Sample records for 31p nmr spectroscopy

  1. Simultaneous 31P NMR spectroscopy and EMG in exercising and recovering human skeletal muscle: technical aspects

    DEFF Research Database (Denmark)

    Vestergaard-Poulsen, P; Thomsen, C; Sinkjaer, T


    . A nonmagnetic ergometer was used for ankle dorsiflexions that activated only the anterior tibial muscle as verified by post exercise imaging. The coil design and the adiabatic sech/tanh pulse improved sensitivity by 45% and 56% respectively, compared with standard techniques. Simultaneous electromyographic......The bioenergetics of human skeletal muscle can be studied by 31P NMR spectroscopy (31P-MRS) and by surface electromyography (SEMG). Simultaneous 31P-MRS and SEMG permit accurate and noninvasive studies of the correlation between metabolic and electrical changes in exercising and recovering human...... skeletal muscle, a relationship that is still poorly understood. This study describes the optimization of skeletal muscle 31P-MRS in a whole-body magnet, involving surface coil design, utilization of adiabatic radio frequency pulses and advanced time-domain fitting, to the technical design of SEMG...

  2. Detoxification of organophosphorus pesticides and nerve agents through RSDL: efficacy evaluation by (31)P NMR spectroscopy. (United States)

    Elsinghorst, Paul W; Worek, Franz; Koller, Marianne


    Intoxication by organophosphorus compounds, especially by pesticides, poses a considerable risk to the affected individual. Countermeasures involve both medical intervention by means of antidotes as well as external decontamination to reduce the risk of dermal absorption. One of the few decontamination options available is Reactive Skin Decontamination Lotion (RSDL), which was originally developed for military use. Here, we present a (31)P NMR spectroscopy based methodology to evaluate the detoxification efficacy of RSDL with respect to a series of organophosphorus pesticides and nerve agents. Kinetic analysis of the obtained NMR data provided degradation half-lives proving that RSDL is also reasonably effective against organophosphorus pesticides. Unexpected observations of different RSDL degradation patterns are presented in view of its reported oximate-catalyzed mechanism of action.

  3. Simultaneous determination of phenolic compounds and triterpenic acids in oregano growing wild in Greece by 31P NMR spectroscopy. (United States)

    Agiomyrgianaki, Alexia; Dais, Photis


    (31)P nuclear magnetic resonance (NMR) spectroscopy was used to detect and quantify simultaneously a large number of phenolic compounds and the two triterpenic acids, ursolic acid and oleanolic acid, extracted from two oregano species Origanum onites and Origanum vulgare ssp. Hirtum using two different organic solvents ethanol and ethyl acetate. This analytical method is based on the derivatization of the hydroxyl and carboxyl groups of these compounds with the phosphorous reagent 2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxa phospholane and the identification of the phosphitylated compounds on the basis of the (31)P chemical shifts. Unambiguous assignment of the (31)P NMR chemical shifts of the dihydroxy- and polyhydroxy-phenols in oregano species as well as those of the triterpenic acids was achieved upon comparison with the chemical shifts of model compounds assigned by using two-dimensional NMR techniques. Furthermore, the integration of the appropriate signals of the hydroxyl derivatives in the corresponding (31)P NMR spectra and the use of the phosphitylated cyclohexanol as an internal standard allowed the quantification of these compounds. The validity of this technique for quantitative measurements was thoroughly examined.

  4. Analysis of monoglycerides, diglycerides, sterols, and free fatty acids in coconut (Cocos nucifera L.) oil by 31P NMR spectroscopy. (United States)

    Dayrit, Fabian M; Buenafe, Olivia Erin M; Chainani, Edward T; de Vera, Ian Mitchelle S


    Phosphorus-31 nuclear magnetic resonance spectroscopy ( (31)P NMR) was used to differentiate virgin coconut oil (VCO) from refined, bleached, deodorized coconut oil (RCO). Monoglycerides (MGs), diglycerides (DGs), sterols, and free fatty acids (FFAs) in VCO and RCO were converted into dioxaphospholane derivatives and analyzed by (31)P NMR. On the average, 1-MG was found to be higher in VCO (0.027%) than RCO (0.019%). 2-MG was not detected in any of the samples down to a detection limit of 0.014%. On the average, total DGs were lower in VCO (1.55%) than RCO (4.10%). When plotted in terms of the ratio [1,2-DG/total DGs] versus total DGs, VCO and RCO samples grouped separately. Total sterols were higher in VCO (0.096%) compared with RCO (0.032%), and the FFA content was 8 times higher in VCO than RCO (0.127% vs 0.015%). FFA determination by (31)P NMR and titration gave comparable results. Principal components analysis shows that the 1,2-DG, 1,3-DG, and FFAs are the most important parameters for differentiating VCO from RCO.

  5. Solid-state 31P NMR spectroscopy of bacteriophage M13 and tobacco mosaic virus.

    NARCIS (Netherlands)

    Magusin, P.C.M.M.


    In this thesis, the results of various 31P NMR experiments observed for intact virus particles of bacteriophage M13 and Tobacco Mosaic Virus (TMV), are presented. To explain the results in a consistent way, models are developed and tested. 31

  6. 31P NMR spectroscopy and electromyography during exercise and recovery in patients with fibromyalgia

    DEFF Research Database (Denmark)

    Vestergaard-Poulsen, P; Thomsen, C; Nørregaard, J


    cross sectional muscle area was evaluated using 1H NMR imaging. The sedentary controls were matched to patients for sex, age and, as far as possible, daily physical activity levels. RESULTS. Patients with FM had reduced maximum voluntary contraction force in relation to the sedentary controls, despite...... with the lower physical activity levels.......OBJECTIVE. To investigate whether patients with fibromyalgia (FM) have normal motor unit recruitment in relation to muscle metabolism during exhausting exercise and recovery, and whether the reduced voluntary muscle force normally seen is related to a smaller muscle size. METHODS. Female patients...

  7. Human calf muscular metabolism study with a home-made ergometer using 31P NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Peynsaert, J.; Achten, E.; Claeys, E. [Ghent University Hospital (Belgium); Rousseaux, M. [Ghent University Hospital (Belgium). Dept. of Sport Medicine


    Phosphorus-31 NMR measurements were performed to examine the variations in the concentration of phosphate metabolites in calf muscle during exercise. Therefore, volunteers, installed in the supine position, were asked to push repetitively on the pedal of a home-made ergometer. The produced work and the changes in phosphorus containing metabolites were measured continuously. Correlations were made between the inorganic phosphate/phosphocreatine ratio and the cumulative work and between the intracellular pH and the cumulative work. The exercise protocol could be changed interactively with respect to the imposed initial pressure, the maximum pressure, the pressure increase per level and the time a certain level was held. The whole experiment could be graphically followed on-line. In the first stadium, the in vitro reproducibility of the ergometer was tested for different protocols. These tests revealed that, though the deviation in produced work was markedly the highest at high working pressures, the relative error never exceeded 3%. Consequently, the ex vitro reproducibility of the data was examined with the equipment placed in the scanner. Generally, same conclusions could be derived. In a next stage, the work will be synchronized with the biochemical data. Extreme precautions will be taken to examine each volunteer every time under the same physical and psychological conditions.

  8. Indirect two-dimensional heteronuclear NMR spectroscopy. (/sup 31/P, /sup 57/Fe) spectra of organoiron complexes

    Energy Technology Data Exchange (ETDEWEB)

    Benn, R.; Brenneke, H.; Frings, A.; Lehmkuhl, H.; Mehler, G.; Rufinska, A.; Wildt, T.


    The indirect heteronuclear two-dimensional (2D) triple-resonance (S,I)-(/sup 1/H) NMR spectroscopy is introduced for measuring the chemical shift and scalar spin-spin coupling constants of an insensitive nucleus I via its scalar coupling J(S,I) by detection of the nucleus S of higher sensitivity. The versatility of this approach is demonstrated by extracting delta(/sup 57/Fe) and J(Fe,X) from (/sup 31/P,/sup 57/Fe)-(/sup 1/H) spectra of various dissolved ((/eta//sup 5/-Cp)(L/sub 2/(R)))Fe, ((/eta//sup 3/-allyl)(/eta//sup 5/-Cp)(L))Fe, and ((/eta//sup 1/,/eta//sup 2/-alkenyl)(/eta//sup 5/-Cp)(L))Fe complexes (R = alkyl, hydride; L = PR/sub 3/). In practice the sensitivity of 2D (/sup 31/P,/sup 57/Fe) spectra was found to be higher than that of the direct observation scheme by at least a factor (..gamma../sub P//..gamma../sub Fe/)/sup 5/2/. Due to the intrinsically higher resolving power of a two-dimensional experiment, small scalar couplings like /sup 2J/(Fe,F) and /sup 1/J(Fe,H) were readily obtained from indirect two-dimensional spectra. Combinations of (/sup 1/H,/sup 57/Fe) and (/sup 31/P,/sup 57/Fe) spectra yielded the relative signs of the J(Fe,X) couplings: /sup 1/J(Fe,P) is positive and increases with increasing ..pi..-acceptor power of the phosphorus ligand L from 55 (L = PMe/sub 3/, R = H) to 149 Hz (L = PF/sub 3/). /sup 1/J(Fe,H) is around +9 Hz (R = H), whereas /sup 2/J(P,H) in these complexes was found to be negative. In all of the allyl complexes investigated, /sup 2J/(Fe,F) (L = PF/sub 3/) is positive and around 3 Hz. In the quasi-tetragonal and -trigonal iron complexes, delta(/sup 57/Fe) varies by about 4000 ppM. This can be rationalized qualitatively by the electronegativity of the atoms directly bonded to iron and the higher oxidation potential in the presence of more basic ligands L via the paramagnetic shielding term. 52 references, 5 figures, 5 tables.

  9. Distinguishing bicontinuous lipid cubic phases from isotropic membrane morphologies using (31)P solid-state NMR spectroscopy. (United States)

    Yang, Yu; Yao, Hongwei; Hong, Mei


    Nonlamellar lipid membranes are frequently induced by proteins that fuse, bend, and cut membranes. Understanding the mechanism of action of these proteins requires the elucidation of the membrane morphologies that they induce. While hexagonal phases and lamellar phases are readily identified by their characteristic solid-state NMR line shapes, bicontinuous lipid cubic phases are more difficult to discern, since the static NMR spectra of cubic-phase lipids consist of an isotropic (31)P or (2)H peak, indistinguishable from the spectra of isotropic membrane morphologies such as micelles and small vesicles. To date, small-angle X-ray scattering is the only method to identify bicontinuous lipid cubic phases. To explore unique NMR signatures of lipid cubic phases, we first describe the orientation distribution of lipid molecules in cubic phases and simulate the static (31)P chemical shift line shapes of oriented cubic-phase membranes in the limit of slow lateral diffusion. We then show that (31)P T2 relaxation times differ significantly between isotropic micelles and cubic-phase membranes: the latter exhibit 2 orders of magnitude shorter T2 relaxation times. These differences are explained by the different time scales of lipid lateral diffusion on the cubic-phase surface versus the time scales of micelle tumbling. Using this relaxation NMR approach, we investigated a DOPE membrane containing the transmembrane domain (TMD) of a viral fusion protein. The static (31)P spectrum of DOPE shows an isotropic peak, whose T2 relaxation times correspond to that of a cubic phase. Thus, the viral fusion protein TMD induces negative Gaussian curvature, which is an intrinsic characteristic of cubic phases, to the DOPE membrane. This curvature induction has important implications to the mechanism of virus-cell fusion. This study establishes a simple NMR diagnostic probe of lipid cubic phases, which is expected to be useful for studying many protein-induced membrane remodeling phenomena

  10. Using solid 13C NMR coupled with solution 31P NMR spectroscopy to investigate molecular species and lability of organic carbon and phosphorus from aquatic plants in Tai Lake, China (United States)

    Aquatic plants are involved in the storage and release capacity for organic matter and nutrients. In this study, solid 13C and solution 31P nuclear magnetic resonance (NMR) spectroscopy were used to characterize the biomass samples of six aquatic plants. Solid 13C NMR spectroscopy revealed the domin...

  11. 2D 31P solid state NMR spectroscopy, electronic structure and thermochemistry of PbP7 (United States)

    Benndorf, Christopher; Hohmann, Andrea; Schmidt, Peer; Eckert, Hellmut; Johrendt, Dirk; Schäfer, Konrad; Pöttgen, Rainer


    Phase pure polycrystalline PbP7 was prepared from the elements via a lead flux. Crystalline pieces with edge-lengths up to 1 mm were obtained. The assignment of the previously published 31P solid state NMR spectrum to the seven distinct crystallographic sites was accomplished by radio-frequency driven dipolar recoupling (RFDR) experiments. As commonly found in other solid polyphosphides there is no obvious correlation between the 31P chemical shift and structural parameters. PbP7 decomposes incongruently under release of phosphorus forming liquid lead as remainder. The thermal decomposition starts at T>550 K with a vapor pressure almost similar to that of red phosphorus. Electronic structure calculations reveal PbP7 as a semiconductor according to the Zintl description and clearly shows the stereo-active Pb-6s2 lone pairs in the electron localization function ELF.

  12. Distribution and mobility of phosphates and sodium ions in cheese by solid-state 31P and double-quantum filtered 23Na NMR spectroscopy. (United States)

    Gobet, Mallory; Rondeau-Mouro, Corinne; Buchin, Solange; Le Quéré, Jean-Luc; Guichard, Elisabeth; Foucat, Loïc; Moreau, Céline


    The feasibility of solid-state magic angle spinning (MAS) (31)P nuclear magnetic resonance (NMR) spectroscopy and (23)Na NMR spectroscopy to investigate both phosphates and Na(+) ions distribution in semi-hard cheeses in a non-destructive way was studied. Two semi-hard cheeses of known composition were made with two different salt contents. (31)P Single-pulse excitation and cross-polarization MAS experiments allowed, for the first time, the identification and quantification of soluble and insoluble phosphates in the cheeses. The presence of a relatively 'mobile' fraction of colloidal phosphates was evidenced. The detection by (23)Na single-quantum NMR experiments of all the sodium ions in the cheeses was validated. The presence of a fraction of 'bound' sodium ions was evidenced by (23)Na double-quantum filtered NMR experiments. We demonstrated that NMR is a suitable tool to investigate both phosphates and Na(+) ions distributions in cheeses. The impact of the sodium content on the various phosphorus forms distribution was discussed and results demonstrated that NMR would be an important tool for the cheese industry for the processes controls.

  13. Characteristics and degradation of carbon and phosphorus from aquatic macrophytes in lakes: Insights from solid-state {sup 13}C NMR and solution {sup 31}P NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Shasha [College of Water Sciences, Beijing Normal University, Beijing 100875 (China); State Key Laboratory of Environment Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); Zhu, Yuanrong, E-mail: [State Key Laboratory of Environment Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); Meng, Wei, E-mail: [State Key Laboratory of Environment Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); He, Zhongqi [USDA-ARS Southern Regional Research Center, 1100 Robert E Lee Blvd, New Orleans, LA 70124 (United States); Feng, Weiying [College of Water Sciences, Beijing Normal University, Beijing 100875 (China); State Key Laboratory of Environment Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); Zhang, Chen [State Key Laboratory of Environment Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); Giesy, John P. [State Key Laboratory of Environment Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); Department of Biomedical and Veterinary Biosciences and Toxicology Centre, University of Saskatchewan, Saskatoon, Saskatchewan (Canada)


    Water extractable organic matter (WEOM) derived from macrophytes plays an important role in biogeochemical cycling of nutrients, including carbon (C), nitrogen (N) and phosphorus (P) in lakes. However, reports of their composition and degradation in natural waters are scarce. Therefore, compositions and degradation of WEOM derived from six aquatic macrophytes species of Tai Lake, China, were investigated by use of solid-state {sup 13}C NMR and solution {sup 31}P NMR spectroscopy. Carbohydrates were the predominant constituents of WEOM fractions, followed by carboxylic acid. Orthophosphate (ortho-P) was the dominant form of P (78.7% of total dissolved P) in the water extracts, followed by monoester P (mono-P) (20.6%) and little diester P (0.65%). The proportion of mono-P in total P species increased with the percentage of O-alkyl and O–C–O increasing in the WEOM, which is likely due to degradation and dissolution of biological membranes and RNA from aquatic plants. Whereas the proportion of mono-P decreased with alkyl-C, NCH/OCH{sub 3} and COO/N–C=O increasing, which may be owing to the insoluble compounds including C functional groups of alkyl-C, NCH/OCH{sub 3} and COO/N–C=O, such as aliphatic biopolymers, lignin and peptides. Based on the results of this study and information in the literature about water column and sediment, we propose that WEOM, dominated by polysaccharides, are the most labile and bioavailable component in debris of macrophytes. Additionally, these WEOMs would also be a potential source for bioavailable organic P (e.g., RNA, DNA and phytate) for lakes. - Highlights: • WEOM derived from aquatic macrophytes was characterized. • C and P in WEOM were characterized by solid {sup 13}C NMR and solution {sup 31}P NMR. • Degradation and transformation of macrophyte-derived C and P were investigated. • Macrophyte-derived WEOM are important source for bioavailable nutrients in lakes.

  14. Simultaneous 31P-NMR spectroscopy and EMG in exercising and recovering human skeletal muscle: a correlation study

    DEFF Research Database (Denmark)

    Vestergaard-Poulsen, P; Thomsen, C; Sinkjaer, T


    of the muscle. Simultaneous 31P-nuclear magnetic resonance spectroscopy and surface electromyography were performed during sustained static exercise and recovery in healthy volunteers and a patient with McArdle's disease. A clear dissociation between the median power frequency of the surface electromyogram...... and pH was seen in the healthy volunteers during recovery and during exercise in the patient with McArdle's disease. The results indicate that proton or lactate accumulation is not primarily responsible for the spectral changes of the surface electromyogram as previously suggested. The motor unit...

  15. Quantitative (31)P NMR spectroscopy and (1)H MRI measurements of bone mineral and matrix density differentiate metabolic bone diseases in rat models. (United States)

    Cao, Haihui; Nazarian, Ara; Ackerman, Jerome L; Snyder, Brian D; Rosenberg, Andrew E; Nazarian, Rosalynn M; Hrovat, Mirko I; Dai, Guangping; Mintzopoulos, Dionyssios; Wu, Yaotang


    In this study, bone mineral density (BMD) of normal (CON), ovariectomized (OVX), and partially nephrectomized (NFR) rats was measured by (31)P NMR spectroscopy; bone matrix density was measured by (1)H water- and fat-suppressed projection imaging (WASPI); and the extent of bone mineralization (EBM) was obtained by the ratio of BMD/bone matrix density. The capability of these MR methods to distinguish the bone composition of the CON, OVX, and NFR groups was evaluated against chemical analysis (gravimetry). For cortical bone specimens, BMD of the CON and OVX groups was not significantly different; BMD of the NFR group was 22.1% (by (31)P NMR) and 17.5% (by gravimetry) lower than CON. For trabecular bone specimens, BMD of the OVX group was 40.5% (by (31)P NMR) and 24.6% (by gravimetry) lower than CON; BMD of the NFR group was 26.8% (by (31)P NMR) and 21.5% (by gravimetry) lower than CON. No significant change of cortical bone matrix density between CON and OVX was observed by WASPI or gravimetry; NFR cortical bone matrix density was 10.3% (by WASPI) and 13.9% (by gravimetry) lower than CON. OVX trabecular bone matrix density was 38.0% (by WASPI) and 30.8% (by gravimetry) lower than CON, while no significant change in NFR trabecular bone matrix density was observed by either method. The EBMs of OVX cortical and trabecular specimens were slightly higher than CON but not significantly different from CON. Importantly, EBMs of NFR cortical and trabecular specimens were 12.4% and 26.3% lower than CON by (31)P NMR/WASPI, respectively, and 4.0% and 11.9% lower by gravimetry. Histopathology showed evidence of osteoporosis in the OVX group and severe secondary hyperparathyroidism (renal osteodystrophy) in the NFR group. These results demonstrate that the combined (31)P NMR/WASPI method is capable of discerning the difference in EBM between animals with osteoporosis and those with impaired bone mineralization.

  16. Hydration behaviour of POPC/C(12)-Bet mixtures investigated by sorption gravimetry, (31)P NMR spectroscopy and X-ray diffraction. (United States)

    Pfeiffer, H; Weichert, H; Klose, G; Heremans, K


    The hydration behaviour of mixtures of the zwitterionic phospholipid 1-palmitoyl-2-oleolyl-sn-glycero-3-phosphocholine (POPC) and the zwitterionic surfactant N,N-dimethyl-N-dodecyl-betain (C(12)-Bet) was investigated by sorption gravimetry, solid-state (31)P NMR-spectroscopy and small angle X-ray diffraction (SAXD). Negative excess hydration (dehydration) was found for almost all hydration degrees investigated. This behaviour is explained by the formation of an inner salt between the dipoles of phospholipid and surfactant headgroups that show a reverse sequence of partial charges with respect to the hydrocarbon backbone. The formation of an inner-salt most probably reduces potential water binding sites. Moreover, NMR data suggest that the incorporation of the zwitterionic surfactant into the phospholipid membrane is correlated with reorientation of the phosphate axis towards the membrane director as well as with reduced lateral and wobbling diffusion.

  17. Oxidative stress-induced metabolic changes in mouse C2C12 myotubes studied with high-resolution 13C, 1H, and 31P NMR spectroscopy

    DEFF Research Database (Denmark)

    Straadt, Ida K; Young, Jette F; Petersen, Bent O;


    In this study, stress in relation to slaughter was investigated in a model system by the use of (13)C, (1)H, and (31)P nuclear magnetic resonance (NMR) spectroscopy for elucidating changes in the metabolites in C2C12 myotubes exposed to H(2)O(2)-induced stress. Oxidative stress resulted in lower...... to lower levels of the unlabeled ((12)C) lactate were identified in the (1)H spectra after stress exposure. These data indicate an increase in de novo synthesis of alanine, concomitant with a release of lactate from the myotubes to the medium at oxidative stress conditions. The changes in the metabolite...... levels of several metabolites, mainly amino acids; however, higher levels of alanine were apparent in the (13)C spectra after incubation with [(13)C(1)]glucose. In the (13)C spectra [(13)C(3)]lactate tended to increase after exposure to increasing concentrations of H(2)O(2); conversely, a tendency...

  18. Oxidative stress-induced metabolic changes in mouse C2C12 myotubes studied with high-resolution 13C, 1H, and 31P NMR spectroscopy. (United States)

    Straadt, Ida K; Young, Jette F; Petersen, Bent O; Duus, Jens Ø; Gregersen, Niels; Bross, Peter; Oksbjerg, Niels; Theil, Peter K; Bertram, Hanne C


    In this study, stress in relation to slaughter was investigated in a model system by the use of (13)C, (1)H, and (31)P nuclear magnetic resonance (NMR) spectroscopy for elucidating changes in the metabolites in C2C12 myotubes exposed to H(2)O(2)-induced stress. Oxidative stress resulted in lower levels of several metabolites, mainly amino acids; however, higher levels of alanine were apparent in the (13)C spectra after incubation with [(13)C(1)]glucose. In the (13)C spectra [(13)C(3)]lactate tended to increase after exposure to increasing concentrations of H(2)O(2); conversely, a tendency to lower levels of the unlabeled ((12)C) lactate were identified in the (1)H spectra after stress exposure. These data indicate an increase in de novo synthesis of alanine, concomitant with a release of lactate from the myotubes to the medium at oxidative stress conditions. The changes in the metabolite levels could possibly be useful as markers for meat quality traits.

  19. Simulated biological effects of microgravity on phospholipid and energy metabolism of chicken embryonic brain cells studied by 31P-NMR spectroscopy

    Institute of Scientific and Technical Information of China (English)


    Levels of phosphomonoester (PME), phosphodiester (PDE), ATP and pH in brain cells of chicken embryos rotated for 24 h in a clinostat during the period of hatching the 13th day (E13) and 15th day (E15) embryos were investigated by using 31P-NMR spectroscopy. Significant increases in the values of PME, ATP and pH were identified after E13 rotating for 24 h. With the same treatment, differences were obtained in the phospholipid and energy metabolism of E15, but no significant levels have been reached . The calorimetric assay (malachite green method) was used for measuring the activity of total ATPase. A dramatic decrease was evident in the activity of ATPase in brain cells of rotated E13 and E15. The former is more sensitive than the latter. All the levels mentioned above could restore in 24 h after the rotation stopped, except that the level of ATP was still higher than the control.

  20. Synthesis, crystal structure, vibrational and 31P-NMR spectroscopy of the thiophosphate NaMg[PO3S]·9H2O (United States)

    Höppe, Henning A.; Scharinger, Stefan W.; Heck, Joachim G.; Gross, Peter; Netzsch, Philip; Kazmierczak, Karolina


    NaMg[PO3S]·9H2O was obtained as single-phase crystalline powder starting from NaOH, PSCl3 and MgCl2·6H2O. At room temperature NaMg[PO3S]·9H2O crystallises in space group Cmc21 (no. 36) (a=638.58(4) pm, b=1632.31(10) pm, c=1217.16(7) pm, Z = 4; Rint = 0.032, Rσ = 0.034, R1 = 0.036, wR2 = 0.071). The data collection at 100 K reveals an ordering of the PO3S tetrahedra by undergoing a symmetry reduction to P21 (no. 4) and an according formation of twins (C1121, unconv. setting of P21, a=631.41(3) pm, b=1630.00(7) pm, c=1219.24(5) pm, γ=90.00(2)°, Z = 4; Rint = 0.115, Rσ = 0.064, R1 = 0.045, wR2 = 0.070). NaMg[PO3S]·9H2O comprises isolated PO3S tetrahedra, distorted MgO6 octahedra and trigonal NaO6 prisms. 31P NMR spectroscopy showed a chemical shift of 33.7 ppm. The vibrational spectra of NaMg[PO3S]·9H2O were recorded and the relevant bands were assigned.

  1. 31P NMR Study on Some Phosphorus-Containing Compounds

    Institute of Scientific and Technical Information of China (English)


    31P NMR has become a widely applied spectroscopic probe of the structure of phosphorus-containing compounds. Meanwhile, the application of 31P NMR has been rapidly expanded to biochemistry and medicinal chemistry of phosphorus-containing compounds because the growing importance of the phosphorus compounds is now widely realized. We report here the results of 31P NMR study on some phosphorus-containing compounds, namely, O-alkyl O-4-nitrophenyl methyl phosphonates with different alkyl chain-length (MePO-n), 4-nitrophenyl alkylphenylphosphinates with different alkyl chain-length (PhP-n), diethyl phosphono- acetonitrile anion and diethyl phosphite anion . Our results indicate that 31P NMR can not only be applied to not only the study of the hydrolytic reactions of MePO-8 and PhP-8 but also be applied to the study of the presence of the anions of diethylphosphonoacetonitrile and diethyl phosphite in nucleophilic reactions.

  2. Hepatic lipid profiling of deer mice fed ethanol using {sup 1}H and {sup 31}P NMR spectroscopy: A dose-dependent subchronic study

    Energy Technology Data Exchange (ETDEWEB)

    Fernando, Harshica; Bhopale, Kamlesh K.; Boor, Paul J.; Ansari, G.A. Shakeel; Kaphalia, Bhupendra S., E-mail:


    Chronic alcohol abuse is a 2nd major cause of liver disease resulting in significant morbidity and mortality. Alcoholic liver disease (ALD) is characterized by a wide spectrum of pathologies starting from fat accumulation (steatosis) in early reversible stage to inflammation with or without fibrosis and cirrhosis in later irreversible stages. Previously, we reported significant steatosis in the livers of hepatic alcohol dehydrogenase (ADH)-deficient (ADH{sup −}) vs. hepatic ADH-normal (ADH{sup +}) deer mice fed 4% ethanol daily for 2 months [Bhopale et al., 2006, Alcohol 39, 179–188]. However, ADH{sup −} deer mice fed 4% ethanol also showed a significant mortality. Therefore, a dose-dependent study was conducted to understand the mechanism and identify lipid(s) involved in the development of ethanol-induced fatty liver. ADH{sup −} and ADH{sup +} deer mice fed 1, 2 or 3.5% ethanol daily for 2 months and fatty infiltration in the livers were evaluated by histology and by measuring dry weights of extracted lipids. Lipid metabolomic changes in extracted lipids were determined by proton ({sup 1}H) and {sup 31}phosphorus ({sup 31}P) nuclear magnetic resonance (NMR) spectroscopy. The NMR data was analyzed by hierarchical clustering (HC) and principle component analysis (PCA) for pattern recognition. Extensive vacuolization by histology and significantly increased dry weights of total lipids found only in the livers of ADH{sup −} deer mice fed 3.5% ethanol vs. pair-fed controls suggest a dose-dependent formation of fatty liver in ADH{sup −} deer mouse model. Analysis of NMR data of ADH{sup −} deer mice fed 3.5% ethanol vs. pair-fed controls shows increases for total cholesterol, esterified cholesterol, fatty acid methyl esters (FAMEs), triacylglycerides and unsaturation, and decreases for free cholesterol, phospholipids and allylic and diallylic protons. Certain classes of neutral lipids (cholesterol esters, fatty acyl chain (-COCH{sub 2}-) and FAMEs) were

  3. Using solid (13)C NMR coupled with solution (31)P NMR spectroscopy to investigate molecular species and lability of organic carbon and phosphorus from aquatic plants in Tai Lake, China. (United States)

    Liu, Shasha; Zhu, Yuanrong; Wu, Fengchang; Meng, Wei; Wang, Hao; He, Zhongqi; Guo, Wenjing; Song, Fanhao; Giesy, John P


    Forms and labilities of plant-derived organic matters (OMs) including carbon (C) and phosphorus (P) were fundamental for understanding their release, degradation and environmental behaviour in lake ecosystems. Thus, solid (13)C and solution (31)P nuclear magnetic resonance (NMR) spectroscopy were used to characterize biomass of six aquatic plants in Tai Lake, China. The results showed that carbohydrates (61.2% of the total C) were predominant C functional group in the solid (13)C NMR spectra of plant biomass, which may indicate high lability and bioavailability of aquatic plants-derived organic matter in lakes. There was 72.6-103.7% of the total P in aquatic plant biomass extracted by NaOH-EDTA extracts. Solution (31)P NMR analysis of these NaOH-EDTA extracts further identified several molecular species of P including orthophosphate (50.1%), orthophosphate monoesters (46.8%), DNA (1.6%) and pyrophosphate (1.4%). Orthophosphate monoesters included β-glycerophosphate (17.7%), hydrolysis products of RNA (11.7%), α-glycerophosphate (9.2%) and other unknown monoesters (2.1%). Additionally, phytate, the major form of organic P in many lake sediments, was detected in floating plant water poppy. These inorganic P (e.g. orthophosphate and pyrophosphate) and organic P (e.g. diester and its degradation products) identified in plant biomass were all labile and bioavailable P, which would play an important role in recycling of P in lakes. These results increased knowledge of chemical composition and bioavailability of OMs derived from aquatic plants in lakes.

  4. Solid-state NMR (31)P paramagnetic relaxation enhancement membrane protein immersion depth measurements. (United States)

    Maltsev, Sergey; Hudson, Stephen M; Sahu, Indra D; Liu, Lishan; Lorigan, Gary A


    Paramagnetic relaxation enhancement (PRE) is a widely used approach for measuring long-range distance constraints in biomolecular solution NMR spectroscopy. In this paper, we show that (31)P PRE solid-state NMR spectroscopy can be utilized to determine the immersion depth of spin-labeled membrane peptides and proteins. Changes in the (31)P NMR PRE times coupled with modeling studies can be used to describe the spin-label position/amino acid within the lipid bilayer and the corresponding helical tilt. This method provides valuable insight on protein-lipid interactions and membrane protein structural topology. Solid-state (31)P NMR data on the 23 amino acid α-helical nicotinic acetylcholine receptor nAChR M2δ transmembrane domain model peptide followed predicted behavior of (31)P PRE rates of the phospholipid headgroup as the spin-label moves from the membrane surface toward the center of the membrane. Residue 11 showed the smallest changes in (31)P PRE (center of the membrane), while residue 22 shows the largest (31)P PRE change (near the membrane surface), when compared to the diamagnetic control M2δ sample. This PRE SS-NMR technique can be used as a molecular ruler to measure membrane immersion depth.

  5. Comparison of the compression strength of human vertebral bodies with the mass and density of apatite: a study by 31P NMR spectroscopy. (United States)

    Brown, C E; Srinivasan, R; Sigmann, P; Myklebust, J B; Battocletti, J H


    The force needed to fracture individual human thoracic and lumbar vertebral bodies is compared with the mass and density of apatite. 31P NMR spectrometry was used to quantify the apatite, because it permits the mineral content of bone to be determined noninvasively with minimal nonspecific interference from the organic matrix or from variations in composition of the marrow. Experiments were performed with bones of similar structure and function from a single individual with no history of trabecular fractures, to compensate for the effects of the other variables that affect bone strength. The coefficient of correlation between compression strength and the volume density (i.e., g/cm3) of apatite was 0.95. The correlation of strength with the mass (i.e., grams) of apatite in a vertebral body also was reasonably good, r = 0.82, but correlations with areal density (i.e., g/cm2) and linear density (i.e., g/cm) were much poorer.

  6. Human in vivo phosphate metabolite imaging with 31P NMR. (United States)

    Bottomley, P A; Charles, H C; Roemer, P B; Flamig, D; Engeseth, H; Edelstein, W A; Mueller, O M


    Phosphorus (31P) spectroscopic images showing the distribution of high-energy phosphate metabolites in the human brain have been obtained at 1.5 T in scan times of 8.5 to 34 min at 27 and 64 cm3 spatial resolution using pulsed phase-encoding gradient magnetic fields and three-dimensional Fourier transform (3DFT) techniques. Data were acquired as free induction decays with a quadrature volume NMR detection coil of a truncated geometry designed to optimize the signal-to-noise ratio on the coil axis on the assumption that the sample noise represents the dominant noise source, and self-shielded magnetic field gradient coils to minimize eddy-current effects. The images permit comparison of metabolic data acquired simultaneously from different locations in the brain, as well as metabolite quantification by inclusion of a vial containing a standard of known 31P concentration in the image array. Values for the NMR visible adenosine triphosphate in three individuals were about 3 mM of tissue. The ratio of NMR detectable phosphocreatine to ATP in brain was 1.15 +/- 0.17 SD in these experiments. Potential sources of random and systematic error in these and other 31P measurements are identified.

  7. 31P NMR for the study of P metabolism and translocation in arbuscular mycorrhizal fungi

    DEFF Research Database (Denmark)

    Rasmussen, N.; Lloyd, D.C.; Ratcliffe, R.G.


    P-31 nuclear magnetic resonance (NMR) spectroscopy was used to study phosphate (P) metabolism in mycorrhizal and nonmycorrhizal roots of cucumber (Cucumis sativus L) and in external mycelium of the arbuscular mycorrhizal (AM) fungus Glomus intraradices Schenck & Smith. The in vivo NMR method allows...... biological systems to be studied non-invasively and non-destructively. (3)1P NMR experiments provide information about cytoplasmic and vacuolar pH, based on the pH-dependent chemical shifts of the signals arising from the inorganic P (P-i) located in the two compartments. Similarly, the resonances arising...... from alpha, beta and gamma phosphates of nucleoside triphosphates (NTP) and nucleoside diphosphates (NDP) supply knowledge about the metabolic activity and the energetic status of the tissue. In addition, the kinetic behaviour of P uptake and storage can be determined with this method. The (3)1P NMR...

  8. Effects of temperature and extracellular pH on metabolites: kinetics of anaerobic metabolism in resting muscle by 31P- and 1H-NMR spectroscopy. (United States)

    Vezzoli, Alessandra; Gussoni, Maristella; Greco, Fulvia; Zetta, Lucia


    Environmental stress, such as low temperature, extracellular acidosis and anoxia, is known to play a key role in metabolic regulation. The aim of the present study was to gain insight into the combined temperature-pH regulation of metabolic rate in frog muscle, i.e. an anoxia-tolerant tissue. The rate of exergonic metabolic processes occurring in resting isolated muscles was determined at 15 degrees C and 25 degrees C as well as at extracellular pH values higher (7.9), similar (7.3) and lower (7.0) than the physiological intracellular pH. (31)P and (1)H nuclear magnetic resonance spectroscopy high-resolution measurements were carried out at 4.7 T in isolated frog (Rana esculenta) gastrocnemius muscle during anoxia to assess, by means of reference compounds, the concentration of all phosphate metabolites and lactate. Intra- and extracellular pH was also determined. In the range of examined temperatures (15-25 degrees C), the temperature dependence of anaerobic glycolysis was found to be higher than that of PCr depletion (Q(10)=2.3). High-energy phosphate metabolism was confirmed to be the initial and preferential energy source. The rate of phosphocreatine hydrolysis did not appear to be affected by extracellular pH changes. By contrast, independent of the intracellular pH value, at the higher temperature (25 degrees C) a lowering of the extracellular pH from 7.9 to 7.0 caused a depression in lactate accumulation. This mechanism was ascribed to the transmembrane proton concentration gradient. This parameter was demonstrated to regulate glycolysis, probably through a reduced lactate efflux, depending on the activity of the lactate-H(+) co-transporter. The calculated intracellular buffer capacity was related to intra- and extracellular pH and temperature. At the experimental extracellular pH of 7.9 and at a temperature of 15 degrees C and 25 degrees C, calculated intracellular buffering capacity was 29.50 micromol g(-1) pH unit(-1) and 69.98 micromol g(-1) pH unit(-1

  9. Simultaneous electromyography and 31P nuclear magnetic resonance spectroscopy--with application to muscle fatigue

    DEFF Research Database (Denmark)

    Vestergaard-Poulsen, P; Thomsen, C; Sinkjaer, T;


    The electromyogram (EMG) is often used to study human muscle fatigue, but the changes in the electromyographic signals during muscle contraction are not well understood in relation to muscle metabolism. The 31P NMR spectroscopy is a semi-quantitative non-invasive method for studying the metabolic...... changes in human muscle. The aim of this study was to develop a method by which EMG and NMR spectroscopy measurements could be performed simultaneously. All measurements were performed in a whole body 1.5 Tesla NMR scanner. A calf muscle ergometer, designed for use in a whole body NMR scanner, was used....... The subject had the left foot strapped to the ergometer. The anterior tibial EMG was recorded by bipolar surface electrodes. A surface coil was strapped to the anterior tibial muscle next to the EMG electrodes. Simultaneous measurements of surface EMG and surface coil 31P NMR spectroscopy were performed...

  10. Importance of the 31-p-nmr-spectroscopy for prediction and early detection of coronary heart disease in patients with diabetes mellitus type I

    CERN Document Server

    Steinboeck, P


    Microvascular abnormalities and dysfunction via thickening of the basement membrane are known to occur in diabetic patients. Myocardial high energy phosphates have been shown to be reduced by ischemia and alterations of the cardiac metabolism are the primary consequence of myocardial ischemia. The present study involved 30 male patients with diabetes mellitus type I and 36 healthy male volunteers as age-matched controls. Phosphorus-31-P-nuclear-magnetic-resonance-spectroscopic-imaging of the heart was performed in all subjects using a 1.5 Tesla whole-body-magnetic-resonance-scanner. The ratios of phosphocreatinine (PCr) to adenosine-triphosphate (ATP) were calculated. Moreover, echocardiographic evaluation and stress tests were performed in all individuals. The myocardium of patients with diabetes mellitus type I showed significantly decreased ratios of PCr/ATP compared with healthy controls. This study demonstrates for the first time a decreased ratio of PCr/ATP in the myocardium of patients with diabetes me...

  11. Use of the Fourier series window protocol with a zig-zag surface coil in 31P NMR human skin spectroscopy. A theoretical study. (United States)

    Bastin, M E; Cowie, A G; Manners, D N; Hands, L J; Styles, P


    The use of a zig-zag surface coil with a three-pulse Fourier Series Window (FSW) has been suggested as a means by which in vivo NMR spectroscopic studies of human skin can be performed. Using direct numerical simulations of the magnetic field profile of a 10 limb zig-zag surface coil, the role of the FSW in reducing NMR signals originating from the deeper skeletal muscle layers is examined theoretically. The extent of muscle signal contamination is determined for different coil inter-limb spacings and pulse width settings. The optimum inter-limb spacing for studying living human skin, that which minimizes signal contamination and maximizes skin signal collected, is shown to be between 4 and 6 mm. These calculations demonstrate that the FSW and zig-zag surface coil offer a protocol for investigating the metabolism of large areas of surface tissue while keeping signal contamination from the deeper skeletal muscle layers down to an acceptable level.

  12. Catalytic mechanism of α-phosphate attack in dUTPase is revealed by X-ray crystallographic snapshots of distinct intermediates, 31P-NMR spectroscopy and reaction path modelling. (United States)

    Barabás, Orsolya; Németh, Veronika; Bodor, Andrea; Perczel, András; Rosta, Edina; Kele, Zoltán; Zagyva, Imre; Szabadka, Zoltán; Grolmusz, Vince I; Wilmanns, Matthias; Vértessy, Beáta G


    Enzymatic synthesis and hydrolysis of nucleoside phosphate compounds play a key role in various biological pathways, like signal transduction, DNA synthesis and metabolism. Although these processes have been studied extensively, numerous key issues regarding the chemical pathway and atomic movements remain open for many enzymatic reactions. Here, using the Mason-Pfizer monkey retrovirus dUTPase, we study the dUTPase-catalyzed hydrolysis of dUTP, an incorrect DNA building block, to elaborate the mechanistic details at high resolution. Combining mass spectrometry analysis of the dUTPase-catalyzed reaction carried out in and quantum mechanics/molecular mechanics (QM/MM) simulation, we show that the nucleophilic attack occurs at the α-phosphate site. Phosphorus-31 NMR spectroscopy ((31)P-NMR) analysis confirms the site of attack and shows the capability of dUTPase to cleave the dUTP analogue α,β-imido-dUTP, containing the imido linkage usually regarded to be non-hydrolyzable. We present numerous X-ray crystal structures of distinct dUTPase and nucleoside phosphate complexes, which report on the progress of the chemical reaction along the reaction coordinate. The presently used combination of diverse structural methods reveals details of the nucleophilic attack and identifies a novel enzyme-product complex structure.

  13. 31P magnetic resonance spectroscopy of skeletal muscle in patients with fibromyalgia

    DEFF Research Database (Denmark)

    Jacobsen, Søren; Jensen, K E; Thomsen, C


    31Phosphorous nuclear magnetic resonance (31P NMR) spectroscopy of painful calf muscle was performed in 12 patients with fibromyalgia (FS) and 7 healthy subjects during rest, aerobic and anaerobic exercising conditions, and postexercise recovery. Ratios of inorganic phosphate and creatinine...

  14. Forms and lability of phosphorus in algae and aquatic macrophytes characterized by solution 31P NMR coupled with enzymatic hydrolysis (United States)

    Increased information on forms and lability of phosphorus (P) in aquatic macrophytes and algae is crucial for better understanding of P biogeochemical cycling in eutrophic lakes. In this work, solution 31P nuclear magnetic resonance (NMR) spectroscopy coupled with enzymatic hydrolysis (EH) was used ...

  15. Decomposition of adsorbed VX on activated carbons studied by 31P MAS NMR. (United States)

    Columbus, Ishay; Waysbort, Daniel; Shmueli, Liora; Nir, Ido; Kaplan, Doron


    The fate of the persistent OP nerve agent O-ethyl S-[2-(diisopropylamino)ethyl] methylphosphonothioate (VX) on granular activated carbons that are used for gas filtration was studied by means of 31P magic angle spinning (MAS) NMR spectroscopy. VX as vapor or liquid was adsorbed on carbon granules, and MAS NMR spectra were recorded periodically. The results show that at least 90% of the adsorbed VX decomposes within 20 days or less to the nontoxic ethyl methylphosphonic acid (EMPA) and bis(S-2-diisopropylaminoethane) {(DES)2}. Decomposition occurred irrespective of the phase from which VX was loaded, the presence of metal impregnation on the carbon surface, and the water content of the carbon. Theoretical and practical aspects of the degradation are discussed.

  16. Decomposition of adsorbed VX on activated carbons studied by {sup 31}P MAS NMR

    Energy Technology Data Exchange (ETDEWEB)

    Ishay Columbus; Daniel Waysbort; Liora Shmueli; Ido Nir; Doron Kaplan [Israel Institute for Biological Research, Ness Ziona (Israel). Departments of Organic Chemistry and Physical Chemistry


    The fate of the persistent OP nerve agent O-ethyl S-(2-(diisopropylamino)ethyl) methylphosphonothioate (VX) on granular activated carbons that are used for gas filtration was studied by means of 31P magic angle spinning (MAS) NMR spectroscopy. Four types of activated carbon were used, including coal-based BPL. VX as vapor or liquid was adsorbed on carbon granules, and MAS NMR spectra were recorded periodically. The results show that at least 90% of the adsorbed VX decomposes within 20 days or less to the nontoxic ethyl methylphosphonic acid (EMPA) and bis(S-2-diisopropylaminoethane) ((DES){sub 2}). Decomposition occurred irrespective of the phase from which VX was loaded, the presence of metal impregnation on the carbon surface, and the water content of the carbon. Theoretical and practical aspects of the degradation are discussed. 17 refs., 6 figs., 3 tabs.

  17. 31P Solid-state NMR based monitoring of permeation of cell penetrating peptides into skin (United States)

    Desai, Pinaki R.; Cormier, Ashley R.; Shah, Punit P.; Patlolla, Ram R.; Paravastu, Anant K.; Singh, Mandip


    The main objective of the current study was to investigate penetration of cell penetrating peptides (CPPs: TAT, R8, R11 and YKA) through skin intercellular lipids using 31P magic angle spinning (MAS) solid-state NMR. In vitro skin permeation studies were performed on rat skin, sections (0–60, 61–120 and 121–180 µm) were collected and analyzed for 31P NMR signal. The concentration dependent shift of 0, 25, 50, 100 and 200 mg/ml of TAT on skin layers, diffusion of TAT, R8, R11 and YKA in the skin and time dependent permeation of R11 was measured on various skin sections using 31P solid-state NMR. Further, CPPs and CPP-tagged fluorescent dye encapsulate liposomes (FLip) in skin layers were tagged using confocal microscopy. The change in 31P NMR chemical shift was found to depend monotonically on the amount of CPP applied on skin, with saturation behavior above 100 mg/ml CPP concentration. R11 and TAT caused more shift in solid-state NMR peaks compared to other peptides. Furthermore, NMR spectra showed R11 penetration up to 180 µm within 30 min. The results of the solid-state NMR study were in agreement with confocal microscopy studies. Thus, 31P solid-state NMR can be used to track CPP penetration into different skin layers. PMID:23702274

  18. Effects of anoxia on 31P NMR spectra of Phycomyces blakesleeanus during development

    Directory of Open Access Journals (Sweden)

    Stanić Marina


    Full Text Available The method of 31P NMR spectroscopy was used to investigate the effects of anoxia on Phycomyces blakesleea­nus mycelium during development. The greatest changes were recorded in the PPc, NADH, and α-ATP signals. Decrease of PPc signal intensity is due to chain length reduction and reduction in number of PPn molecules. Smaller decrease of β-ATP compared to α-ATP signal intensity can be attributed to maintenance of ATP concentration at the expense of PPn hydrolysis. Sensitivity to anoxia varies with the growth stage. It is greatest in 32-h and 44-h mycelium, in which PPn is used as an additional energy source, while the smallest effect was noted for 36-h fungi.

  19. Degradation of black phosphorus: a real-time 31P NMR study (United States)

    Wang, Yue; Yang, Bingchao; Wan, Bensong; Xi, Xuekui; Zeng, Zhongming; Liu, Enke; Wu, Guangheng; Liu, Zhongyuan; Wang, Wenhong


    In this work, degradation behaviors and mechanisms of black phosphorus (BP) crystals in air under ambient conditions were investigated by nuclear magnetic resonance spectroscopy. It has been found that the 31P NMR line intensity for BP decreases exponentially during aging even at the very first several hours, suggesting the origin of the degradation of transport properties. In addition to phosphoric acid, new phosphorous acid was also well resolved in the final aging products. Moreover, BP has been found to be stable in water without the presence of oxygen molecules. These findings are relevant for better understanding of degradation behaviors of BP upon aging and should be helpful for overcoming a barrier that might hamper progress toward applications of BP as a 2D material.

  20. Animal manure phosphorus characterization by sequential chemical fractionation, release kinetics and 31P-NMR analysis

    Directory of Open Access Journals (Sweden)

    Tales Tiecher


    Full Text Available Phosphate release kinetics from manures are of global interest because sustainable plant nutrition with phosphate will be a major concern in the future. Although information on the bioavailability and chemical composition of P present in manure used as fertilizer are important to understand its dynamics in the soil, such studies are still scarce. Therefore, P extraction was evaluated in this study by sequential chemical fractionation, desorption with anion-cation exchange resin and 31P nuclear magnetic resonance (31P-NMR spectroscopy to assess the P forms in three different dry manure types (i.e. poultry, cattle and swine manure. All three methods showed that the P forms in poultry, cattle and swine dry manures are mostly inorganic and highly bioavailable. The estimated P pools showed that organic and recalcitrant P forms were negligible and highly dependent on the Ca:P ratio in manures. The results obtained here showed that the extraction of P with these three different methods allows a better understanding and complete characterization of the P pools present in the manures.

  1. TLC and 31P-NMR analysis of low polarity phospholipids. (United States)

    Vyssotski, Mikhail; MacKenzie, Andrew; Scott, Dawn


    High-performance TLC and (31)P-NMR were assessed as methods of observing the presence of numerous low polarity phospholipids: bis-phosphatidic acid (BPA), semi-lyso bis-phosphatidic acid (SLBPA), N-acyl phosphatidylethanolamine (NAPE), N-(1,1-dimethyl-3-oxo-butyl)-phosphatidylethanolamine (diacetone adduct of PE, DOBPE), N-acetyl PE, phosphatidylmethanol (PM), phosphatidylethanol (PEt), phosphatidyl-n-propanol (PP), phosphatidyl-n-butanol (PB). Both techniques are non-discriminative and do not require the prior isolation of individual lipids. It appears that 2D TLC is superior to (31)P NMR in the analysis of low polarity phospholipids. All phosphatidylalcohols were well separated by 2D TLC. However, some compounds which can present difficulty in separation by 2D-TLC (e.g., SLBPA and NAPE; or DOBPE and N-acetyl PE) were easily distinguished using (31)P NMR so the methods are complimentary. A disadvantage of 2D TLC is that Rf values can vary with different brands and batches of TLC plates. The chemical shifts of (31)P NMR were less variable, and so a library of standards may not be necessary for peak identification. Another advantage of (31)P NMR is the ease of quantification of phospholipids. The applicability of the methods was tested on natural extracts of fish brain and cabbage stem.

  2. Forms and Lability of Phosphorus in Algae and Aquatic Macrophytes Characterized by Solution 31P NMR Coupled with Enzymatic Hydrolysis (United States)

    Feng, Weiying; Zhu, Yuanrong; Wu, Fengchang; He, Zhongqi; Zhang, Chen; Giesy, John P.


    Solution Phosphorus-31 nuclear magnetic resonance (31P NMR) spectroscopy coupled with enzymatic hydrolysis (EH) with commercially available phosphatases was used to characterize phosphorus (P) compounds in extracts of the dominant aquatic macrophytes and algae in a eutrophic lake. Total extractable organic P (Po) concentrations ranged from 504 to 1643 mg kg−1 and 2318 to 8395 mg kg−1 for aquatic macrophytes and algae, respectively. Using 31P NMR spectroscopy, 11 Po species were detected in the mono- and diester region. Additionally, orthophosphate, pyrophosphate and phosphonates were also detected. Using EH, phytate-like P was identified as the prevalent class of enzyme-labile Po, followed by labile monoester- and diester-P. Comparison of the NMR and EH data indicated that the distribution pattern of major P forms in the samples determined by the two methods was similar (r = 0.712, p < 0.05). Additional 31P NMR spectroscopic analysis of extracts following EH showed significant decreases in the monoester and pyrophosphate regions, with a corresponding increase in the orthophosphate signal, as compared to unhydrolyzed extracts. Based on these quantity and hydrolysis data, we proposed that recycling of Po in vegetative biomass residues is an important mechanism for long-term self-regulation of available P for algal blooming in eutrophic lakes. PMID:27849040

  3. Forms and Lability of Phosphorus in Algae and Aquatic Macrophytes Characterized by Solution 31P NMR Coupled with Enzymatic Hydrolysis (United States)

    Feng, Weiying; Zhu, Yuanrong; Wu, Fengchang; He, Zhongqi; Zhang, Chen; Giesy, John P.


    Solution Phosphorus-31 nuclear magnetic resonance (31P NMR) spectroscopy coupled with enzymatic hydrolysis (EH) with commercially available phosphatases was used to characterize phosphorus (P) compounds in extracts of the dominant aquatic macrophytes and algae in a eutrophic lake. Total extractable organic P (Po) concentrations ranged from 504 to 1643 mg kg‑1 and 2318 to 8395 mg kg‑1 for aquatic macrophytes and algae, respectively. Using 31P NMR spectroscopy, 11 Po species were detected in the mono- and diester region. Additionally, orthophosphate, pyrophosphate and phosphonates were also detected. Using EH, phytate-like P was identified as the prevalent class of enzyme-labile Po, followed by labile monoester- and diester-P. Comparison of the NMR and EH data indicated that the distribution pattern of major P forms in the samples determined by the two methods was similar (r = 0.712, p < 0.05). Additional 31P NMR spectroscopic analysis of extracts following EH showed significant decreases in the monoester and pyrophosphate regions, with a corresponding increase in the orthophosphate signal, as compared to unhydrolyzed extracts. Based on these quantity and hydrolysis data, we proposed that recycling of Po in vegetative biomass residues is an important mechanism for long-term self-regulation of available P for algal blooming in eutrophic lakes.

  4. Phosphorus in chronosequence of burnt sugar cane in Brazilian cerrado: humic acid analysis by {sup 31}P NMR; Fosforo em cronossequencia de cana-de-acucar queimada no cerrado goiano: analise de acidos humicos por RMN de {sup 31}P

    Energy Technology Data Exchange (ETDEWEB)

    Rossi, Celeste Q.; Pereira, Marcos G.; Garcia, Andreas C., E-mail: [Universidade Federal Rural do Rio de Janeiro (UFRRJ), Seropedica, RJ (Brazil). Dept. de Solos; Perin, Adriano; Gazolla, Paulo R. [Instituto Federal de Educacao, Ciencia e Tecnologia Goiano, Rio Verde, GO (Brazil); Gonzalez, Antonio P. [Universidade de Coruna, ES (Spain). Faculdad de Ciencias


    The aim of this study was to identify, with the use of {sup 31}P NMR spectroscopy, organic P species in humic acids (HA) in samples from Oxisol cultivated in chronosequence with sugar cane, pasture and Cerrado. The main forms of P-type found were orthophosphate, monoester-P (phosphate sugars) and P-diester (orthophosphate). The {sup 31}P NMR technique proved capable of identifying changes in the areas studied as a function of sugar cane burning time. In areas with 1 and 5 years of burnt cane, a decrease in recalcitrant organic P in humic acids indicated the need for use of P-humic substances for plant nutrition (author)

  5. Optically detected NMR of optically hyperpolarized 31P neutral donors in 28Si

    CERN Document Server

    Steger, M; Yang, A; Saeedi, K; Hayden, M E; Thewalt, M L W; Itoh, K M; Riemann, H; Abrosimov, N V; Becker, P; Pohl, H -J


    The electron and nuclear spins of the shallow donor 31P are promising qubit candidates invoked in many proposed Si-based quantum computing schemes. We have recently shown that the near-elimination of inhomogeneous broadening in highly isotopically enriched 28Si enables an optical readout of both the donor electron and nuclear spins by resolving the donor hyperfine splitting in the near-gap donor bound exciton transitions. We have also shown that pumping these same transitions can very quickly produce large electron and nuclear hyperpolarizations at low magnetic fields, where the equilibrium electron and nuclear polarizations are near zero. Here we show preliminary results of the measurement of 31P neutral donor NMR parameters using this optical nuclear hyperpolarization mechanism for preparation of the 31P nuclear spin system, followed by optical readout of the resulting nuclear spin population after manipulation with NMR pulse sequences. This allows for the observation of single-shot NMR signals with very hi...

  6. Maintenance of high-energy brain phosphorous compounds during insulin-induced hypoglycemia in men. 31P nuclear magnetic resonance spectroscopy study

    DEFF Research Database (Denmark)

    Hilsted, Jannik; Jensen, K E; Thomsen, C;


    31P nuclear magnetic resonance (NMR) spectroscopy allows noninvasive studies of cerebral energy-rich phosphorous compounds in humans. In an attempt to characterize the relationship between peripheral blood glucose concentrations and whole-brain phosphate metabolism during insulin...

  7. Solid-state structures of (R sub 3 P) sub 2 PtX sub 2 complexes as determined by a combination of sup 13 C( sup 1 H) and sup 31 P( sup 1 H) NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Rahn, J.A.; Nelson, J.H. (Univ. of Nevada, Reno (USA)); Baltusis, L. (Varian Instrument Div., Palo Alto, CA (USA))


    Cross-polarization, combined with magic-angle spinning, has been employed to obtain high-resolution solid-state {sup 13}C and {sup 31}P NMR spectra of a series of 31 (R{sub 3}P){sub 2}PtX{sub 2} complexes. These data together with spectra obtained in solution were used to compare the solid-state structures with those in solution. It was found that most of these complexes, which have regular square-planar structures in solution, are distorted in the solid state. The extent of the solid-state distortion is a function of the bulk of the coordinated ligands and increases as the ligand size increases. The solid-state distortions appear to result from intramolecular steric effects for cis-(R{sub 3}P){sub 2}PtX{sub 2} and probably from intermolecular crystal packing forces for trans-(R{sub 3}P){sub 2}PtX{sub 2}. 37 refs., 6 figs., 3 tabs.

  8. CD and 31P NMR studies of tachykinin and MSH neuropeptides in SDS and DPC micelles (United States)

    Schneider, Sydney C.; Brown, Taylor C.; Gonzalez, Javier D.; Levonyak, Nicholas S.; Rush, Lydia A.; Cremeens, Matthew E.


    Secondary structural characteristics of substance P (SP), neurokinin A (NKA), neurokinin B (NKB), α-melanocyte stimulating hormone peptide (α-MSH), γ1-MSH, γ2-MSH, and melittin were evaluated with circular dichroism in phosphite buffer, DPC micelles, and SDS micelles. CD spectral properties of γ1-MSH and γ2-MSH as well as 31P NMR of DPC micelles with all the peptides are reported for the first time. Although, a trend in the neuropeptide/micelle CD data appears to show increased α-helix content for the tachykinin peptides (SP, NKA, NKB) and increased β-sheet content for the MSH peptides (α-MSH, γ1-MSH, γ2-MSH) with increasing peptide charge, the lack of perturbed 31P NMR signals for all neuropeptides could suggest that the reported antimicrobial activity of SP and α-MSH might not be related to a membrane disruption mode of action.

  9. 31p NMR and ESI-MS Studies on Some Intermediates of the Peptide Coupling Reagents Triphenyl-chlorophosphoranes

    Institute of Scientific and Technical Information of China (English)

    Guo TANG; Gui Ji ZHOU; Feng NI; Li Ming HU; Yu Fen ZHAO


    The intermediates of the Appel coupling reagents were studied in acetonitrile,dimethoxyethane and dioxane by 31P NMR, C NMR spectrum and ESI-MS. In dioxane a new high coordinated phosphorous compound with 31p NMR shift at -39 ppm was observed. The ESI-MS showed that it could be a penta-coordinated phosphorous compound containing dioxane. The carboxyl activated intermediates were also studied in three solvents.

  10. Comparing localized and nonlocalized dynamic (31) P magnetic resonance spectroscopy in exercising muscle at 7T

    NARCIS (Netherlands)

    Meyerspeer, M.; Robinson, S.; Nabuurs, C.I.H.C.; Scheenen, T.W.; Schoisengeier, A.; Unger, E.; Kemp, G.J.; Moser, E.


    By improving spatial and anatomical specificity, localized spectroscopy can enhance the power and accuracy of the quantitative analysis of cellular metabolism and bioenergetics. Localized and nonlocalized dynamic (31) P magnetic resonance spectroscopy using a surface coil was compared during aerobic

  11. Exploring new Routes for Identifying Phosphorus Species in Terrestrial and Aquatic Ecosystems with 31P NMR (United States)

    Vestergren, Johan; Persson, Per; Sundman, Annelie; Ilstedt, Ulrik; Giesler, Reiner; Schleucher, Jürgen; Gröbner, Gerhard


    Phosphorus (P) is the primary growth-limiting nutrient in some of the world's biomes. Rock phosphate is a non-renewable resource and the major source of agricultural fertilizers. Predictions of P consumption indicate that rock phosphate mining may peak within 35 years, with severe impacts on worldwide food production1. Organic P compounds constitute a major fraction of soil P, but little is known about the dynamics and bioavailability of organic P species. Our aim is to develop new liquid and solid state 31P-NMR (nuclear magnetic resonance) techniques to identify P-species in water and soils; information required for correlating P speciation with plant and soil processes2, and eventually to improve P use. Soil organic P is frequently extracted using NaOH/EDTA, followed by characterization of the extract by solution 31P-NMR. However, the obtained NMR spectra usually have poor resolution due to line broadening caused by the presence of paramagnetic ions. Therefore, we successfully developed an approach to avoid paramagnetic line broadening by precipitation of metal sulfides. Sulfide precipitation dramatically reduces NMR line widths for soil extracts, without affecting P-composition. The resulting highly improved resolution allowed us to apply for the first time 2D 1H,31P-NMR methods to identify different P monoesters in spectral regions which are extremely crowded in 1D NMR spectra.3 By exploiting 2D 1H-31P NMR spectra of soil extracts we were able to unambiguously identify individual organic P species by combining 31P and 1H chemical shifts and coupling constants. This approach is even suitable for a structural characterization of unknown P-components and for tracing degradation pathways between diesters and monoesters3,4.Currently we apply our approach on boreal4 and tropical soils with focus on Burkina Faso. In addition we also monitor P-species in aqueos ecosystems. For this purpose stream water from the Krycklan catchment in northern Sweden5 has been used to

  12. Phosphorus speciation by {sup 31}P NMR spectroscopy in bracken (Pteridium aquilinum (L.) Kuhn) and bluebell (Hyacinthoides non-scripta (L.) Chouard ex Rothm.) dominated semi-natural upland soil

    Energy Technology Data Exchange (ETDEWEB)

    Ebuele, Victor O.; Santoro, Anna; Thoss, Vera, E-mail:


    Access to P species is a driver for plant community composition based on nutrient acquisition. Here we investigated the distribution and accumulation of soil inorganic P (Pi) and organic P (Po) forms in a bracken and bluebell dominated upland soil for the period between bluebell above ground dominance until biomass is formed from half bluebells and half bracken. Chemical characterisation and {sup 31}P Nuclear Magnetic Resonance spectroscopy was used to determine the organic and inorganic P species. Total P concentration in soils was 0.87 g kg{sup −1}, while in plants (above- and below-ground parts) total P ranged between 0.84–4.0 g kg{sup −1} and 0.14–2.0 g kg{sup −1} for bluebell and bracken, respectively. The P speciation in the plant samples was reflected in the surrounding soil. The main forms of inorganic P detected in the NaOH-EDTA soil extracts were orthophosphate (20.0–31.5%), pyrophosphate (0.6–2.5%) and polyphosphate (0.4–7.0%). Phytate (myo-IP{sub 6}) was the most dominant organic P form (23.6–40.0%). Other major peaks were scyllo-IP{sub 6} and α- and β- glycerophosphate (glyP). In bluebells and bracken the main P form detected was orthophosphate ranging from (21.7–80.4%) and 68.5–81.1%, in above-ground and below-ground biomass, respectively. Other detected forms include α-glyP (4.5–14.4%) and β-glyP (0.9–7.7%) in bluebell, while in bracken they were detected only in stripe and blade in ranges of 2.5–5.5% and 4.4–9.6%, respectively. Pyrophosphate, polyphosphate, scyllo-IP{sub 6}, phosphonates, found in soil samples, were not detected in any plant parts. In particular, the high abundance of phytate in the soil and in bluebell bulbs, may be related to a mechanism through which bluebells create a recalcitrant phosphorus store which form a key part of their adaptation to nutrient poor conditions. - Highlights: • Organic P forms were the dominant P species detected in the bracken (Pteridium aquilinum) and bluebell

  13. The host plant Pinus pinaster exerts specific effects on phosphate efflux and polyphosphate metabolism of the ectomycorrhizal fungus Hebeloma cylindrosporum: a radiotracer, cytological staining and (31) P NMR spectroscopy study. (United States)

    Torres-Aquino, Margarita; Becquer, Adeline; Le Guernevé, Christine; Louche, Julien; Amenc, Laurie K; Staunton, Siobhan; Quiquampoix, Hervé; Plassard, Claude


    Ectomycorrhizal (ECM) association can improve plant phosphorus (P) nutrition. Polyphosphates (polyP) synthesized in distant fungal cells after P uptake may contribute to P supply from the fungus to the host plant if they are hydrolyzed to phosphate in ECM roots then transferred to the host plant when required. In this study, we addressed this hypothesis for the ECM fungus Hebeloma cylindrosporum grown in vitro and incubated without plant or with host (Pinus pinaster) and non-host (Zea mays) plants, using an experimental system simulating the symbiotic interface. We used (32) P labelling to quantify P accumulation and P efflux and in vivo and in vitro nuclear magnetic resonance (NMR) spectroscopy and cytological staining to follow the fate of fungal polyP. Phosphate supply triggered a massive P accumulation as newly synthesized long-chain polyP in H. cylindrosporum if previously grown under P-deficient conditions. P efflux from H. cylindrosporum towards the roots was stimulated by both host and non-host plants. However, the host plant enhanced (32) P release compared with the non-host plant and specifically increased the proportion of short-chain polyP in the interacting mycelia. These results support the existence of specific host plant effects on fungal P metabolism able to provide P in the apoplast of ectomycorrhizal roots.

  14. Using 31P-NMR to investigate dynamics of soil phosphorus compounds in the Rothamsted Long Term Experiments (United States)

    Blackwell, Martin; Turner, Ben; Granger, Steve; Hooper, Tony; Darch, Tegan; Hawkins, Jane; Yuan, Huimin; McGrath, Steve


    The technique of 31P-NMR spectroscopy has done more to advance the knowledge of phosphorus forms (especially organic phosphorus) in environmental samples than any other method. The technique has advanced such that specific compounds can be identified where previously only broad categories such as orthophosphate monoesters and diesters were distinguishable. The Soil Archive and Long Term Experiments at Rothamsted Research, UK, potentially provides an unequalled opportunity to use this technique to observe changes in soil phosphorus compounds with time and under different treatments, thereby enhancing our understanding of phosphorus cycling and use by plants. Some of the earliest work using this technique on soils was carried out by Hawkes et al. in 1984 and this used soils from two of the oldest Rothamsted Long Term Experiments, namely Highfield and Park Grass. Here we revisit the samples studied in this early work and reanalyse them using current methodology to demonstrate how the 31P-NMR technique has advanced. We also present results from a study on the phosphorus chemistry in soils along the Hoosfield acid strip (Rothamsted, UK), where a pH gradient from 3.7 to 7.8 occurs in a single soil with little variation in total phosphorus (mean ± standard deviation 399 ± 27 mg P kg-1). Soil pH was found to be an important factor in determining the proportion of phosphomonoesters and phosphodiesters in the soil organic phosphorus, although total organic phosphorus concentrations were a relatively consistent proportion of the total soil phosphorus (36 ± 2%) irrespective of soil pH. Key words. 31P-NMR, soil organic phosphorus, long term experiments, Hoosfield acid strip

  15. Lateral diffusion of bilayer lipids measured via (31)P CODEX NMR. (United States)

    Saleem, Qasim; Lai, Angel; Morales, Hannah H; Macdonald, Peter M


    We have employed (31)P CODEX (centre-band-only-detection-of-exchange) NMR to measure lateral diffusion coefficients of phospholipids in unilamellar lipid bilayer vesicles consisting of 1-palmitoyl-2-oleoyl-phosphatidylcholine (POPC), alone or in mixtures with 30 mol% 1-palmitoyl-2-oleoyl-phosphatidylglycerol (POPG) or cholesterol (CHOL). The lateral diffusion coefficients of POPC and POPG were extracted from experimental CODEX signal decays as a function of increasing mixing time, after accounting for the vesicle's size and size distribution, as determined via dynamic light scattering, and the viscosity of the vesicular suspension, as determined via (1)H pulsed field gradient NMR. Lateral diffusion coefficients for POPC and POPG determined in this fashion fell in the range 1.0-3.2 × 10(-12) m(2) s(-1) at 10 °C, depending on the vesicular composition, in good agreement with accepted values. Thus, two advantages of (31)P CODEX NMR for phospholipid lateral diffusion measurements are demonstrated: no labelling of the molecule of interest is necessary, and multiple lateral diffusion coefficients can be measured simultaneously. It is expected that this approach will prove particularly useful in diagnosing heterogeneities in lateral diffusion behaviours, such as might be expected for specific lipid-lipid or lipid-protein interactions, and thermotropic or electrostatically induced phase inhomogeneities.

  16. Metabolism of perfused pig intercostal muscles evaluated by 31P-magnetic resonance spectroscopy

    DEFF Research Database (Denmark)

    Pedersen, Brian Lindegaard; Arendrup, Henrik; Secher, Niels H


    consumption and 31P-magnetic resonance spectroscopy (31P-MRS). When perfused at rest with Krebs-Ringer buffer, the preparation maintained physiological levels of phosphocreatine (PCr), inorganic phosphate (Pi), ATP and pH at a stable oxygen consumption of 0.51 +/- 0.01 micromol min(-1) g(-1) for more than 2 h...

  17. Membrane interactions in small fast-tumbling bicelles as studied by 31P NMR. (United States)

    Bodor, Andrea; Kövér, Katalin E; Mäler, Lena


    Small fast-tumbling bicelles are ideal for studies of membrane interactions at molecular level; they allow analysis of lipid properties using solution-state NMR. In the present study we used 31P NMR relaxation to obtain detailed information on lipid head-group dynamics. We explored the effect of two topologically different membrane-interacting peptides on bicelles containing either dimyristoylphosphocholine (DMPC), or a mixture of DMPC and dimyristoylphosphoglycerol (DMPG), and dihexanoylphosphocholine (DHPC). KALP21 is a model transmembrane peptide, designed to span a DMPC bilayer and dynorphin B is a membrane surface active neuropeptide. KALP21 causes significant increase in bicelle size, as evidenced by both dynamic light scattering and 31P T2 relaxation measurements. The effect of dynorphin B on bicelle size is more modest, although significant effects on T2 relaxation are observed at higher temperatures. A comparison of 31P T1 values for the lipids with and without the peptides showed that dynorphin B has a greater effect on lipid head-group dynamics than KALP21, especially at elevated temperatures. From the field-dependence of T1 relaxation data, a correlation time describing the overall lipid motion was derived. Results indicate that the positively charged dynorphin B decreases the mobility of the lipid molecules--in particular for the negatively charged DMPG--while KALP21 has a more modest influence. Our results demonstrate that while a transmembrane peptide has severe effects on overall bilayer properties, the surface bound peptide has a more dramatic effect in reducing lipid head-group mobility. These observations may be of general importance for understanding peptide-membrane interactions.

  18. A chelate-stabilized ruthenium(sigma-pyrrolato) complex: resolving ambiguities in nuclearity and coordination geometry through 1H PGSE and 31P solid-state NMR studies. (United States)

    Foucault, Heather M; Bryce, David L; Fogg, Deryn E


    Reaction of RuCl2(PPh3)3 with LiNN' (NN' = 2-[(2,6-diisopropylphenyl)imino]pyrrolide) affords a single product, with the empirical formula RuCl[(2,6-iPr2C6H3)N=CHC4H3N](PPh3)2. We identify this species as a sigma-pyrrolato complex, [Ru(NN')(PPh3)2]2(mu-Cl)2 (3b), rather than mononuclear RuCl(NN')(PPh3)2 (3a), on the basis of detailed 1D and 2D NMR characterization in solution and in the solid state. Retention of the chelating, sigma-bound iminopyrrolato unit within 3b, despite the presence of labile (dative) chloride and PPh3 donors, indicates that the chelate effect is sufficient to inhibit sigma --> pi isomerization of 3b to a piano-stool, pi-pyrrolato structure. 2D COSY, SECSY, and J-resolved solid-state 31P NMR experiments confirm that the PPh3 ligands on each metal center are magnetically and crystallographically inequivalent, and 31P CP/MAS NMR experiments reveal the largest 99Ru-31P spin-spin coupling constant (1J(99Ru,31P) = 244 +/- 20 Hz) yet measured. Finally, 31P dipolar-chemical shift spectroscopy is applied to determine benchmark phosphorus chemical shift tensors for phosphine ligands in hexacoordinate ruthenium complexes.

  19. 31P NMR Studies on the Ligand Dissociation of Trinuclear Molybde-num Cluster Compounds

    Institute of Scientific and Technical Information of China (English)

    李兆基; 覃业燕; 姚元根; 唐艳红; 康遥; 夏继波; 陈忠; 吴棱


    A series of carboxylate-substituted trinudear molybdenum dus-ter compounds formulated as Mo3S4(DTP)3(RCO2)(L), where RffiH, CH3, C2H5, CH2Cl, CCl3, R1C6H4(R1 is the group on the benzene ring of aromatic carboxylate ), L=pyridine,CH3CN, DMF, have been synthesized by the ligand substitu-tion reaction. The dissociation of the loosely-coordinated ligand L from the cluster core was studied by 31p NMR. The dissocia-tion process of L is related to the solvent, temperature, and acidity of carboxylate groups, so as to affect the solution struc-ture and reactive properties of the duster. The long-distance in-teraction between ligands RCO2 and L is transported by Mo3S4 core.

