WorldWideScience

Sample records for sensitivity 1h-nmr spectroscopy

  1. High sensitivity 1H-NMR spectroscopy of homeopathic remedies made in water

    Science.gov (United States)

    Anick, David J

    2004-01-01

    Background The efficacy of homeopathy is controversial. Homeopathic remedies are made via iterated shaking and dilution, in ethanol or in water, from a starting substance. Remedies of potency 12 C or higher are ultra-dilute (UD), i.e. contain zero molecules of the starting material. Various hypotheses have been advanced to explain how a UD remedy might be different from unprepared solvent. One such hypothesis posits that a remedy contains stable clusters, i.e. localized regions where one or more hydrogen bonds remain fixed on a long time scale. High sensitivity proton nuclear magnetic resonance spectroscopy has not previously been used to look for evidence of differences between UD remedies and controls. Methods Homeopathic remedies made in water were studied via high sensitivity proton nuclear magnetic resonance spectroscopy. A total of 57 remedy samples representing six starting materials and spanning a variety of potencies from 6 C to 10 M were tested along with 46 controls. Results By presaturating on the water peak, signals could be reliably detected that represented H-containing species at concentrations as low as 5 μM. There were 35 positions where a discrete signal was seen in one or more of the 103 spectra, which should theoretically have been absent from the spectrum of pure water. Of these 35, fifteen were identified as machine-generated artifacts, eight were identified as trace levels of organic contaminants, and twelve were unexplained. Of the unexplained signals, six were seen in just one spectrum each. None of the artifacts or unexplained signals occurred more frequently in remedies than in controls, using a p < .05 cutoff. Some commercially prepared samples were found to contain traces of one or more of these small organic molecules: ethanol, acetate, formate, methanol, and acetone. Conclusion No discrete signals suggesting a difference between remedies and controls were seen, via high sensitivity 1H-NMR spectroscopy. The results failed to support

  2. [Rapid analysis of suppositories by quantitative 1H NMR spectroscopy].

    Science.gov (United States)

    Abramovich, R A; Kovaleva, S A; Goriainov, S V; Vorob'ev, A N; Kalabin, G A

    2012-01-01

    Rapid analysis of suppositories with ibuprofen and arbidol by quantitative 1H NMR spectroscopy was performed. Optimal conditions for the analysis were developed. The results are useful for design of rapid methods for quality control of suppositories with different components

  3. 1H NMR spectroscopy-based interventional metabolic phenotyping

    DEFF Research Database (Denmark)

    Lauridsen, Michael B; Bliddal, Henning; Christensen, Robin

    2010-01-01

    1H NMR spectroscopy-based metabolic phenotyping was used to identify biomarkers in the plasma of patients with rheumatoid arthritis (RA). Forty-seven patients with RA (23 with active disease at baseline and 24 in remission) and 51 healthy subjects were evaluated during a one-year follow-up with a......1H NMR spectroscopy-based metabolic phenotyping was used to identify biomarkers in the plasma of patients with rheumatoid arthritis (RA). Forty-seven patients with RA (23 with active disease at baseline and 24 in remission) and 51 healthy subjects were evaluated during a one-year follow......-up with assessments of disease activity (DAS-28) and 1H NMR spectroscopy of plasma samples. Discriminant analysis provided evidence that the metabolic profiles predicted disease severity. Cholesterol, lactate, acetylated glycoprotein, and lipid signatures were found to be candidate biomarkers for disease severity.......0007). However, after 31 days of optimized therapy, the two patient groups were not significantly different (P=0.91). The metabolic profiles of both groups of RA patients were different from the healthy subjects. 1H NMR-based metabolic phenotyping of plasma samples in patients with RA is well suited...

  4. Grape juice quality control by means of {sup 1}H NMR spectroscopy and chemometric analyses

    Energy Technology Data Exchange (ETDEWEB)

    Grandizoli, Caroline Werner Pereira da Silva; Campos, Francinete Ramos; Simonelli, Fabio; Barison, Andersson [Universidade Federal do Paraná (UFPR), Curitiba (Brazil). Departamento de Química

    2014-07-01

    This work shows the application of {sup 1}H NMR spectroscopy and chemometrics for quality control of grape juice. A wide range of quality assurance parameters were assessed by single {sup 1}H NMR experiments acquired directly from juice. The investigation revealed that conditions and time of storage should be revised and indicated on all labels. The sterilization process of homemade grape juices was efficient, making it possible to store them for long periods without additives. Furthermore, chemometric analysis classified the best commercial grape juices to be similar to homemade grape juices, indicating that this approach can be used to determine the authenticity after adulteration. (author)

  5. Structural analysis of the carbohydrate chains of glycoproteins by 500-MHz 1H-NMR spectroscopy

    International Nuclear Information System (INIS)

    Mutsaers, J.H.G.M.

    1986-01-01

    This thesis deals with the structural analysis by 500-MHz 1 H-NMR spectroscopy of carbohydrate chains obtained from glycoproteins. In the chapters 1 to 6 the structural analysis of N-glycosidically linked carbohydrate chains is described. The chapters 7 to 10 describe the structural analysis of O-glycosidically linked carbohydrate chains. 381 refs.; 44 figs.; 24 tabs.; 7 schemes

  6. Interaction of primaquine and chloroquine with ionic micelles: 1 H NMR and electronic absorption spectroscopy

    International Nuclear Information System (INIS)

    Perussi, Janice R.; Monte, Shirley C.; Imasato, Hidetake; Tabak, Marcel; Yushmanov, Victor E.

    1995-01-01

    The characteristic of binding of primaquine (PQ) and chloroquine (CQ) to micelles of surfactants with different charge of headgroups were studied by 1 H-NMR and optical absorption spectroscopy. Cetyltrimethylammonium (CTAC) was used as a cationic surfactant, sodium dodecylsulfate (SDS) as an anionic surfactant and N-hexadecyl-N, N-dimethyl-3-ammonio-1-propanesulfonate (HPS) as zwitterionic. The pK values and binding constants were estimated. (author)

  7. Detection of Apoptosis and Necrosis in Normal Human Lung Cells Using 1H NMR Spectroscopy

    Science.gov (United States)

    Shih, Chwen-Ming; Ko, Wun-Chang; Yang, Liang-Yo; Lin, Chien-Ju; Wu, Jui-Sheng; Lo, Tsui-Yun; Wang, Shwu-Huey; Chen, Chien-Tsu

    2005-05-01

    This study aimed to detect apoptosis and necrosis in MRC-5, a normal human lung cell line, by using noninvasive proton nuclear magnetic resonance (1H NMR). Live MRC-5 cells were processed first for 1H NMR spectroscopy; subsequently their types and the percentage of cell death were assessed on a flow cytometer. Cadmium (Cd) and mercury (Hg) induced apoptosis and necrosis in MRC-5 cells, respectively, as revealed by phosphatidylserine externalization on a flow cytometer. The spectral intensity ratio of methylene (CH2) resonance (at 1.3 ppm) to methyl (CH3) resonance (at 0.9 ppm) was directly proportional to the percentage of apoptosis and strongly and positively correlated with PI staining after Cd treatment (r2 = 0.9868, P In contrast, this ratio only increased slightly within 2-h Hg treatment, and longer Hg exposure failed to produce further increase. Following 2-h Hg exposure, the spectral intensity of choline resonance (at 3.2 ppm) was abolished, but this phenomenon was absent in Cd-induced apoptosis. These findings together demonstrate that 1H NMR is a novel tool with a quantitative potential to distinguish apoptosis from necrosis as early as the onset of cell death in normal human lung cells.

  8. Quantitative 1H-NMR Spectroscopy for Profiling Primary Metabolites in Mulberry Leaves

    Directory of Open Access Journals (Sweden)

    Qianqian Liang

    2018-03-01

    Full Text Available The primary metabolites in aqueous extract of mulberry (Morus alba L. leaves were characterized by using proton nuclear magnetic resonance (1H-NMR spectroscopy. With the convenience of resonance assignment, GABA together with the other 10 primary metabolites was simultaneously identified and quantified in one 1H-NMR spectrum. In this study, external calibration curves for metabolites were employed to calculate the concentrations of interests. The proposed quantitative approach was demonstrated with good linearity (r2 ranged in the interval of 0.9965–0.9999, precision, repeatability, stability (RSD values in the ranges of 0.35–4.89%, 0.77–7.13% and 0.28–2.33%, respectively and accuracy (recovery rates from 89.2% to 118.5%. The established 1H-NMR method was then successfully applied to quantify 11 primary metabolites in mulberry leaves from different geographical regions within a rapid analysis time and a simple sample preparation procedure.

  9. Rapid Determination of Total Thujone in Absinthe Using 1H NMR Spectroscopy

    OpenAIRE

    Yulia B. Monakhova; Thomas Kuballa; Dirk W. Lachenmeier

    2011-01-01

    1H NMR spectroscopy is utilized to quantify total thujone (sum of alpha- and beta-isomers) in absinthe. For sample preparation, a simple dilution with buffer is required. Thujone produces a distinct peak of the CH2 group in the cyclopentanone moiety in the 2.13–2.11 ppm range. No overlap with other typical constituents such as anethole or fenchone occurs. The detection limit of 0.3 mg/L is adequate to control the EU maximum limit. The relative standard deviation was 6%, and linearity was obse...

  10. Pectins from apple pomace - characterization by 13C and 1H NMR spectroscopy

    International Nuclear Information System (INIS)

    Marcon, M.V.; Carneiro, P.I.B.; Wosiacki, G.; Beleski-Carneiro, E.; Petkowicz, C.L.O.

    2005-01-01

    Pectins were extracted from apple pomace flour with 5% (w/v) aqueous citric acid solutions under different time and temperature according to an experimental design (factorial 2 2 with triplicate of central point). Monosaccharide composition of fractions was determined by colorimetric analysis and gas chromatography. The structure of pectins was studied by NMR spectroscopy. The degree of esterification (DE=30.5-55.9), determined by FT-IR spectroscopy, was indirectly correlated with increasing temperature and time of extraction, showing that drastic conditions for extraction promote hydrolysis of esterified units. High content of galacturonic acid is consistent with the smooth region of the polysaccharide. 13 C and 1 H NMR spectroscopy confirmed the presence of uronic acids in the free and methyl ester forms. NMR data also showed the presence of arabinan and galactan as side chains. (author)

  11. Assessment of metabolic phenotypic variability in children’s urine using 1H NMR spectroscopy

    Science.gov (United States)

    Maitre, Léa; Lau, Chung-Ho E.; Vizcaino, Esther; Robinson, Oliver; Casas, Maribel; Siskos, Alexandros P.; Want, Elizabeth J.; Athersuch, Toby; Slama, Remy; Vrijheid, Martine; Keun, Hector C.; Coen, Muireann

    2017-04-01

    The application of metabolic phenotyping in clinical and epidemiological studies is limited by a poor understanding of inter-individual, intra-individual and temporal variability in metabolic phenotypes. Using 1H NMR spectroscopy we characterised short-term variability in urinary metabolites measured from 20 children aged 8-9 years old. Daily spot morning, night-time and pooled (50:50 morning and night-time) urine samples across six days (18 samples per child) were analysed, and 44 metabolites quantified. Intraclass correlation coefficients (ICC) and mixed effect models were applied to assess the reproducibility and biological variance of metabolic phenotypes. Excellent analytical reproducibility and precision was demonstrated for the 1H NMR spectroscopic platform (median CV 7.2%). Pooled samples captured the best inter-individual variability with an ICC of 0.40 (median). Trimethylamine, N-acetyl neuraminic acid, 3-hydroxyisobutyrate, 3-hydroxybutyrate/3-aminoisobutyrate, tyrosine, valine and 3-hydroxyisovalerate exhibited the highest stability with over 50% of variance specific to the child. The pooled sample was shown to capture the most inter-individual variance in the metabolic phenotype, which is of importance for molecular epidemiology study design. A substantial proportion of the variation in the urinary metabolome of children is specific to the individual, underlining the potential of such data to inform clinical and exposome studies conducted early in life.

  12. Authentication of beef versus horse meat using 60 MHz 1H NMR spectroscopy

    Science.gov (United States)

    Jakes, W.; Gerdova, A.; Defernez, M.; Watson, A.D.; McCallum, C.; Limer, E.; Colquhoun, I.J.; Williamson, D.C.; Kemsley, E.K.

    2015-01-01

    This work reports a candidate screening protocol to distinguish beef from horse meat based upon comparison of triglyceride signatures obtained by 60 MHz 1H NMR spectroscopy. Using a simple chloroform-based extraction, we obtained classic low-field triglyceride spectra from typically a 10 min acquisition time. Peak integration was sufficient to differentiate samples of fresh beef (76 extractions) and horse (62 extractions) using Naïve Bayes classification. Principal component analysis gave a two-dimensional “authentic” beef region (p = 0.001) against which further spectra could be compared. This model was challenged using a subset of 23 freeze–thawed training samples. The outcomes indicated that storing samples by freezing does not adversely affect the analysis. Of a further collection of extractions from previously unseen samples, 90/91 beef spectra were classified as authentic, and 16/16 horse spectra as non-authentic. We conclude that 60 MHz 1H NMR represents a feasible high-throughput approach for screening raw meat. PMID:25577043

  13. Authentication of beef versus horse meat using 60 MHz 1H NMR spectroscopy.

    Science.gov (United States)

    Jakes, W; Gerdova, A; Defernez, M; Watson, A D; McCallum, C; Limer, E; Colquhoun, I J; Williamson, D C; Kemsley, E K

    2015-05-15

    This work reports a candidate screening protocol to distinguish beef from horse meat based upon comparison of triglyceride signatures obtained by 60 MHz (1)H NMR spectroscopy. Using a simple chloroform-based extraction, we obtained classic low-field triglyceride spectra from typically a 10 min acquisition time. Peak integration was sufficient to differentiate samples of fresh beef (76 extractions) and horse (62 extractions) using Naïve Bayes classification. Principal component analysis gave a two-dimensional "authentic" beef region (p=0.001) against which further spectra could be compared. This model was challenged using a subset of 23 freeze-thawed training samples. The outcomes indicated that storing samples by freezing does not adversely affect the analysis. Of a further collection of extractions from previously unseen samples, 90/91 beef spectra were classified as authentic, and 16/16 horse spectra as non-authentic. We conclude that 60 MHz (1)H NMR represents a feasible high-throughput approach for screening raw meat. Copyright © 2014 The Authors. Published by Elsevier Ltd.. All rights reserved.

  14. Determination of rate constants of N-alkylation of primary amines by 1H NMR spectroscopy.

    Science.gov (United States)

    Li, Chenghong

    2013-09-05

    Macromolecules containing N-diazeniumdiolates of secondary amines are proposed scaffolds for controlled nitrogen oxide (NO) release medical applications. Preparation of these compounds often involves converting primary amine groups to secondary amine groups through N-alkylation. However, N-alkylation results in not only secondary amines but tertiary amines as well. Only N-diazeniumdiolates of secondary amines are suitable for controlled NO release; therefore, the yield of secondary amines is crucial to the total NO load of the carrier. In this paper, (1)H NMR spectroscopy was used to estimate the rate constants for formation of secondary amine (k1) and tertiary amine (k2) for alkylation reagents such as propylene oxide (PO), methyl acrylate (MA), and acrylonitrile (ACN). At room temperature, the ratio of k2/k1 for the three reactions was found to be around 0.50, 0.026, and 0.0072.

  15. Chemically Methylated and Reduced Pectins: Preparation and Characterisation by 1H-NMR Spectroscopy, Enzymatic Degradation and Gelling Properties

    DEFF Research Database (Denmark)

    Rosenbohm, Christoph; Lundt, Inge; Christensen, T.M.I.E.

    2003-01-01

    with lower DM. A simple method for determination of DM by 1H-NMR spectroscopy is presented. New modified pectins have been prepared by treatment of pectins having different DM’s with NaBH4 to reduce selectively the methyl esters to primary alcohols in the presence of free acids. The degree of reduction (DR......) and the DM of the remaining carboxylic acids could likewise be determined by 1H-NMR spectroscopy. The new reduced pectins can be tolerated by the pectin degrading enzymes polygalacturonase PGI and PGII as well as by pectin lyase, all from Aspergillus niger, but the enzymes exhibit lower specific activities...

  16. Structure determination of the single glycan of rabbit serotransferrin by methylation analysis and 360 MHz /sup 1/H NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Leger, D; Tordera, V; Spik, G [Lille-1 Univ., 59 - Villeneuve-d' Ascq (France); Dorland, L; Haverkamp, J; Vliegenthart, J F.G. [Rijksuniversiteit Utrecht (Netherlands)

    1978-09-15

    The glycopeptide fraction of rabbit serotransferrin (STF) has been investigated applying an original method for the determination of glycan primary structure combining monosaccharide determination, permethylation and 360 MHz /sup 1/H NMR. It is concluded that the highly purified rabbit transferrin contains only 1 glycan chain/molecule. A heterogeneity of the glycan moiety in the sialic acid residues was observed on isolation by paper electrophoresis of a disialylglycopeptide G-1 and a monosialylglycopeptide 2. The primary structure of glycopeptide G-1 deduced on the basis of the data of carbohydrate composition, permethylation analysis and 360 MHz /sup 1/H NMR spectroscopy is identical to the primary structure of human serotransferrin glycan and the glycopeptide G-2 was shown by /sup 1/H NMR spectroscopy, to be a mixture of two isomeric monosialylglycopeptides.

  17. Structure determination of the single glycan of rabbit serotransferrin by methylation analysis and 360 MHz 1H NMR spectroscopy

    International Nuclear Information System (INIS)

    Leger, D.; Tordera, V.; Spik, G.; Dorland, L.; Haverkamp, J.; Vliegenthart, J.F.G.

    1978-01-01

    The glycopeptide fraction of rabbit serotransferrin (STF) has been investigated applying an original method for the determination of glycan primary structure combining monosaccharide determination, permethylation and 360 MHz 1 H NMR. It is concluded that the highly purified rabbit transferrin contains only 1 glycan chain/molecule. A heterogeneity of the glycan moiety in the sialic acid residues was observed on isolation by paper electrophoresis of a disialylglycopeptide G-1 and a monosialylglycopeptide 2. The primary structure of glycopeptide G-1 deduced on the basis of the data of carbohydrate composition, permethylation analysis and 360 MHz 1 H NMR spectroscopy is identical to the primary structure of human serotransferrin glycan and the glycopeptide G-2 was shown by 1 H NMR spectroscopy, to be a mixture of two isomeric monosialylglycopeptides. (Auth.)

  18. Secondary structure determination of human. beta. -endorphin by /sup 1/H NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Lichtarge, O.; Jardetzky, O.; Li, C.H.

    1987-09-08

    The /sup 1/H NMR spectra of human ..beta..-endorphin indicate that the peptide exists in random-coil form in aqueous solution but becomes helical in mixed solvent. Thermal denaturation NMR experiments show that in water there is no transition between 24 and 75/sup 0/C, while a slow noncooperative thermal unfolding is observed in a 60% methanol-40% water mixed solvent in the same temperature range. These findings are consistent with circular dichroism studies by other workers concluding that ..beta..-endorphin is a random coil in water but that it forms 50% ..cap alpha..-helix or more in mixed solvents. The peptide in the mixed water-methanol solvent was further studied by correlated spectroscopy (COSY) and nuclear Overhauser effect spectroscopy (NOESY) experiments. These allow a complete set of assignments to be made and establish two distinct stretches over which the solvent induces formation of ..cap alpha..-helices: the first occurs between Tyr-1 and Thr-12 and the second between Leu-14 and extending to Lys-28. There is evidence that the latter is capped by a turn occurring between Lys-28 and Glu-31. These helices form at the enkephalin receptor binding site, which is at the amino terminus, and at the morphine receptor binding site, located at the carboxyl terminus. The findings suggest that these two receptors may specifically recognize ..cap alpha..-helices.

  19. Chemical exchange in novel spirobicyclic zwitterionic Janovsky complexes using dynamic 1H NMR spectroscopy.

    Science.gov (United States)

    Culf, A S; Cuperlović-Culf, M; Ouellette, R J

    2009-02-01

    Highly coloured Janovsky complexes have been known for over 120 years, being used in many colourimetric analytical procedures. In this present study, two novel and stable nitrocyclohexadienyl spirobicyclic, zwitterionic Janovsky anionic hydantoin sigma-complexes, rac-1,3-diisopropyl-6-nitro-2,4-dioxo-1,3-diazaspiro[4.5]deca-6,9-dien-8-ylideneazinate, ammonium internal salt (1) and 1,3-diisopropyl-2,4-dioxo-1,3-diazaspiro[4.5]deca-6,9-dien-8-ylideneazinate, ammonium internal salt (2) have been prepared and characterised by NMR, electrospray ionization mass spectrometry (ESI-MS) and UV/visible methods. For the p-mononitro-substituted complex (2), we discovered chemical exchange behaviour using 1D saturation transfer and 2D exchange spectroscopy (EXSY) (1)H NMR techniques. The coalescence temperature was determined to be 62 degrees C in d(3)-acetonitrile. Analysis of these data provided a Gibbs free energy of activation, DeltaG double dagger, of + 67 kJ mole(-1), a rate constant, k, coalescence of 220 Hz and an equilibrium constant, K(eqm), of 0.98 as estimates of the exchange process in this solvent. Of the two mechanisms proposed for this fluxional behaviour, ring opening to a substituted benzene or proton exchange, a further theoretical modelling study of 1D (1)H NMR spectra was able to confirm that simple proton exchange between the two nitrogen sites of the hydantoin ring provided an accurate simulation of the observed experimental evidence. Interestingly, the o,p-dinitro-substituted complex (1) did not show any chemical exchange behaviour up to 150 degrees C in d(3)-acetonitrile (to 75 degrees C) and d(6)-dimethyl sulfoxide (DMSO). Molecular modelling at the MM2 level suggests that steric collisions of an N-acyl isopropyl substituent of the hydantoin ring with the ortho-nitro group of the spirofused cyclohexadienyl ring prevents the proposed proton exchange mechanism occurring in this case. 2008 Crown in the right of Canada. Published by John Wiley & Sons, Ltd.

  20. Analysis of the hydrolysis of inulin using real time 1H NMR spectroscopy

    Science.gov (United States)

    Barclay, Thomas; Ginic-Markovic, Milena; Johnston, Martin R.; Cooper, Peter D.; Petrovsky, Nikolai

    2012-01-01

    The hydrolysis of various carbohydrates was investigated under acidic conditions in real time by 1H NMR spectroscopy, with a focus on the polysaccharide inulin. Sucrose was used as a model compound to illustrate the applicability of this technique. The hydrolysis of sucrose was shown to follow pseudo first order kinetics and have an activation energy of 107.0 kJ.mol−1 (s.d. 1.7 kJ.mol−1). Inulin, pullulan and glycogen also all followed pseudo first order kinetics, but had an initiation phase at least partially generated by the protonation of the glycosidic bonds. It was also demonstrated that polysaccharide chain length has an effect on the hydrolysis of inulin. For short chain inulin (DPn 18, s.d. 0.70) the activation energy calculated for the hydrolytic cleavage of glucose was similar to sucrose at 108.5 kJ.mol−1 (std. dev. 0.60). For long chain inulin (DPn 30, s.d. 1.3) the activation energy for the hydrolytic cleavage of glucose was reduced to 80.5 kJ.mol−1 (s.d. 2.3 kJ.mol−1). This anomaly has been attributed to varied conformations for the two different lengths of inulin chain in solution. PMID:22464225

  1. 1H NMR Spectroscopy and MVA Analysis of Diplodus sargus Eating the Exotic Pest Caulerpa cylindracea.

    Science.gov (United States)

    De Pascali, Sandra A; Del Coco, Laura; Felline, Serena; Mollo, Ernesto; Terlizzi, Antonio; Fanizzi, Francesco P

    2015-06-05

    The green alga Caulerpa cylindracea is a non-autochthonous and invasive species that is severely affecting the native communities in the Mediterranean Sea. Recent researches show that the native edible fish Diplodus sargus actively feeds on this alga and cellular and physiological alterations have been related to the novel alimentary habits. The complex effects of such a trophic exposure to the invasive pest are still poorly understood. Here we report on the metabolic profiles of plasma from D. sargus individuals exposed to C. cylindracea along the southern Italian coast, using 1H NMR spectroscopy and multivariate analysis (Principal Component Analysis, PCA, Orthogonal Partial Least Square, PLS, and Orthogonal Partial Least Square Discriminant Analysis, OPLS-DA). Fish were sampled in two seasonal periods from three different locations, each characterized by a different degree of algal abundance. The levels of the algal bisindole alkaloid caulerpin, which is accumulated in the fish tissues, was used as an indicator of the trophic exposure to the seaweed and related to the plasma metabolic profiles. The profiles appeared clearly influenced by the sampling period beside the content of caulerpin, while the analyses also supported a moderate alteration of lipid and choline metabolism related to the Caulerpa-based diet.

  2. Rapid Determination of Total Thujone in Absinthe Using 1H NMR Spectroscopy

    Directory of Open Access Journals (Sweden)

    Yulia B. Monakhova

    2011-01-01

    Full Text Available 1H NMR spectroscopy is utilized to quantify total thujone (sum of α- and β-isomers in absinthe. For sample preparation, a simple dilution with buffer is required. Thujone produces a distinct peak of the CH2 group in the cyclopentanone moiety in the 2.13–2.11 ppm range. No overlap with other typical constituents such as anethole or fenchone occurs. The detection limit of 0.3 mg/L is adequate to control the EU maximum limit. The relative standard deviation was 6%, and linearity was observed from 1 to 100 mg/L. Applicability was proven by analysis of 69 authentic absinthes. The correlation between NMR and our previous method consisting of liquid-liquid extraction followed by GC/MS was significant (P<0.0001,R=0.93. The simple and cheap NMR method can be used for rapid screening of absinthes for total thujone content while chromatographic techniques are recommended for more specific (α- and β-thujone isomers analysis if required.

  3. Determination of the intracellular pH of intact erythrocytes by 1H NMR spectroscopy

    International Nuclear Information System (INIS)

    Rabenstein, D.L.; Isab, A.A.

    1982-01-01

    A method is described for determining the intracellular pH of intact erythrocytes by 1 H NMR. The determination is based on the pH dependence of the chemical shifts of resonances for carbon-bounded protons of an indicator molecule (imidazole) in intact cells. The imidazole is introduced into the erythrocytes by incubation in an isotonic saline solution of the indicator. The pH dependence of the chemical shifts of the imidazole resonances is calibrated from 1 H NMR spectra of the imidazole-containing red cell lysates whose pH is varied by the addition of acid or base and measured directly with a pH electrode. To reduce in intensity or eliminate the much more intense envelope of resonances from the hemoglobin, the 1 H NMR measurements are made by either the spin-echo Fourier transform technique or by the transfer-or-saturation by cross-relaxation method

  4. Predicting Fuel Ignition Quality Using 1H NMR Spectroscopy and Multiple Linear Regression

    KAUST Repository

    Abdul Jameel, Abdul Gani

    2016-09-14

    An improved model for the prediction of ignition quality of hydrocarbon fuels has been developed using 1H nuclear magnetic resonance (NMR) spectroscopy and multiple linear regression (MLR) modeling. Cetane number (CN) and derived cetane number (DCN) of 71 pure hydrocarbons and 54 hydrocarbon blends were utilized as a data set to study the relationship between ignition quality and molecular structure. CN and DCN are functional equivalents and collectively referred to as D/CN, herein. The effect of molecular weight and weight percent of structural parameters such as paraffinic CH3 groups, paraffinic CH2 groups, paraffinic CH groups, olefinic CH–CH2 groups, naphthenic CH–CH2 groups, and aromatic C–CH groups on D/CN was studied. A particular emphasis on the effect of branching (i.e., methyl substitution) on the D/CN was studied, and a new parameter denoted as the branching index (BI) was introduced to quantify this effect. A new formula was developed to calculate the BI of hydrocarbon fuels using 1H NMR spectroscopy. Multiple linear regression (MLR) modeling was used to develop an empirical relationship between D/CN and the eight structural parameters. This was then used to predict the DCN of many hydrocarbon fuels. The developed model has a high correlation coefficient (R2 = 0.97) and was validated with experimentally measured DCN of twenty-two real fuel mixtures (e.g., gasolines and diesels) and fifty-nine blends of known composition, and the predicted values matched well with the experimental data.

  5. Quantitative Analysis of Chemically Modified Starches by 1H-NMR Spectroscopy

    NARCIS (Netherlands)

    Graaf, R.A. de; Lammers, G.; Janssen, L.P.B.M.; Beenackers, A.A.C.M.

    1995-01-01

    A quantitative 1H-NMR method for the determination of the Molar Substitution (MS) of acetylated and hydroxypropylated starches was developed and tested for MS ranging from 0.09 to 0.5. Results were checked using the Johnson method and a titration method for hydroxypropylated and acetylated starch,

  6. Metabolic profiling of human lung cancer blood plasma using 1H NMR spectroscopy

    Science.gov (United States)

    Kokova, Daria; Dementeva, Natalia; Kotelnikov, Oleg; Ponomaryova, Anastasia; Cherdyntseva, Nadezhda; Kzhyshkowska, Juliya

    2017-11-01

    Lung cancer (both small cell and non-small cell) is the second most common cancer in both men and women. The article represents results of evaluating of the plasma metabolic profiles of 100 lung cancer patients and 100 controls to investigate significant metabolites using 400 MHz 1H NMR spectrometer. The results of multivariate statistical analysis show that a medium-field NMR spectrometer can obtain the data which are already sufficient for clinical metabolomics.

  7. Interlaboratory Comparison Test as an Evaluation of Applicability of an Alternative Edible Oil Analysis by 1H NMR Spectroscopy.

    Science.gov (United States)

    Zailer, Elina; Holzgrabe, Ulrike; Diehl, Bernd W K

    2017-11-01

    A proton (1H) NMR spectroscopic method was established for the quality assessment of vegetable oils. To date, several research studies have been published demonstrating the high potential of the NMR technique in lipid analysis. An interlaboratory comparison was organized with the following main objectives: (1) to evaluate an alternative analysis of edible oils by using 1H NMR spectroscopy; and (2) to determine the robustness and reproducibility of the method. Five different edible oil samples were analyzed by evaluating 15 signals (free fatty acids, peroxides, aldehydes, double bonds, and linoleic and linolenic acids) in each spectrum. A total of 21 NMR data sets were obtained from 17 international participant laboratories. The performance of each laboratory was assessed by their z-scores. The test was successfully passed by 90.5% of the participants. Results showed that NMR spectroscopy is a robust alternative method for edible oil analysis.

  8. Metabolic profiling of lymph from pigs fed with ß-glucan by high-resolution 1H NMR spectroscopy

    DEFF Research Database (Denmark)

    Larsen, Flemming Hofmann; Jørgensen, Henry Johs. Høgh; Engelsen, Søren Balling

    2010-01-01

    To gain information about the effect of ingesting different β-glucan sources on intestinal lymph metabolic profile, 10 growing pigs (30-36 kg) were fitted with a catheter in the jejunal lymphatic trunk, and lymph samples collected continuously -1 to 8 h postprandial and again at 24 h after feeding...... a diet containing either 0.4% added yeast or barley β-glucan and compared to a Control diet. The lymph samples were analysed by proton nuclear magnetic resonance (1H NMR) spectroscopy and subsequently subjected to chemometric analysis. The dominant resonances in the 1H NMR spectra of lymph arose...... of increased lymph viscosity induced by barley β-glucan compared to yeast β-glucan were observed...

  9. Thermal heterogeneity within aqueous materials quantified by 1H NMR spectroscopy: Multiparametric validation in silico and in vitro

    Science.gov (United States)

    Lutz, Norbert W.; Bernard, Monique

    2018-02-01

    We recently suggested a new paradigm for statistical analysis of thermal heterogeneity in (semi-)aqueous materials by 1H NMR spectroscopy, using water as a temperature probe. Here, we present a comprehensive in silico and in vitro validation that demonstrates the ability of this new technique to provide accurate quantitative parameters characterizing the statistical distribution of temperature values in a volume of (semi-)aqueous matter. First, line shape parameters of numerically simulated water 1H NMR spectra are systematically varied to study a range of mathematically well-defined temperature distributions. Then, corresponding models based on measured 1H NMR spectra of agarose gel are analyzed. In addition, dedicated samples based on hydrogels or biological tissue are designed to produce temperature gradients changing over time, and dynamic NMR spectroscopy is employed to analyze the resulting temperature profiles at sub-second temporal resolution. Accuracy and consistency of the previously introduced statistical descriptors of temperature heterogeneity are determined: weighted median and mean temperature, standard deviation, temperature range, temperature mode(s), kurtosis, skewness, entropy, and relative areas under temperature curves. Potential and limitations of this method for quantitative analysis of thermal heterogeneity in (semi-)aqueous materials are discussed in view of prospective applications in materials science as well as biology and medicine.

  10. Intermolecular Interactions between Eosin Y and Caffeine Using 1H-NMR Spectroscopy

    Directory of Open Access Journals (Sweden)

    Macduff O. Okuom

    2013-01-01

    Full Text Available DETECHIP has been used in testing analytes including caffeine, cocaine, and tetrahydrocannabinol (THC from marijuana, as well as date rape and club drugs such as flunitrazepam, gamma-hydroxybutyric acid (GHB, and methamphetamine. This study investigates the intermolecular interaction between DETECHIP sensor eosin Y (DC1 and the analyte (caffeine that is responsible for the fluorescence and color changes observed in the actual array. Using 1H-NMR, 1H-COSY, and 1H-DOSY NMR methods, a proton exchange from C-8 of caffeine to eosin Y is proposed.

  11. Quality assurance in the pre-analytical phase of human urine samples by (1)H NMR spectroscopy.

    Science.gov (United States)

    Budde, Kathrin; Gök, Ömer-Necmi; Pietzner, Maik; Meisinger, Christine; Leitzmann, Michael; Nauck, Matthias; Köttgen, Anna; Friedrich, Nele

    2016-01-01

    Metabolomic approaches investigate changes in metabolite profiles, which may reflect changes in metabolic pathways and provide information correlated with a specific biological process or pathophysiology. High-resolution (1)H NMR spectroscopy is used to identify metabolites in biofluids and tissue samples qualitatively and quantitatively. This pre-analytical study evaluated the effects of storage time and temperature on (1)H NMR spectra from human urine in two settings. Firstly, to evaluate short time effects probably due to acute delay in sample handling and secondly, the effect of prolonged storage up to one month to find markers of sample miss-handling. A number of statistical procedures were used to assess the differences between samples stored under different conditions, including Projection to Latent Structure Discriminant Analysis (PLS-DA), non-parametric testing as well as mixed effect linear regression analysis. The results indicate that human urine samples can be stored at 10 °C for 24 h or at -80 °C for 1 month, as no relevant changes in (1)H NMR fingerprints were observed during these time periods and temperature conditions. However, some metabolites most likely of microbial origin showed alterations during prolonged storage but without facilitating classification. In conclusion, the presented protocol for urine sample handling and semi-automatic metabolite quantification is suitable for large-scale epidemiological studies. Copyright © 2015 Elsevier Inc. All rights reserved.

  12. Sequence-specific 1H NMR assignments and secondary structure of the Arc repressor of bacteriophage P22, as determined by two-dimensional 1H NMR spectroscopy

    International Nuclear Information System (INIS)

    Breg, J.N.; Boelens, R.; George, A.V.E.; Kaptein, R.

    1989-01-01

    The Arc repressor of bacteriophage P22 is a DNA binding protein that does not belong to any of the known classes of such proteins. The authors have undertaken a 1 H NMR study of the protein with the aim of elucidating its three-dimensional structure in solution and its mode of binding of operator DNA. Here the authors present the 1 H nuclear magnetic resonance (NMR) assignments of all backbone protons an most of the side-chain protons of Arc repressor. Elements of secondary structure have been identified on the basis of networks of characteristics sequential and medium-range nuclear Overhauser enhancements (NOEs). Two α-helical regions have been found in the peptide regions 16-29 and 35-45. The ends of the helices could not yet be firmly established and could extend to residue 31 for the first helix and to residue 49 for the second. Immediately before the first helix, between residues 8 and 14, a region is present with β-sheet characteristics dominated by a close proximity of the α-protons of residues 9 and 13. Because of the dimeric nature of the protein there are still two possible ways in which the NOEs in the β-sheet region can be interpreted. While the data presently do not allow an unambiguous choice between these two possibilities, some evidence is discussed that favors the latter (β-sheet between monomers). Since the N-terminal region of Arc is responsible for the sequence-specific recognition of its operator, the findings suggest the existence of a DNA binding motif in which a β-sheet region is present

  13. Metabolic profiling studies on the toxicological effects of realgar in rats by 1H NMR spectroscopy

    International Nuclear Information System (INIS)

    Wei Lai; Liao Peiqiu; Wu Huifeng; Li Xiaojing; Pei Fengkui; Li Weisheng; Wu Yijie

    2009-01-01

    The toxicological effects of realgar after intragastrical administration (1 g/kg body weight) were investigated over a 21 day period in male Wistar rats using metabonomic analysis of 1 H NMR spectra of urine, serum and liver tissue aqueous extracts. Liver and kidney histopathology examination and serum clinical chemistry analyses were also performed. 1 H NMR spectra and pattern recognition analyses from realgar treated animals showed increased excretion of urinary Kreb's cycle intermediates, increased levels of ketone bodies in urine and serum, and decreased levels of hepatic glucose and glycogen, as well as hypoglycemia and hyperlipoidemia, suggesting the perturbation of energy metabolism. Elevated levels of choline containing metabolites and betaine in serum and liver tissue aqueous extracts and increased serum creatine indicated altered transmethylation. Decreased urinary levels of trimethylamine-N-oxide, phenylacetylglycine and hippurate suggested the effects on the gut microflora environment by realgar. Signs of impairment of amino acid metabolism were supported by increased hepatic glutamate levels, increased methionine and decreased alanine levels in serum, and hypertaurinuria. The observed increase in glutathione in liver tissue aqueous extracts could be a biomarker of realgar induced oxidative injury. Serum clinical chemistry analyses showed increased levels of lactate dehydrogenase, aspartate aminotransferase, and alkaline phosphatase as well as increased levels of blood urea nitrogen and creatinine, indicating slight liver and kidney injury. The time-dependent biochemical variations induced by realgar were achieved using pattern recognition methods. This work illustrated the high reliability of NMR-based metabonomic approach on the study of the biochemical effects induced by traditional Chinese medicine

  14. Metabolic characterization of natural and cultured Ophicordyceps sinensis from different origins by 1H NMR spectroscopy.

    Science.gov (United States)

    Zhang, Jianshuang; Zhong, Xin; Li, Shaosong; Zhang, Guren; Liu, Xin

    2015-11-10

    Ophicordyceps sinensis is a well-known traditional Chinese medicine and cultured mycelium is a substitute for wild O. sinensis. Metabolic profiles of wild O. sinensis from three geographical locations and cultivated mycelia derived from three origins were investigated using (1)H nuclear magnetic resonance (NMR) analysis combined with multivariate statistical analysis. A total of 56 primary metabolites were identified and quantified from O. sinensis samples. The principle component analysis (PCA) showed significant differences between natural O. sinensis and fermentation mycelia. Seven metabolites responsible for differentiation were screened out by orthogonal partial least squares discriminant analysis (OPLS-DA). The concentrations of mannitol, trehalose, arginine, trans-4-hydroxyproline, alanine and glucitol were significantly different between wild and cultured groups. The variation in metabolic profiling among artificial mycelia was greater than that among wild O. sinensis. Furthermore, wild samples from different origins were clearly distinguished by the levels of mannitol, trehalose and some amino acids. This study indicates that (1)H NMR-based metabolomics is useful for fingerprinting and discriminating O. sinensis of different geographical regions and cultivated mycelia of different strains. The present study provided an efficient approach for investigating chemical compositions and evaluating the quality of medicine and health food derived from O. sinensis. Copyright © 2015 Elsevier B.V. All rights reserved.

  15. Experimental and analytical variation in human urine in 1H NMR spectroscopy-based metabolic phenotyping studies.

    Science.gov (United States)

    Maher, Anthony D; Zirah, Séverine F M; Holmes, Elaine; Nicholson, Jeremy K

    2007-07-15

    1H NMR spectroscopy potentially provides a robust approach for high-throughput metabolic screening of biofluids such as urine and plasma, but sample handling and preparation need careful optimization to ensure that spectra accurately report biological status or disease state. We have investigated the effects of storage temperature and time on the 1H NMR spectral profiles of human urine from two participants, collected three times a day on four different days. These were analyzed using modern chemometric methods. Analytical and preparation variation (tested between -40 degrees C and room temperature) and time of storage (to 24 h) were found to be much less influential than biological variation in sample classification. Statistical total correlation spectroscopy and discriminant function methods were used to identify the specific metabolites that were hypervariable due to preparation and biology. Significant intraindividual variation in metabolite profiles were observed even for urine collected on the same day and after at least 6 h fasting. The effect of long-term storage at different temperatures was also investigated, showing urine is stable if frozen for at least 3 months and that storage at room temperature for long periods (1-3 months) results in a metabolic profile explained by bacterial activity. Presampling (e.g., previous day) intake of food and medicine can also strongly influence the urinary metabolic profiles indicating that collective detailed participant historical meta data are important for interpretation of metabolic phenotypes and for avoiding false biomarker discovery.

  16. Characterization of the serum metabolic profile of dairy cows with milk fever using 1H-NMR spectroscopy.

    Science.gov (United States)

    Sun, Yuhang; Xu, Chuchu; Li, Changsheng; Xia, Cheng; Xu, Chuang; Wu, Ling; Zhang, Hongyou

    2014-01-01

    Milk fever (MF) is a common calcium metabolism disorder in perinatal cows. Currently, information regarding the detailed metabolism in cows suffering from MF is scant. The purpose was to study the metabolic profiling of serum samples from cows with MF in comparison to control cows, and thereby exploring other underlying pathological mechanisms of this disease. In the current study, we compared the serum metabolomic profile of dairy cows with MF (n = 8) to that of healthy dairy cows (n = 24) using a 500-MHz digital (1)H-nuclear magnetic resonance ((1)H-NMR) spectrometer. Based on their clinical presentation and serum calcium concentration, cows were assigned either to the control group (no MF symptoms and serum calcium concentration >2.5 mmol/L) or to the MF group (MF symptoms and serum calcium concentration cows with MF. Most of these were carbohydrates and amino acids involved in various energy metabolism pathways. The different metabolites in cows with MF reflected the pathological features of negative energy balance and fat mobilization, suggesting that MF is associated with altered energy metabolism. The (1)H-NMR spectroscopy can be used to understand the pathogenesis of MF and identify biomarkers of the disease.

  17. Metabolic Characterization of Peripheral Host Responses to Drainage-Resistant Klebsiella pneumoniae Liver Abscesses by Serum 1H-NMR Spectroscopy

    Directory of Open Access Journals (Sweden)

    Zhihui Chang

    2018-06-01

    Full Text Available Purpose: To explore the metabolic characterization of host responses to drainage-resistant Klebsiella pneumoniae liver abscesses (DRKPLAs with serum 1H-nuclear magnetic resonance (NMR spectroscopy.Materials and Methods: The hospital records of all patients with a diagnosis of a liver abscess between June 2015 and December 2016 were retrieved from an electronic hospital database. Eighty-six patients with Klebsiella pneumoniae (K. pneumoniae liver abscesses who underwent percutaneous drainage were identified. Twenty patients with confirmed DRKPLAs were studied. Moreover, we identified 20 consecutive patients with drainage-sensitive Klebsiella pneumoniae liver abscesses (DSKPLAs as controls. Serum samples from the two groups were analyzed with 1H NMR spectroscopy. Partial least squares discriminant analysis (PLS-DA was used to perform 1H NMR metabolic profiling. Metabolites were identified using the Human Metabolome Database, and pathway analysis was performed with MetaboAnalyst 3.0.Results: The PLS-DA test was able to discriminate between the two groups. Five key metabolites that contributed to their discrimination were identified. Glucose, lactate, and 3-hydroxybutyrate were found to be upregulated in DRKPLAs, whereas glutamine and alanine were downregulated compared with the DSKPLAs. Pathway analysis indicated that amino acid metabolisms were significantly different between the DRKPLAs and the DSKPLAs. The D-glutamine and D-glutamate metabolisms exhibited the greatest influences.Conclusions: The five key metabolites identified in our study may be potential targets for guiding novel therapeutics of DRKPLAs and are worthy of additional investigation.

  18. Predicting Fuel Ignition Quality Using 1H NMR Spectroscopy and Multiple Linear Regression

    KAUST Repository

    Abdul Jameel, Abdul Gani; Naser, Nimal; Emwas, Abdul-Hamid M.; Dooley, Stephen; Sarathy, Mani

    2016-01-01

    An improved model for the prediction of ignition quality of hydrocarbon fuels has been developed using 1H nuclear magnetic resonance (NMR) spectroscopy and multiple linear regression (MLR) modeling. Cetane number (CN) and derived cetane number (DCN

  19. Association between the metabolome and low bone mineral density in Taiwanese women determined by (1)H NMR spectroscopy.

    Science.gov (United States)

    You, Ying-Shu; Lin, Ching-Yu; Liang, Hao-Jan; Lee, Shen-Hung; Tsai, Keh-Sung; Chiou, Jeng-Min; Chen, Yen-Ching; Tsao, Chwen-Keng; Chen, Jen-Hau

    2014-01-01

    Osteoporosis is related to the alteration of specific circulating metabolites. However, previous studies on only a few metabolites inadequately explain the pathogenesis of this complex syndrome. To date, no study has related the metabolome to bone mineral density (BMD), which would provide an overview of metabolism status and may be useful in clinical practice. This cross-sectional study involved 601 healthy Taiwanese women aged 40 to 55 years recruited from MJ Health Management Institution between 2009 and 2010. Participants were classified according to high (2nd tertile plus 3rd tertile) and low (1st tertile) BMD groups. The plasma metabolome was evaluated by proton nuclear magnetic resonance spectroscopy ((1) H NMR). Principal components analysis (PCA), partial least-squares discriminant analysis (PLS-DA), and logistic regression analysis were used to assess the association between the metabolome and BMD. The high and low BMD groups could be differentiated by PLS-DA but not PCA in postmenopausal women (Q(2)  = 0.05, ppermutation  = 0.04). Among postmenopausal women, elevated glutamine was significantly associated with low BMD (adjusted odds ratio [AOR] = 5.10); meanwhile, elevated lactate (AOR = 0.55), acetone (AOR = 0.51), lipids (AOR = 0.04), and very low-density lipoprotein (AOR = 0.49) protected against low BMD. To the best of our knowledge, this study is the first to identify a group of metabolites for characterizing low BMD in postmenopausal women using a (1) H NMR-based metabolomic approach. The metabolic profile may be useful for predicting the risk of osteoporosis in postmenopausal women at an early age. © 2014 American Society for Bone and Mineral Research.

  20. 1H NMR Spectroscopy and Multivariate Analysis of Monovarietal EVOOs as a Tool for Modulating Coratina-Based Blends

    Directory of Open Access Journals (Sweden)

    Laura Del Coco

    2014-04-01

    Full Text Available Coratina cultivar-based olives are very common among 100% Italian extra virgin olive oils (EVOOs. Often, the very spicy character of this cultivar, mostly due to the high polyphenols concentration, requires blending with other “sweetener” oils. In this work, monovarietal EVOO samples from the Coratina cultivar (Apulia, Italy were investigated and compared with monovarietal EVOO from native or recently introduced Apulian (Italy cultivars (Ogliarola Garganica, Ogliarola Barese, Cima di Mola, Peranzana, Picholine, from Calabria (Italy (Carolea and Rossanese and from other Mediterranean countries, such as Spain (Picual and Greece (Kalamata and Koroneiki by 1H NMR spectroscopy and multivariate analysis (principal component analysis (PCA. In this regard, NMR signals could allow a first qualitative evaluation of the chemical composition of EVOO and, in particular, of its minor component content (phenols and aldehydes, an intrinsic behavior of EVOO taste, related to the cultivar and geographical origins. Moreover, this study offers an opportunity to address blended EVOOs tastes by using oils from a specific region or country of origin.

  1. [superscript 1]H NMR Spectroscopy-Based Configurational Analysis of Mono- and Disaccharides and Detection of ß-Glucosidase Activity: An Undergraduate Biochemistry Laboratory

    Science.gov (United States)

    Periyannan, Gopal R.; Lawrence, Barbara A.; Egan, Annie E.

    2015-01-01

    A [superscript 1]H NMR spectroscopy-based laboratory experiment explores mono- and disaccharide structural chemistry, and the enzyme-substrate specificity of glycosidic bond cleavage by ß-glucosidase towards cellobiose (ß-linked gluco-disaccharide) and maltose (a-linked gluco-disaccharide). Structural differences between cellobiose, maltose, and…

  2. Fraction of free-base nicotine in fresh smoke particulate matter from the Eclipse "cigarette" by 1H NMR spectroscopy.

    Science.gov (United States)

    Pankow, James F; Barsanti, Kelley C; Peyton, David H

    2003-01-01

    Solution 1H NMR (proton-NMR) spectroscopy was used to measure the distribution of nicotine between its free-base and protonated forms at 20 degrees C in (a) water; (b) glycerin/water mixtures; and (c) puff-averaged "smoke" particulate matter (PM) produced by the Eclipse cigarette, a so-called "harm reduction" cigarette manufactured by R. J. Reynolds (RJR) Tobacco Co. Smoke PM from the Eclipse contains glycerin, water, nicotine, and numerous other components. Smoke PM from the Eclipse yielded a signal for the three N-methyl protons on nicotine at a chemical shift of delta (ppm) = 2.79 relative to a trimethylsilane standard. With alpha fb = fraction of the total liquid nicotine in free-base form, and alpha a = fraction in the acidic, monoprotonated NicH+ form, then alpha a + alpha fb approximately 1. (The diprotonated form of nicotine was assumed negligible.) When the three types of solutions were adjusted so that alpha a approximately 1, the N-methyl protons yielded delta a = 2.82 (Eclipse smoke PM); 2.79 (35% water/65% glycerin); and 2.74 (water). When the solutions were adjusted so that alpha fb approximately 1, the N-methyl protons yielded delta fb = 2.16 (Eclipse smoke PM); 2.13 (35% water/65% glycerin); and 2.10 (water). In all of the solutions, the rate of proton exchange between NicH+ and Nic was fast relative to the 1H-NMR chemical shift difference in hertz. Each solution containing both NicH+ and Nic thus yielded a single N-methyl peak at a delta given by delta = alpha a delta a + alpha fb delta fb so that delta varied linearly between delta a and delta fb. Since alpha fb = (delta a-delta)/(delta a-delta fb), then delta = 2.79 for the unadjusted Eclipse smoke PM indicates alpha fb approximately 0.04. The effective pH of the Eclipse smoke PM at 20 degrees C may then be calculated as pHeff = 8.06 + log[alpha fb/(1-alpha fb)] = 6.69, where 8.06 is the pKa of NicH+ in water at 20 degrees C. The measurements obtained for the puff-averaged Eclipse smoke PM

  3. Determination and Comparison of Seed Oil Triacylglycerol Composition of Various Soybeans (Glycine max (L. Using 1H-NMR Spectroscopy

    Directory of Open Access Journals (Sweden)

    Won Woo Kim

    2013-11-01

    Full Text Available Seed oil triacylglycerol (TAG composition of 32 soybean varieties were determined and compared using 1H-NMR. The contents of linolenic (Ln, linoleic (L, and oleic (O ranged from 10.7% to 19.3%, 37.4%–50.1%, and 15.7%–34.1%, respectively. As is evident, linoleic acid was the major fatty acid of soybean oil. Compositional differences among the varieties were observed. Natural oils containing unsaturated groups have been regarded as important nutrient and cosmetic ingredients because of their various biological activities. The TAG profiles of the soy bean oils could be useful for distinguishing the origin of seeds and controlling the quality of soybean oils. To the best of our knowledge, this is the first study in which the TAG composition of various soybean oils has been analyzed using the 1H-NMR method.

  4. Simultaneous determination of six quality parameters of biodiesel through 1H NMR spectroscopy and partial least squares.

    Science.gov (United States)

    Shimamoto, Gustavo G; Tubino, Matthieu

    2018-03-01

    Biodiesel quality is checked by determining several parameters. Considering the large number of analyses in this verification, as well as the disadvantages of the use of toxic solvents and waste generation, multivariate calibration is suggested to reduce the number of tests. In this work, hydrogen nuclear magnetic resonance ( 1 H NMR) spectra were used to build multivariate models, from partial least squares (PLS), in order to perform simultaneous determination of six important quality parameters of biodiesel: density at 20°C, kinematic viscosity at 40°C, iodine value, acid number, oxidative stability, and water content. 1 H NMR spectrum reflects the structures of the compounds present in biodiesel and showed suitable correlations with the six parameters. In addition, the models were appropriate to predict all parameters for external samples. Thus, the alliance between 1 H NMR spectra and PLS was shown to be applicable to extract a lot of information about biodiesel quality, significantly reducing analysis time, reagent and solvent consumption, and waste generation. Copyright © 2017 Elsevier B.V. All rights reserved.

  5. Identification and quantification of the main organic components of vinegars by high resolution 1H NMR spectroscopy

    International Nuclear Information System (INIS)

    Caligiani, A.; Acquotti, D.; Palla, G.; Bocchi, V.

    2007-01-01

    A detailed analysis of the proton high-field NMR spectra of vinegars (in particular of Italian balsamic vinegars) is reported. A large number of organic substances belonging to different classes, such as carbohydrates, alcohols, organic acids, volatile compounds and amino acids, were assigned. The possibility of quantification of the substances identified in the whole vinegar sample, without extraction or pre-concentration steps, was also tested. The data validity was demonstrated in terms of precision, accuracy, repeatability and inter-day reproducibility. The effects of the most critical experimental parameters (sample concentration, water suppression and relaxation time) on the analysis response were also discussed. 1 H NMR results were compared with those obtained by traditional techniques (GC-MS, titrations), and good correlations were obtained. The results showed that 1 H NMR with water suppression allows a rapid, simultaneous determination of carbohydrates (glucose and fructose), organic acids (acetic, formic, lactic, malic, citric, succinic and tartaric acids), alcohols and polyols (ethanol, acetoin, 2,3-butanediol, hydroxymethylfurfural), and volatile substances (ethyl acetate) in vinegar samples. On the contrary, the amino acid determination without sample pre-concentration was critical. The 1 H NMR method proposed was applied to different samples of vinegars, allowing, in particular, the discrimination of vinegars and balsamic vinegars

  6. UV-visible-DAD and 1H-NMR spectroscopy data fusion for studying the photodegradation process of azo-dyes using MCR-ALS.

    Science.gov (United States)

    Fernández, Cristina; Pilar Callao, M; Larrechi, M Soledad

    2013-12-15

    The photodegradation process of three azo-dyes - Acid Orange 61, Acid Red 97 and Acid Brown 425 - was monitored simultaneously by ultraviolet-visible spectroscopy with diode array detector (UV-vis-DAD) and (1)H-nuclear magnetic resonance ((1)H-NMR). Multivariate curve resolution-alternating least squares (MCR-ALS) was applied to obtain the concentration and spectral profile of the chemical compounds involved in the process. The analysis of the H-NMR data suggests there are more intermediate compounds than those obtained with the UV-vis-DAD data. The fusion of UV-vis-DAD and the (1)H-NMR signal before the multivariate analysis provides better results than when only one of the two detector signals was used. It was concluded that three degradation products were present in the medium when the three azo-dyes had practically degraded. This study is the first application of UV-vis-DAD and (1)H-NMR spectroscopy data fusion in this field and illustrates its potential as a quick method for evaluating the evolution of the azo-dye photodegradation process. © 2013 Elsevier B.V. All rights reserved.

  7. Application of 1H NMR spectroscopy for determination of the interaction energy of cells with the water medium

    International Nuclear Information System (INIS)

    Turov, V.V.; Gorbik, S.P.; Chujko, A.A.

    2002-01-01

    The characteristics of bound water layers and the values of interface energy (γ s ) in live cell suspensions of bread yeast are determined by the method of 1 H NMR with the application of the liquid phase freezing technique. The concentrations of intracellular and extracellular bound water are determined. In terms of the dependence of γ s on the concentration of extracellular water, the energy of the intercellular interaction is determined as 109 J/g of dried cellular mass. In the cell suspension, a phase transition of the sol-gel type is registered. It is observed for the cell mass concentration equal to 10-12 mass%

  8. Development and Validation of Quantitative (1)H NMR Spectroscopy for the Determination of Total Phytosterols in the Marine Seaweed Sargassum.

    Science.gov (United States)

    Zhang, Xiu-Li; Wang, Cong; Chen, Zhen; Zhang, Pei-Yu; Liu, Hong-Bing

    2016-08-10

    Knowledge of phytosterol (PS) contents in marine algae is currently lacking compared to those in terrestrial plants. The present studies developed a quantitative (1)H NMR method for the determination of the total PSs in Sargassum. The characteristic proton signal H-3α in PSs was used for quantification, and 2,3,4,5-tetrachloro-nitrobenzene was used as an internal standard. Seaweed samples could be recorded directly after total lipid extraction and saponification. The results showed that the PS contents in Sargassum fusiforme (788.89-2878.67 mg/kg) were significantly higher than those in Sargassum pallidum (585.33-1596.00 mg/kg). The variable contents in both species suggested that fixed raw materials are very important for future research and development. Orthogonal projection to latent structures discriminant analysis was carried out in the spectral region of δ 3.00-6.50 in the (1)H NMR spectrum. S. fusiforme and S. pallidum could be separated well, and the key sterol marker was fucosterol.

  9. Simple methods via Mid-IR or {sup 1}H NMR spectroscopy for the determination of the iodine value of vegetable oils

    Energy Technology Data Exchange (ETDEWEB)

    Shimamoto, Gustavo G.; Favaro, Martha M.A.; Tubino, Matthieu, E-mail: tubino@iqm.unicamp.br [Universidade Estadual de Campinas (UNICAMP), Campinas, SP (Brazil). Instituto de Química

    2015-07-01

    Two methods for determining the iodine value in vegetable oils are described. One employs mid-infrared (mid-IR) spectroscopy and the other uses hydrogen nuclear magnetic resonance ({sup 1}H NMR). The determination of the iodine value is based on either the transmittance intensity of mid-IR signals or on the {sup 1}H NMR signal integration and multivariate calibration. Both of the methods showed adequate coefficients of determination (r{sup 2} = 0.9974 and 0.9978, respectively) when compared to Wijs method, which is recommended by the norm EN 14111. A statistical comparison between the results from the proposed methods and from Wijs method shows that both instrumental methods offer equivalent results and greater precision compared to Wijs method. The regressions obtained from the constructed models were considered statistically significant and useful for making predictions. The proposed methods present several advantages compared to Wijs method because they significantly reduce analysis time, reagent consumption and waste generation. Furthermore, an analyst can choose between the mid-IR or {sup 1}H NMR to determine the iodine value. (author)

  10. High-resolution 1H NMR spectroscopy of fish muscle, eggs and small whole fish via Hadamard-encoded intermolecular multiple-quantum coherence.

    Directory of Open Access Journals (Sweden)

    Honghao Cai

    Full Text Available BACKGROUND AND PURPOSE: Nuclear magnetic resonance (NMR spectroscopy has become an important technique for tissue studies. Since tissues are in semisolid-state, their high-resolution (HR spectra cannot be obtained by conventional NMR spectroscopy. Because of this restriction, extraction and high-resolution magic angle spinning (HR MAS are widely applied for HR NMR spectra of tissues. However, both of the methods are subject to limitations. In this study, the feasibility of HR (1H NMR spectroscopy based on intermolecular multiple-quantum coherence (iMQC technique is explored using fish muscle, fish eggs, and a whole fish as examples. MATERIALS AND METHODS: Intact salmon muscle tissues, intact eggs from shishamo smelt and a whole fish (Siamese algae eater are studied by using conventional 1D one-pulse sequence, Hadamard-encoded iMQC sequence, and HR MAS. RESULTS: When we use the conventional 1D one-pulse sequence, hardly any useful spectral information can be obtained due to the severe field inhomogeneity. By contrast, HR NMR spectra can be obtained in a short period of time by using the Hadamard-encoded iMQC method without shimming. Most signals from fatty acids and small metabolites can be observed. Compared to HR MAS, the iMQC method is non-invasive, but the resolution and the sensitivity of resulting spectra are not as high as those of HR MAS spectra. CONCLUSION: Due to the immunity to field inhomogeneity, the iMQC technique can be a proper supplement to HR MAS, and it provides an alternative for the investigation in cases with field distortions and with samples unsuitable for spinning. The acquisition time of the proposed method is greatly reduced by introduction of the Hadamard-encoded technique, in comparison with that of conventional iMQC method.

  11. 1H NMR-based spectroscopy detects metabolic alterations in serum of patients with early-stage ulcerative colitis

    International Nuclear Information System (INIS)

    Zhang, Ying; Lin, Lianjie; Xu, Yanbin; Lin, Yan; Jin, Yu; Zheng, Changqing

    2013-01-01

    Highlights: •Twenty ulcerative colitis patients and nineteen healthy controls were enrolled. •Increased 3-hydroxybutyrate, glucose, phenylalanine, and decreased lipid were found. •We report early stage diagnosis of ulcerative colitis using NMR-based metabolomics. -- Abstract: Ulcerative colitis (UC) has seriously impaired the health of citizens. Accurate diagnosis of UC at an early stage is crucial to improve the efficiency of treatment and prognosis. In this study, proton nuclear magnetic resonance ( 1 H NMR)-based metabolomic analysis was performed on serum samples collected from active UC patients (n = 20) and healthy controls (n = 19), respectively. The obtained spectral profiles were subjected to multivariate data analysis. Our results showed that consistent metabolic alterations were present between the two groups. Compared to healthy controls, UC patients displayed increased 3-hydroxybutyrate, β-glucose, α-glucose, and phenylalanine, but decreased lipid in serum. These findings highlight the possibilities of NMR-based metabolomics as a non-invasive diagnostic tool for UC

  12. Characterization of the concurrent metabolic changes in brain and plasma during insulin-induced moderate hypoglycemia using 1H NMR spectroscopy in juvenile rats.

    Science.gov (United States)

    Ennis, Kathleen; Lusczek, Elizabeth; Rao, Raghavendra

    2017-07-13

    Treatment of hypoglycemia in children is currently based on plasma glucose measurements. This approach may not ensure neuroprotection since plasma glucose does not reflect the dynamic state of cerebral energy metabolism. To determine whether cerebral metabolic changes during hypoglycemia could be better characterized using plasma metabolomic analysis, insulin-induced acute hypoglycemia was induced in 4-week-old rats. Brain tissue and concurrent plasma samples were collected from hypoglycemic (N=7) and control (N=7) rats after focused microwave fixation to prevent post-mortem metabolic changes. The concentration of 29 metabolites in brain and 34 metabolites in plasma were determined using 1 H NMR spectroscopy at 700MHz and examined using partial least squares-discriminant analysis. The sensitivity of plasma glucose for detecting cerebral energy failure was assessed by determining its relationship to brain phosphocreatine. The brain and plasma metabolite profiles of the hypoglycemia group were distinct from the control group (brain: R 2 =0.92, Q 2 =0.31; plasma: R 2 =0.95, Q 2 =0.74). Concentration differences in glucose, ketone bodies and amino acids were responsible for the intergroup separation. There was 45% concordance between the brain and plasma metabolite profiles. Brain phosphocreatine correlated with brain glucose (control group: R 2 =0.86; hypoglycemia group: R 2 =0.59; pplasma glucose. The results confirm that plasma glucose is an insensitive biomarker of cerebral energy changes during hypoglycemia and suggest that a plasma metabolite profile is superior for monitoring cerebral metabolism. Copyright © 2017 Elsevier B.V. All rights reserved.

  13. Effect of UV-A and UV-B irradiation on the metabolic profile of aqueous humor in rabbits analyzed by 1H NMR spectroscopy.

    Science.gov (United States)

    Tessem, May-Britt; Bathen, Tone F; Cejková, Jitka; Midelfart, Anna

    2005-03-01

    This study was conducted to investigate metabolic changes in aqueous humor from rabbit eyes exposed to either UV-A or -B radiation, by using (1)H nuclear magnetic resonance (NMR) spectroscopy and unsupervised pattern recognition methods. Both eyes of adult albino rabbits were irradiated with UV-A (366 nm, 0.589 J/cm(2)) or UV-B (312 nm, 1.667 J/cm(2)) radiation for 8 minutes, once a day for 5 days. Three days after the last irradiation, samples of aqueous humor were aspirated, and the metabolic profiles analyzed with (1)H NMR spectroscopy. The metabolic concentrations in the exposed and control materials were statistically analyzed and compared, with multivariate methods and one-way ANOVA. UV-B radiation caused statistically significant alterations of betaine, glucose, ascorbate, valine, isoleucine, and formate in the rabbit aqueous humor. By using principal component analysis, the UV-B-irradiated samples were clearly separated from the UV-A-irradiated samples and the control group. No significant metabolic changes were detected in UV-A-irradiated samples. This study demonstrates the potential of using unsupervised pattern recognition methods to extract valuable metabolic information from complex (1)H NMR spectra. UV-B irradiation of rabbit eyes led to significant metabolic changes in the aqueous humor detected 3 days after the last exposure.

  14. Application of chemometrics in quality control of Turmeric (Curcuma longa) based on Ultra-violet, Fourier transform-infrared and 1H NMR spectroscopy.

    Science.gov (United States)

    Gad, Haidy A; Bouzabata, Amel

    2017-12-15

    Turmeric (Curcuma longa L.) belongs to the family Zingiberaceae that is widely used as a spice in food preparations in addition to its biological activities. UV, FT-IR, 1 H NMR in addition to HPLC were applied to construct a metabolic fingerprint for Turmeric in an attempt to assess its quality. 30 samples were analyzed, and then principal component analysis (PCA) and hierarchical clustering analysis (HCA) were utilized to assess the differences and similarities between collected samples. PCA score plot based on both HPLC and UV spectroscopy showed the same discriminatory pattern, where the samples were segregated into four main groups depending on their total curcuminoids content. The results revealed that UV could be utilized as a simple and rapid alternative for HPLC. However, FT-IR failed to discriminate between the same species. By applying 1 H NMR, the metabolic variability between samples was more evident in the essential oils/fatty acid region. Copyright © 2017 Elsevier Ltd. All rights reserved.

  15. Quantitative analysis of sesquiterpene lactone cnicin in seven Centaurea species wild-growing in Serbia and Montenegro using 1H-NMR spectroscopy

    Directory of Open Access Journals (Sweden)

    IRIS DJORDJEVIC

    2007-12-01

    Full Text Available 1H-NMR spectroscopy was applied for the quantitative analysis of cnicin, a bioactive germacranolide type sesquiterpene lactone, in the aerial parts of seven wild-growing Centaurea species collected in Serbia and Montenegro. The analysis was performed by comparison of the integral of the one-proton signal of cnicin (H-13, δ 5.75 with that of the two-proton singlet (δ 6.98 of 2,6-bis(1,1-dimethylethyl-4-methylphenol (BHT, used as the internal standard. Cnicin, within concentration the range 1.06–6.12 mg/g, calculated per weight of the fresh plant material was detected in six species, the exception being C. salonitana. This method allows the rapid and simple quantification of cnicin without any pre-purification step.

  16. Application of 1H NMR spectroscopy-based metabonomics to feces of cervical cancer patients with radiation-induced acute intestinal symptoms.

    Science.gov (United States)

    Chai, Yanlan; Wang, Juan; Wang, Tao; Yang, Yunyi; Su, Jin; Shi, Fan; Wang, Jiquan; Zhou, Xi; He, Bin; Ma, Hailin; Liu, Zi

    2015-11-01

    Radiation-induced acute intestinal symptoms (RIAISs) are a common complication of radiotherapy for cervical cancer. The aim of this study was to use (1)H nuclear magnetic resonance ((1)H NMR) combined with chemometric analysis to develop a metabolic profile of patients with RIAISs. Fecal samples were collected from 66 patients with cervical cancer before and after pelvic radiotherapy. After radiotherapy, RIAISs occurred in eleven patients. We selected another 11 patients from participants without RIAISs whose age, stage, histological type and treatment methods are matched with RIAIS patients as the control group. (1)H NMR spectroscopy combined with multivariate pattern recognition analysis was used to generate metabolic profile data, as well as to establish a RIAIS-specific metabolic phenotype. Orthogonal partial least-squares discriminant analysis was used to distinguish samples between the pre- and post-radiotherapy RIAIS patients and between RIAIS patients and controls. Fecal samples from RIAIS patients after pelvic radiotherapy were characterized by increased concentrations of α-ketobutyrate, valine, uracil, tyrosine, trimethylamine N-oxide, phenylalanine, lysine, isoleucine, glutamine, creatinine, creatine, bile acids, aminohippurate, and alanine, accompanied by reduced concentrations of α-glucose, n-butyrate, methylamine, and ethanol relative to samples from RIAIS patients before pelvic radiotherapy, while in RIAIS patients relative to controls, trimethylamine, n-butyrate, fumarate and acetate were down-regulated and valine, TMAO, taurine, phenylalanine, lactate, isoleucine and creatinine were up-regulated. We obtained the metabolic profile of RIAIS patients from fecal samples using NMR-based metabonomics. This profile has the potential to be developed into a novel clinical tool for RIAIS diagnosis or therapeutic monitoring, and could contribute to an improved understanding of the disease mechanism. However, because of the limitations of methods, technique

  17. Rapid approach to identify the presence of Arabica and Robusta species in coffee using 1H NMR spectroscopy.

    Science.gov (United States)

    Monakhova, Yulia B; Ruge, Winfried; Kuballa, Thomas; Ilse, Maren; Winkelmann, Ole; Diehl, Bernd; Thomas, Freddy; Lachenmeier, Dirk W

    2015-09-01

    NMR spectroscopy was used to verify the presence of Arabica and Robusta species in coffee. Lipophilic extracts of authentic roasted and green coffees showed the presence of established markers for Robusta (16-O-methylcafestol (16-OMC)) and for Arabica (kahweol). The integration of the 16-OMC signal (δ 3.165 ppm) was used to estimate the amount of Robusta in coffee blends with an approximate limit of detection of 1-3%. The method was successfully applied for the analysis of 77 commercial coffee samples (coffee pods, coffee capsules, and coffee beans). Furthermore, principal component analysis (PCA) was applied to the spectra of lipophilic and aqueous extracts of 20 monovarietal authentic samples. Clusters of the two species were observed. NMR spectroscopy can be used as a rapid prescreening tool to discriminate Arabica and Robusta coffee species before the confirmation applying the official method. Copyright © 2015 Elsevier Ltd. All rights reserved.

  18. Evaluation of chemical changes during Myrciaria cauliflora (jabuticaba fruit) fermentation by {sup 1}H NMR spectroscopy and chemometric analyses

    Energy Technology Data Exchange (ETDEWEB)

    Fortes, Gilmara A.C.; Naves, Sara S.; Ferri, Pedro H.; Santos, Suzana C., E-mail: suzana.quimica.ufg@hotmail.com [Universidade Federal de Goias (UFG), Goiania, GO (Brazil). Inst. de Quimica. Lab. de Bioatividade Molecular

    2012-10-15

    Organic acids, sugars, alcohols, phenolic compounds, color properties, pH and titratable acidity were monitored during the commercial fermentation of jabuticaba (Myrciaria cauliflora) by {sup 1}H nuclear magnetic resonance (NMR) spectroscopy, spectrophotometric assays and standard methods of analysis. Data collected was analyzed by principal component (PCA), hierarchical cluster (HCA) and canonical correlation (CCA) analyses. Two sample groups were distinguished and the variables responsible for separation were sugars, anthocyanins, alcohols, hue and acetic and succinic acids. The canonical correlation analysis confirmed the influence of alcohols (ethanol, methanol and glycerol), organic acids (citric, succinic and acetic acids), pH and titratable acidity on the extraction and stability of anthocyanins and co pigments. As a result, color properties were also affected by phenolic variation throughout the fermentative process. (author)

  19. Hepatocarcinogenesis tumor grading correlated with in vivo image-guided 1H-NMR spectroscopy in a rat model

    International Nuclear Information System (INIS)

    Towner, Rheal A.; Foley, Lesley M.; Painter, Dorothy M.

    2005-01-01

    Hepatocellular carcinoma (HCC) is a common malignancy worldwide, the occurrence of which is unevenly distributed. Most hepatocellular carcinoma cases present late and have a poor prognosis; therefore, early diagnosis is essential to prolong survival. Differential diagnosis with magnetic resonance imaging (MRI) is difficult. We studied the feasibility of using magnetic resonance spectroscopy (MRS) at 7.0 T for the diagnosis and grading of liver tumors. An animal model of hepatocarcinogenesis was used, which allowed tumor progression from precancerous lesions to hepatocellular carcinomas. This study was focused primarily on the grading of the tumors and its correlation with the ratio between the MRS peaks arising from MRS-detected lipid hydrogens (0.9, 1.3 and 5.3 ppm) and compared to the γ-methylene hydrogens of glutamate (Glu) and glutamine (Gln) which was used as an internal reference (2.4 ppm). The lipid methylene hydrogen (1.3 ppm) to (Glu + Gln) ratio was found to correlate with the formation of differentiated small foci and (precancerous) hepatic nodules, whereas the unsaturated olefinic lipid hydrogen (5.3 ppm) to (Glu + Gln) ratio was able to correlate with the formation of late stage tumors such as adenomas and hepatocellular carcinomas. The results of our study suggest that MRS-detected alterations in lipid metabolism can be correlated with the grading of liver tumor tissue at different stages during the carcinogenesis process

  20. The Effect of Season on the Metabolic Profile of the European Clam Ruditapes decussatus as Studied by 1H-NMR Spectroscopy

    Directory of Open Access Journals (Sweden)

    Violetta Aru

    2017-07-01

    Full Text Available In this study, the metabolome of Ruditapes decussatus, an economically and ecologically important marine bivalve species widely distributed in the Mediterranean region, was characterized by using proton Nuclear Magnetic Resonance (1H-NMR spectroscopy. Significant seasonal variations in the content of carbohydrates and free amino acids were observed. The relative amounts of alanine and glycine were found to exhibit the same seasonal pattern as the temperature and salinity at the harvesting site. Several putative sex-specific biomarkers were also discovered. Substantial differences were found for alanine and glycine, whose relative amounts were higher in males, while acetoacetate, choline and phosphocholine were more abundant in female clams. These findings reveal novel insights into the baseline metabolism of the European clam and represent a step forward towards a comprehensive metabolic characterization of the species. Besides providing a holistic view on the prominent nutritional components, the characterization of the metabolome of this bivalve represents an important prerequisite for elucidating the underlying metabolic pathways behind the environment-organism interactions.

  1. Study of the contact charge transfer behavior between cryptophanes (A and E) and fullerene by absorption, fluorescence and {sup 1}H NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Zhang Caihong; Shen Weili; Fan Ruying; Zhang Guomei; Shangguan Lingzhi; Chao Jianbin; Shuang Shaomin [Research Center of Environmental Science and Engineering, School of Chemistry and Chemical Engineering, Shanxi University, Taiyuan 030006 (China); Dong Chuan, E-mail: dc@sxu.edu.cn [Research Center of Environmental Science and Engineering, School of Chemistry and Chemical Engineering, Shanxi University, Taiyuan 030006 (China); Choi, Martin M.F., E-mail: mfchoi@hkbu.edu.hk [Department of Chemistry, Hong Kong Baptist University, Kowloon Tong (Hong Kong)

    2009-09-14

    A group of novel cage-like compounds cryptophanes A and E were synthesized from vanillin by a three-step method. The intermolecular interaction between cryptophanes (A and E) and fullerene (C{sub 60}) was investigated in detail by absorption, fluorescence and {sup 1}H NMR spectroscopy. The absorption of C{sub 60} at 410-650 nm decreased in the presence of cryptophanes A or E. The decrease in absorption intensity was proportional to the concentration of cryptophanes A or E. On the other hand, the fluorescence intensity of cryptophanes A or E decreased and the emission maxima were blue-shifted with the increase in C{sub 60} concentration. These results suggest that contact charge transfer (CCT) complexes can be formed from C{sub 60} with cryptophanes A or E. In addition, the electrochemical behavior of cryptophanes (A and E) and C{sub 60} was studied by cyclic voltammetry. The redox currents of cryptophanes (A and E) decreased and the peak potentials were shifted on addition of C{sub 60}. The changes in the chemical shifts ({Delta}{delta}) of aromatic protons of cryptophanes (A and E) in their NMR spectra further support that CCT complexes were formed with cryptophanes as the electron donors and C{sub 60} as the electron acceptor.

  2. Determination of the content of fatty acid methyl esters (FAME) in biodiesel samples obtained by esterification using 1H-NMR spectroscopy.

    Science.gov (United States)

    Mello, Vinicius M; Oliveira, Flavia C C; Fraga, William G; do Nascimento, Claudia J; Suarez, Paulo A Z

    2008-11-01

    Three different calibration curves based on (1)H-NMR spectroscopy (300 MHz) were used for quantifying the reaction yield during biodiesel synthesis by esterification of fatty acids mixtures and methanol. For this purpose, the integrated intensities of the hydrogens of the ester methoxy group (3.67 ppm) were correlated with the areas related to the various protons of the alkyl chain (olefinic hydrogens: 5.30-5.46 ppm; aliphatic: 2.67-2.78 ppm, 2.30 ppm, 1.96-2.12 ppm, 1.56-1.68 ppm, 1.22-1.42 ppm, 0.98 ppm, and 0.84-0.92 ppm). The first curve was obtained using the peaks relating the olefinic hydrogens, a second with the parafinic protons and the third curve using the integrated intensities of all the hydrogens. A total of 35 samples were examined: 25 samples to build the three different calibration curves and ten samples to serve as external validation samples. The results showed no statistical differences among the three methods, and all presented prediction errors less than 2.45% with a co-efficient of variation (CV) of 4.66%. 2008 John Wiley & Sons, Ltd.

  3. Determination of partition coefficients using 1 H NMR spectroscopy and time domain complete reduction to amplitude-frequency table (CRAFT) analysis.

    Science.gov (United States)

    Soulsby, David; Chica, Jeryl A M

    2017-08-01

    We have developed a simple, direct and novel method for the determination of partition coefficients and partitioning behavior using 1 H NMR spectroscopy combined with time domain complete reduction to amplitude-frequency tables (CRAFT). After partitioning into water and 1-octanol using standard methods, aliquots from each layer are directly analyzed using either proton or selective excitation NMR experiments. Signal amplitudes for each compound from each layer are then extracted directly from the time domain data in an automated fashion and analyzed using the CRAFT software. From these amplitudes, log P and log D 7.4 values can be calculated directly. Phase, baseline and internal standard issues, which can be problematic when Fourier transformed data are used, are unimportant when using time domain data. Furthermore, analytes can contain impurities because only a single resonance is examined and need not be UV active. Using this approach, we examined a variety of pharmaceutically relevant compounds and determined partition coefficients that are in excellent agreement with literature values. To demonstrate the utility of this approach, we also examined salicylic acid in more detail demonstrating an aggregation effect as a function of sample loading and partition coefficient behavior as a function of pH value. This method provides a valuable addition to the medicinal chemist toolbox for determining these important constants. Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

  4. Analysis of the backbone dynamics of interleukin-1β using two-dimensional inverse detected heteronuclear 15N-1H NMR spectroscopy

    International Nuclear Information System (INIS)

    Clore, G.M.; Driscoll, P.C.; Wingfield, P.T.; Gronenborn, A.M.

