Technetium-99m hexamethylpropylene amine oxime single-photon emission tomography of regional cerebral blood flow in insulin-dependent diabetes

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Keymeulen, B. [Dept. of Internal Medicine, Academic Hospital VUB, Brussels (Belgium); Metz, K. de [Dept. of Nuclear Medicine, Academic Hospital VUB, Brussels (Belgium); Cluydts, R. [Dept. of Psychology, Academic Hospital VUB, Brussels (Belgium); Bossuyt, A. [Dept. of Nuclear Medicine, Academic Hospital VUB, Brussels (Belgium); Somers, G.

1996-02-01

The study was performed to investigate subclinical abnormalities in regional cerebral blood flow (rCBF) in patients with insulin-dependent diabetes mellitus (IDDM) and to correlate them with patients` characteristics. After intravenous injection of technetium-99m hexamethylpropylene amine oxime (HMPAO), tracer uptake of the prefrontal, frontal and parieto-occipital zones was measured with a triple-head single-photon emission tomography (SPET) camera system in 35 IDDM patients outside an episode of hypolycaemia. Tracer uptake values in 16 age- and sex-matched healthy volunteers served as reference values. Compared with healthy subjects, increased tracer uptake of both prefrontal regions and the left frontal region could be shown in diabetes. Tracer uptake was negatively correlated with the duration of diabetes in all investigated regions. In diabetic patients with a disease duration of more than 5 years (n=26), stepwise regression analysis revealed a significant positive correlation between their HbA1c levels and tracer uptake. Long-term diabetic patients with reduced (pre)frontal tracer uptake (n=8) had lower HbA1c levels than those without (8.4%{+-}0.2% vs 9.3%{+-}0.3%, P<0.05) and tended to have more frequently a history of hypoglycaemic coma (6/8 v 6/18, P=0.06). It can be concluded that duration of diabetes contributes to subclinical changes in basal rCBF in IDDM as detected with HMPAO SPET of the brain. The positive correlation between the presence of regional hypoperfusion and lower HbA1c levels in long-term diabetic patients may be interpreted in the light of presumed higher incidence of hypoglycaemia as metabolic control improves. (orig.)

A technetium-99m hexamethylpropylene amine oxime brain single-photon emission tomography study in adolescent patients with major depressive disorder

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Tutus, A. [Department of Nuclear Medicine, Erciyes University School of Medicine, Kayseri (Turkey); Kibar, M. [Department of Nuclear Medicine, Cukurova University School of Medicine, Kayseri (Turkey); Sofuoglu, S.; Basturk, M.; Goenuel, A.S. [Department of Psychiatry, Erciyes University School of Medicine, Kayseri (Turkey)

1998-06-01

We have not encountered any brain single-photon emission tomography (SPET) study performed in adolescent depressed patients in the literature. Therefore, we used technetium-99m hexamethylpropylene amine oxime ({sup 99m}Tc-HMPAO) brain SPET in adolescent patients with major depressive disorder (MDD) to examine the possible changes in cerebral perfusion and the possible association between perfusion indices and clinical variables. Fourteen adolescent out-patients (nine females, five males; mean{+-}SD age: 13.11{+-}1.43 years; range: 11-15 years) fulfilling the DSM-IV criteria for MDD and 11 age-matched healthy control subjects (six females, five males; mean{+-}SD age: 13.80{+-}1.60 years; range: 12-15 years) were included in the study. {sup 99}Tc-HMPAO brain SPET was performed twice in the patient group and once in the control group. The first SPET investigation was performed under non-medicated conditions and the second was performed after depressive symptoms had subsided. A relative perfusion index (PI) was calculated as the ratio of regional cortical activity to the whole brain activity. We found significant differences between the PI values of the untreated depressed patients and those of the controls, indicating relatively reduced perfusion in the left anterofrontal and left temporal cortical areas. No significant differences in regional PI values were found between the remitted depressed patients and the controls. Our study suggests that adolescent patients with MDD may have regional cerebral blood flow deficits in frontal regions and a greater anterofrontal right-left perfusion asymmetry compared with normal subjects. The fact that these abnormalities in perfusion indices have a trend toward normal values with symptomatic improvement suggests that they may be state-dependent markers for adolescent MDD. (orig.) With 3 figs., 2 tabs., 37 refs.

A technetium-99m hexamethylpropylene amine oxime brain single-photon emission tomography study in adolescent patients with major depressive disorder

International Nuclear Information System (INIS)

Tutus, A.; Kibar, M.; Sofuoglu, S.; Basturk, M.; Goenuel, A.S.

1998-01-01

We have not encountered any brain single-photon emission tomography (SPET) study performed in adolescent depressed patients in the literature. Therefore, we used technetium-99m hexamethylpropylene amine oxime ( 99m Tc-HMPAO) brain SPET in adolescent patients with major depressive disorder (MDD) to examine the possible changes in cerebral perfusion and the possible association between perfusion indices and clinical variables. Fourteen adolescent out-patients (nine females, five males; mean±SD age: 13.11±1.43 years; range: 11-15 years) fulfilling the DSM-IV criteria for MDD and 11 age-matched healthy control subjects (six females, five males; mean±SD age: 13.80±1.60 years; range: 12-15 years) were included in the study. 99 Tc-HMPAO brain SPET was performed twice in the patient group and once in the control group. The first SPET investigation was performed under non-medicated conditions and the second was performed after depressive symptoms had subsided. A relative perfusion index (PI) was calculated as the ratio of regional cortical activity to the whole brain activity. We found significant differences between the PI values of the untreated depressed patients and those of the controls, indicating relatively reduced perfusion in the left anterofrontal and left temporal cortical areas. No significant differences in regional PI values were found between the remitted depressed patients and the controls. Our study suggests that adolescent patients with MDD may have regional cerebral blood flow deficits in frontal regions and a greater anterofrontal right-left perfusion asymmetry compared with normal subjects. The fact that these abnormalities in perfusion indices have a trend toward normal values with symptomatic improvement suggests that they may be state-dependent markers for adolescent MDD. (orig.)

Parameters influencing SPET regional brain uptake of technetium-99m hexamethylpropylene amine oxime measured by calibrated point sources as an external standard

International Nuclear Information System (INIS)

Dierckx, R.A.; Dobbeleir, A.; Maes, M.; Pickut, B.A.; Vervaet, A.; Deyn, P.P. de

1994-01-01

Using calibrated point sources as an external standard to convert SPET brain counts into absolute values of regional brain uptake (rBU) of technetium-99m hexamethylpropylene amine oxime (HMPAO), the relative contribution of different parameters to interindividual variability of cerebellar rBU was examined in 33 healthy volunteers. Stepwise regression analysis identified body surface as the most important factor underlying interindividual variability, when compared with brain volume. In the normal volunteer population presented, age decrement of rBU corrected for body surface and brain volume equalled 60.5-0.20xage. Based on the data of eight normal volunteers, including four test-retest studies with heart rate (HR) differences greater than 5 units and four test-stress studies with doubling of heart rate after bicycle exercise, influence of heart rate may be expressed by the equation ΔrBU = 0.35 ΔHR. Clinically, estimation of the relative influence of different factors allows normalization and extension of the applicability of the rBU quantification method used from longitudinal studies to group comparisons. Interestingly, results of the Daily Stress Inventory Scale and a subjective rating scale suggest the absence of a significant influence of minor stress on rBU. When using one vial per patient, chromatography may be omitted in clinical routine practice and lipophilicity may be estimated as 90% of the injected dose, if administered within 10 min after preparation. Finally, sensitivity of the quantification method was tested in eight volunteers using acetazolamide brain activation and showed a mean increase in cerebellar rBU of 30.2%, varying between 14.1% and 75.9%. (orig./MG)

Normal regional distribution of cerebral blood flow in dogs: comparison between (99m) Tc-ethylcysteinate dimer and (99m) Tc- hexamethylpropylene amine oxime single photon emission computed tomography.

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Adriaens, Antita; Polis, Ingeborgh; Waelbers, Tim; Vandermeulen, Eva; Dobbeleir, André; De Spiegeleer, Bart; Peremans, Kathelijne

2013-01-01

Functional imaging provides important insights into canine brain pathologies such as behavioral problems. Two (99m) Tc-labeled single photon emission computed tomography (SPECT) cerebral blood flow tracers-ethylcysteinate dimer (ECD) and hexamethylpropylene amine oxime (HMPAO)-are commonly used in human medicine and have been used previously in dogs but intrasubject comparison of both tracers in dogs is lacking. Therefore, this study investigated whether regional distribution differences between both tracers occur in dogs as is reported in humans. Eight beagles underwent two SPECT examinations first with (99m) Tc-ECD and followed by (99m) Tc-HMPAO. SPECT scanning was performed with a triple head gamma camera equipped with ultrahigh resolution parallel hole collimators. Images were reconstructed using filtered backprojection with a Butterworth filter. Emission data were fitted to a template permitting semiquantification using predefined regions or volumes of interest (VOIs). For each VOI, perfusion indices were calculated by normalizing the regional counts per voxel to total brain counts per voxel. The obtained perfusion indices for each region for both tracers were compared with a paired Student's T-test. Significant (P < 0.05) regional differences were seen in the subcortical region and the cerebellum. Both tracers can be used to visualize regional cerebral blood flow in dogs, however, due to the observed regional differences, they are not entirely interchangeable. © 2013 Veterinary Radiology & Ultrasound.

Improving the diagnosis of acute appendicitis in children with atypical clinical findings using the technetium-99m hexamethylpropylene amine oxime-labelled white-blood-cell abdomen scan

International Nuclear Information System (INIS)

Yan Dahchin; Shiau Yuchien; Wang Jhijoung; Ho Shungtai; Kao Chiahung

2002-01-01

Heading AbstractBackground. Diagnosing acute appendicitis in children with equivocal signs and symptoms may be difficult. The usual approach is hospital observation and frequent re-examination. However, many surgeons are reluctant to delay surgery because of the risk of perforation and a negative laparotomy.Objective. To assess and compare the value of the technetium-99m hexamethylpropylene amine oxime ( 99m Tc-HMPAO)-labelled white-blood-cell (WBC) abdomen scan in the diagnosis of acute appendicitis in children with atypical clinical presentation.Patients and methods. Fifty children with acute right lower quadrant abdominal pain and possible acute appendicitis, but atypical findings were included. After IV injection of 99m Tc-HMPAO-labelled WBCs, serial anterior abdomen scans were obtained using a gamma camera.Results. Thirty-three children underwent surgery, while 17 children were managed conservatively and were followed up for at least 1 month. Four children had false-positive results and one child had a false-negative scan result. The overall sensitivity, specificity, accuracy, positive predictive value and negative predictive value of the scan to diagnose acute appendicitis in children with atypical findings was 96.7, 80.0, 90.0, 87.8 and 94.1%, respectively.Conclusions. The 99m Tc-HMPAO WBC abdomen scan is a potential tool for diagnosing acute appendicitis in children with atypical clinical findings. The high sensitivity and negative predictive value allows early discharge from the emergency department to avoid costly observation in hospital and potentially unnecessary surgery in those patients with negative scans. (orig.)

Evaluation of technetium 99m cyclobutylpropylene amine oxime as a potential brain perfusion imaging agent for SPET

International Nuclear Information System (INIS)

Bacciottini, L.; Pupi, A.; Formiconi, A.R.; De Cristofaro, M.T.R.; Petti, A.R.M.; Meldolesi, U.

1990-01-01

99m Tc-labelled d,l-cyclobutylpropylene amine oxime ( 99m Tc-CBPAO) has been developed as a brain imaging agent for single photon emission tomography (SPET). 99m Tc-CBPAO can be prepared using a simple labelling procedure suitable for routine clinical use. It has a high in vitro stability, as has been demonstrated by high-pressure liquid chromatography (HPCL) analysis. This shows that 3 h after labelling, less than 5% of the primary lipophilic complex which is capable of crossing the blood-brain barrier (BBB) converts to a secondary hydrophilic complex. Brain uptake (% dose/g wet tissue) of 99m Tc-CBPAO, determined at 5 and 30 min after injection in two groups of six adult male Sprague-Dawley rats, was found to be 0.74±0.06 and 0.73±0.13 (mean±SD), respectively. These values are not significantly different from those obtained repeating the experiment with 99m Tc-labelled hexamethylpropylene amine oxime ( 99m Tc-HMPAO) (0.72±0.15 at 5 min and 0.88±0.24 at 30 min after injection). Since the rat brain uptake of 99m Tc-CBPAO remained unchanged for a period of time suitable for tomographic study, the comparison of the two tracers was extended to two groups of ten patients. The latter were affected by neurological and psychiatric disorders and were studied with SPET. Human brain uptake (% dose/cc cortical grey matter) of 99m Tc-CBPAO and 99m Tc-HMPAO were 3.04±0.57 and 4.22±0.46 (mean x 10 -3 ±SD x 10 -3 ), respectively, with a 32% significant difference. In two other groups of five patients, the first transit time-activity curves of the two tracers were compared. From the analysis of these curves we suggest that 99m Tc-CBPAO has a higher binding effect on blood components and/or a higher degradation rate in blood than that of 99m Tc-HMPAO. This may account for the reduced human brain uptake. In conclusion, SPET images of 99m Tc-CBPAO reflect blood perfusion, and they have a good diagnostic quality. The main advantage of 99m Tc-CBPAO is its in vitro stability

Oxidation of primary amines to oximes with molecular oxygen using 1,1-diphenyl-2-picrylhydrazyl and WO3/Al2O3 as catalysts.

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Suzuki, Ken; Watanabe, Tomonari; Murahashi, Shun-Ichi

2013-03-15

The oxidative transformation of primary amines to their corresponding oximes proceeds with high efficiency under molecular oxygen diluted with molecular nitrogen (O2/N2 = 7/93 v/v, 5 MPa) in the presence of the catalysts 1,1-diphenyl-2-picrylhydrazyl (DPPH) and tungusten oxide/alumina (WO3/Al2O3). The method is environmentally benign, because the reaction requires only molecular oxygen as the terminal oxidant and gives water as a side product. Various alicyclic amines and aliphatic amines can be converted to their corresponding oximes in excellent yields. It is noteworthy that the oxidative transformation of primary amines proceeds chemoselectively in the presence of other functional groups. The key step of the present oxidation is a fast electron transfer from the primary amine to DPPH followed by proton transfer to give the α-aminoalkyl radical intermediate, which undergoes reaction with molecular oxygen and hydrogen abstraction to give α-aminoalkyl hydroperoxide. Subsequent reaction of the peroxide with WO3/Al2O3 gives oximes. The aerobic oxidation of secondary amines gives the corresponding nitrones. Aerobic oxidative transformation of cyclohexylamines to cyclohexanone oximes is important as a method for industrial production of ε-caprolactam, a raw material for Nylon 6.

A neutral lipophilic complex of sup(99m)Tc with a multidentate amine oxime

International Nuclear Information System (INIS)

Troutner, D.E.; Volkert, W.A.; Hoffman, T.J.; Holmes, R.A.

1984-01-01

Propylene amine oxime, 3,3'-(1,3-propanediyldiimino)bis(3-methyl-2-butanone)dioxime, (PnAO) forms a neutral lipophilic complex with sup(99m)Tc in >95% yield at room temperature at pH 5-10. The complex can be prepared with generator produced sup(99m)Tc using 10 -5 M SnC 4 H 4 O 6 as the reducing agent at ligand concentrations as low as 3 x 10 -5 M. It is stable in saline solutions for as long as 24 h. [Sup(99m)Tc]PnAO may be useful as an imaging agent which passively diffuses across the blood brain barrier. (author)

The relation between crossed cerebellar blood flow and severities of hemiplegia. A technetium-99m hexamethylpropylene amine oxine SPECT study using Patlak plot method

International Nuclear Information System (INIS)

Watanabe, Hiromi; Niwa, Naoki; Kanai, Masanori; Sasaki, Setuo.

1996-01-01

Crossed cerebellar diaschisis (CCD), decrease in crossed cerebellar blood flow (CCBF) (ml/100 g/min), is often observed in the cerebral blood flow imaging of hemiplegic patients. We studied the relations between severities of hemiplegia and degrees of CCD. Severities of hemiplegia were evaluated by Brunnstrom stages (Br. stage) of lower limbs. Degree of CCD was evaluated as CCBF and asymmetry index (ASI) (%) of CCBF, which were calculated from technetium- 99m hexamethylpropylene amine oxine ( 99m Tc HMPAO) SPECT study using Patlak plot method (Matsuda et al. 1992, 1993). We have studied twenty consecutive patients. The CCBF was significantly different between Br. stage II and IV (p=0.0357), III and IV (p<0.001) and III and V (p<0.001). ASI was significantly different between II and IV (p=0.0357), III and IV (p<0.001) and III and VI (p=0.0238). Both of CCBF and ASI of the group of II and III were significantly lower than those of the group of IV, V and VI (p=0.0033 for CCBF and p=0.0087 for ASI). We conclude that this study indicate a close correlation between the severities of hemplegia and the degrees of CCD. (author)

Centrally Acting Oximes in Reactivation of Tabun-Phosphoramidated AChE

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Kovarik, Zrinka; Maček, Nikolina; Sit, Rakesh K.; Radić, Zoran; Fokin, Valery V.; Sharpless, K. Barry; Taylor, Palmer

2012-01-01

Organophosphates (OP) inhibit acetylcholinesterase (AChE, E.C.3.1.1.7), both in peripheral tissues and central nervous system (CNS), causing adverse and sometimes fatal effects due to the accumulation of neurotransmitter acetylcholine (ACh). The currently used therapy, focusing on the reactivation of inhibited AChE, is limited to peripheral tissues because commonly used quaternary pyridinium oxime reactivators do not cross the blood brain barrier (BBB) at therapeutically relevant levels. A directed library of thirty uncharged oximes that contain tertiary amine or imidazole protonable functional groups that should cross the BBB as unionized species was tested as tabun-hAChE conjugate reactivators along with three reference oximes: DAM (diacetylmonoxime), MINA (monoisonitrosoacetone), and 2-PAM. The oxime RS150D [N-((1-(3-(2-((hydroxyimino)methyl)-1H-imidazol-1-yl)propyl)-1H-1,2,3-triazol-4-yl)methyl)benzamide] was highlighted as the most promising reactivator of the tabun-hAChE conjugate. We also observed that oximes RS194B [N-(2-(azepan-1-yl)ethyl)-2-(hydroxyimino)acetamide] and RS41A [2-(hydroxyimino)-N-(2-(pyrrolidin-1-yl)ethyl)acetamide], which emerged as lead uncharged reactivators of phosphylated hAChE with other OPs (sarin, cyclosarin and VX), exhibited only moderate reactivation potency for tabun inhibited hAChE. This implies that geometry of oxime access to the phosphorus atom conjugated to the active serine is an important criterion for efficient reactivation, along with the chemical nature of the conjugated moiety: phosphorate, phosphonate, or phosphoramidate. Moreover, modification of the active center through mutagenesis enhances the rates of reactivation. The phosphoramidated-hAChE choline-binding site mutant Y337A showed three-times enhanced reactivation capacity with non-triazole imidazole containing aldoximes (RS113B, RS113A and RS115A) and acetamide derivative (RS194B) than with 2PAM. PMID:22960624

Ruthenium-Catalyzed Aerobic Oxidation of Amines.

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Ray, Ritwika; Hazari, Arijit Singha; Lahiri, Goutam Kumar; Maiti, Debabrata

2018-01-18

Amine oxidation is one of the fundamental reactions in organic synthesis as it leads to a variety of value-added products such as oximes, nitriles, imines, and amides among many others. These products comprise the key N-containing building blocks in the modern chemical industry, and such transformations, when achieved in the presence of molecular oxygen without using stoichiometric oxidants, are much preferred as they circumvent the production of unwanted wastes. In parallel, the versatility of ruthenium catalysts in various oxidative transformations is well-documented. Herein, this review focuses on aerobic oxidation of amines specifically by using ruthenium catalysts and highlights the major achievements in this direction and challenges that still need to be addressed. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Measurement of cerebral perfusion after zolpidem administration in the baboon model.

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Clauss, R P; Dormehl, I C; Oliver, D W; Nel, W H; Kilian, E; Louw, W K

2001-01-01

A recent report showed that zolpidem (CAS 82626-48-0) can lead to the arousal of a semi-comatosed patient. Zolpidem is clinically used for the treatment of insomnia. It belongs to the imidazopyridine chemical class and is a non benzodiazepine drug. It illicits its pharmacological action via the GABA receptor system through stimulation of particularly the omega 1 receptors. In this study, the effect of zolpidem on brain perfusion was examined by 99mTc hexamethyl-propylene amine oxime (HMPAO) split dose brain SPECT on four normal baboons and in one baboon with abnormal neurological behaviour. The global and regional brain perfusion was not significantly affected in the normal brains. In some regions of the abnormal baboon brain, however, there was a disproportionate increase in perfusion after zolpidem.

{sup 18}FDG PET and acetazolamide-enhanced {sup 99m}Tc-HMPAO SPET in systemic lupus erythematosus

Energy Technology Data Exchange (ETDEWEB)

Gruenwald, F. [Bonn Univ. (Germany). Inst. fuer Klinische und Experimentelle Nuklearmedizin; Schomburg, A. [Bonn Univ. (Germany). Inst. fuer Klinische und Experimentelle Nuklearmedizin; Badali, A. [Dept. of Dermatology, Univ. of Bonn (Germany); Ruhlmann, J. [Bonn Univ. (Germany). Inst. fuer Klinische und Experimentelle Nuklearmedizin; Pavics, L. [Bonn Univ. (Germany). Inst. fuer Klinische und Experimentelle Nuklearmedizin; Biersack, H.J. [Bonn Univ. (Germany). Inst. fuer Klinische und Experimentelle Nuklearmedizin

1995-09-01

In this report, we present the case of a 70-year-old female patient, suffering from SLE without symptoms of CNS involvement. In addition to a SPET study using technetium-99m hexamethylpropylene amine oxime ({sup 99m}Tc-HMPAO) and a PET scan with fluorine-18 deoxyglucose ({sup 18}FDG), a SPET study after acetazolamide injection was performed in order to assess the cerebral perfusion reserve. While the PET scan showed no major abnormalities, and the baseline SPET study revealed only minor changes, the acetazolamide-enhanced SPET study revealed a marked reduction of the cortical perfusion reserve, particularly in both frontal lobes. It is concluded that ``preclinical`` CNS involvement, mainly caused by pathological mechanisms involving the cerebral blood vessels, can be considered to exist in this patient with SLE. (orig.). With 2 figs.

Regional cerebral blood flow assessed by single photon emission computed tomography (SPECT) in dogs with congenital portosystemic shunt and hepatic encephalopathy.

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Or, Matan; Peremans, Kathelijne; Martlé, Valentine; Vandermeulen, Eva; Bosmans, Tim; Devriendt, Nausikaa; de Rooster, Hilde

2017-02-01

Regional cerebral blood flow (rCBF) in eight dogs with congenital portosystemic shunt (PSS) and hepatic encephalopathy (HE) was compared with rCBF in eight healthy control dogs using single photon emission computed tomography (SPECT) with a 99m technetium-hexamethylpropylene amine oxime ( 99m Tc-HMPAO) tracer. SPECT scans were abnormal in all PSS dogs. Compared to the control group, rCBF in PSS dogs was significantly decreased in the temporal lobes and increased in the subcortical (thalamic and striatal) area. Brain perfusion imaging alterations observed in the dogs with PSS and HE are similar to those in human patients with HE. These findings suggest that dogs with HE and PSS have altered perfusion of mainly the subcortical and the temporal regions of the brain. Copyright © 2016 Elsevier Ltd. All rights reserved.

Efficacious Oxime for Organophosphorus Poisoning: A Minireview ...

African Journals Online (AJOL)

Oximes are well known as acetylcholinesterase reactivators and are used in organophosphorus poisoning to reactivate inhibited acetylcholinesterase. Therapeutically available oximes, namely, pralidoxime (2-PAM), obidoxime, trimedoxime and Hagedorn oxime (HI-6), have no broad-spectrum activity against structurally ...

Evolution of technetium-99m-HMPAO SPECT and brain mapping in a patient presenting with echolalia and palilalia.

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Dierckx, R A; Saerens, J; De Deyn, P P; Verslegers, W; Marien, P; Vandevivere, J

1991-08-01

A 78-yr-old woman presented with transient echolalia and palilalia. She had suffered from Parkinson's disease for 2 yr. Routine laboratory examination showed hypotonic hyponatremia, but was otherwise unremarkable. Brain mapping revealed a bifrontal delta focus, more pronounced on the right. Single photon emission computed tomography (SPECT) of the brain with technetium-99m labeled d,l hexamethylpropylene-amine oxime (99mTc-HMPAO), performed during the acute episode showed relative frontoparietal hypoactivity. Brain mapping performed after disappearance of the echolalia and palilalia, which persisted only for 1 day, was normal. By contrast, SPECT findings persisted for more than 3 wk. Features of particular interest in the presented patient are the extensive defects seen on brain SPECT despite the absence of morphologic lesions, the congruent electrophysiologic changes and their temporal relationship with the clinical evolution.

Diagnosis of infected bone and joint diseases with 99mTc-HM-PAO labeled leukocytes

International Nuclear Information System (INIS)

Kanegae, Kakuko; Itoh, Kazuo; Tsukamoto, Eriko; Nagao, Kazuhiko; Nakada, Kunihiro; Hurudate, Masayori

1992-01-01

The usefulness of 99m Tc-hexamethylpropylene amine oxime (HM-PAO) labeled leukocytes scans was studied in 15 patients with suspected infection of the bone and joints. All spot images of lesions were obtained 4 and 24 hours after injection of 70.3-236.8 MBq (a mean, 149.5 MBq). 99m Tc-HM-PAO leukocytes scans were positive in 5 patients, negative in 8, and equivocal in 2. It had a sensitivity of 83% (5/6), specificity of 100% (6/6), and accuracy of 93% (14/15) for diagnosing infections. Equivocal uptake, seen on the 4-hr image in 2 patients, became negative on the 24-hr image. In view of ready availability and simple labeling procedure, 99m Tc-HM-PAO labeled leukocytes scans can be used as one of the specific diagnostic procedures for infections. (N.K.)

Efficacious Oxime for Organophosphorus Poisoning: A Minireview

African Journals Online (AJOL)

Erah

Abstract. Oximes are well known as acetylcholinesterase reactivators and are used in ... activity against structurally different kinds of organophosphorus ... serious threat with regard to occupational .... choose an oxime for unknown OPC exposure. Secondly, there is a lack of .... oximes, and hence cannot pass the blood.

Native and tabun-inhibited cholinesterase interactions with oximes

International Nuclear Information System (INIS)

Kovarik, Z.; Katalinic, M.; Sinko, G.

2009-01-01

The phosphorylation of the serine hydroxyl group in the active site of acetylcholinesterase (AChE) inactivates this essential enzyme in neurotransmission. Its related enzyme butyrylcholinesterase (BChE) also interacts with organophosphorus compounds (OP) scavenging anti-cholinesterase agents and protects synaptic AChE from inhibition. Oximes are reactivators of AChE phosphorylated by OP including insecticides and nerve agents. The effectiveness of oxime-assisted reactivation is primarily attributed to the nucleophilic displacement rate of organophosphate, but efficiency varies with the structure of the bound organophosphate, the structure of the oxime as well as rates of several other cholinesterase's reactions. Besides reactivating cholinesterases, oximes also reversibly inhibit both cholinesterases and protect them from phosphorylation by OP. We tested oximes varying in the type of ring (pyridinium and/or imidazolium), the length and type of the linker between rings, and in the position of the oxime group on the ring to find more effective oximes to reactivate tabun-inhibited human erythrocyte AChE and plasma BChE. Herein we bring an overview of in vitro interactions of native and tabun-inhibited AChE and BChE with oximes together with conformational analysis of the oximes relating molecular properties to their reactivation potency.(author)

Refinement of Structural Leads for Centrally Acting Oxime Reactivators of Phosphylated Cholinesterases*

Science.gov (United States)

Radić, Zoran; Sit, Rakesh K.; Kovarik, Zrinka; Berend, Suzana; Garcia, Edzna; Zhang, Limin; Amitai, Gabriel; Green, Carol; Radić, Božica; Fokin, Valery V.; Sharpless, K. Barry; Taylor, Palmer

2012-01-01

We present a systematic structural optimization of uncharged but ionizable N-substituted 2-hydroxyiminoacetamido alkylamine reactivators of phosphylated human acetylcholinesterase (hAChE) intended to catalyze the hydrolysis of organophosphate (OP)-inhibited hAChE in the CNS. Starting with the initial lead oxime RS41A identified in our earlier study and extending to the azepine analog RS194B, reactivation rates for OP-hAChE conjugates formed by sarin, cyclosarin, VX, paraoxon, and tabun are enhanced severalfold in vitro. To analyze the mechanism of intrinsic reactivation of the OP-AChE conjugate and penetration of the blood-brain barrier, the pH dependence of the oxime and amine ionizing groups of the compounds and their nucleophilic potential were examined by UV-visible spectroscopy, 1H NMR, and oximolysis rates for acetylthiocholine and phosphoester hydrolysis. Oximolysis rates were compared in solution and on AChE conjugates and analyzed in terms of the ionization states for reactivation of the OP-conjugated AChE. In addition, toxicity and pharmacokinetic studies in mice show significantly improved CNS penetration and retention for RS194B when compared with RS41A. The enhanced intrinsic reactivity against the OP-AChE target combined with favorable pharmacokinetic properties resulted in great improvement of antidotal properties of RS194B compared with RS41A and the standard peripherally active oxime, 2-pyridinealdoxime methiodide. Improvement was particularly noticeable when pretreatment of mice with RS194B before OP exposure was combined with RS194B reactivation therapy after the OP insult. PMID:22343626

Gamma irradiation of cholestenone oximes

International Nuclear Information System (INIS)

Uenseren, Envare.

1976-01-01

Irradiation of cholest-4-en-3-one and cholest-5-en-3-one oximes with cobalt-60 gamma-rays in different solvents at different doses gave a mixture of products from which ketones corresponding to the starting oximes, Beckmann type rearrangement products, and some other radiolysis products have been isolated and identified

Detection of a possible epilepsy focus in a preoperated patient by perfusion SPECT and computer-aided subtraction analysis

International Nuclear Information System (INIS)

Apostolova, I.; Wilke, F.; Clausen, M.; Buchert, R.; Lindenau, M.; Stodieck, S.; Fiehler, J.; Heese, O.

2008-01-01

Ictal perfusion SPECT with either 9 9mTc-hexamethylpropylene amine oxime (HMPAO) or 9 9mTc-ethylcysteinate dimer (ECD) has been reported to provide very good sensitivity for the determination of the SOA in fTLE. Sensitivity of interictal perfusion SPECT is much lower. However, interictal perfusion SPECT might enhance the specificity of ictal SPECT findings by improving the discrimination between seizure related local hyperperfusion and intersubject variability of perfusion (physiologic hyperperfusion). In addition, the combination of interictal and ictal perfusion SPECT might provide improved sensitivity compared to ictal SPECT alone, particularly when computer-aided subtraction of ictal and interictal SPECT is used instead of traditional side-by-side visual comparison. The combination of ictal and interictal perfusion SPECT eliminates not only physiological inter-subject variance, but it can also eliminate severe partial volume effects. Computer-aided subtraction analysis appears particularly useful in this case

Detection of a possible epilepsy focus in a preoperated patient by perfusion SPECT and computer-aided subtraction analysis

Energy Technology Data Exchange (ETDEWEB)

Apostolova, I.; Wilke, F.; Clausen, M.; Buchert, R. [Univ. Medical Center Hamburg-Eppendorf (Germany). Dept. of Nuclear Medicine; Lindenau, M.; Stodieck, S. [Protestant Hospital Alsterdorf, Hamburg (Germany). Dept. of Neurology and Epileptology; Fiehler, J. [Univ. Medical Center Hamburg-Eppendorf (Germany). Dept. of Neuroradiology; Heese, O. [Univ. Medical Center Hamburg-Eppendorf (Germany). Neurological Surgery

2008-07-01

Ictal perfusion SPECT with either {sup 9}9mTc-hexamethylpropylene amine oxime (HMPAO) or {sup 9}9mTc-ethylcysteinate dimer (ECD) has been reported to provide very good sensitivity for the determination of the SOA in fTLE. Sensitivity of interictal perfusion SPECT is much lower. However, interictal perfusion SPECT might enhance the specificity of ictal SPECT findings by improving the discrimination between seizure related local hyperperfusion and intersubject variability of perfusion (physiologic hyperperfusion). In addition, the combination of interictal and ictal perfusion SPECT might provide improved sensitivity compared to ictal SPECT alone, particularly when computer-aided subtraction of ictal and interictal SPECT is used instead of traditional side-by-side visual comparison. The combination of ictal and interictal perfusion SPECT eliminates not only physiological inter-subject variance, but it can also eliminate severe partial volume effects. Computer-aided subtraction analysis appears particularly useful in this case.

A Highly Efficient Catalyst for Oxime Ligation and Hydrazone-Oxime Exchange Suitable for Bioconjugation

OpenAIRE

Rashidian, Mohammad; Mahmoodi, Mohammad M.; Shah, Rachit; Dozier, Jonathan K.; Wagner, Carston R.; Distefano, Mark D.

2013-01-01

Imine-based reactions are useful for a wide range of bioconjugation applications. Although aniline is known to catalyze the oxime ligation reaction under physiological conditions, it suffers from slow reaction kinetics, specifically when a ketone is being used or when hydrazone-oxime exchange is performed. Here, we report on the discovery of a new catalyst that is up to 15 times more efficient than aniline. That catalyst, m-phenylenediamine (mPDA), was initially used to analyze the kinetics o...

Improvement of brain single photon emission tomography (SPET) using transmission data acquisition in a four-head SPET scanner

International Nuclear Information System (INIS)

Murase, Kenya; Tanada, Shuji; Inoue, Takeshi; Sugawara, Yoshifumi; Hamamoto, Ken

1993-01-01

Attenuation coefficient maps (μ-maps) are a useful way to compensate for non-uniform attenuation when performing single photon emission tomography (SPET). A new method was developed to record single photon transmission data and a μ-map for the brain was produced using a four-head SPET scanner. Transmission data were acquired by a gamma camera of opposite to a flood radioactive source attached to one of four gamma cameras in the four-head SPET scanner. Attenuation correction was performed using the iterative expectation maximization algorithm and the μ-map. Phantom studies demonstrated that this method could reconstruct the distribution of radioactivity more accurately than conventional methods, even for a severely non-uniform μ-map, and could improve the quality of SPET images. Clinical application to technetium-99m hexamethyl-propylene amine oxime (HMPAO) brain SPET also demonstrated the usefulness of this method. Thus, this method appears to be promising for improvement in the image quality and quantitative accuracy of brain SPET. (orig.)

A new prognostic index - leucocyte infiltration - in human cerebral infarcts by 99Tcm-HMPAO-labelled white blood cell brain SPECT

International Nuclear Information System (INIS)

Kao, C.H.; Wang, P.Y.; Wang, Y.L.; Chang, L.; Wang, S.J.; Yeh, S.H.

1991-01-01

Twenty-six patients with acute cerebral infarction were imaged by 99 Tc m -hexamethylpropylene-amine oxime (HMPAO)-labelled white blood cell brain (Tc-WBC) single photon emission computed tomography (SPECT). The regions of interest were equally placed in the whole hemispheres of both sides with summation of all transaxial slices in the Tc-WBC SPECT. The asymmetric indices (AI) were calculated as 200 [|(right -left)|/(right + left)]. Grouping of patients with cerebral infarction was based on activities of daily living (ADL) at outcome. The results showed that the poor outcome patient group had a higher AI of Tc-WBC than that of the other patients (13.0 ± 3.0 S.E.M. versus 5.4 ± 1.0 S.E.M., and P < 0.05 by Wilcoxon rank sum test). In conclusion, the Tc-WBC SPECT may be considered as a new prognostic index to predict patient outcome in human cerebral ischaemic infarctions consistent with newly established ischaemic injury theories. (author)

The Preparation and Intramolecular Radical Cyclisation Reactions of Chiral Oxime Ethers

Directory of Open Access Journals (Sweden)

Booth Susan E.

1998-01-01

Full Text Available Chiral oxime ether 2 and Oxime ester 4 have been prepared by alkylation and esterification of the oxime 1. Racemic hydroxylamine 6 and chiral hydroxylamine 10 have been synthesised from N-hydroxysuccinimide and the corresponding alcohol in the presence of diethylazodicarboxylate, the two products were converted into the oxime ethers 7 and 11 respectively. The intramolecular radical cyclisation reactions of these oxime ethers and esters has been studied, successful reaction was observed to produce alkyl hydroxylamines 3, 8 and 12.

Synthesis, spectra and X-ray crystallography of dipyridin-2-ylmethanone oxime and its CuX2(oxime)2 complexes: Thermal, Hirshfeld surface and DFT analysis

Science.gov (United States)

Warad, Ismail; Abdoh, Muneer; Al Ali, Anas; Shivalingegowda, Naveen; Kumara, Karthik; Zarrouk, Abdelkader; Lokanath, Neartur Krishnappagowda

2018-02-01

Dipyridin-2-ylmethanone oxime (C11H9N3O), was prepared using di-2-pyridyl ketone. The oxime ligand and its neutral CuX2 (oxime)2 (X = Cl or Br) complexes have been identified with the aid of several spectroscopic techniques such as: IR, EI-MS, EA, UV-visible, TG, 1H-NMR and finally the structure of the free oxime ligand was confirmed by X-ray diffraction studies. The oxime crystallizes in the monoclinic space group P21/c, with cell parameters a = 8.8811 (8) Å, b = 10.6362 (8) Å, c = 11.2050 (8) Å, β = 109.085 (4) º, V = 1000.26 (14) Å3 and Z = 4. The molecular conformation is stabilized by a strong intramolecular Osbnd H⋯N hydrogen bonding between the hydroxyl group of the oxime moiety and the nitrogen of the pyridine ring. Since the oxime structure was solved by XRD, the ligand structure parameters like bond length and angles were compared to the DFT computed one, the UV-visible to TD-SCF and Hirshfeld surface to MEP analysis.