  20. (31)P NMR of apicomplexans and the effects of risedronate on Cryptosporidium parvum growth. (United States)

    Moreno, B; Bailey, B N; Luo, S; Martin, M B; Kuhlenschmidt, M; Moreno, S N; Docampo, R; Oldfield, E


    High-resolution 303.6 MHz (31)P NMR spectra have been obtained of perchloric acid extracts of Plasmodium berghei trophozoites, Toxoplasma gondii tachyzoites, and Cryptosporidium parvum oocysts. Essentially complete resonance assignments have been made based on chemical shifts and by coaddition of authentic reference compounds. Signals corresponding to inorganic pyrophosphate were detected in all three species. In T. gondii and C. parvum, additional resonances were observed corresponding to linear triphosphate as well as longer chain polyphosphates. Spectra of P. berghei and T. gondii also indicated the presence of phosphomonoesters and nucleotide phosphates. We also report that the pyrophosphate analog drug, risedronate (used in bone resorption therapy), inhibits the growth of C. parvum in a mouse xenograft model. When taken together, our results indicate that all the major disease-causing apicomplexan parasites contain extensive stores of condensed phosphates and that as with Plasmodium falciparum and T. gondii, the pyrophosphate analog drug risedronate is an inhibitor of C. parvum cell growth.

  1. Effects of adrenaline on glycogenolysis in resting anaerobic frog muscles studied by 31P-NMR. (United States)

    Kikuchi, Kimio; Yamada, Takenori; Sugi, Haruo


    The effects of adrenaline (also called epinephrine) on glycogenolysis in living anaerobic muscles were examined based on time-dependent changes of (31)P-NMR spectra of resting frog skeletal muscles with and without iodoacetate treatments. The phosphate-metabolite concentration and the intracellular pH determined from the NMR spectra changed with time, reflecting the advancement of various phosphate metabolic reactions coupled with residual ATPase reactions to keep the ATP concentration constant. The results could be explained semi-qualitatively as the ATP regenerative reactions, creatine kinase reaction and glycogenolysis, advanced with time showing the characteristic two phases. Thus, it was clarified for living muscles that adrenaline activates the phosphorylase step of glycogenolysis, and the adrenaline-activated glycogenolysis is further regulated at the phosphofructokinase step by PCr and also possibly by AMP. Associated with the adrenaline-activated glycogenolysis in the examined muscles, the P(i) concentration and the intracellular pH, factors affecting the muscle force, changed significantly, suggesting complicated effects of adrenaline on the muscle contractility.

  2. Study of hereditary fructose intolerance by use of 31P magnetic resonance spectroscopy. (United States)

    Oberhaensli, R D; Rajagopalan, B; Taylor, D J; Radda, G K; Collins, J E; Leonard, J V; Schwarz, H; Herschkowitz, N


    The effect of fructose on liver metabolism in patients with hereditary fructose intolerance (HFI) and in heterozygotes for HFI was studied by 31P magnetic resonance spectroscopy (31P-MRS). In patients with HFI (n = 5) ingestion of small amounts of fructose was followed by an increase in sugar phosphates and decrease in inorganic phosphate (Pi) in the liver that could be detected by 31P-MRS. 31P-MRS could be used to diagnose fructose intolerance and to monitor the patients' compliance with a fructose-restricted diet. In heterozygotes (n = 8) 50 g fructose given orally led to accumulation of sugar phosphates and depletion of Pi in the liver. Fructose also induced a larger increase in plasma urate in heterozygotes than in control subjects. The effect of fructose on liver Pi and plasma urate was most pronounced in heterozygotes with gout (n = 3). Heterozygosity for HFI may predispose to hyperuricaemia.

  3. Improved energy kinetics following high protein diet in McArdle's syndrome. A 31P magnetic resonance spectroscopy study

    DEFF Research Database (Denmark)

    Jensen, K E; Jakobsen, J; Thomsen, C;


    A patient with McArdle's syndrome was examined using bicycle ergometry and 31P NMR spectroscopy during exercise. The patients working capacity was approximately half the expected capacity of controls. Muscle energy kinetics improved significantly during intravenous glucose infusion and after 6...... weeks of high protein diet. During intravenous infusion of amino acids, no changes in working capacity could be detected. No decrease was seen in intracellular muscle pH during aerobic exercise. A significant decrease in muscle pH during aerobic exercise was detected in all controls....

  4. Lipid Dynamics Studied by Calculation of 31P Solid-State NMR Spectra Using Ensembles from Molecular Dynamics Simulations

    DEFF Research Database (Denmark)

    Hansen, Sara Krogh; Vestergaard, Mikkel; Thøgersen, Lea;


    We present a method to calculate 31P solid-state NMR spectra based on the dynamic input from extended molecular dynamics (MD) simulations. The dynamic information confered by MD simulations is much more comprehensive than the information provided by traditional NMR dynamics models based on......, for example, order parameters. Therefore, valuable insight into the dynamics of biomolecules may be achieved by the present method. We have applied this method to study the dynamics of lipid bilayers containing the antimicrobial peptide alamethicin, and we show that the calculated 31P spectra obtained...

  5. In vivo 31P NMR OSIRIS of bioenergetic changes in rabbit kidneys during and after ischaemia: effect of pretreatment with an indeno-indole compound. (United States)

    Sørensen, V; Jonsson, O; Pettersson, S; Scherstén, T; Soussi, B


    Changes in energy phosphates of rabbit kidneys subjected to ischaemia-reperfusion have been measured in vivo with volume selective 31P NMR spectroscopy. The effects of pretreatment with a new lipid peroxidation inhibitor (indeno-indol derivate--code name H290/51) on the bioenergetic changes were analysed. The left kidney was moved to a subcutaneous pocket to facilitate exact positioning over the surface coil. A 1H NMR image was acquired and a 3.5-mL cube selected for 31P NMR spectra. 31P NMR spectra were recorded before occlusion of the left renal artery, during 1 h of ischaemia and 2 hours of reperfusion. Ischaemia induced drastic changes in the levels of inorganic phosphates and ATP as well as intracellular acidosis. A normalization was observed during reperfusion. Two hours after reperfusion significantly higher values for beta-ATP/Pi and intracellular pH were recorded in the animals pretreated with H290/51. The present technique allows quantitative analyses of changes in kidney bioenergetics in vivo during different experimental conditions. The importance of ischaemia-reperfusion induced lipid peroxidation for mitochondrial function is emphasized.

  6. (31)P NMR study of post mortem changes in pig muscle. (United States)

    Miri, A; Talmant, A; Renou, J P; Monin, G


    The rate and the extent of post mortem pH changes in pig muscle largely determine pork quality. Fast pH fall combined with low ultimate pH leads to pale soft exudative (PSE) meat; high ultimate pH leads to dark firm dry (DFD) meat. Post mortem metabolism was studied in pig muscle using(31)P NMR. Fifteen pigs, i.e. 7 Large White pigs and 8 Pietrain pigs, were used. Five pigs of each breed were slaughtered, taking care to minimize preslaughter stress. The other pigs (3 Large Whites and 2 Pietrains) were injected with 0·1 mg adrenaline per kg liveweight before slaughter, in order to increase meat ultimate pH. All the animals were killed by electronarcosis and exsanguination. Three of the adrenaline-treated pigs (1 Large White and 2 Pietrains) gave meat with ultimate pH above 6 (DFD meat). The pigs with normal muscle ultimate pH, i.e. 6 Large Whites and 6 Pietrains, had very variable rates of post mortem muscle metabolism (pH at 30 min after slaughter: 6·17-6·85 in Large Whites; 6·04-6·23 in Pietrains). The relationships between pH and ATP changes were similar in all pigs showing normal muscle ultimate pH, whereas ATP disappeared at a high pH value (on average pH 6·4) in pigs with high ultimate pH. The course of post mortem biochemical changes in a given animal could be predicted rather well by examination of a single(31)P NMR spectrum obtained around 30 min after death. At this time, muscle with a low rate of metabolism simultaneously showed medium to high pH, high ATP content (4-6·8 μmol/g) and rather low Pi content (6-14 μmol/g); muscle with a fast rate of metabolism (PSE-prone muscle) had low pH, low to medium ATP content (1·1-4 μmol/g) and generally high phosphomonoester (PME) content (9-23 μmol/g); muscle with high ultimate pH (DFD-prone muscle) had high pH, low PME content (4-8 μmol/g) and high Pi content (22-27 μmol/g).

  7. Simultaneous electromyography and 31P nuclear magnetic resonance spectroscopy--with application to muscle fatigue

    DEFF Research Database (Denmark)

    Vestergaard-Poulsen, P; Thomsen, C; Sinkjaer, T;


    changes in human muscle. The aim of this study was to develop a method by which EMG and NMR spectroscopy measurements could be performed simultaneously. All measurements were performed in a whole body 1.5 Tesla NMR scanner. A calf muscle ergometer, designed for use in a whole body NMR scanner, was used...

  8. /sup 31/P-NMR studies of a case of type III glycogenosis

    Energy Technology Data Exchange (ETDEWEB)

    Kawai, Mitsuru; Aizawa, Hitoshi; Itoh, Masamitsu; Yoshikawa, Kohki; Murase, Toshio


    /sup 31/P-NMR spectra of skeletal muscles were obtained from a patient of type III glycogenosis (33 y.o. man, reported by one of the authors, T. Murase, in 1973) and the control subject (32 y.o. man), using a superconducting whole body MR (Magnetom, Siemens). Two parameters, 1. muscle pH calculated from the chemical shift of Pi (inorganic phosphate) and PCr (creatine phosphate) and 2. PCr/Pi ratio were monitored before and after the aerobic or ischemic exercise. In resting state, the spectra were normal except for the muscle pH of thigh extensors (7.3), which was obviously higher than that of the control subject (7.0). Significant reduction of PCr/Pi ratio (from 7.0 to 4.1) was observed after the aerobic exercise in thigh extensors. Such a reduction was not recognized in the control subject. The ischemic exercise of forearm muscles revealed slight decrease in muscle pH (from 7.1 to 6.9), which was less prominent than that of the control subject. These results were compatible with the abnormality in the energy metabolism of this disorder, the block in the pathway of glycogenolysis.

  9. /sup 31/P NMR characterization of graded traumatic brain injury in rats

    Energy Technology Data Exchange (ETDEWEB)

    Vink, R.; McIntosh, T.K.; Yamakami, I.; Faden, A.I.


    Irreversible tissue injury following central nervous system trauma is believed to result from both mechanical disruption at the time of primary insult, and more delayed autodestructive processes. These delayed events are associated with various biochemical changes, including alterations in phosphate energy metabolism and intracellular pH. Using /sup 31/P NMR, we have monitored the changes in phosphorus energy metabolism and intracellular pH in a single hemisphere of the rat brain over an 8-h period following graded, traumatic, fluid percussion-induced brain injury. Following trauma the ratio of phosphocreatine to inorganic phosphate (PCr/Pi) declined in each injury group. This decline was transitory with low injury (1.0 +/- 0.5 atm), biphasic with moderate (2.1 +/- 0.4 atm) and high (3.9 +/- 0.9 atm) injury, and sustained following severe injury (5.9 +/- 0.7 atm). The initial PCr/Pi decline in the moderate and high injury groups was associated with intracellular acidosis; however, the second decline occurred in the absence of any pH changes. Alterations in ATP occurred only in severely injured animals and such changes were associated with marked acidosis and 100% mortality rate. After 4h, the posttraumatic PCr/Pi ratio correlated linearly with the severity of injury. We suggest that a reduced posttraumatic PCr/Pi ratio may be indicative of altered mitochondrial energy production and may predict a reduced capacity of the cell to recover from traumatic injury.

  10. 31P NMR studies on the effect of phosphite on Phytophthora palmivora. (United States)

    Niere, J O; Griffith, J M; Grant, B R


    31P NMR spectra were obtained from perchloric acid (PCA) and KOH extracts of Phytophthora palmivora mycelium. Signals indicating the presence of large amounts of short-chain polyphosphate were observed in the spectra of PCA extracts of mycelia grown under both low (0.1 mM) and high (10 mM) phosphate conditions. The mean chain length of polyphosphate was calculated from the relative areas of signals arising from terminal and internal P nuclei in the polyphosphate chain. The small amount of polyphosphate evident in the KOH extract had an average chain length similar to PCA-soluble polyphosphate. 32P tracer studies indicated that phosphorus in the PCA fraction accounted for between 50 and 60% of total phosphorus, the bulk of the remainder being divided between the lipid and KOH extracts. The presence of the fungicide phosphorous acid markedly reduced the average chain length of acid-soluble polyphosphate. This reduction occurred both under low-phosphate conditions, in which treatment with phosphorous acid retards growth, and under high-phosphate conditions, in which no significant growth retardation is observed. Treatment with phosphorous acid perturbed phosphorus distribution and lipid composition under low-phosphate conditions.

  11. Towards the versatile DFT and MP2 computational schemes for 31P NMR chemical shifts taking into account relativistic corrections. (United States)

    Fedorov, Sergey V; Rusakov, Yury Yu; Krivdin, Leonid B


    The main factors affecting the accuracy and computational cost of the calculation of (31)P NMR chemical shifts in the representative series of organophosphorous compounds are examined at the density functional theory (DFT) and second-order Møller-Plesset perturbation theory (MP2) levels. At the DFT level, the best functionals for the calculation of (31)P NMR chemical shifts are those of Keal and Tozer, KT2 and KT3. Both at the DFT and MP2 levels, the most reliable basis sets are those of Jensen, pcS-2 or larger, and those of Pople, 6-311G(d,p) or larger. The reliable basis sets of Dunning's family are those of at least penta-zeta quality that precludes their practical consideration. An encouraging finding is that basically, the locally dense basis set approach resulting in a dramatic decrease in computational cost is justified in the calculation of (31)P NMR chemical shifts within the 1-2-ppm error. Relativistic corrections to (31)P NMR absolute shielding constants are of major importance reaching about 20-30 ppm (ca 7%) improving (not worsening!) the agreement of calculation with experiment. Further better agreement with the experiment by 1-2 ppm can be obtained by taking into account solvent effects within the integral equation formalism polarizable continuum model solvation scheme. We recommend the GIAO-DFT-KT2/pcS-3//pcS-2 scheme with relativistic corrections and solvent effects taken into account as the most versatile computational scheme for the calculation of (31)P NMR chemical shifts characterized by a mean absolute error of ca 9 ppm in the range of 550 ppm.

  12. Assessment of preparation methods for organic phosphorus analysis in phosphorus-polluted Fe/Al-rich Haihe river sediments using solution 31P-NMR.

    Directory of Open Access Journals (Sweden)

    Wenqiang Zhang

    Full Text Available Fe/Al-rich river sediments that were highly polluted with phosphorus (P were used in tests to determine the optimum preparation techniques for measuring organic P (Po using solution (31P nuclear magnetic resonance spectroscopy ((31P-NMR. The optimum pre-treatment, extraction time, sediment to solution ratio and sodium hydroxide-ethylenediaminetetraacetic acid (NaOH-EDTA extractant solution composition were determined. The total P and Po recovery rates were higher from freeze- and air-dried samples than from fresh samples. An extraction time of 16 h was adequate for extracting Po, and a shorter or longer extraction time led to lower recoveries of total P and Po, or led to the degradation of Po. An ideal P recovery rate and good-quality NMR spectra were obtained at a sediment:solution ratio of 1:10, showing that this ratio is ideal for extracting Po. An extractant solution of 0.25 M NaOH and 50 mM EDTA was found to be more appropriate than either NaOH on its own, or a more concentrated NaOH-EDTA mixture for (31P-NMR analysis, as this combination minimized interference from paramagnetic ions and was appropriate for the detected range of Po concentrations. The most appropriate preparation method for Po analysis, therefore, was to extract the freeze-dried and ground sediment sample with a 0.25 M NaOH and 50 mM EDTA solution at a sediment:solution ratio of 1:10, for 16 h, by shaking. As lyophilization of the NaOH-EDTA extracts proved to be an optimal pre-concentration method for Po analysis in the river sediment, the extract was lyophilized as soon as possible, and analyzed by (31P-NMR.

  13. Ab Initio Calculations of 31P NMR Chemical Shielding Anisotropy Tensors in Phosphates: Variations Due to Ring Formation

    Directory of Open Access Journals (Sweden)

    Todd M. Alam


    Full Text Available Abstract: Ring formation in phosphate systems is expected to influence both the magnitude and orientation of the phosphorus (31P nuclear magnetic resonance (NMR chemical shielding anisotropy (CSA tensor. Ab initio calculations of the 31P CSA tensor in both cyclic and acyclic phosphate clusters were performed as a function of the number of phosphate tetrahedral in the system. The calculation of the 31P CSA tensors employed the GAUSSIAN 98 implementation of the gauge-including atomic orbital (GIAO method at the Hartree-Fock (HF level. It is shown that both the 31P CSA tensor anisotropy, and the isotropic chemical shielding can be used for the identification of cyclic phosphates. The differences between the 31P CSA tensor in acyclic and cyclic phosphate systems become less pronounced with increasing number of phosphate groups within the ring. The orientation of the principal components for the 31P CSA tensor shows some variation due to cyclization, most notably with the smaller, highly strained ring systems.

  14. Gated /sup 31/P NMR study of tetanic contraction in rat muscle depleted of phosphocreatine

    Energy Technology Data Exchange (ETDEWEB)

    Shoubridge, E.A.; Radda, G.K.


    Rats were fed a diet containing 1% ..beta..-guanidino-propionic acid (GPA) for 6-12 wk to deplete their muscles of phosphocreatine (PCr). Gated /sup 31/P nuclear magnetic resonance (NMR) spectra were obtained from the gastrocnemius-plantaris muscle at various time points during either a 1- or 3-s isometric tetanic contraction using a surface coil. The energy cost of a 1-s tetanus in unfatigued control rat muscle was 48.4 ATP x g dry wt/sup -1/ x s/sup -1/ and was largely supplied by PCr; anaerobic glycogenolysis was negligible. In GPA-fed rats PCr was undetectable after 400 ms. This had no effect on initial force generated per gram, which was not significantly different from controls. Developed tension in a 3-s tetanus in GPA-fed rats could be divided into a peak phase (duration 0.8-0.9 s) and a plateau phase (65% peak tension) in which PCr was undetectable and the (ATP) was < 20% of that in control muscle. Energy from glycogenolysis was sufficient to maintain force generation at this submaximal level. Mean net glycogen utilization per 3-s tetanus was 78% greater than in control muscle. However, the observed decrease in intracellular pH was less than that expected from energy budget calculations, suggesting either increased buffering capacity or modulation of ATP hydrolysis in the muscles of GPA-fed rats. The results demonstrate that the transport role of PCr is not essential in contracting muscle in GPA-fed rats. PCr is probably important in this regard in the larger fibers of control muscle. Although fast-twitch muscles depleted of PCr have nearly twice the glycogen reserves of control muscle, glycogenolysis is limited in its capacity to fill the role of PCr as an energy buffer under conditions of maximum ATP turnover.

  15. 1H MAS and 1H --> 31P CP/MAS NMR study of human bone mineral. (United States)

    Kaflak-Hachulska, A; Samoson, A; Kolodziejski, W


    Chemical structure of human bone mineral was studied by solid-state nuclear magnetic resonance (NMR) with magic-angle spinning (MAS). Trabecular and cortical bone samples from adult subjects were compared with mineral standards: hydroxyapatite (HA), hydrated and calcined, carbonatoapatite of type B with 9 wt% of CO3(2-) (CHA-B), brushite (BRU) and mixtures of HA with BRU. Proton spectra were acquired with excellent spectral resolution provided by ultra-high speed MAS at 40 kHz. 2D 1H-31P NMR heteronuclear correlation was achieved by cross-polarization (CP) under fast MAS at 12 kHz. 31P NMR was applied with CP from protons under slow MAS at 1 kHz. Appearance of 31P rotational sidebands together with their CP kinetics were analyzed. It was suggested that the sidebands of CP spectra are particularly suitable for monitoring the state of apatite crystal surfaces. The bone samples appeared to be deficient in structural hydroxyl groups analogous to those in HA. We found no direct evidence that the HPO4(2-) brushite-like ions are present in bone mineral. The latter problem is extensively discussed in the literature. The study proves there is a similarity between CHA-B and bone mineral expressed by their similar NMR behavior.

  16. Feasibility of Rapid-Sequence {sup 31}P Magnetic Resonance Spectroscopy in Cardiac Patients

    Energy Technology Data Exchange (ETDEWEB)

    Chida, K.; Otani, H.; Saito, H.; Nagasaka, T.; Kagaya, Y.; Kohzuki, M.; Zuguchi, M.; Shirato, K. [Tohoku Univ., School of Health Sciences, Sendai (Japan). Dept. of Radiological Technology


    Purpose: To determine the clinical feasibility of rapid-sequence phosphorus-31 magnetic resonance spectroscopy ({sup 31}P -MRS) of the heart with cardiac patients using a 5T clinical MR system. Material and Methods: Twenty cardiac patients, i.e. dilated cardiomyopathy (DCM)3 cases, hypertrophic cardiomyopathy (HCM) 3 cases, hypertensive heart diseases (HHD) 3 cases, and aortic regurgitation (AR) case were examined using rapid cardiac {sup 31}P-MRS. Complete three-dimensional localization was performed using a two-dimensional phosphorus chemical-shift imaging sequence in combination with 30-mm axial slice-selective excitation. The rapid-sequence {sup 31}P-MRS procedure was phase encoded in arrays of 8x8 steps with an average of 4 acquisitions. The total examination time, including proton imaging and shimming, for the rapid cardiac {sup 31}P-MRS procedure, ranged from 0 to 5 min, depending on the heart rate. Student's t test was used to compare creatine phosphate (PCr)/adenosine triphosphate (ATP) ratios from the cardiac patients with those of the control subjects (n{approx_equal}13). Results: The myocardial PCr/ATP ratio obtained by rapid {sup 31}P-MRS was significantly lower (P <0.001) in DCM patients (1.82{+-}0.33, mean{+-}SD), and in patients with global myocardial dysfunction (combined data for 20 patients:.89{+-}0.32) than in normal volunteers (2.96{+-}0.59). These results are similar to previous studies. Conclusion: Rapid-sequence {sup 31}P-MRS may be a valid diagnostic tool for patients with cardiac disease.

  17. {sup 31}P-MR spectroscopy in children and adolescents with a familial risk of schizophrenia

    Energy Technology Data Exchange (ETDEWEB)

    Rzanny, R.; Reichenbach, J.R.; Pfleiderer, S.O.R.; Kaiser, W.A. [Institut fuer Diagnostische und Interventionelle Radiologie, Abteilung MT, Klinikum der Friedrich-Schiller-Universitaet Jena, Philosophenweg 3, 07741 Jena (Germany); Klemm, S.; Blanz, B. [Klinik fuer Kinder- und Jugendpsychiatrie, Klinikum der Friedrich-Schiller-Universitaet Jena, Bachstrasse 18, 07741 Jena (Germany); Schmidt, B.; Volz, H.-P. [Klinik fuer Psychiatrie, Klinikum der Friedrich-Schiller-Universitaet Jena, Bachstrasse 18, 07741 Jena (Germany)


    Based on a previous report [9] on alterations of membrane phosphorus metabolism in asymptomatic family members of schizophrenic patients, the aim of the present study was to extend and improve the evaluation and data processing of {sup 31}P spectroscopic data obtained from a larger study population by including an analysis of the broad spectral component (BC) of membrane phospholipids (PL). Eighteen children and siblings of patients with schizophrenia and a gender- and age-matched control group of 18 healthy subjects without familial schizophrenia were investigated with phosphorus magnetic resonance spectroscopy ({sup 31}P-MRS) by using image selected in vivo spectroscopy (ISIS) in the dorsolateral prefrontal regions (DLPFR) of the brain. Spectral analysis was performed by using both the full and truncated FID to estimate metabolic peak ratios of different {sup 31}P metabolites and the intensity and linewidth of the broad component. A significantly higher PDE level (p<0.01) and increased linewidth of the PDE components were observed for the high-risk group compared with the control group (p=0.02). No significant differences were observed for PME as well as for other {sup 31}P-metabolites. No differences were observed between the left and right hemispheres for different normalised {sup 31}P-metabolic levels. Decreased intensities (p=0.03) and smaller linewidths (p=0.01) were obtained for the broad component in the high-risk group. Impairments of membrane metabolism that are typical for schizophrenic patients are partially observed in adolescent asymptomatic family members of schizophrenics, including increased levels of low molecular PDE compounds indicating increased membrane degradation processes, no changes for PME, and decreased intensities and linewidths of the BC indicating changes in the composition and fluidity of membrane phospholipids. Despite limitations to completely suppress fast-relaxing components by dismissing initial FID data points, the

  18. In vivo magnetic resonance imaging and 31P spectroscopy of large human brain tumours at 1.5 tesla

    DEFF Research Database (Denmark)

    Thomsen, C; Jensen, K E; Achten, E;


    31P MR spectroscopy of human brain tumours is one feature of magnetic resonance imaging. Eight patients with large superficial brain tumours and eight healthy volunteers were examined with 31P spectroscopy using an 8 cm surface coil for volume selection. Seven frequencies were resolved in our spe...

  19. Muscle metabolism of professional athletes using {sup 31}P-spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Maeurer, J.; Soellner, O.; Ehrenstein, T.; Knollmann, F.; Vogl, T.J.; Felix, R. [Humboldt-Universitaet, Berlin (Germany). Strahlenklinik und Poliklinik; Konstanczak, P. [Medizinische Univ. Luebeck (Germany). Inst. fuer Radiologie; Wolff, R. [Humboldt-Universitaet Berlin (Germany). Dept. of Sports Medicine


    Purpose: The aim of the study was to examine muscle metabolism in athletes by {sup 31}P-spectroscopy (MRS) and to evaluate to what degree the respective resonance spectrum correlates with the kind of muscle exercise. Material and Methods: Twelve runners and 12 young ice skaters were studied by {sup 31}P-spectroscopy of the gastrocnemic medialis muscle and the vastus medialis muscle using a surface coil at 1.5 T. Results: Sprinters displayed a higher phosphocreatinine/inorganic phosphate (PCr/Pi) and PCr/{beta}-ATP ratios than marathon runners. The respective parameters for middle distance runners were in between. Ice skaters could prospectively be divided into sprint- and long-distance runners by our results which correlated with the athletes` training performance. Conclusion: {sup 31}P-spectroscopy can evaluate the distribution of muscle fiber types. Thus, the athlete`s potential for sprint- or long-distance running can be determined. Additional studies will have to demonstrate to what extent training may change muscle fiber distribution. (orig.)

  20. 31P NMR study of magnetic phase transitions of MnP single crystal under 2 GPa pressure (United States)

    Fan, GuoZhi; Zhao, Bo; Wu, Wei; Zheng, Ping; Luo, JianLin


    Superconductivity on the border of the long-range magnetic order has been discovered in MnP under high pressures. In order to investigate the nature of the magnetic properties adjacent to the superconducting state, we performed zero-field 31P NMR for MnP single crystal under ambient and hydrostatic pressure of 2 GPa, respectively. Radio frequency power level was used to determine whether NMR signal originates from a helical state or not. When 2 GPa pressure was applied, the signal from helical state exists even above 160 K, while that from the ferromagnetic phase was not observed. Our NMR results indicate that the magnetic phase which is adjacent to the superconducting state is in a helical magnetic structure.

  1. La{sub 3}Cu{sub 4}P{sub 4}O{sub 2} and La{sub 5}Cu{sub 4}P{sub 4}O{sub 4}Cl{sub 2}. Synthesis, structure and {sup 31}P solid state NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Bartsch, Timo; Eul, Matthias; Poettgen, Rainer [Muenster Univ. (Germany). Inst. fuer Anorganische und Analytische Chemie; Benndorf, Christopher; Eckert, Hellmut [Muenster Univ. (Germany). Inst. fuer Physikalische Chemie; Sao Paulo Univ., Sao Carlos, SP (Brazil). Inst. of Physics


    The phosphide oxides La{sub 3}Cu{sub 4}P{sub 4}O{sub 2} and La{sub 5}Cu{sub 4}P{sub 4}O{sub 4}Cl{sub 2} were synthesized from lanthanum, copper(I) oxide, red phosphorus, and lanthanum(III) chloride through a ceramic technique. Single crystals can be grown in a NaCl/KCl flux. Both structures were refined from single crystal X-ray diffractometer data: I4/mmm, a = 403.89(4), c = 2681.7(3) pm, wR2 = 0.0660, 269 F{sup 2} values, 19 variables for La{sub 3}Cu{sub 4}P{sub 4}O{sub 2} and a = 407.52(5), c = 4056.8(7) pm, wR2 = 0.0905, 426 F{sup 2} values, 27 variables for La{sub 5}Cu{sub 4}P{sub 4}O{sub 4}Cl{sub 2}. Refinement of the occupancy parameters revealed full occupancy for the oxygen sites in both compounds. The structures are composed of cationic (La{sub 2}O{sub 2}){sup 2+} layers and covalently bonded (Cu{sub 4}P{sub 4}){sup 5-} polyanionic layers with metallic characteristics, and an additional La{sup 3+} between two adjacent (Cu{sub 4}P{sub 4}){sup 5-} layers. The structure of La{sub 5}Cu{sub 4}P{sub 4}O{sub 4}Cl{sub 2} comprises two additional LaOCl slabs per unit cell. Temperature-dependent magnetic susceptibility studies revealed Pauli paramagnetism. The phosphide substructure of La{sub 3}Cu{sub 4}P{sub 4}O{sub 2} was studied by {sup 31}P solid state NMR spectroscopy. By using a suitable dipolar re-coupling approach the two distinct resonances belonging to the P{sub 2}{sup 4-} and the P{sup 3-} units could be identified.

  2. ({sup 1} H, {sup 13} C and {sup 31} P) NMR of phosphonic acid derivatives; Ressonancia magnetica nuclear ({sup 1} H, {sup 13} C, {sup 31} P) de derivados do acido fosfonico

    Energy Technology Data Exchange (ETDEWEB)

    Campos, Valdevino; Costa, Valentim E. Uberti [Rio Grande do Sul Univ., Porto Alegre, RS (Brazil). Inst. de Quimica


    In the last years the development of phosphates analogues in the medical and agricultural pesticides has being very expressive. {sup 1} H, {sup 13} C and mainly {sup 31} P NMR are used for stereochemical and conformational analysis, and reactivity studies on the compounds resulting from those chemical processes 2 refs., 4 figs., 1 tab.

  3. 新型有机磷阻燃剂的31P NMR分析%The Analysis of the 31P NMR of Novel Organic Phosphorus Flame Retardants

    Institute of Scientific and Technical Information of China (English)

    王小芳; 范润兰; 王利生


    利用31P核磁共振仪对7种新型有机磷阻燃剂(CEPPA、DPPA、ODOPB、TODP、PPDC、PPDCO和DCPP)进行了测定和分析,提供了这些阻燃剂的31P NMR化学位移数据,这些数据可用于鉴定阻燃剂结构,通过峰的数量及面积可测定阻燃剂的纯度和杂质含量.结果表明31P NMR分析是检验有机磷阻燃剂纯度的有效方法.

  4. Small angle X-ray scattering and 31P NMR studies on the phase behavior of phospholipid bilayered mixed micelles (United States)

    Bolze, Jörg; Fujisawa, Tetsuro; Nagao, Takashi; Norisada, Kazushi; Saitô, Hazime; Naito, Akira


    The phase behavior of lipid bilayered micelles (`bicelles') (dimyristoyl-phosphatidylcholine, DMPC/dihexanoyl-phosphatidyl-choline, DHPC 2.6/1) has been studied by small angle X-ray scattering and 31P NMR. Below 3% w/v the bilayers are arranged in tightly packed stacks. At intermediate concentrations single units are observed, whereas at 24% w/v and higher, weak stacking occurs again. The DMPC/DHPC ratio in the bicelles strongly increases at low concentration, which is correlated with an increase in the bicelle size and stacking. The increase of the order parameter in a magnetic field is related to the stack formation. Below 297 K there is no stacking at any concentration and no magnetic alignment.

  5. Preservation of bilayer structure in human erythrocytes and erythrocyte ghosts after phospholipase treatment. A 31P-NMR study. (United States)

    van Meer, G; de Kruijff, B; op den Kamp, J A; van Deenen, L L


    1. Fresh human erythrocytes were treated with lytic and non-lytic combinations of phospholipases A2, C and sphingomyelinase. The 31P-NMR spectra of ghosts derived from such erythrocytes show that, in all cases, the residual phospholipids and lysophospholipids remain organized in a bilayer configuration. 2. A bilayer configuration of the (lyso)phospholipids was also observed after treatment of erythrocyte ghosts with various phospholipases even in the case that 98% of the phospholipid was converted into lysophospholipid (72%) and ceramides (26%). 3. A slightly decreased order of the phosphate group of phospholipid molecules, seen as reduced effective chemical shift anisotropy in the 31P-NMR spectra, was found following the formation of diacyglycerols and ceramides in the membrane of intact erythrocytes. Treatment of ghosts always resulted in an extensive decrease in the order of the phosphate groups. 4. The results allow the following conclusions to made: a. Hydrolysis of phospholipids in intact red cells and ghosts does not result in the formation of non-bilayer configuration of residual phospholipids and lysophospholipids. b. Haemolysis, which is obtained by subsequent treatment of intact cells with sphingomyelinase and phospholipase A2, or with phospholipase C, cannot be ascribed to the formation of non-bilayer configuration of phosphate-containing lipids. c. Preservation of bilayer structure, even after hydrolysis of all phospholipid, shows that other membrane constitutents, e.g. cholesterol and/or membrane proteins play an important role in stabilizing the structure of the erythrocyte membrane. d. A major prerequisite for the application of phospholipases in lipid localization studies, the preservation of a bilayer configuration during phospholipid hydrolysis, is met for the erythrocyte membrane.

  6. Influence of the computerized {sup 31}P NMR spectra processing on the tissues pH determination precision; Wplyw obrobki cyfrowej widm {sup 31}P MRJ na dokladnosc pomiaru pH tkanek

    Energy Technology Data Exchange (ETDEWEB)

    Kupka, T. [Inst. Chemii, Univ. Slaski, Katowice (Poland)]|[Zaklad Ciala Stalego, Polska Akademia Nauk, Zabrze (Poland); Religa, Z.; Zembala, M.; Nozynski, J.; Wojtek, P. [Slaska Akademia Medyczna, Zabrze (Poland); Pasterna, G. [Inst. Fizyki, Univ. Slaski, Katowice (Poland); Makhyanov, N. [Nizhnekamskneftekhym, Nizhnekamsk, Tatarstan (Russian Federation)


    The {sup 31}P NMR spectra of different tissues have been measured. To improve the spectra resolution two method of Fourier transformation have been used and namely the CDRE (Convulsion Difference Resolution Enhancement) and LGM (Lorentz-to-Gaussian Multiplication). It was shown that these procedures allow one to improve the quality of measured spectra what results in better precision of the tissues pH determination. 5 refs, 2 figs.

  7. sup 13 C and sup 31 P NMR studies of myocardial metabolism

    Energy Technology Data Exchange (ETDEWEB)

    Laughlin, M.R.


    The fluxes through two enzyme systems have been measured in perfused or in in vivo heart using NMR: phosphocreatine kinase, and glycogen synthase and phosphorylase. The rates of synthesis and degradation of glycogen were monitored in vivo in fed, fasted, and diabetic rat heart during infusions of {sup 13}C-1-glucose and insulin using proton-decoupled {sup 13}C-NMR at 1.9 and 4.7 tesla. The enzyme activities of glycogen synthase and glycogen phosphorylase were also measured in this tissue which had been freeze clamped at the end of the experiment, for comparison with the synthetic rates. For normal fed, fasted, and diabetic animals, synthesis rates were 0.28, 0.16, and 0.15 {mu}mol/min.gww respectively. Glycogen synthase i activity was 0.23, 0.14, and 0.14 {mu}mol/min.gww in these hearts at the end of the experiment, when measured at appropriate substrate and activator concentrations, and follow activation time courses that are consistent with being the main rate determinant for net synthesis in all cases. Turnover of glycogen was studied by observing the preformed {sup 13}C-1-glycogen signal during infusion of {sup 12}C-glucose and insulin, and was found to be close to zero. Extracted phosphorylase a activity was approximately ten times that of synthase i under these circumstances. In order to fully interpret the turnover studies, glycogenolysis of preformed {sup 13}C-glycogen was observed after a bolus of glucagon. The glycogen had either been synthesized from {sup 13}C-1-glucose for a single hour, or during an hour of {sup 13}C-glucose and a subsequent hour of {sup 12}C-glucose infusion. The author observed that breakdown follows an exponential time course related to the phosphorylase a activation state and that the last synthesized glycogen breaks down at the rate of 2.5 {mu}mol/min.gww, five times faster than that synthesized an hour earlier.

  8. (31)P Solid-State NMR study of the chemical setting process of a dual-paste injectable brushite cements. (United States)

    Legrand, A P; Sfihi, H; Lequeux, N; Lemaître, J


    The composition and evolution of a brushite-type calcium phosphate cement was investigated by Solid-State NMR and X-ray during the setting process. The cement is obtained by mixing beta-tricalcium phosphate [Ca(3)(PO(4))(2), beta-TCP] and monocalcium phosphate monohydrate [Ca(H(2)PO(4))(2).H(2)O, MCPM] in presence of water, with formation of dicalcium phosphate dihydrate or brushite [CaHPO(2).2H(2)O, DCPD]. Analysis of the initial beta-TCP paste has shown the presence of beta-calcium pyrophosphate [Ca(2)P(2)O(7), beta-CPy] and that of the initial MCPM a mixture of MCPM and dicalcium phosphate [CaHPO(4), DCP]. Follow-up of the chemical composition by (31)P Solid-State NMR enables to show that the chemical setting process appeared to reach an end after 20 min. The constant composition observed at the end of the process was similarly determined.

  9. Exercise-induced 31P-NMR metabolic response of human wrist flexor muscles during partial neuromuscular blockade. (United States)

    Mizuno, M; Horn, A; Secher, N H; Quistorff, B


    The effects of a depolarizing (decamethonium, DECA) and a nondepolarizing neuromuscular blocking agent (vecuronium, VECU) on the phosphorus-31 nuclear magnetic resonance (31P-NMR)-detected metabolic response to muscle contractions were studied separately in six healthy untrained males. Subjects who showed splitting of the P(i) peak during graded rhythmic forearm exercise without the drugs were selected. It was found that both drugs abolished the P(i) peak splitting during exercise. Despite a similar reduction in phosphocreatine (PCr) during exercise with each drug, a smaller increase in P(i) was observed with DECA than with VECU (P VECU (6.79 +/- 0.11) (P VECU, respectively (P < 0.05). On the basis of the concept that depolarizing and nondepolarizing agents have a preferential effect on fast- and slow-twitch muscle fibers, respectively, the present results support the hypothesis that the NMR-observed splitting of the P(i) peak reflects the metabolic differences between the two major fiber types of human skeletal muscle.

  10. Annual reports on NMR spectroscopy

    CERN Document Server

    Webb, Graham A; McCarthy, M J


    Over recent years, no other technique has grown to such importance as that of NMR spectroscopy. It is used in all branches of science where precise structural determination is required and where the nature of interactions and reactions in solution is being studied. Annual Reports on NMR Spectroscopy has established itself as a means for the specialist and non-specialist alike to become familiar with new applications of the technique in all branches of chemistry, including biochemistry, and pharmaceutics. This volume focuses on theoretical aspects of NMR nuclear shielding and on applications of

  11. Fundamentals of Protein NMR Spectroscopy

    CERN Document Server

    Rule, Gordon S


    NMR spectroscopy has proven to be a powerful technique to study the structure and dynamics of biological macromolecules. Fundamentals of Protein NMR Spectroscopy is a comprehensive textbook that guides the reader from a basic understanding of the phenomenological properties of magnetic resonance to the application and interpretation of modern multi-dimensional NMR experiments on 15N/13C-labeled proteins. Beginning with elementary quantum mechanics, a set of practical rules is presented and used to describe many commonly employed multi-dimensional, multi-nuclear NMR pulse sequences. A modular analysis of NMR pulse sequence building blocks also provides a basis for understanding and developing novel pulse programs. This text not only covers topics from chemical shift assignment to protein structure refinement, as well as the analysis of protein dynamics and chemical kinetics, but also provides a practical guide to many aspects of modern spectrometer hardware, sample preparation, experimental set-up, and data pr...

  12. Quantitative analysis of energy metabolism in human muscle using SLOOP {sup 31}P-MR-spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Beer, M.; Koestler, H.; Buchner, S.; Sandstede, J.; Hahn, D. [Wuerzburg Univ. (Germany). Inst. fuer Roentgendiagnostik; Schneider, C.; Toyka, K.V. [Neurologische Klinik und Poliklinik der Univ. Wuerzburg (Germany)


    Objective: Energy metabolism is vital for regular muscle function. In humans, in vivo analysis using {sup 31}P-MR-spectroscopy (MRS) is mostly restricted to semiquantitative parameters due to technical demands. We applied spatial localization with optimal pointspread function (SLOOP) for quantification in human skeletal and cardiac muscle. Subjects/Methods: 10 healthy volunteers and 4 patients with myotonic dystrophy type 1 were examined using a 1.5 T system (Magnetom VISION) and chemical shift imaging (CSI) for data collection. Concentrations of PCr, ATP and P{sub i} as well as PCr/ATP ratios were calculated by SLOOP. Results: Concentrations of PCr, ATP and P{sub i} were 29.9{+-}3.4, 7.1{+-}0.9 and 5.7{+-}1.2 [mmol/kg] in normal skeletal muscle, corresponding to previously published studies. Two of the patients with a duration of disease longer than 10 years and a pronounced muscle weakness showed a significant decrease of PCr and ATP in skeletal muscle below 10 and 5 mmol/kg. One of these patients had an additional reduction of PCr in cardiac muscle. (orig.) [German] Ziel: Voraussetzung fuer eine regulaere Muskelfunktion ist ein intakter Energiestoffwechsel. Beim Menschen beschraenkten sich bisherige Untersuchungen mittels der {sup 31}P-MR-Spektroskopie (MRS), welche eine In-Vivo-Analyse erlaubt, jedoch zumeist auf die Analyse semiquantitativer Parameter. Wir verwendeten Spatial Localization with Optimal Pointspread Function (SLOOP), um den Stoffwechsel des Skelettmuskels wie des Herzens zu quantifizieren. Patienten/Methoden: 10 Probanden und 4 Patienten mit myotoner Dystrophie Typ 1 wurden an einem 1.5-T-System (Magnetom VISION) mittels der chemical shift imaging (CSI)-Technik untersucht. Die Berechnung der Konzentrationen von PCr, ATP und P{sub 1} sowie des PCr/ATP Verhaeltnisses erfolgte mittels SLOOP. Ergebnisse: Im Skelettmuskel gesunder Probanden betrugen die Absolutkonzentrationen fuer PCr, ATP und P{sub i} 29,9{+-}3.4, 7,1{+-}0,9 und 5,7{+-}1,2 [mmol

  13. Semi-LASER localized dynamic 31P magnetic resonance spectroscopy in exercising muscle at ultra-high magnetic field.

    NARCIS (Netherlands)

    Meyerspeer, M.; Scheenen, T.W.J.; Schmid, A.I.; Mandl, T.; Unger, E.; Moser, E.


    Magnetic resonance spectroscopy (MRS) can benefit from increased signal-to-noise ratio (SNR) of high magnetic fields. In this work, the SNR gain of dynamic 31P MRS at 7 T was invested in temporal and spatial resolution. Using conventional slice selective excitation combined with localization by adia

  14. Phytate Hydrolysis in Rat Gastrointestinal Tracts, as Observed by 31P Fourier Transform Nuclear Magnetic Resonance Spectroscopy


    Wise, Alan; Richards, Colin P.; Trimble, Mary L.


    Phytate hydrolysis was followed through rat gastrointestinal tracts by 31P nuclear magnetic resonance spectroscopy. No phytate hydrolysis products were detected in the diet, stomach, or small intestine. It was concluded that cecal bacteria were responsible for phytate hydrolysis, which continued in the colon and fecal pellet.


    NARCIS (Netherlands)



    31P Magnetic Resonance-Spectroscopy was performed at the site of tender points in the trapezius muscle of patients with primary fibromyalgia syndrome. Earlier, in vitro studies have reported changes in the high energy phosphate-metabolism in biopsies taken from tender points of fibromyalgia patients

  16. Spectroscopic quantification of soil phosphorus forms by 31p-nmr after nine years of organic or mineral fertilization

    Directory of Open Access Journals (Sweden)

    Luciano Colpo Gatiboni


    Full Text Available Long-standing applications of mineral fertilizers or types of organic wastes such as manure can cause phosphorus (P accumulation and changes in the accumulated P forms in the soil. The objective of this research was to evaluate the forms of P accumulated in soils treated with mineral fertilizer or different types of manure in a long-term experiment. Soil was sampled from the 0-5 cm layer of plots fertilized with five different nutrient sources for nine years: 1 control without fertilizer; 2 mineral fertilizer at recommended rates for local conditions; 3 5 t ha-1 year-1 of moist poultry litter; 4 60 m³ ha-1 year-1 of liquid cattle manure and 5 40 m³ ha-1 year-1 of liquid swine manure. The 31P-NMR spectra of soil extracts detected the following P compounds: orthophosphate, pyrophosphate, inositol phosphate, glycerophosphate, and DNA. The use of organic or mineral fertilizer over nine years did not change the soil P forms but influenced their concentration. Fertilization with mineral or organic fertilizers stimulated P accumulation in inorganic forms. Highest inositol phosphate levels were observed after fertilization with any kind of manure and highest organic P concentration in glycerophosphate form in after mineral or no fertilization.

  17. Spectroscopic quantification of soil phosphorus forms by {sup 31}P-NMR after nine years of organic or mineral fertilization

    Energy Technology Data Exchange (ETDEWEB)

    Gatiboni, Luciano Colpo, E-mail: [Universidade Estadual de Santa Catarina (UDESC), Lages, SC (Brazil); Brunetto, Gustavo; Rheinheimer, Danilo dos Santos; Kaminski, Joao; Flores, Alex Fabiani Claro; Lima, Maria Angelica Silveira; Girotto, Eduardo; Copetti, Andre Carlos Cruz, E-mail:, E-mail:, E-mail:, E-mail:, E-mail:, E-mail: [Universidade Federal de Santa Maria (UFSM), RS (Brazil); Pandolfo, Carla Maria; Veiga, Milton, E-mail:, E-mail: [Empresa de Pesquisa Agropecuaria e Extensao Rural de Santa Catarina (EPAGRI), Campos Novos, SC (Brazil)


    Long-standing applications of mineral fertilizers or types of organic wastes such as manure can cause phosphorus (P) accumulation and changes in the accumulated P forms in the soil. The objective of this research was to evaluate the forms of P accumulated in soils treated with mineral fertilizer or different types of manure in a long-term experiment. Soil was sampled from the 0-5 cm layer of plots fertilized with five different nutrient sources for nine years: 1) control without fertilizer; 2) mineral fertilizer at recommended rates for local conditions; 3) 5 t ha{sup -1} year{sup -1} of moist poultry litter; 4) 60 m{sup 3} ha{sup -1} year{sup -1} of liquid cattle manure and 5) 40 m{sup 3} ha{sup -1} year{sup -1} of liquid swine manure. The {sup 31}P-NMR spectra of soil extracts detected the following P compounds: orthophosphate, pyrophosphate, inositol phosphate, glycerophosphate, and DNA. The use of organic or mineral fertilizer over nine years did not change the soil P forms but influenced their concentration. Fertilization with mineral or organic fertilizers stimulated P accumulation in inorganic forms. Highest inositol phosphate levels were observed after fertilization with any kind of manure and highest organic P concentration in glycerophosphate form in after mineral or no fertilization. (author)

  18. Dynamic structures of intact chicken erythrocyte chromatins as studied by 1H-31P cross-polarization NMR. (United States)

    Akutsu, H; Nishimoto, S; Kyogoku, Y


    The dynamic properties of DNA in intact chicken erythrocyte cells, nuclei, nondigested chromatins, digested soluble chromatins, H1, H5-depleted soluble chromatins and nucleosome cores were investigated by means of single-pulse and 1H-31P cross-polarization NMR. The temperature dependence of the phosphorus chemical shift anisotropy was identical for the former three in the presence of 3 mM MgCl2, suggesting that the local higher order structure is identical for these chromatins. The intrinsic phosphorus chemical shift anisotropy of the nucleosome cores was -159 ppm. The chemical shift anisotropy of DNA in the chromatins can be further averaged by the motion of the linker DNA. The spin-lattice relaxation time in the rotating frame of the proton spins (T1p) of the nondigested chromatins was measured at various locking fields. The result was analyzed on the assumption of the isotropic motion to get a rough value of the correlation time of the motion efficient for the relaxation, which was eventually ascribed to the segmental motion of the linker DNA with restricted amplitude. The 30 nm filament structure induced by NaCl was shown to be dynamically different from that induced by MgCl2. Side-by-side compaction of 30-nm filaments was suggested to be induced in the MgCl2 concentration range higher than 0.3 mM. Biological significance of the dynamic structure was discussed in connection with the results obtained.

  19. Quantitative 31P NMR analysis of solid wood offers an insight into the acetylation of its components. (United States)

    Sadeghifar, Hasan; Dickerson, James P; Argyropoulos, Dimitris S


    As a solid substrate, wood and its components are almost invariably examined via spectroscopic or indirect methods of analysis. Unlike earlier approaches, in this effort we dissolve pulverized wood in ionic liquid and then directly derive its functional group contents by quantitative (31)P NMR. As such, this novel analytical methodology is thoroughly examined and an insight into the detailed way acetylation proceeds on solid wood and its components is provided as a function of wood density and within its various anatomical features. As anticipated, the efficiency of acetylation was found to be greater within low density wood than in high density wood. The lignin, the cellulose and the hemicelluloses of the low density wood was found to be acetylated nearly twice as fast with remarkable differences in their quantitative degree of acetylation amongst them. This direct analytical data validates the applied methodology and confirms, for the first time, that the order of acetylation in solid wood is lignin>hemicellulose>cellulose and no reactivity differences exist between early wood and late wood.

  20. Fractioning of sodium polyphosphate and characterization by {sup 31}P NMR: a experience to physical-chemistry lessons; Fracionamento de polifosfato de sodio e caracterizacao por RMN de 31P: um experimento para aulas de Fisico-Quimica

    Energy Technology Data Exchange (ETDEWEB)

    Lima, Emilia Celma de Oliveira; Alcantara, Glaucia Braz Alcantara; Damasceno, Fernando Cruvinel, E-mail: elima@quimica.ufg.b [Universidade Federal de Goias (UFG), Goiania, GO (Brazil). Inst. de Quimica; Moita Neto, Jose Machado [Universidade Federal do Piaui (UFPI), Teresina, PI (Brazil). Dept. de Quimica; Galembeck, Fernando [Universidade Estadual de Campinas (UNICAMP), SP (Brazil). Inst. de Quimica


    This text describes an experiment on fractional precipitation of a polymer together with determination of average degree of polymerization by NMR. Commercial sodium polyphosphate was fractionated by precipitation from aqueous solution by adding increasing amounts of acetone. The polydisperse salt and nine fractions obtained from it were analyzed by {sup 31}P nuclear magnetic resonance and the degree of polymerization of the salts and of the fractions were calculated. Long-chain sodium polyphosphate was also synthesized and analyzed. This experiment was tested in a PChem lab course but it can be used also to illustrate topics of inorganic polymers and analytical chemistry. (author)

  1. Characterization of soybean phosphatidylcholine purity by {sup 1}H and {sup 31}P NMR; Caracterizacao da pureza de fosfatidilcolina da soja atraves de RMN de {sup 1}H e de {sup 31}P

    Energy Technology Data Exchange (ETDEWEB)

    Mertins, Omar; Sebben, Marcelo; Schneider, Paulo Henrique; Pohlmann, Adriana Raffin; Silveira, Nadya Pesce da [Universidade Federal do Rio Grande do Sul (UFRGS), Porto Alegre, RS (Brazil). Dept. de Quimica]. E-mail:


    A strategy is proposed to evaluate the purity of phosphatidylcholine from soybean lecithin, obtained by extraction or column chromatography, using the integrals ratio of {sup 1}H NMR spectra. Integrals of methylene signals, around 1.3 and 1.6 ppm, are added and divided by the integral of the choline methyl groups, around 3.3 ppm. Before purification, a ratio of 19.68 {+-} 1.37 was determined. Using extraction, a ratio of 10.70 {+-} 0.61 was found, while from column chromatography, a value of 2.99 {+-} 0.25 was detected. {sup 31}P NMR of standard phosphatidylcholine showed signals at -0.2 and -0.9 ppm, whereas the purified one showed a single signal at -0.9 ppm. (author)

  2. Caracterização da pureza de fosfatidilcolina da soja através de RMN de ¹H e de 31P Characterization of soybean phosphatidylcholine purity by ¹H and 31P NMR

    Directory of Open Access Journals (Sweden)

    Omar Mertins


    Full Text Available A strategy is proposed to evaluate the purity of phosphatidylcholine from soybean lecithin, obtained by extraction or column chromatography, using the integrals ratio of ¹H NMR spectra. Integrals of methylene signals, around 1.3 and 1.6 ppm, are added and divided by the integral of the choline methyl groups, around 3.3 ppm. Before purification, a ratio of 19.68±1.37 was determined. Using extraction, a ratio of 10.70±0.61 was found, while from column chromatography, a value of 2.99±0.25 was detected. 31P NMR of standard phosphatidylcholine showed signals at -0.2 and -0.9 ppm, whereas the purified one showed a single signal at -0.9 ppm.

  3. A comparison of MR elastography and {sup 31}P MR spectroscopy with histological staging of liver fibrosis

    Energy Technology Data Exchange (ETDEWEB)

    Godfrey, Edmund M. [St James' Hospital, Leeds (United Kingdom); St James' Hospital, Department of Radiology, Leeds (United Kingdom); Patterson, Andrew J.; Priest, Andrew N.; Davies, Susan E.; Joubert, Ilse; Krishnan, Anant S.; Shaw, Ashley S.; Alexander, Graeme J.; Allison, Michael E.; Griffiths, William J.H.; Gimson, Alexander E.S. [Addenbrooke' s Hospital, Cambridge (United Kingdom); Griffin, Nyree [St Thomas' s Hospital, London (United Kingdom); Lomas, David J. [University of Cambridge, Department of Radiology, Cambridge (United Kingdom)


    Conventional imaging techniques are insensitive to liver fibrosis. This study assesses the diagnostic accuracy of MR elastography (MRE) stiffness values and the ratio of phosphomonoesters (PME)/phosphodiesters (PDE) measured using {sup 31}P spectroscopy against histological fibrosis staging. The local research ethics committee approved this prospective, blinded study. A total of 77 consecutive patients (55 male, aged 49 {+-} 11.5 years) with a clinical suspicion of liver fibrosis underwent an MR examination with a liver biopsy later the same day. Patients underwent MRE and {sup 31}P spectroscopy on a 1.5 T whole body system. The liver biopsies were staged using an Ishak score for chronic hepatitis or a modified NAS fibrosis score for fatty liver disease. MRE increased with and was positively associated with fibrosis stage (Spearman's rank = 0.622, P < 0.001). PME/PDE was not associated with fibrosis stage (Spearman's rank = -0.041, p = 0.741). Area under receiver operating curves for MRE stiffness values were high (range 0.75-0.97). The diagnostic utility of PME/PDE was no better than chance (range 0.44-0.58). MRE-estimated liver stiffness increases with fibrosis stage and is able to dichotomise fibrosis stage groupings. We did not find a relationship between {sup 31}P MR spectroscopy and fibrosis stage. circle Magnetic resonance elastography (MRE) and MR spectroscopy can both assess the liver. (orig.)

  4. Correcting human heart 31P NMR spectra for partial saturation. Evidence that saturation factors for PCr/ATP are homogeneous in normal and disease states (United States)

    Bottomley, Paul A.; Hardy, Christopher J.; Weiss, Robert G.

    Heart PCr/ATP ratios measured from spatially localized 31P NMR spectra can be corrected for partial saturation effects using saturation factors derived from unlocalized chest surface-coil spectra acquired at the heart rate and approximate Ernst angle for phosphor creatine (PCr) and again under fully relaxed conditions during each 31P exam. To validate this approach in studies of normal and disease states where the possibility of heterogeneity in metabolite T1 values between both chest muscle and heart and normal and disease states exists, the properties of saturation factors for metabolite ratios were investigated theoretically under conditions applicable in typical cardiac spectroscopy exams and empirically using data from 82 cardiac 31P exams in six study groups comprising normal controls ( n = 19) and patients with dilated ( n = 20) and hypertrophic ( n = 5) cardiomyopathy, coronary artery disease ( n = 16), heart transplants ( n = 19), and valvular heart disease ( n = 3). When TR ≪ T1,(PCr), with T1(PCr) ⩾ T1(ATP), the saturation factor for PCr/ATP lies in the range 1.5 ± 0.5, regardless of the T1 values. The precise value depends on the ratio of metabolite T1 values rather than their absolute values and is insensitive to modest changes in TR. Published data suggest that the metabolite T1 ratio is the same in heart and muscle. Our empirical data reveal that the saturation factors do not vary significantly with disease state, nor with the relative fractions of muscle and heart contributing to the chest surface-coil spectra. Also, the corrected myocardial PCr/ATP ratios in each normal or disease state bear no correlation with the corresponding saturation factors nor the fraction of muscle in the unlocalized chest spectra. However, application of the saturation correction (mean value, 1.36 ± 0.03 SE) significantly reduced scatter in myocardial PCr/ATP data by 14 ± 11% (SD) ( p ⩽ 0.05). The findings suggest that the relative T1 values of PCr and ATP are

  5. Metabolic abnormalities in skeletal muscle of patients receiving zidovudine therapy observed by 31P in vivo magnetic resonance spectroscopy.


    Sinnwell, T M; Sivakumar, K.; Soueidan, S; Jay, C; Frank, J.A.; McLaughlin, A C; Dalakas, M C


    Patients on long-term zidovudine (AZT) therapy experience muscle fatigue and weakness attributed to AZT-induced mitochondrial toxicity in skeletal muscle. To determine if the clinico-pathological abnormalities in these patients correspond to abnormal muscle energy metabolism, we used 31P in vivo magnetic resonance spectroscopy to follow phosphorylated metabolites during exercise. We studied 19 normal volunteers, 6 HIV-positive patients never treated with AZT, and 9 HIV-positive patients who h...

  6. "Solvent Effects" in 1H NMR Spectroscopy. (United States)

    Cavaleiro, Jose A. S.


    Describes a simple undergraduate experiment in chemistry dealing with the "solvent effects" in nuclear magnetic resonance (NMR) spectroscopy. Stresses the importance of having students learn NMR spectroscopy as a tool in analytical chemistry. (TW)

  7. Geographical characterization of greek virgin olive oils (cv. Koroneiki) using 1H and 31P NMR fingerprinting with canonical discriminant analysis and classification binary trees. (United States)

    Petrakis, Panos V; Agiomyrgianaki, Alexia; Christophoridou, Stella; Spyros, Apostolos; Dais, Photis


    This work deals with the prediction of the geographical origin of monovarietal virgin olive oil (cv. Koroneiki) samples from three regions of southern Greece, namely, Peloponnesus, Crete, and Zakynthos, and collected in five harvesting years (2001-2006). All samples were chemically analyzed by means of 1H and 31P NMR spectroscopy and characterized according to their content in fatty acids, phenolics, diacylglycerols, total free sterols, free acidity, and iodine number. Biostatistical analysis showed that the fruiting pattern of the olive tree complicates the geographical separation of oil samples and the selection of significant chemical compounds. In this way the inclusion of the harvesting year improved the classification of samples, but increased the dimensionality of the data. Discriminant analysis showed that the geographical prediction at the level of three regions is very high (87%) and becomes (74%) when we pass to the thinner level of six sites (Chania, Sitia, and Heraklion in Crete; Lakonia and Messinia in Peloponnesus; Zakynthos). The use of classification and binary trees made possible the construction of a geographical prediction algorithm for unknown samples in a self-improvement fashion, which can be readily extended to other varieties and areas.

  8. Functional pools of fast and slow twitch fibers observed by /sup 31/P-NMR during exercise of flexor wrist muscles in man

    Energy Technology Data Exchange (ETDEWEB)

    Park, J.H.; Park, C.R.; Brown, R.L.; Chance, B.


    Functional compartments of fast and slow twitch fibers have been observed by /sup 31/P-NMR spectroscopy during exercise of the wrist flexor muscles in a sedentary, young male subject. Values of Pi, phosphocreatine (PCr) and adenine nucleotides were determined at rest and during an exercise protocol. The subject flexed his wrist muscles at 20% of maximum strength every 5 sec for 6 min and then increased his effort in the next two 6 min intervals to 40% and 60% of maximum. With exercise, the Pi/PCr rose rapidly to the exceptionally high value of 2.2 at 60% effort. As the Pi increased, the initial single peak (pH 7.0-6.9) split into two distinct components with pH values of 6.8 and 6.3. Quantitatively, distribution of the Pi was 40% in the pH 6.8 peak and 60% in the pH 6.3 peak as determined by area estimation following curve fitting. This presumably reflects two pools of Pi corresponding to the oxidative (slow twitch, high pH) and glycolytic (fast twitch, low pH) fibers. In the second identical exercise sequence which followed immediately, only one Pi peak (pH 6.8-6.9) appeared. This suggested that the glycolytic contribution to energy production was largely exhausted and the residual energy was derived from oxidative metabolism. During exercise at high levels, total phosphate decreased due primarily to loss of NMR visible adenine nucleotides. Similar phenomena have been observed in three other sedentary individuals, but not in trained athletes.

  9. Differently saturated fatty acids can be differentiated by 31P NMR subsequent to derivatization with 2-chloro-4,4,5,5-tetramethyldioxaphospholane: a cautionary note. (United States)

    Eibisch, Mandy; Riemer, Thomas; Fuchs, Beate; Schiller, Jürgen


    The analysis of free fatty acid (FFA) mixtures is a very important but, even nowadays, challenging task. This particularly applies as the so far most commonly used technique-gas chromatography/mass spectrometry (GC/MS)-is tedious and time-consuming. It has been convincingly shown ( Spyros, A.; Dais, P. J. Agric. Food Chem. 2000, 48, 802 - 5) that FFA may be analyzed by (31)P NMR subsequent to derivatization with 2-chloro-4,4,5,5-tetramethyldioxaphospholane (CTDP). However, it was also indicated that differently unsaturated FFAs result in the same (31)P NMR chemical shift and cannot be differentiated. Therefore, only the overall fatty acid content of a sample can be determined by the CTDP assay. In contrast, we will show here by using high-field NMR (600 MHz spectrometer, i.e., 242.884 MHz for (31)P) that the CTDP assay may be used to differentiate FFAs that have pronounced differences in their double bond contents: saturated fatty acids (16:0), moderately unsaturated (18:1, 18:2), highly unsaturated (20:4), and extremely unsaturated fatty acids (22:6) result in slightly different chemical shifts. The same applies for oxidized fatty acids. Finally, it will also be shown that the CTDP derivatization products decompose in a time-dependent manner. Therefore, all investigations must adhere to a strict time regime.

  10. Vacuolar glyphosate-sequestration correlates with glyphosate resistance in ryegrass (Lolium spp.) from Australia, South America, and Europe: a 31P NMR investigation. (United States)

    Ge, Xia; d'Avignon, D André; Ackerman, Joseph J H; Collavo, Alberto; Sattin, Maurizio; Ostrander, Elizabeth L; Hall, Erin L; Sammons, R Douglas; Preston, Christopher


    Lolium spp., ryegrass, variants from Australia, Brazil, Chile, and Italy showing differing levels of glyphosate resistance were examined by (31)P NMR. Extents of glyphosate (i) resistance (LD(50)), (ii) inhibition of 5-enopyruvyl-shikimate-3-phosphate synthase (EPSPS) activity (IC(50)), and (iii) translocation were quantified for glyphosate-resistant (GR) and glyphosate-sensitive (GS) Lolium multiflorum Lam. variants from Chile and Brazil. For comparison, LD(50) and IC(50) data for Lolium rigidum Gaudin variants from Italy were also analyzed. All variants showed similar cellular uptake of glyphosate by (31)P NMR. All GR variants showed glyphosate sequestration within the cell vacuole, whereas there was minimal or no vacuole sequestration in the GS variants. The extent of vacuole sequestration correlated qualitatively with the level of resistance. Previous (31)P NMR studies of horseweed ( Conyza canadensis (L.) Cronquist) revealed that glyphosate sequestration imparted glyphosate resistance. Data presented herein suggest that glyphosate vacuolar sequestration is strongly contributing, if not the major contributing, resistance mechanism in ryegrass as well.

  11. In vivo measurement of intracellular pH in human brain during different tensions of carbon dioxide in arterial blood. A 31P-NMR study

    DEFF Research Database (Denmark)

    Jensen, K E; Thomsen, C; Henriksen, O


    The effect of changes in carbon dioxide tension in arterial blood upon intracellular pH in brain tissue was studied in seven healthy volunteers, aged 22-45 years. The pH changes were monitored by use of 31P nuclear magnetic resonance spectroscopy, performed on a whole-body 1.5 Tesla Siemens imaging...

  12. Studies on metabolic regulation using NMR spectroscopy. (United States)

    Bachelard, H; Badar-Goffer, R; Ben-Yoseph, O; Morris, P; Thatcher, N


    The effects of hypoxia and hypoglycaemia on cerebral metabolism and calcium have been studied using multinuclear magnetic resonance spectroscopy. 13C MRS showed that severe hypoxia did not cause any further increase in metabolic flux into lactate seen in mild hypoxia, but there was a further increase in 13C labelling of alanine and glycerol 3-phosphate. These results are discussed in terms of the ability of lactate dehydrogenase to maintain normal levels of NADH in mild hypoxia, but not in severe hypoxia. We conclude that glycerol 3-phosphate and alanine may provide novel means of monitoring severe hypoxia whereas lactate is a reliable indicator only of mild hypoxia. 19F- and 31P NMR spectroscopy showed that neither hypoxia nor hypoglycaemia alone caused any significant change in [Ca2+]i. Combined sequential insults (hypoxia, followed by hypoxia plus hypoglycaemia), or vice versa, produced a 100% increase in [Ca2+]i, whereas immediate exposure to the combined insult (hypoxia plus hypoglycaemia) resulted in a large 5-fold increase in [Ca2+]i, with severe irreversible effects on the energy state. These results are discussed in terms of metabolic adaptation to the single type of insult, which renders the tissue less vulnerable to the combined insult. The effects of this combined insult are far more severe than those caused by glutamate or NMDA, which throws doubt on the current excitoxic hypothesis of cell damage.

  13. The use of {sup 1}H-{sup 31}P GHMBC and covariance NMR to unambiguously determine phosphate ester linkages in complex polysaccharide mixtures

    Energy Technology Data Exchange (ETDEWEB)

    Zartler, Edward R., E-mail: [Merck Research Labs, Merck and Co., Vaccine Analytical Development (United States); Martin, Gary E. [Merck Research Labs, Merck and Co., Structure Elucidation Group (United States)


    Poly- and oligo-saccharides are commonly employed as antigens in many vaccines. These antigens contain phosphoester structural elements that are crucial to the antigenicity, and hence the effectiveness of the vaccine. Nuclear Magnetic Resonance (NMR) is a powerful tool for the site-specific identification of phosphoesters in saccharides. We describe here two advances in the characterization of phosphoesters in saccharides: (1) the use of {sup 1}H-{sup 31}P GHMBC to determine the site-specific identity of phosphoester moieties in heterogeneous mixtures and (2) the use of Unsymmetrical/Generalized Indirect Covariance (U/GIC) to calculate a carbon-phosphorus 2D spectrum. The sensitivity of the {sup 1}H-{sup 31}P GHMBC is far greater than the 'standard' {sup 1}H-{sup 31}P GHSQC and allows long-range {sup 3-5}J{sub HP} couplings to be readily detected. This is the first example to be reported of using U/GIC to calculate a carbon-phosphorus spectrum. The U/GIC processing affords, in many cases, a fivefold to tenfold or greater increase in signal-to-noise ratios in the calculated spectrum. When coupled with the high sensitivity of {sup 1}H-{sup 31}P HMBC, U/GIC processing allows the complete and unambiguous assignments of phosphoester moieties present in heterogeneous samples at levels of {approx}5% (or less) of the total sample, expanding the breadth of samples that NMR can be used to analyze. This new analytical technique is generally applicable to any NMR-observable phosphoester.

  14. Hyperpolarized 131Xe NMR spectroscopy (United States)

    Stupic, Karl F.; Cleveland, Zackary I.; Pavlovskaya, Galina E.; Meersmann, Thomas


    Hyperpolarized (hp) 131Xe with up to 2.2% spin polarization (i.e., 5000-fold signal enhancement at 9.4 T) was obtained after separation from the rubidium vapor of the spin-exchange optical pumping (SEOP) process. The SEOP was applied for several minutes in a stopped-flow mode, and the fast, quadrupolar-driven T1 relaxation of this spin I = 3/2 noble gas isotope required a rapid subsequent rubidium removal and swift transfer into the high magnetic field region for NMR detection. Because of the xenon density dependent 131Xe quadrupolar relaxation in the gas phase, the SEOP polarization build-up exhibits an even more pronounced dependence on xenon partial pressure than that observed in 129Xe SEOP. 131Xe is the only stable noble gas isotope with a positive gyromagnetic ratio and shows therefore a different relative phase between hp signal and thermal signal compared to all other noble gases. The gas phase 131Xe NMR spectrum displays a surface and magnetic field dependent quadrupolar splitting that was found to have additional gas pressure and gas composition dependence. The splitting was reduced by the presence of water vapor that presumably influences xenon-surface interactions. The hp 131Xe spectrum shows differential line broadening, suggesting the presence of strong adsorption sites. Beyond hp 131Xe NMR spectroscopy studies, a general equation for the high temperature, thermal spin polarization, P, for spin I⩾1/2 nuclei is presented.

  15. Fructose-induced aberration of metabolism in familial gout identified by sup 31 P magnetic resonance spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Seegmiller, J.E. (John Radcliffe Hospital, Oxford (England) Univ. of California, San Diego (United States)); Dixon, R.M.; Kemp, G.J.; Rajagopalan, B.; Radda, G.K. (John Radcliffe Hospital, Oxford (England)); Angus, P.W. (John Radcliffe Hospital, Oxford (England) Austin Hospital, Heidelburg, Victoria (Australia)); McAlindon, T.E.; Dieppe, P. (Univ. of Bristol (England))


    The hyperuricemia responsible for the development of gouty arthritis results from a wide range of environmental factors and underlying genetically determined aberrations of metabolism. {sup 31}P magnetic resonance spectroscopy studies of children with hereditary fructose intolerance revealed a readily detectable rise in phosphomonoesters with a marked fall in inorganic phosphate in their liver in vivo and a rise in serum urate in response to very low doses of oral fructose. Parents and some family members heterozygous for this enzyme deficiency showed a similar pattern when given a substantially larger dose of fructose. Three of the nine heterozygotes thus identified also had clinical gout, suggesting the possibility of this defect being a fairly common cause of gout. In the present study this same noninvasive technology was used to identify the same spectral pattern in 2 of the 11 families studied with hereditary gout. In one family, the index patient's three brothers and his mother all showed the fructose-induced abnormality of metabolism, in agreement with the maternal inheritance of metabolism, in agreement with the maternal inheritance of the gout in this family group. The test dose of fructose used produced a significantly larger increment in the concentration of serum urate in the patients showing the changes in {sup 31}P magnetic resonance spectra than in the other patients with familial gout or in nonaffected members, thus suggesting a simpler method for initial screening for the defect.

  16. Wilson's disease: {sup 31}P and {sup 1}H MR spectroscopy and clinical correlation

    Energy Technology Data Exchange (ETDEWEB)

    Sinha, Sanjib; Taly, A.B.; Prashanth, L.K. [National Institute of Mental Health and Neurosciences (NIMHANS), Department of Neurology, Bangalore (India); Ravishankar, S.; Vasudev, M.K. [National Institute of Mental Health and Neurosciences (NIMHANS), Department of Neuroimaging and Interventional Radiology, Bangalore (India)


    Proton ({sup 1}H) magnetic resonance spectroscopy (MRS) changes are noted in Wilson's disease (WD). However, there are no studies regarding membrane phospholipid abnormality using {sup 31}P MRS in these patients. We aimed to analyze the striatal spectroscopic abnormalities using {sup 31}P and {sup 1}H MRS in WD. Forty patients of WD (treated, 29; untreated,11) and 30 controls underwent routine MR image sequences and in vivo 2-D {sup 31}P and {sup 1}H MRS of basal ganglia using an image-selected technique on a 1.5-T MRI scanner. Statistical analysis was done using Student's t test. The mean durations of illness and treatment were 6.2 {+-} 7.4 and 4.8 {+-} 5.9 years, respectively. MRI images were abnormal in all the patients. {sup 1}H MRS revealed statistically significant reduction of N-acetyl aspartate (NAA)/choline (Cho) and NAA/creatine ratios in striatum ({sup 1}H MRS) of treated patients compared to controls. The mean values of phosphomonoesters (PME) (p < 0.0001), phosphodiesters (PDE) (p < 0.0001), and total phosphorus (TPh) (p < 0.0001) were elevated in patients compared to controls. Statistically significant elevated levels of ratio of PME/PDE (p = 0.05) observed in the striatum were noted in treated patients as compared to controls in the {sup 31}P MRS study. The duration of illness correlated well with increased PME/PDE [p < 0.001], PME/TPh [p < 0.05], and PDE/TPh [p < 0.05] and decreased NAA/Cho [p < 0.05] ratios. There was correlation of MRI score and reduced NAA/Cho ratio with disease severity. The PME/PDE ratio (right) was elevated in the treated group [p < 0.001] compared to untreated group. There is reduced breakdown and/or increased synthesis of membrane phospholipids and increased neuronal damage in basal ganglia in patients with WD. (orig.)