    1990-01-01

    The backbone dynamics of uniformly 15 N-labeled interleukin-1β are investigated by using two-dimensional inverse detected heteronuclear 15 N- 1 H NMR spectroscopy. 15 N T 1 , T 2 , and NOE data at a spectrometer frequency of 600 MHz are obtained for 90% of the backbone amide groups. The data provide evidence for motions on three time scales. All the residues exhibit very fast motions on a time scale of approx-lt 20-50 ps that can be characterized by a single-order parameter with an average value of 0.82 ± 0.05. Thirty-two residues also display motions on a time scale of 0.5-4 ns, slightly less than the overall rotational correlation time of the protein (8.3 ns). While the simple formulation can account for the 15 N T 1 and T 2 data, it fails to account for the 15 N- 1 H NOE data and yields calculated values for the NOEs that are either too small or negative, whereas the observed NOEs are positive. Another 42 residues are characterized by some sort of motion on the 30-ns-10-ms time scale, which results in 15 N line broadening due to chemical exchange between different conformational substates with distinct 15 N chemical shifts. In general, the motions on both the 0.5-4-ns and 30-ns-10-ms time scales are localized in surface-accessible loops and turns connecting the β-strands, as well as at the beginning and end of strands. Finally, the kinetic and equilibrium properties of a slow conformational equilibrium between a major and a minor species, involving at least 19 residues and located on one contiguous face of the molecule, are characterized by using 1 H- 15 N correlation spectroscopy, 1 H- 15 N heteronuclear multiple quantum coherence-nuclear Overhauser enhancement spectroscopy, and 1 H- 1 H nuclear Overhauser enhancement spectroscopy

  5. Whole Blood Reveals More Metabolic Detail of the Human Metabolome than Serum as Measured by 1H-NMR Spectroscopy: Implications for Sepsis Metabolomics

    Science.gov (United States)

    Stringer, Kathleen A.; Younger, John G.; McHugh, Cora; Yeomans, Larisa; Finkel, Michael A.; Puskarich, Michael A.; Jones, Alan E.; Trexel, Julie; Karnovsky, Alla

    2015-01-01

    Serum is a common sample of convenience for metabolomics studies. Its processing time can be lengthy and may result in the loss of metabolites including those of red blood cells (RBC). Unlike serum, whole blood (WB) is quickly processed, minimizing the influence of variable hemolysis while including RBC metabolites. To determine differences between serum and WB metabolomes, both sample types, collected from healthy volunteers, were assayed by 1H-NMR spectroscopy. A total of 34 and 50 aqueous metabolites were quantified from serum and WB, respectively. Free hemoglobin (Hgb) levels in serum were measured and the correlation between Hgb and metabolite concentrations was determined. All metabolites detected in serum were at higher concentrations in WB with the exception of acetoacetate and propylene glycol. The 18 unique metabolites of WB included adenosine, AMP, ADP and ATP, which are associated with RBC metabolism. The use of serum results in the underrepresentation of a number of metabolic pathways including branched chain amino acid degradation and glycolysis and gluconeogenesis. The range of free Hgb in serum was 0.03-0.01 g/dL and 8 metabolites were associated (p ≤ 0.05) with free Hgb. The range of free Hgb in serum samples from 18 sepsis patients was 0.02-0.46 g/dL. WB and serum have unique aqueous metabolite profiles but the use of serum may introduce potential pathway bias. Use of WB for metabolomics may be particularly important for studies in diseases like sepsis in which RBC metabolism is altered and mechanical and sepsis-induced hemolysis contributes to variance in the metabolome. PMID:26009817

  6. Conformational analysis of the Sda determinant-containing tetrasaccharide and two mimics in aqueous solution by using 1H NMR ROESY spectroscopy in combination with MD simulations

    International Nuclear Information System (INIS)

    Blanco, Jose L. Jimenez; Rooijen, Johannes J.M. van; Erbel, Paul J.A.; Leeflang, Bas R.; Kamerling, Johannis P.; Vliegenthart, Johannes F.G.

    2000-01-01

    The conformational behaviour of the spacer-linked synthetic Sd a tetrasaccharide β-d-GalpNAc-(1 → 4)-[α-Neu5Ac-(2 → 3)]-β-d-Galp-(1 → 4)-β-d-GlcpNAc-(1 → O) (CH 2 ) 5 NH 2 (1) and the two mimics β-d-Galp-(1 → 4)-[α-Neu5Ac-(2 → 3)]-β-d-Galp-(1 → 4)-β-d-GlcpNAc-(1 → O)(CH 2 ) 5 NH 2 (2) and β-d-GlcpNAc-(1 → 4)-[α-Neu5Ac-(2 → 3)]-β-d-Galp-(1 → 4)-β-d-GlcpNAc-(1 → O) (CH 2 ) 5 NH 2 (3) were investigated by 1 H NMR spectroscopy in combination with molecular dynamics (MD) simulations in water. Experimental 2D 1 H ROESY cross-peak intensities (ROEs) of the tetrasaccharides were compared with calculated ROEs derived from MD trajectories using the CROSREL program. Analysis of these data indicated that the oligosaccharidic skeletons of the compounds 1-3 are rather rigid, especially the β-d-Hex(NAc)-(1 → 4)-[α-Neu5Ac-(2 → 3)]-β-d-Galp fragments. The α- Neu5-Ac-(2 → 3)-β-d-Galp linkage occurred in two different energy minima in the three-dimensional structure of the compounds 1-3 in aqueous solution. Experimental data and dynamics simulations supported the finding that the higher energy rotamer (CHEAT forcefield) was abundant in compounds 1 and 3 due to the existence of a hydrogen bond between the carboxyl group of the sialic acid and the acetamido group of the terminal monosaccharide (GalNAc or GlcNAc) unit. The conformational similarity between 1 and 3 leads to the suggestion that also their activities will be alike.

  7. High-resolution magic angle spinning (1)H NMR spectroscopy of metabolic changes in rabbit lens after treatment with dexamethasone combined with UVB exposure

    Czech Academy of Sciences Publication Activity Database

    Seather, O.; Risa, O.; Čejková, Jitka; Krane, J.; Midelfart, A.

    2004-01-01

    Roč. 242, - (2004), s. 1000-1007 ISSN 0721-832X R&D Projects: GA ČR GA304/03/0419 Institutional research plan: CEZ:AV0Z5008914 Keywords : HR-MAS 1H NMR Subject RIV: FF - HEENT, Dentistry Impact factor: 1.513, year: 2004

  8. The use of 1H-NMR spectroscopy and refractometry for investigation of the distribution of nonelectrolytes of N-alcohol series between human red blood cells and extracellular medium.

    Science.gov (United States)

    Kucherenko, Y U; Moiseev, V A

    2000-01-01

    Comparative analysis of 1H NMR spectroscopy and refractometry with respect to their application for investigating the distribution of nonelectrolytes of n-alcohol series (ethanol, 1,2-propanediol, glycerol) and polyethylene glycols (PEGs) with molecular masses of 400, 600, 1500 between human erythrocytes and extracellular medium was performed. The distribution coefficients (Q) for solutions of ethanol, 1,2-propanediol, glycerol, PEG-400, PEG-600 and PEG-1500 were obtained. The Q values decreased with the increase in the nonelectrolyte molecular mass from 1.23+/-0.12 for ethanol to 0.40+/-0.08 for PEG-1500 (1H NMR spectroscopy) and from 2.6+/-0.12 for ethanol to 0.23+/-0.03 for PEG-1500 (refractometry). It was shown that 1H-NMR high-resolution spectroscopy ensures more precise determination of Q values for nonelectrolytes with low molecular masses; for PEGs with high molecular masses, the accuracy of Q value calculation by this method was about 20%. On the contrary, refractometry can be used for investigating substances with high molecular masses; the error of Q value determination for solution of low-refractive substances, such as ethanol, may be more than 50%.

  9. 1H-NMR urinalysis

    International Nuclear Information System (INIS)

    Yamamoto, Hideaki; Yamaguchi, Shuichi

    1988-01-01

    In an effort to examine the usefulness of 1 H-nuclear magnetic resonance (NMR) urinalysis in the diagnosis of congenital metabolic disorders, 70 kinds of urinary metabolites were analysed in relation to the diagnosis of inborn errors of amino acid and organic acid disorders. Homogated decoupling (HMG) method failed to analyze six metabolites within the undetectable range. When non-decoupling method (NON), in which the materials are dissolved in dimethyl sulfoxide, was used, the identification of signals became possible. The combination of HMG and NON methods was, therefore, considered to identify all of the metabolites. When the urine samples, which were obtained from patients with hyperglycerolemia, hyperornithinemia, glutaric acidemia type II, or glycerol kinase deficiency, were analysed by using both HMG and NON methods, abnormally increased urinary metabolites were detected. 1 H-NMR urinalysis, if used in the combination of HMG and NON methods, may allow simultanenous screening of inborn errors of metabolism of amino acid and organic acid disorders. (Namekawa, K.)

  10. Mobile sequences in the pyruvate dehydrogenase complex, the E2 component, the catalytic domain and the 2-oxogluturate dehydrogenase complex of Azotobacter vinelandii, as detected by 600 MHz 1H-NMR spectroscopy

    International Nuclear Information System (INIS)

    Hanemaaijer, R.; Vervoort, J.; Westphal, A.H.; Kok, A. de.; Veeger, C.

    1988-01-01

    600 MHz 1 H-NMR spectroscopy demonstrates that the pyruvate dehydrogenase complex of Azotobacter vinelandii contains regions of the polypeptide chain with intramolecular mobility. This mobility is located in the E 2 component and can probably be ascribed to alanine-proline-rich regions that link the lipoyl sibdiomains to each other as well as to the E 1 and E 3 binding domain. In the catalytic domain of E 2 which is thought to form a compact, rigid core, also conformational flexibility is observed. It is conceivable that the N-terminal region of the catalytic domain, which contains many alanine residues, is responsible for the observed mobility. In the low-field region of the 1 H-NMR spectrum of E 2 specific resonances are found, which can be ascribed to mobile phenylalanine, histidine and/or tyrosine residues which are located in the E 1 and E 3 binding domain that links the lipoyl domain to the catalytic domain. In the 1 H-NMR spectrum of the intact complex, these resonances cannot be observed, indicating a decreased mobility of the E 1 and E 3 binding domain. (author). 24 refs.; 2 figs

  11. Applying 1H NMR Spectroscopy to Detect Changes in the Urinary Metabolite Levels of Chinese Half-Pipe Snowboarders after Different Exercises

    Directory of Open Access Journals (Sweden)

    Fuqiu Wang

    2015-01-01

    Full Text Available Monitoring physical training is important for the health and performance of athletes, and real-time assessment of fatigue is crucial to improve training efficiency. The relationship between key biomarkers and exercise has been reported. The aim of this study was to determine the effects of different levels of training exercises on the urine metabolome. 1H NMR-based metabolomics analysis was performed on urine samples from half-pipe snowboarders, and spectral profiles were subjected to PCA and PLS-DA. Our results show that metabolic profiles varied during different stages of exercises. Lactate, alanine, trimethylamine, malonate, taurine, and glycine levels decreased while TMAO and phenylalanine levels increased in the stage with higher amount and intensity of exercise. Although the amount of exercise was reduced in subsequent stage, no significant variations of metabolic profile were found. Metabolic changes induced by training level were analyzed with related metabolic pathway. Studying metabolome changes can provide a better understanding of the physiology of athletes and could aid in adjusting training.

  12. Metabolomic profiling of the phytomedicinal constituents of Carica papaya L. leaves and seeds by 1H NMR spectroscopy and multivariate statistical analysis.

    Science.gov (United States)

    Gogna, Navdeep; Hamid, Neda; Dorai, Kavita

    2015-11-10

    Extracts from the Carica papaya L. plant are widely reported to contain metabolites with antibacterial, antioxidant and anticancer activity. This study aims to analyze the metabolic profiles of papaya leaves and seeds in order to gain insights into their phytomedicinal constituents. We performed metabolite fingerprinting using 1D and 2D 1H NMR experiments and used multivariate statistical analysis to identify those plant parts that contain the most concentrations of metabolites of phytomedicinal value. Secondary metabolites such as phenyl propanoids, including flavonoids, were found in greater concentrations in the leaves as compared to the seeds. UPLC-ESI-MS verified the presence of significant metabolites in the papaya extracts suggested by the NMR analysis. Interestingly, the concentration of eleven secondary metabolites namely caffeic, cinnamic, chlorogenic, quinic, coumaric, vanillic, and protocatechuic acids, naringenin, hesperidin, rutin, and kaempferol, were higher in young as compared to old papaya leaves. The results of the NMR analysis were corroborated by estimating the total phenolic and flavonoid content of the extracts. Estimation of antioxidant activity in leaves and seed extracts by DPPH and ABTS in-vitro assays and antioxidant capacity in C2C12 cell line also showed that papaya extracts exhibit high antioxidant activity. Copyright © 2015 Elsevier B.V. All rights reserved.

  13. Metabolite profiling of tomato (Lycopersicon esculentum) using 1H NMR spectroscopy as a tool to detect potential unintended effects following a genetic modification.

    Science.gov (United States)

    Le Gall, Gwénaëlle; Colquhoun, Ian J; Davis, Adrienne L; Collins, Geoff J; Verhoeyen, Martine E

    2003-04-23

    The maize transcription factors LC and C1 were simultaneously overexpressed in tomato with the aim of producing lines with increased amounts of flavonols. The metabolite composition of these genetically modified tomatoes has been compared with that of azygous (nonmodified) controls grown side-by-side under the same conditions. It has been possible to observe metabolic changes in both types at different stages of maturity. (1)H NMR spectra showed that the levels of glutamic acid, fructose, and some nucleosides and nucleotides gradually increase from the immature to the ripe stage, whereas some amino acids such as valine and gamma-aminobutyric acid were present in higher amounts in unripe tomatoes. Apart from the significantly increased content of six main flavonoid glycosides (mainly kaempferol-3-O-rutinoside, with additional increases in kaempferol-3,7-di-O-glucoside (1), kaempferol-3-O-rutinoside-7-O-glucoside (2), kaempferol-3-O-glucoside, a dihydrokaempferol-O-hexoside (3), and naringenin-7-O-glucoside), the levels of at least 15 other metabolites were found to be different between the two types of red tomato. Among them were citric acid, sucrose, phenylalanine, and trigonelline. However, although statistically significant, these changes in mean values were relatively minor (less than 3-fold) and within the natural variation that would be observed in a field-grown crop. Nevertheless, this study clearly showed that NMR combined with chemometrics and univariate statistics can successfully trace even small differences in metabolite levels between plants and therefore represents a powerful tool to detect potential unintended effects in genetically modified crops.

  14. 1H NMR spectroscopy-based metabolomics analysis for the diagnosis of symptomatic E. coli-associated urinary tract infection (UTI).

    Science.gov (United States)

    Lussu, Milena; Camboni, Tania; Piras, Cristina; Serra, Corrado; Del Carratore, Francesco; Griffin, Julian; Atzori, Luigi; Manzin, Aldo

    2017-09-21

    Urinary tract infection (UTI) is one of the most common diagnoses in girls and women, and to a lesser extent in boys and men younger than 50 years. Escherichia coli, followed by Klebsiella spp. and Proteus spp., cause 75-90% of all infections. Infection of the urinary tract is identified by growth of a significant number of a single species in the urine, in the presence of symptoms. Urinary culture is an accurate diagnostic method but takes several hours or days to be carried out. Metabolomics analysis aims to identify biomarkers that are capable of speeding up diagnosis. Urine samples from 51 patients with a prior diagnosis of Escherichia coli-associated UTI, from 21 patients with UTI caused by other pathogens (bacteria and fungi), and from 61 healthy controls were analyzed. The 1 H-NMR spectra were acquired and processed. Multivariate statistical models were applied and their performance was validated using permutation test and ROC curve. Orthogonal Partial Least Squares-discriminant Analysis (OPLS-DA) showed good separation (R 2 Y = 0.76, Q2=0.45, p UTI caused by Escherichia coli and healthy controls. Acetate and trimethylamine were identified as discriminant metabolites. The concentrations of both metabolites were calculated and used to build the ROC curves. The discriminant metabolites identified were also evaluated in urine samples from patients with other pathogens infections to test their specificity. Acetate and trimethylamine were identified as optimal candidates for biomarkers for UTI diagnosis. The conclusions support the possibility of a fast diagnostic test for Escherichia coli-associated UTI using acetate and trimethylamine concentrations.

  15. High-resolution magic angle spinning 1H-NMR spectroscopy studies on the renal biochemistry in the bank vole (Clethrionomys glareolus) and the effects of arsenic (As3+) toxicity.

    Science.gov (United States)

    Griffin, J L; Walker, L; Shore, R F; Nicholson, J K

    2001-06-01

    1. High-resolution magic angle spinning (MAS) 1H-NMR spectroscopy was used to study renal metabolism and the toxicity of As3+, a common environmental contaminant, in the bank vole (Clethrionomys glareolus), a wild species of rodent. 2. Following a 14-day exposure to an environmentally relevant dose of As2O3 (28 mg kg(-1) feed), voles displayed tissue damage at autopsy. MAS 1H spectra indicated abnormal lipid profiles in these samples. 3. Tissue necrosis was also evident from measurements of the apparent diffusion coefficient of water in the intact tissue using MAS 1H diffusion-weighted spectroscopy, its first application to toxicology. 4. Comparison of renal tissue from the wood mouse (Apodemus sylvaticus) exposed to identical exposure levels of As3+ suggested that the bank vole is particularly vulnerable to As3+ toxicity.

  16. Comparative 1H NMR-based metabonomic analysis of HIV-1 sera

    International Nuclear Information System (INIS)

    Philippeos, C.; Steffens, F. E.; Meyer, D.

    2009-01-01

    1 H NMR spectroscopy of sera from HIV-1 infected and uninfected individuals was performed on 300 and 600 MHz instruments. The resultant spectra were automatically data reduced to 90 and 180 integral segments of equal length. Analysis of variance identified significant differences between the sample groups, especially for the samples analyzed on 600 MHz and reduced to fewer segments. Linear discriminant analysis correctly classified 100% of the samples analyzed on the 300 MHz NMR (reduced to 180 segments); an increase in instrument sensitivity resulted in lower percentages of correctly classified samples. Multinomial logistic regression (MLR) resulted in 100% correct classification of all samples from both instruments. Thus 1 H-NMR metabonomics on either instrument distinguishes HIV-positive individuals using or not using anti retroviral therapy, but the sensitivity of the instrument impacts on data reduction. Furthermore, MLR is a novel multivariate statistical technique for improved classification of biological data analyzed in NMR

  17. Comparative {sup 1}H NMR-based metabonomic analysis of HIV-1 sera

    Energy Technology Data Exchange (ETDEWEB)

    Philippeos, C. [University of Johannesburg, Department of Biochemistry (South Africa); Steffens, F. E. [University of Pretoria, Department of Statistics (South Africa); Meyer, D. [University of Pretoria, Department of Biochemistry (South Africa)], E-mail: debra.meyer@up.ac.za

    2009-07-15

    {sup 1}H NMR spectroscopy of sera from HIV-1 infected and uninfected individuals was performed on 300 and 600 MHz instruments. The resultant spectra were automatically data reduced to 90 and 180 integral segments of equal length. Analysis of variance identified significant differences between the sample groups, especially for the samples analyzed on 600 MHz and reduced to fewer segments. Linear discriminant analysis correctly classified 100% of the samples analyzed on the 300 MHz NMR (reduced to 180 segments); an increase in instrument sensitivity resulted in lower percentages of correctly classified samples. Multinomial logistic regression (MLR) resulted in 100% correct classification of all samples from both instruments. Thus {sup 1}H-NMR metabonomics on either instrument distinguishes HIV-positive individuals using or not using anti retroviral therapy, but the sensitivity of the instrument impacts on data reduction. Furthermore, MLR is a novel multivariate statistical technique for improved classification of biological data analyzed in NMR.

  18. Identification and quantitation of 3,4-methylenedioxy-N-methylamphetamine (MDMA, ecstasy) in human urine by 1H NMR spectroscopy. Application to five cases of intoxication.

    Science.gov (United States)

    Liu, Jonathan; Decatur, John; Proni, Gloria; Champeil, Elise

    2010-01-30

    Identification of 3,4-methylenedioxy-N-methylamphetamine (MDMA, ecstasy) in five cases of intoxication using nuclear magnetic resonance (NMR) spectroscopy of human urine is reported. A new water suppression technique PURGE (Presaturation Utilizing Relaxation Gradients and Echoes) was used. A calibration curve was obtained using spiked samples. The method gave a linear response (correlation coefficient of 0.992) over the range 0.01-1mg/mL. Subsequently, quantitation of the amount of MDMA present in the samples was performed. The benefit and reliability of NMR investigations of human urine for cases of intoxication with MDMA are discussed. Published by Elsevier Ireland Ltd.

  19. Sensitivity of 1H NMR analysis of rat urine in relation to toxicometabonomics. Part I: Dose-dependent toxic fffects of Bromobenzene and paracetamol

    NARCIS (Netherlands)

    Schoonen, W.G.E.J.; Kloks, C.P.A.M.; Ploemen, J.P.H.T.M.; Horbach, G.J.; Smit, M.J.; Zandberg, P.; Mellema, J.R.; Zuylen, C.T. van; Tas, A.C.; Nesselrooij, J.H.J. van; Vogels, J.T.W.E.

    2007-01-01

    1H nuclear magnetic resonance (NMR) spectroscopy of rat urine in combination with pattern recognition analysis was evaluated for early noninvasive detection of toxicity of investigational chemical entities. Bromobenzene (B) and paracetamol (P) were administered at five single oral dosages between 2

  20. Comparison of Metabolite Concentrations in the Left Dorsolateral Prefrontal Cortex, the Left Frontal White Matter, and the Left Hippocampus in Patients in Stable Schizophrenia Treated with Antipsychotics with or without Antidepressants. 1H-NMR Spectroscopy Study

    Directory of Open Access Journals (Sweden)

    Dominik Strzelecki

    2015-10-01

    Full Text Available Managing affective, negative, and cognitive symptoms remains the most difficult therapeutic problem in stable phase of schizophrenia. Efforts include administration of antidepressants. Drugs effects on brain metabolic parameters can be evaluated by means of proton nuclear magnetic resonance (1H-NMR spectroscopy. We compared spectroscopic parameters in the left prefrontal cortex (DLPFC, the left frontal white matter (WM and the left hippocampus and assessed the relationship between treatment and the spectroscopic parameters in both groups. We recruited 25 patients diagnosed with schizophrenia (DSM-IV-TR, with dominant negative symptoms and in stable clinical condition, who were treated with antipsychotic and antidepressive medication for minimum of three months. A group of 25 patients with schizophrenia, who were taking antipsychotic drugs but not antidepressants, was matched. We compared metabolic parameters (N-acetylaspartate (NAA, myo-inositol (mI, glutamatergic parameters (Glx, choline (Cho, and creatine (Cr between the two groups. All patients were also assessed with the Positive and Negative Syndrome Scale (PANSS and the Calgary Depression Scale for Schizophrenia (CDSS. In patients receiving antidepressants we observed significantly higher NAA/Cr and NAA/Cho ratios within the DLPFC, as well as significantly higher mI/Cr within the frontal WM. Moreover, we noted significantly lower values of parameters associated with the glutamatergic transmission—Glx/Cr and Glx/Cho in the hippocampus. Doses of antipsychotic drugs in the group treated with antidepressants were also significantly lower in the patients showing similar severity of psychopathology.

  1. Primary structure determination of five sialylated oligosaccharides derived from bronchial- mucus glycoproteins of patients suffering from cystic fibrosis. The occurrence of the NeuAcα(2→3)Galα(1→4)[Fucα(1→3)]GlcNAcα(1→.) structural element revealed by 500-MHz 1H NMR spectroscopy

    NARCIS (Netherlands)

    Vliegenthart, J.F.G.; Lamblin, G.; Boersma, A.; Klein, A.; Roussel, P.; Halbeek, H. van

    1984-01-01

    The structure of sialylated carbohydrate units of bronchial mucins obtained from cystic fibrosis patients was investigated by 500-MHz 1H NMR spectroscopy in conjunction with sugar analysis. After subjecting the mucins to alkaline borohydride degradation, sialylated oligosaccharide-alditols were

  2. The 1H NMR profile of healthy dog cerebrospinal fluid.

    Directory of Open Access Journals (Sweden)

    Mihai Musteata

    Full Text Available The availability of data for reference values in cerebrospinal fluid for healthy humans is limited due to obvious practical and ethical issues. The variability of reported values for metabolites in human cerebrospinal fluid is quite large. Dogs present great similarities with humans, including in cases of central nervous system pathologies. The paper presents the first study on healthy dog cerebrospinal fluid metabolomic profile using (1H NMR spectroscopy. A number of 13 metabolites have been identified and quantified from cerebrospinal fluid collected from a group of 10 mix breed healthy dogs. The biological variability as resulting from the relative standard deviation of the physiological concentrations of the identified metabolites had a mean of 18.20% (range between 9.3% and 44.8%. The reported concentrations for metabolites may be used as normal reference values. The homogeneity of the obtained results and the low biologic variability show that the (1H NMR analysis of the dog's cerebrospinal fluid is reliable in designing and interpreting clinical and therapeutic trials in dogs with central nervous system pathologies.

  3. Observation by flow 1H NMR and dimerization kinetics and products of reactive ortho-quinodimethanes and benzocyclobutadiene

    International Nuclear Information System (INIS)

    Fischer, D.

    1990-01-01

    The reactive o-quinodimethanes, 1,2-dimethylene-1,2-dihydronaphthalene (9) and o-xylylene (1) were observed by flow 1 H NMR spectroscopy at room temperature. The 1 H NMR spectrum of 9 was obtained in the absence of precursor and dimers. However, the 1 H NMR spectrum of the more reactive 1, generated in a similar manner from [o-((trimethylsilyl)methyl)benzyl]trimethylammonium iodide (5.) could be obtained only in the presence of its stable [4 + 2] and [4 + 4] dimers. The dimerization kinetics of 3-methyl- (5'), 3,6-dimethyl- (11), 3-isopropyl- (12), and 3,6-diisoproply-1,2-xylylene (13) in acetonitrile (CH 3 CN) were studied by stopped-flow UV-visible spectroscopy. Fluoride ion induced 1,2-elimination from 2-elimination from 2-trimethylsilylbenzocyclobutenyl-1 mesylate (26) was used to generate the reactive molecule benzocyclobutadiene (1') in CD 3 CN, which was observed by flow 1 H NMR spectroscopy at room temperature. The 1 H NMR spectrum (in CD 3 CN) of 1,2-dimethylene-1,2-dihydrothiophene (1 double-prime), obtained by fluoride ion induced 1,4-elimination from 3-(trimethylammoniummethyl)-2-(trimethylsilylmethyl)thiophene iodine was observed by flow 1 H NMR spectroscopy at room temperature. The dimerization rate of 1 double-prime in CH 3 CN, generated in the same manner, was measured by UV-visible spectroscopy. 166 refs., 7 figs., 7 tabs

  4. Quantitative produced water analysis using mobile 1H NMR

    International Nuclear Information System (INIS)

    Wagner, Lisabeth; Fridjonsson, Einar O; May, Eric F; Stanwix, Paul L; Graham, Brendan F; Carroll, Matthew R J; Johns, Michael L; Kalli, Chris

    2016-01-01

    Measurement of oil contamination of produced water is required in the oil and gas industry to the (ppm) level prior to discharge in order to meet typical environmental legislative requirements. Here we present the use of compact, mobile 1 H nuclear magnetic resonance (NMR) spectroscopy, in combination with solid phase extraction (SPE), to meet this metrology need. The NMR hardware employed featured a sufficiently homogeneous magnetic field, such that chemical shift differences could be used to unambiguously differentiate, and hence quantitatively detect, the required oil and solvent NMR signals. A solvent system consisting of 1% v/v chloroform in tetrachloroethylene was deployed, this provided a comparable 1 H NMR signal intensity for the oil and the solvent (chloroform) and hence an internal reference 1 H signal from the chloroform resulting in the measurement being effectively self-calibrating. The measurement process was applied to water contaminated with hexane or crude oil over the range 1–30 ppm. The results were validated against known solubility limits as well as infrared analysis and gas chromatography. (paper)

  5. LipSpin: A New Bioinformatics Tool for Quantitative 1H NMR Lipid Profiling.

    Science.gov (United States)

    Barrilero, Rubén; Gil, Miriam; Amigó, Núria; Dias, Cintia B; Wood, Lisa G; Garg, Manohar L; Ribalta, Josep; Heras, Mercedes; Vinaixa, Maria; Correig, Xavier

    2018-02-06

    The structural similarity among lipid species and the low sensitivity and spectral resolution of nuclear magnetic resonance (NMR) have traditionally hampered the routine use of 1 H NMR lipid profiling of complex biological samples in metabolomics, which remains mostly manual and lacks freely available bioinformatics tools. However, 1 H NMR lipid profiling provides fast quantitative screening of major lipid classes (fatty acids, glycerolipids, phospholipids, and sterols) and some individual species and has been used in several clinical and nutritional studies, leading to improved risk prediction models. In this Article, we present LipSpin, a free and open-source bioinformatics tool for quantitative 1 H NMR lipid profiling. LipSpin implements a constrained line shape fitting algorithm based on voigt profiles and spectral templates from spectra of lipid standards, which automates the analysis of severely overlapped spectral regions and lipid signals with complex coupling patterns. LipSpin provides the most detailed quantification of fatty acid families and choline phospholipids in serum lipid samples by 1 H NMR to date. Moreover, analytical and clinical results using LipSpin quantifications conform with other techniques commonly used for lipid analysis.

  6. Photochemical generation and 1H NMR detection of alkyl allene oxides in solution

    International Nuclear Information System (INIS)

    Breen, L.E.; Schepp, N.P.; Tan, C.-H.E.

    2005-01-01

    Irradiation of substituted 5-alkyl-4,5-epoxyvalerophenones leads to the formation of alkyl allene oxides that, in some cases, are sufficiently long-lived to be detected at room temperature by 1 H NMR spectroscopy. Absolute lifetime measurements show that the size of the alkyl group has a significant influence on the reactivity of the allene oxide, with tert-butyl allene oxide having a lifetime of 24 h in CD 3 CN at room temperature that is considerably longer than the 1.5 h lifetime of the ethyl allene oxide. The allene oxides react rapidly with water to give α-hydroxyketones. The mechanism involves nucleophilic attack to the epoxide carbon to give an enol, which can also be detected as an intermediate by 1 H NMR spectroscopy. (author)

  7. Utilization of 1H NMR in the determination of absolute configuration of alcohols

    International Nuclear Information System (INIS)

    Barreiros, Marizeth L.; David, Jorge M.; David, Juceni P. . E-juceni@ufba.br

    2005-01-01

    This review reports the determination of absolute configuration of primary and secondary alcohols by 1 H NMR spectroscopy, using the Mosher method. This method consists in the derivatization of an alcohol possessing unknown absolute configuration with one or both enantiomers of an auxiliary reagent. The resulting diastereoisomer spectra are registered and compared, and the chemical shift differences (Δδ R,S = δ R - δ S ) are measured. The determination of the absolute configuration of the alcohol molecule is based on the correlation between its chiral center and the auxiliary reagent's chiral center. Therefore, the determination of the absolute configuration depends on aromatic ring shielding effects on the substituents of the alcohol as evidenced by the 1 H NMR spectrum. (author)

  8. Discrimination of Aurantii Fructus Immaturus and Fructus Poniciri Trifoliatae Immaturus by Flow Injection UV Spectroscopy (FIUV) and 1H NMR using Partial Least-squares Discriminant Analysis (PLS-DA)

    Science.gov (United States)

    Two simple fingerprinting methods, flow-injection UV spectroscopy (FIUV) and 1H nuclear magnetic resonance (NMR), for discrimination of Aurantii FructusImmaturus and Fructus Poniciri TrifoliataeImmaturususing were described. Both methods were combined with partial least-squares discriminant analysis...

  9. Novel 1H NMR approach to quantitative tissue oximetry using hexamethyldisiloxane.

    Science.gov (United States)

    Kodibagkar, Vikram D; Cui, Weina; Merritt, Matthew E; Mason, Ralph P

    2006-04-01

    19F NMR spin-lattice relaxometry of hexafluorobenzene (HFB) has been shown to be a highly sensitive indicator of tumor oxygenation. In this study hexamethyldisiloxane (HMDSO) was identified as a proton NMR analog, and its potential as a probe for investigating dynamic changes in tissue oxygen tension (pO2) was evaluated. HMDSO has a single proton resonance (delta= -0.3 ppm) and the spin-lattice relaxation rate, Rl (= 1/T1) exhibits a linear dependence on pO2: R1 (s(-1)) = 0.1126 + 0.0013* pO2 (torr) at 37 degrees C. To demonstrate application in vivo, HMDSO was administered into healthy rat thigh muscle (100 microl) and tumors (50 microl). Local pO2 was determined by using pulse-burst saturation recovery (PBSR) 1H NMR spectroscopy to assess R1. Water and fat signals were effectively suppressed by frequency-selective excitation of the HMDSO resonance. Rat thigh muscle had a mean baseline pO2 of 35 +/- 11 torr, with a typical stability of +/-3 torr over 20 min, when the rats breathed air. Altering the inhaled gas to oxygen produced a significant increase in pO2 to 100-200 torr. In tumors, altering the inspired gas also produced significant (albeit generally smaller) changes. This new pO2 reporter molecule offers a potentially valuable new tool for investigating pO2 in vivo. (c) 2006 Wiley-Liss, Inc.

  10. 1H-NMR, 1H-NMR T2-edited, and 2D-NMR in bipolar disorder metabolic profiling.

    Science.gov (United States)

    Sethi, Sumit; Pedrini, Mariana; Rizzo, Lucas B; Zeni-Graiff, Maiara; Mas, Caroline Dal; Cassinelli, Ana Cláudia; Noto, Mariane N; Asevedo, Elson; Cordeiro, Quirino; Pontes, João G M; Brasil, Antonio J M; Lacerda, Acioly; Hayashi, Mirian A F; Poppi, Ronei; Tasic, Ljubica; Brietzke, Elisa

    2017-12-01

    The objective of this study was to identify molecular alterations in the human blood serum related to bipolar disorder, using nuclear magnetic resonance (NMR) spectroscopy and chemometrics. Metabolomic profiling, employing 1 H-NMR, 1 H-NMR T 2 -edited, and 2D-NMR spectroscopy and chemometrics of human blood serum samples from patients with bipolar disorder (n = 26) compared with healthy volunteers (n = 50) was performed. The investigated groups presented distinct metabolic profiles, in which the main differential metabolites found in the serum sample of bipolar disorder patients compared with those from controls were lipids, lipid metabolism-related molecules (choline, myo-inositol), and some amino acids (N-acetyl-L-phenyl alanine, N-acetyl-L-aspartyl-L-glutamic acid, L-glutamine). In addition, amygdalin, α-ketoglutaric acid, and lipoamide, among other compounds, were also present or were significantly altered in the serum of bipolar disorder patients. The data presented herein suggest that some of these metabolites differentially distributed between the groups studied may be directly related to the bipolar disorder pathophysiology. The strategy employed here showed significant potential for exploring pathophysiological features and molecular pathways involved in bipolar disorder. Thus, our findings may contribute to pave the way for future studies aiming at identifying important potential biomarkers for bipolar disorder diagnosis or progression follow-up.

  11. Metabolite profiling of leek (Allium porrum L) cultivars by (1) H NMR and HPLC-MS.

    Science.gov (United States)

    Soininen, Tuula H; Jukarainen, Niko; Soininen, Pasi; Auriola, Seppo O K; Julkunen-Tiitto, Riitta; Oleszek, Wieslaw; Stochmal, Anna; Karjalainen, Reijo O; Vepsäläinen, Jouko J

    2014-01-01

    Leek (Allium ampeloprasum var. porrum) is consumed as a vegetable throughout the world. However, little is known about the metabolites of leek cultivars, especially those with potentially important beneficial properties for human health. We provide new information for the overall metabolite composition of several leek cultivars grown in Europe by using HPLC-MS and (1) H NMR. The use of a novel CTLS/NMR (constrained total-line-shape nuclear magnetic resonance) approach was found to be capable of reliable quantification, even with overlapping metabolite signals in the (1) H NMR of plant metabolites. Additionally, a new application for leek flavonoids was optimised for HPLC-MS. The total concentration of carbohydrates (glucose, fructose, kestose/nystose and sucrose) and nine amino acids varied by fourfold in leek juice from different cultivars, while the total concentrations of four organic acids were similar in all cultivars. All the quantified flavonols were kaempferol derivatives or quercetin derivatives and threefold differences in flavonol concentrations were detected between cultivars. In this study, various phytochemical profiles were determined for several leek cultivars by (1) H NMR spectroscopy with CTLS combined with HPLC-MS. The wide variation in bioactive compounds among commercial leek cultivars offers promising opportunities for breeders to raise the levels of important biochemical compounds in leek breeding lines, and also provides some objective measure for quality assurance for the leek industry. Copyright © 2014 John Wiley & Sons, Ltd.

  12. Criterious Preparation and Characterization of Earthworm-composts in View of Animal Waste Recycling: Part II. A Synergistic Utilization of EPR and 1H NMR Spectroscopies on the Characterization of Humic Acids from Vermicomposts

    Directory of Open Access Journals (Sweden)

    Guimarães Elisete

    2001-01-01

    Full Text Available Humic acids (HA extracted from sheep (SHHA, cow (COHA, goat (GOHA and rabbit (RAHA vermicomposted manure were analyzed by electron paramagnetic resonance and hydrogen nuclear magnetic resonance spectroscopies. Carboxylic acids, amine, amide, ester, ether and phenol functions bonded to saturated aliphatic, unsaturated aliphatic conjugated double and single bonds, and aromatic chains constitute the backbone structure of these fresh humic substances (HS. Mn2+ outer sphere complexes (SHHA, COHA, Fe3+ axial (COHA, RAHA or rhombic (SHAHA, COHA, GOHA, RAHA complexes and Cu2+ as weak field (COHA, GOHA, RAHA and strong field (SHAHA, COHA, GOHA, RAHA complexes were characterized.

  13. Applications of 1H-NMR relaxometry in experimental liver studies

    International Nuclear Information System (INIS)

    Holzmueller, P.

    1992-01-01

    Purpose of this study was to investigate applications of proton nuclear magnetic resonance ( 1 H-NMR) relaxometry in experimental medicine. Relaxometry was performed by measurements of spin-lattice (T 1 ) and spin-spin (T 2 ) relaxation time parameters on liver biopsies up to four hours after biopsy excision. Variations of relaxation times due to species and strain, different sample handling and different liver damage models, ethionine fatty liver and paracetamol liver necrosis, were investigated. Cell integrity effects were studied on homogenized liver samples. Relaxation time parameters, especially 'main' components T 1A and T 2A of biexponential model fit, were identified to react very sensitive after tissue damages as well as to cell viability. Thus, investigation of stored liver grafts was performed in order to evaluate the possibility of a rapid liver graft viability testing method for human liver transplantation surgery by 1 H-NMR relaxometry. Another series of measurements was performed to investigate the applicability of isoflurane anesthesia for in vivo NMR experiments. This study proved the good appropriateness of isoflurane for that purpose provided that physiological monitoring and individual adjustment of anesthesia are performed. In these investigations it could be revealed that mainly T 1A and T 2A are influenced by tissue condition and that different information is inherent in these two parameters, with T 2A reflecting tissue viability and changes of tissue conditions very sensitively but rather unspecifically in respect to the damage applied. Based on these results the following future applications of 1 H-NMR relaxometry are suggested : (1) model investigations, (2) investigation of given pathologies, (3) investigation of basic requirements for in vivo NMR and (4) application in a liver graft viability testing protocol, which seems to be the most important future application of 1 H-NMR relaxometry in medicine. (author)

  14. 31P-edited diffusion-ordered 1H NMR spectroscopy for the spectral isolation and identification of organophosphorus compounds related to chemical weapons agents and their degradation products.

    Science.gov (United States)

    Mayer, Brian P; Valdez, Carlos A; Hok, Saphon; Chinn, Sarah C; Hart, Bradley R

    2012-12-04

    Organophosphorus compounds represent a large class of molecules that include pesticides, flame-retardants, biologically relevant molecules, and chemical weapons agents (CWAs). The detection and identification of organophosphorus molecules, particularly in the cases of pesticides and CWAs, are paramount to the verification of international treaties by various organizations. To that end, novel analytical methodologies that can provide additional support to traditional analyses are important for unambiguous identification of these compounds. We have developed an NMR method that selectively edits for organophosphorus compounds via (31)P-(1)H heteronuclear single quantum correlation (HSQC) and provides an additional chromatographic-like separation based on self-diffusivities of the individual species via (1)H diffusion-ordered spectroscopy (DOSY): (1)H-(31)P HSQC-DOSY. The technique is first validated using the CWA VX (O-ethyl S-[2-(diisopropylamino)ethyl] methylphosphonothioate) by traditional two-dimensional DOSY spectra. We then extend this technique to a complex mixture of VX degradation products and identify all the main phosphorus-containing byproducts generated after exposure to a zinc-cyclen organometallic homogeneous catalyst.

  15. Side-chain dynamics of a detergent-solubilized membrane protein: Measurement of tryptophan and glutamine hydrogen-exchange rates in M13 coat protein by 1H NMR spectroscopy

    International Nuclear Information System (INIS)

    O'Neil, J.D.J.; Sykes, B.D.

    1989-01-01

    M13 coat protein is a small (50 amino acids) lipid-soluble protein that becomes an integral membrane protein during the infection stage of the life cycle of the M13 phage and is therefore used as a model membrane protein. To study side-chain dynamics in the protein, the authors have measured individual hydrogen-exchange rates for a primary amide in the side chain of glutamine-15 and for the indole amine of tryptophan-26. The protein was solubilized with the use of perdeuteriated sodium dodecyl sulfate (SDS), and hydrogen-exchange rates were measured by using 1 H nuclear magnetic resonance spectroscopy. The glutamine-15 syn proton exchanged at a rate identical with that in glutamine model peptides except that the pH corresponding to minimum exchange was elevated by about 1.5 pH units. The tryptophan-26 indole amine proton exchange was biphasic, suggesting that two populations of tryptophan-26 exist. It is suggested that the two populations may reflect protein dimerization or aggregation in the SDS micelles. The pH values of minimum exchange for tryptophan-26 in both environments were also elevated by 1.3-1.9 pH units. This phenomenon is reproduced when small tryptophan- and glutamine-containing hydrophobic peptides are dissolved in the presence of SDS micelles. The electrostatic nature of this phenomenon is proven by showing that the minimum pH for exchange can be reduced by dissolving the hydrophobic peptides in the positively charged detergent micelle dodecyltrimethylammonium bromide

  16. Evaluation of mineral oil saturated hydrocarbons (MOSH and mineral oil aromatic hydrocarbons (MOAH in pure mineral hydrocarbon-based cosmetics and cosmetic raw materials using 1H NMR spectroscopy [version 2; referees: 3 approved

    Directory of Open Access Journals (Sweden)

    Dirk W. Lachenmeier

    2017-08-01

    Full Text Available Mineral hydrocarbons consist of two fractions, mineral oil saturated hydrocarbons (MOSH and mineral oil aromatic hydrocarbons (MOAH. MOAH is a potential public health hazard because it may include carcinogenic polycyclic compounds. In the present study, 400 MHz nuclear magnetic resonance (NMR spectroscopy was introduced, in the context of official controls, to measure MOSH and MOAH in raw materials or pure mineral hydrocarbon final products (cosmetics and medicinal products. Quantitative determination (qNMR has been established using the ERETIC methodology (electronic reference to access in vivo concentrations based on the PULCON principle (pulse length based concentration determination. Various mineral hydrocarbons (e.g., white oils, paraffins or petroleum jelly were dissolved in deuterated chloroform. The ERETIC factor was established using a quantification reference sample containing ethylbenzene and tetrachloronitrobenzene. The following spectral regions were integrated: MOSH δ 3.0 – 0.2 ppm and MOAH δ 9.2 - 6.5, excluding solvent signals. Validation showed a sufficient precision of the method with a coefficient of variation <6% and a limit of detection <0.1 g/100 g. The applicability of the method was proven by analysing 27 authentic samples with MOSH and MOAH contents in the range of 90-109 g/100 g and 0.02-1.10 g/100 g, respectively. It is important to distinguish this new NMR-approach from the hyphenated liquid chromatography-gas chromatography methodology previously used to characterize MOSH/MOAH amounts in cosmetic products. For mineral hydrocarbon raw materials or pure mineral hydrocarbon-based cosmetic products, NMR delivers higher specificity without any sample preparation besides dilution. Our sample survey shows that previous methods may have overestimated the MOAH amount in mineral oil products and opens new paths to characterize this fraction. Therefore, the developed method can be applied for routine monitoring of consumer

  17. SU-E-I-34: Intermittent Low- and High-Dose Ethanol Exposure Alters Neurochemical Responses in Adult Rat Brain: An Ex Vivo 1H NMR Spectroscopy at 11.7 T

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Do-Wan; Kim, Sang-Young; Song, Kyu-Ho; Choe, Bo-Young [Department of Biomedical Engineering, and Research Institute of Biomedical Engineering, The Catholic University of Korea College of Medicine, Seoul (Korea, Republic of)

    2014-06-01

    Purpose: The first goal of this study was to determine the influence of the dose-dependent effects of intermittent ethanol intoxication on cerebral neurochemical responses among sham controls and low- and high-dose-ethanol-exposed rats with ex vivo high-resolution spectra. The second goal of this study was to determine the correlations between the metabolite-metabolite levels (pairs-of-metabolite levels) from all of the individual data from the frontal cortex of the intermittent ethanol-intoxicated rats. Methods: Eight-week-old male Wistar rats were divided into 3 groups. Twenty rats in the LDE (n = 10) and the HDE (n = 10) groups received ethanol doses of 1.5 g/kg and 2.5 g/kg, respectively, through oral gavage every 8-h for 4 days. At the end of the 4-day intermittent ethanol exposure, one-dimensional ex vivo 500-MHz proton nuclear magnetic resonance spectra were acquired from 30 samples of the frontal cortex region (from the 3 groups). Results: Normalized total-N-acetylaspartate (tNAA: NAA + NAAG [N-acetylaspartyl-glutamate]), gamma-aminobutyric acid (GABA), and glutathione (GSH) levels were significantly lower in the frontal cortex of the HDE-exposed rats than that of the LDE-exposed rats. Moreover, compared to the CNTL group, the LDE rats exhibited significantly higher normalized GABA levels. The 6 pairs of normalized metabolite levels were positively (+) or negatively (−) correlated in the rat frontal cortex as follows: tNAA and GABA (+), tNAA and Aspartate (Asp) (−), myo-Inositol (mIns) and Asp (−), mIns and Alanine (+), mIns and Taurine (+), and mIns and tNAA (−). Conclusion: Our results suggested that repeated intermittent ethanol intoxication might result in neuronal degeneration and dysfunction, changes in the rate of GABA synthesis, and oxidative stress in the rat frontal cortex. Our ex vivo 1H high-resolution-magic angle spinning nuclear magnetic resonance spectroscopy results suggested some novel metabolic markers for the dose

  18. SU-E-I-34: Intermittent Low- and High-Dose Ethanol Exposure Alters Neurochemical Responses in Adult Rat Brain: An Ex Vivo 1H NMR Spectroscopy at 11.7 T

    International Nuclear Information System (INIS)

    Lee, Do-Wan; Kim, Sang-Young; Song, Kyu-Ho; Choe, Bo-Young

    2014-01-01

    Purpose: The first goal of this study was to determine the influence of the dose-dependent effects of intermittent ethanol intoxication on cerebral neurochemical responses among sham controls and low- and high-dose-ethanol-exposed rats with ex vivo high-resolution spectra. The second goal of this study was to determine the correlations between the metabolite-metabolite levels (pairs-of-metabolite levels) from all of the individual data from the frontal cortex of the intermittent ethanol-intoxicated rats. Methods: Eight-week-old male Wistar rats were divided into 3 groups. Twenty rats in the LDE (n = 10) and the HDE (n = 10) groups received ethanol doses of 1.5 g/kg and 2.5 g/kg, respectively, through oral gavage every 8-h for 4 days. At the end of the 4-day intermittent ethanol exposure, one-dimensional ex vivo 500-MHz proton nuclear magnetic resonance spectra were acquired from 30 samples of the frontal cortex region (from the 3 groups). Results: Normalized total-N-acetylaspartate (tNAA: NAA + NAAG [N-acetylaspartyl-glutamate]), gamma-aminobutyric acid (GABA), and glutathione (GSH) levels were significantly lower in the frontal cortex of the HDE-exposed rats than that of the LDE-exposed rats. Moreover, compared to the CNTL group, the LDE rats exhibited significantly higher normalized GABA levels. The 6 pairs of normalized metabolite levels were positively (+) or negatively (−) correlated in the rat frontal cortex as follows: tNAA and GABA (+), tNAA and Aspartate (Asp) (−), myo-Inositol (mIns) and Asp (−), mIns and Alanine (+), mIns and Taurine (+), and mIns and tNAA (−). Conclusion: Our results suggested that repeated intermittent ethanol intoxication might result in neuronal degeneration and dysfunction, changes in the rate of GABA synthesis, and oxidative stress in the rat frontal cortex. Our ex vivo 1H high-resolution-magic angle spinning nuclear magnetic resonance spectroscopy results suggested some novel metabolic markers for the dose

  19. MetIDB: A Publicly Accessible Database of Predicted and Experimental 1H NMR Spectra of Flavonoids

    NARCIS (Netherlands)

    Mihaleva, V.V.; Beek, te T.A.; Zimmeren, van F.; Moco, S.I.A.; Laatikainen, R.; Niemitz, M.; Korhonen, S.P.; Driel, van M.A.; Vervoort, J.

    2013-01-01

    Identification of natural compounds, especially secondary metabolites, has been hampered by the lack of easy to use and accessible reference databases. Nuclear magnetic resonance (NMR) spectroscopy is the most selective technique for identification of unknown metabolites. High quality 1H NMR (proton

  20. Polymer Molecular Weight Analysis by [Superscript 1]H NMR Spectroscopy

    Science.gov (United States)

    Izunobi, Josephat U.; Higginbotham, Clement L.

    2011-01-01

    The measurement and analysis of molecular weight and molecular weight distribution remain matters of fundamental importance for the characterization and physical properties of polymers. Gel permeation chromatography (GPC) is the most routinely used method for the molecular weight determination of polymers whereas matrix-assisted laser…

  1. {sup 1}H NMR investigation of self-association of vanillin in aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Bogdan, Mircea; Floare, Calin G; PIrnau, Adrian, E-mail: mircea.bogdan@itim-cj.r [National Institute for Research and Development of Isotopic and Molecular Technologies, 65-103 Donath, 400293 Cluj-Napoca (Romania)

    2009-08-01

    A self-association of vanillin have been studied by {sup 1}H NMR spectroscopy using the analysis of proton chemical shifts changes in aqueous solution as a function of concentration. The experimental results have been analysed using indefinite non-cooperative and cooperative models of molecular self-association, enabling the determination of equilibrium constants, parameters of cooperativity and the limiting values of vanillin proton chemical shifts in the complex. It was found that the dimer formation creates energetically favourable conditions for subsequent molecular association.

  2. 1H NMR investigation of self-association of vanillin in aqueous solution

    International Nuclear Information System (INIS)

    Bogdan, Mircea; Floare, Calin G; PIrnau, Adrian

    2009-01-01

    A self-association of vanillin have been studied by 1 H NMR spectroscopy using the analysis of proton chemical shifts changes in aqueous solution as a function of concentration. The experimental results have been analysed using indefinite non-cooperative and cooperative models of molecular self-association, enabling the determination of equilibrium constants, parameters of cooperativity and the limiting values of vanillin proton chemical shifts in the complex. It was found that the dimer formation creates energetically favourable conditions for subsequent molecular association.

  3. 1H NMR visibility of mammalian glycogen in solution

    International Nuclear Information System (INIS)

    Zang, L.H.; Rothman, D.L.; Shulman, R.G.

    1990-01-01

    High-resolution 1 H NMR spectra of rabbit liver glycogen in 2 H 2 O were obtained at 500 MHz, and several resonances were assigned by comparison with the chemical shifts of α-linked diglucose molecules. The NMR relaxation times T 1 and T 2 of glycogen in 2 H 2 O were determined to be 1.1 and 0.029 s, respectively. The measured natural linewidth of the carbon-1 proton is in excellent agreement with that calculated from T 2 . The visibility measurements made by digesting glycogen and comparing glucose and glycogen signal intensities demonstrate that in spite of the very high molecular weight, all of the proton nuclei in glycogen contribute to the NMR spectrum. The result is not unexpected, since 100% NMR visibility was previously observed from the carbon nuclei of glycogen, due to the rapid intramolecular motions

  4. Discrimination of sugarcane according to cultivar by 1H NMR and chemometric analyses

    Energy Technology Data Exchange (ETDEWEB)

    Alves Filho, Elenilson G.; Silva, Lorena M.A.; Choze, Rafael; Liao, Luciano M. [Laboratorio de Ressonancia Magnetica Nuclear, Instituto de Quimica, Universidade Federal de Goias (UFG), Goiania, GO (Brazil); Honda, Neli K.; Alcantara, Glaucia B. [Departamento de Quimica, Universidade Federal de Mato Grosso do Sul (UFMS), Campo Grande, MS (Brazil)

    2012-07-01

    Several technologies for the development of new sugarcane cultivars have mainly focused on the increase in productivity and greater disease resistance. Sugarcane cultivars are usually identified by the organography of the leaves and stems, the analysis of peroxidase and esterase isoenzyme activities and the total soluble protein as well as soluble solid content. Nuclear magnetic resonance (NMR) associated with chemometric analysis has proven to be a valuable tool for cultivar assessment. Thus, this article describes the potential of chemometric analysis applied to 1H high resolution magic angle spinning (HRMAS) and NMR in solution for the investigation of sugarcane cultivars. For this purpose, leaves from eight different cultivars of sugarcane were investigated by {sup 1}H NMR spectroscopy in combination with chemometric analysis. The approach shows to be a useful tool for the distinction and classification of different sugarcane cultivars as well as to access the differences on its chemical composition. (author)

  5. Novel determination of the total phenolic content in crude plant extracts by the use of 1H NMR of the -OH spectral region

    International Nuclear Information System (INIS)

    Nerantzaki, A.A.; Tsiafoulis, C.G.; Charisiadis, P.; Kontogianni, V.G.; Gerothanassis, I.P.

    2011-01-01

    A novel method for the determination of the total phenolic content using 1 H NMR spectroscopy in the -OH spectral region is presented. The use of DMSO-d 6 , which is an aprotic and strongly hydrogen bonding solvent, allows the 'appearance' of the relative sharp resonances of phenolic hydroxyl protons in the region of 8-14 ppm. The determination of the total phenolic -OH content requires three steps: (i) a 1D 1 H NMR spectrum is obtained in DMSO-d 6 ; (ii) a subsequent 1D 1 H NMR spectrum is recorded with irradiation of the residual water signal which results in the elimination or reduction of the phenolic -OH groups, due to proton exchange; and (iii) 1D 1 H NMR spectra are recorded with the addition of a progressively increased amount of salt, NaHCO 3 , which results in extensive linebroadening of the COOH resonances thus allowing the discrimination of the phenolic from the carboxylic acid signals. Integration, with respect to the internal standard TSP-d 4 , of the signal resonances between 14 and 8 ppm in spectrum (i) which are either eliminated or reduced in intensity in steps (ii) and (iii) allows the quantitation of the total phenolic content. The method was applied to model compounds, a mixture of them and several extracts of natural products. The results of the proposed 1 H NMR method were compared to the Folin-Ciocalteu (FC) reagent method. Additionally, since 1 H NMR refers to the total phenolic hydroxyl protons, a reaction factor, A e , is proposed that corresponds to the hydroxyl reactivity. The 1 H NMR method is rapid and accurate bearing the inherent advantages of the NMR spectroscopy and can be applied directly in complex extracts. Furthermore, it can be applied in a wide range of matrixes from crude plant extracts and food products to biological samples.

  6. 1H NMR of High-Potential Iron-Sulfur Protein from the Purple Non-Sulfur Bacterium Rhodoferax fermentans

    DEFF Research Database (Denmark)

    Ciurli, Stefano; Cremonini, Mauro Andrea; Kofod, Pauli

    1996-01-01

    residues bound to the [4Fe-4S]3+/2+ cluster have been performed using one-dimensional NOE and exchange spectroscopy experiments. 1H-NMR hyperfine shifts and relaxation rates of cluster-bound Cys β-CH2 protons indicate that in the [4Fe-4S]3+ cluster one iron ion can be formally described as Fe(III), while......Oxidized and reduced forms of high-potential iron-sulfur protein (HiPIP) from the purple non-sulfur photosynthetic bacterium Rhodoferux fermentans have been characterized using 1H-NMR spectroscopy. Pairwise and sequence-specific assignments of hyperfine-shifted 1H-NMR signals to protons of cysteine...... longitudinal relaxation rates of Cys β-CH2 protons in HiPIPs from six different sources as a function of the Fe-S-Cβ-Cα dihedral angle, indicate that the major contribution is due to a dipolar metal-centered mechanism, with a non-negligeable contribution from a ligand-centered dipolar mechanism which involves...

  7. Reliability of ^1^H NMR analysis for assessment of lipid oxidation at frying temperatures

    Science.gov (United States)

    The reliability of a method using ^1^H NMR analysis for assessment of oil oxidation at a frying temperature was examined. During heating and frying at 180 °C, changes of soybean oil signals in the ^1^H NMR spectrum including olefinic (5.16-5.30 ppm), bisallylic (2.70-2.88 ppm), and allylic (1.94-2.1...

  8. A novel Bayesian approach to quantify clinical variables and to determine their spectroscopic counterparts in 1H NMR metabonomic data

    Directory of Open Access Journals (Sweden)

    Kaski Kimmo

    2007-05-01

    Full Text Available Abstract Background A key challenge in metabonomics is to uncover quantitative associations between multidimensional spectroscopic data and biochemical measures used for disease risk assessment and diagnostics. Here we focus on clinically relevant estimation of lipoprotein lipids by 1H NMR spectroscopy of serum. Results A Bayesian methodology, with a biochemical motivation, is presented for a real 1H NMR metabonomics data set of 75 serum samples. Lipoprotein lipid concentrations were independently obtained for these samples via ultracentrifugation and specific biochemical assays. The Bayesian models were constructed by Markov chain Monte Carlo (MCMC and they showed remarkably good quantitative performance, the predictive R-values being 0.985 for the very low density lipoprotein triglycerides (VLDL-TG, 0.787 for the intermediate, 0.943 for the low, and 0.933 for the high density lipoprotein cholesterol (IDL-C, LDL-C and HDL-C, respectively. The modelling produced a kernel-based reformulation of the data, the parameters of which coincided with the well-known biochemical characteristics of the 1H NMR spectra; particularly for VLDL-TG and HDL-C the Bayesian methodology was able to clearly identify the most characteristic resonances within the heavily overlapping information in the spectra. For IDL-C and LDL-C the resulting model kernels were more complex than those for VLDL-TG and HDL-C, probably reflecting the severe overlap of the IDL and LDL resonances in the 1H NMR spectra. Conclusion The systematic use of Bayesian MCMC analysis is computationally demanding. Nevertheless, the combination of high-quality quantification and the biochemical rationale of the resulting models is expected to be useful in the field of metabonomics.

  9. Complete 1H NMR spectral analysis of ten chemical markers of Ginkgo biloba.

    Science.gov (United States)

    Napolitano, José G; Lankin, David C; Chen, Shao-Nong; Pauli, Guido F

    2012-08-01

    The complete and unambiguous (1)H NMR assignments of ten marker constituents of Ginkgo biloba are described. The comprehensive (1)H NMR profiles (fingerprints) of ginkgolide A, ginkgolide B, ginkgolide C, ginkgolide J, bilobalide, quercetin, kaempferol, isorhamnetin, isoquercetin, and rutin in DMSO-d(6) were obtained through the examination of 1D (1)H NMR and 2D (1)H,(1)H-COSY data, in combination with (1)H iterative full spin analysis (HiFSA). The computational analysis of discrete spin systems allowed a detailed characterization of all the (1)H NMR signals in terms of chemical shifts (δ(H)) and spin-spin coupling constants (J(HH)), regardless of signal overlap and higher order coupling effects. The capability of the HiFSA-generated (1)H fingerprints to reproduce experimental (1)H NMR spectra at different field strengths was also evaluated. As a result of this analysis, a revised set of (1)H NMR parameters for all ten phytoconstituents was assembled. Furthermore, precise (1)H NMR assignments of the sugar moieties of isoquercetin and rutin are reported for the first time. Copyright © 2012 John Wiley & Sons, Ltd.

  10. UV-vis, IR and 1H NMR spectroscopic studies and characterization of ionic-pair crystal violet-oxytetracycline

    Science.gov (United States)

    Orellana, Sandra; Soto, César; Toral, M. Inés

    2010-01-01

    The present study shows the formation and characterization of the ionic-pair between the antibiotic oxytetracycline and the dye crystal violet in ammonia solution pH 9.0 ± 0.2 extracted into chloroform. The characterization was demonstrated using UV-vis spectrophotometry, 1H NMR, measurement of relaxation times T1 and IR spectroscopy, using a comparison between the signals of individual pure compounds with the signals with the mixture CV-OTC in different alkaline media. The formation of ionic-pair was also corroborated by new signals and chemical shifts. (2D) NMR spectroscopy experiments show that the interaction is electrostatic.

  11. Complete 1H NMR spectral analysis of ten chemical markers of Ginkgo biloba

    OpenAIRE

    Napolitano, José G.; Lankin, David C.; Chen, Shao-Nong; Pauli, Guido F.

    2012-01-01

    The complete and unambiguous 1H NMR assignments of ten marker constituents of Ginkgo biloba are described. The comprehensive 1H NMR profiles (fingerprints) of ginkgolide A, ginkgolide B, ginkgolide C, ginkgolide J, bilobalide, quercetin, kaempferol, isorhamnetin, isoquercetin, and rutin in DMSO-d6 were obtained through the examination of 1D 1H NMR and 2D 1H,1H-COSY data, in combination with 1H iterative Full Spin Analysis (HiFSA). The computational analysis of discrete spin systems allowed a ...

  12. On the {sup 1}H NMR spectra of 2-substituted benzoquinones

    Energy Technology Data Exchange (ETDEWEB)

    Tedeschi, E.; Rezende, D. B. [Universidade de Sao Paulo (USP), SP (Brazil). Inst. de Quimica; Arruda Campos, I.P. de, E-mail: ipdacamp@uol.com.br [Universidade Paulista, Sao Paulo, SP (Brazil). Inst. de Ciencias Exatas e Tecnologia. Programa de Pos-Graduacao em Engenharia de Producao

    2009-07-01

    The novel complete analysis of the {sup 1}H NMR spectra of six monosubstituted benzoquinones is reported herein, together with a brief but complete review of the scanty previously published data on benzoquinone and its monosubstituded derivatives. (author)

  13. 1H NMR analysis of the heteroassociation of antitumor antibiotics novotrone and actinomycin D in aqueous solution

    International Nuclear Information System (INIS)

    Evstigneev, M.P.; Rozvadovskaya, A.O.; Kisurkin, D.V.; Dehvis, D.B.; Veselkov, A.N.

    2004-01-01

    The heteroassociation of antitumor antibiotics novotrone (NOV) and actinomycin D (AMD) in aqueous solution has been studied by one- and two-dimensional 1 H-NMR spectroscopy (500 MHz) in order to elucidate the molecular mechanism of the action of antibiotics in combination. It has been shown that heterocomplexes become predominant in the mixed solution at r > 12. It is concluded that aromatic antibiotics (e. g. novotrone and actinomycin D) may form energetically stable heteroassociation complexes in aqueous solution and hence affect their medical-biological activity

  14. Assessment of 1H NMR-based metabolomics analysis for normalization of urinary metals against creatinine.

    Science.gov (United States)

    Cassiède, Marc; Nair, Sindhu; Dueck, Meghan; Mino, James; McKay, Ryan; Mercier, Pascal; Quémerais, Bernadette; Lacy, Paige

    2017-01-01

    Proton nuclear magnetic resonance ( 1 H NMR, or NMR) spectroscopy and inductively coupled plasma-mass spectrometry (ICP-MS) are commonly used for metabolomics and metal analysis in urine samples. However, creatinine quantification by NMR for the purpose of normalization of urinary metals has not been validated. We assessed the validity of using NMR analysis for creatinine quantification in human urine samples in order to allow normalization of urinary metal concentrations. NMR and ICP-MS techniques were used to measure metabolite and metal concentrations in urine samples from 10 healthy subjects. For metabolite analysis, two magnetic field strengths (600 and 700MHz) were utilized. In addition, creatinine concentrations were determined by using the Jaffe method. Creatinine levels were strongly correlated (R 2 =0.99) between NMR and Jaffe methods. The NMR spectra were deconvoluted with a target database containing 151 metabolites that are present in urine. A total of 50 metabolites showed good correlation (R 2 =0.7-1.0) at 600 and 700MHz. Metal concentrations determined after NMR-measured creatinine normalization were comparable to previous reports. NMR analysis provided robust urinary creatinine quantification, and was sufficient for normalization of urinary metal concentrations. We found that NMR-measured creatinine-normalized urinary metal concentrations in our control subjects were similar to general population levels in Canada and the United Kingdom. Copyright © 2016 Elsevier B.V. All rights reserved.

  15. 1H NMR-based metabolic profiling for evaluating poppy seed rancidity and brewing.

    Science.gov (United States)

    Jawień, Ewa; Ząbek, Adam; Deja, Stanisław; Łukaszewicz, Marcin; Młynarz, Piotr

    2015-12-01

    Poppy seeds are widely used in household and commercial confectionery. The aim of this study was to demonstrate the application of metabolic profiling for industrial monitoring of the molecular changes which occur during minced poppy seed rancidity and brewing processes performed on raw seeds. Both forms of poppy seeds were obtained from a confectionery company. Proton nuclear magnetic resonance (1H NMR) was applied as the analytical method of choice together with multivariate statistical data analysis. Metabolic fingerprinting was applied as a bioprocess control tool to monitor rancidity with the trajectory of change and brewing progressions. Low molecular weight compounds were found to be statistically significant biomarkers of these bioprocesses. Changes in concentrations of chemical compounds were explained relative to the biochemical processes and external conditions. The obtained results provide valuable and comprehensive information to gain a better understanding of the biology of rancidity and brewing processes, while demonstrating the potential for applying NMR spectroscopy combined with multivariate data analysis tools for quality control in food industries involved in the processing of oilseeds. This precious and versatile information gives a better understanding of the biology of these processes.

  16. Automatic 1H-NMR Screening of Fatty Acid Composition in Edible Oils

    Directory of Open Access Journals (Sweden)

    David Castejón

    2016-02-01

    Full Text Available In this work, we introduce an NMR-based screening method for the fatty acid composition analysis of edible oils. We describe the evaluation and optimization needed for the automated analysis of vegetable oils by low-field NMR to obtain the fatty acid composition (FAC. To achieve this, two scripts, which automatically analyze and interpret the spectral data, were developed. The objective of this work was to drive forward the automated analysis of the FAC by NMR. Due to the fact that this protocol can be carried out at low field and that the complete process from sample preparation to printing the report only takes about 3 min, this approach is promising to become a fundamental technique for high-throughput screening. To demonstrate the applicability of this method, the fatty acid composition of extra virgin olive oils from various Spanish olive varieties (arbequina, cornicabra, hojiblanca, manzanilla, and picual was determined by 1H-NMR spectroscopy according to this protocol.

  17. Spatially localized 1H NMR spectra of metabolites in the human brain

    International Nuclear Information System (INIS)

    Hanstock, C.C.; Rothman, D.L.; Jue, T.; Shulman, R.G.; Prichard, J.W.

    1988-01-01

    Using a surface coil, the authors have obtained 1 H NMR spectra from metabolites in the human brain. Localization was achieved by combining depth pulses with image-selected in vivo spectroscopy magnetic field gradient methods. 1 H spectra in which total creatine (3.03 ppm) has a signal/noise ratio of 95:1 were obtained in 4 min from 14 ml of brain. A resonance at 2.02 ppm consisting predominantly of N-acetylaspartate was measured relative to the creatine peak in gray and white matter, and the ratio was lower in the white matter. The spin-spin relaxation times of N-acetylaspartate and creatine were measured in white and gray matter and while creatine relaxation times were the same in both, the N-acetylaspartate relaxation time was longer in white matter. Lactate was detected in the normoxic brain and the average of three measurements was ∼0.5 mM from comparison with the creatine plus phosphocreatine peak, which was assumed to be 10.5 mM

  18. Resolution Improvements in in Vivo1H NMR Spectra with Increased Magnetic Field Strength

    Science.gov (United States)

    Gruetter, Rolf; Weisdorf, Sally A.; Rajanayagan, Vasantham; Terpstra, Melissa; Merkle, Hellmut; Truwit, Charles L.; Garwood, Michael; Nyberg, Scott L.; Ugurbil, Kâmil

    1998-11-01

    The measurement of cerebral metabolites using highly homologous localization techniques and similar shimming methods was performed in the human brain at 1.5 and 4 T as well as in the dog and rat brain at 9.4 T. In rat brain, improved resolution was achieved by shimming all first- and second-order shim coils using a fully adiabatic FASTMAP sequence. The spectra showed a clear improvement in spectral resolution for all metabolite resonances with increased field strength. Changes in cerebral glutamine content were clearly observed at 4 T compared to 1.5 T in patients with hepatic encephalopathy. At 9.4 T, glutamine H4 at 2.46 ppm was fully resolved from glutamate H4 at 2.37 ppm, as was the potential resonance from γ-amino-butyric acid at 2.30 ppm and N-acetyl-aspartyl-glutamate at 2.05 ppm. Singlet linewidths were found to be as low as 6 Hz (0.015 ppm) at 9.4 T, indicating a substantial decrease in ppm linewidth with field strength. Furthermore, the methylene peak of creatine was partially resolved from phosphocreatine, indicating a close to 1:1 relationship in gray matter. We conclude that increasing the magnetic field strength increases spectral resolution also for1H NMR, which can lead to more than linear sensitivity gains.

  19. Unambiguous Metabolite Identification in High-Throughput Metabolomics by Hybrid 1H-NMR/ESI-MS1 Approach

    Energy Technology Data Exchange (ETDEWEB)

    2016-10-18

    The invention improves accuracy of metabolite identification by combining direct infusion ESI-MS with one-dimensional 1H-NMR spectroscopy. First, we apply a standard 1H-NMR metabolite identification protocol by matching the chemical shift, J-coupling and intensity information of experimental NMR signals against the NMR signals of standard metabolites in a metabolomics reference libraries. This generates a list of candidate metabolites. The list contains both false positive and ambiguous identifications. The software tool (the invention) takes the list of candidate metabolites, generated from NMRbased metabolite identification, and then calculates, for each of the candidate metabolites, the monoisotopic mass-tocharge (m/z) ratios for each commonly observed ion, fragment and adduct feature. These are then used to assign m/z ratios in experimental ESI-MS spectra of the same sample. Detection of the signals of a given metabolite in both NMR and MS spectra resolves the ambiguities, and therefore, significantly improves the confidence of the identification.

  20. Detailed Source-Specific Molecular Composition of Ambient Aerosol Organic Matter Using Ultrahigh Resolution Mass Spectrometry and 1H NMR

    Directory of Open Access Journals (Sweden)

    Amanda S. Willoughby

    2016-06-01

    Full Text Available Organic aerosols (OA are universally regarded as an important component of the atmosphere that have far-ranging impacts on climate forcing and human health. Many of these impacts are related to OA molecular characteristics. Despite the acknowledged importance, current uncertainties related to the source apportionment of molecular properties and environmental impacts make it difficult to confidently predict the net impacts of OA. Here we evaluate the specific molecular compounds as well as bulk structural properties of total suspended particulates in ambient OA collected from key emission sources (marine, biomass burning, and urban using ultrahigh resolution mass spectrometry (UHR-MS and proton nuclear magnetic resonance spectroscopy (1H NMR. UHR-MS and 1H NMR show that OA within each source is structurally diverse, and the molecular characteristics are described in detail. Principal component analysis (PCA revealed that (1 aromatic nitrogen species are distinguishing components for these biomass burning aerosols; (2 these urban aerosols are distinguished by having formulas with high O/C ratios and lesser aromatic and condensed aromatic formulas; and (3 these marine aerosols are distinguished by lipid-like compounds of likely marine biological origin. This study provides a unique qualitative approach for enhancing the chemical characterization of OA necessary for molecular source apportionment.

  1. Determination of Monomers Reactivity Ratios in Ethyl Acrylate-Methacrylic Acid Copolymerization by Off-Line 1H NMR

    Directory of Open Access Journals (Sweden)

    Samaneh Ashenagar

    2017-03-01

    Full Text Available The physical, chemical and mechanical properties of polymer systems depend on the micro-structural characteristics of their macromolecular chains. Along with the most characteristic kinetic parameters in copolymerization reactions are the reactivity ratios, which give a clear idea of the average composition and the monomer sequence distribution in copolymer systems. This research studies the solution radical copolymerization of methacrylic acid (MAA-ethyl acrylate (EA system at low conversion with 2,2'-azobisisobutyronitrile (AIBN as thermal initiator at 60°C in deuterated dimethyl sulfoxide (DMSO-d6 as a reaction solvent. In this case, the monomer reactivity ratios were determined using linear off-line 1H nuclear magnetic resonance spectroscopy (1H NMR methods such as Mayo-Louis, Finemann-Ross, Inverted Finemann-Ross , Ezrielev-Brokhina-Roskin, Joshi-Joshi, Kelen-Tudos, extended Kelen- Tudos, Mao-Huglin at low and high conversions. The next estimation process in off-line 1H NMR methods were performed by applying techniques based on ordinary least square (OLS and generalized least square (GLS. The results showed that the GLS approach compared to the OLS increased regression coefficients (R2 and the order of magnitude of parameter variances obtained from GLS was many times lower than that obtained from OLS. In addition, the monomer reactivity ratios obtained by the Mao-Huglin method and the GLS approach showed the best linear estimation.

  2. 1H-NMR studies on the interaction of calmodulin with melittin

    International Nuclear Information System (INIS)

    Seeholzer, S.H.; Cohn, M.; Wand, A.J.

    1986-01-01

    Melittin (Mel), a basic amphipathic peptide from bee venom binds to Ca ++ -calmodulin (CaM) with high affinity and competitively inhibits the activation of enzymes by CaM. The CaM:Mel complex is being studied as a model system for understanding the nature of CaM's interaction with other tight binding peptides and target enzymes. The authors report here some preliminary results. Gel filtration experiments have shown that CaM binds 2 Mels with high affinity at pH 6.5 in the absence of salt yet it binds only 1 Mel in the presence of 0.15 M KC1. Hence, electrostatic forces may dominate the binding of the second Mel. The titration of CaM with from 0 to 2 Mels/CaM was followed by 1 H-NMR spectroscopy. The major changes in chemical shift of CaM resonances occur upon binding of the first Mel. Relatively fewer and smaller effects attend binding of the second Mel. Titration of CaM with from 0 through 1 Mel/CaM shifts the relative proportion of the His107-H2 resonance from 8.07 to 7.92 ppm. These two resonances are in slow exchange, the titration is complete at 1 Mel/CaM, and pH titrations are planned to see if these data are consistent with a Mel-induced pK shift of 0.5 pH units. The trimethyllysine resonance is shifted from 3.104 to 3.092 ppm by Mel. The relative proportion of these slowly exchanging peaks continuously changes during the titration from 0 to 2 Mels/CaM, being about 50% of each at 1 Mel/CaM. Data regarding the assignment and structure of Mel in various model solvent systems will also be reported

  3. Metabolic responses of the isopod Porcellionides pruinosus to nickel exposure assessed by (1)H NMR metabolomics.

    Science.gov (United States)

    Ferreira, Nuno G C; Saborano, Raquel; Morgado, Rui; Cardoso, Diogo N; Rocha, Cláudia M; Soares, Amadeu M V M; Loureiro, Susana; Duarte, Iola F

    2016-03-30

    This work aimed at characterizing the metabolome of the isopod Porcellionides pruinosus and at assessing its variations over 14 days under laboratory culture conditions and upon exposure to the contaminant metal Nickel (Ni). The spectral profiles obtained by (1)H NMR spectroscopy were thoroughly assigned and subjected to multivariate analysis in order to highlight consistent changes. Over 50 metabolites could be identified, providing considerable new knowledge on the metabolome of these model organisms. Several metabolites changed non-linearly with Ni dose and exposure time, showing distinct variation patterns for initial (4 days) and later time points (7 and 14 days). In particular, at day 4, several amino acids were increased and sugars were decreased (compared to controls), whereas these variations were inverted for longer exposure, possibly reflecting earlier and more intensive moulting. Other variations, namely in betaines and choline-containing compounds, were suggested to relate with osmoregulation and detoxification mechanisms. Ni also had a marked effect on several nucleotides (increased upon exposure) and a moderate impact on lipids (decreased upon exposure). Overall, this study has provided new information on the Ni-induced metabolic adaptations of the P. pruinosus isopod, paving the way for improved mechanistic understanding of how these model organisms handle soil contamination. This study provided, for the first time to our knowledge, a detailed picture of the NMR-detectable metabolome of terrestrial isopods and of its fluctuations in time and upon exposure to the contaminant metal Nickel. Several time- and dose-dependent changes were highlighted, providing mechanistic insight into how these important model organisms handle Ni contamination.

  4. 1H NMR- based metabolomics approaches as non- invasive tools for diagnosis of endometriosis

    Directory of Open Access Journals (Sweden)

    Negar Ghazi

    2016-01-01

    Full Text Available Background: So far, non-invasive diagnostic approaches such as ultrasound, magnetic resonance imaging, or blood tests do not have sufficient diagnostic power for endometriosis disease. Lack of a non-invasive diagnostic test contributes to the long delay between onset of symptoms and diagnosis of endometriosis. Objective: The present study focuses on the identification of predictive biomarkers in serum by pattern recognition techniques and uses partial least square discriminant analysis, multi-layer feed forward artificial neural networks (ANNs and quadratic discriminant analysis (QDA modeling tools for the early diagnosis of endometriosis in a minimally invasive manner by 1H- NMR based metabolomics. Materials and Methods: This prospective cohort study was done in Pasteur Institute, Iran in June 2013. Serum samples of 31 infertile women with endometriosis (stage II and III who confirmed by diagnostic laparoscopy and 15 normal women were collected and analyzed by nuclear magnetic resonance spectroscopy. The model was built by using partial least square discriminant analysis, QDA, and ANNs to determine classifier metabolites for early prediction risk of disease. Results: The levels of 2- methoxyestron, 2-methoxy estradiol, dehydroepiandrostion androstendione, aldosterone, and deoxy corticosterone were enhanced significantly in infertile group. While cholesterol and primary bile acids levels were decreased. QDA model showed significant difference between two study groups. Positive and negative predict value levels obtained about 71% and 78%, respectively. ANNs provided also criteria for detection of endometriosis. Conclusion: The QDA and ANNs modeling can be used as computational tools in noninvasive diagnose of endometriosis. However, the model designed by QDA methods is more efficient compared to ANNs in diagnosis of endometriosis patients.

  5. /sup 1/H-NMR studies on the interaction of calmodulin with melittin

    Energy Technology Data Exchange (ETDEWEB)

    Seeholzer, S.H.; Cohn, M.; Wand, A.J.