Reaction of the oximes of aliphatic aldehydes and ketones with alkoxyethenes

International Nuclear Information System (INIS)

Voronkov, M.G.; Keiko, N.A.; Shuvashev, Yu.A.; Kalikhman, I.D.; Keiko, V.V.

1987-01-01

In the reaction of acetone oxime with alkyl vinyl ethers in the presence of zinc chloride variable amounts of acetone 0,0'-(2-propylidene)dioxime, acetaldehyde dialkyl acetal, acetaldehyde 0-(1-alkoxyethyl)oxide, and acetone 0-(1-alkoxy-1-methylethyl)oxime, depending on the reaction conditions, are formed in addition to acetone 0-(1-alkoxyethyl)oxime (the initial addition product). In the reaction of acetaldehyde oxime with alkyl vinyl ethers in the presence of zinc chloride acetaldehyde oxime with alkyl vinyl ethers in the presence of zinc chloride acetaldehyde dialkyl acetal was isolated in addition to acetaldehyde 0-(1-alkoxyethyl)oxime. A mechanism for the formation of the obtained compounds is proposed

A structure-activity analysis of the variation in oxime efficacy against nerve agents

International Nuclear Information System (INIS)

Maxwell, Donald M.; Koplovitz, Irwin; Worek, Franz; Sweeney, Richard E.

2008-01-01

A structure-activity analysis was used to evaluate the variation in oxime efficacy of 2-PAM, obidoxime, HI-6 and ICD585 against nerve agents. In vivo oxime protection and in vitro oxime reactivation were used as indicators of oxime efficacy against VX, sarin, VR and cyclosarin. Analysis of in vivo oxime protection was conducted with oxime protective ratios (PR) from guinea pigs receiving oxime and atropine therapy after sc administration of nerve agent. Analysis of in vitro reactivation was conducted with second-order rate contants (k r2 ) for oxime reactivation of agent-inhibited acetylcholinesterase (AChE) from guinea pig erythrocytes. In vivo oxime PR and in vitro k r2 decreased as the volume of the alkylmethylphosphonate moiety of nerve agents increased from VX to cyclosarin. This effect was greater with 2-PAM and obidoxime (> 14-fold decrease in PR) than with HI-6 and ICD585 ( r2 as the volume of the agent moiety conjugated to AChE increased was consistent with a steric hindrance mechanism. Linear regression of log (PR-1) against log (k r2 · [oxime dose]) produced two offset parallel regression lines that delineated a significant difference between the coupling of oxime reactivation and oxime protection for HI-6 and ICD585 compared to 2-PAM and obidoxime. HI-6 and ICD585 appeared to be 6.8-fold more effective than 2-PAM and obidoxime at coupling oxime reactivation to oxime protection, which suggested that the isonicotinamide group that is common to both of these oximes, but absent from 2-PAM and obidoxime, is important for oxime efficacy

21 CFR 524.1446 - Milbemycin oxime solution.

Science.gov (United States)

2010-04-01

... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Milbemycin oxime solution. 524.1446 Section 524...) ANIMAL DRUGS, FEEDS, AND RELATED PRODUCTS OPHTHALMIC AND TOPICAL DOSAGE FORM NEW ANIMAL DRUGS § 524.1446 Milbemycin oxime solution. (a) Specifications. Each tube contains 0.25 milliliter of a 0.1 percent solution...

Functionalised Oximes: Emergent Precursors for Carbon-, Nitrogen- and Oxygen-Centred Radicals

Directory of Open Access Journals (Sweden)

John C. Walton

2016-01-01

Full Text Available Oxime derivatives are easily made, are non-hazardous and have long shelf lives. They contain weak N–O bonds that undergo homolytic scission, on appropriate thermal or photochemical stimulus, to initially release a pair of N- and O-centred radicals. This article reviews the use of these precursors for studying the structures, reactions and kinetics of the released radicals. Two classes have been exploited for radical generation; one comprises carbonyl oximes, principally oxime esters and amides, and the second comprises oxime ethers. Both classes release an iminyl radical together with an equal amount of a second oxygen-centred radical. The O-centred radicals derived from carbonyl oximes decarboxylate giving access to a variety of carbon-centred and nitrogen-centred species. Methods developed for homolytically dissociating the oxime derivatives include UV irradiation, conventional thermal and microwave heating. Photoredox catalytic methods succeed well with specially functionalised oximes and this aspect is also reviewed. Attention is also drawn to the key contributions made by EPR spectroscopy, aided by DFT computations, in elucidating the structures and dynamics of the transient intermediates.

α-Diazo oxime ethers for N-heterocycle synthesis.

Science.gov (United States)

Choi, Subin; Ha, Sujin; Park, Cheol-Min

2017-06-01

This Feature Article introduces the preparation and synthetic utility of α-diazo oxime ethers. α-Oximino carbenes are useful synthons for N-heterocycles, and can be easily prepared from α-diazo oxime ethers as precursors. We begin with the preparation of α-diazo oxime ethers and their application in [3+2] cycloaddition. It turns out that the nature of metals bound to carbenes plays a crucial role in modulating the reactivity of α-oximino carbenes, in which copper carbenes smoothly react with enamines, whereas the less reactive enol ethers and nitriles require gold carbenes. In Section 3.2, a discussion on N-O and C-H bond activation is presented. Carbenes derived from diazo oxime ethers show unique reactivity towards N-O and C-H bond activation, in which the proximity of the two functionalities, carbene and oxime ether, dictates the preferred reaction pathways toward pyridines, pyrroles, and 2H-azirines. In Section 3.3, the development of tandem reactions based on α-diazo oxime ethers is discussed. The nature of carbenes in which whether free carbenes or metal complexes are involved dissects the pathway and forms different types of 2H-azirines. The 2H-azirine formation turned out to be an excellent platform for the tandem synthesis of N-heterocycles including pyrroles and pyridines. In the last section, we describe the electrophilic activation of 2H-azirines with vinyl carbenes and oximino carbenes. The resulting azirinium species undergo rapid ring expansion rearrangements to form pyridines and pyrazines.

The use of technetium-99m hexamethylpropylene amine oxime labelled white blood cells to detect subclinical inflammation of the heart after cardiopulmonary bypass in children with congenital heart disease

International Nuclear Information System (INIS)

Kao Chiahung; Wang Yenliang; Wang Shyhjen; Hsieh Kaisheng

1992-01-01

Ten children (6 boys and 4 girls, aged 1-9 years old) underwent operations with a cardiopulmonary bypass, and the technetium-99m hexamehtylpropylene amine oxine ( 99m Tc-HMPAO) labelled white blood cell (WBC) heart scans were used to detect postoperative leukocyte infiltration in the hearts. The results showed that 80% (8/10) of the cases had subclinical inflammation in the hearts (grading of WBC scans ≥score 2), and a positive correlation (R=0.77) was noted between the severity of the inflammation (grading of the WBC scans) and the duration of the cardiopulmonary bypass in the operations. Another control group (9 boys and 2 girls, aged 2-13 years old) underwent operations without a cardiopulmonary bypass, and subclinical inflammation of hearts was demonstrated in only 1 case (9%) by the 99m Tc-HMPAO labelled WBC scans (grading of WBC scans 99m Tc-HMPAO labelled WBC heart scans may provide non-invasive and directly discernible evidence of subclinical inflammation in the heart due to a transient ischaemic state during a cardiopulmonary bypass, even if the clinical symptoms and signs of carditis are not apparent. (orig.)

A comparison of the neuroprotective efficacy of individual oxime (HI-6) and combinations of oximes (HI-6+trimedoxime, HI-6+K203) in soman-poisoned rats.

Science.gov (United States)

Kassa, Jiri; Karasova, Jana Zdarova; Tesarova, Sandra

2011-07-01

The ability of two combinations of oximes (HI-6+trimedoxime, HI-6+K203) to reduce soman-induced acute neurotoxic signs and symptoms was compared with the neuroprotective efficacy of the oxime HI-6 alone, using a functional observational battery. Soman-induced neurotoxicity and the neuroprotective effects of HI-6 alone and HI-6 combined with trimedoxime or K203 in rats poisoned with soman at a sublethal dose (90 μg/kg intramuscularly, i.m.; 80% of LD₅₀ value) were monitored by the functional observational battery at 24 hours following soman administration. The results indicate that both tested oxime mixtures combined with atropine were able to allow soman-poisoned rats to survive 24 hours following soman challenge, while 4 nontreated soman-poisoned rats and 1 soman-poisoned rat treated with oxime HI-6 alone combined with atropine died within 24 hours following soman poisoning. While the oxime HI-6 alone combined with atropine treatment was able to eliminate a few soman-induced neurotoxic signs and symptoms, both oxime mixtures showed higher neuroprotective efficacy in soman-poisoned rats. Especially, the combination of HI-6 with trimedoxime was able to eliminate most soman-induced neurotoxic signs and symptoms and markedly reduce acute neurotoxicity of soman in rats. Thus, both tested mixtures of oximes combined with atropine were able to increase the neuroprotective effectiveness of antidotal treatment of acute soman poisonings, compared to the individual oxime.

Less common patterns of reduction of some oximes

Czech Academy of Sciences Publication Activity Database

Celik, H.; Ludvík, Jiří; Zuman, P.

2007-01-01

Roč. 52, č. 5 (2007), s. 1990-2000 ISSN 0013-4686 R&D Projects: GA MŠk 1P05ME785 Institutional research plan: CEZ:AV0Z40400503 Keywords : polarography * benzaldehyde oximes * acetophenone oximes * isomeric monoximes Subject RIV: CG - Electrochemistry Impact factor: 2.848, year: 2007

Simple, Efficient and Green Synthesis of Oximes under Ultrasound ...

African Journals Online (AJOL)

NICO

Faculty of Chemistry, Bu-Ali Sina University, Hamadan 65174, Iran. ... The condensation of aldehydes and ketones with hydroxylamine hydrochloride gives oximes in 81–95 ... Oximes are important in organic synthesis not only for protec-.

A Structure-Activity Analysis of the Variation in Oxime Efficacy Against Nerve Agents

Science.gov (United States)

2008-01-01

cyclosarin. Analysis of in vivo oxime protection was conducted with oxime protective ratios (PR) from guinea pigs receiving oxime and atropine therapy ...in our study confirmed previous assessments that oxime protection varies drama - tically against different military nerve agents (Aas, 2003; Dawson... therapy ofacutepoisonings inducedbyanti-cholinesterase neuroparalytic substances. In:Monov, A., Dishovsky, C. (Eds.), Medical Aspects of Chemical and

Adsorption equilibrium of uranium from seawater on chelating resin containing amide oxime group

International Nuclear Information System (INIS)

Hori, Takahiro; Saito, Kyoichi; Furusaki, Shintaro; Sugo, Takanobu; Okamoto, Jiro.

1987-01-01

Chelating resins containing amide oxime group were synthesized by radiation-induced graft polymerization. The amount of the amide oxime groups was controlled below about 0.1 mol per kg of base polymer. The adsorption equilibrium of uranium from seawater on this resin was investigated. It was suggested that two neighboring amide oxime groups on the grafted chain captured one uranyl ion, and that single amide oxime ligand had little capacity for the adsorption of uranium. The adsorption equilibrium was correlated by a Langmuir-type equation. The content of neighboring amide oxime groups was 0.406 x 10 -3 mol per kg of base polymer, which corresponded to 0.39 % of the total amount of amide oxime groups. The apparent stoichiometric stability constant for the complex of uranyl ion with the neighboring amide oxime groups in seawater was calculated to be 10 -21.7 . (author)

Development of new Czech autoinjector with oxime HI-6 DMS

International Nuclear Information System (INIS)

Kuca, K; Jun, D.; Kassa, J.; Marek, J.; Stodulka, P.; Musilek, K.; Dolezal, D.; Povraznik, J.

2009-01-01

Oxime HI-6 (1-(2-(hydroxyiminomethyl)pyridinium) -3-(4-carbamoylpyridinium)-2-oxapropane) is considered to be currently the most universal oxime for the potential use as antidote against nerve agents (sarin, cyclosarin, VX, etc.). None of other commercially available oximes (pralidoxime, obidoxime, trimedoxime, MMB4) has broader antidotal effect. Due to this, development of the appropriate salt of this oxime together with its application form (eg. autoinjector) was the main aim of our departments and several private Czech companies (VAKOS XT as., Decomkov Praha sro., ChemProtect as.). In our contribution, we would like to summarize all the steps which were already done. We would like to thank to the Ministry of Industry and Trade of the Czech Republic for the Project No. FIIM2/104.(author)

A comparison of the reactivating and therapeutic efficacy of two novel bispyridinium oximes (K727, K733) with the oxime HI-6 and obidoxime in sarin-poisoned rats and mice.

Science.gov (United States)

Kassa, Jiri; Sepsova, Vendula; Matouskova, Lenka; Horova, Anna; Musilek, Kamil

2015-03-01

The ability of two novel bispyridinium oximes K727 and K733 and currently available oximes (HI-6, obidoxime) to reactivate sarin-inhibited acetylcholinesterase and to reduce acute toxicity of sarin was evaluated. To investigate the reactivating efficacy of the oximes, the rats were administered intramuscularly with atropine and oximes in equitoxic doses corresponding to 5% of their LD50 values at 1 min after the intramuscular administration of sarin at a dose of 24 µg/kg (LD50). The activity of acetylcholinesterase was measured at 60 min after sarin poisoning. The LD50 value of sarin in non-treated and treated mice was assessed using probit-logarithmical analysis of death occurring within 24 h after intramuscular administration of sarin at five different doses. In vivo determined percentage of reactivation of sarin-inhibited rat blood, diaphragm and brain acetylcholinesterase showed that the potency of both novel oximes K727 and K733 to reactivate sarin-inhibited acetylcholinesterase roughly corresponds to the reactivating efficacy of obidoxime. On the other hand, the oxime HI-6 was found to be the most efficient reactivator of sarin-inhibited acetylcholinesterase. While the oxime HI-6 was able to reduce the acute toxicity of sarin >3 times, both novel oximes and obidoxime decreased the acute toxicity of sarin HI-6 and, therefore, they are not suitable for the replacement of the oxime HI-6 for the antidotal treatment of acute sarin poisoning.

The use of technetium-99m hexamethylpropylene amine oxime labelled white blood cells to detect subclinical inflammation of the heart after cardiopulmonary bypass in children with congenital heart disease

Energy Technology Data Exchange (ETDEWEB)

Kao Chiahung; Wang Yenliang; Wang Shyhjen (Taichung Veterans General Hospital (Taiwan). Dept. of Nuclear Medicine); Hsieh Kaisheng (Taichung Veterans General Hospital (Taiwan). Dept. of Pediatrics)

1992-11-01

Ten children (6 boys and 4 girls, aged 1-9 years old) underwent operations with a cardiopulmonary bypass, and the technetium-99m hexamehtylpropylene amine oxine ({sup 99m}Tc-HMPAO) labelled white blood cell (WBC) heart scans were used to detect postoperative leukocyte infiltration in the hearts. The results showed that 80% (8/10) of the cases had subclinical inflammation in the hearts (grading of WBC scans {>=}score 2), and a positive correlation (R=0.77) was noted between the severity of the inflammation (grading of the WBC scans) and the duration of the cardiopulmonary bypass in the operations. Another control group (9 boys and 2 girls, aged 2-13 years old) underwent operations without a cardiopulmonary bypass, and subclinical inflammation of hearts was demonstrated in only 1 case (9%) by the {sup 99m}Tc-HMPAO labelled WBC scans (grading of WBC scans

Cerebral blood flow measurement in patients with impaired consciousness: usefulness of {sup 99m}Tc-HMPAO single-photon emission tomography in clinical practice

Energy Technology Data Exchange (ETDEWEB)

Chang Chia-Cheng; Kuwana, Nobumasa; Noji, Masato; Tanabe, Yutaka; Koike, Y. [Department of Neurosurgery, Yokohama Minami Kyosai Hospital, Yokohama (Japan); Ikegami, Tadashi [Department of Radiology, Yokohama Minami Kyosai Hospital, Yokohama (Japan)

1998-09-01

The relationship between impairment of consciousness and quantitative cerebral blood flow (CBF) was investigated. The mean CBF of the whole brain was measured by the Patlak-plot method using technetium-99m hexamethylpropylene amine oxime single-photon emission tomography ({sup 99m}Tc-HMPAO SPET) in patients with the following diseases: cerebral infarction, intraparenchymal haemorrhage, subarachnoid haemorrhage, brain tumour and cerebral contusion. The clinical symptoms were evaluated according to the severity of impaired consciousness, aphasia and dementia. Four hundred and eighty-five CBF measurements were performed. Patients with alert consciousness showed an age-related decline in mean CBF. Patients with aphasia showed a significant reduction in mean CBF compared with those without aphasia. Impaired consciousness was proportional to reduction in mean CBF regardless of types of pathology, and the size of lesion did not influence the mean CBF. Patients with dementia showed a significant reduction in mean CBF proportional to the severity of dementia. The quantitative measurement of CBF using {sup 99m}Tc-HMPAO SPET is reliable in clinical evaluations. (orig.) With 3 tabs., 10 refs.

Cerebral blood flow measurement in patients with impaired consciousness: usefulness of 99mTc-HMPAO single-photon emission tomography in clinical practice

International Nuclear Information System (INIS)

Chang Chia-Cheng; Kuwana, Nobumasa; Noji, Masato; Tanabe, Yutaka; Koike, Y.; Ikegami, Tadashi

1998-01-01

The relationship between impairment of consciousness and quantitative cerebral blood flow (CBF) was investigated. The mean CBF of the whole brain was measured by the Patlak-plot method using technetium-99m hexamethylpropylene amine oxime single-photon emission tomography ( 99m Tc-HMPAO SPET) in patients with the following diseases: cerebral infarction, intraparenchymal haemorrhage, subarachnoid haemorrhage, brain tumour and cerebral contusion. The clinical symptoms were evaluated according to the severity of impaired consciousness, aphasia and dementia. Four hundred and eighty-five CBF measurements were performed. Patients with alert consciousness showed an age-related decline in mean CBF. Patients with aphasia showed a significant reduction in mean CBF compared with those without aphasia. Impaired consciousness was proportional to reduction in mean CBF regardless of types of pathology, and the size of lesion did not influence the mean CBF. Patients with dementia showed a significant reduction in mean CBF proportional to the severity of dementia. The quantitative measurement of CBF using 99m Tc-HMPAO SPET is reliable in clinical evaluations. (orig.)

Artificial neural networks that use single-photon emission tomography to identify patients with probable Alzheimer`s disease

Energy Technology Data Exchange (ETDEWEB)

Dawson, M R.W. [Dept. of Psychology, Univ. of Alberta, Edmonton (Canada); Dobbs, A [Dept. of Psychology, Univ. of Alberta, Edmonton (Canada); Hooper, H R [Dept. of Nuclear Medicine, Cross Cancer Inst., Edmonton, AB (Canada); McEwan, A J.B. [Dept. of Radiology and Diagnostic Imaging, Univ. of Alberta, Edmonton (Canada); Triscott, J [Dept. of Family Medicine and Div. of Geriatric Medicine, Univ. of Alberta, Edmonton (Canada); Cooney, J [Dept. of Psychiatry, Univ. of Alberta, Edmonton (Canada)

1994-12-01

Single-photon emission tomographic (SPET) images using technetium-99m labelled hexamethylpropylene amine oxime were obtained from 97 patients diagnosed as having Alzheimer`s disease, as well as from a comparison group of 64 normal subjects. Multiple linear regression was used to predict subject type (Alzheimer`s vs comparison) using scintillation counts from 14 different brain regions as predictors. These results were disappointing: the regression equation accounted for only 33.5% of the variance between subjects. However, the same data were also used to train parallel distributed processing (PDP) networks of different sizes to classify subjects. In general, the PDP networks accounted for substantially more (up to 95%) of the variance in the data, and in many instances were able to distinguish perfectly between the two subjects. These results suggest two conclusions. First, SPET images do provide sufficient information to distinguish patients with Alzheimer`s disease from a normal comparison group. Second, to access this diagnostic information, it appears that one must take advantage of the ability of PDP networks to detect higher-order nonlinear relationships among the predictor variables. (orig.)

Artificial neural networks that use single-photon emission tomography to identify patients with probable Alzheimer's disease

International Nuclear Information System (INIS)

Dawson, M.R.W.; Dobbs, A.; Hooper, H.R.; McEwan, A.J.B.; Triscott, J.; Cooney, J.

1994-01-01

Single-photon emission tomographic (SPET) images using technetium-99m labelled hexamethylpropylene amine oxime were obtained from 97 patients diagnosed as having Alzheimer's disease, as well as from a comparison group of 64 normal subjects. Multiple linear regression was used to predict subject type (Alzheimer's vs comparison) using scintillation counts from 14 different brain regions as predictors. These results were disappointing: the regression equation accounted for only 33.5% of the variance between subjects. However, the same data were also used to train parallel distributed processing (PDP) networks of different sizes to classify subjects. In general, the PDP networks accounted for substantially more (up to 95%) of the variance in the data, and in many instances were able to distinguish perfectly between the two subjects. These results suggest two conclusions. First, SPET images do provide sufficient information to distinguish patients with Alzheimer's disease from a normal comparison group. Second, to access this diagnostic information, it appears that one must take advantage of the ability of PDP networks to detect higher-order nonlinear relationships among the predictor variables. (orig.)

Binding of reactive organophosphate by oximes via hydrogen bond

Indian Academy of Sciences (India)

In this contribution, the ability of simple oximes to bind a well-known nerve agent simulant (dimethylmethylphosphonate, DMMP) via hydrogen bond is reported. UV/Vis measurements indicate the formation of 1:1 complexes. 1H-, 31P-NMR titrations and T-ROESY experiments confirm that oximes bind the organophosphate ...

Fluoren-9-one oxime

Directory of Open Access Journals (Sweden)

Bernhard Bugenhagen

2014-03-01

Full Text Available In the title molecule, C13H9NO, the fluorene system and the oxime group non-H atoms are essentially coplanar, with a maximum deviation from the fluorene mean plane of 0.079 (2 Å for the oxime O atom. A short intramolecular C—H...O generates an S(6 ring. In the crystal, molecules related by a twofold screw axis are connected by O—H...N hydrogen bonds, forming [100] chains Within these chains, molecules related by a unit translation along [100] show π–π stacking interactions between their fluorene ring systems with an interplanar distance of 3.347 (2 Å. The dihedral angle between the fluorene units of adjacent molecules along the helix is 88.40 (2°. There is a short C—H...π contact between the fluorene groups belonging to neighbouring chains.

A comprehensive evaluation of novel oximes in creation of butyrylcholinesterase-based nerve agent bioscavengers

Energy Technology Data Exchange (ETDEWEB)

Katalinić, Maja; Maček Hrvat, Nikolina [Institute for Medical Research and Occupational Health, POB 291, HR-10001 Zagreb (Croatia); Baumann, Krešimir; Morasi Piperčić, Sara; Makarić, Sandro; Tomić, Srđanka; Jović, Ozren; Hrenar, Tomica [Department of Chemistry, Faculty of Science, University of Zagreb, HR-10001 Zagreb (Croatia); Miličević, Ante [Institute for Medical Research and Occupational Health, POB 291, HR-10001 Zagreb (Croatia); Jelić, Dubravko [Fidelta Ltd., HR-10001 Zagreb (Croatia); Žunec, Suzana [Institute for Medical Research and Occupational Health, POB 291, HR-10001 Zagreb (Croatia); Primožič, Ines, E-mail: ines.primozic@chem.pmf.hr [Department of Chemistry, Faculty of Science, University of Zagreb, HR-10001 Zagreb (Croatia); Kovarik, Zrinka, E-mail: zkovarik@imi.hr [Institute for Medical Research and Occupational Health, POB 291, HR-10001 Zagreb (Croatia)

2016-11-01

A well-considered treatment of acute nerve agents poisoning involves the exogenous administration of butyrylcholinesterase (BChE, EC 3.1.1.8) as a stoichiometric bioscavenger efficient in preventing cholinergic crises caused by acetylcholinesterase (AChE, EC 3.1.1.7) inhibition. An additional improvement in medical countermeasures would be to use oximes that could reactivate BChE as well to upgrade bioscavenging from stoichiometric to oxime-assisted catalytic. Therefore, in this paper we investigated the potency of 39 imidazolium and benzimidazolium oximes (36 compounds synthesized for the first time) to be considered as the reactivators specifically designed for reactivation of phosphylated human BChE. Their efficiency in the reactivation of paraoxon-, VX-, and tabun-inhibited human BChE, as well as human AChE was tested and compared with the efficiencies of HI-6 and obidoxime, used in medical practice today. A comprehensive analysis was performed for the most promising oximes defining kinetic parameters of reactivation as well as interactions with uninhibited BChE. Furthermore, experimental data were compared with computational studies (docking, QSAR analysis) as a starting point in future oxime structure refinement. Considering the strict criteria set for in vivo applications, we determined the cytotoxicity of lead oximes on two cell lines. Among the tested oxime library, one imidazolium compound was selected for preliminary in vivo antidotal study in mice. The obtained protection in VX poisoning outlines its potential in development oxime-assisted OP-bioscavenging with BChE. - Highlights: • 36 new imidazolium and benzimidazolium oximes were designed and synthesized. • In vitro reactivation kinetics of phosphylated butyrylcholinesterase was studded. • The modes of actions were elucidated by QSAR and docking simulations. • Protection in VX poisoning was 6.3 × LD{sub 50} in in vivo antidotal study in mice. • Imidazolium oxime-assisted catalysis is

A comprehensive evaluation of novel oximes in creation of butyrylcholinesterase-based nerve agent bioscavengers

International Nuclear Information System (INIS)

Katalinić, Maja; Maček Hrvat, Nikolina; Baumann, Krešimir; Morasi Piperčić, Sara; Makarić, Sandro; Tomić, Srđanka; Jović, Ozren; Hrenar, Tomica; Miličević, Ante; Jelić, Dubravko; Žunec, Suzana; Primožič, Ines; Kovarik, Zrinka

2016-01-01

A well-considered treatment of acute nerve agents poisoning involves the exogenous administration of butyrylcholinesterase (BChE, EC 3.1.1.8) as a stoichiometric bioscavenger efficient in preventing cholinergic crises caused by acetylcholinesterase (AChE, EC 3.1.1.7) inhibition. An additional improvement in medical countermeasures would be to use oximes that could reactivate BChE as well to upgrade bioscavenging from stoichiometric to oxime-assisted catalytic. Therefore, in this paper we investigated the potency of 39 imidazolium and benzimidazolium oximes (36 compounds synthesized for the first time) to be considered as the reactivators specifically designed for reactivation of phosphylated human BChE. Their efficiency in the reactivation of paraoxon-, VX-, and tabun-inhibited human BChE, as well as human AChE was tested and compared with the efficiencies of HI-6 and obidoxime, used in medical practice today. A comprehensive analysis was performed for the most promising oximes defining kinetic parameters of reactivation as well as interactions with uninhibited BChE. Furthermore, experimental data were compared with computational studies (docking, QSAR analysis) as a starting point in future oxime structure refinement. Considering the strict criteria set for in vivo applications, we determined the cytotoxicity of lead oximes on two cell lines. Among the tested oxime library, one imidazolium compound was selected for preliminary in vivo antidotal study in mice. The obtained protection in VX poisoning outlines its potential in development oxime-assisted OP-bioscavenging with BChE. - Highlights: • 36 new imidazolium and benzimidazolium oximes were designed and synthesized. • In vitro reactivation kinetics of phosphylated butyrylcholinesterase was studded. • The modes of actions were elucidated by QSAR and docking simulations. • Protection in VX poisoning was 6.3 × LD 50 in in vivo antidotal study in mice. • Imidazolium oxime-assisted catalysis is feasible

Studies on the polymerization of acrolein oxime, 6

International Nuclear Information System (INIS)

Masuda, Seizo; Tamai, Harumi; Ota, Tadatoshi; Torii, Munetomo; Tanaka, Masami.

1979-01-01

Radiation-induced polymerization and copolymerization of acrolein oxime are investigated in different solvents and at a wide range of temperature for obtaining information on the reaction mechanism. Acrolein oxime is polymerized ionically, irrespective of dryness of the sample. Arrhenius plots for the polymerization rate, which do not yield a linear relation, can be adequately approximated by two straight lines. An anionic mechanism is operative above the room temperature, while a cationic mechanism predominates below -23 0 C. The reaction in the intermediate temperature range proceeds by a competitive mechanism, and the rate of the anionic and cationic polymerizations becomes equal at the temperature near -5 0 C. The reaction rate is proportional to the square root of dose rate at room temperature and -23 0 C. On the basis of these data, it is proposed that the polymerization of acrolein oxime by γ-irradiation proceeds by free-ionic mechanisms. (author)

Evaluation of oxime efficacy in nerve agent poisoning: Development of a kinetic-based dynamic model

International Nuclear Information System (INIS)

Worek, Franz; Szinicz, Ladislaus; Eyer, Peter; Thiermann, Horst

2005-01-01

The widespread use of organophosphorus compounds (OP) as pesticides and the repeated misuse of highly toxic OP as chemical warfare agents (nerve agents) emphasize the necessity for the development of effective medical countermeasures. Standard treatment with atropine and the established acetylcholinesterase (AChE) reactivators, obidoxime and pralidoxime, is considered to be ineffective with certain nerve agents due to low oxime effectiveness. From obvious ethical reasons only animal experiments can be used to evaluate new oximes as nerve agent antidotes. However, the extrapolation of data from animal to humans is hampered by marked species differences. Since reactivation of OP-inhibited AChE is considered to be the main mechanism of action of oximes, human erythrocyte AChE can be exploited to test the efficacy of new oximes. By combining enzyme kinetics (inhibition, reactivation, aging) with OP toxicokinetics and oxime pharmacokinetics a dynamic in vitro model was developed which allows the calculation of AChE activities at different scenarios. This model was validated with data from pesticide-poisoned patients and simulations were performed for intravenous and percutaneous nerve agent exposure and intramuscular oxime treatment using published data. The model presented may serve as a tool for defining effective oxime concentrations and for optimizing oxime treatment. In addition, this model can be useful for the development of meaningful therapeutic animal models

Dose response toxic effects of different oximes in vivo: pathohystological evaluation

International Nuclear Information System (INIS)

Jacevic, V.

2009-01-01

The acute toxicity of oximes is crucial for the assessment of a dose applied as a treatment for organophosphorus intoxications. This is why we decided to investigate which morphological lesions could be produced in Wistar rats after treatment with increasing doses of HI-6, Obidoxime, K027, K048, and K075. In the first part of this study, tested oximes were preliminarily tested in order to obtain their LD50 values. Survival rates were monitored 24 hours after application of each oxime. In separate experiment animals were sacrificed 7 days after single im application of 0.1 LD50 and 0.5 LD50 of each oxime, and hearts, diaphragms and musculus popliteus were obtained for pathohistological analysis. Tissue damage score (TDS) was based on an estimation scale from 0 (no damage) to 5 (strong damage, massive necrotic fields). In rats treated with of 0.1 LD50 of HI-6 and K027 microscopic findings were similar to those evaluated in the control groups, only. More intensive alterations, but still mild and reversible degenerative and vascular changes, were established in tissue samples after treatment with 0.1 LD50 of Obidoxime, K048 and K075, but their values were also similar to the control group. Acute lesions were developed in tissue samples within 7 days following treatment with 0.5 LD50 of all oximes. The most severe tissue alterations were found in rats treated with 0.5 LD50 of K048 and K075 (p < 0.001 vs. control and HI-6). These observations of the earliest tissues events are helping to guide of applications of novel development oximes.(author)

New Cinchona Oximes Evaluated as Reactivators of Acetylcholinesterase and Butyrylcholinesterase Inhibited by Organophosphorus Compounds

Directory of Open Access Journals (Sweden)

Maja Katalinić

2017-07-01

Full Text Available For the last six decades, researchers have been focused on finding efficient reactivators of organophosphorus compound (OP-inhibited acetylcholinesterase (AChE and butyrylcholinesterase (BChE. In this study, we have focused our research on a new oxime scaffold based on the Cinchona structure since it was proven to fit the cholinesterases active site and reversibly inhibit their activity. Three Cinchona oximes (C1, C2, and C3, derivatives of the 9-oxocinchonidine, were synthesized and investigated in reactivation of various OP-inhibited AChE and BChE. As the results showed, the tested oximes were more efficient in the reactivation of BChE and they reactivated enzyme activity to up to 70% with reactivation rates similar to known pyridinium oximes used as antidotes in medical practice today. Furthermore, the oximes showed selectivity towards binding to the BChE active site and the determined enzyme-oxime dissociation constants supported work on the future development of inhibitors in other targeted studies (e.g., in treatment of neurodegenerative disease. Also, we monitored the cytotoxic effect of Cinchona oximes on two cell lines Hep G2 and SH-SY5Y to determine the possible limits for in vivo application. The cytotoxicity results support future studies of these compounds as long as their biological activity is targeted in the lower micromolar range.

Recent advances in evaluation of oxime efficacy in nerve agent poisoning by in vitro analysis

International Nuclear Information System (INIS)

Worek, F.; Eyer, P.; Aurbek, N.; Szinicz, L.; Thiermann, H.

2007-01-01

The availability of highly toxic organophosphorus (OP) warfare agents (nerve agents) underlines the necessity for an effective medical treatment. Acute OP toxicity is primarily caused by inhibition of acetylcholinesterase (AChE). Reactivators (oximes) of inhibited AChE are a mainstay of treatment, however, the commercially available compounds, obidoxime and pralidoxime, are considered to be rather ineffective against various nerve agents, e.g. soman and cyclosarin. This led to the synthesis and investigation of numerous oximes in the past decades. Reactivation of OP-inhibited AChE is considered to be the most important reaction of oximes. Clinical data from studies with pesticide-poisoned patients support the assumption that the various reactions between AChE, OP and oxime, i.e. inhibition, reactivation and aging, can be investigated in vitro with human AChE. In contrast to animal experiments such in vitro studies with human tissue enable the evaluation of oxime efficacy without being affected by species differences. In the past few years numerous in vitro studies were performed by different groups with a large number of oximes and methods were developed for extrapolating in vitro data to different scenarios of human nerve agent poisoning. The present status in the evaluation of new oximes as antidotes against nerve agent poisoning will be discussed

Biological basis of social anxiety disorder

International Nuclear Information System (INIS)

Izumi, Takeshi; Yoshioka, Mitsuhiro; Koyama, Tsukasa

2007-01-01

Reviewed are functional imaging studies of the brain in social anxiety disorder (SAD) which are being under remarkable progress, to discuss the disease in relation to the neuronal network. Current consensuses on results, their meta-analysis and consideration of regions suggested in those studies are as follows. In MRI and single photon emission computed tomography (SPECT) studies, cerebral morphology and blood flow at rest with 99m Tc-hexamethylpropylene amine oxime (HMPAO) are normal in SAD. Many studies of SAD by positron emission tomography (PET) with probes such as 15 O-H 2 O and by fMRI have shown an anxiety-induced excess reaction in the amygdaloid body and insula, and certain studies, a reaction change in frontal lobe or cingulate gyrus. Pattern change of cerebral blood flow is observable by SPECT and PET with 11 C-WAY-100635 after treatment of SAD with SSRI (serotonin-selective reuptake inhibitor). Image findings of brain functions in SAD are not contradictory to clinical findings. Discussion of SAD is also made here in relation to posttraumatic stress and panic disorders, and their image findings. (R.T.)

Oxime Ethers of (E)-11-Isonitrosostrychnine as Highly Potent Glycine Receptor Antagonists

DEFF Research Database (Denmark)

Mohsen, Amal M Y; Mandour, Yasmine M; Sarukhanyan, Edita

2016-01-01

of the crystal structure of the α3 glycine receptor indicated the same orientation of the strychnine core for all analogues. For the most potent oxime ethers, the ether substituent was accommodated in a lipophilic receptor binding pocket. The findings identify the oxime hydroxy group as a suitable attachment...

Comparison of oxime reactivation and aging of nerve agent-inhibited monkey and human acetylcholinesterases.

Science.gov (United States)

Luo, Chunyuan; Tong, Min; Maxwell, Donald M; Saxena, Ashima

2008-09-25

Non-human primates are valuable animal models that are used for the evaluation of nerve agent toxicity as well as antidotes and results from animal experiments are extrapolated to humans. It has been demonstrated that the efficacy of an oxime primarily depends on its ability to reactivate nerve agent-inhibited acetylcholinesterase (AChE). If the in vitro oxime reactivation of nerve agent-inhibited animal AChE is similar to that of human AChE, it is likely that the results of an in vivo animal study will reliably extrapolate to humans. Therefore, the goal of this study was to compare the aging and reactivation of human and different monkey (Rhesus, Cynomolgus, and African Green) AChEs inhibited by GF, GD, and VR. The oximes examined include the traditional oxime 2-PAM, two H-oximes HI-6 and HLo-7, and the new candidate oxime MMB4. Results indicate that oxime reactivation of all three monkey AChEs was very similar to human AChE. The maximum difference in the second-order reactivation rate constant between human and three monkey AChEs or between AChEs from different monkey species was 5-fold. Aging rate constants of GF-, GD-, and VR-inhibited monkey AChEs were very similar to human AChE except for GF-inhibited monkey AChEs, which aged 2-3 times faster than the human enzyme. The results of this study suggest that all three monkey species are suitable animal models for nerve agent antidote evaluation since monkey AChEs possess similar biochemical/pharmacological properties to human AChE.