  17. NMR Spectroscopy and Its Value: A Primer (United States)

    Veeraraghavan, Sudha


    Nuclear magnetic resonance (NMR) spectroscopy is widely used by chemists. Furthermore, the use of NMR spectroscopy to solve structures of macromolecules or to examine protein-ligand interactions is popular. Yet, few students entering graduate education in biological sciences have been introduced to this method or its utility. Over the last six…

  18. Enzyme dynamics from NMR spectroscopy. (United States)

    Palmer, Arthur G


    CONSPECTUS: Biological activities of enzymes, including regulation or coordination of mechanistic stages preceding or following the chemical step, may depend upon kinetic or equilibrium changes in protein conformations. Exchange of more open or flexible conformational states with more closed or constrained states can influence inhibition, allosteric regulation, substrate recognition, formation of the Michaelis complex, side reactions, and product release. NMR spectroscopy has long been applied to the study of conformational dynamic processes in enzymes because these phenomena can be characterized over multiple time scales with atomic site resolution. Laboratory-frame spin-relaxation measurements, sensitive to reorientational motions on picosecond-nanosecond time scales, and rotating-frame relaxation-dispersion measurements, sensitive to chemical exchange processes on microsecond-millisecond time scales, provide information on both conformational distributions and kinetics. This Account reviews NMR spin relaxation studies of the enzymes ribonuclease HI from mesophilic (Escherichia coli) and thermophilic (Thermus thermophilus) bacteria, E. coli AlkB, and Saccharomyces cerevisiae triosephosphate isomerase to illustrate the contributions of conformational flexibility and dynamics to diverse steps in enzyme mechanism. Spin relaxation measurements and molecular dynamics (MD) simulations of the bacterial ribonuclease H enzymes show that the handle region, one of three loop regions that interact with substrates, interconverts between two conformations. Comparison of these conformations with the structure of the complex between Homo sapiens ribonuclease H and a DNA:RNA substrate suggests that the more closed state is inhibitory to binding. The large population of the closed conformation in T. thermophilus ribonuclease H contributes to the increased Michaelis constant compared with the E. coli enzyme. NMR spin relaxation and fluorescence spectroscopy have characterized a

  19. 31P NMR characterization and efficiency of new types of water-insoluble phosphate fertilizers to supply plant-available phosphorus in diverse soil types. (United States)

    Erro, Javier; Baigorri, Roberto; Yvin, Jean-Claude; Garcia-Mina, Jose M


    Hydroponic plant experiments demonstrated the efficiency of a type of humic acid-based water-insoluble phosphate fertilizers, named rhizosphere controlled fertilizers (RCF), to supply available phosphorus (P) to different plant species. This effect was well correlated to the root release of specific organic acids. In this context, the aims of this study are (i) to study the chemical nature of RCF using solid-state (31)P NMR and (ii) to evaluate the real efficiency of RCF matrix as a source of P for wheat plants cultivated in an alkaline and acid soil in comparison with traditional water-soluble (simple superphosphate, SSP) and water-insoluble (dicalcium phosphate, DCP) P fertilizers. The (31)P NMR study revealed the formation of multimetal (double and triple, MgZn and/or MgZnCa) phosphates associated with chelating groups of the humic acid through the formation of metal bridges. With regard to P fertilizer efficiency, the results obtained show that the RCF matrix produced higher plant yields than SSP in both types of soil, with DCP and the water-insoluble fraction from the RCF matrix (WI) exhibiting the best results in the alkaline soil. By contrast, in the acid soil, DCP showed very low efficiency, WI performed on a par with SSP, and RCF exhibited the highest efficiency, thus suggesting a protector effect of humic acid from soil fixation.

  20. Complex Mixture Analysis of Organic Compounds in Yogurt by NMR Spectroscopy

    Directory of Open Access Journals (Sweden)

    Yi Lu


    Full Text Available 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.

  1. Biochemical metabolic changes assessed by 31P magnetic resonance spectroscopy after radiation-induced hepatic injury in rabbits

    Institute of Scientific and Technical Information of China (English)

    Ri-Sheng Yu; Liang Hao; Fei Dong; Jian-Shan Mao; Jian-Zhong Sun; Ying Chen; Min Lin; Zhi-Kang Wang; Wen-Hong Ding


    AIM:To compare the features of biochemical metabolic changes detected by hepatic phosphorus-31 magnetic resonance spectroscopy (31P MRS) with the liver damage score (LDS) and pathologic changes in rabbits and to investigate the diagnostic value of 31P MRS in acute hepatic radiation injury.METHODS:A total of 30 rabbits received different radiation doses (ranging 5-20 Gy) to establish acute hepatic injury models.Blood biochemical tests,31P MRS and pathological examinations were carried out 24 h after irradiation.The degree of injury was evaluated according to LDS and pathology.Ten healthy rabbits served as controls.The MR examination was performed on a 1.5 T imager using a 1H/31P surface coil by the 2D chemical shift imaging technique.The relative quantities of phosphomonoesters (PME),phosphodiesters (PDE),inorganic phosphate (Pi) and adenosine triphosphate (ATP) were measured.The data were statistically analyzed.RESULTS:(1) Relative quantification of phosphorus metabolites:(a) ATP:there were significant differences (P<0.05) (LDS-groups:control group vs mild group vs moderate group vs severe group,1.83±0.33 vs 1.55±0.24 vs 1.27±0.09 vs 0.98±0.18;pathological groups:control group vs mild group vs moderate group vs severe group,1.83±0.33 vs 1.58±0.25 vs 1.32±0.07 vs 1.02 ± 0.18) of ATP relative quantification among control group,mild injured group,moderate injured group,and severe injured group according to both LDS grading and pathological grading,respectively,and it decreased progressively with the increased degree of injury (r=-0.723,P=0.000).(b) PME and Pi;the relative quantification of PME and Pi decreased significantly in the severe injured group,and the difference between the control group and severe injured group was significant (P<0.05) (PME:LDScontrol group vs LDS-severe group,0.86±0.23 vs 0.58±0.22,P=0.031;pathological control group vs pathological severe group,0.86±0.23 vs 0.60±0.21,P=0.037;Pi:LDS-control group vs LDS-severe group,0.74±0.18 vs

  2. Reproducibility of creatine kinase reaction kinetics in human heart: a (31) P time-dependent saturation transfer spectroscopy study. (United States)

    Bashir, Adil; Gropler, Robert


    Creatine kinase (CK) is essential for the buffering and rapid regeneration of adenosine triphosphate (ATP) in heart tissue. Herein, we demonstrate a (31) P MRS protocol to quantify CK reaction kinetics in human myocardium at 3 T. Furthermore, we sought to quantify the test-retest reliability of the measured metabolic parameters. The method localizes the (31) P signal from the heart using modified one-dimensional image-selected in vivo spectroscopy (ISIS), and a time-dependent saturation transfer (TDST) approach was used to measure CK reaction parameters. Fifteen healthy volunteers (22 measurements in total) were tested. The CK reaction rate constant (kf ) was 0.32 ± 0.05 s(-1) and the coefficient of variation (CV) was 15.62%. The intrinsic T1 for phosphocreatine (PCr) was 7.36 ± 1.79 s with CV = 24.32%. These values are consistent with those reported previously. The PCr/ATP ratio was equal to 1.94 ± 0.15 with CV = 7.73%, which is within the range of healthy subjects. The reproducibility of the technique was tested in seven subjects and inferred parameters, such as kf and T1 , exhibited good reliability [intraclass correlation coefficient (ICC) of 0.90 and 0.79 for kf and T1 , respectively). The reproducibility data provided in this study will enable the calculation of the power and sample sizes required for clinical and research studies. The technique will allow for the examination of cardiac energy metabolism in clinical and research studies, providing insight into the relationship between energy deficit and functional deficiency in the heart.

  3. Different early effect of irradiation in brain and small cell lung cancer examined by in vivo 31P-magnetic resonance spectroscopy

    DEFF Research Database (Denmark)

    Kristjansen, P E; Pedersen, A G; Quistorff, B


    Early effects of irradiation were evaluated by non-invasive in vivo 31P-magnetic resonance spectroscopy (31P-MRS) of two small cell lung cancer (SCLC) tumor lines CPH SCCL 54A and 54B, in nude mice. The tumors were originally derived from the same patient and have similar morphology and growth...... characteristics, but a different radiosensitivity. The 54A tumors are twice as radiosensitive as the 54B's. In the present study the tumors were treated with 2.5, 10, and 40 Gy. For comparison, nude mice were given cranial irradiation at the same three doses, and the effect was evaluated by in vivo 31P-MRS...... in ATP/Pi. The differential effect on tumors and brain might be relevant for monitoring irradiation effects by in vivo 31P-MRS in patients with brain metastases....

  4. Intra- and extracellular pH of the brain in vivo studied by 31P-NMR during hyper- and hypocapnia

    DEFF Research Database (Denmark)

    Portman, M A; Lassen, N A; Cooper, T G;


    Studies were performed to determine the pH relationships among the extracellular, intracellular, and arterial blood compartments in the brain in vivo. Resolution of the extracellular monophosphate resonance peak from the intracellular peak in 31P nuclear magnetic resonance (NMR) spectra of sheep...... brain with the calvarium intact enabled pH measurement in these respective compartments. Sheep were then subjected to both hyper- and hypoventilation, which resulted in a wide range of arterial PCO2 and pH values. Linear regression analysis of pH in these compartments yielded slopes of 0.56 +/- 0...... of the extracellular space from the vascular space may be a function of the blood-brain barrier, which contributes to the buffering capability of the extracellular compartment. A marked decrease in the pH gradient between the extracellular and intracellular space occurs during hypercarbia and may influence mechanisms...

  5. Analysis of brain metabolism changes induced by acute potassium cyanide intoxication by 31P NMR in vivo using chronically implanted surface coils. (United States)

    Decorps, M; Lebas, J F; Leviel, J L; Confort, S; Remy, C; Benabid, A L


    Chronic implantation of surface coils on the skull has been developed to record 31P NMR spectra of the brain in unanesthetized rats. Intraperitoneal sublethal potassium cyanide doses induce strong and reversible changes in high-energy phosphate compounds in the brain, similar in part to those induced by ischemia. These effects are dose-dependent as far as phosphocreatine, inorganic orthophosphates and pH are concerned; ATP does not seem to be altered by KCN doses ranging from 3 to 5 mg/kg but starts decreasing at a dose of 6 mg/kg. The fraction of Mg2+ complexed ATP which could be estimated as about 90% was not affected by KCN intoxication. For high doses (6 mg/kg) a new peak, appearing on the upfield side of the inorganic phosphate peak, may correspond to an acidic compartment, the significance of which is discussed.

  6. 31P NMR analysis of intracellular pH of Swiss Mouse 3T3 cells: effects of extracellular Na+ and K+ and mitogenic stimulation. (United States)

    Civan, M M; Williams, S R; Gadian, D G; Rozengurt, E


    Swiss mouse 3T3 cells grown on microcarrier beads were superfused with electrolyte solution during continuous NMR analysis. Conventional 31P and 19F probes of intracellular pH (pHc) were found to be impracticable. Cells were therefore superfused with 1 to 4 mM 2-deoxyglucose, producing a large intracellular, pH-sensitive signal of 2-deoxyglucose phosphate (2DGP). The intracellular incorporation of 2DGP inhibited the Embden-Meyerhof pathway. However, intracellular ATP was at least in part retained and the cellular responsivity to changes in extracellular ionic composition and to the application of growth factors proved intact. Transient replacement of external Na+ with choline or K+ reversibly acidified the intracellular fluids. Quiescent cells and mitogenically stimulated cells displayed the same dependence of shifts in pHc on external Na+ concentration (CoNa). PHc also depended on intracellular Na+ concentration (CcNa). Increasing ccNa by withdrawing external K+ (thereby inhibiting the Na,K-pump) caused reversible intracellular acidification; subsequently reducing CoNa produced a larger acid shift in pHc than with external K+ present. Comparison of separate preparations indicated that pHc was higher in stimulated than in quiescent cells. Transient administration of mitogens also reversibly alkalinized quiescent cells studied continuously. This study documents the feasibility of monitoring pHc of Swiss mouse 3T3 cells using 31P NMR analysis of 2DGP. The results support the concept of a Na/H antiport operative in these cells, both in quiescence and after mitogenic stimulation. The data document by an independent technique that cytoplasmic alkalinization is an early event in mitogenesis, and that full activity of the Embden-Meyerhof pathway is not required for the expression of this event.

  7. Semi-LASER localized dynamic 31P magnetic resonance spectroscopy in exercising muscle at ultra-high magnetic field. (United States)

    Meyerspeer, Martin; Scheenen, Tom; Schmid, Albrecht Ingo; Mandl, Thomas; Unger, Ewald; Moser, Ewald


    Magnetic resonance spectroscopy (MRS) can benefit from increased signal-to-noise ratio (SNR) of high magnetic fields. In this work, the SNR gain of dynamic 31P MRS at 7 T was invested in temporal and spatial resolution. Using conventional slice selective excitation combined with localization by adiabatic selective refocusing (semi-LASER) with short echo time (TE = 23 ms), phosphocreatine quantification in a 38 mL voxel inside a single exercising muscle becomes possible from single acquisitions, with SNR = 42 ± 4 in resting human medial gastrocnemius. The method was used to quantify the phosphocreatine time course during 5 min of plantar flexion exercise and recovery with a temporal resolution of 6 s (the chosen repetition time for moderate T1 saturation). Quantification of inorganic phosphate and pH required accumulation of consecutively acquired spectra when (resting) Pi concentrations were low. The localization performance was excellent while keeping the chemical shift displacement acceptably small. The SNR and spectral line widths with and without localization were compared between 3T and 7 T systems in phantoms and in vivo. The results demonstrate that increased sensitivity of ultra-high field can be used to dynamically acquire metabolic information from a clearly defined region in a single exercising muscle while reaching a temporal resolution previously available with MRS in non-localizing studies only. The method may improve the interpretation of dynamic muscle MRS data.

  8. A 31P magnetic resonance spectroscopy study of mitochondrial function in skeletal muscle of patients with Parkinson's disease. (United States)

    Taylor, D J; Krige, D; Barnes, P R; Kemp, G J; Carroll, M T; Mann, V M; Cooper, J M; Marsden, C D; Schapira, A H


    The activity of complex I of the respiratory chain is decreased in the substantia nigra of patients with Parkinson's disease (PD) but the presence of this defect in skeletal muscle is controversial. Therefore, the mitochondrial function of skeletal muscle in patients with PD was investigated in vivo using 31P magnetic resonance spectroscopy. Results from 7 PD patients, 11 age matched controls and 9 mitochondrial myopathy patients with proven complex I deficiency were obtained from finger flexor muscle at rest, during exercise and in recovery from exercise. In resting muscle, the patients with mitochondrial myopathy showed a low PCr/ATP ratio, a low phosphorylation potential, a high P(i)/PCr ratio and a high calculated free [ADP]. During exercise, stores of high energy phosphate were depleted more rapidly than normal, while in recovery, the concentration of phosphocreatine and free ADP returned to pre-exercise values more slowly than normal. In contrast, the patients with PD were not significantly different from normal for any of these variables, and no abnormality of muscle energetics was detected. Three of the PD patients also had mitochondrial function assessed biochemically in muscle biopsies. No respiratory chain defect was identified in any of these patients by polarography or enzyme analysis when compared with age-matched controls. These results suggest that skeletal muscle is not a suitable tissue for the investigation and identification of the biochemical basis of the nigral complex I deficiency in PD.

  9. Kinetics of 1H --> 31P NMR cross-polarization in bone apatite and its mineral standards. (United States)

    Kaflak, Agnieszka; Kolodziejski, Waclaw


    Kinetics of NMR cross-polarization (CP) from protons to phosphorus-31 nuclei was studied in the following samples: mineral of whole human bone, apatite prepared from bone, natural brushite, synthetic hydroxyapatite (hydrated and calcined), and synthetic carbonatoapatite of type B with 9 wt% of CO(3) (2-). In order to avoid an effect of magic angle spinning on CP and relaxation, the experiments were carried out on static samples. Parameters of the CP kinetics were discussed for trabecular and cortical bone tissue from adult subjects in comparison to the synthetic mineral standards. It was found that carbonatoapatite shows similar CP behavior to the bone mineral. Both materials undergo two-component CP kinetics. The fast-relaxing classical component is from the surface of apatite crystals and the slow-relaxing nonclassical component comes from the crystal interior. The components have been unambiguously assigned using inverse CP from phosphorus-31 to protons. The study provides information on a structured water layer, which covers crystal surface of carbonato- and bone apatite. The layer encompasses ca 40% of apatite phosphorus and its thickness is more than ca 2 nm.

  10. NMR spectroscopy using liquid crystal solvents

    CERN Document Server

    Emsley, JW


    NMR Spectroscopy using Liquid Crystal Solvents covers the importance of using a liquid crystal solvent in NMR to derive nuclear dipolar spin-spin coupling constants. This book is composed of ten chapters, and begins with a brief description of the features and benefits of liquid crystal in NMR spectroscopic analysis. The succeeding chapters deal with the mode of operation of nuclear spin Hamiltonian for partially oriented molecules and the analysis of NMR spectra of partially oriented molecules, as well as the determination of rigid molecule structure. These topics are followed by discussions

  11. A Guided Inquiry Approach to NMR Spectroscopy (United States)

    Parmentier, Laura E.; Lisensky, George C.; Spencer, Brock


    We present a novel way to introduce NMR spectroscopy into the general chemistry curriculum as part of a week-long aspirin project in our one-semester introductory course. Aspirin is synthesized by reacting salicylic acid and acetic anhydride. Purity is determined by titration and IR and NMR spectroscopy. Students compare IR and NMR spectra of their aspirin product to a series of reference spectra obtained by the class. Students are able to interpret the IR spectra of their aspirin using IR data from previous experiments. NMR is introduced by having students collect 1H NMR spectra of a series of reference compounds chosen to include some of the structural features of aspirin and compare spectra and structures of the reference compounds to develop a correlation chart for chemical shifts. This process is done in small groups using shared class data and is guided by a series of questions designed to relate the different kinds of hydrogen atoms to number and position of peaks in the NMR spectrum. Students then identify the peaks in the NMR spectrum of their aspirin product and relate percent purity by titration with spectral results and percent yield. This is an enjoyable project that combines the synthesis of a familiar material with a guided inquiry-based introduction to NMR spectroscopy.

  12. 31P MR Spectroscopy Imaging of Liver : Initial Clinical Study%31P MR波谱成像在肝脏的初步临床应用研究

    Institute of Scientific and Technical Information of China (English)

    刘于宝; 梁长虹; 张忠林; 余元新; 谢淑飞; 林韩斌; 王秋实; 郑君惠


    目的探讨31P MRS成像技术在肝脏的初步临床应用.方法对5例健康志愿者、5例乙型肝炎肝功能正常病例、5例慢性活动性肝炎肝硬化、5例原发性肝细胞癌病例行常规MR扫描、31P MRS成像.采用GE公司波谱分析软件(spectroscopy analysis GE)校正,并计算细胞内pH值,分析各峰峰值及各比值变化特征.结果正常组5例中4例肝脏31P波谱提供的6种代谢物峰从左至右为:磷酸单脂(PME)、无机磷(Pi)、磷酸二脂(PDE)、三磷酸腺苷(γ-ATP、α-ATP、β- ATP)6种.其中1例出现7种峰,多出一种因受腹壁肌肉影响产生的磷酸肌酸(PCr)峰.轻度肝炎组,PME轻度升高,PDE轻度减低,PME/PDE值较正常组略高.慢活肝-肝硬化组6个共振峰中仅PME明显升高.原发性肝细胞癌病例中,PME均明显增高,细胞内pH值呈碱性.结论 31P MRS对检测肝脏代谢变化具有重要价值.

  13. A Wet-Lab Approach to Stereochemistry Using [superscript 31]P NMR Spectroscopy (United States)

    Fenton, Owen S.; Sculimbrene, Bianca R.


    Understanding stereochemistry is an important and difficult task for students to master in organic chemistry. In both introductory and advanced courses, students are encouraged to explore the spatial relationships between molecules, but this exploration is often limited either to the lecture hall or the confines of the library. As such, we sought…

  14. 31P MAS-NMR study of flux-grown rare-earth element orthophosphate (monazite/xenotime) solid solutions: Evidence of random cation distribution from paramagnetically shifted NMR resonances

    Energy Technology Data Exchange (ETDEWEB)

    Palke, A. C. [Stanford University; Stebbins, J. F. [Stanford University; Boatner, Lynn A [ORNL


    We present 31P magic angle spinning nuclear magnetic resonance (MAS-NMR) spectra of flux-grown solid solutions of La1-xCexPO4 ( x between 0.027 and 0.32) having the monoclinic monazite structure, and of Y1-xMxPO4 (M = Vn+, Ce3+, Nd3+, x between 0.001 and 0.014) having the tetragonal zircon structure. Paramagnetically shifted NMR resonances are observed in all samples due to the presence of paramagnetic Vn+, Ce3+, and Nd3+ in the diamagnetic LaPO4 or YPO4. As a first-order observation, the number and relative intensity of these peaks is related to the symmetry and structure of the diamagnetic host phase. The presence of paramagnetic shifts allows for increased resolution between NMR resonances for distinct atomic species which leads to the observation of low intensity peaks related to PO4 species having more than one paramagnetic neighbor two or four atomic bonds away. Through careful analysis of peak areas and comparison with predictions for simple models, it was determined that solid solutions in the systems examined here are characterized by complete disorder (random distribution) of diamagnetic La3+ or Y3+ with the paramagnetic substitutional species Ce3+ and Nd3+. The increased resolution given by the paramagnetic interactions also leads to the observation of splitting of specific resonances in the 31P NMR spectra that may be caused by local, small-scale distortions from the substitution of ions having dissimilar ionic radii.

  15. Characterizing mixed phosphonic acid ligand capping on CdSe/ZnS quantum dots using ligand exchange and NMR spectroscopy. (United States)

    Davidowski, Stephen K; Lisowski, Carmen E; Yarger, Jeffery L


    The ligand capping of phosphonic acid functionalized CdSe/ZnS core-shell quantum dots (QDs) was investigated with a combination of solution and solid-state (31) P nuclear magnetic resonance (NMR) spectroscopy. Two phosphonic acid ligands were used in the synthesis of the QDs, tetradecylphosphonic acid and ethylphosphonic acid. Both alkyl phosphonic acids showed broad liquid and solid-state (31) P NMR resonances for the bound ligands, indicative of heterogeneous binding to the QD surface. In order to quantify the two ligand populations on the surface, ligand exchange facilitated by phenylphosphonic acid resulted in the displacement of the ethylphosphonic acid and tetradecylphosphonic acid and allowed for quantification of the free ligands using (31) P liquid-state NMR. After washing away the free ligand, two broad resonances were observed in the liquids' (31) P NMR corresponding to the alkyl and aromatic phosphonic acids. The washed samples were analyzed via solid-state (31) P NMR, which confirmed the ligand populations on the surface following the ligand exchange process. Copyright © 2015 John Wiley & Sons, Ltd.

  16. Facilitated transport of Mn2+ in sycamore (Acer pseudoplatanus) cells and excised maize root tips. A comparative 31P n.m.r. study in vivo. (United States)

    Roby, C; Bligny, R; Douce, R; Tu, S I; Pfeffer, P E


    Movement of paramagnetic Mn2+ into sycamore (Acer pseudoplatanus) cells has been indirectly examined by observing the line broadening exhibited in its 31P n.m.r. spectra. Mn2+ was observed to pass into the vacuole, while exhibiting a very minor accumulation in the cytoplasm. With time, gradual leakage of phosphate from the vacuole to the cytoplasm was observed along with an increase in glucose-6-phosphate. Anoxia did not appear to affect the relative distribution of Mn2+ in the cytoplasm and vacuole. Under hypoxic conditions restriction of almost all movement of Mn2+ across the plasmalemma as well as the tonoplast was observed. In contrast, maize root tips showed entry and complete complexation of nucleotide triphosphate by Mn2+ during hypoxia. The rate of passage of Mn2+ across the tonoplast in both sycamore and maize root cells is approximately the same. However, the rates of facilitated movement across the respective plasma membranes appear to differ. More rapid movement of Mn2+ across the plasmalemma in maize root tip cells allows a gradual build-up of metal ion in the cytoplasm prior to its diffusion across the tonoplast. Sycamore cells undergo a slower uptake of Mn2+ into their cytoplasms (comparable with the rate of diffusion through the tonoplast), so little or no observable accumulation of Mn2+ is observed in this compartment.

  17. Insight into the protonation and K(I)-interaction of the inositol 1,2,3-trisphosphate as provided by 31P NMR and theoretical calculations (United States)

    Veiga, Nicolás; Torres, Julia; González, Gabriel; Gómez, Kerman; Mansell, David; Freeman, Sally; Domínguez, Sixto; Kremer, Carlos


    Animal cells contain a pool of inositol phosphates whose biological function is still under current investigation. Ins(1,2,3) P3 is probably an important safe chelator of iron cations not strongly bound to proteins. In order to clarify its biological functions, Ins(1,2,3) P3 chemistry under physiological conditions must be completely elucidated. The protonation and complexation behaviour of Ins(1,2,3) P3 has been recently studied under these conditions by potentiometry. Under simulated physiological conditions it forms the protonated species H 2L 4- and H 3L 3-. The presence of high concentrations of potassium in intracellular compartments causes the formation of two predominant Ins(1,2,3) P3 complexes: [K(HL)] 4- and [K(H 2L)] 3-, in the absence of iron. In this work we expand part of this macroscopic knowledge to the inframolecular level, by 31P NMR measurements and focusing on the protonation and complexation of this biologically relevant molecule to potassium. We complete this study with theoretical calculations which lead us to predict the geometries of every form of the ligand and their relative stabilities. The influence of the ring conformation in protonated and complexed forms is also discussed.

  18. In vivo 31P MRS of human brain at high/ultrahigh fields: a quantitative comparison of NMR detection sensitivity and spectral resolution between 4 T and 7 T. (United States)

    Qiao, Hongyan; Zhang, Xiaoliang; Zhu, Xiao-Hong; Du, Fei; Chen, Wei


    The primary goal of this study was to establish a rigorous approach for determining and comparing the NMR detection sensitivity of in vivo 31P MRS at different field strengths (B0). This was done by calculating the signal-to-noise ratio (SNR) achieved within a unit sampling time at a given field strength. In vivo 31P spectra of human occipital lobe were acquired at 4 and 7 T under similar experimental conditions. They were used to measure the improvement of the human brain 31P MRS when the field strength increases from 4 to 7 T. The relaxation times and line widths of the phosphocreatine (PCr) resonance peak and the RF coil quality factors (Q) were also measured at these two field strengths. Their relative contributions to SNR at a given field strength were analyzed and discussed. The results show that in vivo 31P sensitivity was significantly improved at 7 T as compared with 4 T. Moreover, the line-width of the PCr resonance peak showed less than a linear increase with increased B0, which leads to a significant improvement in 31P spectral resolution. These findings indicate the advantage of high-field strength to improve in vivo 31P MRS quality in both sensitivity and spectral resolution. This advantage should improve the reliability and applicability of in vivo 31P MRS in studying high-energy phosphate metabolism, phospholipid metabolism and cerebral biogenetics in the human at both normal and diseased states noninvasively. Finally, the approach used in this study for calculating in vivo 31P MRS sensitivity provides a general tool in estimating the relative NMR detection sensitivity for any nuclear spin at a given field strength.

  19. {sup 31}P magnetic resonance spectroscopy to measure in vivo cardiac energetics in normal myocardium and hypertrophic cardiomyopathy: Experiences at 3 T

    Energy Technology Data Exchange (ETDEWEB)

    Shivu, Ganesh Nallur [Department of Cardiovascular Medicine, University of Birmingham, Vincent Drive, Edgbaston, Birmingham B15 2TT (United Kingdom)], E-mail:; Abozguia, Khalid; Phan, Thanh Trung; Ahmed, Ibrar [Department of Cardiovascular Medicine, University of Birmingham, Vincent Drive, Edgbaston, Birmingham B15 2TT (United Kingdom); Henning, Anke [Institute for Biomedical Engineering, University and ETH Zurich, Gloriastrasse 35, CH-8092, Zurich CH ETZ F97 (Switzerland); Frenneaux, Michael [Department of Cardiovascular Medicine, University of Birmingham, Vincent Drive, Edgbaston, Birmingham B15 2TT (United Kingdom)


    Background: {sup 31}P magnetic resonance spectroscopy (MRS) allows measurement of in vivo high-energy phosphate kinetics in the myocardium. While traditionally {sup 31}P cardiac spectroscopy is performed at 1.5 T, cardiac MRS at higher field strength can theoretically increase signal to noise ratio (SNR) and spectral resolution therefore improving sensitivity and specificity of the cardiac spectra. The reproducibility and feasibility of performing cardiac spectroscopy at 3 T is presented here in this study in healthy volunteers and patients with hypertrophic cardiomyopathy. Methods: Cardiac spectroscopy was performed using a Phillips 3T Achieva scanner in 37 healthy volunteers and 26 patients with hypertrophic cardiomyopathy (HCM) to test the feasibility of the protocol. To test the reproducibility a single volunteer was scanned eight times on separate occasions. A single voxel {sup 31}P MRS was performed using Image Selected In vivo Spectroscopy (ISIS) volume localization. Results: The mean phosphocreatine/adenosine triphosphate (PCr/ATP) ratio of the eight measurements performed on one individual was 2.11 {+-} 0.25. Bland Altman plots showed a variance of 12% in the measurement of PCr/ATP ratios. The PCr/ATP ratio was significantly reduced in HCM patients compared to controls, 1.42 {+-} 0.51 and 2.11 {+-} 0.57, respectively, P < 0.0001. (All results are expressed as mean {+-} standard deviation). Conclusions: Here we demonstrate that cardiac {sup 31}P MRS at 3 T is a reliable method of measuring in vivo high-energy phosphate kinetics in the myocardium for clinical studies and diagnostics. Based on our data an impairment of cardiac energetic state in patients with hypertrophic cardiomyopathy is indisputable.

  20. Cumulative "roof effect" in high-resolution in vivo 31P NMR spectra of human calf muscle and the Clebsch-Gordan coefficients of ATP at 1.5 T. (United States)

    Schröder, Leif; Schmitz, Christian; Bachert, Peter


    NMR spectra of non-weakly coupled spin systems exhibit asymmetries in line intensities known as "roof effect" in 1D spectroscopy. Due to limited spectral resolution, this effect has not been paid much attention so far in in vivo spectroscopy. But when high-quality spectra are obtained, this effect should be taken into account to explain the quantum-mechanical fine structure of the system. Adenosine 5'-triphosphate (ATP) represents a 31P spin system with multiple line splittings which are caused by J-couplings of medium strength at 1.5 T. We analyzed the ATP roof effect in vivo, especially for the beta-ATP multiplet. The intensities of its outer resonances deviate by ca. 12.5% from a symmetrical triplet. As this asymmetry reflects the transition from Paschen-Back to Zeeman effect with total spin that is largely broken up, the Clebsch-Gordan coefficients of the system can be indicated in analogy to the hyperfine structure of hydrogen. Taking the roof effect into account, the chi2 of fitting in vivo ATP resonances is reduced by ca. 9% (p<0.005).

  1. Cumulative “roof effect” in high-resolution in vivo 31P NMR spectra of human calf muscle and the Clebsch Gordan coefficients of ATP at 1.5 T (United States)

    Schröder, Leif; Schmitz, Christian; Bachert, Peter


    NMR spectra of non-weakly coupled spin systems exhibit asymmetries in line intensities known as "roof effect" in 1D spectroscopy. Due to limited spectral resolution, this effect has not been paid much attention so far in in vivo spectroscopy. But when high-quality spectra are obtained, this effect should be taken into account to explain the quantum-mechanical fine structure of the system. Adenosine 5'-triphosphate (ATP) represents a 31P spin system with multiple line splittings which are caused by J-couplings of medium strength at 1.5 T. We analyzed the ATP roof effect in vivo, especially for the β-ATP multiplet. The intensities of its outer resonances deviate by ca. 12.5% from a symmetrical triplet. As this asymmetry reflects the transition from Paschen-Back to Zeeman effect with total spin that is largely broken up, the Clebsch-Gordan coefficients of the system can be indicated in analogy to the hyperfine structure of hydrogen. Taking the roof effect into account, the χ2 of fitting in vivo ATP resonances is reduced by ca. 9% ( p < 0.005).

  2. 31P nuclear magnetic resonance in vivo spectroscopy of the metabolic changes induced in the awake rat brain during KCN intoxication and its reversal by hydroxocobalamine. (United States)

    Benabid, A L; Decorps, M; Remy, C; Le Bas, J F; Confort, S; Leviel, J L


    Radiofrequency surface coils were chronically implanted in rats, which were subsequently subjected to 31P nuclear magnetic resonance (NMR) investigations at 4.7 T. The implanted coil allowed study of the animals without need for anesthesia, which is a prerequisite for studies of normal brain metabolism. The animals may be kept in the NMR probe for several hours. During subsequent experiments, they may be placed in the same position, therefore allowing follow-up studies for periods as long as 2 months. This method has been used in the study of sublethal KCN intoxication. KCN, a cytochrome c oxidase inhibitor, induces a blockade of cell respiratory processes, which is reflected, in a dose-dependent manner, by a decrease in phosphocreatine content and pH and an increase in inorganic phosphate content, whereas ATP levels remain constant until high doses of KCN (6 mg/kg i.p.) are reached. 31P NMR allows the time course of these metabolic changes to be followed. For high KCN doses, a new peak, termed X, is observed, which is interpreted as being due to a pool of inorganic phosphate at very low pH (5.65), corresponding to a subset of cells that did not survive KCN injury. Hydroxocobalamine, a specific antidote of KCN, suppresses the metabolic changes due to 6 mg/kg of KCN.

  3. Medical applications of NMR imaging and NMR spectroscopy with stable isotopes. Summary

    Energy Technology Data Exchange (ETDEWEB)

    Matwiyoff, N.A.


    The current status of NMR imaging and NMR spectroscopy are summarized. For the most part examples from the March 1983 Puerto Rico symposium are used to illustrate the utility of NMR in medicine. 18 refs., 5 figs.

  4. 31P magic angle spinning NMR study of flux-grown rare-earth element orthophosphate (monazite/xenotime) solid solutions: evidence of random cation distribution from paramagnetically shifted NMR resonances. (United States)

    Palke, Aaron C; Stebbins, Jonathan F; Boatner, Lynn A


    We present (31)P magic angle spinning nuclear magnetic resonance spectra of flux-grown solid solutions of La(1-x)Ce(x)PO4 (x between 0.027 and 0.32) having the monoclinic monazite structure, and of Y(1-x)M(x)PO4 (M = V(n+), Ce(3+), Nd(3+), x between 0.001 and 0.014) having the tetragonal zircon structure. Paramagnetically shifted NMR resonances are observed in all samples due to the presence of paramagnetic V(n+), Ce(3+), and Nd(3+) in the diamagnetic LaPO4 or YPO4. As a first-order observation, the number and relative intensities of these peaks are related to the symmetry and structure of the diamagnetic host phase. The presence of paramagnetic shifts allows for increased resolution between NMR resonances for distinct atomic species which leads to the observation of low intensity peaks related to PO4 species having more than one paramagnetic neighbor two or four atomic bonds away. Through careful analysis of peak areas and comparison with predictions for simple models, it was determined that solid solutions in the systems examined here are characterized by complete disorder (random distribution) of diamagnetic La(3+) or Y(3+) with the paramagnetic substitutional species Ce(3+) and Nd(3+). The increased resolution given by the paramagnetic interactions also leads to the observation of splitting of specific resonances in the (31)P NMR spectra that may be caused by local, small-scale distortions from the substitution of ions having dissimilar ionic radii.

  5. {sup 31}P MR spectroscopy to evaluate the efficacy of hepatic artery embolizatio in the treatment of neuroendocrine liver metastases

    Energy Technology Data Exchange (ETDEWEB)

    Ljungberg, Maria; Vikhoff-Baaz, Barbro; Starck, Goeran; Forssell-Aronsson, Eva [Department of Radiation Physics, Institute of Clinical Sciences, The Sahlgrenska Academy at the University of Gothenburg, Gothenburg (Sweden); Department of Medical Physics and Biomedical Engineering, MR Centre, Sahlgrenska University Hospital, Gothenburg (Sweden)], E-mail:; Westberg, Gunnel; Waengberg, Bo; Ahlman, Haakan [Department of Surgery, Institute of Clinical Sciences, The Sahlgrenska Academy at University of Gothenburg, Gothenburg (Sweden); Ekholm, Sven [Department of Radiology, Institute of Clinical Sciences, The Sahlgrenska Academy at University of Gothenburg, Gothenburg, Sweden (Sweden)


    Background. It is common to treat patients with metastatic disease from gastrointestinal neuroendocrine (NE) tumors with surgical reduction to prolong survival. This can be combined with hepatic arterial embolization (HAE) and medical treatment to reduce hormonal symptoms. Today there are no rapid and reliable methods to evaluate the efficacy of HAE in the treatment of neuroendocrine liver metastasis. Purpose. To investigate metabolic changes in hepatic metastases of NE tumors following HAE, and to establish if there are any early spectral patterns that might indicate therapeutic efficacy based on in vivo {sup 31}P MRS data. Material and Methods. Volume selective {sup 31}P MRS was used to study 11 patients with disseminated NE tumors with regional lymph nodes and bilobar liver metastases. Measurements were performed before and 1 and 3 days after HAE. Results. Non-responders had significantly higher PME/Pi and {alpha}NTP/{Sigma}NTP ratios than the responders before HAE (P < 0.05). Three days after HAE, non-responders still had significantly higher {alpha}NTP/{Sigma}NTP than the responders did (P < 0.05). We also observed trends for increased PME ratios 3 days after HAE, decreased ATP-levels, and liberated Pi in responders. Conclusion. This {sup 31}P-MRS study showed significant differences in PME/Pi and {alpha}NTP/{Sigma}P ratios between responders and non-responders on the day before HAE, which is an interesting finding that may reflect intrinsic properties of the tumor tissue. We also observed trends for cell membrane renewal and increased energy consumption in responders after HAE. These results demonstrate potentials for {sup 31}P-MRS to predict individual responsiveness prior to HAE.

  6. Quantitative ATP synthesis in human liver measured by localized 31P spectroscopy using the magnetization transfer experiment. (United States)

    Schmid, A I; Chmelík, M; Szendroedi, J; Krssák, M; Brehm, A; Moser, E; Roden, M


    The liver plays a central role in intermediate metabolism. Accumulation of liver fat (steatosis) predisposes to various liver diseases. Steatosis and abnormal muscle energy metabolism are found in insulin-resistant and type-2 diabetic states. To examine hepatic energy metabolism, we measured hepatocellular lipid content, using proton MRS, and rates of hepatic ATP synthesis in vivo, using the 31P magnetization transfer experiment. A suitable localization scheme was developed and applied to the measurements of longitudinal relaxation times (T1) in six healthy volunteers and the ATP-synthesis experiment in nine healthy volunteers. Liver 31P spectra were modelled and quantified successfully using a time domain fit and the AMARES (advanced method for accurate, robust and efficient spectral fitting of MRS data with use of prior knowledge) algorithm describing the essential components of the dataset. The measured T1 relaxation times are comparable to values reported previously at lower field strengths. All nine subjects in whom saturation transfer was measured had low hepatocellular lipid content (1.5 +/- 0.2% MR signal; mean +/- SEM). The exchange rate constant (k) obtained was 0.30 +/- 0.02 s(-1), and the rate of ATP synthesis was 29.5 +/- 1.8 mM/min. The measured rate of ATP synthesis is about three times higher than in human skeletal muscle and human visual cortex, but only about half of that measured in perfused rat liver. In conclusion, 31P MRS at 3 T provides sufficient sensitivity to detect magnetization transfer effects and can therefore be used to assess ATP synthesis in human liver.

  7. Localized Semi-LASER Dynamic 31P Magnetic Resonance Spectroscopy of the Soleus During and Following Exercise at 7 T

    CERN Document Server

    Fiedler, Georg B; Schmid, Albrecht I; Goluch, Sigrun; Schewzow, Kiril; Laistler, Elmar; Mirzahosseini, Arash; Niess, Fabian; Unger, Ewald; Wolzt, Michael; Moser, Ewald


    Object This study demonstrates the applicability of semi-LASER localized dynamic $^{31}$P MRS to deeper lying areas of the exercising human soleus muscle (SOL). The effect of accurate localization and high temporal resolution on data specificity is investigated. Materials and Methods To achieve high signal-to-noise ratio (SNR) at a temporal resolution of 6 s, a custom-built calf coil array was used at 7T. The kinetics of phosphocreatine (PCr) and intracellular pH were quantified separately in SOL and gastrocnemius medialis (GM) muscle of 9 volunteers, during rest, plantar flexion exercise and recovery. Results The average SNR of PCr at rest was 64$\\pm$15 in SOL (83$\\pm$12 in GM). End exercise PCr depletion in SOL (19$\\pm$9%) was far lower than in GM (74$\\pm$14%). pH in SOL increased rapidly and, in contrast to GM, remained elevated until the end of exercise. Conclusion $^{31}$P MRS in single-shots every 6 s localized in the deeper lying SOL enabled quantification of PCr recovery times at low depletions and of...

  8. Probing the interaction of U(vi) with phosphonate-functionalized mesoporous silica using solid-state NMR spectroscopy. (United States)

    Uribe, Eva C; Mason, Harris E; Shusterman, Jennifer A; Bruchet, Anthony; Nitsche, Heino


    The fundamental interaction of U(vi) with diethylphosphatoethyl triethoxysilane functionalized SBA-15 mesoporous silica is studied by macroscopic batch experiments and solid-state NMR spectroscopy. DPTS-functionalized silica has been shown to extract U(vi) from nitric acid solutions at or above pH 3. Extraction is dependent on pH and ionic strength. Single-pulse (31)P NMR on U(vi) contacted samples revealed that U(vi) only interacts with a fraction of the ligands present on the surface. At pH 4 the U(vi) extraction capacity of the material is limited to 27-37% of the theoretical capacity, based on ligand loading. We combined single pulse (31)P NMR on U(vi)-contacted samples with batch studies to measure a ligand-to-metal ratio of approximately 2 : 1 at pH 3 and 4. Batch studies and cross-polarization NMR measurements reveal that U(vi) binds to deprotonated phosphonate and/or silanol sites. We use (31)P-(31)P DQ-DRENAR NMR studies to compare the average dipolar coupling between phosphorus spins for both U(vi)-complexed and non-complexed ligand environments. These measurements reveal that U(vi) extraction is not limited by inadequate surface distribution of ligands, but rather by low stability of the surface phosphonate complex.

  9. Effect of prior exercise in Pi/PC ratio and intracellular pH during a standardized exercise. A study on human muscle using [31P]NMR. (United States)

    Laurent, D; Authier, B; Lebas, J F; Rossi, A


    Seven subjects underwent a standard localized exercise of calf muscles in order to investigate whether the metabolic exercise-induced steady-state, as revealed by the evaluation of inorganic phosphate/phosphocreatine ratio, depends on the conditioning of the muscle just prior to the exercise. The experimental protocols consisted of two separate experiments using first [31P]nuclear magnetic resonance spectroscopy and second (on 3 subjects) infrared oxyphotometry to respectively follow variation of energy metabolism and tissular deoxygenation. The exercise consisted of 240 successive plantar flexions (0.5 Hz frequency) against a high load equivalent to 80% of the maximal voluntary contraction. This exercise was accomplished before cold exercise and after warm exercise, a warming-up period bringing to approximately 50% of VO2max. The results showed that: (1) steady-state level of phosphate/phosphocreatine and intracellular acidosis was significantly lowered by warming-up; (2) cold and warm exercise steady-state of calculated adenosine diphosphate values were not significantly different; (3) cold exercise rapidly induced a high tissular deoxygenation that is not observed during warm exercise; and (4) time-constant of phosphocreatine resynthesis is lowered after warm exercise but the initial slope of time-evolution is not modified. Parallel experiments also showed that phosphate/phosphocreatine steady-state was not modified in comparison with warm exercise when the same power of exercise was reached by stepwise incrementation of the charge. From these results we postulate that a better tissue oxygenation due to a global or localized warming-up allows to reach the same mechanical performance with a lower decrease of PCr content, owing to a faster adjustment of oxidative metabolism during the transitional period.(ABSTRACT TRUNCATED AT 250 WORDS)

  10. HPLC and 31P NMR characterization of the reaction between antitumor platinum agents and the phosphorothioate chemoprotective agent S-2-(3-aminopropylamino)ethylphosphorothioic acid (WR-2721). (United States)

    Thompson, D C; Wyrick, S D; Holbrook, D J; Chaney, S G


    In prior studies, we examined the effects of the radioprotective and chemoprotective agent WR-2721 [S-2-(3-aminopropylamino)ethylphosphorothioic acid] on the in vivo biotransformation of the cisplatin [cis-diamminedichloroplatinum(II)] analog ormaplatin [(d,I)trans-1,2-diaminocyclohexanetetrachloroplatinum(IV), Pt(dach)Cl4, (formerly called tetraplatin)]. Those data suggested that a direct interaction between WR-2721 and ormaplatin and/or the corresponding Pt(II) drug, Pt(dach)Cl2, may be occurring in vivo. This would be in contrast to the generally accepted hypothesis that WR-2721 is a prodrug that must first be converted by alkaline phosphatase to a free thiol compound, WR-1065, before any appreciable reactivity would be evident. However, the major biotransformation product observed in the peritoneal fluid, plasma, and all tissues was Pt(dach)(WR-1065). We report here on further investigations into the in vitro reactivity of Pt(dach) compounds with WR-2721 and WR-1065. Separation of reaction products resulting from incubation of Pt(dach)(malonato) with either WR-2721 or WR-1065 under physiological conditions gave profiles that were indistinguishable by reverse phase HPLC and cation exchange HPLC at two different pHs. 31P NMR characterization of the dephosphorylation of WR-2721 revealed essentially no loss of inorganic phosphate for up to 24 hr when incubated in unbuffered water at 30 degrees. In contrast, when incubated with a 1:1 molar ratio of cisplatin under the same conditions, the WR-2721 signal was decreased markedly in the first 5 min, and had disappeared almost completely by 1 hr. The signal corresponding to inorganic phosphate increased in parallel to the decrease in the WR-2721 signal. No intermediate formation of a complex containing both platinum and phosphate could be detected at any time. These data suggest that the reaction between WR-2721 and platinum complexes results in rapid dephosphorylation of WR-2721, and, consequently, that the reaction

  11. Value of dynamic 31p magnetic resonance spectroscopy technique in in vivo assessment of the skeletal muscle mitochondrial function in type 2 diabetes

    Institute of Scientific and Technical Information of China (English)

    WU Fei-yun; TU Hui-juan; QIN Bin; CHEN Ting; XU Hua-feng; QI Jing; WANG De-hang


    Background Phosphorous magnetic resonance spectroscopy (31p-MRS) has been successfully applied to study intracellular membrane compounds and high-energy phosphate metabolism.This study aimed to evaluate the capability of dynamic 31p-MRS for assessing energy metabolism and mitochondrial function in skeletal muscle from type 2 diabetic patients.Methods Dynamic 31p-MRS was performed on 22 patients with type 2 diabetes and 26 healthy volunteers.Spectra were acquired from quadriceps muscle while subjects were in a state of rest,at exercise and during recovery.The peak areas of inorganic phosphate (Pi),phosphocreatine (PCr),and adenosine triphosphate (ATP) were measured.The concentration of adenosine diphosphate (ADP) and the intracellular pH value were calculated from the biochemistry reaction equilibrium.The time constant and recovery rates of Pi,PCr,and ADP were analyzed using exponential curve fitting.Results As compared to healthy controls,type 2 diabetes patients had significantly lower skeletal muscle concentrations of Pi,PCr and β-ATP,and higher levels of ADP and Pi/PCr.During exercise,diabetics experienced a significant Pi peak increase and PCr peak decrease,and once the exercise was completed both Pi and PCr peaks returned to resting levels.Quantitatively,the mean recovery rates of Pi and PCr in diabetes patients were (10.74±1.26) mmol/s and (4.74±2.36) mmol/s,respectively,which was significantly higher than in controls.Conclusions Non-invasive quantitative 31P-MRS is able to detect energy metabolism inefficiency and mitochondrial function impairment in skeletal muscle of type 2 diabetics.

  12. Analysis of 3.0T 31P-MR spectroscopy:gastrocnemius of healthy adults in the resting state%静息状态健康成人腓肠肌3.0T31P-MRS分析

    Institute of Scientific and Technical Information of China (English)

    朱凯; 由长城; 张晓凡; 曾立红; 刘鹏飞


    目的 应用3.0T 31P-MRS对不同年龄组左腓肠肌磷代谢物定量分析,评估其磷代谢物特点,并为腓肠肌31P-MRS检查参数优化提供依据.方法 32例健康志愿者,在静息状态下进行31P-MRS单体素扫描,分别显示7个代谢产物波峰,同时计算pH值、PME/β-ATP、PCr/PME、β-ATP/Pi、PME/Pi、PDE/β-ATP相对定量分析.结果 健康成人静息状态下显示7个代谢物.PME、PCr、Pi、总ATP、PCr/PME、PME/Pi青年组和与老年组有统计学差异.中老年组PME、PME/β-ATP、β-ATP/Pi、PME/Pi、PDE/β-ATP男性与女性有统计学差异.结论 3.0T 31P-MRS可无创量化健康成人不同年龄、各组不同性别静息状态腓肠肌磷代谢产物.%Objective To evaluate different age groups of phosphatides metabolism features using 3. OT 31P-MRS, so that to provide the basis for optimization of 31P-MRS examinating gastrocnemius. Methods Single factor 31P-MRS was carried out at the resting state in 32 healthy volunteers, 7 metabolites peaks of gastrocnemius, including pH, PME/13-ATP, PCr/PME,|3-ATP/Pi, PME/Pi and PDE/|3-ATP were showed to implement the relative quantitative analysis. Results MRS showed that the PME, PCr, Pi, total ATP,PCr/PME,PME/Pi in the healthy resting state were significantly different between youth group and the old group. PME, PME/(3-ATP,(3-ATP/Pi, PME/Pi and PDE/(3-ATP were significantly different between men and women in the elderly group. Conclusion 3. OT 31 P-MRS can noninvasively quantify the resting gastrocnemius phosphorus metabolites in healthy adults in different ages and different genders.

  13. Early Detection of Myocardial Bioenergetic Deficits: A 9.4 Tesla Complete Non Invasive 31P MR Spectroscopy Study in Mice with Muscular Dystrophy.

    Directory of Open Access Journals (Sweden)

    Weina Cui

    Full Text Available Duchenne muscular dystrophy (DMD is the most common fatal form of muscular dystrophy characterized by striated muscle wasting and dysfunction. Patients with DMD have a very high incidence of heart failure, which is increasingly the cause of death in DMD patients. We hypothesize that in the in vivo system, the dystrophic cardiac muscle displays bioenergetic deficits prior to any functional or structural deficits. To address this we developed a complete non invasive 31P magnetic resonance spectroscopy (31P MRS approach to measure myocardial bioenergetics in the heart in vivo.Six control and nine mdx mice at 5 months of age were used for the study. A standard 3D -Image Selected In vivo Spectroscopy (3D-ISIS sequence was used to provide complete gradient controlled three-dimensional localization for heart 31P MRS. These studies demonstrated dystrophic hearts have a significant reduction in PCr/ATP ratio compare to normal (1.59±0.13 vs 2.37±0.25, p<0.05.Our present study provides the direct evidence of significant cardiac bioenergetic deficits in the in vivo dystrophic mouse. These data suggest that energetic defects precede the development of significant hemodynamic or structural changes. The methods provide a clinically relevant approach to use myocardial energetics as an early marker of disease in the dystrophic heart. The new method in detecting the in vivo bioenergetics abnormality as an early non-invasive marker of emerging dystrophic cardiomyopathy is critical in management of patients with DMD, and optimized therapies aimed at slowing or reversing the cardiomyopathy.

  14. On an accidental degeneracy in the {sup 31}P{l_brace}{sup 1}H{r_brace} NMR chemical shifts in ruthenium diphosphine complexes; Sobre uma degenerescencia acidental nos deslocamentos quimicos de RMN {sup 31}P{l_brace}{sup 1}H{r_brace} em complexos difosfinicos de rutenio

    Energy Technology Data Exchange (ETDEWEB)

    Valle, Eliana Maira Agostini; Nascimento, Fabio Batista do; Ferreira, Antonio Gilberto; Batista, Alzir A. [Universidade Federal de Sao Carlos (UFSCar), SP (Brazil). Dept. de Quimica]. E-mail:; Monteiro, Marcos Claudio Rodrigues; Machado, Sergio de Paula [Universidade Federal do Rio de Janeiro (UFRJ), Rio de Janeiro, RJ (Brazil). Inst. de Quimica. Dept. de Quimica Inorganica; Ellena, Javier; Castellano, Eduardo E.; Azevedo, Eduardo Ribeiro de [Universidade de Sao Paulo (USP), Sao Carlos, SP (Brazil). Inst. de Fisica


    The [RuCl(bipy)(dppb)(4-pic)]PF{sub 6} complex was prepared and fully characterized. The X-ray crystal structure of this complex was determined in order to make an unambiguous distinction between the two possible positions of the 4-methylpyridine ligand (4-pic) in the compound: trans to phosphorus atom or trans to nitrogen atom. The [RuCl(bipy)(dppb)(4-pic)]PF{sub 6} complex exhibits an unusual temperature-dependent accidental degeneracy of the {sup 31}P chemical shifts in its solution NMR spectrum. (author)

  15. Comparison of the clinical state and its changes in patients with Duchenne and Becker muscular dystrophy with results of in vivo {sup 31}P magnetic resonance spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Hajek, M. [MR Unit, Inst. for Clinical and Experimental Medicine, Prague (Czech Republic); Grosmanova, A. [Dept. of Neuropediatrics, Thomayer`s Hospital, Prague (Czech Republic); Horska, A. [MR Unit, Inst. for Clinical and Experimental Medicine, Prague (Czech Republic); Urban, P. [Dept. of Analytical Chemistry, Prague Inst. of Chemical Technology (Czech Republic)


    A total of 14 boys with the Duchenne and Becker forms of muscular dystrophy (DMD, BMD) were examined using {sup 31}P magnetic resonance (MR) spectroscopy; 12 boys were examined repeatedly. The results were correlated with clinical findings (including those of genetic tests) and with data obtained from examinations of an age-matched control group. Evaluation of results using principal component analysis revealed maximum variability in the following ratios: phosphocreatine/inorganic phosphate (PCr/Pi), phosphocreatine/phosphodiesters (PCr/PDe) and phosphocreatine/phosphomonoesters (PCr/PMe). A decrease in PCr/Pi correlates with weakness of the hip girdle and of the lower part of the shoulder girdle in DMD/BMD patients. The values of all ratios in the group of patients with the DMD phenotype differ significantly from results obtained in the group with the BMD phenotype. Continuous follow-up of patients using {sup 31}P MR spectroscopy revealed a marked decrease in PCr/Pi in DMD/BMD patients at an age that could be expected in subjects with a typical clinical course of DMD/BMD. An attempt to manage a concomitant disease with prednisone and carnitene was followed by an increase in PCr/Pi in 3 cases. A rise in the PCr/Pi ratio signalled clinical improvement in the patients. A decrease in PCr/Pi was found after controlled physical training, a finding consistent with data obtained from clinical observations describing an adverse effect of physical stress on the dystrophic process. (orig.)

  16. Separation of advanced from mild fibrosis in diffuse liver disease using {sup 31}P magnetic resonance spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Noren, Bengt [Department of Radiology, Linkoeping University, SE-581 85 Linkoeping (Sweden); Dahlqvist, Olof [Department of Radiation Physics, Linkoeping University, SE-581 85 Linkoeping (Sweden); Center for Medical Image Science and Visualization (CMIV), Linkoeping University, SE-581 85 Linkoeping (Sweden); Lundberg, Peter [Department of Radiology, Linkoeping University, SE-581 85 Linkoeping (Sweden); Department of Radiation Physics, Linkoeping University, SE-581 85 Linkoeping (Sweden); Center for Medical Image Science and Visualization (CMIV), Linkoeping University, SE-581 85 Linkoeping (Sweden)], E-mail:; Almer, Sven [Department of Gastroenterology and Hepatology, Linkoeping University, SE-581 85 Linkoeping (Sweden); Kechagias, Stergios [Department of Internal Medicine, Linkoeping University, SE-581 85 Linkoeping (Sweden); Ekstedt, Mattias [Department of Gastroenterology and Hepatology, Linkoeping University, SE-581 85 Linkoeping (Sweden); Franzen, Lennart [Medilab, SE-183 53 Taeby Sweden (Sweden); Wirell, Staffan [Department of Radiology, Linkoeping University, SE-581 85 Linkoeping (Sweden); Smedby, Orjan [Department of Radiology, Linkoeping University, SE-581 85 Linkoeping (Sweden); Center for Medical Image Science and Visualization (CMIV), Linkoeping University, SE-581 85 Linkoeping (Sweden)


    {sup 31}P-MRS using DRESS was used to compare absolute liver metabolite concentrations (PME, Pi, PDE, {gamma}ATP, {alpha}ATP, {beta}ATP) in two distinct groups of patients with chronic diffuse liver disorders, one group with steatosis (NAFLD) and none to moderate inflammation (n = 13), and one group with severe fibrosis or cirrhosis (n = 16). All patients underwent liver biopsy and extensive biochemical evaluation. A control group (n = 13) was also included. Absolute concentrations and the anabolic charge, AC = {l_brace}PME{r_brace}/({l_brace}PME{r_brace} + {l_brace}PDE{r_brace}), were calculated. Comparing the control and cirrhosis groups, lower concentrations of PDE (p = 0.025) and a higher AC (p < 0.001) were found in the cirrhosis group. Also compared to the NAFLD group, the cirrhosis group had lower concentrations of PDE (p = 0.01) and a higher AC (p = 0.009). No significant differences were found between the control and NAFLD group. When the MRS findings were related to the fibrosis stage obtained at biopsy, there were significant differences in PDE between stage F0-1 and stage F4 and in AC between stage F0-1 and stage F2-3. Using a PDE concentration of 10.5 mM as a cut-off value to discriminate between mild, F0-2, and advanced, F3-4, fibrosis the sensitivity and specificity were 81% and 69%, respectively. An AC cut-off value of 0.27 showed a sensitivity of 93% and a specificity of 54%. In conclusion, the results suggest that PDE is a marker of liver fibrosis, and that AC is a potentially clinically useful parameter in discriminating mild fibrosis from advanced.

  17. Interaction Study of an Amorphous Solid Dispersion of Cyclosporin A in Poly-Alpha-Cyclodextrin with Model Membranes by 1H-, 2H-, 31P-NMR and Electron Spin Resonance

    Directory of Open Access Journals (Sweden)

    Jean-Claude Debouzy


    Full Text Available The properties of an amorphous solid dispersion of cyclosporine A (ASD prepared with the copolymer alpha cyclodextrin (POLYA and cyclosporine A (CYSP were investigated by 1H-NMR in solution and its membrane interactions were studied by 1H-NMR in small unilamellar vesicles and by 31P 2H NMR in phospholipidic dispersions of DMPC (dimyristoylphosphatidylcholine in comparison with those of POLYA and CYSP alone. 1H-NMR chemical shift variations showed that CYSP really interacts with POLYA, with possible adduct formation, dispersion in the solid matrix of the POLYA, and also complex formation. A coarse approach to the latter mechanism was tested using the continuous variations method, indicating an apparent 1 : 1 stoichiometry. Calculations gave an apparent association constant of log Ka = 4.5. A study of the interactions with phospholipidic dispersions of DMPC showed that only limited interactions occurred at the polar head group level (31P. Conversely, by comparison with the expected chain rigidification induced by CYSP, POLYA induced an increase in the fluidity of the layer while ASD formation led to these effects almost being overcome at 298 K. At higher temperature, while the effect of CYSP seems to vanish, a resulting global increase in chain fluidity was found in the presence of ASD.

  18. Neither moderate hypoxia nor mild hypoglycaemia alone causes any significant increase in cerebral [Ca2+]i: only a combination of the two insults has this effect. A 31P and 19F NMR study. (United States)

    Badar-Goffer, R S; Thatcher, N M; Morris, P G; Bachelard, H S


    (1) The energy state and free intracellular calcium concentration ([Ca2+]i) of superfused cortical slices were measured in moderate hypoxia (approximately 65 microM O2), in mild hypoglycaemia (0.5 mM glucose), and in combinations of the two insults using 19F and 31P NMR spectroscopy. (2) Neither hypoxia nor hypoglycaemia alone caused any significant change in [Ca2+]i. Hypoxia caused a 40% fall in phosphocreatine (PCr) content but not in ATP level, and hypoglycaemia produced a slight fall in both (as expected from previous studies). These changes in the energy state recovered on return to control conditions. (3) A combined sequential insult (hypoxia, followed by hypoxia plus hypoglycaemia) produced a 100% increase in [Ca2+]i and a decrease in PCr level to approximately 25% of control. The reverse combined sequential insult (hypoglycaemia, followed by hypoglycaemia plus hypoxia) had the same effect. On return to control conditions there was some decrease in [Ca2+]i and a small increase in PCr content, but neither recovered to control levels. (4) Exposure of the tissue to the combined simultaneous insult (hypoxia plus hypoglycaemia) immediately after the control spectra had been recorded resulted in a fivefold increase in [Ca2+]i and a similar decrease in PCr level to 20-25% of control. There was little if any change of [Ca2+]i or PCr level on return to control conditions. (5) These results are discussed in terms of metabolic adaptation of some but not all of the cortical cells to the single type of insult, which renders the tissues less vulnerable to the combined insult.

  19. Reduced rate of adenosine triphosphate synthesis by in vivo 31P nuclear magnetic resonance spectroscopy and downregulation of PGC-1beta in distal skeletal muscle following burn. (United States)

    Tzika, A Aria; Mintzopoulos, Dionyssios; Padfield, Katie; Wilhelmy, Julie; Mindrinos, Michael N; Yu, Hongue; Cao, Haihui; Zhang, Qunhao; Astrakas, Loukas G; Zhang, Jiangwen; Yu, Yong-Ming; Rahme, Laurence G; Tompkins, Ronald G


    Using a mouse model of burn trauma, we tested the hypothesis that severe burn trauma corresponding to 30% of total body surface area (TBSA) causes reduction in adenosine triphosphate (ATP) synthesis in distal skeletal muscle. We employed in vivo 31P nuclear magnetic resonance (NMR) in intact mice to assess the rate of ATP synthesis, and characterized the concomitant gene expression patterns in skeletal muscle in burned (30% TBSA) versus control mice. Our NMR results showed a significantly reduced rate of ATP synthesis and were complemented by genomic results showing downregulation of the ATP synthase mitochondrial F1 F0 complex and PGC-1beta gene expression. Our findings suggest that inflammation and muscle atrophy in burns are due to a reduced ATP synthesis rate that may be regulated upstream by PGC-1beta. These findings implicate mitochondrial dysfunction in distal skeletal muscle following burn injury. That PGC-1beta is a highly inducible factor in most tissues and responds to common calcium and cyclic adenosine monophosphate (cAMP) signaling pathways strongly suggests that it may be possible to develop drugs that can induce PGC-1beta.

  20. Bioenergy recovery phenomenon in the myocardium following ischemia and factors contributing to the recovery studied by /sup 31/P magnetic resonance spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Yoshiyama, Minoru


    Metabolism in ischemic and post-ischemic myocardium was studied by the use of /sup 31/P magnetic resonance spectroscopy (/sup 31/P-MRS) to identify factors that cause recovery of ATP levels in post-ischemic hearts. Perfused guinea-pig hearts were treated to 30 or 60 min of ischemia and reperfused by one of three perfusates, one with 200 adenosine (ADO30 for 30 min ischemia), one with 200 inosine (INO30 for 30 min ischemia, and INO60 for 60 min ischemia), and the third without adenine uncleoside. After 4 hours of reperfusion, ATP levels in INO30 were 95.5% of preischemic level, and in ADO30, 113.5% at 4 hours. However, ATP levels in the control increased only up to 70.2%. ATP levels in INO60 improved to 73.4% after 4 hours and then became stable. Left ventricular maximal positive dp/dt also recovered to 82.4% (control, 43.1%) after 6 hours. In an in vivo study, ATP levels depressed after ischemia did not recover after 4 hours of reperfusion. However, ATP levels recovered from 70.2% to 86.6% after the administration of adenosine into the left ventricle (0.1 mmol of adenosine per hour) for 2 hours. Administration of inosine or adenosine to the post-ischemic heart should be useful to improve the myocardial metabolism and cardiac function.

  1. Changes in energy metabolism in the quadriceps femoris after a single bout of acute exhaustive swimming in rats: a 31p-magnetic resonance spectroscopy study

    Institute of Scientific and Technical Information of China (English)

    Sun Yingwei; Pan Shinong; Chen Zhian; Zhao Heng; Ma Ying; Zheng Liqiang; Li Qi


    Background Little is known about the value of 31P-magnetic resonance spectroscopy (31P-MRS) in in vivo assessment of exhaustive exercise-induced injury in skeletal muscle.We aimed to evaluate the value of a 31P-MRS study using the quadriceps femoris after a single bout of acute exhaustive swimming in rats,and the correlation between 31P-MRS and histological changes.Methods Sixty male Sprague-Dawley rats were randomly assigned to control,half-exhaustive,and exhaustive exercise groups.31P-MRS of the quadriceps femoris of the right lower limb was performed immediately after swimming exercise to detect Pi,PCr,and β-ATP.The Pi/PCr,Pi/β-ATP,PCr/β-ATP,and PCr/(PCr+Pi) were calculated and pH measured.Areas under the receiver operating characteristic curve (AUCs) were calculated to evaluate the diagnostic potential of 31P-MRS in identifying and distinguishing the three groups.HE staining,electron microscopy and desmin immunostaining after imaging of the muscle were used as a reference standard.The correlation between 31P-MRS and the mean absorbance (A value) of desmin staining were analyzed with the Pearson correlation test.Results Pi,PCr,Pi/PCr,and PCr/(PCr+Pi) showed statistically significant intergroup differences (P<0.05).AUCs of Pi,PCr,Pi/PCr,and PCr/(PCr+Pi) were 0.905,0.848,0.930,and 0.930 for the control and half-exhaustive groups,while sensitivity and specificity were 90%/85%,95%/55%,95%/80%,and 90%/85%,respectively.The AUCs of Pi,PCr,Pi/PCr and PCr/(PCr+Pi) were 0.995,0.980,1.000,and 1.000 for the control and exhaustive groups,while sensitivity and specificity were 95%/90%,100%/90%,100%/95%,and 100%/95%,respectively.The AUCs of Pi,PCr,Pi/PCr,and PCr/(PCr+Pi) were 0.735,0.865,0.903,and 0.903 for the half-exhaustive and exhaustive groups,while sensitivity and specificity were 80%/60%,90%/75%,95%/65%,and 95%/70%,respectively.In the half-exhaustive group,some muscle fibers exhibited edema in HE staining,and the

  2. Fósforo num Cambissolo cultivado com cana-de-açúcar por longo tempo: II - análise de ácidos húmicos por RMN 31P Phosphorus in an Inceptsoil under long-term sugarcane: II - humic acid analysis by NMR 31P

    Directory of Open Access Journals (Sweden)

    Jader Galba Busato


    Full Text Available Sistemas de manejo da lavoura de cana-de-açúcar que favoreçam a matéria orgânica do solo podem aumentar o conteúdo de nutrientes disponíveis e diminuir a necessidade de aplicação de fertilizantes industriais. Apesar da importância dos componentes orgânicos no fornecimento de P, pouco se conhece sobre a sua dinâmica em ambientes tropicais. O objetivo deste trabalho foi identificar, por meio da ressonância magnética nuclear (RMN 31P, as espécies de P nos ácidos húmicos de um Cambissolo Háplico Ta eutrófico vértico, localizado no Município de Campos dos Goytacazes, norte do Estado do Rio de Janeiro, e cultivado com cana-de-açúcar com preservação do palhiço e adição de vinhaça por longo tempo. Por meio da análise de RMN 31P foi possível observar acúmulo de P orgânico em formas mais facilmente mineralizadas nas áreas com preservação de matéria orgânica, tal como P em ligações diésteres. Nas áreas de cana queimada, houve maior participação de espécies orgânicas mais estáveis, como o ortofosfato em ligações monoésteres. Os resultados da espectroscopia de RMN 31P mostram que, nas áreas com maior aporte de resíduo orgânico (i.e., cana crua e cana queimada com adição de vinhaça, os ácidos húmicos constituem uma reserva importante de P orgânico prontamente disponível. Já, nas áreas de cana queimada, o acúmulo de P orgânico recalcitrante nos ácidos húmicos indica utilização do P-lábil das substâncias húmicas como fonte importante para nutrição das plantas.Crop management systems that favor soil organic matter can improve the available nutrient content for plants and reduce the use of industrial fertilizer. Despite the importance of organic compounds as a P source, little is known about its dynamics in tropical environments. The objective of this study was to identify organic P species present in humic acids by NMR 31P analysis in a fine clay Fluventic Eutrochrepts in Campos dos

  3. 核磁共振磷谱在有机化合物草甘膦合成过程中的监控%The Application of 31^P-NMR Spectrum in Monitoring the Synthesis of Glyphosate

    Institute of Scientific and Technical Information of China (English)

    赵黎黎; 王敏; 钟江春; 林吉柏


    The 31^P-NMR is one of important technologies of Nuclear magnetic resonance; it plays a very important role in the quality and quantity of compound in organic chemistry and monitoring the synthesis. The article makes a brief introduction for the tested method in the Synthesis of Glyphosate by 31^P-NMR to supply a reference for the application of NMR in the field of organic pesticide.%磷谱是核磁共振的一项重要应用,它在有机化学的定性、定量以及合成过程的监控实验中具有非常重要的作用。本文开发了利用核磁共振磷谱进行有机农药草甘磷部分合成过程监控的实验方法。为草甘膦质量控制和品质提升提供方法支持,同时为进一步扩大核磁共振在有机农药化合物研究领域中的应用提供参考。

  4. Investigation of the cerebral energy status in patients with glutaric aciduria type I by 31P magnetic resonance spectroscopy. (United States)

    Möller, H E; Koch, H G; Weglage, J; Freudenberg, F; Ullrich, K


    In vivo phosphorus magnetic resonance spectroscopy (MRS) was used to investigate markers of the cerebral energy status in two patients with glutaric aciduria type I (GA-I). Besides an increased concentration of phosphomonoesters in one patient, no other significant alterations from controls were found. This might indicate increased resynthesis of dendritic processes secondary to preceding metabolic crises. In contrast to previous cell-culture studies, no cerebral depletion of phosphocreatine (PCr) was observed. In conclusion, a severe global and permanent depletion of cerebral energy supplies must be ruled out. The benefit of a permanent creatine substitution to stabilize mitochondrial energy metabolism seems thus questionable. However, as MRS was performed during stable clinical conditions, the possibility of a PCr decrease during acute metabolic crises cannot be assessed.

  5. NMR spectroscopy: a tool for conformational analysis

    Energy Technology Data Exchange (ETDEWEB)

    Tormena, Claudio F.; Cormanich, Rodrigo A.; Rittner, Roberto, E-mail: [Universidade Estadual de Campinas (UNICAMP), SP (Brazil). Inst. de Quimica. Lab. de Fisico-Quimica Organica; Freitas, Matheus P. [Universidade Federal de Lavras (UFLA), MG (Brazil). Dept. de Qumica


    The present review deals with the application of NMR data to the conformational analysis of simple organic compounds, together with other experimental methods like infrared spectroscopy and with theoretical calculations. Each sub-section describes the results for a group of compounds which belong to a given organic function like ketones, esters, etc. Studies of a single compound, even of special relevance, were excluded since the main goal of this review is to compare the results for a given function, where different substituents were used or small structural changes were introduced in the substrate, in an attempt to disclose their effects in the conformational equilibrium. Moreover, the huge amount of data available in the literature, on this research field, imposed some limitations which will be detailed in the Introduction, but it can be reminded in advance that these limitations include mostly the period when these results were published. (author)

  6. Non-invasive assessment of phosphate metabolism and oxidative capacity in working skeletal muscle in healthy young Chinese volunteers using 31P Magnetic Resonance Spectroscopy

    Directory of Open Access Journals (Sweden)

    Ming Li


    Full Text Available Background. Generally, males display greater strength and muscle capacity than females while performing a task. Muscle biopsy is regarded as the reference method of evaluating muscle functions; however, it is invasive and has sampling errors, and is not practical for longitudinal studies and dynamic measurement during excise. In this study, we built an in-house force control and gauge system for quantitatively applying force to quadriceps while the subjects underwent 31P Magnetic Resonance Spectroscopy (31P-MRS; our aim was to investigate if there is a sex difference of phosphate metabolite change in working muscles in young heathy Chinese volunteers. Methods. Volunteers performed knee-extending excises using a force control and gauge system while lying prone in a Philips 3T Magnetic Resonance (MR scanner. The 31P-MRS coil was firmly placed under the middle of the quadriceps . 31P-MRS measurements of inorganic phosphate (Pi, phosphocreatine (PCr and adenosine triphosphate (ATP were acquired from quadriceps while subjects were in a state of pre-, during- and post-exercise. The PCr, Pi, PCr/Pi, PCr/ATP, pH, work/energy cost ratio (WE, kPCr and oxidative capacity were compared between males and females. Results. A total of 17 volunteers underwent the study. Males: N = 10, age = 23.30 ± 1.25years; females: N = 7, age = 23.57 ± 0.79 years. In this study, males had significantly greater WE (16.33 ± 6.46 vs. 7.82 ± 2.16, p = 0.002 than females. Among PCr, Pi, PCr/Pi, PCr/ATP, pH, kPCr and oxidative capacity at different exercise status, only PCr/Pi (during-exercise, males = 5.630 ± 1.647, females = 4.014 ± 1.298, p = 0.047, PCr/ATP (during-exercise, males =1.273 ± 0.219, females = 1.523 ± 0.167, p = 0.025, and ATP (post-exercise, males = 24.469 ± 3.911 mmol/kg, females = 18.353 ± 4.818 mmol/kg, p = 0.035 had significant sex differences. Males had significantly greater PCr/Pi, but less PCr/ATP than females during exercise, suggesting males had

  7. Quantitative 31P NMR for Simultaneous Trace Analysis of Organophosphorus Pesticides in Aqueous Media Using the Stir Bar Sorptive Extraction Method (United States)

    Ansari, S.; Talebpour, Z.; Molaabasi, F.; Bijanzadeh, H. R.; Khazaeli, S.