    1986-05-01

    Melittin (Mel), a basic amphipathic peptide from bee venom binds to Ca/sup + +/-calmodulin (CaM) with high affinity and competitively inhibits the activation of enzymes by CaM. The CaM:Mel complex is being studied as a model system for understanding the nature of CaM's interaction with other tight binding peptides and target enzymes. The authors report here some preliminary results. Gel filtration experiments have shown that CaM binds 2 Mels with high affinity at pH 6.5 in the absence of salt yet it binds only 1 Mel in the presence of 0.15 M KC1. Hence, electrostatic forces may dominate the binding of the second Mel. The titration of CaM with from 0 to 2 Mels/CaM was followed by /sup 1/H-NMR spectroscopy. The major changes in chemical shift of CaM resonances occur upon binding of the first Mel. Relatively fewer and smaller effects attend binding of the second Mel. Titration of CaM with from 0 through 1 Mel/CaM shifts the relative proportion of the His107-H2 resonance from 8.07 to 7.92 ppm. These two resonances are in slow exchange, the titration is complete at 1 Mel/CaM, and pH titrations are planned to see if these data are consistent with a Mel-induced pK shift of 0.5 pH units. The trimethyllysine resonance is shifted from 3.104 to 3.092 ppm by Mel. The relative proportion of these slowly exchanging peaks continuously changes during the titration from 0 to 2 Mels/CaM, being about 50% of each at 1 Mel/CaM. Data regarding the assignment and structure of Mel in various model solvent systems will also be reported.

  6. Evaluation of 1H NMR metabolic profiling using biofluid mixture design.

    Science.gov (United States)

    Athersuch, Toby J; Malik, Shahid; Weljie, Aalim; Newton, Jack; Keun, Hector C

    2013-07-16

    A strategy for evaluating the performance of quantitative spectral analysis tools in conditions that better approximate background variation in a metabonomics experiment is presented. Three different urine samples were mixed in known proportions according to a {3, 3} simplex lattice experimental design and analyzed in triplicate by 1D (1)H NMR spectroscopy. Fifty-four urinary metabolites were subsequently quantified from the sample spectra using two methods common in metabolic profiling studies: (1) targeted spectral fitting and (2) targeted spectral integration. Multivariate analysis using partial least-squares (PLS) regression showed the latent structure of the spectral set recapitulated the experimental mixture design. The goodness-of-prediction statistic (Q(2)) of each metabolite variable in a PLS model was calculated as a metric for the reliability of measurement, across the sample compositional space. Several metabolites were observed to have low Q(2) values, largely as a consequence of their spectral resonances having low s/n or strong overlap with other sample components. This strategy has the potential to allow evaluation of spectral features obtained from metabolic profiling platforms in the context of the compositional background found in real biological sample sets, which may be subject to considerable variation. We suggest that it be incorporated into metabolic profiling studies to improve the estimation of matrix effects that confound accurate metabolite measurement. This novel method provides a rational basis for exploiting information from several samples in an efficient manner and avoids the use of multiple spike-in authentic standards, which may be difficult to obtain.

  7. The utility of biomarkers in hepatocellular carcinoma: review of urine-based 1H-NMR studies – what the clinician needs to know

    Directory of Open Access Journals (Sweden)

    Cartlidge CR

    2017-11-01

    Full Text Available Caroline R Cartlidge,1 M R Abellona U,2 Alzhraa M A Alkhatib,2 Simon D Taylor-Robinson1 1Department of Surgery and Cancer, Liver Unit, Division of Digestive Health, 2Department of Surgery and Cancer, Division of Computational and Systems Medicine, Faculty of Medicine, Imperial College London, London, UK Abstract: Hepatocellular carcinoma (HCC is the fifth most common malignancy, the third most common cause of cancer death, and the most common primary liver cancer. Overall, there is a need for more reliable biomarkers for HCC, as those currently available lack sensitivity and specificity. For example, the current gold-standard biomarker, serum alpha-fetoprotein, has a sensitivity of roughly only 70%. Cancer cells have different characteristic metabolic signatures in biofluids, compared to healthy cells; therefore, metabolite analysis in blood or urine should lead to the detection of suitable candidates for the detection of HCC. With the advent of metabonomics, this has increased the potential for new biomarker discovery. In this article, we look at approaches used to identify biomarkers of HCC using proton nuclear magnetic resonance (1H-NMR spectroscopy of urine samples. The various multivariate statistical analysis techniques used are explained, and the process of biomarker identification is discussed, with a view to simplifying the knowledge base for the average clinician. Keywords: hepatocellular carcinoma, biomarkers, metabonomics, urine, proton nuclear magnetic resonance spectroscopy, 1H-NMR 

  8. 1H NMR analysis of complexation of hydrotropic agents nicotinamide and caffeine with aromatic biologically active molecules in aqueous solution

    Science.gov (United States)

    Lantushenko, Anastasia O.; Mukhina, Yulia V.; Veselkov, Kyrill A.; Davies, David B.; Veselkov, Alexei N.

    2004-07-01

    NMR spectroscopy has been used to elucidate the molecular mechanism of solubilization action of hydrotropic agents nicotinamide (NA) and caffeine (CAF). Hetero-association of NA with riboflavine-mononucleotide (FMN) and CAF with low soluble in aqueous solution synthetic analogue of antibiotic actinomycin D, actinocyl-bis-(3-dimethylaminopropyl) amine (Actill), has been investigated by 500 MHz 1H NMR spectroscopy. Concentration and temperature dependences of proton chemical shifts have been analysed in terms of a statistical-thermodynamic model of indefinite self- and heteroassociation of aromatic molecules. The obtained results enable to conclude that NA-FMN and CAF-Actill intermolecular complexes are mainly stabilized by the stacking interactions of the aromatic chromophores. Hetero-association of the investigated molecules plays an important role in solubilization of aromatic drugs by hydrotropic agents nicotinamide and caffeine.

  9. Metabolite profiling of Clinacanthus nutans leaves extracts obtained from different drying methods by 1H NMR-based metabolomics

    Science.gov (United States)

    Hashim, Noor Haslinda Noor; Latip, Jalifah; Khatib, Alfi

    2016-11-01

    The metabolites of Clinacanthus nutans leaves extracts and their dependence on drying process were systematically characterized using 1H nuclear magnetic resonance spectroscopy (NMR) multivariate data analysis. Principal component analysis (PCA) and partial least square-discriminant analysis (PLS-DA) were able to distinguish the leaves extracts obtained from different drying methods. The identified metabolites were carbohydrates, amino acid, flavonoids and sulfur glucoside compounds. The major metabolites responsible for the separation in PLS-DA loading plots were lupeol, cycloclinacosides, betulin, cerebrosides and choline. The results showed that the combination of 1H NMR spectroscopy and multivariate data analyses could act as an efficient technique to understand the C. nutans composition and its variation.

  10. Synthesis of Zinc Diethyldithiocarbamate (ZDEC) and Structure Characterization using Decoupling 1H NMR

    International Nuclear Information System (INIS)

    Sujarit, Jenjira; Phutdhawong, Weerachai

    2003-10-01

    A synthesis of zinc diethyldithiocarbamate (ZDEC) has been studied. The optimization mole ratio of the synthetic process was 2: 2: 2: 1 of diethylamine, carbondisulfide, sodium hydroxide, and zinc chloride. Characterization was carried out mainly by analyzing its spectroscopic properties especially decoupling 1 H NMR technique. ZDEC was obtained in 48.5% yield

  11. Evaluation of 1H NMR relaxometry for the assessment of pore size distribution in soil samples

    NARCIS (Netherlands)

    Jaeger, F.; Bowe, S.; As, van H.; Schaumann, G.E.

    2009-01-01

    1H NMR relaxometry is used in earth science as a non-destructive and time-saving method to determine pore size distributions (PSD) in porous media with pore sizes ranging from nm to mm. This is a broader range than generally reported for results from X-ray computed tomography (X-ray CT) scanning,

  12. Modelling the acid/base 1H NMR chemical shift limits of metabolites in human urine.

    Science.gov (United States)

    Tredwell, Gregory D; Bundy, Jacob G; De Iorio, Maria; Ebbels, Timothy M D

    2016-01-01

    Despite the use of buffering agents the 1 H NMR spectra of biofluid samples in metabolic profiling investigations typically suffer from extensive peak frequency shifting between spectra. These chemical shift changes are mainly due to differences in pH and divalent metal ion concentrations between the samples. This frequency shifting results in a correspondence problem: it can be hard to register the same peak as belonging to the same molecule across multiple samples. The problem is especially acute for urine, which can have a wide range of ionic concentrations between different samples. To investigate the acid, base and metal ion dependent 1 H NMR chemical shift variations and limits of the main metabolites in a complex biological mixture. Urine samples from five different individuals were collected and pooled, and pre-treated with Chelex-100 ion exchange resin. Urine samples were either treated with either HCl or NaOH, or were supplemented with various concentrations of CaCl 2 , MgCl 2 , NaCl or KCl, and their 1 H NMR spectra were acquired. Nonlinear fitting was used to derive acid dissociation constants and acid and base chemical shift limits for peaks from 33 identified metabolites. Peak pH titration curves for a further 65 unidentified peaks were also obtained for future reference. Furthermore, the peak variations induced by the main metal ions present in urine, Na + , K + , Ca 2+ and Mg 2+ , were also measured. These data will be a valuable resource for 1 H NMR metabolite profiling experiments and for the development of automated metabolite alignment and identification algorithms for 1 H NMR spectra.

  13. Isolation and quantification of pinitol in Argyrolobium roseum plant, by 1H-NMR

    Directory of Open Access Journals (Sweden)

    Neha Sharma

    2016-01-01

    Full Text Available Chemical investigations on ethanolic extract of Argyrolobium roseum led to the isolation of Pinitol as the major constituent of the plant. Pinitol is chemically known as 3-O-methyl-D-Chiro-inositol and has been found to possess anti-diabetic activity. It helps in the regeneration of beta cells, present in the areas of the pancreas called as islets – of Langerhans. These cells make and release insulin, a hormone which controls the level of glucose in the blood. Pinitol was isolated from the ethanolic extract of the plant and a sensitive & reliable method, based on Proton Nuclear Magnetic Resonance (PNMR, was developed and used as an analytical tool for quantification and identification of this relatively UV insensitive compound in the alcoholic extract of the plant. The method involves the use of pyrazinamide (an anti-tuberculosis drug, as a reference. Validation of the method was carried out by preparing a known concentration of an artificial mixture of pinitol and pyrazinamide. The recovery of pinitol in the mixture was in the range of 98.5–101.3%. Pinitol in pure form was isolated from the ethanolic extract of A. roseum by repeated column chromatography over silica gel followed by crystallization in methanol. Pinitol isolated from the plant was identified on the basis of 1H-NMR, 13C-NMR, DEPT (45°, 90° and 135° experiments and mass spectral data. The method was successfully applied for the quantitation of pinitol in various extracts of the said plant.

  14. 1H NMR and PCA-based analysis revealed variety dependent changes in phenolic contents of apple fruit after drying.

    Science.gov (United States)

    Francini, Alessandra; Romeo, Stefania; Cifelli, Mario; Gori, Daniele; Domenici, Valentina; Sebastiani, Luca

    2017-04-15

    Dry and fresh apples have been studied monitoring their polyphenolic profiles through 1 H NMR, antioxidant capacity and total polyphenol content. Six ancient and underutilized apple varieties (Mantovana, Mora, Nesta, Cipolla, Ruggina, Sassola) and a commercial one (Golden Delicious) were dried with an air-drying system at 45°C for 19h. Although some of their polyphenol constituents were lost during drying, the antioxidant capacity of some apple varieties remained higher compared to Golden Delicious. This result is very important for ancient and underutilized varieties that are not consumed on large scale as fresh product since they have low attractiveness, due to their ugly appearance. Combining quantitative NMR spectroscopy with principal component analysis we have identified and quantified several polyphenols (such as catechin, epicathechin, and chlorogenic acid) that are important to establish the nutraceutical value of the different investigated apple varieties. Copyright © 2016 Elsevier Ltd. All rights reserved.

  15. Untangle soil-water-mucilage interactions: 1H NMR Relaxometry is lifting the veil

    Science.gov (United States)

    Brax, Mathilde; Buchmann, Christian; Schaumann, Gabriele Ellen

    2017-04-01

    Mucilage is mainly produced at the root tips and has a high water holding capacity derived from highly hydrophilic gel-forming substances. The objective of the MUCILAGE project is to understand the mechanistic role of mucilage for the regulation of water supply for plants. Our subproject investigates the chemical and physical properties of mucilage as pure gel and mixed with soil. 1H-NMR Relaxometry and PFG NMR represent non-intrusive powerful methods for soil scientific research by allowing quantification of the water distribution as well as monitoring of the water mobility in soil pores and gel phases.Relaxation of gel water differs from the one of pure water due to additional interactions with the gel matrix. Mucilage in soil leads to a hierarchical pore structure, consisting of the polymeric biohydrogel network surrounded by the surface of soil particles. The two types of relaxation rates 1/T1 and 1/T2 measured with 1H-NMR relaxometry refer to different relaxation mechanisms of water, while PFG-NMR measures the water self-diffusion coefficient. The objective of our study is to distinguish in situ water in gel from pore water in a simplified soil system, and to determine how the "gel effect" affects both relaxation rates and the water self-diffusion coefficient in porous systems. We demonstrate how the mucilage concentration and the soil solution alter the properties of water in the respective gel phases and pore systems in model soils. To distinguish gel-inherent processes from classical processes, we investigated the variations of the water mobility in pure chia mucilage under different conditions by using 1H-NMR relaxometry and PFG NMR. Using model soils, the signals coming from pore water and gel water were differentiated. We combined the equations describing 1H-NMR relaxation in porous systems and our experimental results, to explain how the presence of gel in soil affects 1H-NMR relaxation. Out of this knowledge we propose a method, which determines in

  16. Study on 1H-NMR fingerprinting of Rhodiolae Crenulatae Radix et Rhizoma.

    Science.gov (United States)

    Wen, Shi-yuan; Zhou, Jiang-tao; Chen, Yan-yan; Ding, Li-qin; Jiang, Miao-miao

    2015-07-01

    Nuclear magnetic resonance (1H-NMR) fingerprint of Rhodiola rosea medicinal materials was established, and used to distinguish the quality of raw materials from different sources. Pulse sequence for water peak inhibition was employed to acquire 1H-NMR spectra with the temperature at 298 K and spectrometer frequency of 400.13 MHz. Through subsection integral method, the obtained NMR data was subjected to similarity analysis and principal component analysis (PCA). 10 batches raw materials of Rhodiola rosea from different origins were successfully distinguished by PCA. The statistical results indicated that rhodiola glucoside, butyl alcohol, maleic acid and alanine were the main differential ingredients. This method provides an auxiliary method of Chinese quality approach to evaluate the quality of Rhodiola crenulata without using natural reference substances.

  17. Evaluation of saffron (Crocus sativus L.) adulteration with plant adulterants by (1)H NMR metabolite fingerprinting.

    Science.gov (United States)

    Petrakis, Eleftherios A; Cagliani, Laura R; Polissiou, Moschos G; Consonni, Roberto

    2015-04-15

    In the present work, a preliminary study for the detection of adulterated saffron and the identification of the adulterant used by means of (1)H NMR and chemometrics is reported. Authentic Greek saffron and four typical plant-derived materials utilised as bulking agents in saffron, i.e., Crocus sativus stamens, safflower, turmeric, and gardenia were investigated. A two-step approach, relied on the application of both OPLS-DA and O2PLS-DA models to the (1)H NMR data, was adopted to perform authentication and prediction of authentic and adulterated saffron. Taking into account the deficiency of established methodologies to detect saffron adulteration with plant adulterants, the method developed resulted reliable in assessing the type of adulteration and could be viable for dealing with extensive saffron frauds at a minimum level of 20% (w/w). Copyright © 2014 Elsevier Ltd. All rights reserved.

  18. 1H-NMR METABONOMICS ANALYSIS OF SERA DIFFERENTIATES BETWEEN MAMMARY TUMOR-BEARING MICE AND HEALTHY CONTROLS

    Science.gov (United States)

    Global analysis of 1H-NMR spectra of serum is an appealing approach for the rapid detection of cancer. To evaluate the usefulness of this method in distinguishing between mammary tumor-bearing mice and healthy controls, we conducted 1H-NMR metabonomic analyses on serum samples ob...

  19. Computer-aided structure elucidation Pt. 2. /sup 1/H-NMR data interpretation

    Energy Technology Data Exchange (ETDEWEB)

    Szalontai, G; Recsey, Zs; Csapo, Z [Nehezvegyipari Kutato Intezet, Veszprem (Hungary)

    1982-01-01

    A computerized /sup 1/H-NMR data interpretation system has been developed using the artificial intelligence approach. An attempt has been made to overcome the difficulties of interpreting higher order spin systems. Proton-containing functional groups are divided into subgroups according to their spectroscopic behaviour and the information they bear. Spin simulation is used to study the effect of substituents on the higher order splitting patterns. Illustrative examples are given.

  20. Application of {sup 1}H-NMR-based metabolomics for detecting injury induced by long-term microwave exposure in Wistar rats' urine

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Li-Feng; Peng, Rui-Yun; Wang, Shui-Ming; Gao, Ya-Bing; Dong, Ji; Zhao, Li; Li, Xiang; Zuo, Hong-Yan; Wang, Chang-Zhen [Beijing Institute of Radiation Medicine, Laboratory of Pathology, Beijing (China); Hu, Xiang-Jun [Beijing Institute of Radiation Medicine, Beijing (China); Gao, Rong-Lian [Beijing Institute of Radiation Medicine, Laser Medicine, Beijing (China); Su, Zhen-Tao [Beijing Institute of Radiation Medicine, Radiation Protection, Beijing (China); Feng, Xin-Xing [Chinese Academy of Medical Sciences, Endocrine and Cardiovascular Center, Fuwai Hospital and Cardiovascular Institute, Beijing (China)

    2012-07-15

    There has been growing public concern regarding exposure to microwave fields as a potential human health hazard. This study aimed to identify sensitive biochemical indexes for the detection of injury induced by microwave exposure. Male Wistar rats were exposed to microwaves for 6 min per day, 5 days per week over a period of 1 month at an average power density of 5 mW/cm{sup 2} (specific absorption rate of 2.1 W/kg). Urine specimens were collected over 24 h in metabolic cages at 7 days, 21 days, 2 months, and 6 months after exposure. {sup 1}H NMR spectroscopy data were analyzed using multivariate statistical techniques. Urine metabolic profiles of rats after long-term microwave exposure were significantly differentiated from those of sham-treated controls using principal component analysis or partial least squares discriminant analysis. Significant differences in low molecular weight metabolites (acetate, succinate, citrate, ketoglutarate, glucose, taurine, phenylalanine, tyrosine, and hippurate) were identified in the 5 mW/cm{sup 2} microwave exposure group compared with the sham-treated controls at 7 days, 21 days, and 2 months. Metabolites returned to normal levels by 6 months after exposure. These data indicated that these metabolites were related to the perturbations of energy metabolism particularly in the tricarboxylic acid cycle, and the metabolism of amino acids, monoamines, and choline in urine represent potential indexes for the detection of injury induced by long-term microwave exposure. (orig.)

  1. Positional enrichment by proton analysis (PEPA). A one-dimensional "1H-NMR approach for "1"3C stable isotope tracer studies in metabolomics

    International Nuclear Information System (INIS)

    Vinaixa, Maria; Yanes, Oscar; Rodriguez, Miguel A.; Capellades, Jordi; Aivio, Suvi; Stracker, Travis H.; Gomez, Josep; Canyellas, Nicolau

    2017-01-01

    A novel metabolomics approach for NMR-based stable isotope tracer studies called PEPA is presented, and its performance validated using human cancer cells. PEPA detects the position of carbon label in isotopically enriched metabolites and quantifies fractional enrichment by indirect determination of "1"3C-satellite peaks using 1D-"1H-NMR spectra. In comparison with "1"3C-NMR, TOCSY and HSQC, PEPA improves sensitivity, accelerates the elucidation of "1"3C positions in labeled metabolites and the quantification of the percentage of stable isotope enrichment. Altogether, PEPA provides a novel framework for extending the high-throughput of "1H-NMR metabolic profiling to stable isotope tracing in metabolomics, facilitating and complementing the information derived from 2D-NMR experiments and expanding the range of isotopically enriched metabolites detected in cellular extracts. (copyright 2017 The Authors. Published by Wiley-VCH Verlag GmbH and Co. KGaA.)

  2. Positional enrichment by proton analysis (PEPA). A one-dimensional {sup 1}H-NMR approach for {sup 13}C stable isotope tracer studies in metabolomics

    Energy Technology Data Exchange (ETDEWEB)

    Vinaixa, Maria; Yanes, Oscar [Department of Electronic Engineering-Universitat Rovira i Virgili, Spanish Biomedical Research Center in Diabetes and Associated Metabolic Disorders (CIBERDEM), Reus (Spain); Rodriguez, Miguel A.; Capellades, Jordi [Universitat Rovira i Virgili, Spanish Biomedical Research Center in Diabetes and Associated Metabolic Disorders (CIBERDEM), Reus (Spain); Aivio, Suvi; Stracker, Travis H. [Institute for Research in Biomedicine (IRB Barcelona), Barcelona Institute of Science and Technology (Spain); Gomez, Josep; Canyellas, Nicolau [Department of Electronic Engineering-, Universitat Rovira i Virgili, Tarragona (Spain)

    2017-03-20

    A novel metabolomics approach for NMR-based stable isotope tracer studies called PEPA is presented, and its performance validated using human cancer cells. PEPA detects the position of carbon label in isotopically enriched metabolites and quantifies fractional enrichment by indirect determination of {sup 13}C-satellite peaks using 1D-{sup 1}H-NMR spectra. In comparison with {sup 13}C-NMR, TOCSY and HSQC, PEPA improves sensitivity, accelerates the elucidation of {sup 13}C positions in labeled metabolites and the quantification of the percentage of stable isotope enrichment. Altogether, PEPA provides a novel framework for extending the high-throughput of {sup 1}H-NMR metabolic profiling to stable isotope tracing in metabolomics, facilitating and complementing the information derived from 2D-NMR experiments and expanding the range of isotopically enriched metabolites detected in cellular extracts. (copyright 2017 The Authors. Published by Wiley-VCH Verlag GmbH and Co. KGaA.)

  3. From proton nuclear magnetic resonance spectra to pH. Assessment of {sup 1}H NMR pH indicator compound set for deuterium oxide solutions

    Energy Technology Data Exchange (ETDEWEB)

    Tynkkynen, Tuulia, E-mail: tuulia.tynkkynen@uku.fi [Laboratory of Chemistry, Department of Biosciences, University of Kuopio, PO Box 1627, 70211 Kuopio (Finland); Tiainen, Mika; Soininen, Pasi; Laatikainen, Reino [Laboratory of Chemistry, Department of Biosciences, University of Kuopio, PO Box 1627, 70211 Kuopio (Finland)

    2009-08-19

    In this study, a protocol for pH determination from D{sub 2}O samples using {sup 1}H NMR pH indicator compounds was developed and assessed by exploring the pH-dependency of 13 compounds giving pH-dependent {sup 1}H NMR signals. The indicators cover the pH range from pH* 0 to 7.2. Equations to transform the indicator chemical shifts to pH estimates are given here for acetic acid, formic acid, chloroacetic acid, dichloroacetic acid, creatine, creatinine, glycine, histidine, 1,2,4-triazole, and TSP (2,2,3,3-tetradeutero-3-(trimethylsilyl)-propionic acid). To characterize the method in presence of typical solutes, the effects of common metabolites, albumin and ionic strength were also evaluated. For the ionic strengths, the effects were also modelled. The experiments showed that the use of pH sensitive {sup 1}H NMR chemical shifts allows the pH determination of typical metabolite solutions with accuracy of 0.01-0.05 pH units. Also, when the ionic strength is known with accuracy better than 0.1 mol dm{sup -3} and the solute concentrations are low, pH{sub nmr}{sup *} (the NMR estimate of pH) can be assumed to be within 0.05 pH units from potentiometrically determined pH.

  4. Synergistic effect of the simultaneous chemometric analysis of {sup 1}H NMR spectroscopic and stable isotope (SNIF-NMR, {sup 18}O, {sup 13}C) data: Application to wine analysis

    Energy Technology Data Exchange (ETDEWEB)

    Monakhova, Yulia B., E-mail: yul-monakhova@mail.ru [Chemisches und Veterinäruntersuchungsamt (CVUA) Karlsruhe, Weissenburger Strasse 3, Karlsruhe 76187 (Germany); Bruker Biospin GmbH, Silberstreifen, Rheinstetten 76287 (Germany); Department of Chemistry, Saratov State University, Astrakhanskaya Street 83, Saratov 410012 (Russian Federation); Godelmann, Rolf [Chemisches und Veterinäruntersuchungsamt (CVUA) Karlsruhe, Weissenburger Strasse 3, Karlsruhe 76187 (Germany); Hermann, Armin [Landesuntersuchungsamt -Institut für Lebensmittelchemie und Arzneimittelprüfung, Emy-Roeder-Straße 1, Mainz 55129 (Germany); Kuballa, Thomas [Chemisches und Veterinäruntersuchungsamt (CVUA) Karlsruhe, Weissenburger Strasse 3, Karlsruhe 76187 (Germany); Cannet, Claire; Schäfer, Hartmut; Spraul, Manfred [Bruker Biospin GmbH, Silberstreifen, Rheinstetten 76287 (Germany); Rutledge, Douglas N. [AgroParisTech, UMR 1145, Ingénierie Procédés Aliments, 16 rue Claude Bernard, Paris F-75005 (France)

    2014-06-23

    Highlights: • {sup 1}H NMR profilings of 718 wines were fused with stable isotope analysis data (SNIF-NMR, {sup 18}O, {sup 13}C). • The best improvement was obtained for prediction of the geographical origin of wine. • Certain enhancement was also obtained for the year of vintage (from 88 to 97% for {sup 1}H NMR to 99% for the fused data). • Independent component analysis was used as an alternative chemometric tool for classification. - Abstract: It is known that {sup 1}H NMR spectroscopy represents a good tool for predicting the grape variety, the geographical origin, and the year of vintage of wine. In the present study we have shown that classification models can be improved when {sup 1}H NMR profiles are fused with stable isotope (SNIF-NMR, {sup 18}O, {sup 13}C) data. Variable selection based on clustering of latent variables was performed on {sup 1}H NMR data. Afterwards, the combined data of 718 wine samples from Germany were analyzed using linear discriminant analysis (LDA), partial least squares-discriminant analysis (PLS-DA), factorial discriminant analysis (FDA) and independent components analysis (ICA). Moreover, several specialized multiblock methods (common components and specific weights analysis (ComDim), consensus PCA and consensus PLS-DA) were applied to the data. The best improvement in comparison with {sup 1}H NMR data was obtained for prediction of the geographical origin (up to 100% for the fused data, whereas stable isotope data resulted only in 60–70% correct prediction and {sup 1}H NMR data alone in 82–89% respectively). Certain enhancement was obtained also for the year of vintage (from 88 to 97% for {sup 1}H NMR to 99% for the fused data), whereas in case of grape varieties improved models were not obtained. The combination of {sup 1}H NMR data with stable isotope data improves efficiency of classification models for geographical origin and vintage of wine and can be potentially used for other food products as well.

  5. Comparison between the efficacy of two cleanup methods for the 1H NMR analysis of food samples contaminated with Cypermethrin

    International Nuclear Information System (INIS)

    Silva, M.M.; Figueroa-Villar, J.D.; Aguiar, A.P.; Riehl, C.A.S.

    2004-01-01

    This work aimed to study the use of 1 H NMR for the identification of cypermethrin in cooked foods. 1 H NMR is not commonly used in these cases, because food samples ready for consumption have complex substances, mainly lipids, which usually interfere with the identification of cypermethrin. Thus, we drew a comparison between the most applied method for the treatment of those samples and an alternative route that made possible the use of 1 H NMR in the identification of cypermethrin in a matrix consisting of rice, bean, and chicken, which allows the Forensic work for such cases.(author)

  6. 1H NMR study of fermented cocoa (Theobroma cacao L.) beans.

    Science.gov (United States)

    Caligiani, Augusta; Acquotti, Domenico; Cirlini, Martina; Palla, Gerardo

    2010-12-08

    This study reports for the first time the metabolic profile of cocoa (Theobroma cacao L.) beans using the (1)H NMR technique applied to polar extracts of fermented cocoa beans. The simultaneous detection and quantification of amino acids, polyalcohols, organic acids, sugars, methylxanthines, catechins, and phenols were obtained by assigning the major signals of the spectra for different varieties of cocoa beans (Forastero, Criollo, and Trinitario) from different countries (Ecuador, Ghana, Grenada, and Trinidad). The data set obtained, representative of all classes of soluble compounds of cocoa, was useful to characterize the fermented cocoa beans as a function of the variety and geographic origin.

  7. sup(1)H-NMR study of restricted rotation in dithiophosphoromethyl acetanilides

    International Nuclear Information System (INIS)

    Kovacs, Zs.

    1985-01-01

    sup(1)H-NMR spectra of a series of dithiophosphoromethyl acetanilide derivatives were investigated. The presence of an ortho substituted aryl group bonded to the nitrogen atom of the amide group allowed the observation of restricted internal rotation around the aryl-nitrogen bond. Coalescence temperature and the values of the free energy of activation were determined from the temperature dependent NMR behaviour of these molecules. The possibility of cis-trans isomerism about the nitrogen carbonyl bond was also studied, and the assignment of the conformation of the existing isomer was also made using the aromatic solvent induced shift. (author)

  8. 1H-NMR of human blood lipids in cases of malignant and benign tumors

    International Nuclear Information System (INIS)

    Yushmanov, V.E.; Kotrikadze, N.G.; Pershin, A.D.; Dzhishkariani, O.S.; Tsartsidze, M.A.; Lomsadze, B.A.; Sibel'dina, L.A.

    1989-01-01

    High resolution 1 H-NMR (360MH z ) combined with thin-layer chromatography was used to study profile and molecular structure changes of inverted micelles of human blood developing in patients with malignant and benign tumors of the breast and uterus. Alterations were demonstrated in relative intensities of some lipid NMR peaks in tumor, as compared to normal blood. Changes in blood - lipid levels, e.g. cholesterol, in tumor affect lipid structural and dynamical status thus elucidating NMR-regularities obtained

  9. 1H NMR metabolomics of earthworm exposure to sub-lethal concentrations of phenanthrene in soil

    International Nuclear Information System (INIS)

    Brown, Sarah A.E.; McKelvie, Jennifer R.; Simpson, Andre J.; Simpson, Myrna J.

    2010-01-01

    1 H NMR metabolomics was used to monitor earthworm responses to sub-lethal (50-1500 mg/kg) phenanthrene exposure in soil. Total phenanthrene was analyzed via soxhlet extraction, bioavailable phenanthrene was estimated by hydroxypropyl-β-cyclodextrin (HPCD) and 1-butanol extractions and sorption to soil was assessed by batch equilibration. Bioavailable phenanthrene (HPCD-extracted) comprised ∼65-97% of total phenanthrene added to the soil. Principal component analysis (PCA) showed differences in responses between exposed earthworms and controls after 48 h exposure. The metabolites that varied with exposure included amino acids (isoleucine, alanine and glutamine) and maltose. PLS models indicated that earthworm response is positively correlated to both total phenanthrene concentration and bioavailable (HPCD-extracted) phenanthrene in a freshly spiked, unaged soil. These results show that metabolomics is a powerful, direct technique that may be used to monitor contaminant bioavailability and toxicity of sub-lethal concentrations of contaminants in the environment. These initial findings warrant further metabolomic studies with aged contaminated soils. - 1 H NMR metabolomics is used to directly monitor metabolic responses of Eisenia fetida after 48 h of exposure to sub-lethal concentrations of phenanthrene in soil.

  10. Discriminating binding and positioning of amphiphiles to lipid bilayers by {sup 1}H NMR

    Energy Technology Data Exchange (ETDEWEB)

    Evanics, F. [Department of Chemistry, University of Toronto, UTM, 3359 Mississauga Rd. North Mississauga, Ont., L5L 1C6 (Canada); Prosser, R.S. [Department of Chemistry, University of Toronto, UTM, 3359 Mississauga Rd. North Mississauga, Ont., L5L 1C6 (Canada)]. E-mail: sprosser@utm.utoronto.ca

    2005-04-04

    The binding and positioning in lipid bilayers of three well-known drugs--imipramine, nicotine, and caffeine--have been studied using {sup 1}H NMR. The membrane model system consisted of 'fast-tumbling' lipid bicelles, in which a bilayered lipid domain, composed of the unsaturated lipid, 1,2-dimyristelaidoyl-sn-glycero-3-phosphocholine (DMLPC) was surrounded by a rim of deuterated detergent-like lipids, consisting of 1,2-dihexanoyl-sn-glycero-3-phosphocholine (DHPC-d22). Binding and immersion depth information was obtained by three experiments. (1) {sup 1}H chemical shift perturbations, upon transfer of the amphiphiles from water to a bicelle mixture, were used to estimate regions of the amphiphiles that interact with the membrane. (2) Water contact to resolvable protons was measured through a Nuclear Overhauser Effect (NOE) between water and resolvable drug and lipid resonances. In the case of both lipids and membrane bound drugs, positive NOEs with large cross-relaxation rates were measured for most resonances originating from the membrane hydrophilic region, while negative NOEs were observed predominantly to resonances in the hydrophobic region of the membrane. (3) {sup 1}H NMR measurements of oxygen-induced (paramagnetic) spin-lattice relaxation rates, which are known to increase with membrane immersion depth, were used to corroborate conclusions based on chemical shift perturbations and water-ligand NOEs.

  11. A chiral aluminum solvating agent (CASA) for 1H NMR chiral analysis of alcohols at low temperature.

    Science.gov (United States)

    Seo, Min-Seob; Jang, Sumin; Kim, Hyunwoo

    2018-03-16

    A chiral aluminum solvating agent (CASA) was demonstrated to be a general and efficient reagent for 1H NMR chiral analysis of alcohols. The sodium salt of the CASA (CASA-Na) showed a complete baseline peak separation of the hydroxyl group for various chiral alcohols including primary, secondary, and tertiary alcohols with alkyl and aryl substituents in CD3CN. Due to the weak intermolecular interaction, 1H NMR measurement at low temperature (-40 to 10 °C) was required.

  12. Combined chemometric analysis of (1)H NMR, (13)C NMR and stable isotope data to differentiate organic and conventional milk.

    Science.gov (United States)

    Erich, Sarah; Schill, Sandra; Annweiler, Eva; Waiblinger, Hans-Ulrich; Kuballa, Thomas; Lachenmeier, Dirk W; Monakhova, Yulia B

    2015-12-01

    The increased sales of organically produced food create a strong need for analytical methods, which could authenticate organic and conventional products. Combined chemometric analysis of (1)H NMR-, (13)C NMR-spectroscopy data, stable-isotope data (IRMS) and α-linolenic acid content (gas chromatography) was used to differentiate organic and conventional milk. In total 85 raw, pasteurized and ultra-heat treated (UHT) milk samples (52 organic and 33 conventional) were collected between August 2013 and May 2014. The carbon isotope ratios of milk protein and milk fat as well as the α-linolenic acid content of these samples were determined. Additionally, the milk fat was analyzed by (1)H and (13)C NMR spectroscopy. The chemometric analysis of combined data (IRMS, GC, NMR) resulted in more precise authentication of German raw and retail milk with a considerably increased classification rate of 95% compared to 81% for NMR and 90% for IRMS using linear discriminate analysis. Copyright © 2015 Elsevier Ltd. All rights reserved.

  13. Does the 1H-NMR plasma metabolome reflect the host-tumor interactions in human breast cancer?

    Science.gov (United States)

    Richard, Vincent; Conotte, Raphaël; Mayne, David; Colet, Jean-Marie

    2017-07-25

    Breast cancer (BC) is the most common diagnosed cancer and the leading cause of cancer death in women worldwide. There is an obvious need for a better understanding of BC biology. Alterations in the serum metabolome of BC patients have been identified but their clinical significance remains elusive. We evaluated by 1H-Nuclear Magnetic Resonance (1H-NMR) spectroscopy, filtered plasma metabolome of 50 early (EBC) and 15 metastatic BC (MBC) patients. Using Principal Component Analysis, Partial Least-Squares Discriminant Analysis and Hierarchical Clustering we show that plasma levels of glucose, lactate, pyruvate, alanine, leucine, isoleucine, glutamate, glutamine, valine, lysine, glycine, threonine, tyrosine, phenylalanine, acetate, acetoacetate, β-hydroxy-butyrate, urea, creatine and creatinine are modulated across patients clusters. In particular lactate levels are inversely correlated with the tumor size in the EBC cohort (Pearson correlation r = -0.309; p = 0.044). We suggest that, in BC patients, tumor cells could induce modulation of the whole patient's metabolism even at early stages. If confirmed in a lager study these observations could be of clinical importance.

  14. Identification of the compositional changes in Orthosiphon stamineus leaves triggered by different drying techniques using 1 H NMR metabolomics.

    Science.gov (United States)

    Pariyani, Raghunath; Ismail, Intan Safinar; Ahmad Azam, Amalina; Abas, Faridah; Shaari, Khozirah

    2017-09-01

    Java tea is a well-known herbal infusion prepared from the leaves of Orthosiphon stamineus (OS). The biological properties of tea are in direct correlation with the primary and secondary metabolite composition, which in turn largely depends on the choice of drying method. Herein, the impact of three commonly used drying methods, i.e. shade, microwave and freeze drying, on the metabolite composition and antioxidant activity of OS leaves was investigated using proton nuclear magnetic resonance ( 1 H NMR) spectroscopy combined with multivariate classification and regression analysis tools. A total of 31 constituents comprising primary and secondary metabolites belonging to the chemical classes of fatty acids, amino acids, sugars, terpenoids and phenolic compounds were identified. Shade-dried leaves were identified to possess the highest concentrations of bioactive secondary metabolites such as chlorogenic acid, caffeic acid, luteolin, orthosiphol and apigenin, followed by microwave-dried samples. Freeze-dried leaves had higher concentrations of choline, amino acids leucine, alanine and glutamine and sugars such as fructose and α-glucose, but contained the lowest levels of secondary metabolites. Metabolite profiling coupled with multivariate analysis identified shade drying as the best method to prepare OS leaves as Java tea or to include in traditional medicine preparation. © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry.

  15. Quantitative determination of carboxylic acids, amino acids, carbohydrates, ethanol and hydroxymethylfurfural in honey by (1)H NMR.

    Science.gov (United States)

    del Campo, Gloria; Zuriarrain, Juan; Zuriarrain, Andoni; Berregi, Iñaki

    2016-04-01

    A method using (1)H NMR spectroscopy has been developed to quantify simultaneously thirteen analytes in honeys without previous separation or pre-concentration steps. The method has been successfully applied to determine carboxylic acids (acetic, formic, lactic, malic and succinic acids), amino acids (alanine, phenylalanine, proline and tyrosine), carbohydrates (α- and β-glucose and fructose), ethanol and hydroxymethylfurfural in eucalyptus, heather, lavender, orange blossom, thyme and rosemary honeys. Quantification was performed by using the area of the signal of each analyte in the honey spectra, together with external standards. The regression analysis of the signal area against concentration plots, used for the calibration of each analyte, indicates a good linearity over the concentration ranges found in honeys, with correlation coefficients higher than 0.985 for the thirteen quantified analytes. The recovery studies give values over the 93.7-105.4% range with relative standard deviations lower than 7.4%. Good precision, with relative standard deviations over the range of 0.78-5.21% is obtained. Copyright © 2015 Elsevier Ltd. All rights reserved.

  16. 1H NMR studies of human lysozyme: Spectral assignment and comparison with hen lysozyme

    International Nuclear Information System (INIS)

    Redfield, C.; Dobson, C.M.

    1990-01-01

    Complete main-chain (NH and αCH) 1 H NMR assignments are reported for the 130 residues of human lysozyme, along with extensive assignments for side-chain protons. Analysis of 2-D NOESY experiments shows that the regions of secondary structure for human lysozyme in solution are essentially identical with those found previously in a similar study of hen lysozyme and are in close accord with the structure of the protein reported previously from x-ray diffraction studies in the crystalline state. Comparison of the chemical shifts, spin-spin coupling constants, and hydrogen exchange behavior are also consistent with closely similar structures for the two proteins in solution. In a number of cases specific differences in the NMR parameters between hen and human lysozymes can be correlated with specific differences observed in the crystal structures

  17. Characterization of cellulose acetate obtained from sugarcane bagasse by 1H-NMR

    International Nuclear Information System (INIS)

    Cerqueira, Daniel A.; Rodrigues Filho, Guimes; Carvalho, Rui A.; Valente, Artur J.M.

    2009-01-01

    Cellulose from sugarcane bagasse was used for synthesizing cellulose acetate with different degrees of substitution, which were characterized by 1 H-NMR through the relationship between the peak areas of the hydrogen atoms present at the acetate groups (-(C=O)OCH 3 ) and the peaks of the hydrogen bonded to the carbon atoms of the glycosidic rings. Suppression was carried out in order to remove the peak of residual water in the materials and the peak related to impurities in cellulose triacetate. Degree of substitution values obtained through the resonance deconvolution were compared to those obtained by chemical determination through an acid-base titration. The determined degrees of substitution of the cellulose samples were 2.94 and 2.60. (author)

  18. 1H NMR quantification in very dilute toxin solutions: application to anatoxin-a analysis.

    Science.gov (United States)

    Dagnino, Denise; Schripsema, Jan

    2005-08-01

    A complete procedure is described for the extraction, detection and quantification of anatoxin-a in biological samples. Anatoxin-a is extracted from biomass by a routine acid base extraction. The extract is analysed by GC-MS, without the need of derivatization, with a detection limit of 0.5 ng. A method was developed for the accurate quantification of anatoxin-a in the standard solution to be used for the calibration of the GC analysis. 1H NMR allowed the accurate quantification of microgram quantities of anatoxin-a. The accurate quantification of compounds in standard solutions is rarely discussed, but for compounds like anatoxin-a (toxins with prices in the range of a million dollar a gram), of which generally only milligram quantities or less are available, this factor in the quantitative analysis is certainly not trivial. The method that was developed can easily be adapted for the accurate quantification of other toxins in very dilute solutions.

  19. Complete 1H NMR assignments of pyrrolizidine alkaloids and a new eudesmanoid from Senecio polypodioides.

    Science.gov (United States)

    Villanueva-Cañongo, Claudia; Pérez-Hernández, Nury; Hernández-Carlos, Beatriz; Cedillo-Portugal, Ernestina; Joseph-Nathan, Pedro; Burgueño-Tapia, Eleuterio

    2014-05-01

    Chemical investigation of the aerial parts of Senecio polypodioides lead to the isolation of the new eudesmanoid 1β-angeloyloxyeudesm-7-ene-4β,9α-diol (1) and the known dirhamnosyl flavonoid lespidin (3), while from roots, the known 7β-angeloyloxy-1-methylene-8α-pyrrolizidine (5) and sarracine N-oxide (6), as well as the new neosarracine N-oxide (8), were obtained. The structure of 1 and 8 was elucidated by spectral means. Complete assignments of the (1)H NMR data for 5, 6, sarracine (7), and 8 were made using one-dimensional and two-dimensional NMR experiments and by application of the iterative full spin analysis of the PERCH NMR software. Copyright © 2014 John Wiley & Sons, Ltd.

  20. Multivariate modelling with 1H NMR of pleural effusion in murine cerebral malaria

    Directory of Open Access Journals (Sweden)

    Ghosh Soumita

    2011-11-01

    Full Text Available Abstract Background Cerebral malaria is a clinical manifestation of Plasmodium falciparum infection. Although brain damage is the predominant pathophysiological complication of cerebral malaria (CM, respiratory distress, acute lung injury, hydrothorax/pleural effusion are also observed in several cases. Immunological parameters have been assessed in pleural fluid in murine models; however there are no reports of characterization of metabolites present in pleural effusion. Methods 1H NMR of the sera and the pleural effusion of cerebral malaria infected mice were analyzed using principal component analysis, orthogonal partial least square analysis, multiway principal component analysis, and multivariate curve resolution. Results It has been observed that there was 100% occurrence of pleural effusion (PE in the mice affected with CM, as opposed to those are non-cerebral and succumbing to hyperparasitaemia (NCM/HP. An analysis of 1H NMR and SDS-PAGE profile of PE and serum samples of each of the CM mice exhibited a similar profile in terms of constituents. Multivariate analysis on these two classes of biofluids was performed and significant differences were detected in concentrations of metabolites. Glucose, creatine and glutamine contents were high in the PE and lipids being high in the sera. Multivariate curve resolution between sera and pleural effusion showed that changes in PE co-varied with that of serum in CM mice. The increase of glucose in PE is negatively correlated to the glucose in serum in CM as obtained from the result of multiway principal component analysis. Conclusions This study reports for the first time, the characterization of metabolites in pleural effusion formed during murine cerebral malaria. The study indicates that the origin of PE metabolites in murine CM may be the serum. The loss of the components like glucose, glutamine and creatine into the PE may worsen the situation of patients, in conjunction with the enhanced

  1. Identification of fucans from four species of sea cucumber by high temperature 1H NMR

    Science.gov (United States)

    Wu, Nian; Chen, Shiguo; Ye, Xingqian; Li, Guoyun; Yin, Li'ang; Xue, Changhu

    2014-10-01

    Acidic polysaccharide, which has various biological activities, is one of the most important components of sea cucumber. In the present study, crude polysaccharide was extracted from four species of sea cucumber from three different geographical zones, Pearsonothuria graeffei ( Pg) from Indo-Pacific, Holothuria vagabunda ( Hv) from Norwegian Coast, Stichopus tremulu ( St) from Western Indian Ocean, and Isostichopus badionotu ( Ib) from Western Atlantic. The polysaccharide extract was separated and purified with a cellulose DEAE anion-exchange column to obtain corresponding sea cucumber fucans (SC-Fucs). The chemical property of these SC-Fucs, including molecular weight, monosaccharide composition and sulfate content, was determined. Their structure was compared simply with fourier infrared spectrum analyzer and identified with high temperature 1H nuclear magnetic resonance spectrum analyzer (NMR) and room temperature 13C NMR. The results indicated that Fuc- Pg obtained from the torrid zone mainly contained 2,4-O-disulfated and non-sulfated fucose residue, whereas Fuc- Ib from the temperate zone contained non-, 2-O- and 2,4-O-disulfated fucose residue; Fuc- St from the frigid zone and Fuc- Hv from the torrid zone contained mainly non-sulfated fucose residue. The proton of SC-Fucs was better resolved via high temperature 1H NMR than via room temperature 1H NMR. The fingerprint of sea cucumber in different sea regions was established based on the index of anomer hydrogen signal in SC-Fucs. Further work will help to understand whether there exists a close relationship between the geographical area of sea cucumber and the sulfation pattern of SC-Fucs.

  2. Metabolic effects of dinoseb, diazinon and esfenvalerate in eyed eggs and alevins of Chinook salmon (Oncorhynchus tshawytscha) determined by 1H NMR metabolomics

    International Nuclear Information System (INIS)

    Viant, Mark R.; Pincetich, Christopher A.; Tjeerdema, Ronald S.

    2006-01-01

    Pesticide pulses in the Sacramento River, California, originate from storm-water discharges and non-point source aquatic pollution that can last from a few days to weeks. The Sacramento River and its tributaries have historically supported the majority of California's Chinook salmon (Oncorhynchus tshawytscha) spawning grounds. Three pesticides currently used in the Sacramento Valley - dinoseb, diazinon, and esfenvalerate - were chosen to model the exposure of salmon embryos to storm-water discharges. Static-renewal (96 h) exposures to eyed eggs and alevins resulted in both toxicity and significant changes in metabolism assessed in whole-embryo extracts by 1 H nuclear magnetic resonance (NMR) spectroscopy based metabolomics and HPLC with UV detection (HPLC-UV). The 96-h LC 5 values of eyed eggs and alevins exposed to dinoseb were 335 and 70.6 ppb, respectively, and the corresponding values for diazinon were 545 and 29.5 ppm for eyed eggs and alevins, respectively. The 96-h LC 5 of eyed eggs exposed to esfenvalerate could not be determined due to lack of mortality at the highest exposure concentration, but in alevins was 16.7 ppb. All esfenvalerate exposed alevins developed some degree of lordosis or myoskeletal abnormality and did not respond to stimulus or exhibit normal swimming behavior. ATP concentrations measured by HPLC-UV decreased significantly in eyed eggs due to 250 ppb dinoseb and 10 and 100 ppb esfenvalerate (p 1 H NMR metabolite fingerprints of eyed egg and alevin extracts revealed both dose-dependent and mechanism of action-specific metabolic effects induced by the pesticides. Furthermore, NMR based metabolomics proved to be more sensitive than HPLC-UV in identifying significant changes in sublethal metabolism of pesticide exposed alevins. In conclusion, we have demonstrated several benefits of a metabolomics approach for chemical risk assessment, when used in conjunction with a fish embryo assay, and have identified significant metabolic perturbations

  3. Characterizing source fingerprints and ageing processes in laboratory-generated secondary organic aerosols using proton-nuclear magnetic resonance (1H-NMR) analysis and HPLC HULIS determination

    Science.gov (United States)

    Zanca, Nicola; Lambe, Andrew T.; Massoli, Paola; Paglione, Marco; Croasdale, David R.; Parmar, Yatish; Tagliavini, Emilio; Gilardoni, Stefania; Decesari, Stefano

    2017-09-01

    The study of secondary organic aerosol (SOA) in laboratory settings has greatly increased our knowledge of the diverse chemical processes and environmental conditions responsible for the formation of particulate matter starting from biogenic and anthropogenic volatile compounds. However, characteristics of the different experimental setups and the way they impact the composition and the timescale of formation of SOA are still subject to debate. In this study, SOA samples were generated using a potential aerosol mass (PAM) oxidation flow reactor using α-pinene, naphthalene and isoprene as precursors. The PAM reactor facilitated exploration of SOA composition over atmospherically relevant photochemical ageing timescales that are unattainable in environmental chambers. The SOA samples were analyzed using two state-of-the-art analytical techniques for SOA characterization - proton nuclear magnetic resonance (1H-NMR) spectroscopy and HPLC determination of humic-like substances (HULIS). Results were compared with previous Aerodyne aerosol mass spectrometer (AMS) measurements. The combined 1H-NMR, HPLC, and AMS datasets show that the composition of the studied SOA systems tend to converge to highly oxidized organic compounds upon prolonged OH exposures. Further, our 1H-NMR findings show that only α-pinene SOA acquires spectroscopic features comparable to those of ambient OA when exposed to at least 1 × 1012 molec OH cm-3 × s OH exposure, or multiple days of equivalent atmospheric OH oxidation. Over multiple days of equivalent OH exposure, the formation of HULIS is observed in both α-pinene SOA and in naphthalene SOA (maximum yields: 16 and 30 %, respectively, of total analyzed water-soluble organic carbon, WSOC), providing evidence of the formation of humic-like polycarboxylic acids in unseeded SOA.

  4. Characterizing source fingerprints and ageing processes in laboratory-generated secondary organic aerosols using proton-nuclear magnetic resonance (1H-NMR analysis and HPLC HULIS determination

    Directory of Open Access Journals (Sweden)

    N. Zanca

    2017-09-01

    Full Text Available The study of secondary organic aerosol (SOA in laboratory settings has greatly increased our knowledge of the diverse chemical processes and environmental conditions responsible for the formation of particulate matter starting from biogenic and anthropogenic volatile compounds. However, characteristics of the different experimental setups and the way they impact the composition and the timescale of formation of SOA are still subject to debate. In this study, SOA samples were generated using a potential aerosol mass (PAM oxidation flow reactor using α-pinene, naphthalene and isoprene as precursors. The PAM reactor facilitated exploration of SOA composition over atmospherically relevant photochemical ageing timescales that are unattainable in environmental chambers. The SOA samples were analyzed using two state-of-the-art analytical techniques for SOA characterization – proton nuclear magnetic resonance (1H-NMR spectroscopy and HPLC determination of humic-like substances (HULIS. Results were compared with previous Aerodyne aerosol mass spectrometer (AMS measurements. The combined 1H-NMR, HPLC, and AMS datasets show that the composition of the studied SOA systems tend to converge to highly oxidized organic compounds upon prolonged OH exposures. Further, our 1H-NMR findings show that only α-pinene SOA acquires spectroscopic features comparable to those of ambient OA when exposed to at least 1  ×  1012 molec OH cm−3  ×  s OH exposure, or multiple days of equivalent atmospheric OH oxidation. Over multiple days of equivalent OH exposure, the formation of HULIS is observed in both α-pinene SOA and in naphthalene SOA (maximum yields: 16 and 30 %, respectively, of total analyzed water-soluble organic carbon, WSOC, providing evidence of the formation of humic-like polycarboxylic acids in unseeded SOA.

  5. Serum 1H-NMR metabolomic fingerprints of acute-on-chronic liver failure in intensive care unit patients with alcoholic cirrhosis.

    Directory of Open Access Journals (Sweden)

    Roland Amathieu

    Full Text Available INTRODUCTION: Acute-on-chronic liver failure is characterized by acute deterioration of liver function in patients with compensated or decompensated, but stable, cirrhosis. However, there is no accurate definition of acute-on-chronic liver failure and physicians often use this term to describe different clinical entities. Metabolomics investigates metabolic changes in biological systems and identifies the biomarkers or metabolic profiles. Our study assessed the metabolomic profile of serum using proton nuclear magnetic resonance ((1H-NMR spectroscopy to identify metabolic changes related to acute-on-chronic liver failure. PATIENTS: Ninety-three patients with compensated or decompensated cirrhosis (CLF group but stable liver function and 30 patients with cirrhosis and hospitalized for the management of an acute event who may be responsible of acute-on-chronic liver failure (ACLF group, were fully analyzed. Blood samples were drawn at admission, and sera were separated and stored at -80°C until (1H-NMR spectral analysis. Using orthogonal projection to latent-structure discriminant analyses, various metabolites contribute to the complete separation between these both groups. RESULTS: The predictability of the model was 0.73 (Q(2 Y and the explained variance was 0.63 (R(2 Y. The main metabolites that had increased signals related to acute-on-chronic liver failure were lactate, pyruvate, ketone bodies, glutamine, phenylalanine, tyrosine, and creatinine. High-density lipids were lower in the ALCF group than in CLF group. CONCLUSION: A serum metabolite fingerprint for acute-on-chronic liver failure, obtained with (1H-NMR, was identified. Metabolomic profiling may aid clinical evaluation of patients with cirrhosis admitted into intensive care units with acute-on-chronic liver failure, and provide new insights into the metabolic processes involved in acute impairment of hepatic function.

  6. Metabolomics study of Saw palmetto extracts based on 1H NMR spectroscopy.

    Science.gov (United States)

    de Combarieu, Eric; Martinelli, Ernesto Marco; Pace, Roberto; Sardone, Nicola

    2015-04-01

    Preparations containing Saw palmetto extracts are used in traditional medicine to treat benign prostatic hyperplasia. According to the European and the American Pharmacopoeias, the extract is obtained from comminuted Saw palmetto berries by a suitable extracting procedure using ethanol or supercritical carbon dioxide or a mixture of n-hexane and methylpentanes. In the present study an approach to metabolomics profiling using nuclear magnetic resonance (NMR) has been used as a finger-printing tool to assess the overall composition of the extracts. The phytochemical analysis coupled with principal component analysis (PCA) showed the same composition of the Saw palmetto extracts obtained with carbon dioxide and hexane with minor not significant differences for extracts obtained with ethanol. In fact these differences are anyhow lower than the batch-to-batch variability ascribable to the natural-occurring variability in the Saw palmetto fruits' phytochemical composition. The fingerprinting analysis combined with chemometric method, is a technique, which would provide a tool to comprehensively assess the quality control of Saw palmetto extracts. Copyright © 2015 Elsevier B.V. All rights reserved.

  7. Metabonomic study of human serum in gallbladder cancer by 1H NMR spectroscopy

    International Nuclear Information System (INIS)

    Sonkar, Kanchan; Sinha, Neeraj; Behari, Anu; Kapoor, V.K.

    2012-01-01

    Gallbladder carcinoma (GBC) is one of the most lethal malignancies of upper gastrointestinal tract and it has the highest mortality rate in Chile and India. It has a very high incidence rates in northern India therefore it is also called as an Indian disease. There are several factors which play important role in development of gallbladder cancer including long-standing stones in gallbladder and alterations in composition of bile. Studies on gallstones and gallbladder tissues revealed that benign group can easily be discriminated from malignant group. Many proteomic studies have been performed for different cancers and several responsible serum protein markers have been identified but there is no such metabonomics study that shows the presence of any biomarker associated with gallbladder carcinoma. Identification of such biomarker would help immensely in the diagnostic of GBC. For this study we have collected blood samples (70; including patients from Chronic Cholecystitis (CC), XanthoGranulomatous Cholecystitis (XGC) and Gallbladder Cancer (GBC)) post-operatively (immediately after surgery) from patient undergoing cholecystectomy in Department of Surgical Gastroenterology, SGPGIMS. Control samples were also collected from 20 volunteers after 12 hrs of fasting. 4 ml of blood sample was collected and was allowed to clot in plastic tube for 30 min at room temperature in incubator. The serum was collected by centrifugation and samples were stored at -80 deg C till NMR experiments. 400 μL of serum was used for recording NMR spectra. NMR spectra were recorded at Bruker Avance 800 MHz spectrometer using CPMG pulse sequence with water presaturation. Control serum shows presence of various amino acids and low molecular weight metabolites. Detailed multivariate analysis along with markers found in serum associated with GBC will be presented. (author)

  8. (1H-NMR spectroscopy revealed Mycobacterium tuberculosis caused abnormal serum metabolic profile of cattle.

    Directory of Open Access Journals (Sweden)

    Yingyu Chen

    Full Text Available To re-evaluate virulence of Mycobacterium tuberculosis (M. tb in cattle, we experimentally infected calves with M. tb andMycobacterium bovisvia intratracheal injection at a dose of 2.0×10(7 CFU and observed the animals for 33 weeks. The intradermal tuberculin test and IFN-γin vitro release assay showed that both M. tb and M. bovis induced similar responses. Immunohistochemical staining of pulmonary lymph nodes indicated that the antigen MPB83 of both M. tb and M. bovis were similarly distributed in the tissue samples. Histological examinations showed all of the infected groups exhibited neutrophil infiltration to similar extents. Although the infected cattle did not develop granulomatous inflammation, the metabolic profiles changed significantly, which were characterized by a change in energy production pathways and increased concentrations of N-acetyl glycoproteins. Glycolysis was induced in the infected cattle by decreased glucose and increased lactate content, and enhanced fatty acid β-oxidation was induced by decreased TG content, and decreased gluconeogenesis indicated by the decreased concentration of glucogenic and ketogenic amino acids promoted utilization of substances other than glucose as energy sources. In addition, an increase in acute phase reactive serum glycoproteins, together with neutrophil infiltration and increased of IL-1β production indicated an early inflammatory response before granuloma formation. In conclusion, this study indicated that both M. tb and M.bovis were virulent to cattle. Therefore, it is likely that cattle with M. tb infections would be critical to tuberculosis transmission from cattle to humans. Nuclear magnetic resonance was demonstrated to be an efficient method to systematically evaluate M. tb and M. bovi sinfection in cattle.

  9. 2D COSY sup 1 H NMR; A new tool for studying in sity brain metabolism in the living animal

    Energy Technology Data Exchange (ETDEWEB)

    Barrere, B.; Peres, M.; Seulaz, J. (Universite Paris 7 (France). Laboratoire de Physiologie et Physiopathologie Cerebrovasculaire INSERM U 182 CNRS UA 641, Paris (France)); Gillet, B.; Mergui, S.; Beloeil, J.-C. (Centre National de la Recherche Scientifique, 91 - Gif-sur-Yvette (France). Inst. de Chimie des Substances Naturelles)

    1990-05-21

    2D COSY {sup 1}H NMR with surface coil has been used to resolve and assign cerebral metabolites which had previously been detected but could not be resolved or assigned in situ in the living animal by conventional 1D {sup 1}H NMR. A wide range of cerebral metabolites, including alanine, N-acetyl asparate, asparate, choline derivatives, creatine/phosphocreatine pool, GABA, glucose, glutamate/glutamine pool, inositol, lactate and taurine were simultaneously resolved and assigned in situ in the whole animal using the 2D COSY correlation graphs. Global irreversible ischemia caused the appearance and the disappearance of cross-peaks in the 2D COSY {sup 1}H NMR map, corresponding to increases in alanine, GABA and lactate and glucose depletion. (author). 21 refs.; 3 figs.

  10. 1H NMR methods for the noninvasive study of metabolism and other processes involving small molecules in intact erythrocytes

    International Nuclear Information System (INIS)

    Rabenstein, D.L.

    1984-01-01

    1 H NMR methods are described with which resolved resonances can be obtained for many of the small molecules in intact erythrocytes. In one method, the more intense hemoglobin resonances are suppressed by transfer of saturation throughout the hemoglobin spin system by cross relaxation following a selective saturation pulse. In a second method, the hemoglobin resonances are eliminated with the spin-echo pulse sequence by using a between-pulse delay time long enough for complete elimination of the hemoglobin resonances by spin-spin relaxation. Selected examples of the study of erythrocyte biochemistry by 1 H NMR are discussed. (Auth.)

  11. Improving Visualization and Interpretation of Metabolome-Wide Association Studies: An Application in a Population-Based Cohort Using Untargeted 1H NMR Metabolic Profiling.

    Science.gov (United States)

    Castagné, Raphaële; Boulangé, Claire Laurence; Karaman, Ibrahim; Campanella, Gianluca; Santos Ferreira, Diana L; Kaluarachchi, Manuja R; Lehne, Benjamin; Moayyeri, Alireza; Lewis, Matthew R; Spagou, Konstantina; Dona, Anthony C; Evangelos, Vangelis; Tracy, Russell; Greenland, Philip; Lindon, John C; Herrington, David; Ebbels, Timothy M D; Elliott, Paul; Tzoulaki, Ioanna; Chadeau-Hyam, Marc

    2017-10-06

    1 H NMR spectroscopy of biofluids generates reproducible data allowing detection and quantification of small molecules in large population cohorts. Statistical models to analyze such data are now well-established, and the use of univariate metabolome wide association studies (MWAS) investigating the spectral features separately has emerged as a computationally efficient and interpretable alternative to multivariate models. The MWAS rely on the accurate estimation of a metabolome wide significance level (MWSL) to be applied to control the family wise error rate. Subsequent interpretation requires efficient visualization and formal feature annotation, which, in-turn, call for efficient prioritization of spectral variables of interest. Using human serum 1 H NMR spectroscopic profiles from 3948 participants from the Multi-Ethnic Study of Atherosclerosis (MESA), we have performed a series of MWAS for serum levels of glucose. We first propose an extension of the conventional MWSL that yields stable estimates of the MWSL across the different model parameterizations and distributional features of the outcome. We propose both efficient visualization methods and a strategy based on subsampling and internal validation to prioritize the associations. Our work proposes and illustrates practical and scalable solutions to facilitate the implementation of the MWAS approach and improve interpretation in large cohort studies.

  12. Efficient 1H-NMR Quantitation and Investigation of N-Acetyl-D-glucosamine (GlcNAc and N,N'-Diacetylchitobiose (GlcNAc2 from Chitin

    Directory of Open Access Journals (Sweden)

    Huey-Lang Yang

    2011-09-01

    Full Text Available A quantitative determination method of N-acetyl-D-glucosamine (GlcNAc and N,N'-diacetylchitobiose (GlcNAc2 is proposed using a proton nuclear magnetic resonance experiment. N-acetyl groups of GlcNAc and (GlcNAc2 are chosen as target signals, and the deconvolution technique is used to determine the concentration of the corresponding compound. Compared to the HPLC method, 1H-NMR spectroscopy is simple and fast. The method can be used for the analysis of chitin hydrolyzed products with real-time analysis, and for quantifying the content of products using internal standards without calibration curves. This method can be used to quickly evaluate chitinase activity. The temperature dependence of 1H-NMR spectra (VT-NMR is studied to monitor the chemical shift variation of acetyl peak. The acetyl groups of products are involved in intramolecular H-bonding with the OH group on anomeric sites. The rotation of the acetyl group is closely related to the intramolecular hydrogen bonding pattern, as suggested by the theoretical data (molecular modeling.

  13. Composition and Quantitation of Microalgal Lipids by ERETIC 1H NMR Method

    Directory of Open Access Journals (Sweden)

    Angelo Fontana

    2013-09-01

    Full Text Available Accurate characterization of biomass constituents is a crucial aspect of research in the biotechnological application of natural products. Here we report an efficient, fast and reproducible method for the identification and quantitation of fatty acids and complex lipids (triacylglycerols, glycolipids, phospholipids in microalgae under investigation for the development of functional health products (probiotics, food ingredients, drugs, etc. or third generation biofuels. The procedure consists of extraction of the biological matrix by modified Folch method and direct analysis of the resulting material by proton nuclear magnetic resonance (1H NMR. The protocol uses a reference electronic signal as external standard (ERETIC method and allows assessment of total lipid content, saturation degree and class distribution in both high throughput screening of algal collection and metabolic analysis during genetic or culturing studies. As proof of concept, the methodology was applied to the analysis of three microalgal species (Thalassiosira weissflogii, Cyclotella cryptica and Nannochloropsis salina which drastically differ for the qualitative and quantitative composition of their fatty acid-based lipids.

  14. Towards high resolution ^1H NMR spectra of tannin colloidal aggregates

    Science.gov (United States)

    Mirabel, M.; Glories, Y.; Pianet, I.; Dufourc, E. J.

    1999-10-01

    The time dependent colloidal formation of tannins in hydro-alcoholic medium has been studied by 1H-NMR. Line broadening observed with time can be cancelled by making use of magic angle sample spinning (MASS) thus yielding sharp lines that allow structural studies. We used as an example catechin, a constitutive monomer of Bordeaux young red wine tannins. Chemical shift variations of polyphenol protons allow monitoring the time course of aggregation. La formation de tanins colloïdaux au cours du temps, en milieu hydroalcoolique, a été suivie par RMN-^1H. Un élargissement marqué des résonances est observé et peut être supprimé par la rotation de l'échantillon à l'angle magique ce qui ouvre tout un champ d'études structurales sur ces composés colloïdaux. L'exemple proposé est celui de la catéchine, monomère constitutif de tannins présents en grande quantité dans les vins rouges jeunes de Bordeaux. Des variations du déplacement chimique de certains protons polyphénoliques permettent de suivre l'évolution temporelle de l'agrégation.

  15. Relativistic force field: parametric computations of proton-proton coupling constants in (1)H NMR spectra.

    Science.gov (United States)

    Kutateladze, Andrei G; Mukhina, Olga A

    2014-09-05

    Spin-spin coupling constants in (1)H NMR carry a wealth of structural information and offer a powerful tool for deciphering molecular structures. However, accurate ab initio or DFT calculations of spin-spin coupling constants have been very challenging and expensive. Scaling of (easy) Fermi contacts, fc, especially in the context of recent findings by Bally and Rablen (Bally, T.; Rablen, P. R. J. Org. Chem. 2011, 76, 4818), offers a framework for achieving practical evaluation of spin-spin coupling constants. We report a faster and more precise parametrization approach utilizing a new basis set for hydrogen atoms optimized in conjunction with (i) inexpensive B3LYP/6-31G(d) molecular geometries, (ii) inexpensive 4-31G basis set for carbon atoms in fc calculations, and (iii) individual parametrization for different atom types/hybridizations, not unlike a force field in molecular mechanics, but designed for the fc's. With the training set of 608 experimental constants we achieved rmsd <0.19 Hz. The methodology performs very well as we illustrate with a set of complex organic natural products, including strychnine (rmsd 0.19 Hz), morphine (rmsd 0.24 Hz), etc. This precision is achieved with much shorter computational times: accurate spin-spin coupling constants for the two conformers of strychnine were computed in parallel on two 16-core nodes of a Linux cluster within 10 min.

  16. Plaster mortars with polymer fibers and additives investigated by 1H NMR relaxometry

    Science.gov (United States)

    Mustea, Andrei; Manea, Daniela L.; Jumate, Elena; Orbán, Yvette A.; Fechete, Radu

    2017-12-01

    Plaster mortars with polypropylene (pp) fibers and/or additives were investigated by 1H NMR relaxometry. Two recipes are proposed and are based on a commercially available mortar or are self-prepared and have different content of polypropylene fibers, which play the role of reinforcement agent, and/or Sika additive which is a waterproofing agent. The distributions of transverse relaxation times, T2 were obtained at 1, 3, 7 and 28 days after preparation. For the majority of T2-distributions four peaks are observed and, are associated with the hydration water (to the mineralogical components) and water in small, medium and large pores. The evolution in time, from 1 to 28 days, of the T2-distributions indicates the effects of pp fibers and Sika additive in the formation of pore microstructure. The degree of homogeneity of prepared receipts was evaluated from the relative peak-width and compared with mechanical measurements. Finally, we shown that the inverse of the transverse relaxation time values, T2-1, characteristic to the hydration water depends linearly on the resistance at compression measured for the 1÷28 days period, proving the important role of hydrations to the mechanical properties of the final product.

  17. 1H NMR Metabolic Profiling of Biofluids from Rats with Gastric Mucosal Lesion and Electroacupuncture Treatment

    Directory of Open Access Journals (Sweden)

    Jingjing Xu

    2015-01-01

    Full Text Available Gastric mucosal lesion (GML is a common gastrointestinal disorder with multiple pathogenic mechanisms in clinical practice. In traditional Chinese medicine (TCM, electroacupuncture (EA treatment has been proven as an effective therapy for GML, although the underlying healing mechanism is not yet clear. Here, we used proton nuclear magnetic resonance- (1H NMR- based metabolomic method to investigate the metabolic perturbation induced by GML and the therapeutic effect of EA treatment on stomach meridian (SM acupoints. Clear metabolic differences were observed between GML and control groups, and related metabolic pathways were discussed by means of online metabolic network analysis toolbox. By comparing the endogenous metabolites from GML and GML-SM groups, the disturbed pathways were partly recovered towards healthy state via EA treated on SM acupoints. Further comparison of the metabolic variations induced by EA stimulated on SM and the control gallbladder meridian (GM acupoints showed a quite similar metabolite composition except for increased phenylacetylglycine, 3,4-dihydroxymandelate, and meta-hydroxyphenylacetate and decreased N-methylnicotinamide in urine from rats with EA treated on SM acupoints. The current study showed the potential application of metabolomics in providing further insight into the molecular mechanism of acupuncture.

  18. Understanding the microstructure of coal during carbonization using rheometry and {sup 1}H NMR

    Energy Technology Data Exchange (ETDEWEB)

    Karen M. Steel; Miguel C. Diaz; John W. Patrick; Colin E. Snape [University of Nottingham, Nottingham (United Kingdom). Nottingham Fuel and Energy Centre, School of Chemical, Environmental and Mining Engineering

    2005-07-01

    High-temperature rheometry and {sup 1}H NMR have been combined to assess the microstructural changes taking place during carbonization of four coals with varying volatile matter contents. A linear relationship exists between the logarithm of the material's complex viscosity and the fraction of hydrogen present in rigid structures for the resolidification region in which the material is liquid-like with small amounts of dispersed solid. The Krieger-Dougherty suspension equation fits the data, however, the fit parameters are not realistic. This is thought to be due to the fact that the solid which forms does not entirely behave like a suspension, as the solid regions join together rather than pack together. The relationship is best characterized by the Arrhenius viscosity equation and bears similarity with thermosetting polymer networks. Results suggest that resolidification occurs through progressive crosslinking and cyclization reactions within the liquid medium, giving rise to a network structure leading to a gel point. Horizontal positioning of the curves depends on the relative proportions of solid material arising from unsoftened coal and from resolidified structures. Correcting the curves to neglect the contribution from unsoftened coal indicates that while the unsoftened material has a fairly equant shape, the resolidified material has a much higher hydrodynamic volume. The gel point occurs when the ratio of hydrogen present in resolidified structures to that still present in liquid form is 2:3. 27 refs., 8 figs., 4 tabs.

  19. 1H NMR structural characterization of a recombinant kringle 2 domain from human tissue-type plasminogen activator

    International Nuclear Information System (INIS)

    Byeon, I.J.L.; Llinas, M.; Kelley, R.F.

    1989-01-01

    The kringle 2 domain of human tissue-type plasminogen activator (t-PA) has been characterized via 1 H NMR spectroscopy at 300 and 620 MHz. The experiments were performed on the isolated domain obtained by expression of the 174-263 portion of t-PA in Escherichia coli. The spectrum of t-Pa kringle 2 is characteristic of a globular structure and shows overall similarity to that of the plasminogen (PGN) kringle 4. Spectral comparison with human and bovine PGN kringle 4 identified side-chain resonances from Leu 46 , which afford a fingerprint of kringle folding, and from most of the aromatic ring spin systems. Ligand-binding studies confirm that t-PA kringle 2 binds L-lysine with an association constant K a ∼ 11.9 mM -1 . The data indicate that homologous or conserved residues relative to those that compose the lysine-binding sites of PGN kringles 1 and 4 are involved in the binding of L-lysine to t-PA kringle 2. These include Tyr 36 and, within the kringle inner loop, Trp 62 , His 64 , Trp 72 , and Tyr 74 . Several labile NH protons of t-PA kringle 2 exhibit retarded H-exchange kinetics, requiring more than a week in 2 H 2 O for full deuteration in the presence of L-lysine at 37 degree C. This reveals that kringle 2 is endowed with a compact, dynamically stable conformation. Proton Overhauser experiments in 1 H 2 O, centered on well-resolved NH resonances between 9.8 and 12 ppm, identify signals arising from the His 48a imidazole NH3 proton and the three Trp indole NH1 protons. Overall, the data indicate a highly structured conformation for the recombinant t-PA kringle 2 that is closely related to that of the previously investigated PGN kringles 1, 4, and 5

  20. Extraction and [superscript 1]H NMR Analysis of Fats from Convenience Foods: A Laboratory Experiment for Organic Chemistry

    Science.gov (United States)

    Hartel, Aaron M.; Moore, Amy C.

    2014-01-01

    The extraction and analysis of fats from convenience foods (crackers, cookies, chips, candies) has been developed as an experiment for a second-year undergraduate organic chemistry laboratory course. Students gravimetrically determine the fat content per serving and then perform a [superscript 1]H NMR analysis of the recovered fat to determine the…

  1. The effect of standardized food intake on the association between BMI and 1H-NMR metabolites

    NARCIS (Netherlands)

    Schutte, A.M.; Akker, van den Erik B.; Deelen, Joris; Rest, van de O.; Heemst, van D.; Feskens, E.J.M.; Beekman, M.; Slagboom, P.E.

    2016-01-01

    Multiple studies have shown that levels of 1H-NMR metabolites are associated with disease and risk factors of disease such as BMI. While most previous investigations have been performed in fasting samples, meta-analysis often includes both cohorts with fasting and non-fasting blood samples. In the

  2. Structure of the oligosaccharide of hen phosvitin as determined by two-dimensional 1H NMR of the intact glycoprotein

    International Nuclear Information System (INIS)

    Brockbank, R.L.; Vogel, H.J.

    1990-01-01

    The major form of the oligosaccharide of hen phosvitin was studied with two-dimensional 1 H NMR of the intact glycoprotein. Its structure was determined from an analysis of the chemical shifts of the structural reporter groups, and it was further confirmed by comparison to several related model oligosaccharides. The oligosaccharide is N-linked and is present in a 1:1 stoichiometry to the protein. It has a complex type 1 triantennary structure with two NeuAcα2,6Ga1β1,4G1cNAcβ1,2 arms linked to the Man-4 and Man-4' and a third Ga1β1,4G1cNAcβ1, 4 arm attached to the Man-4. the oligosaccharide contains the common core sequence which is present in all N-linked glycoproteins [Manα1,3(Manα1,6)Manβ1,4G1cNAcβ1,4G1cNAcβ1,N]. In the course of this study, we have found that unique spin systems for the G1cNAc and NeuAc are obtained for spectra recorded in 90% H 2 O. Their NH peaks were assigned at low pH, and these assignments proved useful for confirming the identify of cross-peaks in the anomeric region. In addition, the protons of G1cNAc-1 could be correlated to the NH of the asparagine link. The cross-peak patterns determined in phase-sensitive 2D experiments for the H1,H2 protons have a different appearance for each type of monosaccharide, and this information was also used for making first-order assignments. A comparison with model compounds suggests that the solution conformation of the oligosaccharide is not affected by its attachment to the protein

  3. Insights into the mechanisms underlying mercury-induced oxidative stress in gills of wild fish (Liza aurata) combining "1H NMR metabolomics and conventional biochemical assays

    International Nuclear Information System (INIS)

    Cappello, Tiziana; Brandão, Fátima; Guilherme, Sofia; Santos, Maria Ana; Maisano, Maria; Mauceri, Angela; Canário, João; Pacheco, Mário; Pereira, Patrícia

    2016-01-01

    be sensitive and effective towards a mechanistically based assessment of Hg toxicity in gills of wild fish, providing new insights into the toxicological pathways underlying the oxidative stress. - Highlights: • Mercury-induced oxidative stress was investigated in gills of wild fish Liza aurata. • "1H NMR-based metabolomics and oxidative stress biomarkers were applied. • Hg interfered with the antioxidant protection but lipid peroxidation was prevented. • Activation of membrane repair processes suggested cell membrane ability to recover. • The combined approach is a sensitive and effective tool in ecotoxicological studies.

  4. Insights into the mechanisms underlying mercury-induced oxidative stress in gills of wild fish (Liza aurata) combining {sup 1}H NMR metabolomics and conventional biochemical assays

    Energy Technology Data Exchange (ETDEWEB)

    Cappello, Tiziana, E-mail: tcappello@unime.it [Department of Biological and Environmental Sciences, University of Messina, 98166 Messina (Italy); Brandão, Fátima, E-mail: fatimabrandao@ua.pt [Department of Biology and CESAM, University of Aveiro, 3810-193 Aveiro (Portugal); Guilherme, Sofia; Santos, Maria Ana [Department of Biology and CESAM, University of Aveiro, 3810-193 Aveiro (Portugal); Maisano, Maria; Mauceri, Angela [Department of Biological and Environmental Sciences, University of Messina, 98166 Messina (Italy); Canário, João [Centro de Química Estrutural, Instítuto Superíor Técnico, Universidade de Lisboa, 1049-001 Lisbon (Portugal); Pacheco, Mário; Pereira, Patrícia [Department of Biology and CESAM, University of Aveiro, 3810-193 Aveiro (Portugal)

    2016-04-01

    be sensitive and effective towards a mechanistically based assessment of Hg toxicity in gills of wild fish, providing new insights into the toxicological pathways underlying the oxidative stress. - Highlights: • Mercury-induced oxidative stress was investigated in gills of wild fish Liza aurata. • {sup 1}H NMR-based metabolomics and oxidative stress biomarkers were applied. • Hg interfered with the antioxidant protection but lipid peroxidation was prevented. • Activation of membrane repair processes suggested cell membrane ability to recover. • The combined approach is a sensitive and effective tool in ecotoxicological studies.