Fast and low-temperature sintering of silver complex using oximes as a potential reducing agent for solution-processible, highly conductive electrodes

International Nuclear Information System (INIS)

Yoo, Ji Hoon; Park, Su Bin; Kim, Ji Man; Han, Dae Sang; Chae, Jangwoo; Kwak, Jeonghun

2014-01-01

Highly conductive, solution-processed silver thin-films were obtained at a low sintering temperature of 100 °C in a short sintering time of 10 min by introducing oximes as a potential reductant for silver complex. The thermal properties and reducibility of three kinds of oximes, acetone oxime, 2-butanone oxime, and one dimethylglyoxime, were investigated as a reducing agent, and we found that the thermal decomposition product of oximes (ketones) accelerated the conversion of silver complex into highly conductive silver at low sintering temperature in a short time. Using the acetone oxime, the silver thin-film exhibited the lowest surface resistance (0.91 Ω sq −1 ) compared to those sing other oximes. The silver thin-film also showed a high reflectance of 97.8%, which is comparable to evaporated silver films. We also demonstrated inkjet printed silver patterns with the oxime-added silver complex inks. (paper)

A Development of Rapid, Practical and Selective Process for Preparation of Z-Oximes

International Nuclear Information System (INIS)

Kim, Bo Ram; Sung, Gi Hyeon; Yoon, Yongjin; Kim, Jeumjong

2013-01-01

Oximes are important functional groups in organic chemistry due to their synthetic utility as protecting groups for carbonyl groups and their ability to form other functionalities, and their biological activity. Oximes are commonly prepared by condensing aldehydes and ketones with hydroxylamines. These reactions do not always go to completion and reaction times can be long, and therefore there has been interest in more convenient and efficient methods. To avoid the typical disadvantage, conversion of aldehydes and ketones to the corresponding oximes was accomplished by using various catalysts such as organic acid/bases, AcONa, alumina, TiO 2 /SO 4 silica gel, Oxone, NaOH, basic ionic liquid 1-butyl-3-methylimidazolium hydroxide, polyoxometalates, Na 2 SO 4 , and CuSO 4 /K 2 CO 3 under the solvent, the solvent-free or the microwave conditions. These are one and more drowbacks such as long reaction time, use of catalysts, inconvenients due to solid-sate reaction, low yields and limitaion of some carbonyl compounds. On the other hand, H. Sharghi, et al.,14 reported the catalysis of the stereoselectivity of CuSO 4 and K 2 CO 3 in the oximation of aldehydes and ketones under solvent-free conditions. Although this method show high selectivity, it is inconvenient for the large scale experiments and the industrial process due to the solvent-free condition. Therefore, we attempted to develop a more convenient and efficient solution method. According to the literatures, treatment of potassium carbonate with methanol generates slightly the potassium methoxide, which may be useful for forming the free NH 2 OH from its salts. We describe the oximation of aldehyde and ketone using NH 2 OH·HCl/K 2 CO 3 in methanol solvent. We selected oximation of acetophenone (1a) with hydroxylamine hydrochloride as a model and its behavior was investigated in seven solvents involving methanol (Table 1). As shown in the Entry 2 in Table 1, compound 1a was treated with hydroxylamine

A Development of Rapid, Practical and Selective Process for Preparation of Z-Oximes

Energy Technology Data Exchange (ETDEWEB)

Kim, Bo Ram; Sung, Gi Hyeon; Yoon, Yongjin [Gyeongsang National Univ., Jinju (Korea, Republic of); Kim, Jeumjong [Electronic and Telecommunications Research Institute, Daejeon (Korea, Republic of)

2013-04-15

Oximes are important functional groups in organic chemistry due to their synthetic utility as protecting groups for carbonyl groups and their ability to form other functionalities, and their biological activity. Oximes are commonly prepared by condensing aldehydes and ketones with hydroxylamines. These reactions do not always go to completion and reaction times can be long, and therefore there has been interest in more convenient and efficient methods. To avoid the typical disadvantage, conversion of aldehydes and ketones to the corresponding oximes was accomplished by using various catalysts such as organic acid/bases, AcONa, alumina, TiO{sub 2}/SO{sub 4} silica gel, Oxone, NaOH, basic ionic liquid 1-butyl-3-methylimidazolium hydroxide, polyoxometalates, Na{sub 2}SO{sub 4}, and CuSO{sub 4}/K{sub 2}CO{sub 3} under the solvent, the solvent-free or the microwave conditions. These are one and more drowbacks such as long reaction time, use of catalysts, inconvenients due to solid-sate reaction, low yields and limitaion of some carbonyl compounds. On the other hand, H. Sharghi, et al.,14 reported the catalysis of the stereoselectivity of CuSO{sub 4} and K{sub 2}CO{sub 3} in the oximation of aldehydes and ketones under solvent-free conditions. Although this method show high selectivity, it is inconvenient for the large scale experiments and the industrial process due to the solvent-free condition. Therefore, we attempted to develop a more convenient and efficient solution method. According to the literatures, treatment of potassium carbonate with methanol generates slightly the potassium methoxide, which may be useful for forming the free NH{sub 2}OH from its salts. We describe the oximation of aldehyde and ketone using NH{sub 2}OH·HCl/K{sub 2}CO{sub 3} in methanol solvent. We selected oximation of acetophenone (1a) with hydroxylamine hydrochloride as a model and its behavior was investigated in seven solvents involving methanol (Table 1). As shown in the Entry 2 in

76 FR 12563 - Oral Dosage Form New Animal Drugs; Spinosad and Milbemycin Oxime

Science.gov (United States)

2011-03-08

... spinosad and milbemycin oxime in dogs for the treatment and prevention of flea infestations and for the... and milbemycin oxime) Chewable Tablets in dogs for the treatment and prevention of flea infestations... Friday. Under section 512(c)(2)(F)(ii) of the Federal Food, Drug, and Cosmetic Act (21 U.S.C. 360b(c)(2...

Chromatographic analysis of toxic phosphylated oximes (POX): a brief overview.

Science.gov (United States)

Becker, Christian; Worek, Franz; John, Harald

2010-10-01

Poisoning with organophosphorus compounds (OP), e.g. pesticides and nerve agents, causes inhibition of acetylcholinesterase (AChE) by phosphylation of the active site serine residue. Consequently, accumulation of stimulating acetylcholine in the synaptic cleft induces cholinergic crisis which ultimately may lead to death. For standard causal therapy, enzyme reactivators are administered representing oxime derivatives of quarternary pyridinium compounds, e.g. pralidoxime (2-PAM), obidoxime and HI 6. The mechanism of action includes removal of the phosphyl moiety by a nucleophilic attack of the oximate molecule substituting the enzyme and forming a phosphylated oxime (POX). POX is produced in stoichiometric amounts of reactivated enzyme and exhibits a significantly enhanced toxicity (inhibition rate constant) when compared to the parent OP. However, stability of POX under physiological conditions appears to be highly limited. Nevertheless, the presence of POX reveals a potential critical issue for both therapeutic efficacy in vivo and pharmacokinetic and pharmacodynamic (PK-PD) modelling based on cholinesterase activity data. Detailed characterization represents an important need for elaboration of the entire oxime pharmacology.Nevertheless, reports on POX toxicity and analysis are quite rare and may therefore be indicative of the challenge of POX analysis. This review provides a concise overview of chromatographic approaches applied to POX separation. Chromatography represents the key technology for POX purification and quantification in kinetic in vitro studies using buffers and biological fluids. Applications based on reversed-phase chromatography (RPC), ion pair chromatography (IPC) and an affinity approach as well as thin layer chromatography (TLC) are discussed and novel applications and data are presented. Copyright © 2010 John Wiley & Sons, Ltd.

Organic Process Technology Valuation: Cyclohexanone Oxime Syntheses

Science.gov (United States)

Cannon, Kevin C.; Breen, Maureen P.

2010-01-01

Three contemporary processes for cyclohexanone oxime synthesis are evaluated in a case study. The case study introduces organic chemistry students to basic cost accounting to determine the most economical technology. Technical and financial aspects of these processes are evaluated with problem-based exercises that may be completed by students…

Inhibition of the voltage-dependent chloride channel of Torpedo electric organ by diisopropylfluorophosphate and its reversal by oximes

International Nuclear Information System (INIS)

Abalis, I.M.; Chiang, P.K.; Wirtz, R.A.; Andre, R.G.

1986-01-01

Diisopropylfluorophosphate (DFP), a potent organophosphate inhibitor of cholinesterases, was found to inhibit the specific binding of [ 35 S]t-butylbicyclophosphorothionate (TBPS), specific chloride channels ligand, to the electric organ membranes of Torpedo, with a Ki of 21 +/- 3 μM. The binding sites of [ 35 S]TBPS in the Torpedo membranes were found not to be GABA receptors or nicotinic acetylcholine receptors as previously described. Interestingly, a stimulation of the binding of [ 35 S]TBPS was observed in the presence of atropine and three oximes, monopyridinium oxime 2-PAM, bispyridinium bis-oxime TMB-4 and H-oxime HI-6. The maximal stimulation was 300-500% of control, after which, the stimulation was reversed at higher concentrations. The three oximes protected by more than 95% the inhibition by 1 mM DFP of the binding of [ 35 S]TBPS to the voltage-dependent chloride channel. However, atropine protected only 20% of the inhibited channel. These results, thus, suggest that the protection against the toxic effects of DFP or other anticholinesterase agents by the tested oximes may not be solely a result of the reactivation of cholinesterases but also the protection of the voltage-dependent chloride channel

Methods of evaluating SPECT images. The usefulness of the Matsuda`s method by the Patlak plot method in children

Energy Technology Data Exchange (ETDEWEB)

Takaishi, Yasuko [Nippon Medical School, Tokyo (Japan); Hashimoto, Kiyoshi; Fujino, Osamu [and others

1998-11-01

Single photon emission computed tomography (SPECT) is a tool to study cerebral blood flow (CBF) kinetics. There are three methods of evaluating SPECT images: visual, semi-quantitative (evaluation of the radioactivity ratio of the cerebral region to the cerebellum (R/CE) or to the thalamus (R/TH)) and quantitative (Matsuda`s method by Patlak plot method using {sup 99m}Tc-hexamethylpropylene amine oxime radionuclide angiography). We evaluated SPECT images by the quantitative method in 14 patients with neurological disorders and examined the correlation of the results to those obtained by the semi-quantitative method. There was no significant correlation between the R/CE or R/TH ratio and regional CBF except two regions. The evaluation by the semi-quantitative method may have been inappropriate, probably because the cerebellar or thalamic blood flow was not constant in each case. Evaluation by the quantitative method, on the other hand, seemed to be useful not only for the comparison of CBF among normal subjects, but also in the demonstration of progressive changes of CBF in the same case. The Matsuda`s method by the Patlak plot method is suitable for examination of children, since it dose not require aortic blood sampling. (author)

Preparation of phenacylchloride, morpholinophenacyl and N-Piperidinophenacyl oximes and study of their complexation with Copper (II) and Cobalt (II) ions

International Nuclear Information System (INIS)

Ali, Kamal Eldin Ahmed

1999-01-01

The aim of the present work is to prepare phenacyl chloride oxime and phenacyl of N-Piperidine and morpholine derivatives, and mainly to study their complexes with Cu(II) and Co(II) ions with objective ascertaining that one of these ligands can be used in quantitative extraction of these metal ions from the aqueous solution. Copper (II) salts form 1:1 complexes with the phenyacyl oximes of N-piperidine and morpholine and 1:2 complex with phenacyl chloride oxime. However, cobalt(II) salts form 1:2 complexes with phenacyl oxime of N-piperidine and morpholine but does not complex with phenacyl chloride oxime. The stoichiometry of these complexes were determined by UV/VIS spectrophotometry using the mole ratio, continuous variation and slope ratio methods.The stability constants of the five complexes were calculated from aberrances using Job's method. They showed that the copper (II) and cobalt (II) complexes with N-piperidinophenacy oxime are more stable than those with morpholinophenacyl oxime. Copper (II) complexes with any of these two ligands are more stable than those of cobalt (II). IR spectra of the complexes of copper (II) and cobalt (II) with phenacyl oxime of N-piperidine and morpholine show diminished peaks of hydrogen bonds between N and O atoms of the ligand. Specific extractabilities using amylalcohol of copper (II) complexes with the three ligands increase from PH4 to reach its maximum at PH8. The high value for N-piperidinophenacyl oxime ligand (96%-97%) indicates that, this ligand can be used as analytical reagent for the quantitative spectrophotometric determination of copper (II) salts in aqueous media. Cobalt (II) complexes were formed and extracted from solution only at PH6 (specific PH). The extractabilities ranging from 81.6-87.2% warrants the use of these ligands in quantitative spectrophotometric determination of cobalt (II).(Author)

Deprotection of oximes using urea nitrate under microwave irradiation

Indian Academy of Sciences (India)

Abstract. A new mild and efficient method for the cleavage of oximes to carbonyl compounds using readily available urea nitrate in acetonitrile-water (95 : 5), under microwave irradiation within 2 min, in good yields is reported.

Cutaneous exposure to vesicant phosgene oxime: Acute effects on the skin and systemic toxicity

International Nuclear Information System (INIS)

Tewari-Singh, Neera; Goswami, Dinesh G; Kant, Rama; Croutch, Claire R; Casillas, Robert P; Orlicky, David J; Agarwal, Rajesh

2017-01-01

Phosgene Oxime (CX), an urticant or nettle agent categorized as a vesicant, is a potential chemical warfare and terrorist weapon. Its exposure can result in widespread and devastating effects including high mortality due to its fast penetration and ability to cause immediate severe cutaneous injury. It is one of the least studied chemical warfare agents with no effective therapy available. Thus, our goal was to examine the acute effects of CX following its cutaneous exposure in SKH-1 hairless mice to help establish a relevant injury model. Results from our study show that topical cutaneous exposure to CX vapor causes blanching of exposed skin with an erythematous ring, necrosis, edema, mild urticaria and erythema within minutes after exposure out to 8 h post-exposure. These clinical skin manifestations were accompanied with increases in skin thickness, apoptotic cell death, mast cell degranulation, myeloperoxidase activity indicating neutrophil infiltration, p53 phosphorylation and accumulation, and an increase in COX-2 and TNFα levels. Topical CX-exposure also resulted in the dilatation of the peripheral vessels with a robust increase in RBCs in vessels of the liver, spleen, kidney, lungs and heart tissues. These events could cause a drop in blood pressure leading to shock, hypoxia and death. Together, this is the first report on effects of CX cutaneous exposure, which could help design further comprehensive studies evaluating the acute and chronic skin injuries from CX topical exposure and elucidate the related mechanism of action to aid in the identification of therapeutic targets and mitigation of injury. - Highlights: • Phosgene oxime cutaneous exposure causes skin blanching, edema and urticaria. • Penetration of phosgene oxime causes dilation of vasculature in internal organs. • Mast cells could play an important role in phosgene oxime-induced skin injury. • Phosgene oxime could induce low blood pressure and hypoxia leading to mortality. • Data is

Cutaneous exposure to vesicant phosgene oxime: Acute effects on the skin and systemic toxicity

Energy Technology Data Exchange (ETDEWEB)

Tewari-Singh, Neera, E-mail: Neera.tewari-singh@ucdenver.edu [Department of Pharmaceutical Sciences, Skaggs School of Pharmacy and Pharmaceutical Sciences, University of Colorado Anschutz Medical Campus, Aurora, CO 80045 (United States); Goswami, Dinesh G; Kant, Rama [Department of Pharmaceutical Sciences, Skaggs School of Pharmacy and Pharmaceutical Sciences, University of Colorado Anschutz Medical Campus, Aurora, CO 80045 (United States); Croutch, Claire R; Casillas, Robert P [MRIGlobal, Kansas City, MO 64110 (United States); Orlicky, David J [Department of Pathology, School of Medicine, University of Colorado Anschutz Medical Campus, Aurora, CO 80045 (United States); Agarwal, Rajesh [Department of Pharmaceutical Sciences, Skaggs School of Pharmacy and Pharmaceutical Sciences, University of Colorado Anschutz Medical Campus, Aurora, CO 80045 (United States)

2017-02-15

Phosgene Oxime (CX), an urticant or nettle agent categorized as a vesicant, is a potential chemical warfare and terrorist weapon. Its exposure can result in widespread and devastating effects including high mortality due to its fast penetration and ability to cause immediate severe cutaneous injury. It is one of the least studied chemical warfare agents with no effective therapy available. Thus, our goal was to examine the acute effects of CX following its cutaneous exposure in SKH-1 hairless mice to help establish a relevant injury model. Results from our study show that topical cutaneous exposure to CX vapor causes blanching of exposed skin with an erythematous ring, necrosis, edema, mild urticaria and erythema within minutes after exposure out to 8 h post-exposure. These clinical skin manifestations were accompanied with increases in skin thickness, apoptotic cell death, mast cell degranulation, myeloperoxidase activity indicating neutrophil infiltration, p53 phosphorylation and accumulation, and an increase in COX-2 and TNFα levels. Topical CX-exposure also resulted in the dilatation of the peripheral vessels with a robust increase in RBCs in vessels of the liver, spleen, kidney, lungs and heart tissues. These events could cause a drop in blood pressure leading to shock, hypoxia and death. Together, this is the first report on effects of CX cutaneous exposure, which could help design further comprehensive studies evaluating the acute and chronic skin injuries from CX topical exposure and elucidate the related mechanism of action to aid in the identification of therapeutic targets and mitigation of injury. - Highlights: • Phosgene oxime cutaneous exposure causes skin blanching, edema and urticaria. • Penetration of phosgene oxime causes dilation of vasculature in internal organs. • Mast cells could play an important role in phosgene oxime-induced skin injury. • Phosgene oxime could induce low blood pressure and hypoxia leading to mortality. • Data is

Conversion of Natural Aldehydes from Eucalyptus citriodora, Cymbopogon citratus, and Lippia multiflora into Oximes: GC-MS and FT-IR Analysis †

Directory of Open Access Journals (Sweden)

Igor W. Ouédraogo

2009-08-01

Full Text Available Three carbonyl-containing extracts of essential oils from Eucalyptus citriodora (Myrtaceae, Cymbopogon citratus (Gramineae and Lippia multiflora (Verbenaceae were used for the preparation of oximes. The reaction mixtures were analyzed by GC-MS and different compounds were identified on the basis of their retention times and mass spectra. We observed quantitative conversion of aldehydes to their corresponding oximes with a purity of 95 to 99%. E and Z stereoisomers of the oximes were obtained and separated by GC-MS. During GC analysis, the high temperature in the injector was shown to cause partial dehydratation of oximes and the resulting nitriles were readily identified. Based on FT-IR spectroscopy, that revealed the high stability and low volatility of these compounds, the so-obtained oximes could be useful for future biological studies.

Impacts of Different Functional Groups on the Kinetic Rates of α-Amine Ketoximesilanes Hydrolysis in the Preparation of Room Temperature Vulcanized Silicone Rubber.

Science.gov (United States)

Xu, Huihui; Liu, Zihou; Liu, Qingyang; Bei, Yiling; Zhu, Qingzeng

2018-05-13

α-Amine ketoximesilanes are proven to be effective crosslinkers in the preparation of ketone-oxime one-component room temperature vulcanized (RTV) silicone rubber without the use of toxic metal catalyst. This work aimed to investigate the hydrolysis kinetic of α-amine ketoximesilanes, which is vitally important for the preparation of RTV silicone rubber. Five kinds of α-amine ketoximesilanes, namely α-(N,N-diethyl)aminomethyltri(methylethylketoxime)silane (DEMOS), α-(N,N-di-n-butyl)aminomethyltri(methylethylketoxime)silane (DBMOS), α-(N-n-butyl)aminomethyltri(methylethylketoxime)silane (n-BMOS), α-(N-cyclohexyl)aminomethyltri(methylethylketoxime)silane (CMOS) and α-(β-aminomethyl)aminomethyltri(methylethylketoxime)silane (AEMOS), were successfully obtained and confirmed using Fourier transform infrared spectrometer (FT-IR) and hydrogen-1 nuclear magnetic resonance ( ¹H NMR). Kinetics of hydrolysis reactions were measured by FT-IR and conductivity. Our results illustrated that the kinetic constant rates ranged from 12.2 × 10 −4 s −1 to 7.6 × 10 −4 s −1 , with the decreasing order of DEMOS > n-BMOS > DBMOS > CMOS > AEMOS at the given temperature and humidity. Better performances of thermal stability could be achieved when using the α-amine ketoximesilanes as crosslinkers in the preparation of RTV silicon rubber than that of RTV silicone rubber with the use of methyltri(methylethylketoxime)silane (MOS) as a crosslinker and organic tin as a catalyst.

Peripheral site ligand conjugation to a non-quaternary oxime enhances reactivation of nerve agent-inhibited human acetylcholinesterase

NARCIS (Netherlands)

Koning, M.C. de; Grol, M. van; Noort, D.

2011-01-01

Commonly employed pyridinium-oxime (charged) reactivators of nerve agent inhibited acetylcholinesterase (AChE) do not readily pass the blood brain barrier (BBB) because of the presence of charge(s). Conversely, non-ionic oxime reactivators often suffer from a lack of reactivating potency due to a

Synthesis of 2-hydroxy-3-(2-methyl-propenyl-1,4-naphthoquinone and related oxime derivatives

Directory of Open Access Journals (Sweden)

Patricia S. Oliveira

2012-06-01

Full Text Available The condensation reaction of commercial 2-hydroxy-1 ,4-naphthoquinone 1 (lawsone with isobutyraldehyde 2 furnishs norlapachol 3 (2-hydroxy-3-(2-methyl-propenyl -1,4-naphthoquinone with yields ranging from 66 to 93% depending on the different conditions tested, and a reaction temperature factor determinant for the formation of the desired product. It was treated with hydroxylamine hydrochloride in alkaline (NaOH to provide the oxime 4 from regioselective modification of the carbonyl C-1 with 91% yield. The regioselectivity of the reaction can be explained by analyzing the different resonance structures which can be seen that the carbonyl C-4 is less electrophilic than C-1. In this work was also obtained the oxime 5, 6 and 7 from lapachol, αlpha and β-lapachone, respectively, in yields of 64-85%. The oximes of αlpha and β-norlapachone, 8 and 9 are in obtention. All the products were analyzed by IR and NMR, and were observed that oximes of lapachol and norlapachol are isolated as E/Z mixtures. Two-dimensional NOE-type experiments of the corresponding acylated derivative will be made to help identify the proportion of the mixture.

A comprehensive evaluation of the efficacy of leading oxime therapies in guinea pigs exposed to organophosphorus chemical warfare agents or pesticides

Energy Technology Data Exchange (ETDEWEB)

Wilhelm, Christina M., E-mail: wilhelmc@battelle.org [Battelle, 505 King Avenue, JM-7, Columbus, OH 43201-2693 (United States); Snider, Thomas H., E-mail: snidert@battelle.org [Battelle, 505 King Avenue, JM-7, Columbus, OH 43201-2693 (United States); Babin, Michael C., E-mail: babinm@battelle.org [Battelle, 505 King Avenue, JM-7, Columbus, OH 43201-2693 (United States); Jett, David A., E-mail: jettd@ninds.nih.gov [National Institutes of Health/National Institute of Neurological Disorders and Stroke, Bethesda, MD 20892 (United States); Platoff, Gennady E., E-mail: platoffg@niaid.nih.gov [National Institutes of Health/National Institute of Allergy and Infectious Diseases, Bethesda, MD 20892 (United States); Yeung, David T., E-mail: dy70v@nih.gov [National Institutes of Health/National Institute of Neurological Disorders and Stroke, Bethesda, MD 20892 (United States)

2014-12-15

The currently fielded pre-hospital therapeutic regimen for the treatment of organophosphorus (OP) poisoning in the United States (U.S.) is the administration of atropine in combination with an oxime antidote (2-PAM Cl) to reactivate inhibited acetylcholinesterase (AChE). Depending on clinical symptoms, an anticonvulsant, e.g., diazepam, may also be administered. Unfortunately, 2-PAM Cl does not offer sufficient protection across the range of OP threat agents, and there is some question as to whether it is the most effective oxime compound available. The objective of the present study is to identify an oxime antidote, under standardized and comparable conditions, that offers protection at the FDA approved human equivalent dose (HED) of 2-PAM Cl against tabun (GA), sarin (GB), soman (GD), cyclosarin (GF), and VX, and the pesticides paraoxon, chlorpyrifos oxon, and phorate oxon. Male Hartley guinea pigs were subcutaneously challenged with a lethal level of OP and treated at approximately 1 min post challenge with atropine followed by equimolar oxime therapy (2-PAM Cl, HI-6 DMS, obidoxime Cl{sub 2}, TMB-4, MMB4-DMS, HLö-7 DMS, MINA, and RS194B) or therapeutic-index (TI) level therapy (HI-6 DMS, MMB4-DMS, MINA, and RS194B). Clinical signs of toxicity were observed for 24 h post challenge and blood cholinesterase [AChE and butyrylcholinesterase (BChE)] activity was analyzed utilizing a modified Ellman's method. When the oxime is standardized against the HED of 2-PAM Cl for guinea pigs, the evidence from clinical observations, lethality, quality of life (QOL) scores, and cholinesterase reactivation rates across all OPs indicated that MMB4 DMS and HLö-7 DMS were the two most consistently efficacious oximes. - Highlights: • First comprehensive evaluation of leading AChE oxime reactivators • All oximes are compared against current U.S. therapy 2-PAM Cl. • Relative therapeutic oxime efficacies against OP CWNA and pesticides • Contribution to more effective

Quantum Chemical and Physicochemical Studies of Oximes (Prophylactics against and Reactivators of Phosphorylated AChE).

Science.gov (United States)

1984-10-25

crystal structure of nicotinic acid ,. and we used the ether bridge from the crystal structure of dimethyl ether. We are investigating various rotamers...observations were made: - The titration curve (after the subtraction of the blank curve) shows only one titrable group, i.e. the oxime moiety. - The...subtraction of the blank curve, shows two titrable groups, i.e. the two oxime moieties. The results are as follows: Temperature Conditions PKa pK2

Efficacy of the Tertiary Oxime Monoisonitrosoacetone (MINA) Against Lethal Sarin Intoxication in the Guinea Pig

Science.gov (United States)

2007-10-01

Sarin 5a. CONTRACT NUMBER Intoxication in the Guinea Pig 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S) Koplovitz, I and...efficacy of MINA as a treatment for lethal sarin (GB) intoxication in guinea pigs . Male animals were challenged subcutaneously (s.c.) with 2 LD50s...oximes that are readily able to enter the brain. 15. SUBJECT TERMS oximes, brain, sarin, reactivation, nerve agents, guinea pigs 16. SECURITY

Prediction of effectiveness of shunting in patients with normal pressure hydrocephalus by cerebral blood flow measurement and computed tomography cisternography

Energy Technology Data Exchange (ETDEWEB)

Chang, Chia-Cheng; Kuwana, Nobumasa; Ito, Susumu; Ikegami, Tadashi [Yokohama Minami Kyosai Hospital (Japan)

1999-11-01

Measurement of cerebral blood flow (CBF) and computed tomography (CT) cisternography were performed in 37 patients with a tentative diagnosis of normal pressure hydrocephalus (NPH) to predict their surgical outcome. The mean CBF of the whole brain was measured quantitatively by single photon emission computed tomography with technetium-99m-hexamethylpropylene amine oxime before surgery. The results of CT cisternography were classified into four patients: type I, no ventricular stasis at 24 hours; type II, no ventricular stasis with delayed clearance of cerebral blush; type III, persistent ventricular stasis with prominent cerebral blush; type IV, persistent ventricular stasis with diminished cerebral blush and/or asymmetrical filling of the sylvian fissures. The mean CBF was significantly lower than that of age-matched controls (p<0.005). Patients with a favorable outcome had a significantly higher mean CBF than patients with an unfavorable outcome (p<0.005). Patients with the type I pattern did not respond to shunting. Some patients with type II and III patterns responded to shunting but improvement was unsatisfactory. Patients with type IV pattern responded well to shunting, and those with a mean CBF of 35 ml/100 g/min or over achieved a favorable outcome. The combination of CBF measurement and CT cisternography can improve the prediction of surgical outcome in patients with suspected NPH. (author)

Vascular risk factors, atherosclerosis, cerebral white matter lesions and cerebral perfusion in a population-based study

International Nuclear Information System (INIS)

Claus, J.J.; Breteler, M.M.B.; Hasan, D.; Krenning, E.P.; Bots, M.L.; Grobbee, D.E.; Swieten, J.C. van; Harskamp, F. van; Hofman, A.

1996-01-01

We studied risk factors for cerebral vascular disease (blood pressure and hypertension, factor VIIc, factor VIIIc, fibrinogen), indicators of atherosclerosis (intima-media thickness and plaques in the carotid artery) and cerebral white matter lesions in relation to regional cerebral blood flow (rCBF) in 60 persons (aged 65-85 years) recruited from a population-based study. rCBF was assessed with single-photon emission tomography using technetium-99m d,l-hexamethylpropylene amine oxime ( 99m Tc-HMPAO). Statistical analysis was performed with multiple linear regression with adjustment for age, sex and ventricle-to-brain ratio. A significant positive association was found between systolic and diastolic blood pressure and temporo-parietal rCBF. In analysis with quartiles of the distribution, we found a threshold effect for the relation of low diastolic blood pressure (≤60 mmHg) and low temporo-parietal rCBF. Levels of plasma fibrinogen were inversely related to parietal rCBF, with a threshold effect of high fibrinogen levels (>3.2 g/l) and low rCBF. Increased atherosclerosis was related to low rCBF in all cortical regions, but these associations were not significant. No consistent relation was observed between severity of cerebral white matter lesions and rCBF. Our results may have implications for blood pressure control in the elderly population. (orig.)

Differences in 99mTc-HMPAO brain SPET perfusion imaging between Tourette's syndrome and chronic tic disorder in children

International Nuclear Information System (INIS)

Chiu, N.-T.; Lee, B.-F.; Chang, Y.-C.; Huang, C.-C.; Wang, S.-T.

2001-01-01

Early differential diagnosis between Tourette's syndrome and chronic tic disorder is difficult but important because both the outcome and the treatment of these two childhood-onset diseases are distinct. We assessed the sensitivity and specificity of brain single-photon emission tomography (SPET) perfusion imaging in distinguishing the two diseases, and characterized their different cerebral perfusion patterns. Twenty-seven children with Tourette's syndrome and 11 with chronic tic disorder (mean age 9.5 and 8.6 years, respectively) underwent brain SPET with technetium-99m hexamethylpropylene amine oxime (HMPAO). Visual interpretation and semi-quantitative analysis of SPET images were performed. On visual interpretation, 22 of 27 (82%) of the Tourette's syndrome group had lesions characterized by decreased perfusion. The left hemisphere was more frequently involved. None of the children with chronic tic disorder had a visible abnormality. Semi-quantitative analysis showed that, compared with children with chronic tic disorder, children with Tourette's syndrome had significantly lower perfusion in the left lateral temporal area and asymmetric perfusion in the dorsolateral frontal, lateral and medial temporal areas. In conclusion, using the visual approach, brain SPET perfusion imaging is sensitive and specific in differentiating Tourette's syndrome and chronic tic disorder. The perfusion difference between the two groups, demonstrated by semi-quantitative analysis, may be related more to the co-morbidity in Tourette's syndrome than to tics per se. (orig.)

Resting state rCBF mapping with single-photon emission tomography and positron emission tomography: magnitude and origin of differences

International Nuclear Information System (INIS)

Jonsson, C.; Kimiaei, S.; Larsson, S.A.; Pagani, M.; Ingvar, M.; Thurfjell, L.; Jacobsson, H.

1998-01-01

Single-photon emission tomography (SPET), using technetium-99m hexamethylpropylene amine oxime, and positron emission tomography (PET), using oxygen-15 butanol were compared in six healthy male volunteers with regard to the mapping of resting state regional cerebral blood flow (rCBF). A computerized brain atlas was utilized for 3D regional analyses and comparison of 64 selected and normalized volumes of interest (VOIs). The normalized mean rCBF values in SPET, as compared to PET, were higher in most of the Brodmann areas in the frontal and parietal lobes (4.8% and 8.7% respectively). The average differences were small in the temporal (2.3%) and occipital (1.1%) lobes. PET values were clearly higher in small VOIs like the thalamus (12.3%), hippocampus (12.3%) and basal ganglia (9.9%). A resolution phantom study showed that the in-plane SPET/PET system resolution was 11.0/7.5 mm. In conclusion, SPET and PET data demonstrated a fairly good agreement despite the superior spatial resolution of PET. The differences between SPET and PET rCBF are mainly due to physiological and physical factors, the data processing, normalization and co-registration methods. In order to further improve mapping of rCBF with SPET it is imperative not only to improve the spatial resolution but also to apply accurate correction techniques for scatter, attenuation and non-linear extraction. (orig.)

Brain perfusion and cognitive function changes in hypertensive patients

International Nuclear Information System (INIS)

Efimova, I.Y.; Efimova, N.Y.; Triss, S.V.; Lishmanov, Y.B.

2008-01-01

The aim of our study was to estimate brain perfusion and cognitive function (CF) in patients with arterial hypertension (AH) before and after hypotensive therapy. The study included 15 patients (mean age, 53.0±5.7 years) with previously untreated or ineffectively treated essential hypertension of the second degree. All patients underwent brain single photon emission computed tomography (SPECT) scanning with 99m Tc-hexamethylpropylene amine oxime ( 99m Tc-HMPAO) and comprehensive neuropsychological testing before and after 24 weeks of hypotensive therapy (angiotensin-converting enzyme [ACE] inhibitor or diuretics). The brain perfusion was significantly lower (15-22%) in all regions of AH patients. These patients showed a 25% decrease in attention and psychomotor speed as well as a 14% decrease in mentation. Six months of hypotensive therapy led to an increase in brain perfusion by an average of 7-11% in all brain regions. After treatment these patients demonstrated an average 11-18% improvements in attention and psychomotor speed, as well as an average 10% improvement in abstract mentation. Marked signs of brain hypoperfusion and impaired CF: decrease in attention, slowing psychomotor speed and mentation was found in hypertensive patients even without focal neurological symptomatology. Twenty-four weeks of hypotensive treatment with ACE inhibitors or diuretics had a positive effect on cerebral perfusion and led to CF improvement. (author)

Prediction of effectiveness of shunting in patients with normal pressure hydrocephalus by cerebral blood flow measurement and computed tomography cisternography

International Nuclear Information System (INIS)

Chang, Chia-Cheng; Kuwana, Nobumasa; Ito, Susumu; Ikegami, Tadashi

1999-01-01

Measurement of cerebral blood flow (CBF) and computed tomography (CT) cisternography were performed in 37 patients with a tentative diagnosis of normal pressure hydrocephalus (NPH) to predict their surgical outcome. The mean CBF of the whole brain was measured quantitatively by single photon emission computed tomography with technetium-99m-hexamethylpropylene amine oxime before surgery. The results of CT cisternography were classified into four patients: type I, no ventricular stasis at 24 hours; type II, no ventricular stasis with delayed clearance of cerebral blush; type III, persistent ventricular stasis with prominent cerebral blush; type IV, persistent ventricular stasis with diminished cerebral blush and/or asymmetrical filling of the sylvian fissures. The mean CBF was significantly lower than that of age-matched controls (p<0.005). Patients with a favorable outcome had a significantly higher mean CBF than patients with an unfavorable outcome (p<0.005). Patients with the type I pattern did not respond to shunting. Some patients with type II and III patterns responded to shunting but improvement was unsatisfactory. Patients with type IV pattern responded well to shunting, and those with a mean CBF of 35 ml/100 g/min or over achieved a favorable outcome. The combination of CBF measurement and CT cisternography can improve the prediction of surgical outcome in patients with suspected NPH. (author)

Labeling of autologous monocytes with 99mTc-HMPAO at very high specific radioactivity

International Nuclear Information System (INIS)

Hemert, Formijn J. van; Thurlings, Rogier; Dohmen, Serge E.; Voermans, Carlijn; Tak, Paul P.; Eck-Smit, Berthe L.F. van; Bennink, Roelof J.