    The analysis of pesticides in water samples is of primary concern for quality control laboratories due to the toxicity of these compounds and their associated public health risk. A novel analytical method based on stir bar sorptive extraction (SBSE), followed by 31P quantitative nuclear magnetic resonance (31P QNMR), has been developed for simultaneously monitoring and determining four organophosphorus pesticides (OPPs) in aqueous media. The effects of factors on the extraction efficiency of OPPs were investigated using a Draper-Lin small composite design. An optimal sample volume of 4.2 mL, extraction time of 96 min, extraction temperature of 42°C, and desorption time of 11 min were obtained. The results showed reasonable linearity ranges for all pesticides with correlation coefficients greater than 0.9920. The limit of quantification (LOQ) ranged from 0.1 to 2.60 mg/L, and the recoveries of spiked river water samples were from 82 to 94% with relative standard deviation (RSD) values less than 4%. The results show that this method is simple, selective, rapid, and can be applied to other sample matrices.

  8. Recent Advances in Multinuclear NMR Spectroscopy for Chiral Recognition of Organic Compounds

    Directory of Open Access Journals (Sweden)

    Márcio S. Silva


    Full Text Available Nuclear magnetic resonance (NMR is a powerful tool for the elucidation of chemical structure and chiral recognition. In the last decade, the number of probes, media, and experiments to analyze chiral environments has rapidly increased. The evaluation of chiral molecules and systems has become a routine task in almost all NMR laboratories, allowing for the determination of molecular connectivities and the construction of spatial relationships. Among the features that improve the chiral recognition abilities by NMR is the application of different nuclei. The simplicity of the multinuclear NMR spectra relative to 1H, the minimal influence of the experimental conditions, and the larger shift dispersion make these nuclei especially suitable for NMR analysis. Herein, the recent advances in multinuclear (19F, 31P, 13C, and 77Se NMR spectroscopy for chiral recognition of organic compounds are presented. The review describes new chiral derivatizing agents and chiral solvating agents used for stereodiscrimination and the assignment of the absolute configuration of small organic compounds.

  9. Bone and Soft Tissue Tumors:Study of 3.0T31P MR Spectroscopy%3.0T31P-MRS对骨与软组织肿瘤的诊断价值

    Institute of Scientific and Technical Information of China (English)

    齐滋华; 李传福; 马祥兴; 李振峰; 张凯; 于德新


    目的 探讨超高场31P-MRS对骨与软组织肿瘤的成像特点.方法 对病理证实的骨与软组织肿瘤41例用磷表面线圈进行31P-MRS分析,测量波谱中各代谢产物的峰下面积,分别以三磷酸腺苷β峰(β-ATP)、三磷酸核苷(NTP)、磷酸肌酸(Pcr)为参照计算各代谢产物的相对比值,根据无机磷(Pi)相对于Pcr化学位移的变化计算细胞内pH值,进行相对定量分析.根据峰下面积计算各代谢产物与β-ATP、三磷酸核苷(NTP=ATP+Pi+Pcr)、Pcr的相对值PME/β-ATP、PDE/β-ATP、β-ATP/Pi、PME/NTP、PDE/NTP、Pcr/Pi及Pcr/PME.并运用SPSS11.5 for Windows软件包进行统计学处理,采用多个独立样本的非参数检验.结果 良、恶性肿瘤组的Pcr/PME、PME/NTP较对照组均有显著性差异(P<0.05).良、恶性肿瘤组PME/β-ATP、PME/NTP的差异有显著性意义(P<0.05).与正常组比较,良、恶性肿瘤组的PME和PDE及Pi峰升高,Pcr峰降低.结论 31P-MRS测得的Pcr/PME、PME/NTP与骨、软组织肿瘤相关,PME/β-ATP、PME/NTP在骨与软组织肿瘤的诊断和鉴别诊断中发挥重要的作用.

  10. Energy Deregulation Precedes Alteration in Heart Energy Balance in Young Spontaneously Hypertensive Rats: A Non Invasive In Vivo 31P-MR Spectroscopy Follow-Up Study (United States)

    Deschodt-Arsac, Veronique; Arsac, Laurent; Magat, Julie; Naulin, Jerome; Quesson, Bruno; Dos Santos, Pierre


    Introduction Gradual alterations in cardiac energy balance, as assessed by the myocardial PCr/ATP-ratio, are frequently associated with the development of cardiac disease. Despite great interest for the follow-up of myocardial PCr and ATP content, cardiac MR-spectroscopy in rat models in vivo is challenged by sensitivity issues and cross-contamination from other organs. Methods Here we combined MR-Imaging and MR-Spectroscopy (Bruker BioSpec 9.4T) to follow-up for the first time in vivo the cardiac energy balance in the SHR, a genetic rat model of cardiac hypertrophy known to develop early disturbances in cytosolic calcium dynamics. Results We obtained consistent 31P-spectra with high signal/noise ratio from the left ventricle in vivo by using a double-tuned (31P/1H) surface coil. Reasonable acquisition time (<3.2min) allowed assessing the PCr/ATP-ratio comparatively in SHR and age-matched control rats (WKY): i) weekly from 12 to 21 weeks of age; ii) in response to a bolus injection of the ß-adrenoreceptor agonist isoproterenol at age 21 weeks. Discussion Along weeks, the cardiac PCr/ATP-ratio was highly reproducible, steady and similar (2.35±0.06) in SHR and WKY, in spite of detectable ventricular hypertrophy in SHR. At the age 21 weeks, PCr/ATP dropped more markedly (-17.1%±0.8% vs. -3,5%±1.4%, P<0.001) after isoproterenol injection in SHR and recovered slowly thereafter (time constant 21.2min vs. 6.6min, P<0.05) despite similar profiles of tachycardia among rats. Conclusion The exacerbated PCr/ATP drop under ß-adrenergic stimulation indicates a defect in cardiac energy regulation possibly due to calcium-mediated abnormalities in the SHR heart. Of note, defects in energy regulation were present before detectable abnormalities in cardiac energy balance at rest. PMID:27622548

  11. The Doppler effect in NMR spectroscopy. (United States)

    Guéron, Maurice


    An NMR sample may be subject to motions, such as those due to sample spinning or to liquid flow. Is the spectrum of such a sample affected by the Doppler effect? The question arises because, instrumental dimensions being much shorter than the wavelength, it is the near-field of the precessing magnetic moment which couples to the receiver coil, rather than the radiated far-field. We expand the near-field into plane propagating waves. For each such wave there is another one with the same amplitude, propagating in the opposite direction. The Doppler shifts are therefore equal and opposite. In the model case of a small fluid sample moving with constant velocity, this leads to a distribution of Doppler shifts which is symmetrical with respect to the unshifted frequency: there is no net spectral shift. We examine the possibility of observing the Doppler distribution in this case. We also consider the case of thermal motion of a gas. We draw attention to the resolved Doppler splitting of molecular rotational transitions in a supersonic burst as observed in a microwave resonator. We also mention briefly the Doppler effect in molecular beam spectroscopy.

  12. Analyzing Ph value, energy and phospholipid metabolism of various cerebral tumors and normal brain tissue with 31P magnetic resonance spectroscopy

    Institute of Scientific and Technical Information of China (English)

    Wei Tan; Guangyao Wu; Junmo Sun


    BACKGROUND: 31P magnetic resonance spectroscopy (31P MRS) can be used to non-injuredly and dynamicly detect various metabolites including phosphorus in organis and reflect changes of phospholipid metabolism and energy metabolism in tissue and pH value in cells.OBJECTIVE: To observe changes of pH value, phospholipid metabolism and energy metabolism of various cerebral tumors and normal brain tissue with 31P MRS.DESIGN: Semi-quantitative contrast observation.PARTICIPANTS: A total of 44 patients with cerebral tumor diagnosed with surgery operation were selected from the Department of Magnetic Resonance, Central South Hospital, Wuhan University from September 2004 to June 2006. All the subjects had complete 31P MRS data before steroid and operation. Among them,16 patients had glioma of grade Ⅱ-Ⅲ, 12 spongioblastoma and 16 meningioma. The mean age was (45±6)years. Another 36 subjects without focus on cerebral MRI were regarded as normal group, including 19 males and 18 females, and the mean age was (41±4) years. Included subjects were consent.METHODS: Eclipse1.5T MRS (Philips Company) was used to collect wave spectrum; jMRUI(1.3) was used to analyze experimental data and calculate pH value in voxel and ratios of phosphocreatine (PCr)/inorganic phosphate (Pi), PCr/phosphodiesterase (PDE) and phosphomonoesterase (PME)/β-adenosine triphosphate (β-ATP) of various metabolites. 31P MRS results were compared with t test between tumor patients and normal subjects.MAIN OUTCOME MEASURES: Changes of phospholipid metabolism (PME/PDE), energy metabolism (PCr/ATP) and pH value of various cerebral tumors and normal brain tissues.RESULTS: A total of 44 cases with cerebral tumor and 36 normal subjects were involved in the final analysis. pH value and semi-quantitative measurements of normal brain tissues and various cerebral tumors: ① pH value at top occipital region and temple occipital region of normal brain tissue was 7.04±0.02;PCt/β-ATP was 1.51 ±0.03; PCt/Pi was 2.85

  13. NMR Analysis of Unknowns: An Introduction to 2D NMR Spectroscopy (United States)

    Alonso, David E.; Warren, Steven E.


    A study combined 1D (one-dimensional) and 2D (two-dimensional) NMR spectroscopy to solve structural organic problems of three unknowns, which include 2-, 3-, and 4-heptanone. Results showed [to the first power]H NMR and [to the thirteenth power]C NMR signal assignments for 2- and 3-heptanone were more challenging than for 4-heptanone owing to the…

  14. High-resolution NMR spectroscopy under the fume hood. (United States)

    Küster, Simon K; Danieli, Ernesto; Blümich, Bernhard; Casanova, Federico


    This work reports the possibility to acquire high-resolution (1)H NMR spectra with a fist-sized NMR magnet directly installed under the fume hood. The small NMR sensor based on permanent magnets was used to monitor the trimerization of propionaldehyde catalyzed by indium trichloride in real time by continuously circulating the reaction mixture through the magnet bore in a closed loop with the help of a peristaltic pump. Thanks to the chemical selectivity of NMR spectroscopy the progress of the reaction can be monitored on-line by determining the concentrations of both reactant and product from the area under their respective lines in the NMR spectra as a function of time. This in situ measurement demonstrates that NMR probes can be used in chemistry laboratories, e.g. for reaction optimization, or installed at specific points of interest along industrial process lines. Therefore, it will open the door for the implementation of feedback control based on spectroscopic NMR data.

  15. In vivo 31 P NMR Spectroscopy for the study of P Pools and their Dynamics in Arbuscular Mycorrhizal Fungi

    DEFF Research Database (Denmark)

    Viereck, Nanna

    large amounts and is often limiting to plant growth. The availability of P is limited by the slow rate of diffusion of inorganic orthopliospliate (Pi) through the soil. As plants remove Pi from the soil solution close to the root an area suii-ounding the root drained for soluble Pi may be formed (the P....... The extraradical mycelium of an AM fungus forms an extensive hyphal network and allows the plant to access Pi in tlie soil solution beyond the P-depletion zone. Once the association is established, the fungus takes up Pi from the soil through the extraradical mycelium in an active process like plants. However, Pi....... Furthermore, an attempt was made to measure phospliatase activity in the extraradical mycelium and mycorrhizal roots using the enzyme-iabeled-fluorescence (ELF) method in order to localize aspects of P metabolism. Alkaline phosphatase activity was observed in all species af AM fungi used, which indicated...

  16. Carbon-13 NMR spectroscopy of biological systems

    CERN Document Server

    Beckmann, Nicolau


    This book is intended to provide an in-depth understanding of 13C NMR as a tool in biological research. 13C NMR has provided unique information concerning complex biological systems, from proteins and nucleic acids to animals and humans. The subjects addressed include multidimensional heteronuclear techniques for structural studies of molecules in the liquid and solid states, the investigation of interactions in model membranes, the elucidation of metabolic pathwaysin vitro and in vivo on animals, and noninvasive metabolic studies performed on humans. The book is a unique mix of NMR methods and biological applications which makes it a convenient reference for those interested in research in this interdisciplinary area of physics, chemistry, biology, and medicine.Key Features* An interdisciplinary text with emphasis on both 13C NMR methodology and the relevant biological and biomedical issues* State-of-the-art 13C NMR techniques are described; Whenever possible, their advantages over other approaches are empha...

  17. Applications of NMR spectroscopy to systems biochemistry. (United States)

    Fan, Teresa W-M; Lane, Andrew N


    The past decades of advancements in NMR have made it a very powerful tool for metabolic research. Despite its limitations in sensitivity relative to mass spectrometric techniques, NMR has a number of unparalleled advantages for metabolic studies, most notably the rigor and versatility in structure elucidation, isotope-filtered selection of molecules, and analysis of positional isotopomer distributions in complex mixtures afforded by multinuclear and multidimensional experiments. In addition, NMR has the capacity for spatially selective in vivo imaging and dynamical analysis of metabolism in tissues of living organisms. In conjunction with the use of stable isotope tracers, NMR is a method of choice for exploring the dynamics and compartmentation of metabolic pathways and networks, for which our current understanding is grossly insufficient. In this review, we describe how various direct and isotope-edited 1D and 2D NMR methods can be employed to profile metabolites and their isotopomer distributions by stable isotope-resolved metabolomic (SIRM) analysis. We also highlight the importance of sample preparation methods including rapid cryoquenching, efficient extraction, and chemoselective derivatization to facilitate robust and reproducible NMR-based metabolomic analysis. We further illustrate how NMR has been applied in vitro, ex vivo, or in vivo in various stable isotope tracer-based metabolic studies, to gain systematic and novel metabolic insights in different biological systems, including human subjects. The pathway and network knowledge generated from NMR- and MS-based tracing of isotopically enriched substrates will be invaluable for directing functional analysis of other 'omics data to achieve understanding of regulation of biochemical systems, as demonstrated in a case study. Future developments in NMR technologies and reagents to enhance both detection sensitivity and resolution should further empower NMR in systems biochemical research.

  18. Developments of RF Coil for P in vivo NMR Spectroscopy .

    Directory of Open Access Journals (Sweden)

    S. Khushu


    Full Text Available RF receiver coils are very important parts of an NMR System. The design of these coils is very critical and has a dramatic effect on the SNR of the NMR signal and are generally developed in TRA/REC mode. This paper reports the developments of a 3.5 cm TRA/REC 26 MHz RF coil for P spectroscopy of small organs like thyroid. The coil is small in size, fits well in the neck for thyroid spectroscopy and is successfully working with the 1.5 tesla whole body Superconducting NMR System available at INMAS.

  19. Evidence for a "metabolically inactive" inorganic phosphate pool in adenosine triphosphate synthase reaction using localized 31P saturation transfer magnetic resonance spectroscopy in the rat brain at 11.7 T. (United States)

    Tiret, Brice; Brouillet, Emmanuel; Valette, Julien


    With the increased spectral resolution made possible at high fields, a second, smaller inorganic phosphate resonance can be resolved on (31)P magnetic resonance spectra in the rat brain. Saturation transfer was used to estimate de novo adenosine triphosphate synthesis reaction rate. While the main inorganic phosphate pool is used by adenosine triphosphate synthase, the second pool is inactive for this reaction. Accounting for this new pool may not only help us understand (31)P magnetic resonance spectroscopy metabolic profiles better but also better quantify adenosine triphosphate synthesis.

  20. Changes of liver metabolite concentrations in adults with disorders of fructose metabolism after intravenous fructose by 31P magnetic resonance spectroscopy. (United States)

    Boesiger, P; Buchli, R; Meier, D; Steinmann, B; Gitzelmann, R


    A novel 31P magnetic resonance spectroscopy procedure allows the estimation of absolute concentrations of certain phosphorus-containing compounds in liver. We have validated this approach by measuring ATP, phosphomonesters, and inorganic phosphate (Pi) during fasting and after an i.v. fructose bolus in healthy adults and in three adults with disorders of fructose metabolism and by comparing results with known metabolic concentrations measured chemically. During fasting, the ATP concentration averaged 2.7 +/- 0.3 (SD, n = 9) mmol/L, which, after due correction for other nucleoside triphosphates, was 2.1 mmol/L and corresponded well with known concentrations. Fructose-1-phosphate (F-1-P) could not be measured during fasting; its concentration after fructose was calculated from the difference of the phosphomonester signals before (2.9 +/- 0.2 mmol/L) and after fructose. Pi was 1.4 +/- 0.3 mmol/L and represented the one fourth of Pi visible in magnetic resonance spectra. In the three healthy controls after fructose (200 mg/kg, 20% solution, 2.5 min), the fructokinase-mediated increase of F-1-P was rapid, reaching 4.9 mmol/L within 3 min, whereas the uncorrected ATP decreased from 2.7 to 1.8 mmol/L and the Pi from 1.4 to 0.3 mmol/L. The subsequent decrease of F-1-P, mediated by fructaldolase, was accompanied by an overshooting rise of Pi to 2.7 mmol/L. In the patient with essential fructosuria, the concentrations of F-1-P, ATP, and Pi remained unchanged, confirming that fructokinase was indeed inactive. In the patient with hereditary fructose intolerance, initial metabolic changes were the same as in the controls, but baseline concentrations were not yet reestablished after 7 h, indicating weak fructaldolase activity.(ABSTRACT TRUNCATED AT 250 WORDS)

  1. A primer to nutritional metabolomics by NMR spectroscopy and chemometrics

    DEFF Research Database (Denmark)

    Savorani, Francesco; Rasmussen, Morten Arendt; Mikkelsen, Mette Skau


    This paper outlines the advantages and disadvantages of using high throughput NMR metabolomics for nutritional studies with emphasis on the workflow and data analytical methods for generation of new knowledge. The paper describes one-by-one the major research activities in the interdisciplinary...... metabolomics platform and highlights the opportunities that NMR spectra can provide in future nutrition studies. Three areas are emphasized: (1) NMR as an unbiased and non-destructive platform for providing an overview of the metabolome under investigation, (2) NMR for providing versatile information and data...... structures for multivariate pattern recognition methods and (3) NMR for providing a unique fingerprint of the lipoprotein status of the subject. For the first time in history, by combining NMR spectroscopy and chemometrics we are able to perform inductive nutritional research as a complement to the deductive...

  2. Solid-State NMR Spectroscopy for the Physical Chemistry Laboratory (United States)

    Kinnun, Jacob J.; Leftin, Avigdor; Brown, Michael F.


    Solid-state nuclear magnetic resonance (NMR) spectroscopy finds growing application to inorganic and organic materials, biological samples, polymers, proteins, and cellular membranes. However, this technique is often neither included in laboratory curricula nor typically covered in undergraduate courses. On the other hand, spectroscopy and…

  3. Facing and Overcoming Sensitivity Challenges in Biomolecular NMR Spectroscopy

    DEFF Research Database (Denmark)

    Ardenkjær-Larsen, Jan Henrik; Boebinger, Gregory S.; Comment, Arnaud


    enhance the sensitivity of solid‐ and liquid‐state experiments. While substantial advances have been made in all these areas, numerous challenges remain in the quest of endowing NMR spectroscopy with the sensitivity that has characterized forms of spectroscopies based on electrical or optical measurements....... These challenges, and the ways by which scientists and engineers are striving to solve them, are also addressed....

  4. NMR Spectroscopy: Processing Strategies (by Peter Bigler) (United States)

    Mills, Nancy S.


    Peter Bigler. VCH: New York, 1997. 249 pp. ISBN 3-527-28812-0. $99.00. This book, part of a four-volume series planned to deal with all aspects of a standard NMR experiment, is almost the exact book I have been hoping to find. My department has acquired, as have hundreds of other undergraduate institutions, high-field NMR instrumentation and the capability of doing extremely sophisticated experiments. However, the training is often a one- or two-day experience in which the material retained by the faculty trained is garbled and filled with holes, not unlike the information our students seem to retain. This text, and the accompanying exercises based on data contained on a CD-ROM, goes a long way to fill in the gaps and clarify misunderstandings about NMR processing.

  5. Cell signaling, post-translational protein modifications and NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Theillet, Francois-Xavier [In-cell NMR Group, Department of NMR-Supported Structural Biology, Leibniz Institute of Molecular Pharmacology (FMP Berlin) (Germany); Smet-Nocca, Caroline [Universite Lille Nord de France, CNRS UMR 8576 (France); Liokatis, Stamatios; Thongwichian, Rossukon; Kosten, Jonas [In-cell NMR Group, Department of NMR-Supported Structural Biology, Leibniz Institute of Molecular Pharmacology (FMP Berlin) (Germany); Yoon, Mi-Kyung; Kriwacki, Richard W. [St. Jude Children' s Research Hospital, Department of Structural Biology (United States); Landrieu, Isabelle; Lippens, Guy [Universite Lille Nord de France, CNRS UMR 8576 (France); Selenko, Philipp, E-mail: [In-cell NMR Group, Department of NMR-Supported Structural Biology, Leibniz Institute of Molecular Pharmacology (FMP Berlin) (Germany)


    Post-translationally modified proteins make up the majority of the proteome and establish, to a large part, the impressive level of functional diversity in higher, multi-cellular organisms. Most eukaryotic post-translational protein modifications (PTMs) denote reversible, covalent additions of small chemical entities such as phosphate-, acyl-, alkyl- and glycosyl-groups onto selected subsets of modifiable amino acids. In turn, these modifications induce highly specific changes in the chemical environments of individual protein residues, which are readily detected by high-resolution NMR spectroscopy. In the following, we provide a concise compendium of NMR characteristics of the main types of eukaryotic PTMs: serine, threonine, tyrosine and histidine phosphorylation, lysine acetylation, lysine and arginine methylation, and serine, threonine O-glycosylation. We further delineate the previously uncharacterized NMR properties of lysine propionylation, butyrylation, succinylation, malonylation and crotonylation, which, altogether, define an initial reference frame for comprehensive PTM studies by high-resolution NMR spectroscopy.

  6. Metabolic Changes in Rats with Photochemically Induced Cerebral Infarction and the Effects of Batroxobin: A Study by Magnetic Resonance Imaging, 1H- and 31P- Magnetic Resonance Spectroscopy

    Institute of Scientific and Technical Information of China (English)

    管兴志; 吴卫平; 匡培根; 匡培梓; 高杨; 管林初; 李丽云; 毛希安; 刘买利


    Metabolic changes in rats with photochemically induced cerebral infarction and the effects of batroxobin were investigated 1, 3, 5 and 7 days after infarction by means of magnetic resonance imaging (MRI), 1H- and 31P- magnetic resonance spectroscopy (MRS). A region of T2 hyperintensity was observed in left temporal neocortex in infarction group and batroxobin group 1, 3, 5 and 7 days after infarction. The volume of the region gradually decreased from 1 day to 7 days after infarction. The ratio of NAA/Cho+Cr in the region of T2 hyperintensity in the infarction group was significantly lower than that in the corresponding region in the sham-operated group 3, 5 and 7 days after infarction respectively (P<0.05). Lac appeared in the region of T2 hyperintensity in the infarction group 1, 3, 5 and 7 days after infarction, but it was not observed in the corresponding region in sham-operated group at all time points. Compared with the sham-operated group, the ratios of bATP/PME+PDE and PCr/PME+PDE of the whole brain in the infarction group were significantly lower 1, 3 and 5 days after infarction respectively (P<0.05), and the ratio of bATP/PCr also was significantly lower 1 day after infarction (P<0.05). Batroxobin significantly decreased the volume of the region of T2 hyperintensity 1 and 3 days after infarction (P<0.05), significantly increased the ratio of NAA/Cho+Cr in the region 5 and 7 days after infarction (P<0.05), significantly decreased the ratios of Lac/Cho+Cr and Lac/NAA in the region 5 and 7 days after infarction (P<0.05), and significantly increased the ratios of bATP/PME+PDE and bATP/PCr in the whole brain 1 day after infarction (P<0.05). The results indicated that the infracted region had severe edema, increased Lac and apparent neuronal dysfunction and death, and energy metabolism of the whole brain decreased after focal infarction, and that batroxobin effectively ameliorated the above-mentioned abnormal changes.

  7. Analyzing protein-ligand interactions by dynamic NMR spectroscopy. (United States)

    Mittermaier, Anthony; Meneses, Erick


    Nuclear magnetic resonance (NMR) spectroscopy can provide detailed information on protein-ligand interactions that is inaccessible using other biophysical techniques. This chapter focuses on NMR-based approaches for extracting affinity and rate constants for weakly binding transient protein complexes with lifetimes of less than about a second. Several pulse sequences and analytical techniques are discussed, including line-shape simulations, spin-echo relaxation dispersion methods (CPMG), and magnetization exchange (EXSY) experiments.

  8. Room temperature chiral discrimination in paramagnetic NMR spectroscopy

    CERN Document Server

    Soncini, Alessandro


    A recently proposed theory of chiral discrimination in NMR spectroscopy based on the detection of a molecular electric polarization $\\mathbf{P}$ rotating in a plane perpendicular to the NMR magnetic field [A. D. Buckingham, J. Chem. Phys. $\\mathbf{140}$, 011103 (2014)], is here generalized to paramagnetic systems. Our theory predicts new contributions to $\\mathbf{P}$, varying as the square of the inverse temperature. Ab initio calculations for ten Dy$^{3+}$ complexes, at 293K, show that in strongly anisotropic paramagnetic molecules $\\mathbf{P}$ can be more than 1000 times larger than in diamagnetic molecules, making paramagnetic NMR chiral discrimination amenable to room temperature detection.

  9. /sup 31/P nuclear magnetic resonance study of renal allograft rejection in the rat

    Energy Technology Data Exchange (ETDEWEB)

    Shapiro, J.I.; Haug, C.E.; Shanley, P.F.; Weil, R. III; Chan, L.


    Phosphorus (/sup 31/P) nuclear magnetic resonance (NMR) spectroscopy was used to serially evaluate heterotopic renal allograft rejection in the rat. Renal allografts transplanted to the groin of recipient animals were studied using a 1.89 Tesla horizontal bore magnet. The relative intracellular concentrations of phosphorus metabolites such as adenosine triphosphate and inorganic phosphate as well as intracellular pH were determined by /sup 31/P NMR on days 4, 7, 10, and 14 following transplantation across a major histocompatibility mismatch. Recipient rats chosen to be rejectors received no immunosuppression while animals chosen to be nonrejectors received cyclosporine during the first 7 days following transplantation. By day 7, all rejector rats could be distinguished from nonrejector rats by their higher relative concentration of inorganic phosphate and their lower relative concentration of adenosine triphosphate. These NMR findings correlated with histologic findings of renal infarction probably related to vascular rejection in the allografts. /sup 31/P NMR spectroscopy may have application as a noninvasive tool in the differential diagnosis of posttransplantation renal insufficiency.

  10. Phosphatation of zeolite H-ZSM-5 : A combined microscopy and spectroscopy study

    NARCIS (Netherlands)

    Van Der Bij, Hendrik E.; Aramburo, Luis R.; Arstad, Bjørnar; Dynes, James J.; Wang, Jian; Weckhuysen, Bert M.


    A variety of phosphated zeolite H-ZSM-5 samples are investigated by using a combination of Fourier transfer infrared (FTIR) spectroscopy, single pulse 27Al, 29Si, 31P, 1H-31P cross polarization (CP), 27Al-31P CP, and 27Al 3Q magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy, sca

  11. Phosphorus Speciation of Sequential Extracts of Organic Amendments using NMR Spectroscopy (United States)

    Akinremi, O.


    O.O. 1Akinremi Babasola Ajiboye and Donald N. Flaten 1Department of Soil Science, University of Manitoba, Winnipeg, R3T 2NT, Canada We carried out this study in order to determine the forms of phosphorus in various organic amendments using state-of-the art spectroscopic technique. Anaerobically digested biosolids (BIO), hog (HOG), dairy (DAIRY), beef (BEEF) and poultry (POULTRY) manures were subjected to sequential extraction. The extracts were analyzed by solution 31P nuclear magnetic resonance (NMR) spectroscopy. Most of the total P analysed by inductively coupled plasma-optical emission spectroscopy (ICP-OES) in the sequential extracts of organic amendments were orthophosphate, except POULTRY, which was dominated by organic P. The labile P fraction in all the organic amendments, excluding POULTRY, was mainly orthophosphate P from readily soluble calcium and some aluminum phosphates. In the poultry litter, however, Ca phytate was the main P species controlling P solubility. Such knowledge of the differences in the chemical forms of phosphorus in organic amendments are essential for proper management of these amendments for agro-environmental purposes Key words: organic amendments, solution NMR, sequential fractionation, labile phosphorus

  12. 31P-MRS评价肝细胞癌代谢水平及其与临床、病理特征的关系%Relationship between clinical-pathological features and metabolic status of hepatocellular carcinoma detected by 31p magnetic resonance spectroscopy

    Institute of Scientific and Technical Information of China (English)

    于德新; 马祥兴; 李笃民; 张晓明; 王茜; 李传福


    Objective To examine the relationship between clinical-pathological features and metabolic status of hepato-cellular carcinoma (HCC) using in vivo 3IP magnetic resonance spectroscopy (31P-MRS). Methods 31P-MRS scanning with a single voxel was carried out on 32 HCC lesions. Groups were formed for the following: with and without capsula, with and without cirrhosis, and with and without infiltration (intrahepatic daughter foci, tumor-emboli in portal veins and lymphatic metastasis). Another group was formed according to the pathological grades of the lesions. Intra-cellular pH value (pHi), and metabolic parameters including phosphomonoester (PME), phosphodiester (PDE), inorganic phosphate (Pi), y-ATP, 0-ATP, a-ATP, lower energetic phosphate (LEP), and the ratios PME/ATP, Pi/ ATP, PME/PDE, PME/Pi, PDE/Pi and PDE/ATP were calculated. Differences in the metabolic parameters between different groups were analyzed. Results HCC exhibited higher values for pHi, Pi, Pi/ATP and LEP, but lower values for o-ATP and PDE/Pi, than the liver (P 0.05). Conclusion Some phosphorus metabolites in HCC are related to clinical-pathological features, and 3IP-MRS can be used to evaluate the biological behavior of HCC in a non-invasive fashion.%目的 利用31 P-MRS检测肝细胞癌(HCC),探讨各代谢参数与临床及病理特征的关系.方法 对32个肝细胞癌病灶进行单体素31P-MRS扫描.根据手术及病理结果显示有无包膜、肝硬化、侵袭转移性以及恶性程度分别进行分组.根据31P-MRS扫描结果计算肝细胞内pH值(pHi)、磷酸单脂(PME)、磷酸双脂(PDE)、无机磷(Pi)、γ-ATP、β-ATP、α-ATP、PME/ATP、Pi/ATP、PME/PDE、PME/Pi、PDE/Pi、PDE/ATP和低能磷酸盐(LEP)等参数.分析以上代谢参数在各分组之间差异.结果 HCC的pHi、Pi、Pi/ATP、LEP均明显大于周围肝组织,α-ATP和PDE/Pi则相反(P<0.05).包膜组病灶的β-ATP小于无包膜组(t=2.290,P=0.029).肝硬化组HCC病灶pHi大于无

  13. Biomolecular recognition mechanisms studied by NMR spectroscopy and MD simulations

    NARCIS (Netherlands)

    Hsu, Shang-Te Danny


    This thesis describes the use of solution Nuclear Magnetic Resonance (NMR) spectroscopy and Molecular Dynamics (MD) simulations to study the mechanism of biomolecular recognition with two model systems: i) lipid II-binding lantibiotics (lanthionine-containing antibiotics) and ii) the human immunodef

  14. Theoretical Studies on the Fe-M Interactions and 31p NMR in Fe(CO)3(EtPhPpy)2MX2 (X=NCS, SCN, CI; M=Zn, Cd, Hg)

    Institute of Scientific and Technical Information of China (English)

    Xiao-xuan Huang; Xuan Xu; Mei-xiang Xie


    To study the Fe-M interactions and their effects on 31p NMR, the structures of Fe(CO)3(EtPhPpy)21,Fe(CO)3(EtPhPpy)2M(NCS)2 (2: M=Zn, 3: M=Cd, 4: M=Hg) and Fe(CO)3(EtPhPpy)2CdX2 (5: X=CI,6: X=SCN) were investigated by density functional theory (DFT) PBE0 method. The stabilities S of complexes follow S(2)>S(3)>S(4) and S(3)~S(6)>S(5), indicating that 6 is stable and may be synthesized.The complexes with thiocyanate are more stable than that with chloride in Fe(CO)3(EtPhPpy)2CdX2.The strength I of Fe-M interactions follows I(2)≈I(3)31p chemical shifts are caused (compared with mononuclear complex 1).

  15. Recovering Invisible Signals by Two-Field NMR Spectroscopy. (United States)

    Cousin, Samuel F; Kadeřávek, Pavel; Haddou, Baptiste; Charlier, Cyril; Marquardsen, Thorsten; Tyburn, Jean-Max; Bovier, Pierre-Alain; Engelke, Frank; Maas, Werner; Bodenhausen, Geoffrey; Pelupessy, Philippe; Ferrage, Fabien


    Nuclear magnetic resonance (NMR) studies have benefited tremendously from the steady increase in the strength of magnetic fields. Spectacular improvements in both sensitivity and resolution have enabled the investigation of molecular systems of rising complexity. At very high fields, this progress may be jeopardized by line broadening, which is due to chemical exchange or relaxation by chemical shift anisotropy. In this work, we introduce a two-field NMR spectrometer designed for both excitation and observation of nuclear spins in two distinct magnetic fields in a single experiment. NMR spectra of several small molecules as well as a protein were obtained, with two dimensions acquired at vastly different magnetic fields. Resonances of exchanging groups that are broadened beyond recognition at high field can be sharpened to narrow peaks in the low-field dimension. Two-field NMR spectroscopy enables the measurement of chemical shifts at optimal fields and the study of molecular systems that suffer from internal dynamics, and opens new avenues for NMR spectroscopy at very high magnetic fields.

  16. Spanning or looping? The order and conformation of bipolar phospholipids in lipid membranes using 2H NMR spectroscopy. (United States)

    Cuccia, L A; Morin, F; Beck, A; Hébert, N; Just, G; Lennox, R B


    Solid-state 2H NMR spectroscopy was used to study and characterize the conformation and order of bolaform lipid membranes. A series of 2H-labeled bolaform phosphatidylcholines has been synthesized and their properties compared to a [D4]dimyristoylphosphatidylcholine (DMPC) and a [D8]-32 macrocyclic phosphatidylcholine. 31P NMR measurements establish that the aqueous dispersions of these lipids adopt lamellar phases. Computational dePakeing was used to extract the spectrum of the oriented system from spectra consisting of a superposition of randomly oriented domains in an unoriented sample. A large (> 90 %) and constant value for the normalized segmental order parameter (Smol) was observed for all positions along the diacyl chain of the bolaform lipids and only a small population ( 90%) of the bolaform lipids is assigned to a highly ordered, spanning conformer.

  17. Characteristics and degradation of carbon and phosphorus from aquatic macrophytes in lakes: insights from solid-state 13C NMR and solution 31P NMR spectroscopy (United States)

    Water extractable organic matter (WEOM) derived from macrophytes plays an important role in biogeochemical cycling of nutrients, including carbon (C), nitrogen (N) and phosphorus (P) in lakes. However, reports of their composition and degradation in natural waters are scarce. Therefore, compositions...

  18. The solubilisation of boar sperm membranes by different detergents - a microscopic, MALDI-TOF MS, 31P NMR and PAGE study on membrane lysis, extraction efficiency, lipid and protein composition

    Directory of Open Access Journals (Sweden)

    Müller Karin


    Full Text Available Abstract Background Detergents are often used to isolate proteins, lipids as well as "detergent-resistant membrane domains" (DRMs from cells. Different detergents affect different membrane structures according to their physico-chemical properties. However, the effects of different detergents on membrane lysis of boar spermatozoa and the lipid composition of DRMs prepared from the affected sperm membranes have not been investigated so far. Results Spermatozoa were treated with the selected detergents Pluronic F-127, sodium cholate, CHAPS, Tween 20, Triton X-100 and Brij 96V. Different patterns of membrane disintegration were observed by light and electron microscopy. In accordance with microscopic data, different amounts of lipids and proteins were released from the cells by the different detergents. The biochemical methods to assay the phosphorus and cholesterol contents as well as 31P NMR to determine the phospholipids were not influenced by the presence of detergents since comparable amounts of lipids were detected in the organic extracts from whole cell suspensions after exposure to each detergent. However, matrix-assisted laser desorption and ionization time-of-flight mass spectrometry applied to identify phospholipids was essentially disturbed by the presence of detergents which exerted particular suppression effects on signal intensities. After separation of the membrane fractions released by detergents on a sucrose gradient only Triton X-100 and sodium cholate produced sharp turbid DRM bands. Only membrane solubilisation by Triton X-100 leads to an enrichment of cholesterol, sphingomyelin, phosphatidylinositol and phosphatidylethanolamine in a visible DRM band accompanied by a selective accumulation of proteins. Conclusion The boar sperm membranes are solubilised to a different extent by the used detergents. Particularly, the very unique DRMs isolated after Triton X-100 exposure are interesting candidates for further studies regarding the

  19. Development and application of a membrane cyclone reactor for in vivo NMR spectroscopy with high microbial cell densities. (United States)

    Hartbrich, A; Schmitz, G; Weuster-Botz, D; de Graaf, A A; Wandrey, C


    A new bioreactor system has been developed for in vivo NMR spectroscopy of microorganisms under defined physiological conditions. This cyclone reactor with an integrated NMR flow cell is continuously operated in the magnet of a 400-MHz wide-bore NMR spectrometer system. The residence times of medium and cells are decoupled by a circulation-integrated cross-flow microfiltration module to achieve higher cell densities as compared to continuous fermentations without cell retention (increase in cell density up to a factor of 10 in steady state). Volumetric mass transfer coefficients k(L)a of more than 1.0 s(-1) are possible in the membrane cyclone reactor, ensuring adequate oxygen supply [oxygen transfer rate >15,000 mg O(2) .(L h)(-1)] of high cell densities. With the aid of the membrane cyclone reactor we were able to show, using continuous in vivo (31)P NMR spectroscopy of anaerobic glucose fermentation by Zymomonas mobilis, that the NMR signal intensity was directly proportional to the cell concentration in the reactor. The concentration profiles of intracellular inorganic phosphate, NAD(H), NDP, NTP, UDP-sugar, a cyclic pyrophosphate, two sugar phosphate pools, and extracellular inorganic phosphate were recorded after a shift from one steady state to another. The intracellular cyclic pyrophosphate had not been detected before in in vitro measurements of Zymomonas mobilis extracts due to the high instability of this compound. Using continuous in vivo (13)C NMR spectroscopy of aerobic glucose utilization by Corynebacterium glutamicum at a density of 25 g(cell dry weight) . L(-1), the membrane cyclone reactor served to measure the different dynamics of labeling in the carbon atoms of L-lactate, L-glutamate, succinate, and L-lysine with a time resolution of 10 min after impressing a [1-(13)C]-glucose pulse.

  20. NMR clinical imaging and spectroscopy: Its impact on nuclear medicine

    Energy Technology Data Exchange (ETDEWEB)


    This is a collection of four papers describing aspects of past and future use of nuclear magnetic resonance as a clinical diagnostic tool. The four papers are entitled (1) What Does NMR Offer that Nuclear Medicine Does Not by Jerry W. Froelich, (2) Oncological Imaging: Now, Future and Impact Jerry W. Froelich, (3) Magnetic Resonance Spectroscopy/Spectroscopic Imaging and Nuclear Medicine: Past, Present and Future by H. Cecil Charles, and (4) MR Cardiology: Now, Future and Impact by Robert J. Herfkens.

  1. NMR clinical imaging and spectroscopy: Its impact on nuclear medicine

    Energy Technology Data Exchange (ETDEWEB)


    This is a collection of four papers describing aspects of past and future use of nuclear magnetic resonance as a clinical diagnostic tool. The four papers are entitled (1) What Does NMR Offer that Nuclear Medicine Does Not? by Jerry W. Froelich, (2) Oncological Imaging: Now, Future and Impact Jerry W. Froelich, (3) Magnetic Resonance Spectroscopy/Spectroscopic Imaging and Nuclear Medicine: Past, Present and Future by H. Cecil Charles, and (4) MR Cardiology: Now, Future and Impact by Robert J. Herfkens.

  2. 1999 Rose Site 31P (United States)

    US Fish and Wildlife Service, Department of the Interior — Underwater Site 31P was established off Rose Atoll, American Samoa by Dr. James Maragos, U.S. Fish & Wildlife Service, on August 22, 1999. The site was...

  3. 2005 Rose Site 31P (United States)

    US Fish and Wildlife Service, Department of the Interior — Underwater Site 31P was established off Rose Atoll, American Samoa by Dr. James Maragos, U.S. Fish (5) = between meters 4 and 5). Quantitative analysis of the...

  4. 2012 Rose Site 31P (United States)

    US Fish and Wildlife Service, Department of the Interior — Underwater Site 31P was established off Rose Atoll, American Samoa by Dr. James Maragos, U.S. Fish & Wildlife Service, on August 22, 1999. The site was...

  5. 2006 Rose Site 31P (United States)

    US Fish and Wildlife Service, Department of the Interior — Underwater Site 31P was established off Rose Atoll, American Samoa by Dr. James Maragos, U.S. Fish & Wildlife Service, on August 22, 1999. The site was...

  6. 2004 Rose Site 31P (United States)

    US Fish and Wildlife Service, Department of the Interior — Underwater Site 31P was established off Rose Atoll, American Samoa by Dr. James Maragos, U.S. Fish & Wildlife Service, on August 22, 1999. The site was...

  7. Insulin induces a positive relationship between the rates of ATP and glycogen changes in isolated rat liver in presence of glucose; a 31P and 13C NMR study

    Directory of Open Access Journals (Sweden)

    Gin Henri


    Full Text Available Abstract Background There is an emerging theory suggesting that insulin, which is known to be the predominant postprandial anabolic hormone, is also a major regulator of mitochondrial oxidative phosphorylation in human skeletal muscle. However, little is known about its effects in the liver. Since there is a theoretical relationship between glycogen metabolism and energy status, a simultaneous and continuous investigation of hepatic ATP and glycogen content was performed in intact and isolated perfused liver by 31P and 13C nuclear magnetic resonance (NMR The hepatic rates of ATP and glycogen changes were evaluated with different concentrations of insulin and glucose during continuous and short-term supply. Results Liver from rats fed ad libitum were perfused with Krebs-Henseleit Buffer (KHB(controls or KHB containing 6 mM glucose, 30 mM glucose, insulin alone, insulin + 6 mM glucose, insulin + 30 mM glucose. In the control, glycogenolysis occurred at a rate of -0.53 ± 0.021 %·min-1 and ATP content decreased at a rate of -0.28 ± 0.029 %·min-1. In the absence of insulin, there was a close proportional relationship between the glycogen flux and the glucose concentration, whereas ATP rates never varied. With insulin + glucose, both glycogen and ATP rates were strongly related to the glucose concentration; the magnitude of net glycogen flux was linearly correlated to the magnitude of net ATP flux: fluxglycogen = 72.543(fluxATP + 172.08, R2 = 0.98. Conclusion Only the co-infusion of 30 mM glucose and insulin led to (i a net glycogen synthesis, (ii the maintenance of the hepatic ATP content, and a strong positive correlation between their net fluxes. This has never previously been reported. The specific effect of insulin on ATP change is likely related to a rapid stimulation of the hepatic mitochondrial oxidative phosphorylation. We propose that variations in the correlation between rates of ATP and glycogen changes could be a probe for insulin

  8. Structural Characterization of Intrinsically Disordered Proteins by NMR Spectroscopy

    Directory of Open Access Journals (Sweden)

    Peter Tompa


    Full Text Available Recent advances in NMR methodology and techniques allow the structural investigation of biomolecules of increasing size with atomic resolution. NMR spectroscopy is especially well-suited for the study of intrinsically disordered proteins (IDPs and intrinsically disordered regions (IDRs which are in general highly flexible and do not have a well-defined secondary or tertiary structure under functional conditions. In the last decade, the important role of IDPs in many essential cellular processes has become more evident as the lack of a stable tertiary structure of many protagonists in signal transduction, transcription regulation and cell-cycle regulation has been discovered. The growing demand for structural data of IDPs required the development and adaption of methods such as 13C-direct detected experiments, paramagnetic relaxation enhancements (PREs or residual dipolar couplings (RDCs for the study of ‘unstructured’ molecules in vitro and in-cell. The information obtained by NMR can be processed with novel computational tools to generate conformational ensembles that visualize the conformations IDPs sample under functional conditions. Here, we address NMR experiments and strategies that enable the generation of detailed structural models of IDPs.

  9. Extracting protein dynamics information from overlapped NMR signals using relaxation dispersion difference NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Konuma, Tsuyoshi [Icahn School of Medicine at Mount Sinai, Department of Structural and Chemical Biology (United States); Harada, Erisa [Suntory Foundation for Life Sciences, Bioorganic Research Institute (Japan); Sugase, Kenji, E-mail:, E-mail: [Kyoto University, Department of Molecular Engineering, Graduate School of Engineering (Japan)


    Protein dynamics plays important roles in many biological events, such as ligand binding and enzyme reactions. NMR is mostly used for investigating such protein dynamics in a site-specific manner. Recently, NMR has been actively applied to large proteins and intrinsically disordered proteins, which are attractive research targets. However, signal overlap, which is often observed for such proteins, hampers accurate analysis of NMR data. In this study, we have developed a new methodology called relaxation dispersion difference that can extract conformational exchange parameters from overlapped NMR signals measured using relaxation dispersion spectroscopy. In relaxation dispersion measurements, the signal intensities of fluctuating residues vary according to the Carr-Purcell-Meiboon-Gill pulsing interval, whereas those of non-fluctuating residues are constant. Therefore, subtraction of each relaxation dispersion spectrum from that with the highest signal intensities, measured at the shortest pulsing interval, leaves only the signals of the fluctuating residues. This is the principle of the relaxation dispersion difference method. This new method enabled us to extract exchange parameters from overlapped signals of heme oxygenase-1, which is a relatively large protein. The results indicate that the structural flexibility of a kink in the heme-binding site is important for efficient heme binding. Relaxation dispersion difference requires neither selectively labeled samples nor modification of pulse programs; thus it will have wide applications in protein dynamics analysis.

  10. New generation NMR bioreactor coupled with high-resolution NMR spectroscopy leads to novel discoveries in Moorella thermoaceticum metabolic profiles

    Energy Technology Data Exchange (ETDEWEB)

    Xue, Junfeng; Isern, Nancy G.; Ewing, R James; Liyu, Andrey V.; Sears, Jesse A.; Knapp, Harlan; Iversen, Jens; Sisk, Daniel R.; Ahring, Birgitte K.; Majors, Paul D.


    An in-situ nuclear magnetic resonance (NMR) bioreactor was developed and employed to monitor microbial metabolism under batch-growth conditions in real time. We selected Moorella thermoacetica ATCC 49707 as a test case. M. thermoacetica (formerly Clostridium thermoaceticum) is a strictly anaerobic, thermophilic, acetogenic, gram-positive bacterium with potential for industrial production of chemicals. The metabolic profiles of M. thermoacetica were characterized during growth in batch mode on xylose (a component of lignocellulosic biomass) using the new generation NMR bioreactor in combination with high-resolution, high sensitivity NMR (HR-NMR) spectroscopy. In-situ NMR measurements were performed using water-suppressed H-1 NMR spectroscopy at an NMR frequency of 500 MHz, and aliquots of the bioreactor contents were taken for 600 MHz HR-NMR spectroscopy at specific intervals to confirm metabolite identifications and expand metabolite coverage. M. thermoacetica demonstrated the metabolic potential to produce formate, ethanol and methanol from xylose, in addition to its known capability of producing acetic acid. Real-time monitoring of bioreactor conditions showed a temporary pH decrease, with a concomitant increase in formic acid during exponential growth. Fermentation experiments performed outside of the magnet showed that the strong magnetic field employed for NMR detection did not significantly affect cell metabolism. Use of the in-situ NMR bioreactor facilitated monitoring of the fermentation process in real time, enabling identification of intermediate and end-point metabolites and their correlation with pH and biomass produced during culture growth. Real-time monitoring of culture metabolism using the NMR bioreactor in combination with the HR-NMR spectroscopy will allow optimization of the metabolism of microorganisms producing valuable bioproducts.

  11. {sup 31}P-MR spectroscopy of the brain in patients with anorexia nervosa: characteristic differences in the spectra between patients and healthy control subjects; {sup 31}P-MRS des Hirns bei Anorexia nervosa: charakteristische Unterschiede in den Spektren von Patienten und gesunden Vergleichspersonen

    Energy Technology Data Exchange (ETDEWEB)

    Rzanny, R.; Reichenbach, J.R.; Mentzel, H.J.; Pfleiderer, S.O.R.; Kaiser, W.A. [Inst. fuer Diagnostische und Interventionelle Radiologie, Klinikum der Friedrich-Schiller-Univ. Jena (Germany); Freesmeyer, D.; Klemm, S.; Gerhard, U.J.; Blanz, B. [Klinik fuer Kinder- und Jugendpsychiatrie, Klinikum der Friedrich-Schiller-Univ. Jena (Germany)


    Purpose: To investigate whether {sup 31}P-MR spectroscopy can detect reduced concentrations of high-energy phosphates, like PCr and NTP, caused by decreased metabolic activity in the brain of patients with anorexia nervosa (AN) and, furthermore, whether any impairment of the cerebral membrane metabolism can be derived from the spectra. Material and Methods: 10 female patients, age range 12 - 20 years and mean BMI (body mass index) of 14.8 {+-} 1.6 kg/m{sup 2}, with clinically diagnosed AN (ICD-10, F50.0) and 10 healthy control subjects, age range 12 - 21 years and mean BMI 19.0 {+-} 2.1 kg/m{sup 2}, without nutritional disturbances: were investigated. {sup 31}P-MR spectroscopy was performed with a 1.5 T MRI unit using single volume selection in the frontal/prefrontal region of brain. Relative metabolic concentrations were quantified by normalizing the peak areas of the metabolites with the total area of the complete phosphorous spectrum, P{sub tot}, as well as with the peak area of β-NTP. Results: Significant differences between the two groups were observed for the metabolic ratios PDE/P{sub tot}, PDE/β-NTP and {alpha}-NTP/P{sub tot} which were lower in the patient group except for {alpha}-NTP/P{sub tot}. These ratios also revealed a statistically significant correlation with the BMI (r{sub PDE/Ptot} = 0.747, r{sub PDE/β-NTP} = 0.57, r{sub {alpha}}{sub -NTP/Ptot} = -0.56; p {<=} 0.1). Reduced relative concentrations of PCr/P{sub tot}, β-NTP/P{sub tot} or Pi/P{sub tot} were not encountered. Conclusion: The lowered PDE/P{sub tot} ratio for patients with AN and its correlation with BMI suggests that decreased BMI induces compositional changes of the phospholipids in the brain, which decrease the fraction of mobile phospholipids. (orig.) [German] Problemstellung: Das Ziel dieser Studie war es zu untersuchen, ob mit Hilfe der {sup 31}P-MR-Spektroskopie ({sup 31}P-MRS) im Gehirn von Patienten mit Anorexia nervosa (AN) verringerte Konzentrationen an

  12. New generation NMR bioreactor coupled with high-resolution NMR spectroscopy leads to novel discoveries in Moorella thermoacetica metabolic profiles. (United States)

    Xue, Junfeng; Isern, Nancy G; Ewing, R James; Liyu, Andrei V; Sears, Jesse A; Knapp, Harlan; Iversen, Jens; Sisk, Daniel R; Ahring, Birgitte K; Majors, Paul D


    An in situ nuclear magnetic resonance (NMR) bioreactor was developed and employed to monitor microbial metabolism under batch growth conditions in real time. We selected Moorella thermoacetica ATCC 49707 as a test case. M. thermoacetica (formerly Clostridium thermoaceticum) is a strictly anaerobic, thermophilic, acetogenic, gram-positive bacterium with potential for industrial production of chemicals. The metabolic profiles of M. thermoacetica were characterized during growth in batch mode on xylose (a component of lignocellulosic biomass) using the new generation NMR bioreactor in combination with high-resolution NMR (HR-NMR) spectroscopy. In situ NMR measurements were performed using water-suppressed H-1 NMR spectroscopy at 500 MHz, and aliquots of the bioreactor contents were taken for 600-MHz HR-NMR spectroscopy at specific intervals to confirm metabolite identifications and expand metabolite coverage. M. thermoacetica demonstrated the metabolic potential to produce formate, ethanol, and methanol from xylose, in addition to its known capability of producing acetic acid. Real-time monitoring of bioreactor conditions showed a temporary pH decrease, with a concomitant increase in formic acid during exponential growth. Fermentation experiments performed outside of the magnet showed that the strong magnetic field employed for NMR detection did not significantly affect cell metabolism. Use of the in situ NMR bioreactor facilitated monitoring of the fermentation process, enabling identification of intermediate and endpoint metabolites and their correlation with pH and biomass produced during culture growth. Real-time monitoring of culture metabolism using the NMR bioreactor in combination with HR-NMR spectroscopy will allow optimization of the metabolism of microorganisms producing valuable bioproducts.

  13. Changes of high-energy phosphorous compounds in skeletal muscle during glucose-induced thermogenesis in man. A 31P MR spectroscopy study

    DEFF Research Database (Denmark)

    Thomsen, C; Jensen, Karl Erik; Astrup, A


    spectroscopy during an oral glucose load in healthy lean subjects. The inorganic phosphate concentration increased gradually (P less than 0.05) after glucose intake. The phosphocreatine/inorganic phosphate rate decreased (P less than 0.05) and the estimated ADP concentration increased. ATP and intracellular p......H remained unchanged after the glucose administration. No changes were seen in the control experiments. The processes responsible for the decreased energy state of the skeletal muscle cell may be an obligatory conversion of glucose to glycogen. Also, facultative processes, such as sodium/potassium pumping...

  14. Report on neptunium speciation by NMR and optical spectroscopies

    Energy Technology Data Exchange (ETDEWEB)

    Tait, C.D.; Palmer, P.D.; Ekberg, S.A.; Clark, D.L.


    Hydrolysis and carbonate complexation reactions were examined for NpO{sub 2}{sup 2+} and NpO{sub 2}{sup +} ions by a variety of techniques including potentiometric titration, UV-Vis-NIR and NMR spectroscopy. The equilibrium constant for the reaction 3NpO{sub 2}(CO{sub 3}){sub 3}{sup 4{minus}} + 3H{sup +} {rightleftharpoons} (NpO{sub 2}){sub 3}(CO{sub 3}){sub 6}{sup 6{minus}} + 3HCO{sub 3}{sup {minus}} was determined to be logK = 19.7 ({plus_minus} 0.8) (I = 2.5 m). {sup 17}O NMR spectroscopy of NpO{sub 2}{sup n+} ions (n = 1,2) reveals a readily observable {sup 17}O resonance for n = 2, but not for n = 1. The first hydrolysis constant for NpO{sub 2}{sup +} was studied as a function of temperature, and the functional form for the temperature-dependent equilibrium constant for the reaction written as NpO{sub 2}{sup +} + H{sub 2}O {rightleftharpoons} NpO{sub 2}OH + H{sup +} was found to be logK = 2.28 {minus} 3780/T, where T is in {degree}K. Finally, the temperature dependence of neptunium(V) carbonate complexation constants was studied. For the first carbonate complexation constant, the appropriate functional form was found to be log{beta}{sub 01} = 1.47 + 786/T.

  15. Potential of NMR Spectroscopy in the Characterization of Nonconventional Oils

    Directory of Open Access Journals (Sweden)

    Abdul Majid


    Full Text Available NMR spectroscopy was applied for the characterization of two biomass based pyrolysis oil samples. The samples were extracted in various solvents and the extracts were investigated by both 1H and 13C NMR spectroscopy. Subsequent evaluation of the integrated analytical data revealed chemical information regarding semiquantitative estimation of various functional groups. This information could not have been obtained readily from the individual spectroscopic techniques. Semiquantitative estimation of the various functional groups allowed a comparison of the extraction efficiency of these groups in various solvents. The method is based on the premise that although the number of individual molecular species in pyrolysis oil liquid is large, most of these species are composed of a limited number of functional groups. The methodology provided information on the concentration of chemical functionalities that are potentially useful for synthetic modifications and may help to guide the use of pyrolysis oil as a chemical feedstock. The approach described is expected to be generally applicable to complex mixture of hydrocarbon oils such as bio-oils, oil sands bitumen, and coal pyrolysis oils.

  16. 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


    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)

  17. Phospholipid composition and organization of cytochrome c oxidase preparations as determined by 31P-nuclear magnetic resonance. (United States)

    Seelig, A; Seelig, J


    The molecular organization as well as the composition of the phospholipids in cytochrome c oxidase preparations (bovine heart) were investigated by 31P-nuclear magnetic resonance. In the so-called 'lipid-rich' preparation the lipids were found to form a fluid bilayer around the enzyme since the 31P-NMR spectrum was characteristic of a fast, axially symmetric motion of the phosphate groups with a chemical shift anisotropy of delta sigma = -45 ppm. In contrast, the 'lipid-depleted' cytochrome c oxidase gave rise to a broader spectrum where the motion of the phospholipids was no longer axially symmetric. Nevertheless, the total width of the spectrum was still considerably narrower than observed for immobilized phospholipids in solid crystals. Both enzyme preparations were dissolved in 1% detergent solution and used for high-resolution 31P-NMR spectroscopy. Narrow lines of about 20 Hz linewidth were obtained for both types of enzyme preparations, and well-resolved resonances could be assigned to cardiolipin, phosphatidylethanolamin and phosphatidylcholine. The major differences between lipid-rich and lipid-depleted cytochrome c oxidase were the absolute amount of phospholipid associated with the protein and the relative contribution of the individual lipid classes to the 31P-NMR spectrum. For lipid-rich cytochrome c oxidase about 130 molecules phospholipid were bound per enzyme (approx. 11 cardiolipins, 54 phosphatidylethanolamines and 64 phosphatidylcholines). For lipid-depleted cytochrome c oxidase only 6-18 lipids were bound per enzyme (1 or 2 cardiolipins, 3-8 phosphatidylethanolamines and 2-8 phosphatidylcholines). In contrast to earlier suggestions that cardiolipin is the only remaining lipid in lipid-depleted cytochrome c oxidase, the 31P-NMR studies demonstrate that all three lipids remain associated with the protein.

  18. Ageing of Starch Based Systems as observed with FT-IR and Solid State NMR Spectroscopy

    NARCIS (Netherlands)

    Smits, A.L.M.; Ruhnau, F.C.; Vliegenthart, J.F.G.; Soest, van J.J.G.


    The retrogradation and physical ageing of model starch systems with respect to their glass transition temperatures Tg have been investigated by Fourier transform infrared spectroscopy and solid state NMR spectroscopy. Diffuse reflectance Fourier transform infrared (DRIFT) spectra demonstrate the com

  19. Ageing of starch based systems as observed with FT-IR and solid state NMR spectroscopy

    NARCIS (Netherlands)

    Vliegenthart, J.F.G.; Smits, A.L.M.; Ruhnau, F.C.; Soest, J.J.G. van


    The retrogradation and physical ageing of model starch systems with respect to their glass transition temperatures Tg have been investigated by Fourier transform infrared Spectroscopy and solid state NMR spectroscopy. Diffuse reflectance Fourier transform infrared (DRIFT) spectra demonstrate the com

  20. Photochromism of indolino-benzopyrans studied by NMR and UV-visible spectroscopy

    Directory of Open Access Journals (Sweden)

    S. Delbaere


    is described. The structures of photomerocyanines elucidated by NMR spectroscopy and spectrokinetic data (λmax⁡ of colored form, colorability, and rate constant of bleaching obtained by UV-visible spectroscopy are reported.

  1. Multiplicative or t1 Noise in NMR Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Granwehr, Josef


    The signal in an NMR experiment is highly sensitive to fluctuations of the environment of the sample. If, for example, the static magnetic field B{sub 0}, the amplitude and phase of radio frequency (rf) pulses, or the resonant frequency of the detection circuit are not perfectly stable and reproducible, the magnetic moment of the spins is altered and becomes a noisy quantity itself. This kind of noise not only depends on the presence of a signal, it is in fact proportional to it. Since all the spins at a particular location in a sample experience the same environment at any given time, this noise primarily affects the reproducibility of an experiment, which is mainly of importance in the indirect dimensions of a multidimensional experiment, when intense lines are suppressed with a phase cycle, or for difference spectroscopy techniques. Equivalently, experiments which are known to be problematic with regard to their reproducibility, like flow experiments or experiments with a mobile target, tend to be affected stronger by multiplicative noise. In this article it is demonstrated how multiplicative noise can be identified and characterized using very simple, repetitive experiments. An error estimation approach is developed to give an intuitive, yet quantitative understanding of its properties. The consequences for multidimensional NMR experiments are outlined, implications for data analysis are shown, and strategies for the optimization of experiments are summarized.

  2. Metabolomic insight into soy sauce through (1)H NMR spectroscopy. (United States)

    Ko, Bong-Kuk; Ahn, Hyuk-Jin; van den Berg, Frans; Lee, Cherl-Ho; Hong, Young-Shick


    Soy sauce, a well-known seasoning in Asia and throughout the world, consists of many metabolites that are produced during fermentation or aging and that have various health benefits. However, their comprehensive assessment has been limited due to targeted or instrumentally specific analysis. This paper presents for the first time a metabolic characterization of soy sauce, especially that aged up to 12 years, to obtain a global understanding of the metabolic variations through (1)H NMR spectroscopy coupled with multivariate pattern recognition techniques. Elevated amino acids and organic acids and the consumption of carbohydrate were associated with continuous involvement of microflora in aging for 12 years. In particular, continuous increases in the levels of betaine were found during aging for up to 12 years, demonstrating that microbial- or enzyme-related metabolites were also coupled with osmotolerant or halophilic bacteria present during aging. This work provides global insights into soy sauce through a (1)H NMR-based metabolomic approach that enhances the current understanding of the holistic metabolome and allows assessment of soy sauce quality.

  3. Determination of gluconeogenesis in man by the use of deuterium-NMR-spectroscopy

    CERN Document Server

    Rosian, E


    The aim of this dissertation is the quantification of the deuterium--distribution in human glucose by the use of the deuterium NMR spectroscopy of deuteriated water. The glucose production in human organism is composed of gluconeogenesis and glycolysis. The quantification of the part of gluconeogenesis on the total glucose production was determined by the use of deuterium NMR spectroscopy. (boteke)

  4. An Oil Spill in a Tube: An Accessible Approach for Teaching Environmental NMR Spectroscopy (United States)

    Simpson, Andre´ J.; Mitchell, Perry J.; Masoom, Hussain; Mobarhan, Yalda Liaghati; Adamo, Antonio; Dicks, Andrew P.


    NMR spectroscopy has great potential as an instrumental method for environmental chemistry research and monitoring but may be underused in teaching laboratories because of its complexity and the level of expertise required in operating the instrument and interpreting data. This laboratory experiment introduces environmental NMR spectroscopy to…

  5. Applications of high-resolution solid-state NMR spectroscopy in food science. (United States)

    Bertocchi, Fabio; Paci, Maurizio


    The principal applications of high-resolution solid-state NMR spectroscopy, in the field of food science, are reviewed, after a short general introduction, mainly focusing on the potential of these investigations, which are, today, routine tools for resolving technological problems. Selected examples of the applications in the field of food science of high-resolution solid-state NMR spectroscopy both in (13)C and in (1)H NMR particularly illustrative of the results obtainable are reported in some detail.

  6. Characterization of plant-derived carbon and phosphorus in lakes by sequential fractionation and NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Shasha [College of Water Sciences, Beijing Normal University, Beijing 100875 (China); State Key Laboratory of Environment Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); Zhu, Yuanrong, E-mail: [State Key Laboratory of Environment Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); Wu, Fengchang, E-mail: [State Key Laboratory of Environment Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); Meng, Wei [State Key Laboratory of Environment Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); He, Zhongqi [USDA-ARS Southern Regional Research Center, 1100 Robert E Lee Blvd, New Orleans, LA 70124 (United States); Giesy, John P. [State Key Laboratory of Environment Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); Department of Biomedical and Veterinary Biosciences and Toxicology Centre, University of Saskatchewan, Saskatoon, Saskatchewan (Canada)


    Although debris from aquatic macrophytes is one of the most important endogenous sources of organic matter (OM) and nutrients in lakes, its biogeochemical cycling and contribution to internal load of nutrients in eutrophic lakes are still poorly understood. In this study, sequential fractionation by H{sub 2}O, 0.1 M NaOH and 1.0 M HCl, combined with {sup 13}C and {sup 31}P NMR spectroscopy, was developed and used to characterize organic carbon (C) and phosphorus (P) in six aquatic plants collected from Tai Lake (Ch: Taihu), China. Organic matter, determined by total organic carbon (TOC), was unequally distributed in H{sub 2}O (21.2%), NaOH (29.9%), HCl (3.5%) and residual (45.3%) fractions. For P in debris of aquatic plants, 53.3% was extracted by H{sub 2}O, 31.9% by NaOH, and 11% by HCl, with 3.8% in residual fractions. Predominant OM components extracted by H{sub 2}O and NaOH were carbohydrates, proteins and aliphatic acids. Inorganic P (P{sub i}) was the primary form of P in H{sub 2}O fractions, whereas organic P (P{sub o}) was the primary form of P in NaOH fractions. The subsequent HCl fractions extracted fewer species of C and P. Some non-extractable carbohydrates, aromatics and metal phytate compounds remained in residual fractions. Based on sequential extraction and NMR analysis, it was proposed that those forms of C (54.7% of TOC) and P (96.2% of TP) in H{sub 2}O, NaOH and HCl fractions are potentially released to overlying water as labile components, while those in residues are stable and likely preserved in sediments of lakes. These results will be helpful in understanding internal loading of nutrients from debris of aquatic macrophytes and their recycling in lakes. - Highlights: • Sequential fractionation combined with NMR analysis was applied on aquatic plants. • Labile and stable C and P forms in aquatic plants were characterized. • 54.7% of OM and 96.2% of P in aquatic plants are potentially available. • 45.3% of OM and 3.8% of P in aquatic

  7. In vivo 31P nuclear magnetic resonance investigation of tellurite toxicity in Escherichia coli. (United States)

    Lohmeier-Vogel, Elke M; Ung, Shiela; Turner, Raymond J


    Here we compare the physiological state of Escherichia coli exposed to tellurite or selenite by using the noninvasive technique of phosphorus-31 nuclear magnetic resonance (NMR) spectroscopy. We studied glucose-fed Escherichia coli HB101 cells containing either a normal pUC8 plasmid with no tellurite resistance determinants present or the pTWT100 plasmid which contains the resistance determinants tehAB. No differences could be observed in intracellular ATP levels, the presence or absence of a transmembrane pH gradient, or the levels of phosphorylated glycolytic intermediates when resistant cells were studied by 31P NMR in the presence or absence of tellurite. In the sensitive strain, we observed that the transmembrane pH gradient was dissipated and intracellular ATP levels were rapidly depleted upon exposure to tellurite. Only the level of phosphorylated glycolytic intermediates remained the same as observed with resistant cells. Upon exposure to selenite, no differences could be observed by 31P NMR between resistant and sensitive strains, suggesting that the routes for selenite and tellurite reduction within the cells differ significantly, since only tellurite is able to collapse the transmembrane pH gradient and lower ATP levels in sensitive cells. The presence of the resistance determinant tehAB, by an as yet unidentified detoxification event, protects the cells from uncoupling by tellurite.

  8. 31-phosphorus magnetic resonance spectroscopy in diagnosis of the benign and malignant masses in liver%~(31)P-MRS在肝脏良、恶性占位性病变中的诊断价值

    Institute of Scientific and Technical Information of China (English)

    于德新; 刘成; 李传福; 张晓明; 马祥兴


    目的 探讨~(31)P磁共振波谱成像(MRS)在肝脏良、恶性占位性病变诊断中的价值.方法分别对35个(其中肝脓肿13个)肝脏良性病灶及62个恶性病灶进行单体素~(31)P-MRS扫描,计算肝细胞内pH值(pHi)、磷酸单脂(PME)、磷酸双脂(PDE)、无机磷(Pi)、γ-、β-、及α-三磷酸腺苷(ATP)、PME/ATP、Pi/ATP、PME/PDE、PME/Pi、PDE/Pi、PDE/ATP和低能磷酸盐(LEP)等参数.分析以上代谢参数在良、恶性病变之间差异.结果在良、恶性病变之间,γ-ATP分别为1279.46±432.21和758.22±240.79,Pi/A1P分别为3.98±0.86和5.36±0.96,差异均有统计学意义(P0.05).结论~(31)P-MRS代谢物γ-ATP和Pi/ATP可作为鉴别肝脏良、恶性病变的参数,pHi值有助于肝脓肿与肝脏肿瘤的鉴别.%Objective To probe the clinical value of 31-phosphorus magnetic resonance spectroscopy(~(31)P-MRS) in vivo at 3.0 Tesla in diagnosis of the benign and malignant masses. Methods~(31)P-MRS scanning with a single voxel was carried out on 35 benign tumors, 62 malignant ones and 13 hepatic abscesses. Intracellular pH value (pHi), and some metabolic parameters in-cluding phosphomonoester (PME), phosphodiester (PDE), inorganic phosphate (Pi), γ-,β-, and α- adenosine triphosphate (ATP), lower energetic phosphate (LEP), and the ratios of PME/ATP, Pi/ATP, PME/PDE, PME/Pi, PDE/Pi and PDE/ATP were calculated. The differences in the metabolic parameters above between benign and malignant groups were analyzed. Results The differences inγ-ATP, which were 1279.46±432.21 and 758.22±240.79 in benign and malignant lesions respectively, and Pi/ATP, 3.98±0.8 and 5.36±0.96, were identified statistically (P0.05). Conclusion Such phosphorus metabolites as γ-ATP and Pi/ATP in HCC may be used to differentiate the benign and malignant masses, while pHi is helpful for the diagnosis of hepatic abscesses.

  9. Ion counting in supercapacitor electrodes using NMR spectroscopy. (United States)

    Griffin, John M; Forse, Alexander C; Wang, Hao; Trease, Nicole M; Taberna, Pierre-Louis; Simon, Patrice; Grey, Clare P


    (19)F NMR spectroscopy has been used to study the local environments of anions in supercapacitor electrodes and to quantify changes in the populations of adsorbed species during charging. In the absence of an applied potential, anionic species adsorbed within carbon micropores (in-pore) are distinguished from those in large mesopores and spaces between particles (ex-pore) by a characteristic nucleus-independent chemical shift (NICS). Adsorption experiments and two-dimensional exchange experiments confirm that anions are in dynamic equilibrium between the in- and ex-pore environments with an exchange rate in the order of tens of Hz. (19)F in situ NMR spectra recorded at different charge states reveal changes in the intensity and NICS of the in-pore resonances, which are interpreted in term of changes in the population and local environments of the adsorbed anions that arise due to the charge-storage process. A comparison of the results obtained for a range of electrolytes reveals that several factors influence the charging mechanism. For a tetraethylammonium tetrafluoroborate electrolyte, positive polarisation of the electrode is found to proceed by anion adsorption at a low concentration, whereas increased ion exchange plays a more important role for a high concentration electrolyte. In contrast, negative polarization of the electrode proceeds by cation adsorption for both concentrations. For a tetrabutylammonium tetrafluoroborate electrolyte, anion expulsion is observed in the negative charging regime; this is attributed to the reduced mobility and/or access of the larger cations inside the pores, which forces the expulsion of anions in order to build up ionic charge. Significant anion expulsion is also observed in the negative charging regime for alkali metal bis(trifluoromethane)sulfonimide electrolytes, suggesting that more subtle factors also affect the charging mechanism.

  10. Nuclear Magnetic Resonance (NMR) Spectroscopy For Metabolic Profiling of Medicinal Plants and Their Products. (United States)

    Kumar, Dinesh


    NMR spectroscopy has multidisciplinary applications, including excellent impact in metabolomics. The analytical capacity of NMR spectroscopy provides information for easy qualitative and quantitative assessment of both endogenous and exogenous metabolites present in biological samples. The complexity of a particular metabolite and its contribution in a biological system are critically important for understanding the functional state that governs the organism's phenotypes. This review covers historical aspects of developments in the NMR field, its applications in chemical profiling, metabolomics, and quality control of plants and their derived medicines, foods, and other products. The bottlenecks of NMR in metabolic profiling are also discussed, keeping in view the future scope and further technological interventions.

  11. Multidimensional solid-state NMR spectroscopy of plant cell walls. (United States)

    Wang, Tuo; Phyo, Pyae; Hong, Mei


    Plant biomass has become an important source of bio-renewable energy in modern society. The molecular structure of plant cell walls is difficult to characterize by most atomic-resolution techniques due to the insoluble and disordered nature of the cell wall. Solid-state NMR (SSNMR) spectroscopy is uniquely suited for studying native hydrated plant cell walls at the molecular level with chemical resolution. Significant progress has been made in the last five years to elucidate the molecular structures and interactions of cellulose and matrix polysaccharides in plant cell walls. These studies have focused on primary cell walls of growing plants in both the dicotyledonous and grass families, as represented by the model plants Arabidopsis thaliana, Brachypodium distachyon, and Zea mays. To date, these SSNMR results have shown that 1) cellulose, hemicellulose, and pectins form a single network in the primary cell wall; 2) in dicot cell walls, the protein expansin targets the hemicellulose-enriched region of the cellulose microfibril for its wall-loosening function; and 3) primary wall cellulose has polymorphic structures that are distinct from the microbial cellulose structures. This article summarizes these key findings, and points out future directions of investigation to advance our fundamental understanding of plant cell wall structure and function.