  5. Determination of 1,2/1,3-diglycerides in Sicilian extra-virgin olive oils by 1H-NMR over a one-year storage period.

    Science.gov (United States)

    Salvo, Andrea; Rotondo, Archimede; La Torre, Giovanna Loredana; Cicero, Nicola; Dugo, Giacomo

    2017-04-01

    This study is aimed to monitor by 1 H NMR spectroscopy the effect of a 12-month storage period on the 1,2-diglycerides over 1,3-diglycerides ratio for five mono-cultivar 'extra virgin olive oils' (EVOO) (Arbequina, Arbosana, Cerasuola, Nocellara and FS17) and one blend of two different cultivars (Nocellara + Biancolilla) preserved in the dark and at room temperature. These quantifications, at 500 MHz, are readily extracted through a specific and original integration difference method. Albeit it was known that the isomerisation rate is affected by the free acidity, we here demonstrate that it also depends on the presence of specific macromolecules (lipases), indeed, different EVOO cultivars with similar free acidity, show different isomerisation rate. Our results are consistent with similar diglyceride monitoring performed on Greek and Spanish EVOOs by 31 P NMR.

  6. Tissue metabolic profiling of human gastric cancer assessed by 1H NMR

    International Nuclear Information System (INIS)

    Wang, Huijuan; Zhang, Hailong; Deng, Pengchi; Liu, Chunqi; Li, Dandan; Jie, Hui; Zhang, Hu; Zhou, Zongguang; Zhao, Ying-Lan

    2016-01-01

    Gastric cancer is the fourth most common cancer and the second most deadly cancer worldwide. Study on molecular mechanisms of carcinogenesis will play a significant role in diagnosing and treating gastric cancer. Metabolic profiling may offer the opportunity to understand the molecular mechanism of carcinogenesis and help to identify the potential biomarkers for the early diagnosis of gastric cancer. In this study, we reported the metabolic profiling of tissue samples on a large cohort of human gastric cancer subjects (n = 125) and normal controls (n = 54) based on 1 H nuclear magnetic resonance ( 1 H NMR) together with multivariate statistical analyses (PCA, PLS-DA, OPLS-DA and ROC curve). The OPLS-DA model showed adequate discrimination between cancer tissues and normal controls, and meanwhile, the model excellently discriminated the stage-related of tissue samples (stage I, 30; stage II, 46; stage III, 37; stage IV, 12) and normal controls. A total of 48 endogenous distinguishing metabolites (VIP > 1 and p < 0.05) were identified, 13 of which were changed with the progression of gastric cancer. These modified metabolites revealed disturbance of glycolysis, glutaminolysis, TCA, amino acids and choline metabolism, which were correlated with the occurrence and development of human gastric cancer. The receiver operating characteristic diagnostic AUC of OPLS-DA model between cancer tissues and normal controls was 0.945. And the ROC curves among different stages cancer subjects and normal controls were gradually improved, the corresponding AUC values were 0.952, 0.994, 0.998 and 0.999, demonstrating the robust diagnostic power of this metabolic profiling approach. As far as we know, the present study firstly identified the differential metabolites in various stages of gastric cancer tissues. And the AUC values were relatively high. So these results suggest that the metabolic profiling of gastric cancer tissues has great potential in detecting this disease and helping

  7. Metabolic effects of dinoseb, diazinon and esfenvalerate in eyed eggs and alevins of Chinook salmon (Oncorhynchus tshawytscha) determined by {sup 1}H NMR metabolomics

    Energy Technology Data Exchange (ETDEWEB)

    Viant, Mark R [School of Biosciences, The University of Birmingham, Edgbaston, Birmingham, B15 2TT (United Kingdom); Pincetich, Christopher A [Department of Environmental Toxicology, College of Agricultural and Environmental Sciences, University of California, One Shields Avenue, Davis, CA 95616-8588 (United States); Tjeerdema, Ronald S [Department of Environmental Toxicology, College of Agricultural and Environmental Sciences, University of California, One Shields Avenue, Davis, CA 95616-8588 (United States)

    2006-05-25

    Pesticide pulses in the Sacramento River, California, originate from storm-water discharges and non-point source aquatic pollution that can last from a few days to weeks. The Sacramento River and its tributaries have historically supported the majority of California's Chinook salmon (Oncorhynchus tshawytscha) spawning grounds. Three pesticides currently used in the Sacramento Valley - dinoseb, diazinon, and esfenvalerate - were chosen to model the exposure of salmon embryos to storm-water discharges. Static-renewal (96 h) exposures to eyed eggs and alevins resulted in both toxicity and significant changes in metabolism assessed in whole-embryo extracts by {sup 1}H nuclear magnetic resonance (NMR) spectroscopy based metabolomics and HPLC with UV detection (HPLC-UV). The 96-h LC{sub 5} values of eyed eggs and alevins exposed to dinoseb were 335 and 70.6 ppb, respectively, and the corresponding values for diazinon were 545 and 29.5 ppm for eyed eggs and alevins, respectively. The 96-h LC{sub 5} of eyed eggs exposed to esfenvalerate could not be determined due to lack of mortality at the highest exposure concentration, but in alevins was 16.7 ppb. All esfenvalerate exposed alevins developed some degree of lordosis or myoskeletal abnormality and did not respond to stimulus or exhibit normal swimming behavior. ATP concentrations measured by HPLC-UV decreased significantly in eyed eggs due to 250 ppb dinoseb and 10 and 100 ppb esfenvalerate (p < 0.05). Phosphocreatine, as measured by HPLC-UV, decreased significantly in eyed eggs due to 250 ppb dinoseb, 10 and 100 ppb esfenvalerate, and 100 ppm diazinon (p < 0.05). Principal components analyses of {sup 1}H NMR metabolite fingerprints of eyed egg and alevin extracts revealed both dose-dependent and mechanism of action-specific metabolic effects induced by the pesticides. Furthermore, NMR based metabolomics proved to be more sensitive than HPLC-UV in identifying significant changes in sublethal metabolism of pesticide

  8. Metabolic effects of dinoseb, diazinon and esfenvalerate in eyed eggs and alevins of Chinook salmon (Oncorhynchus tshawytscha) determined by {sup 1}H NMR metabolomics

    Energy Technology Data Exchange (ETDEWEB)

    Viant, Mark R. [School of Biosciences, The University of Birmingham, Edgbaston, Birmingham, B15 2TT (United Kingdom)]. E-mail: M.Viant@bham.ac.uk; Pincetich, Christopher A. [Department of Environmental Toxicology, College of Agricultural and Environmental Sciences, University of California, One Shields Avenue, Davis, CA 95616-8588 (United States); Tjeerdema, Ronald S. [Department of Environmental Toxicology, College of Agricultural and Environmental Sciences, University of California, One Shields Avenue, Davis, CA 95616-8588 (United States)

    2006-05-25

    Pesticide pulses in the Sacramento River, California, originate from storm-water discharges and non-point source aquatic pollution that can last from a few days to weeks. The Sacramento River and its tributaries have historically supported the majority of California's Chinook salmon (Oncorhynchus tshawytscha) spawning grounds. Three pesticides currently used in the Sacramento Valley - dinoseb, diazinon, and esfenvalerate - were chosen to model the exposure of salmon embryos to storm-water discharges. Static-renewal (96 h) exposures to eyed eggs and alevins resulted in both toxicity and significant changes in metabolism assessed in whole-embryo extracts by {sup 1}H nuclear magnetic resonance (NMR) spectroscopy based metabolomics and HPLC with UV detection (HPLC-UV). The 96-h LC{sub 5} values of eyed eggs and alevins exposed to dinoseb were 335 and 70.6 ppb, respectively, and the corresponding values for diazinon were 545 and 29.5 ppm for eyed eggs and alevins, respectively. The 96-h LC{sub 5} of eyed eggs exposed to esfenvalerate could not be determined due to lack of mortality at the highest exposure concentration, but in alevins was 16.7 ppb. All esfenvalerate exposed alevins developed some degree of lordosis or myoskeletal abnormality and did not respond to stimulus or exhibit normal swimming behavior. ATP concentrations measured by HPLC-UV decreased significantly in eyed eggs due to 250 ppb dinoseb and 10 and 100 ppb esfenvalerate (p < 0.05). Phosphocreatine, as measured by HPLC-UV, decreased significantly in eyed eggs due to 250 ppb dinoseb, 10 and 100 ppb esfenvalerate, and 100 ppm diazinon (p < 0.05). Principal components analyses of {sup 1}H NMR metabolite fingerprints of eyed egg and alevin extracts revealed both dose-dependent and mechanism of action-specific metabolic effects induced by the pesticides. Furthermore, NMR based metabolomics proved to be more sensitive than HPLC-UV in identifying significant changes in sublethal metabolism of pesticide

  9. Ehrlich and sarcoma 180 tumour characterisation and early detection by 1H NMR-based metabonomics of mice serum

    International Nuclear Information System (INIS)

    Grandizoli, Caroline W.P. da S.; Simonelli, Fabio; Nagata, Noemi; Barison, Andersson; Carrenho, Luise Z.B.; Francisco, Thais M.G. de; Campos, Francinete R.; Santana Filho, Arquimedes P. de; Sassaki, Guilherme L.; Kreuger, Maria R.O.

    2014-01-01

    The success of cancer treatment is directly related to early detection before symptoms emerge, although nowadays few cancers can be detected early. In this sense, 1 H nuclear magnetic resonance ( 1 H NMR)-based metabonomics was used to identify metabolic changes in biofluid as a consequence of tumours growing in mice. Through partial least squares discriminant analysis (PLS-DA) analysis of 1 H NMR spectra from serum samples it was possible to diagnose Ehrlich ascites and Sarcoma 180 tumours five and ten days after cell inoculation, respectively. Lipids, lipoproteins and lactate were the main biomarkers at onset as well as in the progress of carcinogenic process. Thus, NMR-based metabonomics can be a valuable tool to study the effects of tumour establishment on the chemical composition of biofluids. (author)

  10. The use of IRMS, (1)H NMR and chemical analysis to characterise Italian and imported Tunisian olive oils.

    Science.gov (United States)

    Camin, Federica; Pavone, Anita; Bontempo, Luana; Wehrens, Ron; Paolini, Mauro; Faberi, Angelo; Marianella, Rosa Maria; Capitani, Donatella; Vista, Silvia; Mannina, Luisa

    2016-04-01

    Isotope Ratio Mass Spectrometry (IRMS), (1)H Nuclear Magnetic Resonance ((1)H NMR), conventional chemical analysis and chemometric elaboration were used to assess quality and to define and confirm the geographical origin of 177 Italian PDO (Protected Denomination of Origin) olive oils and 86 samples imported from Tunisia. Italian olive oils were richer in squalene and unsaturated fatty acids, whereas Tunisian olive oils showed higher δ(18)O, δ(2)H, linoleic acid, saturated fatty acids β-sitosterol, sn-1 and 3 diglyceride values. Furthermore, all the Tunisian samples imported were of poor quality, with a K232 and/or acidity values above the limits established for extra virgin olive oils. By combining isotopic composition with (1)H NMR data using a multivariate statistical approach, a statistical model able to discriminate olive oil from Italy and those imported from Tunisia was obtained, with an optimal differentiation ability arriving at around 98%. Copyright © 2015 Elsevier Ltd. All rights reserved.

  11. Ehrlich and sarcoma 180 tumour characterisation and early detection by {sup 1}H NMR-based metabonomics of mice serum

    Energy Technology Data Exchange (ETDEWEB)

    Grandizoli, Caroline W.P. da S.; Simonelli, Fabio; Nagata, Noemi; Barison, Andersson [Universidade Federal do Parana (UFPR), Curitiba, PR (Brazil). Dept. de Quimica; Carrenho, Luise Z.B.; Francisco, Thais M.G. de; Campos, Francinete R. [Universidade Federal do Parana (UFPR), Curitiba, PR (Brazil). Dept. de Farmacia; Santana Filho, Arquimedes P. de; Sassaki, Guilherme L. [Universidade Federal do Parana (UFPR), Curitiba, PR (Brazil). Dept. de Bioquimica; Kreuger, Maria R.O. [Universidade do Vale do Itajai (UNIVALI), (Brazil). Centro de Ciencias da Saude

    2014-05-15

    The success of cancer treatment is directly related to early detection before symptoms emerge, although nowadays few cancers can be detected early. In this sense, {sup 1}H nuclear magnetic resonance ({sup 1}H NMR)-based metabonomics was used to identify metabolic changes in biofluid as a consequence of tumours growing in mice. Through partial least squares discriminant analysis (PLS-DA) analysis of {sup 1}H NMR spectra from serum samples it was possible to diagnose Ehrlich ascites and Sarcoma 180 tumours five and ten days after cell inoculation, respectively. Lipids, lipoproteins and lactate were the main biomarkers at onset as well as in the progress of carcinogenic process. Thus, NMR-based metabonomics can be a valuable tool to study the effects of tumour establishment on the chemical composition of biofluids. (author)

  12. Structural analysis of flavonoids in solution through DFT 1H NMR chemical shift calculations: Epigallocatechin, Kaempferol and Quercetin

    Science.gov (United States)

    De Souza, Leonardo A.; Tavares, Wagner M. G.; Lopes, Ana Paula M.; Soeiro, Malucia M.; De Almeida, Wagner B.

    2017-05-01

    In this work, we showed that comparison between experimental and theoretical 1H NMR chemical shift patterns, calculated using Density Functional Theory (DFT), can be used for the prediction of molecular structure of flavonoids in solution, what is experimentally accessible for gas phase (electron diffraction methods) and solid samples (X-ray diffraction). The best match between B3LYP/6-31G(d,p)-PCM 1H NMR calculations for B ring rotated structures and experimental spectra can provide information on the conformation adopted by polyphenols in solution (usually DMSO-d6, acetone-d6 as solvents), which may differ from solid state and gas phase observed structures, and also DFT optimized geometry in the vacuum.

  13. 1H NMR-based metabolomics of time-dependent responses of Eisenia fetida to sub-lethal phenanthrene exposure

    International Nuclear Information System (INIS)

    Lankadurai, Brian P.; Wolfe, David M.; Simpson, Andre J.; Simpson, Myrna J.

    2011-01-01

    1 H NMR-based metabolomics was used to examine the response of the earthworm Eisenia fetida after exposure to sub-lethal concentrations of phenanthrene over time. Earthworms were exposed to 0.025 mg/cm 2 of phenanthrene (1/64th of the LC 50 ) via contact tests over four days. Earthworm tissues were extracted using a mixture of chloroform, methanol and water, resulting in polar and non-polar fractions that were analyzed by 1 H NMR after one, two, three and four days. NMR-based metabolomic analyses revealed heightened E. fetida responses with longer phenanthrene exposure times. Amino acids alanine and glutamate, the sugar maltose, the lipids cholesterol and phosphatidylcholine emerged as potential indicators of phenanthrene exposure. The conversion of succinate to fumarate in the Krebs cycle was also interrupted by phenanthrene. Therefore, this study shows that NMR-based metabolomics is a powerful tool for elucidating time-dependent relationships in addition to the mode of toxicity of phenanthrene in earthworm exposure studies. - Highlights: → NMR-based earthworm metabolomic analysis of the mode of action of phenanthrene is presented. → The earthworm species E. fetida were exposed to sub-lethal phenanthrene concentrations. → Both polar and non-polar metabolites of E. fetida tissue extracts were analyzed by 1 H NMR. → Longer phenanthrene exposure times resulted in heightened earthworm responses. → An interruption of the Krebs cycle was also observed due to phenanthrene exposure. - 1 H NMR metabolomics is used to determine the relationship between phenanthrene exposure and the metabolic response of the earthworm E. fetida over time and also to elucidate the phenanthrene mode of toxicity.

  14. Novel spin dynamics in ferrimagnetic molecular chains from 1H NMR and μSR spin-lattice relaxation measurements

    International Nuclear Information System (INIS)

    Micotti, E.; Lascialfari, A.; Rigamonti, A.; Aldrovandi, S.; Caneschi, A.; Gatteschi, D.; Bogani, L.

    2004-01-01

    The spin dynamics in the helical chain Co(hfac) 2 NITPhOMe has been investigated by 1 H NMR and μSR relaxation. In the temperature range 15< T<60 K, the results are consistent with the relaxation of the homogeneous magnetization. For T≤15 K, NMR and μSR evidence a second spin relaxation mechanism, undetected by the magnetization measurements. From the analysis of these data, insights on this novel relaxation process are derived

  15. Novel spin dynamics in ferrimagnetic molecular chains from 1H NMR and μSR spin-lattice relaxation measurements

    Science.gov (United States)

    Micotti, E.; Lascialfari, A.; Rigamonti, A.; Aldrovandi, S.; Caneschi, A.; Gatteschi, D.; Bogani, L.

    2004-05-01

    The spin dynamics in the helical chain Co(hfac) 2NITPhOMe has been investigated by 1H NMR and μSR relaxation. In the temperature range 15

  16. Application of 1H NMR for the characterisation of cocoa beans of different geographical origins and fermentation levels.

    Science.gov (United States)

    Caligiani, Augusta; Palla, Luigi; Acquotti, Domenico; Marseglia, Angela; Palla, Gerardo

    2014-08-15

    This study reports for the first time the use of (1)H NMR technique combined with chemometrics to study the metabolic profile of cocoa (Theobroma cacao L.) beans of different varieties, origin and fermentation levels. Results of PCA applied to cocoa bean (1)H NMR dataset showed that the main factor influencing the cocoa bean metabolic profile is the fermentation level. In fact well fermented brown beans form a group clearly separated from unfermented, slaty, and underfermented, violet, beans, independently of the variety or geographical origin. Considering only well fermented beans, the metabolic profile obtained by (1)H NMR permitted to discriminate between some classes of samples. The National cocoa of Ecuador, known as Arriba, showed the most peculiar characteristics, while the samples coming from the African region showed some similar traits. The dataset obtained, representative of all the classes of soluble compounds of cocoa, was therefore useful to characterise fermented cocoa beans as a function of their origin and fermentation level. Copyright © 2014 Elsevier Ltd. All rights reserved.

  17. Determination of the overall migration from silicone baking moulds into simulants and food using 1H-NMR techniques.

    Science.gov (United States)

    Helling, Ruediger; Mieth, Anja; Altmann, Stefan; Simat, Thomas Joachim

    2009-03-01

    Different silicone baking moulds (37 samples) were characterized with respect to potential migrating substances using 1H-NMR, RP-HPLC-UV/ELSD and GC techniques. In all cases cyclic organosiloxane oligomers with the formula [Si(CH3)2-O]n were identified (n = 6 ... 50). Additionally, linear, partly hydroxyl-terminated organosiloxanes HO-[Si(CH3)2-O]n-H (n = 7 ... 20) were found in 13 samples. No substances other than siloxanes could be detected, meaning the migrants mainly consist of organopolysiloxanes. Based on this knowledge, a 1H-NMR quantification method for siloxanes was established for the analysis of both simulants and foodstuffs. Validation of the 1H-NMR method gave suitable performance characteristics: limit of detection 8.7 mg kg(-1) oil, coefficient of variation 7.8% (at a level of 1.0 mg kg(-1) food). Migration studies were carried out with simulants (olive oil, isooctane, ethanol (95%), Tenax) as well as preparation of different cakes. From the 1st to 10th experiment, siloxane migration into cakes only slightly decreased, with a significant dependence on fat content. Migration never exceeded a level of 21 mg kg(-1) (3 mg dm(-2)) and was, therefore, well below the overall migration limit of 60 mg kg(-1) (10 mg dm(-2)). However, migration behaviour into simulants differed completely from these results.

  18. 1H NMR method for simultaneous identification and determination of caffeine and theophylline in human serum and pharmaceutical preparations

    International Nuclear Information System (INIS)

    Talebpour, Z.; Bijanzadeh, H.R.; Haghgoo, S.; Shamsipur, M.

    2004-01-01

    A 1 H NMR method for simultaneous identification and determination of caffeine and theophylline in pharmaceutical preparations and human serum has been developed. 1 H NMR spectrum of caffeine exhibits three sharp singlets at 2.75, 2.93 and 3.4 ppm, while that of theophyline shows two singlet peaks at 2.77 and 2.97 ppm. For the purpose of quantitative analyses of the mixtures of these two alkaloids 1 H NMR spectra of caffeine and theophylline was compared to that of maleic acid as an internal standard at the constant temperature. The suitable peaks were selected and standard deviation and reproducibility of the results were studied applying the full factorial design method. The obtained detection limits are 1.6 μgL - 1 and 1.43 μg L 1 for caffeine and theophylline, respectively. The average recoveries of the studied applying compounds in various samples, pharmaceutical preparations and human serum ranged from 90.2 to 107.5% (author)

  19. A resorcinarene-based “turn-off” fluorescence sensor for 4-nitrotoluene: Insights from fluorescence and {sup 1}H NMR titration with computational approach

    Energy Technology Data Exchange (ETDEWEB)

    Panchal, Urvi; Modi, Krunal; Dey, Shuvankar; Prajapati, Usha [Department of Chemistry, University School of Sciences, Gujarat University, Ahmedabad 380009, Gujarat (India); Patel, Chirag [Department of Bioinformatics, Applied Botany Centre (ABC), University School of Sciences, Gujarat University, Ahmedabad 380009, Gujarat (India); Jain, V.K., E-mail: drvkjain@hotmail.com [Department of Chemistry, University School of Sciences, Gujarat University, Ahmedabad 380009, Gujarat (India)

    2017-04-15

    A new Tetra-Methoxy Resorcinarene-N-(2-ethyl) Phthalimide (TMRN2Ph) has been synthesized for the selective and sensitive recognition of 4-nitrotoluene (4-NT) among various nitroaromatic compounds (NACs) by using a spectrofluorimetric method. Strong quenching in the fluorescence intensity of TMRN2Ph was displayed upon the addition of 4-NT in the linear concentration range of 50 µM to 1 mM. The complexation between TMRN2Ph and 4-NT is supported by ESI-MS and {sup 1}H NMR analysis. The complex of TMRN2Ph with 4-NT has been investigated by computational methods such as molecular docking and molecular dynamics to determine the binding interactions and conformational changes. The detection of 4-NT from a water sample has also been performed successfully.

  20. Comparison between the efficacy of two cleanup methods for the {sup 1}H NMR analysis of food samples contaminated with Cypermethrin

    Energy Technology Data Exchange (ETDEWEB)

    Silva, M.M.; Figueroa-Villar, J.D.; Aguiar, A.P. [Instituto Militar de Engenharia (IME), Rio de Janeiro, RJ (Brazil). Dept. de Quimica; Riehl, C.A.S. [Universidade Federal do Rio de Janeiro (UFRJ), RJ (Brazil). Inst. de Quimica. Dept. de Quimica Analitica]. E-mail: riehl@iq.ufrj

    2004-07-01

    This work aimed to study the use of {sup 1}H NMR for the identification of cypermethrin in cooked foods. {sup 1}H NMR is not commonly used in these cases, because food samples ready for consumption have complex substances, mainly lipids, which usually interfere with the identification of cypermethrin. Thus, we drew a comparison between the most applied method for the treatment of those samples and an alternative route that made possible the use of {sup 1}H NMR in the identification of cypermethrin in a matrix consisting of rice, bean, and chicken, which allows the Forensic work for such cases.(author)

  1. Human urine as test material in 1H NMR-based metabonomics: recommendations for sample preparation and storage.

    Science.gov (United States)

    Lauridsen, Michael; Hansen, Steen H; Jaroszewski, Jerzy W; Cornett, Claus

    2007-02-01

    Metabonomic approaches are believed to have the capability of revolutionizing diagnosis of diseases and assessment of patient conditions after medical interventions. In order to ensure comparability of metabonomic 1H NMR data from different studies, we suggest validated sample preparation guidelines for human urine based on a stability study that evaluates effects of storage time and temperature, freeze-drying, and the presence of preservatives. The results indicated that human urine samples should be stored at or below -25 degrees C, as no changes in the 1H NMR fingerprints have been observed during storage at this temperature for 26 weeks. Formation of acetate, presumably due to microbial contamination, was occasionally observed in samples stored at 4 degrees C without addition of a preservative. Addition of a preserving agent is not mandatory provided that the samples are stored at -25 degrees C. Thus, no differences were observed between 1H NMR spectra of nonpreserved urines and urines with added sodium azide and stored at -25 degrees C, whereas the presence of sodium fluoride caused a shift of especially citrate resonances. Freeze-drying of urine and reconstitution in D2O at pH 7.4 resulted in the disappearance of the creatinine CH2 signal at delta 4.06 due to deuteration. A study evaluating the effects of phosphate buffer concentration on signal variability and assessment of the probability of citrate or creatinine resonances crossing bucket border (a boundary between adjacent integrated regions) led to the conclusion that a minimum buffer concentration of 0.3 M is adequate for normal urines used in this study. However, final buffer concentration of 1 M will be required for very concentrated urines.

  2. Functional Group and Structural Characterization of Unmodified and Functionalized Lignin by Titration, Elemental Analysis, 1H NMR and FTIR Techniques

    Directory of Open Access Journals (Sweden)

    Ramin Bairami Habashi

    2017-11-01

    Full Text Available Lignin is the second most abundant polymer in the world after cellulose. Therefore, characterization of the structure and functional groups of lignin in order to assess its potential applications in various technical fields has become a necessity. One of the major problems related to the characterization of lignin is the lack of well-defined protocols and standards. In this paper, systematic studies have been done to characterize the structure and functional groups of lignin quantitatively using different techniques such as elemental analysis, titration and 1H NMR and FTIR techniques. Lignin as a black liquor was obtained from Choka Paper Factory and it was purified before any test. The lignin was reacted with α-bromoisobutyryl bromide to calculate the number of hydroxyl and methoxyl moles. Using 1H NMR spectroscopic method on α-bromoisobutyrylated lignin (BiBL in the presence of a given amount of N,N-dimethylformamide (DMF as an internal standard, the number of moles of hydroxyl and methoxyl groups per gram of lignin was found to be 6.44 mmol/g and 6.64 mmol/g, respectively. Using aqueous titration, the number of moles of phenolic hydroxyl groups and carboxyl groups of the lignin were calculated as 3.13 mmol/g and 2.84 mmol/g, respectively. The findings obtained by 1H NMR and elemental analysis indicated to phenyl propane unit of the lignin with C9 structural formula as C9 HAl 3.84HAr2.19S0.2O0.8(OH1.38(OCH31.42. Due to poor solubility of the lignin in tetrahydrofuran (THF, acetylated lignin was used in the GPC analysis, by which number-average molecular weight  of the lignin was calculated as 992 g/mol.

  3. 1H NMR study of the solvent THF concerning their structural and dynamical properties in chemically Li-intercalated SWNT

    KAUST Repository

    Schmid, Marc R.

    2011-09-01

    Structural and dynamical properties of the THF solvent in single-walled carbon nanotubes intercalated with lithium are investigated by NMR. 1H NMR experiments reveal the existence of two types of inequivalent THF solvent molecules with different chemical environments and dynamical behavior. At low temperatures THF molecules perpendicularly arranged in between adjacent SWNT presumably exhibit a restricted rotation around their dipolar axis. At higher temperatures THF molecules are isotropically rotating and diffusing along the interstitial channels of the SWNT bundles. © 2011 Elsevier B.V. All rights reserved.

  4. Hydrogen cluster/network in tobermorite as studied by multiple-quantum spin counting {sup 1}H NMR

    Energy Technology Data Exchange (ETDEWEB)

    Mogami, Yuuki [Division of Chemistry, Graduate School of Science, Kyoto University, Kyoto 606-8502 (Japan); Yamazaki, Satoru; Matsuno, Shinya [Analysis and Simulation Center, Asahi Kasei Corporation, Fuji, Shizuoka 416-8501 (Japan); Matsui, Kunio [Products and Marketing Development Dept., Asahi Kasei Construction Materials Corporation, Sakai-machi, Ibaraki 306-0493 (Japan); Noda, Yasuto [Division of Chemistry, Graduate School of Science, Kyoto University, Kyoto 606-8502 (Japan); Takegoshi, K., E-mail: takeyan@kuchem.kyoto-u.ac.jp [Division of Chemistry, Graduate School of Science, Kyoto University, Kyoto 606-8502 (Japan)

    2014-12-15

    Proton multiple-quantum (MQ) spin-counting experiment has been employed to study arrangement of hydrogen atoms in 9 Å/11 Å natural/synthetic tobermorites. Even though all tobermorite samples give similar characterless, broad static-powder {sup 1}H NMR spectra, their MQ spin-counting spectra are markedly different; higher quanta in 11 Å tobermorite do not grow with the MQ excitation time, while those in 9 Å one do. A statistical analysis of the MQ results recently proposed [26] is applied to show that hydrogens align in 9 Å tobermorite one dimensionally, while in 11 Å tobermorite they exist as a cluster of 5–8 hydrogen atoms.

  5. Sequence-specific assignments in the 1H NMR spectrum of the human inflammatory protein C5a

    International Nuclear Information System (INIS)

    Zuiderweg, E.R.P.; Mollison, K.W.; Henkin, J.; Carter, G.W.

    1988-01-01

    Full sequence-specific assignments for the 1 H NMR lines of the backbone protons of the human complement factor C5a are described and documented. The results were obtained by largely following the methodology developed by Wuethrich et al. Assignments for the majority of the amino acid side chain protons were obtained by using a comparison of double- and triple-quantum-filtered two-dimensional correlated experiments together with the analysis of relayed coherence transfer spectra. The assignments provide the basis for the determination of the thus far unknown three-dimensional structure of C5a from nuclear Overhauser enhancement distance constraints

  6. 1H NMR study of the solvent THF concerning their structural and dynamical properties in chemically Li-intercalated SWNT

    KAUST Repository

    Schmid, Marc R.; Goze-Bac, Christophe; Bouhrara, Mohamed; Saih, Youssef; Mehring, Michael; Abou-Hamad, Edy

    2011-01-01

    Structural and dynamical properties of the THF solvent in single-walled carbon nanotubes intercalated with lithium are investigated by NMR. 1H NMR experiments reveal the existence of two types of inequivalent THF solvent molecules with different chemical environments and dynamical behavior. At low temperatures THF molecules perpendicularly arranged in between adjacent SWNT presumably exhibit a restricted rotation around their dipolar axis. At higher temperatures THF molecules are isotropically rotating and diffusing along the interstitial channels of the SWNT bundles. © 2011 Elsevier B.V. All rights reserved.

  7. {sup 1}H NMR metabolomics of earthworm exposure to sub-lethal concentrations of phenanthrene in soil

    Energy Technology Data Exchange (ETDEWEB)

    Brown, Sarah A.E.; McKelvie, Jennifer R.; Simpson, Andre J. [Department of Physical and Environmental Sciences, University of Toronto, 1265 Military Trail Toronto, Ontario, M1C 1A4 (Canada); Simpson, Myrna J., E-mail: myrna.simpson@utoronto.c [Department of Physical and Environmental Sciences, University of Toronto, 1265 Military Trail Toronto, Ontario, M1C 1A4 (Canada)

    2010-06-15

    {sup 1}H NMR metabolomics was used to monitor earthworm responses to sub-lethal (50-1500 mg/kg) phenanthrene exposure in soil. Total phenanthrene was analyzed via soxhlet extraction, bioavailable phenanthrene was estimated by hydroxypropyl-beta-cyclodextrin (HPCD) and 1-butanol extractions and sorption to soil was assessed by batch equilibration. Bioavailable phenanthrene (HPCD-extracted) comprised approx65-97% of total phenanthrene added to the soil. Principal component analysis (PCA) showed differences in responses between exposed earthworms and controls after 48 h exposure. The metabolites that varied with exposure included amino acids (isoleucine, alanine and glutamine) and maltose. PLS models indicated that earthworm response is positively correlated to both total phenanthrene concentration and bioavailable (HPCD-extracted) phenanthrene in a freshly spiked, unaged soil. These results show that metabolomics is a powerful, direct technique that may be used to monitor contaminant bioavailability and toxicity of sub-lethal concentrations of contaminants in the environment. These initial findings warrant further metabolomic studies with aged contaminated soils. - {sup 1}H NMR metabolomics is used to directly monitor metabolic responses of Eisenia fetida after 48 h of exposure to sub-lethal concentrations of phenanthrene in soil.

  8. {sup 1}H NMR-based metabolomics reveals sub-lethal toxicity of a mixture of diabetic and lipid-regulating pharmaceuticals on amphibian larvae

    Energy Technology Data Exchange (ETDEWEB)

    Melvin, Steven D., E-mail: s.melvin@griffith.edu.au [Australian Rivers Institute, Griffith University, Southport, QLD 4222 (Australia); Habener, Leesa J. [Griffith School of Environment, Griffith University, Southport, QLD 4222 (Australia); Leusch, Frederic D.L. [Australian Rivers Institute, Griffith University, Southport, QLD 4222 (Australia); Griffith School of Environment, Griffith University, Southport, QLD 4222 (Australia); Carroll, Anthony R. [Griffith School of Environment, Griffith University, Southport, QLD 4222 (Australia)

    2017-03-15

    expected response patterns may be explained by differences in the receptivity or uptake of the compounds in non-mammalian species. Proton nuclear magnetic resonance ({sup 1}H NMR) spectroscopy revealed evidence of broad metabolic dysregulation in exposed animals, and possible interaction between the solvent and mixture. Specifically, increased lactic acid and branched-chain amino acids were observed, with responses tending to follow a non-monotonic pattern. Overall, results demonstrate that a mixture of drugs commonly prescribed to treat human metabolic syndrome is capable of eliciting physiological and developmental effects on larval amphibians. Importantly, outcomes further suggest that it may not be possible to predict toxicological effects in non-target wildlife based on our knowledge of how these compounds act in humans.

  9. "1H NMR-based metabolomics reveals sub-lethal toxicity of a mixture of diabetic and lipid-regulating pharmaceuticals on amphibian larvae

    International Nuclear Information System (INIS)

    Melvin, Steven D.; Habener, Leesa J.; Leusch, Frederic D.L.; Carroll, Anthony R.

    2017-01-01

    expected response patterns may be explained by differences in the receptivity or uptake of the compounds in non-mammalian species. Proton nuclear magnetic resonance ("1H NMR) spectroscopy revealed evidence of broad metabolic dysregulation in exposed animals, and possible interaction between the solvent and mixture. Specifically, increased lactic acid and branched-chain amino acids were observed, with responses tending to follow a non-monotonic pattern. Overall, results demonstrate that a mixture of drugs commonly prescribed to treat human metabolic syndrome is capable of eliciting physiological and developmental effects on larval amphibians. Importantly, outcomes further suggest that it may not be possible to predict toxicological effects in non-target wildlife based on our knowledge of how these compounds act in humans.

  10. Detection of counterfeit brand spirits using 1H NMR fingerprints in comparison to sensory analysis.

    Science.gov (United States)

    Kuballa, Thomas; Hausler, Thomas; Okaru, Alex O; Neufeld, Maria; Abuga, Kennedy O; Kibwage, Isaac O; Rehm, Jürgen; Luy, Burkhard; Walch, Stephan G; Lachenmeier, Dirk W

    2018-04-15

    Beverage fraud involving counterfeiting of brand spirits is an increasing problem not only due to deception of the consumer but also because it poses health risks e.g. from possible methanol admixture. Suspicious spirit samples from Russia and Kenya were analysed using 1 H nuclear magnetic resonance (NMR) spectroscopy in comparison to authentic products. Using linear regression analysis of spectral integral values, 4 counterfeited samples from Russia and 2 from Kenya were easily identifiable with R 2  counterfeited and authentic samples but the assessors were unable to correctly identify the counterfeited product in the majority of cases. An important conclusion is that consumers cannot assumed to be self-responsible when consuming counterfeit alcohol because there is no general ability to organoleptically detect counterfeit alcohol. Copyright © 2017 Elsevier Ltd. All rights reserved.

  11. Global host metabolic response to Plasmodium vivax infection: a 1H NMR based urinary metabonomic study

    Directory of Open Access Journals (Sweden)

    Sengupta Arjun

    2011-12-01

    Full Text Available Abstract Background Plasmodium vivax is responsible for the majority of malarial infection in the Indian subcontinent. This species of the parasite is generally believed to cause a relatively benign form of the disease. However, recent reports from different parts of the world indicate that vivax malaria can also have severe manifestation. Host response to the parasite invasion is thought to be an important factor in determining the severity of manifestation. In this paper, attempt was made to determine the host metabolic response associated with P. vivax infection by means of NMR spectroscopy-based metabonomic techniques in an attempt to better understand the disease pathology. Methods NMR spectroscopy of urine samples from P. vivax-infected patients, healthy individuals and non-malarial fever patients were carried out followed by multivariate statistical analysis. Two data analysis techniques were employed, namely, Principal Component Analysis [PCA] and Orthogonal Projection to Latent Structure Discriminant Analysis [OPLS-DA]. Several NMR signals from the urinary metabolites were further selected for univariate comparison among the classes. Results The urine metabolic profiles of P. vivax-infected patients were distinct from those of healthy individuals as well as of non-malarial fever patients. A highly predictive model was constructed from urine profile of malarial and non-malarial fever patients. Several metabolites were found to be varying significantly across these cohorts. Urinary ornithine seems to have the potential to be used as biomarkers of vivax malaria. An increasing trend in pipecolic acid was also observed. The results suggest impairment in the functioning of liver as well as impairment in urea cycle. Conclusions The results open up a possibility of non-invasive analysis and diagnosis of P. vivax using urine metabolic profile. Distinct variations in certain metabolites were recorded, and amongst these, ornithine may have the

  12. X-ray and 1H-NMR spectroscopic studies of the structures and conformations of the new nootropic agents RU-35929, RU-47010 and RU-35965

    Science.gov (United States)

    Amato, Maria E.; Bandoli, Giuliano; Casellato, Umberto; Pappalardo, Giuseppe C.; Toja, Emilio

    1990-10-01

    The crystal and molecular structures of the nootropics (±)1-benzenesulphonyl-2-oxo-5-ethoxypyrrolidine ( 1), (±)1-(3-pyridinylsulphonyl)-2-oxo-5-ethoxypyrrolidine ( 2) and (±)1-benzenesulphonyl-2-oxo-5-isopropyloxypyrrolidine ( 3) have been determined by X-ray analysis. The solution conformation of 1, 2 and 3 has been investigated by 1H NMR spectroscopy. In the solid state, the main feature consists of the similar structural parameters and conformations, with the exception of the conformation adopted by the 5-ethoxy moiety which changes on passing from 1 to 2. The solid state overall enveloped conformation of the 2-pyrrolidinone ring for the three nootropics is found to be retained in solution on the basis of NMR evidence. Comparison between calculated and experimental coupling constant values shows that one of the two possible puckered opposite conformational isomers (half-chair shapes) occurs in solution. The relative pharmacological potencies of 1, 2 and 3 cannot therefore be interpreted in terms of the different conformation features presently detectable by available experimental methods.

  13. Study the chemical composition and biological outcomes resulting from the interaction of the hormone adrenaline with heavy elements: Infrared, Raman, electronic, 1H NMR, XRD and SEM studies

    Science.gov (United States)

    Ibrahim, Omar B.; Mohamed, Mahmoud A.; Refat, Moamen S.

    2014-01-01

    Heavy metal adrenaline complexes formed from the reaction of adrenaline with Al3+, Zn2+, Sn2+, Sb3+, Pb2+and Bi3+ ions in methanolic solvent at 60 °C. The final reaction products have been isolated and characterization using elemental analyses (% of carbon, hydrogen and nitrogen), conductivity measurements, mid infrared, Raman laser, UV-Vis, 1H NMR spectra, X-ray powder diffraction, scanning electron microscopy and energy-dispersive X-ray spectroscopy (EDX). Upon the spectroscopic, conductivity and elemental analyses, the stoichiometric reactions indicated that the data obtained refer to 1:2 (M:L) for Zn2+, Sn2+, Pb2+and Bi3+ complexes [Zn(Adr)2(Cl)2], [Sn(Adr)2]Cl2, [Pb(Adr)2](NO3)2 and [Bi(Adr)2(Cl)2]Cl, while the molar ratio 1:3 (M:L) for Al3+ and Sb3+ with formulas [Al(Adr)3](NO3)3 and [Sb(Adr)3]Cl3. The infrared and Raman laser spectra interpreted the mode of interactions which associated through the two phenolic groups of catechol moiety. The adrenaline chelates have been screened for their in vitro antibacterial activity against four bacteria, Gram-positive (Bacillus subtilis and Staphylococcus aureus) and Gram-negative (Escherichia coli and Pseudomonas aeruginosa) and two strains of fungus (Aspergillus flavus and Candida albicans). The metal chelates were shown to possess more antibacterial and antifungal activities than the free adrenaline chelate.

  14. Statistical removal of background signals from high-throughput 1H NMR line-broadening ligand-affinity screens

    International Nuclear Information System (INIS)

    Worley, Bradley; Sisco, Nicholas J.; Powers, Robert

    2015-01-01

    NMR ligand-affinity screens are vital to drug discovery, are routinely used to screen fragment-based libraries, and used to verify chemical leads from high-throughput assays and virtual screens. NMR ligand-affinity screens are also a highly informative first step towards identifying functional epitopes of unknown proteins, as well as elucidating the biochemical functions of protein–ligand interaction at their binding interfaces. While simple one-dimensional 1 H NMR experiments are capable of indicating binding through a change in ligand line shape, they are plagued by broad, ill-defined background signals from protein 1 H resonances. We present an uncomplicated method for subtraction of protein background in high-throughput ligand-based affinity screens, and show that its performance is maximized when phase-scatter correction is applied prior to subtraction

  15. 1H-NMR/13C-NMR studies of branched structures in PVC obtained at atmospheric pressure

    International Nuclear Information System (INIS)

    Braun, D.; Holzer, G.; Hjertberg, T.

    1981-01-01

    The 1 H-NMR-spectra of raw poly (vinyl cloride) obtained at atmospheric pressure (U-PVC) have revealed the presence of high concentrations of branches. The content of labile chlorine was determined by reaction with phenole in order to estimate the branch points with tertiary chlorine. The branch length of reductively dehalogenated U-PVC by 13 C-NMR analysis have provided evidence for both short chain branches including chloromethyl groups and 2.4-dichloro-n-butyl groups and long chain branching. For a number of U-polymers the total amount of branching ranges from 7.5 to 13.5/1000 C. The 13 C-NMR measurements point to a ratio of methyl/butyl branches of 1:1 and short chains/long chains of 6:1. (orig.)

  16. Correlations between the 1H NMR chemical shieldings and the pKa values of organic acids and amines.

    Science.gov (United States)

    Lu, Juanfeng; Lu, Tingting; Zhao, Xinyun; Chen, Xi; Zhan, Chang-Guo

    2018-06-01

    The acid dissociation constants and 1 H NMR chemical shieldings of organic compounds are important properties that have attracted much research interest. However, few studies have explored the relationship between these two properties. In this work, we theoretically studied the NMR chemical shifts of a series of carboxylic acids and amines in the gas phase and in aqueous solution. It was found that the negative logarithms of the experimental acid dissociation constants (i.e., the pK a values) of the organic acids and amines in aqueous solution correlate almost linearly with the corresponding calculated NMR chemical shieldings. Key factors that affect the theoretically predicted pK a values are discussed in this paper. The present work provides a new way to predict the pK a values of organic/biochemical compounds. Graphical abstract The chemical shielding values of organic acids and amines correlate near linearly with their corresponding pK a values.

  17. Effect of rootstock on the scion of Hevea brasiliensis through metabolic analysis of latex samples by 1H NMR

    Directory of Open Access Journals (Sweden)

    Eduardo Sanches Pereira do Nascimento

    2011-01-01

    Full Text Available In this study, the effect of rootstock on grafting through metabolomic analysis of latex (Hevea brasiliensis samples was verified by 1H nuclear magnetic resonance (NMR and multivariate data analysis. Sixteen metabolites present in the latex cytosol were characterized by NMR. PCA analysis showed that the latex samples of the RR and GR groups can be differentiated. The GR group samples present a metabolic profile similar to the RR group samples, while the RG group is in an intermediate position between RR and GG groups. Sucrose and formate contributed greatly to the separation obtained by PCA, presenting a good correlation between the results. 1H NMR was an efficient technique to differentiate latex samples from different types of rootstocks and grafting and in the future could be used to predict rubber production by latex analysis.

  18. Assignment strategies in homonuclear three-dimensional 1H NMR spectra of proteins

    International Nuclear Information System (INIS)

    Vuister, G.W.; Boelens, R.; Padilla, A.; Kleywegt, G.J.; Kaptein, R.

    1990-01-01

    The increase in dimensionality of three-dimensional (3D) NMR greatly enhances the spectral resolution in comparison to 2D NMR. It alleviates the problem of resonance overlap and may extend the range of molecules amenable to structure determination by high-resolution NMR spectroscopy. Here, the authors present strategies for the assignment of protein resonances from homonuclear nonselective 3D NOE-HOHAHA spectra. A notation for connectivities between protons, corresponding to cross peaks in 3D spectra, is introduced. They show how spin systems can be identified by tracing cross-peak patterns in cross sections perpendicular to the three frequency axes. The observable 3D sequential connectivities in proteins are tabulated, and estimates for the relative intensities of the corresponding cross peaks are given for α-helical and β-sheet conformations. Intensities of the cross peaks in the 3D spectrum of pike III paravalbumin follow the predictions. The sequential-assignment procedure is illustrated for loop regions, extended and α-helical conformations for the residues Ala 54-Leu 63 of paravalbumin. NOEs that were not previously identified in 2D spectra of paravalbumin due to overlap are found

  19. (1)H NMR-based metabonomics revealed protective effect of Naodesheng bioactive extract on ischemic stroke rats.

    Science.gov (United States)

    Luo, Lan; Zhen, Lifeng; Xu, Yatao; Yang, Yongxia; Feng, Suxiang; Wang, Shumei; Liang, Shengwang

    2016-06-20

    Stroke is a leading cause of death and disability in the world. However, current therapies are limited. Naodesheng, a widely used traditional Chinese medicine prescription, has shown a good clinical curative effect on ischemic stroke. Also, Naodesheng has been suggested to have neuroprotective effect on focal cerebral ischemia rats, but the underlying molecular mechanism remains unclear. The present study was designed to evaluate the effect of Naodesheng bioactive extract on the metabolic changes in brain tissue, plasma and urine induced by cerebral ischemia perfusion injury, and explore the possible metabolic mechanisms by using a (1)H NMR-based metabonomics approach. A middle cerebral artery occlusion rat model was established and confirmed by the experiments of neurobehavioral abnormality evaluation, brain tissue TTC staining and pathological examination. The metabolic changes in brain tissue, plasma and urine were then assessed by a (1)H NMR technique combined with multivariate statistical analysis method. These NMR data showed that cerebral ischemia reperfusion induced great metabolic disorders in brain tissue, plasma and urine metabolisms. However, Naodesheng bioactive extract could reverse most of the imbalanced metabolites. Meanwhile, it was found that both the medium and high dosages of Naodesheng bioactive extract were more effective on the metabolic changes than the low dosage, consistent with histopathological assessments. These results revealed that Naodesheng had protective effect on ischemic stroke rats and the underlying mechanisms involved multiple metabolic pathways, including energy metabolism, amino acid metabolism, oxidative stress and inflammatory injury. The present study could provide evidence that metabonomics revealed its capacity to evaluate the holistic efficacy of traditional Chinese medicine and explore the underlying mechanisms. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

  20. 1H NMR metabolic fingerprinting to probe temporal postharvest changes on qualitative attributes and phytochemical profile of sweet cherry fruit

    Directory of Open Access Journals (Sweden)

    Vlasios eGoulas

    2015-11-01

    Full Text Available Sweet cherry fruits (Prunus avium cvs. ‘Canada Giant’, ‘Ferrovia’ were harvested at commercial maturity stage and analyzed at harvest and after maintenance at room temperature (storage at ~ 20°C, shelf life for 1, 2, 4, 6 and 8 days, respectively. Fruit were initially analyzed for respiration rate, qualitative attributes and textural properties: ‘Canada Giant’ fruit were characterized by higher weight losses and stem browning index, being more intense over the late stages of shelf life period; meanwhile ‘Ferrovia’ possessed appreciably better performance even after extended shelf life period. A gradual decrease of respiration rate was monitored in both cultivars, culminated after 8 days at 20°C. The sweet cherry fruit nutraceutical profile was monitored using an array of instrumental techniques (spectrophotometric assays, HPLC, 1H-NMR. Fruit antioxidant capacity was enhanced with the progress of shelf life period, concomitant with the increased levels of total anthocyanin and of phenolic compounds. ‘Ferrovia’ fruit presented higher contents of neochlorogenic acid and p-coumarolquinic acid throughout the shelf life period. We further developed an 1H-NMR method that allows the study of primary and secondary metabolites in a single running, without previous separation and isolation procedures. Diagnostic peaks were located in the aliphatic region for sugars and organic acids, in the aromatic region for phenolic compounds and at 8.2 to 8.6 ppm for anthocyanins. This NMR-based methodology provides a unifying tool for quantitative and qualitative characterization of metabolite changes of sweet cherry fruits; it is also expected to be further exploited for monitoring temporal changes in other fleshy fruits.

  1. 1H NMR Metabolic Fingerprinting to Probe Temporal Postharvest Changes on Qualitative Attributes and Phytochemical Profile of Sweet Cherry Fruit

    Science.gov (United States)

    Goulas, Vlasios; Minas, Ioannis S.; Kourdoulas, Panayiotis M.; Lazaridou, Athina; Molassiotis, Athanassios N.; Gerothanassis, Ioannis P.; Manganaris, George A.

    2015-01-01

    Sweet cherry fruits (Prunus avium cvs. ‘Canada Giant’, ‘Ferrovia’) were harvested at commercial maturity stage and analyzed at harvest and after maintenance at room temperature (storage at ∼20°C, shelf life) for 1, 2, 4, 6, and 8 days, respectively. Fruit were initially analyzed for respiration rate, qualitative attributes and textural properties: ‘Canada Giant’ fruit were characterized by higher weight losses and stem browning index, being more intense over the late stages of shelf life period; meanwhile ‘Ferrovia’ possessed appreciably better performance even after extended shelf life period. A gradual decrease of respiration rate was monitored in both cultivars, culminated after 8 days at 20°C. The sweet cherry fruit nutraceutical profile was monitored using an array of instrumental techniques (spectrophotometric assays, HPLC, 1H-NMR). Fruit antioxidant capacity was enhanced with the progress of shelf life period, concomitant with the increased levels of total anthocyanin and of phenolic compounds. ‘Ferrovia’ fruit presented higher contents of neochlorogenic acid and p-coumaroylquinic acid throughout the shelf life period. We further developed an 1H-NMR method that allows the study of primary and secondary metabolites in a single running, without previous separation and isolation procedures. Diagnostic peaks were located in the aliphatic region for sugars and organic acids, in the aromatic region for phenolic compounds and at 8.2–8.6 ppm for anthocyanins. This NMR-based methodology provides a unifying tool for quantitative and qualitative characterization of metabolite changes of sweet cherry fruits; it is also expected to be further exploited for monitoring temporal changes in other fleshy fruits. PMID:26617616

  2. (1)H NMR Metabolic Fingerprinting to Probe Temporal Postharvest Changes on Qualitative Attributes and Phytochemical Profile of Sweet Cherry Fruit.

    Science.gov (United States)

    Goulas, Vlasios; Minas, Ioannis S; Kourdoulas, Panayiotis M; Lazaridou, Athina; Molassiotis, Athanassios N; Gerothanassis, Ioannis P; Manganaris, George A

    2015-01-01

    Sweet cherry fruits (Prunus avium cvs. 'Canada Giant', 'Ferrovia') were harvested at commercial maturity stage and analyzed at harvest and after maintenance at room temperature (storage at ∼20°C, shelf life) for 1, 2, 4, 6, and 8 days, respectively. Fruit were initially analyzed for respiration rate, qualitative attributes and textural properties: 'Canada Giant' fruit were characterized by higher weight losses and stem browning index, being more intense over the late stages of shelf life period; meanwhile 'Ferrovia' possessed appreciably better performance even after extended shelf life period. A gradual decrease of respiration rate was monitored in both cultivars, culminated after 8 days at 20°C. The sweet cherry fruit nutraceutical profile was monitored using an array of instrumental techniques (spectrophotometric assays, HPLC, (1)H-NMR). Fruit antioxidant capacity was enhanced with the progress of shelf life period, concomitant with the increased levels of total anthocyanin and of phenolic compounds. 'Ferrovia' fruit presented higher contents of neochlorogenic acid and p-coumaroylquinic acid throughout the shelf life period. We further developed an (1)H-NMR method that allows the study of primary and secondary metabolites in a single running, without previous separation and isolation procedures. Diagnostic peaks were located in the aliphatic region for sugars and organic acids, in the aromatic region for phenolic compounds and at 8.2-8.6 ppm for anthocyanins. This NMR-based methodology provides a unifying tool for quantitative and qualitative characterization of metabolite changes of sweet cherry fruits; it is also expected to be further exploited for monitoring temporal changes in other fleshy fruits.

  3. Quantitative Quantum Mechanical Spectral Analysis (qQMSA) of (1)H NMR spectra of complex mixtures and biofluids.

    Science.gov (United States)

    Tiainen, Mika; Soininen, Pasi; Laatikainen, Reino

    2014-05-01

    The quantitative interpretation of (1)H NMR spectra of mixtures like the biofluids is a demanding task due to spectral complexity and overlap. Complications may arise also from water suppression, T2-editing, protein interactions, relaxation differences of the species, experimental artifacts and, furthermore, the spectra may contain unknown components and macromolecular background which cannot be easily separated from baseline. In this work, tools and strategies for quantitative Quantum Mechanical Spectral Analysis (qQMSA) of (1)H NMR spectra from complex mixtures were developed and systematically assessed. In the present approach, the signals of well-defined, stoichiometric components are described by a QM model, while the background is described by a multiterm baseline function and the unknown signals using optimizable and adjustable lines, regular multiplets or any spectral structures which can be composed from spectral lines. Any prior knowledge available from the spectrum can also be added to the model. Fitting strategies for weak and strongly overlapping spectral systems were developed and assessed using two basic model systems, the metabolite mixtures without and with macromolecular (serum) background. The analyses show that if the spectra are measured in high-throughput manner, the consistent absolute quantification demands some calibration to compensate the different response factors of the protons and compounds. On the other hand, the results show that also the T2-edited spectra can be measured so that they obey well the QM rules. In general, qQMSA exploits and interprets the spectral information in maximal way taking full advantage from the QM properties of the spectra and, at the same time, offers chemical confidence which means that individual components can be identified with high confidence on the basis of their accurate spectral parameters. Copyright © 2014 Elsevier Inc. All rights reserved.

  4. I. The synthesis and characterization of annulated uranocenes. II. The variable temperature 1H NMR of uranocenes

    International Nuclear Information System (INIS)

    Luke, W.D.

    1980-01-01

    A general synthetic route to alkyl annulated cyclooctatetraene dianions and the corresponding annulated uranocenes has been developed. Dideprotonation of bicyclooctatrienes, resulting from reaction of cyclooctatetraene dianion with l,n-dialkylbromides or methanesulfonates, affords alkyl annulated cyclooctatetraene dianions in moderate yields. Dicyclopenteno-, bisdimethylcyclopenteno- and dicyclohexenouranocene were prepared from the corresponding cyclooctatetraene dianions and UCl 4 . The structures of dicyclobuteno- and dicyclopentenouranocene were elucidated by single crystal X-ray diffraction, and the effects of annulation on the uranocene skeleton are discussed. Attempted synthesis of benzocyclooctatetraene and a benzannulated uranocene is reported. The variable temperature 1 H NMR spectrum of uranocene has been reinvestigated from -100 to 100 0 C. The isotropic shift was found to be linear in T -1 with an extrapolated intercept of 0 at T -1 = 0. Variable temperature 1 H NMR spectra, from -80 to 70 0 C, of 17 substituted uranocenes are reported. The energy barrier to ring rotation in 1,1', 4,4'-tetra-t-butyl-uranocene was determined to be 8.24 +- 0.5 kcal/mole while the barrier in the corresponding 1,1', 3,3'-tetra-t-butylferrocene was determined to be 13.1 kcal/mole. Alkyl substitution is shown to have little effect on the electronic and magnetic properties of the uranocene skeleton, and thus alkyl substituted uranocenes are treated as having effective axial symmetry in analysis of the observed isotropic shifts. Using diannulated uranocenes as model systems an analysis of the contact and pseudocontact components of the observed isotropic shifts in uranocene and alkyl substituted uranocenes is presented

  5. Principal component analysis for verifying 1H NMR spectral assignments. The case of 3-aryl (1,2,4)-oxadiazole-5-carbohydrazide benzylidene

    International Nuclear Information System (INIS)

    Silva, Joao Bosco P. da; Malvestiti, Ivani; Hallwass, Fernando; Ramos, Mozart N.; Leite, Lucia F.C. da Costa; Barreiro, Eliezer J.

    2005-01-01

    The 1 H NMR data set of a series of 3-aryl (1,2,4)-oxadiazole-5-carbohydrazide benzylidene derivatives synthesized in our group was analyzed using the chemometric technique of principal component analysis (PCA). Using the original 1H NMR data PCA allowed identifying some misassignments of the proton aromatic chemical shifts. As a consequence of this multivariate analysis, nuclear Overhauser difference experiments were performed to investigate the ambiguity of other assignments of the ortho and meta aromatic hydrogens for the compound with the bromine substituent. The effect of the 1,2,4-oxadiazole group as an electron acceptor, mainly for the hydrogens 12,13, has been highlighted. (author)

  6. 1H NMR metabolomics identification of markers of hypoxia-induced metabolic shifts in a breast cancer model system

    International Nuclear Information System (INIS)

    Weljie, Aalim M.; Bondareva, Alla; Zang, Ping; Jirik, Frank R.

    2011-01-01

    Hypoxia can promote invasive behavior in cancer cells and alters the response to therapeutic intervention as a result of changes in the expression many genes, including genes involved in intermediary metabolism. Although metabolomics technologies are capable of simultaneously measuring a wide range of metabolites in an untargeted manner, these methods have been relatively under utilized in the study of cancer cell responses to hypoxia. Thus, 1 H NMR metabolomics was used to examine the effects of hypoxia in the MDA-MB-231 human breast cancer cell line, both in vitro and in vivo. Cell cultures were compared with respect to their metabolic responses during growth under either hypoxic (1% O 2 ) or normoxic conditions. Orthogonal partial least squares discriminant analysis (OPLS-DA) was used to identify a set of metabolites that were responsive to hypoxia. Via intracardiac administration, MDA-MB-231 cells were also used to generate widespread metastatic disease in immuno-compromised mice. Serum metabolite analysis was conducted to compare animals with and without a large tumor burden. Intriguingly, using a cross-plot of the OPLS loadings, both the in vitro and in vivo samples yielded a subset of metabolites that were significantly altered by hypoxia. These included primarily energy metabolites and amino acids, indicative of known alterations in energy metabolism, and possibly protein synthesis or catabolism. The results suggest that the metabolite pattern identified might prove useful as a marker for intra-tumoral hypoxia.

  7. 1H NMR-based metabolic profiling reveals inherent biological variation in yeast and nematode model systems

    International Nuclear Information System (INIS)

    Szeto, Samuel S. W.; Reinke, Stacey N.; Lemire, Bernard D.

    2011-01-01

    The application of metabolomics to human and animal model systems is poised to provide great insight into our understanding of disease etiology and the metabolic changes that are associated with these conditions. However, metabolomic studies have also revealed that there is significant, inherent biological variation in human samples and even in samples from animal model systems where the animals are housed under carefully controlled conditions. This inherent biological variability is an important consideration for all metabolomics analyses. In this study, we examined the biological variation in 1 H NMR-based metabolic profiling of two model systems, the yeast Saccharomyces cerevisiae and the nematode Caenorhabditis elegans. Using relative standard deviations (RSD) as a measure of variability, our results reveal that both model systems have significant amounts of biological variation. The C. elegans metabolome possesses greater metabolic variance with average RSD values of 29 and 39%, depending on the food source that was used. The S. cerevisiae exometabolome RSD values ranged from 8% to 12% for the four strains examined. We also determined whether biological variation occurs between pairs of phenotypically identical yeast strains. Multivariate statistical analysis allowed us to discriminate between pair members based on their metabolic phenotypes. Our results highlight the variability of the metabolome that exists even for less complex model systems cultured under defined conditions. We also highlight the efficacy of metabolic profiling for defining these subtle metabolic alterations.

  8. (1)H-NMR-based metabolomic analysis of the effect of moderate wine consumption on subjects with cardiovascular risk factors.

    Science.gov (United States)

    Vázquez-Fresno, Rosa; Llorach, Rafael; Alcaro, Francesca; Rodríguez, Miguel Ángel; Vinaixa, Maria; Chiva-Blanch, Gemma; Estruch, Ramon; Correig, Xavier; Andrés-Lacueva, Cristina

    2012-08-01

    Moderate wine consumption is associated with health-promoting activities. An H-NMR-based metabolomic approach was used to identify urinary metabolomic differences of moderate wine intake in the setting of a prospective, randomized, crossover, and controlled trial. Sixty-one male volunteers with high cardiovascular risk factors followed three dietary interventions (28 days): dealcoholized red wine (RWD) (272mL/day, polyphenol control), alcoholized red wine (RWA) (272mL/day) and gin (GIN) (100mL/day, alcohol control). After each period, 24-h urine samples were collected and analyzed by (1) H-NMR. According to the results of a one-way ANOVA, significant markers were grouped in four categories: alcohol-related markers (ethanol); gin-related markers; wine-related markers; and gut microbiota markers (hippurate and 4-hydroxphenylacetic acid). Wine metabolites were classified into two groups; first, metabolites of food metabolome: tartrate (RWA and RWD), ethanol, and mannitol (RWA); and second, biomarkers that relates to endogenous modifications after wine consumption, comprising branched-chain amino acid (BCAA) metabolite (3-methyl-oxovalerate). Additionally, a possible interaction between alcohol and gut-related biomarkers has been identified. To our knowledge, this is the first time that this approach has been applied in a nutritional intervention with red wine. The results show the capacity of this approach to obtain a comprehensive metabolome picture including food metabolome and endogenous biomarkers of moderate wine intake. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. IR, 1H NMR, mass, XRD and TGA/DTA investigations on the ciprofloxacin/iodine charge-transfer complex.

    Science.gov (United States)

    Refat, Moamen S; El-Hawary, W F; Moussa, Mohamed A A

    2011-05-01

    The charge-transfer complex (CTC) of ciprofloxacin drug (CIP) as a donor with iodine (I(2)) as a sigma acceptor has been studied spectrophotometrically in CHCl(3). At maximum absorption bands, the stoichiometry of CIP:iodine system was found to be 1:1 ratio according to molar ratio method. The essential spectroscopic data like formation constant (K(CT)), molar extinction coefficient (ɛ(CT)), standard free energy (ΔG°), oscillator strength (f), transition dipole moment (μ), resonance energy (R(N)) and ionization potential (I(D)) were estimated. The spectroscopic techniques such as IR, (1)H NMR, mass and UV-vis spectra and elemental analyses (CHN) as well as TG-DTG and DTA investigations were used to characterize the chelating behavior of CIP/iodine charge-transfer complex. The iodine CT interaction was associated with a presence of intermolecular hydrogen bond. The X-ray investigation was carried out to investigate the iodine doping in the synthetic CT complex. Copyright © 2011 Elsevier B.V. All rights reserved.

  10. Serum metabolomics of Indian women with polycystic ovary syndrome using 1H NMR coupled with a pattern recognition approach.

    Science.gov (United States)

    RoyChoudhury, Sourav; Mishra, Biswa Prasanna; Khan, Tila; Chattopadhayay, Ratna; Lodh, Indrani; Datta Ray, Chaitali; Bose, Gunja; Sarkar, Himadri S; Srivastava, Sudha; Joshi, Mamata V; Chakravarty, Baidyanath; Chaudhury, Koel

    2016-10-18

    Polycystic ovary syndrome (PCOS) is one of the most commonly occurring metabolic and endocrinological disorders affecting women of reproductive age. Metabolomics is an emerging field that holds promise in understanding disease pathophysiology. Recently, a few metabolomics based studies have been attempted in PCOS patients; however, none of them have included patients from the Indian population. The main objective of this study was to investigate the serum metabolomic profile of Indian women with PCOS and compare them with controls. Proton nuclear magnetic resonance ( 1 H NMR) was used to first identify the differentially expressed metabolites among women with PCOS from the Eastern region of India during the discovery phase and further validated in a separate cohort of PCOS and control subjects. Multivariate analysis of the binned spectra indicated 16 dysregulated bins in the sera of these women with PCOS. Out of these 16 bins, 13 identified bins corresponded to 12 metabolites including 8 amino acids and 4 energy metabolites. Amongst the amino acids, alanine, valine, leucine and threonine and amongst the energy metabolites, lactate and acetate were observed to be significantly up-regulated in women with PCOS when compared with controls. The remaining 4 amino acids, l-glutamine, proline, glutamate and histidine were down-regulated along with 2 energy metabolites: glucose and 3-hydroxybutyric acid. Our findings showed dysregulations in the expression of different metabolites in the serum of women with PCOS suggesting the involvement of multiple pathways including amino acid metabolism, carbohydrate/lipid metabolism, purine and pyrimidine metabolism and protein synthesis.

  11. 1H NMR studies of plastocyanin from Scenedesmus obliquus: Complete sequence-specific assignment, secondary structure analysis, and global fold

    International Nuclear Information System (INIS)

    Moore, J.M.; Chazin, W.J.; Wright, P.E.; Powls, R.

    1988-01-01

    Two-dimensional 1 H NMR methods have been used to make sequence-specific resonance assignments for the 97 amino acid residues of the plastocyanin from the green alga Scenedesmus obliquus. Assignments were obtained for all backbone protons and the majority of the side-chain protons. Spin system identification relied heavily on the observation of relayed connectivities to the backbone amide proton. Sequence-specific assignments were made by using the sequential assignment procedure. During this process, an extra valine residue was identified that had not been detected in the original amino acid sequence. Elements of regular secondary structure were identified from characteristic NOE connectivities between backbone protons, coupling constant values, and the observation of slowly exchanging amide protons. The protein in solution contains eight β-strands, one short segment of helix, five reverse turns, and five loops. The β-strands may be arranged into two βsheets on the basis of extensive cross-strand NOE connectivities. The chain-folding topology determined from the NMR experiments is that of a Greek key β-barrel and is similar to that observed for French bean plastocyanin in solution and poplar plastocyanin in the crystalline state. While the overall structures are similar, several differences in local structure between the S. obliquus and higher plant plastocyanins have been identified

  12. /sup 1/H-NMR urinalysis. Simultaneous screening of inborn errors of metabolism of amino acid and organic acid disorders

    Energy Technology Data Exchange (ETDEWEB)

    Yamamoto, Hideaki; Yamaguchi, Shuichi

    1988-02-01

    In an effort to examine the usefulness of /sup 1/H-nuclear magnetic resonance (NMR) urinalysis in the diagnosis of congenital metabolic disorders, 70 kinds of urinary metabolites were analysed in relation to the diagnosis of inborn errors of amino acid and organic acid disorders. Homogated decoupling (HMG) method failed to analyze six metabolites within the undetectable range. When non-decoupling method (NON), in which the materials are dissolved in dimethyl sulfoxide, was used, the identification of signals became possible. The combination of HMG and NON methods was, therefore, considered to identify all of the metabolites. When the urine samples, which were obtained from patients with hyperglycerolemia, hyperornithinemia, glutaric acidemia type II, or glycerol kinase deficiency, were analysed by using both HMG and NON methods, abnormally increased urinary metabolites were detected. /sup 1/H-NMR urinalysis, if used in the combination of HMG and NON methods, may allow simultanenous screening of inborn errors of metabolism of amino acid and organic acid disorders. (Namekawa, K.).

  13. Classification of Coffee Beans by GC-C-IRMS, GC-MS, and 1H-NMR

    Science.gov (United States)

    Arana, Victoria Andrea; Esseiva, Pierre; Pazos, Diego

    2016-01-01

    In a previous work using 1H-NMR we reported encouraging steps towards the construction of a robust expert system for the discrimination of coffees from Colombia versus nearby countries (Brazil and Peru), to assist the recent protected geographical indication granted to Colombian coffee in 2007. This system relies on fingerprints acquired on a 400 MHz magnet and is thus well suited for small scale random screening of samples obtained at resellers or coffee shops. However, this approach cannot easily be implemented at harbour's installations, due to the elevated operational costs of cryogenic magnets. This limitation implies shipping the samples to the NMR laboratory, making the overall approach slower and thereby more expensive and less attractive for large scale screening at harbours. In this work, we report on our attempt to obtain comparable classification results using alternative techniques that have been reported promising as an alternative to NMR: GC-MS and GC-C-IRMS. Although statistically significant information could be obtained by all three methods, the results show that the quality of the classifiers depends mainly on the number of variables included in the analysis; hence NMR provides an advantage since more molecules are detected to obtain a model with better predictions. PMID:27516919

  14. Classification of Coffee Beans by GC-C-IRMS, GC-MS, and (1)H-NMR.

    Science.gov (United States)

    Arana, Victoria Andrea; Medina, Jessica; Esseiva, Pierre; Pazos, Diego; Wist, Julien

    2016-01-01

    In a previous work using (1)H-NMR we reported encouraging steps towards the construction of a robust expert system for the discrimination of coffees from Colombia versus nearby countries (Brazil and Peru), to assist the recent protected geographical indication granted to Colombian coffee in 2007. This system relies on fingerprints acquired on a 400 MHz magnet and is thus well suited for small scale random screening of samples obtained at resellers or coffee shops. However, this approach cannot easily be implemented at harbour's installations, due to the elevated operational costs of cryogenic magnets. This limitation implies shipping the samples to the NMR laboratory, making the overall approach slower and thereby more expensive and less attractive for large scale screening at harbours. In this work, we report on our attempt to obtain comparable classification results using alternative techniques that have been reported promising as an alternative to NMR: GC-MS and GC-C-IRMS. Although statistically significant information could be obtained by all three methods, the results show that the quality of the classifiers depends mainly on the number of variables included in the analysis; hence NMR provides an advantage since more molecules are detected to obtain a model with better predictions.

  15. Magnetization transfer from macromolecules to water protons in murine dental tissues as revealed by 500 MHz 1H-NMR

    International Nuclear Information System (INIS)

    Nakamura, Koji; Era, Seiichi; Nagai, Naoki; Sogami, Masaru; Takasaki, Akihiko; Kato, Kazuo.

    1997-01-01

    Although much is known about magnetization transfer phenomena in biological soft tissues, little is known about those in hard tissues. Using a 500 MHz 1 H-NMR spectrometer, we studied the spin-lattice relaxation time (T 1 (H 2 O)) and the intermolecular cross-relaxation times (T IS (H 2 O)) from irradiated macromolecular protons to observed water protons in murine lower incisors (hard tissue) and compared with those in murine lens tissue (soft tissue). Mean values for the water content (%) of murine lower incisors and lens tissue were 16.02±2.39 (n=14) and 67.20±4.60 (n=15), respectively. These findings were consistent with the large different in water content between soft tissues and hard tissues. T IS (H 2 O) values obtained by f 2 -irradiation at 7.13 or -4.00 ppm showed no significant difference between lower incisors and lens tissue. Plots of 1/T IS (H 2 O) values vs. tissue dry weight (W(%)) for lower incisor tissue approximated a straight line with slope approximately equal for that obtained for lens tissue. These results suggest that the state of water in hard tissue may be similar to that in soft tissues, in spite of the significant difference in water content. Thus, saturation transfer NMR techniques such as measurement of T IS (H 2 O) values may be applicable to the study of water-macromolecule interactions in both biological soft and hard tissues. (author)

  16. {sup 1}H NMR-based metabolic profiling reveals inherent biological variation in yeast and nematode model systems

    Energy Technology Data Exchange (ETDEWEB)

    Szeto, Samuel S. W.; Reinke, Stacey N.; Lemire, Bernard D., E-mail: bernard.lemire@ualberta.ca [University of Alberta, Department of Biochemistry, School of Molecular and Systems Medicine (Canada)

    2011-04-15

    The application of metabolomics to human and animal model systems is poised to provide great insight into our understanding of disease etiology and the metabolic changes that are associated with these conditions. However, metabolomic studies have also revealed that there is significant, inherent biological variation in human samples and even in samples from animal model systems where the animals are housed under carefully controlled conditions. This inherent biological variability is an important consideration for all metabolomics analyses. In this study, we examined the biological variation in {sup 1}H NMR-based metabolic profiling of two model systems, the yeast Saccharomyces cerevisiae and the nematode Caenorhabditis elegans. Using relative standard deviations (RSD) as a measure of variability, our results reveal that both model systems have significant amounts of biological variation. The C. elegans metabolome possesses greater metabolic variance with average RSD values of 29 and 39%, depending on the food source that was used. The S. cerevisiae exometabolome RSD values ranged from 8% to 12% for the four strains examined. We also determined whether biological variation occurs between pairs of phenotypically identical yeast strains. Multivariate statistical analysis allowed us to discriminate between pair members based on their metabolic phenotypes. Our results highlight the variability of the metabolome that exists even for less complex model systems cultured under defined conditions. We also highlight the efficacy of metabolic profiling for defining these subtle metabolic alterations.

  17. Simultaneous, simple and rapid determination of five bioactive free anthraquinones in Radix et Rhizoma Rhei by quantitative 1H NMR

    International Nuclear Information System (INIS)

    Dong, Jian-Wei; Cai, Le; Fang, Yun-Shan; Duan, Wei-He; Li, Zhen-Jie; Ding, Zhong-Tao

    2016-01-01

    Radix et Rhizoma Rhei has been recognized for centuries in traditional medicine for its multiple pharmacological actions. The free anthraquinones including physcion, chrysophanol, emodin, rhein, and aloe-emodin are the main bioactive components in Radix et Rhizoma Rhei. In the present study, a fast quantitative 1 H nuclear magnetic resonance (q-HNMR) method for the determination and quantitation of five free anthraquinones in Radix et Rhizoma Rhei was developed. Validation of the quantitative method was performed in terms of specificity, accuracy, precision, and stability. The results showed that the solvent acetone-d 6 enabled satisfactory separation of the signals to be integrated. Five anthraquinones in Radix et Rhizoma Rhei could be quantified accurately using featured signals from 1 H NMR. This work implied that q-HNMR represents a feasible alternative to high-performance liquid chromatography (HPLC)-based methods for quantitation of anthraquinones in Radix et Rhizoma Rhei and is suitable for the quality control of Radix et Rhizoma Rhei. (author)

  18. Global Metabolic Stress of Isoeffort Continuous and High Intensity Interval Aerobic Exercise: A Comparative 1H NMR Metabonomic Study.

    Science.gov (United States)

    Zafeiridis, Andreas; Chatziioannou, Anastasia Chrysovalantou; Sarivasiliou, Haralambos; Kyparos, Antonios; Nikolaidis, Michalis G; Vrabas, Ioannis S; Pechlivanis, Alexandros; Zoumpoulakis, Panagiotis; Baskakis, Constantinos; Dipla, Konstantina; Theodoridis, Georgios A

    2016-12-02

    The overall metabolic/energetic stress that occurs during an acute bout of exercise is proposed to be the main driving force for long-term training adaptations. Continuous and high-intensity interval exercise protocols (HIIE) are currently prescribed to acquire the muscular and metabolic benefits of aerobic training. We applied 1 H NMR-based metabonomics to compare the overall metabolic perturbation and activation of individual bioenergetic pathways of three popular aerobic exercises matched for effort/strain. Nine men performed continuous, long-interval (3 min), and short-interval (30 s) bouts of exercise under isoeffort conditions. Blood was collected before and after exercise. The multivariate PCA and OPLS-DA models showed a distinct separation of pre- and postexercise samples in three protocols. The two models did not discriminate the postexercise overall metabolic profiles of the three exercise types. Analysis focused on muscle bioenergetic pathways revealed an extensive upregulation of carbohydrate-lipid metabolism and the TCA cycle in all three protocols; there were only a few differences among protocols in the postexercise abundance of molecules when long-interval bouts were performed. In conclusion, continuous and HIIE exercise protocols, when performed with similar effort/strain, induce comparable global metabolic response/stress despite their marked differences in work-bout intensities. This study highlights the importance of NMR metabonomics in comprehensive monitoring of metabolic consequences of exercise training in the blood of athletes and exercising individuals.

  19. Quantitative determination and validation of octreotide acetate using 1 H-NMR spectroscopy with internal standard method.

    Science.gov (United States)

    Yu, Chen; Zhang, Qian; Xu, Peng-Yao; Bai, Yin; Shen, Wen-Bin; Di, Bin; Su, Meng-Xiang

    2018-01-01

    Quantitative nuclear magnetic resonance (qNMR) is a well-established technique in quantitative analysis. We presented a validated 1 H-qNMR method for assay of octreotide acetate, a kind of cyclic octopeptide. Deuterium oxide was used to remove the undesired exchangeable peaks, which was referred to as proton exchange, in order to make the quantitative signals isolated in the crowded spectrum of the peptide and ensure precise quantitative analysis. Gemcitabine hydrochloride was chosen as the suitable internal standard. Experimental conditions, including relaxation delay time, the numbers of scans, and pulse angle, were optimized first. Then method validation was carried out in terms of selectivity, stability, linearity, precision, and robustness. The assay result was compared with that by means of high performance liquid chromatography, which is provided by Chinese Pharmacopoeia. The statistical F test, Student's t test, and nonparametric test at 95% confidence level indicate that there was no significant difference between these two methods. qNMR is a simple and accurate quantitative tool with no need for specific corresponding reference standards. It has the potential of the quantitative analysis of other peptide drugs and standardization of the corresponding reference standards. Copyright © 2017 John Wiley & Sons, Ltd.

  20. Automated Control of the Organic and Inorganic Composition of Aloe vera Extracts Using (1)H NMR Spectroscopy.

    Science.gov (United States)

    Monakhova, Yulia B; Randel, Gabriele; Diehl, Bernd W K

    2016-09-01

    Recent classification of Aloe vera whole-leaf extract by the International Agency for Research and Cancer as a possible carcinogen to humans as well as the continuous adulteration of A. vera's authentic material have generated renewed interest in controlling A. vera. The existing NMR spectroscopic method for the analysis of A. vera, which is based on a routine developed at Spectral Service, was extended. Apart from aloverose, glucose, malic acid, lactic acid, citric acid, whole-leaf material (WLM), acetic acid, fumaric acid, sodium benzoate, and potassium sorbate, the quantification of Mg(2+), Ca(2+), and fructose is possible with the addition of a Cs-EDTA solution to sample. The proposed methodology was automated, which includes phasing, baseline-correction, deconvolution (based on the Lorentzian function), integration, quantification, and reporting. The NMR method was applied to 41 A. vera preparations in the form of liquid A. vera juice and solid A. vera powder. The advantages of the new NMR methodology over the previous method were discussed. Correlation between the new and standard NMR methodologies was significant for aloverose, glucose, malic acid, lactic acid, citric acid, and WLM (P vera.

  1. A (1H NMR-Based Metabonomic Investigation of Time-Related Metabolic Trajectories of the Plasma, Urine and Liver Extracts of Hyperlipidemic Hamsters.