2007-01-01

Rheumatoid arthritis of joints involves the accumulation of monocyte-derived macrophages in the affected synovial tissue. This process of cell migration can be portrayed scintigraphically in order to monitor noninvasive effects of therapy on the progress of the disease. Scintigraphic detection of inflammation by means of technetium 99m-hexamethylpropylene amine oxime ( 99m Tc-HMPAO)-labeled leukocytes provides a classic example. Present state-of-the-art methods in cell biology allow the isolation of cells like lymphocytes or monocytes, which are less abundant than main blood constituents but, instead, harbor particular functions like specific homing properties. To facilitate scintigraphic imaging of the cell functions involved, the relatively small population of cells must be labeled to radioactive yields as high as possible. We demonstrate that autologous monocytes isolated from 100 ml of peripheral blood can be radiolabeled to a yield of 10 (instead of 1) Bq per cell, allowing scintigraphic analysis of rheumatoid arthritis up to 20 h post injection of patients. The method is based on the instantaneous distribution of lipophilic 99m Tc-HMPAO between the hydrophobic inside of cells and the hydrophilic (aqueous) surrounding of cells, followed by decomposition of the radiopharmaceutical into compounds that are unable to cross the cellular membrane. The procedure provides a method of choice for cell-mediated scintigraphy at low availability of cells with the correct homing properties

Usefulness of hybrid SPECT/CT for the {sup 99m}Tc-HMPAO-labeled leukocyte scintigraphy in a case of cranial osteomyelitis

Energy Technology Data Exchange (ETDEWEB)

Bruni, Chiara; Padovano, Federico; Travascio, Laura; Schillaci, Orazio; Simonetti, Giovanni [University of Rome Tor Vergata, Rome (Italy). Dept. of Diagnostic Imaging, Molecular Imaging, Interventional Radiology and Radiotherapy]. E-mail: chiarabruni79@hotmail.com

2008-12-15

Cranial osteomyelitis is a potentially fatal lesion. White blood cell scanning (WBC) with {sup 99m}Tc-hexamethylpropylene amine oxime (HMPAO) has proven highly sensitive and specific in the diagnosis and follow-up of patients with suspected osteomyelitis. In this report we show the usefulness of SPECT and transmission CT performed simultaneously using a hybrid imaging device for the functional anatomic mapping of soft tissue and cranial bone infections. {sup 99m}Tc-HMPAO-labeled leukocytes scintigraphy was performed on an elderly diabetic man with an intracranial mass lesion and with suspected temporal bone infection. Planar scans were acquired 30 min, 4 h, and 24 h after injection. SPECT/CT was obtained 6 h after tracer injection, using a dual-head camera coupled with a low-power X-ray tube. The scintigraphic results were matched with the results of surgery and of clinical follow-up. The planar images alone were true-positives for abscess in this patient. SPECT/CT improves the accuracy of {sup 99m}Tc- HMPAO scintigraphy especially in discriminating between soft-tissue and bone involvement. In fact, SPECT/CT also showed temporal bone osteomyelitis. This result indicates that SPECT/CT performed using a hybrid device can improve imaging with {sup 99m}Tc-HMPAO-labeled leukocytes in patients with suspected osteomyelitis by providing accurate anatomic localization and precise definition of the extent of infection. (author)

Usefulness of hybrid SPECT/CT for the 99mTc-HMPAO-labeled leukocyte scintigraphy in a case of cranial osteomyelitis

Directory of Open Access Journals (Sweden)

Chiara Bruni

Full Text Available Cranial osteomyelitis is a potentially fatal lesion. White blood cell scanning (WBC with 99mTc-hexamethylpropylene amine oxime (HMPAO has proven highly sensitive and specific in the diagnosis and follow-up of patients with suspected osteomyelitis. In this report we show the usefulness of SPECT and transmission CT performed simultaneously using a hybrid imaging device for the functional anatomic mapping of soft tissue and cranial bone infections. 99mTc-HMPAO-labeled leukocytes scintigraphy was performed on an elderly diabetic man with an intracranial mass lesion and with suspected temporal bone infection. Planar scans were acquired 30 min, 4 h, and 24 h after injection. SPECT/CT was obtained 6 h after tracer injection, using a dual-head camera coupled with a low-power X-ray tube. The scintigraphic results were matched with the results of surgery and of clinical follow-up. The planar images alone were true-positives for abscess in this patient. SPECT/CT improves the accuracy of99mTc-HMPAO scintigraphy especially in discriminating between soft-tissue and bone involvement. In fact, SPECT/CT also showed temporal bone osteomyelitis. This result indicates that SPECT/CT performed using a hybrid device can improve imaging with 99mTc-HMPAO-labeled leukocytes in patients with suspected osteomyelitis by providing accurate anatomic localization and precise definition of the extent of infection.

Comparison of simultaneous 99mTc-HMPAO and 111In oxine labelled white cell scans in the assessment of inflammatory bowel disease

International Nuclear Information System (INIS)

Allan, R.A.; Bassingham, S.; Lazarus, C.; Clarke, S.E.M.; Fogelman, I.; Sladen, G.E.

1993-01-01

Forty-seven patients, 29 with chronic inflammatory bowel disease (IBD) and 18 with presumed irritable bowel syndrome, including one with uncomplicated diverticular disease, were studied with simultaneous technetium-99m hexamethylpropylene amine oxime and indium-III oxine labelled leucocyte scans performed at 1, 3 and 24 h. Twenty-seven patients with IBD had active disease as judged by clinical and laboratory criteria and all of these had positive scans with both agents. No false positive studies were obtained. The 1-h 99m Tc-HMPAO WBC scans showed the same distribution to disease as the 3-h 111 -In WBC scans, with no difference in intensity (P 111 -In scans. The 3-h 99m Tc-HMPAO WBC scans showed more extensive disease (P 111 In WBC scans. Physiological bowel activity on 3-h 99m Tc-HMPAO WBC scans was present in 12 patients but was faint and did not interfere with assessment of disease extent and activity. It is concluded that in terms of isotope availability, radiation dosimetry and image quality, 99m Tc-HMPAO is the agent of choice in detecting active IBD, with localization of disease possible at 1-h after re-injection and optimal resolution and definition of disease extent at 3 h. A negative scan reliably excludes active disease. (orig.)

t-3-Benzyl-r-2,c-6-diphenylpiperidin-4-one oxime

Directory of Open Access Journals (Sweden)

R. Arulraj

2016-12-01

Full Text Available In the title compound, C24H24N2O [systematic name: (E-3-benzyl-2,6-diphenylpiperidin-4-one oxime], the piperidine ring adopts a slightly distorted chair conformation and the phenyl rings and the benzyl group substituents are attached equatorially. The oxime group makes a dihedral angle of 42.88 (12° with the piperidine ring. The dihedral angle between the phenyl rings is 71.96 (8°. The benzyl ring makes dihedral angles of 63.01 (8 and 59.35 (8° with the two phenyl rings. In the crystal, molecules are linked by O—H...N hydrogen bonds, forming C(7 chains along the c axis. The chains are linked by C—H...π interactions, forming slabs lying parallel to the bc plane.

Binding of Reactive Organophosphate by Oximes via Hydrogen Bond

Indian Academy of Sciences (India)

Giuseppe Trusso

Stoichiometries of the complexes were investigated by the Job plot method using spectrophotometric measurements. The samples were prepared by mixing equimolecular stock solutions (3.7 x 10. -3. M) in dry CH3CN of the appropriate oxime and DMMP to cover the whole range of molar fractions keeping constant the total ...

Theoretical NMR and conformational analysis of solvated oximes for organophosphates-inhibited acetylcholinesterase reactivation

Science.gov (United States)

da Silva, Jorge Alberto Valle; Modesto-Costa, Lucas; de Koning, Martijn C.; Borges, Itamar; França, Tanos Celmar Costa

2018-01-01

In this work, quaternary and non-quaternary oximes designed to bind at the peripheral site of acetylcholinesterase previously inhibited by organophosphates were investigated theoretically. Some of those oximes have a large number of degrees of freedom, thus requiring an accurate method to obtain molecular geometries. For this reason, the density functional theory (DFT) was employed to refine their molecular geometries after conformational analysis and to compare their 1H and 13C nuclear magnetic resonance (NMR) theoretical signals in gas-phase and in solvent. A good agreement with experimental data was achieved and the same theoretical approach was employed to obtain the geometries in water environment for further studies.

Spectrophotometric determination of pKa's of 1-hydroxybenzotriazole and oxime derivatives in 95% acetonitrile-water

International Nuclear Information System (INIS)

Fathallah, M.F.; Khattab, S.N.

2011-01-01

1-hydroxybenzotriazole derivatives are used with carbodiimide as additives to generate active esters during peptide bond formation. They are also used as additives during the peptide bond formation. Dissociation constants of the 1-hydroxybenzotriazole (HOBt) and its derivatives, 1-hydroxy-6-chloro benzotriazole, 1-hydroxy-6-trifluoro methylbenzotriazole, 1-hydroxy-6-nitrobenzo-triazole were determined spectrophotometrically in 95% acetonitrile-water. In addition, 7-aza-1-hydroxybenzotriazole (7-HOAt) and 4-aza-1-hydroxybenzotriazole (4-HOAt) were also studied. Recently, oxyma was reported as a good replacement for the benzotriazole derivatives. As alcoholic components of active esters, the oximes seem to be good leaving groups. Therefore it was expected, that the strongly acidic and nucleophilic oximes, which possess electron-withdrawing groups in the molecule, are suitable as additives during the peptide bond formation. The dissociation constant of some oximes, such as diethyl 2-(hydroxyimino)malonate, ethyl 2-cyano-2-(hydroxyimino)acetate (oxyma), hydroxycarbonimidoyl dicyanide and N-hydroxypicolinimidoyl cyanide in 95% acetonitrile-water are reported. (author)

Design and Biological Evaluation of Antifouling Dihydrostilbene Oxime Hybrids.

Science.gov (United States)

Moodie, Lindon W K; Cervin, Gunnar; Trepos, Rozenn; Labriere, Christophe; Hellio, Claire; Pavia, Henrik; Svenson, Johan

2018-04-01

By combining the recently reported repelling natural dihydrostilbene scaffold with an oxime moiety found in many marine antifoulants, a library of nine antifouling hybrid compounds was developed and biologically evaluated. The prepared compounds were shown to display a low antifouling effect against marine bacteria but a high potency against the attachment and growth of microalgae down to MIC values of 0.01 μg/mL for the most potent hybrid. The mode of action can be characterized as repelling via a reversible non-toxic biostatic mechanism. Barnacle cyprid larval settlement was also inhibited at low μg/mL concentrations with low levels or no toxicity observed. Several of the prepared compounds performed better than many reported antifouling marine natural products. While several of the prepared compounds are highly active as antifoulants, no apparent synergy is observed by incorporating the oxime functionality into the dihydrostilbene scaffold. This observation is discussed in light of recently reported literature data on related marine natural antifoulants and antifouling hybrids as a potentially general strategy for generation of improved antifoulants.

Glycoconjugate Oxime Formation Catalyzed at Neutral pH: Mechanistic Insights and Applications of 1,4-Diaminobenzene as a Superior Catalyst for Complex Carbohydrates.

Science.gov (United States)

Østergaard, Mads; Christensen, Niels Johan; Hjuler, Christian T; Jensen, Knud J; Thygesen, Mikkel B

2018-04-18

The reaction of unprotected carbohydrates with aminooxy reagents to provide oximes is a key method for the construction of glycoconjugates. Aniline and derivatives serve as organocatalysts for the formation of oximes from simple aldehydes, and we have previously reported that aniline also catalyzes the formation of oximes from the more complex aldehydes, carbohydrates. Here, we present a comprehensive study of the effect of aniline analogues on the formation of carbohydrate oximes and related glycoconjugates depending on organocatalyst structure, pH, nucleophile, and carbohydrate, covering more than 150 different reaction conditions. The observed superiority of the 1,4-diaminobenzene (PDA) catalyst at neutral pH is rationalized by NMR analyses and DFT studies of reaction intermediates. Carbohydrate oxime formation at pH 7 is demonstrated by the formation of a bioactive glycoconjugate from a labile, decorated octasaccharide originating from exopolysaccharides of the soil bacterium Mesorhizobium loti. This study of glycoconjugate formation includes the first direct comparison of aniline-catalyzed reaction rates and equilibrium constants for different classes of nucleophiles, including primary oxyamines, secondary N-alkyl oxyamines, as well as aryl and arylsulfonyl hydrazides. We identified 1,4-diaminobenzene as a superior catalyst for the construction of oxime-linked glycoconjugates under mild conditions.

SPECT with [99mTc]-d,l-hexamethyl-propylene amine oxime (HM-PAO) compared with regional cerebral blood flow measured by PET

DEFF Research Database (Denmark)

Yonekura, Y; Nishizawa, S; Mukai, Thomas Søgaard

1988-01-01

In order to validate the use of technetium-99m-d,l-hexamethylpropyleneamine oxime (HM-PAO) as a flow tracer, a total of 21 cases were studied with single photon emission computerized tomography (SPECT), and compared to regional cerebral blood flow (rCBF) measured by position emission tomography...... (PET) using the oxygen-15 CO2 inhalation technique. Although HM-PAO SPECT and rCBF PET images showed a similar distribution pattern the HM-PAO SPECT image showed less contrast between high and low activity flow regions than the rCBF image and a nonlinear relationship between HM-PAO activity and r......CBF was shown. Based on the assumption of flow-dependent backdiffusion of HM-PAO from the brain, we applied a "linearization algorithm" to correct the HM-PAO SPECT images. The corrected HM-PAO SPECT images revealed a good linear correlation with rCBF (r = 0.901, p less than 0.001). The results indicated HM-PAO...

Reaction of Non-Symmetric Schiff Base Metallo-Ligand Complexes Possessing an Oxime Function with Ln Ions

Directory of Open Access Journals (Sweden)

Jean-Pierre Costes

2018-03-01

Full Text Available The preparation of non-symmetric Schiff base ligands possessing one oxime function that is associated to a second function such as pyrrole or phenol function is first described. These ligands, which possess inner N4 or N3O coordination sites, allow formation of cationic or neutral non-symmetric CuII or NiII metallo-ligand complexes under their mono- or di-deprotonated forms. In presence of Lanthanide ions the neutral complexes do not coordinate to the LnIII ions, the oxygen atom of the oxime function being only hydrogen-bonded to a water molecule that is linked to the LnIII ion. This surprising behavior allows for the isolation of LnIII ions by non-interacting metal complexes. Reaction of cationic NiII complexes possessing a protonated oxime function with LnIII ions leads to the formation of original and dianionic (Gd(NO352− entities that are well separated from each other. This work highlights the preparation of well isolated mononuclear LnIII entities into a matrix of diamagnetic metal complexes. These new complexes complete our previous work dealing with the complexing ability of the oxime function toward Lanthanide ions. It could open the way to the synthesis of new entities with interesting properties, such as single-ion magnets for example.

Synthesis and antimicrobial activities of new oxime carbamates of 3 ...

Indian Academy of Sciences (India)

Abstract. S-alkylation of 3-aryl-2-thioquinazolin-4(3H)-one (1) with chloroacetone gave 2-(propanonyl thio)-3-arylquinazol-4(3H)ones (2). Further, the treatment of compound (2) with hydroxylamine hydrochloride gave the corresponding oximes (3) which on reaction with phenyl isocyanate in THF yielded corresponding.

Diprotonated hydrazones and oximes as reactive intermediates in electrochemical reductions

Czech Academy of Sciences Publication Activity Database

Baymak, M. S.; Celik, H.; Ludvík, Jiří; Lund, H.; Zuman, P.

2004-01-01

Roč. 45, č. 26 (2004), s. 5113-5115 ISSN 0040-4039 R&D Projects: GA ČR GA203/01/1093; GA AV ČR IAA4040304 Institutional research plan: CEZ:AV0Z4040901 Keywords : hydrazones * oximes * diprotonation Subject RIV: CG - Electrochemistry Impact factor: 2.484, year: 2004

Selective Tandem Synthesis of Oximes from Benzylic Alcohols Catalyzed with 2, 3-Dichloro-5, 6-dicyanobenzoquinone

Energy Technology Data Exchange (ETDEWEB)

Aghapour, Ghasem; Mohamadian, Samaneh [Damghan University, Damghan (Iran, Islamic Republic of)

2012-04-15

In spite of many reports in the literature concerning with oxidation of benzylic alcohols to carbonyl compounds with 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ) in stoichiometric amounts or even more, we surprisingly found that benzylic alcohols are directly oxidized to oximes using a catalytic amount of DDQ in the presence of hydroxylamine hydrochloride under solvent-free conditions. The present tandem catalytic method can be efficiently used for preparation of oximes in the presence of some other functional groups with excellent chemoselectivity

Eco-friendly synthesis, physicochemical studies, biological assay and molecular docking of steroidal oxime-ethers

Science.gov (United States)

Alam, Mahboob; Lee, Dong-Ung

2015-01-01

The aim of this study was to report the synthesis of biologically active compounds; 7-(2′-aminoethoxyimino)-cholest-5-ene (4), a steroidal oxime-ether and its derivatives (5, 6) via a facile microwave assisted solvent free reaction methodology. This new synthetic, eco-friendly, sustainable protocol resulted in a remarkable improvement in the synthetic efficiency (85-93 % yield) and high purity using basic alumina. The synthesized compounds were screened for their antibacterial against six bacterial strains by disc diffusion method and antioxidant potential by DPPH assay. The binding capabilities of a compound 6 exhibiting good antibacterial potential were assessed on the basis of molecular docking studies and four types of three-dimensional molecular field descriptors. Moreover the structure-antimicrobial activity relationships were studied using some physicochemical and quantum-chemical parameters with GAMESS interface as well as WebMO Job Manager by using the basic level of theory. Hence, this synthetic approach is believed to provide a better scope for the synthesis of steroidal oxime-ether analogues and will be a more practical alternative to the presently existing procedures. Moreover, detailed in silico docking studies suggested the plausible mechanism of steroidal oxime-ethers as effective antimicrobial agents. PMID:27330525

Insights into the mechanism and catalysis of oxime coupling chemistry at physiological pH.

Science.gov (United States)

Wang, Shujiang; Gurav, Deepanjali; Oommen, Oommen P; Varghese, Oommen P

2015-04-07

The dynamic covalent-coupling reaction involving α-effect nucleophiles has revolutionized bioconjugation approaches, due to its ease and high efficiency. Key to its success is the discovery of aniline as a nucleophilic catalyst, which made this reaction feasible under physiological conditions. Aniline however, is not so effective for keto substrates. Here, we investigate the mechanism of aniline activation in the oxime reaction with aldehyde and keto substrates. We also present carboxylates as activating agents that can promote the oxime reaction with both aldehyde and keto substrates at physiological pH. This rate enhancement circumvents the influence of α-effect by forming H-bonds with the rate-limiting intermediate, which drives the reaction to completion. The combination of aniline and carboxylates had a synergistic effect, resulting in a ∼14-31-fold increase in reaction rate at pD 7.4 with keto substrates. The biocompatibility and efficiency of carboxylate as an activating agent is demonstrated by performing cell-surface oxime labeling at physiological pH using acetate, which showed promising results that were comparable with aniline. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Efficient Conversion of Oximes to the Corresponding Carbonyl Compounds with Tetrabutylammonium Chromate under Aprotic Conditions

International Nuclear Information System (INIS)

Pourali, Ali Reza; Goli, Arezou

2006-01-01

The solubility in several solvents, mildness, simple work-up and absence of side reactions provide advantages of using TBAC in deoximation reactions. This is an efficient and selective method for homogeneous deoximation of structurally different compounds under the moderately acidic and aprotic conditions in high yields. Regeneration of ketones and aldehydes from their oximes has assumed added importance since the discovery of the Barton reaction in which oximes are produced at non-activated hydrocarbon sites. Also, their synthesis from non-carbonyl compounds, such as by nitrosation of an active methylene group, nitrosation of an α-halo carbonyl compound and condensation of a nitro-alkene with an aldehyde provides a valid alternative pathway to carbonyl compounds. Therefore, there has been a continued interest in the effective regeneration of carbonyl compounds from the corresponding oximes especially under mild conditions. Oxidative and reductive methods have been found to show advantages over the classical hydrolytic methods. Although many oxidizing agents have been used, only a limited number of methods are efficient because of the low solubility of these metallic reagents in most organic solvents

Clinical experience with sup(99m)Tc-hexamethylpropylene-amineoxime for labelling leucocytes and imaging inflammation

Energy Technology Data Exchange (ETDEWEB)

Peters, A.M.; Danpure, H.J.; Osman, S.; Hawker, R.J.; Henderson, B.L.; Hodgson, H.J.; Kelly, J.D.; Neirinckx, R.D.; Lavender, J.P.

1986-10-25

Hexamethylpropylene-amineoxime (HMPAO) forms a lipid-soluble neutral complex with sup(99m)Tc which is rapidly incorporated into leucocytes in vitro. In six patients with suspected or known inflammatory disease, a 'mixed' leucocyte suspension isolated from 85 ml blood anticoagulated with acid-citrate-dextrose was labelled by sup(99m)Tc-HMPAO with a mean efficiency of 47% (SE2%), of which 78% (3) was taken up by granulocytes. Activity eluted more rapidly from other cell types in vitro than from granulocytes, which remained firmly labelled. Mean initial biodistribution of the label and granulocyte recovery in blood of 32% (8) at 30-40 min showed that the granulocytes were not significantly activated during labelling. All six patients were positive for inflammatory disease, as early as 30 min in five patients and at 3 h in the sixth; they all remained positive at 20-24 h. Four patients also received /sup 111/In-labelled 'pure' granulocytes. In terms of detail, the sup(99m)Tc images were comparable or superior to the /sup 111/In images.

Iridium-Catalyzed Condensation of Primary Amines To Form Secondary Amines

DEFF Research Database (Denmark)

Lorentz-Petersen, Linda Luise Reeh; Jensen, Paw; Madsen, Robert

2009-01-01

Symmetric secondary amines are readily obtained by heating a neat primary amine with 0.5 mol% of bis(dichloro[eta(5)-pentamethylcyclopentadienyl]iridium). The products are isolated by direct distillation in good yields.......Symmetric secondary amines are readily obtained by heating a neat primary amine with 0.5 mol% of bis(dichloro[eta(5)-pentamethylcyclopentadienyl]iridium). The products are isolated by direct distillation in good yields....

Two reduction waves of oximes and imine formation in acidic media

Czech Academy of Sciences Publication Activity Database

Celik, H.; Ludvík, Jiří; Zuman, P.

2006-01-01

Roč. 51, č. 26 (2006), s. 5845-5852 ISSN 0013-4686 R&D Projects: GA MŠk 1P05ME785 Institutional research plan: CEZ:AV0Z40400503 Keywords : oximes * electroreduction * polarography Subject RIV: CG - Electrochemistry Impact factor: 2.955, year: 2006

Indirubin-3-Oxime Prevents H2O2-Induced Neuronal Apoptosis via Concurrently Inhibiting GSK3β and the ERK Pathway.

Science.gov (United States)

Yu, Jie; Zheng, Jiacheng; Lin, Jiajia; Jin, Linlu; Yu, Rui; Mak, Shinghung; Hu, Shengquan; Sun, Hongya; Wu, Xiang; Zhang, Zaijun; Lee, Mingyuen; Tsim, Wahkeung; Su, Wei; Zhou, Wenhua; Cui, Wei; Han, Yifan; Wang, Qinwen

2017-05-01

Oxidative stress-induced neuronal apoptosis plays an important role in many neurodegenerative disorders. In this study, we have shown that indirubin-3-oxime, a derivative of indirubin originally designed for leukemia therapy, could prevent hydrogen peroxide (H 2 O 2 )-induced apoptosis in both SH-SY5Y cells and primary cerebellar granule neurons. H 2 O 2 exposure led to the increased activities of glycogen synthase kinase 3β (GSK3β) and extracellular signal-regulated kinase (ERK) in SH-SY5Y cells. Indirubin-3-oxime treatment significantly reversed the altered activity of both the PI3-K/Akt/GSK3β cascade and the ERK pathway induced by H 2 O 2 . In addition, both GSK3β and mitogen-activated protein kinase inhibitors significantly prevented H 2 O 2 -induced neuronal apoptosis. Moreover, specific inhibitors of the phosphoinositide 3-kinase (PI3-K) abolished the neuroprotective effects of indirubin-3-oxime against H 2 O 2 -induced neuronal apoptosis. These results strongly suggest that indirubin-3-oxime prevents H 2 O 2 -induced apoptosis via concurrent inhibiting GSK3β and the ERK pathway in SH-SY5Y cells, providing support for the use of indirubin-3-oxime to treat neurodegenerative disorders caused or exacerbated by oxidative stress.

Efficacy of two anthelmintic treatments, spinosad/milbemycin oxime and ivermectin/praziquantel in dogs with natural Toxocara spp. infection.

Science.gov (United States)

Heredia Cardenas, Rafael; Romero Núñez, Camilo; Miranda Contreras, Laura

2017-11-30

Toxocara canis is one of the most important zoonotic parasites of dogs. The aim of the present study was to compare the efficacy of spinosad/milbemycin oxime and ivermectin/praziquantel in dogs naturally infected with Toxocara spp. We studied 200 dogs with a positive diagnosis of Toxocara spp. Through coproparasitoscopic analysis, two study groups of 100 dogs each were assigned: spinosad/milbemycin oxime at a dose of 30-60mg/kg and 0.75-1.0mg/kg, respectively, or ivermectin/praziquantel administered at a dose of 0.2mg/kg and 5mg/kg, respectively. Both groups received a single dose. Three stool samples, one at day 0 before treatment, and at 14 and 28days post-treatment were examined using concentration-flotation techniques. In both treatments, the number of Toxocara spp. eggs decreased; with spinosad/milbemycin oxime treatment, eggs decreased by 87% at 14days (P=0.008) and 94% at 28days after treatment, compared with 71% at day 14 and 88% at day 28 in dogs medicated with ivermectin/praziquantel. The spinosad/milbemycin oxime treated group showed a greater decrease in the number of Toxocara spp. positive dogs compared to the group receiving ivermectin/praziquantel. Copyright © 2017 Elsevier B.V. All rights reserved.

The Efficacy Of Milbemycin Oxime In The Treatment Of Naturally Acquired Infestations Of Sarcoptes Scabiei On Dogs

OpenAIRE

Xu Q; Guo S; Li J; Wang Y; Shen Z; Yanping Wang; Ying Z; Zhang Z; Fu S; Ma L; Yang L; Wang J; Duanhui Ma

2013-01-01

Milbemycin oxime tablets were evaluated for efficacy against sarcoptic mange mites in naturally infested dogs. Sixty-five dogs were allocated to two groups and were housed individually. Fifty of the dogs were treated orally with milbemycin oxime at the proposed dose. The other fifteen were treated orally with vehicle. Study day 0 was defined as the first day of treatment administration. Dogs were treated on days 0, 7 and 14, and efficacy was assessed by counting viable mites recovered from sk...

Multiple QSAR models, pharmacophore pattern and molecular docking analysis for anticancer activity of α, β-unsaturated carbonyl-based compounds, oxime and oxime ether analogues

Science.gov (United States)

Masand, Vijay H.; El-Sayed, Nahed N. E.; Bambole, Mukesh U.; Quazi, Syed A.

2018-04-01

Multiple discrete quantitative structure-activity relationships (QSARs) models were constructed for the anticancer activity of α, β-unsaturated carbonyl-based compounds, oxime and oxime ether analogues with a variety of substituents like sbnd Br, sbnd OH, -OMe, etc. at different positions. A big pool of descriptors was considered for QSAR model building. Genetic algorithm (GA), available in QSARINS-Chem, was executed to choose optimum number and set of descriptors to create the multi-linear regression equations for a dataset of sixty-nine compounds. The newly developed five parametric models were subjected to exhaustive internal and external validation along with Y-scrambling using QSARINS-Chem, according to the OECD principles for QSAR model validation. The models were built using easily interpretable descriptors and accepted after confirming statistically robustness with high external predictive ability. The five parametric models were found to have R2 = 0.80 to 0.86, R2ex = 0.75 to 0.84, and CCCex = 0.85 to 0.90. The models indicate that frequency of nitrogen and oxygen atoms separated by five bonds from each other and internal electronic environment of the molecule have correlation with the anticancer activity.

Successful oxime therapy one hour after soman intoxication in the rat

NARCIS (Netherlands)

Wolthuis, O.L.; Kepner, L.A.

1978-01-01

The bisquarternary mono-oxime HI-6, and to a lesser extent HS-6, caused functional recovery of neuromuscular transmission in vivo and in vitro when given 60 min after soman, i.e. when the soman-cholinesterase (AChE) complex is said to be fully 'aged'. Atropinised rats, with the tracheas intubated,

Altered cerebral blood flow in chronic neck pain patients but not in whiplash patients: a 99mTc-HMPAO rCBF study.

Science.gov (United States)

Sundström, Torbjörn; Guez, Michel; Hildingsson, Christer; Toolanen, Göran; Nyberg, Lars; Riklund, Katrine

2006-08-01

A cross-sectional study to investigate regional cerebral blood flow (rCBF) in patients with chronic whiplash syndrome and chronic neck pain patients without previous history of trauma along with a healthy control group. Chronic neck pain is a common disorder and a history of cervical spine injury including whiplash trauma constitute a risk factor for persistent neck pain. The aetiology of the late whiplash syndrome is unknown with no specific diagnostic criteria based on imaging, physiological, or psychological examination. Earlier studies indicate a parieto-occipital hypoperfusion but it is unclear if the hypoperfusion represents a response to chronic pain. The rCBF was monitored in 45 patients with chronic neck pain: 27 cases with chronic whiplash syndrome and 18 age and gender matched cases with non-traumatic chronic neck pain. The rCBF was estimated with single-photon emission computed tomography (SPECT) using technetium-99m hexamethylpropylene amine oxime (HMPAO). The non-traumatic patients displayed rCBF changes in comparison with the whiplash group and the healthy control group. These changes included rCBF decreases in a right temporal region close to hippocampus, and increased rCBF in left insula. The whiplash group displayed no significant differences in rCBF in comparison with the healthy controls. The present study suggests different pain mechanisms in patients with chronic neck pain of non-traumatic origin compared to those with chronic neck pain due to a whiplash trauma.

Resting state rCBF mapping with single-photon emission tomography and positron emission tomography: magnitude and origin of differences

Energy Technology Data Exchange (ETDEWEB)

Jonsson, C.; Kimiaei, S.; Larsson, S.A. [Section of Nuclear Medicine, Department of Hospital Physics, Karolinska Hospital and Department of Medical Radiation Physics, Stockholm University, Stockholm (Sweden); Pagani, M. [Institute of Experimental Medicine, CNR, Rome (Italy); Ingvar, M. [Section of Cognitive Neurophysiology, Karolinska Hospital, Stockholm (Sweden); Thurfjell, L. [Center of Image Analysis, Uppsala University, Uppsala (Sweden); Jacobsson, H. [Department of Diagnostic Radiology, Karolinska Hospital, Stockholm (Sweden)

1998-02-01

Single-photon emission tomography (SPET), using technetium-99m hexamethylpropylene amine oxime, and positron emission tomography (PET), using oxygen-15 butanol were compared in six healthy male volunteers with regard to the mapping of resting state regional cerebral blood flow (rCBF). A computerized brain atlas was utilized for 3D regional analyses and comparison of 64 selected and normalized volumes of interest (VOIs). The normalized mean rCBF values in SPET, as compared to PET, were higher in most of the Brodmann areas in the frontal and parietal lobes (4.8% and 8.7% respectively). The average differences were small in the temporal (2.3%) and occipital (1.1%) lobes. PET values were clearly higher in small VOIs like the thalamus (12.3%), hippocampus (12.3%) and basal ganglia (9.9%). A resolution phantom study showed that the in-plane SPET/PET system resolution was 11.0/7.5 mm. In conclusion, SPET and PET data demonstrated a fairly good agreement despite the superior spatial resolution of PET. The differences between SPET and PET rCBF are mainly due to physiological and physical factors, the data processing, normalization and co-registration methods. In order to further improve mapping of rCBF with SPET it is imperative not only to improve the spatial resolution but also to apply accurate correction techniques for scatter, attenuation and non-linear extraction. (orig.) With 6 figs., 3 tabs., 23 refs.

Differences in {sup 99m}Tc-HMPAO brain SPET perfusion imaging between Tourette's syndrome and chronic tic disorder in children

Energy Technology Data Exchange (ETDEWEB)

Chiu, N.-T.; Lee, B.-F. [Dept. of Nuclear Medicine, College of Medicine, National Cheng Kung University, Tainan, Taiwan (Taiwan); Chang, Y.-C. [Dept. of Pediatrics, Kaohsiung Chang Kang Children' s Hospital, Kaohsiung, Taiwan (Taiwan); Huang, C.-C. [Dept. of Pediatrics, College of Medicine, National Cheng Kung University, Tainan (Taiwan); Wang, S.-T. [Dept. of Public Health, College of Medicine, National Cheng Kung University, Tainan, Taiwan (Taiwan)

2001-02-01

Early differential diagnosis between Tourette's syndrome and chronic tic disorder is difficult but important because both the outcome and the treatment of these two childhood-onset diseases are distinct. We assessed the sensitivity and specificity of brain single-photon emission tomography (SPET) perfusion imaging in distinguishing the two diseases, and characterized their different cerebral perfusion patterns. Twenty-seven children with Tourette's syndrome and 11 with chronic tic disorder (mean age 9.5 and 8.6 years, respectively) underwent brain SPET with technetium-99m hexamethylpropylene amine oxime (HMPAO). Visual interpretation and semi-quantitative analysis of SPET images were performed. On visual interpretation, 22 of 27 (82%) of the Tourette's syndrome group had lesions characterized by decreased perfusion. The left hemisphere was more frequently involved. None of the children with chronic tic disorder had a visible abnormality. Semi-quantitative analysis showed that, compared with children with chronic tic disorder, children with Tourette's syndrome had significantly lower perfusion in the left lateral temporal area and asymmetric perfusion in the dorsolateral frontal, lateral and medial temporal areas. In conclusion, using the visual approach, brain SPET perfusion imaging is sensitive and specific in differentiating Tourette's syndrome and chronic tic disorder. The perfusion difference between the two groups, demonstrated by semi-quantitative analysis, may be related more to the co-morbidity in Tourette's syndrome than to tics per se. (orig.)

Physical assessment of the GE/CGR Neurocam and comparison with a single rotating gamma-camera

International Nuclear Information System (INIS)

Kouris, K.; Jarritt, P.H.; Costa, D.C.; Ell, P.J.

1992-01-01

The GE/CGR Neurocam is a triple-headed single photon emission tomography (SPET) system dedicated to multi-slice brain tomography. We have assessed its physical performance in terms of sensitivity and resolution, and its clinical efficacy in comparison with a modern, single, rotating gamma-camera (GE 400XCT). Using a water-filled cylinder containing TC-99m, the tomographic volume sensitivity of the Neurocam was 30.0 and 50.7 kcps/MBq.ml.cm for the high-resolution and general-purpose collimators, respectively; the corresponding values for the single rotating camera were 7.6 and 12.8 kcps/MBq.ml.cm. Tomographic resolution was measured in air and in water. In air, the Neurocam resolution at the centre of the field-of-view is 9.0 and 10.7 mm full width at half-maximum (FWHM) with the collimators, respectively, and is isotropic in the three orthogonal planes; the resolution of the GE 400XCT with its 13-cm radius of rotation is 10.3 and 11.7 mm, respectively. For the Neurocam with the HR collimator, the transaxial FWHM values in water were 9.7 mm at the centre and 9.5 mm radial (6.6 mm tangential) at 8 cm from the centre. The physical characteristics of the Neurocam enable the routine acquisition of brain perfusion data with Tc-99m hexamethyl-propylene amine oxime in about 14 min, yielding better image quality than with a single rotating camera in 40 min. (orig./HP)

Studies on the polymerization of acrolein oxime, 13

International Nuclear Information System (INIS)

Ota, Tadatoshi; Mori, Yoshikazu; Tamai, Harumi; Masuda, Seizo; Tanaka, Masami.

1980-01-01

The radiation-induced polymerization of acrolein oxime was carried out at temperatures ranging from room temperature to -78 0 C, and the resulting low molecular products were analyzed by gas chromatography-mass spectrometry. Acetaldoxime, propionaldoxime, propenylhydroxylamines, dioximes etc. were obtained. Initial processes of the polymerization are discussed on the basis of these reaction products. The present work offers further corroborating evidence for the already-described postulation that an anionic mechanism is operative above room temperature, and a cationic mechanism is predominant below -23 0 C. (author)

Catalytic activity of some oxime-based Pd(II-complexes in Suzuki coupling of aryl and heteroaryl bromides in water

Directory of Open Access Journals (Sweden)

Kamal M. Dawood

2017-05-01

Full Text Available The catalytic activity of four Pd(II-complexes of benzoazole-oximes was extensively studied in Suzuki–Miyaura C–C cross coupling reactions in water, as an eco-friendly green solvent, under both thermal heating as well as microwave irradiation conditions. The cross-coupling reactions included different activated and deactivated aryl- or heteroaryl-bromides with several arylboronic acids. The protected oxime-complexes were found to be more efficient than the free ones.

Novel bioreducible poly(amido amine)s for highly efficient gene delivery

NARCIS (Netherlands)

Lin, C.; Zhong, Zhiyuan; Lok, Martin C.; Jiang, Xulin; Hennink, Wim E.; Feijen, Jan; Engbersen, Johannes F.J.

2007-01-01

A series of novel bioreducible poly(amido amine)s containing multiple disulfide linkages (SS-PAAs) were synthesized and evaluated as nonviral gene vectors. These linear SS-PAAs could be easily obtained by Michael-type polyaddition of various primary amines to the disulfide-containing cystamine

Inhibition, recovery and oxime-induced reactivation of muscle esterases following chlorpyrifos exposure in the earthworm Lumbricus terrestris

International Nuclear Information System (INIS)

Collange, B.; Wheelock, C.E.; Rault, M.; Mazzia, C.; Capowiez, Y.; Sanchez-Hernandez, J.C.