  12. 骨和软组织肿瘤的3.0T磁共振磷谱变化研究%Changes of 3-tesla 31P-MR spectroscopy of bone and soft tissue tumors

    Institute of Scientific and Technical Information of China (English)

    齐滋华; 李传福; 马祥兴; 李振峰; 张凯; 于德新


    Objective To study the characteristic changes of 31P-MR spectroscopy of bone and soft tissue tumors. Methods 41 patients were examined by phosphorus surface coil of 3 tesla MR machine, including 18 benign tumor foci and 28 malignant foci, and adjacent normal muscles. The areas under the peaks of various metabolites in the spectra were measured, including phosphomonoester(PME), inorganic phosphours (Pi), phosphodiester(PDE), phosphocreatine ( Pcr ), adenosine triphosphate (ATP) γ, α, β. The ratios of the metabolites to β-ATP, NTP and Pcr were calculated. Intracellular pH was calculated according to the chemical shift change of Pi relative to Per. Results The ratios of Pcr/PME and PME/NTP in benign and malignant tumor groups were significantly different from those of the normal group ( P < 0.05). Between benign and malignant tumor groups, the ratios of PME/β-ATP and PME/NTP were significantly different (P < 0.05). Conclusion Pcr/PME and PME/NTP are potential diagnostic indexes of bone and soft tissue tumors. PME/β-ATP and PME/NTP are potential indexes of differential diagnosis of bone and soft tissue tumors.%目的 探讨骨和软组织肿瘤磁共振磷谱(31P-MRS)的变化特点.方法 对41例经病理证实的骨和软组织肿瘤患者的18个良性肿瘤病灶、28个恶性肿瘤病灶及其相邻部位正常肌肉组织,应用3.0T MR机进行31P-MRS分析,测量波谱中磷酸单酯(PME)、无机磷(Pi)、磷酸二酯(PDE)、磷酸肌酸(Pcr)、三磷酸腺苷γ-峰(γ-ATP)、α-峰(α-ATP)和β-峰(β-ATP)的峰下面积.分别以β-ATP、三磷酸核苷(NTP)和Pcr为参照,计算各代谢产物的相对比值.根据Pi相对于Pcr化学位移的变化计算细胞内pH值.结果 良、恶性肿瘤组中Pcr/PME、PME/NTP与正常对照组比较,差异均有统计学意义(P<0.05).良、恶性肿瘤组中PME/β-ATP与PME/NTP比较,差异有统计学意义(P<0.05).结论 Pcr/PME和PME/NTP是诊断骨和软组织肿瘤的潜在指标,PME/β-ATP和PME/NTP是

  13. Thermodynamic and structural behaviour of equimolar POPC/CnE4 (n=8, 12, 16) mixtures by sorption gravimetry, 2H NMR spectroscopy and X-ray diffraction. (United States)

    Pfeiffer, H; Klose, G; Heremans, K


    The hydration behaviour of equimolar mixtures of phospholipids and nonionic surfactants with different chain length was investigated by gravimetric sorption, NMR spectroscopy and X-ray diffraction. At the most hydration degrees investigated, the incorporation of nonionic surfactants in a phospholipid bilayer leads to an increase of the hydrophilicity, which can be shown by the presence of excess hydration. The increased hydrophilicity could be explained by the excavation of additional water binding sites due to the "dilution" of the dipole field of the phospholipid bilayer. Another related contribution arises from the increase of the accessible surface area due to the increase of gauche conformers that result from the steric mismatch when surfactants are incorporated into the phospholipid matrix. (2)H NMR spectroscopy was used to determine the quadrupolar splitting representing a measure of the order state of water. The swelling behaviour could be assessed by small-angle X-ray diffraction. (31)P NMR spectroscopy was applied for the assignment of phase structures to the respective hydration range.

  14. Characterizations of Some N-Substituted-salicylhydrazide in Mixtures by NMR Diffusion Ordered Spectroscopy

    Institute of Scientific and Technical Information of China (English)

    张芳; 于贤勇; 陈忠; 林深; 刘世雄


    Several novel N-substituted-salicylhydrazide ligands, most of which are difficult to be purified or recrystallized so that their chemical configurations can not be confirmed by conventional NMR and/or X-ray diffraction techniques, were synthesized in this experiment, and their chemical configurations in mixture were analyzed and characterized by 2D NMR diffusion ordered spectroscopy (DOSY), a labor-saving virtual separation based on diffusion properties,together with several routine NMR techniques.

  15. Studies of Molecular Dynamics by Solid State Deuterium NMR Spectroscopy (United States)

    Zhao, Baiyi

    The rotational dynamics of molecules in a number of solid systems were followed by variable temperature deuterium (^2H), nuclear magnetic resonance (NMR) spectroscopy via changes in the spectral lineshapes and spin-lattice relaxation times (T _1). First the pure solid trimethylamine-borane adduct, (CH_3)_3NBH_3, was studied. For a methyl deuterated sample, T _1 measurements yielded two T_1 minima, 6.9 ms and 4.3 ms corresponding to the slowing of methyl and trimethyl rotation, respectively, with decreasing temperature. Activation energies for methyl and trimethyl rotation, obtained from fitting the T _1 curve as a function of temperature, were 32.8 and 15.0 kJ/mol, respectively; simulations of the spectral lineshapes gave 26.6 and 18.9 kT/mol, respectively. Fitting of the ^2H T_1 curve for the borane deuterated sample gave a BH _3 rotation activation energy of 14.1 kT/mol and a ^2H quadrupolar coupling constant, chi, of 101 kHz. The activation energy for BH_3 rotation obtained from the spectral lineshape simulations gave 12.6 kT/mol. A series of deuterated organic chalcogen cations: (CH_3)_3S^+, (CH_3)_3Se^+ and (CH_3)_3Te^+, were ion exchanged into the cavities of sodium Mordenite LZ-M5 and the dynamics of these guests within the hydrated zeolite were followed by ^2H NMR. All three undergo isotropic motion above about -80 to -90^circC. Below this temperature two superimposed ^2H powder spectra appear; the broad lineshape is consistent with only methyl rotation in a hindered, coordinated site, and the other narrow lineshape is due to both methyl and trimethyl rotation in a less hindered, uncoordinated site. As the temperature is lowered the population of the lower energy coordinated site increases. Relative peak areas yield adsorption enthalpies of 6.7, 7.8 and 10.0 kJ/mol for (CH_3)_3S^+, (CH_3)_3Se^+ and (CH_3)_3Te^+, respectively. The series of methyl deuterated ammonium and phosphonium cations: (CH_3)NH_3^+ , (CH_3)_2NH^+ , (CH_3)_3NH^+ and (CH_3)_4P^+ , were

  16. 健康成人延迟性肌肉酸痛31P-MR波谱及其与肌酸激酶、酸痛指数相关性分析%The changes of healthy adults delayed onset muscle soreness 31P-MR spectroscopy and correlation between serum creatine kinase and soreness index

    Institute of Scientific and Technical Information of China (English)

    王希海; 陈超; 卢昊宁; 孟帆; 李飞; 王子文; 富聪聪; 夏丽莹; 富西湖


    目的 分析健康志愿者股四头肌延迟性肌肉酸痛(DOMS)31P-MRS影像特征,及其与肌酸激酶(CK)、酸痛指数相关性.方法 选取10名健康志愿者.所有受试者运用短距离重复跑运动模式进行训练以获得DOMS模型,且在运动前,运动后即刻、1、2、3、5、7d对右侧股四头肌进行31 P-MRS扫描、血清学CK浓度检查、肌肉酸痛指数评分,分别测量31P-MRS无机磷酸盐(Pi)、磷酸肌酸(PCr)和三磷酸腺苷(ATP)峰下面积,并计算Pi/PCr、PCr/ATP、Pi/ATP比值.运用重复测量资料的方差分析对各指标不同时间上的变化的特点进行分析.用Spearman秩相关分析对31P-MRS测量结果与CK值、酸痛指数进行相关性分析.结果 10名健康志愿者右侧股四头肌31P-MRS检查显示Pi峰下面积、Pi/PCr在运动后随时间逐渐增加,在运动后1~2 d达到最大值(分别为0.33 ±0.04、0.27±0.03),两者在时间上有一致性.PCr及ATP峰下面积在运动后即刻较运动前明显下降,在运动后1d逐渐恢复到运动前水平(分别为0.28±0.05、1.22 ±0.04).CK在运动后即刻轻度增高,运动后1d血清中CK[(577±223) U/L]明显增高达到峰值,运动后2 d[(483 ±229) U/L]逐渐下降但仍明显高于运动前水平[(86±30) U/L],运动后7dCK逐渐恢复到运动前水平.Pi峰下面积及Pi/PCr与CK均呈正相关(r值分别为0.631、0.614,P值均<0.01).PCr峰下面积、ATP峰下面积与CK值无相关性(r值分别为0.044、0.188,P值均>0.05).Pi峰下面积、Pi/PCr、Pi/ATP与酸痛指数相呈正相关(r值分别为0.762、0.758,0.616,P值均<0.05).结论 31P-MRS能够有效评估DOMS后骨骼肌代谢产物的变化规律,31P-MRS与血清学指标、肌肉酸痛指数能够对DOMS进行综合评价,十分有助于为运动训练提供科学的理论依据和指导.

  17. Integration of screening and identifying ligand(s) from medicinal plant extracts based on target recognition by using NMR spectroscopy



    Authors: Yalin Tang, Qian Shang, Junfeng Xiang, Qianfan Yang, Qiuju Zhou, Lin Li, Hong Zhang, Qian Li, Hongxia Sun, Aijiao Guan, Wei Jiang & Wei Gai ### Abstract This protocol presents the screening of ligand(s) from medicinal plant extracts based on target recognition by using NMR spectroscopy. A detailed description of sample preparation and analysis process is provided. NMR spectroscopies described here are 1H NMR, diffusion-ordered spectroscopy (DOSY), relaxation-edited NMR, ...

  18. Development of a micro flow-through cell for high field NMR spectroscopy.

    Energy Technology Data Exchange (ETDEWEB)

    Alam, Todd Michael; McIntyre, Sarah K.


    A highly transportable micro flow-through detection cell for nuclear magnetic resonance (NMR) spectroscopy has been designed, fabricated and tested. This flow-through cell allows for the direct coupling between liquid chromatography (LC) and gel permeation chromatography (GPC) resulting in the possibility of hyphenated LC-NMR and GPC-NMR. The advantage of the present flow cell design is that it is independent and unconnected to the detection probe electronics, is compatible with existing commercial high resolution NMR probes, and as such can be easily implemented at any NMR facility. Two different volumes were fabricated corresponding to between {approx}3.8 and 10 {micro}L detection volume. Examples of the performance of the cell on different NMR instruments, and using different NMR detection probes were demonstrated.

  19. Structure elucidation of glycoprotein glycans and of polysaccharides by NMR spectroscopy

    NARCIS (Netherlands)

    Vliegenthart, J.F.G.; Leeflang, B.R.; Faber, E.J.; Erbel, P.J.A.


    The applicability of 1H-NMR spectroscopy for the determination of the primary and tertiary structure of carbohydrate-containing molecules is demonstrated. For classes of known compounds the characterization can be based on chemical shifts observed in 1D NMR spectra with or without the aid of a compu

  20. Measurement of Solution Viscosity via Diffusion-Ordered NMR Spectroscopy (DOSY) (United States)

    Li, Weibin; Kagan, Gerald; Hopson, Russell; Williard, Paul G.


    Increasingly, the undergraduate chemistry curriculum includes nuclear magnetic resonance (NMR) spectroscopy. Advanced NMR techniques are often taught including two-dimensional gradient-based experiments. An investigation of intermolecular forces including viscosity, by a variety of methods, is often integrated in the undergraduate physical and…

  1. The neurochemical profile quantified by in vivo(1)H NMR spectroscopy


    João M N Duarte; Lei, Hongxia; Mlynárik, Vladimír; Gruetter, Rolf


    Proton NMR spectroscopy is emerging from translational and preclinical neuroscience research as an important tool for evidence based diagnosis and therapy monitoring. It provides biomarkers that offer fingerprints of neurological disorders even in cases where a lesion is not yet observed in MR images. The collection of molecules used as cerebral biomarkers that are detectable by (1)H NMR spectroscopy define the so-called "neurochemical profile". The non-invasive quality of this technique make...

  2. Bringing NMR and IR Spectroscopy to High Schools (United States)

    Bonjour, Jessica L.; Hass, Alisa L.; Pollock, David W.; Huebner, Aaron; Frost, John A.


    Development of benchtop, portable Fourier transform nuclear magnetic resonance (NMR) and infrared (IR) spectrometers has opened up opportunities for creating university-high school partnerships that provide high school students with hands-on experience with NMR and IR instruments. With recent changes to the international baccalaureate chemistry…

  3. Value of 31P MR spectroscopy in monitoring the early response of hepatocellular carcinoma to transcatheter arterial chemoembolization%31P-MR波谱分析技术评价化疗栓塞治疗肝细胞癌疗效的初步研究

    Institute of Scientific and Technical Information of China (English)

    袁正; 叶晓丹; 董生; 许立超; 孙志超; 肖湘生


    目的 评价MR磷谱分析(31P-MRS)早期监测肝细胞癌(HCC)化疗栓塞治疗疗效的价值.方法 对15例因HCC接受化疗栓塞治疗的患者(共17个癌灶)分别在治疗前和治疗后48 h内进行31P-MRS检查,5名健康志愿者也接受相同参数的检查以作为对照.比较肝癌组织和正常肝组织中的磷酸单酯(PME)和磷酸二酯(PDE)水平;分别计算化疗栓塞前后PME、PDE、与三磷酸核苷比值(PME/NPT)、PDE/NPT,并对治疗前、后数据进行统计学处理.与临床随访资料比较,考量各指标在早期评价疗效中的价值.结果 HCC治疗后PME水平(中位数:1.38×107;范围:0.665×107~6.21×107)低于治疗前(中位数:2.98×107;范围:0.846×107~102.5×107)(P<0.05).临床随访发现冶疗有效病灶31P-MRS中,治疗后48 h内与治疗前相比PME/NPT(P<0.01)和PME/PDE/NPT(P<0.01)比值均下降;临床随访中治疗无效的病灶,PME/NPT比值下降(P<0.05),而PDE/NPT比值轻度上升,但差异无统计学意义(P<0.05).结论 在肝细胞肝癌化疗栓塞治疗前和治疗后48 h内,31P-MRS中PME/NPT和PDE/NPT的比值变化对早期评价疗效和指导后续治疗有指导意义.

  4. (17)O NMR and Raman Spectroscopies of Green Tea Infusion with Nanomaterial to Investigate Their Properties. (United States)

    Zhou, Changyan; Zhang, Huiping; Yan, Ying; Zhang, Xinya


    (17)O NMR and Raman spectrograms of green tea infusions with nanomaterial were investigated. Different green tea infusions were prepared by steeping tea powder with different concentrations of nanomaterial aqueous solution. The tea infusions were tested with (17)O NMR and Raman spectroscopies. The (17)O NMR results showed that line width increased to 90 in the tea infusions after nanomaterial was added as a result of the effects of the self-association of Ca(2+) and tea polyphenol. The results of Raman spectroscopy showed that, in tea infusions, the enhancement of C─C and C─O stretching vibrations suggest an increase in the number of effective components in water.

  5. Temperature-induced transitions in disordered proteins probed by NMR spectroscopy

    DEFF Research Database (Denmark)

    Kjærgaard, Magnus; Poulsen, Flemming Martin; Kragelund, Birthe Brandt


    Intrinsically disordered proteins are abundant in nature and perform many important physiological functions. Multidimensional NMR spectroscopy has been crucial for the understanding of the conformational properties of disordered proteins and is increasingly used to probe their conformational...... ensembles. Compared to folded proteins, disordered proteins are more malleable and more easily perturbed by environmental factors. Accordingly, the experimental conditions and especially the temperature modify the structural and functional properties of disordered proteins. NMR spectroscopy allows analysis...... of temperature-induced structural changes at residue resolution using secondary chemical shift analysis, paramagnetic relaxation enhancement, and residual dipolar couplings. This chapter discusses practical aspects of NMR studies of temperature-induced structural changes in disordered proteins....

  6. Labelling analysis for ¹³C MFA using NMR spectroscopy. (United States)

    Jouhten, Paula; Maaheimo, Hannu


    NMR spectroscopy is an efficient method for analyzing (13)C labelling of cellular metabolites. The strength of it is especially the ability to provide direct quantitative positional information on the (13)C labelling status of carbon atoms in metabolites. NMR spectroscopic methods allow also for detection of contiguously (13)C-labelled fragments in the carbon backbones of the metabolites. Furthermore, the recent developments of NMR spectroscopy hardware have substantially improved the sensitivity of the methods. In this chapter we describe a method for analyzing the (13)C labelling of the biomass amino acids for metabolic flux analysis, sample preparation for NMR spectroscopy, acquiring and processing the NMR spectra, and extracting the (13)C labelling information from the NMR data. Different NMR methods are applied depending on the (13)C labelling strategy chosen. These strategies include uniform (13)C labelling, positional (13)C labelling, or a combination of both. Not only the preparation of sample for analysis of (13)C labelling in proteinogenic amino acids in biomass is described, but also the necessary modifications to the method when analysis of (13)C labelling in free metabolic intermediates is of interest. Finally the strategies for using the different NMR-detected (13)C labelling data in (13)C MFA are discussed.

  7. Ultra fast magic angle spinning solid - state NMR spectroscopy of intact bone. (United States)

    Singh, Chandan; Rai, Ratan Kumar; Kayastha, Arvind M; Sinha, Neeraj


    Ultra fast magic angle spinning (MAS) has been a potent method to significantly average out homogeneous/inhomogeneous line broadening in solid-state nuclear magnetic resonance (ssNMR) spectroscopy. It has given a new direction to ssNMR spectroscopy with its different applications. We present here the first and foremost application of ultra fast MAS (~60 kHz) for ssNMR spectroscopy of intact bone. This methodology helps to comprehend and elucidate the organic content in the intact bone matrix with resolution and sensitivity enhancement. At this MAS speed, amino protons from organic part of intact bone start to appear in (1) H NMR spectra. The experimental protocol of ultra-high speed MAS for intact bone has been entailed with an additional insight achieved at 60 kHz.

  8. 31-P-Magnetresonanztomographie der menschlichen Leber



    Die 31-P-Magnetresonanz-Spektroskopie (31-P-MRS) ist eine nicht-invasive Methode, welche einen direkten Einblick in den Phospholipid-Haushalt der menschlichen Leber erlaubt. Mit der 31-P-MR-Spektroskopie wurden Spektren von 10 Patienten mit Leberzirrhose sowie von 13 gesunden Probanden in Kombination mit dem Lokalisationsverfahren 3D-CSI und dem Nachbearbeitungsprogramm SLOOP (Spectral Localization with Optimal Pointspread Funktion) gewonnen. Die Ergebnisse dieser Studie ergaben signifikante ...

  9. Analysis of human urine metabolites using SPE and NMR spectroscopy

    Institute of Scientific and Technical Information of China (English)


    Nuclear magnetic resonance (NMR) spectroscopic analysis of metabonome/metabolome has widespread applications in biomedical science researches. However, most of NMR resonances for urinary metabolites remain to be fully assigned. In the present study, human urine samples from two healthy volunteers were pre-treated with C18 solid-phase extraction and the resultant 5 sub-fractions were subjected to one- and two-dimensional NMR studies, including 1H J-Resolved, 1H-1H COSY, 1H-1H TOCSY, 1H-13C HSQC, and HMBC 2D NMR. More than 70 low molecular weight metabolites were identified, and complete assignments of 1H and 13C resonances including many complex coupled spin systems were obtained.

  10. Sol-gel chemistry synthesis and DTA-TGA, XRPD, SIC and {sup 7}Li, {sup 31}P, {sup 29}Si MAS-NMR studies on the Li-NASICON Li{sub 3}Zr{sub 2-y}Si{sub 2-4y}P{sub 1+4y}O{sub 12} (0 Less-Than-Or-Slanted-Equal-To y Less-Than-Or-Slanted-Equal-To 0.5) system

    Energy Technology Data Exchange (ETDEWEB)

    Belam, W., E-mail: [Chemistry Department, Bizerta Science Faculty, 7021 Jarzouna, Bizerta (Tunisia)


    Highlights: Black-Right-Pointing-Pointer The samples of Li-NASICON were elaborated by sol-gel chemistry. Black-Right-Pointing-Pointer The calcined temperatures of the studied samples were deduced from their thermograms. Black-Right-Pointing-Pointer The recorded X-ray powder diffractograms were indexed in the rhombohedral system. Black-Right-Pointing-Pointer The synthesized Li-NASICON materials are excellent lithium fast cation conductors. - Abstract: Five selected compounds of Li-NASICON, Li{sub 3}Zr{sub 2-y}Si{sub 2-4y}P{sub 1+4y}O{sub 12} (0 Less-Than-Or-Slanted-Equal-To y Less-Than-Or-Slanted-Equal-To 0.5), were synthesized by sol-gel chemistry in order to obtain pure polycrystalline powder and then analyzed by different physicochemical characterizations such as coupled DTA (differential thermal analysis)-TGA (thermogravimetric analysis), XRPD (X-ray powder diffraction), CIS (complex impedance spectroscopy) and MAS (magic angle spinning)-NMR (nuclear magnetic resonance). So the calcined temperature of each sample has been deduced from its corresponding DTA-TGA thermogram. However, the recorded X-ray powder diffractograms were indexed in the rhombohedral system with R3{sup Macron }c space group which corresponds to the ideal structure of NASICON. Whereas, the complex impedance spectroscopy study showed that these Li-NASICON materials are excellent lithium fast cation conductors with total electric conductivity maximal value 1.97 Multiplication-Sign 10{sup -3} S cm{sup -1} at 293 K in the case of Li{sub 3}Zr{sub 1.5}P{sub 3}O{sub 12}. Furthermore, {sup 7}Li, {sup 31}P and {sup 29}Si MAS-NMR spectroscopy study and DFT/B3LYP theoretical calculations of chemical shifts were performed to discuss the ambiguousness that exists between the resonance peak number in the experimental spectrum and the crystallographic site number relative to Li{sub 3}Zr{sub 2}Si{sub 2}PO{sub 12}.

  11. Structural investigations on betacyanin pigments by LC NMR and 2D NMR spectroscopy. (United States)

    Stintzing, Florian C; Conrad, Jürgen; Klaiber, Iris; Beifuss, Uwe; Carle, Reinhold


    Four betacyanin pigments were analysed by LC NMR and subjected to extensive NMR characterisation after isolation. Previously, low pH values were applied for NMR investigations of betalains resulting in rapid degradation of the purified substances thus preventing extensive NMR studies. Consequently, up to now only one single (13)C NMR spectrum of a betalain pigment, namely that of neobetanin (=14,15-dehydrobetanin), was available. Because of its sufficient stability under highly acidic conditions otherwise detrimental for betacyanins, this pigment remained an exemption. Since betalains are most stable in the pH range of 5-7, a new solvent system has been developed allowing improved data acquisition through improved pigment stability at near neutral pH. Thus, not only (1)H, but for the first time also partial (13)C data of betanin, isobetanin, phyllocactin and hylocerenin isolated from red-purple pitaya [Hylocereus polyrhizus (Weber) Britton & Rose, Cactaceae] could be indirectly obtained by gHSQC- and gHMQC-NMR experiments.

  12. Continuous Flow 1H and 13C NMR Spectroscopy in Microfluidic Stripline NMR Chips (United States)


    Microfluidic stripline NMR technology not only allows for NMR experiments to be performed on small sample volumes in the submicroliter range, but also experiments can easily be performed in continuous flow because of the stripline’s favorable geometry. In this study we demonstrate the possibility of dual-channel operation of a microfluidic stripline NMR setup showing one- and two-dimensional 1H, 13C and heteronuclear NMR experiments under continuous flow. We performed experiments on ethyl crotonate and menthol, using three different types of NMR chips aiming for straightforward microfluidic connectivity. The detection volumes are approximately 150 and 250 nL, while flow rates ranging from 0.5 μL/min to 15 μL/min have been employed. We show that in continuous flow the pulse delay is determined by the replenishment time of the detector volume, if the sample trajectory in the magnet toward NMR detector is long enough to polarize the spin systems. This can considerably speed up quantitative measurement of samples needing signal averaging. So it can be beneficial to perform continuous flow measurements in this setup for analysis of, e.g., reactive, unstable, or mass-limited compounds. PMID:28194934

  13. Phosphorus speciation in calcite speleothems determined from solid-state NMR spectroscopy (United States)

    Mason, Harris E.; Frisia, Silvia; Tang, Yuanzhi; Reeder, Richard J.; Phillips, Brian L.


    Variations in speleothem P concentration show cyclic patterns that have important implications for high resolution palaeoclimate and palaeoenvironmental reconstructions. However, little is known about the speciation of P in calcite speleothems. Here we employ solid-state 31P and 1H magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopic techniques as a non-destructive method for analyzing the distribution of P in speleothems. The 31P MAS NMR results show three peaks indicating the presence of three primary types of phosphate species in samples from the Grotta di Ernesto (northeastern Italy): a broad peak at a chemical shift δP-31 = 3.1 to 3.7 ppm from individual phosphate ions incorporated within calcite, a narrow set of peaks near δP-31 = - 0.9 ppm from crystalline monetite and a narrow peak at δP-31 = 2.9 ppm from an unidentified crystalline phosphate phase. Essentially identical results were obtained for a synthetic calcite/phosphate coprecipitate. Spectra collected for a sample from Grotte de Clamouse (southern France) show only a broad peak near 3.5 ppm suggesting a possible limit for phosphate incorporation into the calcite structure. These data suggest that P in this system can interact to form calcium phosphate surface precipitates during infiltration events and are subsequently enclosed during calcite growth.

  14. Photochromism of indolino-benzopyrans studied by NMR and UV-visible spectroscopy

    Directory of Open Access Journals (Sweden)


    Full Text Available The synthesis of photochromic 3,3-di( 4 ′ -fluorophenyl-3H-benzopyrans fused to an indole moiety is described. The structures of photomerocyanines elucidated by NMR spectroscopy and spectrokinetic data ( λ max⁡ of colored form, colorability, and rate constant of bleaching obtained by UV-visible spectroscopy are reported.

  15. Toward contrast-enhanced, optically-detected NMR spectroscopy (United States)

    Meriles, Carlos; Pagliero, Daniela


    Optical detection of Nuclear Magnetic Resonance (NMR) takes place via a two-step process that relies on the interaction between optical photons and electrons on the one hand, and the hyperfine coupling between electrons and nuclear spins on the other. The latter depends on the material system under consideration while the former is dominated by the difference between the illumination and optical transition wavelengths. Here we use optical Faraday rotation to monitor nuclear spins in real time after resonant radio-frequency excitation at high-magnetic field. Comparison between inductively and optically detected NMR spectra in model sample fluids indicates that each of these mechanisms can lead to alternate forms of spectral contrast. Extension of these findings may find application in solvent suppression protocols, sensitivity-enhanced NMR of metalloproteins, or the characterization of molecular orbitals in diamagnetic systems. We acknowledge support from the National Science Foundation.

  16. Ligand screening by saturation-transfer difference (STD) NMR spectroscopy.

    Energy Technology Data Exchange (ETDEWEB)

    Krishnan, V V


    NMR based methods to screen for high-affinity ligands have become an indispensable tool for designing rationalized drugs, as these offer a combination of good experimental design of the screening process and data interpretation methods, which together provide unprecedented information on the complex nature of protein-ligand interactions. These methods rely on measuring direct changes in the spectral parameters, that are often simpler than the complex experimental procedures used to study structure and dynamics of proteins. The goal of this review article is to provide the basic details of NMR based ligand-screening methods, with particular focus on the saturation transfer difference (STD) experiment. In addition, we provide an overview of other NMR experimental methods and a practical guide on how to go about designing and implementing them.

  17. Evaluation of liver function status in patients with obstructive jaundice using in vivo 31-phosphorus magnetic resonance spectroscopy%31p-MRS无创评估梗阻性黄疸肝功能损害的价值

    Institute of Scientific and Technical Information of China (English)

    于德新; 马祥兴; 张晓明; 张宗利; 李传福



  18. NMR spectroscopy of experimentally shocked single crystal quartz: A reexamination of the NMR shock barometer (United States)

    Fiske, P. S.; Gratz, A. J.; Nellis, W. J.


    Cygan and others report a broadening of the Si-29 nuclear magnetic resonance (NMR) peak for synthetic quartz powders with increasing shock pressure which they propose as a shock wave barometer for natural systems. These results are expanded by studying single crystal quartz shocked to 12 and 33 GPa using the 6.5 m two-stage light-gas gun at Lawrence Livermore National Laboratories. Our NMR results differ substantially from those of Cygan and others and suggest that the proposed shock wave barometer may require refinement. The difference in results between this study and that of Cygan and others is most likely caused by different starting materials (single crystal vs. powder) and different shock loading histories. NMR results from single crystal studies may be more applicable to natural systems.

  19. Forensic examination of electrical tapes using high resolution magic angle spinning ¹H NMR spectroscopy. (United States)

    Schoenberger, Torsten; Simmross, Ulrich; Poppe, Christian


    The application of high resolution magic angle spinning (HR-MAS) (1)H NMR spectroscopy is ideally suited for the differentiation of plastics. In addition to the actual material composition, the different types of polymer architectures and tacticity provide characteristic signals in the fingerprint of the (1)H NMR spectra. The method facilitates forensic comparison, as even small amounts of insoluble but swellable plastic particles are utilized. The performance of HR-MAS NMR can be verified against other methods that were recently addressed in various articles about forensic tape comparison. In this study samples of the 90 electrical tapes already referenced by the FBI laboratory were used. The discrimination power of HR-MAS is demonstrated by the fact that more tape groups can be distinguished by NMR spectroscopy than by using the combined evaluation of several commonly used analytical techniques. An additional advantage of this robust and quick method is the very simple sample preparation.

  20. Profiling formulated monoclonal antibodies by (1)H NMR spectroscopy. (United States)

    Poppe, Leszek; Jordan, John B; Lawson, Ken; Jerums, Matthew; Apostol, Izydor; Schnier, Paul D


    Nuclear magnetic resonance (NMR) is arguably the most direct methodology for characterizing the higher-order structure of proteins in solution. Structural characterization of proteins by NMR typically utilizes heteronuclear experiments. However, for formulated monoclonal antibody (mAb) therapeutics, the use of these approaches is not currently tenable due to the requirements of isotope labeling, the large size of the proteins, and the restraints imposed by various formulations. Here, we present a new strategy to characterize formulated mAbs using (1)H NMR. This method, based on the pulsed field gradient stimulated echo (PGSTE) experiment, facilitates the use of (1)H NMR to generate highly resolved spectra of intact mAbs in their formulation buffers. This method of data acquisition, along with postacquisition signal processing, allows the generation of structural and hydrodynamic profiles of antibodies. We demonstrate how variation of the PGSTE pulse sequence parameters allows proton relaxation rates and relative diffusion coefficients to be obtained in a simple fashion. This new methodology can be used as a robust way to compare and characterize mAb therapeutics.

  1. Insights into the metabolic response to traumatic brain injury as revealed by 13C NMR spectroscopy.

    Directory of Open Access Journals (Sweden)

    Brenda eBartnik-Olson


    Full Text Available The present review highlights critical issues related to cerebral metabolism following traumatic brain injury (TBI and the use of 13C labeled substrates and nuclear magnetic resonance (NMR spectroscopy to study these changes. First we address some pathophysiologic factors contributing to metabolic dysfunction following TBI. We then examine how 13C NMR spectroscopy strategies have been used to investigate energy metabolism, neurotransmission, the intracellular redox state, and neuroglial compartmentation following injury. 13C NMR spectroscopy studies of brain extracts from animal models of TBI have revealed enhanced glycolytic production of lactate, evidence of pentose phosphate pathway (PPP activation, and alterations in neuronal and astrocyte oxidative metabolism that are dependent on injury severity. Differential incorporation of label into glutamate and glutamine from 13C labeled glucose or acetate also suggest TBI-induced adaptations to the glutamate-glutamine cycle.

  2. Solid-State NMR Spectroscopy of Metal–Organic Framework Compounds (MOFs

    Directory of Open Access Journals (Sweden)

    Stefan Kaskel


    Full Text Available Nuclear Magnetic Resonance (NMR spectroscopy is a well-established method for the investigation of various types of porous materials. During the past decade, metal–organic frameworks have attracted increasing research interest. Solid-state NMR spectroscopy has rapidly evolved into an important tool for the study of the structure, dynamics and flexibility of these materials, as well as for the characterization of host–guest interactions with adsorbed species such as xenon, carbon dioxide, water, and many others. The present review introduces and highlights recent developments in this rapidly growing field.

  3. In vivo 31P magnetic resonance spectroscopy and 1H magnetic resonance imaging of human bladder carcinoma on nude mice: effects of tumour growth and treatment with cis-dichloro-diamine platinum

    DEFF Research Database (Denmark)

    De Certaines, J D; Albrectsen, J; Larsen, V A;


    phosphate and phosphomonoesters and a decrease of phosphocreatine. Fast growing tumours and early stage of regrowth after treatment presented a higher phosphocreatine/beta NTP ratio. Following CDDP treatment, 31P metabolite ratios and pH were significantly altered compared with age-matched controls......, as early as 6 hours after treatment. Although necrotic area was clearly visible in MRI, no treatment effect could be detected on the images of treated tumours....

  4. In vivo 31P magnetic resonance spectroscopy and 1H magnetic resonance imaging of human bladder carcinoma on nude mice: effects of tumour growth and treatment with cis-dichloro-diamine platinum

    DEFF Research Database (Denmark)

    De Certaines, J D; Albrectsen, J; Larsen, V A;


    phosphate and phosphomonoesters and a decrease of phosphocreatine. Fast growing tumours and early stage of regrowth after treatment presented a higher phosphocreatine/beta NTP ratio. Following CDDP treatment, 31P metabolite ratios and pH were significantly altered compared with age-matched controls......, as early as 6 hours after treatment. Although necrotic area was clearly visible in MRI, no treatment effect could be detected on the images of treated tumours....

  5. Discovering [superscript 13]C NMR, [superscript 1]H NMR, and IR Spectroscopy in the General Chemistry Laboratory through a Sequence of Guided-Inquiry Exercises (United States)

    Iler, H. Darrell; Justice, David; Brauer, Shari; Landis, Amanda


    This sequence of three guided-inquiry labs is designed for a second-semester general chemistry course and challenges students to discover basic theoretical principles associated with [superscript 13]C NMR, [superscript 1]H NMR, and IR spectroscopy. Students learn to identify and explain basic concepts of magnetic resonance and vibrational…

  6. The effects of intramolecular and intermolecular coordination on (31)P nuclear shielding: phosphorylated azoles. (United States)

    Chernyshev, Kirill A; Larina, Ludmila I; Chirkina, Elena A; Krivdin, Leonid B


    The effects of intramolecular and intermolecular coordination on (31)P nuclear shielding have been investigated in the series of tetracoordinated, pentacoordinated and hexacoordinated N-vinylpyrazoles and intermolecular complexes of N-vinylimidazole and 1-allyl-3,5-dimethylpyrazole with phosphorous pentachloride both experimentally and theoretically. It was shown that either intramolecular or intermolecular coordination involving phosphorous results in a dramatic (31)P nuclear shielding amounting to approximately 150 ppm on changing the phosphorous coordination number by one. A major importance of solvent effects on (31)P nuclear shielding of intramolecular and intermolecular complexes involving N → P coordination bond has been demonstrated. It was found that the zeroth-order regular approximation-gauge-including atomic orbital-B1PW91/DZP method was sufficiently accurate for the calculation of (31)P NMR chemical shifts, provided relativistic corrections are taken into account, the latter being of crucial importance in the description of (31)P nuclear shielding.

  7. Theory of mirrored time domain sampling for NMR spectroscopy. (United States)

    Ghosh, Arindam; Wu, Yibing; He, Yunfen; Szyperski, Thomas


    A generalized theory is presented for novel mirrored hypercomplex time domain sampling (MHS) of NMR spectra. It is the salient new feature of MHS that two interferograms are acquired with different directionality of time evolution, that is, one is sampled forward from time t=0 to the maximal evolution time tmax, while the second is sampled backward from t=0 to -tmax. The sampling can be accomplished in a (semi) constant time or non constant-time manner. Subsequently, the two interferograms are linearly combined to yield a complex time domain signal. The manifold of MHS schemes considered here is defined by arbitrary settings of sampling phases ('primary phase shifts') and amplitudes of the two interferograms. It is shown that, for any two given primary phase shifts, the addition theorems of trigonometric functions yield the unique linear combination required to form the complex signal. In the framework of clean absorption mode (CAM) acquisition of NMR spectra being devoid of residual dispersive signal components, 'secondary phase shifts' represent time domain phase errors which are to be eliminated. In contrast, such secondary phase shifts may be introduced by experimental design in order to encode additional NMR parameters, a new class of NMR experiments proposed here. For generalization, it is further considered that secondary phase shifts may depend on primary phase shifts and/or sampling directionality. In order to compare with MHS theory, a correspondingly generalized theory is derived for widely used hypercomplex ('States') sampling (HS). With generalized theory it is shown, first, that previously introduced 'canonical' schemes, characterized by primary phases being multiples of π/4, afford maximal intensity of the desired absorptive signals in the absence of secondary phase shifts, and second, how primary phases can be adjusted to maximize the signal intensity provided that the secondary phase shifts are known. Third, it is demonstrated that theory enables

  8. Simultaneous 19F-1H medium resolution NMR spectroscopy for online reaction monitoring (United States)

    Zientek, Nicolai; Laurain, Clément; Meyer, Klas; Kraume, Matthias; Guthausen, Gisela; Maiwald, Michael


    Medium resolution nuclear magnetic resonance (MR-NMR) spectroscopy is currently a fast developing field, which has an enormous potential to become an important analytical tool for reaction monitoring, in hyphenated techniques, and for systematic investigations of complex mixtures. The recent developments of innovative MR-NMR spectrometers are therefore remarkable due to their possible applications in quality control, education, and process monitoring. MR-NMR spectroscopy can beneficially be applied for fast, non-invasive, and volume integrating analyses under rough environmental conditions. Within this study, a simple 1/16″ fluorinated ethylene propylene (FEP) tube with an ID of 0.04″ (1.02 mm) was used as a flow cell in combination with a 5 mm glass Dewar tube inserted into a benchtop MR-NMR spectrometer with a 1H Larmor frequency of 43.32 MHz and 40.68 MHz for 19F. For the first time, quasi-simultaneous proton and fluorine NMR spectra were recorded with a series of alternating 19F and 1H single scan spectra along the reaction time coordinate of a homogeneously catalysed esterification model reaction containing fluorinated compounds. The results were compared to quantitative NMR spectra from a hyphenated 500 MHz online NMR instrument for validation. Automation of handling, pre-processing, and analysis of NMR data becomes increasingly important for process monitoring applications of online NMR spectroscopy and for its technical and practical acceptance. Thus, NMR spectra were automatically baseline corrected and phased using the minimum entropy method. Data analysis schemes were designed such that they are based on simple direct integration or first principle line fitting, with the aim that the analysis directly revealed molar concentrations from the spectra. Finally, the performance of 1/16″ FEP tube set-up with an ID of 1.02 mm was characterised regarding the limit of detection (LOQ (1H) = 0.335 mol L-1 and LOQ (19F) = 0.130 mol L-1 for trifluoroethanol in

  9. 2D-Cosy NMR Spectroscopy as a Quantitative Tool in Biological Matrix: Application to Cyclodextrins. (United States)

    Dufour, Gilles; Evrard, Brigitte; de Tullio, Pascal


    Classical analytical quantifications in biological matrices require time-consuming sample pre-treatments and extractions. Nuclear magnetic resonance (NMR) analysis does not require heavy sample treatments or extractions which therefore increases its accuracy in quantification. In this study, even if quantitative (q)NMR could not be applied to 2D spectra, we demonstrated that cross-correlations and diagonal peak intensities have a linear relationship with the analyzed pharmaceutical compound concentration. This work presents the validation process of a 2D-correlation spectroscopy (COSY) NMR quantification of 2-hydroxypropyl-β-cyclodextrin in plasma. Specificity, linearity, precision (repeatability and intermediate precision), trueness, limits of quantification (LOQs), and accuracy were used as validation criteria. 2D-NMR could therefore be used as a valuable and accurate analytical technique for the quantification of pharmaceutical compounds, including hardly detectable compounds such as cyclodextrins or poloxamers, in complex biological matrices based on a calibration curve approach.

  10. Slow-spinning low-sideband HR-MAS NMR spectroscopy: delicate analysis of biological samples (United States)

    Renault, Marie; Shintu, Laetitia; Piotto, Martial; Caldarelli, Stefano


    High-Resolution Magic-Angle Spinning (HR-MAS) NMR spectroscopy has become an extremely versatile analytical tool to study heterogeneous systems endowed with liquid-like dynamics. Spinning frequencies of several kHz are however required to obtain NMR spectra, devoid of spinning sidebands, with a resolution approaching that of purely isotropic liquid samples. An important limitation of the method is the large centrifugal forces that can damage the structure of the sample. In this communication, we show that optimizing the sample preparation, particularly avoiding air bubbles, and the geometry of the sample chamber of the HR-MAS rotor leads to high-quality low-sideband NMR spectra even at very moderate spinning frequencies, thus allowing the use of well-established solution-state NMR procedures for the characterization of small and highly dynamic molecules in the most fragile samples, such as live cells and intact tissues.

  11. Ultrasensitive anion detection by NMR spectroscopy: a supramolecular strategy based on modulation of chemical exchange rate. (United States)

    Perruchoud, Loïse H; Hadzovic, Alen; Zhang, Xiao-An


    NMR spectroscopy is a powerful tool for monitoring molecular interactions and is widely used to characterize supramolecular systems at the atomic level. NMR is limited for sensing purposes, however, due to low sensitivity. Dynamic processes such as conformational changes or binding events can induce drastic effects on NMR spectra in response to variations in chemical exchange (CE) rate, which can lead to new strategies in the design of supramolecular sensors through the control and monitoring of CE rate. Here, we present an indirect NMR anion sensing technique in which increased CE rate, due to anion-induced conformational flexibility of a relatively rigid structure of a novel sensor, allows ultrasensitive anion detection as low as 120 nM.

  12. Clathrate Structure Determination by Combining Crystal Structure Prediction with Computational and Experimental (129) Xe NMR Spectroscopy. (United States)

    Selent, Marcin; Nyman, Jonas; Roukala, Juho; Ilczyszyn, Marek; Oilunkaniemi, Raija; Bygrave, Peter J; Laitinen, Risto; Jokisaari, Jukka; Day, Graeme M; Lantto, Perttu


    An approach is presented for the structure determination of clathrates using NMR spectroscopy of enclathrated xenon to select from a set of predicted crystal structures. Crystal structure prediction methods have been used to generate an ensemble of putative structures of o- and m-fluorophenol, whose previously unknown clathrate structures have been studied by (129) Xe NMR spectroscopy. The high sensitivity of the (129) Xe chemical shift tensor to the chemical environment and shape of the crystalline cavity makes it ideal as a probe for porous materials. The experimental powder NMR spectra can be used to directly confirm or reject hypothetical crystal structures generated by computational prediction, whose chemical shift tensors have been simulated using density functional theory. For each fluorophenol isomer one predicted crystal structure was found, whose measured and computed chemical shift tensors agree within experimental and computational error margins and these are thus proposed as the true fluorophenol xenon clathrate structures.

  13. NMR difference spectroscopy with a dual saddle-coil difference probe. (United States)

    Macnaughtan, Megan A; Smith, Aaron P; Goldsbrough, Peter B; Santini, Robert E; Raftery, Daniel


    A new difference probe for nuclear magnetic resonance (NMR) spectroscopy is presented. The difference probe uses two saddle-shaped coils to excite and detect two samples simultaneously. The samples are held in a specially modified 3-mm NMR tube with an Ultem plastic disk to separate the samples. The probe's resonant circuit contains two crossed diodes that passively switch the relative phase of each coil during the NMR experiment. The result is a difference spectrum from the two samples. The degree of cancellation of common signals was determined to be approximately 90%, and the application of the probe to relaxation-edited difference spectroscopy for identifying protein-ligand interactions was demonstrated using glutathione and glutathione S-transferase binding protein.

  14. Online T5 learning model to enhance chemistry students’ understanding of NMR spectroscopy

    Directory of Open Access Journals (Sweden)

    Saksri Supasorn


    Full Text Available Regular lecture-based teaching approaches sometimes fail to enhance students’ understanding of some practice-based chemistry topics such as Nuclear Magnetic Resonance (NMR spectroscopy. A new task-based approach called the T5 learning model was introduced for 48 students studying NMR in the Spectroscopic Methods for Chemical Identification course in 2011. Four different NMR learning environments based on T5 learning models were developed. The students were requested to participate in the following online processes in each environment: 1 complete an individual task, 2 provide feedback and evaluate three anonymous peer tasks, 3 adjust their individual task and evaluate peer feedback, 4 complete a team task and evaluate the effort of each group member, and 5 get feedback from instructor to fulfill understanding. The result showed that the students obtained post-achievement NMR score (mean 24.25, SD 4.80 statistically significantly higher than pre- achievement score (mean 12.29, SD 1.69 at p-value of 0.05. In addition, the implementation of T5-D4LP NMR course in each year during 2010-2012 showed that the students achieved high score (about 70% in the NMR topics. The student evaluation of the T5 NMR learning environments revealed that they agreed that peer feedback with instructor facilitation engaged them in deep learning and effectively promoted their conceptual understanding.


    Solution-state NMR spectroscopy provides a powerful tool for understanding the formation of chemical bonds between wood components and adhesives. Finely ground cell wall (CW) material fully dissolves in a solvent system containing dimethylsulfoxide (DMSO-d6) and N-methyl¬imidazole (NMI-d6), keeping ...

  16. Structural investigation of bistrifluron using x-ray crystallography, NMR spectroscopy, and molecular modeling

    CERN Document Server

    Moon, J K; Rhee, S K; Kim, G B; Yun, H S; Chung, B J; Lee, S S; Lim, Y H


    A new insecticide, bistrifluron acts as an inhibitor of insect development and interferes with the cuticle formation of insects. Since it shows low acute oral and dermal toxicities, it can be one of potent insecticides. Based on X-ray crystallography, NMR spectroscopy and molecular modeling, the structural studies of bistrifluron have been carried out.

  17. Structure Determination of Unknown Organic Liquids Using NMR and IR Spectroscopy: A General Chemistry Laboratory (United States)

    Pavel, John T.; Hyde, Erin C.; Bruch, Martha D.


    This experiment introduced general chemistry students to the basic concepts of organic structures and to the power of spectroscopic methods for structure determination. Students employed a combination of IR and NMR spectroscopy to perform de novo structure determination of unknown alcohols, without being provided with a list of possible…

  18. NMR imaging and spectroscopy of the mammalian central nervous system after heavy ion radiation

    Energy Technology Data Exchange (ETDEWEB)

    Richards, T.


    NMR imaging, NMR spectroscopic, and histopathologic techniques were used to study the proton relaxation time and related biochemical changes in the central nervous system after helium beam in vivo irradiation of the rodent brain. The spectroscopic observations reported in this dissertation were made possible by development of methods for measuring the NMR parameters of the rodent brain in vivo and in vitro. The methods include (1) depth selective spectroscopy using an optimization of rf pulse energy based on a priori knowledge of N-acetyl aspartate and lipid spectra of the normal brain, (2) phase-encoded proton spectroscopy of the living rodent using a surface coil, and (3) dual aqueous and organic tissue extraction technique for spectroscopy. Radiation induced increases were observed in lipid and p-choline peaks of the proton spectrum, in vivo. Proton NMR spectroscopy measurements on brain extracts (aqueous and organic solvents) were made to observe chemical changes that could not be seen in vivo. Radiation-induced changes were observed in lactate, GABA, glutamate, and p-choline peak areas of the aqueous fraction spectra. In the organic fraction, decreases were observed in peak area ratios of the terminal-methyl peaks, the N-methyl groups of choline, and at a peak at 2.84 ppM (phosphatidyl ethanolamine and phosphatidyl serine resonances) relative to TMS. With histology and Evans blue injections, blood-brain barrier alternations were seen as early as 4 days after irradiation. 83 references, 53 figures.

  19. High-Resolution Solid-State NMR Spectroscopy: Characterization of Polymorphism in Cimetidine, a Pharmaceutical Compound (United States)

    Pacilio, Julia E.; Tokarski, John T.; Quiñones, Rosalynn; Iuliucci, Robbie J.


    High-resolution solid-state NMR (SSNMR) spectroscopy has many advantages as a tool to characterize solid-phase material that finds applications in polymer chemistry, nanotechnology, materials science, biomolecular structure determination, and others, including the pharmaceutical industry. The technology associated with achieving high resolution…

  20. Using NMR Spectroscopy to Investigate the Solution Behavior of Nerve Agents and Their Binding to Acetylcholinesterase (United States)


    USING NMR SPECTROSCOPY TO INVESTIGATE THE SOLUTION BEHAVIOR OF NERVE AGENTS AND THEIR BINDING TO...Solution Behavior of Nerve Agents and Their Binding to Acetylcholinesterase 5a. CONTRACT NUMBER CB3889 5b. GRANT NUMBER 5c. PROGRAM ELEMENT...dynamics (MD) Nerve agent Nuclear magnetic relaxation Nuclear Overhauser effect (NOE) Solution behavior 16

  1. Stereochemical investigation of selegiline HCl with /sup 1/H and /sup 13/C NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Podanyi, B. (CHINOIN Gyogyszer- es Vegyeszeti Termekek Gyara, Budapest (Hungary))


    Selegiline HCl, the bioactive substance of the antiparkinsonic medicine, JUMEX was investigated by NMR spectroscopy. The dominant conformer was determined. Optically active shift-reagent was used for the determination of optical purity. The /sup 13/C spectrum was analyzed, and molecular dynamics was investigated at different temperatures.

  2. 1H NMR spectroscopy-based interventional metabolic phenotyping

    DEFF Research Database (Denmark)

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


    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...

  3. 1H NMR spectroscopy-based interventional metabolic phenotyping: a cohort study of rheumatoid arthritis patients

    DEFF Research Database (Denmark)

    Lauridsen, Michael Brændgaard; Bliddal, Henning; Christensen, Robin Daniel Kjersgaard;


    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...

  4. Musculoskeletal metabolism in patients with liver cirrhosis by 31-phosphorus magnetic resonance spectroscopy at 3.0 Tesla in vivo%~(31)P-MR波谱对肝硬化时骨骼肌能量代谢的评估

    Institute of Scientific and Technical Information of China (English)

    于德新; 马祥兴; 李笃民; 张晓明; 王茜; 李传福


    目的 探讨~(31)P-MRS技术评估肝硬化对骨骼肌代谢的影响.方法 分别对35例肝硬化患者及30例正常对照组的大腿后方骨骼肌进行单体素~(31)P-MRS扫描,计算骨骼肌细胞内pH值(pHi)、磷酸单酯(PME)、磷酸双酯(PDE)、无机磷(Pi)、磷酸肌酸(PCr)、γ-ATP、β-ATP、α-ATP、Pi/ATP、PCr/ATP、PCr/PME、PCr/PDE、PCr/Pi、PME/ATP、PME/PDE、PME/Pi、PDE/ATP、PDE/Pi等指标.分析肝硬化及其分级对骨骼肌~(31)P-MRS指标的影响.结果 肝硬化组骨骼肌的PME、PCr、β-ATP、PME/PDE及Pcr/PDE均大于正常对照组,而PDE/ATP则相反(P<0.05).在Child-Pugh分级A、B、C级患者骨骼肌的pHi分别为7.18±0.10、7.20±0.10、7.41±0.08,具有统计学差异(P=0.041,F=4.629);PME/PDE分别为0.57±0.26、0.68±0.24、1.16±0.24,也存在明显差异(P=0.047,F=4.254),而其余代谢物指标未见统计学差异(P>0.05).结论 ~(31)P-MRS可以对肝硬化患者骨骼肌的异常代谢进行无创评估,骨骼肌pHi及PME/PDE随肝硬化Child-Pugh分级的增加而上升.

  5. Dynamic Nuclear Polarization (DNP) solid-state NMR spectroscopy, a new approach to study humic material? (United States)

    Knicker, Heike; Lange, Sascha; van Rossum, Barth; Oschkinat, Hartmut


    Compared to solution NMR spectroscopy, solid-state NMR spectra suffer from broad resonance lines and low resolution. This could be overcome by the use of 2-dimenstional solid-state NMR pulse sequences. Until recently, this approach has been unfeasible as a routine tool in soil chemistry, mainly because of the low NMR sensitivity of the respective samples. A possibility to circumvent those sensitivity problems represents high-field Dynamic Nuclear Polarization (DNP) solid-state NMR spectroscopy (Barnes et al., 2008), allowing considerable signal enhancements (Akbey et al., 2010). This is achieved by a microwave-driven transfer of polarization from a paramagnetic center to nuclear spins. Application of DNP to MAS spectra of biological systems (frozen solutions) showed enhancements of the factor 40 to 50 (Hall et al., 1997). Enhancements of this magnitude, thus may enable the use of at least some of the 2D solid-state NMR techniques that are presently already applied for pure proteins but are difficult to apply to soil peptides in their complex matrix. After adjusting the required acquisition parameters to the system "soil organic matter", lower but still promising enhancement factors were achieved. Additional optimization was performed and allowed the acquisition of 2D 13C and 15N solid-state NMR spectra of humified 13C and 15N enriched plant residues. Within the present contribution, the first solid-state DNP NMR spectra of humic material are presented. Those data demonstrate the great potential of this approach which certainly opens new doors for a better understanding of biochemical processes in soils, sediments and water. Akbey, Ü., Franks, W.T., Linden, A., Lange, S., Griffin, R.G., van Rossum, B.-J., Oschkinat, H., 2010. Dynamic nuclear polarization of deuterated proteins. Angewandte Chemie International Edition 49, 7803-7806. Barnes, A.B., De Paëpe, G., van der Wel, P.C.A., Hu, K.N., Joo, C.G., Bajaj, V.S., Mak-Jurkauskas, M.L., Sirigiri, J.R., Herzfeld, J

  6. Evaluation of Liver Cirrhosis and Its Child-Pugh Stage Using Vivo 31-phosphorus Magnetic Resonance Spectroscopy at 3.0 Tesla%31P-MRS在评估肝硬化及其分级中的价值

    Institute of Scientific and Technical Information of China (English)

    于德新; 马祥兴; 李笃民; 张晓明; 王茜; 李传福


    目的 探讨31P-磁共振波谱(MRS)无创评估肝硬化及其分级的价值.资料与方法 分别对53例肝硬化患者及28名正常对照组进行单体素31P-MRS扫描,计算肝细胞内pH值(pHi)、磷酸单酯(PME)、磷酸双酯(PDE)、无机磷(Pi)、磷酸肌酸(PCr)、γ-ATP、β-ATP、α-ATP、PME/ATP、Pi/ATP、PCr/ATP、PME/PDE、PME/Pi、PDE/Pi、PDE/ATP比值和低能磷酸盐(LEP)等代谢指标.探讨以上各参数在肝硬化及其Child-Pugh分级中的异同.结果 在肝硬化组,PME、PME/ATP、PME/PDE及PME/Pi均大于正常对照组(P0.05).结论 肝硬化时PME相关参数明显升高,PME、Pi和PME/Pi可对肝硬化的程度进行评估.

  7. Hadamard NMR spectroscopy for two-dimensional quantum information processing and parallel search algorithms. (United States)

    Gopinath, T; Kumar, Anil


    Hadamard spectroscopy has earlier been used to speed-up multi-dimensional NMR experiments. In this work, we speed-up the two-dimensional quantum computing scheme, by using Hadamard spectroscopy in the indirect dimension, resulting in a scheme which is faster and requires the Fourier transformation only in the direct dimension. Two and three qubit quantum gates are implemented with an extra observer qubit. We also use one-dimensional Hadamard spectroscopy for binary information storage by spatial encoding and implementation of a parallel search algorithm.

  8. Quantification of organic and amino acids in beer by 1H NMR spectroscopy. (United States)

    Nord, Lars I; Vaag, Pia; Duus, Jens Ø


    The quantification of organic and amino acids in beer using 1H NMR spectroscopy is demonstrated. Quantification was made both by integration of signals in the spectra together with use of calibration references and by use of partial least-squares (PLS) regression. Results from the NMR quantifications were compared with those obtained from determinations by amino acid analysis on HPLC and organic acid analysis by capillary electrophoresis. The described NMR-based methods could satisfactorily be used for quantification of several of the investigated metabolites in beer down to approximately 10 mg/L and for most with a good to high accuracy compared to results obtained by HPLC and capillary electrophoresis (R2 0.90-0.99). This was achieved with a simple sample preparation and one-dimensional 1H NMR spectra obtained in a few minutes. The use of PLS clearly improves the accuracy of the quantifications, based on comparison to results obtained by HPLC and capillary electrophoresis, and furthermore permits the determination of components with partially overlapped signals in the spectrum. NMR spectroscopy in combination with PLS will be a useful tool for the quantification of metabolites, not only in beer but also in other beverages and biofluids.

  9. New methods and applications in solid-state NMR spectroscopy of quadrupolar nuclei. (United States)

    Ashbrook, Sharon E; Sneddon, Scott


    Solid-state nuclear magnetic resonance (NMR) spectroscopy has long been established as offering unique atomic-scale and element-specific insight into the structure, disorder, and dynamics of materials. NMR spectra of quadrupolar nuclei (I > (1)/2) are often perceived as being challenging to acquire and to interpret because of the presence of anisotropic broadening arising from the interaction of the electric field gradient and the nuclear electric quadrupole moment, which broadens the spectral lines, often over several megahertz. Despite the vast amount of information contained in the spectral line shapes, the problems with sensitivity and resolution have, until very recently, limited the application of NMR spectroscopy of quadrupolar nuclei in the solid state. In this Perspective, we provide a brief overview of the quadrupolar interaction, describe some of the basic experimental approaches used for acquiring high-resolution NMR spectra, and discuss the information that these spectra can provide. We then describe some interesting recent examples to showcase some of the more exciting and challenging new applications of NMR spectra of quadrupolar nuclei in the fields of energy materials, microporous materials, Earth sciences, and biomaterials. Finally, we consider the possible directions that this highly informative technique may take in the future.

  10. Intramolecular hydrogen-bonding studies by NMR spectroscopy

    CERN Document Server

    Cantalapiedra, N A


    o-methoxybenzamide and N-methyl-o-methylbenzamide, using the pseudo-contact shifts calculated from the sup 1 H and sup 1 sup 3 C NMR spectra. The main conformation present in solution for o-fluorobenzamide was the one held by an intramolecular N-H...F hydrogen bond. Ab-initio calculations (at the RHF/6-31G* level) have provided additional data for the geometry of the individual molecules. A conformational equilibrium study of some nipecotic acid derivatives (3-substituted piperidines: CO sub 2 H, CO sub 2 Et, CONH sub 2 , CONHMe, CONEt sub 2) and cis-1,3-disubstituted cyclohexane derivatives (NHCOMe/CO sub 2 Me, NHCOMe/CONHMe, NH sub 2 /CO sub 2 H) has been undertaken in a variety of solvents, in order to predict the intramolecular hydrogen-bonding energies involved in the systems. The conformer populations were obtained by direct integration of proton peaks corresponding to the equatorial and axial conformations at low temperature (-80 deg), and by geometrically dependent coupling constants ( sup 3 J sub H s...

  11. Li mobility in fast ion conductors followed by NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Sanz, J.


    Structural features that enhance Li mobility in fast ion conductors with perovskite (Li{sub 3}xLa{sub 2}/3-xTiO{sub 3} series) and Nasicon structure (Li{sub 1}+xTi{sub 2}-xAl{sub x} (PO{sub 4}){sub 3} series) have been investigated. From the analysis of quadrupolar interactions, the local symmetry and exchange processes between structural sites occupied by lithium have been deduced to investigate local motions of lithium in conduction paths of analyzed compounds. The study of spin-lattice (T{sub 1}) and spin-spin (T{sub 2}) relaxation times made possible the analysis of the temperature dependence of Li residence times at structural sites. The comparison of these values with those deduced from conductivity (ac and dc-measurements) allowed the study of Li-motion mechanisms. The onset of long range motions requires the analysis of low frequency measurements (T{sub 2} relaxation and dc-conductivity). The non- Arrhenius behaviour, often observed in fast ion conductors, has been ascribed to order/disorder transitions. At increasing temperatures, Li motions become less correlated, producing the decrement of activation energy. In analyzed compounds, a direct measurement of diffusion coefficients has been obtained from NMR experiments performed with the pulse field gradient (PFG) technique. Finally, it is emphasized the importance of the vacancy percolation in conductivity processes. (Author)

  12. Evaluation of biochemical metabolites by ~(31)P MR spectroscopy in leukemic infiltration of liver%急性白血病肝浸润~(31)P磁共振波谱学分析及临床意义

    Institute of Scientific and Technical Information of China (English)

    孙建忠; 王志康; 余日胜; 黄连生; 徐秀芳; 张敏鸣


    目的:通过对白血病肝脏浸润(LIL)病例与正常对照组的肝脏二维化学位移磁共振31磷波谱成像(2D CSI ~(31)P MRS)对照研究,探讨LIL的肝脏磷化合物代谢特征变化.方法:收集LIL 15例,并与12例正常肝脏作对照,进行2D CSI ~(31)P MRS肝脏扫描,检测各种磷代谢物包括磷酸单酯(PME)、磷酸双酯(PDE)、三磷酸腺苷(ATP)、无机磷(Pi)的相对值,经体模所测校正系数校正后,分析PME、PDE、Pi、ATP的校正相对值(以下简称相对值),及PME/PDE、PME/ATP、PDE/ATP、Pi/ATP、 PME/(PME+PDE)的比值变化.结果:在所测的肝脏磷代谢物相对值中,仅LIL组的PME相对值升高,为1.992±0.876,与对照组(1.167±0.427)相比有显著性差异,P<0.05;其它各磷代谢物相对值均无差异.比较LIL与正常对照组之间磷代谢物比值,发现LIL组中与PME相关的比值包括PME/PDE、PME/ATP和PME/(PME+PDE)比值升高,分别为0.551±0.339、1.402±0.654和0.326±0.13,与对照组(分别为0.254±0.059、0.792±0.232和0.199±0.049)相比有显著性差异,P<0.01;LIL组的其它磷代谢物比值与对照组相比均无显著差异.结论:肝~(31)P MRS检查为LIL提供新的非创伤性检测和评价方法,肝脏PME相对值及其相应比值升高提示白血病患者肝浸润存在的可能.

  13. Disclosing the multi-faceted world of weakly interacting inorganic systems by means of NMR spectroscopy. (United States)

    Rocchigiani, Luca; Macchioni, Alceo


    The potential of NMR spectroscopy to investigate inorganic systems assembled by, or whose reactivity is affected by, non-covalent interactions is described. Subjects that have received particular attention in recent years (halogen bonding and Frustrated Lewis Pairs) and more classical subjects that remain under-explored (self-aggregation of ion pairs in low polar solvents, behavior of MAO containing metallocenium ion pairs, and hydrogen bonding/ion pairing effects in Au(i) catalysis) are considered, using an innovative approach, always focusing on the crucial information that can be provided by NMR.

  14. Synthesis and proton NMR spectroscopy of intra-vesicular gamma-aminobutyric acid (GABA). (United States)

    Wang, Luke Y-J; Tong, Rong; Kohane, Daniel S


    We report the synthesis of vesicles containing gamma-aminobutyric acid (GABA), and their proton nuclear magnetic resonance ((1)H NMR) spectra. These vesicles were constructed to more closely mimic the intracellular environment wherein GABA exists. For this study, these GABA-containing vesicles were examined under (1)H NMR as a potential platform for future studies on the differences between aqueous phantoms, ex vivo brain extracts, and in vivo magnetic resonance spectroscopy results. We found that intra-vesicular GABA faithfully yielded the chemical shifts and J-coupling constants of free aqueous GABA, alongside the chemical shift signals of the vesicle wall.

  15. Grape juice quality control by means of ¹H nmr spectroscopy and chemometric analyses

    Directory of Open Access Journals (Sweden)

    Caroline Werner Pereira da Silva Grandizoli


    Full Text Available This work shows the application of ¹H NMR spectroscopy and chemometrics for quality control of grape juice. A wide range of quality assurance parameters were assessed by single ¹H 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.

  16. Solid-phase enolate chemistry investigated using HR-MAS NMR spectroscopy. (United States)

    Fruchart, Jean-Sébastien; Lippens, Guy; Kuhn, Cyrille; Gras-Masse, Hélène; Melnyk, Oleg


    Supported P4-t-Bu enolate chemistry of phenylacetyloxymethyl polystyrene (PS) resin was investigated using high-resolution magic angle spinning (HR-MAS) NMR spectroscopy. Direct analysis of the crude reaction suspensions through the use of a diffusion filter (DF) allowed a rapid selection of the optimal experimental conditions, but also the characterization of the enolate on the solid phase. Comparison with solution experiments and literature data allowed us to address partially the structure of the enolate. HR-MAS NMR spectra of the enolate revealed also a tight interaction of P4-t-Bu base with the polymer matrix.

  17. Characterization of phosphate sequestration by a lanthanum modified bentonite clay: A solid-state NMR, EXAFS and PXRD study

    DEFF Research Database (Denmark)

    Dithmer, Line; Lipton, Andrew S; Reitzel, Kasper;


    Phosphate (Pi) sequestration by a lanthanum (La) exchanged clay mineral (La-Bentonite), which is extensively used in chemical lake restoration, was investigated on the molecular level using a combination of 31P and 139La solid state NMR spectroscopy (SSNMR), extended X-ray absorption spectroscopy...

  18. Magnesium and Calcium Aluminate Liquids: In Situ High-Temperature 27Al NMR Spectroscopy. (United States)

    Poe, B T; McMillan, P F; Coté, B; Massiot, D; Coutures, J P


    The use of high-temperature nuclear magnetic resonance (NMR) spectroscopy provides a means of investigating the structure of refractory aluminate liquids at temperatures up to 2500 K. Time-averaged structural information indicates that the average aluminum coordination for magnesium aluminate (MgAl(2)O(4)) liquid is slightly greater than for calcium aluminate (CaAl(2)O(4)) liquid and that in both liquids it is close to four. Ion dynamics simulations for these liquids suggest the presence of four-, five-, and six-coordinated aluminate species, in agreement with NMR experiments on fast-quenched glasses. These species undergo rapid chemical exchange in the high-temperature liquids, which is evidenced by a single Lorentzian NMR line.

  19. Bis(pentamethylcyclopentadienyl)ytterbium: An investigation of weak interactions in solution using multinuclear NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Schwartz, D.J.


    NMR spectroscopy is ideal for studying weak interactions (formation enthalpy {le}20 kcal/mol) in solution. The metallocene bis(pentamethylcyclopentadienyl)ytterbium, Cp*{sub 2}Yb, is ideal for this purpose. cis-P{sub 2}PtH{sub 2}complexes (P = phosphine) were used to produce slow-exchange Cp*{sub 2}YbL adducts for NMR study. Reversible formation of (P{sub 2}PtH){sub 2} complexes from cis-P{sub 2}PtH{sub 2} complexes were also studied, followed by interactions of Cp*{sub 2}Yb with phosphines, R{sub 3}PX complexes. A NMR study was done on the interactions of Cp*{sub 2}Yb with H{sub 2}, CH{sub 4}, Xe, CO, silanes, stannanes, C{sub 6}H{sub 6}, and toluene.

  20. Functional MRI and NMR spectroscopy of an operating gas-liquid-solid catalytic reactor. (United States)

    Koptyug, Igor V; Lysova, Anna A; Kulikov, Alexander V; Kirillov, Valery A; Parmon, Valentin N; Sagdeev, Renad Z


    A dynamic in situ study of alpha-methylstyrene catalytic hydrogenation on a single catalyst pellet or in a granular bed is performed using 1H MRI and spatially resolved 1H NMR spectroscopy. Owing to reaction exothermicity, a reciprocating motion of the liquid front within the pellet accompanied by pellet temperature oscillations has been observed. Spatially resolved information on the reactant to product conversion within the catalyst bed has been obtained for a steady-state regime. Two-dimensional 27Al NMR images of alumina catalyst supports and other alumina-containing materials have been detected using moderate magnetic field gradients (80 G/cm) and a two-pulse spin-echo sequence. Temperature dependence of signal intensity and 27Al T1 time of alumina are considered as possible temperature sensors for NMR thermometry applications.

  1. Structures of larger proteins in solution: Three- and four-dimensional heteronuclear NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Gronenborn, A.M.; Clore, G.M. [National Institutes of Health, Bethesda, MD (United States)


    Complete understanding of a protein`s function and mechanism of action can only be achieved with a knowledge of its three-dimensional structure at atomic resolution. At present, there are two methods available for determining such structures. The first method, which has been established for many years, is x-ray diffraction of protein single crystals. The second method has blossomed only in the last 5 years and is based on the application of nuclear magnetic resonance (NMR) spectroscopy to proteins in solution. This review paper describes three- and four-dimensional NMR methods applied to protein structure determination and was adapted from Clore and Gronenborn. The review focuses on the underlying principals and practice of multidimensional NMR and the structural information obtained.

  2. Fast acquisition of high-resolution 2D NMR spectroscopy in inhomogeneous magnetic fields (United States)

    Lin, Liangjie; Wei, Zhiliang; Zeng, Qing; Yang, Jian; Lin, Yanqin; Chen, Zhong


    High-resolution nuclear magnetic resonance (NMR) spectroscopy plays an important role in chemical and biological analyses. In this study, we combine the J-coupling coherence transfer module with the echo-train acquisition technique for fast acquisition of high-resolution 2D NMR spectra in magnetic fields with unknown spatial variations. The proposed method shows satisfactory performance on a 5 mM ethyl 3-bromopropionate sample, under a 5-kHz (10 ppm at 11.7 T) B0 inhomogeneous field, as well as under varying degrees of pulse-flip-angle deviations. Moreover, a simulative ex situ NMR measurement is also conducted to show the effectiveness of the proposed pulse sequence.

  3. High-resolution NMR and diffusion-ordered spectroscopy of port wine. (United States)

    Nilsson, Mathias; Duarte, Iola F; Almeida, Cláudia; Delgadillo, Ivonne; Goodfellow, Brian J; Gil, Ana M; Morris, Gareth A


    The use of high-resolution NMR and high-resolution diffusion-ordered spectroscopy (DOSY) for the characterization of selected Port wine samples of different ages with the aim of identifying changes in composition is described. Conventional 1D and 2D NMR methods enabled the identification of about 35 compounds, including minor components such as some medium-chain alcohols, amino acids, and organic acids. High-resolution (HR) DOSY extended sample characterization, increasing the number of compounds identified and NMR assignments made, by providing information on the relative molecular sizes of the metabolites present. Port wines of different ages were found to differ mainly in their content of (a) organic acids and some amino acids, (b) an unidentified possible disaccharide, and (c) large aromatic species. The relative amount of these last high Mw aromatics is seen to decrease significantly in the oldest wine, as expected from the known formation and precipitation of anthocyanin-based polymers during red wine aging.

  4. Remeasuring HEWL pKa values by NMR spectroscopy 

    DEFF Research Database (Denmark)

    Webb, Helen; Tynan-Connolly, Barbara Mary; Lee, Gregory M;


    protonated carbons and protons in this protein. We extracted pK(a) values from the resulting titration curves using standard fitting methods, and compared these values to each other, and with those measured previously by ¹H NMR (Bartik et al., Biophys J 1994;66:1180–1184). This analysis gives insights......Site-specific pK(a) values measured by NMR spectroscopy provide essential information on protein electrostatics, the pH-dependence of protein structure, dynamics and function, and constitute an important benchmark for protein pK(a) calculation algorithms. Titration curves can be measured...... by tracking the NMR chemical shifts of several reporter nuclei versus sample pH. However, careful analysis of these curves is needed to extract residue-specific pK(a) values since pH-dependent chemical shift changes can arise from many sources, including through-bond inductive effects, through-space electric...

  5. Chemical-shift-resolved ¹⁹F NMR spectroscopy between 13.5 and 135 MHz: Overhauser-DNP-enhanced diagonal suppressed correlation spectroscopy. (United States)

    George, Christy; Chandrakumar, Narayanan


    Overhauser-DNP-enhanced homonuclear 2D (19)F correlation spectroscopy with diagonal suppression is presented for small molecules in the solution state at moderate fields. Multi-frequency, multi-radical studies demonstrate that these relatively low-field experiments may be operated with sensitivity rivalling that of standard 200-1000 MHz NMR spectroscopy. Structural information is accessible without a sensitivity penalty, and diagonal suppressed 2D NMR correlations emerge despite the general lack of multiplet resolution in the 1D ODNP spectra. This powerful general approach avoids the rather stiff excitation, detection, and other special requirements of high-field (19)F NMR spectroscopy.

  6. In situ solid-state NMR spectroscopy of electrochemical cells: batteries, supercapacitors, and fuel cells. (United States)

    Blanc, Frédéric; Leskes, Michal; Grey, Clare P


    Electrochemical cells, in the form of batteries (or supercapacitors) and fuel cells, are efficient devices for energy storage and conversion. These devices show considerable promise for use in portable and static devices to power electronics and various modes of transport and to produce and store electricity both locally and on the grid. For example, high power and energy density lithium-ion batteries are being developed for use in hybrid electric vehicles where they improve the efficiency of fuel use and help to reduce greenhouse gas emissions. To gain insight into the chemical reactions involving the multiple components (electrodes, electrolytes, interfaces) in the electrochemical cells and to determine how cells operate and how they fail, researchers ideally should employ techniques that allow real-time characterization of the behavior of the cells under operating conditions. This Account reviews the recent use of in situ solid-state NMR spectroscopy, a technique that probes local structure and dynamics, to study these devices. In situ NMR studies of lithium-ion batteries are performed on the entire battery, by using a coin cell design, a flat sealed plastic bag, or a cylindrical cell. The battery is placed inside the NMR coil, leads are connected to a potentiostat, and the NMR spectra are recorded as a function of state of charge. (7)Li is used for many of these experiments because of its high sensitivity, straightforward spectral interpretation, and relevance to these devices. For example, (7)Li spectroscopy was used to detect intermediates formed during electrochemical cycling such as LixC and LiySiz species in batteries with carbon and silicon anodes, respectively. It was also used to observe and quantify the formation and growth of metallic lithium microstructures, which can cause short circuits and battery failure. This approach can be utilized to identify conditions that promote dendrite formation and whether different electrolytes and additives can help

  7. Variability within intramuscular fat content of pigs as measured by gravimetry, FTIR and NMR spectroscopy. (United States)

    Geers, R; Decanniere, C; Villé, H; Van Hecke, P; Bosschaerts, L


    In order to determine in vivo intramuscular fat content of pigs' biceps femoris, three methods were compared. Gravimetry and FTIR spectroscopy after total fat extraction from a biopsy (about 400 mg skeletal muscle tissue) and in vivo (1)H NMR spectroscopy after imaging and volume of interest selection were used. Mean values (g fat/100 g fresh tissue) were, respectively, 1·47 ± 0·35 (gravimetry), 1·26 ± 0·33 (FTIR) and 0·51 ± 0·19 (NMR); but NMR-values represented only triglycerides. Within an intramuscular fat range from 1·1 to 2·7 g per 100 g fresh muscle tissue, possible to estimate a calibration line between the in vitro and in vivo data for hybrid piglets of about 18 kg. Repeated in vivo NMR measurements on the same muscle volume showed a mean coefficient of variation of 5·5 ± 2·7%. The coefficient of variation of measurements on different volumes within the same muscle was 14 ± 10%. The mean intramuscular fat content of 18 kg or 100 kg pigs was, respectively, 1·64 ± 0·46 (biceps femoris) and 1·32 ± 0·1 (longissimus dorsi) g per 100 g fresh muscle tissue.