    Directory of Open Access Journals (Sweden)

    Chun-Ying Jiang

    Full Text Available The hamster has been previously found to be a suitable model to study the changes associated with diet-induced hyperlipidemia in humans. Traditionally, studies of hyperlipidemia utilize serum- or plasma-based biochemical assays and histopathological evaluation. However, unbiased metabonomic technologies have the potential to identify novel biomarkers of disease. Thus, to obtain a better understanding of the progression of hyperlipidemia and discover potential biomarkers, we have used a proton nuclear magnetic resonance spectroscopy ((1H-NMR-based metabonomics approach to study the metabolic changes occurring in the plasma, urine and liver extracts of hamsters fed a high-fat/high-cholesterol diet. Samples were collected at different time points during the progression of hyperlipidemia, and individual proton NMR spectra were visually and statistically assessed using two multivariate analyses (MVA: principal component analysis (PCA and orthogonal partial least squares-discriminant analysis (OPLS-DA. Using the commercial software package Chenomx NMR suite, 40 endogenous metabolites in the plasma, 80 in the urine and 60 in the water-soluble fraction of liver extracts were quantified. NMR analysis of all samples showed a time-dependent transition from a physiological to a pathophysiological state during the progression of hyperlipidemia. Analysis of the identified biomarkers of hyperlipidemia suggests that significant perturbations of lipid and amino acid metabolism, as well as inflammation, oxidative stress and changes in gut microbiota metabolites, occurred following cholesterol overloading. The results of this study substantially broaden the metabonomic coverage of hyperlipidemia, enhance our understanding of the mechanism of hyperlipidemia and demonstrate the effectiveness of the NMR-based metabonomics approach to study a complex disease.

  2. Aggregation Number in Water/n-Hexanol Molecular Clusters Formed in Cyclohexane at Different Water/n-Hexanol/Cyclohexane Compositions Calculated by Titration 1H NMR.

    Science.gov (United States)

    Flores, Mario E; Shibue, Toshimichi; Sugimura, Natsuhiko; Nishide, Hiroyuki; Moreno-Villoslada, Ignacio

    2017-11-09

    Upon titration of n-hexanol/cyclohexane mixtures of different molar compositions with water, water/n-hexanol clusters are formed in cyclohexane. Here, we develop a new method to estimate the water and n-hexanol aggregation numbers in the clusters that combines integration analysis in one-dimensional 1 H NMR spectra, diffusion coefficients calculated by diffusion-ordered NMR spectroscopy, and further application of the Stokes-Einstein equation to calculate the hydrodynamic volume of the clusters. Aggregation numbers of 5-15 molecules of n-hexanol per cluster in the absence of water were observed in the whole range of n-hexanol/cyclohexane molar fractions studied. After saturation with water, aggregation numbers of 6-13 n-hexanol and 0.5-5 water molecules per cluster were found. O-H and O-O atom distances related to hydrogen bonds between donor/acceptor molecules were theoretically calculated using density functional theory. The results show that at low n-hexanol molar fractions, where a robust hydrogen-bond network is held between n-hexanol molecules, addition of water makes the intermolecular O-O atom distance shorter, reinforcing molecular association in the clusters, whereas at high n-hexanol molar fractions, where dipole-dipole interactions dominate, addition of water makes the intermolecular O-O atom distance longer, weakening the cluster structure. This correlates with experimental NMR results, which show an increase in the size and aggregation number in the clusters upon addition of water at low n-hexanol molar fractions, and a decrease of these magnitudes at high n-hexanol molar fractions. In addition, water produces an increase in the proton exchange rate between donor/acceptor molecules at all n-hexanol molar fractions.

  3. Gas phase 1H NMR studies and kinetic modeling of dihydrogen isotope equilibration catalyzed by Ru-nanoparticles under normal conditions: dissociative vs. associative exchange.

    Science.gov (United States)

    Limbach, Hans-Heinrich; Pery, Tal; Rothermel, Niels; Chaudret, Bruno; Gutmann, Torsten; Buntkowsky, Gerd

    2018-04-25

    The equilibration of H2, HD and D2 between the gas phase and surface hydrides of solid organic-ligand-stabilized Ru metal nanoparticles has been studied by gas phase 1H NMR spectroscopy using closed NMR tubes as batch reactors at room temperature and 800 mbar. When two different nanoparticle systems, Ru/PVP (PVP ≡ polyvinylpyrrolidone) and Ru/HDA (HDA ≡ hexadecylamine) were exposed to D2 gas, only the release of HD from the hydride containing surface could be detected in the initial stages of the reaction, but no H2. In the case of Ru/HDA also the reverse experiment was performed where surface deuterated nanoparticles were exposed to H2. In that case, the conversion of H2 into gaseous HD was detected. In order to analyze the experimental kinetic and spectroscopic data, we explored two different mechanisms taking into account potential kinetic and equilibrium H/D isotope effects. Firstly, we explored the dissociative exchange mechanism consisting of dissociative adsorption of dihydrogen, fast hydride surface diffusion and associative desorption of dihydrogen. It is shown that if D2 is the reaction partner, only H2 will be released in the beginning of the reaction, and HD only in later reaction stages. The second mechanism, dubbed here associative exchange consists of the binding of dihydrogen to Ru surface atoms, followed by a H-transfer to or by H-exchange with an adjacent hydride site, and finally of the associative desorption of dihydrogen. In that case, in the exchange with D2, only HD will be released in the beginning of the reaction. Our experimental results are not compatible with the dissociative exchange but can be explained in terms of the associative exchange. Whereas the former will dominate at low temperatures and pressures, the latter will prevail around room temperature and normal pressures where transition metal nanoparticles are generally used as reaction catalysts.

  4. 1H NMR-based serum metabolomics reveals erythromycin-induced liver toxicity in albino Wistar rats

    Directory of Open Access Journals (Sweden)

    Atul Rawat

    2016-01-01

    Full Text Available Introduction: Erythromycin (ERY is known to induce hepatic toxicity which mimics other liver diseases. Thus, ERY is often used to produce experimental models of drug-induced liver-toxicity. The serum metabolic profiles can be used to evaluate the liver-toxicity and to further improve the understanding of underlying mechanism. Objective: To establish the serum metabolic patterns of Erythromycin induced hepatotoxicity in albino wistar rats using 1H NMR based serum metabolomics. Experimental: Fourteen male rats were randomly divided into two groups (n = 7 in each group: control and ERY treated. After 28 days of intervention, the metabolic profiles of sera obtained from ERY and control groups were analyzed using high-resolution 1D 1H CPMG and diffusion-edited nuclear magnetic resonance (NMR spectra. The histopathological and SEM examinations were employed to evaluate the liver toxicity in ERY treated group. Results: The serum metabolic profiles of control and ERY treated rats were compared using multivariate statistical analysis and the metabolic patterns specific to ERY-induced liver toxicity were established. The toxic response of ERY was characterized with: (a increased serum levels of Glucose, glutamine, dimethylamine, malonate, choline, phosphocholine and phospholipids and (b decreased levels of isoleucine, leucine, valine, alanine, glutamate, citrate, glycerol, lactate, threonine, circulating lipoproteins, N-acetyl glycoproteins, and poly-unsaturated lipids. These metabolic alterations were found to be associated with (a decreased TCA cycle activity and enhanced fatty acid oxidation, (b dysfunction of lipid and amino acid metabolism and (c oxidative stress. Conclusion and Recommendations: Erythromycin is often used to produce experimental models of liver toxicity; therefore, the established NMR-based metabolic patterns will form the basis for future studies aiming to evaluate the efficacy of anti-hepatotoxic agents or the hepatotoxicity of new

  5. Evidence for network formation during the carbonization of coal from the combination of rheometry and {sup 1}H NMR techniques

    Energy Technology Data Exchange (ETDEWEB)

    Karen M. Steel; Miguel C. Diaz; John W. Patrick; Colin E. Snape [University of Nottingham, Nottingham (United Kingdom). Nottingham Fuel and Energy Centre, School of Chemical, Environmental and Mining Engineering

    2006-09-15

    High-temperature rheometry and {sup 1}H NMR have been combined to assess the microstructural changes taking place during carbonization of a number of different coals. A linear relationship exists between the logarithm of the material's complex viscosity ({eta}{sup {asterisk}}) and the fraction of hydrogen present in rigid structures ({phi}{sub rh}) for the resolidification region in which the material is liquid-like with small amounts of dispersed solid. The relationship is best characterized by the Arrhenius viscosity equation given by {eta}{sup {asterisk}} = {eta}{sub 0}{sup {asterisk}} exp(({eta}){phi}{sub rh}) where {eta}{sub 0}{sup {asterisk}} is the complex viscosity of the liquid medium and {eta} is the intrinsic viscosity of the resolidified material. Attempts to fit the Krieger-Dougherty suspension equation showed that the solid regions formed do not pack together like a normal suspension. Instead, it is more likely that cross-linking and cyclization reactions within the liquid medium give rise to a network structure of solid material and a characteristic gel point. The ratio of hydrogen present in rigid structures to that still present in liquid form at the gel point is approximately 2:3. The resolidified material was found to have a higher {eta} than the components of the coal that remained unsoftened, which suggests that while the unsoftened components have a fairly equant shape, the resolidified components have a much higher hydrodynamic volume. The resolidification process bears similarity with thermosetting polymer networks and the measurements taken for a blend of two coals follow a common two-component polymer blending rule. 35 refs., 13 figs., 4 tabs.

  6. Experimental (FT-IR, FT-Raman, 1H NMR) and theoretical study of magnesium, calcium, strontium, and barium picolinates.

    Science.gov (United States)

    Swiderski, G; Kalinowska, M; Wojtulewski, S; Lewandowski, W

    2006-05-01

    The experimental IR, Raman, and 1H NMR spectra of picolinic acid, as well as magnesium, calcium, strontium, and barium picolinates were registered, assigned and studied. Characteristic changes in the spectra of metal picolinates in comparison with the spectrum of ligand were observed, which lead to the conclusion that perturbation of the aromatic system of picolinates increases along with the series Mg-->Ca-->Sr-->Ba. Theoretical structures of beryllium and magnesium picolinates, as well as theoretical IR spectrum of magnesium picolinate were calculated in B3PW91/6-311++G(d, p) level. On the basis of calculated bond lengths in pyridine ring geometric, aromaticity indexes HOMA were calculated. The idea of these indexes is based on the fact that the essential factor in aromatic stabilization is the pi delocalization manifested in: planar geometry, equalization of the bond lengths and angles, and symmetry. The decidedly lower value of HOMA for magnesium picolinate (i.e. 0.545; 0.539) than that for beryllium picolinate (i.e. 0.998; 0.998) indicate higher aromatic properties of Be picolinate than of Mg picolinate. The comparison of theoretical and literature experimental structures of magnesium picolinate was done. The experimental structure contains two water molecules, so the calculations for hydrated magnesium picolinate were carried on, and the influence of coordinated water molecule on the structure of picolinates was discussed. The HOMAs for hydrated experimental and calculated Mg picolinate amount to 0.870; 0.743, and 0.900; 0.890, respectively, whereas for anhydrous structure, it is as described above, i.e. 0.545; 0.539. Thus, the calculations clearly showed that water molecules coordinated to the central atom weakens the effect of metal on the electronic system of ligand.

  7. 1H NMR spectrum of the native human insulin monomer. Evidence for conformational differences between the monomer and aggregated forms.

    Science.gov (United States)

    Roy, M; Lee, R W; Brange, J; Dunn, M F

    1990-04-05

    The effects of high dilution on the 1H Fourier transform NMR spectrum of native human insulin at pH* 8.0 and 9.3 have been examined at 500 MHz resolution. The dependence of the spectrum on concentration and comparison with the spectrum of a biologically highly potent monomeric insulin mutant (SerB9----Asp) establish that at 36 microM (pH* 9.3) or 18 microM (pH* 8) and no added buffer or salts, human insulin is monomeric. Under these conditions of dilution, ionic strength, and pH*, human insulin and the SerB9----Asp mutant exhibit nearly identical 1H NMR spectra. At higher concentrations (i.e. greater than 36 microM to 0.91 mM), native human insulin dimerizes, and this aggregation causes a change in insulin conformation. Although there are many changes in the spectrum, the TyrB26 ring H3,5 proton signals located at 6.63 ppm and the methyl signal located at 0.105 ppm (characteristics of monomeric insulin) are particularly distinct signatures of the conformation change that accompanies dimerization. Magnetization transfer experiments show that the 0.105 ppm methyl signal shifts downfield to a new position at 0.45 ppm. We conclude that the 0.105 ppm methyl signal is due to a conformation in which a Leu methyl group is centered over and in van der Waals contact with the ring of an aromatic side chain. Dimerization causes a conformation change that alters this interaction, thereby causing the downfield shift. Nuclear Overhauser studies indicate that the methyl group involved is located within a cluster of aromatic side chains and that the closest ring-methyl group interaction is with the ring of PheB24.

  8. 1H NMR spectra of N-methyl-4-tolyl-1-(4-bromonaphthylamine and N-phenyl-1-(4-bromonaphthylamine: a combined experimental and theoretical study

    Directory of Open Access Journals (Sweden)

    Sergiy I. Okovytyy

    2014-03-01

    Full Text Available Theoretical investigations of the conformational properties and 1H NMR chemical shifts for N-methyl-4-tolyl-1-(4-bromonaphthylamine and N-phenyl-1-(4-bromonaphthylamine are reported. The calculations were performed at the DFT level (PBE1PBE functional using magnetically consistent 6-31G## and STO##-3Gmag basis sets. Conformational properties of the amines were studied using potential energy surface scanning. Chemical shifts were calculated using the GIAO and CSGT methods and averaged in proportion to the population of the corresponding conformations. Solvent effects (CDCl3 were accounted via PCM method. The obtained results allowed to assign the 1H NMR signals for the naphthalene moiety, which could not be done based on the experimental data alone.

  9. Sequence-specific 1H NMR resonance assignments of Bacillus subtilis HPr: Use of spectra obtained from mutants to resolve spectral overlap

    International Nuclear Information System (INIS)

    Wittekind, M.; Klevit, R.E.; Reizer, J.

    1990-01-01

    On the basis of an analysis of two-dimensional 1 H NMR spectra, the complete sequence-specific 1 H NMR assignments are presented for the phosphocarrier protein HPr from the Gram-positive bacterium Bacillus subtilis. During the assignment procedure, extensive use was made of spectra obtained from point mutants of HPr in order to resolve spectral overlap and to provide verification of assignments. Regions of regular secondary structure were identified by characteristic patterns of sequential backbone proton NOEs and slowly exchanging amide protons. B subtilis HPr contains four β-strands that form a single antiparallel β-sheet and two well-defined α-helices. There are two stretches of extended backbone structure, one of which contains the active site His 15 . The overall fold of the protein is very similar to that of Escherichia coli HPr determined by NMR studies

  10. Direct study of minor extra-virgin olive oil components without any sample modification. 1H NMR multisupression experiment: A powerful tool.

    Science.gov (United States)

    Ruiz-Aracama, Ainhoa; Goicoechea, Encarnación; Guillén, María D

    2017-08-01

    Proton Nuclear Magnetic Resonance ( 1 H NMR) was employed to study monovarietal commercial Spanish extra-virgin olive oils (EVOO) (Arbequina, Arroniz, Cornicabra, Hojiblanca and Picual). Each sample was analyzed by a standard pulse and by an experiment suppressing the main lipid signals, enabling the detection of signals of minor components. The aim was to determine the possibilities of both 1 H NMR approaches to characterize EVOO composition, focusing on acyl groups, squalene, sterols, triterpene acids/esters, fatty alcohols, wax esters and phenols (lignans, tyrosol, hydroxytyrosol, oleocanthal, oleacein, oleokoronal, oleomissional, ligstrodials and oleuropeindials), and to determine hydrolysis and oxidation levels. The signal assignments (in deuterated chloroform) are thoroughly described, identifying for the first time those of the protons of esters of phytol and of geranylgeraniol. Correct signal assignment is fundamental for obtaining sound results when interpreting statistical data from metabolomic studies of EVOO composition and adulteration, making it possible to differentiate and classify oils. Copyright © 2017 Elsevier Ltd. All rights reserved.

  11. Unified integration intervals for the structural characterization of oil, coal or fractions there of by 1h NMR and 13c NMR

    International Nuclear Information System (INIS)

    Avella, Eliseo; Fierro, Ricardo

    2010-01-01

    Based on an analysis of publications reported between 1972 and 2006, it became clear that there are inaccuracies in the limits of the ranges of integration that the authors assigned to signals in nuclear magnetic resonance (NMR) to the structural characterization of petroleum, coals and their derived fractions, from their hydrogen (1H NMR) and carbon (13C NMR) spectra. Consequently, consolidated limits were determined for the integration of 1H NMR spectra and 13C NMR of these samples using a statistical treatment applied to the limits of integration intervals already published. With these unified limits, correlation NMR charts were developed that are useful for the allocation of the integral at such intervals, and at smaller intervals defined in terms of the intersection between different assignments. Also raised equations needed to establish the integral attributable to specific fragments in an attempt to make a more accurate structural characterization from NMR spectra of oil, coal or fractions derived.

  12. Ameliorating effects of Mango (Mangifera indica L.) fruit on plasma ethanol level in a mouse model assessed with 1H-NMR based metabolic profiling

    Science.gov (United States)

    Kim, So-Hyun; K. Cho, Somi; Min, Tae-Sun; Kim, Yujin; Yang, Seung-Ok; Kim, Hee-Su; Hyun, Sun-Hee; Kim, Hana; Kim, Young-Suk; Choi, Hyung-Kyoon

    2011-01-01

    The ameliorating effects of Mango (Mangifera indica L.) flesh and peel samples on plasma ethanol level were investigated using a mouse model. Mango fruit samples remarkably decreased mouse plasma ethanol levels and increased the activities of alcohol dehydrogenase and acetaldehyde dehydrogenase. The 1H-NMR-based metabolomic technique was employed to investigate the differences in metabolic profiles of mango fruits, and mouse plasma samples fed with mango fruit samples. The partial least squares-discriminate analysis of 1H-NMR spectral data of mouse plasma demonstrated that there were clear separations among plasma samples from mice fed with buffer, mango flesh and peel. A loading plot demonstrated that metabolites from mango fruit, such as fructose and aspartate, might stimulate alcohol degradation enzymes. This study suggests that mango flesh and peel could be used as resources for functional foods intended to decrease plasma ethanol level after ethanol uptake. PMID:21562641

  13. Novel spin dynamics in ferrimagnetic molecular chains from {sup 1}H NMR and {mu}SR spin-lattice relaxation measurements

    Energy Technology Data Exchange (ETDEWEB)

    Micotti, E. E-mail: micotti@fisicavolta.unipv.it; Lascialfari, A.; Rigamonti, A.; Aldrovandi, S.; Caneschi, A.; Gatteschi, D.; Bogani, L

    2004-05-01

    The spin dynamics in the helical chain Co(hfac){sub 2}NITPhOMe has been investigated by {sup 1}H NMR and {mu}SR relaxation. In the temperature range 15

  14. {sup 1}H NMR-based metabolomics of time-dependent responses of Eisenia fetida to sub-lethal phenanthrene exposure

    Energy Technology Data Exchange (ETDEWEB)

    Lankadurai, Brian P.; Wolfe, David M.; Simpson, Andre J. [Department of Chemistry, University of Toronto, 1265 Military Trail, Toronto, Ontario M1C 1A4 Canada (Canada); Simpson, Myrna J., E-mail: myrna.simpson@utoronto.ca [Department of Chemistry, University of Toronto, 1265 Military Trail, Toronto, Ontario M1C 1A4 Canada (Canada)

    2011-10-15

    {sup 1}H NMR-based metabolomics was used to examine the response of the earthworm Eisenia fetida after exposure to sub-lethal concentrations of phenanthrene over time. Earthworms were exposed to 0.025 mg/cm{sup 2} of phenanthrene (1/64th of the LC{sub 50}) via contact tests over four days. Earthworm tissues were extracted using a mixture of chloroform, methanol and water, resulting in polar and non-polar fractions that were analyzed by {sup 1}H NMR after one, two, three and four days. NMR-based metabolomic analyses revealed heightened E. fetida responses with longer phenanthrene exposure times. Amino acids alanine and glutamate, the sugar maltose, the lipids cholesterol and phosphatidylcholine emerged as potential indicators of phenanthrene exposure. The conversion of succinate to fumarate in the Krebs cycle was also interrupted by phenanthrene. Therefore, this study shows that NMR-based metabolomics is a powerful tool for elucidating time-dependent relationships in addition to the mode of toxicity of phenanthrene in earthworm exposure studies. - Highlights: > NMR-based earthworm metabolomic analysis of the mode of action of phenanthrene is presented. > The earthworm species E. fetida were exposed to sub-lethal phenanthrene concentrations. > Both polar and non-polar metabolites of E. fetida tissue extracts were analyzed by {sup 1}H NMR. > Longer phenanthrene exposure times resulted in heightened earthworm responses. > An interruption of the Krebs cycle was also observed due to phenanthrene exposure. - {sup 1}H NMR metabolomics is used to determine the relationship between phenanthrene exposure and the metabolic response of the earthworm E. fetida over time and also to elucidate the phenanthrene mode of toxicity.

  15. Use of hydrogen-deuterium exchange for contrast in {sup 1}H NMR microscopy investigations of an operating PEM fuel cell

    Energy Technology Data Exchange (ETDEWEB)

    Feindel, Kirk W.; Bergens, Steven H.; Wasylishen, Roderick E. [Department of Chemistry, Gunning/Lemieux Chemistry Centre, University of Alberta, Edmonton, Alta. T6G 2G2 (Canada)

    2007-11-08

    The use of hydrogen-deuterium (H-D) exchange as a method to introduce contrast in {sup 1}H NMR microscopy images and to investigate the dynamic distribution of water throughout an operating H{sub 2}/O{sub 2} polymer electrolyte membrane fuel cell, PEMFC, is demonstrated. Cycling D{sub 2}O(l) through the flow channels of a PEMFC causes H-D exchange with water in the PEM to result in a D{sub 2}O-saturated PEM and thus concomitant removal of the {sup 1}H NMR signal. Subsequent operation of the PEMFC with H{sub 2}(g) enables visualization of the redistribution of water from wet or flooded conditions as H-D exchange occurs with D{sub 2}O in the PEM and results in recovery of the {sup 1}H NMR signal. Alternating between H{sub 2}(g) and D{sub 2}(g) as fuel allows observation of water distributions in the PEM while the cell is operating at a steady-state under low relative humidity. At similar currents, the rate of observable H-D exchange in the PEM during fuel cell operation was faster when the PEM was saturated with water than when under low relative humidity. These results are consistent with the known proportions of the conductive hydrophilic and nonconductive hydrophobic domains of Nafion when exposed to different relative humidities. (author)

  16. Characterizing Radiation-Aged Polysiloxane-Silica Composites: Identifying Changes in Network Topology via 1H NMR

    International Nuclear Information System (INIS)

    Mayer, B.; Chinn, S.C.; Maxwell, R.S.; Reimer, J.

    2008-01-01

    Characterizing and quantifying changes in elastomeric materials upon exposure to harsh environments is important in the estimation of device lifetimes. Nuclear magnetic resonance (NMR) spectroscopy has been used effectively in the analysis of such materials and has proved to be both sensitive to micro- and macroscopic changes associated with material 'aging'. Traditional analyses, however, rely on empirical formulae containing a large number of (often arbitrary) independent variables. This ambiguity can be circumvented largely by developing models of NMR observables that are based on basic polymer physics. We compare two such models, one previously published and one derived herein, along with empirical expressions that describe the proton transverse magnetization decay associated with complex polymer networks. One particular extracted parameter, the proton-proton residual dipolar coupling (RDC), can be directly related to network topology, and a comparison of the extracted RDCs reveals high consistency among the models. An expression derived from the properties of a static Gaussian chain can minimize the number of parameters necessarily to describe the solid-like, networked proton population to a single independent parameter, the average residual dipolar coupling, D avg .

  17. Profiling the metabolome changes caused by cranberry procyanidins in plasma of female rats using (1) H NMR and UHPLC-Q-Orbitrap-HRMS global metabolomics approaches.

    Science.gov (United States)

    Liu, Haiyan; Garrett, Timothy J; Tayyari, Fariba; Gu, Liwei

    2015-11-01

    The objective was to investigate the metabolome changes in female rats gavaged with partially purified cranberry procyanidins (PPCP) using (1) H NMR and UHPLC-Q-Orbitrap-HRMS metabolomics approaches, and to identify the contributing metabolites. Twenty-four female Sprague-Dawley rats were randomly separated into two groups and administered PPCP or partially purified apple procyanidins (PPAP) for three times using a 250 mg extracts/kg body weight dose. Plasma was collected 6 h after the last gavage and analyzed using (1) H NMR and UHPLC-Q-Orbitrap-HRMS. No metabolome difference was observed using (1) H NMR metabolomics approach. However, LC-HRMS metabolomics data show that metabolome in the plasma of female rats administered PPCP differed from those gavaged with PPAP. Eleven metabolites were tentatively identified from a total of 36 discriminant metabolic features based on accurate masses and/or product ion spectra. PPCP caused a greater increase of exogenous metabolites including p-hydroxybenzoic acid, phenol, phenol-sulphate, catechol sulphate, 3, 4-dihydroxyphenylvaleric acid, and 4'-O-methyl-(-)-epicatechin-3'-O-beta-glucuronide in rat plasma. Furthermore, the plasma level of O-methyl-(-)-epicatechin-O-glucuronide, 4-hydroxy-5-(hydroxyphenyl)-valeric acid-O-sulphate, 5-(hydroxyphenyl)-ϒ-valerolactone-O-sulphate, 4-hydroxydiphenylamine, and peonidin-3-O-hexose were higher in female rats administered with PPAP. The metabolome changes caused by cranberry procyanidins were revealed using an UHPLC-Q-Orbitrap-HRMS global metabolomics approach. Exogenous and microbial metabolites were the major identified discriminate biomarkers. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Profiling the Metabolome Changes Caused by Cranberry Procyanidins in Plasma of Female Rats using 1H NMR and UHPLC-Q-Orbitrap-HRMS Global Metabolomics Approaches

    Science.gov (United States)

    Liu, Haiyan; Garrett, Timothy J.; Tayyari, Fariba; Gu, Liwei

    2015-01-01

    Scope The objective was to investigate the metabolome changes in female rats gavaged with partially purified cranberry procyanidins (PPCP) using 1H NMR and UHPLC-Q-Orbitrap-HRMS metabolomics approaches, and to identify the contributing metabolites. Methods and results Twenty four female Sprague-Dawley rats were randomly separated into two groups and administered PPCP or partially purified apple procyanidins (PPAP) for 3 times using a 250 mg extracts/kg body weight dose. Plasma were collected six hours after the last gavage and analyzed using 1H NMR and UHPLC-Q-Orbitrap-HRMS. No metabolome difference was observed using 1H NMR metabolomics approach. However, LC-HRMS metabolomics data show that metabolome in plasma of female rats administered PPCP differed from those gavaged with PPAP. Eleven metabolites were tentatively identified from a total of 36 discriminant metabolic features based on accurate masses and/or product ion spectra. PPCP caused a greater increase of exogenous metabolites including p-hydroxybenzoic acid, phenol, phenol-sulfate, catechol sulphate, 3, 4-dihydroxyphenylvaleric acid, and 4′-O-methyl-(−)-epicatechin-3′-O-beta-glucuronide in rat plasma. Furthermore, the plasma level of O-methyl-(−)-epicatechin-O-glucuronide, 4-hydroxy-5-(hydroxyphenyl)-valeric acid-O-sulphate, 5-(hydroxyphenyl)-γ-valerolactone-O-sulphate, 4-hydroxydiphenylamine, and peonidin-3-O-hexose were higher in female rats administered with PPAP. Conclusion The metabolome changes caused by cranberry procyanidins were revealed using an UHPLC-Q-Orbitrap-HRMS global metabolomics approach. Exogenous and microbial metabolites were the major identified discriminate biomarkers. PMID:26264887

  19. 1H NMR-Based Metabolomic Analysis of Sub-Lethal Perfluorooctane Sulfonate Exposure to the Earthworm, Eisenia fetida, in Soil

    Directory of Open Access Journals (Sweden)

    Myrna J. Simpson

    2013-08-01

    Full Text Available 1H NMR-based metabolomics was used to measure the response of Eisenia fetida earthworms after exposure to sub-lethal concentrations of perfluorooctane sulfonate (PFOS in soil. Earthworms were exposed to a range of PFOS concentrations (five, 10, 25, 50, 100 or 150 mg/kg for two, seven and fourteen days. Earthworm tissues were extracted and analyzed by 1H NMR. Multivariate statistical analysis of the metabolic response of E. fetida to PFOS exposure identified time-dependent responses that were comprised of two separate modes of action: a non-polar narcosis type mechanism after two days of exposure and increased fatty acid oxidation after seven and fourteen days of exposure. Univariate statistical analysis revealed that 2-hexyl-5-ethyl-3-furansulfonate (HEFS, betaine, leucine, arginine, glutamate, maltose and ATP are potential indicators of PFOS exposure, as the concentrations of these metabolites fluctuated significantly. Overall, NMR-based metabolomic analysis suggests elevated fatty acid oxidation, disruption in energy metabolism and biological membrane structure and a possible interruption of ATP synthesis. These conclusions obtained from analysis of the metabolic profile in response to sub-lethal PFOS exposure indicates that NMR-based metabolomics is an excellent discovery tool when the mode of action (MOA of contaminants is not clearly defined.

  20. Monitoring Metabolite Profiles of Cannabis sativa L. Trichomes during Flowering Period Using 1H NMR-Based Metabolomics and Real-Time PCR.

    Science.gov (United States)

    Happyana, Nizar; Kayser, Oliver

    2016-08-01

    Cannabis sativa trichomes are glandular structures predominantly responsible for the biosynthesis of cannabinoids, the biologically active compounds unique to this plant. To the best of our knowledge, most metabolomic works on C. sativa that have been reported previously focused their investigations on the flowers and leaves of this plant. In this study, (1)H NMR-based metabolomics and real-time PCR analysis were applied for monitoring the metabolite profiles of C. sativa trichomes, variety Bediol, during the last 4 weeks of the flowering period. Partial least squares discriminant analysis models successfully classified metabolites of the trichomes based on the harvest time. Δ (9)-Tetrahydrocannabinolic acid (1) and cannabidiolic acid (2) constituted the vital differential components of the organic preparations, while asparagine, glutamine, fructose, and glucose proved to be their water-extracted counterparts. According to RT-PCR analysis, gene expression levels of olivetol synthase and olivetolic acid cyclase influenced the accumulation of cannabinoids in the Cannabis trichomes during the monitoring time. Moreover, quantitative (1)H NMR and RT-PCR analysis of the Cannabis trichomes suggested that the gene regulation of cannabinoid biosynthesis in the C. sativa variety Bediol is unique when compared with other C. sativa varieties. Georg Thieme Verlag KG Stuttgart · New York.

  1. Discriminative Analysis of Different Grades of Gaharu (Aquilaria malaccensis Lamk. via 1H-NMR-Based Metabolomics Using PLS-DA and Random Forests Classification Models

    Directory of Open Access Journals (Sweden)

    Siti Nazirah Ismail

    2017-09-01

    Full Text Available Gaharu (agarwood, Aquilaria malaccensis Lamk. is a valuable tropical rainforest product traded internationally for its distinctive fragrance. It is not only popular as incense and in perfumery, but also favored in traditional medicine due to its sedative, carminative, cardioprotective and analgesic effects. The current study addresses the chemical differences and similarities between gaharu samples of different grades, obtained commercially, using 1H-NMR-based metabolomics. Two classification models: partial least squares-discriminant analysis (PLS-DA and Random Forests were developed to classify the gaharu samples on the basis of their chemical constituents. The gaharu samples could be reclassified into a ‘high grade’ group (samples A, B and D, characterized by high contents of kusunol, jinkohol, and 10-epi-γ-eudesmol; an ‘intermediate grade’ group (samples C, F and G, dominated by fatty acid and vanillic acid; and a ‘low grade’ group (sample E and H, which had higher contents of aquilarone derivatives and phenylethyl chromones. The results showed that 1H- NMR-based metabolomics can be a potential method to grade the quality of gaharu samples on the basis of their chemical constituents.

  2. Toxic actions of dinoseb in medaka (Oryzias latipes) embryos as determined by in vivo 31P NMR, HPLC-UV and 1H NMR metabolomics.

    Science.gov (United States)

    Viant, Mark R; Pincetich, Christopher A; Hinton, David E; Tjeerdema, Ronald S

    2006-03-10

    Changes in metabolism of Japanese medaka (Oryzias latipes) embryos exposed to dinoseb (2-sec-butyl-4,6-dinitrophenol), a substituted dinitrophenol herbicide, were determined by in vivo (31)P NMR, high-pressure liquid chromatography (HPLC)-UV, and (1)H NMR metabolomics. ATP and phosphocreatine (PCr) metabolism were characterized within intact embryos by in vivo (31)P NMR; concentrations of ATP, GTP, ADP, GDP, AMP and PCr were determined by HPLC-UV; and changes in numerous polar metabolites were characterized by (1)H NMR-based metabolomics. Rangefinding exposures determined two sublethal doses of dinoseb, 50 and 75 ppb, in which embryos survived from 1-day post fertilization (DPF) through the duration of embryogenesis. In vivo (31)P NMR data were acquired from 900 embryos in 0, 50, and 75 ppb dinoseb at 14, 62, and 110 h (n = 6 groups) after initiation of exposure. After 110 h, embryos were observed for normal development and hatching success, then either preserved in 10% formalin for growth analysis or flash frozen and extracted for HPLC-UV and (1)H NMR analysis. Dinoseb exposure at both concentrations resulted in significant declines in [ATP] and [PCr] at 110 h as measured by in vivo (31)P NMR (p fashion. Metabolic effects measured by in vivo (31)P NMR showed a significant increase in orthophosphate levels (P(i); p < 0.05), and significant decreases in [ATP], [PCr] and the PCr/P(i) ratio (p < 0.05). Metabolomics revealed a dose-response relationship between dinoseb and endogenous metabolite changes, with both dinoseb concentrations producing significantly different metabolic profiles from controls (p < 0.05). Metabolic changes included decreased concentrations of ATP, PCr, alanine and tyrosine, and increased concentrations of lactate with medaka embryotoxicity. This study demonstrated that medaka embryos respond to dinoseb with significant changes in metabolism, reduced growth and heart rates, and increased abnormal development and post-exposure mortality. All

  3. Two-dimensional 1H NMR experiments show that the 23-residue magain in antibiotic peptide is an α-helix in dodecylphosphocholine micelles, sodium dodecylsulfate micelles, and trifluoroethanol/water solution

    International Nuclear Information System (INIS)

    Gesell, Jennifer; Zasloff, Michael; Opella, Stanley J.

    1997-01-01

    Magainin2 is a 23-residue antibiotic peptide that disrupts the ionic gradient across certain cell membranes. Two-dimensional 1H NMR spectroscopy was used to investigate the structure of the peptide in three of the membrane environments most commonly employed in biophysical studies. Sequence-specific resonance assignments were determined for the peptide in perdeuterated dodecylphosphocholine (DPC) and sodium dodecylsulfate micelles and confirmed for the peptide in 2,2,2-trifluoroethanol solution. The secondary structure is shown to be helical in all of the solvent systems. The NMR data were used as a set of restraints for a simulated annealing protocol that generated a family of three-dimensional structures of the peptide in DPC micelles, which superimposed best between residues 4 and 20. For these residues, the mean pairwise rms difference for the backbone atoms is 0.47 ± 0.10A from the average structure. The calculated peptide structures appear to be curved,with the bend centered at residues Phe12 and Gly13

  4. UV-vis, IR and 1H NMR spectroscopic studies of some mono- and bis-azo-compounds based on 2,7-dihydroxynaphthalene and aniline derivatives

    Science.gov (United States)

    Issa, Raafat M.; Fayed, Tarek A.; Awad, Mohammed K.; El-Kony, Sanaa M.

    2005-12-01

    The absorption spectra of mono- and bis-azo-derivatives obtained by coupling the diazonium salts of aromatic amines and 2,7-dihydroxynaphthalene have been studied in six organic solvents. The different absorption bands have been assigned and the effect of solvents on the charge transfer band is also discussed. The diagnostic IR spectral bands and 1H NMR signals are assigned and discussed in relation to molecular structure. Also, semi-empirical molecular orbital calculations using the atom superposition and electron delocalization molecular orbital (ASED-MO) theory have been performed to investigate the molecular and electronic structures of these compounds. According to these calculations, an intramolecular hydrogen bonding is essential for stabilization of such molecules.

  5. 1H NMR-based metabolomic fingerprinting to determine metabolite levels in serrano peppers (Capsicum annum L.) grown in two different regions.

    Science.gov (United States)

    Becerra-Martínez, Elvia; Florentino-Ramos, Elideth; Pérez-Hernández, Nury; Gerardo Zepeda-Vallejo, L; Villa-Ruano, Nemesio; Velázquez-Ponce, Manuel; García-Mendoza, Felipe; Bañuelos-Hernández, Angel E

    2017-12-01

    Chili pepper (Capsicum annuum) is the most important and emblematic condiment in Mexican food. Serrano pepper is a variety of C. annuum that is traditionally cultivated in Mexico and commercialized in local markets. The aim of this study was to describe the 1 H NMR metabolomic profiling of the aqueous phase of serrano peppers harvested from two distinct regions, in the states of Veracruz and Oaxaca, Mexico. According to the current results, aspartate citrate, lactate, leucine and sucrose were found at higher amount in the serrano peppers from Veracruz. On the other hand, acetate, formate, fumarate, malonate, phosphocholine, pyruvate and succinate showed the highest abundance in this product from Oaxaca. These are the main metabolites that distinguish one group from the other. The spectrometric method reported presently is characterized by great simplicity, robustness and reproducibility. Thus, this technique can be used for establishing reliable metabolomic fingerprints of serrano peppers grown under different environmental conditions. Copyright © 2017 Elsevier Ltd. All rights reserved.

  6. Metabolic trajectories based on 1H NMR spectra of urines from sheep exposed to nutritional challenges during prenatal and early postnatal life

    DEFF Research Database (Denmark)

    Nyberg, Nils; Nielsen, Mette Benedicte Olaf; Jaroszewski, Jerzy W.

    2010-01-01

    1H NMR metabolic profiles of urine from sheep exposed to prenatal nutritional restriction (n = 19) and a control group with normal prenatal nutritional requirements (n = 19), followed by either conventional (n = 10 + 10) or high carbohydrate high fat postnatal diet (n = 9 + 9), were studied. Urine...... undernutrition followed by normal postnatal diet showed metabolic patters that are ahead in time on the metabolic trajectory relative to the prenatal control group. No long-term effects of fetal undernutrition, alone or in combination with postnatal hypernutrition were observed....... amount of glucose, indicative of monogastric-like metabolism, and exhibiting concomitant increase of metabolites related to rumen microflora (mainly glycine conjugates of benzoic and phenylacetic acid) as the ruminal metabolism developed. Urines from young (2-month-old) animals exposed to prenatal...

  7. Study of crude and plasma-treated heavy oil by low- and high-field 1H NMR

    Energy Technology Data Exchange (ETDEWEB)

    Honorato, Hercilio D. A.; Silva, Renzo C.; Junior, Valdemar Lacerda; Castro, Eustaquio V. R. de; Freitas, Jair C. C. [Research and Methodology Development Laboratory for Crude Oil Analysis - LabPetro, Department of Chemistry, Federal University of Espirito Santo (Brazil)], email: jairccfreitas@yahoo.com.br; Piumbini, Cleiton K.; Cunha, Alfredo G.; Emmerich, Francisco G. [Department of Physics, Federal University of Espirito Santo (Brazil); Souza, Andre A. de; Bonagamba, Tito J. [Institute of Physics of Sao Carlos, University of Sao Paulo (Brazil)

    2010-07-01

    This document is intended to describe the combination of H low-field NMR and thermogravimetry (TG), rheological measurement and H high-field NMR to assess the physical and chemical changes that can occur in a heavy crude oil from treatment in a plasma reactor. This research was done using a heavy crude oil, API gravity of 10.1, which was treated in a double dielectric barrier (DDB) plasma reactor using different plasma gases: natural gas (NG), C02 or H2. The low-field HNMR experiments were conducted in a Maran Ultra spectrometer, from Oxford Instruments, at 27.5? C. After rheological analysis, a reduction in the viscosity of the plasma-treated oils in comparison to that of the crude oil was observed. Finally, it was confirmed that the use of H low-field NMR relaxometry and H high-field NMR spectroscopy allowed a separate analysis of the effects of the plasma treatment on the water and oil fractions to be made.

  8. Quantitative evaluation of polymer concentration profile during swelling of hydrophilic matrix tablets using 1H NMR and MRI methods.

    Science.gov (United States)

    Baumgartner, Sasa; Lahajnar, Gojmir; Sepe, Ana; Kristl, Julijana

    2005-02-01

    Many pharmaceutical tablets are based on hydrophilic polymers, which, after exposure to water, form a gel layer around the tablet that limits the dissolution and diffusion of the drug and provides a mechanism for controlled drug release. Our aim was to determine the thickness of the swollen gel layer of matrix tablets and to develop a method for calculating the polymer concentration profile across the gel layer. MR imaging has been used to investigate the in situ swelling behaviour of cellulose ether matrix tablets and NMR spectroscopy experiments were performed on homogeneous hydrogels with known polymer concentration. The MRI results show that the thickest gel layer was observed for hydroxyethylcellulose tablets, followed by definitely thinner but almost equal gel layer for hydroxypropylcellulose and hydroxypropylmethylcellulose of both molecular weights. The water proton NMR relaxation parameters were combined with the MRI data to obtain a quantitative description of the swelling process on the basis of the concentrations and mobilities of water and polymer as functions of time and distance. The different concentration profiles observed after the same swelling time are the consequence of the different polymer characteristics. The procedure developed here could be used as a general method for calculating polymer concentration profiles on other similar polymeric systems.

  9. Hydrogen Bonding, (1)H NMR, and Molecular Electron Density Topographical Characteristics of Ionic Liquids Based on Amino Acid Cations and Their Ester Derivatives.

    Science.gov (United States)

    Rao, Soniya S; Bejoy, Namitha Brijit; Gejji, Shridhar P

    2015-08-13

    Amino acid ionic liquids (AAILs) have attracted significant attention in the recent literature owing to their ubiquitous applications in diversifying areas of modern chemistry, materials science, and biosciences. The present work focuses on unraveling the molecular interactions underlying AAILs. Electronic structures of ion pairs consisting of amino acid cations ([AA(+)], AA = Gly, Ala, Val, Leu, Ile, Pro, Ser, Thr) and their ester substituted derivatives [AAE(+)] interacting with nitrate anion [NO3(-)] have been obtained from the dispersion corrected M06-2x density functional theory. The formation of ion pair is accompanied by the transfer of proton from quaternary nitrogen to anion facilitated via hydrogen bonding. The [Ile], [Pro], [Ser], and [Thr] and their esters reveal relatively strong inter- as well as intramolecular hydrogen-bonding interactions. Consequently, the hierarchy in binding energies of [AA][NO3] ion pairs and their ester analogues turns out to be [Gly] > [Ala] > [Ser] ∼ [Val] ∼ [Ile] > [Leu] ∼ [Thr] > [Pro]. The work underlines how the interplay of intra- as well as intermolecular hydrogen-bonding interactions in [AA]- and [AAE]-based ILs manifest in their infrared and (1)H NMR spectra. Substitution of -OCH3 functional group in [AA][NO3] ILs lowers the melting point attributed to weaker hydrogen-bonding interactions, making them suitable for room temperature applications. As opposed to gas phase structures, the presence of solvent (DMSO) does not bring about any proton transfer in the ion pairs or their ester analogues. Calculated (1)H NMR chemical shifts of the solvated structures agree well with those from experiment. Correlations of decomposition temperatures in [AA]- and [AAE]-based ILs with binding energies and electron densities at the bond critical point(s) in molecular electron density topography, have been established.

  10. Vicinal 1H-1H NMR coupling constants from density functional theory as reliable tools for stereochemical analysis of highly flexible multichiral center molecules.

    Science.gov (United States)

    López-Vallejo, Fabian; Fragoso-Serrano, Mabel; Suárez-Ortiz, Gloria Alejandra; Hernández-Rojas, Adriana C; Cerda-García-Rojas, Carlos M; Pereda-Miranda, Rogelio

    2011-08-05

    A protocol for stereochemical analysis, based on the systematic comparison between theoretical and experimental vicinal (1)H-(1)H NMR coupling constants, was developed and applied to a series of flexible compounds (1-8) derived from the 6-heptenyl-5,6-dihydro-2H-pyran-2-one framework. The method included a broad conformational search, followed by geometry optimization at the DFT B3LYP/DGDZVP level, calculation of the vibrational frequencies, thermochemical parameters, magnetic shielding tensors, and the total NMR spin-spin coupling constants. Three scaling factors, depending on the carbon atom hybridizations, were found for the (1)H-C-C-(1)H vicinal coupling constants: f((sp3)-(sp3)) = 0.910, f((sp3)-(sp2)) = 0.929, and f((sp2)-(sp2))= 0.977. A remarkable correlation between the theoretical (J(pre)) and experimental (1)H-(1)H NMR (J(exp)) coupling constants for spicigerolide (1), a cytotoxic natural product, and some of its synthetic stereoisomers (2-4) demonstrated the predictive value of this approach for the stereochemical assignment of highly flexible compounds containing multiple chiral centers. The stereochemistry of two natural 6-heptenyl-5,6-dihydro-2H-pyran-2-ones (14 and 15) containing diverse functional groups in the heptenyl side chain was also analyzed by application of this combined theoretical and experimental approach, confirming its reliability. Additionally, a geometrical analysis for the conformations of 1-8 revealed that weak hydrogen bonds substantially guide the conformational behavior of the tetraacyloxy-6-heptenyl-2H-pyran-2-ones.

  11. A solid-phase extraction procedure coupled to 1H NMR, with chemometric analysis, to seek reliable markers of the botanical origin of honey

    International Nuclear Information System (INIS)

    Beretta, Giangiacomo; Caneva, Enrico; Regazzoni, Luca; Bakhtyari, Nazanin Golbamaki; Maffei Facino, Roberto

    2008-01-01

    The aim of this work was to establish an analytical method for identifying the botanical origin of honey, as an alternative to conventional melissopalynological, organoleptic and instrumental methods (gas-chromatography coupled to mass spectrometry (GC-MS), high-performance liquid chromatography HPLC). The procedure is based on the 1 H nuclear magnetic resonance (NMR) profile coupled, when necessary, with electrospray ionisation-mass spectrometry (ESI-MS) and two-dimensional NMR analyses of solid-phase extraction (SPE)-purified honey samples, followed by chemometric analyses. Extracts of 44 commercial Italian honeys from 20 different botanical sources were analyzed. Honeydew, chestnut and linden honeys showed constant, specific, well-resolved resonances, suitable for use as markers of origin. Honeydew honey contained the typical resonances of an aliphatic component, very likely deriving from the plant phloem sap or excreted into it by sap-sucking aphids. Chestnut honey contained the typical signals of kynurenic acid and some structurally related metabolite. In linden honey the 1 H NMR profile gave strong signals attributable to the mono-terpene derivative cyclohexa-1,3-diene-1-carboxylic acid (CDCA) and to its 1-O-β-gentiobiosyl ester (CDCA-GBE). These markers were not detectable in the other honeys, except for the less common nectar honey from rosa mosqueta. We compared and analyzed the data by multivariate techniques. Principal component analysis found different clusters of honeys based on the presence of these specific markers. The results, although obviously only preliminary, suggest that the 1 H NMR profile (with HPLC-MS analysis when necessary) can be used as a reference framework for identifying the botanical origin of honey

  12. A solid-phase extraction procedure coupled to {sup 1}H NMR, with chemometric analysis, to seek reliable markers of the botanical origin of honey

    Energy Technology Data Exchange (ETDEWEB)

    Beretta, Giangiacomo [Istituto di Chimica Farmaceutica e Tossicologica ' Pietro Pratesi' , Faculty of Pharmacy, University of Milan, via Mangiagalli 25, 20133 Milan (Italy)], E-mail: giangiacomo.beretta@unimi.it; Caneva, Enrico [Ciga - Centro Interdipartimentale Grandi Apparecchiature, University of Milan, via Golgi 19, 20133 Milan (Italy); Regazzoni, Luca; Bakhtyari, Nazanin Golbamaki; Maffei Facino, Roberto [Istituto di Chimica Farmaceutica e Tossicologica ' Pietro Pratesi' , Faculty of Pharmacy, University of Milan, via Mangiagalli 25, 20133 Milan (Italy)

    2008-07-14

    The aim of this work was to establish an analytical method for identifying the botanical origin of honey, as an alternative to conventional melissopalynological, organoleptic and instrumental methods (gas-chromatography coupled to mass spectrometry (GC-MS), high-performance liquid chromatography HPLC). The procedure is based on the {sup 1}H nuclear magnetic resonance (NMR) profile coupled, when necessary, with electrospray ionisation-mass spectrometry (ESI-MS) and two-dimensional NMR analyses of solid-phase extraction (SPE)-purified honey samples, followed by chemometric analyses. Extracts of 44 commercial Italian honeys from 20 different botanical sources were analyzed. Honeydew, chestnut and linden honeys showed constant, specific, well-resolved resonances, suitable for use as markers of origin. Honeydew honey contained the typical resonances of an aliphatic component, very likely deriving from the plant phloem sap or excreted into it by sap-sucking aphids. Chestnut honey contained the typical signals of kynurenic acid and some structurally related metabolite. In linden honey the {sup 1}H NMR profile gave strong signals attributable to the mono-terpene derivative cyclohexa-1,3-diene-1-carboxylic acid (CDCA) and to its 1-O-{beta}-gentiobiosyl ester (CDCA-GBE). These markers were not detectable in the other honeys, except for the less common nectar honey from rosa mosqueta. We compared and analyzed the data by multivariate techniques. Principal component analysis found different clusters of honeys based on the presence of these specific markers. The results, although obviously only preliminary, suggest that the {sup 1}H NMR profile (with HPLC-MS analysis when necessary) can be used as a reference framework for identifying the botanical origin of honey.

  13. New findings on the in vivo antioxidant activity of Curcuma longa extract by an integrated (1)H NMR and HPLC-MS metabolomic approach.

    Science.gov (United States)

    Dall'Acqua, Stefano; Stocchero, Matteo; Boschiero, Irene; Schiavon, Mariano; Golob, Samuel; Uddin, Jalal; Voinovich, Dario; Mammi, Stefano; Schievano, Elisabetta

    2016-03-01

    Curcuminoids possess powerful antioxidant activity as demonstrated in many chemical in vitro tests and in several in vivo trials. Nevertheless, the mechanism of this activity is not completely elucidated and studies on the in vivo antioxidant effects are still needed. Metabolomics may be used as an attractive approach for such studies and in this paper, we describe the effects of oral administration of a Curcuma longa L. extract (150 mg/kg of total curcuminoids) to 12 healthy rats with particular attention to urinary markers of oxidative stress. The experiment was carried out over 33 days and changes in the 24-h urine samples metabolome were evaluated by (1)H NMR and HPLC-MS. Both techniques produced similar representations for the collected samples confirming our previous study. Modifications of the urinary metabolome lead to the observation of different variables proving the complementarity of (1)H NMR and HPLC-MS for metabolomic purposes. The urinary levels of allantoin, m-tyrosine, 8-hydroxy-2'-deoxyguanosine, and nitrotyrosine were decreased in the treated group thus supporting an in vivo antioxidant effect of the oral administration of Curcuma extract to healthy rats. On the other hand, urinary TMAO levels were higher in the treated compared to the control group suggesting a role of curcumin supplementation on microbiota or on TMAO urinary excretion. Furthermore, the urinary levels of the sulphur containing compounds taurine and cystine were also changed suggesting a role for such constituents in the biochemical pathways involved in Curcuma extract bioactivity and indicating the need for further investigation on the complex role of antioxidant curcumin effects. Copyright © 2015 Elsevier B.V. All rights reserved.

  14. Diagnosis of coinfection by schistosomiasis and viral hepatitis B or C using 1H NMR-based metabonomics.

    Science.gov (United States)

    Gouveia, Liana Ribeiro; Santos, Joelma Carvalho; Silva, Ronaldo Dionísio; Batista, Andrea Dória; Domingues, Ana Lúcia Coutinho; Lopes, Edmundo Pessoa de Almeida; Silva, Ricardo Oliveira

    2017-01-01

    Diagnosis of liver involvement due to schistosomiasis in asymptomatic patients from endemic areas previously diagnosed with chronic hepatitis B (HBV) or C (HCV) and periportal fibrosis is challenging. H-1 Nuclear Magnetic Resonance (NMR)-based metabonomics strategy is a powerful tool for providing a profile of endogenous metabolites of low molecular weight in biofluids in a non-invasive way. The aim of this study was to diagnose periportal fibrosis due to schistosomiasis mansoni in patients with chronic HBV or HCV infection through NMR-based metabonomics models. The study included 40 patients divided into two groups: (i) 18 coinfected patients with schistosomiasis mansoni and HBV or HCV; and (ii) 22 HBV or HCV monoinfected patients. The serum samples were analyzed through H-1 NMR spectroscopy and the models were based on Principal Component Analysis (PCA) and Partial Least Squares-Discriminant Analysis (PLS-DA). Ultrasonography examination was used to ascertain the diagnosis of periportal fibrosis. Exploratory analysis showed a clear separation between coinfected and monoinfected samples. The supervised model built from PLS-DA showed accuracy, R2 and Q2 values equal to 100%, 98.1% and 97.5%, respectively. According to the variable importance in the projection plot, lactate serum levels were higher in the coinfected group, while the signals attributed to HDL serum cholesterol were more intense in the monoinfected group. The metabonomics models constructed in this study are promising as an alternative tool for diagnosis of periportal fibrosis by schistosomiasis in patients with chronic HBV or HCV infection from endemic areas for Schistosoma mansoni.

  15. Is 1H NMR metabolomics becoming the promising early biomarker for neonatal sepsis and for monitoring the antibiotic toxicity?

    Science.gov (United States)

    Noto, Antonio; Mussap, Michele; Fanos, Vassilios

    2014-06-01

    Metabolomics, the latest of omics disciplines, has been successfully used in various fields of basic research such as pharmacology and toxicology. Recently, this new science has gained an important role in the translational research of diagnostics. In this regard, the challenge for neonatologists and medical laboratories is to diagnose neonatal sepsis, a disease with high mortality and morbidity due to the difficulty in diagnosing it. Metabolomics, through its ability to identify perturbations caused by this condition, aims at recognizing metabolites that characterize neonatal sepsis with high specificity and sensitivity. The purpose of this review is to highlight the ability of metabolomics to find early biomarkers for this condition, as well as to predict the toxic effects caused by antibiotics.

  16. Nuclear magnetic resonance studies on brain edema. Time course of /sup 1/H-NMR relaxation times

    Energy Technology Data Exchange (ETDEWEB)

    Naruse, S; Horikawa, Y; Tanaka, C; Hirakawa, K; Nishikawa, H [Kyoto Prefectural Univ. of Medicine (Japan)

    1981-06-01

    1. The state of water in normal and edematous brain tissue was studied by measurement of proton longitudinal (T/sub 1/) and transverse (T/sub 2/) relaxation times using pulsed nuclear magnetic resonance (NMR) technique. 2. In control rats, T/sub 1/ and T/sub 2/ of water showed one component, which was more fast in white matter. Those values displayed 1.07 - 1.18 sec. of T/sub 1/ and 75 - 76 msec. of T/sub 2/. 3. When rat brain was injured by cold, T/sub 1/ was observed to become longer (1.18 - 1.27 sec.), and T/sub 2/ was observed be separated into two components, the faster T/sub 2/ (45 - 50 msec.) and slower T/sub 2/ (100 - 105 msec.), in both gray and white matter of the injured side. 4. In triethyltin (TET) induced brain edema, elongation of T/sub 1/ (1.2 sec.) and remarkable separation of T/sub 2/, faster T/sub 2/ (75 msec.) and slower T/sub 2/ (400 - 450 msec.), were observed in white matter. 5. In both cold and TET induced edema, slower T/sub 2/ fraction is suggested to be the extracellular space and faster T/sub 2/ fraction, intracellular. 6. T/sub 2/ changes precede the water content changes in cold injury, and parallel in TET induced edema. Those changes of relaxation times are reversible. 7. T/sub 2/ changes of water is more sensitive than the T/sub 1/ for the detection of production and disappearance of brain edema. 8. These results disclose the dynamic movements of water during the course of brain edema and offered significant information of the clinical application of NMR-CT.

  17. Volatile-Compound Fingerprinting by Headspace-Gas-Chromatography Ion-Mobility Spectrometry (HS-GC-IMS) as a Benchtop Alternative to 1H NMR Profiling for Assessment of the Authenticity of Honey.

    Science.gov (United States)

    Gerhardt, Natalie; Birkenmeier, Markus; Schwolow, Sebastian; Rohn, Sascha; Weller, Philipp

    2018-02-06

    This work describes a simple approach for the untargeted profiling of volatile compounds for the authentication of the botanical origins of honey based on resolution-optimized HS-GC-IMS combined with optimized chemometric techniques, namely PCA, LDA, and kNN. A direct comparison of the PCA-LDA models between the HS-GC-IMS and 1 H NMR data demonstrated that HS-GC-IMS profiling could be used as a complementary tool to NMR-based profiling of honey samples. Whereas NMR profiling still requires comparatively precise sample preparation, pH adjustment in particular, HS-GC-IMS fingerprinting may be considered an alternative approach for a truly fully automatable, cost-efficient, and in particular highly sensitive method. It was demonstrated that all tested honey samples could be distinguished on the basis of their botanical origins. Loading plots revealed the volatile compounds responsible for the differences among the monofloral honeys. The HS-GC-IMS-based PCA-LDA model was composed of two linear functions of discrimination and 10 selected PCs that discriminated canola, acacia, and honeydew honeys with a predictive accuracy of 98.6%. Application of the LDA model to an external test set of 10 authentic honeys clearly proved the high predictive ability of the model by correctly classifying them into three variety groups with 100% correct classifications. The constructed model presents a simple and efficient method of analysis and may serve as a basis for the authentication of other food types.

  18. Elucidation of the sequence selective binding mode of the DNA minor groove binder adozelesin, by high-field 1H NMR and restrained molecular dynamics

    International Nuclear Information System (INIS)

    Cameron, L.

    1999-01-01

    Adozelesin (formerly U73-975, The Upjohn Co.) is a covalent, minor-groove binding analogue of the antitumour antibiotic (+)CC-1065. Adozelesin consists of a cyclopropapyrroloindole alkylating sub-unit identical to (+)CC-1065, plus indole and benzofuran sub-units which replace the more complex pyrroloindole B and C sub-units, respectively, of (+)CC-1065. Adozelesin is a clinically important drug candidate, since it does not contain the ethylene bridge moieties on the B and C sub-units which are thought to be responsible for the unusual delayed hepatotoxicity exhibited by (+)CC-1065. Sequencing techniques identified two consensus sequences for adozelesin binding as p(dA) and 5'(T/A)(T/A)T-A*(C/G)G. This suggests that adozelesin spans a total of five base-pairs and shows a preference for A=T base-pair rich sequences, thus avoiding steric crowding around the exocyclic NH 2 of guanine and a wide minor groove. In this project, the covalent modification of two DNA sequences, i.e. 5'd(CGTAAGCGCTTA*CG) 2 and 5'-d(CGAAAAA*CGG)· 5'-d(CCGTTTTTCG), by adozelesin was examined by high-field NMR and restrained molecular mechanics and dynamics. Previous studies of minor groove binding drugs, using techniques as diverse as NMR, X-ray crystallography and molecular modelling, indicate that the incorporation of a guanine into the consensus sequence sterically hinders binding and, more importantly, produces a wider minor groove which is a 'slack' fit for the ligand. The aim of this investigation was to provide an insight into the sequence selective binding of adozelesin to 5'-AAAAA*CG and 5'-GCTTA*CG. The 1 H NMR data revealed that, in both cases, β-helical structure and Watson-Crick base-pairing was maintained on adduct formation. The 5'-GCTTA*CG adduct displayed significant distortion of the guanine base on the non-covalently modified strand. This distortion resulted from an amalgamation of two factors. Firstly, the presence of a strong hydrogen-bond between the amide linker of the

  19. Multivariate analysis of fingerprinting of majority secondary metabolites of propolis of Costa Rica using proton nuclear magnetic resonance (1H-NMR)

    International Nuclear Information System (INIS)

    Umana Rojas, Eduardo

    2013-01-01

    Propolis is produced by Apis mellifera bees from resins of plants that are found around the apiary. The chemical composition is highly variable and Costa Rica has reported without studies of characterization to define the types of propolis in the country. 119 samples were collected from beekeeping areas of the country. The spectrum of 1 H-NMR and its antioxidant activity against DPPH radical were measured. The spectra have been divided into 243 blocks of 0,04 ppm and processed with the Minitab software for multivariate analysis. 99 of the samples collected were used for construction of models for the valuation of the predictive ability of the model have been used coefficients of determination (R 2 ) of prediction by the software and the remaining 20 samples. The existence of three types of propolis with chemically different metabolomes were determined by principal component analysis (PCA). A prediction model was constructed by analysis of partial least squares (PLS). The prediction model has allowed to classify a propolis according to the level of anti-oxidant activity (AAO), high (type I and II) or low (type III) from the spectrum of 1 H-NMR. The R 2 has been 0.88 and R 2 prediction of 0, 718 for new samples. The n-coniferyl benzoate of group I and nemorosone of the group II as two discriminated antioxidants among the groups I and II were isolated and high concentration levels of these compounds have been differentiated with respect to type III. This has allowed the construction of a linear discriminant model with a success rate of 100% for the samples used for formulation and 92,9 for the prediction of different samples. The classification systems could be applied to the standardization of the quality of propolis from Costa Rica for future medicinal or cosmetic applications that take advantage of its antioxidant properties. Also, the methylated derivative has isolated and identified of the n-coniferyl benzoate thereof propolis than was obtained his counterpart

  20. Monitoring changes in the structure and properties of humic substances following ozonation using UV-Vis, FTIR and (1)H NMR techniques.

    Science.gov (United States)

    Rodríguez, Francisco J; Schlenger, Patrick; García-Valverde, María

    2016-01-15

    The main objective of this work is to conduct a comprehensive structural characterization of humic substances using the following experimental techniques: FTIR, 1H NMR and several UV–Vis parameters (Specific UV Absorbance at 254 nm or SUVA254, SUVA280, A400, the absorbance ratios A210/254, A250/365, A254/203, A254/436, A265/465, A270/400, A280/350, A465/665, the Absorbance Slope Index (ASI), the spectral slopes S275–295, S350–400 and the slope ratio SR). These UV–Vis parameters have also been correlated with key properties of humic substances such as aromaticity, molecular weight (MW) and trihalomethane formation potential (THMFP). An additional objective of this work is also to evaluate the usefulness of these techniques to monitor structural changes in humic substances produced by the ozonation treatment. Four humic substances were studied in this work: three of them were provided by the International Humic Substances Society (Suwannee River Fulvic Acid Standard: SRFA, Suwannee River Humic Acid Standard: SRHA and Nordic Reservoir Fulvic Acid Reference: NLFA) and the other one was a terrestrial humic acid widely used as a surrogate for aquatic humic substances in various studies (Aldrich Humic Acid: AHA). The UV–Vis parameters showing the best correlations with aromaticity in this study were SUVA254, SUVA280, A280/A350 ratio and A250/A364 ratio. The best correlations with molecular weight were for SUVA254, SUVA280 and A280/A350 ratio. Finally, in the case of the THMFP it was STHMFP-per mol HS the parameter showing good correlations with most of the UV–Vis parameters studied (especially with A280/A350 ratio, A265/A465 ratio and A270/A400 ratio) whereas STHMFP-per mg C showed poor correlations in most cases. On the whole, the UV–Vis parameter showing the best results was A280/A350 ratio as it showed excellent correlations for the three properties studied (aromaticity, MW and THMFP). A decrease in aromaticity following ozonation of humic substances can

  1. An Investigation into the Antiobesity Effects of Morinda citrifolia L. Leaf Extract in High Fat Diet Induced Obese Rats Using a 1H NMR Metabolomics Approach

    Science.gov (United States)

    Gooda Sahib Jambocus, Najla; Saari, Nazamid; Ismail, Amin; Mahomoodally, Mohamad Fawzi; Abdul Hamid, Azizah

    2016-01-01

    The prevalence of obesity is increasing worldwide, with high fat diet (HFD) as one of the main contributing factors. Obesity increases the predisposition to other diseases such as diabetes through various metabolic pathways. Limited availability of antiobesity drugs and the popularity of complementary medicine have encouraged research in finding phytochemical strategies to this multifaceted disease. HFD induced obese Sprague-Dawley rats were treated with an extract of Morinda citrifolia L. leaves (MLE 60). After 9 weeks of treatment, positive effects were observed on adiposity, fecal fat content, plasma lipids, and insulin and leptin levels. The inducement of obesity and treatment with MLE 60 on metabolic alterations were then further elucidated using a 1H NMR based metabolomics approach. Discriminating metabolites involved were products of various metabolic pathways, including glucose metabolism and TCA cycle (lactate, 2-oxoglutarate, citrate, succinate, pyruvate, and acetate), amino acid metabolism (alanine, 2-hydroxybutyrate), choline metabolism (betaine), creatinine metabolism (creatinine), and gut microbiome metabolism (hippurate, phenylacetylglycine, dimethylamine, and trigonelline). Treatment with MLE 60 resulted in significant improvement in the metabolic perturbations caused obesity as demonstrated by the proximity of the treated group to the normal group in the OPLS-DA score plot and the change in trajectory movement of the diseased group towards the healthy group upon treatment. PMID:26798649

  2. The influence of different diets on metabolism and atherosclerosis processes-A porcine model: Blood serum, urine and tissues 1H NMR metabolomics targeted analysis.

    Directory of Open Access Journals (Sweden)

    Adam Zabek

    Full Text Available The global epidemic of cardiovascular diseases leads to increased morbidity and mortality caused mainly by myocardial infarction and stroke. Atherosclerosis is the major pathological process behind this epidemic. We designed a novel model of atherosclerosis in swine. Briefly, the first group (11 pigs received normal pig feed (balanced diet group-BDG for 12 months, the second group (9 pigs was fed a Western high-calorie diet (unbalanced diet group-UDG for 12 months, the third group (8 pigs received a Western type high-calorie diet for 9 months later replaced by a normal diet for 3 months (regression group-RG. Clinical measurements included zoometric data, arterial blood pressure, heart rate and ultrasonographic evaluation of femoral arteries. Then, the animals were sacrificed and the blood serum, urine and skeletal muscle tissue were collected and 1H NMR based metabolomics studies with the application of fingerprinting PLS-DA and univariate analysis were done. Our results have shown that the molecular disturbances might overlap with other diseases such as onset of diabetes, sleep apnea and other obesity accompanied diseases. Moreover, we revealed that once initiated, molecular changes did not return to homeostatic equilibrium, at least for the duration of this experiment.

  3. Simplifying the complex 1H NMR spectra of fluorine-substituted benzamides by spin system filtering and spin-state selection: multiple-quantum-single-quantum correlation.

    Science.gov (United States)

    Baishya, Bikash; Reddy, G N Manjunatha; Prabhu, Uday Ramesh; Row, T N Guru; Suryaprakash, N

    2008-10-23

    The proton NMR spectra of fluorine-substituted benzamides are very complex (Figure 1) due to severe overlap of (1)H resonances from the two aromatic rings, in addition to several short and long-range scalar couplings experienced by each proton. With no detectable scalar couplings between the inter-ring spins, the (1)H NMR spectra can be construed as an overlap of spectra from two independent phenyl rings. In the present study we demonstrate that it is possible to separate the individual spectrum for each aromatic ring by spin system filtering employing the multiple-quantum-single-quantum correlation methodology. Furthermore, the two spin states of fluorine are utilized to simplify the spectrum corresponding to each phenyl ring by the spin-state selection. The demonstrated technique reduces spectral complexity by a factor of 4, in addition to permitting the determination of long-range couplings of less than 0.2 Hz and the relative signs of heteronuclear couplings. The technique also aids the judicious choice of the spin-selective double-quantum-single-quantum J-resolved experiment to determine the long-range homonuclear couplings of smaller magnitudes.

  4. Comparison of earthworm responses to petroleum hydrocarbon exposure in aged field contaminated soil using traditional ecotoxicity endpoints and 1H NMR-based metabolomics

    International Nuclear Information System (INIS)

    Whitfield Åslund, Melissa; Stephenson, Gladys L.; Simpson, André J.; Simpson, Myrna J.

    2013-01-01

    1 H NMR metabolomics and conventional ecotoxicity endpoints were used to examine the response of earthworms exposed to petroleum hydrocarbons (PHCs) in soil samples collected from a site that was contaminated with crude oil from a pipeline failure in the mid-1990s. The conventional ecotoxicity tests showed that the soils were not acutely toxic to earthworms (average survival ≥90%), but some soil samples impaired reproduction endpoints by >50% compared to the field control soil. Additionally, metabolomics revealed significant relationships between earthworm metabolic profiles (collected after 2 or 14 days of exposure) and soil properties including soil PHC concentration. Further comparisons by partial least squares regression revealed a significant relationship between the earthworm metabolomic data (collected after only 2 or 14 days) and the reproduction endpoints (measured after 63 days). Therefore, metabolomic responses measured after short exposure periods may be predictive of chronic, ecologically relevant toxicity endpoints for earthworms exposed to soil contaminants. -- Highlights: •Earthworm response to petroleum hydrocarbon exposure in soil is examined. •Metabolomics shows significant changes to metabolic profile after 2 days. •Significant relationships observed between metabolomic and reproduction endpoints. •Metabolomics may have value as a rapid screening tool for chronic toxicity. -- Earthworm metabolomic responses measured after 2 and 14 days are compared to traditional earthworm ecotoxicity endpoints (survival and reproduction) in petroleum hydrocarbon contaminated soil

  5. Study on the effects of wheat bran incorporation on water mobility and biopolymer behavior during bread making and storage using time-domain 1H NMR relaxometry.

    Science.gov (United States)

    Hemdane, S; Jacobs, P J; Bosmans, G M; Verspreet, J; Delcour, J A; Courtin, C M

    2017-12-01

    Water binding is suggested to be key in the deleterious effect of wheat bran on bread quality. This study investigates water mobility and biopolymer behavior during bran-rich bread making and storage, using 1 H NMR. Coarse, ground, and pericarp-enriched bran were incorporated in bread dough, and their impact on freshly baked and stored bread properties was assessed. Compared to wheat flour control dough, bran incorporation resulted in a progressive immobilization of water during dough resting, which could be linked to changes in evolution of dough height during fermentation and oven rise. This, together with modified starch gelatinization behavior upon baking, can be related with the inferior quality of bran-rich breads. The impact was most pronounced with pericarp-enriched bran. Textural quality during storage was less affected for coarse or ground bran-rich bread compared to wheat flour bread, which could be principally attributed to retardation of amylopectin retrogradation in the presence of bran. Copyright © 2017 Elsevier Ltd. All rights reserved.

  6. An Investigation into the Antiobesity Effects of Morinda citrifolia L. Leaf Extract in High Fat Diet Induced Obese Rats Using a 1H NMR Metabolomics Approach

    Directory of Open Access Journals (Sweden)

    Najla Gooda Sahib Jambocus

    2016-01-01

    Full Text Available The prevalence of obesity is increasing worldwide, with high fat diet (HFD as one of the main contributing factors. Obesity increases the predisposition to other diseases such as diabetes through various metabolic pathways. Limited availability of antiobesity drugs and the popularity of complementary medicine have encouraged research in finding phytochemical strategies to this multifaceted disease. HFD induced obese Sprague-Dawley rats were treated with an extract of Morinda citrifolia L. leaves (MLE 60. After 9 weeks of treatment, positive effects were observed on adiposity, fecal fat content, plasma lipids, and insulin and leptin levels. The inducement of obesity and treatment with MLE 60 on metabolic alterations were then further elucidated using a 1H NMR based metabolomics approach. Discriminating metabolites involved were products of various metabolic pathways, including glucose metabolism and TCA cycle (lactate, 2-oxoglutarate, citrate, succinate, pyruvate, and acetate, amino acid metabolism (alanine, 2-hydroxybutyrate, choline metabolism (betaine, creatinine metabolism (creatinine, and gut microbiome metabolism (hippurate, phenylacetylglycine, dimethylamine, and trigonelline. Treatment with MLE 60 resulted in significant improvement in the metabolic perturbations caused obesity as demonstrated by the proximity of the treated group to the normal group in the OPLS-DA score plot and the change in trajectory movement of the diseased group towards the healthy group upon treatment.

  7. Analysis of the Effects of δ-Tocopherol on RAW264.7 and K562 Cells Based on 1H NMR Metabonomics.

    Science.gov (United States)

    Lu, Yang; Li, Hui; Geng, Yue

    2018-01-31

    δ-Tocopherol (δ-TOH) is a form of vitamin E with higher bioactivity. In this study, we studied the bioactivity of δ-TOH using the IC 50 of δ-TOH on RAW264.7 (80 μM) and K562 (110 μM) cells. We compared the differential metabolites from the cell lines with and without δ-TOH treatment by 1 H NMR metabonomics analysis. It was found that δ-TOH affected the protein biosynthesis, betaine metabolism, and urea cycle in various ways in both cell lines. Metabolic levels of the cell lines were changed after treatment with δ-TOH as differential metabolites were produced. The betaine level in RAW264.7 cells was reduced significantly, while the l-lactic acid level in K562 cells was significantly enhanced. The metabolic changes might contribute to the switch of the respiration pattern from aerobic respiration to anaerobic respiration in K562 cells. These results are helpful in further understanding the subtoxicity of δ-TOH.

  8. A 1H-NMR-Based Metabonomic Study on the Anti-Depressive Effect of the Total Alkaloid of Corydalis Rhizoma

    Directory of Open Access Journals (Sweden)

    Hongwei Wu

    2015-05-01

    Full Text Available Corydalis Rhizoma, named YuanHu in China, is the dried tuber of Corydalis yanhusuo W.T. Wang which is used in Traditional Chinese Medicine for pain relief and blood activation. Previous pharmacological studies showed that apart from analgesics, the alkaloids from YuanHu may be useful in the therapy of depression by acting on the GABA, dopamine and benzodiazepine receptors. In this study, the antidepressive effect of the total alkaloid of YuanHu (YHTA was investigated in a chronic unpredictable mild stress (CUMS rat model using 1H-NMR-based metabonomics. Plasma metabolic profiles were analyzed and multivariate data analysis was applied to discover the metabolic biomarkers in CUMS rats. Thirteen biomarkers of CUMS-introduced depression were identified, which are myo-inositol, glycerol, glycine, creatine, glutamine, glutamate, β-glucose, α-glucose, acetoacetate, 3-hydroxybutyrate, leucine and unsaturated lipids (L7, L9. Moreover, a metabolic network of the potential biomarkers in plasma perturbed by CUMS was detected. After YHTA treatment, clear separation between the model group and YHTA-treated group was achieved. The levels of all the abnormal metabolites mentioned above showed a tendency of restoration to normal levels. The results demonstrated the therapeutic efficacy of YHTA against depression and suggested that NMR-based metabolomics can provide a simple and easy tool for the evaluation of herbal therapeutics.

  9. Photochemical Degradation of the Anticancer Drug Bortezomib by V-UV/UV (185/254 nm) Investigated by (1)H NMR Fingerprinting: A Way to Follow Aromaticity Evolution.

    Science.gov (United States)

    Martignac, Marion; Balayssac, Stéphane; Gilard, Véronique; Benoit-Marquié, Florence

    2015-06-18

    We have investigated the removal of bortezomib, an anticancer drug prescribed in multiple myeloma, using the photochemical advanced oxidation process of V-UV/UV (185/254 nm). We used two complementary analytical techniques to follow the removal rate of bortezomib. Nuclear magnetic resonance (NMR) is a nonselective method requiring no prior knowledge of the structures of the byproducts and permits us to provide a spectral signature (fingerprinting approach). This untargeted method provides clues to the molecular structure changes and information on the degradation of the parent drug during the irradiation process. This holistic NMR approach could provide information for monitoring aromaticity evolution. We use liquid chromatography, coupled with high-resolution mass spectrometry (LC-MS), to correlate results obtained by (1)H NMR and for accurate identification of the byproducts, in order to understand the mechanistic degradation pathways of bortezomib. The results show that primary byproducts come from photoassisted deboronation of bortezomib at 254 nm. A secondary byproduct of pyrazinecarboxamide was also identified. We obtained a reliable correlation between these two analytical techniques.

  10. α-Glucosidase inhibition and antioxidant activity of an oenological commercial tannin. Extraction, fractionation and analysis by HPLC/ESI-MS/MS and (1)H NMR.

    Science.gov (United States)

    Muccilli, Vera; Cardullo, Nunzio; Spatafora, Carmela; Cunsolo, Vincenzo; Tringali, Corrado

    2017-01-15

    Two batches of the oenological tannin Tan'Activ R, (toasted oak wood - Quercus robur), were extracted with ethanol. A fractionation on XAD-16 afforded four fractions for each extract. Extracts and fractions were evaluated for antioxidant activity (DPPH), polyphenol content (GAE) and yeast α-glucosidase inhibitory activity. Comparable results were obtained for both columns, fractions X1B and X2B showing the highest antioxidant activity. Fractions X1C and X2C notably inhibited α-glucosidase, with IC50=9.89 and 8.05μg/mL, respectively. Fractions were subjected to HPLC/ESI-MS/MS and (1)H NMR analysis. The main phenolic constituents of both X1B and X2B were a monogalloylglucose isomer (1), a HHDP-glucose isomer (2), castalin (3) gallic acid (4), vescalagin (5), and grandinin (or its isomer roburin E, 6). X1C and X2C showed a complex composition, including non-phenolic constituents. Fractionation of X2C gave a subfraction, with enhanced α-glucosidase inhibitory activity (IC50=6.15μg/mL), with castalagin (7) as the main constituent. Copyright © 2016 Elsevier Ltd. All rights reserved.

  11. 1H NMR metabonomics indicates continued metabolic changes and sexual dimorphism post-parasite clearance in self-limiting murine malaria model.

    Directory of Open Access Journals (Sweden)

    Arjun Sengupta

    Full Text Available Malaria, a mosquito-borne disease caused by Plasmodium spp. is considered to be a global threat, specifically for the developing countries. In human subjects considerable information exists regarding post-malarial physiology. However, most murine malarial models are lethal, and most studies deal with acute phases occurring as disease progresses. Much less is known regarding physiological status post-parasite clearance. We have assessed the physiological changes at the organ levels using (1H NMR based metabonomics in a non lethal self-clearing murine malarial model of P. chabaudi parasites and Balb/C, far beyond the parasite clearance point. The results showed distinct metabolic states between uninfected and infected mice at the peak parasitemia, as well as three weeks post-parasite clearance. Our data also suggests that the response at the peak infection as well as recovery exhibited distinct sexual dimorphism. Specifically, we observed accumulation of acetylcholine in the brain metabolic profile of both the sexes. This might have important implication in understanding the pathophysiology of the post malarial neurological syndromes. In addition, the female liver showed high levels of glucose, dimethylglycine, methylacetoacetate and histidine after three weeks post-parasite clearance, while the males showed accumulation of branched chain amino acids, lysine, glutamine and bile acids.