2010-01-01

Assessment of wildlife exposure to organophosphorus (OP) pesticides generally involves the measurement of cholinesterase (ChE) inhibition, and complementary biomarkers (or related endpoints) are rarely included. Herein, we investigated the time course inhibition and recovery of ChE and carboxylesterase (CE) activities in the earthworm Lumbricus terrestris exposed to chlorpyrifos, and the ability of oximes to reactivate the phosphorylated ChE activity. Results indicated that these esterase activities are a suitable multibiomarker scheme for monitoring OP exposure due to their high sensitivity to OP inhibition and slow recovery to full activity levels following pesticide exposure. Moreover, oximes reactivated the inhibited ChE activity of the earthworms exposed to 12 and 48 mg kg -1 chlorpyrifos during the first week following pesticide exposure. This methodology is useful for providing evidence for OP-mediated ChE inhibition in individuals with a short history of OP exposure (≤1 week); resulting a valuable approach for assessing multiple OP exposure episodes in the field. - Esterase inhibition combined with oxime reactivation methods is a suitable approach for monitoring organophosphate contamination

Inhibition, recovery and oxime-induced reactivation of muscle esterases following chlorpyrifos exposure in the earthworm Lumbricus terrestris

Energy Technology Data Exchange (ETDEWEB)

Collange, B. [Universite d' Avignon et des Pays de Vaucluse, UMR 406 Abeilles et Environnement, Site AGROPARC, F-84914, Avignon Cede 09 (France); Wheelock, C.E. [Division of Physiological Chemistry II, Department of Medical Biochemistry and Biophysics, Karolinska Institutet, SE 171 77, Stockholm (Sweden); Rault, M.; Mazzia, C. [Universite d' Avignon et des Pays de Vaucluse, UMR 406 Abeilles et Environnement, Site AGROPARC, F-84914, Avignon Cede 09 (France); Capowiez, Y. [INRA, Unite PSH, Site AGROPARC, F-84914 Avignon Cedex 09 (France); Sanchez-Hernandez, J.C., E-mail: juancarlos.sanchez@uclm.e [Laboratory of Ecotoxicology, Faculty of Environmental Science, University of Castilla-La Mancha, Avda. Carlos III s/n, 45071, Toledo (Spain)

2010-06-15

Assessment of wildlife exposure to organophosphorus (OP) pesticides generally involves the measurement of cholinesterase (ChE) inhibition, and complementary biomarkers (or related endpoints) are rarely included. Herein, we investigated the time course inhibition and recovery of ChE and carboxylesterase (CE) activities in the earthworm Lumbricus terrestris exposed to chlorpyrifos, and the ability of oximes to reactivate the phosphorylated ChE activity. Results indicated that these esterase activities are a suitable multibiomarker scheme for monitoring OP exposure due to their high sensitivity to OP inhibition and slow recovery to full activity levels following pesticide exposure. Moreover, oximes reactivated the inhibited ChE activity of the earthworms exposed to 12 and 48 mg kg{sup -1} chlorpyrifos during the first week following pesticide exposure. This methodology is useful for providing evidence for OP-mediated ChE inhibition in individuals with a short history of OP exposure (<=1 week); resulting a valuable approach for assessing multiple OP exposure episodes in the field. - Esterase inhibition combined with oxime reactivation methods is a suitable approach for monitoring organophosphate contamination

Selective and Efficient Solvent Extraction of Copper(II Ions from Chloride Solutions by Oxime Extractants

Directory of Open Access Journals (Sweden)

Zahra Kaboli Tanha

2016-06-01

Full Text Available Oxime extractants 3-tert-butyl-2-hydroxy-5-methyl benzaldehyde oxime (HL1 and 3-tert-butyl-2-hydroxy-5-methoxy benzaldehyde oxime (HL2 were synthesized and characterized by conventional spectroscopic methods. Suitable lipophilic nature of the prepared extractants allowed examining the ability of these molecules for extraction-separation of copper from its mixture with normally associated metal ions by performing competitive extraction experiments of Cu(II, Co(II, Ni(II, Zn(II, Cd(II and Pb(II ions from chloride solutions. Both ligands transfer selectively the copper ions into dichloromethane by a cation exchange mechanism. Conventional log-log analysis and isotherm curves showed that Cu(II ions are extracted as the complexes with 1:2 metal to ligand ratio by both extractants. Verification of the effect of the organic diluent used in the extraction of copper ions by HL1 and HL2 demonstrated that the extraction efficiency varies as: dichloromethane ~ dichloroethane > toluene > xylene > ethylacetate. Time dependency investigation of the extraction processes revealed that the kinetics of the extraction of copper by HL2 is more rapid than that of HL1. The application of the ligands for extraction-separation of copper ions from leach solutions of cobalt and nickel-cadmium filter-cakes of a zinc production plants was evaluated.

Synthesis of Imidazopyridines via Copper-Catalyzed, Formal Aza-[3 + 2] Cycloaddition Reaction of Pyridine Derivatives with α-Diazo Oxime Ethers.

Science.gov (United States)

Park, Sangjune; Kim, Hyunseok; Son, Jeong-Yu; Um, Kyusik; Lee, Sooho; Baek, Yonghyeon; Seo, Boram; Lee, Phil Ho

2017-10-06

The Cu-catalyzed, formal aza-[3 + 2] cycloaddition reaction of pyridine derivatives with α-diazo oxime ethers in trifluoroethanol was used to synthesize imidazopyridines via the release of molecular nitrogen and elimination of alcohol. These methods enabled modular synthesis of a wide range of N-heterobicyclic compounds such as imidazopyridazines, imidazopyrimidines, and imidazopyrazines with an α-imino Cu-carbenoid generated from the α-diazo oxime ethers and copper.

Scintigraphic evaluation of brain death with 99mTc-d,l-hexamethyl-propyleneamine oxime (HMPAO)

International Nuclear Information System (INIS)

Takehara, Yasuo; Isoda, Haruo; Sakai, Tsuneo; Tanaka, Tokutaro; Sato, Haruhiko; Yamamoto, Takamichi; Takahashi, Motoichiro; Kaneko, Masao.

1989-01-01

Lately, the criteria of brain death is being discussed. Cerebral scintigram, especially scintigraphic evaluation of brain death by dynamic study, has been previously reported. Cerebral imaging using radiolabeled amines such as 123 I-IMP N-isopropyl-p-iodoamphetamin (IMP) or 99m Tc d, l-hexamethyl-propyleneamine oxime (HMPAO) offers a significant information of brain death by the finding of 'non visualized brain'. However, the dynamic scintigram acquired during the bolus injection of 99m Tc-HMPAO provides an additional information of brain death by classical 'hot nose sign'. 99m Tc-HMPAO is able to be administered relatively in a large amount of dose. This cerebral perfusion tracer is lipophilic and remains in the central nervous system, which characterize its role as a reliable indicator of cerebral blood flow. As a result, this compound became suitable for the non-invasive study of brain circulation when the diagnosis of brain death is uncertain. We report a case of brain death in which diagnosis was made by the classical 'hot nose sign' in dynamic scintigraphy performed when 99 mTc-HMPAO was injected as well as the SPECT which showed a lack of cerebral visualization at the equilibrium state. As far as we are informed, this additional procedure used in the diagnosis of brain death has not reported before. The importance of performing a dynamic scintigram at the administration of 99m Tc-HMPAO is also discussed in this report. (author)

Development and validation of a FIA/UV-vis method for pK(a) determination of oxime based acetylcholinesterase reactivators.

Science.gov (United States)

Musil, Karel; Florianova, Veronika; Bucek, Pavel; Dohnal, Vlastimil; Kuca, Kamil; Musilek, Kamil

2016-01-05

Acetylcholinesterase reactivators (oximes) are compounds used for antidotal treatment in case of organophosphorus poisoning. The dissociation constants (pK(a1)) of ten standard or promising acetylcholinesterase reactivators were determined by ultraviolet absorption spectrometry. Two methods of spectra measurement (UV-vis spectrometry, FIA/UV-vis) were applied and compared. The soft and hard models for calculation of pK(a1) values were performed. The pK(a1) values were recommended in the range 7.00-8.35, where at least 10% of oximate anion is available for organophosphate reactivation. All tested oximes were found to have pK(a1) in this range. The FIA/UV-vis method provided rapid sample throughput, low sample consumption, high sensitivity and precision compared to standard UV-vis method. The hard calculation model was proposed as more accurate for pK(a1) calculation. Copyright © 2015 Elsevier B.V. All rights reserved.

Electrochemical determination of 5-dodecylsalicylaldoxime and 2′-hydroxy-5′-nonylacetophenone oxime in commercial extractants

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Elizalde María P.

2017-01-01

Full Text Available A differential pulse voltammetric method using a hanging mercury drop electrode (HMDE was optimized for the determination of 5-dodecylsalicylaldoxime in hydro-alcoholic solutions using factorial and central composite designs. The Taguchi design methodology was used to extend the formerly optimized method to the determination of 2′-hydroxy-5′-nonylacetophenone oxime. The method was successfully applied to quantify 5-dodecylsalicylaldoxime and 2′-hydroxy-5′-nonylacetophenone oxime in samples of commercial extractants over the concentration range 0.05–2.45 and 0.07–0.82 mg L-1, respectively, with detection limits of 0.034 and 0.019 mg L-1, respectively.

Synthesis and Antifungal Activity of Novel 3-Caren-5-One Oxime Esters.

Science.gov (United States)

Huang, Min; Duan, Wen-Gui; Lin, Gui-Shan; Li, Kun; Hu, Qiong

2017-09-12

A series of novel 3-caren-5-one oxime esters were designed and synthesized by multi-step reactions in an attempt to develop potent antifungal agents. Two E - Z stereoisomers of the intermediate 3-caren-5-one oxime were separated by column chromatography for the first time. The structures of all the intermediates and target compounds were confirmed by UV-Vis, FTIR, NMR, ESI-MS, and elemental analysis. The antifungal activity of the target compounds was preliminarily evaluated by the in vitro method against Fusarium oxysporum f. sp. cucumerinum , Physalospora piricola , Alternaria solani , Cercospora arachidicola , Gibberella zeae, Rhizoeotnia solani , Bipolaris maydis , and Colleterichum orbicalare at 50 µg/mL. The target compounds exhibited best antifungal activity against P. piricola , in which compounds ( Z )- 4r (R = β -pyridyl), ( Z )- 4q (R = α -thienyl), ( E )- 4f' (R = p -F Ph), ( Z )- 4i (R = m -Me Ph), ( Z )- 4j (R = p -Me Ph), and ( Z )- 4p (R = α -furyl) had inhibition rates of 97.1%, 87.4%, 87.4%, 85.0%, 81.9%, and 77.7%, respectively, showing better antifungal activity than that of the commercial fungicide chlorothanil. Also, compound ( Z )- 4r (R = β -pyridyl) displayed remarkable antifungal activity against all the tested fungi, with inhibition rates of 76.7%, 82.7%, 97.1%, 66.3%, 74.7%, 93.9%, 76.7% and 93.3%, respectively, showing better or comparable antifungal activity than that of the commercial fungicide chlorothanil. Besides, the E-Z isomers of the target oxime esters were found to show obvious differences in antifungal activity. These results provide an encouraging framework that could lead to the development of potent novel antifungal agents.

SYNTHESIS OF OXIMES WITH THE DOPED POTASSIUM FLUORIDE ANIMAL BONE MEAL AS A CATALYST

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M. AIT TALEB

2017-12-01

Full Text Available The potassium fluoride doped Animal Bone Meal (KF/ABM was prepared and characterized using several techniques to identify the structural properties. After, it has been used as a new and eco-friendly catalyst for the preparation of from aldehydes and ketones oximes under solvent-free conditions. It is clearly shown that this reaction (using this catalyst can lead to the corresponding oximes in good yields (80 % to excellent yields (96 %. In the case of dissymmetric aldehydes and ketones, this catalyst can lead to a mixture of Z- and E- isomers (Z/E = 86/14–90/10. The remarkable advantages of this catalyst are high conversion, short reaction times, cleaner reaction profiles, reusability up to 8 times without significant loss of activity, and reduction in catalyst toxicity.

Synthesis and Antifungal Activity of Novel 3-Caren-5-One Oxime Esters

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Min Huang

2017-09-01

Full Text Available A series of novel 3-caren-5-one oxime esters were designed and synthesized by multi-step reactions in an attempt to develop potent antifungal agents. Two E-Z stereoisomers of the intermediate 3-caren-5-one oxime were separated by column chromatography for the first time. The structures of all the intermediates and target compounds were confirmed by UV-Vis, FTIR, NMR, ESI-MS, and elemental analysis. The antifungal activity of the target compounds was preliminarily evaluated by the in vitro method against Fusarium oxysporum f. sp. cucumerinum, Physalospora piricola, Alternaria solani, Cercospora arachidicola, Gibberella zeae, Rhizoeotnia solani, Bipolaris maydis, and Colleterichum orbicalare at 50 µg/mL. The target compounds exhibited best antifungal activity against P. piricola, in which compounds (Z-4r (R = β-pyridyl, (Z-4q (R = α-thienyl, (E-4f′ (R = p-F Ph, (Z-4i (R = m-Me Ph, (Z-4j (R = p-Me Ph, and (Z-4p (R = α-furyl had inhibition rates of 97.1%, 87.4%, 87.4%, 85.0%, 81.9%, and 77.7%, respectively, showing better antifungal activity than that of the commercial fungicide chlorothanil. Also, compound (Z-4r (R = β-pyridyl displayed remarkable antifungal activity against all the tested fungi, with inhibition rates of 76.7%, 82.7%, 97.1%, 66.3%, 74.7%, 93.9%, 76.7% and 93.3%, respectively, showing better or comparable antifungal activity than that of the commercial fungicide chlorothanil. Besides, the E-Z isomers of the target oxime esters were found to show obvious differences in antifungal activity. These results provide an encouraging framework that could lead to the development of potent novel antifungal agents.

Synthesis and Bioactivities of Novel Pyrazole Oxime Derivatives Containing a 5-Trifluoromethylpyridyl Moiety

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Hong Dai

2016-02-01

Full Text Available In this study, in order to find novel biologically active pyrazole oxime compounds, a series of pyrazole oxime derivatives containing a 5-trifluoromethylpyridyl moiety were synthesized. Preliminary bioassays indicated that most title compounds were found to display good to excellent acaricidal activity against Tetranychus cinnabarinus at a concentration of 200 μg/mL, and some designed compounds still showed excellent acaricidal activity against Tetranychus cinnabarinus at the concentration of 10 μg/mL, especially since the inhibition rates of compounds 8e, 8f, 8l, 8m, 8n, 8p, and 8q were all 100.00%. Interestingly, some target compounds exhibited moderate to good insecticidal activities against Plutella xylostella and Aphis craccivora at a concentration of 200 μg/mL; furthermore, compounds 8e and 8l possessed outstanding insecticidal activities against Plutella xylostella under the concentration of 50 μg/mL.

Selective N-alkylation of amines using nitriles under hydrogenation conditions: facile synthesis of secondary and tertiary amines.

Science.gov (United States)

Ikawa, Takashi; Fujita, Yuki; Mizusaki, Tomoteru; Betsuin, Sae; Takamatsu, Haruki; Maegawa, Tomohiro; Monguchi, Yasunari; Sajiki, Hironao

2012-01-14

Nitriles were found to be highly effective alkylating reagents for the selective N-alkylation of amines under catalytic hydrogenation conditions. For the aromatic primary amines, the corresponding secondary amines were selectively obtained under Pd/C-catalyzed hydrogenation conditions. Although the use of electron poor aromatic amines or bulky nitriles showed a lower reactivity toward the reductive alkylation, the addition of NH(4)OAc enhanced the reactivity to give secondary aromatic amines in good to excellent yields. Under the same reaction conditions, aromatic nitro compounds instead of the aromatic primary amines could be directly transformed into secondary amines via a domino reaction involving the one-pot hydrogenation of the nitro group and the reductive alkylation of the amines. While aliphatic amines were effectively converted to the corresponding tertiary amines under Pd/C-catalyzed conditions, Rh/C was a highly effective catalyst for the N-monoalkylation of aliphatic primary amines without over-alkylation to the tertiary amines. Furthermore, the combination of the Rh/C-catalyzed N-monoalkylation of the aliphatic primary amines and additional Pd/C-catalyzed alkylation of the resulting secondary aliphatic amines could selectively prepare aliphatic tertiary amines possessing three different alkyl groups. According to the mechanistic studies, it seems reasonable to conclude that nitriles were reduced to aldimines before the nucleophilic attack of the amine during the first step of the reaction.

Azobisisobutyronitrile initiated aerobic oxidative transformation of amines: coupling of primary amines and cyanation of tertiary amines.

Science.gov (United States)

Liu, Lianghui; Wang, Zikuan; Fu, Xuefeng; Yan, Chun-Hua

2012-11-16

In the presence of a catalytic amount of radical initiator AIBN, primary amines are oxidatively coupled to imines and tertiary amines are cyanated to α-aminonitriles. These "metal-free" aerobic oxidative coupling reactions may find applications in a wide range of "green" oxidation chemistry.

The effect of the conditions of amidoximation on the adsorptive characteristics of amide oxime resin for uranium recovery from seawater

International Nuclear Information System (INIS)

Hori, Takahiro; Furusaki, Shintaro; Sugo, Takanobu; Okamoto, Jiro.

1987-01-01

A hollow-fiber type chelating resin containing the amide oxime group for the recovery of uranium from seawater was synthesized by radiation-induced graft polymerization. The effect of the conditions of amidoximation on the amount and/or distribution of the functional groups and on the durability to the recycle adsorption was investigated. The amount of adsorbed copper on the resin increased with the reaction time of the amidoximation, but that of adsorbed hydrochloric acid gradually decreased after reaching the maximum. From the results of elemental analysis, infrared adsorption spectra, visible light and ultraviolet adsorption spectra and the observation of coloration of the resin by alkaline treatment, the amidoximation was found to be a consecutive reaction. The results also suggested that, after the introduction of the amide oxime group, the acidic amide, hydroxamic acid and/or cyclic functional groups were formed. From the measurement of the distribution of adsorbed copper by X-ray microanalyzer, it was confirmed that the amidoximation occured uniformly across the resin. An experiment was carried out on the recycle adsorption of the amide oxime resin using natural seawater, and the sufficient durability was recognized for the case that the resin was taken out from the hydroxylamine solution at the time when the amount of adsorbed hydrochloric acid reached the maximum. In this case the resin contained the largest amount of the amide oxime group and least amount of the by-products formed from the secondary reactions. (author)

Bioreducible poly(amido amine)s for non-viral gene delivery

NARCIS (Netherlands)

Lin, C.

2008-01-01

This thesis describes the design and development of bioreducible poly(amido amine)s as non-viral vectors for gene delivery in vitro and in vivo. The structural influences of these polymers on their physico-chemical properties and gene delivery properties, transfection capability and cytotoxicity in

Assessment of changes in regional cerebral blood flow in patients with major depression using the 99mTc-HMPAO single photon emission tomography method

International Nuclear Information System (INIS)

Yazici, K.; Kapucu, Oe.; Erbas, B.; Varoglu, E.; Guelec, C.; Bekdik, C.F.; Hacettepe Univ., Ankara

1992-01-01

Regional cerebral blood flow was investigated in 14 patients with major depression diagnosed according to the DSM-III-R criteria (six patients with single and eight patients with recurrent episodes) and in ten healthy volunteers. The mean ages of the patients and the controls were 33.5±2.7 and 31.6±2.6 years, respectively. The severity of the depression was assessed using the 17-item Hamiltonian Depression Scale (mean: 23.2±1.5). None of the patients was under medication. After administration of 500 MBq technetium-99m hexamethylpropylene amine oxime, a single photon emission tomography study was performed and then transaxial, sagittal and coronal slices were obtained. For the semiquantitative analysis of the data, the ratios of the mean counts/pixel to the whole slice were calculated for 24 regions on three consecutive transaxial slices in the orbitomeatal plane. Additionally, left/right and frontal/occipital ratios were calculated. Both sides of the temporal region had a significantly decreased cerebral blood flow (CBF) when compared to the controls. The left/right ratio of the prefrontal region was also significantly lower in the patients than in the controls. The Hamilton score had a negative correlation with blood flow in the anterofrontal and left prefrontal regions. According to our results, regional CBF seems to be decreased in the left prefrontal and in both temporal regions in major depression. The severity of depression is correlated with the reduction in CBF in the regions of the anterofrontal and left prefrontal cortex. (orig.)

Comparison of simultaneous [sup 99m]Tc-HMPAO and [sup 111]In oxine labelled white cell scans in the assessment of inflammatory bowel disease

Energy Technology Data Exchange (ETDEWEB)

Allan, R.A.; Bassingham, S.; Lazarus, C.; Clarke, S.E.M.; Fogelman, I. (Guy' s Hospital, London (United Kingdom). Dept. of Nuclear Medicine); Sladen, G.E. (Guy' s Hospital, London (United Kingdom). Dept. of Gastroenterology)

1993-03-01

Forty-seven patients, 29 with chronic inflammatory bowel disease (IBD) and 18 with presumed irritable bowel syndrome, including one with uncomplicated diverticular disease, were studied with simultaneous technetium-99m hexamethylpropylene amine oxime and indium-III oxine labelled leucocyte scans performed at 1, 3 and 24 h. Twenty-seven patients with IBD had active disease as judged by clinical and laboratory criteria and all of these had positive scans with both agents. No false positive studies were obtained. The 1-h [sup 99m]Tc-HMPAO WBC scans showed the same distribution to disease as the 3-h [sup 111]-In WBC scans, with no difference in intensity (P<0.92); they showed more extensive disease (P<0.02) and more intense uptake (P<0.001) than did the 1-h [sup 111]-In scans. The 3-h [sup 99m]Tc-HMPAO WBC scans showed more extensive disease (P<0.002), with greater intensity (P<0.0005), than did the 3-h [sup 111]In WBC scans. Physiological bowel activity on 3-h [sup 99m]Tc-HMPAO WBC scans was present in 12 patients but was faint and did not interfere with assessment of disease extent and activity. It is concluded that in terms of isotope availability, radiation dosimetry and image quality, [sup 99m]Tc-HMPAO is the agent of choice in detecting active IBD, with localization of disease possible at 1-h after re-injection and optimal resolution and definition of disease extent at 3 h. A negative scan reliably excludes active disease. (orig.).

Diagnosis of pyogenic pelvic inflammatory diseases by {sup 99m}Tc-HMPAO leucocyte scintigraphy

Energy Technology Data Exchange (ETDEWEB)

Rachinsky, I.; Boguslavsky, L.; Golan, H.; Lantsberg, S. [Department of Nuclear Medicine, Ben-Gurion Univ. of the Negev (Israel); Goldstein, D.; Pak, I.; Katz, M. [Department of Obstetrics and Gynecology, Ben-Gurion Univ. of the Negev, Beer-Sheva (Israel)

2000-12-01

Pelvic inflammatory disease (PID) is one of the major health problems of women of child-bearing age. Among the most serious complications of PID is the formation of a tubo-ovarian abscess (TOA). Early diagnosis of this condition may prevent serious surgical complications such as peritonitis and sepsis, which may be fatal. The purpose of this study was to investigate the efficacy of technetium-99m hexamethylpropylene amine oxime (HMPAO) leucocyte scintigraphy in the diagnosis of TOA. Twenty women with high clinical suspicion of TOA underwent {sup 99m}Tc-HMPAO leucocyte scintigraphy. The labelling of leucocytes with {sup 99m}Tc-HMPAO was performed according to a standard protocol. Scans were obtained at 1, 3 and 24 h following the injection of the labelled leucocytes. In eight cases the early and/or late scan was positive, in 11 cases it was negative, and in one case of ovarian cyst torsion, confirmed by laparoscopy, it showed slight uptake in the capsule of the cyst (false-positive). The sensitivity of {sup 99m}Tc-HMPAO leucocyte scintigraphy was 100%, specificity 91.6%, positive predictive value 89%, negative predictive value 100% and overall accuracy 95%. It is concluded that leucocyte scintigraphy is a non-invasive, safe, physiological and accurate procedure for the diagnosis of TOA. The 24-h scan is crucial, since in some cases the abscess was not clearly visualized on the early scan. Leucocyte scintigraphy may reduce the need for CT, diagnostic laparoscopy and unnecessary invasive surgical procedures. (orig.)

Extraordinary arousal from semi-comatose state on zolpidem ...

African Journals Online (AJOL)

propylene amine oxime (99mTc HMPAO) brain single photon emission computed tomography (SPECf) before and after administration of the gamma-aminobutyric acid (GABA) agonist zolpidem. It was observed that 15 minutes after application ...

The economics of amine usage

International Nuclear Information System (INIS)

Fountain, M.J.

1994-01-01

The EPRI computer programm, 'Aminemod', a PWR chemistry model, has been used to compare the technical advantages of the 'advanced' amines, ethanolamine, 1,2 diaminoethane and 5 aminopentanol over morpholine in generating an elevated pH in the moisture separator and the economics of using these amines has been assessed by using an MS Excel spreadsheet in conjunction with Aminemod. The advanced amines are capable of achieving 1 pH unit above neutrality, the EPRI target for prevention of erosion-corrison, at acceptable cost and, compared with 'conventional' amines, at considerably reduced ionic load on the condensate polisher. The exercise demonstrates that it is essential to evaluate the effect of an amine dosing regime on the total operating cost and that it is not possible to prejudge the economic outcome on the basis of an amine's purchase price. (orig.)

Synthesis and 5α-Reductase Inhibitory Activity of C21 Steroids Having 1,4-diene or 4,6-diene 20-ones and 4-Azasteroid 20-Oximes

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Eunsook Ma

2011-12-01

Full Text Available The synthesis and evaluation of 5α-reductase inhibitory activity of some 4-azasteroid-20-ones and 20-oximes and 3β-hydroxy-, 3β-acetoxy-, or epoxy-substituted C21 steroidal 20-ones and 20-oximes having double bonds in the A and/or B ring are described. Inhibitory activity of synthesized compounds was assessed using 5α-reductase enzyme and [1,2,6,7-3H]testosterone as substrate. All synthesized compounds were less active than finasteride (IC50: 1.2 nM. Three 4-azasteroid-2-oximes (compounds 4, 6 and 8 showed good inhibitory activity (IC50: 26, 10 and 11 nM and were more active than corresponding 4-azasteroid 20-ones (compounds 3, 5 and 7. 3β-Hydroxy-, 3β-acetoxy- and 1α,2α-, 5α,6α- or 6α,7α-epoxysteroid-20-one and -20-oxime derivatives having double bonds in the A and/or B ring showed no inhibition of 5α-reductase enzyme.

In Vitro Ability of Currently Available Oximes to Reactivate Organophosphate Pesticide-Inhibited Human Acetylcholinesterase and Butyrylcholinesterase

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Kamil Musilek

2011-03-01

Full Text Available We have in vitro tested the ability of common, commercially available, cholinesterase reactivators (pralidoxime, obidoxime, methoxime, trimedoxime and HI-6 to reactivate human acetylcholinesterase (AChE, inhibited by five structurally different organophosphate pesticides and inhibitors (paraoxon, dichlorvos, DFP, leptophos-oxon and methamidophos. We also tested reactivation of human butyrylcholinesterase (BChE with the aim of finding a potent oxime, suitable to serve as a “pseudocatalytic” bioscavenger in combination with this enzyme. Such a combination could allow an increase of prophylactic and therapeutic efficacy of the administered enzyme. According to our results, the best broad-spectrum AChE reactivators were trimedoxime and obidoxime in the case of paraoxon, leptophos-oxon, and methamidophos-inhibited AChE. Methamidophos and leptophos-oxon were quite easily reactivatable by all tested reactivators. In the case of methamidophos-inhibited AChE, the lower oxime concentration (10−5 M had higher reactivation ability than the 10−4 M concentration. Therefore, we evaluated the reactivation ability of obidoxime in a concentration range of 10−3–10−7 M. The reactivation of methamidophos-inhibited AChE with different obidoxime concentrations resulted in a bell shaped curve with maximum reactivation at 10−5 M. In the case of BChE, no reactivator exceeded 15% reactivation ability and therefore none of the oximes can be recommended as a candidate for “pseudocatalytic” bioscavengers with BChE.

Bacterial degradation of monocyclic aromatic amines

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Pankaj Kumar Arora

2015-08-01

Full Text Available Aromatic amines are an important group of industrial chemicals, which are widely used for manufacturing of dyes, pesticides, drugs, pigments, and other industrial products. These compounds have been considered highly toxic to human beings due to their carcinogenic nature. Three groups of aromatic amines have been recognized: monocyclic, polycyclic and heterocyclic aromatic amines. Bacterial degradation of several monocyclic aromatic compounds has been studied in a variety of bacteria, which utilizes monocyclic aromatic amines as their sole source of carbon and energy. Several degradation pathways have been proposed and the related enzymes and genes have also been characterized. Many reviews have been reviewed toxicity of monocyclic aromatic amines; however, there is lack of review on biodegradation of monocyclic aromatic amines. The aim of this review is to summarize bacterial degradation of monocyclic aromatic amines. This review will increase our current understanding of biochemical and molecular basis of bacterial degradation of monocyclic aromatic amines.

Amine Measurements in Boreal Forest Air

Science.gov (United States)

Hemmilä, Marja; Hellén, Heidi; Makkonen, Ulla; Hakola, Hannele

2015-04-01

Amines are reactive, volatile bases in the air with a general formula of RNH2, R2NH or R3N. Especially small amines can stabilize sulphuric acid clusters and hence affect nucleation. Amines react rapidly with hydroxyl radical (OH˙) thus affecting oxidative capacity of the atmosphere. The amine concentrations are higher in forest air than in urban air (Hellén et al., 2014), but the sources are not known. In order to get more information concerning amine sources, we conducted a measurement campaign in a boreal forest. At SMEAR II station at Hyytiälä, Southern Finland (61°510'N, 24°170'E, 180 m a.s.l.) The measurements cover seven months, from June to December 2014. For sampling and measuring we used MARGA (The instrument for Measuring AeRosols and Gases in Ambient air) which is an on-line ion chromatograph (IC) connected to a sampling system. The IC component of the MARGA system was coupled to an electrospray ionization quadrupole mass spectrometer (MS) to improve sensitivity of amine measurements. This new set-up enabled amine concentration measurements in ambient air both in aerosol and gas phases with a time resolution of only 1 hour. With MARGA-MS we analysed 7 different amines: monomethylamine (MMA), dimethylamine (DMA), trimethylamine (TMA), ethylamine (EA), diethylamine (DEA), propylamine (PA) and butylamine (BA). In preliminary data-analysis we found out, that in June and July most of the measured amines were in gas phase, and particle phase amine concentrations were mostly under detection limits (<1.7 pptv). In June the gaseous amine concentrations were higher than in July. The measured concentrations of gaseous amines followed temperature variation, which could indicate that amines are produced and emitted from the environment or re-emitted from the surfaces as temperature rises after deposition during night-time. All measured amines had similar diurnal variation with maxima during afternoon and minima during night. Results from other months will also

The Design, Synthesis and Screening of Potential Pyridinium Oxime Prodrugs

Science.gov (United States)

1984-02-01

Our intent is to take advantage of this trapping mechanism using nucleophiles (X) such as SCN, SO3H, I, Br and OCN, which we hope will be as labile...pH 3.5-10.5. The advantage of the system stemmed from the fact that each pyridinium oxime regenerator has a discrete -max which is pH dependent. 2-PAM...with matching 3 cm guard columns. Normal phase analysis was performed "on an Alltech 0.5 x 25 cm silica gel 10 p column with 3 cm guard column and

Cp*Co(III) Catalyzed Site-Selective C-H Activation of Unsymmetrical O-Acyl Oximes: Synthesis of Multisubstituted Isoquinolines from Terminal and Internal Alkynes.

Science.gov (United States)

Sun, Bo; Yoshino, Tatsuhiko; Kanai, Motomu; Matsunaga, Shigeki

2015-10-26

The synthesis of isoquinolines by site-selective C-H activation of O-acyl oximes with a Cp*Co(III) catalyst is described. In the presence of this catalyst, the C-H activation of various unsymmetrically substituted O-acyl oximes selectively occurred at the sterically less hindered site, and reactions with terminal as well as internal alkynes afforded the corresponding products in up to 98 % yield. Whereas the reactions catalyzed by the Cp*Co(III) system proceeded with high site selectivity (15:1 to 20:1), use of the corresponding Cp*Rh(III) catalysts led to low selectivities and/or yields when unsymmetrical O-acyl oximes and terminal alkynes were used. Deuterium labeling studies indicate a clear difference in the site selectivity of the C-H activation step under Cp*Co(III) and Cp*Rh(III) catalysis. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Efficient Construction of Energetic Materials via Nonmetallic Catalytic Carbon-Carbon Cleavage/Oxime-Release-Coupling Reactions.

Science.gov (United States)

Zhao, Gang; He, Chunlin; Yin, Ping; Imler, Gregory H; Parrish, Damon A; Shreeve, Jean'ne M

2018-03-14

The exploitation of C-C activation to facilitate chemical reactions is well-known in organic chemistry. Traditional strategies in homogeneous media rely upon catalyst-activated or metal-mediated C-C bonds leading to the design of new processes for applications in organic chemistry. However, activation of a C-C bond, compared with C-H bond activation, is a more challenging process and an underdeveloped area because thermodynamics does not favor insertion into a C-C bond in solution. Carbon-carbon bond cleavage through loss of an oxime moiety has not been reported. In this paper, a new observation of self-coupling via C-C bond cleavage with concomitant loss of oxime in the absence of metals (either metal-complex mediation or catalysis) results in dihydroxylammonium 5,5-bistetrazole-1,10-diolate (TKX-50) as well as N, N'-([3,3'-bi(1,2,4-oxadiazole)]-5,5'-diyl)dinitramine, a potential candidate for a new generation of energetic materials.

Energetics of Ortho-7 (oxime drug translocation through the active-site gorge of tabun conjugated acetylcholinesterase.

Directory of Open Access Journals (Sweden)

Vivek Sinha

Full Text Available Oxime drugs translocate through the 20 Å active-site gorge of acetylcholinesterase in order to liberate the enzyme from organophosphorus compounds' (such as tabun conjugation. Here we report bidirectional steered molecular dynamics simulations of oxime drug (Ortho-7 translocation through the gorge of tabun intoxicated enzyme, in which time dependent external forces accelerate the translocation event. The simulations reveal the participation of drug-enzyme hydrogen bonding, hydrophobic interactions and water bridges between them. Employing nonequilibrium theorems that recovers the free energy from irreversible work done, we reconstruct potential of mean force along the translocation pathway such that the desired quantity represents an unperturbed system. The potential locates the binding sites and barriers for the drug to translocate inside the gorge. Configurational entropic contribution of the protein-drug binding entity and the role of solvent translational mobility in the binding energetics is further assessed.

Sillica Gel-Amine from Geothermal Sludge

Science.gov (United States)

Muljani, S.; Pujiastuti, C.; Wicaksono, P.; Lutfianingrum, R.

2018-01-01

Silica Gel-Amine (SGA) has been made from geothermal sludge by grafting amine method. Sodium silicate solution is prepared by extracted geothermal sludge powder using sodium hidroxide solution then acidification in the range of pH 5 - 9 by using tartaric acid 1N. The grafting process uses 1 ml of ammonia solution and 10 ml of toluene at a rate of 0.1 ml min-1 accompanied by a reflux process. The amine grafting is done in two methods. The first method is grafting amine in silicate solution and the second method is grafting amine in washed gel. Product SGA was confirmed by FTIR, TGA-DTG and BET characterization. The results show that the pH affects the amount of amine that is grafted onto silica gel. Differences in grafting method affect the size of the pore and surface area. SGA product prepared by grafting washed gel at pH 8 have pore diameter of 12.06 nm, surface area of 173.44 m2g-1, and mass of decomposed amine compound 0.4 mg. In the presence of amine groups on the silica gel surface, these adsorbents may be able to selectively adsorb CO2 gas from natural gas.

The economics of amine usage

International Nuclear Information System (INIS)

Fountain, M.J.

1994-01-01

Research carried out over the past decade in the USA (funded by EPRI) and by the CEGB/Nuclear Electric in the UK has identified several thermally stable, low-toxicity 'advanced' amines with good high-temperature basicity and low steam-water distribution ratio. As a direct result of this work several US PWR stations are now evaluating monoethanolamine (ETA) and Nuclear Electric's Wylfa Power Station (magnox) now doses 5 aminopentanol (5AP) instead of AMP, which had successfully combated erosion-corrosion for the past nine years. It has recently been stated that the use of 5AP ''...could save Nuclear Electric up to 1.5M pounds per year''. To provide US power station chemists with a tool for tailoring amine dosage to their own plant requirements EPRI has developed a computer model, Aminmod, which can, with user-defined circuit parameters and amine feed concentrations, calculate amine concentrations and pH(t) values at various points around the circuit. To complement this model a user-friendly spreadsheet program is being developed which will work in conjunction with Aminmod, via active links, to calculate the total operating cost associated with the selected amine dosing regime and compare alternative scenarios. This paper discusses the relationship between the technical and economic aspects of choosing an amine dosing regime and draws on combined Aminmod/spreadsheet results to illustrate how differences in amine properties can influence the optimum economic solution for a typical PWR. (author). 3 figs., 2 tabs., 5 refs

Amines, Astrocytes and Arousal

OpenAIRE

Bazargani, N.; Attwell, D.

2017-01-01

Amine neurotransmitters, such as noradrenaline, mediate arousal, attention, and reward in the CNS. New data suggest that, from flies to mammals, a major mechanism for amine transmitter action is to raise astrocyte [Ca2+]i and release gliotransmitters that modulate neuronal activity and behavior.

Extraction of sulphates by long chain amines; Extraction des sulfates par les amines a longues chaines

Energy Technology Data Exchange (ETDEWEB)

Boirie, Ch [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

1959-05-15

The extraction of sulphuric acid by long chain amines in organic solution has been studied with a view to determining the value of the stability constants of the amine sulphates and bi-sulphates formed. We have concentrated chiefly on uranium sulphate and thorium sulphate. The formulae of the complexes extractable with amines have been established, as well as the corresponding dissociation constants. We have observed that for uranium sulphate the formula of the complex depends only on the nature of the amine, whereas for thorium this formula varies with the amine structure. From the formulae determined and the value of the constants calculated, we have been able to establish the best conditions for uranium and thorium extraction and also for a separation of these two elements. Finally we propose an application of this study to the determination of uranium in ores, where the separation of uranium by this method is particularly easy and complete. (author) [French] L'extraction de l'acide sulfurique par des amines a longues chaines en solution organique a ete etudiee en vue de la determination de la valeur des constantes de stabilite des sulfates et bisulfates d'amines formes. Parmi les sulfates, nous nous sommes particulierement interesses au sulfate d'uranium et au sulfate de thorium. Nous avons determine les formules des complexes extractibles avec les amines, ainsi que les constantes de dissociation correspondantes. Nous avons remarque que pour le sulfate d'uranium, la formule du complexe ne depend que de la nature de l'amine, alors que pour le thorium cette formule varie avec la structure de l'amine. Les formules determinees et la valeur des constantes calculees, nous ont permis de decrire les meilleures conditions d'extraction de l'uranium et du thorium ainsi que celles d'une separation de ces deux elements. Nous proposons enfin une application de cette etude au dosage de l'uranium dans les minerais, ou la separation de l'uranium par cette methode est

Synthesis of a hollow fiber type porous chelating resin containing the amide oxime group by radiation induced graft polymerization for the uranium recovery

International Nuclear Information System (INIS)

Hori, Takahiro; Saito, Kyoichi; Furusaki, Shintaro; Sugo, Takanobu; Okamoto, Jiro.