  8. Conformational equilibrium of phenylacetic acid and its halogenated analogues through theoretical studies, NMR and IR spectroscopy (United States)

    Levandowski, Mariana N.; Rozada, Thiago C.; Melo, Ulisses Z.; Basso, Ernani A.; Fiorin, Barbara C.


    This paper presents a study on the conformational preferences of phenylacetic acid (PA) and its halogenated analogues (FPA, CPA, BPA). To clarify the effects that rule these molecules' behaviour, theoretical calculations were used, for both the isolated phase and solution, combined with nuclear magnetic resonance (NMR) and infrared (IR) spectroscopy. Most conformations of phenylacetic acid and its halogenated derivatives are stabilized through the hyperconjugative effect, which rules the conformational preference. NMR analyses showed that even with the variation in medium polarity, there was no significant change in the conformation population. Infrared spectroscopy showed similar results for all compounds under study. In most spectra, two bands were found through the carbonyl deconvolution, which is in accordance with the theoretical data. It was possible to prove that variation in the nature of the substituent in the ortho position had no significant influence on the conformational equilibrium.

  9. Analysis and aging of unsaturated polyester resins in contemporary art installations by NMR spectroscopy. (United States)

    Stamatakis, Georgios; Knuutinen, Ulla; Laitinen, Kai; Spyros, Apostolos


    Two original art installations constructed from unsaturated polyester resins (UPR) and four different reference UPR products (before and after UVB aging) were analyzed by high-resolution 1D and 2D nuclear magnetic resonance (NMR) spectroscopy. Breaking strain studies were also conducted for the four UPR model products before and after different aging procedures (moisture, UVB exposure, melt/freeze). NMR analysis of the chemical composition of the UPR resin extracts showed they contain several low MW organic compounds and oligomers rich in polar -OH groups that play a significant role in the degradation behavior of the composite UPR materials. Statistical analysis of the NMR compositional data showed that styrene and benzaldehyde contents can be used to differentiate between fresh and aged UPR samples. The phthalate and propylene glycol unit speciation (esterified, primary or secondary -OH) of the extracts provided evidence that UPR resin C was used in the construction of the two art installations, and direct comparison of (1)H and (13)C NMR spectra verified this compositional similarity. UPR resin C was shown by both NMR and breaking strain studies to be the reference UPR most susceptible to degradation by different aging procedures, a characteristic attributed to the lower styrene content of resin C.

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


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


    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 t...

  11. 1H to 13C Energy Transfer in Solid State NMR Spectroscopy of Natural Organic Systems (United States)

    Berns, Anne E.; Conte, Pellegrino


    Cross polarization (CP) magic angle spinning (MAS) 13C-NMR spectroscopy is a solid state NMR technique widely used to study chemical composition of organic materials with low or no solubility in the common deuterated solvents used to run liquid state NMR experiments. Based on the magnetization transfer from abundant nuclei (with spin of 1 -2) having a high gyromagnetic ratio (γ), such as protons, to the less abundant 13C nuclei with low γ values, 13C-CPMAS NMR spectroscopy is often applied in environmental chemistry to obtain quantitative information on the chemical composition of natural organic matter (NOM) (Conte et al., 2004), although its quantitative assessment is still matter of heavy debates. Many authors (Baldock et al., 1997; Conte et al., 1997, 2002; Dria et al., 2002; Kiem et al., 2000; Kögel-Knabner, 2000; Preston, 2001), reported that the application of appropriate instrument setup as well as the use of special pulse sequences and correct spectra elaboration may provide signal intensities that are directly proportional to the amount of nuclei creating a NMR signal. However, many other papers dealt with the quantitative unsuitability of 13C-CPMAS NMR spectroscopy. Among those, Mao et al. (2000), Smernik and Oades (2000 a,b), and Preston (2001) reported that cross-polarized NMR techniques may fail in a complete excitation of the 13C nuclei. In fact, the amount of observable carbons via 13C-CPMAS NMR spectroscopy appeared, in many cases, lower than that measured by a direct observation of the 13C nuclei. As a consequence, cross-polarized NMR techniques may provide spectra where signal distribution may not be representative of the quantitative distribution of the different natural organic matter components. Cross-polarization is obtained after application of an initial 90° x pulse on protons and a further spin lock pulse (along the y axis) having a fixed length (contact time) for both nuclei (1H and 13C) once the Hartmann-Hahn condition is matched

  12. Investigating the interaction between peptides of the amphipathic helix of Hcf106 and the phospholipid bilayer by solid-state NMR spectroscopy (United States)

    Zhang, Lei; Liu, Lishan; Maltsev, Sergey; Lorigan, Gary A.; Dabney-Smith, Carole


    The chloroplast twin arginine translocation (cpTat) system transports highly folded precursor proteins into the thylakoid lumen using the protonmotive force as its only energy source. Hcf106, as one of the core components of the cpTat system, is part of the precursor receptor complex and functions in the initial precursor-binding step. Hcf106 is predicted to contain a single amino terminal transmembrane domain followed by a Pro-Gly hinge, a predicted amphipathic α-helix (APH), and a loosely structured carboxy terminus. Hcf106 has been shown biochemically to insert spontaneously into thylakoid membranes. To better understand the membrane active capabilities of Hcf106, we used solid-state NMR spectroscopy to investigate those properties of the APH. In this study, synthesized peptides of the predicted Hcf106 APH (amino acids 28–65) were incorporated at increasing mol% into 1-palmitoyl-2-oleoyl-sn-glycero-phosphocholine (POPC) and POPC/MGDG (monogalactosyldiacylglycerol; mole ratio 85:15) multilamellar vesicles (MLVs) to probe the peptide-lipid interaction. Solid-state 31P NMR and 2H NMR spectroscopic experiments revealed that the peptide perturbs the headgroup and the acyl chain regions of phospholipids as indicated by changes in spectral lineshape, chemical shift anisotropy (CSA) line width, and 2H order SCD parameters. In addition, the comparison between POPC MLVs and POPC/MGDG MLVs indicated that the lipid bilayer composition affected peptide perturbation of the lipids, and such perturbation appeared to be more intense in a system more closely mimicking a thylakoid membrane. PMID:24144541

  13. Carbon-dot organic surface modifier analysis by solution-state NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Philippidis, Aggelos; Spyros, Apostolos, E-mail:; Anglos, Demetrios [University of Crete, NMR Laboratory, Department of Chemistry (Greece); Bourlinos, Athanasios B. [University of Ioannina, Physics Department (Greece); Zboril, Radek [Palacky University in Olomouc, Regional Centre of Advanced Technologies and Materials, Department of Physical Chemistry, Faculty of Science (Czech Republic); Giannelis, Emmanuel P. [Cornell University, Department of Materials Science and Engineering (United States)


    Carbon dots (C-dots) represent a new class of carbon-based materials that were discovered recently and have drawn the interest of the scientific community, particularly because of their attractive optical properties and their potential as fluorescent sensors. Investigation of the chemical structure of C-dots is extremely important for correlating the surface modifier composition with C-dot optical properties and allow for structure-properties fine tuning. In this article, we report the structural analysis of the surface modifiers of three different types of C-dot nanoparticles (Cwax, Cws, and Csalt) by use of 1D- and 2D-high-resolution NMR spectroscopy in solution. We unambiguously verify that the structure of the modifier chains remains chemically unchanged during the passivation procedure, and confirm the covalent attachment of the modifiers to the nanoparticle core, which contributes no signal to the solution-state NMR spectra. To our knowledge, this is the first study confirming the full structural assignment of C-dot organic surface modifiers by use of solution NMR spectroscopy.

  14. NMR Spectroscopy of Human Eye Tissues: A New Insight into Ocular Biochemistry

    Directory of Open Access Journals (Sweden)

    Tomasz Kryczka


    Full Text Available Background. The human eye is a complex organ whose anatomy and functions has been described very well to date. Unfortunately, the knowledge of the biochemistry and metabolic properties of eye tissues varies. Our objective was to reveal the biochemical differences between main tissue components of human eyes. Methods. Corneas, irises, ciliary bodies, lenses, and retinas were obtained from cadaver globes 0-1/2 hours postmortem of 6 male donors (age: 44–61 years. The metabolic profile of tissues was investigated with HR MAS 1H NMR spectroscopy. Results. A total of 29 metabolites were assigned in the NMR spectra of the eye tissues. Significant differences between tissues were revealed in contents of the most distant eye-tissues, while irises and ciliary bodies showed minimal biochemical differences. ATP, acetate, choline, glutamate, lactate, myoinositol, and taurine were identified as the primary biochemical compounds responsible for differentiation of the eye tissues. Conclusions. In this study we showed for the first time the results of the analysis of the main human eye tissues with NMR spectroscopy. The biochemical contents of the selected tissues seemed to correspond to their primary anatomical and functional attributes, the way of the delivery of the nutrients, and the location of the tissues in the eye.

  15. Characterization of the insertase BamA in three different membrane mimetics by solution NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Morgado, Leonor; Zeth, Kornelius; Burmann, Björn M.; Maier, Timm; Hiller, Sebastian, E-mail: [University of Basel, Biozentrum (Switzerland)


    The insertase BamA is the central protein of the Bam complex responsible for outer membrane protein biogenesis in Gram-negative bacteria. BamA features a 16-stranded transmembrane β-barrel and five periplasmic POTRA domains, with a total molecular weight of 88 kDa. Whereas the structure of BamA has recently been determined by X-ray crystallography, its functional mechanism is not well understood. This mechanism comprises the insertion of substrates from a dynamic, chaperone-bound state into the bacterial outer membrane, and NMR spectroscopy is thus a method of choice for its elucidation. Here, we report solution NMR studies of different BamA constructs in three different membrane mimetic systems: LDAO micelles, DMPC:DiC{sub 7}PC bicelles and MSP1D1:DMPC nanodiscs. The impact of biochemical parameters on the spectral quality was investigated, including the total protein concentration and the detergent:protein ratio. The barrel of BamA is folded in micelles, bicelles and nanodiscs, but the N-terminal POTRA5 domain is flexibly unfolded in the absence of POTRA4. Measurements of backbone dynamics show that the variable insertion region of BamA, located in the extracellular lid loop L6, features high local flexibility. Our work establishes biochemical preparation schemes for BamA, which will serve as a platform for structural and functional studies of BamA and its role within the Bam complex by solution NMR spectroscopy.

  16. Stereochemistry of 16a-Hydroxyfriedelin and 3-Oxo-16-methylfriedel-16-ene Established by 2D NMR Spectroscopy

    Directory of Open Access Journals (Sweden)

    Vagner Fernandes Knupp


    Full Text Available Friedelin (1, 3b-friedelinol (2, 28-hydroxyfriedelin (3, 16a-hydroxyfriedelin (4, 30-hydroxyfriedelin (5 and 16a,28-dihydroxyfriedelin (6 were isolated through fractionation of the hexane extract obtained from branches of Salacia elliptica. After a week in CDCl3 solution, 16a-hydroxyfriedelin (4 reacted turning into 3-oxo-16-methylfriedel-16-ene (7. This is the first report of a dehydration followed by a Nametkin rearrangement of a pentacyclic triterpene in CDCl3 solution occurring in the NMR tube. These seven pentacyclic triterpenes was identified through NMR spectroscopy and the stereochemistry of compound 4 and 7 was established by 2D NMR (NOESY spectroscopy and mass spectrometry (GC-MS. It is also the first time that all the 13C-NMR and 2D NMR spectral data are reported for compounds 4 and 7.

  17. Determination of the biogenic secondary organic aerosol fraction in the boreal forest by NMR spectroscopy

    Directory of Open Access Journals (Sweden)

    E. Finessi


    Full Text Available The study investigates the sources of fine organic aerosol (OA in the boreal forest, based on measurements including both filter sampling (PM1 and online methods and carried out during a one-month campaign held in Hyytiälä, Finland, in spring 2007. Two aerosol mass spectrometers (Q-AMS, ToF-AMS were employed to measure on-line concentrations of major non-refractory aerosol species, while the water extracts of the filter samples were analyzed by nuclear magnetic resonance (NMR spectroscopy for organic functional group characterization of the polar organic fraction of the aerosol. AMS and NMR spectra were processed separately by non-negative factorization algorithms, in order to apportion the main components underlying the submicrometer organic aerosol composition and depict them in terms of both mass fragmentation patterns and functional group compositions.

    The NMR results supported the AMS speciation of oxidized organic aerosol (OOA into two main fractions, which could be generally labelled as more and less oxidized organics. The more oxidized component was characterized by a mass spectrum dominated by the m/z 44 peak, and in parallel by a NMR spectrum showing aromatic and aliphatic backbones highly substituted with oxygenated functional groups (carbonyls/carboxyls and hydroxyls. Such component, contributing on average 50% of the OA mass throughout the observing period, was associated with pollution outbreaks from the Central Europe. The less oxidized component was enhanced in concomitance with air masses originating from the North-to-West sector, in agreement with previous investigations conducted at this site. NMR factor analysis was able to separate two distinct components under the less oxidized fraction of OA. One of these NMR-factors was associated with the formation of terrestrial biogenic secondary organic aerosol (BSOA, based on the comparison with spectral profiles obtained from laboratory experiments of

  18. Protolytic properties of polyamine wasp toxin analogues studied by 13C NMR spectroscopy

    DEFF Research Database (Denmark)

    Strømgaard, Kristian; Piazzi, Lorna; Olsen, Christian A;


    Acid-base properties of the natural polyamine wasp toxin PhTX-433 (1) and seven synthetic analogues [PhTX-343 (2), PhTX-334 (3), PhTX-443 (4), PhTX-434 (5), PhTX-344 (6), PhTX-444 (7), and PhTX-333 (8)], each having four protolytic sites, were characterized by 13C NMR spectroscopy. Nonlinear......, multiparameter, simultaneous fit of all chemical shift data obtained from the NMR titration curves yielded macroscopic pKa values as well as intrinsic chemical shift data of all differently protonated macrospecies. Analyses of the chemical shift data demonstrated strong interactions between all four sites...... and provided information about complex relationships between chemical shift values and protonation state. Deprotonation of fully protonated forms starts at the central amino group of the polyamine moiety, and the extent of this trend depends on the distance to the flanking, protonated amino groups. The pKa1...

  19. Methyl labeling and TROSY NMR spectroscopy of proteins expressed in the eukaryote Pichia pastoris

    Energy Technology Data Exchange (ETDEWEB)

    Clark, Lindsay; Zahm, Jacob A.; Ali, Rustam [University of Texas Southwestern Medical Center, Department of Biophysics (United States); Kukula, Maciej; Bian, Liangqiao [University of Texas at Arlington, Shimadzu Center for Advanced Analytical Chemistry (United States); Patrie, Steven M. [University of Texas Southwestern Medical Center, Department of Pathology (United States); Gardner, Kevin H. [CUNY Advanced Science Research Center, Structural Biology Initiative (United States); Rosen, Michael K.; Rosenbaum, Daniel M., E-mail: [University of Texas Southwestern Medical Center, Department of Biophysics (United States)


    {sup 13}C Methyl TROSY NMR spectroscopy has emerged as a powerful method for studying the dynamics of large systems such as macromolecular assemblies and membrane proteins. Specific {sup 13}C labeling of aliphatic methyl groups and perdeuteration has been limited primarily to proteins expressed in E. coli, preventing studies of many eukaryotic proteins of physiological and biomedical significance. We demonstrate the feasibility of efficient {sup 13}C isoleucine δ1-methyl labeling in a deuterated background in an established eukaryotic expression host, Pichia pastoris, and show that this method can be used to label the eukaryotic protein actin, which cannot be expressed in bacteria. This approach will enable NMR studies of previously intractable targets.

  20. Classification of Wines Based on Combination of 1H NMR Spectroscopy and Principal Component Analysis

    Institute of Scientific and Technical Information of China (English)

    DU, Yuan-Yuan; BAI, Guo-Yun; ZHANG, Xu; LIU, Mai-Li


    A combination of 1H nuclear magnetic resonance (NMR) spectroscopy and principal component analysis (PCA)has shown the potential for being a useful method for classification of type, production origin or geographic origin of wines. In this preliminary study, twenty-one bottled wines were classified/separated for their location of production in Shacheng, Changli and Yantai, and the types of the blended, medium dry, dry white and dry red wines, using the NMR-PCA method. The wines were produced by three subsidiary companies of an enterprise according to the same national standard. The separation was believed to be mainly due to the fermentation process for different wines and environmental variations, such as local climate, soil, underground water, sunlight and rainfall. The major chemicals associated with the separation were identified.

  1. Metabolic Profiling of Food Protective Cultures by in vitro NMR Spectroscopy

    DEFF Research Database (Denmark)

    Ebrahimi, Parvaneh

    D project is mainly focused on the application of in vitro NMR spectroscopy for studying the metabolism of protective cultures. As an important part of this work, an analytical protocol was developed for realtime in vitro NMR measurements of bacterial fermentation, which includes guidelines from the sample......Food spoilage is of major concern to the food industry, because it leads to considerable economic losses, a deteriorated environmental food-print, and to possible public health hazards. In order to limit food spoilage, research on the preservation of food products has always received particular......-called protective cultures) has unexploited potential to inhibit the growth of pathogenic microorganisms and enhance the shelf life of the final food product. In order to apply biopreservation in food products effectively, detailed knowledge on the metabolism of protective cultures is required. The present Ph...

  2. Reactive surface organometallic complexes observed using dynamic nuclear polarization surface enhanced NMR spectroscopy

    KAUST Repository

    Pump, Eva


    Dynamic Nuclear Polarization Surface Enhanced NMR Spectroscopy (DNP SENS) is an emerging technique that allows access to high-sensitivity NMR spectra from surfaces. However, DNP SENS usually requires the use of radicals as an exogenous source of polarization, which has so far limited applications for organometallic surface species to those that do not react with the radicals. Here we show that reactive surface species can be studied if they are immobilized inside porous materials with suitably small windows, and if bulky nitroxide bi-radicals (here TEKPol) are used as the polarization source and which cannot enter the pores. The method is demonstrated by obtaining significant DNP enhancements from highly reactive complelxes [(equivalent to Si-O-)W(Me)(5)] supported on MCM-41, and effects of pore size (6.0, 3.0 and 2.5 nm) on the performance are discussed.

  3. Refolding of ribonuclease A monitored by real-time photo-CIDNP NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Day, Iain J. [University of Sussex, Department of Chemistry and Biochemistry, School of Life Sciences (United Kingdom); Maeda, Kiminori; Paisley, Howard J. [University of Oxford, Department of Chemistry, Physical and Theoretical Chemistry Laboratory (United Kingdom); Mok, K. Hun [University of Dublin, Trinity College, School of Biochemistry and Immunology (Ireland)], E-mail:; Hore, P. J. [University of Oxford, Department of Chemistry, Physical and Theoretical Chemistry Laboratory (United Kingdom)], E-mail:


    Photo-CIDNP NMR spectroscopy is a powerful method for investigating the solvent accessibility of histidine, tyrosine and tryptophan residues in a protein. When coupled to real-time NMR, this technique allows changes in the environments of these residues to be used as a probe of protein folding. In this paper we describe experiments performed to monitor the refolding of ribonuclease A following dilution from a high concentration of chemical denaturant. These experiments provide a good example of the utility of this technique which provides information that is difficult to obtain by other biophysical methods. Real-time photo-CIDNP measurements yield residue-specific kinetic data pertaining to the folding reaction, interpreted in terms of current knowledge of the folding of bovine pancreatic ribonuclease A.

  4. Characterization of metabolites in different kiwifruit varieties by NMR and fluorescence spectroscopy. (United States)

    Abdul Hamid, Nur Ashikin; Mediani, Ahmed; Maulidiani, M; Abas, Faridah; Park, Yong Seo; Leontowicz, Hanna; Leontowicz, Maria; Namiesnik, Jacek; Gorinstein, S


    It is known from our previous studies that kiwifruits, which are used in common human diet, have preventive properties of coronary artery disease. This study describes a combination of (1)H NMR spectroscopy, multivariate data analyses and fluorescence measurements in differentiating of some kiwifruit varieties, their quenching and antioxidant properties. A total of 41 metabolites were identified by comparing with literature data Chenomx database and 2D NMR. The binding properties of the extracted polyphenols against HSA showed higher reactivity of studied two cultivars in comparison with the common Hayward. The results showed that the fluorescence of HSA was quenched by Bidan as much as twice than by other fruits. The correlation between the binding properties of polyphenols in the investigated fruits, their relative quantification and suggested metabolic pathway was established. These results can provide possible application of fruit extracts in pharmaceutical industry.

  5. Microfabricated inserts for magic angle coil spinning (MACS wireless NMR spectroscopy.

    Directory of Open Access Journals (Sweden)

    Vlad Badilita

    Full Text Available This article describes the development and testing of the first automatically microfabricated probes to be used in conjunction with the magic angle coil spinning (MACS NMR technique. NMR spectroscopy is a versatile technique for a large range of applications, but its intrinsically low sensitivity poses significant difficulties in analyzing mass- and volume-limited samples. The combination of microfabrication technology and MACS addresses several well-known NMR issues in a concerted manner for the first time: (i reproducible wafer-scale fabrication of the first-in-kind on-chip LC microresonator for inductive coupling of the NMR signal and reliable exploitation of MACS capabilities; (ii improving the sensitivity and the spectral resolution by simultaneous spinning the detection microcoil together with the sample at the "magic angle" of 54.74° with respect to the direction of the magnetic field (magic angle spinning - MAS, accompanied by the wireless signal transmission between the microcoil and the primary circuit of the NMR spectrometer; (iii given the high spinning rates (tens of kHz involved in the MAS methodology, the microfabricated inserts exhibit a clear kinematic advantage over their previously demonstrated counterparts due to the inherent capability to produce small radius cylindrical geometries, thus tremendously reducing the mechanical stress and tearing forces on the sample. In order to demonstrate the versatility of the microfabrication technology, we have designed MACS probes for various Larmor frequencies (194, 500 and 700 MHz testing several samples such as water, Drosophila pupae, adamantane solid and LiCl at different magic angle spinning speeds.

  6. Separation of 2H MAS NMR Spectra by Two-Dimensional Spectroscopy (United States)

    Kristensen, J. H.; Bildsøe, H.; Jakobsen, H. J.; Nielsen, N. C.


    New methods for optimum separation of 2H MAS NMR spectra are presented. The approach is based on hypercomplex spectroscopy that is useful for sign discrimination and phase separation. A new theoretical formalism is developed for the description of hypercomplex experiments. This exploits the properties of Lie algebras and hypercomplex numbers to obtain a solution to the Liouville-von Neumann equation. The solution is expressed in terms of coherence transfer functions that describe the allowed coherence transfer pathways in the system. The theoretical formalism is essential in order to understand all the features of hypercomplex experiments. The method is applied to the development of two-dimensional quadrupole-resolved 2H MAS NMR spectroscopy. The important features of this technique are discussed and two different versions are presented with widely different characteristics. An improved version of two-dimensional double-quantum 2H MAS NMR spectroscopy is developed. The conditions under which the double-quantum experiment is useful are discussed and its performance is compared with that observed for the quadrupole-resolved experiments. A general method is presented for evaluating the optimum pulse sequence parameters consistent with maximum sensitivity and resolution. This approach improves the performance of the experiments and is essential for any further development of the techniques. The effects of finite pulse width and hypercomplex data processing may lead to both intensity and phase distortions in the spectra. These effects are analyzed and general correction procedures are suggested. The techniques are applied to polycrystalline malonic-acid-2H4 for which the spinning sideband manifolds from the carboxyl and methylene deuterons are separated. The spinning sideband manifolds are simulated to determine the quadrupole parameters. The values are consistent with previous results, indicating that the techniques are both accurate and reliable.

  7. Metabolic response to exogenous ethanol in yeast: An in vivo statistical total correlation NMR spectroscopy approach

    Indian Academy of Sciences (India)

    Maso Ricci; Marianna Aggravi; Claudia Bonechi; Silvia Martini; Anna Maria; Claudio Rossi


    In vivo NMR spectroscopy, together with selectively 13C-labelled substrates and ‘statistical total correlation spectroscopy’ analysis (STOCSY), are valuable tools to collect and interpret the metabolic responses of a living organism to external stimuli. In this study, we applied this approach to evaluate the effects of increasing concentration of exogenous ethanol on the Saccharomyces cerevisiae fermentative metabolism. We show that the STOCSY analysis correctly identifies the different types of correlations among the enriched metabolites involved in the fermentation, and that these correlations are quite stable even in presence of a stressing factor such as the exogenous ethanol.

  8. Stereochemical investigations on the diketopiperazine derivatives of enalapril and lisinopril by NMR spectroscopy (United States)

    Demeter, Ádám; Fodor, Tamás; Fischer, János


    Stereochemical analysis of epimeric diketopiperazine (DKP) derivatives of enalapril and lisinopril has been performed by NMR spectroscopy. The present study focuses on the configurational assignment and conformational characteristics of the epimeric DKPs obtained from cyclization and subsequent base-catalyzed hydrolysis. We report full 1H and 13C assignments as obtained by a concerted use of 1D and 2D methods. The configuration of the respective stereogenic centres and the main conformational features were derived from the measured scalar and NOE connections. One conspicuous conformational feature of the sidechain is its tendency to bend over the piperazinedione ring.

  9. Probing the Pu4 + magnetic moment in PuF4 with 19F NMR spectroscopy (United States)

    Capan, Cigdem; Dempsey, Richard J.; Sinkov, Sergey; McNamara, Bruce K.; Cho, Herman


    The magnetic fields produced by Pu4 + centers have been measured by 19F NMR spectroscopy to elucidate the Pu-F electronic interactions in polycrystalline PuF4. Spectra acquired at applied fields of 2.35 and 7.05 T reveal a linear scaling of the 19F line shape. A model is presented that treats the line broadening and shifts as due to dipolar fields produced by Pu valence electrons in localized noninteracting orbitals. Alternative explanations for the observed line shape involving covalent Pu-F bonding, superexchange interactions, and electronic configurations with enhanced magnetic moments are considered.

  10. Employing NMR Spectroscopy To Evaluate Transmission of Electronic Effects in 4-Substituted Chalcones (United States)

    Wachter-Jurcsak, Nanette; Zamani, Hossein


    Described is an organic synthesis experiment that demonstrates the electronic transmission by substituents. The effect of substitution at the para-position of the styryl ring of 1,3-diphenyl-2-propenones (chalcones) by typical electron-donating or -accepting groups can be observed by proton and carbon-13 NMR spectroscopy. A linear correlation is observed when the differences in chemical shift measurements for H are plotted against the corresponding Hammett substituent constant values. Good correlation between carbon-13 chemical shifts of the alpha carbon are also observed. The syntheses of the 4-substituted chalcones is presented as well as a brief discussion of the theory.

  11. Dynamic processes and chemical composition of Lepidium sativum seeds determined by means of field-cycling NMR relaxometry and NMR spectroscopy. (United States)

    Rachocki, A; Latanowicz, L; Tritt-Goc, J


    Proton nuclear magnetic resonance (NMR) techniques, such as field-cycling relaxometry, wide-line NMR spectroscopy, and magic angle spinning NMR spectroscopy, were applied to study the seeds of cress, Lepidium sativum. Field-cycling NMR relaxometry was used for the first time to investigate the properties of the whole molecular system of dry cress seeds. This method not only allowed the dynamics to be studied, but was also successful in the differentiation among the solid (i.e., carbohydrates, proteins, or fats forming a solid form of lipids) and liquid-like (oil compounds) components of the seeds. The (1)H NMR relaxation dispersion of oils was interpreted as a superposition of intramolecular and intermolecular contributions. The intramolecular part was described in terms of a Lorentzian spectral density function, whereas a log-Gaussian distribution of correlation times was applied for the intermolecular dipole-dipole contribution. The models applied led to very good agreement with the experimental data and demonstrate that the contribution of the intermolecular relaxation to the overall relaxation should not be disregarded, especially at low frequencies. A power-law frequency dependence of the proton relaxation dispersion was used for the interpretation of the solid components. From the analysis of the (1)H wide-line NMR spectra of the liquid-like component of hydrated cress seeds, we can conclude that the contribution of oil protons should always be taken into account when evaluating the spin-lattice relaxation times values or measuring the moisture and oil content. The application of (1)H magic angle spinning NMR significantly improves resolution in the liquid-like spectrum of seeds and allows the determination of the chemical composition of cress seeds.

  12. Optimization of sample preparation for accurate results in quantitative NMR spectroscopy (United States)

    Yamazaki, Taichi; Nakamura, Satoe; Saito, Takeshi


    Quantitative nuclear magnetic resonance (qNMR) spectroscopy has received high marks as an excellent measurement tool that does not require the same reference standard as the analyte. Measurement parameters have been discussed in detail and high-resolution balances have been used for sample preparation. However, the high-resolution balances, such as an ultra-microbalance, are not general-purpose analytical tools and many analysts may find those balances difficult to use, thereby hindering accurate sample preparation for qNMR measurement. In this study, we examined the relationship between the resolution of the balance and the amount of sample weighed during sample preparation. We were able to confirm the accuracy of the assay results for samples weighed on a high-resolution balance, such as the ultra-microbalance. Furthermore, when an appropriate tare and amount of sample was weighed on a given balance, accurate assay results were obtained with another high-resolution balance. Although this is a fundamental result, it offers important evidence that would enhance the versatility of the qNMR method.

  13. Bis(pentamethylcyclopentadienyl)ytterbium: An investigation of weak interactions in solution using multinuclear NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Schwartz, David Joel [Univ. of California, Berkeley, CA (United States)


    NMR spectroscopy is ideal for studying weak interactions (formation enthalpy ≤20 kcal/mol) in solution. The metallocene bis(pentamethylcyclopentadienyl)ytterbium, Cp*2Yb, is ideal for this purpose. cis-P2PtH2complexes (P = phosphine) were used to produce slow-exchange Cp*2YbL adducts for NMR study. Reversible formation of (P2PtH)2 complexes from cis-P2PtH2 complexes were also studied, followed by interactions of Cp*2Yb with phosphines, R3PX complexes. A NMR study was done on the interactions of Cp*2Yb with H2, CH4, Xe, CO, silanes, stannanes, C6H6, and toluene.

  14. Advanced Structural Determination of Diterpene Esters Using Molecular Modeling and NMR Spectroscopy. (United States)

    Nothias-Scaglia, Louis-Félix; Gallard, Jean-François; Dumontet, Vincent; Roussi, Fanny; Costa, Jean; Iorga, Bogdan I; Paolini, Julien; Litaudon, Marc


    Three new jatrophane esters (1-3) were isolated from Euphorbia amygdaloides ssp. semiperfoliata, including an unprecedented macrocyclic jatrophane ester bearing a hemiketal substructure, named jatrohemiketal (3). The chemical structures of compounds 1-3 and their relative configurations were determined by spectroscopic analysis. The absolute configuration of compound 3 was determined unambiguously through an original strategy combining NMR spectroscopy and molecular modeling. Conformational search calculations were performed for the four possible diastereomers 3a-3d differing in their C-6 and C-9 stereocenters, and the lowest energy conformer was used as input structure for geometry optimization. The prediction of NMR parameters ((1)H and (13)C chemical shifts and (1)H-(1)H coupling constants) by density functional theory (DFT) calculations allowed identifying the most plausible diastereomer. Finally, the stereostructure of 3 was solved by comparison of the structural features obtained by molecular modeling for 3a-3d with NMR-derived data (the values of dihedral angles deduced from the vicinal proton-proton coupling constants ((3)JHH) and interproton distances determined by ROESY). The methodology described herein provides an efficient way to solve or confirm structural elucidation of new macrocyclic diterpene esters, in particular when no crystal structure is available.

  15. Investigation of Oxidative Degradation in Polymers Using (17)O NMR Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Alam, Todd M.; Celina, Mathew; Assink, Roger A.; Clough, Roger L.; Gillen, Kenneth T.; Wheeler David R.


    The thermal oxidation of pentacontane (C{sub 50}H{sub 102}), and of the homopolymer polyisoprene, has been investigated using {sup 17}O NMR spectroscopy. By performing the oxidation using {sup 17}O labeled O{sub 2} gas, it is possible to easily identify degradation products, even at relatively low concentrations. It is demonstrated that details of the degradation mechanism can be obtained from analysis of the {sup 17}O NMR spectra as a function of total oxidation. Pentacontane reveals the widest variety of reaction products, and exhibits changes in the relative product distributions with increasing O{sub 2} consumption. At low levels of oxygen incorporation, peroxides are the major oxidation product, while at later stages of degradation these species are replaced by increasing concentrations of ketones, alcohols, carboxylic acids and esters. Analyzing the product distribution can help in identification of the different free-radical decomposition pathways of hydroperoxides, including recombination, proton abstraction and chain scission, as well as secondary reactions. The {sup 17}O NMR spectra of thermally oxidized polyisoprene reveal fewer degradation functionalities, but exhibit an increased complexity in the type of observed degradation species due to structural features such as unsaturation and methyl branching. Alcohols and ethers formed from hydrogen abstraction and free radical termination.

  16. Symmetry Breaking in NMR Spectroscopy: The Elucidation of Hidden Molecular Rearrangement Processes

    Directory of Open Access Journals (Sweden)

    Michael J. McGlinchey


    Full Text Available Variable-temperature NMR spectroscopy is probably the most convenient and sensitive technique to monitor changes in molecular structure in solution. Rearrangements that are rapid on the NMR time-scale exhibit simplified spectra, whereby non-equivalent nuclear environments yield time-averaged resonances. At lower temperatures, when the rate of exchange is sufficiently reduced, these degeneracies are split and the underlying “static” molecular symmetry, as seen by X-ray crystallography, becomes apparent. Frequently, however, such rearrangement processes are hidden, even when they become slow on the NMR time-scale, because the molecular point group remains unchanged. Judicious symmetry breaking, such as by substitution of a molecular fragment by a similar, but not identical moiety, or by the incorporation of potentially diastereotopic (chemically non-equivalent nuclei, allows the elucidation of the kinetics and energetics of such processes. Examples are chosen that include a wide range of rotations, migrations and other rearrangements in organic, inorganic and organometallic chemistry.

  17. Structural Characterization of Lignins Isolated from Caragana sinica Using FT-IR and NMR Spectroscopy

    Institute of Scientific and Technical Information of China (English)

    XIAOLing-ping; SHIZheng-jun; XUFeng; SUN Run-cang; Amar Kmohanty


    In order to efficiently explore and use woody biomass,six lignin fractions were isolated from dewaxed Caragana sinica via successive extraction with organic.solvents and alkaline solutions.The lignin structures were characterized by Fourier transform infrared spectroscopy (FT-IR) and 1D and 2D Nuclear Magnetic Resonance (NMR).FT-IR spectra revealed that the “core” of the lignin structure did not significantly change during the treatment under the conditions given.The results of 1 H and 13C NMR demonstrated that the lignin fraction L2,isolated with 70% ethanol containing 1% NaOH,was mainly composed of β-O-4 ether bonds together with G and S units and trace p-hydroxyphenyl unit.Based on the 2D HSQC NMR spectrum,the ethanol organosolv lignin fraction L1,extracted with 70% ethanol,presents a predominance of β-O-4' arylether linkages (61% of total side chains),and a low abundance of condensed carbon-carbon linked structures (such as β-β',β-1',and β-5') and a lower S/G ratio.Furthermore,a small percentage (ca.9%) of the linkage side chain was found to be acylated at the γ-carbon.

  18. Novel monosaccharide fermentation products in Caldicellulosiruptor saccharolyticus identified using NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Isern, Nancy G.; Xue, Junfeng; Rao, Jaya V.; Cort, John R.; Ahring, Birgitte K.


    Profiles of metabolites produced by the thermophilic obligately anaerobic cellulose-degrading Gram-positive bacterium Caldicellulosiruptor saccharolyticus DSM 8903 strain following growth on different monosaccharides (D-glucose, D-mannose, L-arabinose, D-arabinose, D-xylose, L-fucose, and D-fucose) as carbon sources revealed several unexpected fermentation products, suggesting novel metabolic capacities and unexplored metabolic pathways in this organism. Both 1H and 13C nuclear magnetic resonance (NMR) spectroscopy were used to determine intracellular and extracellular metabolite profiles. Metabolite profiles were determined from 1-D 1H NMR spectra by curve fitting against spectral libraries provided in Chenomx software. To reduce uncertainties due to unassigned, overlapping, or poorly-resolved peaks, metabolite identifications were confirmed with 2-D homonuclear and heteronuclear NMR experiments. In addition to expected metabolites such as acetate, lactate, glycerol, and ethanol, several novel fermentation products were identified: ethylene glycol (from growth on D-arabinose, though not L-arabinose), acetoin and 2,3-butanediol (from D-glucose and L-arabinose), and hydroxyacetone (from D-mannose and L-arabinose). Production of ethylene glycol from D-arabinose was particularly notable, with around 10% of the substrate carbon converted into this uncommon fermentation product. The novel products have not previously been reported to be produced by C. saccharolyticus, nor would they be easily predicted from the current genome annotation, and show new potentials for using this strain for production of bioproducts.

  19. Optimization of identity operation in NMR spectroscopy via genetic algorithm: Application to the TEDOR experiment (United States)

    Manu, V. S.; Veglia, Gianluigi


    Identity operation in the form of π pulses is widely used in NMR spectroscopy. For an isolated single spin system, a sequence of even number of π pulses performs an identity operation, leaving the spin state essentially unaltered. For multi-spin systems, trains of π pulses with appropriate phases and time delays modulate the spin Hamiltonian to perform operations such as decoupling and recoupling. However, experimental imperfections often jeopardize the outcome, leading to severe losses in sensitivity. Here, we demonstrate that a newly designed Genetic Algorithm (GA) is able to optimize a train of π pulses, resulting in a robust identity operation. As proof-of-concept, we optimized the recoupling sequence in the transferred-echo double-resonance (TEDOR) pulse sequence, a key experiment in biological magic angle spinning (MAS) solid-state NMR for measuring multiple carbon-nitrogen distances. The GA modified TEDOR (GMO-TEDOR) experiment with improved recoupling efficiency results in a net gain of sensitivity up to 28% as tested on a uniformly 13C, 15N labeled microcrystalline ubiquitin sample. The robust identity operation achieved via GA paves the way for the optimization of several other pulse sequences used for both solid- and liquid-state NMR used for decoupling, recoupling, and relaxation experiments.

  20. Biological effects and physical safety aspects of NMR imaging and in vivo spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Tenforde, T.S.; Budinger, T.F.


    An assessment is made of the biological effects and physical hazards of static and time-varying fields associated with the NMR devices that are being used for clinical imaging and in vivo spectroscopy. A summary is given of the current state of knowledge concerning the mechanisms of interaction and the bioeffects of these fields. Additional topics that are discussed include: (1) physical effects on pacemakers and metallic implants such as aneurysm clips, (2) human health studies related to the effects of exposure to nonionizing electromagnetic radiation, and (3) extant guidelines for limiting exposure of patients and medical personnel to the fields produced by NMR devices. On the basis of information available at the present time, it is concluded that the fields associated with the current generation of NMR devices do not pose a significant health risk in themselves. However, rigorous guidelines must be followed to avoid the physical interaction of these fields with metallic implants and medical electronic devices. 476 refs., 5 figs., 2 tabs.

  1. Sensitivity and resolution enhancement in solid-state NMR spectroscopy of bicelles (United States)

    Dvinskikh, Sergey V.; Yamamoto, Kazutoshi; Dürr, Ulrich H. N.; Ramamoorthy, Ayyalusamy


    Magnetically aligned bicelles are becoming attractive model membranes to investigate the structure, dynamics, geometry, and interaction of membrane-associated peptides and proteins using solution- and solid-state NMR experiments. Recent studies have shown that bicelles are more suitable than mechanically aligned bilayers for multidimensional solid-state NMR experiments. In this work, we describe experimental aspects of the natural abundance 13C and 14N NMR spectroscopy of DMPC/DHPC bicelles. In particular, approaches to enhance the sensitivity and resolution and to quantify radio-frequency heating effects are presented. Sensitivity of 13C detection using single pulse excitation, conventional cross-polarization (CP), ramp-CP, and NOE techniques are compared. Our results suggest that the proton decoupling efficiency of the FLOPSY pulse sequence is better than that of continuous wave decoupling, TPPM, SPINAL, and WALTZ sequences. A simple method of monitoring the water proton chemical shift is demonstrated for the measurement of sample temperature and calibration of the radio-frequency-induced heating in the sample. The possibility of using 14N experiments on bicelles is also discussed.

  2. Ground-state properties of K-isotopes from laser and $\\beta$-NMR spectroscopy

    CERN Multimedia

    Lievens, P; Rajabali, M M; Krieger, A R

    By combining high-resolution laser spectroscopy with $\\beta$-NMR spectroscopy on polarized K-beams we aim to establish the ground-state spins and magnetic moments of the neutron-rich $^{48,49,50,51}$K isotopes from N=29 to N=32. Spins and magnetic moments of the odd-K isotopes up to N=28 reveal an inversion of the ground-state, from the normal $\\,{I}$=3/2 ($\\pi{d}_{3/2}^{-1}$) in $^{41-45}$K$\\to\\,{I}$=1/2 ($\\pi{s}_{1/2}^{-1}$) in $^{47}$K. This inversion of the proton single particle levels is related to the strong proton $d_{3/2}$ - neutron $f_{7/2}$ interaction which lowers the energy of the $\\pi{d}_{3/2}$ single particle state when filling the $\

  3. Impact of salbutamol on muscle metabolism assessed by ³¹P NMR spectroscopy. (United States)

    Decorte, N; Lamalle, L; Carlier, P G; Giacomini, E; Guinot, M; Levy, P; Verges, S; Wuyam, B


    The potential ergogenic effects of oral salbutamol intake were demonstrated for decades but the underlying mechanisms remain to elucidate. We hypothesized that improved exercise performance after acute oral salbutamol administration is associated with changes in muscle metabolism. Twelve healthy, nonasthmatic, moderately trained, male subjects were recruited to compare in a double-blind crossover randomized study, an oral dose of salbutamol (4 mg) and a placebo. After treatment administration, subjects performed repetitive plantar flexions to exhaustion in a 3T magnet. Continuous (31) P nuclear magnetic resonance spectroscopy assessment of the calf muscles was performed at rest, during exercise, and during recovery. No significant difference between treatments was detected in metabolite concentration at rest (P > 0.05). Creatine phosphate and inorganic phosphate changes during and immediately after exercise were similar between treatments (P > 0.05). Intramuscular pH (pHi) was significantly higher at rest, at submaximal exercise but not at exhaustion with salbutamol (pHi at 50% of exercise duration, 6.8 ± 0.1/6.9 ± 0.1 for placebo and salbutamol, respectively, P salbutamol. Salbutamol induced significant improvement in calf muscle endurance with similar metabolic responses during exercise, except slight differences in pHi. Other mechanisms than changes in muscle metabolism may be responsible for the ergogenic effect of salbutamol administration.

  4. Improved compositional analysis of block copolymers using diffusion ordered NMR spectroscopy. (United States)

    Viel, Stéphane; Mazarin, Michaël; Giordanengo, Rémi; Phan, Trang N T; Charles, Laurence; Caldarelli, Stefano; Bertin, Denis


    Block copolymers constitute a fascinating class of polymeric materials that are used in a broad range of applications. The performance of these materials is highly coupled to the physical and chemical properties of the constituting block copolymers. Traditionally, the composition of block copolymers is obtained by 1H NMR spectroscopy on purified copolymer fractions. Specifically, the integrals of a properly selected set of 1H resonances are compared and used to infer the number average molecular weight (M(n)) of one of the block from the (typically known) M(n) value of the other. As a corollary, compositional determinations achieved on imperfectly purified samples lead to serious errors, especially when isolation of the block copolymer from the initial macro initiator is tedious. This investigation shows that Diffusion Ordered NMR Spectroscopy (DOSY) can be used to provide a way to assess the advancement degree of the copolymerization purification/reaction, in order to optimize it and hence contribute to an improved compositional analysis of the resulting copolymer. To this purpose, a series of amphiphilic polystyrene-b-poly(ethylene oxide) block copolymers, obtained by controlled free-radical nitroxide mediated polymerization, were analyzed and it is shown that, under proper experimental conditions, DOSY allows for an improved compositional analysis of these block copolymers.

  5. Identification and quantitative determination of lignans in Cedrus atlantica resins using 13C NMR spectroscopy. (United States)

    Nam, Anne-Marie; Paoli, Mathieu; Castola, Vincent; Casanova, Joseph; Bighelli, Ange


    Identification and quantitative determination of individual components of resin collected on the trunk of 28 Cedrus atlantica trees, grown in Corsica, has been carried out using 13C NMR spectroscopy. Eight resin acids bearing either the pimarane or abietane skeleton, two monoterpene hydrocarbons and four oxygenated neutral diterpenes have been identified, as well as three lignans, scarcely found in resins. Three groups could be distinguished within the 28 resin samples. The nine samples of Group I had their composition dominated by diterpene acids (33.7-45.8%), with abietic acid (6.2-18.7%) and isopimaric acid (5.1-12.6%) being the major components. The four samples of Group II contained resin acids (main components) and lignans in moderate amounts (up to 10.3%). Conversely, lignans (38.8-63.8%) were by far the major components of the 15 samples of Group III. Depending on the sample, the major component was pinoresinol (18.1-38.9%), lariciresinol (17.2-33.7%) or lariciresinol 9'-acetate (16.9-29.1%). Finally, due to the high biological interest in lignans, a rapid procedure, based on 1H NMR spectroscopy, was developed for quantification of lignans in resins of C. atlantica.

  6. Evidence for cross-linking in tomato cutin using HR-MAS NMR spectroscopy. (United States)

    Deshmukh, Ashish P; Simpson, André J; Hatcher, Patrick G


    Cutin is a polyester biopolymer component of plant leaf and fruit cuticles, most often associated with waxes and cuticular polysaccharides, and sometimes with another aliphatic biopolymer called cutan. Insolubility of these cuticular biopolymers has made it difficult to apply traditional analytical techniques for structure determination, because most techniques providing molecular level details require solubility. By using the relatively new technique of one and two-dimensional high-resolution magic angle spinning (HR-MAS) NMR spectroscopy, with added information from solid-state 13C NMR spectroscopy, detailed through-bond connectivities and assignments are made for cutin from Lycopersicon esculentum (tomato) fruit. Based on the data obtained, tomato cutin is found to be predominantly an aliphatic polyester with some olefinic and aromatic moieties, consistent with previous studies that employed various degradative approaches. Aside from esters, there are free primary and secondary alcohol groups, as well as free fatty acids. A significant finding is the presence of alpha-branched fatty acids/esters. Mid-chain hydroxyls appear to be generally unesterified, but esters of mid-chain hydroxyls have been identified. The alpha-branched fatty acids/esters and esters of mid-chain hydroxyls could point towards cross-linking.

  7. Postharvest ripening study of sweet lime (Citrus limettioides) in situ by volume-localized NMR spectroscopy. (United States)

    Banerjee, Abhishek; George, Christy; Bharathwaj, Sathyamoorthy; Chandrakumar, Narayanan


    Spatially resolved NMR--especially volume-localized spectroscopy (VLS)is useful in various fields including clinical diagnosis, process monitoring, etc. VLS carries high significance because of its ability to identify molecular species and hence track molecular events. This paper reports the application of VLS at 200 MHz to study the postharvest ripening of sweet lime ( Citrus limettioides ) in situ, including a comparative study of normal and acetylene-mediated ripening. Localization to a cubic voxel of 64 microL was achieved with point-resolved spectroscopy (PRESS). Glucose, sucrose, fructose, and citric acid are found to be among the main constituents in the fruit. In the natural process, the sugar to acid ratio increases with ripening. Ethanol generation is seen to occur at a faster rate in acetylene-mediated ripening. Whereas NMR imaging experiments including parametric imaging (e.g., T(1) or T(2) maps) may be employed for "macro" monitoring of processes such as these, this work demonstrates that the molecular imprint of the process may be tracked noninvasively by VLS.

  8. Structural investigation of aluminium doped ZnO nanoparticles by solid-state NMR spectroscopy. (United States)

    Avadhut, Yamini S; Weber, Johannes; Hammarberg, Elin; Feldmann, Claus; Schmedt auf der Günne, Jörn


    The electrical conductivity of aluminium doped zinc oxide (AZO, ZnO:Al) materials depends on doping induced defects and grain structure. This study aims at relating macroscopic electrical conductivity of AZO nanoparticles with their atomic structure, which is non-trivial because the derived materials are heavily disordered and heterogeneous in nature. For this purpose we synthesized AZO nanoparticles with different doping levels and narrow size distribution by a microwave assisted polyol method followed by drying and a reductive treatment with forming gas. From these particles electrically conductive, optically transparent films were obtained by spin-coating. Characterization involved energy-dispersive X-ray analysis, wet chemical analysis, X-ray diffraction, electron microscopy and dynamic light scattering, which provided a basis for a detailed structural solid-state NMR study. A multinuclear ((27)Al, (13)C, (1)H) spectroscopic investigation required a number of 1D MAS NMR and 2D MAS NMR techniques (T(1)-measurements, (27)Al-MQMAS, (27)Al-(1)H 2D-PRESTO-III heteronuclear correlation spectroscopy), which were corroborated by quantum chemical calculations with an embedded cluster method (EEIM) at the DFT level. From the combined data we conclude that only a small part of the provided Al is incorporated into the ZnO structure by substitution of Zn. The related (27)Al NMR signal undergoes a Knight shift when the material is subjected to a reductive treatment with forming gas. At higher (formal) doping levels Al forms insulating (Al, H and C containing) side-phases, which cover the surface of the ZnO:Al particles and increase the sheet resistivity of spin-coated material. Moreover, calculated (27)Al quadrupole coupling constants serve as a spectroscopic fingerprint by which previously suggested point-defects can be identified and in their great majority be ruled out.

  9. Confirming the 3D Solution Structure of a Short Double-Stranded DNA Sequence Using NMR Spectroscopy (United States)

    Ruhayel, Rasha A.; Berners-Price, Susan J.


    2D [superscript 1]H NOESY NMR spectroscopy is routinely used to give information on the closeness of hydrogen atoms through space. This work is based on a 2D [superscript 1]H NOESY NMR spectrum of a 12 base-pair DNA duplex. This 6-h laboratory workshop aims to provide advanced-level chemistry students with a basic, yet solid, understanding of how…

  10. Formation of diphosphates. A NMR study on the mechanism and stereochemistry of diphosphate formation from chiral dioxaphosphorinanes

    NARCIS (Netherlands)

    Hulst, R; Visser, J.M.; De Vries, N.K.; Zijlstra, R.W J; Kooijman, H.; Smeets, W.J.J.; Spek, A.L.; Feringa, B.L.


    During the use of chiral 2-oxo-1,3,2-dioxaphosphorinanes as derivatizing reagents in the enantiomeric excess determination of amines, alcohols, and unprotected amino acids, minor traces of side reaction products were observed by 1H and 31P NMR spectroscopy. Analysis of the reaction mixture showed th

  11. A structural study of epoxidized natural rubber (ENR-50) and its cyclic dithiocarbonate derivative using NMR spectroscopy techniques. (United States)

    Hamzah, Rosniza; Bakar, Mohamad Abu; Khairuddean, Melati; Mohammed, Issam Ahmed; Adnan, Rohana


    A structural study of epoxidized natural rubber (ENR-50) and its cyclic dithiocarbonate derivative was carried out using NMR spectroscopy techniques. The overlapping (1)H-NMR signals of ENR-50 at δ 1.56, 1.68-1.70, 2.06, 2.15-2.17 ppm were successfully assigned. In this work, the C=S and quaternary carbon of cyclic dithiocarbonate. All other (1)H- and (13)C-NMR chemical shifts of the derivative remain unchanged with respect to the ENR-50.

  12. In vivo NMR spectroscopy of the liver. Spectroscopie RMN du foie in vivo

    Energy Technology Data Exchange (ETDEWEB)

    Jehenson, P.; Cuenod, C.A.; Syrota, A. (CEA, 91 - Orsay (FR). Service Hospitalier Frederic Joliot)


    The application of in vivo MR spectroscopy to the study of the liver is currently an expanding field of research. Owing to technical difficulties, the results obtained thus far were mainly those of animal observations. Several nuclei have been considered: hydrogen, phosphorus, carbon or fluorine. This non-traumatic method allows following and quantifying the various metabolic pathways, especially during hepatic diseases. The major metabolic pathways, i.e. neoglycogenesis, glycogenolysis, Krebs' cycle, etc., are studied, as well as their alterations during diseases such as ischemia, diabetes or alcoholism. The development of this promising technique requires the cooperation of various clinical and fundamental disciplines.

  13. Unilateral NMR, 13C CPMAS NMR spectroscopy and micro-analytical techniques for studying the materials and state of conservation of an ancient Egyptian wooden sarcophagus. (United States)

    Proietti, Noemi; Presciutti, Federica; Di Tullio, Valeria; Doherty, Brenda; Marinelli, Anna Maria; Provinciali, Barbara; Macchioni, Nicola; Capitani, Donatella; Miliani, Costanza


    A multi-technique approach was employed to study a decorated Egyptian wooden sarcophagus (XXV-XXVI dynasty, Third Intermediate Period), belonging to the Museo del Vicino Oriente of the Sapienza University of Rome. Portable non-invasive unilateral NMR was applied to evaluate the conservation state of the sarcophagus. Moreover, using unilateral NMR, a non-invasive analytical protocol was established to detect the presence of organic substances on the surface and/or embedded in the wooden matrix. This protocol allowed for an educated sampling campaign aimed at further investigating the state of degradation of the wood and the presence of organic substances by (13)C cross polarization magic angle spinning (CPMAS) NMR spectroscopy. The composition of the painted layer was analysed by optical microscopy (OM), scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS), Raman and surface enhanced (resonance) Raman spectroscopy (SERS/SERRS), infrared and GC-MS techniques, evidencing original components such as clay minerals, Egyptian green, indigo, natural gums, and also highlighting restoration pigments and alteration compounds. The identification of the wood, of great value for the reconstruction of the history of the artwork, was achieved by means of optical microscopy.

  14. Study by ³¹P NMR spectroscopy of the triacylglycerol degradation processes in olive oil with different heat-transfer mechanisms. (United States)

    Lucas-Torres, Covadonga; Pérez, Angel; Cabañas, Beatriz; Moreno, Andrés


    The thermal degradation of olive oil using conventional and microwave heating under the same experimental conditions were compared. A powerful identification and quantification technique based on (31)P NMR has been developed to characterise the differences between the minor components including diacylglycerol and free fatty acids in the heated samples. The (31)P NMR spectra of the degraded olive oils, which contain OH groups derivatised with a phosphorus reagent, showed that conventional heating is more detrimental to the oil than microwave technique. Conventional heating leads to a significant increase in the diacylglycerol and free fatty acid contents as well as in the number of degradation compounds, which damage the olive oil quality. However, the main process that takes place on using microwave heating is isomerisation between diacylglycerols, a change that could give a potential longer shelf life to the olive oil.

  15. Rapid determination of coenzyme Q10 in food supplements using 1H NMR spectroscopy. (United States)

    Monakhova, Yulia B; Ruge, Ingrid; Kuballa, Thomas; Lerch, Christiane; Lachenmeier, Dirk W


    A methodology utilizing 1H NMR spectroscopy has been developed to measure the concentration of coenzyme Q10 (CoQ10) in dietary supplements. For sample preparation, a very simple dilution with deuterated chloroform and addition of internal standard is sufficient. CoQ10 produces a distinct peak of the CH groups in the isoprene side chain of the molecule in the δ 5.15 - 5.05 ppm range, where it can be distinguished from other matrix compounds. The method was shown to be of adequate sensitivity with a limit of detection (LOD) of 7.8 mg/L, to control the CoQ10 content in the majority of the products. The precision expressed as relative standard deviation was around 5 %; linearity was observed from 14 to 2000 mg/L (R = 0.99). The developed methodology was applied for the analysis of 21 food supplements (capsules, tablets, and liquid products). On the basis of the labeled amounts, only two products contained substantially lower concentrations of CoQ10 (57 % and 51 %). All other concentrations varied between 83 % and 190 % with respect to labeling. The developed NMR method may be used by quality assurance laboratories for routine control of CoQ10 products.

  16. XRD, TEM, IR, Raman and NMR Spectroscopy of In Situ Crystallization of Lithium Disilicate Glass (United States)

    Fuss, T.; Mogus-Milankovic, A.; Ray, C. S.; Lesher, C. E.; Youngman, R.; Day, D. E.


    The structure of a Li2O-2SiO2 (LS2) glass was investigated as a function of pressure and temperature up to 6 GPa and 750 C respectively, using XRD, TEM, IR, Raman and NMR spectroscopy. Glass densified at 6 GPa has an average Si-O-Si bond angle approx.7deg lower than that found in glass processed at 4.5 GPa. At 4.5 GPa, lithium disilicate crystallizes from the glass, while at 6 GPa a new high pressure form of lithium metasilicate crystallizes. The new phase, while having lithium metasilicate crystal symmetry, contains at least 4 different Si sites. NMR results for 6 GPa sample indicate the presence of Q4 species with (Q(sup 4))Si-O-Si(Q(sup 4)) bond angles of approx.157deg. This is the first reported occurrence of Q(sup 4) species with such large bond angles in alumina free alkali silicate glass. No five- or six- coordinated Si are found.

  17. Microstructure determination of 2-hydroxy ethyl methacrylate and methyl acrylate copolymers by NMR spectroscopy (United States)

    Brar, A. S.; Hooda, Sunita; Goyal, Ashok Kumar


    Copolymers of 2-Hydroxy ethyl methacrylate and methyl acrylate (H/M) of different compositions were synthesized by free radical bulk polymerization using azobisisobutyronitrile (AIBN) as an initiator under nitrogen atmosphere. The copolymers compositions were calculated from 1H NMR spectra. The reactivity ratios for H/M copolymers obtained from a linear Kelen-Tudos method (KT) and nonlinear error-in-variables method (EVM) are rH = 3.31 ± 0.08, rM = 0.23 ± 0.00 and rH = 3.32, rM = 0.23, respectively. The complete spectral assignment of methine, methylene, methyl and carbonyl carbon regions in terms of compositional and configurational sequences of H/M copolymers was done with the help of 13C{ 1H} NMR, distortionless enhancement by polarization transfer (DEPT), two-dimensional heteronuclear single quantum coherence (HSQC) along with total correlated spectroscopy (TOCSY). Further, the assignments of carbonyl region were made with the help of heteronuclear multiple bond coherence (HMBC) spectrum.

  18. Authentication of beef versus horse meat using 60 MHz 1H NMR spectroscopy. (United States)

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


    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.

  19. Low-field (1)H NMR spectroscopy for distinguishing between arabica and robusta ground roast coffees. (United States)

    Defernez, Marianne; Wren, Ella; Watson, Andrew D; Gunning, Yvonne; Colquhoun, Ian J; Le Gall, Gwénaëlle; Williamson, David; Kemsley, E Kate


    This work reports a new screening protocol for addressing issues of coffee authenticity using low-field (60MHz) bench-top (1)H NMR spectroscopy. Using a simple chloroform-based extraction, useful spectra were obtained from the lipophilic fraction of ground roast coffees. It was found that 16-O-methylcafestol (16-OMC, a recognized marker compound for robusta beans) gives rise to an isolated peak in the 60MHz spectrum, which can be used as an indicator of the presence of robusta beans in the sample. A total of 81 extracts from authenticated coffees and mixtures were analysed, from which the detection limit of robusta in arabica was estimated to be between 10% and 20% w/w. Using the established protocol, a surveillance exercise was conducted of 27 retail samples of ground roast coffees which were labelled as "100% arabica". None were found to contain undeclared robusta content above the estimated detection limit.

  20. Quantitative analysis of sesquiterpene lactones in extract of Arnica montana L. by 1H NMR spectroscopy. (United States)

    Staneva, Jordanka; Denkova, Pavletta; Todorova, Milka; Evstatieva, Ljuba


    (1)H NMR spectroscopy was used as a method for quantitative analysis of sesquiterpene lactones present in a crude lactone fraction isolated from Arnica montana. Eight main components - tigloyl-, methacryloyl-, isobutyryl- and 2-methylbutyryl-esters of helenalin (H) and 11α,13-dihydrohelenalin (DH) were identified in the studied sample. The method allows the determination of the total amount of sesquiterpene lactones and the quantity of both type helenalin and 11α,13-dihydrohelenalin esters separately. Furthermore, 6-O-tigloylhelenalin (HT, 1), 6-O-methacryloylhelenalin (HM, 2), 6-O-tigloyl-11α,13-dihydrohelenalin (DHT, 5), and 6-O-methacryloyl-11α,13-dihydrohelenalin (DHM, 6) were quantified as individual components.

  1. Carbon-deuterium rotational-echo double-resonance NMR spectroscopy of lyophilized aspartame formulations. (United States)

    Luthra, Suman A; Utz, Marcel; Gorman, Eric M; Pikal, Michael J; Munson, Eric J; Lubach, Joseph W


    In this study, changes in the local conformation of aspartame were observed in annealed lyophilized glasses by monitoring changes in the distance between two labeled sites using C-(2)H rotational-echo double-resonance (REDOR) nuclear magnetic resonance (NMR) spectroscopy. Confirmation that the REDOR experiments were producing accurate distance measurement was ensured by measuring the (13)C-(15)N distance in glycine. The experiment was further verified by measuring the REDOR dephasing curve on (13)C-(2)H methionine. (13)C-(2)H REDOR dephasing curves were then measured on lyophilized aspartame-disaccharide formulations. In aspartame-sucrose formulation, the internuclear distances increased upon annealing, which correlated with decreased chemical reactivity. By contrast, annealing had only a minimal effect on the dephasing curve in aspartame-trehalose formulation. The results show that stability is a function of both mobility and local structure (conformation), even in a small molecule system such as lyophilized aspartame-sucrose.

  2. Bacterial expression and isotope labeling of AIMP1/p43 codosome protein for structural studies by multidimensional NMR spectroscopy

    Directory of Open Access Journals (Sweden)

    Vorobyova N. V.


    Full Text Available AIMP1/p43 protein is a structural component of multisynthetase complex (codosome in eukaryotes, which reveals both tRNA binding and cytokine activities. Aim. Bacterial expression and purification of isotopically-labeled recombinant AIMP1/p43 protein in E. coli cells for studying its solution structure by multidimensional NMR spectroscopy. Methods. AIMP1/p43 protein was expressed in E. coli BL21(DE3pLysE cells on M9 minimal medium with 15N isotope labeling and purified by metal-chelated chromatography. Heteronuclear 2D 1H-15N NMR experiments were performed in solution at 293 K on Agilent DDR2 800 NMR spectrometer. Results. The AIMP1/p43 protein was obtained in uniformly 15N-labeled form as an NMR sample. A high dispersion of resonance signals in the 2D 1H-15N HSQC NMR spectra confirmed the presence of its compact 3D protein structure. The NMR spectrum of AIMP1/p43 demonstrated a high signal-to-noise ratio and sufficient stability to acquire other multidimensional NMR data sets for determination of the structure of AIMP1/p43 protein in solution. Conclusions. The 15N-labeled AIMP1/p43 protein was stable for 4–7 days, which makes possible acquiring the critical NMR experimental data for detailed structural analysis in solution. Our data on the initial NMR spectra indicated the presence of some additional signals in comparison with the NMR spectrum of EMAP II which could be assigned to amino acids of the N-terminal α-helical fragment of AIMP1/p43.

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

    KAUST Repository

    Abdul Jameel, Abdul Gani


    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.

  4. Investigation of multiaxial molecular dynamics by 2H MAS NMR spectroscopy. (United States)

    Kristensen, J H; Hoatson, G L; Vold, R L


    The technique of 2H MAS NMR spectroscopy is presented for the investigation of multiaxial molecular dynamics. To evaluate the effects of discrete random reorientation a Lie algebraic formalism based on the stochastic Liouville-von Neumann equation is developed. The solution to the stochastic Liouville-von Neumann equation is obtained both in the presence and absence of rf irradiation. This allows effects of molecular dynamics to be evaluated during rf pulses and extends the applicability of the formalism to arbitrary multiple pulse experiments. Theoretical methods are presented for the description of multiaxial dynamics with particular emphasis on the application of vector parameters to represent molecular rotations. Numerical time and powder integration algorithms are presented that are both efficient and easy to implement computationally. The applicability of 2H MAS NMR spectroscopy for investigating molecular dynamics is evaluated from theoretical spectra. To demonstrate the potential of the technique the dynamics of thiourea-2H4 is investigated experimentally. From a series of variable temperature MAS and quadrupole echo spectra it has been found that the dynamics can be described by composite rotation about the CS and CN bonds. Both experiments are sensitive to the fast CS rotation which is shown to be described by the Arrhenius parameters E(CS) = 46.4 +/- 2.3 kJ mol(-1) and ln(A(CS))= 32.6 +/- 0.9. The MAS experiment represents a significant improvement by simultaneously allowing the dynamics of the slow CN rotation to be fully characterized in terms of E(CN) = 56.3 +/- 3.4 kJ mol(-1) and ln(A(CN)) = 25.3 +/- 1.1.

  5. Synthesis and Resolution of the Atropisomeric 1,1'-Bi-2-Naphthol: An Experiment in Organic Synthesis and 2-D NMR Spectroscopy (United States)

    Mak, Kendrew K. W.


    NMR spectroscopy is presented. It is seen that the experiment regarding the synthesis and resolution of 1,1'-Bi-2-naphtol presents a good experiment for teaching organic synthesis and NMR spectroscopy and provides a strategy for obtaining enantiopure compounds from achiral starting materials.

  6. Evaluation of mitochondrial function of skeletal muscle in type 2 diabetic patients offspring using dynamic 31p magnetic resonance spectroscopy%磁共振动态磷谱技术评估2型糖尿病患者子女的骨骼肌线粒体功能

    Institute of Scientific and Technical Information of China (English)

    涂慧娟; 吴飞云; 秦斌; 陈婷; 齐静


    目的:评价磁共振动态磷谱技术对评估2型糖尿病患者子女骨骼肌能量代谢和线粒体功能的价值.方法:对21名2型糖尿病患者子女和18名健康志愿者的股四头肌进行磁共振动态磷谱检查,获取静息、运动、恢复3个状态的波谱数据.对无机磷(Pi)、磷酸肌酸(PCr)、三磷酸腺苷(ATP)等化合物的峰下面积进行定量分析,通过生化反应平衡公式计算二磷酸腺苷(ADP)和细胞内pH值,并利用指数曲线拟合分析Pi、PCr和ADP的时间常数和恢复速率.结果:糖尿病患者子女组及正常对照组静息期Pi、PCr、ADP、β-ATP的含量及Pi/PCr无统计学差异.运动末期糖尿病患者子女组β-ATP低于正常对照组.恢复期糖尿病患者子女组多帧波谱PCr、β-ATP、pH均低于正常对照组,第3帧Pi/PCr比值比对照组高.恢复期糖尿病患者子女组PCr恢复速率明显低于正常对照组PCr恢复速率.结论:磁共振动态磷谱技术可以无创性检测2型糖尿病患者子女的能量代谢受损及线粒体功能状态.%Objective: To evaluate the energy metabolism and mitochondrial function of skeletal muscle in type 2 diabetic patients offspring using dynamic 31P magnetic resonance spectroscopy(31P-MRS). Methods; Dynamic 31P-MRS was performed on 21 type 2 diabetes patients offsprings and 18 healthy volunteers. Spectra were acquired from quadriceps muscle while subjects were at rest,exercise and recovery. The peak area of inorganic phosphate (Pi),phosphocreatine (PCr) and adenosine triphosphate (ATP) were measured. The concentration of adenosine diphosphate (ADP) and intracellular pH value were calculated from the biochemistry reaction equilibrium. The time constant and recovery rate of PCr,Pi and ADP were analyzed using exponential curve fit. Results; There were no significance differences of Pi,PCr,ADP,β-ATP and the ratio of Pi/PCr between the type 2 diabetes patients offsprings and the healthy volunteers at rest. The type 2

  7. TG/DTG, FT-ICR Mass Spectrometry, and NMR Spectroscopy Study of Heavy Fuel Oil

    KAUST Repository

    Elbaz, Ayman M.


    There is an increasing interest in the comprehensive study of heavy fuel oil (HFO) due to its growing use in furnaces, boilers, marines, and recently in gas turbines. In this work, the thermal combustion characteristics and chemical composition of HFO were investigated using a range of techniques. Thermogravimetric analysis (TGA) was conducted to study the nonisothermal HFO combustion behavior. Chemical characterization of HFO was accomplished using various standard methods in addition to direct infusion atmospheric pressure chemical ionization Fourier transform ion cyclotron resonance mass spectrometry (APCI-FTICR MS), high resolution 1H nuclear magnetic resonance (NMR), 13C NMR, and two-dimensional heteronuclear multiple bond correlation (HMBC) spectroscopy. By analyzing thermogravimetry and differential thermogravimetry (TG/DTG) results, three different reaction regions were identified in the combustion of HFO with air, specifically, low temperature oxidation region (LTO), fuel deposition (FD), and high temperature oxidation (HTO) region. At the high end of the LTO region, a mass transfer resistance (skin effect) was evident. Kinetic analysis in LTO and HTO regions was conducted using two different kinetic models to calculate the apparent activation energy. In both models, HTO activation energies are higher than those for LTO. The FT-ICR MS technique resolved thousands of aromatic and sulfur containing compounds in the HFO sample and provided compositional details for individual molecules of three major class species. The major classes of compounds included species with one sulfur atom (S1), with two sulfur atoms (S2), and purely hydrocarbons (HC). The DBE (double bond equivalent) abundance plots established for S1 and HC provided additional information on their distributions in the HFO sample. The 1H NMR and 13C NMR results revealed that nearly 59% of the 1H nuclei were distributed as paraffinic CH2 and 5% were in aromatic groups. Nearly 21% of 13C nuclei were

  8. LEGO-NMR spectroscopy: a method to visualize individual subunits in large heteromeric complexes. (United States)

    Mund, Markus; Overbeck, Jan H; Ullmann, Janina; Sprangers, Remco


    Seeing the big picture: Asymmetric macromolecular complexes that are NMR active in only a subset of their subunits can be prepared, thus decreasing NMR spectral complexity. For the hetero heptameric LSm1-7 and LSm2-8 rings NMR spectra of the individual subunits of the complete complex are obtained, showing a conserved RNA binding site. This LEGO-NMR technique makes large asymmetric complexes accessible to detailed NMR spectroscopic studies.

  9. High-resolution 1H-NMR spectroscopy of free and glycosidically linked O-acetylated sialic acids

    NARCIS (Netherlands)

    Vliegenthart, J.F.G.; Haverkamp, J.; Halbeek, H. van; Dorland, L.; Pfeil, R.; Schauer, R.


    A number of naturally occurring and synthetic, partially O-acetylated derivatives of N-acetylneuraminic and N-glycoloylneuraminic acids have been investigated by 360-MHz 1H-NMR spectroscopy. O-Acetylation causes strong downfield shifts for the resonances of neighbouring sugar-skeleton protons. The c

  10. Response to the Letter to the Editor regarding "Determination of the fatty acid profile by 1H-NMR spectroscopy." (United States)

    In expansion of previous work (G. Knothe, J.A. Kenar, Determination of the fatty acid profile by 1H-NMR spectroscopy, Eur. J. Lipid Sci. Technol. 2004, 106, 88-96), an additional approach is discussed for quantitating saturated fatty acids in the fatty acid profiles of common vegetable oils by 1H-NM...

  11. Multinuclear nanoliter one-dimensional and two-dimensional NMR spectroscopy with a single non-resonant microcoil

    NARCIS (Netherlands)

    Fratila, R.M.; Gomez, M.V.; Sykora, S.; Velders, A.H.


    Nuclear magnetic resonance (NMR) spectroscopy is a powerful analytical technique, but its low sensitivity and highly sophisticated, costly, equipment severely constrain more widespread applications. Here we show that a non-resonant planar transceiver microcoil integrated in a microfluidic chip (dete

  12. NMR and IR Spectroscopy for the Structural Characterization of Edible Fats and Oils: An Instrumental Analysis Laboratory (United States)

    Crowther, Molly W.


    This article describes an upper-level instrumental laboratory for undergraduates that explores the complementary nature of IR and NMR spectroscopy for analysis of several edible fats and oils that are structurally similar but differ in physical properties and health implications. Five different fats and oils are analyzed for average chain length,…

  13. A multi-metabolite analysis of serum by H-1 NMR spectroscopy: Early systemic signs of Alzheimer's disease

    NARCIS (Netherlands)

    Tukiainen, T.; Tynkkynen, T.; Mäkinen, V.P.; Jylänki, P.P.; Kangas, A.J.; Hokkanen, J.; Vehtari, A.; Grohn, O.; Hallikainen, M.; Soininen, H.; Kivipelto, M.; Groop, P.H.; Kaski, K.; Laatikainen, R.; Soininen, P.; Pirttilä, T.; Ala-Korpela, M.