  12. Simultaneous, simple and rapid determination of five bioactive free anthraquinones in Radix et Rhizoma Rhei by quantitative {sup 1}H NMR

    Energy Technology Data Exchange (ETDEWEB)

    Dong, Jian-Wei; Cai, Le; Fang, Yun-Shan; Duan, Wei-He; Li, Zhen-Jie; Ding, Zhong-Tao, E-mail: ztding@ynu.edu.cn, E-mail: caile@ynu.edu.cn [Key Laboratory of Medicinal Chemistry for Natural Resource, Ministry of Education, School of Chemical Science and Technology, Yunnan University, Kunming (China)

    2016-07-01

    Radix et Rhizoma Rhei has been recognized for centuries in traditional medicine for its multiple pharmacological actions. The free anthraquinones including physcion, chrysophanol, emodin, rhein, and aloe-emodin are the main bioactive components in Radix et Rhizoma Rhei. In the present study, a fast quantitative {sup 1}H nuclear magnetic resonance (q-HNMR) method for the determination and quantitation of five free anthraquinones in Radix et Rhizoma Rhei was developed. Validation of the quantitative method was performed in terms of specificity, accuracy, precision, and stability. The results showed that the solvent acetone-d{sub 6} enabled satisfactory separation of the signals to be integrated. Five anthraquinones in Radix et Rhizoma Rhei could be quantified accurately using featured signals from {sup 1}H NMR. This work implied that q-HNMR represents a feasible alternative to high-performance liquid chromatography (HPLC)-based methods for quantitation of anthraquinones in Radix et Rhizoma Rhei and is suitable for the quality control of Radix et Rhizoma Rhei. (author)

  13. DNA hairpin structures in solution: 500-MHz two-dimensional 1H NMR studies on d(CGCCGCAGC) and d(CGCCGTAGC)

    International Nuclear Information System (INIS)

    Gupta, G.; Sarma, M.H.; Sarma, R.H.

    1987-01-01

    A hairpin structure contains two conformationally distinct domains: a double-helical stem with Watson-Crick base pairs and a single-stranded loop that connects the two arms of the stem. By extensive 1D and 2D 500-MHz 1 H NMR studies in H 2 O and D 2 O, it has been demonstrated that the DNA oligomers d(CGCCGCAGC) and d(CGCCGTAGC) form hairpin structures under conditions of low concentration, 0.5 mM in DNA strand, and low salt (20 mM NaCl, pH 7). From examination of the nuclear Overhauser effect (NOE) between base protons H8/H6 and sugar protons H1' and H2'/H2'', it was concluded that in D(CGCCGCAGC) and d(CGCCCTAGC) all the nine nucleotides display average (C2'-endo,anti) geometry. The NMR data in conjunction with molecular model building and solvent accessibility studies were used to derive a working model for the hairpins

  14. 1H NMR-based metabolomics investigation on the effects of petrochemical contamination in posterior adductor muscles of caged mussel Mytilus galloprovincialis.

    Science.gov (United States)

    Cappello, Tiziana; Maisano, Maria; Mauceri, Angela; Fasulo, Salvatore

    2017-08-01

    Environmental metabolomics is a high-throughout approach that provides a snapshot of the metabolic status of an organism. In order to elucidate the biological effects of petrochemical contamination on aquatic invertebrates, mussels Mytilus galloprovincialis were caged at the "Augusta-Melilli-Priolo" petrochemical area and Brucoli (Sicily, south Italy), chosen as the reference site. After confirming the elevated concentrations of polycyclic aromatic hydrocarbons (PAHs) and mercury (Hg) in Augusta sediments in our previous work (Maisano et al., 2016a), herein an environmental metabolomics approach based on protonic nuclear magnetic resonance ( 1 H NMR), coupled with chemometrics, was applied on the mussel posterior adductor muscle (PAM), the main muscular system in bivalve molluscs. Amino acids, osmolytes, energy storage compounds, tricarboxylic acid cycle intermediates, and nucleotides, were found in PAM NMR spectra. Principal Component Analysis (PCA) indicated that mussels caged at the polluted site clustered separately from mussels from the control area, suggesting a clear differentiation between their metabolic profiles. Specifically, disorders in energy metabolism, alterations in amino acids metabolism, and disturbance in the osmoregulatory processes were observed in mussel PAM. Overall, findings from this work demonstrated the usefulness of applying an active biomonitoring strategy for environmental risk assessment, and the effectiveness of metabolomics in elucidating changes in metabolic pathways of aquatic organisms caged at sites differentially contaminated, and thus its suitability to be applied in ecotoxicological studies. Copyright © 2017 Elsevier Inc. All rights reserved.

  15. Solution 1H NMR investigation of the active site molecular and electronic structures of substrate-bound, cyanide-inhibited HmuO, a bacterial heme oxygenase from Corynebacterium diphtheriae.

    Science.gov (United States)

    Li, Yiming; Syvitski, Ray T; Chu, Grace C; Ikeda-Saito, Masao; Mar, Gerd N La

    2003-02-28

    The molecular structure and dynamic properties of the active site environment of HmuO, a heme oxygenase (HO) from the pathogenic bacterium Corynebacterium diphtheriae, have been investigated by (1)H NMR spectroscopy using the human HO (hHO) complex as a homology model. It is demonstrated that not only the spatial contacts among residues and between residues and heme, but the magnetic axes that can be related to the direction and magnitude of the steric tilt of the FeCN unit are strongly conserved in the two HO complexes. The results indicate that very similar contributions of steric blockage of several meso positions and steric tilt of the attacking ligand are operative. A distal H-bond network that involves numerous very strong H-bonds and immobilized water molecules is identified in HmuO that is analogous to that previously identified in hHO (Li, Y., Syvitski, R. T., Auclair, K., Wilks, A., Ortiz de Montellano, P. R., and La Mar, G. N. (2002) J. Biol. Chem. 277, 33018-33031). The NMR results are completely consistent with the very recent crystal structure of the HmuO.substrate complex. The H-bond network/ordered water molecules are proposed to orient the distal water molecule near the catalytically key Asp(136) (Asp(140) in hHO) that stabilizes the hydroperoxy intermediate. The dynamic stability of this H-bond network in HmuO is significantly greater than in hHO and may account for the slower catalytic rate in bacterial HO compared with mammalian HO.

  16. 1H-NMR-based metabolic analysis of human serum reveals novel markers of myocardial energy expenditure in heart failure patients.

    Directory of Open Access Journals (Sweden)

    Zhiyong Du

    Full Text Available OBJECTIVE: Elevated myocardial energy expenditure (MEE is related with reduced left ventricular ejection fraction, and has also been documented as an independent predictor of cardiovascular mortality. However, the serum small-molecule metabolite profiles and pathophysiological mechanisms of elevated MEE in heart failure (HF are still lacking. Herein, we used 1H-NMR-based metabolomics analysis to screen for potential biomarkers of MEE in HF. METHODS: A total of 61 subjects were enrolled, including 46 patients with heart failure and 15 age-matched controls. Venous serum samples were collected from subjects after an 8-hour fast. An INOVA 600 MHz nuclear magnetic resonance spectrometer with Carr-Purcell-Melboom-Gill (CPMG pulse sequence was employed for the metabolomics analysis and MEE was calculated using colored Doppler echocardiography. Metabolomics data were processed using orthogonal signal correction and regression analysis was performed using the partial least squares method. RESULTS: The mean MEE levels of HF patients and controls were 139.61±58.18 cal/min and 61.09±23.54 cal/min, respectively. Serum metabolomics varied with MEE changed, and 3-hydroxybutyrate, acetone and succinate were significantly elevated with the increasing MEE. Importantly, these three metabolites were independent of administration of angiotensin converting enzyme inhibitor, β-receptor blockers, diuretics and statins (P>0.05. CONCLUSIONS: These results suggested that in patients with heart failure, MEE elevation was associated with significant changes in serum metabolomics profiles, especially the concentration of 3-hydroxybutyrate, acetone and succinate. These compounds could be used as potential serum biomarkers to study myocardial energy mechanism in HF patients.

  17. Serum metabonomics study of the hepatoprotective effect of Corydalis saxicola Bunting on carbon tetrachloride-induced acute hepatotoxicity in rats by (1)H NMR analysis.

    Science.gov (United States)

    Liang, Yong-Hong; Tang, Chao-Ling; Lu, Shi-Yin; Cheng, Bang; Wu, Fang; Chen, Zhao-Ni; Song, Fangming; Ruan, Jun-Xiang; Zhang, Hong-Ye; Song, Hui; Zheng, Hua; Su, Zhi-Heng

    2016-09-10

    Corydalis saxicola Bunting (CS), a traditional Chinese folk medicine, has been effectively used for treating liver disease in Zhuang nationality in South China. However, the exact hepatoprotective mechanism of CS was still looking forward to further elucidation by far. In present work, metabonomic study of biochemical changes in the serum of carbon tetrachloride (CCl4)-induced acute liver injury rats after CS treatment were performed using proton nuclear magnetic resonance ((1)H-NMR) analysis. Metabolic profiling by means of principal components analysis (PCA) and partial least squares-discriminate analysis (PLS-DA) indicated that the metabolic perturbation caused by CCl4 was reduced by CS treatment. A total of 9 metabolites including isoleucine (1), lactate (2), alanine (3), glutamine (4), acetone (5), succinate (6), phosphocholine (7), d-glucose (8) and glycerol (9) were considered as potential biomarkers involved in the development of CCl4-induced acute liver injury. According to pathway analysis by metabolites identified and correlation network construction by Pearson's correlation coefficency matrix, alanine, aspartate and glutamate metabolism and glycerolipid metabolism were recognized as the most influenced metabolic pathways associated with CCl4 injury. As a result, notably, deviations of metabolites 1, 3, 4, 7 and 9 in the process of CCl4-induced acute liver injury were improved by CS treatment, which suggested that CS mediated synergistically abnormalities of the metabolic pathways, composed of alanine, aspartate and glutamate metabolism and glycerolipid metabolism. In this study, it was the first report to investigate the hepatoprotective effect of the CS based on metabonomics strategy, which may be a potentially powerful tool to interpret the action mechanism of traditional Chinese folk medicines. Copyright © 2016 Elsevier B.V. All rights reserved.

  18. Urinary metabonomics study of the hepatoprotective effects of total alkaloids from Corydalis saxicola Bunting on carbon tetrachloride-induced chronic hepatotoxicity in rats using 1H NMR analysis.

    Science.gov (United States)

    Wu, Fang; Zheng, Hua; Yang, Zheng-Teng; Cheng, Bang; Wu, Jin-Xia; Liu, Xu-Wen; Tang, Chao-Ling; Lu, Shi-Yin; Chen, Zhao-Ni; Song, Fang-Ming; Ruan, Jun-Xiang; Zhang, Hong-Ye; Liang, Yong-Hong; Song, Hui; Su, Zhi-Heng

    2017-06-05

    Chronic liver injury has been shown to cause liver fibrosis due to the sustained pathophysiological wound healing response of the liver, and eventually progresses to cirrhosis. The total alkaloids of Corydalis saxicola Bunting (TACS), a collection of important bioactive ingredients derived from the traditional Chinese folk medicine Corydalis saxicola Bunting (CS), have been reported to have protective effects on the liver. However, the underlying molecular mechanisms need further elucidation. In this study, the urinary metabonomics and the biochemical changes in rats with carbon tetrachloride (CCl 4 )-induced chronic liver injury due to treatment TACS or administration of the positive control drug-bifendate were studied via proton nuclear magnetic resonance ( 1 H NMR) analysis. Partial least squares-discriminate analysis (PLS-DA) suggested that metabolic perturbation caused by CCl 4 damage was recovered with TACS and bifendate treatment. A total of seven metabolites including 2-oxoglutarate, citrate, dimethylamine, taurine, phenylacetylglycine, creatinine and hippurate were considered as potential biomarkers involved in the development of CCl 4 -induced chronic liver injury. According to pathway analysis using identified metabolites and correlation network construction, the tricarboxylic acid (TCA) cycle, gut microbiota metabolism and taurine and hypotaurine metabolism were recognized as the most affected metabolic pathways associated with CCl 4 chronic hepatotoxicity. Notably, the changes in 2-oxoglutarate, citrate, taurine and hippurate during the process of CCl 4 -induced chronic liver injury were significantly restored by TACS treatment, which suggested that TACS synergistically mediated the regulation of multiple metabolic pathways including the TCA cycle, gut microbiota metabolism and taurine and hypotaurine metabolism. This study could bring valuable insight to evaluating the efficacy of TACS intervention therapy, help deepen the understanding of the

  19. Recommended strategies for spectral processing and post-processing of 1D 1H-NMR data of biofluids with a particular focus on urine

    KAUST Repository

    Emwas, Abdul-Hamid M.

    2018-02-12

    1H NMR spectra from urine can yield information-rich data sets that offer important insights into many biological and biochemical phenomena. However, the quality and utility of these insights can be profoundly affected by how the NMR spectra are processed and interpreted. For instance, if the NMR spectra are incorrectly referenced or inconsistently aligned, the identification of many compounds will be incorrect. If the NMR spectra are mis-phased or if the baseline correction is flawed, the estimated concentrations of many compounds will be systematically biased. Furthermore, because NMR permits the measurement of concentrations spanning up to five orders of magnitude, several problems can arise with data analysis. For instance, signals originating from the most abundant metabolites may prove to be the least biologically relevant while signals arising from the least abundant metabolites may prove to be the most important but hardest to accurately and precisely measure. As a result, a number of data processing techniques such as scaling, transformation and normalization are often required to address these issues. Therefore, proper processing of NMR data is a critical step to correctly extract useful information in any NMR-based metabolomic study. In this review we highlight the significance, advantages and disadvantages of different NMR spectral processing steps that are common to most NMR-based metabolomic studies of urine. These include: chemical shift referencing, phase and baseline correction, spectral alignment, spectral binning, scaling and normalization. We also provide a set of recommendations for best practices regarding spectral and data processing for NMR-based metabolomic studies of biofluids, with a particular focus on urine.

  20. Leucine-rich diet alters the 1H-NMR based metabolomic profile without changing the Walker-256 tumour mass in rats.

    Science.gov (United States)

    Viana, Laís Rosa; Canevarolo, Rafael; Luiz, Anna Caroline Perina; Soares, Raquel Frias; Lubaczeuski, Camila; Zeri, Ana Carolina de Mattos; Gomes-Marcondes, Maria Cristina Cintra

    2016-10-03

    Cachexia is one of the most important causes of cancer-related death. Supplementation with branched-chain amino acids, particularly leucine, has been used to minimise loss of muscle tissue, although few studies have examined the effect of this type of nutritional supplementation on the metabolism of the tumour-bearing host. Therefore, the present study evaluated whether a leucine-rich diet affects metabolomic derangements in serum and tumour tissues in tumour-bearing Walker-256 rats (providing an experimental model of cachexia). After 21 days feeding Wistar female rats a leucine-rich diet, distributed in L-leucine and LW-leucine Walker-256 tumour-bearing groups, we examined the metabolomic profile of serum and tumour tissue samples and compared them with samples from tumour-bearing rats fed a normal protein diet (C - control; W - tumour-bearing groups). We utilised 1 H-NMR as a means to study the serum and tumour metabolomic profile, tumour proliferation and tumour protein synthesis pathway. Among the 58 serum metabolites examined, we found that 12 were altered in the tumour-bearing group, reflecting an increase in activity of some metabolic pathways related to energy production, which diverted many nutrients toward tumour growth. Despite displaying increased tumour cell activity (i.e., higher Ki-67 and mTOR expression), there were no differences in tumour mass associated with changes in 23 metabolites (resulting from valine, leucine and isoleucine synthesis and degradation, and from the synthesis and degradation of ketone bodies) in the leucine-tumour group. This result suggests that the majority of nutrients were used for host maintenance. A leucine rich-diet, largely used to prevent skeletal muscle loss, did not affect Walker 256 tumour growth and led to metabolomic alterations that may partially explain the positive effects of leucine for the whole tumour-bearing host.

  1. Host-guest complexes of 2-hydroxypropyl-β-cyclodextrin/β-cyclodextrin and nifedipine: 1H NMR, molecular modeling, and dissolution studies

    Science.gov (United States)

    de Araújo, Márcia Valéria Gaspar; Vieira, João Victor Francisco; da Silva, Caroline W. P.; Barison, Andersson; Andrade, George Ricardo Santana; da Costa, Nivan Bezerra; Barboza, Fernanda Malaquias; Nadal, Jessica Mendes; Novatski, Andressa; Farago, Paulo Vitor; Zawadzki, Sônia Faria

    2017-12-01

    Nifedipine (NIF) is a hydrophobic drug widely used for treating cardiovascular diseases. This calcium channel blocker can present a higher apparent solubility by its inclusion into different cyclodextrins (CDs) as host-guest complexes. This paper focused on the structural investigation and dissolution behavior of inclusion complexes prepared with 2-hydroxypropyl-β-cyclodextrin (HPβCD) or β-cyclodextrin (βCD) and NIF. Drug amorphization was observed for HPβCD/NIF and βCD/NIF inclusion complexes by X-ray diffractometry (XRD). The sharp endothermic peak of NIF was not observed for these both host-guest complexes by differential scanning calorimetry (DSC). These results of XRD and DSC provide evidences of complexation between drug and the investigated CDs. 1H and saturation transfer difference nuclear magnetic resonance studies revealed the enhancement in the signal at 2.27 ppm for HPβCD/NIF and βCD/NIF inclusion complexes that corresponded to the methyl groups of NIF from the non-aromatic ring. This result suggested that non-aromatic ring of NIF was inserted into HPβCD and βCD cavities. Considering the mathematical simulations, it was observed that the inclusion process can occur in the both NH-in or NH-out forms. However, since it was used aqueous medium, it is possible to indicate that the obtained host-guest complexes HPβCD/NIF and βCD/NIF are in NH-in form which corresponded to the previous results obtained by 1H NMR experiments. Dissolution assays demonstrated that NIF inclusion complexes improved the drug release nevertheless without changing its biexponential release behavior. These host-guest complexes can be further used as feasible NIF carriers in solid dosage forms.

  2. Recommended strategies for spectral processing and post-processing of 1D 1H-NMR data of biofluids with a particular focus on urine

    KAUST Repository

    Emwas, Abdul-Hamid M.; Saccenti, Edoardo; Gao, Xin; McKay, Ryan T.; dos Santos, Vitor A. P. Martins; Roy, Raja; Wishart, David S.

    2018-01-01

    1H NMR spectra from urine can yield information-rich data sets that offer important insights into many biological and biochemical phenomena. However, the quality and utility of these insights can be profoundly affected by how the NMR spectra are processed and interpreted. For instance, if the NMR spectra are incorrectly referenced or inconsistently aligned, the identification of many compounds will be incorrect. If the NMR spectra are mis-phased or if the baseline correction is flawed, the estimated concentrations of many compounds will be systematically biased. Furthermore, because NMR permits the measurement of concentrations spanning up to five orders of magnitude, several problems can arise with data analysis. For instance, signals originating from the most abundant metabolites may prove to be the least biologically relevant while signals arising from the least abundant metabolites may prove to be the most important but hardest to accurately and precisely measure. As a result, a number of data processing techniques such as scaling, transformation and normalization are often required to address these issues. Therefore, proper processing of NMR data is a critical step to correctly extract useful information in any NMR-based metabolomic study. In this review we highlight the significance, advantages and disadvantages of different NMR spectral processing steps that are common to most NMR-based metabolomic studies of urine. These include: chemical shift referencing, phase and baseline correction, spectral alignment, spectral binning, scaling and normalization. We also provide a set of recommendations for best practices regarding spectral and data processing for NMR-based metabolomic studies of biofluids, with a particular focus on urine.

  3. Epitope diversity of N-glycans from bovine peripheral myelin glycoprotein P0 revealed by mass spectrometry and nano probe magic angle spinning 1H NMR spectroscopy

    NARCIS (Netherlands)

    Vliegenthart, J.F.G.; Gutiérrez Gallego, R.; Jiménez Blanco, J.L.; Thijssen-van Zuylen, C.W.E.M.; Gotfredsen, C.H.; Voshol, H.; Duus, J.Ø.; Schachner, M.

    2001-01-01

    The carbohydrate structures present on the glycoproteins in the central and peripheral nerve systems are essential in many cell adhesion processes. The P0 glycoprotein, expressed by myelinating Schwann cells, plays an important role during the formation and maintenance of myelin, and it is the most

  4. Conformational Analysis of Indole Alkaloids Corynantheine and Dihydrocorynantheine by Dynamic 1H NMR Spectroscopy and Computational Methods: Steric Effects of Ethyl vs Vinyl Group

    DEFF Research Database (Denmark)

    Stærk, Dan; Norrby, Per-Ola; Jaroszewski, Jerzy W.

    2001-01-01

    H-1 NMR (400 MHz) spectra of the indole alkaloid dihydrocorynantheine recorded at room temperature show the presence of two conformers near coalescence. Low temperature H-1 NMR allowed characterization of the conformational equilibrium, which involves rotation of the 3-methoxypropenoate side chain...... bulk of the vinyl and the ethyl group. The conformational equilibria involving the side chain rotation as well as inversion of the bridgehead nitrogen in corynantheine and dihydrocorynantheine was studied by force-field (Amber(*) and MMFF) and ab initio (density-functional theory at the B3LYP/6-31G...

  5. Investigation of urine metabolic profiles in newborns with prenatally diagnosedunilateral urinary tract dilatation using 1H NMR spectroscopy and metabolomic analysis

    OpenAIRE

    Scalabre , Aurélien

    2017-01-01

    The prenatal finding of unilateral Urinary Tract Dilatation (UTD) can be transient or represent a significant urinary flow impairment that would lead to progressive deterioration of renal function. Identifying urinary biomarkers could help to differentiate uropathy requiring surgical management from transient dilatation at an early stage.Metabolic phenotyping studies provide untargeted quantification of all detectable low molecular-weight molecules by profiling without any a priori the metabo...

  6. Structural determination of the carbohydrate chains from arthropod and mollusc hemocyanin by means of 500-MHz 1H-NMR spectroscopy

    International Nuclear Information System (INIS)

    Kuik, J.A. van.

    1987-01-01

    In this thesis carbohydrate structures of hemocyanins of arthropods and molluscs are studied. Hemocyanins are high-molecular-mass, copper-containing oxygen-transport proteins. The function of these carbohydrate chains are yet still unknown. It is not probable that they play a role in the oxygen-binding processes. They are rather thought to have a function in the build-up of the hemocyanin molecules. 286 refs.; 30 figs.; 25 tabs

  7. Analysis of immediate changes of water-soluble metabolites in alkali-burned rabbit cornea, aqueous humor and lens by high-resolution 1H-NMR spectroscopy

    Czech Academy of Sciences Publication Activity Database

    Risa, O.; Saether, O.; Midelfart, A.; Krane, J.; Čejková, Jitka

    2002-01-01

    Roč. 240, - (2002), s. 49-55 ISSN 0721-832X R&D Projects: GA ČR GA304/00/1635 Institutional research plan: CEZ:AV0Z5039906 Keywords : aqueous humor * alkali-burned eyes Subject RIV: FF - HEENT, Dentistry Impact factor: 1.191, year: 2002

  8. Quantitative 1H NMR metabolomics reveals extensive metabolic reprogramming of primary and secondary metabolism in elicitor-treated opium poppy cell cultures

    Directory of Open Access Journals (Sweden)

    Vogel Hans J

    2008-01-01

    Full Text Available Abstract Background Opium poppy (Papaver somniferum produces a diverse array of bioactive benzylisoquinoline alkaloids and has emerged as a model system to study plant alkaloid metabolism. The plant is cultivated as the only commercial source of the narcotic analgesics morphine and codeine, but also produces many other alkaloids including the antimicrobial agent sanguinarine. Modulations in plant secondary metabolism as a result of environmental perturbations are often associated with the altered regulation of other metabolic pathways. As a key component of our functional genomics platform for opium poppy we have used proton nuclear magnetic resonance (1H NMR metabolomics to investigate the interplay between primary and secondary metabolism in cultured opium poppy cells treated with a fungal elicitor. Results Metabolite fingerprinting and compound-specific profiling showed the extensive reprogramming of primary metabolic pathways in association with the induction of alkaloid biosynthesis in response to elicitor treatment. Using Chenomx NMR Suite v. 4.6, a software package capable of identifying and quantifying individual compounds based on their respective signature spectra, the levels of 42 diverse metabolites were monitored over a 100-hour time course in control and elicitor-treated opium poppy cell cultures. Overall, detectable and dynamic changes in the metabolome of elicitor-treated cells, especially in cellular pools of carbohydrates, organic acids and non-protein amino acids were detected within 5 hours after elicitor treatment. The metabolome of control cultures also showed substantial modulations 80 hours after the start of the time course, particularly in the levels of amino acids and phospholipid pathway intermediates. Specific flux modulations were detected throughout primary metabolism, including glycolysis, the tricarboxylic acid cycle, nitrogen assimilation, phospholipid/fatty acid synthesis and the shikimate pathway, all of which

  9. Optimized slice-selective 1H NMR experiments combined with highly accurate quantitative 13C NMR using an internal reference method

    Science.gov (United States)

    Jézéquel, Tangi; Silvestre, Virginie; Dinis, Katy; Giraudeau, Patrick; Akoka, Serge

    2018-04-01

    Isotope ratio monitoring by 13C NMR spectrometry (irm-13C NMR) provides the complete 13C intramolecular position-specific composition at natural abundance. It represents a powerful tool to track the (bio)chemical pathway which has led to the synthesis of targeted molecules, since it allows Position-specific Isotope Analysis (PSIA). Due to the very small composition range (which represents the range of variation of the isotopic composition of a given nuclei) of 13C natural abundance values (50‰), irm-13C NMR requires a 1‰ accuracy and thus highly quantitative analysis by 13C NMR. Until now, the conventional strategy to determine the position-specific abundance xi relies on the combination of irm-MS (isotopic ratio monitoring Mass Spectrometry) and 13C quantitative NMR. However this approach presents a serious drawback since it relies on two different techniques and requires to measure separately the signal of all the carbons of the analyzed compound, which is not always possible. To circumvent this constraint, we recently proposed a new methodology to perform 13C isotopic analysis using an internal reference method and relying on NMR only. The method combines a highly quantitative 1H NMR pulse sequence (named DWET) with a 13C isotopic NMR measurement. However, the recently published DWET sequence is unsuited for samples with short T1, which forms a serious limitation for irm-13C NMR experiments where a relaxing agent is added. In this context, we suggest two variants of the DWET called Multi-WET and Profiled-WET, developed and optimized to reach the same accuracy of 1‰ with a better immunity towards T1 variations. Their performance is evaluated on the determination of the 13C isotopic profile of vanillin. Both pulse sequences show a 1‰ accuracy with an increased robustness to pulse miscalibrations compared to the initial DWET method. This constitutes a major advance in the context of irm-13C NMR since it is now possible to perform isotopic analysis with high

  10. A correction method for systematic error in (1)H-NMR time-course data validated through stochastic cell culture simulation.

    Science.gov (United States)

    Sokolenko, Stanislav; Aucoin, Marc G

    2015-09-04

    as 2.5 % under a wide range of conditions. Both the simulation framework and error correction method represent examples of time-course analysis that can be applied to further developments in (1)H-NMR methodology and the more general application of quantitative metabolomics.

  11. Understanding the generation and maintenance of supersaturation during the dissolution of amorphous solid dispersions using modulated DSC and 1H NMR.

    Science.gov (United States)

    Baghel, Shrawan; Cathcart, Helen; O'Reilly, Niall J

    2018-01-30

    In this study, the dissolution behaviour of dipyridamole (DPM) and cinnarizine (CNZ) spray-dried amorphous solid dispersions (ASDs) using polyvinyl pyrrolidone (PVP) and polyacrylic acid (PAA) as a carrier matrix were evaluated and compared. The drug concentrations achieved from the dissolution of PVP and PAA solid dispersions were significantly greater than the equilibrium solubility of crystalline DPM and CNZ in phosphate buffer pH 6.8 (PBS 6.8). The maximum drug concentration achieved by dissolution of PVP and PAA solid dispersions did not exceed the theoretically calculated apparent solubility of amorphous DPM and CNZ. However, the degree of supersaturation of DPM and CNZ increased considerably as the polymer weight fraction within the solid dispersion increased. In addition, the supersaturation profile of DPM and CNZ were studied in the presence and absence of the polymers. PAA was found to maintain a higher level of supersaturation compared to PVP. The enhanced drug solution concentration following dissolution of ASDs can be attributed to the reduced crystal growth rates of DPM and CNZ at an equivalent supersaturation. We have also shown that, for drugs having high crystallization tendency and weak drug-polymer interaction, the feasible way to increase dissolution might be increase the polymer weight fraction in the ASD. Solution 1 H NMR spectra were used to understand dissolution mechanism and to identify drug-polymer interaction. The change in electron densities of proton attached to different groups in DPM and CNZ suggested drug-polymer interaction in solution. The relative intensities of peak shift and nature of interaction between drug and polymer in different systems are different. These different effects suggest that DPM and CNZ interacts in a different way with PVP and PAA in solution which goes some way towards explaining the different polymeric effect, particularly in terms of inhibition of drug recrystallization and dissolution of DPM and CNZ ASDs

  12. A new Schiff base compound N,N'-(2,2-dimetylpropane)-bis(dihydroxylacetophenone): synthesis, experimental and theoretical studies on its crystal structure, FTIR, UV-visible, 1H NMR and 13C NMR spectra.

    Science.gov (United States)

    Saheb, Vahid; Sheikhshoaie, Iran

    2011-10-15

    The Schiff base compound, N,N'-(2,2-dimetylpropane)-bis(dihydroxylacetophenone) (NDHA) is synthesized through the condensation of 2-hydroxylacetophenone and 2,2-dimethyl 1,3-amino propane in methanol at ambient temperature. The yellow crystalline precipitate is used for X-ray single-crystal determination and measuring Fourier transform infrared (FTIR), UV-visible, (1)H NMR and (13)C NMR spectra. Electronic structure calculations at the B3LYP, PBEPBE and PW91PW91 levels of theory are performed to optimize the molecular geometry and to calculate the FTIR, (1)H NMR and (13)C NMR spectra of the compound. Time-dependent density functional theory (TDDFT) method is used to calculate the UV-visible spectrum of NDHA. Vibrational frequencies are determined experimentally and compared with those obtained theoretically. Vibrational assignments and analysis of the fundamental modes of the compound are also performed. All theoretical methods can well reproduce the structure of the compound. The (1)H NMR and (13)C NMR chemical shifts calculated by all DFT methods are consistent with the experimental data. However, the NMR shielding tensors computed at the B3LYP/6-31+G(d,p) level of theory are in better agreement with experimental (1)H NMR and (13)C NMR spectra. The electronic absorption spectrum calculated at the B3LYP/6-31+G(d,p) level by using TD-DFT method is in accordance with the observed UV-visible spectrum of NDHA. In addition, some quantum descriptors of the molecule are calculated and conformational analysis is performed and the results were compared with the crystallographic data. Copyright © 2011 Elsevier B.V. All rights reserved.

  13. Tensiometric, fluorescence and 1H NMR study of mixed micellization of non-steroidal anti-inflammatory drug sodium salt of ibuprofen in the presence of non-ionic surfactant in aqueous/urea solutions

    International Nuclear Information System (INIS)

    Rub, Malik Abdul; Khan, Farah; Sheikh, Mohmad Shafi; Azum, Naved; Asiri, Abdullah M.

    2016-01-01

    Highlights: • Interaction between (IBF + TX-100) mixtures has been investigated. • (IBF + TX-100) mixtures exhibit synergistic behavior. • Urea increases the surface charge of the micelles resulting halt of the micelles formation. • N agg , K sv and dielectric constant of mixed systems have also been evaluated. • 1 H NMR data suggested that IBF and TX-100 interacts through hydrophobic as well as hydrophillic interaction. - Abstract: The desirable surface/bulk properties for specific applications of drug sodium salt of ibuprofen (IBF) and Triton X-100 (TX-100) can be achieved by adjusting mainly the composition of these systems. The interactions of anionic drug IBF with non-ionic surfactant TX-100 micelles have been investigated using tensiometry, fluorometry and 1 H NMR in aqueous as well in 250 mmol⋅kg −1 urea solutions. Different theoretical models like Clint, Rubingh, and Rosen, etc. were utilized to get information about the nature of interaction between these two in bulk and at the interface. These models disclose that the non-ideal behavior with attractive interaction in bulk and at the interface exists. The steady-state fluorescence quenching study was employed to evaluate micelle aggregation numbers (N agg ), which signify the involvement of surfactant was forever higher compared to IBF. Stern–Volmer binding constants (K sv ), micropolarity (I 1 /I 3 ) and dielectric constant (D exp ) of the mixtures are also obtained using fluorescence method. By the addition of urea raise in the surface charge of the micelles was observed followed by halt of the micellization of drug and surfactant as well as their mixture, therefore cmc values increases followed by decrease in aggregation number. The 1 H NMR resonance intensity variations were paralleled by upfield shifts in the resonance frequencies, due to an increased shielding of IBF happening from closeness of the non-ionic TX-100 surfactant.

  14. 1H NMR and SPME-GC/MS study of hydrolysis, oxidation and other reactions occurring during in vitro digestion of non-oxidized and oxidized sunflower oil. Formation of hydroxy-octadecadienoates.

    Science.gov (United States)

    Nieva-Echevarría, Bárbara; Goicoechea, Encarnación; Manzanos, María J; Guillén, María D

    2017-01-01

    Both fresh and slightly oxidized sunflower oils, as models of omega-6 rich lipids, were submitted to in vitro gastrointestinal digestion and studied by 1 H NMR and SPME-GC/MS. Changes in lipolysis degree, lipid composition and oxidative level were studied by 1 H NMR. Three quantitative approaches were used and several equations were newly developed. In oxidized oil digestates slightly lower hydrolysis and a higher advance of oxidation took place during digestion. This latter was evidenced by a greater decrease of lipid unsaturation degree and enhanced generation of oxidation products (cis,trans-hydroperoxy-octadecadienoates, cis,trans- and trans,trans-hydroxy-octadecadienoates). For the first time, the generation of hydroxy-octadecadienoates during in vitro digestion is reported. Furthermore, SPME-GC/MS study of non-digested and digested samples headspaces confirmed that lipid oxidation occurred: abundances of volatile markers increased (including potentially toxic alpha,beta-unsaturated aldehydes), especially in oxidized oils digestates. Markers of Maillard-type and esterification reactions were also detected in the digestates. Copyright © 2016 Elsevier Ltd. All rights reserved.

  15. 1H-NMR and HPLC studies of the changes involved in volume regulation in the muscle fibres of the crab, Hemigrapsus edwardsi.

    Science.gov (United States)

    Bedford, J J; Smith, R A; Thomas, M; Leader, J P

    1991-01-01

    1. The process of cell volume readjustment, during adaptation to salinity changes, in muscle fibres of the euryhaline New Zealand shore crab, Hemigrapsus edwardsi, involve large changes in the amounts of free amino acid. 2. These are taurine, proline, alanine, arginine, glutamic acid, glycine and serine. 3. These changes may be quantified by High Performance Liquid Chromatography, and qualitatively demonstrated by proton nuclear magnetic resonance spectroscopy.

  16. Two-dimensional nuclear magnetic resonance spectroscopy

    International Nuclear Information System (INIS)

    Bax, A.; Lerner, L.

    1986-01-01

    Great spectral simplification can be obtained by spreading the conventional one-dimensional nuclear magnetic resonance (NMR) spectrum in two independent frequency dimensions. This so-called two-dimensional NMR spectroscopy removes spectral overlap, facilitates spectral assignment, and provides a wealth of additional information. For example, conformational information related to interproton distances is available from resonance intensities in certain types of two-dimensional experiments. Another method generates 1 H NMR spectra of a preselected fragment of the molecule, suppressing resonances from other regions and greatly simplifying spectral appearance. Two-dimensional NMR spectroscopy can also be applied to the study of 13 C and 15 N, not only providing valuable connectivity information but also improving sensitivity of 13 C and 15 N detection by up to two orders of magnitude. 45 references, 10 figures

  17. Achieving sensitive, high-resolution laser spectroscopy at CRIS

    Energy Technology Data Exchange (ETDEWEB)

    Groote, R. P. de [Instituut voor Kern- en Stralingsfysica, KU Leuven (Belgium); Lynch, K. M., E-mail: kara.marie.lynch@cern.ch [EP Department, CERN, ISOLDE (Switzerland); Wilkins, S. G. [The University of Manchester, School of Physics and Astronomy (United Kingdom); Collaboration: the CRIS collaboration

    2017-11-15

    The Collinear Resonance Ionization Spectroscopy (CRIS) experiment, located at the ISOLDE facility, has recently performed high-resolution laser spectroscopy, with linewidths down to 20 MHz. In this article, we present the modifications to the beam line and the newly-installed laser systems that have made sensitive, high-resolution measurements possible. Highlights of recent experimental campaigns are presented.

  18. 1H NMR and Multivariate Analysis for Geographic Characterization of Commercial Extra Virgin Olive Oil: A Possible Correlation with Climate Data

    Directory of Open Access Journals (Sweden)

    Domenico Rongai

    2017-11-01

    Full Text Available 1H Nuclear Magnetic Resonance (NMR spectroscopy coupled with multivariate analysis has been applied in order to investigate metabolomic profiles of more than 200 extravirgin olive oils (EVOOs collected in a period of over four years (2009–2012 from different geographic areas. In particular, commercially blended EVOO samples originating from different Italian regions (Tuscany, Sicily and Apulia, as well as European (Spain and Portugal and non-European (Tunisia, Turkey, Chile and Australia countries. Multivariate statistical analysis (Principal Component Analisys (PCA and Orthogonal Partial Least Squares Discriminant Analysis (OPLS-DA applied on the NMR data revealed the existence of marked differences between Italian (in particular from Tuscany, Sicily and Apulia regions and foreign (in particular Tunisian EVOO samples. A possible correlation with available climate data has been also investigated. These results aim to develop a powerful NMR-based tool able to protect Italian olive oil productions.

  19. Stereochemistry of C18 monounsaturated cork suberin acids determined by spectroscopic techniques including (1) H-NMR multiplet analysis of olefinic protons.

    Science.gov (United States)

    Santos, Sara; Graça, José

    2014-01-01

    Suberin is a biopolyester responsible for the protection of secondary plant tissues, and yet its molecular structure remains unknown. The C18:1 ω-hydroxyacid and the C18:1 α,ω-diacid are major monomers in the suberin structure, but the configuration of the double bond remains to be elucidated. To unequivocally define the configuration of the C18:1 suberin acids. Pure C18:1 ω-hydroxyacid and C18:1 α,ω-diacid, isolated from cork suberin, and two structurally very close C18:1 model compounds of known stereochemistry, methyl oleate and methyl elaidate, were analysed by NMR spectroscopy, Fourier transform infrared (FTIR) and Raman spectroscopy, and GC-MS. The GC-MS analysis showed that both acids were present in cork suberin as only one geometric isomer. The analysis of dimethyloxazoline (DMOX) and picolinyl derivatives proved the double bond position to be at C-9. The FTIR spectra were concordant with a cis-configuration for both suberin acids, but their unambiguous stereochemical assignment came from the NMR analysis: (i) the chemical shifts of the allylic (13) C carbons were shielded comparatively to the trans model compound, and (ii) the complex multiplets of the olefinic protons could be simulated only with (3) JHH and long-range (4) JHH coupling constants typical of a cis geometry. The two C18:1 suberin acids in cork are (Z)-18-hydroxyoctadec-9-enoic acid and (Z)-octadec-9-enedoic acid. Copyright © 2013 John Wiley & Sons, Ltd.

  20. {sup 1}H-NMR characterization of cellulose acetate obtained from sugarcane bagasse; Caracterizacao de acetato de celulose obtido a partir do bagaco de cana-de-acucar por {sup 1}H-RMN

    Energy Technology Data Exchange (ETDEWEB)

    Cerqueira, Daniel A., E-mail: daniel.cerqueira@ufba.b [Universidade Federal da Bahia (UFBA), Salvador, BA (Brazil). Inst. de Ciencias Ambientais e Desenvolvimento Sustentavel; Rodrigues Filho, Guimes [Universidade Federal de Uberlandia (UFU), MG (Brazil). Inst. de Quimica; Carvalho, Rui de A. [Universidade de Coimbra (Portugal). Dept. de Bioquimica; Valente, Artur J.M. [Universidade de Coimbra (Portugal). Dept. de Quimica

    2010-07-01

    Cellulose from sugarcane bagasse was used for synthesizing cellulose acetate with different degrees of substitution, which were characterized by {sup 1}H-NMR through the relationship between the peak areas of the hydrogen atoms of the acetate groups (-(C=O)OCH{sub 3}) and the peaks of the hydrogen bonded to the carbon atoms of the glycosidic rings. Suppression of some signals was carried out in order to remove the residual water resonance in the materials and those related to impurities in cellulose triacetate as well. A deconvolution method for the computation of the degree of substitution of acetylation is proposed. The degrees of substitution for the cellulose samples were 2.94 and 2.60, in good agreement with those obtained by chemical determination through an acid-base titration. (author)

  1. Characterization of cellulose acetate obtained from sugarcane bagasse by {sup 1}H-NMR; Caracterizacao de acetato de celulose obtido a partir do bagaco de cana-de-acucar por {sup 1}H-RMN

    Energy Technology Data Exchange (ETDEWEB)

    Cerqueira, Daniel A.; Rodrigues Filho, Guimes, E-mail: d.a.cerqueira@gmail.co [Universidade Federal de Uberlendia (IQ/UFU), MG (Brazil). Inst. de Quimica; Carvalho, Rui A. [Universidade de Coimbra (UC) (Portugal). Dept. de Bioquimica; Valente, Artur J.M. [Universidade de Coimbra (UC) (Portugal). Dept. de Quimica

    2009-07-01

    Cellulose from sugarcane bagasse was used for synthesizing cellulose acetate with different degrees of substitution, which were characterized by {sup 1}H-NMR through the relationship between the peak areas of the hydrogen atoms present at the acetate groups (-(C=O)OCH{sub 3} ) and the peaks of the hydrogen bonded to the carbon atoms of the glycosidic rings. Suppression was carried out in order to remove the peak of residual water in the materials and the peak related to impurities in cellulose triacetate. Degree of substitution values obtained through the resonance deconvolution were compared to those obtained by chemical determination through an acid-base titration. The determined degrees of substitution of the cellulose samples were 2.94 and 2.60. (author)

  2. The Serum Metabolite Response to Diet Intervention with Probiotic Acidified Milk in Irritable Bowel Syndrome Patients Is Indistinguishable from that of Non-Probiotic Acidified Milk by 1H NMR-Based Metabonomic Analysis

    Directory of Open Access Journals (Sweden)

    Ulla Svensson

    2010-11-01

    Full Text Available The effects of a probiotic acidified milk product on the blood serum metabolite profile of patients suffering from Irritable Bowel Syndrome (IBS compared to a non-probiotic acidified milk product was investigated using 1H NMR metabonomics. For eight weeks, IBS patients consumed 0.4 L per day of a probiotic fermented milk product or non-probiotic acidified milk. Both diets resulted in elevated levels of blood serum l-lactate and 3-hydroxybutyrate. Our results showed identical effects of acidified milk consumption independent of probiotic addition. A similar result was previously obtained in a questionnaire-based evaluation of symptom relief. A specific probiotic effect is thus absent both in the patient subjective symptom evaluations and at the blood serum metabolite level. However, there was no correspondence between symptom relief and metabolite response on the patient level.

  3. Metabolite Profiling of the Microalgal Diatom Chaetoceros Calcitrans and Correlation with Antioxidant and Nitric Oxide Inhibitory Activities via 1H NMR-Based Metabolomics

    Directory of Open Access Journals (Sweden)

    Awanis Azizan

    2018-05-01

    Full Text Available Microalgae are promising candidate resources from marine ecology for health-improving effects. Metabolite profiling of the microalgal diatom, Chaetoceros calcitrans was conducted by using robust metabolomics tools, namely 1H nuclear magnetic resonance (NMR spectroscopy coupled with multivariate data analysis (MVDA. The unsupervised data analysis, using principal component analysis (PCA, resolved the five types of extracts made by solvents ranging from polar to non-polar into five different clusters. Collectively, with various extraction solvents, 11 amino acids, cholesterol, 6 fatty acids, 2 sugars, 1 osmolyte, 6 carotenoids and 2 chlorophyll pigments were identified. The fatty acids and both carotenoid pigments as well as chlorophyll, were observed in the extracts made from medium polar (acetone, chloroform and non-polar (hexane solvents. It is suggested that the compounds were the characteristic markers that influenced the separation between the clusters. Based on partial least square (PLS analysis, fucoxanthin, astaxanthin, violaxanthin, zeaxanthin, canthaxanthin, and lutein displayed strong correlation to 2,2-diphenyl-1-picrylhydrazyl (DPPH free radical scavenging and nitric oxide (NO inhibitory activity. This metabolomics study showed that solvent extractions are one of the main bottlenecks for the maximum recovery of bioactive microalgal compounds and could be a better source of natural antioxidants due to a high value of metabolites.

  4. “Omics” Prospective Monitoring of Bariatric Surgery: Roux-En-Y Gastric Bypass Outcomes Using Mixed-Meal Tolerance Test and Time-Resolved 1H NMR-Based Metabolomics

    Science.gov (United States)

    Lopes, Thiago I.B.; Geloneze, Bruno; Pareja, José C.; Calixto, Antônio R.; Ferreira, Márcia M.C.

    2016-01-01

    Abstract Roux-en-Y gastric bypass (RYGB) surgery goes beyond weight loss to induce early beneficial hormonal changes that favor glycemic control. In this prospective study, ten obese subjects diagnosed with type 2 diabetes underwent bariatric surgery. Mixed-meal tolerance test was performed before and 12 months after RYGB, and the outcomes were investigated by a time-resolved hydrogen nuclear magnetic resonance (1H NMR)-based metabolomics. To the best of our knowledge, no previous omics-driven study has used time-resolved 1H NMR-based metabolomics to investigate bariatric surgery outcomes. Our results presented here show a significant decrease in glucose levels after bariatric surgery (from 159.80 ± 61.43 to 100.00 ± 22.94 mg/dL), demonstrating type 2 diabetes remission (p < 0.05). The metabolic profile indicated lower levels of lactate, alanine, and branched chain amino acids for the operated subject at fasting state after the surgery. However, soon after food ingestion, the levels of these metabolites increased faster in operated than in nonoperated subjects. The lipoprotein profile achieved before and after RYGB at fasting was also significantly different, but converging 180 min after food ingestion. For example, the very low-density lipoprotein, low-density lipoprotein, N-acetyl-glycoproteins, and unsaturated lipid levels decreased after RYGB, while phosphatidylcholine and high-density lipoprotein increased. This study provides important insights on RYGB surgery and attendant type 2 diabetes outcomes using an “omics” systems science approach. Further research on metabolomic correlates of RYGB surgery in larger study samples is called for. PMID:27428253

  5. Differentiation of Organically and Conventionally Grown Tomatoes by Chemometric Analysis of Combined Data from Proton Nuclear Magnetic Resonance and Mid-infrared Spectroscopy and Stable Isotope Analysis.

    Science.gov (United States)

    Hohmann, Monika; Monakhova, Yulia; Erich, Sarah; Christoph, Norbert; Wachter, Helmut; Holzgrabe, Ulrike

    2015-11-04

    Because the basic suitability of proton nuclear magnetic resonance spectroscopy ((1)H NMR) to differentiate organic versus conventional tomatoes was recently proven, the approach to optimize (1)H NMR classification models (comprising overall 205 authentic tomato samples) by including additional data of isotope ratio mass spectrometry (IRMS, δ(13)C, δ(15)N, and δ(18)O) and mid-infrared (MIR) spectroscopy was assessed. Both individual and combined analytical methods ((1)H NMR + MIR, (1)H NMR + IRMS, MIR + IRMS, and (1)H NMR + MIR + IRMS) were examined using principal component analysis (PCA), partial least squares discriminant analysis (PLS-DA), linear discriminant analysis (LDA), and common components and specific weight analysis (ComDim). With regard to classification abilities, fused data of (1)H NMR + MIR + IRMS yielded better validation results (ranging between 95.0 and 100.0%) than individual methods ((1)H NMR, 91.3-100%; MIR, 75.6-91.7%), suggesting that the combined examination of analytical profiles enhances authentication of organically produced tomatoes.

  6. Non-linear modeling of 1H NMR metabonomic data using kernel-based orthogonal projections to latent structures optimized by simulated annealing

    International Nuclear Information System (INIS)

    Fonville, Judith M.; Bylesjoe, Max; Coen, Muireann; Nicholson, Jeremy K.; Holmes, Elaine; Lindon, John C.; Rantalainen, Mattias

    2011-01-01

    Highlights: → Non-linear modeling of metabonomic data using K-OPLS. → automated optimization of the kernel parameter by simulated annealing. → K-OPLS provides improved prediction performance for exemplar spectral data sets. → software implementation available for R and Matlab under GPL v2 license. - Abstract: Linear multivariate projection methods are frequently applied for predictive modeling of spectroscopic data in metabonomic studies. The OPLS method is a commonly used computational procedure for characterizing spectral metabonomic data, largely due to its favorable model interpretation properties providing separate descriptions of predictive variation and response-orthogonal structured noise. However, when the relationship between descriptor variables and the response is non-linear, conventional linear models will perform sub-optimally. In this study we have evaluated to what extent a non-linear model, kernel-based orthogonal projections to latent structures (K-OPLS), can provide enhanced predictive performance compared to the linear OPLS model. Just like its linear counterpart, K-OPLS provides separate model components for predictive variation and response-orthogonal structured noise. The improved model interpretation by this separate modeling is a property unique to K-OPLS in comparison to other kernel-based models. Simulated annealing (SA) was used for effective and automated optimization of the kernel-function parameter in K-OPLS (SA-K-OPLS). Our results reveal that the non-linear K-OPLS model provides improved prediction performance in three separate metabonomic data sets compared to the linear OPLS model. We also demonstrate how response-orthogonal K-OPLS components provide valuable biological interpretation of model and data. The metabonomic data sets were acquired using proton Nuclear Magnetic Resonance (NMR) spectroscopy, and include a study of the liver toxin galactosamine, a study of the nephrotoxin mercuric chloride and a study of

  7. Rearrangement of the distal pocket accompanying E7 His → Gln substitution in elephant carbonmonoxy- and oxymyoglobin: 1H NMR identification of a new aromatic residue in the heme pocket

    International Nuclear Information System (INIS)

    Yu, L.P.; La Mar, G.N.; Mizukami, H.

    1990-01-01

    Two-dimensional 1 H NMR methods have been used to assign side-chain resonances for the residues in the distal heme pocket of elephant carbonmonoxymyoglobin (MbCO) and oxymyoglobin (MbO 2 ). It is shown that, while the other residues in the heme pocket are minimally perturbed, the Phe CD4 residue in elephant MbCO and MbO 2 resonates considerably upfield compared to the corresponding residue in sperm whale MbCO. The new NOE connectivities to Val E11 and heme-induced ring current calculations indicate that Phe CD4 has been inserted into the distal heme pocket by reorienting the aromatic side chain and moving the CD corner closer to the heme. The CζH proton of the Phe CD4 was found to move toward the iron of the heme by ∼4 angstrom relative to the position in sperm whale MbCO, requiring minimally a 3-angstrom movement of the CD helical backbone. The significantly altered distal conformation in elephant myoglobin, rather than the single distal E7 substitution, forms a plausible basis for its altered functional properties of lower autoxidation rate, higher redox potential, and increased affinity for CO ligand. These results demonstrate that one-to-one interpretation of amino acid residue substitution (E7 His → Gln) is oversimplified and that conformational changes of substituted proteins which are not readily predicted have to be considered for interpretation of their functional properties

  8. Highly sensitive high resolution Raman spectroscopy using resonant ionization methods

    International Nuclear Information System (INIS)

    Owyoung, A.; Esherick, P.

    1984-05-01

    In recent years, the introduction of stimulated Raman methods has offered orders of magnitude improvement in spectral resolving power for gas phase Raman studies. Nevertheless, the inherent weakness of the Raman process suggests the need for significantly more sensitive techniques in Raman spectroscopy. In this we describe a new approach to this problem. Our new technique, which we call ionization-detected stimulated Raman spectroscopy (IDSRS), combines high-resolution SRS with highly-sensitive resonant laser ionization to achieve an increase in sensitivity of over three orders of magnitude. The excitation/detection process involves three sequential steps: (1) population of a vibrationally excited state via stimulated Raman pumping; (2) selective ionization of the vibrationally excited molecule with a tunable uv source; and (3) collection of the ionized species at biased electrodes where they are detected as current in an external circuit

  9. Spectroscopy 101: A Practical Introduction to Spectroscopy and Analysis for Undergraduate Organic Chemistry Laboratories

    Science.gov (United States)

    Morrill, Lucas A.; Kammeyer, Jacquelin K.; Garg, Neil K.

    2017-01-01

    An undergraduate organic chemistry laboratory that provides an introduction to various spectroscopic techniques is reported. Whereas organic spectroscopy is most often learned and practiced in the context of reaction analyses, this laboratory experiment allows students to become comfortable with [superscript 1]H NMR, [superscript 13]C NMR, and IR…

  10. Sensitivity of Raman spectroscopy to normal patient variability

    Science.gov (United States)

    Vargis, Elizabeth; Byrd, Teresa; Logan, Quinisha; Khabele, Dineo; Mahadevan-Jansen, Anita

    2011-11-01

    Many groups have used Raman spectroscopy for diagnosing cervical dysplasia; however, there have been few studies looking at the effect of normal physiological variations on Raman spectra. We assess four patient variables that may affect normal Raman spectra: Race/ethnicity, body mass index (BMI), parity, and socioeconomic status. Raman spectra were acquired from a diverse population of 75 patients undergoing routine screening for cervical dysplasia. Classification of Raman spectra from patients with a normal cervix is performed using sparse multinomial logistic regression (SMLR) to determine if any of these variables has a significant effect. Results suggest that BMI and parity have the greatest impact, whereas race/ethnicity and socioeconomic status have a limited effect. Incorporating BMI and obstetric history into classification algorithms may increase sensitivity and specificity rates of disease classification using Raman spectroscopy. Studies are underway to assess the effect of these variables on disease.

  11. Sensitivity Increases for the TITAN Decay Spectroscopy Program

    Directory of Open Access Journals (Sweden)

    Leach K.G.

    2015-01-01

    Full Text Available The TITAN facility at TRIUMF has recently initiated a program of performing decay spectroscopy measurements in an electron-beam ion-trap (EBIT. The unique environment of the EBIT provides backingfree storage of the radioactive ions, while guiding charged decay particles from the trap centre via the strong magnetic field. This measurement technique is able to provide a significant increase in detection sensitivity for photons which result from radioactive decay. A brief overview of this device is presented, along with methods of improving the signal-to-background ratio for photon detection by reducing Compton scattered events, and eliminating vibrational noise.

  12. Coordinate-sensitive charged particle detector for spectroscopy

    Directory of Open Access Journals (Sweden)

    Sidorenko V. P.

    2016-10-01

    Full Text Available The authors have designed, manufactured and tested a coordinate-sensitive detector for charged particle spectroscopy. The detector can be used in the devices for the elemental analysis of materials, providing simultaneous analysis of all the elemental composition with high sensitivity and precision. The designed device is based on an integrated circuit (IC and a microchannel plate (MCP electron multiplier. The IC is mounted on a ceramic substrate. Ions fall on the MCP mounted above the IC. Giving rise to a pulse which typically exceeds 106 electrons, each ion falls on the detector electrodes and these pulses are counted. In this research, a two stage stack of MCPs (Hamamatsu was used. The MCPs have a channel diameter of 12 μm on a 15 μm pitch. The results of tests carried out in a mass spectrometer are presented. The designed detector is small, light, and low-power.

  13. Dye-sensitized solar cells with natural dyes extracted from achiote seeds

    Energy Technology Data Exchange (ETDEWEB)

    Gomez-Ortiz, N.M.; Vazquez-Maldonado, I.A.; Azamar-Barrios, J.A.; Oskam, G. [Departamento de Fisica Aplicada, CINVESTAV-IPN, Merida, Yuc. 97310 (Mexico); Perez-Espadas, A.R.; Mena-Rejon, G.J. [Laboratorio de Quimica Organica de Investigacion, Facultad de Quimica, Universidad Autonoma de Yucatan, Merida, Yuc. 97150 (Mexico)

    2010-01-15

    We have explored the application of natural dyes extracted from the seeds of the achiote shrub (Bixa orellana L.) in dye-sensitized solar cells (DSCs). The main pigments are bixin and norbixin, which were obtained by separation and purification from the dark-red extract (annatto). The dyes were characterized using {sup 1}H-NMR, FTIR spectroscopy, and UV-Vis spectrophotometry. Solar cells were prepared using TiO{sub 2} and ZnO nanostructured, mesoporous films and the annatto, bixin, and norbixin as sensitizers. The best results were obtained with bixin-sensitized TiO{sub 2} solar cells with efficiencies of up to 0.53%, illustrating the importance of purification of dyes from natural extracts. (author)

  14. Principal component analysis for verifying {sup 1}H NMR spectral assignments. The case of 3-aryl (1,2,4)-oxadiazole-5-carbohydrazide benzylidene; Aplicacao de analise de componentes principais para verificacao de atribuicoes de sinais nos espetros de RMN 1H. O caso dos 3-aril (1,2,4)-oxadiazol-5-carboidrazida benzilidenos

    Energy Technology Data Exchange (ETDEWEB)

    Silva, Joao Bosco P. da; Malvestiti, Ivani; Hallwass, Fernando; Ramos, Mozart N. [Pernambuco Univ., Recife, PE (Brazil). Dept. de Quimica Fundamental]. E-mail: paraiso@ufpe.br; Leite, Lucia F.C. da Costa [Universidade Catolica de Pernambuco, Recife, PE (Brazil). Dept. de Quimica; Barreiro, Eliezer J. [Universidade Federal, Rio de Janeiro, RJ (Brazil). Faculdade de Farmacia

    2005-06-01

    The {sup 1}H NMR data set of a series of 3-aryl (1,2,4)-oxadiazole-5-carbohydrazide benzylidene derivatives synthesized in our group was analyzed using the chemometric technique of principal component analysis (PCA). Using the original 1H NMR data PCA allowed identifying some misassignments of the proton aromatic chemical shifts. As a consequence of this multivariate analysis, nuclear Overhauser difference experiments were performed to investigate the ambiguity of other assignments of the ortho and meta aromatic hydrogens for the compound with the bromine substituent. The effect of the 1,2,4-oxadiazole group as an electron acceptor, mainly for the hydrogens 12,13, has been highlighted. (author)

  15. Structure determination by 1H NMR spectroscopy of (sulfated) sialylated N-linked carbohydrate chains released from porcine thyroglobulin by peptide-N4-(N-acetyl-β-glucosaminyl)asparagine amidase-F

    NARCIS (Netherlands)

    Vliegenthart, J.F.G.; Waard, P. de; Koorevaar, A.; Kamerling, J.P.

    1991-01-01

    The N-linked carbohydrate chains of porcine thyroglobulin were released by peptide-N4-(N-acetyl-β-glucosaminyl)asparagine amidase-F (PNGase- F). The resulting oligosaccharides were fractionated by a combination of fast protein liquid chromatography and high performance liquid chromatography and

  16. Highly Functionalised Cyclopentanes by Radical Cyclisation of Unsaturated Bromolactones III. Preparation of Carbaaldohexofuranoses. - Determination of the Relative Configuration at C-4/C-5 of 2,3-Unsaturated heptono-1,4-lactones by Means of 1-H NMR Spectroscopy

    DEFF Research Database (Denmark)

    Lundt, Inge; Horneman, Anne Marie

    1999-01-01

    Two new carbaaldohexofuranoses, carba--D-glucofuranose and carba--L-mannofuranose have been prepared using 5,6-O-isopropylidene-D-glycero-L-galacto-heptono-1,4-lactone (6) as the starting material. The key step was a highly stereoselective intramolecular 5-exo-trig radical cyclisation of C-2......-substituted 2,3-unsaturated 7-bromo-7-deoxy-heptono-1,4-lactones promoted by tributyltin hydride. Assignment of the configuration of the unsaturated lactones was based upon NMR data of related compounds. The starting material, compound 6, was obtained by chain elongation of D-gulose, and a facile method...

  17. Chiral discrimination of sibutramine enantiomers by capillary electrophoresis and proton nuclear magnetic resonance spectroscopy.

    Science.gov (United States)

    Lee, Yong-Jae; Choi, Seungho; Lee, Jinhoo; Nguyen, NgocVan Thi; Lee, Kyungran; Kang, Jong Seong; Mar, Woongchon; Kim, Kyeong Ho

    2012-03-01

    Capillary electrophoresis (CE) and proton nuclear magnetic resonance spectroscopy ((1)H-NMR) have been used to discriminate the enantiomers of sibutramine using cyclodextrin derivatives. Possible correlation between CE and (1)H-NMR was examined. Good correlation between the (1)H-NMR shift non-equivalence data for sibutramine and the degree of enantioseparation in CE was observed. In CE study, a method of enantiomeric separation and quantitation of sibutramine was developed using enantiomeric standards. The method was based on the use of 50 mM of phosphate buffer of pH 3.0 with 10 mM of methyl-beta-cyclodextrin (M-β-CD). 0.05% of LOD, 0.2% of LOQ for S-sibutramine enantiomer was achieved, and the method was validated and applied to the quantitative determination of sibutramine enantiomers in commercial drugs. On a 600 MHz (1)H-NMR analysis, enantiomer signal separation of sibutramine was obtained by fast diastereomeric interaction with a chiral selector M-β-CD. For chiral separation and quantification, N-methyl proton peaks (at 2.18 ppm) were selected because of its being singlet and simple for understanding of diastereomeric interaction. Effects of temperature and concentration of chiral selector on enantiomer signal separation were investigated. The optimum condition was 0.5 mg/mL of sibutramine and 10 mg/mL of M-β-CD at 10°C. Distinguishment of 0.5% of S-sibutramine in R-sibutramine was found to be possible by (1)H-NMR with M-β-CD as chiral selector. Host-guest interaction between sibutramine and M-β-CD was confirmed by (1)H-NMR studies and CE studies. A Structure of the inclusion complex was proposed considering (1)H-NMR and 2D ROESY studies.

  18. 1H NMR relaxometry and quadrupole relaxation enhancement as a sensitive probe of dynamical properties of solids—[C(NH2)3]3Bi2I9 as an example

    International Nuclear Information System (INIS)

    Florek-Wojciechowska, M.; Wojciechowski, M.; Brym, Sz.; Kruk, D.; Jakubas, R.

    2016-01-01

    1 H nuclear magnetic resonance relaxometry has been applied to reveal information on dynamics and structure of Gu 3 Bi 2 I 9 ([Gu = C(NH 2 ) 3 ] denotes guanidinium cation). The data have been analyzed in terms of a theory of quadrupole relaxation enhancement, which has been extended here by including effects associated with quadrupole ( 14 N) spin relaxation caused by a fast fluctuating component of the electric field gradient tensor. Two motional processes have been identified: a slow one occurring on a timescale of about 8 × 10 −6 s which has turned out to be (almost) temperature independent, and a fast process in the range of 10 −9 s. From the 1 H- 14 N relaxation contribution (that shows “quadrupole peaks”) the quadrupole parameters, which are a fingerprint of the arrangement of the anionic network, have been determined. It has been demonstrated that the magnitude of the quadrupole coupling considerably changes with temperature and the changes are not caused by phase transitions. At the same time, it has been shown that there is no evidence of abrupt changes in the cationic dynamics and the anionic substructure upon the phase transitions

  19. 1H NMR relaxometry and quadrupole relaxation enhancement as a sensitive probe of dynamical properties of solids—[C(NH2)3]3Bi2I9 as an example

    Science.gov (United States)

    Florek-Wojciechowska, M.; Wojciechowski, M.; Jakubas, R.; Brym, Sz.; Kruk, D.

    2016-02-01

    1H nuclear magnetic resonance relaxometry has been applied to reveal information on dynamics and structure of Gu3Bi2I9 ([Gu = C(NH2)3] denotes guanidinium cation). The data have been analyzed in terms of a theory of quadrupole relaxation enhancement, which has been extended here by including effects associated with quadrupole (14N) spin relaxation caused by a fast fluctuating component of the electric field gradient tensor. Two motional processes have been identified: a slow one occurring on a timescale of about 8 × 10-6 s which has turned out to be (almost) temperature independent, and a fast process in the range of 10-9 s. From the 1H-14N relaxation contribution (that shows "quadrupole peaks") the quadrupole parameters, which are a fingerprint of the arrangement of the anionic network, have been determined. It has been demonstrated that the magnitude of the quadrupole coupling considerably changes with temperature and the changes are not caused by phase transitions. At the same time, it has been shown that there is no evidence of abrupt changes in the cationic dynamics and the anionic substructure upon the phase transitions.

  20. Improvement of sensitivity in high-resolution Rutherford backscattering spectroscopy

    International Nuclear Information System (INIS)

    Hashimoto, H.; Nakajima, K.; Suzuki, M.; Kimura, K.; Sasakawa, K.

    2011-01-01

    The sensitivity (limit of detection) of high-resolution Rutherford backscattering spectroscopy (HRBS) is mainly determined by the background noise of the spectrometer. There are two major origins of the background noise in HRBS, one is the stray ions scattered from the inner wall of the vacuum chamber of the spectrometer and the other is the dark noise of the microchannel plate (MCP) detector which is commonly used as a focal plane detector of the spectrometer in HRBS. In order to reject the stray ions, several barriers are installed inside the spectrometer and a thin Mylar foil is mounted in front of the detector. The dark noise of the MCP detector is rejected by the coincidence measurement with the secondary electrons emitted from the Mylar foil upon the ion passage. After these improvements, the background noise is reduced by a factor of 200 at a maximum. The detection limit can be improved down to 10 ppm for As in Si at a measurement time of 1 h under ideal conditions.

  1. Interaction and transport of cysteamine (MEA) through membrane models. {sup 15}N-NMR et {sup 1}H-NMR; Interaction et transport de la cysteamine (MEA) a travers des membranes modeles. Etude par {sup 15}N-RMN et {sup 1}H-RMN

    Energy Technology Data Exchange (ETDEWEB)

    Lagoueyte, C.; Subra, G.; Bonnet, P.A.; Chapat, J.P.; Debouzy, J.C.; Fauvelle, F.; Berleur, F.; Roman, V.; Fatome, M.; Fernandez, J.P.

    1995-12-31

    We investigated by {sup 15}N-NMR the interactions of [{sup 15}N]-MEA, a radio-protecting aminothiol, with model membranes (SUVs and LUVs) of egg yolk phosphatidylcholine and phosphatidic acid. We prepared LUVs with a pH gradient between the intravesicular space and the bulk medium. Even though the external pH was low, MEA penetrates into the vesicles. With SUVs, {sup 1}H-NMR revealed that the interactions of unlabeled MEA within the hydrophobic core of the bilayer vary with external pH value. (author). 5 refs.

  2. Využití axiálně chirálních karbamátů a karbonátů pro stanovení absolutní konfigurace aminů a alkoholů metodou 1H NMR

    Czech Academy of Sciences Publication Activity Database

    Hartwich, Petr; Streinz, Ludvík

    2006-01-01

    Roč. 100, č. 5 (2006), s. 382-382 ISSN 0009-2770. [Mezioborové setkání mladých vědeckých a výzkumných pracovníků z oboru chemie, biochemie, molekulární biologie a oborů příbuzných. Konference Sigma-Aldrich /6./. 14.06.2006-17.06.2006, Devět skal] Institutional research plan: CEZ:AV0Z50070508 Keywords : 1H NMR method Subject RIV: CB - Analytical Chemistry, Separation

  3. In vivo 31P and 1H NMR studies of rat brain tumor pH and blood flow during acute hyperglycemia: Differential effects between subcutaneous and intracerebral locations

    International Nuclear Information System (INIS)

    Ross, B.D.; Mitchell, S.L.; Merkle, H.; Garwood, M.

    1989-01-01

    Surface coil NMR spectroscopy was used to monitor the hyperglycemia-induced alterations in pH and blood flow in vivo in C6 gliomas implanted both subcutaneously and intracerebrally in rats. Tumor pH was calculated from the chemical shift difference between PCr and Pi in the 31 P NMR spectra. Subcutaneous glioma pH decreased 0.8 units by 1 h after intraperitoneal administration of an aqueous 50% glucose solution (6 g glucose per kg body weight). In contrast, hyperglycemia failed to significantly alter the pH of intracerebral gliomas which were monitored for 90 min following administration of glucose. Tumor blood flow (TBF) was determined both pre- and post-glucose administration using deuterium NMR by monitoring the time course of D2O washout following intratumoral injection of saline D2O. Subcutaneous and intracerebral TBF were found to have an average change of -78.1% (range -47.4 to -93.3%, n = 5) and -21.1% (range +6.0 to -37.8%, n = 9), respectively. In addition, laser Doppler blood flow measurements of rat skin and subcutaneous glioma revealed a dramatic reduction in blood flow in both tissues following glucose administration. These results indicate that the effects of acute hyperglycemia are site dependent and that hyperglycemia alone is not beneficial for inducing intracellular acidosis in intracerebral tumors

  4. Sensitivity-enhanced 13C MR spectroscopy of the human brain at 3 Tesla.

    NARCIS (Netherlands)

    Klomp, D.W.J.; Renema, W.K.J.; Graaf, M. de; Galan, B.E. de; Kentgens, A.P.M.; Heerschap, A.

    2006-01-01

    A new coil design for sensitivity-enhanced 13C MR spectroscopy (MRS) of the human brain is presented. The design includes a quadrature transmit/receive head coil optimized for 13C MR sensitivity. Loss-less blocking circuits inside the coil conductors allow this coil to be used inside a homogeneous

  5. Sensitivity-enhanced C-13 MR spectroscopy of the human brain at 3 Tesla

    NARCIS (Netherlands)

    Klomp, D.W.J.; Renema, W.K.J.; Graaf, M. van der; Galan, B.E. de; Kentgens, A.P.M.; Heerschap, A.

    2006-01-01

    A new coil design for sensitivity-enhanced C-13 MR spectroscopy (MRS) of the human brain is presented. The design includes a quadrature transmit/receive head coil optimized for C-13 MR sensitivity. Loss-less blocking circuits inside the coil conductors allow this coil to be used inside a homogeneous

  6. Resonance raman spectroscopy of an ultraviolet-sensitive insect rhodopsin

    International Nuclear Information System (INIS)

    Pande, C.; Deng, H.; Rath, P.; Callender, R.H.; Schwemer, J.

    1987-01-01

    The authors present the first visual pigment resonance Raman spectra from the UV-sensitive eyes of an insect, Ascalaphus macaronius (owlfly). This pigment contains 11-cis-retinal as the chromophore. Raman data have been obtained for the acid metarhodopsin at 10 0 C in both H 2 O and D 2 O. The C=N stretching mode at 1660 cm -1 in H 2 O shifts to 1631 cm -1 upon deuteriation of the sample, clearly showing a protonated Schiff base linkage between the chromophore and the protein. The structure-sensitive fingerprint region shows similarities to the all-trans-protonated Schiff base of model retinal chromophores, as well as to the octopus acid metarhodopsin and bovine metarhodopsin I. Although spectra measured at -100 0 C with 406.7-nm excitation, to enhance scattering from rhodopsin (λ/sub max/ 345 nm), contain a significant contribution from a small amount of contaminants [cytochrome(s) and/or accessory pigment] in the sample, the C=N stretch at 1664 cm -1 suggests a protonated Schiff base linkage between the chromophore and the protein in rhodopsin as well. For comparison, this mode also appears at ∼ 1660 cm -1 in both the vertebrate (bovine) and the invertebrate (octopus) rhodopsins. These data are particularly interesting since the absorption maximum of 345 nm for rhodopsin might be expected to originate from an unprotonated Schiff base linkage. That the Schiff base linkage in the owlfly rhodopsin, like in bovine and in octopus, is protonated suggests that a charged chromophore is essential to visual transduction

  7. Sensitivity of near-infrared spectroscopy and diffuse correlation spectroscopy to brain hemodynamics: simulations and experimental findings during hypercapnia

    Science.gov (United States)

    Selb, Juliette; Boas, David A.; Chan, Suk-Tak; Evans, Karleyton C.; Buckley, Erin M.; Carp, Stefan A.

    2014-01-01

    Abstract. Near-infrared spectroscopy (NIRS) and diffuse correlation spectroscopy (DCS) are two diffuse optical technologies for brain imaging that are sensitive to changes in hemoglobin concentrations and blood flow, respectively. Measurements for both modalities are acquired on the scalp, and therefore hemodynamic processes in the extracerebral vasculature confound the interpretation of cortical hemodynamic signals. The sensitivity of NIRS to the brain versus the extracerebral tissue and the contrast-to-noise ratio (CNR) of NIRS to cerebral hemodynamic responses have been well characterized, but the same has not been evaluated for DCS. This is important to assess in order to understand their relative capabilities in measuring cerebral physiological changes. We present Monte Carlo simulations on a head model that demonstrate that the relative brain-to-scalp sensitivity is about three times higher for DCS (0.3 at 3 cm) than for NIRS (0.1 at 3 cm). However, because DCS has higher levels of noise due to photon-counting detection, the CNR is similar for both modalities in response to a physiologically realistic simulation of brain activation. Even so, we also observed higher CNR of the hemodynamic response during graded hypercapnia in adult subjects with DCS than with NIRS. PMID:25453036

  8. Sensitivity of near-infrared spectroscopy and diffuse correlation spectroscopy to brain hemodynamics: simulations and experimental findings during hypercapnia.

    Science.gov (United States)

    Selb, Juliette; Boas, David A; Chan, Suk-Tak; Evans, Karleyton C; Buckley, Erin M; Carp, Stefan A

    2014-07-01

    Near-infrared spectroscopy (NIRS) and diffuse correlation spectroscopy (DCS) are two diffuse optical technologies for brain imaging that are sensitive to changes in hemoglobin concentrations and blood flow, respectively. Measurements for both modalities are acquired on the scalp, and therefore hemodynamic processes in the extracerebral vasculature confound the interpretation of cortical hemodynamic signals. The sensitivity of NIRS to the brain versus the extracerebral tissue and the contrast-to-noise ratio (CNR) of NIRS to cerebral hemodynamic responses have been well characterized, but the same has not been evaluated for DCS. This is important to assess in order to understand their relative capabilities in measuring cerebral physiological changes. We present Monte Carlo simulations on a head model that demonstrate that the relative brain-to-scalp sensitivity is about three times higher for DCS (0.3 at 3 cm) than for NIRS (0.1 at 3 cm). However, because DCS has higher levels of noise due to photon-counting detection, the CNR is similar for both modalities in response to a physiologically realistic simulation of brain activation. Even so, we also observed higher CNR of the hemodynamic response during graded hypercapnia in adult subjects with DCS than with NIRS.

  9. The Use and Evaluation of Scaffolding, Student Centered-Learning, Behaviorism, and Constructivism to Teach Nuclear Magnetic Resonance and IR Spectroscopy in a Two-Semester Organic Chemistry Course

    Science.gov (United States)

    Livengood, Kimberly; Lewallen, Denver W.; Leatherman, Jennifer; Maxwell, Janet L.

    2012-01-01

    Since 2002, infrared spectroscopy (IR) and nuclear magnetic resonance (NMR) spectrometry have been introduced at the beginning of the first-semester organic chemistry lab course at this university. Starting in 2008, each individual student was given 20 unique homework problems that consisted of multiple-choice [superscript 1]H NMR and IR problems…

  10. Resolving molecular vibronic structure using high-sensitivity two-dimensional electronic spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Bizimana, Laurie A.; Brazard, Johanna; Carbery, William P.; Gellen, Tobias; Turner, Daniel B., E-mail: dturner@nyu.edu [Department of Chemistry, New York University, 100 Washington Square East, New York, New York 10003 (United States)

    2015-10-28

    Coherent multidimensional optical spectroscopy is an emerging technique for resolving structure and ultrafast dynamics of molecules, proteins, semiconductors, and other materials. A current challenge is the quality of kinetics that are examined as a function of waiting time. Inspired by noise-suppression methods of transient absorption, here we incorporate shot-by-shot acquisitions and balanced detection into coherent multidimensional optical spectroscopy. We demonstrate that implementing noise-suppression methods in two-dimensional electronic spectroscopy not only improves the quality of features in individual spectra but also increases the sensitivity to ultrafast time-dependent changes in the spectral features. Measurements on cresyl violet perchlorate are consistent with the vibronic pattern predicted by theoretical models of a highly displaced harmonic oscillator. The noise-suppression methods should benefit research into coherent electronic dynamics, and they can be adapted to multidimensional spectroscopies across the infrared and ultraviolet frequency ranges.

  11. Secondary structure of bovine albumin as studied by polarization-sensitive multiplex CARS spectroscopy

    NARCIS (Netherlands)

    Voroshilov, A.; Voroshilov, Artemy; Otto, Cornelis; Greve, Jan

    1996-01-01

    The first application of polarization-sensitive multiplex coherent anti-Stokes Raman spectroscopy (MCARS) in the absence of resonance enhancement to the resolution of the secondary structure of a protein in solution is reported. Polarization MCARS spectra of bovine albumin in D2O were obtained in

  12. New enhanced sensitivity infrared laser spectroscopy techniques applied to reactive plasmas and trace gas detection

    NARCIS (Netherlands)

    Welzel, S.

    2009-01-01

    Infrared laser absorption spectroscopy (IRLAS) employing both tuneable diode and quantum cascade lasers (TDLs, QCLs) has been applied with both high sensitivity and high time resolution to plasma diagnostics and trace gas measurements. TDLAS combined with a conventional White type multiple pass cell

  13. Sensitivity Analysis and Requirements for Temporally and Spatially Resolved Thermometry Using Neutron Resonance Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Fernandez, Juan Carlos [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Barnes, Cris William [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Mocko, Michael Jeffrey [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Zavorka, Lukas [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2018-01-31

    This report is intended to examine the use of neutron resonance spectroscopy (NRS) to make time- dependent and spatially-resolved temperature measurements of materials in extreme conditions. Specifically, the sensitivities of the temperature estimate on neutron-beam and diagnostic parameters is examined. Based on that examination, requirements are set on a pulsed neutron-source and diagnostics to make a meaningful measurement.

  14. Improved Sensitivity of Spectroscopic Quantification of Stable Isotope Content Using Capillary Absorption Spectroscopy

    Science.gov (United States)

    Moran, J.; Wilcox Freeburg, E.; Kriesel, J.; Linley, T. J.; Kelly, J.; Coleman, M. L.; Christensen, L. E.; Vance, S.

    2016-12-01

    Spectroscopy-based platforms have recently risen to the forefront for making stable isotope measurements of methane, carbon dioxide, water, or other analytes. These spectroscopy systems can be relatively straightforward to operate (versus a mass spectrometry platform), largely relieve the analyst of mass interference artifacts, and many can be used in the field. Despite these significant advantages, however, existing spectroscopy techniques suffer from a lack of measurement sensitivity that can ultimately limit select applications including spatially resolved and compound-specific measurements. Here we present a capillary absorption spectroscopy (CAS) system that is designed to mitigate sensitivity issues in spectroscopy-based stable isotope evaluation. The system uses mid-wave infrared excitation generated from a continuous wave quantum cascade laser. Importantly, the sample `chamber' is a flexible capillary with a total volume of less than one cc. Proprietary coatings on the internal surface of the fiber improve optical performance, guiding the light to a detector and facilitating high levels of interaction between the laser beam and gaseous analytes. We present data demonstrating that a tapered hollow fiber cell, with an internal diameter that broadens toward the detector, reduces optical feedback to further improve measurement sensitivity. Sensitivity of current hollow fiber / CAS systems enable measurements of only 10's of picomoles CO2 while theoretical improvements should enable measurements of as little as 10's of femtomoles. Continued optimization of sample introduction and improvements to optical feedback are being explored. Software is being designed to provide rapid integration of data and generation of processed isotope measurements using a graphical user interface. Taken together, the sensitivity improvements of the CAS system under development could, when coupled to a laser ablation sampling device, enable up to 2 µm spatial resolution (roughly the

  15. A 1H NMR-based metabolomics approach to evaluate the geographical authenticity of herbal medicine and its application in building a model effectively assessing the mixing proportion of intentional admixtures: A case study of Panax ginseng: Metabolomics for the authenticity of herbal medicine.