1986-01-01

A hollow fiber type porous chelating resin containing amide oxime as a functional group was synthesized and used as an adsorbent for the recovery of uranium. Hollow fiber type porous polyethylene was used as a base polymer. Acrylonitrile was grafted onto it by the radiation-induced graft polymerization. By changing the reaction time, four kinds of graft polymer were obtained. The degree of grafting ranged from 79 % to 127 %. Each resin was soaked in hydroxylamine solution, and the cyano group was converted to amide oxime group. By elemental analysis, the amount of nitrogen introduced on the graft polymer resin in amidoximation was determined to range from 4.3 mmol to 8.5 mmol per 1 g of base polymer. Most of the nitrogen is considered to belong to the amide oxime group. The pore radius, which was initially distributed broadly from about 500 A to 10000 A for the base polymer, was changed to about 1000 A with narrow distribution by the grafting. The pore volume was 1.2 ∼ 1.4 cm 3 per 1 gram of the amide oxime resin, which was about half of that of the initial base polymer. But the pore volume per 1 g base polymer of the amide oxime resin increased with an increase in the grafting degree, e.g. 4.5 cm 3 /g base polymer at 127 % of grafting degree. Specific surface area, which was 30 m 2 /g in base polymer, decreased with an increase in the grafting degree, e.g. 15 m 2 /g at 127 % of grafting degree. Both the amounts of the adsorbed hydrochloric acid and the adsorbed copper were about 1.5 times of the amount of nitrogen introduced in the amidoximation. The reason is considered to be caused by the formation of hydroxamic acid and amide from the measurements of the IR spectra. The amount of uranium adsorbed on the resin was 64 % of the amount of nitrogen introduced in the amidoximation. (author)

1H, 13C and 13N chemical shifts and 1H-15N and 13C-15N heteronuclear spin-spin coupling constants n the NMR spectra of 5-substituted furfural oximes

International Nuclear Information System (INIS)

Popelis, Yu.Yu.; Liepin'sh, E.E.; Lukevits, E.Ya.

1986-01-01

The 1 H, 13 C, and 15 N NMR spectra of 15 N-enriched 5-substituted furfural oximes were investigated. It was shown that the chemical shifts of the ring atoms and the oxime group correlate satisfactorily with the F and R substituent constants, whereas their sensitivity to the effect of the substituents is lower than in monosubstituted furan derivatives. The constants of spin-spin coupling between the ring protons and the oxime group were determined. An analysis of the 1 H- 1 H spin-spin coupling constants (SSCC) on the basis of their stereospecificity indicates that the E isomers have primarily an s-trans conformation in polar dimethyl sulfoxide, whereas the Z isomers, on the other hand, have an s-cis conformation. The signs of the direct and geminal 13 C- 15 N SSCC were determined for 5-trimethylsilylfurfural oxime

Kinetic analysis of interactions of paraoxon and oximes with human, Rhesus monkey, swine, rabbit, rat and guinea pig acetylcholinesterase.

Science.gov (United States)

Worek, Franz; Aurbek, Nadine; Wille, Timo; Eyer, Peter; Thiermann, Horst

2011-01-15

Previous in vitro studies showed marked species differences in the reactivating efficiency of oximes between human and animal acetylcholinesterase (AChE) inhibited by organophosphorus (OP) nerve agents. These findings provoked the present in vitro study which was designed to determine the inhibition, aging, spontaneous and oxime-induced reactivation kinetics of the pesticide paraoxon, serving as a model compound for diethyl-OP, and the oximes obidoxime, pralidoxime, HI 6 and MMB-4 with human, Rhesus monkey, swine, rabbit, rat and guinea pig erythrocyte AChE. Comparable results were obtained with human and monkey AChE. Differences between human, swine, rabbit, rat and guinea pig AChE were determined for the inhibition and reactivation kinetics. A six-fold difference of the inhibitory potency of paraoxon with human and guinea pig AChE was recorded while only moderate differences of the reactivation constants between human and animal AChE were determined. Obidoxime was by far the most effective reactivator with all tested species. Only minor species differences were found for the aging and spontaneous reactivation kinetics. The results of the present study underline the necessity to determine the inhibition, aging and reactivation kinetics in vitro as a basis for the development of meaningful therapeutic animal models, for the proper assessment of in vivo animal data and for the extrapolation of animal data to humans. Copyright © 2010 Elsevier Ireland Ltd. All rights reserved.

Memory functions and rCBF {sup 99m}Tc-HMPAO SPET: developing diagnostics in Alzheimer's disease

Energy Technology Data Exchange (ETDEWEB)

Elgh, Eva; Naesman, Birgitta [Department of Community Medicine and Rehabilitation, Geriatric Medicine, Umeaa University, 901 85 Umeaa (Sweden); Sundstroem, Torbjoern; Aahlstroem, Katrine Riklund [Department of Radiation Sciences, Diagnostic Radiology, Umeaa University, Umeaa (Sweden); Nyberg, Lars [Department of Psychology, Umeaa University, Umeaa (Sweden)

2002-09-01

Alzheimer's disease (AD) is a primary degenerative disease of the brain. The prevalence increases with age, with devastating consequences for the individual and society. The aim of this study was to evaluate whether patients with early AD show an altered regional cerebral blood flow (rCBF) compared with control persons. Furthermore, we aimed to investigate the correlation between rCBF in sublobar volumes of the brain and performance on memory tests. Memory tests were chosen to evaluate episodic and semantic memory. Fourteen patients (aged 75.2{+-}8.8 years) with early AD and 15 control persons (aged 71.4{+-}3.2 years) were included. rCBF measurements with single-photon emission tomography (SPET) using technetium-99m hexamethylpropylene amine oxime (HMPAO) were performed. The rCBF {sup 99m}Tc-HMPAO SPET images were spatially transformed to fit a brain atlas and normalised for differences in rCBF (Computerised Brain Atlas software). Cortical and subcortical volumes of interest (VOIs) were analysed and compared. Compared with the controls, AD patients showed a significantly lower rCBF ratio in temporoparietal regions, including the left hippocampus. The diagnostic sensitivity and specificity for AD were high in temporoparietal regions. AD patients had significantly reduced performance on semantic and, in particular, episodic memory tests compared with age-matched normative data, and their performance on several episodic tests correlated with rCBF ratios in parietal and temporal regions, including the left hippocampus. The correlation between rCBF ratio and level of episodic memory performance suggests that abnormalities in rCBF pattern underlie impaired episodic memory functioning in AD. (orig.)

Memory functions and rCBF 99mTc-HMPAO SPET: developing diagnostics in Alzheimer's disease

International Nuclear Information System (INIS)

Elgh, Eva; Naesman, Birgitta; Sundstroem, Torbjoern; Aahlstroem, Katrine Riklund; Nyberg, Lars

2002-01-01

Alzheimer's disease (AD) is a primary degenerative disease of the brain. The prevalence increases with age, with devastating consequences for the individual and society. The aim of this study was to evaluate whether patients with early AD show an altered regional cerebral blood flow (rCBF) compared with control persons. Furthermore, we aimed to investigate the correlation between rCBF in sublobar volumes of the brain and performance on memory tests. Memory tests were chosen to evaluate episodic and semantic memory. Fourteen patients (aged 75.2±8.8 years) with early AD and 15 control persons (aged 71.4±3.2 years) were included. rCBF measurements with single-photon emission tomography (SPET) using technetium-99m hexamethylpropylene amine oxime (HMPAO) were performed. The rCBF 99m Tc-HMPAO SPET images were spatially transformed to fit a brain atlas and normalised for differences in rCBF (Computerised Brain Atlas software). Cortical and subcortical volumes of interest (VOIs) were analysed and compared. Compared with the controls, AD patients showed a significantly lower rCBF ratio in temporoparietal regions, including the left hippocampus. The diagnostic sensitivity and specificity for AD were high in temporoparietal regions. AD patients had significantly reduced performance on semantic and, in particular, episodic memory tests compared with age-matched normative data, and their performance on several episodic tests correlated with rCBF ratios in parietal and temporal regions, including the left hippocampus. The correlation between rCBF ratio and level of episodic memory performance suggests that abnormalities in rCBF pattern underlie impaired episodic memory functioning in AD. (orig.)

Clinical usefulness of scatter and attenuation correction for brain single photon emission computed tomography (SPECT) in pediatrics

International Nuclear Information System (INIS)

Adachi, Itaru; Doi, Kenji; Komori, Tsuyoshi; Hou, Nobuyoshi; Tabuchi, Koujirou; Matsui, Ritsuo; Sueyoshi, Kouzou; Utsunomiya, Keita; Narabayashi, Isamu

1998-01-01

This investigation was undertaken to study clinical usefulness of scatter and attenuation correction (SAC) of brain SPECT in infants to compare the standard reconstruction (STD). The brain SPECT was performed in 31 patients with 19 epilepsy, 5 cerebro-vascular disease, 2 brain tumor, 3 meningitis, 1 hydrocephalus and psychosis (mean age 5.0±4.9 years old). Many patients was necessary to be injected sedatives for restraining body motion after Technetium-99m hexamethylpropylene amine oxime ( 99m Tc-HMPAO) was injected at the convulsion or rest. Brain SPECT data were acquired with triple detector gamma camera (GCA-9300 Toshiba Japan). These data were reconstructed by filtered backprojection after the raw data were corrected by triple energy windows method of scatter correction and Chang filtered method of attenuation correction. The same data was reconstructed by filtered backprojection without these corrections. Both SAC and STD SPECT images were analyzed by the visual interpretation. The uptake ratio of cerebral basal nuclei was calculated by the counts of the thalamus or lenticular nuclei divided by the cortex. All images of SAC method were excellent than that of STD method. The thalamic uptake ratio in SAC method was higher than that of STD method (1.22±0.09>0.87±0.22 p 1.02±0.16 p<0.01). Transmission scan is the most suitable method of absorption correction. But the transmission scan is not adequate for examination of children, because this scan needs a lot of time and the infants are exposed by the line source radioisotope. It was concluded that these scatter and absorption corrections were most suitable method for brain SPECT in pediatrics. (author)

99Tcm brain imaging for the assessment of patients with intractable partial epilepsy - our experience

International Nuclear Information System (INIS)

Schlicht, S.; Bruns, M.; Booth, R.; Octigan, K.; Karamoskos, P.; Cook, M.; O'Brien, T.

2000-01-01

Full text: 99 Tc m - Ethyl Cysteinate Diethylester (ECD) or Bicisate is a new radiopharmaceutical used for the assessment of cerebral perfusion. Unlike 99 Tc m Hexamethylpropylene Amine Oxime ( 99 Tc m - HMPAO) which is unstable and needs to be reconstituted immediately prior to injection, 99 Tc m -ECD is stable for up to eight hours following reconstitution. Therefore, 99 Tc m -ECD does not require mixing just prior to injection and is readily available on a daily inpatient basis to the epilepsy unit, facilitating earlier and faster injections, and the acquisition of true ictal studies. This is particularly important with patients who have extra temporal seizures which are typically brief in duration. 45 patients have undergone 99 Tc m -ECD studies for epilepsy in our department over a period of one year. Image acquisition routinely commences within two hours of injection, and consists of a 360 degree elliptical SPECT using an ADAC Dual Headed Gamma Camera. Patients undergo both ictal and inter ictal SPECT studies, and an MRI. Visual comparison of the ictal, inter ictal and MRI images is performed, as well as subtraction and co-registration. The SISCOM analysis technique is used which allows subtraction of the SPECTs and co registration with MRI. This has the advantage of improved specificity, sensitivity, and accurate anatomical localisation. The results of our experience with 99Tcm-ECD will be presented. In conclusion, we have found that 99 Tc m -ECD is ideally suited for peri-ictal SPECT studies as part of the pre-operative assessment of patients with intractable partial epilepsy. Copyright (2000) The Australian and New Zealand Society of Nuclear Medicine Inc

Assessment of cerebral perfusion with single-photon emission tomography in normal subjects and in patients with Alzheimer's disease: effects of region of interest selection

Energy Technology Data Exchange (ETDEWEB)

Claus, J J [Dept. of Neurology, Univ. Hospital, Rotterdam (Netherlands) Dept. of Epidemiology and Biostatistics, Erasmus Univ. Medical School, Rotterdam (Netherlands); Harskamp, F van [Dept. of Neurology, Univ. Hospital, Rotterdam (Netherlands); Breteler, M M.B. [Dept. of Epidemiology and Biostatistics, Erasmus Univ. Medical School, Rotterdam (Netherlands); Krenning, E P [Dept. of Nuclear Medicine, Univ. Hospital, Rotterdam (Netherlands); Cammen, T.J.M. van der (Dept. of Geriatric Medicine, Univ. Hospital, Rotterdam (Netherlands)); Hofman, A [Dept. of Epidemiology and Biostatistics, Erasmus Univ. Medical School, Rotterdam (Netherlands); Hasan, D [Dept. of Neurology, Univ. Hospital, Rotterdam (Netherlands)

1994-10-01

We compared three different ROIs in a SPET study with 60 controls and in 48 patients with probable Alzheimer's disease diagnosed according to the NINCDS-ADRDA criteria. Regional cerebral blood flow (rCBF) was assessed with SPET using technetium-99m d,l-hexamethylpropylene amine oxime ([sup 99m]Tc-HMPAO), normalized to the mean activity in a cerebellar reference slice. The three different ROIs were: a multi-slice and a single-slice ROI with reference to the normal brain anatomy (using an anatomical atlas), and a rectangular (2x4 pixels) ROI in the frontal, temporal, temporoparietal and occipital cortices. No differences were observed for the means of rCBF values between the single-slice and multi-slice ROI's with reference to the normal anatomy, but some variability was present for individual comparisons. In contrast, significantly higher mean rCBF values were obtained with the single-slice rectangular ROIs in all four regions for both patients and controls and considerable variability was shown for individual subjects. After analysis with multivariate logistic regression and receiver operator characteristic curves, the ability of SPET to discriminate between controls and Alzheimer patients was similar in the three methods for mild and moderate Alzheimer patients (Global Deterioration Scale = GDS of 3 and 4). However, with increasing dementia severity (GDS>4) the rectangular ROIs showed lower ability to discriminate between groups compared to the single-slice and multi-slice anatomically defined ROIs. This study suggests that results of rCBF assessment with SPET using [sup 99m]Tc-HMPAO in patients with severe Alzheimer's disease are influenced by the shape and size of the ROI. (orig.)

Changes in local cerebral blood flow by neuroactivation and vasoactivation in patients with impaired cognitive function

International Nuclear Information System (INIS)

Knapp, W.H.; Dannenberg, C.; Marschall, B.; Zedlick, D.; Loeschmann, K.; Bettin, S.; Barthel, H.; Seese, A.

1996-01-01

Imaging of local cerebral blood flow (lCBF) may serve as an important supplementary tool in the aetiological assessment of dementias. In early or preclinical disease, however, there are less characteristic changes in lCBF. In the present study it was investigated whether vasoactivation or neuroactivation may produce more pronounced local lCBF deficits. Local CBF was investigated by using technetium-99m hexamethylpropylene amine oxime and single-photon emission tomography (SPET) in 80 patients (50 with mild cognitive impairment and 30 with dementia of Alzheimer type (DAT), all without evidence of cerebrovascular disease) at rest (baseline) and during activation. In 31 studies patients underwent vasomotor activation with acetazolamide, while 62 studies were performed under cognitive challenge (neuroactivation by labyrinth task). Cortical activity relative to that of cerebellum increased significantly in a right temporal region and tended to increase in other cortical regions upon vasoactivation. In contrast, neuroactivation reduced cortical activity relative to that of cerebellum in several left and right temporal and in left parietal regions. Visual classification of SPET images of patients with probable DAT by three observers resulted in a reduction of the number of definitely abnormal patterns from 9/12 to 4/12 by vasoactivation and an increase from 10/18 to 15/18 by neuroactivation. Correspondingly, abnormal ratings in patients with mild cognitive dysfunction were reduced form 7/19 to 5/19 by vasoactivation and were increased from 12/21 to 18/21 by neuroactivation. In conclusion, vasoactivation does not enhance local relative perfusion deficits in patients with cognitive impairment of non-vascular aetiology, whereas neuroactivation by labyrinth task produces more pronounced local flow differences and enhances abnormal patterns in lCBF imaging. (orig.)

Acetylcholine muscarinic receptors and response to anti-cholinesterase therapy in patients with Alzheimer's disease

International Nuclear Information System (INIS)

Brown, Derek; Chisholm, Jennifer A.; Patterson, Jim; Wyper, David; Owens, Jonathan; Pimlott, Sally

2003-01-01

An acetylcholine deficit remains the most consistent neurotransmitter abnormality found in Alzheimer's disease and various therapeutic agents have been targeted at this. In this study we investigated the action of Donepezil, a cholinesterase inhibitor that has few side-effects. In particular we set out to investigate whether muscarinic acetylcholine receptor (mAChR) availability influences the response to this therapy. We used the novel single-photon emission tomography (SPET) tracer (R,R)[ 123 I]I-quinuclidinyl benzilate (R,R[ 123 I]I-QNB), which has high affinity for the M1 subtype of mAChR. Regional cerebral perfusion was also assessed using technetium-99m hexamethylpropylene amine oxime. We investigated 20 patients on Donepezil treatment and ten age-matched controls. The results showed a reduction in (R,R)[ 123 I]I-QNB binding in the caudal anterior cingulate in patients compared with controls and relatively high binding in the putamen and rostral anterior cingulate, suggesting a relative sparing of mAChR in these regions. The main finding of the study was that mAChR availability as assessed by (R,R)[ 123 I]I-QNB binding did not distinguish responders from non-responders. Interestingly, we found that the extent of cognitive improvement showed no positive correlation with (R,R)[ 123 I]I-QNB binding in any brain region but was inversely related to binding in the insular cortex. This suggests that, within the advised cognitive performance band for use of Donepezil, response is greater in those patients with evidence of a more marked cholinergic deficit. A larger study should investigate this. (orig.)

Memory-provoked rCBF-SPECT as a diagnostic tool in Alzheimer's disease?

International Nuclear Information System (INIS)

Sundstroem, Torbjoern; Riklund, Katrine Aa.; Elgh, Eva; Naesman, Birgitta; Larsson, Anne; Nyberg, Lars

2006-01-01

Alzheimer's disease (AD) is a primary degenerative disease that progressively affects all brain functions, with devastating consequences for the patient, the patient's family and society. Rest regional cerebral blood flow (rCBF) could have a strategic role in differentiating between AD patients and normal controls, but its use for this purpose has a low discriminatory capacity. The purpose of this study was to evaluate whether the diagnostic sensitivity of rCBF single-photon emission computed tomography (SPECT) could be increased by using an episodic memory task provocation, i.e. memory-provoked rCBF-SPECT (MP-SPECT). Eighteen persons (73.2±4.8 years) with mild AD and 18 healthy elderly (69.4±3.9 years) were included in the study. The subjects were injected with 99m Tc-hexamethylpropylene amine oxime (HMPAO) during memory provocation with faces and names, followed by an rCBF-SPECT study. The rCBF 99m Tc-HMPAO SPECT images were analysed using statistical parametric mapping (SPM2). Peaks with a false discovery rate corrected value of 0.05 were considered significant. On MP-SPECT, the AD group showed a significant rCBF reduction in the left parietal cortex in comparison with healthy elderly. At rest, no significant group differences were seen. Memory provocation increased the sensitivity of rCBF-SPECT for the detection of AD-related blood flow changes in the brain at the group level. Further studies are needed to evaluate MP-SPECT as a diagnostic tool at the individual level. If a higher sensitivity for AD at the individual level is verified in future studies, a single MP-SPECT study might be sufficient in the clinical setting. (orig.)

Clinical validation of the avidin/indium-111 biotin approach for imaging infection/inflammation in orthopaedic patients

International Nuclear Information System (INIS)

Lazzeri, E.; Molea, N.; Bodei, L.; Bianchi, R.; Manca, M.; Marchetti, S.; Consoli, V.; Chinol, M.; Paganelli, G.; Mariani, G.

1999-01-01

We report here the results of a validation study of the avidin/indium-111 biotin approach in patients with skeletal lesions. This study involved 54 patients with orthopaedic conditions: 20 patients with intermediate suspected osteomyelitis of the trunk, 19 patients with infection/inflammation of prosthetic joint replacements, and 15 patients with suspected osteomyelitis of appendicular bones. Avidin (3 mg) was injected as an i.v. bolus, followed 4 h later by 111 In-biotin; imaging was acquired 30 min and 16-18 h after administration of 111 In-biotin. Technetium-99m hexamethylpropylene amine oxime ( 99m Tc-HMPAO)-labelled leucocyte scintigraphy was performed in 39/54 patients. The overall sensitivity of the avidin/ 111 In-biotin scan was 97.7% (versus 88.9% for 99m Tc-HMPAO leucocyte scintigraphy). While the diagnostic performance of avidin/ 111 In-biotin scintigraphy was similar to that of 99m Tc-HMPAO leucocyte scintigraphy in patients with prosthetic joint replacements or osteomyelitis of appendicular bones, the avidin/ 111 In-biotin approach clearly performed better than 99m Tc-HMPAO leucocyte scintigraphy in patients with suspected osteomyelitis of the trunk (100% sensitivity, specificity and accuracy versus 50% sensitivity, 100% specificity and 66.7% accuracy for 99m Tc-HMPAO-leucocyte scintigraphy). These results demonstrate the feasibility of the avidin/ 111 In-biotin approach for imaging sites of infection/inflammation in the clinical setting. Although no systematic advantages of avidin/ 111 In-biotin scintigraphy were found versus 99m Tc-HMPAO leucocyte scintigraphy, the newer scintigraphic method is more practicable and involves lower biological risk for the operators. (orig.)

Assessment of cerebral perfusion with single-photon emission tomography in normal subjects and in patients with Alzheimer's disease: effects of region of interest selection

International Nuclear Information System (INIS)

Claus, J.J.; Harskamp, F. van; Breteler, M.M.B.; Krenning, E.P.; Cammen, T.J.M. van der; Hofman, A.; Hasan, D.

1994-01-01

We compared three different ROIs in a SPET study with 60 controls and in 48 patients with probable Alzheimer's disease diagnosed according to the NINCDS-ADRDA criteria. Regional cerebral blood flow (rCBF) was assessed with SPET using technetium-99m d,l-hexamethylpropylene amine oxime ( 99m Tc-HMPAO), normalized to the mean activity in a cerebellar reference slice. The three different ROIs were: a multi-slice and a single-slice ROI with reference to the normal brain anatomy (using an anatomical atlas), and a rectangular (2x4 pixels) ROI in the frontal, temporal, temporoparietal and occipital cortices. No differences were observed for the means of rCBF values between the single-slice and multi-slice ROI's with reference to the normal anatomy, but some variability was present for individual comparisons. In contrast, significantly higher mean rCBF values were obtained with the single-slice rectangular ROIs in all four regions for both patients and controls and considerable variability was shown for individual subjects. After analysis with multivariate logistic regression and receiver operator characteristic curves, the ability of SPET to discriminate between controls and Alzheimer patients was similar in the three methods for mild and moderate Alzheimer patients (Global Deterioration Scale = GDS of 3 and 4). However, with increasing dementia severity (GDS>4) the rectangular ROIs showed lower ability to discriminate between groups compared to the single-slice and multi-slice anatomically defined ROIs. This study suggests that results of rCBF assessment with SPET using 99m Tc-HMPAO in patients with severe Alzheimer's disease are influenced by the shape and size of the ROI. (orig.)

Docking and molecular dynamics studies of peripheral site ligand–oximes as reactivators of sarin-inhibited human acetylcholinesterase

NARCIS (Netherlands)

Almeida, J.S.F.D. de; Cuya Guizado, T.R.; Guimarães, A.P.; Ramalho, T.C.; Gonçalves, A.S.; Koning, M.C. de; França, T.C.C.

2016-01-01

In the present work, we performed docking and molecular dynamics simulations studies on two groups of long-tailored oximes designed as peripheral site binders of acetylcholinesterase (AChE) and potential penetrators on the blood brain barrier. Our studies permitted to determine how the tails anchor

Steric control of reactivity: formation of oximes, benzodiazepinone N-oxides and isoxazoloquinolinones

OpenAIRE

Heaney, Frances; Bourke, Sharon; Cunningham, Desmond; McArdle, Patrick

1998-01-01

Reaction of the alkenyl carbonyl compounds 1 with hydroxylamine can lead to the formation of the oximes 2, the benzodiazepinone N-oxides 3 or the isoxazoloquinolinones 5. The product(s) of reaction are shown to depend on the electronic nature of the terminal olefinic substituent R3 and the space filling capacity of the substituents R1, R2 and R4. When the olefinic centre is electron poor (R3 = CO2Et) ketocarbonyls convert exclusively to bicyclic nitrones 3 whereas aldehydes are more sensitive...

Oxidation of amines by flavoproteins.

Science.gov (United States)

Fitzpatrick, Paul F

2010-01-01

Many flavoproteins catalyze the oxidation of primary and secondary amines, with the transfer of a hydride equivalent from a carbon-nitrogen bond to the flavin cofactor. Most of these amine oxidases can be classified into two structural families, the D-amino acid oxidase/sarcosine oxidase family and the monoamine oxidase family. This review discusses the present understanding of the mechanisms of amine and amino acid oxidation by flavoproteins, focusing on these two structural families. Copyright 2009 Elsevier Inc. All rights reserved.

Controlling Nitrosamines, Nitramines, and Amines in Amine-Based CO₂ Capture Systems with Continuous Ultraviolet and Ozone Treatment of Washwater.

Science.gov (United States)

Dai, Ning; Mitch, William A

2015-07-21

Formation of nitrosamines and nitramines from reactions between flue gas NOx and the amines used in CO2 capture units has arisen as a significant concern. Washwater scrubbers can capture nitrosamines and nitramines. They can also capture amines, preventing formation of nitrosamines and nitramines downwind by amine reactions with ambient NOx. The continuous application of UV alone, or a combination of UV and ozone to the return line of a washwater treatment unit was evaluated to control the accumulation of nitrosamines, nitramines and amines in a laboratory-scale washwater unit. With model secondary amine solvents ranging from nonvolatile diethanolamine to volatile morpholine, application of 272-537 mJ/cm(2) UV incident fluence alone reduced the accumulation of nitrosamines and nitramines by approximately an order of magnitude. Modeling indicated that the gains achieved by UV treatment should increase over time, because UV treatment converts the time dependence of nitrosamine accumulation from a quadratic to a linear function. Ozone (21 mg/L) maintained low steady-state concentrations of amines in the washwater. While modeling indicated that more than 80% of nitrosamine accumulation in the washwater was associated with reaction of washwater amines with residual NOx, a reduction in nitrosamine accumulation rates due to ozone oxidation of amines was not fully realized because the ozonation products of amines reduced nitrosamine photolysis rates by competing for photons.

Metal and base free synthesis of primary amines via ipso amination of organoboronic acids mediated by [bis(trifluoroacetoxy)iodo]benzene (PIFA).

Science.gov (United States)

Chatterjee, Nachiketa; Goswami, Avijit

2015-08-07

A metal and base free synthesis of primary amines has been developed at ambient temperature through ipso amination of diversely functionalized organoboronic acids, employing a combination of [bis(trifluoroacetoxy)iodo]benzene (PIFA)-N-bromosuccinimide (NBS) and methoxyamine hydrochloride as the aminating reagent. The amines were primarily obtained as their trifluoroacetate salts which on subsequent aqueous alkaline work up provided the corresponding free amines. The combination of PIFA-NBS is found to be the mildest choice compared to the commonly used strong bases (e.g. n-BuLi, Cs2CO3) for activating the aminating agent. The reaction is expected to proceed via activation of the aminating reagent followed by B-N 1,2-aryl migration.

Extraction of some acids using aliphatic amines; Extraction de quelques acides par des amines aliphatiques

Energy Technology Data Exchange (ETDEWEB)

Matutano, L [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

1964-06-01

Hydrochloric, nitric, sulphuric, perchloric, phosphoric, acetic and formic acids in aqueous solution (0.05 to 10 M) are extracted by amberlite LA2 and trilaurylamine in solution, 5 per cent by volume, in kerosene and xylene respectively. The extraction process consists of: neutralization of the amine salt; a 'molecular extraction', i.e. an extraction using an excess of acid with respect to the stoichiometry of the amine salt. According to the behaviour of the acid during the extraction, three groups may be distinguished: completely dissociated acids, carboxylic acids, phosphoric acid. This classification is also valid for the extraction of the water which occurs simultaneously with that of the acid. An extraction mechanism is put forward for formic acid and the formation constant of its amine salt is calculated. (author) [French] Les acides chlorhydrique, nitrique, sulfurique, perchlorique, phosphorique, acetique et formique, en solution aqueuse - 0,05 a 10 M - sont extraits par l'amberlite LA2 et la trilaurylamine en solution, a 5 pour cent en volume, dans le kerosene et le xylene respectivement. L'extraction comprend: une neutralisation de l'amine par l'acide avec formation d'un sel d'amine; une 'extraction moleculaire', c'est-a-dire une extraction d'acide en exces par rapport a la stoechiometrie du sel d'amine. Suivant le comportement des acides au cours de l'extraction nous distinguons trois groupes: acides entierement dissocies, acides carboxyliques, acide phosphorique. Cette classification est egalement valable pour l'extraction de l'eau qui est simultanee a celle de l'acide. Un mecanisme d'extraction pour l'acide formique est propose et nous calculons la constante de formation de son sel d'amine. (auteur)

Original Article. Protection studies of new bis quaternary 2-(hydroxyimino-N-(pyridin-3yl acetamide derivatives (HNK-series oximes against acute poisoning by dichlorvos (DDVP in Swiss albino mice

Directory of Open Access Journals (Sweden)

Kumar Pravin

2016-12-01

Full Text Available The available antidotal therapy against acute poisoning by organophosphates involves the use of atropine alone or in combination with one of the oximes, e.g. 2-PAM, Obidoxime, TMB-4 or HI-6. Each of these oximes has some limitation, raising the question of the universal antidotal efficacy against poisoning by all OPs/nerve agents. In the present study, newly synthesized bis quaternary 2-(hydroxyimino-N-(pyridin-3yl acetamide derivatives (HNK-series oximes were evaluated for their antidotal efficacy against DDVP intoxicated Swiss mice, in terms of the Protection Index (PI and AChE reactivation in brain and serum. The inhibition concentration (IC50 was determined in brain and serum after optimizing the time point for maximum inhibition (60 min post DDVP exposure. AChE reactivation efficacy of the HNK series was evaluated at IC50 and compared with 2-PAM. HNK-102 showed a ~2 times better Protection Index (PI as compared to 2-PAM against DDVP toxicity. IC50 at 60 min DDVP post exposure was found to be approximately one fifth and one half of the LD50 dose for brain and serum AChE, respectively. Out of three HNK oximes, HNK-102 & 106 at 0.20 LD50 dose significantly reactivated DDVP intoxicated brain AChE (p<0.05 as compared to 2-PAM at double IC50 dose of DDVP. In light of double PI and higher AChE reactivation, HNK 102 was found to be a better oxime than 2-PAM in the treatment of acute poisoning by DDVP.

Theoretical study of the nucleophilic addition of oximes to the nitrile complexes trans-/cis-[ReCl4(NCCH3)2

International Nuclear Information System (INIS)

Klestova-Nadeeva, E. A.; Kuznetsov, M. L.; Dement'ev, A. I.

2005-01-01

The reaction of nucleophilic addition of oximes (HON=CRR 1 ) to organic nitriles coordinated in the rhenium complexes trans-/cis-[ReCl 4 (NCCH 3 ) 2 ] was theoretically studied by the Hartree-Fock and density functional theory (B3LYP) methods. The reaction mechanism involves (I) the initial change of the oxime conformation; (II) the formation of the orientation complex with the coordinated nitrile molecule, which transforms into a four-membered transition state; (III) the formation of the addition product in a less stable conformation; and (IV) the formation of the ultimate addition product. The calculations make it possible to interpret the activation of nitriles in terms of the activated complex theory as a result of stabilization of the transition state in going from the free to the coordinated nitrile [ru

Chemoselective organocatalytic aerobic oxidation of primary amines to secondary imines.

Science.gov (United States)

Wendlandt, Alison E; Stahl, Shannon S

2012-06-01

Biomimetic aerobic oxidation of primary benzylic amines has been achieved by using a quinone catalyst. Excellent selectivity is observed for primary, unbranched benzylic amines relative to secondary/tertiary amines, branched benzylic amines, and aliphatic amines. The exquisite selectivity for benzylic amines enables oxidative self-sorting within dynamic mixtures of amines and imines to afford high yields of cross-coupled imine products.

Enantioselective Direct α-Amination of Aldehydes via a Photoredox Mechanism: A Strategy for Asymmetric Amine Fragment Coupling

OpenAIRE

Cecere, Giuseppe; Koenig, Christian M.; Alleva, Jennifer L.; MacMillan, David W. C.

2013-01-01

The direct, asymmetric α-amination of aldehydes has been accomplished via a combination of photoredox and organocatalysis. Photon-generated, nitrogen-centered radicals undergo enantioselective α-addition to catalytically formed chiral enamines to directly produce stable α-amino aldehyde adducts bearing synthetically useful amine substitution patterns. Incorporation of a photolabile group on the amine precursor obviates the need to employ a photoredox catalyst in this transformation. Important...

Amine synergism in uranium extraction

International Nuclear Information System (INIS)

Rinelli, G.; Abbruzzese, C.

1977-01-01

Commercial products based on C 8 to C 12 tertiary amine mixtures are now widely used in the solvent extraction of uranium from sulphuric pregnant solutions. The satisfactory results generally obtained have never required an analysis of the synergistic effects of amine combinations similar to that carried out for the organo-phosphorus compounds. In the research described the increase in the extraction power of an organic phase composed of an amine binary mixture was studied with regard to an aqueous solution from the sulphuric acid treatment of uranium ore. On the basis of the experimental results obtained, it is possible to select the best composition of the amine mixture to ensure a percentage increase in uranium recovery. Bearing in mind the tendency for the yellow-cake price to rise, the study is considered to be a useful contribution in the context of commercial products currently available on the market. (author)

General Dialdehyde Click Chemistry for Amine Bioconjugation.

Science.gov (United States)

Elahipanah, Sina; O'Brien, Paul J; Rogozhnikov, Dmitry; Yousaf, Muhammad N

2017-05-17

The development of methods for conjugating a range of molecules to primary amine functional groups has revolutionized the fields of chemistry, biology, and material science. The primary amine is a key functional group and one of the most important nucleophiles and bases used in all of synthetic chemistry. Therefore, tremendous interest in the synthesis of molecules containing primary amines and strategies to devise chemical reactions to react with primary amines has been at the core of chemical research. In particular, primary amines are a ubiquitous functional group found in biological systems as free amino acids, as key side chain lysines in proteins, and in signaling molecules and metabolites and are also present in many natural product classes. Due to its abundance, the primary amine is the most convenient functional group handle in molecules for ligation to other molecules for a broad range of applications that impact all scientific fields. Because of the primary amine's central importance in synthetic chemistry, acid-base chemistry, redox chemistry, and biology, many methods have been developed to efficiently react with primary amines, including activated carboxylic acids, isothiocyanates, Michael addition type systems, and reaction with ketones or aldehydes followed by in situ reductive amination. Herein, we introduce a new traceless, high-yield, fast click-chemistry method based on the rapid and efficient trapping of amine groups via a functionalized dialdehyde group. The click reaction occurs in mild conditions in organic solvents or aqueous media and proceeds in high yield, and the starting dialdehyde reagent and resulting dialdehyde click conjugates are stable. Moreover, no catalyst or dialdehyde-activating group is required, and the only byproduct is water. The initial dialdehyde and the resulting conjugate are both straightforward to characterize, and the reaction proceeds with high atom economy. To demonstrate the broad scope of this new click

Differential pulse polarographic determination of molybdenum (VI) in phosphoric medium by benzoin alpha oxime

International Nuclear Information System (INIS)

Chergouche, S.

1992-02-01

The extraction of Molybdenum (VI) using both 4-Methylpentane-2-one (hexone) and chloroform dissolved Benzoin-alpha-oxime has been investigated in order to develop a simple and sensitive polarographic method allowing the analysis of Molybdenum (VI) contained in industrial phosphoric acid produced in ANNABA (Eastern Algeria). The investigation takes into account various parameters such as: The stirring time, solvent rate, the number of stages ... as well as the organic phase conditioning during the polarographic analysis

Biogenic amines degradation by microorganisms isolated from cheese

Directory of Open Access Journals (Sweden)

Irena Butor

2017-01-01

Full Text Available The aim of this study was the isolation and characterization of microorganisms able to degrade biogenic amines and their identification. Individual microorganisms were obtained by isolation from commercially available foodstuffs and food produced in the technological laboratories of Faculty of Technology, Tomas Bata University in Zlín and subsequently identified by MALDI-TOF MS. The results of MALDI-TOF MS identification were verified by 16S rRNA sequenation. In this work was studied the ability of 5 bacterial strains positive to biogenic amines degradation isolated from dairy products to decrease biogenic amines content in vitro and quantified reduction in the concentration of biogenic amines tryptamine, β-phenylethylamine, putrescine, cadaverine, histamine and tyramine. The level of degradation (decrease of biogenic amines was determined on the base of the ability to grow in media with biogenic amines as the sole source carbon and nitrogen. The isolated strains with the ability of degradation of one or more biogenic amines were cultured in medium supplemented with relevant biogenic amines, the media derivatized with dansyl chloride and these amines separated by HPLC at a wavelength of 254 nm. From five tested strains identified as Bacillus subtilis, Bacillus pumilus, Enterobacter cloacae, Rhizobium radiobacter and Acinetobacter pitii, isolated from gouda type cheese, the greatest ability of degradation was observed in Bacillus subtilis, which was capable to degrade almost all amount of histamine, cadaverine and putrescine. Other four strains showed a lower rate of degradation than Bacillus subtilis, but the ability to degrade biogenic amines with these microorganisms was still significant.