    A three-molecular-window approach for H-1 NMR spectroscopy of serum is presented to obtain specific molecular data on lipoproteins, Various low-molecular-weight metabolites, and individual lipid molecules together with their degree of (poly)(un)saturation. The multiple data were analysed with self-o

  14. Functional dynamics of human FKBP12 revealed by methyl C-13 rotating frame relaxation dispersion NMR spectroscopy

    NARCIS (Netherlands)

    Brath, U; Akke, M; Yang, DW; Kay, LE; Mulder, FAA


    Transverse relaxation dispersion NMR spectroscopy can provide atom-specific information about time scales, populations, and the extent of structural reorganization in proteins under equilibrium conditions. A method is described that uses side-chain methyl groups as local reporters for conformational

  15. 31P-MRS of skeletal muscle is not a sensitive diagnostic test for mitochondrial myopathy

    DEFF Research Database (Denmark)

    Jeppesen, Tina Dysgaard; Quistorff, Bjørn; Wibrand, Flemming


    Clinical phenotypes of persons with mitochondrial DNA (mtDNA) mutations vary considerably. Therefore, diagnosing mitochondrial myopathy (MM) patients can be challenging and warrants diagnostic guidelines. (31)phosphorous magnetic resonance spectroscopy ((31)P-MRS) have been included as a minor...... investigated for the following: 1) (31)P-MRS of lower arm and leg muscles before and after exercise, 2) resting and peak-exercise induced increases of plasma lactate, 3) muscle morphology and -mitochondrial enzyme activity, 4) maximal oxygen uptake (VO(2max)), 5) venous oxygen desaturation during handgrip...... impaired citrate synthase-corrected complex I activity. Resting PCr/P(i) ratio and leg P(i) recovery were lower in MM patients vs. healthy subjects. PCr and ATP production after exercise were similar in patients and healthy subjects. Although the specificity for MM of some (31)P-MRS variables was as high...

  16. Probing site-specific 13C/15N-isotope enrichment of spider silk with liquid-state NMR spectroscopy. (United States)

    Shi, Xiangyan; Yarger, Jeffery L; Holland, Gregory P


    Solid-state nuclear magnetic resonance (NMR) has been extensively used to elucidate spider silk protein structure and dynamics. In many of these studies, site-specific isotope enrichment is critical for designing particular NMR methods for silk structure determination. The commonly used isotope analysis techniques, isotope-ratio mass spectroscopy and liquid/gas chromatography-mass spectroscopy, are typically not capable of providing the site-specific isotope information for many systems because an appropriate sample derivatization method is not available. In contrast, NMR does not require any sample derivatization or separation prior to analysis. In this article, conventional liquid-state (1)H NMR was implemented to evaluate incorporation of (13)C/(15)N-labeled amino acids in hydrolyzed spider dragline silk. To determine site-specific (13)C and (15)N isotope enrichments, an analysis method was developed to fit the (1)H-(13)C and (1)H-(15)N J-splitting (J CH and J NH) (1)H NMR peak patterns of hydrolyzed silk fiber. This is demonstrated for Nephila clavipes spiders, where [U-(13)C3,(15)N]-Ala and [1-(13)C,(15)N]-Gly were dissolved in their water supplies. Overall, contents for Ala and Gly isotopomers are extracted for these silk samples. The current methodology can be applied to many fields where site-specific tracking of isotopes is of interest.

  17. A strategy for co-translational folding studies of ribosome-bound nascent chain complexes using NMR spectroscopy. (United States)

    Cassaignau, Anaïs M E; Launay, Hélène M M; Karyadi, Maria-Evangelia; Wang, Xiaolin; Waudby, Christopher A; Deckert, Annika; Robertson, Amy L; Christodoulou, John; Cabrita, Lisa D


    During biosynthesis on the ribosome, an elongating nascent polypeptide chain can begin to fold, in a process that is central to all living systems. Detailed structural studies of co-translational protein folding are now beginning to emerge; such studies were previously limited, at least in part, by the inherently dynamic nature of emerging nascent chains, which precluded most structural techniques. NMR spectroscopy is able to provide atomic-resolution information for ribosome-nascent chain complexes (RNCs), but it requires large quantities (≥10 mg) of homogeneous, isotopically labeled RNCs. Further challenges include limited sample working concentration and stability of the RNC sample (which contribute to weak NMR signals) and resonance broadening caused by attachment to the large (2.4-MDa) ribosomal complex. Here, we present a strategy to generate isotopically labeled RNCs in Escherichia coli that are suitable for NMR studies. Uniform translational arrest of the nascent chains is achieved using a stalling motif, and isotopically labeled RNCs are produced at high yield using high-cell-density E. coli growth conditions. Homogeneous RNCs are isolated by combining metal affinity chromatography (to isolate ribosome-bound species) with sucrose density centrifugation (to recover intact 70S monosomes). Sensitivity-optimized NMR spectroscopy is then applied to the RNCs, combined with a suite of parallel NMR and biochemical analyses to cross-validate their integrity, including RNC-optimized NMR diffusion measurements to report on ribosome attachment in situ. Comparative NMR studies of RNCs with the analogous isolated proteins permit a high-resolution description of the structure and dynamics of a nascent chain during its progressive biosynthesis on the ribosome.

  18. An in vitro model for the in vivo mobilization of cadmium by chelating agents using 113Cd-NMR spectroscopy. (United States)

    Beaty, J A; Jones, M M; Wilson, D J; Ma, L


    An in vitro method, based on 113Cd-NMR spectroscopy, that provides an alternative to the use of animals for an initial screening of cadmium antagonists is presented. The relative values of the effective stability constants of potential chelating antagonists for cadmium are estimated by using 113Cd-NMR spectroscopy to determine the concentrations of the cadmium species involved in appropriate competitive equilibria. This is accomplished via an examination of the competition between the proposed antagonist and EDTA (ethylenediaminetetraacetic acid) for cadmium-113; previously, EDTA has been shown to be capable of removing cadmium from such in vivo binding sites as metallothionein. The reactions proceed via the stepwise addition of three dithiocarbamate groups to the cadmium accompanied by the concurrent stepwise release of donor groups from the EDTA. The resulting 113Cd-NMR data allow for the determination of the overall stability constant for the complex formed between cadmium and N-methyl-D-glucamine dithiocarbamate, iminodiacetic acid dithiocarbamate, proline dithiocarbamate, sarcosine dithiocarbamate. The use of 113Cd-NMR spectroscopy has the potential for providing direct evidence on the effectiveness of chelate antagonists to compete with endogenous ligands for other toxic metal ions. This technique could prove very useful for other compounds that are not stable enough toward acid and/or base to be examined by standard titrimetric methods.

  19. "Pulse pair technique in high resolution NMR" a reprint of the historical 1971 lecture notes on two-dimensional spectroscopy. (United States)

    Jeener, Jean; Alewaeters, Gerrit


    The review articles published in "Progress in NMR Spectroscopy" are usually invited treatments of topics of current interest, but occasionally the Editorial Board may take an initiative to publish important historical material that is not widely available. The present article represents just such a case. Jean Jeener gave a lecture in 1971 at a summer school in Basko Polje, in what was then called Yugoslavia. As is now widely known, Jean Jeener laid down the foundations in that lecture of two - and higher - dimensional NMR spectroscopy by proposing the homonuclear COSY experiment. Jeener realized that the new proposal would open the door towards protein NMR and molecular structure determinations, but he felt that useful versions of such experiments could not be achieved with the NMR, computer and electronics technology available at that time, so that copies of the lecture notes were circulated (the Basko Polje lecture notes by J. Jeener and G. Alewaeters), but no formal publication followed. Fortunately, Ernst, Freeman, Griffin, and many others were more far-sighted and optimistic. An early useful extension was Ernst's proposal to replace the original projection/reconstruction technique of MRI by the widely adopted Fourier transform method inspired by the Basko Polje lecture. Later, the pulse method spread over many fields of spectroscopy as soon as the required technology became available. Jean Jeener, Emeritus professor, Université Libre de Bruxelles. Geoffrey Bodenhausen, Ecole Normale Supérieure, Paris.

  20. Transport Properties of Ibuprofen Encapsulated in Cyclodextrin Nanosponge Hydrogels: A Proton HR-MAS NMR Spectroscopy Study. (United States)

    Ferro, Monica; Castiglione, Franca; Punta, Carlo; Melone, Lucio; Panzeri, Walter; Rossi, Barbara; Trotta, Francesco; Mele, Andrea


    The chemical cross-linking of β-cyclodextrin (β-CD) with ethylenediaminetetraacetic dianhydride (EDTA) led to branched polymers referred to as cyclodextrin nanosponges (CDNSEDTA). Two different preparations are described with 1:4 and 1:8 CD-EDTA molar ratios. The corresponding cross-linked polymers were contacted with 0.27 M aqueous solution of ibuprofen sodium salt (IP) leading to homogeneous, colorless, drug loaded hydrogels. The systems were characterized by high resolution magic angle spinning (HR-MAS) NMR spectroscopy. Pulsed field gradient spin echo (PGSE) NMR spectroscopy was used to determine the mean square displacement (MSD) of IP inside the polymeric gel at different observation times td. The data were further processed in order to study the time dependence of MSD: MSD = f(td). The proposed methodology is useful to characterize the different diffusion regimes that, in principle, the solute may experience inside the hydrogel, namely normal or anomalous diffusion. The full protocols including the polymer preparation and purification, the obtainment of drug-loaded hydrogels, the NMR sample preparation, the measurement of MSD by HR-MAS NMR spectroscopy and the final data processing to achieve the time dependence of MSD are here reported and discussed. The presented experiments represent a paradigmatic case and the data are discussed in terms of innovative approach to the characterization of the transport properties of an encapsulated guest within a polymeric host of potential application for drug delivery.

  1. Binding of phenol and differently halogenated phenols to dissolved humic matter as measured by NMR spectroscopy. (United States)

    Smejkalová, Daniela; Spaccini, Riccardo; Fontaine, Barbara; Piccolo, Alessandro


    1H- and 19F-NMR measurements of spin-lattice (T1) and spin-spin (T2) relaxationtimes and diffusion ordered spectroscopy (DOSY) were applied to investigate the association of nonsubstituted (phenol (P)) and halogen-substituted (2,4-dichlorophenol (DCP); 2,4,6-trichlorophenol (TCP), and 2,4,6-trifluorophenol (TFP) phenols with a dissolved humic acid (HA). T1 and T2 values for both 1H and 19F in phenols decreased with enhancing HA concentration, indicating reduction in molecular mobility due to formation of noncovalent interactions. Moreover, correlation times (tau c) for different hydrogen and fluorine atoms in phenols showed that anisotropic mobility turned into isotropic motion with HA additions. Changes in relaxation times suggested that DCP and TCP were more extensively bound to HA than P and TFP. This was confirmed by diffusion measurements which showed full association of DCP and TCP to a less amount of HA than that required for entire complexation of P and TFP. Calculated values of binding constants (Ka) reflected the overall NMR behavior, being significantly larger for DCP- and TCP-HA (10.04 +/- 1.32 and 4.47 +/- 0.35 M(-1), respectively) than for P- and TFP-HA complexes (0.57 +/- 0.03 and 0.28 +/- 0.01 M(-1), respectively). Binding increased with decreasing solution pH, thus indicating a dependence on the fraction of protonated form (alpha) of phenols in solution. However, it was found that the hydrophobicity conferred to phenols by chlorine atoms on aromatic rings is a stronger drive than alpha for the phenols repartition within the HA hydrophobic domains.

  2. Identification of the Glycosaminoglycan Binding Site of Interleukin-10 by NMR Spectroscopy. (United States)

    Künze, Georg; Köhling, Sebastian; Vogel, Alexander; Rademann, Jörg; Huster, Daniel


    The biological function of interleukin-10 (IL-10), a pleiotropic cytokine with an essential role in inflammatory processes, is known to be affected by glycosaminoglycans (GAGs). GAGs are highly negatively charged polysaccharides and integral components of the extracellular matrix with important functions in the biology of many growth factors and cytokines. The molecular mechanism of the IL-10/GAG interaction is unclear. In particular, experimental evidence about IL-10/GAG binding sites is lacking, despite its importance for understanding the biological role of the interaction. Here, we report the experimental determination of a GAG binding site of IL-10. Although no co-crystal structure of the IL-10·GAG complex could be obtained, its structural characterization was possible by NMR spectroscopy. Chemical shift perturbations of IL-10 induced by GAG binding were used to narrow down the location of the binding site and to assess the affinity for different GAG molecules. Subsequent observation of NMR pseudocontact shifts of IL-10 and its heparin ligand, as induced by a protein-attached lanthanide spin label, provided structural restraints for the protein·ligand complex. Using these restraints, pseudocontact shift-based rigid body docking together with molecular dynamics simulations yielded a GAG binding model. The heparin binding site is located at the C-terminal end of helix D and the adjacent DE loop and coincides with a patch of positively charged residues involving arginines 102, 104, 106, and 107 and lysines 117 and 119. This study represents the first experimental characterization of the IL-10·GAG complex structure and provides the starting point for revealing the biological significance of the interaction of IL-10 with GAGs.

  3. Two-dimensional NMR spectroscopy strongly enhances soil organic matter composition analysis (United States)

    Soucemarianadin, Laure; Erhagen, Björn; Öquist, Mats; Nilsson, Mats; Hedenström, Mattias; Schleucher, Jürgen


    Soil organic matter (SOM) is the largest terrestrial carbon pool and strongly affects soil properties. With climate change, understanding SOM processes and turnover and how they could be affected by increasing temperatures becomes critical. This is particularly key for organic soils as they represent a huge carbon pool in very sensitive ecosystems, like boreal ecosystems and peatlands. Nevertheless, characterization of SOM molecular composition, which is essential to elucidate soil carbon processes, is not easily achieved, and further advancements in that area are greatly needed. Solid-state one-dimensional (1D) 13C nuclear magnetic resonance (NMR) spectroscopy is often used to characterize its molecular composition, but only provides data on a few major functional groups, which regroup many different molecular fragments. For instance, 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. Here we show that two-dimensional (2D) liquid-state 1H-13C NMR spectra provided much richer data on the composition of boreal plant litter and organic surface soil. The 2D spectra indeed resolved overlaps observed in 1D 13C spectra and displayed signals from hundreds of identifiable molecular groups. For example, in the aromatics region, signals from individual lignin units could be recognized. It was hence possible to follow the fate of specific structural moieties in soils. We observed differences between litter and soil samples, and were able to relate them to the decomposition of identifiable moieties. Sample preparation and data acquisition were both simple and fast. Further, using multivariate data analysis, we aimed at linking the detailed chemical fingerprints of SOM to turnover rates in a soil incubation experiment. With the multivariate models, we were able to identify specific molecular

  4. Indirectly detected chemical shift correlation NMR spectroscopy in solids under fast magic angle spinning

    Energy Technology Data Exchange (ETDEWEB)

    Mao, Kanmi [Iowa State Univ., Ames, IA (United States)


    The development of fast magic angle spinning (MAS) opened up an opportunity for the indirect detection of insensitive low-γ nuclei (e.g., 13C and 15N) via the sensitive high-{gamma} nuclei (e.g., 1H and 19F) in solid-state NMR, with advanced sensitivity and resolution. In this thesis, new methodology utilizing fast MAS is presented, including through-bond indirectly detected heteronuclear correlation (HETCOR) spectroscopy, which is assisted by multiple RF pulse sequences for 1H-1H homonuclear decoupling. Also presented is a simple new strategy for optimization of 1H-1H homonuclear decoupling. As applications, various classes of materials, such as catalytic nanoscale materials, biomolecules, and organic complexes, are studied by combining indirect detection and other one-dimensional (1D) and two-dimensional (2D) NMR techniques. Indirectly detected through-bond HETCOR spectroscopy utilizing refocused INEPT (INEPTR) mixing was developed under fast MAS (Chapter 2). The time performance of this approach in 1H detected 2D 1H{l_brace}13C{r_brace} spectra was significantly improved, by a factor of almost 10, compared to the traditional 13C detected experiments, as demonstrated by measuring naturally abundant organic-inorganic mesoporous hybrid materials. The through-bond scheme was demonstrated as a new analytical tool, which provides complementary structural information in solid-state systems in addition to through-space correlation. To further benefit the sensitivity of the INEPT transfer in rigid solids, the combined rotation and multiple-pulse spectroscopy (CRAMPS) was implemented for homonuclear 1H decoupling under fast MAS (Chapter 3). Several decoupling schemes (PMLG5m$\\bar{x}$, PMLG5mm$\\bar{x}$x and SAM3) were analyzed to maximize the performance of through-bond transfer based

  5. Styrylpyrylium Salts: 1H and 13C NMR High-Resolution Spectroscopy (1D and 2D

    Directory of Open Access Journals (Sweden)

    Jean Claude W. Ouédraogo


    Full Text Available 1H and 13C NMR high-resolution spectroscopy (1D and 2D (1H, 1H-COSY, HSQC, HMBC for four styrylpyrylium perchlorates were carried out and signal attributions are reported. Chemical shifts observed on 13C NMR spectra for the styrylpyrylium salts were compared with net atomic charge for carbon obtained by AM1 semiempirical calculations. The position of the styryl group present low effect on chemical shifts for carbon atoms, while the presence of methyl group led to the unshielding of the substituted carbon.

  6. Enhanced detection of aldehydes in Extra-Virgin Olive Oil by means of band selective NMR spectroscopy (United States)

    Dugo, Giacomo; Rotondo, Archimede; Mallamace, Domenico; Cicero, Nicola; Salvo, Andrea; Rotondo, Enrico; Corsaro, Carmelo


    High resolution Nuclear Magnetic Resonance (NMR) spectroscopy is a very powerful tool for comprehensive food analyses and especially for Extra-Virgin Olive Oils (EVOOs). We use the NMR technique to study the spectral region of aldehydes (8-10 ppm) for EVOOs coming from the south part of Italy. We perform novel experiments by using mono and bidimensional band selective spin-echo pulse sequences and identify four structural classes of aldehydes in EVOOs. For the first time such species are identified in EVOOs without any chemical treatment; only dilution with CDCl3 is employed. This would allow the discrimination of different EVOOs for the aldehydes content increasing the potentiality of the NMR technique in the screening of metabolites for geographical characterization of EVOOs.

  7. Revealing the metabonomic variation of rosemary extracts using 1H NMR spectroscopy and multivariate data analysis. (United States)

    Xiao, Chaoni; Dai, Hui; Liu, Hongbing; Wang, Yulan; Tang, Huiru


    The molecular compositions of rosemary ( Rosmarinus officinalis L.) extracts and their dependence on extraction solvents, seasons, and drying processes were systematically characterized using NMR spectroscopy and multivariate data analysis. The results showed that the rosemary metabonome was dominated by 33 metabolites including sugars, amino acids, organic acids, polyphenolic acids, and diterpenes, among which quinate, cis-4-glucosyloxycinnamic acid, and 3,4,5-trimethoxyphenylmethanol were found in rosemary for the first time. Compared with water extracts, the 50% aqueous methanol extracts contained higher levels of sucrose, succinate, fumarate, malonate, shikimate, and phenolic acids, but lower levels of fructose, glucose, citrate, and quinate. Chloroform/methanol was an excellent solvent for selective extraction of diterpenes. From February to August, the levels of rosmarinate and quinate increased, whereas the sucrose level decreased. The sun-dried samples contained higher concentrations of rosmarinate, sucrose, and some amino acids but lower concentrations of glucose, fructose, malate, succinate, lactate, and quinate than freeze-dried ones. These findings will fill the gap in the understanding of rosemary composition and its variations.

  8. Differentiating brown and white adipose tissues by high-resolution diffusion NMR spectroscopy. (United States)

    Verma, Sanjay Kumar; Nagashima, Kaz; Yaligar, Jadegoud; Michael, Navin; Lee, Swee Shean; Xianfeng, Tian; Gopalan, Venkatesh; Sadananthan, Suresh Anand; Anantharaj, Rengaraj; Velan, S Sendhil


    There are two types of fat tissues, white adipose tissue (WAT) and brown adipose tissue (BAT), which essentially perform opposite functions in whole body energy metabolism. There is a large interest in identifying novel biophysical properties of WAT and BAT by a quantitative and easy-to-run technique. In this work, we used high-resolution pulsed field gradient diffusion NMR spectroscopy to study the apparent diffusion coefficient (ADC) of fat molecules in rat BAT and WAT samples. The ADC of fat in BAT and WAT from rats fed with a chow diet was compared with that of rats fed with a high-fat diet to monitor how the diffusion properties change due to obesity-associated parameters such as lipid droplet size, fatty acid chain length, and saturation. Feeding a high-fat diet resulted in increased saturation, increased chain lengths, and reduced ADC of fat in WAT. The ADC of fat was lower in BAT relative to WAT in rats fed both chow and high-fat diets. Diffusion of fat was restricted in BAT due to the presence of small multilocular lipid droplets. Our findings indicate that in vivo diffusion might be a potential way for better delineation of BAT and WAT in both lean and obese states.

  9. 1H NMR Spectroscopy and MVA Analysis of Diplodus sargus Eating the Exotic Pest Caulerpa cylindracea

    Directory of Open Access Journals (Sweden)

    Sandra A. De Pascali


    Full Text Available 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.

  10. 1H NMR Spectroscopy and MVA Analysis of Diplodus sargus Eating the Exotic Pest Caulerpa cylindracea (United States)

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


    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. PMID:26058009

  11. Fast proton exchange in histidine: measurement of rate constants through indirect detection by NMR spectroscopy. (United States)

    Sehgal, Akansha Ashvani; Duma, Luminita; Bodenhausen, Geoffrey; Pelupessy, Philippe


    Owing to its imidazole side chain, histidine participates in various processes such as enzyme catalysis, pH regulation, metal binding, and phosphorylation. The determination of exchange rates of labile protons for such a system is important for understanding its functions. However, these rates are too fast to be measured directly in an aqueous solution by using NMR spectroscopy. We have obtained the exchange rates of the NH3(+) amino protons and the labile NH(ε2) and NH(δ1) protons of the imidazole ring by indirect detection through nitrogen-15 as a function of temperature (272 KExchange rates up to 8.5×10(4) s(-1) could be determined (i.e., lifetimes as short as 12 μs). The three chemical shifts δH(i) of the invisible exchanging protons H(i) and the three one-bond scalar coupling constants (1)J(N,H(i)) could also be determined accurately.

  12. Quantification of Water-Soluble Metabolites in Medicinal Mushrooms Using Proton NMR Spectroscopy. (United States)

    Lo, Yu-Chang; Chien, Shih-Chang; Mishchuk, Darya O; Slupsky, Carolyn M; Mau, Jeng-Leun


    The water-soluble metabolites in 5 mushrooms were identified and quantified using proton nuclear magnetic resonance (NMR) spectroscopy and software for targeted metabolite detection and quantification. In total, 35 compounds were found in Agaricus brasiliensis, 25 in Taiwanofungus camphoratus, 23 in Ganoderma lucidum (Taiwan) and Lentinus edodes, and 16 in G. lucidum (China). Total amounts of all identified metabolites in A. brasiliensis, T. camphoratus, G. lucidum, G. lucidum (China), and L. edodes were 149,950.51, 12,834.18, 9,549.09, 2,788.41, and 111,726.51 mg/kg dry weight, respectively. These metabolites were categorized into 4 groups: free amino acids and derivatives, carbohydrates, carboxylic acids, and nucleosides. Carbohydrates were the most abundant metabolites among all 4 groups, with mannitol having the highest concentration among all analyzed metabolites (848-94,104 mg/kg dry weight). Principal components analysis (PCA) showed obvious distinction among the metabolites of the 5 different kinds of mushrooms analyzed in this study. Thus PCA could provide an optional analytical way of identifying and recognizing the compositions of flavor products. Furthermore, the results of this study demonstrate that NMRbased metabolomics is a powerful tool for differentiating between various medicinal mushrooms.

  13. Thermodynamic Study on the Protonation Reactions of Glyphosate in Aqueous Solution: Potentiometry, Calorimetry and NMR spectroscopy. (United States)

    Liu, Bijun; Dong, Lan; Yu, Qianhong; Li, Xingliang; Wu, Fengchang; Tan, Zhaoyi; Luo, Shunzhong


    Glyphosate [N-(phosphonomethyl)glycine] has been described as the ideal herbicide because of its unique properties. There is some conflicting information concerning the structures and conformations involved in the protonation process of glyphosate. Protonation may influence the chemical and physical properties of glyphosate, modifying its structure and the chemical processes in which it is involved. To better understand the species in solution associated with changes in pH, thermodynamic study (potentiometry, calorimetry and NMR spectroscopy) about the protonation pathway of glyphosate is performed. Experimental results confirmed that the order of successive protonation sites of totally deprotonated glyphosate is phosphonate oxygen, amino nitrogen, and finally carboxylate oxygen. This trend is in agreement with the most recent theoretical work in the literature on the subject (J. Phys. Chem. A 2015, 119, 5241-5249). The result is important because it confirms that the protonated site of glyphosate in pH range 7-8, is not on the amino but on the phosphonate group instead. This corrected information can improve the understanding of the glyphosate chemical and biochemical action.

  14. Development of an integrated system for high-pressure NMR spectroscopy on proteins

    Energy Technology Data Exchange (ETDEWEB)

    Kremer, Werner; Beck Erlach, Markus; Munte, Claudia E.; Ernst, T.; Hartl, Rainer; Arnold, M.; Rochelt, Doerte; Niesner, Dieter; Kalbitzer, Hans Robert [Institute of Biophysics and Physical Biochemistry, Regensburg (Germany)


    High hydrostatic pressure can induce multiple effects on proteins including denaturation, depolymerization, and changes of side chain protonation state. Pressure induced structural changes can be investigated with high pressure NMR spectroscopy, because different conformers in the energy-landscape of proteins are accessible via their different specific volume. Therefore static pressure in the range from 4-200 MPa has been applied to proteins and peptides. In addition the application of pressure jumps with a microprocessor controlled on-line pressure system has been performed in order to analyze possible structural intermediates which are not accessible by the utilization of static pressure. Quartz, sapphire or ceramic cells are used to handle the proteins in aqueous solutions during the experiment. The best results can be obtained with ceramic cells because they can withstand high pressures and can be easily handled. A completely new autoclave for these ceramic cells has been constructed, including an improved method for pressure transmission, an integrated safety jacket and a fast closing emergency valve.

  15. 1H NMR Spectroscopy and MVA Analysis of Diplodus sargus Eating the Exotic Pest Caulerpa cylindracea. (United States)

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


    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.

  16. Utilizing NMR and EPR spectroscopy to probe the role of copper in prion diseases

    KAUST Repository

    Emwas, Abdul-Hamid M.


    Copper is an essential nutrient for the normal development of the brain and nervous system, although the hallmark of several neurological diseases is a change in copper concentrations in the brain and central nervous system. Prion protein (PrP) is a copper-binding, cell-surface glycoprotein that exists in two alternatively folded conformations: a normal isoform (PrPC) and a disease-associated isoform (PrPSc). Prion diseases are a group of lethal neurodegenerative disorders that develop as a result of conformational conversion of PrPC into PrPSc. The pathogenic mechanism that triggers this conformational transformation with the subsequent development of prion diseases remains unclear. It has, however, been shown repeatedly that copper plays a significant functional role in the conformational conversion of prion proteins. In this review, we focus on current research that seeks to clarify the conformational changes associated with prion diseases and the role of copper in this mechanism, with emphasis on the latest applications of NMR and EPR spectroscopy to probe the interactions of copper with prion proteins. Copyright © 2013 John Wiley & Sons, Ltd.

  17. Reconsidering the activation entropy for anomerization of glucose and mannose in water studied by NMR spectroscopy (United States)

    Kosaka, Ami; Aida, Misako; Katsumoto, Yukiteru


    The anomerization of monosaccharides is a very important process to understand how their stereoisomers are stabilized in aqueous solutions. For glucose and mannose, it has been known that α- and β-anomers of hexopyranose exist as the major components. In order to examine the anomerization pathway for glucose and mannose in aqueous solutions, it is indispensable to determine the thermodynamic parameters such as the activation energy, the activation Gibbs free energy (ΔG‡), enthalpy (ΔH‡), and entropy (ΔS‡). Although several research groups reported these quantities in aqueous solution, they have still been controversial especially for ΔS‡. In this paper, we employ 1H NMR spectroscopy for monitoring the population of both α- and β-anomers of glucose and mannose. The contribution of ΔS‡ to ΔG‡ for glucose in water is estimated to be ca. 30%, while that for mannose is 8.0%. The large difference in ΔS‡ suggests that the anomerization pathway is not the same for glucose and mannose.

  18. Analysis of Ascarosides from Caenorhabditis elegans Using Mass Spectrometry and NMR Spectroscopy (United States)

    Zhang, Xinxing; Noguez, Jaime H.; Zhou, Yue; Butcher, Rebecca A.


    The nematode Caenorhabditis elegans secretes a family of water-soluble small molecules, known as the ascarosides, into its environment and uses these ascarosides in chemical communication. The ascarosides are derivatives of the 3,6-dideoxysugar ascarylose, modified with different fatty acid-derived side chains. C. elegans uses specific ascarosides, which are together known as the dauer pheromone, to trigger entry into the stress-resistant dauer larval stage. In addition, C. elegans uses specific ascarosides to control certain behaviors, including mating attraction, aggregation, and avoidance. Although in general the concentration of the ascarosides in the environment increases with population density, C. elegans can vary the types and amounts of ascarosides that it secretes depending on the culture conditions under which it has been grown and its developmental history. Here, we describe how to grow high-density worm cultures and the bacterial food for those cultures, as well as how to extract the culture medium to generate a crude pheromone extract. Then, we discuss how to analyze the types and amounts of ascarosides in that extract using mass spectrometry and NMR spectroscopy. PMID:24014355

  19. Application of 13C NMR spectroscopy to characterize organic chemical components of decomposing coarse woody debris from different climatic regions

    Directory of Open Access Journals (Sweden)

    Takuya Hishinuma


    Full Text Available Solid-state 13C nuclear magnetic resonance (NMR spectroscopy was applied to coarse woody debris (CWD in different stages of decomposition and collected from forest floor of a subtropical, a cool temperate, and a subalpine forest in Japan. The purpose was to test its applicability to characterize organic chemical composition of CWD of broad-leaved and coniferous trees from different climatic conditions. O-alkyl-C, mainly representing carbohydrates, was the predominant component of CWD at the three sites, accounting for 43.5-58.1% of the NMR spectra. Generally, the relative area under the signals for aromatic-C and phenolic-C, mainly representing lignin, increased, whereas the relative area for O-alkyl-C decreased, as the decay class advanced. The relative area under NMR chemical shift regions was significantly correlated with the chemical properties examined with proximate analyses. That is, O-alkyl-C and di-O-alkyl-C NMR signal areas were positively correlated with the volumetric density of CWD and the content of total carbohydrates. Methoxyl-C, aromatic-C, phenolic-C, carboxyl-C, and carbonyl-C were positively correlated with the contents of acid-unhydrolyzable residues (lignin, tannins, and cutin and nitrogen. Lignin-C calculated from NMR signals increased, and polysaccharide-C decreased, with the decay class of CWD at the three study sites. A review of previous studies on 13C NMR spectroscopy for decomposing CWD suggested further needs of its application to broad-leaved trees from tropical and subtropical regions.

  20. Metabolic profiling for studying chemotype variations in Withania somnifera (L.) Dunal fruits using GC-MS and NMR spectroscopy. (United States)

    Bhatia, Anil; Bharti, Santosh K; Tewari, Shri K; Sidhu, Om P; Roy, Raja


    Withania somnifera (L.) Dunal (Solanaceae), commonly known as Ashwagandha, is one of the most valued Indian medicinal plant with several pharmaceutical and nutraceutical applications. Metabolic profiling was performed by GC-MS and NMR spectroscopy on the fruits obtained from four chemotypes of W. somnifera. A combination of (1)H NMR spectroscopy and GC-MS identified 82 chemically diverse metabolites consisting of organic acids, fatty acids, aliphatic and aromatic amino acids, polyols, sugars, sterols, tocopherols, phenolic acids and withanamides in the fruits of W. somnifera. The range of metabolites identified by GC-MS and NMR of W. somnifera fruits showed various known and unknown metabolites. The primary and secondary metabolites observed in this study represent MVA, DOXP, shikimic acid and phenylpropanoid biosynthetic metabolic pathways. Squalene and tocopherol have been rated as the most potent naturally occurring compounds with antioxidant properties. These compounds have been identified by us for the first time in the fruits of W. somnifera. Multivariate principal component analysis (PCA) on GC-MS and NMR data revealed clear distinctions in the primary and secondary metabolites among the chemotypes. The variation in the metabolite concentration among different chemotypes of the fruits of W. somnifera suggest that specific chemovars can be used to obtain substantial amounts of bioactive ingredients for use as potential pharmacological and nutraceuticals agents.

  1. Human in vivo cardiac phosphorus NMR spectroscopy at 3.0 Tesla (United States)

    Bruner, Angela Properzio

    One of the newest methods with great potential for use in clinical diagnosis of heart disease is human, cardiac, phosphorus NMR spectroscopy (cardiac p 31 MRS). Cardiac p31 MRS is able to provide quantitative, non-invasive, functional information about the myocardial energy metabolites such as pH, phosphocreatine (PCr), and adenosinetriphosphate (ATP). In addition to the use of cardiac p3l MRS for other types of cardiac problems, studies have shown that the ratio of PCr/ATP and pH are sensitive and specific markers of ischemia at the myocardial level. In human studies, typically performed at 1.5 Tesla, PCr/ATP has been relatively easy to measure but often requires long scan times to provide adequate signal-to-noise (SNR). In addition, pH which relies on identification of inorganic phosphate (Pi), has rarely been obtained. Significant improvement in the quality of cardiac p31 MRS was achieved through the use of the General Electric SIGNATM 3.0 Tesla whole body magnet, improved coil designs and optimized pulse sequences. Phantom and human studies performed on many types of imaging and spectroscopy sequences, identified breathhold gradient-echo imaging and oblique DRESS p31 spectroscopy as the best compromises between SNR, flexibility and quality localization. Both single-turn and quadrature 10-cm diameter, p31 radiofrequency coils, were tested with the quadrature coil providing greater SNR, but at a greater depth to avoid skeletal muscle contamination. Cardiac p31 MRS obtained in just 6 to 8 minutes, gated, showed both improved SNR and discernment of Pi allowing for pH measurement. A handgrip, in-magnet exerciser was designed, created and tested at 1.5 and 3.0 Tesla on volunteers and patients. In ischemic patients, this exercise was adequate to cause a repeated drop in PCr/ATP and pH with approximately eight minutes of isometric exercise at 30% maximum effort. As expected from literature, this exercise did not cause a drop in PCr/ATP for reference volunteers.

  2. 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.;


    The gelling properties of pectin are known to be closely related to the degree of methylation (DM) and the distribution of the ester groups. In order to investigate this dependency, a natural citrus pectin (DM=64%) has been methylated to pectins with higher DM’s or saponified to achieve pectins...... than with unmodified pectin. The new reduced pectins exhibit high gelling properties. Keywords: Pectin; Methylation; Deesterification; Reduction; DM and DR by 1H-NMR spectroscopy; Reduced Pectin; Pectinases; Gelling properties....

  3. Light induced E-Z isomerization in a multi-responsive organogel: elucidation from (1)H NMR spectroscopy. (United States)

    Mondal, Sanjoy; Chakraborty, Priyadarshi; Bairi, Partha; Chatterjee, Dhruba P; Nandi, Arun K


    A multiresponsive organogel of (E)-N'-(anthracene-10-ylmethylene)-3,4,5-tris(dodecyloxy)benzohydrazide (I) showed a decrease of fluorescence intensity, decrease in mechanical strength and a change in gel morphology on irradiation with a wavelength of 365 nm. This is attributed to the E-Z isomerization across the C=N bond of I as evidenced from (1)H NMR spectroscopy.

  4. Proton chemical shift tensors determined by 3D ultrafast MAS double-quantum NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Rongchun; Mroue, Kamal H.; Ramamoorthy, Ayyalusamy, E-mail: [Biophysics and Department of Chemistry, The University of Michigan, Ann Arbor, Michigan 48109-1055 (United States)


    Proton NMR spectroscopy in the solid state has recently attracted much attention owing to the significant enhancement in spectral resolution afforded by the remarkable advances in ultrafast magic angle spinning (MAS) capabilities. In particular, proton chemical shift anisotropy (CSA) has become an important tool for obtaining specific insights into inter/intra-molecular hydrogen bonding. However, even at the highest currently feasible spinning frequencies (110–120 kHz), {sup 1}H MAS NMR spectra of rigid solids still suffer from poor resolution and severe peak overlap caused by the strong {sup 1}H–{sup 1}H homonuclear dipolar couplings and narrow {sup 1}H chemical shift (CS) ranges, which render it difficult to determine the CSA of specific proton sites in the standard CSA/single-quantum (SQ) chemical shift correlation experiment. Herein, we propose a three-dimensional (3D) {sup 1}H double-quantum (DQ) chemical shift/CSA/SQ chemical shift correlation experiment to extract the CS tensors of proton sites whose signals are not well resolved along the single-quantum chemical shift dimension. As extracted from the 3D spectrum, the F1/F3 (DQ/SQ) projection provides valuable information about {sup 1}H–{sup 1}H proximities, which might also reveal the hydrogen-bonding connectivities. In addition, the F2/F3 (CSA/SQ) correlation spectrum, which is similar to the regular 2D CSA/SQ correlation experiment, yields chemical shift anisotropic line shapes at different isotropic chemical shifts. More importantly, since the F2/F1 (CSA/DQ) spectrum correlates the CSA with the DQ signal induced by two neighboring proton sites, the CSA spectrum sliced at a specific DQ chemical shift position contains the CSA information of two neighboring spins indicated by the DQ chemical shift. If these two spins have different CS tensors, both tensors can be extracted by numerical fitting. We believe that this robust and elegant single-channel proton-based 3D experiment provides useful atomistic

  5. Encoded loop-lanthanide-binding tags for long-range distance measurements in proteins by NMR and EPR spectroscopy. (United States)

    Barthelmes, Dominic; Gränz, Markus; Barthelmes, Katja; Allen, Karen N; Imperiali, Barbara; Prisner, Thomas; Schwalbe, Harald


    We recently engineered encodable lanthanide binding tags (LBTs) into proteins and demonstrated their applicability in Nuclear Magnetic Resonance (NMR) spectroscopy, X-ray crystallography and luminescence studies. Here, we engineered two-loop-LBTs into the model protein interleukin-1β (IL1β) and measured (1)H, (15)N-pseudocontact shifts (PCSs) by NMR spectroscopy. We determined the Δχ-tensors associated with each Tm(3+)-loaded loop-LBT and show that the experimental PCSs yield structural information at the interface between the two metal ion centers at atomic resolution. Such information is very valuable for the determination of the sites of interfaces in protein-protein-complexes. Combining the experimental PCSs of the two-loop-LBT construct IL1β-S2R2 and the respective single-loop-LBT constructs IL1β-S2, IL1β-R2 we additionally determined the distance between the metal ion centers. Further, we explore the use of two-loop LBTs loaded with Gd(3+) as a novel tool for distance determination by Electron Paramagnetic Resonance spectroscopy and show the NMR-derived distances to be remarkably consistent with distances derived from Pulsed Electron-Electron Dipolar Resonance.

  6. Area per lipid and cholesterol interactions in membranes from separated local-field (13)C NMR spectroscopy. (United States)

    Leftin, Avigdor; Molugu, Trivikram R; Job, Constantin; Beyer, Klaus; Brown, Michael F


    Investigations of lipid membranes using NMR spectroscopy generally require isotopic labeling, often precluding structural studies of complex lipid systems. Solid-state (13)C magic-angle spinning NMR spectroscopy at natural isotopic abundance gives site-specific structural information that can aid in the characterization of complex biomembranes. Using the separated local-field experiment DROSS, we resolved (13)C-(1)H residual dipolar couplings that were interpreted with a statistical mean-torque model. Liquid-disordered and liquid-ordered phases were characterized according to membrane thickness and average cross-sectional area per lipid. Knowledge of such structural parameters is vital for molecular dynamics simulations, and provides information about the balance of forces in membrane lipid bilayers. Experiments were conducted with both phosphatidylcholine (dimyristoylphosphatidylcholine (DMPC) and palmitoyloleoylphosphatidylcholine (POPC)) and egg-yolk sphingomyelin (EYSM) lipids, and allowed us to extract segmental order parameters from the (13)C-(1)H residual dipolar couplings. Order parameters were used to calculate membrane structural quantities, including the area per lipid and bilayer thickness. Relative to POPC, EYSM is more ordered in the ld phase and experiences less structural perturbation upon adding 50% cholesterol to form the lo phase. The loss of configurational entropy is smaller for EYSM than for POPC, thus favoring its interaction with cholesterol in raftlike lipid systems. Our studies show that solid-state (13)C NMR spectroscopy is applicable to investigations of complex lipids and makes it possible to obtain structural parameters for biomembrane systems where isotope labeling may be prohibitive.

  7. Structural characterization of homogalacturonan by NMR spectroscopy - assignment of reference compounds

    DEFF Research Database (Denmark)

    Petersen, Bent O.; Meier, Sebastian; Duus, Jens Øllgaard;


    Complete assignment of 1H and 13C NMR of six hexagalactopyranuronic acids with varying degree and pattern of methyl esterification is reported. The NMR experiments were run at room temperature using approximately 2 mg of sample making this method convenient for studying the structure of homogalac......Complete assignment of 1H and 13C NMR of six hexagalactopyranuronic acids with varying degree and pattern of methyl esterification is reported. The NMR experiments were run at room temperature using approximately 2 mg of sample making this method convenient for studying the structure...

  8. Prostate Cancer Diagnosis: experimental and Clinical Studies With HRMAS NMR Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Stenman, Katarina


    approach using 1D and 2D high-resolution magic angle spinning (HRMAS) NMR spectroscopy combined with histopathology on intact prostatectomy specimens was evaluated in this research project. The non-destructive nature of HRMAS NMR enables spectroscopic analysis of intact tissue samples with consecutive histological examinations under light microscope. Metabolomics aids in the unraveling and the discovery of organ-specific endogenous metabolites that have the potential to be reliable indicators of organ function and viability, extrinsic and intrinsic perturbations, as well as valuable markers for treatment response. The results may, therefore, be applied clinically to characterize an organ by utilizing bio-markers that have the capacity to distinguish between disease and health. The aim was to characterize the human and the rat prostate in terms of its intermediary metabolism, which is shown here to differ between species and anatomical regions. Furthermore, the aim is to seek the verification of HRMAS NMR derived metabolites which are known to be a part of the prostate metabolome such as, citrate, choline, and the polyamines which were performed, but also the identification of metabolites not previously identified as part of the local prostate metabolism, such as Omega-6, which was detected in tumors. The extended aim was to elucidate novel bio-markers with clinical potential. In this study, the common phyto-nutrient, inositol, which appears to possess protective properties, was identified as being a potentially important PCa bio-marker for the distinction between the more indolent Gleason score 6 and the more aggressive Gleason score 7 in non-malignant prostate tissues with tumors elsewhere in the organ. Further studies in this area of PCa research are therefore warranted

  9. Compositional differences among Chinese soy sauce types studied by (13)C NMR spectroscopy coupled with multivariate statistical analysis. (United States)

    Kamal, Ghulam Mustafa; Wang, Xiaohua; Bin Yuan; Wang, Jie; Sun, Peng; Zhang, Xu; Liu, Maili


    Soy sauce a well known seasoning all over the world, especially in Asia, is available in global market in a wide range of types based on its purpose and the processing methods. Its composition varies with respect to the fermentation processes and addition of additives, preservatives and flavor enhancers. A comprehensive (1)H NMR based study regarding the metabonomic variations of soy sauce to differentiate among different types of soy sauce available on the global market has been limited due to the complexity of the mixture. In present study, (13)C NMR spectroscopy coupled with multivariate statistical data analysis like principle component analysis (PCA), and orthogonal partial least square-discriminant analysis (OPLS-DA) was applied to investigate metabonomic variations among different types of soy sauce, namely super light, super dark, red cooking and mushroom soy sauce. The main additives in soy sauce like glutamate, sucrose and glucose were easily distinguished and quantified using (13)C NMR spectroscopy which were otherwise difficult to be assigned and quantified due to serious signal overlaps in (1)H NMR spectra. The significantly higher concentration of sucrose in dark, red cooking and mushroom flavored soy sauce can directly be linked to the addition of caramel in soy sauce. Similarly, significantly higher level of glutamate in super light as compared to super dark and mushroom flavored soy sauce may come from the addition of monosodium glutamate. The study highlights the potentiality of (13)C NMR based metabonomics coupled with multivariate statistical data analysis in differentiating between the types of soy sauce on the basis of level of additives, raw materials and fermentation procedures.

  10. [Effect of rehabilitation after myocardial infarction on muscular metabolism. Contribution of phosphorus 31 NMR spectroscopy]. (United States)

    Cottin, Y; Marcer, I; Walker, P; Verges, B; Caillaux, B X; Louis, P; Didier, J P; Casillas, J M; Brunotte, F; Wolf, J E


    P 31 NMR spectroscopy is a recent technique which allows a non-invasive and direct analysis of oxidative metabolism and pH changes, an indicator of acidosis due to lactic acid accumulation in the skeletal muscles. The authors investigated oxidative muscular metabolism of the sural triceps in 10 patients after myocardial infarction by performing a study after the acute phase and repeating the study after a programme of physical training. At rest, there were no significant differences. On the other hand, for the same level of maximal effort, the depletion in phosphocreatinine (PCr) and the accumulation of inorganic phosphate (Pi) were significantly lower after physical training: the PCr/PCr + Pi increased from 0.467 +/- 0.179 to 0.538 +/- 0.20 (p < 0.02) and the Pi/PCr ratio decreased from 1.570 +/- 1.440 to 1.181 +/- 1.069 (p < 0.05). The pH at the same level of maximal exercise did not change significantly between the two periods: 6.85 +/- 0.16 vs 6.88 +/- 0.15 (NS). The peak oxygen consumption (VO2) measured during bicycle ergometry increased significantly from 23.4 +/- 10.5 to 28.3 +/- 12.14 ml/min/kg after exercise training (p < 0.01). In addition, a correlation was observed between the improvement of the peripheral parameters (PCr/PCr + Pi) and the increase in VO2 max (r = 0.757, p < 0.01). The authors results confirm the effects of physical training on oxidative metabolisms of the peripheral muscles and its influence on improvement of global performance of coronary patients.

  11. Structural characterization of homogalacturonan by NMR spectroscopy-assignment of reference compounds. (United States)

    Petersen, Bent O; Meier, Sebastian; Duus, Jens Ø; Clausen, Mads H


    Complete assignment of (1)H and (13)C NMR of six hexagalactopyranuronic acids with varying degree and pattern of methyl esterification is reported. The NMR experiments were run at room temperature using approximately 2mg of sample making this method convenient for studying the structure of homogalacturonan oligosaccharides.

  12. Organic Spectroscopy Laboratory: Utilizing IR and NMR in the Identification of an Unknown Substance (United States)

    Glagovich, Neil M.; Shine, Timothy D.


    A laboratory experiment that emphasizes the interpretation of both infrared (IR) and nuclear magnetic resonance (NMR) spectra in the elucidation of the structure of an unknown compound was developed. The method helps students determine [to the first power]H- and [to the thirteenth power]C-NMR spectra from the structures of compounds and to…

  13. Establishing resolution-improved NMR spectroscopy in high magnetic fields with unknown spatiotemporal variations

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Zhiyong; Cai, Shuhui; Zheng, Zhenyao; Lin, Yulan, E-mail:, E-mail:; Chen, Zhong, E-mail:, E-mail: [Department of Electronic Science, State Key Laboratory of Physical Chemistry of Solid Surfaces, Xiamen University, Xiamen (China); Smith, Pieter E. S. [Chemical Physics Department, Weizmann Institute of Science, Rehovot (Israel)


    A half-century quest for higher magnetic fields has been an integral part of the progress undergone in the Nuclear Magnetic Resonance (NMR) study of materials’ structure and dynamics. Because 2D NMR relies on systematic changes in coherences’ phases as a function of an encoding time varied over a series of independent experiments, it generally cannot be applied in temporally unstable fields. This precludes most NMR methods from being used to characterize samples situated in hybrid or resistive magnets that are capable of achieving extremely high magnetic field strength. Recently, “ultrafast” NMR has been developed into an effective and widely applicable methodology enabling the acquisition of a multidimensional NMR spectrum in a single scan; it can therefore be used to partially mitigate the effects of temporally varying magnetic fields. Nevertheless, the strong interference of fluctuating fields with the spatial encoding of ultrafast NMR still severely restricts measurement sensitivity and resolution. Here, we introduce a strategy for obtaining high resolution NMR spectra that exploits the immunity of intermolecular zero-quantum coherences (iZQCs) to field instabilities and inhomogeneities. The spatial encoding of iZQCs is combined with a J-modulated detection scheme that removes the influence of arbitrary field inhomogeneities during acquisition. This new method can acquire high-resolution one-dimensional NMR spectra in large inhomogeneous and fluctuating fields, and it is tested with fields experimentally modeled to mimic those of resistive and resistive-superconducting hybrid magnets.

  14. 1020MHz single-channel proton fast magic angle spinning solid-state NMR spectroscopy. (United States)

    Pandey, Manoj Kumar; Zhang, Rongchun; Hashi, Kenjiro; Ohki, Shinobu; Nishijima, Gen; Matsumoto, Shinji; Noguchi, Takashi; Deguchi, Kenzo; Goto, Atsushi; Shimizu, Tadashi; Maeda, Hideaki; Takahashi, Masato; Yanagisawa, Yoshinori; Yamazaki, Toshio; Iguchi, Seiya; Tanaka, Ryoji; Nemoto, Takahiro; Miyamoto, Tetsuo; Suematsu, Hiroto; Saito, Kazuyoshi; Miki, Takashi; Ramamoorthy, Ayyalusamy; Nishiyama, Yusuke


    This study reports a first successful demonstration of a single channel proton 3D and 2D high-throughput ultrafast magic angle spinning (MAS) solid-state NMR techniques in an ultra-high magnetic field (1020MHz) NMR spectrometer comprised of HTS/LTS magnet. High spectral resolution is well demonstrated.

  15. Permanent Magnet with Very Low Field Gradient (0.1G/mm) for NMR Spectroscopy (United States)

    Ilic, Ognjen; Issadore, David; Hunt, Tom; Westervelt, Robert


    Nuclear Magnetic Resonance (NMR) is a powerful analytical tool for obtaining chemical, physical and structural information. To produce the uniform fields required, NMR experiments typically employ large, expensive electromagnets and shimming coils. We have developed a small permanent magnet with an iron yoke that produces a field of ˜10 kG with gradient CCNE.

  16. Studies concerning the interaction between local anesthetics and lipid membrane by phosphorus-31, deuterium and proton NMR; Estudo da interacao entre anestesicos locais e membranas lipidicas por ressonancia magnetica de fosforo ({sup 31} P), deuterio ({sup 2} H) e proton ({sup 1} H)

    Energy Technology Data Exchange (ETDEWEB)

    Paula, Eneida de [Universidade Estadual de Campinas (UNICAMP), SP (Brazil). Dept. de Bioquimica; Jarrell, Harold C. [National Research Council of Canada, Ottawa, ON (Canada). Inst. for Biological Sciences; Schreier, Shirley [Sao Paulo Univ., SP (Brazil). Inst. de Quimica


    Local anesthetics block the conduction of nervous stimulus by impeding the entrance of sodium ion and the consequently depolarization of the nervous membrane. The action mechanism of local anesthetics, however, is not fully understood yet. In the present work the interaction between local anesthetics and membranes are studied by the perspective of lipid phase perturbation using NMR to elucidate the mechanism. Results are presented and discussed 5 refs., 1 fig., 1 tab.

  17. Combining 1H NMR spectroscopy and multivariate regression techniques to quantitatively determine falsification of porcine heparin with bovine species. (United States)

    Monakhova, Yulia B; Diehl, Bernd W K


    (1)H NMR spectroscopy was used to distinguish pure porcine heparin and porcine heparin blended with bovine species and to quantify the degree of such adulteration. For multivariate modelling several statistical methods such as partial least squares regression (PLS), ridge regression (RR), stepwise regression with variable selection (SR), stepwise principal component regression (SPCR) were utilized for modeling NMR data of in-house prepared blends (n=80). The models were exhaustively validated using independent test and prediction sets. PLS and RR showed the best performance for estimating heparin falsification regarding its animal origin with the limit of detection (LOD) and root mean square error of validation (RMSEV) below 2% w/w and 1% w/w, respectively. Reproducibility expressed in coefficients of variation was estimated to be below 10% starting from approximately 5% w/w of bovine adulteration. Acceptable calibration model was obtained by SPCR, by its application range was limited, whereas SR is least recommended for heparin matrix. The developed method was found to be applicable also to heparinoid matrix (not purified heparin). In this case root mean square of prediction (RMSEP) and LOD were approximately 7% w/w and 8% w/w, respectively. The simple and cheap NMR method is recommended for screening of heparin animal origin in parallel with official NMR test of heparin authenticity and purity.

  18. Analyzing the adsorption of blood plasma components by means of fullerene-containing silica gels and NMR spectroscopy in solids (United States)

    Melenevskaya, E. Yu.; Mokeev, M. V.; Nasonova, K. V.; Podosenova, N. G.; Sharonova, L. V.; Gribanov, A. V.


    The results from studying the adsorption of blood plasma components (e.g., protein, triglycerides, cholesterol, and lipoproteins of low and high density) using silica gels modified with fullerene molecules (in the form of C60 or the hydroxylated form of C60(OH) x ) and subjected to hydration (or, alternatively, dehydration) are presented. The conditions for preparing adsorbents that allow us to control the adsorption capacity of silica gel and the selectivity of adsorption toward the components of blood plasma, are revealed. The nature and strength of the interactions of the introduced components (fullerene molecules and water) with functional groups on the silica surface are studied by means of solid state NMR spectroscopy (NMR-SS). Conclusions regarding the nature of the centers that control adsorption are drawn on the basis of NMR-SS spectra in combination with direct measurements of adsorption. The interaction of the oxygen of the hydroxyl group of silica gel with fullerene, leading to the formation of electron-donor complexes of C60-H, C60-OH, or C60-OSi type, is demonstrated by the observed changes in the NMR-SS spectra of silica gels in the presence of fullerene.

  19. Identification and quantification of major steviol glycosides in Stevia rebaudiana purified extracts by 1H NMR spectroscopy. (United States)

    Pieri, Valerio; Belancic, Andrea; Morales, Susana; Stuppner, Hermann


    The use of (1)H NMR spectroscopy for the characterization of Stevia rebaudiana extracts is presented. The developed method allows qualitative and quantitative determination of the major steviol glycosides in purified extracts and fractions obtained from various stages of the purification process. Moreover, it proved to be a powerful tool to differentiate between glycosides which are naturally occurring in the stevia plant and artifacts formed in the course of the manufacturing process. Identification of steviol glycosides was achieved by the use of 2D NMR techniques, whereas quantification is based on qHNMR using anthracene as internal standard. The solvent mixture pyridine-d(5)-DMSO-d(6) (6:1) enabled satisfactory separation of the signals to be integrated. Validation of the method was performed in terms of specificity, precision, accuracy, linearity, robustness, and stability. Quantitative results were compared to those obtained with the JECFA HPLC-UV method and were found to be in reasonable agreement. NMR analysis does not rely on the use of reference compounds and enables significantly faster analysis compared to HPLC-UV. Thus, NMR represents a feasible alternative to HPLC-based methods for the quality control of Stevia rebaudiana extracts.

  20. 1H HR-MAS NMR Spectroscopy and the Metabolite Determination of Typical Foods in Mediterranean Diet

    Directory of Open Access Journals (Sweden)

    Carmelo Corsaro


    Full Text Available NMR spectroscopy has become an experimental technique widely used in food science. The experimental procedures that allow precise and quantitative analysis on different foods are relatively simple. For a better sensitivity and resolution, NMR spectroscopy is usually applied to liquid sample by means of extraction procedures that can be addressed to the observation of particular compounds. For the study of semisolid systems such as intact tissues, High-Resolution Magic Angle Spinning (HR-MAS has received great attention within the biomedical area and beyond. Metabolic profiling and metabolism changes can be investigated both in animal organs and in foods. In this work we present a proton HR-MAS NMR study on the typical vegetable foods of Mediterranean diet such as the Protected Geographical Indication (PGI cherry tomato of Pachino, the PGI Interdonato lemon of Messina, several Protected Designation of Origin (PDO extra virgin olive oils from Sicily, and the Traditional Italian Food Product (PAT red garlic of Nubia. We were able to identify and quantify the main metabolites within the studied systems that can be used for their characterization and authentication.

  1. Dynamic nuclear polarization NMR spectroscopy allows high-throughput characterization of microporous organic polymers. (United States)

    Blanc, Frédéric; Chong, Samantha Y; McDonald, Tom O; Adams, Dave J; Pawsey, Shane; Caporini, Marc A; Cooper, Andrew I


    Dynamic nuclear polarization (DNP) solid-state NMR was used to obtain natural abundance (13)C and (15)N CP MAS NMR spectra of microporous organic polymers with excellent signal-to-noise ratio, allowing for unprecedented details in the molecular structure to be determined for these complex polymer networks. Sensitivity enhancements larger than 10 were obtained with bis-nitroxide radical at 14.1 T and low temperature (∼105 K). This DNP MAS NMR approach allows efficient, high-throughput characterization of libraries of porous polymers prepared by combinatorial chemistry methods.

  2. Assessing the fate and transformation of plant residues in the terrestrial environment using HR-MAS NMR spectroscopy (United States)

    Kelleher, Brian P.; Simpson, Myrna J.; Simpson, Andre J.


    Plant litter decomposition plays a fundamental role in carbon and nitrogen cycles, provides key nutrients to the soil environment and represents a potentially large positive feedback to atmospheric CO 2. However, the full details of decomposition pathways and products are unknown. Here we present the first application of HR-MAS NMR spectroscopy on 13C and 15N labeled plant materials, and apply this approach in a preliminary study to monitor the environmental degradation of the pine and wheatgrass residues over time. In HR-MAS, is it possible to acquire very high resolution NMR data of plant biomass, and apply the vast array of multidimensional experiments available in conventional solution-state NMR. High levels of isotopic enrichment combined with HR-MAS significantly enhance the detection limits, and provide a wealth of information that is unattainable by any other method. Diffusion edited HR-MAS NMR data reveal the rapid loss of carbohydrate structures, while two-dimensional (2-D) HR-MAS NMR spectra demonstrate the relatively fast loss of both hydrolysable and condensed tannin structures from all plant tissues studied. Aromatic (partially lignin) and aliphatic components (waxes, cuticles) tend to persist, along with a small fraction of carbohydrate, and become highly functionalized over time. While one-dimensional (1-D) 13C HR-MAS NMR spectra of fresh plant tissue reflect compositional differences between pine and grass, these differences become negligible after decomposition suggesting that recalcitrant carbon may be similar despite the plant source. Two-dimensional 1H- 15N HR-MAS NMR analysis of the pine residue suggests that nitrogen from specific peptides is either selectively preserved or used for the synthesis of what appears to be novel structures. The amount of relevant data generated from plant components in situ using HR-MAS NMR is highly encouraging, and demonstrates that complete assignment will yield unprecedented structural knowledge of plant cell

  3. Cationic complexation with dissolved organic matter: Insights from molecular dynamics computer simulations and NMR spectroscopy (United States)

    Kalinichev, A. G.; Xu, X.; Kirkpatrick, R.


    Dissolved organic matter (DOM) is ubiquitous in soil and surface water and plays many important geochemical and environmental roles acting as a proton donor/acceptor and pH buffer and interacting with metal ions, minerals and organic species to form water-soluble and water-insoluble complexes of widely differing chemical and biological stabilities. There are strong correlations among the concentration of DOM and the speciation, solubility and toxicity of many trace metals in soil and water due to metal-DOM interaction. DOM can also significantly negatively affect the performance of nanofiltration and reverse osmosis membranes used industrially for water purification and desalination, being one of the major causes of a so-called `membrane bio- fouling'. The molecular scale mechanisms and dynamics of the DOM interactions with metals and membranes are, however, quite poorly understood. Methods of computational molecular modeling, combined with element- specific nuclear magnetic resonance (NMR) spectroscopy, can serve as highly effective tools to probe and quantify on a fundamental molecular level the DOM interactions with metal cations in aqueous solutions, and to develop predictive models of the molecular mechanisms responsible for the metal-DOM complexation in the environment. This paper presents the results of molecular dynamics (MD) computer simulations of the interaction of DOM with dissolved Na+, Cs+, Mg2+, and Ca2+. Na+ forms only very weak outer-sphere complexes with DOM. These results and the results of other recent molecular modeling efforts (e.g., Sutton et al., Environmental Toxicology and Chemistry, 24, 1902-1911, 2005), clearly indicate that both the structural and dynamic aspects of the cation-DOM complexation follow a simple trend in terms of the charge/size ratio for the ions. Due to the competition between ion hydration in bulk aqueous solution and adsorption of these cations by the negatively charged DOM functional groups (primarily carboxylate

  4. (1)H NMR spectroscopy-guided isolation of new sucrose esters from Physalis alkekengi var. franchetii and their antibacterial activity. (United States)

    Zhang, Chuan-Yang; Luo, Jian-Guang; Liu, Rui-Huan; Lin, Ru; Yang, Ming-Hua; Kong, Ling-Yi


    Ten new sucrose esters, physakengoses A-J (1-10), were isolated from the aerial parts of Physalis alkekengi var. franchetii under the guidance of (1)H NMR spectroscopy. Their structures were determined by spectroscopic analyses (HRESIMS, 1D and 2D NMR, and ESIMS) and chemical methods. These new compounds were tested for antibacterial activities against Staphylococcus aureus, Bacillus subtilis, Pseudomonas aeruginosa and Escherichia coli. Among them, compounds 2 and 5-8 showed potent inhibitory effects against test strains with MIC values ranging from 3.5 to 14.9μg/mL. These findings may indicate that the P. alkekengi var. franchetii has potential application as an ingredient in pharmaceuticals.

  5. Metabolite Characterization in Peritoneal Dialysis Effluent Using High-resolution 1H and 1H-13C NMR Spectroscopy

    CERN Document Server

    Guleria, Anupam; Rawat, Atul; Khetrapal, C L; Prasad, Narayan; Kumar, Dinesh


    Metabolite analysis of peritoneal dialysis (PD) effluent may provide information regarding onset and progression of complications associated with prolonged PD therapy. In this context, the NMR detectable small metabolites of PD effluent samples were characterized using high resolution 1H and 1H-13C NMR spectroscopy. The various spectra were recorded (at 800 MHz proton frequency) on PD effluent samples obtained after 4 hour (intraperitoneal) dwell time from patients with end stage renal failure (ESRF) and continuing normally on PD therapy. Inspite of devastating spectral feature of PD effluent due to the presence of intense resonances from glucose and lactate, we were able to identify about 53 small endogenous metabolites (including many complex coupled spin systems) and more than 90 % of the total CH cross peaks of 1H-13C HSQC spectrum were identified specific to various metabolites of PD effluent. We foresee that the characteristic fingerprints of various metabolites of control PD effluent samples will be us...

  6. Conformational analysis of 3-(trimethylsilyl)propionic acid by NMR spectroscopy: an unusual expression of the beta-silyl effect. (United States)

    Nkansah, Richard A; Gerken, James B; Roberts, John D


    The rotational freedom of the carbon-carbon single bonds of 1,2-disubstituted ethanes affords the possibility of these compounds existing as a rapidly interconverting mixture of conformers in solution. The conformational preferences of one such compound, 3-(trimethylsilyl)propionic acid, and its anion were studied in water, dimethyl sulfoxide, methanol, ethanol, isopropyl alcohol, tert-butyl alcohol, tetrahydrofuran, and toluene with 1H NMR spectroscopy. The conformational preferences were determined from the vicinal proton-proton coupling constants between the hydrogen nuclei of the CH(2)CH(2) group with the aid of the Altona equations to derive the equilibrium anti and gauche percentages of rotamers from the averaged NMR-time scale couplings. Conformational analyses of 4,4-dimethylpentanoic acid and its anion as well as 2-(trimethylsilyl)ethanesulfonate anion were also conducted to compare the relative structural influences on the conformational preferences of silicon and carbon.

  7. In-situ annotation of carbohydrate diversity, abundance, and degradability in highly complex mixtures using NMR spectroscopy

    DEFF Research Database (Denmark)

    Meier, Sebastian


    Many functions of carbohydrates depend on the detection of short structural motifs, approximately up to hexasaccharide length, by receptors or catalysts. This study investigates the usefulness of state-of-the-art 1H–13C nuclear-magnetic-resonance (NMR) spectroscopy for characterizing the diversity......, abundance, and degradability of such short structural motifs in plant-derived carbohydrates. Assignments of carbohydrate signals for 1H–13C NMR spectra of beer, wine, and fruit juice yield up to >130 assignments in situ, i.e. in individual samples without separation or derivatization. More than 500...... structural motifs can be resolved over a concentration range of ~103 in experiments of a few hours duration. The diversity of carbohydrate units increases according to power laws at lower concentrations for both cereal and fruit-derived samples. Simple graphs resolve the smaller overall contribution of more...

  8. Metabolite profiling of Curcuma species grown in different regions using 1H NMR spectroscopy and multivariate analysis. (United States)

    Jung, Youngae; Lee, Jueun; Kim, Ho Kyoung; Moon, Byeong Cheol; Ji, Yunui; Ryu, Do Hyun; Hwang, Geum-Sook


    Curcuma is used to treat skin diseases and colic inflammatory disorders, and in insect repellants and antimicrobial and antidiabetic medications. Two Curcuma species (C. aromatica and C. longa) grown in Jeju-do and Jin-do were used in this study. Methanolic extracts were analyzed by (1)H NMR spectroscopy, and metabolite profiling coupled with multivariate analysis was applied to characterize the differences between species or origin. PCA analysis showed significantly greater differences between species than origins, and the metabolites responsible for the differences were identified. The concentrations of sugars (glucose, fructose, and sucrose) and essential oils (eucalyptol, curdione, and germacrone) were significantly different between the two species. However, the samples from Jeju-do and Jin-do were different mainly in their concentrations of organic acids (fumarate, succinate, acetate, and formate) and sugars. This study demonstrates that NMR-based metabolomics is an efficient method for fingerprinting and determining differences between Curcuma species or those grown in different regions.

  9. Theoretical NMR spectroscopy of N-heterocyclic carbenes and their metal complexes

    KAUST Repository

    Falivene, Laura


    Recent theoretical analysis of the NMR properties of free N-heterocyclic carbenes (NHC) and Metal-NHC complexes has complemented experiments, allowing the establishment of structure/property relationships and the rationalization of otherwise surprising experimental results. In this review, the main conclusions from recent literature are discussed, with the aim to offer a vision of the potential of theoretical analyses of NMR properties.

  10. Investigating fatty acids inserted into magnetically aligned phospholipid bilayers using EPR and solid-state NMR spectroscopy (United States)

    Nusair, Nisreen A.; Tiburu, Elvis K.; Dave, Paresh C.; Lorigan, Gary A.


    This is the first time 2H solid-state NMR spectroscopy and spin-labeled EPR spectroscopy have been utilized to probe the structural orientation and dynamics of a stearic acid incorporated into magnetically aligned phospholipid bilayers or bicelles. The data gleaned from the two different techniques provide a more complete description of the bilayer membrane system. Both methods provided similar qualitative information on the phospholipid bilayer, high order, and low motion for the hydrocarbon segment close to the carboxyl groups of the stearic acid and less order and more rapid motion at the end towards the terminal methyl groups. However, the segmental order parameters differed markedly due to the different orientations that the nitroxide and C-D bond axes transform with the various stearic acid acyl chain conformations, and because of the difference in dynamic sensitivity between NMR and EPR over the timescales examined. 5-, 7-, 12-, and 16-doxylstearic acids spin-labels were used in the EPR experiments and stearic acid-d 35 was used in the solid-state NMR experiments. The influence of the addition of cholesterol and the variation of temperature on the fatty acid hydrocarbon chain ordering in the DMPC/DHPC phospholipid bilayers was also studied. Cholesterol increased the degree of ordering of the hydrocarbon chains. Conversely, as the temperature of the magnetically aligned phospholipid bilayers increased, the order parameters decreased due to the higher random motion of the acyl chain of the stearic acid. The results indicate that magnetically aligned phospholipid bilayers are an excellent model membrane system and can be used for both NMR and EPR studies.

  11. High-resolution (19)F MAS NMR spectroscopy: structural disorder and unusual J couplings in a fluorinated hydroxy-silicate. (United States)

    Griffin, John M; Yates, Jonathan R; Berry, Andrew J; Wimperis, Stephen; Ashbrook, Sharon E


    High-resolution (19)F magic angle spinning (MAS) NMR spectroscopy is used to study disorder and bonding in a crystalline solid. (19)F MAS NMR reveals four distinct F sites in a 50% fluorine-substituted deuterated hydrous magnesium silicate (clinohumite, 4Mg(2)SiO(4)·Mg(OD(1-x)F(x))(2) with x = 0.5), indicating extensive structural disorder. The four (19)F peaks can be assigned using density functional theory (DFT) calculations of NMR parameters for a number of structural models with a range of possible local F environments generated by F(-)/OH(-) substitution. These assignments are supported by two-dimensional (19)F double-quantum MAS NMR experiments that correlate F sites based on either spatial proximity (via dipolar couplings) or through-bond connectivity (via scalar, or J, couplings). The observation of (19)F-(19)F J couplings is unexpected as the fluorines coordinate Mg atoms and the Mg-F interaction is normally considered to be ionic in character (i.e., there is no formal F-Mg-F covalent bonding arrangement). However, DFT calculations predict significant (19)F-(19)F J couplings, and these are in good agreement with the splittings observed in a (19)F J-resolved MAS NMR experiment. The existence of these J couplings is discussed in relation to both the nature of bonding in the solid state and the occurrence of so-called "through-space" (19)F-(19)F J couplings in solution. Finally, we note that we have found similar structural disorder and spin-spin interactions in both synthetic and naturally occurring clinohumite samples.

  12. Powder-XRD and (14) N magic angle-spinning solid-state NMR spectroscopy of some metal nitrides. (United States)

    Kempgens, Pierre; Britton, Jonathan


    Some metal nitrides (TiN, ZrN, InN, GaN, Ca3 N2 , Mg3 N2 , and Ge3 N4 ) have been studied by powder X-ray diffraction (XRD) and (14) N magic angle-spinning (MAS) solid-state NMR spectroscopy. For Ca3 N2 , Mg3 N2 , and Ge3 N4 , no (14) N NMR signal was observed. Low speed (νr  = 2 kHz for TiN, ZrN, and GaN; νr  = 1 kHz for InN) and 'high speed' (νr  = 15 kHz for TiN; νr  = 5 kHz for ZrN; νr  = 10 kHz for InN and GaN) MAS NMR experiments were performed. For TiN, ZrN, InN, and GaN, powder-XRD was used to identify the phases present in each sample. The number of peaks observed for each sample in their (14) N MAS solid-state NMR spectrum matches perfectly well with the number of nitrogen-containing phases identified by powder-XRD. The (14) N MAS solid-state NMR spectra are symmetric and dominated by the quadrupolar interaction. The envelopes of the spinning sidebands manifold are Lorentzian, and it is concluded that there is a distribution of the quadrupolar coupling constants Qcc 's arising from structural defects in the compounds studied.

  13. A study of transition-metal organometallic complexes combining 35Cl solid-state NMR spectroscopy and 35Cl NQR spectroscopy and first-principles DFT calculations. (United States)

    Johnston, Karen E; O'Keefe, Christopher A; Gauvin, Régis M; Trébosc, Julien; Delevoye, Laurent; Amoureux, Jean-Paul; Popoff, Nicolas; Taoufik, Mostafa; Oudatchin, Konstantin; Schurko, Robert W


    A series of transition-metal organometallic complexes with commonly occurring metal-chlorine bonding motifs were characterized using (35)Cl solid-state NMR (SSNMR) spectroscopy, (35)Cl nuclear quadrupole resonance (NQR) spectroscopy, and first-principles density functional theory (DFT) calculations of NMR interaction tensors. Static (35)Cl ultra-wideline NMR spectra were acquired in a piecewise manner at standard (9.4 T) and high (21.1 T) magnetic field strengths using the WURST-QCPMG pulse sequence. The (35)Cl electric field gradient (EFG) and chemical shielding (CS) tensor parameters were readily extracted from analytical simulations of the spectra; in particular, the quadrupolar parameters are shown to be very sensitive to structural differences, and can easily differentiate between chlorine atoms in bridging and terminal bonding environments. (35)Cl NQR spectra were acquired for many of the complexes, which aided in resolving structurally similar, yet crystallographically distinct and magnetically inequivalent chlorine sites, and with the interpretation and assignment of (35)Cl SSNMR spectra. (35)Cl EFG tensors obtained from first-principles DFT calculations are consistently in good agreement with experiment, highlighting the importance of using a combined approach of theoretical and experimental methods for structural characterization. Finally, a preliminary example of a (35)Cl SSNMR spectrum of a transition-metal species (TiCl4) diluted and supported on non-porous silica is presented. The combination of (35)Cl SSNMR and (35)Cl NQR spectroscopy and DFT calculations is shown to be a promising and simple methodology for the characterization of all manner of chlorine-containing transition-metal complexes, in pure, impure bulk and supported forms.

  14. Refocused continuous-wave decoupling: A new approach to heteronuclear dipolar decoupling in solid-state NMR spectroscopy

    DEFF Research Database (Denmark)

    Vinther, Joachim Møllesøe; Nielsen, Anders B.; Bjerring, Morten


    A novel strategy for heteronuclear dipolar decoupling in magic-angle spinning solid-state NMR spectroscopy is presented, which eliminates residual static high-order terms in the effective Hamiltonian originating from interactions between oscillating dipolar and anisotropic shielding tensors...... rCW decoupling sequences are presented and their performance is compared to state-of-the-art decoupling methods. The rCW decoupling sequences benefit from extreme broadbandedness, tolerance towards rf inhomogeneity, and improved potential for decoupling at relatively low average rf field strengths...