    Science.gov (United States)

    Nguyen, Huy Truong; Lee, Dong-Kyu; Choi, Young-Geun; Min, Jung-Eun; Yoon, Sang Jun; Yu, Yun-Hyun; Lim, Johan; Lee, Jeongmi; Kwon, Sung Won; Park, Jeong Hill

    2016-05-30

    Ginseng, the root of Panax ginseng has long been the subject of adulteration, especially regarding its origins. Here, 60 ginseng samples from Korea and China initially displayed similar genetic makeup when investigated by DNA-based technique with 23 chloroplast intergenic space regions. Hence, (1)H NMR-based metabolomics with orthogonal projections on the latent structure-discrimination analysis (OPLS-DA) were applied and successfully distinguished between samples from two countries using seven primary metabolites as discrimination markers. Furthermore, to recreate adulteration in reality, 21 mixed samples of numerous Korea/China ratios were tested with the newly built OPLS-DA model. The results showed satisfactory separation according to the proportion of mixing. Finally, a procedure for assessing mixing proportion of intentionally blended samples that achieved good predictability (adjusted R(2)=0.8343) was constructed, thus verifying its promising application to quality control of herbal foods by pointing out the possible mixing ratio of falsified samples. Copyright © 2016 Elsevier B.V. All rights reserved.

  16. Voxel-based measurement sensitivity of spatially resolved near-infrared spectroscopy in layered tissues.

    Science.gov (United States)

    Niwayama, Masatsugu

    2018-03-01

    We quantitatively investigated the measurement sensitivity of spatially resolved spectroscopy (SRS) across six tissue models: cerebral tissue, a small animal brain, the forehead of a fetus, an adult brain, forearm muscle, and thigh muscle. The optical path length in the voxel of the model was analyzed using Monte Carlo simulations. It was found that the measurement sensitivity can be represented as the product of the change in the absorption coefficient and the difference in optical path length in two states with different source-detector distances. The results clarified the sensitivity ratio between the surface layer and the deep layer at each source-detector distance for each model and identified changes in the deep measurement area when one of the detectors was close to the light source. A comparison was made with the results from continuous-wave spectroscopy. The study also identified measurement challenges that arise when the surface layer is inhomogeneous. Findings on the measurement sensitivity of SRS at each voxel and in each layer can support the correct interpretation of measured values when near-infrared oximetry or functional near-infrared spectroscopy is used to investigate different tissue structures. (2018) COPYRIGHT Society of Photo-Optical Instrumentation Engineers (SPIE).

  17. Impact of sensor metal thickness on microwave spectroscopy sensitivity for individual particles and biological cells analysis

    OpenAIRE

    Chen , Wenli; Dubuc , David; Grenier , Katia

    2016-01-01

    International audience; This paper focuses on evaluating the impact of metal thickness of a microwave coplanar based sensor dedicated to the microwave dielectric spectroscopy of single particles and individual biological cells. A sensitivity study has therefore been achieved for metal thicknesses comprised between 0.3 and 20 µm. After the validation of electromagnetic simulations with measurements of 10 μm-diameter polystyrene bead, both capacitive and conductive contrasts have been defined f...

  18. Raman spectroscopy differentiates between sensitive and resistant multiple myeloma cell lines

    Science.gov (United States)

    Franco, Domenico; Trusso, Sebastiano; Fazio, Enza; Allegra, Alessandro; Musolino, Caterina; Speciale, Antonio; Cimino, Francesco; Saija, Antonella; Neri, Fortunato; Nicolò, Marco S.; Guglielmino, Salvatore P. P.

    2017-12-01

    Current methods for identifying neoplastic cells and discerning them from their normal counterparts are often nonspecific and biologically perturbing. Here, we show that single-cell micro-Raman spectroscopy can be used to discriminate between resistant and sensitive multiple myeloma cell lines based on their highly reproducible biomolecular spectral signatures. In order to demonstrate robustness of the proposed approach, we used two different cell lines of multiple myeloma, namely MM.1S and U266B1, and their counterparts MM.1R and U266/BTZ-R subtypes, resistant to dexamethasone and bortezomib, respectively. Then, micro-Raman spectroscopy provides an easily accurate and noninvasive method for cancer detection for both research and clinical environments. Characteristic peaks, mostly due to different DNA/RNA ratio, nucleic acids, lipids and protein concentrations, allow for discerning the sensitive and resistant subtypes. We also explored principal component analysis (PCA) for resistant cell identification and classification. Sensitive and resistant cells form distinct clusters that can be defined using just two principal components. The identification of drug-resistant cells by confocal micro-Raman spectroscopy is thus proposed as a clinical tool to assess the development of resistance to glucocorticoids and proteasome inhibitors in myeloma cells.

  19. Preparation of the Fv fragment from a short-chain mouse IgG2a anti-dansyl monoclonal antibody and use of selectively deuterated Fv analogues for two-dimensional 1H NMR analyses fo the antigen-antibody interactions

    International Nuclear Information System (INIS)

    Takahashi, Hideo; Igarashi, Takako; Shimada, Ichio; Arata, Yoji

    1991-01-01

    The Fv fragment, a univalent antigen-binding unit with a molecular weight of 25,000, has successfully been prepared in high yield by limited proteolysis with clostripain of a short-chain mouse IgG2a anti-dansyl monoclonal antibody in which the entire C H 1 domain is deleted. The Fv fragment obtained is stable at room temperature and retains its full antigen-binding capability. It has been shown that selective deuterium labeling of the Fv fragment, which is half the size of the Fab fragment, provides 1 H NMR spectral data at a sufficient resolution for a detailed structural analysis of the antigen-combining site. NOESY spectra of an Fv analogue, in which all aromatic protons except for His C2'-H and Tyr C3',5'-H had been deuterated, were measured in the presence of varying amounts of dansyl-L-lysine. On the basis of the NOESY data obtained, it was possible to assign all the ring proton resonances for the dansly group that is bound to the Fv fragment. It was also possible to obtain information about His and Tyr residues of the Fv fragment in the absence and presence of the antigen. On the basis of the NMR data obtained, the authors have shown that at least two Tyr residues along with one of the amide groups are directly involved in antigen binding. The mode of interaction of the dansyl ring with these residues in the Fv fragment has briefly been discussed

  20. Preparation of the Fv fragment from a short-chain mouse IgG2a anti-dansyl monoclonal antibody and use of selectively deuterated Fv analogues for two-dimensional sup 1 H NMR analyses fo the antigen-antibody interactions

    Energy Technology Data Exchange (ETDEWEB)

    Takahashi, Hideo; Igarashi, Takako; Shimada, Ichio; Arata, Yoji (Univ. of Tokyo (Japan))

    1991-03-19

    The Fv fragment, a univalent antigen-binding unit with a molecular weight of 25,000, has successfully been prepared in high yield by limited proteolysis with clostripain of a short-chain mouse IgG2a anti-dansyl monoclonal antibody in which the entire C{sub H}1 domain is deleted. The Fv fragment obtained is stable at room temperature and retains its full antigen-binding capability. It has been shown that selective deuterium labeling of the Fv fragment, which is half the size of the Fab fragment, provides {sup 1}H NMR spectral data at a sufficient resolution for a detailed structural analysis of the antigen-combining site. NOESY spectra of an Fv analogue, in which all aromatic protons except for His C2{prime}-H and Tyr C3{prime},5{prime}-H had been deuterated, were measured in the presence of varying amounts of dansyl-L-lysine. On the basis of the NOESY data obtained, it was possible to assign all the ring proton resonances for the dansly group that is bound to the Fv fragment. It was also possible to obtain information about His and Tyr residues of the Fv fragment in the absence and presence of the antigen. On the basis of the NMR data obtained, the authors have shown that at least two Tyr residues along with one of the amide groups are directly involved in antigen binding. The mode of interaction of the dansyl ring with these residues in the Fv fragment has briefly been discussed.

  1. Synthesis, spectroscopy, thermal studies and supramolecular ...

    Indian Academy of Sciences (India)

    TECS

    Synthesis, spectroscopy, thermal studies and supramolecular structures of two .... J = 9 Hz), 8∙13 (d, 2H, J = 9 Hz), 7∙69 (s, 1H), 7∙04. (s, 2H). ... 1H NMR (D2O): δ (in ppm); 8∙05 (d, 2H, ..... 86∙33 (2). 86∙92(1). 87∙08(2). V (Ε3). 553∙1(6). 573∙71(5). 561∙56(14). 557∙5(3) .... Mn, Co and Ni complexes.28–30 The observed inter-.

  2. A microwave resonator for limiting depth sensitivity for electron paramagnetic resonance spectroscopy of surfaces.

    Science.gov (United States)

    Sidabras, Jason W; Varanasi, Shiv K; Mett, Richard R; Swarts, Steven G; Swartz, Harold M; Hyde, James S

    2014-10-01

    A microwave Surface Resonator Array (SRA) structure is described for use in Electron Paramagnetic Resonance (EPR) spectroscopy. The SRA has a series of anti-parallel transmission line modes that provides a region of sensitivity equal to the cross-sectional area times its depth sensitivity, which is approximately half the distance between the transmission line centers. It is shown that the quarter-wave twin-lead transmission line can be a useful element for design of microwave resonators at frequencies as high as 10 GHz. The SRA geometry is presented as a novel resonator for use in surface spectroscopy where the region of interest is either surrounded by lossy material, or the spectroscopist wishes to minimize signal from surrounding materials. One such application is in vivo spectroscopy of human finger-nails at X-band (9.5 GHz) to measure ionizing radiation dosages. In order to reduce losses associated with tissues beneath the nail that yield no EPR signal, the SRA structure is designed to limit depth sensitivity to the thickness of the fingernail. Another application, due to the resonator geometry and limited depth penetration, is surface spectroscopy in coating or material science. To test this application, a spectrum of 1.44 μM of Mg(2+) doped polystyrene 1.1 mm thick on an aluminum surface is obtained. Modeling, design, and simulations were performed using Wolfram Mathematica (Champaign, IL; v. 9.0) and Ansys High Frequency Structure Simulator (HFSS; Canonsburg, PA; v. 15.0). A micro-strip coupling circuit is designed to suppress unwanted modes and provide a balanced impedance transformation to a 50 Ω coaxial input. Agreement between simulated and experimental results is shown.

  3. A microwave resonator for limiting depth sensitivity for electron paramagnetic resonance spectroscopy of surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Sidabras, Jason W.; Varanasi, Shiv K.; Hyde, James S. [Department of Biophysics, Medical College of Wisconsin, Milwaukee, Wisconsin 53211 (United States); Mett, Richard R. [Department of Biophysics, Medical College of Wisconsin, Milwaukee, Wisconsin 53211 (United States); Department of Physics and Chemistry, Milwaukee School of Engineering, Milwaukee, Wisconsin 53202 (United States); Swarts, Steven G. [Department of Radiation Oncology, University of Florida, Gainesville, Florida, 32610 (United States); Swartz, Harold M. [Department of Radiology, Geisel Medical School at Dartmouth, Hanover, New Hampshire 03755 (United States)

    2014-10-15

    A microwave Surface Resonator Array (SRA) structure is described for use in Electron Paramagnetic Resonance (EPR) spectroscopy. The SRA has a series of anti-parallel transmission line modes that provides a region of sensitivity equal to the cross-sectional area times its depth sensitivity, which is approximately half the distance between the transmission line centers. It is shown that the quarter-wave twin-lead transmission line can be a useful element for design of microwave resonators at frequencies as high as 10 GHz. The SRA geometry is presented as a novel resonator for use in surface spectroscopy where the region of interest is either surrounded by lossy material, or the spectroscopist wishes to minimize signal from surrounding materials. One such application is in vivo spectroscopy of human finger-nails at X-band (9.5 GHz) to measure ionizing radiation dosages. In order to reduce losses associated with tissues beneath the nail that yield no EPR signal, the SRA structure is designed to limit depth sensitivity to the thickness of the fingernail. Another application, due to the resonator geometry and limited depth penetration, is surface spectroscopy in coating or material science. To test this application, a spectrum of 1.44 μM of Mg{sup 2+} doped polystyrene 1.1 mm thick on an aluminum surface is obtained. Modeling, design, and simulations were performed using Wolfram Mathematica (Champaign, IL; v. 9.0) and Ansys High Frequency Structure Simulator (HFSS; Canonsburg, PA; v. 15.0). A micro-strip coupling circuit is designed to suppress unwanted modes and provide a balanced impedance transformation to a 50 Ω coaxial input. Agreement between simulated and experimental results is shown.

  4. Billion-Fold Enhancement in Sensitivity of Nuclear Magnetic Resonance Spectroscopy for Magnesium Ions in Solution

    CERN Document Server

    Gottberg, Alexander; Kowalska, Magdalena; Bissell, Mark L; Arcisauskaite, Vaida; Blaum, Klaus; Helmke, Alexander; Johnston, Karl; Kreim, Kim; Larsen, Flemming H; Neugart, Rainer; Neyens, Gerda; Garcia Ruiz, Ronald F; Szunyogh, Daniel; Thulstrup, Peter W; Yordanov, Deyan T; Hemmingsen, Lars

    2014-01-01

    β-nuclear magnetic resonance (NMR) spectroscopy is highly sensitive compared to conventional NMR spectroscopy, and may be applied for several elements across the periodic table. β-NMR has previously been successfully applied in the fields of nuclear and solid-state physics. In this work, β-NMR is applied, for the first time, to record an NMR spectrum for a species in solution. 31Mg β-NMR spectra are measured for as few as 107 magnesium ions in ionic liquid (EMIM-Ac) within minutes, as a prototypical test case. Resonances are observed at 3882.9 and 3887.2 kHz in an external field of 0.3 T. The key achievement of the current work is to demonstrate that β-NMR is applicable for the analysis of species in solution, and thus represents a novel spectroscopic technique for use in general chemistry and potentially in biochemistry.

  5. High-speed high-sensitivity infrared spectroscopy using mid-infrared swept lasers (Conference Presentation)

    Science.gov (United States)

    Childs, David T. D.; Groom, Kristian M.; Hogg, Richard A.; Revin, Dmitry G.; Cockburn, John W.; Rehman, Ihtesham U.; Matcher, Stephen J.

    2016-03-01

    Infrared spectroscopy is a highly attractive read-out technology for compositional analysis of biomedical specimens because of its unique combination of high molecular sensitivity without the need for exogenous labels. Traditional techniques such as FTIR and Raman have suffered from comparatively low speed and sensitivity however recent innovations are challenging this situation. Direct mid-IR spectroscopy is being speeded up by innovations such as MEMS-based FTIR instruments with very high mirror speeds and supercontinuum sources producing very high sample irradiation levels. Here we explore another possible method - external cavity quantum cascade lasers (EC-QCL's) with high cavity tuning speeds (mid-IR swept lasers). Swept lasers have been heavily developed in the near-infrared where they are used for non-destructive low-coherence imaging (OCT). We adapt these concepts in two ways. Firstly by combining mid-IR quantum cascade gain chips with external cavity designs adapted from OCT we achieve spectral acquisition rates approaching 1 kHz and demonstrate potential to reach 100 kHz. Secondly we show that mid-IR swept lasers share a fundamental sensitivity advantage with near-IR OCT swept lasers. This makes them potentially able to achieve the same spectral SNR as an FTIR instrument in a time x N shorter (N being the number of spectral points) under otherwise matched conditions. This effect is demonstrated using measurements of a PDMS sample. The combination of potentially very high spectral acquisition rates, fundamental SNR advantage and the use of low-cost detector systems could make mid-IR swept lasers a powerful technology for high-throughput biomedical spectroscopy.

  6. On velocity-space sensitivity of fast-ion D-alpha spectroscopy

    DEFF Research Database (Denmark)

    Salewski, Mirko; Geiger, B.; Moseev, Dmitry

    2014-01-01

    The velocity-space observation regions and sensitivities in fast-ion Dα (FIDA) spectroscopy measurements are often described by so-called weight functions. Here we derive expressions for FIDA weight functions accounting for the Doppler shift, Stark splitting, and the charge-exchange reaction...... and electron transition probabilities. Our approach yields an efficient way to calculate correctly scaled FIDA weight functions and implies simple analytic expressions for their boundaries that separate the triangular observable regions in (v‖, v⊥)-space from the unobservable regions. These boundaries...

  7. Coplanar Electrode Layout Optimized for Increased Sensitivity for Electrical Impedance Spectroscopy

    DEFF Research Database (Denmark)

    Clausen, Casper Hyttel; Skands, Gustav Erik; Bertelsen, Christian Vinther

    2015-01-01

    This work describes an improvement in the layout of coplanar electrodes for electrical impedance spectroscopy. We have developed, fabricated, and tested an improved electrode layout, which improves the sensitivity of an impedance flow cytometry chip. The improved chip was experimentally tested...... and compared to a chip with a conventional electrode layout. The improved chip was able to discriminate 0.5 mu m beads from 1 mu m as opposed to the conventional chip. Furthermore, finite element modeling was used to simulate the improvements in electrical field density and uniformity between the electrodes...... of the new electrode layout. Good agreement was observed between the model and the obtained experimental results....

  8. Laser-based secondary neutral mass spectroscopy: Useful yield and sensitivity

    International Nuclear Information System (INIS)

    Young, C.E.; Pellin, M.J.; Calaway, W.F.; Joergensen, B.; Schweitzer, E.L.; Gruen, D.M.

    1986-01-01

    A variety of problems exist in order to optimally apply resonance ionization spectroscopy (RIS) to the detection of sputtered neutral atoms, however. Several of these problems and their solutions are examined in this paper. First, the possible useful yields obtainable and the dependence of useful yield on various laser parameters for this type of sputtered neutral mass spectrometer (SNMS) are considered. Second, the choice of a mass spectrometer and its effect on the instrumental useful yield is explored in light of the unique ionization region for laser based SNMS. Finally a brief description of noise sources and their effect on the instrumental sensitivity is discussed. 33 refs., 12 figs

  9. High-intensity xenon plasma discharge lamp for bulk-sensitive high-resolution photoemission spectroscopy.

    Science.gov (United States)

    Souma, S; Sato, T; Takahashi, T; Baltzer, P

    2007-12-01

    We have developed a highly brilliant xenon (Xe) discharge lamp operated by microwave-induced electron cyclotron resonance (ECR) for ultrahigh-resolution bulk-sensitive photoemission spectroscopy (PES). We observed at least eight strong radiation lines from neutral or singly ionized Xe atoms in the energy region of 8.4-10.7 eV. The photon flux of the strongest Xe I resonance line at 8.437 eV is comparable to that of the He Ialpha line (21.218 eV) from the He-ECR discharge lamp. Stable operation for more than 300 h is achieved by efficient air-cooling of a ceramic tube in the resonance cavity. The high bulk sensitivity and high-energy resolution of PES using the Xe lines are demonstrated for some typical materials.

  10. Tailored Algorithm for Sensitivity Enhancement of Gas Concentration Sensors Based on Tunable Laser Absorption Spectroscopy.

    Science.gov (United States)

    Vargas-Rodriguez, Everardo; Guzman-Chavez, Ana Dinora; Baeza-Serrato, Roberto

    2018-06-04

    In this work, a novel tailored algorithm to enhance the overall sensitivity of gas concentration sensors based on the Direct Absorption Tunable Laser Absorption Spectroscopy (DA-ATLAS) method is presented. By using this algorithm, the sensor sensitivity can be custom-designed to be quasi constant over a much larger dynamic range compared with that obtained by typical methods based on a single statistics feature of the sensor signal output (peak amplitude, area under the curve, mean or RMS). Additionally, it is shown that with our algorithm, an optimal function can be tailored to get a quasi linear relationship between the concentration and some specific statistics features over a wider dynamic range. In order to test the viability of our algorithm, a basic C 2 H 2 sensor based on DA-ATLAS was implemented, and its experimental measurements support the simulated results provided by our algorithm.

  11. Intracavity optogalvanic spectroscopy. An analytical technique for 14C analysis with subattomole sensitivity.

    Science.gov (United States)

    Murnick, Daniel E; Dogru, Ozgur; Ilkmen, Erhan

    2008-07-01

    We show a new ultrasensitive laser-based analytical technique, intracavity optogalvanic spectroscopy, allowing extremely high sensitivity for detection of (14)C-labeled carbon dioxide. Capable of replacing large accelerator mass spectrometers, the technique quantifies attomoles of (14)C in submicrogram samples. Based on the specificity of narrow laser resonances coupled with the sensitivity provided by standing waves in an optical cavity and detection via impedance variations, limits of detection near 10(-15) (14)C/(12)C ratios are obtained. Using a 15-W (14)CO2 laser, a linear calibration with samples from 10(-15) to >1.5 x 10(-12) in (14)C/(12)C ratios, as determined by accelerator mass spectrometry, is demonstrated. Possible applications include microdosing studies in drug development, individualized subtherapeutic tests of drug metabolism, carbon dating and real time monitoring of atmospheric radiocarbon. The method can also be applied to detection of other trace entities.

  12. Cones fabricated by 3D nanoimprint lithography for highly sensitive surface enhanced Raman spectroscopy

    International Nuclear Information System (INIS)

    Wu Wei; Hu Min; Ou Fungsuong; Li Zhiyong; Williams, R Stanley

    2010-01-01

    We demonstrated a cost-effective and deterministic method of patterning 3D cone arrays over a large area by using nanoimprint lithography (NIL). Cones with tip radius of less than 10 nm were successfully duplicated onto the UV-curable imprint resist materials from the silicon cone templates. Such cone structures were shown to be a versatile platform for developing reliable, highly sensitive surface enhanced Raman spectroscopy (SERS) substrates. In contrast to the silicon nanocones, the SERS substrates based on the Au coated cones made by the NIL offered significant improvement of the SERS signal. A further improvement of the SERS signal was observed when the polymer cones were imprinted onto a reflective metallic mirror surface. A sub-zeptomole detection sensitivity for a model molecule, trans-1,2-bis(4-pyridyl)-ethylene (BPE), on the Au coated NIL cone surfaces was achieved.

  13. Sensitive and ultra-fast species detection using pulsed cavity ringdown spectroscopy

    KAUST Repository

    Alquaity, Awad

    2015-01-01

    Pulsed cavity ringdown spectroscopy (CRDS) is used to develop a novel, ultra-fast, high-sensitivity diagnostic for measuring species concentrations in shock tube experiments. The diagnostic is demonstrated by monitoring trace concentrations of ethylene in the mid-IR region near 949.47 cm-1. Each ringdown measurement is completed in less than 1 μs and the time period between successive pulses is 10 μs. The high sensitivity diagnostic has a noise-equivalent detection limit of 1.08 x 10-5 cm-1 which enables detection of 15 ppm ethylene at fuel pyrolysis conditions (1845 K and 2 bar) and 294 ppb ethylene under ambient conditions (297 K and 1 bar). To our knowledge, this is the first successful application of the cavity ringdown method to the measurement of species time-histories in a shock tube. © 2015 OSA.

  14. Vibrational Spectroscopy on Photoexcited Dye-Sensitized Films via Pump-Degenerate Four-Wave Mixing.

    Science.gov (United States)

    Abraham, Baxter; Fan, Hao; Galoppini, Elena; Gundlach, Lars

    2018-03-01

    Molecular sensitization of semiconductor films is an important technology for energy and environmental applications including solar energy conversion, photocatalytic hydrogen production, and water purification. Dye-sensitized films are also scientifically complex and interesting systems with a long history of research. In most applications, photoinduced heterogeneous electron transfer (HET) at the molecule/semiconductor interface is of critical importance, and while great progress has been made in understanding HET, many open questions remain. Of particular interest is the role of combined electronic and vibrational effects and coherence of the dye during HET. The ultrafast nature of the process, the rapid intramolecular vibrational energy redistribution, and vibrational cooling present complications in the study of vibronic coupling in HET. We present the application of a time domain vibrational spectroscopy-pump-degenerate four-wave mixing (pump-DFWM)-to dye-sensitized solid-state semiconductor films. Pump-DFWM can measure Raman-active vibrational modes that are triggered by excitation of the sample with an actinic pump pulse. Modifications to the instrument for solid-state samples and its application to an anatase TiO 2 film sensitized by a Zn-porphyrin dye are discussed. We show an effective combination of experimental techniques to overcome typical challenges in measuring solid-state samples with laser spectroscopy and observe molecular vibrations following HET in a picosecond time window. The cation spectrum of the dye shows modes that can be assigned to the linker group and a mode that is localized on the Zn-phorphyrin chromophore and that is connected to photoexcitation.

  15. Investigation of the Sensitivity of Transmission Raman Spectroscopy for Polymorph Detection in Pharmaceutical Tablets.

    Science.gov (United States)

    Feng, Hanzhou; Bondi, Robert W; Anderson, Carl A; Drennen, James K; Igne, Benoît

    2017-08-01

    Polymorph detection is critical for ensuring pharmaceutical product quality in drug substances exhibiting polymorphism. Conventional analytical techniques such as X-ray powder diffraction and solid-state nuclear magnetic resonance are utilized primarily for characterizing the presence and identity of specific polymorphs in a sample. These techniques have encountered challenges in analyzing the constitution of polymorphs in the presence of other components commonly found in pharmaceutical dosage forms. Laborious sample preparation procedures are usually required to achieve satisfactory data interpretability. There is a need for alternative techniques capable of probing pharmaceutical dosage forms rapidly and nondestructively, which is dictated by the practical requirements of applications such as quality monitoring on production lines or when quantifying product shelf lifetime. The sensitivity of transmission Raman spectroscopy for detecting polymorphs in final tablet cores was investigated in this work. Carbamazepine was chosen as a model drug, polymorph form III is the commercial form, whereas form I is an undesired polymorph that requires effective detection. The concentration of form I in a direct compression tablet formulation containing 20% w/w of carbamazepine, 74.00% w/w of fillers (mannitol and microcrystalline cellulose), and 6% w/w of croscarmellose sodium, silicon dioxide, and magnesium stearate was estimated using transmission Raman spectroscopy. Quantitative models were generated and optimized using multivariate regression and data preprocessing. Prediction uncertainty was estimated for each validation sample by accounting for all the main variables contributing to the prediction. Multivariate detection limits were calculated based on statistical hypothesis testing. The transmission Raman spectroscopic model had an absolute prediction error of 0.241% w/w for the independent validation set. The method detection limit was estimated at 1.31% w/w. The

  16. Some problems connected with boron determination by atomic absorption spectroscopy and the sensitivity improvement

    Directory of Open Access Journals (Sweden)

    JELENA J. SAVOVIC

    2001-08-01

    Full Text Available Two atomizers were compared: an N2O–C2H2 flame and a stabilized U-shaped DC arc with aerosol supply. Both the high plasma temperature and the reducing atmosphere obtained by acetylene addition to the argon stream substantially increase the sensitivity of boron determination by atomic absorption spectroscopy (AAS when the arc atomizer is used. The results were compared with those for silicon as a control element. The experimental characteristic concentrations for both elements were compared with the computed values. The experimentally obtained characteristic concentration for boron when using the arc atomizer was in better agreement with the calculated value. It was estimated that the influence of stable monoxide formation on the sensitivity for both elements was about the same, but reduction of analyte and formation of non-volatile carbide particles was more important for boron, which is the main reason for the low sensitivity of boron determination using a flame atomizer. The use of an arc atomizer suppresses this interference and significantly improves the sensitivity of the determination.

  17. Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Hellman, Hal

    1968-01-01

    This booklet discusses spectroscopy, the study of absorption of radiation by matter, including X-ray, gamma-ray, microwave, mass spectroscopy, as well as others. Spectroscopy has produced more fundamental information to the study of the detailed structure of matter than any other tools.

  18. Spectroscopy

    CERN Document Server

    Walker, S

    1976-01-01

    The three volumes of Spectroscopy constitute the one comprehensive text available on the principles, practice and applications of spectroscopy. By giving full accounts of those spectroscopic techniques only recently introduced into student courses - such as Mössbauer spectroscopy and photoelectron spectroscopy - in addition to those techniques long recognised as being essential in chemistry teaching - sucha as e.s.r. and infrared spectroscopy - the book caters for the complete requirements of undergraduate students and at the same time provides a sound introduction to special topics for graduate students.

  19. CdS-Sensitized ZnO Nanorod Photoelectrodes: Photoelectrochemistry and Photoinduced Absorption Spectroscopy

    Directory of Open Access Journals (Sweden)

    Idriss Bedja

    2011-01-01

    Full Text Available Thin films of ZnO semiconductor nanorods (ZnO-nr of 6 μm length and thin ZnO nanoparticulate films (ZnO-np have been prepared and modified with Q-dots CdS for comparison study. PIA (photoinduced absorption spectroscopy, a multipurpose tool in the study of dye-sensitized solar cells, is used to study a quantum-dot-modified metal-oxide nanostrucutred electrode. Q-dot CdS-sensitized ZnO-nr (1D network sensitized photoelectrode has demonstrated best performances in both photoelectrical response (IPCE max = 92% and broadening response into far visible comparing to ZnO-np-based CdS solar cell. Preadsorbing ZnO-nr with ZnO-np does not bring further improvement. Time constant for electron injection into ZnO-nr conduction band was relatively fast decay of 6.5 ms, similar to TiO2-coated CdS, and proves at least a well pore filling of ZnO-nr film by ultrafine CdS particles. Unidirectional electron transfer mechanistic in ZnO-nr has played a major role in these performances.

  20. Impedance spectroscopy on pH-sensors with lithium lanthanum titanate sensitive material

    International Nuclear Information System (INIS)

    Bohnke, Cl.; Fourquet, J.-L.

    2003-01-01

    The ceramic Li 3x La 2/3-x , 1/3-2x TiO 3 is used, in an all-solid-state configuration, as pH-sensor in aqueous buffer solution. This ceramic displays a pH sensitivity comparable to the one obtained with a commercial glass electrode and does not show any sensitivity to the redox potential of the solution. This is one of the remarkable properties of this ceramic pH-sensor. It is shown in this paper that the reproducibility and the behaviour of the pH-response depend on the morphology of the grain boundaries particularly on the size of the grains. A so-called 'good' pH-response is obtained with a ceramic showing big and homogeneous grains. Complex impedance spectroscopy reveals that such ceramic has a high grain boundary resistance. Furthermore, this electrochemical technique allows us to determine that the interface reaction involved in the pH detection has a time constant of the order of the second. Several assumptions such as ion exchange or acid-base reaction are proposed to explain the sensitivity of the ceramic material to the pH of the solution

  1. Impedance spectroscopy study of N719-sensitized ZnO-based solar cells

    Energy Technology Data Exchange (ETDEWEB)

    Pauporté, Th., E-mail: thierry-pauporte@chimie-paristech.fr [Laboratoire d' Electrochimie, Chimie des Interfaces et Modélisation pour l' Energie, Ecole Nationale Supérieure de Chimie de Paris, 11 rue P. et M. Curie, 75231 Paris cedex 05 (France); Magne, C. [Laboratoire d' Electrochimie, Chimie des Interfaces et Modélisation pour l' Energie, Ecole Nationale Supérieure de Chimie de Paris, 11 rue P. et M. Curie, 75231 Paris cedex 05 (France); Saint-Gobain Recherche, 39 quai Lucien Lefranc, 93303 Aubervilliers Cedex (France)

    2014-06-02

    ZnO porous films prepared by electrodeposition and by sol–gel techniques have been sensitized by the N719 dye and used as photoelectrode in dye-sensitized solar cells. Similar stationary current–voltage characteristics have been measured for films having two drastically different morphologies and nanostructures. The solar cells have been studied by impedance spectroscopy over large frequency and applied voltage ranges in order to elucidate the inherent correlation between the photoelectrode structure and properties. The electrical response has been analyzed using an ad-hoc electrical model to extrapolate the electronic structure and charge carrier kinetic properties of the photoelectrodes. The two films exhibit very different density distributions of their trap states below the conduction band edge. Moreover, their electron lifetimes and transport times vary differently with the DOS due to different surface and conduction properties. The charge collection efficiency has been calculated by two different approaches, one being derived from first principles. Very high values are reported in all cases. Globally, the limitation of N719/ZnO solar cell performances is related to their open circuit voltage and their short circuit current. The latter point is discussed in the light of our impedance results and photoelectrode light absorption data. - Highlights: • Exponential trap state distribution • Electron transport and recombination depend on oxide preparation route. • Charge collection efficiency modeling • Very high charge collection efficiency in N719/ZnO dye-sensitized solar cells • ZnO cell performance limitations.

  2. Coplanar Electrode Layout Optimized for Increased Sensitivity for Electrical Impedance Spectroscopy

    Directory of Open Access Journals (Sweden)

    Casper Hyttel Clausen

    2014-12-01

    Full Text Available This work describes an improvement in the layout of coplanar electrodes for electrical impedance spectroscopy. We have developed, fabricated, and tested an improved electrode layout, which improves the sensitivity of an impedance flow cytometry chip. The improved chip was experimentally tested and compared to a chip with a conventional electrode layout. The improved chip was able to discriminate 0.5 μm beads from 1 μm as opposed to the conventional chip. Furthermore, finite element modeling was used to simulate the improvements in electrical field density and uniformity between the electrodes of the new electrode layout. Good agreement was observed between the model and the obtained experimental results.

  3. Silver-coated Si nanograss as highly sensitive surface-enhanced Raman spectroscopy substrates

    Energy Technology Data Exchange (ETDEWEB)

    Tang, Jing; Kuo, Huei Pei; Hu, Min; Li, Zhiyong; Williams, R.S. [Hewlett-Packard Laboratories, Information and Quantum Systems Laboratory, Palo Alto, CA (United States); Ou, Fung Suong [Hewlett-Packard Laboratories, Information and Quantum Systems Laboratory, Palo Alto, CA (United States); Rice University, Department of Applied Physics, Houston, TX (United States); Stickle, William F. [Hewlett-Packard Company, Advanced Diagnostic Lab, Corvallis, OR (United States)

    2009-09-15

    We created novel surface-enhanced Raman spectroscopy (SERS) substrates by metalization (Ag) of Si nanograss prepared by a Bosch process which involves deep reactive ion etching of single crystalline silicon. No template or lithography was needed for making the Si nanograss, thus providing a simple and inexpensive method to achieve highly sensitive large-area SERS substrates. The dependence of the SERS effect on the thickness of the metal deposition and on the surface morphology and topology of the substrate prior to metal deposition was studied in order to optimize the SERS signals. We observed that the Ag-coated Si nanograss can achieve uniform SERS enhancement over large area ({proportional_to}1 cm x 1 cm) with an average EF (enhancement factor) of 4.2 x 10{sup 8} for 4-mercaptophenol probe molecules. (orig.)

  4. A position sensitive silicon detector for AEgIS (Antimatter Experiment: Gravity, Interferometry, Spectroscopy)

    CERN Multimedia

    Gligorova, A

    2014-01-01

    The AEḡIS experiment (Antimatter Experiment: Gravity, Interferometry, Spectroscopy) is located at the Antiproton Decelerator (AD) at CERN and studies antimatter. The main goal of the AEḡIS experiment is to carry out the first measurement of the gravitational acceleration for antimatter in Earth’s gravitational field to a 1% relative precision. Such a measurement would test the Weak Equivalence Principle (WEP) of Einstein’s General Relativity. The gravitational acceleration for antihydrogen will be determined using a set of gravity measurement gratings (Moiré deflectometer) and a position sensitive detector. The vertical shift due to gravity of the falling antihydrogen atoms will be detected with a silicon strip detector, where the annihilation of antihydrogen will take place. This poster presents part of the development process of this detector.

  5. High sensitivity and label-free detection of Enterovirus 71 by nanogold modified electrochemical impedance spectroscopy

    Science.gov (United States)

    Wang, Fang-Yu; Li, Hsing-Yuan; Tseng, Shing-Hua; Cheng, Tsai-Mu; Chu, Hsueh-Liang; Yang, Jyh-Yuan; Chang, Chia-Ching

    2013-03-01

    Enterovirus 71 (EV71), which is the most fulminant and invasive species of enterovirus, can cause children neurologic complications and death within 2-3 days after fever and rash developed. Besides, EV71 has high sequence similarity with Coxsackie A 16 (CA16) that makes differential diagnosis difficult in clinic and laboratory. Since conventional viral diagnostic method cannot diagnose EV71 quickly and EV71 can transmit at low viral titer, the patients might delay in treatment. A quick, high sensitive, and high specific test for EV71 detection is pivotal. Electrochemical impedance spectroscopy (EIS) has been applied for detecting bio-molecules as biosensors recently. In this study, we try to build a detection platform for EV71 detection by nanogold modified EIS probe. The result shows that our probe can detect 3.6 VP1/50 μl (one EV71 particle has 60 VP1) in 3 minutes. The test can also distinguish EV71 from CA16 and lysozyme. Diagnosis of enterovirus 71 by electrochemical impedance spectroscopy has the potential to apply in clinic.

  6. Characterization of the Pore Filling of Solid State Dye Sensitized Solar Cells with Photoinduced Absorption Spectroscopy

    Directory of Open Access Journals (Sweden)

    Carol Olson

    2011-01-01

    Full Text Available Near steady-state photoinduced absorption (PIA and UV-Vis absorption spectroscopy are used to characterize the pore filling of spiro-MeOTAD (2,2′,7,7′-tetrakis-(N,N-di-p-methoxyphenylamine9,9′-spirobifluorene into the nanoparticulate TiO2 electrode of a solid-state dye-sensitized solar cell (ssDSC. The volumetric ratio of filled to unfilled pore volumes, as well as the optical signature of interacting chemical species, that is, the hole-transfer yield (HTY, are investigated. PIA spectroscopy is used to measure the HTY, relative to the amount of spiro-MeOTAD present, without needing to determine the extinction coefficients of the dye and spiro-MeOTAD cation species. The Beer-Lambert law is used to relate the relative PIA signal to the penetration length of the hole-conductor in the TiO2 film. For the sample thickness range of 1.4–5 μm investigated here, the optimum characteristic penetration length is determined to be 3.1+0.46 μm, which is compared to 1.4 μm for the 200 mg mL−1 concentration of spiro-MeOTAD conventionally used. Therefore, doubling the effective penetration of spiro-MeOTAD is necessary to functionalize all the dye molecules in a ssDSC.

  7. Depth-sensitive optical spectroscopy for noninvasive diagnosis of oral neoplasia

    Science.gov (United States)

    Schwarz, Richard Alan

    Oral cancer is the 11th most common cancer in the world. Cancers of the oral cavity and oropharynx account for more than 7,500 deaths each year in the United States alone. Major advances have been made in the management of oral cancer through the combined use of surgery, radiotherapy and chemotherapy, improving the quality of life for many patients; however, these advances have not led to a significant increase in survival rates, primarily because diagnosis often occurs at a late stage when treatment is more difficult and less successful. Accurate, objective, noninvasive methods for early diagnosis of oral neoplasia are needed. Here a method is presented to noninvasively evaluate oral lesions using depth-sensitive optical spectroscopy (DSOS). A ball lens coupled fiber-optic probe was developed to enable preferential targeting of different depth regions in the oral mucosa. Clinical studies of the diagnostic performance of DSOS in 157 subjects were carried out in collaboration with the University of Texas M. D. Anderson Cancer Center. An overall sensitivity of 90% and specificity of 89% were obtained for nonkeratinized oral tissue relative to histopathology. Based on these results a compact, portable version of the clinical DSOS device with real-time automated diagnostic capability was developed. The portable device was tested in 47 subjects and a sensitivity of 82% and specificity of 83% were obtained for nonkeratinized oral tissue. The diagnostic potential of multimodal platforms incorporating DSOS was explored through two pilot studies. A pilot study of DSOS in combination with widefield imaging was carried out in 29 oral cancer patients, resulting in a combined sensitivity of 94% and specificity of 69%. Widefield imaging and spectroscopy performed slightly better in combination than each method performed independently. A pilot study of DSOS in combination with the optical contrast agents 2-NBDG, EGF-Alexa 647, and proflavine was carried out in resected tissue

  8. Generation of Small Single Domain Nanobody Binders for Sensitive Detection of Testosterone by Electrochemical Impedance Spectroscopy.

    Science.gov (United States)

    Li, Guanghui; Zhu, Min; Ma, Lu; Yan, Junrong; Lu, Xiaoling; Shen, Yanfei; Wan, Yakun

    2016-06-08

    A phage display library of variable domain of the heavy chain only antibody or nanobody (Nb) was constructed after immunizing a bactrian camel with testosterone. With the smaller molecular size (15 kDa), improved solubility, good stability, high affinity, specificity, and lower immunogenicity, Nbs are a promising tool in the next generation of diagnosis and medical applications. Testosterone is a reproductive hormone, playing an important role in normal cardiac function and being the highly predictive marker for many diseases. Herein, a simple and sensitive immunosensor based on electrochemical impedance spectroscopy (EIS) and Nbs was successfully developed for the determination of testosterone. We successfully isolated the antitestosterone Nbs from an immune phage display library. Moreover, one of the Nbs was biotinylated according to in vivo BirA system, which showed the highest production yield and the most stable case. Further, the EIS immunosensor was set up for testosterone detection by applying the biotinylated antitestosterone Nb. As a result, the biosensor exhibited a linear working range from 0.05 to 5 ng mL(-1) with a detection limit of 0.045 ng mL(-1). In addition, the proposed immunosensor was successfully applied in determining testosterone in serum samples. In conclusion, the proposed immunosensor revealed high specificity of testosterone detection and showed as a potential approach for sensitive and accurate diagnosis of testosterone.

  9. Which experimental model can sensitively indicate brain death by functional near-infrared spectroscopy?

    Science.gov (United States)

    Pan, Boan; Liu, Weichao; Fang, Xiang; Huang, Xiaobo; Li, Ting

    2018-02-01

    Brain death is defined as permanent loss of the brain functions. The evaluation of it has many meanings, such as the relief of organ transplantation stress and family burden. However, it is hard to be judged precisely. The standard clinical tests are expensive, time consuming and even dangerous, and some auxiliary methods have limitations. Functional near infrared spectroscopy (fNIRS), monitoring cerebral hemodynamic responses noninvasively, evaluate brain death in some papers published, but there is no discussion about which experimental mode can monitor brain death patient more sensitively. Here, we attempt to use our fNIRS to evaluate brain death and find which experimental mode is effective. In order to discuss the problem, we detected eleven brain death patients and twenty normal patients under natural state. They were provided different fraction of inspiration O2 (FIO2) in different phase. We found that the ratio of Δ[HbO2] (the concentration changes in oxyhemoglobin) to Δ[Hb] (the concentration changes in deoxyhemoglobin) in brain death patients is significantly higher than normal patients in FIO2 experiment. Combined with the data analysis result, restore oxygen change process and low-high-low paradigm is more sensitively.

  10. Rapid and highly sensitive detection of Enterovirus 71 by using nanogold-enhanced electrochemical impedance spectroscopy

    International Nuclear Information System (INIS)

    Li, Hsing-Yuan; Tseng, Shing-Hua; Cheng, Tsai-Mu; Chu, Hsueh-Liang; Lu, Yu-Ning; Wang, Fang-Yu; Tu, Lung-Chen; Chang, Chia-Ching; Tsai, Li-Yun; Shieh, Juo-Yu; Yang, Jyh-Yuan; Juan, Chien-Chang

    2013-01-01

    Enterovirus 71 (EV71) infection is an emerging infectious disease causing neurological complications and/or death within two to three days after the development of fever and rash. A low viral titre in clinical specimens makes the detection of EV71 difficult. Conventional approaches for detecting EV71 are time consuming, poorly sensitive, or complicated, and cannot be used effectively for clinical diagnosis. Furthermore, EV71 and Coxsackie virus A16 (CA16) may cross react in conventional assays. Therefore, a rapid, highly sensitive, specific, and user-friendly test is needed. We developed an EV71-specific nanogold-modified working electrode for electrochemical impedance spectroscopy in the detection of EV71. Our results show that EV71 can be distinguished from CA16, Herpes simplex virus, and lysozyme, with the modified nanogold electrode being able to detect EV71 in concentrations as low as 1 copy number/50 μl reaction volume, and the duration between sample preparation and detection being 11 min. This detection platform may have the potential for use in point-of-care diagnostics. (paper)

  11. Rapid and highly sensitive detection of Enterovirus 71 by using nanogold-enhanced electrochemical impedance spectroscopy

    Science.gov (United States)

    Li, Hsing-Yuan; Tseng, Shing-Hua; Cheng, Tsai-Mu; Chu, Hsueh-Liang; Lu, Yu-Ning; Wang, Fang-Yu; Tsai, Li-Yun; Shieh, Juo-Yu; Yang, Jyh-Yuan; Juan, Chien-Chang; Tu, Lung-Chen; Chang, Chia-Ching

    2013-07-01

    Enterovirus 71 (EV71) infection is an emerging infectious disease causing neurological complications and/or death within two to three days after the development of fever and rash. A low viral titre in clinical specimens makes the detection of EV71 difficult. Conventional approaches for detecting EV71 are time consuming, poorly sensitive, or complicated, and cannot be used effectively for clinical diagnosis. Furthermore, EV71 and Coxsackie virus A16 (CA16) may cross react in conventional assays. Therefore, a rapid, highly sensitive, specific, and user-friendly test is needed. We developed an EV71-specific nanogold-modified working electrode for electrochemical impedance spectroscopy in the detection of EV71. Our results show that EV71 can be distinguished from CA16, Herpes simplex virus, and lysozyme, with the modified nanogold electrode being able to detect EV71 in concentrations as low as 1 copy number/50 μl reaction volume, and the duration between sample preparation and detection being 11 min. This detection platform may have the potential for use in point-of-care diagnostics.

  12. Pore closure in zeolitic imidazolate frameworks under mechanical pressure† †Electronic supplementary information (ESI) available: Experimental details; synthetic procedures; supplementary data analyses; additional PXRD, thermal and elemental analyses as well as IR and 1H NMR spectroscopy data. See DOI: 10.1039/c7sc04952h

    Science.gov (United States)

    Wharmby, Michael T.; Kieslich, Gregor; Hante, Inke; Schneemann, Andreas; Wu, Yue; Daisenberger, Dominik; Cheetham, Anthony K.

    2018-01-01

    We investigate the pressure-dependent mechanical behaviour of the zeolitic imidazolate framework ZIF-4 (M(im)2; M2+ = Co2+ or Zn2+, im– = imidazolate) with high pressure, synchrotron powder X-ray diffraction and mercury intrusion measurements. A displacive phase transition from a highly compressible open pore (op) phase with continuous porosity (space group Pbca, bulk modulus ∼1.4 GPa) to a closed pore (cp) phase with inaccessible porosity (space group P21/c, bulk modulus ∼3.3–4.9 GPa) is triggered by the application of mechanical pressure. Over the course of the transitions, both ZIF-4 materials contract by about 20% in volume. However, the threshold pressure, the reversibility and the immediate repeatability of the phase transition depend on the metal cation. ZIF-4(Zn) undergoes the op–cp phase transition at a hydrostatic mechanical pressure of only 28 MPa, while ZIF-4(Co) requires about 50 MPa to initiate the transition. Interestingly, ZIF-4(Co) fully returns to the op phase after decompression, whereas ZIF-4(Zn) remains in the cp phase after pressure release and requires subsequent heating to switch back to the op phase. These variations in high pressure behaviour can be rationalised on the basis of the different electron configurations of the respective M2+ ions (3d10 for Zn2+ and 3d7 for Co2+). Our results present the first examples of op–cp phase transitions (i.e. breathing transitions) of ZIFs driven by mechanical pressure and suggest potential applications of these functional materials as shock absorbers, nanodampers, or in mechanocalorics. PMID:29675212

  13. IDENTIFICAÇÃO DE PRODUTOS DA OXIDAÇÃO DE ÓLEOS COMESTÍVEIS ATRAVÉS DA ESPECTROSCOPIA DE RMN DE 1H / IDENTIFICATION OF OXIDATION PRODUCTS IN EDIBLE OIL BY MEANS OF 1H NMR SPECTROSCOPY

    Directory of Open Access Journals (Sweden)

    MARINA COLZATO

    2009-11-01

    Full Text Available A espectroscopia por ressonância magnética nuclear de 1H de alta resolução (RMN de 1H é uma ferramenta útil para monitorar os produtos de oxidação em óleos comestíveis. O método é rápido, relativamente simples e preciso, permitindo o acompanhamento e a caracterização da formação de produtos primários de oxidação, como os hidroperóxidos e os dienos conjugados. Neste trabalho, óleos de canola, azeite de oliva e de macadâmia foram objetos de oxidação acelerada por 30 dias e os produtos de oxidação avaliados por RMN de 1H. Os resultados indicaram uma maior estabilidade (resistência ao estresse térmico, para o óleo de oliva > macadâmia > canola, respectivamente.

  14. Indole-3-acetic acid/diol based pH-sensitive biological macromolecule for antibacterial, antifungal and antioxidant applications.

    Science.gov (United States)

    G, Chitra; D S, Franklin; S, Sudarsan; M, Sakthivel; S, Guhanathan

    2017-02-01

    Indole-3-acetic acid (IAA)/diol based pH-sensitive biopolymeric hydrogels with tunable biological properties (cytotoxicity, anti-oxidant and anti-fungal) have been synthesized via condensation polymerization. The present study focused on the synthesis of heterocyclic hydrogel using citric acid (CA), indole-3-acetic acid (IAA) and diethylene glycol (DEG) by condensation polymerization. The hydrogels revealed a pH-sensitive swelling behaviour, with increased swelling in acidic media, then turns to decreased the swelling in the basic media. The hydrogel samples were tested for antifungal activity against Aspergillus fumigates, Rhizopusoryzae and Candida albicans at different concentrations using ketoconazole as positive control and DMSO as negative control for antifungal activity. Antioxidant activity increasing nature in DPPH than NO radical compared with rutin and confirmed non toxic property using cytotoxicity analysis. The biopolymeric hydrogels were characterized by Fourier transform infrared (FT-IR) spectroscopy, 1 H NMR, 13 C NMR, TGA, DSC followed by scanning electron microscopy (SEM). Such hydrogels with antioxidant properties is recommended for medical applications such as bandages, catheters, drains and tubes to prevent infection. Copyright © 2016 Elsevier B.V. All rights reserved.

  15. Spectroscopy

    DEFF Research Database (Denmark)

    Berg, Rolf W.

    This introductory booklet covers the basics of molecular spectroscopy, infrared and Raman methods, instrumental considerations, symmetry analysis of molecules, group theory and selection rules, as well as assignments of fundamental vibrational modes in molecules.......This introductory booklet covers the basics of molecular spectroscopy, infrared and Raman methods, instrumental considerations, symmetry analysis of molecules, group theory and selection rules, as well as assignments of fundamental vibrational modes in molecules....

  16. Determination of paraquat in water samples using a sensitive fluorescent probe titration method.

    Science.gov (United States)

    Yao, Feihu; Liu, Hailong; Wang, Guangquan; Du, Liming; Yin, Xiaofen; Fu, Yunlong

    2013-06-01

    Paraquat (PQ), a nonselective herbicide, is non-fluorescent in aqueous solutions. Thus, its determination through direct fluorescent methods is not feasible. The supramolecular inclusion interaction of PQ with cucurbit[7]uril was studied by a fluorescent probe titration method. Significant quenching of the fluorescence intensity of the cucurbit[7]uril-coptisine fluorescent probe was observed with the addition of PQ. A new fluorescent probe titration method with high selectivity and sensitivity at the ng/mL level was developed to determine PQ in aqueous solutions with good precision and accuracy based on the significant quenching of the supramolecular complex fluorescence intensity. The proposed method was successfully used in the determination of PQ in lake water, tap water, well water, and ditch water in an agricultural area, with recoveries of 96.73% to 105.77%. The fluorescence quenching values (deltaF) showed a good linear relationship with PQ concentrations from 1.0 x 10(-8) to 1.2 x 10(-5) mol/L with a detection limit of 3.35 x 10(-9) mol/L. In addition, the interaction models of the supramolecular complexes formed between the host and the guest were established using theoretical calculations. The interaction mechanism between the cucurbit[7]uril and PQ was confirmed by 1H NMR spectroscopy.

  17. Synthesis and evaluation of temperature- and glucose-sensitive nanoparticles based on phenylboronic acid and N-vinylcaprolactam for insulin delivery

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Jun-zi [College of Chemistry, Chemical Engineering and Biotechnology, Donghua University, Shanghai, 201620 (China); Bremner, David H. [School of Science, Engineering and Technology, Kydd Building, Abertay University, Dundee DD1 1HG, Scotland (United Kingdom); Li, He-yu; Sun, Xiao-zhu [College of Chemistry, Chemical Engineering and Biotechnology, Donghua University, Shanghai, 201620 (China); Zhu, Li-Min, E-mail: lzhu@dhu.edu.cn [College of Chemistry, Chemical Engineering and Biotechnology, Donghua University, Shanghai, 201620 (China)

    2016-12-01

    Poly N-vinylcaprolactam-co-acrylamidophenylboronic acid p(NVCL-co-AAPBA) was prepared from N-vinylcaprolactam (NVCL) and 3-acrylamidophenylboronic acid (AAPBA), using 2,2-azobisisobutyronitrile (AIBN) as initiator. The synthesis and structure of the polymer were examined by Fourier Transform infrared spectroscopy (FT-IR) and {sup 1}H-NMR. Dynamic light scattering (DLS), lower critical solution temperature (LCST) and transmission electron microscopy (TEM) were utilized to characterize the nanoparticles, CD spectroscopy was used to determine if there were any changes to the conformation of the insulin, and cell and animal toxicity were also investigated. The prepared nanoparticles were found to be monodisperse submicron particles and were glucose- and temperature-sensitive. In addition, the nanoparticles have good insulin-loading characteristics, do not affect the conformation of the insulin and show low-toxicity to cells and animals. These p(NVCL-co-AAPBA) nanoparticles may have some value for insulin or other hypoglycemic protein delivery. - Highlights: • A comprehensive study of a nanoparticles may have some value for insulin or other hypoglycemic protein delivery. • p(NVCL-co-AAPBA)'s synthetic method is simple, convenient to carry out. • NVCL is low toxic and safe. • The evaluation of acute toxicity and chronic toxicity is the most highlight.

  18. Highly sensitive fiber grating chemical sensors: An effective alternative to atomic absorption spectroscopy

    Science.gov (United States)

    Laxmeshwar, Lata. S.; Jadhav, Mangesh S.; Akki, Jyoti. F.; Raikar, Prasad; Kumar, Jitendra; prakash, Om; Raikar, U. S.

    2017-06-01

    Accuracy in quantitative determination of trace elements like Zinc, present in drinking water in ppm level, is a big challenge and optical fiber gratings as chemical sensors may provide a promising solution to overcome the same. This paper presents design of two simple chemical sensors based on the principle of shift in characteristic wavelength of gratings with change in their effective refractive index, to measure the concentration of Zinc in drinking water using etched short period grating (FBG) and Long period grating (LPG) respectively. Three samples of drinking water from different places have been examined for presence of Zinc. Further, the results obtained by our sensors have also been verified with the results obtained by a standard method, Atomic absorption spectroscopy (AAS). The whole experiment has been performed by fixing the fibers in a horizontal position with the sensor regions at the center of the fibers, making it less prone to disturbance and breaking. The sensitivity of LPG sensor is about 205 times that of the FBG sensor. A few advantages of Fiber grating sensors, besides their regular features, over AAS have also been discussed, that make our sensors potential alternatives for existing techniques in determination of trace elements in drinking water.

  19. spectroscopy

    African Journals Online (AJOL)

    Aghomotsegin

    2015-10-14

    Oct 14, 2015 ... characterized by using phenotypic, API and Fourier transform infrared (FTIR) spectroscopy methods. One hundred and fifty-seven (157) strains were isolated from 13 cheese samples, and identification test was performed for 83 strains. At the end of the study, a total of 22 Lactococcus sp., 36 Enterecoccus ...

  20. Laser photoacoustic spectroscopy helps fight terrorism: High sensitivity detection of chemical Warfare Agent and explosives

    Science.gov (United States)

    Patel, C. K. N.

    2008-01-01

    Tunable laser photoacoustic spectroscopy is maturing rapidly in its applications to real world problems. One of the burning problems of the current turbulent times is the threat of terrorist acts against civilian population. This threat appears in two distinct forms. The first is the potential release of chemical warfare agents (CWA), such as the nerve agents, in a crowded environment. An example of this is the release of Sarin by Aum Shinrikyo sect in a crowded Tokyo subway in 1995. An example of the second terrorist threat is the ever-present possible suicide bomber in crowded environment such as airports, markets and large buildings. Minimizing the impact of both of these threats requires early detection of the presence of the CWAs and explosives. Photoacoustic spectroscopy is an exquisitely sensitive technique for the detection of trace gaseous species, a property that Pranalytica has extensively exploited in its CO2 laser based commercial instrumentation for the sub-ppb level detection of a number of industrially important gases including ammonia, ethylene, acrolein, sulfur hexafluoride, phosphine, arsine, boron trichloride and boron trifluoride. In this presentation, I will focus, however, on our recent use of broadly tunable single frequency high power room temperature quantum cascade lasers (QCL) for the detection of the CWAs and explosives. Using external grating cavity geometry, we have developed room temperature QCLs that produce continuously tunable single frequency CW power output in excess of 300 mW at wavelengths covering 5 μm to 12 μm. I will present data that show a CWA detection capability at ppb levels with false alarm rates below 1:108. I will also show the capability of detecting a variety of explosives at a ppb level, again with very low false alarm rates. Among the explosives, we have demonstrated the capability of detecting homemade explosives such as triacetone triperoxide and its liquid precursor, acetone which is a common household

  1. A single optical sensor with high sensitivity for detection of Fe{sup 3+} and CN{sup −} ions

    Energy Technology Data Exchange (ETDEWEB)

    Afshani, Jafar [School of Chemistry, College of Science, University of Tehran, Tehran (Iran, Islamic Republic of); Badiei, Alireza, E-mail: abadiei@khayam.ut.ac.ir [School of Chemistry, College of Science, University of Tehran, Tehran (Iran, Islamic Republic of); Nanobiomedicine Center of Excellence, Nanoscience and Nanotechnology Research Center, University of Tehran, Tehran (Iran, Islamic Republic of); Jafari, Maryam; Shayesteh, Alireza; Karimi, Mehdi; Lashgari, Negar [School of Chemistry, College of Science, University of Tehran, Tehran (Iran, Islamic Republic of); Mohammadi Ziarani, Ghodsi [Department of Chemistry, Alzahra University, Tehran (Iran, Islamic Republic of)

    2016-11-15

    1,2-Bis(2-hydroxymethylphenoxy)ethane was synthesized and characterized by FT-IR and {sup 1}H NMR spectroscopy, and single crystal X-ray diffraction method. The sensing ability of the sensor was studied in the presence of different cations and anions. Following the excitation wavelengths at 275 nm in EtOH/H{sub 2}O (1:9, v/v) and 310 nm in MeCN/H{sub 2}O (1:9, v/v), two distinct emissions at 305 and 356 nm were obtained, respectively. Fe{sup 3+} and CN{sup −} ions were successfully detected in EtOH/H{sub 2}O and MeCN/H{sub 2}O mixtures, respectively. While the fluorescence intensity of the sensor quenched considerably in the presence of Fe{sup 3+} cation at 305 nm, it enhanced in the presence of CN{sup −} anion at 356 nm. Selectivity of the sensor toward these ions was verified in the presence of a variety of common interfering ions. The detection limits of Fe{sup 3+} and CN{sup −} were calculated as 5.4 × 10{sup −9} mol L{sup −1} and 1.9 × 10{sup −8} mol L{sup −1}, respectively which shows the high sensitivity of the sensor toward the target ions. Finally, the interaction of the sensor and CN{sup −} anion was determined by computational studies.

  2. Studies of ultrathin magnetic films and particle-surface interactions with spin-sensitive electron spectroscopies

    International Nuclear Information System (INIS)

    Walters, G.K.; Dunning, F.B.

    1991-06-01

    Research during the current grant year has focused on: Investigation of probing depth in electron scattering from epitaxially grown paramagnetic films by means of Spin-Polarized Electron Energy Loss Spectroscopy; and studies of the dynamics of metastable He(2 3 S) deexcitation at surfaces utilizing Spin-Polarized Metastable Deexcitation Spectroscopy . This report discussed this research

  3. Direct Detection Electron Energy-Loss Spectroscopy: A Method to Push the Limits of Resolution and Sensitivity.

    Science.gov (United States)

    Hart, James L; Lang, Andrew C; Leff, Asher C; Longo, Paolo; Trevor, Colin; Twesten, Ray D; Taheri, Mitra L

    2017-08-15

    In many cases, electron counting with direct detection sensors offers improved resolution, lower noise, and higher pixel density compared to conventional, indirect detection sensors for electron microscopy applications. Direct detection technology has previously been utilized, with great success, for imaging and diffraction, but potential advantages for spectroscopy remain unexplored. Here we compare the performance of a direct detection sensor operated in counting mode and an indirect detection sensor (scintillator/fiber-optic/CCD) for electron energy-loss spectroscopy. Clear improvements in measured detective quantum efficiency and combined energy resolution/energy field-of-view are offered by counting mode direct detection, showing promise for efficient spectrum imaging, low-dose mapping of beam-sensitive specimens, trace element analysis, and time-resolved spectroscopy. Despite the limited counting rate imposed by the readout electronics, we show that both core-loss and low-loss spectral acquisition are practical. These developments will benefit biologists, chemists, physicists, and materials scientists alike.

  4. High sensitivity detection of NO2 employing cavity ringdown spectroscopy and an external cavity continuously tunable quantum cascade laser.

    Science.gov (United States)

    Rao, Gottipaty N; Karpf, Andreas

    2010-09-10

    A trace gas sensor for the detection of nitrogen dioxide based on cavity ringdown spectroscopy (CRDS) and a continuous wave external cavity tunable quantum cascade laser operating at room temperature has been designed, and its features and performance characteristics are reported. By measuring the ringdown times of the cavity at different concentrations of NO(2), we report a sensitivity of 1.2 ppb for the detection of NO(2) in Zero Air.

  5. Highly sensitive analysis of boron and lithium in aqueous solution using dual-pulse laser-induced breakdown spectroscopy.

    Science.gov (United States)

    Lee, Dong-Hyoung; Han, Sol-Chan; Kim, Tae-Hyeong; Yun, Jong-Il

    2011-12-15

    We have applied a dual-pulse laser-induced breakdown spectroscopy (DP-LIBS) to sensitively detect concentrations of boron and lithium in aqueous solution. Sequential laser pulses from two separate Q-switched Nd:YAG lasers at 532 nm wavelength have been employed to generate laser-induced plasma on a water jet. For achieving sensitive elemental detection, the optimal timing between two laser pulses was investigated. The optimum time delay between two laser pulses for the B atomic emission lines was found to be less than 3 μs and approximately 10 μs for the Li atomic emission line. Under these optimized conditions, the detection limit was attained in the range of 0.8 ppm for boron and 0.8 ppb for lithium. In particular, the sensitivity for detecting boron by excitation of laminar liquid jet was found to be excellent by nearly 2 orders of magnitude compared with 80 ppm reported in the literature. These sensitivities of laser-induced breakdown spectroscopy are very practical for the online elemental analysis of boric acid and lithium hydroxide serving as neutron absorber and pH controller in the primary coolant water of pressurized water reactors, respectively.

  6. Depth sensitivity and source-detector separations for near infrared spectroscopy based on the Colin27 brain template.

    Directory of Open Access Journals (Sweden)

    Gary E Strangman

    Full Text Available Understanding the spatial and depth sensitivity of non-invasive near-infrared spectroscopy (NIRS measurements to brain tissue-i.e., near-infrared neuromonitoring (NIN - is essential for designing experiments as well as interpreting research findings. However, a thorough characterization of such sensitivity in realistic head models has remained unavailable. In this study, we conducted 3,555 Monte Carlo (MC simulations to densely cover the scalp of a well-characterized, adult male template brain (Colin27. We sought to evaluate: (i the spatial sensitivity profile of NIRS to brain tissue as a function of source-detector separation, (ii the NIRS sensitivity to brain tissue as a function of depth in this realistic and complex head model, and (iii the effect of NIRS instrument sensitivity on detecting brain activation. We found that increasing the source-detector (SD separation from 20 to 65 mm provides monotonic increases in sensitivity to brain tissue. For every 10 mm increase in SD separation (up to ~45 mm, sensitivity to gray matter increased an additional 4%. Our analyses also demonstrate that sensitivity in depth (S decreases exponentially, with a "rule-of-thumb" formula S=0.75*0.85(depth. Thus, while the depth sensitivity of NIRS is not strictly limited, NIN signals in adult humans are strongly biased towards the outermost 10-15 mm of intracranial space. These general results, along with the detailed quantitation of sensitivity estimates around the head, can provide detailed guidance for interpreting the likely sources of NIRS signals, as well as help NIRS investigators design and plan better NIRS experiments, head probes and instruments.

  7. [The influence of probe geometry on the sensitivity of tissue oximeter using near infra-red spectroscopy].

    Science.gov (United States)

    Wang, F; Ding, H; Lin, F

    2000-08-01

    Based on the modified Lambert-Beer law under scattering media, near infra-red spectroscopy tissue oximeter measures the changes of absorber concentrations (such as oxy-hemoglobin, deoxy-hemoglobin, cytochrome aa3). This is made possible by recording the optical density change under different physiological status. This paper describes the average penetration depth, average photon path-length and spatial sensitive profile in multi-layered tissue model using Monte-Carlo method. The result shows the probe geometry of the sensor, which is the separation between the light source and the detector, has a great influence on the sensitivity of measurement. Increasing this separation properly allows the improvement of the sensitivity of measurement and the increase of the probability of looking at oxygenation deep under the surface tissue. But this improvement is limited by the decrease of signal-noise ratio. Optimum probe spacing should be estimated for special tissue structure.

  8. Cell-specific and pH-sensitive nanostructure hydrogel based on chitosan as a photosensitizer carrier for selective photodynamic therapy.

    Science.gov (United States)

    Belali, Simin; Karimi, Ali Reza; Hadizadeh, Mahnaz

    2018-04-15

    The major problems of porphyrins as promising materials for photodynamic therapy (PDT) are their low solubility, subsequently aggregation in biological environments, and a lack of tumor selectivity. With this in mind, a chitosan-based hydrogel conjugated with tetrakis(4-aminophenyl)porphyrin (NH 2 -TPP) and 2,4,6-tris(p-formylphenoxy)-1,3,5-triazine (TRIPOD) via Schiff base linkage, functionalized with folate was designed and synthesized as a pH-sensitive, self-healable and injectable targeted PS delivery system. This new hydrogel was characterized by FT-IR, 1 H NMR, SEM, UV-vis, fluorescence spectroscopy and zeta potential. Formation of imine bonds with the aldehyde group of TRIPOD and amine group of NH 2 -TPP and chitosan, as a dynamic connection, was approved by rheological analysis. Spectroscopic characterizations revealed that aggregation of porphyrin in aqueous media was eliminated due to diminished π stacking interaction of porphyrin in 3D cross-linked hydrogel structure. Hydrogel 3D microporous structure efficiently transfers the excitation energy to the porphyrin unit, yielding improvement singlet oxygen releases. Cytotoxicity and phototoxicity analysis of the CS/NH 2 -TPP/FA hydrogels indicating an excellent capability to kill cancer cells selectively and prevent damage to normal cells. This work presents a new and efficient model for the preparation of highly efficient and targeting photosensitizer delivery system. Copyright © 2018. Published by Elsevier B.V.

  9. Ultrafast Spectroscopy of Energetic Materials: Toward a Molecular Understanding of Impact Sensitivity

    National Research Council Canada - National Science Library

    Dlott, Dana D

    2005-01-01

    ... with 1.5 Angstrom resolution. With 3D spectroscopy we have studied vibrational energy transfer in water and for the first time we have been able to watch vibrational energy flow across the interface between a molecular nanostructure and its surroundings.

  10. Cationic effect on dye-sensitized solar cell properties using electrochemical impedance and transient absorption spectroscopy techniques

    International Nuclear Information System (INIS)

    Gupta, Ravindra Kumar; Bedja, Idriss

    2017-01-01

    Redox-couple polymer electrolytes, (poly(ethylene oxide)-succinonitrile) blend/MI-I 2 , where M  =  Li or K, were prepared by the solution cast method. Owing to the plasticizing property of K + ions, the K + ion-based electrolyte exhibited better electrical conductivity than the Li + ion-based electrolyte, which did however exhibit better photovoltaic properties. Electrochemical impedance spectroscopy revealed faster redox species diffusions and interfacial processes in the Li + ion-based dye-sensitized solar cells than in the K + ion-based ones. Transient absorption spectroscopy ascertained faster dye-regeneration by the Li + ion-based electrolyte than the K + ion-based electrolyte. (paper)

  11. Wavenumber selection based analysis in Raman spectroscopy improves skin cancer diagnostic specificity at high sensitivity levels (Conference Presentation)

    Science.gov (United States)

    Zhao, Jianhua; Zeng, Haishan; Kalia, Sunil; Lui, Harvey

    2017-02-01

    Background: Raman spectroscopy is a non-invasive optical technique which can measure molecular vibrational modes within tissue. A large-scale clinical study (n = 518) has demonstrated that real-time Raman spectroscopy could distinguish malignant from benign skin lesions with good diagnostic accuracy; this was validated by a follow-up independent study (n = 127). Objective: Most of the previous diagnostic algorithms have typically been based on analyzing the full band of the Raman spectra, either in the fingerprint or high wavenumber regions. Our objective in this presentation is to explore wavenumber selection based analysis in Raman spectroscopy for skin cancer diagnosis. Methods: A wavenumber selection algorithm was implemented using variably-sized wavenumber windows, which were determined by the correlation coefficient between wavenumbers. Wavenumber windows were chosen based on accumulated frequency from leave-one-out cross-validated stepwise regression or least and shrinkage selection operator (LASSO). The diagnostic algorithms were then generated from the selected wavenumber windows using multivariate statistical analyses, including principal component and general discriminant analysis (PC-GDA) and partial least squares (PLS). A total cohort of 645 confirmed lesions from 573 patients encompassing skin cancers, precancers and benign skin lesions were included. Lesion measurements were divided into training cohort (n = 518) and testing cohort (n = 127) according to the measurement time. Result: The area under the receiver operating characteristic curve (ROC) improved from 0.861-0.891 to 0.891-0.911 and the diagnostic specificity for sensitivity levels of 0.99-0.90 increased respectively from 0.17-0.65 to 0.20-0.75 by selecting specific wavenumber windows for analysis. Conclusion: Wavenumber selection based analysis in Raman spectroscopy improves skin cancer diagnostic specificity at high sensitivity levels.

  12. A spirooxazine derivative as a highly sensitive cyanide sensor by means of UV-visible difference spectroscopy.

    Science.gov (United States)

    Zhu, Shaoyin; Li, Minjie; Sheng, Lan; Chen, Peng; Zhang, Yumo; Zhang, Sean Xiao-An

    2012-12-07

    A spirooxazine derivative 2-nitro-5a-(2-(4-dimethylaminophenyl)-ethylene)-6,6-dimethyl-5a,6-dihydro-12H-indolo[2,1-b][1,3]benzooxazine (P1) was explored as a sensitive cyanide probe. Different from conventional spiropyrans, P1 avoided locating the 3H-indolium cation and the 4-nitrophenolate anion in the same conjugated structure, which enhanced the positive charge of 3H-indolium cation so that the sensitivity and reaction speed were improved highly. UV-visible difference spectroscopy using P1 detection solution as a timely reference improved the measurement accuracy, prevented the error caused by the inherent absorption change of P1 solution with time. This enabled the "positive-negative alternative absorption peaks" in difference spectrum to be used as a finger-print to distinguish whether the spectral change was caused by cyanide. Benefiting from the special design of the molecular structure and the strategy of difference spectroscopy, P1 showed high selectivity and sensitivity for CN(-). A detection limit of 0.4 μM and a rate constant of 1.1 s(-1) were achieved.

  13. High-field {sup 1}H NMR microscopy for fundamental biophysical research; Hochfeld {sup 1}H-NMR-Mikroskopie zur biophysikalischen Grundlagenforschung

    Energy Technology Data Exchange (ETDEWEB)

    Haddad, D.

    2003-08-08

    This work has a biophysical background and uses different examples to demonstrate the practical applicability of NMR-Microscopy in the medical and biological sector. Therefore, the different projects are feasibility studies which are used to compare the possibilities and advantages of NMR-Microscopy with other, established examination techniques. In detail, using MR-Microscopy, different living and fixed biological samples have been visualized non-invasively with high spatial resolution. The specific purpose of the studies ranged from the visualization of the invasion of tumor-spheroids into cell aggregates using T2 parameter maps (time constant of the spin-spin relaxation) to the three-dimensional display of the honey bee brain in the intact head capsule and the non-invasive visualization of the anatomy of prenatal dolphins. For all these projects, the non-invasive character of MR-experiments was of utmost importance. The tumor invasion was not to be disturbed by the measurements, the bee brain should be visualized as close to its true natural shape as possible and the examined dolphins represent rare museum specimens which should not be destroyed. The different samples were all imaged with the best possible spatial resolution which was either limited by the necessary signal-to-noise ratio (SNR) or the available scan time. In order to resolve single details and fine structures in the images, it was necessary to optimize the SNR as well as the contrast-to-noise ratio. To guarantee the necessary SNR, the measurements were performed on high field MR-spectrometers with resonance frequencies of 500 and 750 MHz.

  14. Photocurrent Spectroscopy of Perovskite Layers and Solar Cells: A Sensitive Probe of Material Degradation

    KAUST Repository

    Holovský , Jakub; De Wolf, Stefaan; Werner, Jé ré mie; Remeš, Zdeněk; Mü ller, Martin; Neykova, Neda; Ledinský , Martin; Černá , Ladislava; Hrzina, Pavel; Lö per, Philipp; Niesen, Bjoern; Ballif, Christophe

    2017-01-01

    Optical absorptance spectroscopy of polycrystalline CHNHPbI films usually indicates the presence of a PbI phase, either as a preparation residue or due to film degradation, but gives no insight on how this may affect electrical properties. Here, we apply photocurrent spectroscopy to both perovskite solar cells and coplanar-contacted layers at various stages of degradation. In both cases, we find that the presence of a PbI phase restricts charge-carrier transport, suggesting that PbI encapsulates CHNHPbI grains. We also find that PbI injects holes into the CHNHPbI grains, increasing the apparent photosensitivity of PbI. This phenomenon, known as modulation doping, is absent in the photocurrent spectra of solar cells, where holes and electrons have to be collected in pairs. This interpretation provides insights into the photogeneration and carrier transport in dual-phase perovskites.

  15. Photocurrent Spectroscopy of Perovskite Layers and Solar Cells: A Sensitive Probe of Material Degradation

    KAUST Repository

    Holovský, Jakub

    2017-01-25

    Optical absorptance spectroscopy of polycrystalline CHNHPbI films usually indicates the presence of a PbI phase, either as a preparation residue or due to film degradation, but gives no insight on how this may affect electrical properties. Here, we apply photocurrent spectroscopy to both perovskite solar cells and coplanar-contacted layers at various stages of degradation. In both cases, we find that the presence of a PbI phase restricts charge-carrier transport, suggesting that PbI encapsulates CHNHPbI grains. We also find that PbI injects holes into the CHNHPbI grains, increasing the apparent photosensitivity of PbI. This phenomenon, known as modulation doping, is absent in the photocurrent spectra of solar cells, where holes and electrons have to be collected in pairs. This interpretation provides insights into the photogeneration and carrier transport in dual-phase perovskites.

  16. Phase transition behavior of novel pH-sensitive polyaspartamide derivatives grafted with 1-(3-aminopropyl)imidazole.

    Science.gov (United States)

    Seo, Kwangwon; Kim, Dukjoon

    2006-09-15

    New pH-sensitive polyaspartamide derivatives were synthesized by grafting 1-(3-aminopropyl)imidazole and/or O-(2-aminoethyl)-O'-methylpoly(ethylene glycol) 5000 on polysuccinimide for application in intracellular drug delivery systems. The DS of 1-(3-aminopropyl)imidazole was adjusted by the feed molar ratio, and the structure of the prepared polymer was confirmed using FT-IR and 1H NMR spectroscopy. Their pH-sensitive properties were characterized by light transmittance measurements, and the particle size and its distribution were investigated by dynamic light scattering measurements at varying pH values. The pH-sensitive phase transition was clearly observed in polymer solutions with a high substitution of 1-(3-aminopropyl)imidazole. The prepared polymers showed a high buffering capacity between pH 5 and 7, and this increased with the DS of 1-(3-aminopropyl)imidazole. The pH dependence of the aggregation and de-aggregation behavior was examined using a fluorescence spectrometer. For MPEG/imidazole-g-polyaspartamides with a DS of 1-(3-aminopropyl)imidazole over 82%, self aggregates associated with the hydrophobic interactions of the unprotonated imidazole groups were observed at pH values above 7, and their mean size was over 200 nm, while the aggregates of polymers were dissociated at pH values below 7 by the protonation of imidazole groups. These pH-sensitive polyaspartamide derivatives are potential basic candidates for intracellular drug delivery carriers triggered by small pH changes.

  17. A novel aptasensor based on single-molecule force spectroscopy for highly sensitive detection of mercury ions.

    Science.gov (United States)

    Li, Qing; Michaelis, Monika; Wei, Gang; Colombi Ciacchi, Lucio

    2015-08-07

    We have developed a novel aptasensor based on single-molecule force spectroscopy (SMFS) capable of detecting mercury ions (Hg(2+)) with sub-nM sensitivity. The single-strand (ss) DNA aptamer used in this work is rich in thymine (T) and readily forms T-Hg(2+)-T complexes in the presence of Hg(2+). The aptamer was conjugated to an atomic force microscope (AFM) probe, and the adhesion force between the probe and a flat graphite surface was measured by single-molecule force spectroscopy (SMFS). The presence of Hg(2+) ions above a concentration threshold corresponding to the affinity constant of the ions for the aptamer (about 5 × 10(9) M(-1)) could be easily detected by a change of the measured adhesion force. With our chosen aptamer, we could reach an Hg(2+) detection limit of 100 pM, which is well below the maximum allowable level of Hg(2+) in drinking water. In addition, this aptasensor presents a very high selectivity for Hg(2+) over other metal cations, such as K(+), Ca(2+), Zn(2+), Fe(2+), and Cd(2+). Furthermore, the effects of the ionic strength and loading rate on the Hg(2+) detection were evaluated. Its simplicity, reproducibility, high selectivity and sensitivity make our SMFS-based aptasensor advantageous with respect to other current Hg(2+) sensing methods. It is expected that our strategy can be exploited for monitoring the pollution of water environments and the safety of potentially contaminated food.

  18. Resonance-enhanced laser-induced plasma spectroscopy for sensitive elemental analysis: Elucidation of enhancement mechanisms

    International Nuclear Information System (INIS)

    Lui, S.L.; Cheung, N.H.