Metabolism and Biomarkers of Heterocyclic Aromatic Amines in Molecular Epidemiology Studies: Lessons Learned from Aromatic Amines

Science.gov (United States)

2011-01-01

Aromatic amines and heterocyclic aromatic amines (HAAs) are structurally related classes of carcinogens that are formed during the combustion of tobacco or during the high-temperature cooking of meats. Both classes of procarcinogens undergo metabolic activation by N-hydroxylation of the exocyclic amine group, to produce a common proposed intermediate, the arylnitrenium ion, which is the critical metabolite implicated in toxicity and DNA damage. However, the biochemistry and chemical properties of these compounds are distinct and different biomarkers of aromatic amines and HAAs have been developed for human biomonitoring studies. Hemoglobin adducts have been extensively used as biomarkers to monitor occupational and environmental exposures to a number of aromatic amines; however, HAAs do not form hemoglobin adducts at appreciable levels and other biomarkers have been sought. A number of epidemiologic studies that have investigated dietary consumption of well-done meat in relation to various tumor sites reported a positive association between cancer risk and well-done meat consumption, although some studies have shown no associations between well-done meat and cancer risk. A major limiting factor in most epidemiological studies is the uncertainty in quantitative estimates of chronic exposure to HAAs and, thus, the association of HAAs formed in cooked meat and cancer risk has been difficult to establish. There is a critical need to establish long-term biomarkers of HAAs that can be implemented in molecular epidemioIogy studies. In this review article, we highlight and contrast the biochemistry of several prototypical carcinogenic aromatic amines and HAAs to which humans are chronically exposed. The biochemical properties and the impact of polymorphisms of the major xenobiotic-metabolizing enzymes on the biological effects of these chemicals are examined. Lastly, the analytical approaches that have been successfully employed to biomonitor aromatic amines and HAAs, and

Synthesis and characterization of monomeric and dimeric ...

African Journals Online (AJOL)

The two complexes are isostructural, with the central metal atom lying on a crystallographic 2-fold axis. Both complexes are approximately octahedral, the coordination being provided by two trans pyridine nitrogen atoms and two cis amine nitrogen atoms from the oxime ligands, and by two cis chlorides. The dimeric ...

Regional cerebral blood flow distribution in newly diagnosed schizophrenia and schizophreniform disorder

DEFF Research Database (Denmark)

Rubin, P; Holm, S; Madsen, P L

1994-01-01

Regional cerebral blood flow distribution (rCBF) in 24 first admissions with schizophrenia or schizophreniform disorder and in 17 healthy volunteers was examined. Single photon emission computed tomography with a brain-retained tracer, technetium-99m-d,l-hexamethyl-propylene amine oxime, was used...... interrelationship in schizophrenia and schizophreniform disorder....

Amine promoted, metal enhanced degradation of Mirex under high temperature conditions

Energy Technology Data Exchange (ETDEWEB)

Jallad, Karim N. [American University of Sharjah, Department of Chemistry, P.O. Box 26666, Sharjah (United Arab Emirates)]. E-mail: kjallad@runbox.com; Lynn, Bert C. [University of Kentucky, Department of Chemistry, Lexington, KY 40506-055 (United States); Alley, Earl G. [Mississippi State University, Department of Chemistry, MS State, MS 39762 (United States)

2006-07-31

In this study, zero-valent metal dehalogenation of mirex was conducted with amine solvents at high temperatures. Mirex was treated with excess amine in sealed glass tube reactors under nitrogen. The amines used were n-butyl amine (l), ethyl amine (l), dimethyl amine (g), diethyl amine (l), triethyl amine (l), trimethyl amine (g) and ammonia (g). The metals used were copper, zinc, magnesium, aluminum and calcium. The most suitable amine solvent and metal were selected by running a series of reactions with different amines and different zero-valent metals, in order to optimize the conditions under which complete degradation of mirex takes place. These dehalogenation reactions illustrated the role of zero-valent metals as reductants, whereas the amine solvents acted as proton donors. In this study, we report that mirex was completely degraded with diethyl amine (l) in the presence of copper at 100 deg. C and the hydrogenated products accounted for more than 94 of the degraded mirex.

In Vitro Ability of Currently Available Oximes to Reactivate Organophosphate Pesticide-Inhibited Human Acetylcholinesterase and Butyrylcholinesterase

OpenAIRE

Kamil Musilek; Kamil Kuca; Daniel Jun; Lucie Musilova

2011-01-01

We have in vitro tested the ability of common, commercially available, cholinesterase reactivators (pralidoxime, obidoxime, methoxime, trimedoxime and HI-6) to reactivate human acetylcholinesterase (AChE), inhibited by five structurally different organophosphate pesticides and inhibitors (paraoxon, dichlorvos, DFP, leptophos-oxon and methamidophos). We also tested reactivation of human butyrylcholinesterase (BChE) with the aim of finding a potent oxime, suitable to serve as a “pseudocatalytic...

A versatile family of degradable non-viral gene carriers based on hyperbranched poly(ester amine)s

NARCIS (Netherlands)

Zhong, Zhiyuan; Song, Y.; Engbersen, Johannes F.J.; Lok, Martin C.; Hennink, Wim E.; Feijen, Jan

2005-01-01

A variety of degradable hyperbranched poly(ester amine)s containing primary, secondary and tertiary amino groups, were synthesized and evaluated as non-viral gene carriers. The polymers were obtained in high yields through a Michael-type conjugate addition of diacrylate monomers with trifunctional

Cerebral uptake and retention of 99Tcsup(m)-hexamethylpropyleneamine oxime (99Tcsup(m)-HM-PAO)

International Nuclear Information System (INIS)

Holmes, R.A.; Chaplin, S.B.; Royston, K.G.; Missouri Univ., Columbia

1985-01-01

A new radiopharmaceutical, 99 Tcsup(m)-hexamethylpropyleneamine oxime ( 99 Tcsup(m)-HM-PAO) is described. This agent displays considerable promise for imaging cerebral blood flow. In studies in rats and one human volunteer, 99 Tcsup(m)-HM-PAO demonstrates good brain uptake, prolonged retention of activity in the brain, and slow regional redistribution. These properties suggest that this new radiopharmaceutical is ideal for single photon emission tomographic (SPECT) imaging of cerebral blood flow. (author)

Synthesis and bioelectrochemical behavior of aromatic amines.

Science.gov (United States)

Shabbir, Muhammad; Akhter, Zareen; Ahmad, Iqbal; Ahmed, Safeer; Bolte, Michael; McKee, Vickie

2017-12-01

Four aromatic amines 1-amino-4-phenoxybenzene (A 1 ), 4-(4-aminophenyloxy) biphenyl (A 2 ), 1-(4-aminophenoxy) naphthalene (A 3 ) and 2-(4-aminophenoxy) naphthalene (A 4 ) were synthesized and characterized by elemental, spectroscopic (FTIR, NMR), mass spectrometric and single crystal X-ray diffraction methods. The compounds crystallized in monoclinic crystal system with space group P2 1 . Intermolecular hydrogen bonds were observed between the amine group and amine/ether acceptors of neighboring molecules. Electrochemical investigations were done using cyclic voltammetry (CV), square wave voltammetry (SWV) and differential pulse voltammetry (DPV). CV studies showed that oxidation of aromatic amines takes place at about 0.9 V (vs. Ag/AgCl) and the electron transfer (ET) process has irreversible nature. After first scan reactive intermediate were generated electrochemically and some other cathodic and anodic peaks also appeared in the succeeding scans. DPV study revealed that ET process is accompanied by one electron. DNA binding study of aromatic amines was performed by CV and UV-visible spectroscopy. These investigations revealed groove binding mode of interaction of aromatic amines with DNA. Copyright © 2017 Elsevier Inc. All rights reserved.

Can hydroxylamine be a more potent nucleophile for the reactivation of tabun-inhibited AChE than prototype oxime drugs? An answer derived from quantum chemical and steered molecular dynamics studies.

Science.gov (United States)

Lo, Rabindranath; Ganguly, Bishwajit

2014-07-29

Organophosphorus nerve agents are highly toxic compounds which strongly inhibit acetylcholinesterase (AChE) in the blood and in the central nervous system (CNS). Tabun is one of the highly toxic organophosphorus (OP) compounds and is resistant to many oxime drugs formulated for the reactivation of AChE. The reactivation mechanism of tabun-conjugated AChE with various drugs has been examined with density functional theory and ab initio quantum chemical calculations. The presence of a lone-pair located on the amidic group resists the nucleophilic attack at the phosphorus center of the tabun-conjugated AChE. We have shown that the newly designed drug candidate N-(pyridin-2-yl)hydroxylamine, at the MP2/6-31+G*//M05-2X/6-31G* level in the aqueous phase with the polarizable continuum solvation model (PCM), is more effective in reactivating the tabun-conjugated AChE than typical oxime drugs. The rate determining activation barrier with N-(pyridin-2-yl)hydroxylamine was found to be ∼1.7 kcal mol(-1), which is 7.2 kcal mol(-1) lower than the charged oxime trimedoxime (one of the most efficient reactivators in tabun poisonings). The greater nucleophilicity index (ω(-)) and higher CHelpG charge of pyridinylhydroxylamine compared to TMB4 support this observation. Furthermore, we have also examined the reactivation process of tabun-inhibited AChE with some other bis-quaternary oxime drug candidates such as methoxime (MMB4) and obidoxime. The docking analysis suggests that charged bis-quaternary pyridinium oximes have greater binding affinity inside the active-site gorge of AChE compared to the neutral pyridinylhydroxylamine. The peripheral ligand attached to the neutral pyridinylhydroxylamine enhanced the binding with the aromatic residues in the active-site gorge of AChE through effective π-π interactions. Steered molecular dynamics (SMD) simulations have also been performed with the charged oxime (TMB4) and the neutral hydroxylamine. From protein-drug interaction

Amine Swingbed Payload Project Management

Science.gov (United States)

Walsch, Mary; Curley, Su

2013-01-01

The International Space Station (ISS) has been designed as a laboratory for demonstrating technologies in a microgravity environment, benefitting exploration programs by reducing the overall risk of implementing such technologies in new spacecraft. At the beginning of fiscal year 2010, the ISS program manager requested that the amine-based, pressure-swing carbon dioxide and humidity absorption technology (designed by Hamilton Sundstrand, baselined for the Orion Multi-Purpose Crew Vehicle, and tested at the Johnson Space Center in relevant environments, including with humans, since 2005) be developed into a payload for ISS Utilization. In addition to evaluating the amine technology in a flight environment before the first launch of the Orion vehicle, the ISS program wanted to determine the capability of the amine technology to remove carbon dioxide from the ISS cabin environment at the metabolic rate of the full 6 ]person crew. Because the amine technology vents the absorbed carbon dioxide and water vapor to space vacuum (open loop), additional hardware needed to be developed to minimize the amount of air and water resources lost overboard. Additionally, the payload system would be launched on two separate Space Shuttle flights, with the heart of the payload-the swingbed unit itself-launching a full year before the remainder of the payload. This paper discusses the project management and challenges of developing the amine swingbed payload in order to accomplish the technology objectives of both the open -loop Orion application as well as the closed-loop ISS application.

Tandem catalytic allylic amination and [2,3]-Stevens rearrangement of tertiary amines.

Science.gov (United States)

Soheili, Arash; Tambar, Uttam K

2011-08-24

We have developed a catalytic allylic amination involving tertiary aminoesters and allylcarbonates, which is the first example of the use of tertiary amines as intermolecular nucleophiles in metal-catalyzed allylic substitution chemistry. This process is employed in a tandem ammonium ylide generation/[2,3]-rearrangement reaction, which formally represents a palladium-catalyzed Stevens rearrangement. Low catalyst loadings and mild reaction conditions are compatible with an unprecedented substrate scope for the ammonium ylide functionality, and products are generated in high yields and diastereoselectivities. Mechanistic studies suggested the reversible formation of an ammonium intermediate.

{sup 99m}Tc-HMPAO and {sup 99m}Tc-ECD perform differently in typically hypoperfused areas in Alzheimer's disease

Energy Technology Data Exchange (ETDEWEB)

Koulibaly, Pierre Malick [Nuclear Medicine Department, Centre Antoine Lacassagne, University of Nice-Sophia Antipolis (France); Laboratoire de Biophysique, Universite de Nice-Sophia Antipolis, UFR de Medecine, 28 Avenue de Valombrose, 06107, Nice Cedex 2 (France); Nobili, Flavio; Vitali, Paolo; Girtler, Nicola; Rodriguez, Guido [Clinical Neurophysiology, Department of Internal Medicine, University of Genoa (Italy); Migneco, Octave; Darcourt, Jacques [Nuclear Medicine Department, Centre Antoine Lacassagne, University of Nice-Sophia Antipolis (France); Robert, Philippe H. [Memory Center, Federation of Clinical Neuroscience, Centre Hospitalier Universitaire, University of Nice-Sophia Antipolis (France)

2003-07-01

Technetium-99m hexamethylpropylene amine oxime (HMPAO) and {sup 99m}Tc-N,N''-1,2-ethylene diylbis-l-cysteine diethyl ester dihydrochloride (ECD) yield significantly different images of cerebral perfusion owing to their particular pharmacokinetics. The aim of this study was to assess the topography, extension and statistical significance of these differences in Alzheimer's disease (AD). Sixty-four patients with mild to moderate AD were retrospectively selected by two European centres. Two series of patients, including 32 studied with {sup 99m}Tc-HMPAO single-photon emission tomography (SPET) and 32 studied with {sup 99m}Tc-ECD SPET, were matched for sex, age ({+-}3 years) and severity of cognitive impairment as assessed by the Mini-Mental State Examination (MMSE) ({+-}2 points), following a case-control procedure. SPET data were processed using SPM99 software (uncorrected height threshold: P=0.001). {sup 99m}Tc-ECD SPET gave significantly higher uptake ratio values than {sup 99m}Tc-HMPAO SPET in several symmetrical clusters, including the right and left occipital cuneus, the left occipital and parietal precuneus, and the left superior and middle temporal gyri. {sup 99m}Tc-HMPAO SPET gave significantly higher uptake ratio values than ECD in two smaller clusters, including the hippocampus in both hemispheres. In AD, relative brain uptake of {sup 99m}Tc-HMPAO and {sup 99m}Tc-ECD is different in several brain regions, some of which are typically involved in AD, such as the precuneus and the hippocampus. These differences confirm the need for specific normal databases, but their impact on routine SPET reports in AD is not known and deserves an ad hoc investigation. (orig.)

Heterogeneity of cerebral blood flow in frontotemporal lobar degeneration and Alzheimer's disease

International Nuclear Information System (INIS)

Nagao, Michinobu; Sugawara, Yoshifumi; Mochizuki, Teruhito; Miki, Hitoshi; Kikuchi, Takanori; Ikeda, Manabu; Fukuhara, Ryuji; Hokoishi, Kazuhiko; Murase, Kenya

2004-01-01

This study was designed to quantify the heterogeneity on cerebral blood flow single-photon emission tomography (SPET) images in frontotemporal lobar degeneration (FTLD) and Alzheimer's disease (AD) using a three-dimensional fractal analysis. Twenty-one FTLD patients, 21 AD patients and 11 healthy controls underwent technetium-99m hexamethylpropylene amine oxime SPET scanning. Patients with FTLD and AD matched for sex, age and the severity of dementia as estimated with the Clinical Dementia Rating and were determined to be in the early stage of illness. We delineated the SPET images using a 35% cut-off and a 50% cut-off of the maximal voxel radioactivity and measured the number of voxels included in the contours of two different cut-offs. The fractal dimension (FD) was calculated by relating the logarithms of the cut-offs and the numbers of voxels, and it was defined as the heterogeneity of the cerebral perfusion. We divided the SPET images into two sets, anterior and posterior, with equal numbers of coronal SPET slices. We calculated total FD, anterior FD and posterior FD for total, anterior and posterior SPET images. Anterior FDs for FTLD and AD were 1.55±0.34 and 1.24±0.19 (P=0.0002). The ratios of anterior to posterior FD for FTLD and AD were 1.81±0.41 and 1.32±0.14 (P<0.0001). Use of the anterior FD and the ratio of anterior to posterior FD separated FTLD patients from AD patients and controls with a sensitivity of 85.7% and a specificity of 93.8%. Anterior FD and the ratio of anterior to posterior FD may be useful in distinguishing FTLD from AD. (orig.)

Brain single-photon emission tomography with 99mTc-HMPAO in neuropsychiatric systemic lupus erythematosus: relations with EEG and MRI findings and clinical manifestations

International Nuclear Information System (INIS)

Colamussi, P.; Giganti, M.; Cittanti, C.; Dovigo, L.; Trotta, F.; Tola, M.R.; Tamarozzi, R.; Lucignani, G.; Piffanelli, A.

1995-01-01

In the reported study the role of single-photon emission tomography (SPET) with technetium-99m hexamethylpropylene amine oxime (HMPAO) in the evaluation of CNS involvement in SLE was assessed and the relations between SPET perfusion defects, EEG examination, magnetic resonance imaging (MRI) findings and clinical presentation were examined. Twenty SLE patients with different NP manifestations were studied. Multiple areas of hypoperfusion, especially in the territory of the middle cerebral artery, were demonstrated by SPET analysis in all 20 patients. The number of hypoperfused areas and the degree of hypoperfusion, expressed by an asymmetry index (AI), were more marked in patients with multiple NP manifestations. MRI and EEG evaluations were positive for 14 of 18 and for 12 of 20 patients, respectively. In the patients with positive SPET and MRI, 87 MRI focal lesions and 63 hypoperfused areas were found, and for 51 of these 63 at least one MRI lesion was found in the same anatomical region. SPET examination of patients with a normal EEG showed fewer hypoperfused areas and a lower degree of asymmetry compared to patients with an abnormal EEG. SPET of patients with focal EEG abnormalities showed more hypoperfused areas (difference not statistically significant) and a higher AI than did SPET of the patients with diffuse EEG abnormalities. Seven of 11 anatomical regions with focal EEG abnormalities. Seven of 11 anatomical regions with focal EEG abnormalities had co-localized hypoperfused areas and in two of these seven no detectable MRI lesions were found. The analysis of SPET and NP manifestations showed that 12 of 20 patients had at least one positive correlation, always involving the areas with the highest AI. In total, 51/88 (58%) hypoperfused areas correlated with the MRI findings and 31/88 (35%) with NP manifestations; for seven of the latter no concurrent MRI lesions were detected in the same anatomical region. (orig.)

A comparison of 99mTc-HMPAO SPET changes in dementia with Lewy bodies and Alzheimer's disease using statistical parametric mapping

International Nuclear Information System (INIS)

Colloby, Sean J.; Paling, Sean M.; Lobotesis, Kyriakos; Ballard, Clive; McKeith, Ian; O'Brien, John T.; Fenwick, John D.; Williams, David E.

2002-01-01

Differences in regional cerebral blood flow (rCBF) between subjects with Alzheimer's disease (AD), dementia with Lewy bodies (DLB) and healthy volunteers were investigated using statistical parametric mapping (SPM99). Forty-eight AD, 23 DLB and 20 age-matched control subjects participated. Technetium-99m hexamethylpropylene amine oxime (HMPAO) brain single-photon emission tomography (SPET) scans were acquired for each subject using a single-headed rotating gamma camera (IGE CamStar XR/T). The SPET images were spatially normalised and group comparison was performed by SPM99. In addition, covariate analysis was undertaken on the standardised images taking the Mini Mental State Examination (MMSE) scores as a variable. Applying a height threshold of P≤0.001 uncorrected, significant perfusion deficits in the parietal and frontal regions of the brain were observed in both AD and DLB groups compared with the control subjects. In addition, significant temporoparietal perfusion deficits were identified in the AD subjects, whereas the DLB patients had deficits in the occipital region. Comparison of dementia groups (height threshold of P≤0.01 uncorrected) yielded hypoperfusion in both the parietal [Brodmann area (BA) 7] and occipital (BA 17, 18) regions of the brain in DLB compared with AD. Abnormalities in these areas, which included visual cortex and several areas involved in higher visual processing and visuospatial function, may be important in understanding the visual hallucinations and visuospatial deficits which are characteristic of DLB. Covariate analysis indicated group differences between AD and DLB in terms of a positive correlation between cognitive test score and temporoparietal blood flow. In conclusion, we found evidence of frontal and parietal hypoperfusion in both AD and DLB, while temporal perfusion deficits were observed exclusively in AD and parieto-occipital deficits in DLB. (orig.)

Clinical significance of abdominal scintigraphy using {sup 99m}Tc-HMPAO-labelled leucocytes in patients with seronegative spondyloarthropathies

Energy Technology Data Exchange (ETDEWEB)

Alonso Farto, J.C.; Almoguera Arias, I.; Ortega Valle, A.; Perez Vazquez, J.M. [Department of Nuclear Medicine, Univ. Complutense, Madrid (Spain); Lopez Longo, F.J.; Gonzalez Fernandez, C.M.; Monteagudo Saez, I.; Bascones, M.; Carreno Perez, L. [Department of Rheumatology, ' ' Hospital Universitario Gregorio Maranon' ' , Universidad Complutense, Madrid (Spain)

2000-12-01

Abdominal scintigraphy shows silent gut inflammation in patients with spondyloarthropathies (Sp) without clinical evidence of gut inflammation. Abdominal scintigraphy images are different than those obtained in patients with ulcerative colitis or Crohn's disease and are not related to the anti-inflammatory drugs administered. The aim of this study was to examine the clinical associations of findings on abdominal scintigraphy in patients with Sp. A total of 204 Sp patients (European Spondylarthropathy Study Group 1991 criteria) and 54 non-Sp controls receiving non-steroidal anti-inflammatory drugs were studied. Abdominal scintigraphy images were obtained at 30 and 120 min after injection of technetium-99m hexamethylpropylene amine oxime ({sup 99m}Tc-HMPAO)-labelled leucocytes. {sup 99m}Tc-HMPAO-labelled leucocyte scans were positive in 104 Sp patients (50.9%) and in six non-Sp controls (2.9%) (P<0.001; OR=8.32; 95% CI=3.23-22.67). Silent gut inflammation was not associated with any of the following: age of onset, duration of evolution, sex, family history of Sp or psoriasis, articular manifestations, extra-articular manifestations, radiological findings or HLA-B27 positivity. Positive abdominal scintigraphy was associated with active disease (P<0.0001; OR=52.7; 95% CI=19-145.6) and an increase in the C-reactive protein (P<0.005; OR=3.4; 95% CI=1.5-7.4). It is concluded that (a) abdominal scintigraphy using {sup 99m}Tc-HMPAO-labelled leucocytes is of value in detecting the silent gut inflammation in Sp patients, and (b) silent gut inflammation is related to the clinical activity, but is not associated with any particular type of illness or with HLA-B27. (orig.)

Brain single-photon emission tomography with {sup 99m}Tc-HMPAO in neuropsychiatric systemic lupus erythematosus: relations with EEG and MRI findings and clinical manifestations

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Colamussi, P. [Dept. of Nuclear Medicine, Univ. of Ferrara (Italy); Giganti, M. [Dept. of Nuclear Medicine, Univ. of Ferrara (Italy); Cittanti, C. [Dept. of Nuclear Medicine, Univ. of Ferrara (Italy); Dovigo, L. [Inst. of Neurology, Univ. of Ferrara (Italy); Trotta, F. [Inst. of Neurology, Univ. of Ferrara (Italy); Tola, M.R. [Div. of Rheumatology, S. Anna Hospital, Ferrara (Italy); Tamarozzi, R. [Radiology Dept., S. Anna Hospital, Ferrara (Italy); Lucignani, G. [INB-CNR Dept. of Nuclear Medicine, H.S. Raffaele, Milan (Italy); Piffanelli, A. [Dept. of Nuclear Medicine, Univ. of Ferrara (Italy)

1995-01-01

In the reported study the role of single-photon emission tomography (SPET) with technetium-99m hexamethylpropylene amine oxime (HMPAO) in the evaluation of CNS involvement in SLE was assessed and the relations between SPET perfusion defects, EEG examination, magnetic resonance imaging (MRI) findings and clinical presentation were examined. Twenty SLE patients with different NP manifestations were studied. Multiple areas of hypoperfusion, especially in the territory of the middle cerebral artery, were demonstrated by SPET analysis in all 20 patients. The number of hypoperfused areas and the degree of hypoperfusion, expressed by an asymmetry index (AI), were more marked in patients with multiple NP manifestations. MRI and EEG evaluations were positive for 14 of 18 and for 12 of 20 patients, respectively. In the patients with positive SPET and MRI, 87 MRI focal lesions and 63 hypoperfused areas were found, and for 51 of these 63 at least one MRI lesion was found in the same anatomical region. SPET examination of patients with a normal EEG showed fewer hypoperfused areas and a lower degree of asymmetry compared to patients with an abnormal EEG. SPET of patients with focal EEG abnormalities showed more hypoperfused areas (difference not statistically significant) and a higher AI than did SPET of the patients with diffuse EEG abnormalities. Seven of 11 anatomical regions with focal EEG abnormalities. Seven of 11 anatomical regions with focal EEG abnormalities had co-localized hypoperfused areas and in two of these seven no detectable MRI lesions were found. The analysis of SPET and NP manifestations showed that 12 of 20 patients had at least one positive correlation, always involving the areas with the highest AI. In total, 51/88 (58%) hypoperfused areas correlated with the MRI findings and 31/88 (35%) with NP manifestations; for seven of the latter no concurrent MRI lesions were detected in the same anatomical region. (orig.)

99mTc-HMPAO SPECT in pediatric patients with neurological disorders

International Nuclear Information System (INIS)

Yamaoka, Mitsuko

1994-01-01

In 125 pediatric patients with suspected brain diseases, EEG, CT and MRI findings were compared with those obtained with single photon emission computed tomography (SPECT) of the brain using Tc-99m-d, 1-hexamethyl-propylene amine oxime ( 99m Tc-HMPAO), to determine the usefulness of SPECT as an adjunct to EEG, CT and MRI in this age group. The incidences of abnormal finding in the 125 patients were 53.6, 75.2, 60.6 and 51.4% using 99m Tc-HMPAO SPECT, EEG, CT and MRI respectively. In localization-related epilepsy and cerebrovascular diseases, the incidence of abnormality was higher with 99m Tc-HMPAO SPECT than with either CT or MRI. There was a tendency for mean age to be higher and mean IQ or DG lower in patients with more extensive abnormality in comparison to those who had normal or only focally abnormal SPECT findings. Nevertheless, some patients showed focal hypofusion in the frontal or occipital area without significant mental retardation. Epileptic foci detected by EEG corresponded to defects found using 99m Tc-HMPAO SPECT in 34.8% of the symptomatic localization-related epileptic patients. Pathological lesions detected by CT or MRI corresponded with SPECT findings in 48.1% of patients. Furthermore, the incidence of abnormal findings on SPECT was 30% in patients in whom CT or MRI was normal. Epileptic foci detected by EEG did not correspond well with the area of focal hyperfusion found on SPECT. Focal hyperfusion may sometimes occur even in the interictal period or postictal period in childhood seizure disorders. In conclusion, 99m Tc-HMPAO SPECT revealed abnormal findings at a moderate incidence in neuropediatric patients. Correlations with EEG, CT and MRI findings as well as assessment of clinical signs, including the investigation of epileptic foci, are essential for adequate interpretation of brain functions. (author)

Vascular dementia of Binswanger's type: clinical, neuroradiological and 99mTc-HMPAO SPET study

International Nuclear Information System (INIS)

Shyu Woeicherng; Lin Jiannchyun; Shen Chihchieh; Hsu Yawdon; Lee Chauchin; Shiah Ishin; Tsao Wenlong

1996-01-01

In 24 patients with vascular dementia of Binswanger's type (VDBT) and 14 age-matched neurologically normal volunteers, we investigated the relationship between clinical features, white matter lesions (leucoaraiosis) and cerebral atrophy on computed tomographic (CT) scan, and regional cerebral blood flow. All subjects underwent the Mini-Mental State Examination of Taiwan, version 1 (MMSE-T1), for assessing the severity of cognitive impairment. The patients were subdivided into two groups, one with mild to moderate (group I, MMSE-T1 scores: 11-24, n=11), and the other with severe dementia (group II, MMSE-T1 scores: below 10, n=13). White matter degeneration was evaluated with densitometric methods. Loss of brain parenchyma was estimated with seven linear measurements (Evan's ratio, third ventricle ratio, width of temporal horn tip, anterior-posterior length of temporal horn, anterior-posterior length of Sylvian fissure and width of frontal interhemispheric fissure) by CT scans. Regional cerebral blood flow was determined with technetium-99m hexamethylpropylene amine oxime (HMPAO) single-photon emission tomography (SPET). In neuroimaging studies, subcortical leuco-araiosis was localized at the frontal region in group I patients and scattered diffusely in group II patients. 99m Tc-HMPAO SPET analysis revealed reduction of regional cerebral blood flow in the frontal lobe in group I patients and widespread reduction of regional cerebral blood flow in group II patients. A correlation between frontal leuco-araiosis and perfusion defect of the frontal pole was demonstrated in group I patients, showing findings typical of subcortical dementia. There was no difference in frontal athrophic measurements between group I patients and controls. Ratios of volumes of lost brain parenchyma and leuco-araiosis were significantly higher in group II patients than in the age-matched controls, corresponding to a diffuse cerebral perfusion defect. (orig./MG)

Regional cerebral blood flow pattern in normal young and aged volunteers: a 99mTc-HMPAO SPET study

International Nuclear Information System (INIS)

Catafau, A.M.; Lomena, J.; Pavia, J.; Parellada, E.; Bernardo, M.; Setoain, J.; Tolosa, E.

1996-01-01

The aim of this study was to investigate the normal pattern of regional cerebral blood flow (rCBF) distribution in normal young and aged volunteers using technetium-99m hexamethylpropylene amine oxime ( 99m -Tc-HMPAO) as a tracer. The region brain perfusion of young and aged subjects was compared, especially regarding rCBF differences due to age and gender, and interhemispheric rCBF asymmetries. Sixty-eight right-handed normal volunteers -40 young (mean age 29.5±6.3 years) and 28 aged (mean age 71.2±4.3 years) - were included in the study. rCBF was estimated on the basis of a semiquantitative approach by means of a left-right index and two region/reference ratios, using the cerebellum and the whole brain activity as references. A good correlation between these two region/reference ratios was found (P<0.005 in all cerebral regions). The highest rCBF ratios corresponded to the cerebellum, followed by the occipital lobe. The remaining cortical regions (temporal, parietal, frontal and basal ganglia) showed slightly lower values. The white matter showed rCBF ratios substantially lower than the grey matter. In neighter young nor aged subjects were significant rCBF differences between the genders found in any of the two region/reference indices employed. Aged sugjects showed significantly lower rCBF ratios than young subjects in the left frontal lobe and in the posterior region of the left temporal lobe. In both young and aged subjects, lower perfusion was found in the left hemisphere, except for the white matter region in both age groups and the frontal lobe in the young subjects. Aged subjects presented a slightly higher interhemispheric asymmetry in the frontal lobe. However, interhemispheric asymmetry was minimal (-1.01% to 3.14%). Consequently, a symmetrical rCBF distribution can be assumed between homologous regions, independent of age. (orig.)

Memory-provoked rCBF-SPECT as a diagnostic tool in Alzheimer's disease?

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Sundstroem, Torbjoern; Riklund, Katrine Aa. [Umeaa University, Umeaa University Hospital, Department of Radiation Sciences, Diagnostic Radiology, Umeaa (Sweden); Elgh, Eva; Naesman, Birgitta [Umeaa University, Department of Community Medicine and Rehabilitation, Geriatric Medicine, Umeaa (Sweden); Larsson, Anne [Umeaa University, Department of Radiation Sciences, Radiation Physics, Umeaa (Sweden); Nyberg, Lars [Umeaa University, Department of Psychology, Umeaa (Sweden)

2006-01-01

Alzheimer's disease (AD) is a primary degenerative disease that progressively affects all brain functions, with devastating consequences for the patient, the patient's family and society. Rest regional cerebral blood flow (rCBF) could have a strategic role in differentiating between AD patients and normal controls, but its use for this purpose has a low discriminatory capacity. The purpose of this study was to evaluate whether the diagnostic sensitivity of rCBF single-photon emission computed tomography (SPECT) could be increased by using an episodic memory task provocation, i.e. memory-provoked rCBF-SPECT (MP-SPECT). Eighteen persons (73.2{+-}4.8 years) with mild AD and 18 healthy elderly (69.4{+-}3.9 years) were included in the study. The subjects were injected with{sup 99m}Tc-hexamethylpropylene amine oxime (HMPAO) during memory provocation with faces and names, followed by an rCBF-SPECT study. The rCBF{sup 99m}Tc-HMPAO SPECT images were analysed using statistical parametric mapping (SPM2). Peaks with a false discovery rate corrected value of 0.05 were considered significant. On MP-SPECT, the AD group showed a significant rCBF reduction in the left parietal cortex in comparison with healthy elderly. At rest, no significant group differences were seen. Memory provocation increased the sensitivity of rCBF-SPECT for the detection of AD-related blood flow changes in the brain at the group level. Further studies are needed to evaluate MP-SPECT as a diagnostic tool at the individual level. If a higher sensitivity for AD at the individual level is verified in future studies, a single MP-SPECT study might be sufficient in the clinical setting. (orig.)

A comparison of {sup 99m}Tc-HMPAO SPET changes in dementia with Lewy bodies and Alzheimer's disease using statistical parametric mapping

Energy Technology Data Exchange (ETDEWEB)

Colloby, Sean J.; Paling, Sean M.; Lobotesis, Kyriakos; Ballard, Clive; McKeith, Ian; O' Brien, John T. [Wolfson Research Centre, Institute for Ageing and Health, Newcastle upon Tyne (United Kingdom); Fenwick, John D. [Regional Medical Physics Department, Newcastle General Hospital, Newcastle upon Tyne (United Kingdom); Williams, David E. [Regional Medical Physics Department, Sunderland Royal Hospital (United Kingdom)

2002-05-01

Differences in regional cerebral blood flow (rCBF) between subjects with Alzheimer's disease (AD), dementia with Lewy bodies (DLB) and healthy volunteers were investigated using statistical parametric mapping (SPM99). Forty-eight AD, 23 DLB and 20 age-matched control subjects participated. Technetium-99m hexamethylpropylene amine oxime (HMPAO) brain single-photon emission tomography (SPET) scans were acquired for each subject using a single-headed rotating gamma camera (IGE CamStar XR/T). The SPET images were spatially normalised and group comparison was performed by SPM99. In addition, covariate analysis was undertaken on the standardised images taking the Mini Mental State Examination (MMSE) scores as a variable. Applying a height threshold of P{<=}0.001 uncorrected, significant perfusion deficits in the parietal and frontal regions of the brain were observed in both AD and DLB groups compared with the control subjects. In addition, significant temporoparietal perfusion deficits were identified in the AD subjects, whereas the DLB patients had deficits in the occipital region. Comparison of dementia groups (height threshold of P{<=}0.01 uncorrected) yielded hypoperfusion in both the parietal [Brodmann area (BA) 7] and occipital (BA 17, 18) regions of the brain in DLB compared with AD. Abnormalities in these areas, which included visual cortex and several areas involved in higher visual processing and visuospatial function, may be important in understanding the visual hallucinations and visuospatial deficits which are characteristic of DLB. Covariate analysis indicated group differences between AD and DLB in terms of a positive correlation between cognitive test score and temporoparietal blood flow. In conclusion, we found evidence of frontal and parietal hypoperfusion in both AD and DLB, while temporal perfusion deficits were observed exclusively in AD and parieto-occipital deficits in DLB. (orig.)

Regional differences between 99mTc-ECD and 99mTc-HMPAO SPET in perfusion changes with age and gender in healthy adults

International Nuclear Information System (INIS)

Inoue, Kentaro; Nakagawa, Manabu; Goto, Ryoi; Kinomura, Shigeo; Sato, Tachio; Sato, Kazunori; Fukuda, Hiroshi

2003-01-01

A number of studies using single-photon emission tomography (SPET) have shown perfusion changes with age in several cortical and subcortical areas, which might distort the results of perfusion imaging studies of neuropsychiatric disorders. Technetium-99m labelled ethyl cysteinate dimer (ECD) and hexamethylpropylene amine oxime (HMPAO) are both used as markers of cerebral perfusion, but have different pharmacokinetics and retention patterns. The aim of this study was to determine whether age and gender effects on perfusion SPET differ depending on whether 99m Tc-HMPAO or 99m Tc-ECD is used. Forty-five subjects (20 male and 25 female, mean age 52.8±6.6 years) were assigned to 99m Tc-HMPAO SPET (HMPAO group), and 39 subjects (24 male and 15 female, mean age 52.6±6.7 years) to 99m Tc-ECD SPET (ECD group). SPET images were obtained about 10 min after intravenous injection of approximately 800 MBq 99m Tc-HMPAO or 99m Tc-ECD using the same SPET scanner. Three-dimensional volumetric magnetic resonance imaging was performed to as7sess morphological changes in the grey matter. All image processing and statistical analyses were performed using SPM99 software. An area in the right anterior frontal lobe showed an increase in perfusion with age only in the HMPAO group, whereas areas in the bilateral retrosplenial cortex showed decreases in perfusion with age only in the ECD group; neither group showed corresponding changes in the grey matter. The present study shows that different effects of age on perfusion are observed depending on whether 99m Tc-HMPAO and 99m Tc-ECD is used. This suggests that the results of perfusion SPET are differently confounded depending on the tracer used, and that perfusion SPET with these tracers has limitations when used in research on subtle perfusion changes. (orig.)