  15. Identification and quantitative determination of carbohydrates in ethanolic extracts of two conifers using 13C NMR spectroscopy. (United States)

    Duquesnoy, Emilie; Castola, Vincent; Casanova, Joseph


    We developed a method for the direct identification and quantification of carbohydrates in raw vegetable extracts using (13)C NMR spectroscopy without any preliminary step of precipitation or reduction of the components. This method has been validated (accuracy, precision and response linearity) using pure compounds and artificial mixtures before being applied to authentic ethanolic extracts of pine needles, pine wood and pine cones and fir twigs. We determined that carbohydrates represented from 15% to 35% of the crude extracts in which pinitol was the principal constituent accompanied by arabinitol, mannitol, glucose and fructose.


    DEFF Research Database (Denmark)

    Olafsdottir, E. S.; Sorensen, A. M.; Cornett, Claus;


    nonannellated cyclopentane derivatives. The new glucosides were shown, by NMR spectroscopy (including NOE measurements), X-ray crystallography, and enzymatic hydrolysis to the corresponding cyanohydrins, to be (1R,2R,3R,4R)- and (1S,2S,3S,4S)-1-(beta-D-glucopyranosyloxy)-2,3-epoxy-4-hydroxycyclopenta ne-1...... side as the three oxygen substituents. In addition to the glucosides, two amides, (1S,2S,3R,4R)-2,3-epoxy-1,4-dihydroxycyclopentane-1-carboxamide and (1S,4R)-1,4-dihydroxy-2-cyclopentene-1-carboxamide, were isolated from P. suberosa and characterized; the amides are probably artefacts...

  17. Phenylalanine and tyrosine methyl ester intramolecular interactions and conformational analysis by (1)H NMR and infrared spectroscopies and theoretical calculations. (United States)

    Cormanich, Rodrigo A; Ducati, Lucas C; Tormena, Cláudio F; Rittner, Roberto


    Amino acid conformational analysis in solution are scarce, since these compounds present a bipolar zwitterionic structure ((+)H3NCHRCOO(-)) in these media. Also, intramolecular hydrogen bonds have been classified as the sole interactions governing amino acid conformational behavior in the literature. In the present work we propose phenylalanine and tyrosine methyl ester conformational studies in different solvents by (1)H NMR and infrared spectroscopies and theoretical calculations. Both experimental and theoretical results are in agreement and suggest that the conformational behavior of the phenylalanine and tyrosine methyl esters are similar and are dictated by the interplay between steric and hyperconjugative interactions.

  18. New strategy for stable-isotope-aided, multidimensional NMR spectroscopy of DNA oligomers

    Energy Technology Data Exchange (ETDEWEB)

    Ono, Okira; Tate, Shin-Ichi; Kainosho, Masatsune [Tokyo Metropolitan Univ., Tokyo (Japan)


    Nuclear Magnetic Resonance (NMR) is the most efficient method for determining the solution structures of biomolecules. By applying multidimensional heteronuclear NMR techniques to {sup 13}C/{sup 15}N-labeled proteins, we can determine the solution structures of proteins with molecular mass of 20 to 30kDa at an accuracy similar to that of x-ray crystallography. Improvements in NMR instrumentation and techniques as well as the development of protein engineering methods for labeling proteins have rapidly advanced multidimensional heteronuclear NMR of proteins. In contrast, multidimensional heteronuclear NMR studies of nucleic acids is less advanced because there were no efficient methods for preparing large amounts of labeled DNA/RNA oligomers. In this report, we focused on the chemical synthesis of DNA oligomers labeled at specific residue(s). RNA oligomers with specific labels, which are difficult to synthesize by the enzyme method, can be synthesized by the chemical method. The specific labels are useful for conformational analysis of larger molecules such as protein-nucleic acid complexes.

  19. Dynamics and interactions of ibuprofen in cyclodextrin nanosponges by solid-state NMR spectroscopy (United States)

    Ferro, Monica; Pastori, Nadia; Punta, Carlo; Melone, Lucio; Panzeri, Walter; Rossi, Barbara; Trotta, Francesco


    Two different formulations of cyclodextrin nanosponges (CDNS), obtained by polycondensation of β-cyclodextrin with ethylenediaminetetraacetic acid dianhydride (EDTAn), were treated with aqueous solutions of ibuprofen sodium salt (IbuNa) affording hydrogels that, after lyophilisation, gave two solid CDNS-drug formulations. 1H fast MAS NMR and 13C CP-MAS NMR spectra showed that IbuNa was converted in situ into its acidic and dimeric form (IbuH) after freeze-drying. 13C CP-MAS NMR spectra also indicated that the structure of the nanosponge did not undergo changes upon drug loading compared to the unloaded system. However, the 13C NMR spectra collected under variable contact time cross-polarization (VCT-CP) conditions showed that the polymeric scaffold CDNS changed significantly its dynamic regime on passing from the empty CDNS to the drug-loaded CDNS, thus showing that the drug encapsulation can be seen as the formation of a real supramolecular aggregate rather than a conglomerate of two solid components. Finally, the structural features obtained from the different solid-state NMR approaches reported matched the information from powder X-ray diffraction profiles. PMID:28228859

  20. A simple mathematical model and practical approach for evaluating citric acid cycle fluxes in perfused rat hearts by 13C-NMR and 1H-NMR spectroscopy. (United States)

    Tran-Dinh, S; Hoerter, J A; Mateo, P; Bouet, F; Herve, M


    We propose a simple mathematical model and a practical approach for evaluating the flux constant and the absolute value of flux in the citric acid cycle in perfused organs by 13C-NMR and 1H-NMR spectroscopy. We demonstrate that 13C-NMR glutamate spectra are independent of the relative sizes of the mitochondrial and cytosolic compartments and the exchange rates of glutamates, unless there is a difference in 13C chemical shifts of glutamate carbons between the two compartments. Wistar rat hearts (five beating and four KCl-arrested hearts) were aerobically perfused with 100% enriched [2-(13)C]acetate and the kinetics of glutamate carbon labeling from perchloric acid extracts were studied at various perfusion times. Under our experimental conditions, the citric acid cycle flux constant, which represents the fraction of glutamate in exchange with the citric acid cycle per unit time, is about 0.350 +/- 0.003 min(-1) for beating hearts and 0.0741 +/- 0.004 min(-1) for KCl-arrested hearts. The absolute values of the citric acid flux for beating hearts and for KCl-arrested hearts are 1.06 +/- 0.06 micromol x min(-1) x mg(-1) and 0.21 +/- 0.02 micromol x min(-1) x g(-1), respectively. The fraction of unlabeled acetate determined from the proton signal of the methyl group is small and essentially the same in beating and arrested hearts (7.4 +/- 1.7% and 8.8 +/- 2.1%, respectively). Thus, the large difference in the Glu C2/C4 between beating and arrested hearts is not due to the important contribution from anaplerotic sources in arrested hearts but simply to a substantial difference in citric acid cycle fluxes. Our model fits the experimental data well, indicating a fast exchange between 2-oxoglutarate and glutamate in the mitochondria of rat hearts. Analysis of the flux constant, calculated from the half-time of glutamate C4 labeling given in the literature, allows for a comparison of the citric acid flux for various working conditions in different animal species.

  1. New Insights into High-Performance Thermoelectric Tellurides from ^125Te NMR Spectroscopy (United States)

    Levin, E. M.; Hu, Y.-Y.; Cook, B. A.; Harringa, J. L.; Schmidt-Rohr, K.; Kanatzidis, M. G.


    Thermoelectric materials are widely used for direct transformation of heat to electricity (Seebeck effect) and for solid state refrigeration (Peltier effect). Efforts to increase the efficiency of high-performance thermoelectrics, which include narrow-gap, doped tellurium-based semiconductors, require detailed knowledge of their local structure and bonding. We have used ^125Te nuclear magnetic resonance (NMR) as a local probe for obtaining better understanding of these high-performance thermoelectric tellurides, specifically PbTe doped with Ag and Sb (LAST materials) and GeTe doped with Ag and Sb (TAGS materials). The resonance frequencies and line shapes of the NMR spectra, as well as spin-lattice relaxation times and chemical shift anisotropies are highly sensitive to the composition and synthesis conditions of LAST and TAGS materials, enabling studies of the local composition, distortion, bonding, and carrier concentration. Several intriguing phenomena including electronic inhomogeneity and local distortions of the crystal lattice have been observed by NMR.

  2. Mechanisms of Action of (Methacrylates in Hemolytic Activity, in Vivo Toxicity and Dipalmitoylphosphatidylcholine (DPPC Liposomes Determined Using NMR Spectroscopy

    Directory of Open Access Journals (Sweden)

    Seiichiro Fujisawa


    Full Text Available We investigated the quantitative structure-activity relationships between hemolytic activity (log 1/H50 or in vivo mouse intraperitoneal (ip LD50 using reported data for α,β-unsaturated carbonyl compounds such as (methacrylate monomers and their 13C-NMR β-carbon chemical shift (δ. The log 1/H50 value for methacrylates was linearly correlated with the δCβ value. That for (methacrylates was linearly correlated with log P, an index of lipophilicity. The ipLD50 for (methacrylates was linearly correlated with δCβ but not with log P. For (methacrylates, the δCβ value, which is dependent on the π-electron density on the β-carbon, was linearly correlated with PM3-based theoretical parameters (chemical hardness, η; electronegativity, χ; electrophilicity, ω, whereas log P was linearly correlated with heat of formation (HF. Also, the interaction between (methacrylates and DPPC liposomes in cell membrane molecular models was investigated using 1H-NMR spectroscopy and differential scanning calorimetry (DSC. The log 1/H50 value was related to the difference in chemical shift (ΔδHa (Ha: H (trans attached to the β-carbon between the free monomer and the DPPC liposome-bound monomer. Monomer-induced DSC phase transition properties were related to HF for monomers. NMR chemical shifts may represent a valuable parameter for investigating the biological mechanisms of action of (methacrylates.

  3. Direct evaluation of molecular States of piroxicam/poloxamer nanosuspension by suspended-state NMR and Raman spectroscopies. (United States)

    Hasegawa, Yuki; Higashi, Kenjirou; Yamamoto, Keiji; Moribe, Kunikazu


    A nanosuspension of piroxicam (PXC) and poloxamer 407 (poloxamer) prepared by the wet milling method was directly evaluated at the molecular level from the viewpoint of both solution and solid phases. (13)C solution-state NMR measurements revealed a reduction in the concentration of dissolved poloxamer in the nanosuspension. Furthermore, the fraction of dissolved poly(ethylene oxide) (PEO) chain, which is the hydrophilic part of poloxamer, was higher than that of dissolved poly(propylene oxide) (PPO) chain, the hydrophobic part. (13)C suspended-state NMR and Raman spectroscopies detected both solid-state PXC and poloxamer involved in the nanoparticles. Interestingly, the coexistence of crystalline and amorphous PXC in the nanoparticle was demonstrated. The yellow color of the nanosuspension strongly supported the existence of amorphous PXC. Changes in the peak intensity depending on the contact time in the suspended-state NMR spectrum revealed that the PEO chain of poloxamer in the nanoparticle had higher mobility compared with the PPO chain. The PEO chain should project into the water phase and form the outer layer of the nanoparticles, whereas the PPO chain should face the inner side of the nanoparticles. Amorphous PXC could be stabilized by intermolecular interaction with the PPO chain near the surface of the nanoparticles, whereas crystalline PXC could form the inner core.

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

    Directory of Open Access Journals (Sweden)

    Macduff O. Okuom


    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.

  5. Identification of the chemotypes of Ocimum forskolei and Ocimum basilicum by NMR spectroscopy. (United States)

    Fatope, Majekodunmi O; Marwah, Ruchi G; Al Hadhrami, Nabil M; Onifade, Anthony K; Williams, John R


    The chemotypes of Ocimum forskolei Benth and Ocimum basilicum L. growing wild in Oman have been established by (13)C-NMR analyses of the vegetative and floral oils of the plants. The chemotypes, estragole for O. forskolei and linalool for O. basilicum, suggested by (13)C-NMR fingerprinting were also confirmed by GC-FID and GC/MS analyses. The oil of O. forskolei demonstrated better activities against bacteria and dermatophytes. The significance of the presence of estragole and linalool in the volatile oils of plants whose fragrances are traditionally inhaled, added to food, or rubbed on the skin are discussed.

  6. Investigation of zinc alkali pyrophosphate glasses. Part II: Local and medium range orders analysed by 1D/2D NMR

    Energy Technology Data Exchange (ETDEWEB)

    Rajbhandari, P. [UCCS UMR-CNRS 8181, Université de Lille1, Villeneuve d' Ascq (France); Chen, Y. [LASIR UMR-CNRS 8516, Université de Lille1, Villeneuve d' Ascq (France); Doumert, B. [IMMCL CNRS-FR2638, Université de Lille1, Villeneuve d' Ascq (France); Montagne, L. [UCCS UMR-CNRS 8181, Université de Lille1, Villeneuve d' Ascq (France); Tricot, G., E-mail: [UCCS UMR-CNRS 8181, Université de Lille1, Villeneuve d' Ascq (France); LASIR UMR-CNRS 8516, Université de Lille1, Villeneuve d' Ascq (France)


    The structure of the (66-x)ZnO-xNa{sub 2}O-33.4P{sub 2}O{sub 5} composition line, selected for the development of low-Tg and stable glasses, has been investigated by 1D/2D NMR spectroscopy. If standard 1D {sup 31}P MAS-NMR experiments give access to the Q{sup n} speciation and show the presence of Q{sup 0}, Q{sup 1} and Q{sup 2} sites within the glass structure, application of the homonuclear through-space correlation technique ({sup 31}P DQ-SQ) allows for a more accurate description of the phosphate units. Clear distinction between the Q{sup 1} sites involved in dimmers or in longer chains has been derived from 2D NMR correlation maps and leads to the re-assignment of Q{sup 1} into Q{sup 1,1} and Q{sup 1,2} species. {sup 23}Na and {sup 23}Na({sup 31}P) REDOR MAS-NMR experiments have been used to analyse the Na{sup +} ions distribution and its interaction with the phosphate network. {sup 67}Zn static NMR experiments, performed at very high field, were carried out and suggest a constant Zn{sup 2+} coordination state all along the composition line. The results have been used to discuss the impact of the Zn{sup 2+}/Na{sup +} ratio on the extent of disorder within the glass network expressed in terms of Q{sup n} dismutation equilibrium constant and phosphate chain length distribution. - Highlights: • Structure of zinc alkali pyrophosphate glasses have been analysed by 1D/2D NMR. • 2D {sup 31}P experiments allow to separate Q{sup 1,1} and Q{sup 1,2} species. • {sup 67}Zn static NMR shows a constant signal all along the composition line.

  7. Cation size effects in mixed-ion metaphosphate glasses: structural characterization by multinuclear solid state NMR spectroscopy. (United States)

    Schneider, J; Tsuchida, J; Eckert, H


    Metaphosphate glasses with two monovalent species A(1-x)B(x)PO3 (0 ≤x≤ 1) show mixed-ion effects (MIE) in the dc conductivities and glass transition temperatures, which are strongly dependent on the cation size mismatch between the two mobile species. In the present contribution, mixed-ion metaphosphate glasses based on the cation combinations Cs-Li, Rb-Li, and Cs-Ag, exhibiting particularly large size mismatches, are analyzed by (31)P, (87)Rb, (109)Ag and (133)Cs NMR to determine possible correlations between this mismatch and some of the structural properties critical to the development of the MIE: the local environments around the mobile species and their spatial distribution relative to each other. The results are compared with those obtained in the Na-Ag metaphosphate series, which serves as a reference system, with minimized cation mismatch MIE. The local coordination environments of the Ag(+), Rb(+) and Cs(+) ions follow analogous compositional trends as previously observed in Na-based mixed-ion metaphosphate glasses: for a given cation species A, the average A-O distance shows an expansion/compression when this cation is replaced by a second species B with smaller/bigger ionic radius, respectively. This compositional differentiation of the structural sites for the mobile species may contribute to the MIE. Concerning the relative spatial distribution of the mobile ions, results from (7)Li-(133)Cs (SEDOR) experiments indicate a random mixture of Cs and Li in Cs-Li metaphosphate glasses. While this result is in agreement with one of the fundamental hypotheses of the models proposed to describe the MIE, it is at variance with the observation of various partial cation segregation phenomena observed in Na-based mixed alkali glasses. This result suggests that cation size mismatch is not the decisive parameter in determining segregation or non-statistical mixing of cations in the glass. In the Cs-Ag and Na-Ag glasses, (109)Ag spin-echo NMR reveals a progressive

  8. Characterization of pyrogenic organic matter by 2-dimenstional HETeronucleus CORelation solid-state 13C NMR (HETCOR) spectroscopy (United States)

    Knicker, Heike


    During the last years, increasing evidences are provided that the common view of charcoal as a polyaromatic network is too much simplified. Experiments with model compounds indicated that it represents a heterogeneous mixture of thermally altered biomacromolecules with N, O and likely also S substitutions as common features. If produced from a N-rich feedstock, the so called black nitrogen (BN) has to be considered as an integral part of the aromatic charcoal network. In order to study this network one-dimensional (1D) solid-state nuclear magnetic resonance (NMR) spectroscopy is often applied. However, this technique suffers from broad resonance lines and low resolution. Applying 2D techniques can help but until recently, this was unfeasible for natural organic matter (NOM) due to sensitivity problems and the high complexity of the material. On the other hand, during the last decade, the development of stronger magnetic field instruments and advanced pulse sequences has put them into reach for NOM research. Although 2D NMR spectroscopy has many different applications, all pulse sequences are based on the introduction of a preparation time during which the magnetization of a spin system is adjusted into a state appropriate to whatever properties are to be detected in the indirect dimension. Then, the spins are allowed to evolve with the given conditions and after their additional manipulation during a mixing period the modulated magnetization is detected. Assembling several 1D spectra with incrementing evolution time creates a data set which is two-dimensional in time (t1, t2). Fourier transformation of both dimensions leads to a 2D contour plot correlating the interactions detected in the indirect dimension t1 with the signals detected in the direct dimension t2. The so called solid-state heteronuclear correlation (HETCOR) NMR spectroscopy represents a 2D technique allows the determination which protons are interacting with which carbons. In the present work this

  9. Identification of Imitation Cheese and Imitation Ice Cream Based on Vegetable Fat Using NMR Spectroscopy and Chemometrics

    Directory of Open Access Journals (Sweden)

    Yulia B. Monakhova


    Full Text Available Vegetable oils and fats may be used as cheap substitutes for milk fat to manufacture imitation cheese or imitation ice cream. In this study, 400 MHz nuclear magnetic resonance (NMR spectroscopy of the fat fraction of the products was used in the context of food surveillance to validate the labeling of milk-based products. For sample preparation, the fat was extracted using an automated Weibull-Stoldt methodology. Using principal component analysis (PCA, imitation products can be easily detected. In both cheese and ice cream, a differentiation according to the type of raw material (milk fat and vegetable fat was possible. The loadings plot shows that imitation products were distinguishable by differences in their fatty acid ratios. Furthermore, a differentiation of several types of cheese (Edamer, Gouda, Emmentaler, and Feta was possible. Quantitative data regarding the composition of the investigated products can also be predicted from the same spectra using partial least squares (PLS regression. The models obtained for 13 compounds in cheese (R2 0.75–0.95 and 17 compounds in ice cream (R2 0.83–0.99 (e.g., fatty acids and esters were suitable for a screening analysis. NMR spectroscopy was judged as suitable for the routine analysis of dairy products based on milk or on vegetable fat substitutes.

  10. Effect of 1,10-phenanthroline aromaticity in carboxylic acids:1H NMR spectroscopy, GIAO calculations and thermodynamic properties (United States)

    Machado, Camila M. B.; Santos, Vanessa F. C.; Belarmino, Marcia K. D. L.; França, José A. A.; Moura, Gustavo L. C.; Lima, Nathalia B. D.


    Hydrogen bonding represents a class of chemical interactions, which are directly responsible for several physical properties, such as: energetic stabilities, boiling points, vibrational modes, bond lengths, etc. In this article, we examine from the point of view of 1H NMR spectroscopy and GIAO calculations, the effects associated with the process of formation of the hydrogen bonds as they appear in the chemical shifts of the acidic hydrogens in the complexes between nitrogenated compounds, PHEN, BIPY and DIBIPY, and carboxylic acids, HOOCH, HOOCCH3 and HOOCC6H5. All computational simulations were performed using the quantum chemical methods B3LYP/6-31++G(d,p) and ωB97X-D/def2-TZVP. The 1H NMR spectroscopy results showed that, in both cases, the hydrogen nucleus of the OH group is the most affected in the process of hydrogen bond formation. For the complexes involving PHEN we observed that the hydrogen nucleus is more strongly shielded when compared with this signal in the corresponding complexes involving BIPY and DIBIPY.

  11. Variability of cork from Portuguese Quercus suber studied by solid-state (13)C-NMR and FTIR spectroscopies. (United States)

    Lopes, M H; Barros, A S; Pascoal Neto, C; Rutledge, D; Delgadillo, I; Gil, A M


    A new approach is presented for the study of the variability of Portuguese reproduction cork using solid-state (13)C-NMR spectroscopy and photoacoustic (PAS) FTIR (FTIR-PAS) spectroscopy combined with chemometrics. Cork samples were collected from 12 different geographical sites, and their (13)C-cross-polarization with magic angle spinning (CP/MAS) and FTIR spectra were registered. A large spectral variability among the cork samples was detected by principal component analysis and found to relate to the suberin and carbohydrate contents. This variability was independent of the sample geographical origin but significantly dependent on the cork quality, thus enabling the distinction of cork samples according to the latter property. The suberin content of the cork samples was predicted using multivariate regression models based on the (13)C-NMR and FTIR spectra of the samples as reported previously. Finally, the relationship between the variability of the (13)C-CP/MAS spectra with that of the FTIR-PAS spectra was studied by outer product analysis. This type of multivariate analysis enabled a clear correlation to be established between the peaks assigned to suberin and carbohydrate in the FTIR spectrum and those appearing in the (13)C-CP/MAS spectra.

  12. Identification of Imitation Cheese and Imitation Ice Cream Based on Vegetable Fat Using NMR Spectroscopy and Chemometrics. (United States)

    Monakhova, Yulia B; Godelmann, Rolf; Andlauer, Claudia; Kuballa, Thomas; Lachenmeier, Dirk W


    Vegetable oils and fats may be used as cheap substitutes for milk fat to manufacture imitation cheese or imitation ice cream. In this study, 400 MHz nuclear magnetic resonance (NMR) spectroscopy of the fat fraction of the products was used in the context of food surveillance to validate the labeling of milk-based products. For sample preparation, the fat was extracted using an automated Weibull-Stoldt methodology. Using principal component analysis (PCA), imitation products can be easily detected. In both cheese and ice cream, a differentiation according to the type of raw material (milk fat and vegetable fat) was possible. The loadings plot shows that imitation products were distinguishable by differences in their fatty acid ratios. Furthermore, a differentiation of several types of cheese (Edamer, Gouda, Emmentaler, and Feta) was possible. Quantitative data regarding the composition of the investigated products can also be predicted from the same spectra using partial least squares (PLS) regression. The models obtained for 13 compounds in cheese (R (2) 0.75-0.95) and 17 compounds in ice cream (R (2) 0.83-0.99) (e.g., fatty acids and esters) were suitable for a screening analysis. NMR spectroscopy was judged as suitable for the routine analysis of dairy products based on milk or on vegetable fat substitutes.

  13. International school on high field NMR spectroscopy for solids and liquids

    Energy Technology Data Exchange (ETDEWEB)

    Marion, D.; Meier, B.; Keeler, J.; Berthault, P.; Vedrine, P.; Grandinetti, P.; Delsuc, M.A.; Spiess, H


    The aim of the school is to offer high-level pedagogical courses on a wide range of liquid- and solid-state NMR concepts and techniques: theory, instrumentation (magnets and probes), data acquisition, processing and analysis, measurement of dipolar and quadrupolar couplings, spin relaxation and hyper-polarization. This document gathers only the slides of most presentations.

  14. Quantification of lignin-carbohydrate linkages with high-resolution NMR spectroscopy. (United States)

    Balakshin, Mikhail; Capanema, Ewellyn; Gracz, Hanna; Chang, Hou-min; Jameel, Hasan


    A quantitative approach to characterize lignin-carbohydrate complex (LCC) linkages using a combination of quantitative ¹³C NMR and HSQC 2D NMR techniques has been developed. Crude milled wood lignin (MWLc), LCC extracted from MWLc with acetic acid (LCC-AcOH) and cellulolytic enzyme lignin (CEL) preparations were isolated from loblolly pine (Pinus taeda) and white birch (Betula pendula) woods and characterized using this methodology on a routine 300 MHz NMR spectrometer and on a 950 MHz spectrometer equipped with a cryogenic probe. Structural variations in the pine and birch LCC preparations of different types (MWL, CEL and LCC-AcOH) were elucidated. The use of the high field NMR spectrometer equipped with the cryogenic probe resulted in a remarkable improvement in the resolution of the LCC signals and, therefore, is of primary importance for an accurate quantification of LCC linkages. The preparations investigated showed the presence of different amounts of benzyl ether, γ-ester and phenyl glycoside LCC bonds. Benzyl ester moieties were not detected. Pine LCC-AcOH and birch MWLc preparations were preferable for the analysis of phenyl glycoside and ester LCC linkages in pine and birch, correspondingly, whereas CEL preparations were the best to study benzyl ether LCC structures. The data obtained indicate that pinewood contains higher amounts of benzyl ether LCC linkages, but lower amounts of phenyl glycoside and γ-ester LCC moieties as compared to birch wood.

  15. Self-Association of N-Methylacetamide Examined by Infrared and NMR Spectroscopies (United States)

    Schenck, Heather L.; Hui, KaWai


    These spectroscopic experiments investigate polarity and concentration effects on self-association behavior in N-methylacetamide. Inquiry can be limited to the concentration dependence of hydrogen bonding and estimation of dimerization constant (NMR studies) or to the effect of solvent polarity on extent of hydrogen bonding (IR studies). The…

  16. Wild salmon authenticity can be predicted by 1H-NMR spectroscopy

    NARCIS (Netherlands)

    Capuano, E.; Lommen, A.; Heenan, S.P.; Dura, de la A.; Rozijn, M.; Ruth, van S.M.


    The combination of 1H NMR fingerprinting of muscle lipids from fresh and processed (frozen, canned and smoked) Atlantic salmon (Salmo salar) with supervised multivariate analysis was applied to differentiate wild and farmed fish. Soft Independent Modelling of Class Analogy (SIMCA) allowed classifica

  17. 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.


    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, r

  18. Quantitative analysis of chemically modified starches by H-1-NMR spectroscopy

    NARCIS (Netherlands)

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


    A quantitative H-1-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,

  19. Microtesla NMR J-coupling spectroscopy with an unshielded atomic magnetometer

    CERN Document Server

    Bevilacqua, Giuseppe; Baranga, Andrei Ben-Amar; Dancheva, Yordanka; Rossi, Claudio


    We present experimental data and theoretical interpretation of NMR spectra of remotely magnetized samples, detected in an unshielded environment by means of a differential atomic magnetometer. The measurements are performed in an ultra-low-field at an intermediate regime, where the J-coupling and the Zeeman energies have comparable values and produce rather complex line sets, which are satisfactorily interpreted.

  20. Microtesla NMR J-coupling spectroscopy with an unshielded atomic magnetometer. (United States)

    Bevilacqua, Giuseppe; Biancalana, Valerio; Baranga, Andrei Ben-Amar; Dancheva, Yordanka; Rossi, Claudio


    We present experimental data and theoretical interpretation of NMR spectra of remotely magnetized samples, detected in an unshielded environment by means of a differential atomic magnetometer. The measurements are performed in an ultra-low-field at an intermediate regime, where the J-coupling and the Zeeman energies have comparable values and produce rather complex line sets, which are satisfactorily interpreted.

  1. In situ NMR spectroscopy of supercapacitors: insight into the charge storage mechanism. (United States)

    Wang, Hao; Forse, Alexander C; Griffin, John M; Trease, Nicole M; Trognko, Lorie; Taberna, Pierre-Louis; Simon, Patrice; Grey, Clare P


    Electrochemical capacitors, commonly known as supercapacitors, are important energy storage devices with high power capabilities and long cycle lives. Here we report the development and application of in situ nuclear magnetic resonance (NMR) methodologies to study changes at the electrode-electrolyte interface in working devices as they charge and discharge. For a supercapacitor comprising activated carbon electrodes and an organic electrolyte, NMR experiments carried out at different charge states allow quantification of the number of charge storing species and show that there are at least two distinct charge storage regimes. At cell voltages below 0.75 V, electrolyte anions are increasingly desorbed from the carbon micropores at the negative electrode, while at the positive electrode there is little change in the number of anions that are adsorbed as the voltage is increased. However, above a cell voltage of 0.75 V, dramatic increases in the amount of adsorbed anions in the positive electrode are observed while anions continue to be desorbed at the negative electrode. NMR experiments with simultaneous cyclic voltammetry show that supercapacitor charging causes marked changes to the local environments of charge storing species, with periodic changes of their chemical shift observed. NMR calculations on a model carbon fragment show that the addition and removal of electrons from a delocalized system should lead to considerable increases in the nucleus-independent chemical shift of nearby species, in agreement with our experimental observations.

  2. Fast screening of turkish olive oil by NMR spectroscopy for geographical determination and discrimination purposes

    Directory of Open Access Journals (Sweden)

    Ok, S.


    Full Text Available The main goal of this study is to rapidly screen olive oil contents by acquiring one dimensional (1D 1H NMR spectra of 38 samples from Turkey, The Middle East, and Libya. The quantitative analysis of the 1H NMR helped in distinguishing the geographical origin of the olive oil samples. The intensity of 1H NMR variables was submitted to the statistical method, analysis of variance (ANOVA. As a result of combining the NMR data and ANOVA, olive oils were discriminated based on regional origin rather than province. This less time consuming discriminative screening by 1H NMR does not require any further analysis of the olive oil, including oxidative stability measurements or gas chromatography. The possibility of determining authenticity, even in an olive growing area of a small village was also shown. The two-dimensional (2D non-invasive 1H DOSY NMR experiment, known as “NMR chromatography”, was used to determine the olive oil sub-fraction.El objetivo es conocer de manera rápida el contenido de aceite de oliva mediante la adquisición de espectros de 1H RMN de una dimensión (1D. El estudio se ha realizado con 38 muestras procedentes de Turquía, Oriente Medio y Libia. El análisis cuantitativo de 1H RMN ayudó a distinguir el origen geográfico de las muestras de aceites de oliva. La intensidad de las señales de 1H RMN se sometió a estudio estadístico mediante análisis de varianza (ANOVA. Como resultado de la combinación de los datos de RMN y ANOVA, los aceites de oliva fueron discriminados por origen regional antes que por provincia. Esta técnica de discriminación rápida por 1H RMN no requiere ningún análisis adicional de los aceites de oliva mediante estudios de estabilidad a la oxidación o cromatografía de gases. También se demostró la posibilidad de determinar la autenticidad, incluso en el área de cultivo del olivo de una pequeña aldea. Los experimentos de RMN bi-dimensionales (2D no invasiva 1H DOSY, conocido como

  3. Comprehensive multiphase NMR spectroscopy: Basic experimental approaches to differentiate phases in heterogeneous samples (United States)

    Courtier-Murias, Denis; Farooq, Hashim; Masoom, Hussain; Botana, Adolfo; Soong, Ronald; Longstaffe, James G.; Simpson, Myrna J.; Maas, Werner E.; Fey, Michael; Andrew, Brian; Struppe, Jochem; Hutchins, Howard; Krishnamurthy, Sridevi; Kumar, Rajeev; Monette, Martine; Stronks, Henry J.; Hume, Alan; Simpson, André J.


    Heterogeneous samples, such as soils, sediments, plants, tissues, foods and organisms, often contain liquid-, gel- and solid-like phases and it is the synergism between these phases that determine their environmental and biological properties. Studying each phase separately can perturb the sample, removing important structural information such as chemical interactions at the gel-solid interface, kinetics across boundaries and conformation in the natural state. In order to overcome these limitations a Comprehensive Multiphase-Nuclear Magnetic Resonance (CMP-NMR) probe has been developed, and is introduced here, that permits all bonds in all phases to be studied and differentiated in whole unaltered natural samples. The CMP-NMR probe is built with high power circuitry, Magic Angle Spinning (MAS), is fitted with a lock channel, pulse field gradients, and is fully susceptibility matched. Consequently, this novel NMR probe has to cover all HR-MAS aspects without compromising power handling to permit the full range of solution-, gel- and solid-state experiments available today. Using this technology, both structures and interactions can be studied independently in each phase as well as transfer/interactions between phases within a heterogeneous sample. This paper outlines some basic experimental approaches using a model heterogeneous multiphase sample containing liquid-, gel- and solid-like components in water, yielding separate 1H and 13C spectra for the different phases. In addition, 19F performance is also addressed. To illustrate the capability of 19F NMR soil samples, containing two different contaminants, are used, demonstrating a preliminary, but real-world application of this technology. This novel NMR approach possesses a great potential for the in situ study of natural samples in their native state.

  4. Determination of the structural changes by Raman and {sup 13}C CP/MAS NMR spectroscopy on native corn starch with plasticizers

    Energy Technology Data Exchange (ETDEWEB)

    Cozar, O. [Academy of Romanian Scientists, Splaiul Independentei 54, 050094, Bucharest, Romania and National Institute of Research-Development for Machines and Installations Designed to Agriculture and Food Industry - INMA Bucureşti - Cluj-Napoca Branch (Romania); Filip, C.; Tripon, C. [National Institute for Research and Development of Isotopic and Molecular Technologies, 65-103 Donath, 400293 Cluj-Napoca (Romania); Cioica, N.; Coţa, C.; Nagy, E. M. [National Institute of Research-Development for Machines and Installations Designed to Agriculture and Food Industry - INMA Bucureşti - Cluj-Napoca Branch, RO-400458 Cluj-Napoca (Romania)


    The plasticizing - antiplasticizing effect of water and glycerol contents on native corn starch samples is investigated by FT-Raman and {sup 13}C CP/MAS NMR spectroscopy. The presence of both amorphous and crystalline structural phases was evidenced in pure native corn starch and also in the samples containing plasticizers. Among the crystalline starch structures, the A- and V- types were suggested by CP/MAS NMR spectra.

  5. Characterisation of PEGylated PLGA nanoparticles comparing the nanoparticle bulk to the particle surface using UV/vis spectroscopy, SEC, {sup 1}H NMR spectroscopy, and X-ray photoelectron spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Spek, S.; Haeuser, M. [Institute of Pharmaceutical Technology and Biopharmacy, University of Muenster, Corrensstrasse 48, 48149 Muenster (Germany); Schaefer, M.M. [nanoAnalytics, Heisenbergstrasse 11, 48149 Muenster (Germany); Langer, K., E-mail: [Institute of Pharmaceutical Technology and Biopharmacy, University of Muenster, Corrensstrasse 48, 48149 Muenster (Germany)


    Graphical abstract: - Highlights: • We compared nanoparticles prepared on the basis of PLGA and PEG–PLGA for their polymeric composition in the particle bulk and on the surface. • We validated three analytical methods (UV/vis, SEC, {sup 1}H NMR) for quantification of the polymeric stabiliser PVA and {sup 1}H NMR for the quantification of PEG. • In the case of PEG–PLGA as starting material we observed significant PEG contents not only on the surface but even in the particle bulk. • We observed an unexpected accumulation of the polymeric stabiliser PVA on PEGylated particle surfaces. - Abstract: Hypothesis: The bulk and the surface structure of nanoparticles based on poly(lactic-co-glycolic acid) (PLGA) and PLGA–PEG copolymer is expected to consist of different polymer compositions. An enrichment of hydrophilic PEG on the surface in combination with an accumulation of PLGA in the bulk is anticipated. Hence, the imbalance between bulk and surface composition should be detectable by suitable analytical methods. Experiments: Nanoparticles were assembled using an emulsion-evaporation method with polyvinyl alcohol (PVA) as stabiliser. Mixtures of PLGA and PLGA–PEG copolymer were applied to achieve variably PEGylated nanoparticles. The nanoparticle composition was analysed with respect to PLGA, PVA and PEG, comparing the polymer content of the nanoparticle bulk to the surface. For the bulk, PVA was quantified by a UV/vis spectroscopic method as well as size exclusion chromatography (SEC), and {sup 1}H nuclear magnetic resonance (NMR) spectroscopy. PEG determination of the bulk was carried out using quantitative {sup 1}H NMR spectroscopy. Surface composition was investigated by X-ray photoelectron spectroscopy (XPS). Findings: For the characterisation of the polymer composition {sup 1}H NMR, SEC, and XPS-methods were successfully established and validated. Unexpectedly, a significant PEG content was detected within the particle bulk. The comparison of

  6. Solution state structure determination of silicate oligomers by 29SI NMR spectroscopy and molecular modeling. (United States)

    Cho, Herman; Felmy, Andrew R; Craciun, Raluca; Keenum, J Patrick; Shah, Neil; Dixon, David A


    Evidence for nine new solution state silicate oligomers has been discovered by (29)Si NMR homonuclear correlation experiments of (29)Si-enriched samples. In addition to enhancing signal sensitivity, the isotopic enrichment increases the probability of the (29)Si-(29)Si two-bond scalar couplings that are necessary for the observation of internuclear correlations in 2-D experiments. The proposed assignments are validated by comparisons of experimental and simulated cross-peaks obtained with high digital resolution. The internuclear connectivity indicated by the NMR data suggests that several of these oligomers can have multiple stereoisomers, including conformers and/or diastereomers. The stabilities of these oligomers and their possible stereoisomers have been investigated by electronic structure calculations.

  7. Design and application of robust rf pulses for toroid cavity NMR spectroscopy

    CERN Document Server

    Skinner, Thomas E; Woelk, Klaus; Gershenzon, Naum I; Glaser, Steffen J


    We present robust radio frequency (rf) pulses that tolerate a factor of six inhomogeneity in the B1 field, significantly enhancing the potential of toroid cavity resonators for NMR spectroscopic applications. Both point-to-point (PP) and unitary rotation (UR) pulses were optimized for excitation, inversion, and refocusing using the gradient ascent pulse engineering (GRAPE) algorithm based on optimal control theory. In addition, the optimized parameterization (OP) algorithm applied to the adiabatic BIR-4 UR pulse scheme enabled ultra-short (50 microsec) pulses with acceptable performance compared to standard implementations. OP also discovered a new class of non-adiabatic pulse shapes with improved performance within the BIR-4 framework. However, none of the OP-BIR4 pulses are competitive with the more generally optimized UR pulses. The advantages of the new pulses are demonstrated in simulations and experiments. In particular, the DQF COSY result presented here represents the first implementation of 2D NMR sp...

  8. Structural studies of proteins by paramagnetic solid-state NMR spectroscopy (United States)

    Jaroniec, Christopher P.


    Paramagnetism-based nuclear pseudocontact shifts and spin relaxation enhancements contain a wealth of information in solid-state NMR spectra about electron-nucleus distances on the ∼20 Å length scale, far beyond that normally probed through measurements of nuclear dipolar couplings. Such data are especially vital in the context of structural studies of proteins and other biological molecules that suffer from a sparse number of experimentally-accessible atomic distances constraining their three-dimensional fold or intermolecular interactions. This perspective provides a brief overview of the recent developments and applications of paramagnetic magic-angle spinning NMR to biological systems, with primary focus on the investigations of metalloproteins and natively diamagnetic proteins modified with covalent paramagnetic tags.

  9. Structural analysis of complex saponins of Balanites aegyptiaca by 800 MHz 1H NMR spectroscopy. (United States)

    Staerk, Dan; Chapagain, Bishnu P; Lindin, Therese; Wiesman, Zeev; Jaroszewski, Jerzy W


    The main saponin (1) present in the mesocarp of Balanites aegyptiaca fruit is a mixture of 22R and 22S epimers of 26-(O-beta-D-glucopyranosyl)-3-beta-[4-O-(beta-D-glucopyranosyl)-2-O-(alpha-L-rhamnopyranosyl)-beta-D-glucopyranosyloxy]-22,26-dihydroxyfurost-5-ene. This structure differs from a previously reported saponin isolated from this source by the site of attachment of the rhamnosyl residue, and presumably represents a structural revision of the latter. The main saponin (2) present in the kernel is a xylopyranosyl derivative of 1. The use of high-field NMR enabled the practically complete assignment of 1H and 13C chemical shifts of these complex saponins, existing as a mixture of C-22 epimers. Moreover, the work represents a new approach to structural elucidation of saponins: direct preparative-scale HPLC-RID of crude extracts followed by high-field NMR investigations supported by ESI-MSn.

  10. SIMPSON: a general simulation program for solid-state NMR spectroscopy. (United States)

    Bak, M; Rasmussen, J T; Nielsen, N C


    A computer program for fast and accurate numerical simulation of solid-state NMR experiments is described. The program is designed to emulate a NMR spectrometer by letting the user specify high-level NMR concepts such as spin systems, nuclear spin interactions, RF irradiation, free precession, phase cycling, coherence-order filtering, and implicit/explicit acquisition. These elements are implemented using the Tcl scripting language to ensure a minimum of programming overhead and direct interpretation without the need for compilation, while maintaining the flexibility of a full-featured programming language. Basically, there are no intrinsic limitations to the number of spins, types of interactions, sample conditions (static or spinning, powders, uniaxially oriented molecules, single crystals, or solutions), and the complexity or number of spectral dimensions for the pulse sequence. The applicability ranges from simple 1D experiments to advanced multiple-pulse and multiple-dimensional experiments, series of simulations, parameter scans, complex data manipulation/visualization, and iterative fitting of simulated to experimental spectra. A major effort has been devoted to optimizing the computation speed using state-of-the-art algorithms for the time-consuming parts of the calculations implemented in the core of the program using the C programming language. Modification and maintenance of the program are facilitated by releasing the program as open source software (General Public License) currently at The general features of the program are demonstrated by numerical simulations of various aspects for REDOR, rotational resonance, DRAMA, DRAWS, HORROR, C7, TEDOR, POST-C7, CW decoupling, TPPM, F-SLG, SLF, SEMA-CP, PISEMA, RFDR, QCPMG-MAS, and MQ-MAS experiments.

  11. Chemical tagging of chlorinated phenols for their facile detection and analysis by NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Valdez, Carlos A. [Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States); Leif, Roald N. [Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)


    A derivatization method that employs diethyl (bromodifluoromethyl) phosphonate (DBDFP) to efficiently tag the endocrine disruptor pentachlorophenol (PCP) and other chlorinated phenols (CPs) along with their reliable detection and analysis by NMR is presented. The method accomplishes the efficient alkylation of the hydroxyl group in CPs with the difluoromethyl (CF2H) moiety in extremely rapid fashion (5 min), at room temperature and in an environmentally benign manner. The approach proved successful in difluoromethylating a panel of 18 chlorinated phenols, yielding derivatives that displayed unique 1H, 19F NMR spectra allowing for the clear discrimination between isomerically related CPs. Due to its biphasic nature, the derivatization can be applied to both aqueous and organic mixtures where the analysis of CPs is required. Furthermore, the methodology demonstrates that PCP along with other CPs can be selectively derivatized in the presence of other various aliphatic alcohols, underscoring the superiority of the approach over other general derivatization methods that indiscriminately modify all analytes in a given sample. The present work demonstrates the first application of NMR on the qualitative analysis of these highly toxic and environmentally persistent species.

  12. Conformational Analysis of Triazine Dendrimers: Using NMR Spectroscopy To Probe the Choreography of a Dendrimer's Dance. (United States)

    Moreno, Karlos X; Simanek, Eric E


    One-dimensional (1D) and two-dimensional (2D) NMR studies are used to probe the conformation of a melamine dendrimer bearing unique NMR signals from the core to the periphery. Four conceptual anchors for dendrimer conformation emerge from these experiments. First, changes in isomer populations observed by (1)H NMR reveal the onset of globular structure. Second, NOE complexity emerges with globular structure: variable temperature NOESY studies show that the peripheral groups, BOC-protected aliphatic amines, fold back into the globular core of the macromolecule at 75 degrees C in DMSO-d(6). Third, variable temperature coefficients measured for NH protons suggest that solvent is largely excluded from the interior of the dendrimer: the carbamate NH groups of the periphery are most sensitive to temperature while the NHs nearest the core show little temperature dependence. Conformation is influenced by solvent choice: backfolding is observed in DMSO-d(6), but not in either CDCl(3) or CD(3)OD. Finally, relaxation studies show that peripheral groups are more dynamic than groups at the core. These anchors consolidate observations made by many groups on disparate systems within a common architecture.

  13. NMR doesn't lie or how solid-state NMR spectroscopy contributed to a better understanding of the nature and function of soil organic matter (Philippe Duchaufour Medal Lecture) (United States)

    Knicker, Heike


    "Nuclear magnetic resonance (NMR) does not lie". More than anything else, this statement of a former colleague and friend has shaped my relation to solid-state NMR spectroscopy. Indeed, if this technique leads to results which contradict the expectations, it is because i) some parts of the instrument are broken, ii) maladjustment of the acquisition parameters or iii) wrong preparation or confusion of samples. However, it may be even simpler, namely that the expectations were wrong. Of course, for researchers, the latter is the most interesting possibility since it forces to reassess accepted views and to search for new explanations. As my major analytical tool, NMR spectroscopy has confronted me with this challenge often enough to turn this issue into the main subject of my talk and to share with the audience how it formed my understanding of function and nature of soil organic matter (SOM). Already shortly after its introduction into soil science in the 1980's, the data obtained with solid-state 13C NMR spectroscopy opened the stage for ongoing discussions, since they showed that in humified SOM aromatic carbon is considerably less important than previously thought. This finding had major implications regarding the understanding of the origin of SOM and the mechanisms by which it is formed. Certainly, the discrepancy between the new results and previous paradigms contributed to mistrust in the reliability of solid-state NMR techniques. The respective discussion has survived up to our days, although already in the 1980's and 1990's fundamental studies could demonstrate that quantitative solid-state NMR data can be obtained if i) correct acquisition parameters are chosen, ii) the impact of paramagnetic compounds is reduced and iii) the presence of soot in soils can be excluded. On the other hand, this mistrust led to a detailed analysis of the impact of paramagnetics on the NMR behavior of C groups which then improved our understanding of the role of carbohydrates

  14. Characterization of polysulfone and polysulfone/vanillin microcapsules by 1H NMR spectroscopy, solid-state 13C CP/MAS-NMR spectroscopy, and N2 adsorption-desorption analyses. (United States)

    Peña, Brisa; de Ménorval, Louis-Charles; Garcia-Valls, Ricard; Gumí, Tània


    Textile detergent and softener industries have incorporated perfume microencapsulation technology to improve their products. Perfume encapsulation allows perfume protection until use and provides a long-lasting fragrance release. But, certain industrial microcapsules show low encapsulation capacity and low material stability. Polysulfone capsules have been already proposed to solve these drawbacks. Among them, PSf/Vanillin capsules were considered as a desirable system. They present both good material stability and high encapsulation capacity. However, several factors such as the final location of the perfume in the polymeric matrix, the aggregation state that it has in the capsule and its interaction with the capsule components have not been studied yet. These factors can provide vast information about the capsule performance and its improvement. With the aim to characterize these parameters, the physical and chemical properties of PSf/Vanillin capsules have been investigated by nuclear magnetic resonance (NMR) spectroscopy, scanning electron microscopy (SEM), atomic force microscopy (AFM), and N(2) adsorption-desorption measurements. AFM micrograph and N(2) isotherms confirm that the presence of vanillin modify the physical structure of PSf/Vanillin microcapsules as it is trapped in the capsule porosity. NMR results show that vanillin is present in solid state in PSf/Vanillin microcapsules.

  15. Characterization of partitioning relevant lanthanide and actinide complexes by NMR spectroscopy; Charakterisierung von partitioningrelevanten Lanthaniden- und Actinidenkomplexen mittels NMR-Spektroskopie

    Energy Technology Data Exchange (ETDEWEB)

    Adam, Christian


    In the present work the interaction of N-donor ligands, such as 2,6-Bis(5,6-dipropyl-1,2,4-triazin-3-yl)pyridine (nPrBTP) and 2,6-Bis(5-(2,2-dimethylpropyl)1H-pyrazol)-3-yl-pyridine (C5-BPP), with trivalent lanthanide and actinide ions was studied. Ligands of this type show a high selectivity for the separation of trivalent actinide ions over lanthanides from nitric acid solutions. However, the reason for this selectivity, which is crucial for future partitioning and transmutation strategies for radioactive wastes, is still unknown. So far, the selectivity of some N-donor ligands is supposed to be an effect of an increased covalency in the actinide-ligand bond, compared to the lanthanide compounds. NMR spectroscopy on paramagnetic metal complexes is an excellent tool for the elucidation of bonding modes. The overall paramagnetic chemical shift consists of two contributions, the Fermi Contact Shift (FCS), due to electron spin delocalisation through covalent bonds, and the Pseudo Contact Shift (PCS), which describes the dipolar coupling of the electron magnetic moment and the nuclear spin. By assessing the FCS share in the paramagnetic shift, the degree of covalency in the metal-ligand bond can be gauged. Several methods to discriminate FCS and PCS have been used on the data of the nPrBTP- and C5-BPP-complexes and were evaluated regarding their applicability on lanthanide and actinide complexes with N-donor ligands. The study comprised the synthesis of all Ln(III) complexes with the exceptions of Pm(III) and Gd(III) as well as the Am(III) complex as a representative of the actinide series with both ligands. All complexes were fully characterised ({sup 1}H, {sup 13}C and {sup 15}N spectra) using NMR spectroscopy. By isotope enrichment with the NMR-active {sup 15}N in positions 8 and 9 in both ligands, resonance signals of these nitrogen atoms were detected for all complexes. The Bleaneymethod relies on different temperature dependencies for FCS (T{sup -1}) and PCS (T

  16. The Influence of Plant Litter on Soil Water Repellency: Insight from 13C NMR Spectroscopy.

    Directory of Open Access Journals (Sweden)

    Gaspare Cesarano

    Full Text Available Soil water repellency (SWR, i.e. reduced affinity for water owing to the presence of organic hydrophobic coatings on soil particles has relevant hydrological implications because low rates of infiltration enhance water runoff, and untargeted diffusion of fertilizers and pesticides. Previous studies investigated the occurrence of SWR in ecosystems with different vegetation cover but did not clarify its relationships with litter biochemical quality. Here, we investigated the capability of different plant litter types to induce SWR by using fresh and decomposed leaf materials from 12 species, to amend a model sandy soil over a year-long microcosm experiment. Water repellency, measured by the Molarity of an Ethanol Droplet (MED test, was tested for the effects of litter species and age, and compared with litter quality assessed by 13C-CPMAS NMR in solid state and elemental chemical parameters. All litter types were highly water repellent, with MED values of 18% or higher. In contrast, when litter was incorporated into the soil, only undecomposed materials induced SWR, but with a large variability of onset and peak dynamics among litter types. Surprisingly, SWR induced by litter addition was unrelated to the aliphatic fraction of litter. In contrast, lignin-poor but labile C-rich litter, as defined by O-alkyl C and N-alkyl and methoxyl C of 13C-CPMAS NMR spectral regions, respectively, induced a stronger SWR. This study suggests that biochemical quality of plant litter is a major controlling factor of SWR and, by defining litter quality with 13C-CPMAS NMR, our results provide a significant novel contribution towards a full understanding of the relationships between plant litter biochemistry and SWR.

  17. The Influence of Plant Litter on Soil Water Repellency: Insight from 13C NMR Spectroscopy. (United States)

    Cesarano, Gaspare; Incerti, Guido; Bonanomi, Giuliano


    Soil water repellency (SWR, i.e. reduced affinity for water owing to the presence of organic hydrophobic coatings on soil particles) has relevant hydrological implications because low rates of infiltration enhance water runoff, and untargeted diffusion of fertilizers and pesticides. Previous studies investigated the occurrence of SWR in ecosystems with different vegetation cover but did not clarify its relationships with litter biochemical quality. Here, we investigated the capability of different plant litter types to induce SWR by using fresh and decomposed leaf materials from 12 species, to amend a model sandy soil over a year-long microcosm experiment. Water repellency, measured by the Molarity of an Ethanol Droplet (MED) test, was tested for the effects of litter species and age, and compared with litter quality assessed by 13C-CPMAS NMR in solid state and elemental chemical parameters. All litter types were highly water repellent, with MED values of 18% or higher. In contrast, when litter was incorporated into the soil, only undecomposed materials induced SWR, but with a large variability of onset and peak dynamics among litter types. Surprisingly, SWR induced by litter addition was unrelated to the aliphatic fraction of litter. In contrast, lignin-poor but labile C-rich litter, as defined by O-alkyl C and N-alkyl and methoxyl C of 13C-CPMAS NMR spectral regions, respectively, induced a stronger SWR. This study suggests that biochemical quality of plant litter is a major controlling factor of SWR and, by defining litter quality with 13C-CPMAS NMR, our results provide a significant novel contribution towards a full understanding of the relationships between plant litter biochemistry and SWR.

  18. Conformational Study of 8-C-glucosyl-prunetin by Dynamic NMR Spectroscopy

    Institute of Scientific and Technical Information of China (English)


    By means of variable temperature NMR spectra, conformation of 8-C-glucosyl prunetin,isolated from the leaves of Dalbergia hainanensis (Leguminosae), was studied. The restricted rotation around the C (sp3)-C (sp2) bond in the C-glucosides isoflavonoid results in two main conformers (syn and anti). With the help of MM calculation, the preferred conformation A has H-I" gauche to the 7-OCH3. The barrier to rotation was 18.1 kcal/mol. This result agrees with the calculated value 16.2 kcal/mol of free energy of activation for the interconversion between the conformers.

  19. NMR diffusion spectroscopy for the characterization of multicomponent hydrogen-bonded assemblies in solution

    NARCIS (Netherlands)

    Timmerman, Peter; Weidmann, Jean-Luc; Jolliffe, Katrina A.; Prins, Leonard J.; Reinhoudt, David N.; Shinkai, Seiji; Frish, Limor; Cohen, Yoram


    NMR diffusion measurements on 10 different multicomponent hydrogen-bonded assemblies, viz. the three single rosettes SR1–SR3 ( 13· 2a3, 13· 2b3, 13· 2c3) the double rosettes DR1–DR5 ( 3a3· 2a6, 3b3· 2b6, 3c3· 2a6, 3d3· 2a6, 3e3· 2a6), and DR6 ( 4a3· 16), and the tetrarosette TR ( 53· 2a12) are descr

  20. Conformational Study of 8—C—glucosyl—prunetin by Dynamic NMR Spectroscopy

    Institute of Scientific and Technical Information of China (English)

    PeiChengZHANG; YingHongWANG; 等


    By means of variable temperature NMR spectra,conformation of 8-C-glucosyl prunetin, isolated from the leaves of Dalbergia hainanensis (Leguminosae), was studied. The restricted rotation around the C(sp3)-C(sp2) bond in the C-glucosides isoflavonoid results in two main conformers (syn and anti). With the help of MM calculation, the preferred conformation A has H-1″ gauche to the 7-OCH3. The barrier to rotation was 18.1 kcal/mol. This result agrees with the calculated value 16.2 kcal/mol of free energy of activation for the interconversion between the conformers.

  1. Comparative Investigation of the Ionicity of Aprotic and Protic Ionic Liquids in Molecular Solvents by using Conductometry and NMR Spectroscopy. (United States)

    Thawarkar, Sachin; Khupse, Nageshwar D; Kumar, Anil


    Electrical conductivity (σ), viscosity (η), and self-diffusion coefficient (D) measurements of binary mixtures of aprotic and protic imidazolium-based ionic liquids with water, dimethyl sulfoxide, and ethylene glycol were measured from 293.15 to 323.15 K. The temperature dependence study reveals typical Arrhenius behavior. The ionicities of aprotic ionic liquids were observed to be higher than those of protic ionic liquids in these solvents. The aprotic ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate, [bmIm][BF4 ], displays 100 % ionicity in both water and ethylene glycol. The protic ionic liquids in both water and ethylene glycol are classed as good ionic candidates, whereas in DMSO they are classed as having a poor ionic nature. The solvation dynamics of the ionic species of the ionic liquids are illustrated on the basis of the (1) H NMR chemical shifts of the ionic liquids. The self-diffusion coefficients D of the cation and anion of [HmIm][CH3 COO] in D2 O and in [D6 ]DMSO are determined by using (1) H nuclei with pulsed field gradient spin-echo NMR spectroscopy.

  2. Combined Reversed Phase HPLC, Mass Spectrometry, and NMR Spectroscopy for a Fast Separation and Efficient Identification of Phosphatidylcholines

    Directory of Open Access Journals (Sweden)

    Jan Willmann


    Full Text Available In respect of the manifold involvement of lipids in biochemical processes, the analysis of intact and underivatised lipids of body fluids as well as cell and tissue extracts is still a challenging task, if detailed molecular information is required. Therefore, the advantage of combined use of high-pressure liquid chromatography (HPLC, mass spectrometry (MS, and nuclear magnetic resonance (NMR spectroscopy will be shown analyzing three different types of extracts of the ubiquitous membrane component phosphatidylcholine. At first, different reversed phase modifications were tested on phosphatidylcholines (PC with the same effective carbon number (ECN for their applicability in lipid analysis. The results were taken to improve the separation of three natural PC extract types and a new reversed phase (RP-HPLC method was developed. The individual species were characterized by one- and two-dimensional NMR and positive or negative ion mode quadrupole time of flight (q-TOF-MS as well as MS/MS techniques. Furthermore, ion suppression effects during electrospray ionisation (ESI, difficulties, limits, and advantages of the individual analytical techniques are addressed.

  3. Characterization of Alginates by Nuclear Magnetic Resonance (NMR) and Vibrational Spectroscopy (IR, NIR, Raman) in Combination with Chemometrics. (United States)

    Jensen, Henrik Max; Larsen, Flemming Hofmann; Engelsen, Søren Balling


    This chapter describes three different spectroscopic methods for structural characterization of the commercial important hydrocolloid alginate extracted from brown seaweed. The "golden" reference method for characterization of the alginate structure is (1)H liquid-state NMR of depolymerized alginate polymers using a stepwise hydrolysis. Having implemented this method, predictive and rapid non-destructive methods using vibrational spectroscopy and chemometrics can be developed. These methods can predict the M/G-ratio of the intact alginate powder with at least the same precision and accuracy as the reference method in a fraction of the time that is required to measure the alginate using the reference method. The chapter also demonstrates how solid-state (13)C CP/MAS NMR can be used to determine the M/G ratio on the intact sample by the use of multivariate chemometrics and how this method shares the characteristics of the solid-state non-destructive IR method rather than its liquid-state counterpart.

  4. Intermolecular alignment in Y145Stop human prion protein amyloid fibrils probed by solid-state NMR spectroscopy. (United States)

    Helmus, Jonathan J; Surewicz, Krystyna; Apostol, Marcin I; Surewicz, Witold K; Jaroniec, Christopher P


    The Y145Stop mutant of human prion protein, huPrP23-144, has been linked to PrP cerebral amyloid angiopathy, an inherited amyloid disease, and also serves as a valuable in vitro model for investigating the molecular basis of amyloid strains. Prior studies of huPrP23-144 amyloid by magic-angle-spinning (MAS) solid-state NMR spectroscopy revealed a compact β-rich amyloid core region near the C-terminus and an unstructured N-terminal domain. Here, with the focus on understanding the higher-order architecture of huPrP23-144 fibrils, we probed the intermolecular alignment of β-strands within the amyloid core using MAS NMR techniques and fibrils formed from equimolar mixtures of (15)N-labeled protein and (13)C-huPrP23-144 prepared with [1,3-(13)C(2)] or [2-(13)C]glycerol. Numerous intermolecular correlations involving backbone atoms observed in 2D (15)N-(13)C spectra unequivocally suggest an overall parallel in-register alignment of the β-sheet core. Additional experiments that report on intermolecular (15)N-(13)CO and (15)N-(13)Cα dipolar couplings yielded an estimated strand spacing that is within ∼10% of the distances of 4.7-4.8 Å typical for parallel β-sheets.

  5. Investigating sorption on iron-oxyhydroxide soil minerals by solid-state NMR spectroscopy: a 6Li MAS NMR study of adsorption and absorption on goethite

    DEFF Research Database (Denmark)

    Nielsen, Ulla Gro; Paik, Younkee; Julmis, Keinia;


    High-resolution 2H MAS NMR spectra can be obtained for nanocrystalline particles of goethite (alpha-FeOOH, particle size approximately 4-10 nm) at room temperature, facilitating NMR studies of sorption under environmentally relevant conditions. Li sorption was investigated as a function of pH, th...

  6. Determination of structural topology of a membrane protein in lipid bilayers using polarization optimized experiments (POE) for static and MAS solid state NMR spectroscopy. (United States)

    Mote, Kaustubh R; Gopinath, T; Veglia, Gianluigi


    The low sensitivity inherent to both the static and magic angle spinning techniques of solid-state NMR (ssNMR) spectroscopy has thus far limited the routine application of multidimensional experiments to determine the structure of membrane proteins in lipid bilayers. Here, we demonstrate the advantage of using a recently developed class of experiments, polarization optimized experiments, for both static and MAS spectroscopy to achieve higher sensitivity and substantial time-savings for 2D and 3D experiments. We used sarcolipin, a single pass membrane protein, reconstituted in oriented bicelles (for oriented ssNMR) and multilamellar vesicles (for MAS ssNMR) as a benchmark. The restraints derived by these experiments are then combined into a hybrid energy function to allow simultaneous determination of structure and topology. The resulting structural ensemble converged to a helical conformation with a backbone RMSD ~0.44 Å, a tilt angle of 24° ± 1°, and an azimuthal angle of 55° ± 6°. This work represents a crucial first step toward obtaining high-resolution structures of large membrane proteins using combined multidimensional oriented solid-state NMR and magic angle spinning solid-state NMR.

  7. Metabolic analysis of elicited cell suspension cultures of Cannabis sativa L. by (1)H-NMR spectroscopy. (United States)

    Pec, Jaroslav; Flores-Sanchez, Isvett Josefina; Choi, Young Hae; Verpoorte, Robert


    Cannabis sativa L. plants produce a diverse array of secondary metabolites. Cannabis cell cultures were treated with jasmonic acid (JA) and pectin as elicitors to evaluate their effect on metabolism from two cell lines using NMR spectroscopy and multivariate data analysis. According to principal component analysis (PCA) and partial least square-discriminant analysis (PLS-DA), the chloroform extract of the pectin-treated cultures were more different than control and JA-treated cultures; but in the methanol/water extract the metabolome of the JA-treated cells showed clear differences with control and pectin-treated cultures. Tyrosol, an antioxidant metabolite, was detected in cannabis cell cultures. The tyrosol content increased after eliciting with JA.

  8. Solid state 13C NMR and FT-IR spectroscopy of the cocoon silk of two common spiders (United States)

    Bramanti, Emilia; Catalano, Donata; Forte, Claudia; Giovanneschi, Mario; Masetti, Massimo; Veracini, Carlo Alberto


    The structure of the silk from cocoons of two common spiders, Araneus diadematus (family Araneidae) and Achaearanea tepidariorum (family Theridiidae) was investigated by means of 13C solid state NMR and FT-IR spectroscopies. The combined use of these two techniques allowed us to highlight differences in the two samples. The cocoon silk of Achaearanea tepidariorum is essentially constituted by helical and β-sheet structures, whereas that of Araneus diadematus shows a more complex structure, containing also β-strands and β-turns. Moreover, the former silk is essentially crystalline while the latter contains more mobile domains. The structural differences of the two cocoon silks are ascribed to the different habitat of the two species.

  9. 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: [Universidade Federal de Goias (UFG), Goiania, GO (Brazil). Inst. de Quimica. Lab. de Bioatividade Molecular


    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)

  10. An efficient method and device for transfer of semisolid materials into solid-state NMR spectroscopy rotors. (United States)

    Hisao, Grant S; Harland, Michael A; Brown, Robert A; Berthold, Deborah A; Wilson, Thomas E; Rienstra, Chad M


    The study of mass-limited biological samples by magic angle spinning (MAS) solid-state NMR spectroscopy critically relies upon the high-yield transfer of material from a biological preparation into the MAS rotor. This issue is particularly important for maintaining biological activity and hydration of semi-solid samples such as membrane proteins in lipid bilayers, pharmaceutical formulations, microcrystalline proteins and protein fibrils. Here we present protocols and designs for rotor-packing devices specifically suited for packing hydrated samples into Pencil-style 1.6 mm, 3.2 mm standard, and 3.2 mm limited speed MAS rotors. The devices are modular and therefore readily adaptable to other rotor and/or ultracentrifugation tube geometries.

  11. Determination of the (Na+) Sternheimer antishielding factor by 23Na NMR spectroscopy on sodium oxide chloride, Na3OCl. (United States)

    Klösters, G; Jansen, M


    The (Na+) Sternheimer antishielding factor gammainifinity (Na+) was determined by 23Na NMR spectroscopy on sodium oxide-chloride, Na3OCl. The quadrupolar coupling constant of the sodium ion in Na3OCI was determined to QCC = 11.34 MHz, which presents the largest coupling constant of a sodium nucleus observed so far. Applying a simple point charge model, the largest principal value of the electric field gradient at the sodium site was calculated to V(zz) = -6.76762 x 10(20) V/m2. From these values we calculated the (Na+) Sternheimer antishielding factor to gammainifinity (Na+)= -5.36. In sodium oxide, Na2O, we observed an isotropic chemical shift of deltaCS = 55.1 ppm, referenced to 1 M aqueous NaCI (delta = 0 ppm).

  12. NMR methodologies for studying mitochondrial bioenergetics. (United States)

    Alves, Tiago C; Jarak, Ivana; Carvalho, Rui A


    Nuclear magnetic resonance (NMR) spectroscopy is a technique with an increasing importance in the study of metabolic diseases. Its initial important role in the determination of chemical structures (1, 2) has been considerably overcome by its potential for the in vivo study of metabolism (3-5). The main characteristic that makes this technique so attractive is its noninvasiveness. Only nuclei capable of transitioning between energy states, in the presence of an intense and constant magnetic field, are studied. This includes abundant nuclei such as proton ((1)H) and phosphorous ((31)P), as well as stable isotopes such as deuterium ((2)H) and carbon 13 ((13)C). This allows a wide range of applications that vary from the determination of water distribution in tissues (as obtained in a magnetic resonance imaging scan) to the calculation of metabolic fluxes under ex vivo and in vivo conditions without the need to use radioactive tracers or tissue biopsies (as in a magnetic resonance spectroscopy (MRS) scan). In this chapter, some technical aspects of the methodology of an NMR/MRS experiment as well as how it can be used to study mitochondrial bioenergetics are overviewed. Advantages and disadvantages of in vivo MRS versus high-resolution NMR using proton high rotation magic angle spinning (HRMAS) of tissue biopsies and tissue extracts are also discussed.

  13. Direct observation of millisecond to second motions in proteins by dipolar CODEX NMR spectroscopy. (United States)

    Krushelnitsky, Alexey; deAzevedo, Eduardo; Linser, Rasmus; Reif, Bernd; Saalwächter, Kay; Reichert, Detlef


    We present a site-resolved study of slow (ms to s) motions in a protein in the solid (microcrystalline) state performed with the use of a modified version of the centerband-only detection of exchange (CODEX) NMR experiment. CODEX was originally based on measuring changes in molecular orientation by means of the chemical shift anisotropy (CSA) tensor, and in our modification, angular reorientations of internuclear vectors are observed. The experiment was applied to the study of slow (15)N-(1)H motions of the SH3 domain of chicken alpha-spectrin. The protein was perdeuterated with partial back-exchange of protons at labile sites. This allowed indirect (proton) detection of (15)N nuclei and thus a significant enhancement of sensitivity. The diluted proton system also made negligible proton-driven spin diffusion between (15)N nuclei, which interferes with the molecular exchange (motion) and hampers the acquisition of dynamic parameters. The experiment has shown that approximately half of the peaks in the 2D (15)N-(1)H correlation spectrum exhibit exchange in a different extent. The correlation time of the slow motion for most peaks is 1 to 3 s. This is the first NMR study of the internal dynamics of proteins in the solid state on the millisecond to second time scale with site-specific spectral resolution that provides both time-scale and geometry information about molecular motions.


    Directory of Open Access Journals (Sweden)

    Thomas Heinze


    Full Text Available Tert-butyldimethylsilyl cellulose with a degree of substitution (DS of up to 2 could be obtained by homogeneous conversion of the biopolymer with tert-butylchlorosilane in N,N-dimethyl aceteamide/LiCl in the presence of imidazole. The cellulose derivatives were characterized in detail by means of two-dimensional NMR spectroscopic techniques including subsequent derivatization of the original polymer by consecutive methylation-desilyation-acetylation. The very well resolved NMR spectra indicate that dependent on the reaction temperature 2,6-di-O-tert-butyldimethylsilyl moieties are the main repeating units. 3,6-di-O- and 6-mono-O functionalized repeating units were identified in very small amount if the reaction is carried out at room temperature. Additionally, 2,3,6-tri-O-silylated functions appear if reaction is carried out at temperature of 100°C. Thus, a novel path for regioselective protection of position 2 and 6 for cellulose was established.

  15. Ionic Liquid-Solute Interactions Studied by 2D NOE NMR Spectroscopy. (United States)

    Khatun, Sufia; Castner, Edward W


    Intermolecular interactions between a Ru(2+)(bpy)3 solute and the anions and cations of four different ionic liquids (ILs) are investigated by 2D NMR nuclear Overhauser effect (NOE) techniques, including {(1)H-(19)F} HOESY and {(1)H-(1)H} ROESY. Four ILs are studied, each having the same bis(trifluoromethylsulfonyl)amide anion in common. Two of the ILs have aliphatic 1-alkyl-1-methylpyrrolidinium cations, while the other two ILs have aromatic 1-alkyl-3-methylimidazolium cations. ILs with both shorter (butyl) and longer (octyl or decyl) cationic alkyl substituents are studied. NOE NMR results suggest that the local environment of IL anions and cations near the Ru(2+)(bpy)3 solute is rather different from the bulk IL structure. The solute-anion and solute-cation interactions are significantly different both for ILs with short vs long alkyl tails and for ILs with aliphatic vs aromatic cation polar head groups. In particular, the solute-anion interactions are observed to be about 3 times stronger for the cations with shorter alkyl tails relative to the ILs with longer alkyl tails. The Ru(2+)(bpy)3 solute interacts with both the polar head and the nonpolar tail groups of the 1-butyl-1-methylpyrrolidinium cation but only with the nonpolar tail groups of the 1-decyl-1-methylpyrrolidinium cation.

  16. High resolution triple resonance micro magic angle spinning NMR spectroscopy of nanoliter sample volumes. (United States)

    Brauckmann, J Ole; Janssen, J W G Hans; Kentgens, Arno P M


    To be able to study mass-limited samples and small single crystals, a triple resonance micro-magic angle spinning (μMAS) probehead for the application of high-resolution solid-state NMR of nanoliter samples was developed. Due to its excellent rf performance this allows us to explore the limits of proton NMR resolution in strongly coupled solids. Using homonuclear decoupling we obtain unprecedented (1)H linewidths for a single crystal of glycine (Δν(CH2) = 0.14 ppm) at high field (20 T) in a directly detected spectrum. The triple channel design allowed the recording of high-resolution μMAS (13)C-(15)N correlations of [U-(13)C-(15)N] arginine HCl and shows that the superior (1)H resolution opens the way for high-sensitivity inverse detection of heteronuclei even at moderate spinning speeds and rf-fields. Efficient decoupling leads to long coherence times which can be exploited in many correlation experiments.

  17. Solid-state 51V MAS NMR spectroscopy determines component concentration and crystal phase in co-crystallised mixtures of vanadium complexes

    DEFF Research Database (Denmark)

    Nielsen, Ulla Gro; Hazell, Alan Charles; Skibsted, Jørgen Bengaard


    resonances are sensitive to intermolecular interactions specific to each crystal phase. The solid-state V-51 MAS NMR spectroscopic data show that the different phases do not co-precipitate but the concentration of the solute (which can be either 1 or 2) can vary. Thus co-crystallised mixtures of 1 and 2 can...... be classed as a molecular mixture capable of forming continuous solid solutions....... for the vanadium atoms of the two complexes mean that V-51 solution state and MAS NMR spectroscopy can be used to determine the concentration of 1 and 2 in bulk samples. Significantly, however, V-51 MAS NMR spectroscopy also reports on the identity of the crystal phase. This is possible because the isotropic V-51...

  18. Nobel Prize in Chemistry 1991 "for his contributions to the development of the methodology of high resolution nuclear magnetic resonance (NMR) spectroscopy": Richard R. Ernst

    CERN Multimedia


    Prof. Richard R. Ernst presents "The domestication of nuclear spins by chemists and biologists".The usage of nuclear spins in chemistry and biology for exploring the structure and dynamics of matter is discussed. The main emphasis is put on the methodological aspects of multidimensional nuclear magnetic resonance (NMR) spectroscopy that are responsible for the success of this powerful analytical technique.

  19. Detection of adulteration in orange juices by a new screening method using proton NMR spectroscopy in combination with pattern recognition techniques

    NARCIS (Netherlands)

    Vogels, J.T.W.E.; Terwel, L.; Tas, A.C.; Berg, F. van den; Dukel, F.; Greef, J. van der


    This paper describes the application of proton NMR spectroscopy as a screening tool for the determination of the authenticity of orange juices. Principal component and discriminant analyses were used to discriminate between authentic and nonauthentic (suspect) samples. In one set of profiles, additi

  20. Determination and Quantification of the Local Environments in Stoichiometric and Defect Jarosite by Solid-State 2H NMR Spectroscopy

    DEFF Research Database (Denmark)

    Nielsen, Ulla Gro; Grey, Clare P.; Majzlan, Juraj


    The nature and concentrations of the local environments in a series of deuterated jarosite (nominally AFe3(SO4)2(OD)6 with A = K, Na, and D3O) samples with different levels of iron and cation vacancies have been determined by 2H MAS NMR spectroscopy at ambient temperatures. Three different local ...