    2002-01-01

    When performing laser-induced plasma spectroscopy for elemental analysis, the analyte signal-to-noise ratio increased from four to over fifty if the plume was reheated by a dye laser pulse tuned to resonant absorption. Time-resolved studies showed that the enhancement was not due to resonance photoionization. Rather, efficient and controlled rekindling of a larger plume volume was the key mechanism. The signal-to-noise ratio further increased to over a hundred if the atmosphere was replaced by a low-pressure heavy inert gas. The ambient gas helped confine and thermally insulate the expanding vapor

  19. Photocurrent spectroscopy of perovskite layers and solar cells: a sensitive probe of material degradation

    Czech Academy of Sciences Publication Activity Database

    Holovský, Jakub; De Wolf, S.; Werner, J.; Remeš, Zdeněk; Müller, Martin; Neykova, Neda; Ledinský, Martin; Černá, L.; Hrzina, P.; Löper, P.; Niesen, B.; Ballif, C.

    2017-01-01

    Roč. 8, č. 4 (2017), s. 838-843 ISSN 1948-7185 R&D Projects: GA ČR GJ17-26041Y; GA MŠk LM2015087 Grant - others:AV ČR(CZ) KONNECT-007 Program:Bilaterální spolupráce Institutional support: RVO:68378271 Keywords : photocurrent spectroscopy * perovskite layers * solar cells Subject RIV: BM - Solid Matter Physics ; Magnetism OBOR OECD: Condensed matter physics (including formerly solid state physics, supercond.) Impact factor: 9.353, year: 2016

  20. Sensitivity enhancement of 13C nuclei in 2D J-resolved NMR spectroscopy using a recycled-flow system

    International Nuclear Information System (INIS)

    Ha, S.T.K.; Lee, R.W.K.; Wilkins, C.L.

    1987-01-01

    Recycled-flow nuclear magnetic resonance for sensitivity enhancement in 1/2 spin nuclei has been reported previously, achieving several-fold signal enhancement. The success of the method depends upon premagnetization of nuclei prior to flowing into the detector region, obviating the need for delays following data acquisition to allow spin-lattice relaxation and reduce experiment time. The actual gains of sensitivity enhancement for 13 C- 1 H 2D J-resolved NMR using a recycled-flow method are evaluated. Possible enhancements for two types of J-resolved measurements, namely, one-bond 13 C- 1 H and long range J-resolved spectroscopy, are estimated using a simple Carr-Purcell spin-echo approach to quantify the 13 C signals. The pulse sequence is simply 90 0 -t /sub 1/2/-180 0 -t/sub 1/2/-AT-t/sub d/, where t/sub 1/2/ is half the evolution time, AT is the acquisition time, and t/sub d/ the experiment repetition time. In a static 2D NMR experiment, t/sub d/ usually must be the same order of the longest spin-lattice relaxation time (T 1 ) of nuclei. Quantitative measurements using a recycled-flow system indicate t/dub d/ can be reduced to a fraction of T 1 ; hence significant time savings can be achieved. Time-savings of between 2 and 25 can be anticipated for 2D spectroscopy under flow measurement conditions used in the present study. Other types of 2D NMR spectroscopy (autocorrelation and double quantum NMR) are discussed

  1. Low Dose X-Ray Speckle Visibility Spectroscopy Reveals Nanoscale Dynamics in Radiation Sensitive Ionic Liquids

    Science.gov (United States)

    Verwohlt, Jan; Reiser, Mario; Randolph, Lisa; Matic, Aleksandar; Medina, Luis Aguilera; Madsen, Anders; Sprung, Michael; Zozulya, Alexey; Gutt, Christian

    2018-04-01

    X-ray radiation damage provides a serious bottleneck for investigating microsecond to second dynamics on nanometer length scales employing x-ray photon correlation spectroscopy. This limitation hinders the investigation of real time dynamics in most soft matter and biological materials which can tolerate only x-ray doses of kGy and below. Here, we show that this bottleneck can be overcome by low dose x-ray speckle visibility spectroscopy. Employing x-ray doses of 22-438 kGy and analyzing the sparse speckle pattern of count rates as low as 6.7 ×10-3 per pixel, we follow the slow nanoscale dynamics of an ionic liquid (IL) at the glass transition. At the prepeak of nanoscale order in the IL, we observe complex dynamics upon approaching the glass transition temperature TG with a freezing in of the alpha relaxation and a multitude of millisecond local relaxations existing well below TG . We identify this fast relaxation as being responsible for the increasing development of nanoscale order observed in ILs at temperatures below TG .

  2. An efficient digital phase sensitive detector for use in electron spin resonance spectroscopy

    International Nuclear Information System (INIS)

    Vistnes, A.I; Wormald, D.I.; Isachsen, S.

    1983-10-01

    A digital sensitive detector for a modified Bruker electron spin resonance spectrometer, equipped with an Aspect 2000 minicomputer, is described. Magnetic field modulation is derived from a clock in the computer, which makes it possible to perform the data acquisition fully synchronously with the modulation. The resulting high phase accuracy makes it possible to compress the data to a single modulation period before the Fourier transformation. Both the in-phase and the phase-quadrature signals (of the first or second harmonic) are recorded simultaneously. The system makes the data processing, including the Fourier transformation, approximately 1000 times faster than previously reported digital phase sensitive detector systems for electron spin resonance spectrometers

  3. Spectral sensitization of TiO2 by new hemicyanine dyes in dye solar cell yielding enhanced photovoltage: Probing chain length effect on performance

    International Nuclear Information System (INIS)

    Fadadu, Kishan B.; Soni, Saurabh S.

    2013-01-01

    Graphical abstract: New hemicyanine dyes based on indolenine moiety were utilized as light harvesting materials in dye sensitized solar cell. Chain lengths of the molecules were varied in order to study its effect of chain length on the performance of DSSC. Electron transfer kinetic of the solar cell was studied and it was found that the chain length changes the electron transfer kinetic. We have achieved remarkable photovoltage and overall performance of DSSC. Highlights: ► New hemicyanine dyes based on indolenine moiety were utilized as light harvesting materials in dye sensitized solar cell. ► Chain lengths of the molecules were varied in order to study its effect of chain length on the performance of DSSC. ► Electron transfer kinetic of the solar cell was studied and it was found that the chain length changes the electron transfer kinetic. -- Abstract: New hemicyanine dyes having indole nucleus with different alkyl chain length were synthesized and characterized using 1 H NMR and mass spectroscopy. These dyes were used to sensitize the TiO 2 film in dye sensitized solar cell. Nanocrystalline dye solar cells were fabricated and characterized using various electrochemical techniques. It has been found that the alkyl chain length present in the dye molecules greatly affects the overall performance of dye solar cell. Molecules having longer alkyl chain are having better sensitizers which enhance V oc to significant extent. Chain length dependent performance was further investigated using Tafel polarization and impedance method. Hemicyanine dye having hexyl chain has outperformed by attaining 2.9% solar to electricity conversion efficiency

  4. Sensitive and ultra-fast species detection using pulsed cavity ringdown spectroscopy

    KAUST Repository

    Alquaity, Awad; Es-sebbar, Et-touhami; Farooq, Aamir

    2015-01-01

    of ethylene in the mid-IR region near 949.47 cm-1. Each ringdown measurement is completed in less than 1 μs and the time period between successive pulses is 10 μs. The high sensitivity diagnostic has a noise-equivalent detection limit of 1.08 x 10-5 cm-1 which

  5. High-sensitivity ultraviolet photoemission spectroscopy technique for direct detection of gap states in organic thin films

    Energy Technology Data Exchange (ETDEWEB)

    Bussolotti, Fabio, E-mail: fabio@ims.ac.jp

    2015-10-01

    Highlights: • Density of gap states in organic thin film was detected by photoemission spectroscopy. • Inert gas exposure affects the density of gap states in organic thin films. • Density of gap states controls the energy level alignment at the organic/inorganic and organic/organic interfaces. - Abstract: We developed ultrahigh sensitivity, low-background ultraviolet photoemission spectroscopy (UPS) technique which does not introduce detectable radiation damages into organic materials. The UPS allows to detect density of states of the order of ∼10{sup 16} states eV{sup −1} cm{sup −3} even for radiation-sensitive organic films, this results being comparable to electrical measurements of charge trapping centers. In this review we introduce the method of ultrahigh sensitivity photoemission measurement and we present some results on the energy distribution of gap states in pentacene (Pn) films deposited on SiO{sub 2} and Au(1 1 1) substrate. For Pn/SiO{sub 2} thin film the results show that exposure to inert gas (N{sub 2} and Ar) atmosphere produces a sharp rise in gap states from 10{sup 16} to 10{sup 18} states eV{sup −1} cm{sup −3} and pushes the Fermi level closer to the valence band (0.15–0.17 eV), as does exposure to O{sub 2} (0.20 eV), while no such gas-induced effects are observed for Pn/Au(1 1 1) system. The results demonstrate that these gap states originate from small imperfections in the Pn packing structure, which are induced by gas penetration into the film through the Pn crystal grain boundaries. Similar results were obtained for CuPc/F{sub 16}CuPc thin films, a prototypical example of donor/acceptor interface for photovoltaic application.

  6. High sensitivity spectroscopy with tunable diode lasers - detection of O2 quadrupole transitions and 14C

    International Nuclear Information System (INIS)

    Reid, J.

    1981-01-01

    In recent years, tunable lead-salt diode lasers (TDLs) have found widespread application in all fields of infrared spectroscopy. However, most applications of TDLs utilise only the tunability and high resolution of these devices, and few experiments have employed the ability of the TDL to detect very small absorption coefficients. We have developed a laser absorption spectrometer (LAS) which can detect absorption coefficients as small as 10 -6 to 10 -7 m -1 , while retaining the full tunability and resolution of the TDL. This instrument has been used as a point monitoring system for many trace gases of atmospheric significance. In this paper, we describe two additional applications of the LAS: (I) the detection of very weak transitions such as quadrupole lines in oxygen, and (II) the detection of rare isotopes, with 14 C in CO 2 as an example. Details are given in the following sections. (orig.)

  7. Detection sensitivity of laser-induced breakdown spectroscopy for Cr II in liquid samples

    International Nuclear Information System (INIS)

    Rai, Nilesh K.; Rai, Awadhesh K.; Kumar, Akshaya; Thakur, Surya N.

    2008-01-01

    The performance of laser-induced breakdown spectroscopy (LIBS) has been evaluated for detection of toxic metals such as Cr in water. Pure aqueous solutions (unitary matrix) with variable Cr concentration were used to construct calibration curves and to estimate the LIBS limit of detection (LOD). The calibration curves for Cr in a binary matrix (Cr plus Cd) and a tertiary matrix (Cr plus Cd and Co) were used to evaluate the matrix effect on the LOD. The LOD for Cr was found to be 1.1, 1.5, and 2.0 ppm (parts in 10 6 ) in a unitary, binary, and tertiary matrix, respectively. Once calibrated, the system was utilized for the detection and quantification of the Cr in tannery wastewater collected from different locations in the industrial area of Kanpur, India, where Cr concentrations were determined to be far higher than the U.S. Environmental Protection Agency safe drinking water limit of 0.05 ppm

  8. Polarization Sensitive Coherent Anti-Stokes Raman Spectroscopy of DCVJ in Doped Polymer

    Science.gov (United States)

    Ujj, Laszlo

    2014-05-01

    Coherent Raman Microscopy is an emerging technic and method to image biological samples such as living cells by recording vibrational fingerprints of molecules with high spatial resolution. The race is on to record the entire image during the shortest time possible in order to increase the time resolution of the recorded cellular events. The electronically enhanced polarization sensitive version of Coherent anti-Stokes Raman scattering is one of the method which can shorten the recording time and increase the sharpness of an image by enhancing the signal level of special molecular vibrational modes. In order to show the effectiveness of the method a model system, a highly fluorescence sample, DCVJ in a polymer matrix is investigated. Polarization sensitive resonance CARS spectra are recorded and analyzed. Vibrational signatures are extracted with model independent methods. Details of the measurements and data analysis will be presented. The author gratefully acknowledge the UWF for financial support.

  9. Highly sensitive three-dimensional interdigitated microelectrode for microparticle detection using electrical impedance spectroscopy

    International Nuclear Information System (INIS)

    Chang, Fu-Yu; Chen, Ming-Kun; Jang, Ling-Sheng; Wang, Min-Haw

    2016-01-01

    Cell impedance analysis is widely used for monitoring biological and medical reactions. In this study, a highly sensitive three-dimensional (3D) interdigitated microelectrode (IME) with a high aspect ratio on a polyimide (PI) flexible substrate was fabricated for microparticle detection (e.g. cell quantity detection) using electroforming and lithography technology. 3D finite element simulations were performed to compare the performance of the 3D IME (in terms of sensitivity and signal-to-noise ratio) to that of a planar IME for particles in the sensing area. Various quantities of particles were captured in Dulbecco’s modified Eagle medium and their impedances were measured. With the 3D IME, the particles were arranged in the gap, not on the electrode, avoiding the noise due to particle position. For the maximum particle quantities, the results show that the 3D IME has at least 5-fold higher sensitivity than that of the planar IME. The trends of impedance magnitude and phase due to particle quantity were verified using the equivalent circuit model. The impedance (1269 Ω) of 69 particles was used to estimate the particle quantity (68 particles) with 98.6% accuracy using a parabolic regression curve at 500 kHz. (paper)

  10. Application of two-dimensional J-resolved nuclear magnetic resonance spectroscopy to differentiation of beer

    International Nuclear Information System (INIS)

    Khatib, Alfi; Wilson, Erica G.; Kim, Hye Kyong; Lefeber, Alfons W.M.; Erkelens, Cornelis; Choi, Young Hae; Verpoorte, Robert

    2006-01-01

    A number of ingredients in beer that directly or indirectly affect its quality require an unbiased wide-spectrum analytical method that allows for the determination of a wide array of compounds for its efficient control. 1 H nuclear magnetic resonance (NMR) spectroscopy is a method that clearly meets this description as the broad range of compounds in beer is detectable. However, the resulting congestion of signals added to the low resolution of 1 H NMR spectra makes the identification of individual components very difficult. Among two-dimensional (2D) NMR techniques that increase the resolution, J-resolved NMR spectra were successfully applied to the analysis of 2-butanol extracts of beer as overlapping signals in 1 H NMR spectra were fully resolved by the additional axis of the coupling constant. Principal component analysis based on the projected J-resolved NMR spectra showed a clear separation between all of the six brands of pilsner beer evaluated in this study. The compounds responsible for the differentiation were identified by 2D NMR spectra including correlated spectroscopy and heteronuclear multiple bond correlation spectra together with J-resolved spectra. They were identified as nucleic acid derivatives (adenine, uridine and xanthine), amino acids (tyrosine and proline), organic acid (succinic and lactic acid), alcohol (tyrosol and isopropanol), cholines and carbohydrates

  11. Filter paper saturated by urine sample in metabolic disorders detection by proton magnetic resonance spectroscopy.

    Science.gov (United States)

    Blasco, Hélène; Garrigue, Marie-Ange; De Vos, Aymeric; Antar, Catherine; Labarthe, François; Maillot, François; Andres, Christian R; Nadal-Desbarats, Lydie

    2010-02-01

    NMR spectroscopy of urine samples is able to diagnose many inborn errors of metabolism (IEM). However, urinary metabolites have a poor stability, requiring special care for routine analysis (storage of urine at -20 or -80 degrees C, fast transport). The aim of our study was to investigate the reliability of dried urine filter paper for urine storage and transport and to evaluate the ability of NMR to detect several IEM using this method. Urine samples from five healthy subjects were analyzed by (1)H NMR following different storage conditions (-20 vs 4 degrees C vs dried on filter paper) and at different time points (24 h, 48 h, 96 h, and 7 days). Urine pattern of fresh urine was considered as a reference. We analyzed the conservation of some amino acids and organic acids using Bland and Altman plot with intraclass correlation coefficient determination. Then, we evaluated the use of filter paper to detect four different IEM (methylmalonic and isovaleric acidurias, ornithine transcarbamylase deficiency, and cystinuria). Analysis of urine samples from healthy subjects revealed a high stability of studied molecules (ICC > 0.8) even after 7 days of storage on filter paper. Moreover, an excellent preservation of metabolites specifically accumulated in IEM was observed when analysis of dried urine filter paper was compared to fresh urine (coefficient of variation storage of dried urine on filter paper is reliable for (1)H NMR spectroscopy analysis. Preservation of urine molecules over time using that method is convenient for routine clinical practice.

  12. Accelerating two-dimensional nuclear magnetic resonance correlation spectroscopy via selective coherence transfer

    Science.gov (United States)

    Ye, Qimiao; Chen, Lin; Qiu, Wenqi; Lin, Liangjie; Sun, Huijun; Cai, Shuhui; Wei, Zhiliang; Chen, Zhong

    2017-01-01

    Nuclear magnetic resonance (NMR) spectroscopy serves as an important tool for both qualitative and quantitative analyses of various systems in chemistry, biology, and medicine. However, applications of one-dimensional 1H NMR are often restrained by the presence of severe overlap among different resonances. The advent of two-dimensional (2D) 1H NMR constitutes a promising alternative by extending the crowded resonances into a plane and thereby alleviating the spectral congestions. However, the enhanced ability in discriminating resonances is achieved at the cost of extended experimental duration due to necessity of various scans with progressive delays to construct the indirect dimension. Therefore, in this study, we propose a selective coherence transfer (SECOT) method to accelerate acquisitions of 2D correlation spectroscopy by converting chemical shifts into spatial positions within the effective sample length and then performing an echo planar spectroscopic imaging module to record the spatial and spectral information, which generates 2D correlation spectrum after 2D Fourier transformation. The feasibility and effectiveness of SECOT have been verified by a set of experiments under both homogeneous and inhomogeneous magnetic fields. Moreover, evaluations of SECOT for quantitative analyses are carried out on samples with a series of different concentrations. Based on these experimental results, the SECOT may open important perspectives for fast, accurate, and stable investigations of various chemical systems both qualitatively and quantitatively.

  13. Complex Mixture Analysis of Organic Compounds in Yogurt by NMR Spectroscopy

    Science.gov (United States)

    Lu, Yi; Hu, Fangyu; Miyakawa, Takuya; Tanokura, Masaru

    2016-01-01

    NMR measurements do not require separation and chemical modification of samples and therefore rapidly and directly provide non-targeted information on chemical components in complex mixtures. In this study, one-dimensional (1H, 13C, and 31P) and two-dimensional (1H-13C and 1H-31P) NMR spectroscopy were conducted to analyze yogurt without any pretreatment. 1H, 13C, and 31P NMR signals were assigned to 10 types of compounds. The signals of α/β-lactose and α/β-galactose were separately observed in the 1H NMR spectra. In addition, the signals from the acyl chains of milk fats were also successfully identified but overlapped with many other signals. Quantitative difference spectra were obtained by subtracting the diffusion ordered spectroscopy (DOSY) spectra from the quantitative 1H NMR spectra. This method allowed us to eliminate interference on the overlaps; therefore, the correct intensities of signals overlapped with those from the acyl chains of milk fat could be determined directly without separation. Moreover, the 1H-31P HMBC spectra revealed for the first time that N-acetyl-d-glucosamine-1-phosphate is contained in yogurt. PMID:27322339

  14. Study of acute biochemical effects of thallium toxicity in mouse urine by NMR spectroscopy.

    Science.gov (United States)

    Tyagi, Ritu; Rana, Poonam; Khan, Ahmad Raza; Bhatnagar, Deepak; Devi, M Memita; Chaturvedi, Shubhra; Tripathi, Rajendra P; Khushu, Subash

    2011-10-01

    Thallium (Tl) is a toxic heavy metal and its exposure to the human body causes physiological and biochemical changes due to its interference with potassium-dependent biological reactions. A high-resolution (1)H NMR spectroscopy based metabonomic approach has been applied for investigating acute biochemical effects caused by thallium sulfate (Tl(2)SO(4)). Male strain A mice were divided in three groups and received three doses of Tl(2)SO(4) (5, 10 and 20 mg kg(-1) b.w., i.p.). Urine samples collected at 3, 24, 72 and 96 h post-dose time points were analyzed by (1)H NMR spectroscopy. NMR spectral data were processed and analyzed using principal components analysis to represent biochemical variations induced by Tl(2)SO(4). Results showed Tl-exposed mice urine to have distinct metabonomic phenotypes and revealed dose- and time-dependent clustering of treated groups. The metabolic signature of urine analysis from Tl(2)SO(4)-treated animals exhibited an increase in the levels of creatinine, taurine, hippurate and β-hydroxybutyrate along with a decrease in energy metabolites trimethylamine and choline. These findings revealed Tl-induced disturbed gut flora, membrane metabolite, energy and protein metabolism, representing physiological dysfunction of vital organs. The present study indicates the great potential of NMR-based metabonomics in mapping metabolic response for toxicology, which could ultimately lead to identification of potential markers for Tl toxicity. Copyright © 2011 John Wiley & Sons, Ltd.

  15. GIOVE: a new detector setup for high sensitivity germanium spectroscopy at shallow depth

    International Nuclear Information System (INIS)

    Heusser, G.; Weber, M.; Hakenmüller, J.; Laubenstein, M.; Lindner, M.; Maneschg, W.; Simgen, H.; Stolzenburg, D.; Strecker, H.

    2015-01-01

    We report on the development and construction of the high-purity germanium spectrometer setup GIOVE (Germanium Inner Outer VEto), recently built and now operated at the shallow underground laboratory of the Max-Planck-Institut für Kernphysik, Heidelberg. Particular attention was paid to the design of a novel passive and active shield, aiming at efficient rejection of environmental and muon induced radiation backgrounds. The achieved sensitivity level of ≤100 μBq kg -1 for primordial radionuclides from U and Th in typical γ ray sample screening measurements is unique among instruments located at comparably shallow depths and can compete with instruments at far deeper underground sites

  16. GIOVE: a new detector setup for high sensitivity germanium spectroscopy at shallow depth

    Energy Technology Data Exchange (ETDEWEB)

    Heusser, G.; Weber, M.; Hakenmueller, J.; Lindner, M.; Maneschg, W.; Simgen, H.; Stolzenburg, D.; Strecker, H. [Max-Planck-Institut fuer Kernphysik, Heidelberg (Germany); Laubenstein, M. [Laboratori Nazionali del Gran Sasso, Assergi (Italy)

    2015-11-15

    We report on the development and construction of the high-purity germanium spectrometer setup GIOVE (Germanium Inner Outer VEto), recently built and now operated at the shallow underground laboratory of the Max-Planck-Institut fuer Kernphysik, Heidelberg. Particular attention was paid to the design of a novel passive and active shield, aiming at efficient rejection of environmental and muon induced radiation backgrounds. The achieved sensitivity level of ≤ 100μBq kg{sup -1} for primordial radionuclides from U and Th in typical γ ray sample screening measurements is unique among instruments located at comparably shallow depths and can compete with instruments at far deeper underground sites. (orig.)

  17. Highly Sensitive Detection of Clenbuterol in Animal Urine Using Immunomagnetic Bead Treatment and Surface-Enhanced Raman Spectroscopy

    Science.gov (United States)

    Cheng, Jie; Su, Xiao-Ou; Wang, Shi; Zhao, Yiping

    2016-09-01

    Combining surface-enhanced Raman spectroscopy (SERS) of aggregated graphene oxide/gold nanoparticle hybrids with immunomagnetic bead sample preparation method, a highly sensitive strategy to determine the clenbuterol content in animal urine was developed. Based on a linear calibration curve of the SERS characteristic peak intensity of clenbuterol at Δv = 1474 cm-1 versus the spiked clenbuterol concentration in the range of 0.5-20 ng·mL-1, the quantity of clenbuterol in real animal urine samples can be determined and matches well with those determined by LC-MS/MS, while the detection time is significantly reduced to 15 min/sample. The limits of detection and quantification in the urine are 0.5 ng·mL-1 and 1 ng·mL-1, respectively, and the recovery clenbuterol rates are 82.8-92.4% with coefficients of variation farming.

  18. New robust sensitive fluorescence spectroscopy coupled with PLSR for estimation of quercetin in Ziziphus mucronata and Ziziphus sativa

    Science.gov (United States)

    Hussain, Javid; Mabood, Fazal; Al-Harrasi, Ahmed; Ali, Liaqat; Rizvi, Tania Shamim; Jabeen, Farah; Gilani, Syed Abdullah; Shinwari, Shehla; Ahmad, Mushtaq; Alabri, Zahra Khalfan; Al Ghawi, Said Hamood Salim

    2018-04-01

    Flavonoids are natural antioxidants derived from plants and commonly found in a variety of foods to sequester free radicals. Quercetin, belonging to flavonol subclass of flavonoids, has received considerable attention because of its wide uses as a nutritional supplement as well as a phytochemical remedy for a number of diseases. In the current study, quantification of quercetin was carried out in two medicinally important flavonoid rich plant Ziziphus mucronata and Ziziphus sativa. Emission spectroscopy was utilized as a new method coupled with Partial Least Squares Regression (PLSR) and the cross validation was done by UV-Visible spectroscopy. The results indicated the higher quercetin content in Z. mucronata (1.50 ± 0.034%) than Z. sativa (1.21 ± 0.052%), and were further verified through Folin-Ciocalteu Colorimetric method (Z. mucronata; 1.41 ± 0.26% and Z. sativa; 1.13 ± 0.136%). In this study the sensitivity was explained in term of slope i.e. Slope = 0.9973.

  19. Rhodanine dyes for dye-sensitized solar cells : spectroscopy, energy levels and photovoltaic performance.

    Science.gov (United States)

    Marinado, Tannia; Hagberg, Daniel P; Hedlund, Maria; Edvinsson, Tomas; Johansson, Erik M J; Boschloo, Gerrit; Rensmo, Håkan; Brinck, Tore; Sun, Licheng; Hagfeldt, Anders

    2009-01-07

    Three new sensitizers for photoelectrochemical solar cells were synthesized consisting of a triphenylamine donor, a rhodanine-3-acetic acid acceptor and a polyene connection. The conjugation length was systematically increased, which resulted in two effects: first, it led to a red-shift of the optical absorption of the dyes, resulting in an improved spectral overlap with the solar spectrum. Secondly, the oxidation potential decreased systematically. The excited state levels were, however, calculated to be nearly stationary. The experimental trends were in excellent agreement with density functional theory (DFT) computations. The photovoltaic performance of this set of dyes as sensitizers in mesoporous TiO2 solar cells was investigated using electrolytes containing the iodide/triiodide redox couple. The dye with the best absorption characteristics showed the poorest solar cell efficiency, due to losses by recombination of electrons in TiO2 with triiodide. Addition of 4-tert butylpyridine to the electrolyte led to a strongly reduced photocurrent for all dyes due to a reduced electron injection efficiency, caused by a 0.15 V negative shift of the TiO2 conduction band potential.

  20. GIOVE: a new detector setup for high sensitivity germanium spectroscopy at shallow depth

    Energy Technology Data Exchange (ETDEWEB)

    Heusser, G., E-mail: gerd.heusser@mpi-hd.mpg.de; Weber, M., E-mail: marc.weber@mpi-hd.mpg.de; Hakenmüller, J. [Max-Planck-Institut für Kernphysik, Saupfercheckweg 1, 69117, Heidelberg (Germany); Laubenstein, M. [Laboratori Nazionali del Gran Sasso, Via G. Acitelli 22, 67100, Assergi, AQ (Italy); Lindner, M.; Maneschg, W.; Simgen, H.; Stolzenburg, D.; Strecker, H. [Max-Planck-Institut für Kernphysik, Saupfercheckweg 1, 69117, Heidelberg (Germany)

    2015-11-09

    We report on the development and construction of the high-purity germanium spectrometer setup GIOVE (Germanium Inner Outer VEto), recently built and now operated at the shallow underground laboratory of the Max-Planck-Institut für Kernphysik, Heidelberg. Particular attention was paid to the design of a novel passive and active shield, aiming at efficient rejection of environmental and muon induced radiation backgrounds. The achieved sensitivity level of ≤100 μBq kg{sup -1} for primordial radionuclides from U and Th in typical γ ray sample screening measurements is unique among instruments located at comparably shallow depths and can compete with instruments at far deeper underground sites.

  1. Structural Characterization of Amadori Rearrangement Product of Glucosylated Nα-Acetyl-Lysine by Nuclear Magnetic Resonance Spectroscopy

    Directory of Open Access Journals (Sweden)

    Chuanjiang Li

    2014-01-01

    Full Text Available Maillard reaction is a nonenzymatic reaction between reducing sugars and free amino acid moieties, which is known as one of the most important modifications in food science. It is essential to characterize the structure of Amadori rearrangement products (ARPs formed in the early stage of Maillard reaction. In the present study, the Nα-acetyl-lysine-glucose model had been successfully set up to produce ARP, Nα-acetyl-lysine-glucose. After HPLC purification, ARP had been identified by ESI-MS with intense [M+H]+ ion at 351 m/z and the purity of ARP was confirmed to be over 90% by the relative intensity of [M+H]+ ion. Further structural characterization of the ARP was accomplished by using nuclear magnetic resonance (NMR spectroscopy, including 1D 1H NMR and 13C NMR, the distortionless enhancement by polarization transfer (DEPT-135 and 2D 1H-1H and 13C-1H correlation spectroscopy (COSY and 2D nuclear overhauser enhancement spectroscopy (NOESY. The complexity of 1D 1H NMR and 13C NMR was observed due to the presence of isomers in glucose moiety of ARP. However, DEPT-135 and 2D NMR techniques provided more structural information to assign the 1H and 13C resonances of ARP. 2D NOESY had successfully confirmed the glycosylated site between 10-N in Nα-acetyl-lysine and 7′-C in glucose.

  2. A High Sensitivity Preamplifier for Quartz Tuning Forks in QEPAS (Quartz Enhanced PhotoAcoustic Spectroscopy Applications

    Directory of Open Access Journals (Sweden)

    Tomasz Starecki

    2017-11-01

    Full Text Available All the preamplifiers dedicated for Quartz Enhanced PhotoAcoustic Spectroscopy (QEPAS applications that have so far been reported in the literature have been based on operational amplifiers working in transimpedance configurations. Taking into consideration that QEPAS sensors are based on quartz tuning forks, and that quartz has a relatively high voltage constant and relatively low charge constant, it seems that a transimpedance amplifier is not an optimal solution. This paper describes the design of a quartz QEPAS sensor preamplifier, implemented with voltage amplifier configuration. Discussion of an electrical model of the circuit and preliminary measurements are presented. Both theoretical analysis and experiments show that use of the voltage configuration allows for a substantial increase of the output signal in comparison to the transimpedance circuit with the same tuning fork working in identical conditions. Assuming that the sensitivity of the QEPAS technique depends directly on the properties of the preamplifier, use of the voltage amplifier configuration should result in an increase of QEPAS sensitivity by one to two orders of magnitude.

  3. A High Sensitivity Preamplifier for Quartz Tuning Forks in QEPAS (Quartz Enhanced PhotoAcoustic Spectroscopy) Applications.

    Science.gov (United States)

    Starecki, Tomasz; Wieczorek, Piotr Z

    2017-11-03

    All the preamplifiers dedicated for Quartz Enhanced PhotoAcoustic Spectroscopy (QEPAS) applications that have so far been reported in the literature have been based on operational amplifiers working in transimpedance configurations. Taking into consideration that QEPAS sensors are based on quartz tuning forks, and that quartz has a relatively high voltage constant and relatively low charge constant, it seems that a transimpedance amplifier is not an optimal solution. This paper describes the design of a quartz QEPAS sensor preamplifier, implemented with voltage amplifier configuration. Discussion of an electrical model of the circuit and preliminary measurements are presented. Both theoretical analysis and experiments show that use of the voltage configuration allows for a substantial increase of the output signal in comparison to the transimpedance circuit with the same tuning fork working in identical conditions. Assuming that the sensitivity of the QEPAS technique depends directly on the properties of the preamplifier, use of the voltage amplifier configuration should result in an increase of QEPAS sensitivity by one to two orders of magnitude.

  4. High-sensitivity high-selectivity detection of CWAs and TICs using tunable laser photoacoustic spectroscopy

    Science.gov (United States)

    Pushkarsky, Michael; Webber, Michael; Patel, C. Kumar N.

    2005-03-01

    We provide a general technique for evaluating the performance of an optical sensor for the detection of chemical warfare agents (CWAs) in realistic environments and present data from a simulation model based on a field deployed discretely tunable 13CO2 laser photoacoustic spectrometer (L-PAS). Results of our calculations show the sensor performance in terms of usable sensor sensitivity as a function of probability of false positives (PFP). The false positives arise from the presence of many other gases in the ambient air that could be interferents. Using the L-PAS as it exists today, we can achieve a detection threshold of about 4 ppb for the CWAs while maintaining a PFP of less than 1:106. Our simulation permits us to vary a number of parameters in the model to provide guidance for performance improvement. We find that by using a larger density of laser lines (such as those obtained through the use of tunable semiconductor lasers), improving the detector noise and maintaining the accuracy of laser frequency determination, optical detection schemes can make possible CWA sensors having sub-ppb detection capability with TIC detection.

  5. Imaging the electron transfer reaction of Ne2+ with Ar using position-sensitive coincidence spectroscopy

    International Nuclear Information System (INIS)

    Harper, Sarah M; Hu Wanping; Price, Stephen D

    2002-01-01

    A new experiment, employing position-sensitive detection coupled with time-of-flight mass spectrometry, has been used to investigate the single-electron transfer reaction between Ne 2+ and Ar by detecting the resulting pairs of singly charged ions in coincidence. The experimental technique allows the determination of the individual velocity vectors of the ionic products, in the centre-of-mass frame, for each reactive event detected. The experiments show that forward scattering dominates the reactivity, although a bimodal angular distribution is apparent. In addition, the spectra show that at laboratory frame collision energies from 4-14 eV the reactivity is dominated by Ne 2+ (2p 4 , 3 P) accepting an electron from an argon atom to form the ground state of Ne + together with an Ar + ion in an excited electronic level, predominantly arising from the Ar + (3s 2 3p 4 3d) configuration. The form of this reactivity, and the differences between the reactivity observed in these experiments and those performed at higher collision energies, are well reproduced by Landau-Zener theory

  6. Phase sensitive molecular dynamics of self-assembly glycolipid thin films: A dielectric spectroscopy investigation

    Science.gov (United States)

    Velayutham, T. S.; Ng, B. K.; Gan, W. C.; Majid, W. H. Abd.; Hashim, R.; Zahid, N. I.; Chaiprapa, Jitrin

    2014-08-01

    Glycolipid, found commonly in membranes, is also a liquid crystal material which can self-assemble without the presence of a solvent. Here, the dielectric and conductivity properties of three synthetic glycolipid thin films in different thermotropic liquid crystal phases were investigated over a frequency and temperature range of (10-2-106 Hz) and (303-463 K), respectively. The observed relaxation processes distinguish between the different phases (smectic A, columnar/hexagonal, and bicontinuous cubic Q) and the glycolipid molecular structures. Large dielectric responses were observed in the columnar and bicontinuous cubic phases of the longer branched alkyl chain glycolipids. Glycolipids with the shortest branched alkyl chain experience the most restricted self-assembly dynamic process over the broad temperature range studied compared to the longer ones. A high frequency dielectric absorption (Process I) was observed in all samples. This is related to the dynamics of the hydrogen bond network from the sugar group. An additional low-frequency mechanism (Process II) with a large dielectric strength was observed due to the internal dynamics of the self-assembly organization. Phase sensitive domain heterogeneity in the bicontinuous cubic phase was related to the diffusion of charge carriers. The microscopic features of charge hopping were modelled using the random walk scheme, and two charge carrier hopping lengths were estimated for two glycolipid systems. For Process I, the hopping length is comparable to the hydrogen bond and is related to the dynamics of the hydrogen bond network. Additionally, that for Process II is comparable to the bilayer spacing, hence confirming that this low-frequency mechanism is associated with the internal dynamics within the phase.

  7. Synthesis, spectroscopy and photosensitizing properties of hydroxynitrophenyl porphyrins

    Energy Technology Data Exchange (ETDEWEB)

    Maestrin, Ana Paula J.; Tedesco, Antonio Claudio; Neri, Claudio R.; Gandini, Maria Elisa F.; Serra, Osvaldo A.; Iamamoto, Yassuko [Sao Paulo Univ., Ribeirao Preto, SP (Brazil). Faculdade de Filosofia, Ciencias e Letras. Inst. de Quimica]. E-mail: osaserra@usp.br

    2004-10-01

    The hydroxynitrophenyl porphyrins, 5,10,15,20-tetrakis(2-hydroxy-5-nitrophenyl)porphyrin and 5-mono(carboxyphenyl)-10,15,20-tris(2-hydroxy-5-nitrophenyl)porphyrin described in this work were prepared through Adler's method. These compounds were characterized by {sup 1}H NMR and light absorption and emission spectroscopy in the visible region. In order to demonstrate the involvement of {sup 1}O{sub 2} production, the uric (UA) acid test was carried out, which considers the decrease in the absorbance of UA at 293 nm following laser light irradiation of a solution containing UA and a photosensitizer. The results obtained demonstrate that these hydroxynitrophenyl porphyrins can be considered as promising photosensitizers in PDT. (author)

  8. 1 H NMR study and multivariate data analysis of reindeer skin tanning methods.

    Science.gov (United States)

    Zhu, Lizheng; Ilott, Andrew J; Del Federico, Eleonora; Kehlet, Cindie; Klokkernes, Torunn; Jerschow, Alexej

    2017-04-01

    Reindeer skin clothing has been an essential component in the lives of indigenous people of the arctic and sub-arctic regions, keeping them warm during harsh winters. However, the skin processing technology, which often conveys the history and tradition of the indigenous group, has not been well documented. In this study, NMR spectra and relaxation behaviors of reindeer skin samples treated with a variety of vegetable tannin extracts, oils and fatty substances are studied and compared. With the assistance of principal component analysis (PCA), one can recognize patterns and identify groupings of differently treated samples. These methods could be important aids in efforts to conserve museum leather artifacts with unknown treatment methods and in the analysis of reindeer skin tanning processes. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

  9. High-field 1H NMR microscopy for fundamental biophysical research

    International Nuclear Information System (INIS)

    Haddad, D.

    2003-01-01

    This work has a biophysical background and uses different examples to demonstrate the practical applicability of NMR-Microscopy in the medical and biological sector. Therefore, the different projects are feasibility studies which are used to compare the possibilities and advantages of NMR-Microscopy with other, established examination techniques. In detail, using MR-Microscopy, different living and fixed biological samples have been visualized non-invasively with high spatial resolution. The specific purpose of the studies ranged from the visualization of the invasion of tumor-spheroids into cell aggregates using T2 parameter maps (time constant of the spin-spin relaxation) to the three-dimensional display of the honey bee brain in the intact head capsule and the non-invasive visualization of the anatomy of prenatal dolphins. For all these projects, the non-invasive character of MR-experiments was of utmost importance. The tumor invasion was not to be disturbed by the measurements, the bee brain should be visualized as close to its true natural shape as possible and the examined dolphins represent rare museum specimens which should not be destroyed. The different samples were all imaged with the best possible spatial resolution which was either limited by the necessary signal-to-noise ratio (SNR) or the available scan time. In order to resolve single details and fine structures in the images, it was necessary to optimize the SNR as well as the contrast-to-noise ratio. To guarantee the necessary SNR, the measurements were performed on high field MR-spectrometers with resonance frequencies of 500 and 750 MHz

  10. Tunneling splitting of magnetic levels in Fe8 detected by 1H NMR cross relaxation

    Science.gov (United States)

    Furukawa, Y.; Aizawa, K.; Kumagai, K.; Ullu, R.; Lascialfari, A.; Borsa, F.

    2003-05-01

    Measurements of proton NMR and the spin lattice relaxation rate 1/T1 in the octanuclear iron (III) cluster [Fe8(N3C6H15)6O2(OH)12]ṡ[Br8ṡ9H2O], in short Fe8, have been performed at 1.5 K in a powder sample aligned along the main anisotropy z axis, as a function of a transverse magnetic field (i.e., perpendicular to the main easy axis z). A big enhancement of 1/T1 is observed over a wide range of fields (2.5-5 T), which can be attributed to the tunneling dynamics; in fact, when the tunneling splitting of the pairwise degenerate m=±10 states of the Fe8 molecule becomes equal to the proton Larmor frequency a very effective spin lattice relaxation channel for the nuclei is opened. The experimental results are explained satisfactorily by considering the distribution of tunneling splitting resulting from the distribution of the angles in the hard xy plane for the aligned powder, and the results of the direct diagonalization of the model Hamiltonian.

  11. Tunneling splitting of magnetic levels in Fe8 detected by 1H NMR cross relaxation

    OpenAIRE

    Furukawa, Y.; Aizawa, K.; Kumagai, K.; Ullu, R.; Lascialfari, A.; Borsa, F.

    2003-01-01

    Measurements of proton NMR and the spin lattice relaxation rate 1/T1 in the octanuclear iron (III) cluster [Fe8(N3C6H15)6O2(OH)12][Br8 9H2O], in short Fe8, have been performed at 1.5 K in a powder sample aligned along the main anisotropy z axis, as a function of a transverse magnetic field (i.e., perpendicular to the main easy axis z). A big enhancement of 1/T1 is observed over a wide range of fields (2.5-5 T), which can be attributed to the tunneling dynamics; in fact, when the tunneling spl...

  12. IR, 1H-NMR, UV-Vis AND THERMAL STUDIES ON THE ...

    African Journals Online (AJOL)

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    1Department of Chemistry, Faculty of Science, Port Said University, Port Said ... The general chemical structure of Rhodamine 6G donor and acceptors are given in .... atom of the -NH group is involved in the complexation process between ...

  13. Improving the efficiency of quantitative (1)H NMR: an innovative external standard-internal reference approach.

    Science.gov (United States)

    Huang, Yande; Su, Bao-Ning; Ye, Qingmei; Palaniswamy, Venkatapuram A; Bolgar, Mark S; Raglione, Thomas V

    2014-01-01

    The classical internal standard quantitative NMR (qNMR) method determines the purity of an analyte by the determination of a solution containing the analyte and a standard. Therefore, the standard must meet the requirements of chemical compatibility and lack of resonance interference with the analyte as well as a known purity. The identification of such a standard can be time consuming and must be repeated for each analyte. In contrast, the external standard qNMR method utilizes a standard with a known purity to calibrate the NMR instrument. The external standard and the analyte are measured separately, thereby eliminating the matter of chemical compatibility and resonance interference between the standard and the analyte. However, the instrumental factors, including the quality of NMR tubes, must be kept the same. Any deviations will compromise the accuracy of the results. An innovative qNMR method reported herein utilizes an internal reference substance along with an external standard to assume the role of the standard used in the traditional internal standard qNMR method. In this new method, the internal reference substance must only be chemically compatible and be free of resonance-interference with the analyte or external standard whereas the external standard must only be of a known purity. The exact purity or concentration of the internal reference substance is not required as long as the same quantity is added to the external standard and the analyte. The new method reduces the burden of searching for an appropriate standard for each analyte significantly. Therefore the efficiency of the qNMR purity assay increases while the precision of the internal standard method is retained. Copyright © 2013 Elsevier B.V. All rights reserved.

  14. Validation of quantitative 1H NMR method for the analysis of pharmaceutical formulations

    International Nuclear Information System (INIS)

    Santos, Maiara da S.

    2013-01-01

    The need for effective and reliable quality control in products from pharmaceutical industries renders the analyses of their active ingredients and constituents of great importance. This study presents the theoretical basis of ¹H NMR for quantitative analyses and an example of the method validation according to Resolution RE N. 899 by the Brazilian National Health Surveillance Agency (ANVISA), in which the compound paracetamol was the active ingredient. All evaluated parameters (selectivity, linearity, accuracy, repeatability and robustness) showed satisfactory results. It was concluded that a single NMR measurement provides structural and quantitative information of active components and excipients in the sample. (author)

  15. 1H NMR relaxometry as an indicator of setting and water depletion during cement hydration

    International Nuclear Information System (INIS)

    Wang, Biyun; Faure, Paméla; Thiéry, Mickaël; Baroghel-Bouny, Véronique

    2013-01-01

    Proton nuclear magnetic resonance relaxometry has been used to detect setting and microstructure evolution during cement hydration. NMR measurements were performed since casting, during setting and until hardening (from 0 to 3 days). The mobility of water molecules was assessed by an analysis focused on the diagram of longitudinal relaxation time T 1 generated by an Inversion Recovery sequence. The initial stiffening of the solid network was identified by an analysis of the relaxation rate 1/T 1 . The kinetics of water depletion was investigated by using a simple one-pulse acquisition sequence. In parallel, conventional techniques (Vicat needle and temperature monitoring), as well as numerical simulations of hydration, were used to complement and validate these NMR results. Cement pastes and mortars with different water-to-cement ratios made of grey or white OPCs were tested. Furthermore, the effects of the addition of sand, super-plasticizer and silica fume on the hydration kinetics were investigated

  16. Plastering mortar with antibacterial and antifungal properties studied by 1H NMR relaxometry

    Science.gov (United States)

    Jumate, E.; Aciu, C.; Manea, D. L.; Moldovan, D.; Chelcea, R.; Fechete, R.

    2017-12-01

    The Plastering mortars, with good antibacterial (in particular Escherichia coli, Staphylococcus aureus, Enterococcus faecalis, Pseudomonas aeruginosa) and antifungal (Aspergillus niger and Penicillium chrysogenum) properties, were studied by 1D NMR relaxometry and internal humidity measurements. Three recipes based on plastering mortar with variable content (0, 5 and 10 %) of Ag/ZnO nanopowders and with adequate physical characteristics regarding the mechanical strengths (CS IV), good adhesion to the substrate and low water absorption by capillarity (W2) were considered. The distributions of transverse relaxation times T2 were measured at 2 h after preparation (for mortar pasta) and then for the same samples at 2, 7, and 28 days during the hydration of mineralogical components. The T2 distributions are characterized by four components associated with hydration water and water in three types of pores of different dimension. The dimension of pores formed during hydration process are strongly dependent on the Ag/ZnO nanopowders content but finally at 28 days the pores distributions, as resulted from the T2 distributions, looks similar. Finally, the transverse relaxation ratio was linearly correlated to the compressive strength and the hydration behaviour during 132 days measured with a dedicated humidity sensor embedded inside sampled was discussed.

  17. The effects of some parameters on the calculated 1H NMR relaxation times of cell water

    International Nuclear Information System (INIS)

    Koivula, A.; Suominen, K.; Kiviniitty, K.

    1976-01-01

    The effect of some parameters on the longitudinal and transverse relaxation times is calculated and a comparison between the calculated relaxation times with the results of different measurements is made. (M.S.)

  18. 1 H-NMR metabolomics: Profiling method for a rapid and efficient ...

    African Journals Online (AJOL)

    Principal component analysis was used to separate groups of samples and to relate known and unknown metabolites to transgenic events. The screening of 100 samples, from extraction to data mining, took 36 h. Thus, this procedure allows the rapid selection of metabolic phenotypes of interest among about 30 transgenic ...

  19. Communication: Molecular dynamics and {sup 1}H NMR of n-hexane in liquid crystals

    Energy Technology Data Exchange (ETDEWEB)

    Weber, Adrian C. J., E-mail: WeberA@BrandonU.CA [Chemistry Department, Brandon University, 270-18th Street, Brandon, Manitoba R7A 6A9 (Canada); Burnell, E. Elliott, E-mail: elliott.burnell@ubc.ca [Chemistry Department, University of British Columbia, 2036 Main Mall, Vancouver, British Columbia V6T 1Z1 (Canada); Meerts, W. Leo, E-mail: leo.meerts@science.ru.nl [Radboud University, Institute for Molecules and Materials, Heyendaalseweg 135, NL-6525 AJ Nijmegen (Netherlands); Atomic, Molecular and Laser Physics, Vrije Universiteit, De Boelelaan 1081, 1081 HV Amsterdam (Netherlands); Lange, Cornelis A. de, E-mail: c.a.de.lange@vu.nl [Atomic, Molecular and Laser Physics, Vrije Universiteit, De Boelelaan 1081, 1081 HV Amsterdam (Netherlands); Dong, Ronald Y., E-mail: rondong@phas.ubc.ca [Department of Physics and Astronomy, University of British Columbia, 6224 Agricultural Road, Vancouver, British Columbia V6T 1Z1 (Canada); Muccioli, Luca, E-mail: Luca.Muccioli@unibo.it; Pizzirusso, Antonio, E-mail: Antonio.Pizzirusso80@gmail.com; Zannoni, Claudio, E-mail: Claudio.Zannoni@unibo.it [Dipartimento di Chimica Industriale “Toso Montanari,” Università di Bologna and INSTM, viale Risorgimento 4, 40136 Bologna (Italy)

    2015-07-07

    The NMR spectrum of n-hexane orientationally ordered in the nematic liquid crystal ZLI-1132 is analysed using covariance matrix adaptation evolution strategy (CMA-ES). The spectrum contains over 150 000 transitions, with many sharp features appearing above a broad, underlying background signal that results from the plethora of overlapping transitions from the n-hexane as well as from the liquid crystal. The CMA-ES requires initial search ranges for NMR spectral parameters, notably the direct dipolar couplings. Several sets of such ranges were utilized, including three from MD simulations and others from the modified chord model that is specifically designed to predict hydrocarbon-chain dipolar couplings. In the end, only inaccurate dipolar couplings from an earlier study utilizing proton-proton double quantum 2D-NMR techniques on partially deuterated n-hexane provided the necessary estimates. The precise set of dipolar couplings obtained can now be used to investigate conformational averaging of n-hexane in a nematic environment.

  20. Main-chain-directed strategy for the assignment of 1H NMR spectra of proteins

    International Nuclear Information System (INIS)

    Englander, S.W.; Wand, A.J.

    1987-01-01

    A strategy for assigning the resonances in two-dimensional (2D) NMR spectra of proteins is described. The method emphasizes the analysis of through-space relationships between protons by use of the two-dimensional nuclear Overhauser effect (NOE) experiment. NOE patterns used in the algorithm were derived from a statistical analysis of the combinations of short proton-proton distances observed in the high-resolution crystal structures of 21 proteins. One starts with a search for authentic main-chain NH-C/sub α/H-C/sub β/H J-coupled units, which can be found with high reliability. The many main-chain units of a protein are then placed in their proper juxtaposition by recognition of predefined NOE connectivity patterns. To discover these connectivities, the 2D NOE spectrum is examined, in a prescribed order, for the distinct NOE patterns characteristic of helices, sheets, turns, and extended chain. Finally, the recognition of a few amino acid side-chain types places the discovered secondary structure elements within the polypeptide sequences. Unlike the sequential assignment approach, the main-chain-directed strategy does not rely on the difficult task of recognizing many side-chain spin systems in J-correlated spectra, the assignment process is not in general sequential with the polypeptide chain, and the prescribed connectivity patterns are cyclic rather than linear. The latter characteristic avoids ambiguous branch points in the analysis and imposed an internally confirmatory property on each forward step

  1. High-pressure low-field 1H NMR relaxometry in nanoporous materials.

    Science.gov (United States)

    Horch, Carsten; Schlayer, Stefan; Stallmach, Frank

    2014-03-01

    A low-field NMR sensor with NdFeB permanent magnets (B0=118 mT) and a pressure cell made of PEEK (4 cm outer diameter) were designed for (1)H relaxation time studies of adsorbed molecules at pressures of up to 300 bar. The system was used to investigate methane uptake of microporous metal-organic frameworks and nanoporous activated carbon. T2 relaxation time distribution of pure methane and of methane under co-adsorption of carbon dioxide show that the host-guest interaction lead to a relaxation time contrasts, which may be used to distinguish between the gas phase and the different adsorbed phases of methane. Adsorption isotherms, exchange of methane between adsorbent particles and the surrounding gas phase, successive displacement of methane from adsorption sites by co-adsorption of carbon dioxide and CO2/CH4 adsorption separation factors were determined from the observed NMR relaxation time distributions. Copyright © 2014 Elsevier Inc. All rights reserved.

  2. Temperature dependence of 1H NMR chemical shifts and its influence on estimated metabolite concentrations.

    Science.gov (United States)

    Wermter, Felizitas C; Mitschke, Nico; Bock, Christian; Dreher, Wolfgang

    2017-12-01

    Temperature dependent chemical shifts of important brain metabolites measured by localised 1 H MRS were investigated to test how the use of incorrect prior knowledge on chemical shifts impairs the quantification of metabolite concentrations. Phantom measurements on solutions containing 11 metabolites were performed on a 7 T scanner between 1 and 43 °C. The temperature dependence of the chemical shift differences was fitted by a linear model. Spectra were simulated for different temperatures and analysed by the AQSES program (jMRUI 5.2) using model functions with chemical shift values for 37 °C. Large differences in the temperature dependence of the chemical shift differences were determined with a maximum slope of about ±7.5 × 10 -4  ppm/K. For 32-40 °C, only minor quantification errors resulted from using incorrect chemical shifts, with the exception of Cr and PCr. For 1-10 °C considerable quantification errors occurred if the temperature dependence of the chemical shifts was neglected. If 1 H MRS measurements are not performed at 37 °C, for which the published chemical shift values have been determined, the temperature dependence of chemical shifts should be considered to avoid systematic quantification errors, particularly for measurements on animal models at lower temperatures.

  3. 1H nmr spectra of dichloro and dihydroxy derivatives of methylcyclosiloxanes

    International Nuclear Information System (INIS)

    Lavrukhin, B.D.

    1986-01-01

    The authors report on a continuation of an investigation of how the nature of the substituents on the Si atoms influences the character of the spectra. As objects of investigation, the authors took the dichloro and dihydroxy derivatives of cyclosiloxanes with 4 to 8 Si atoms in the ring. Shown are tables of chemical shifts of protons of CH 3 groups in chloromethylcyclosiloxanes, and chemical shifts of protons of CH 3 groups in linear methylsiloxanes and chloromethylsiloxanes. Additivity was demonstrated for chemical shifts of CH 3 group protons in dichloromethylcyclosiloxanes, and the increments of chemical shift were obtained for 8-, 10-, 12-, 14-, and 16-membered rings. It was established that the chemical shifts in the spectra of the dihydroxy derivatives are nonadditive

  4. /sup 1/H-NMR chemical shift imaging suitable for low field systems

    Energy Technology Data Exchange (ETDEWEB)

    Yamamoto, Etsuji; Onodera, Takashi; Shiono, Hidemi; Kohno, Hideki

    1986-12-01

    An echo-time encoding proton NMR chemical shift imaging proposed by Dixon is extended to be applicable to low filed systems. The method utilizes the small phase angle between magnetic vectors of water and lipid protons to decrease the signal decays with spin-spin relaxation. The inevitable phase error caused by the static field inhomogeneity is corrected by using phase images of phantom measured under the same conditions as the actual measurements. The experiments were carried out using CuSO/sub 4/ doped water and vegetable oil at 0.5 T. Two chemical shift images could be clearly resolved with only one scan when the field inhomogeneity was larger than the chemical shift difference.

  5. IR, 1H-NMR, UV-Vis AND THERMAL STUDIES ON THE ...

    African Journals Online (AJOL)

    Preferred Customer

    Charge-transfer complexes using organic species are intensively studied [6, .... 1242 ms. 1698 s. 1647 s. 1608 vs. 1530 s. 1501 s. 1446 mw. 1364 s. 1318 vs .... thermal decomposition process of Rh6G/iodine complex is non-spontaneous, i.e..

  6. Microcomputer utilization for comparison of 1H-NMR spectra with data base standards

    International Nuclear Information System (INIS)

    Vale Rodrigues, G. do; Nagem, T.J.

    1989-01-01

    A new computacional technique for the storage of spectrometric data of natural products listed in the literature and its comparison with data of new compounds isolated as natural products is described here. The programs allow a correlation of two spectra by inverting one relative to the other. The programs again permit the comparison of two NMR spectra in different frequencies. (author) [pt

  7. Complete sequence-specific 1H NMR assignments for human insulin

    International Nuclear Information System (INIS)

    Kline, A.D.; Justice, R.M. Jr.

    1990-01-01

    Solvent conditions where human insulin could be studied by high-resolution NMR were determined. Both low pH and addition of acetonitrile were required to overcome the protein's self-association and to obtain useful spectra. Two hundred eighty-six 1 H resonances were located and assigned to specific sites on the protein by using two-dimensional NMR methods. The presence and position of numerous d NN sequential NOE's indicate that the insulin conformation seen in crystallographic studies is largely retained under these solution conditions. Slowly exchanging protons were observed for seven backbone amide protons and were assigned to positions A15 and A16 and to positions B15-B19. These amides all occur within helical regions of the protein

  8. 1H NMR relaxometry in the TGBA* and TGBC*phases

    Czech Academy of Sciences Publication Activity Database

    Domenici, V.; Gradišek, A.; Apih, T.; Hamplová, Věra; Novotná, Vladimíra; Sebastião, P.J.

    2016-01-01

    Roč. 49, č. 1 (2016), 17-27 ISSN 0015-0193 Grant - others:AVČR(CZ) M100101204 Institutional support: RVO:68378271 Keywords : Ferroelectric liquid crystal * chiral liquid crystals * molecular dynamics * NMR * twist grain boundary phases * spin-lattice Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 0.551, year: 2016

  9. 1H NMR spectra part 31: 1H chemical shifts of amides in DMSO solvent.

    Science.gov (United States)

    Abraham, Raymond J; Griffiths, Lee; Perez, Manuel

    2014-07-01

    The (1)H chemical shifts of 48 amides in DMSO solvent are assigned and presented. The solvent shifts Δδ (DMSO-CDCl3 ) are large (1-2 ppm) for the NH protons but smaller and negative (-0.1 to -0.2 ppm) for close range protons. A selection of the observed solvent shifts is compared with calculated shifts from the present model and from GIAO calculations. Those for the NH protons agree with both calculations, but other solvent shifts such as Δδ(CHO) are not well reproduced by the GIAO calculations. The (1)H chemical shifts of the amides in DMSO were analysed using a functional approach for near ( ≤ 3 bonds removed) protons and the electric field, magnetic anisotropy and steric effect of the amide group for more distant protons. The chemical shifts of the NH protons of acetanilide and benzamide vary linearly with the π density on the αN and βC atoms, respectively. The C=O anisotropy and steric effect are in general little changed from the values in CDCl3. The effects of substituents F, Cl, Me on the NH proton shifts are reproduced. The electric field coefficient for the protons in DMSO is 90% of that in CDCl3. There is no steric effect of the C=O oxygen on the NH proton in an NH…O=C hydrogen bond. The observed deshielding is due to the electric field effect. The calculated chemical shifts agree well with the observed shifts (RMS error of 0.106 ppm for the data set of 257 entries). Copyright © 2014 John Wiley & Sons, Ltd.

  10. Temperature dependence of 1H NMR relaxation time, T2, for intact and neoplastic plant tissues

    Science.gov (United States)

    Lewa, Czesław J.; Lewa, Maria

    Temperature dependences of the spin-spin proton relaxation time, T2, have been shown for normal and tumorous tissues collected from kalus culture Nicotiana tabacum and from the plant Kalanchoe daigremontiana. For neoplastic plant tissues, time T2 was increased compared to that for intact plants, a finding similar to that for animal and human tissues. The temperature dependences obtained were compared to analogous relations observed with animal tissues.

  11. Characterization of urban aerosol using aerosol mass spectrometry and proton nuclear magnetic resonance spectroscopy

    Science.gov (United States)

    Cleveland, M. J.; Ziemba, L. D.; Griffin, R. J.; Dibb, J. E.; Anderson, C. H.; Lefer, B.; Rappenglück, B.

    2012-07-01

    Particulate matter was measured during August and September of 2006 in Houston as part of the Texas Air Quality Study II Radical and Aerosol Measurement Project. Aerosol size and composition were determined using an Aerodyne quadrupole aerosol mass spectrometer. Aerosol was dominated by sulfate (4.1 ± 2.6 μg m-3) and organic material (5.5 ± 4.0 μg m-3), with contributions of organic material from both primary (˜32%) and secondary (˜68%) sources. Secondary organic aerosol appears to be formed locally. In addition, 29 aerosol filter samples were analyzed using proton nuclear magnetic resonance (1H NMR) spectroscopy to determine relative concentrations of organic functional groups. Houston aerosols are less oxidized than those observed elsewhere, with smaller relative contributions of carbon-oxygen double bonds. These particles do not fit 1H NMR source apportionment fingerprints for identification of secondary, marine, and biomass burning organic aerosol, suggesting that a new fingerprint for highly urbanized and industrially influenced locations be established.

  12. Direct metabolic fingerprinting of commercial herbal tinctures by nuclear magnetic resonance spectroscopy and mass spectrometry.

    Science.gov (United States)

    Politi, Matteo; Zloh, Mire; Pintado, Manuela E; Castro, Paula M L; Heinrich, Michael; Prieto, Jose M

    2009-01-01

    Tinctures are widely used liquid pharmaceutical preparations traditionally obtained by maceration of one or more medicinal plants in ethanol-water solutions. Such a process results in the extraction of virtually hundreds of structurally diverse compounds with different polarities. Owing to the large chemical diversity of the constituents present in the herbal tinctures, the analytical tools used for the quality control of tinctures are usually optimised only for the detection of single chemical entities or specific class of compounds. In order to overcome the major limitations of the current methods used for analysis of tinctures, a new methodological approach based on NMR spectroscopy and MS spectrometry has been tested with different commercial tinctures. Diffusion-edited 1H-NMR (1D DOSY) and 1H-NMR with suppression of the ethanol and water signals have been applied here for the first time to the direct analysis of commercial herbal tinctures derived from Echinacea purpurea, Hypericum perforatum, Ginkgo biloba and Valeriana officinalis. The direct injection of the tinctures in the MS detector in order to obtain the corresponding metabolic profiles was also performed. Using both NMR and MS methods it was possible, without evaporation or separation steps, to obtain a metabolic fingerprint able to distinguish between tinctures prepared with different plants. Batch-to-batch homogeneity, as well as degradation after the expiry date of a batch, was also investigated. The techniques proposed here represent fast and convenient direct analyses of medicinal herbal tinctures.

  13. Detection and quantification of phenolic compounds in olive oil by high resolution {sup 1}H nuclear magnetic resonance spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Christophoridou, Stella [NMR Laboratory, Department of Chemistry, University of Crete, P.O. Box 2208, Voutes, 71003 Heraklion, Crete (Greece); Dais, Photis [NMR Laboratory, Department of Chemistry, University of Crete, P.O. Box 2208, Voutes, 71003 Heraklion, Crete (Greece)], E-mail: dais@chemistry.uoc.gr

    2009-02-09

    High resolution {sup 1}H NMR spectroscopy has been employed as a versatile and rapid method to analyze the polar fraction of extra virgin olive oils containing various classes of phenolic compounds. The strategy for identification of phenolic compounds is based on the NMR chemical shifts of a large number of model compounds assigned by using two-dimensional (2D) NMR spectroscopy. Furthermore, 2D NMR was applied to phenolic extracts in an attempt to discover additional phenolic compounds. The {sup 1}H NMR methodology was successful in detecting simple phenols, such as p-coumaric acid, vanillic acid, homovanillyl alcohol, vanillin, free tyrosol, and free hydroxytyrosol, the flavonols apigenin and luteolin, the lignans (+) pinoresinol, (+) 1-acetoxypinoresinol and syringaresinol, two isomers of the aldehydic form of oleuropein and ligstroside, the dialdehydic form of oleuropein and ligstroside lacking a carboxymethyl group, and finally total hydroxytyrosol and total tyrosol reflecting the total amounts of free and esterified hydroxytyrol and tyrosol, respectively. The absolute amount of each phenolic constituent was determined in the polar fraction by using anhydrous 1,3,5-triazine as an internal standard.

  14. Detection and quantification of phenolic compounds in olive oil by high resolution 1H nuclear magnetic resonance spectroscopy

    International Nuclear Information System (INIS)

    Christophoridou, Stella; Dais, Photis

    2009-01-01

    High resolution 1 H NMR spectroscopy has been employed as a versatile and rapid method to analyze the polar fraction of extra virgin olive oils containing various classes of phenolic compounds. The strategy for identification of phenolic compounds is based on the NMR chemical shifts of a large number of model compounds assigned by using two-dimensional (2D) NMR spectroscopy. Furthermore, 2D NMR was applied to phenolic extracts in an attempt to discover additional phenolic compounds. The 1 H NMR methodology was successful in detecting simple phenols, such as p-coumaric acid, vanillic acid, homovanillyl alcohol, vanillin, free tyrosol, and free hydroxytyrosol, the flavonols apigenin and luteolin, the lignans (+) pinoresinol, (+) 1-acetoxypinoresinol and syringaresinol, two isomers of the aldehydic form of oleuropein and ligstroside, the dialdehydic form of oleuropein and ligstroside lacking a carboxymethyl group, and finally total hydroxytyrosol and total tyrosol reflecting the total amounts of free and esterified hydroxytyrol and tyrosol, respectively. The absolute amount of each phenolic constituent was determined in the polar fraction by using anhydrous 1,3,5-triazine as an internal standard

  15. Diffuse Reflectance Spectroscopy (DRS) of radiation-induced re-oxygenation in sensitive and resistant head and neck tumor xenografts

    Science.gov (United States)

    Dadgar, Sina; Rodríguez Troncoso, Joel; Rajaram, Narasimhan

    2018-02-01

    Currently, anatomical assessment of tumor volume performed several weeks after completion of treatment is the clinical standard to determine whether a cancer patient has responded to a treatment. However, functional changes within the tumor could potentially provide information regarding treatment resistance or response much earlier than anatomical changes. We have used diffuse reflectance spectroscopy to assess the short and long-term re-oxygenation kinetics of a human head and neck squamous cell carcinoma xenografts in response to radiation therapy. First, we injected UM-SCC-22B cell line into the flank of 50 mice to grow xenografts. Once the tumor volume reached 200 mm3 (designated as Day 1), the mice were distributed into radiation and control groups. Members of radiation group underwent a clinical dose of radiation of 2 Gy/day on Days 1, 4, 7, and 10 for a cumulative dose of 8 Gy. DRS spectra of these tumors were collected for 14 days during and after therapy, and the collected spectra of each tumor were converted to its optical properties using a lookup table-base inverse model. We found statistically significant differences in tumor growth rate between two groups which is in indication of the sensitivity of this cell line to radiation. We further acquired significantly different contents of hemoglobin and scattering magnitude and size in two groups. The scattering has previously been associated with necrosis. We furthermore found significantly different time-dependent changes in vascular oxygenation and tumor hemoglobin concentration in post-radiation days.

  16. Terahertz spectroscopy

    DEFF Research Database (Denmark)

    Jepsen, Peter Uhd

    2009-01-01

    In this presentation I will review methods for spectroscopy in the THz range, with special emphasis on the practical implementation of the technique known ad THz time-domain spectroscopy (THz-TDS). THz-TDS has revived the old field of far-infrared spectroscopy, and enabled a wealth of new...... activities that promise commercial potential for spectroscopic applications in the THz range. This will be illustrated with examples of spectroscopy of liquids inside their bottles as well as sensitive, quantitative spectroscopy in waveguides....

  17. Sensitive detection of chlorine in iron oxide by single pulse and dual pulse laser-induced breakdown spectroscopy

    Science.gov (United States)

    Pedarnig, J. D.; Haslinger, M. J.; Bodea, M. A.; Huber, N.; Wolfmeir, H.; Heitz, J.

    2014-11-01

    The halogen chlorine is hard to detect in laser-induced breakdown spectroscopy (LIBS) mainly due to its high excited state energies of 9.2 and 10.4 eV for the most intense emission lines at 134.72 nm and 837.59 nm, respectively. We report on sensitive detection of Cl in industrial iron oxide Fe2O3 powder by single-pulse (SP) and dual-pulse (DP) LIBS measurements in the near infrared range in air. In compacted powder measured by SP excitation (Nd:YAG laser, 532 nm) Cl was detected with limit of detection LOD = 440 ppm and limit of quantitation LOQ = 720 ppm. Orthogonal DP LIBS was studied on pressed Fe2O3 pellets and Fe3O4 ceramics. The transmission of laser-induced plasma for orthogonal Nd:YAG 1064 nm and ArF 193 nm laser pulses showed a significant dependence on interpulse delay time (ipd) and laser wavelength (λL). The UV pulses (λL = 193 nm) were moderately absorbed in the plasma and the Cl I emission line intensity was enhanced while IR pulses (λL = 1064 nm) were not absorbed and Cl signals were not enhanced at ipd = 3 μs. The UV laser enhancement of Cl signals is attributed to the much higher signal/background ratio for orthogonal DP excitation compared to SP excitation and to the increased plasma temperature and electron number density. This enabled measurement at a very short delay time of td ≥ 0.1 μs with respect to the re-excitation pulse and detection of the very rapidly decaying Cl emission with higher efficiency.

  18. The clinical utility of nuclear magnetic resonance spectroscopy: recent in vitro, in vivo animal and clinical observations

    International Nuclear Information System (INIS)

    Blackstock, A. William; Kwock, Lester; Mukherji, Suresh K.; Schiro, Sharon; Tepper, Joel E.

    1995-01-01

    Purpose/Objective: Combined radiation and 5-fluorouracil (5-FU) has resulted in improved outcomes in patients treated with gastrointestinal malignancies and squamous cancers of the head and neck. In our first aim, we proposed that the enhanced cell kill and tumor regression observed with the combination of 5-FU and radiation is related to radiation potentiating the anti-tumor effects of 5-FU. Using fluorine-19 ( 19 F) nuclear magnetic resonance (nmr) we non-invasively determined the tumor clearance rates of 5-FU +/- radiation in an animal model and used this research tool to predict tumor response in patients receiving concurrent radiation and 5-FU therapy. Our second aim was to evaluate the use of proton ( 1 H) nmr spectroscopy to non-invasively determine the spectral characteristics of malignant tumors in the head and neck and liver and correlate these clinical observations with in vitro and in vivo data. Materials and Methods: 1 H and 19 F spectroscopic analysis were performed with a 2.0T Otsuka magnetic resonance imaging and spectroscopy system. 1 H nmr patient studies were done on a clinical 1.5T Philips MR system. In vitro magnetic resonance spectroscopy (MRS) studies were performed on a 11 T Bruker nmr system. Animal experiments for the 19 F nmr studies were performed on 3-6 week old female (Nu/Nu) athymic nude mice. Animals were injected s.c. with 10 6 human colon adenocarcinoma (HT-29) cells. At a tumor size of 1.0 cm, animals in the first group received i.v. 5-FU (100 mg/kg) immediately prior to spectroscopic analysis. Animals in the second group were treated with a single radiation dose of either 2 Gy or 10 Gy just prior to the 5-FU injection and subsequent spectroscopy. Spectroscopic analyses were performed at 20-30 minute intervals for 4-6 hr's. Results: 19 F nmr: A decrease in tumor clearance was observed in tumors pre-treated with a single dose of irradiation (2.0 Gy and 10 Gy). The clearance rate of the 5-FU for non-irradiated animals was 0.0178 min

  19. Solid state structural investigations of the bis(chalcone) compound with single crystal X-ray crystallography, DFT, gamma-ray spectroscopy and chemical spectroscopy methods

    Science.gov (United States)

    Yakalı, Gül; Biçer, Abdullah; Eke, Canel; Cin, Günseli Turgut

    2018-04-01

    A bis(chalcone), (2E,6E)-2,6-bis((E)-3phenylallidene)cyclohexanone, was characterized by 1H NMR, 13C NMR, FTIR, UV-Vis spectroscopy, gamma-ray spectroscopy and single crystal X- ray structural analysis. The optimized molecular structure of the compound is calculated using DFT/B3LYP with 6-31G (d,p) level. The calculated geometrical parameters are in good agreement with the experimental data obtained from our reported X-ray structure. The powder and single crystal compounds were gama-irradiated using clinical electron linear accelerator and 60Co gamma-ray source, respectively. Spectral studies (1H NMR, 13C NMR, FTIR and UV-Vis) of powder chalcone compound were also investigated before and after irradiation. Depending on the irradiation notable changes were observed in spectral features powder sample. Single crystal X-ray diffraction investigation shows that both unirradiated and irradiated single crystal samples crystallizes in a orthorhombic crystal system in the centrosymmetric space group Pbcn and exhibits an C-H..O intramolecular and intermolecular hydrogen bonds. The crystal packing is stabilised by strong intermolecular bifurcate C-H..O hydrogen bonds and π…π stacking interactions. The asymmetric unit of the title compound contains one-half of a molecule. The other half of the molecule is generated with (1-x,y,-3/2-z) symmetry operator. The molecule is almost planar due to having π conjugated system of chalcones. However, irradiated single crystal compound showed significant changes lattice parameters, crystal volume and density. According to results of gamma-ray spectroscopy, radioactive elements of powder compound which are 123Sb(n,g),124Sb,57Fe(g,p),56Mn, 55Mn(g,n), and 54Mn were determined using photoactivation analysis. However, the most intensive gamma-ray energy signals are 124Sb.

  20. Combination of 1H nuclear magnetic resonance spectroscopy and principal component analysis to evaluate the lipid fluidity of flutamide-encapsulated lipid nanoemulsions.

    Science.gov (United States)

    Takegami, Shigehiko; Ueyama, Keita; Konishi, Atsuko; Kitade, Tatsuya

    2018-06-06

    The lipid fluidity of various lipid nanoemulsions (LNEs) without and with flutamide (FT) and containing one of two neutral lipids, one of four phosphatidylcholines as a surfactant, and sodium palmitate as a cosurfactant was investigated by the combination of 1 H nuclear magnetic resonance (NMR) spectroscopy and principal component analysis (PCA). In the 1 H NMR spectra, the peaks from the methylene groups of the neutral lipids and surfactants for all LNE preparations showed downfield shifts with increasing temperature from 20 to 60 °C. PCA was applied to the 1 H NMR spectral data obtained for the LNEs. The PCA resulted in a model in which the first two principal components (PCs) extracted 88% of the total spectral variation; the first PC (PC-1) axis and second PC (PC-2) axis accounted for 73 and 15%, respectively, of the total spectral variation. The Score-1 values for PC-1 plotted against temperature revealed the existence of two clusters, which were defined by the neutral lipid of the LNE preparations. Meanwhile, the Score-2 values decreased with rising temperature and reflected the increase in lipid fluidity of each LNE preparation, consistent with fluorescence anisotropy measurements. In addition, the changes of Score-2 values with temperature for LNE preparations with FT were smaller than those for LNE preparations without FT. This indicates that FT encapsulated in LNE particles markedly suppressed the increase in lipid fluidity of LNE particles with rising temperature. Thus, PCA of 1 H NMR spectra will become a powerful tool to analyze the lipid fluidity of lipid nanoparticles. Graphical abstract ᅟ.

  1. NMR spectroscopy study of agar-based polymers electrolytes

    Energy Technology Data Exchange (ETDEWEB)

    Mattos, R.I.; Tambelli, C.E. [Universidade de Sao Paulo (USP), Pirassununga, SP (Brazil). Fac. de Zootecnia e Engenharia de Alimentos; Raphael, E. [Universidade Federal de Sao Joao del-Rey (UFSJ), MG (Brazil). Dept. de Ciencias Naturais; Silva, I.D.A.; Magon, C.J.; Donoso, J.P. [Universidade de Sao Paulo (IFSC/USP), Sao Carlos, SP (Brazil). Inst. de Fisica

    2012-07-01

    Full text: This communication presents the results of preparation and characterization of transparent films obtained from agar and acetic acid. The films were characterized by electrochemical impedance spectroscopy (EIS) and nuclear magnetic resonance (NMR). The film formed by agar (Sigma Aldrich) was dispersed in water and kept under stirring and heating at 100 deg C. Next, glycerol, formaldehyde and different quantities of acetic acid (25 and 50 wt%) were added to this solution. The obtained solution was placed on a glass plate and left to dry for 48 hours in oven at 50 deg C to obtain the films, which were kept under vacuum before characterization. The ionic conductivity of the films display an Arrhenius behavior with activation energy E{sub a} = 78 (25 wt% of acetic acid) and E{sub a} = 87 kJ/mol (50 wt% of acetic acid). The conductivity values were 3:0 X 10{sup -6} and 1:2 X 10{sup -4} S/cm at room temperature and 4:4 X 10{sup -4} and 1:5 X 10{sup -3}S/cm at 70 deg C, for the 25 and 50 wt% of acetic acid respectively. To investigate the mechanism of protonic conduction in the polymer proton conductor proton NMR measurements were performed in the temperature range 200-370 K. The {sup 1}H-NMR results exhibit the qualitative feature associated with the proton mobility, namely the presence of well defined {sup 1}H spin-lattice relaxation maxima at 300 K. Activation energy of the order of 40 kJ/mol was obtained from the {sup 1}H-NMR line narrowing data. The ionic conductivity of the film combined with their transparency, flexibility, homogeneity and good adhesion to the glasses or metals indicate that agar-based SPEs are promising materials for used on optoelectronic applications. (author)

  2. Time-resolved terahertz spectroscopy reveals the influence of charged sensitizing quantum dots on the electron dynamics in ZnO

    Czech Academy of Sciences Publication Activity Database

    Bamini, S.N.; Němec, Hynek; Žídek, Karel; Abdellah, M.; Al-Marri, M.J.; Chábera, P.; Ponseca, C.; Zheng, K.; Pullerits, T.

    2017-01-01

    Roč. 19, č. 8 (2017), s. 6006-6012 ISSN 1463-9076 R&D Projects: GA ČR GA17-03662S Institutional support: RVO:68378271 ; RVO:61389021 Keywords : sensitized semiconductors * ultrafast dynamics * terahertz spectroscopy Subject RIV: BM - Solid Matter Physics ; Magnetism OBOR OECD: Condensed matter physics (including formerly solid state physics , supercond.) Impact factor: 4.123, year: 2016

  3. Two-dimensional NMR spectroscopy links structural moieties of soil organic matter to the temperature sensitivity of its decomposition

    Science.gov (United States)

    Soucemarianadin, Laure; Erhagen, Björn; Öquist, Mats; Nilsson, Mats; Schleucher, Jürgen

    2015-04-01

    Soil organic matter (SOM) represents a huge carbon pool, specifically in boreal ecosystems. Warming-induced release of large amounts of CO2 from the soil carbon pool might become a significant exacerbating feedback to global warming, if decomposition rates of boreal soils were more sensitive to increased temperatures. Despite a large number of studies dedicated to the topic, it has proven difficult to elucidate how the organo-chemical composition of SOM influences its decomposition, or its quality as a substrate for microbial metabolism. A great part of this challenge results from our inability to achieve a detailed characterization of the complex composition of SOM on the level of molecular structural moieties. 13C nuclear magnetic resonance (NMR) spectroscopy is a common tool to characterize SOM. However, SOM is a very complex mixture and the chemical shift regions distinguished in the 13C NMR spectra often represent many different molecular fragments. For example, in the carbohydrates region, signals of all monosaccharides present in many different polymers overlap. This overlap thwarts attempts to identify molecular moieties, resulting in insufficient information to characterize SOM composition. We applied two-dimensional (2D) NMR to characterize SOM with highly increased resolution. We directly dissolved finely ground litters and forest floors'fibric and humic horizons'of both coniferous and deciduous boreal forests in dimethyl sulfoxide and analyzed the resulting solution with a 2D 1H-13C NMR experiment. In the 2D planes of these spectra, signals of CH groups can be resolved based on their 13C and 1H chemical shifts, hence the resolving power and information content of these NMR spectra is hugely increased. The 2D spectra indeed resolved overlaps observed in 1D 13C spectra, so that hundreds of distinct CH groups could be observed and many molecular fragments could be identified. For instance, in the aromatics region, signals from individual lignin units could

  4. Conjugated and Entrapped HPMA-PLA Nano-Polymeric Micelles Based Dual Delivery of First Line Anti TB Drug