Clinical usefulness of scatter and attenuation correction for brain single photon emission computed tomography (SPECT) in pediatrics

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Adachi, Itaru; Doi, Kenji; Komori, Tsuyoshi; Hou, Nobuyoshi; Tabuchi, Koujirou; Matsui, Ritsuo; Sueyoshi, Kouzou; Utsunomiya, Keita; Narabayashi, Isamu [Osaka Medical Coll., Takatsuki (Japan)

1998-01-01

This investigation was undertaken to study clinical usefulness of scatter and attenuation correction (SAC) of brain SPECT in infants to compare the standard reconstruction (STD). The brain SPECT was performed in 31 patients with 19 epilepsy, 5 cerebro-vascular disease, 2 brain tumor, 3 meningitis, 1 hydrocephalus and psychosis (mean age 5.0{+-}4.9 years old). Many patients was necessary to be injected sedatives for restraining body motion after Technetium-99m hexamethylpropylene amine oxime ({sup 99m}Tc-HMPAO) was injected at the convulsion or rest. Brain SPECT data were acquired with triple detector gamma camera (GCA-9300 Toshiba Japan). These data were reconstructed by filtered backprojection after the raw data were corrected by triple energy windows method of scatter correction and Chang filtered method of attenuation correction. The same data was reconstructed by filtered backprojection without these corrections. Both SAC and STD SPECT images were analyzed by the visual interpretation. The uptake ratio of cerebral basal nuclei was calculated by the counts of the thalamus or lenticular nuclei divided by the cortex. All images of SAC method were excellent than that of STD method. The thalamic uptake ratio in SAC method was higher than that of STD method (1.22{+-}0.09>0.87{+-}0.22 p<0.01). The lenticular nuclear uptake ratio in SAC method was higher than that of STD method (1.26{+-}0.15>1.02{+-}0.16 p<0.01). Transmission scan is the most suitable method of absorption correction. But the transmission scan is not adequate for examination of children, because this scan needs a lot of time and the infants are exposed by the line source radioisotope. It was concluded that these scatter and absorption corrections were most suitable method for brain SPECT in pediatrics. (author)

Clinical validation of the avidin/indium-111 biotin approach for imaging infection/inflammation in orthopaedic patients

Energy Technology Data Exchange (ETDEWEB)

Lazzeri, E.; Molea, N.; Bodei, L.; Bianchi, R. [Regional Centre of Nuclear Medicine, University of Pisa, Pisa (Italy); Manca, M.; Marchetti, S.; Consoli, V. [Institute of Orthopedics, University of Pisa, Pisa (Italy); Chinol, M.; Paganelli, G. [Nuclear Medicine Service, European Institute of Oncology, Milan (Italy); Mariani, G. [Nuclear Medicine Service, DIMI, University of Genoa, Genoa (Italy)

1999-06-01

We report here the results of a validation study of the avidin/indium-111 biotin approach in patients with skeletal lesions. This study involved 54 patients with orthopaedic conditions: 20 patients with intermediate suspected osteomyelitis of the trunk, 19 patients with infection/inflammation of prosthetic joint replacements, and 15 patients with suspected osteomyelitis of appendicular bones. Avidin (3 mg) was injected as an i.v. bolus, followed 4 h later by {sup 111}In-biotin; imaging was acquired 30 min and 16-18 h after administration of {sup 111}In-biotin. Technetium-99m hexamethylpropylene amine oxime ({sup 99m}Tc-HMPAO)-labelled leucocyte scintigraphy was performed in 39/54 patients. The overall sensitivity of the avidin/{sup 111}In-biotin scan was 97.7% (versus 88.9% for {sup 99m}Tc-HMPAO leucocyte scintigraphy). While the diagnostic performance of avidin/{sup 111}In-biotin scintigraphy was similar to that of {sup 99m}Tc-HMPAO leucocyte scintigraphy in patients with prosthetic joint replacements or osteomyelitis of appendicular bones, the avidin/{sup 111}In-biotin approach clearly performed better than {sup 99m}Tc-HMPAO leucocyte scintigraphy in patients with suspected osteomyelitis of the trunk (100% sensitivity, specificity and accuracy versus 50% sensitivity, 100% specificity and 66.7% accuracy for {sup 99m}Tc-HMPAO-leucocyte scintigraphy). These results demonstrate the feasibility of the avidin/{sup 111}In-biotin approach for imaging sites of infection/inflammation in the clinical setting. Although no systematic advantages of avidin/{sup 111}In-biotin scintigraphy were found versus {sup 99m}Tc-HMPAO leucocyte scintigraphy, the newer scintigraphic method is more practicable and involves lower biological risk for the operators. (orig.) With 3 figs., 2 tabs., 56 refs.

Measurement of temporal regional cerebral perfusion with single-photon emission tomography predicts rate of decline in language function and survival in early Alzheimer`s disease

Energy Technology Data Exchange (ETDEWEB)

Claus, J.J.; Walstra, G.J.M.; Hijdra, A.; Gool, W.A. van [Department of Neurology, Academic Medical Center, University of Amsterdam, Amsterdam (Netherlands); Royen, E.A. van [Department of Nuclear Medicine, Academic Medical Center, University of Amsterdam (Netherlands); Verbeeten, B. Jr. [Department of Radiology, Academic Medical Center, University of Amsterdam (Netherlands)

1999-03-01

We determined the relationship between regional cerebral blood flow (rCBF) measured with single-photon emission tomography (SPET) and decline in cognitive function and survival in Alzheimer`s disease. In a prospective follow-up study, 69 consecutively referred patients with early probable Alzheimer`s disease (NINCDS/ADRDA criteria) underwent SPET performed at the time of initial diagnosis using technetium-99m-labelled hexamethylpropylene amine oxime. Neuropsychological function was assessed at baseline and after 6 months and survival data were available on all patients, extending to 5.5 years of follow-up. Lower left temporal (P<0.01) and lower left parietal (P<0.01) rCBF were statistically significantly related to decline in language function after 6 months. The association between left temporal rCBF and survival was also statistically significant (P<0.05) using Cox proportional hazards regression analysis. Performing analysis with quartiles of the distribution, we found a threshold effect for low left temporal rCBF (rCBF<73.7%, P<0.01) and high risk of mortality. In this lowest quartile, median survival time was 2.7 years (follow-up to 5.2 years), compared with 4.4 years in the other quartiles (follow-up to 5.5 years). Kaplan-Meier survival curves showed statistically significant (P<0.05, log rank test) survival curves for the lowest versus other quartiles of left temporal rCBF. All results were unaffected by adjustment for age, sex, dementia severity, duration of symptoms, education and ratings of local cortical atrophy. We conclude that left temporal rCBF predicts decline in language function and survival in patients with early probable Alzheimer`s disease, with a threshold effect of low rCBF and high risk of mortality. (orig.) With 3 figs., 3 tabs., 44 refs.

Abdominal scintigraphy using 99mTc-HMPAO-labelled leucocytes in patients with seronegative spondylarthropathies without clinical evidence of inflammatory bowel disease

International Nuclear Information System (INIS)

Alonso, J.C.; Lopez-Longo, F.J.; Lampreave, J.L.; Gonzalez, C.M.; Vegazo, O.; Carreno, L.; Almoguera, I.

1996-01-01

Abdominal scintigraphy with technetium-99m hexamethylpropylene amine oxime ( 99m Tc-HMPAO)-labelled leucocytes is an excellent tool for evaluating disease extent and activity of intestinal lesions in patients with inflammatory bowel disease (IBD). In some cases of seronegative spondylarthropathies (SSp), IBD may remain subclinical. The aim of this study was to evaluate the presence of positive abdominal scintigraphy in patients with SSp and without clinical symptoms or signs of IBD. To this end we studied 32 patients with active SSp (European Spondylarthropathy Study Group 1991 criteria) without clinical evidence of IBD (eight had ankylosing spondylitis, four psoriatic arthritis, three reactive arthritis an 17 undifferentiated SSp) and 11 controls without SSp. All SSp and control patients received similar doses of non-steroidal anti-inflammatory drugs (NSAIDs). Abdominal scintigraphic images were obtained at 30 and 120 min after re-injection of 99m Tc-HMPAO-labelled leucocytes. The 99m Tc-HMPAO-labelled leucocyte scan was positive in 17 patients with SSp (53.1%) (six with ankylosing spondylitis, three with psoriatic arthritis, two with reactive arthritis and six with undifferentiated SSp). Fourteen patients scored from 2 to 4 on the intensity of uptake scale. The colon and terminal ileum were predominantly involved. Axial involvement was more frequent in patients with a positive scan than in patients with negative results (P 99m Tc-HMPAO-labelled leucocyte scan shows increased uptake among patients with SSp without evidence of IBD. These findings provide new evidence linking SSp with intestinal inflammation and suggest that in some cases a bowel-related process could contribute to the development of SSp. Long-term follow-up studies with more patients are necessary to evaluate the diagnostic and therapeutic implications of these results. (orig.). With 3 figs., 3 tabs

Measurement of temporal regional cerebral perfusion with single-photon emission tomography predicts rate of decline in language function and survival in early Alzheimer's disease

International Nuclear Information System (INIS)

Claus, J.J.; Walstra, G.J.M.; Hijdra, A.; Gool, W.A. van; Royen, E.A. van; Verbeeten, B. Jr.

1999-01-01

We determined the relationship between regional cerebral blood flow (rCBF) measured with single-photon emission tomography (SPET) and decline in cognitive function and survival in Alzheimer's disease. In a prospective follow-up study, 69 consecutively referred patients with early probable Alzheimer's disease (NINCDS/ADRDA criteria) underwent SPET performed at the time of initial diagnosis using technetium-99m-labelled hexamethylpropylene amine oxime. Neuropsychological function was assessed at baseline and after 6 months and survival data were available on all patients, extending to 5.5 years of follow-up. Lower left temporal (P<0.01) and lower left parietal (P<0.01) rCBF were statistically significantly related to decline in language function after 6 months. The association between left temporal rCBF and survival was also statistically significant (P<0.05) using Cox proportional hazards regression analysis. Performing analysis with quartiles of the distribution, we found a threshold effect for low left temporal rCBF (rCBF<73.7%, P<0.01) and high risk of mortality. In this lowest quartile, median survival time was 2.7 years (follow-up to 5.2 years), compared with 4.4 years in the other quartiles (follow-up to 5.5 years). Kaplan-Meier survival curves showed statistically significant (P<0.05, log rank test) survival curves for the lowest versus other quartiles of left temporal rCBF. All results were unaffected by adjustment for age, sex, dementia severity, duration of symptoms, education and ratings of local cortical atrophy. We conclude that left temporal rCBF predicts decline in language function and survival in patients with early probable Alzheimer's disease, with a threshold effect of low rCBF and high risk of mortality. (orig.)

Extraction of sulphates by long chain amines

International Nuclear Information System (INIS)

Boirie, Ch.

1959-05-01

The extraction of sulphuric acid by long chain amines in organic solution has been studied with a view to determining the value of the stability constants of the amine sulphates and bi-sulphates formed. We have concentrated chiefly on uranium sulphate and thorium sulphate. The formulae of the complexes extractable with amines have been established, as well as the corresponding dissociation constants. We have observed that for uranium sulphate the formula of the complex depends only on the nature of the amine, whereas for thorium this formula varies with the amine structure. From the formulae determined and the value of the constants calculated, we have been able to establish the best conditions for uranium and thorium extraction and also for a separation of these two elements. Finally we propose an application of this study to the determination of uranium in ores, where the separation of uranium by this method is particularly easy and complete. (author) [fr

Development of lyophilized kit of Tin-Glucoheptonate for in vitro labeling of leucocytes with 99mTc

International Nuclear Information System (INIS)

Nascimento, Rosemeire Fagundes

2007-01-01

The study and localization of inflammatory and infection process in Nuclear Medicine represents a relevant tool in diagnostic procedures. In same cases, the diagnostic is easy and based on anamnesis and clinical observation; in other cases, the patients are asymptomatic or present non specific symptoms that difficult the diagnostic. The early diagnostic of inflammatory or infectious process allow the early introduction of therapy and prevents complications. Farther, the differentiation between inflammation and infection is of extreme importance as well as the localization of the focus. The use of labeled leucocytes, studied and applied in much pathologies, is the method of choice for the visualization of inflammation and infection. The scintigraphy using labeled leucocytes was introduced at 1976 by McAffe and Thakur and since of this is used in the diagnostic of different pathologies related to leucocyte infiltration like intestinal inflammatory disease, bone or prosthetic-vascular infections. The in vitro labeling of leucocytes with 111 In was performed using oxime or tropolone as ligand and with 99m Tc using hexamethylpropylene amine oxime (HMPAO) as ligand, resulting in a lipophilic complex. The 99m Tc-HMPAG complex was preferably employed in many indications and countries do to the ideal physical properties of 99m Tc that results in low dose to the patient. However, the labeling employing the HMPAO complex results in some disadvantages like the low stability of the complex, and some requirements related to the 99m Tc elution (like the time pos elution), beyond the high cost of the compound that is imported. The aim of this work was the development of a tin-glucoheptonate lyophilized kit for in vitro leucocytes labeling with 99m Tc using the pre-stannization method. The optimization of the labeling technique was developed using leucocytes isolated from total blood and employing different volumes of the tinglucoheptonate reagent and different incubation times at

Redox reactions of Cu(II)-amine complexes in aqueous solutions

International Nuclear Information System (INIS)

Kumbhar, A.G.; Kishore, Kamal

2003-01-01

A number of amines can be employed for all volatile treatment (AVT) of steam generator (SG) systems of nuclear power reactors. These amines form complexes with Cu 2+ and Ni 2+ ions which come into water due to corrosion. The redox reactions of a number of Cu(II)-AVT amine complexes and the stability of the transient species formed have been studied by pulse radiolysis technique. Rate constants for the reaction of e aq - with a number of Cu(II)-amine complexes have been determined by following the decay of e aq - absorption. Stability of Cu(I)-amine complexes was studied by following the kinetics of the bleaching signal formed at the λ max of the Cu(II) amine complex. Except for Cu(I)-triethanolamine complex all other Cu(I)-amine complexes were found to be stable. One-electron oxidation of Cu(II) amine complexes was studied using azidyl radicals for the oxidation reaction as OH radicals react with the alcohol groups present in the amines used in this study. Cu(III)-amine complexes were found to be unstable and decayed by second-order kinetics

Separation of fission 99Mo by alpha-benzoin oxime precipitation in nitric medium

International Nuclear Information System (INIS)

Yamaura, Mitiko; Freitas, Antonio A.; Egute, Nayara dos S.; Camilo, Ruth L.; Araujo, Izilda C.; Forbicini, Christina A.L.G. de O.

2011-01-01

Since 2009, the production of generators 99 Mo/ 99 mTc suffers a crisis of global supply due to technical problems of the two reactors which account for 64% of world production of fission 99 Mo. By the project of Brazilian Multipurpose Reactor (RMB), the Brazilian government invests in the construction of the first multipurpose reactor suitable for the domestic production of 99 Mo from LEU targets in order to supply of fission 99 Mo in the coming decades. The IPEN started the research of the technology and production of fission 99 Mo from acid and alkaline dissolutions of Low Enriched Uranium (LEU) targets as well as other used radioisotopes in nuclear medicine. This work is part of the research of the technology of the fission 99 Mo from acid dissolution of the LEU targets that is being developed at the IPEN. In this study the separation of the Mo by precipitation with alpha-benzoin oxime in nitric medium and the recovery by dissolution were investigated. The precipitation studies were performed by batch assays with nitric solution of Mo(VI), containing 99 Mo tracer, and uranyl ions. Influence of concentration of permanganate from 0.03 to 2.5%, dissolution temperature at 30 deg C and 150 deg C and the uranium concentration from 74 g.L -1 to 115 g.L -1 was studied. Results indicated that the precipitation of Mo with alpha-benzoin oxime from nitric medium is highly efficient, and its recovery by dissolution with basic solution of H 2 O 2 gave a high yield. (author)

Innovative approach for the electrochemical detection of non-electroactive organophosphorus pesticides using oxime as electroactive probe

International Nuclear Information System (INIS)

Dong, Jing; Hou, Juying; Jiang, Jianxia; Ai, Shiyun

2015-01-01

Highlights: • Novel approach for electrochemical detection of non-electroactive OPs was proposed. • PAM was used as electroactive probe for the first time. • The detection system displayed high sensitivity and promptness. • The developed sensor was used in real samples with satisfactory results. - Abstract: An innovative approach for sensitive and simple electrochemical detection of non-electroactive organophosphorus pesticides (OPs) was described in this report. The novel strategy emphasized the fabrication of an oxime-based sensor via attaching pralidoxime (PAM) on graphene quantum dots (GQDs) modified glassy carbon electrode. The introduction of GQDs significantly increased the effective electrode area, and then enlarged the immobilization quantity of PAM. Thus, the oxidation current of PAM was obviously increased. Relying on the nucleophilic substitution reaction between oxime and OPs, fenthion was detected using PAM as the electroactive probe. Under optimum conditions, the difference of oxidation current of PAM was proportional to fenthion concentration over the range from 1.0 × 10 −11 M to 5.0 × 10 −7 M with a detection limit of 6.8 × 10 −12 M (S/N = 3). Moreover, the favorable detection performance in water and soil samples heralded the promising applications in on-site OPs detection

Reductive amination with zinc powder in aqueous media

Directory of Open Access Journals (Sweden)

Giovanni B. Giovenzana

2011-08-01

Full Text Available Zinc powder in aqueous alkaline media was employed to perform reductive amination of aldehydes with primary amines. The corresponding secondary amines were obtained in good yields along with minor amounts of hydrodimerization byproducts. The protocol is a green alternative to the use of complex hydrides in chlorinated or highly flammable solvents.

Thermometric titrations of amines with nitrosyl perchlorate in acetonitrile solvent.

Science.gov (United States)

Gündüz, T; Kiliç, E; Cakirer, O

1996-05-01

Thirteen aliphatic and four aromatic amines, namely diethylamine, triethylamine, n-propylamine, di-n-propylamine, tri-n-butylamine, isopropylamine, di-isopropylamine, n-butylamine, di-n-butylamine, tri-n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, aniline, N,N-dimethylaniline, 2-nitroaniline and 4-nitroaniline were titrated thermometrically with nitrosyl perchlorate in acetonitrile solvent. All the aliphatic amines gave very well-shaped thermometric titration curves. The calculated recovery values of the amines were very good. In comparison, the aromatic amines, aniline and N,N-dimethylaniline gave rather well-shaped titration curves, but the recovery values were fairly low. 2-Nitro- and 4-nitro anilines gave no thermometric response at all. The heats of reaction of the amines with nitrosyl perchlorate are rather high. However, the average heat of reaction of the aromatic amines is approximately two-thirds that of the average heat of the aliphatic amines. To support this method all the amines were also titrated potentiometrically and very similar results to those obtained with the thermometric method are seen. The nitrosyl ion is a Lewis acid, strong enough to titrate quantitatively aliphatic amines in acetonitrile solvent, but not strong enough to titrate aromatic amines at the required level in the same solvent.

High performance supercapacitor using N-doped graphene prepared via supercritical fluid processing with an oxime nitrogen source

International Nuclear Information System (INIS)

Balaji, S. Suresh; Elavarasan, A.; Sathish, M.

2016-01-01

Graphical abstract: N-doped graphene prepared via supercritical fluid processing with oxime nitrogen source (DMG) showed enhanced performance in electrochemical supercapacitor application. A maximum specific capacitance of 286 F g"−"1 at a current density of 0.5 A/g was achieved with a high specific capacity retention of 98% after 1000 cycles at 5 A/g. - Highlights: • N-functionalised graphene synthesized via supercritical fluid processing. • DMG, an oxime based nitrogen precursor. • Maximum specific capacitance of 286 F/g at 0.5 A/g in aqueous solution. • Pyridinic as well as quarternary nitrogen for enhanced capacitance. - Abstract: Heteroatom doped graphene has been proved for its promising applications in electrochemical energy storage systems. Here, nitrogen (N) doped graphene was prepared via two different techniques namely supercritical fluid assisted processing and hydrothermal heat treatment using dimethylglyoxime (DMG) as an oxime nitrogen precursor. The FT-IR and Raman spectra showed the N-containing functional group in the graphene. The XRD analysis revealed the complete reduction of graphene oxide during the supercritical fluid processing. The elemental analysis and X-ray photoelectron spectroscopy revealed the amount and nature of N-doping in the graphene, respectively. The surface morphology and physical nature of the samples were analyzed using scanning and transmission electron microscopic analysis. The electrochemical performance of prepared electrode materials was evaluated using cyclic voltammetry, galvanostatic charge-discharge analysis and electrochemical impedance spectroscopy. The N-doped graphene prepared via supercritical fluid assisted processing exhibit enhanced capacitive behaviour with a maximum specific capacitance of 286 F g"−"1 at a current density of 0.5 A/g. The cycling studies showed 98% specific capacity retention with 100% coulombic efficiency over 1000 cycles at 5 A/g. The enhanced specific capacitance of N

Trace Amines and the Trace Amine-Associated Receptor 1: Pharmacology, Neurochemistry and Clinical Implications

Directory of Open Access Journals (Sweden)

Yue ePei

2016-04-01

Full Text Available Biogenic amines are a collection of endogenous molecules that play pivotal roles as neurotransmitters and hormones. In addition to the classical biogenic amines resulting from decarboxylation of aromatic acids, including dopamine (DA, norepinephrine, epinephrine, serotonin (5-HT and histamine, other biogenic amines, present at much lower concentrations in the central nervous system (CNS, and hence referred to as trace amines (TAs, are now recognized to play significant neurophysiological and behavioural functions. At the turn of the century, the discovery of the trace amine-associated receptor 1 (TAAR1, a phylogenetically conserved G protein-coupled receptor that is responsive to both TAs, such as β-phenylethylamine, octopamine and tyramine, and structurally-related amphetamines, unveiled mechanisms of action for TAs other than interference with aminergic pathways, laying the foundations for deciphering the functional significance of TAs and its mammalian CNS receptor, TAAR1. Although its molecular interactions and downstream targets have not been fully elucidated, TAAR1 activation triggers accumulation of intracellular cAMP, modulates PKA and PKC signalling and interferes with the β-arrestin2-dependent pathway via G protein-independent mechanisms. TAAR1 is uniquely positioned to exert direct control over DA and 5-HT neuronal firing and release, which has profound implications for understanding the pathophysiology of, and therefore designing more efficacious therapeutic interventions for, a range of neuropsychiatric disorders that involve aminergic dysregulation, including Parkinson’s disease, schizophrenia, mood disorders and addiction. Indeed, the recent development of novel pharmacological tools targeting TAAR1 has uncovered the remarkable potential of TAAR1-based medications as new generation pharmacotherapies in neuropsychiatry. This review summarizes recent developments in the study of TAs and TAAR1, their intricate neurochemistry and

Tunable, chemoselective amination via silver catalysis.

Science.gov (United States)

Rigoli, Jared W; Weatherly, Cale D; Alderson, Juliet M; Vo, Brian T; Schomaker, Jennifer M

2013-11-20

Organic N-containing compounds, including amines, are essential components of many biologically and pharmaceutically important molecules. One strategy for introducing nitrogen into substrates with multiple reactive bonds is to insert a monovalent N fragment (nitrene or nitrenoid) into a C-H bond or add it directly to a C═C bond. However, it has been challenging to develop well-defined catalysts capable of promoting predictable and chemoselective aminations solely through reagent control. Herein, we report remarkable chemoselective aminations that employ a single metal (Ag) and a single ligand (phenanthroline) to promote either aziridination or C-H insertion by manipulating the coordination geometry of the active catalysts.

Oxidations of N-(3-indoleethyl) cyclic aliphatic amines by horseradish peroxidase: the indole ring binds to the enzyme and mediates electron-transfer amine oxidation.

Science.gov (United States)

Ling, Ke-Qing; Li, Wen-Shan; Sayre, Lawrence M

2008-01-23

Although oxidations of aromatic amines by horseradish peroxidase (HRP) are well-known, typical aliphatic amines are not substrates of HRP. In this study, the reactions of N-benzyl and N-methyl cyclic amines with HRP were found to be slow, but reactions of N-(3-indoleethyl) cyclic amines were 2-3 orders of magnitude faster. Analyses of pH-rate profiles revealed a dominant contribution to reaction by the amine-free base forms, the only species found to bind to the enzyme. A metabolic study on a family of congeneric N-(3-indoleethyl) cyclic amines indicated competition between amine and indole oxidation pathways. Amine oxidation dominated for the seven- and eight-membered azacycles, where ring size supports the change in hybridization from sp3 to sp2 that occurs upon one-electron amine nitrogen oxidation, whereas only indole oxidation was observed for the six-membered ring congener. Optical difference spectroscopic binding data and computational docking simulations suggest that all the arylalkylamine substrates bind to the enzyme through their aromatic termini with similar binding modes and binding affinities. Kinetic saturation was observed for a particularly soluble substrate, consistent with an obligatory role of an enzyme-substrate complexation preceding electron transfer. The significant rate enhancements seen for the indoleethylamine substrates suggest the ability of the bound indole ring to mediate what amounts to medium long-range electron-transfer oxidation of the tertiary amine center by the HRP oxidants. This is the first systematic investigation to document aliphatic amine oxidation by HRP at rates consistent with normal metabolic turnover, and the demonstration that this is facilitated by an auxiliary electron-rich aromatic ring.

Development of I-123-labeled amines for brain studies: localization of I-123 iodophenylalkyl amines in rat brain

International Nuclear Information System (INIS)

Winchell, H.S.; Baldwin, R.M.; Lin, T.H.

1980-01-01

Localization in rat brain of forty iodophenylalkyl amines labeled with I-123 was evaluated in an attempt to develop I-123-labeled amines useful for brain studies. For the amines studied, the highest activity in brain and the brain-to-blood activity ratios ranked p > m > o as related to iodine position on the benzene ring: for alkyl groups the rank order was α-methylethyl > ethyl > methyl > none; for N additions it was single lipophilic group > H > two lipophilic groups. It is suggested that introduction of a halogen into the ring structure of many amines results in greater concentration of the agent in brain than is seen with the nonhalogenated parent compound. The agent N-isopropyl-p-iodoamphetamine was chosen for further study because, in the rat, it showed high brain activity (1.57%/g) and brain-blood ratio (12.6) at 5 min

New insights into controlling tube-bundle fouling using alternative amines

Energy Technology Data Exchange (ETDEWEB)

Turner, C.W.; Klimas, S.J.; Guzonas, D.A.; Fruzzetti, K. [Atomic Energy of Canada Ltd. (Canada); Frattini, P.L. [Electric Power Research Inst. (United States)

2002-07-01

A volatile amine is added to the secondary heat-transport system of a nuclear power plant to reduce the rate of corrosion and corrosion product transport in the feedwater and to protect steam generator (SG) crevices and materials exposed to steam condensate. Volatility and base strength of the amine at the SG operating temperature are two important considerations when choosing the optimum amine (or mixture of amines) for corrosion control in the steam cycle. The investigation has found that the rate of tube-bundle fouling is strongly dependent upon the surface chemistry of the corrosion products. For example, the fouling rates of fully oxidized iron oxides, such as hematite and lepidocrocite, are at least an order of magnitude greater than the fouling rate of magnetite under identical operating conditions. The difference is related to the sign of the surface charge on the corrosion products at temperature. The choice of amine for pH-control also influences the fouling rate. This was originally thought to be a surface-charge effect as well, but recent tests have suggested that it is related to the role that the amine plays in governing the rate of deposit consolidation on the heat-transfer surface. Amines that promote a high rate of deposit consolidation result in a low rate of deposit removal and a high fouling rate. Conversely, amines that tend to inhibit deposit consolidation produce a higher rate of deposit removal and a lower fouling rate. Dimethyl-amine and dodecyl-amine have been identified as two amines that inhibit the rate of deposit consolidation and, consequently, result in fouling rates that are up to 5 times lower than rates measured for amines that promote consolidation. A significant difference between morpholine (high fouling rate) and dimethyl-amine (low fouling rate) is that the latter desorbs more slowly from the surface of magnetite. How to account for a correlation between slow desorption kinetics and lower rate constants for deposition and

New insights into controlling tube-bundle fouling using alternative amines

International Nuclear Information System (INIS)

Turner, C.W.; Klimas, S.J.; Guzonas, D.A.; Fruzzetti, K.; Frattini, P.L.

2002-01-01

A volatile amine is added to the secondary heat-transport system of a nuclear power plant to reduce the rate of corrosion and corrosion product transport in the feedwater and to protect steam generator (SG) crevices and materials exposed to steam condensate. Volatility and base strength of the amine at the SG operating temperature are two important considerations when choosing the optimum amine (or mixture of amines) for corrosion control in the steam cycle. The investigation has found that the rate of tube-bundle fouling is strongly dependent upon the surface chemistry of the corrosion products. For example, the fouling rates of fully oxidized iron oxides, such as hematite and lepidocrocite, are at least an order of magnitude greater than the fouling rate of magnetite under identical operating conditions. The difference is related to the sign of the surface charge on the corrosion products at temperature. The choice of amine for pH-control also influences the fouling rate. This was originally thought to be a surface-charge effect as well, but recent tests have suggested that it is related to the role that the amine plays in governing the rate of deposit consolidation on the heat-transfer surface. Amines that promote a high rate of deposit consolidation result in a low rate of deposit removal and a high fouling rate. Conversely, amines that tend to inhibit deposit consolidation produce a higher rate of deposit removal and a lower fouling rate. Dimethyl-amine and dodecyl-amine have been identified as two amines that inhibit the rate of deposit consolidation and, consequently, result in fouling rates that are up to 5 times lower than rates measured for amines that promote consolidation. A significant difference between morpholine (high fouling rate) and dimethyl-amine (low fouling rate) is that the latter desorbs more slowly from the surface of magnetite. How to account for a correlation between slow desorption kinetics and lower rate constants for deposition and

BIOGENIC AMINES CONTENT IN DIFFERENT WINE SAMPLES

Directory of Open Access Journals (Sweden)

Attila Kántor

2015-02-01

Full Text Available Twenty-five samples of different Slovak wines before and after filtration were analysed in order to determine the content of eight biogenic amines (tryptamine, phenylalanine, putrescine, cadaverine, histamine, tyramine, spermidine and spermine. The method involves extraction of biogenic amines from wine samples with used dansyl chloride. Ultra-high performance liquid chromatography (UHPLC was used for determination of biogenic amines equipped with a Rapid Resolution High Definition (RRHD, DAD detectors and Extend-C18 LC column (50 mm x 3.0 mm ID, 1.8 μm particle size. In this study the highest level of biogenic amine in all wine samples represent tryptamine (TRM with the highest content 170.9±5.3 mg/L in Pinot Blanc wine. Phenylalanine (PHE cadaverine (CAD, histamine (HIS and spermidine (SPD were not detected in all wines; mainly SPD was not detected in 16 wines, HIS not detected in 14 wines, PHE and CAD not detected in 2 wines. Tyramine (TYR, spermine (SPN and putrescine (PUT were detected in all wines, but PUT and SPN in very low concentration. The worst wine samples with high biogenic amine content were Saint Laurent (BF, Pinot Blanc (S and Pinot Noir (AF.

Biogenic amine formation and bacterial contribution in Natto products.

Science.gov (United States)

Kim, Bitna; Byun, Bo Young; Mah, Jae-Hyung

2012-12-01

Twenty-one Natto products currently distributed in Korea were analysed for biogenic amine contents and tested to determine physicochemical and bacterial contributions to biogenic amine formation. Among them, nine products (about 43%) had β-phenylethylamine or tyramine contents greater than the toxic dose (30mg/kg and 100mg/kg, respectively) of each amine, although no products showed total amounts of biogenic amines above the harmful level (1000mg/kg), which indicates that the amounts of biogenic amines in some Natto products are not within the safe level for human health. From four different Natto products, that contained noticeable levels of β-phenylethylamine and tyramine, 80 bacterial strains were isolated. All the strains were identified to be Bacillus subtilis and highly capable of producing β-phenylethylamine and tyramine. Therefore, it seems likely that the remarkable contents of β-phenylethylamine and tyramine in Natto predominantly resulted from the strains highly capable of producing those amines present in the food. Copyright © 2012 Elsevier Ltd. All rights reserved.

Sodium Perborate Oxidation of an Aromatic Amine

Science.gov (United States)

Juestis, Laurence

1977-01-01

Describes an experiment involving the oxidation of aromatic primary amines to the corresponding azo compound; suggests procedures for studying factors that influence the yield of such a reaction, including the choice of solvent and the oxidant-amine ratio. (MLH)

A Catalyst-Free Amination of Functional Organolithium Reagents by Flow Chemistry.

Science.gov (United States)

Kim, Heejin; Yonekura, Yuya; Yoshida, Jun-Ichi

2018-04-03

Reported is the electrophilic amination of functional organolithium intermediates with well-designed aminating reagents under mild reaction conditions using flow microreactors. The aminating reagents were optimized to achieve efficient C-N bond formation without using any catalyst. The electrophilic amination reactions of functionalized aryllithiums were successfully conducted under mild reaction conditions, within 1 minute, by using flow microreactors. The aminating reagent was also prepared by the flow method. Based on stopped-flow NMR analysis, the reaction time for the preparation of the aminating reagent was quickly optimized without the necessity of work-up. Integrated one-flow synthesis consisting of the generation of an aryllithium, the preparation of an aminating reagent, and their combined reaction was successfully achieved to give the desired amine within 5 minutes of total reaction time. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Method for the production of primary amines

NARCIS (Netherlands)

Baldenius, Kai-Uwe; Ditrich, Klaus; Breurer, Michael; Navickas, Vaidotas; Janssen, Dick; Crismaru, Ciprian; Bartsch, Sebastian

2014-01-01

The present invention relates to a novel enzymatically catalyzed method for the production of aliphatic primary amines, which method comprises the enzymatic oxidation of a primary aliphatic alcohol catalyzed by an alcohol dehydrogenase, amination of the resulting oxocompound catalyzed by a

Dual C-H functionalization of N-aryl amines: synthesis of polycyclic amines via an oxidative Povarov approach.

Science.gov (United States)

Min, Chang; Sanchawala, Abbas; Seidel, Daniel

2014-05-16

Iminium ions generated in situ via copper(I) bromide catalyzed oxidation of N-aryl amines readily undergo [4 + 2] cycloadditions with a range of dienophiles. This method involves the functionalization of both a C(sp(3))-H and a C(sp(2))-H bond and enables the rapid construction of polycyclic amines under relatively mild conditions.

Direct electrochemical imidation of aliphatic amines via anodic oxidation.

Science.gov (United States)

Zhang, Li; Su, Ji-Hu; Wang, Sujing; Wan, Changfeng; Zha, Zhenggen; Du, Jiangfeng; Wang, Zhiyong

2011-05-21

Direct electrochemical synthesis of sulfonyl amidines from aliphatic amines and sulfonyl azides was realized with good to excellent yields. Traditional tertiary amine substrates were broadened to secondary and primary amines. The reaction intermediates were observed and a reaction mechanism was proposed and discussed. © The Royal Society of Chemistry 2011

40 CFR 721.6660 - Polymer of alkanepolyol and poly-alkyl-poly-iso-cyan-ato-car-bo-mo-no-cycle, acetone oxime...

Science.gov (United States)

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Polymer of alkanepolyol and poly-alkyl... Polymer of alkanepolyol and poly-alkyl-poly-iso-cyan-ato-car-bo-mo-no-cycle, acetone oxime-blocked... substance identified generically as a polymer of alkane-polyol and polyalkylpolyisocyanatocarbomonocy- cle...

Catalytic Ester and Amide to Amine Interconversion: Nickel-Catalyzed Decarbonylative Amination of Esters and Amides by C−O and C−C Bond Activation

KAUST Repository

Yue, Huifeng

2017-03-15

An efficient nickel-catalyzed decarbonylative amination reaction of aryl and heteroaryl esters has been achieved for the first time. The new amination protocol allows the direct interconversion of esters and amides into the corresponding amines and represents a good alternative to classical rearrangements as well as cross coupling reactions.

Transition Metal Free C-N Bond Forming Dearomatizations and Aryl C-H Aminations by in Situ Release of a Hydroxylamine-Based Aminating Agent.

Science.gov (United States)

Farndon, Joshua J; Ma, Xiaofeng; Bower, John F

2017-10-11

We outline a simple protocol that accesses directly unprotected secondary amines by intramolecular C-N bond forming dearomatization or aryl C-H amination. The method is dependent on the generation of a potent electrophilic aminating agent released by in situ deprotection of O-Ts activated N-Boc hydroxylamines.

Catalytic Ester and Amide to Amine Interconversion: Nickel-Catalyzed Decarbonylative Amination of Esters and Amides by C−O and C−C Bond Activation

KAUST Repository

Yue, Huifeng; Guo, Lin; Liao, Hsuan-Hung; Cai, Yunfei; Zhu, Chen; Rueping, Magnus

2017-01-01

An efficient nickel-catalyzed decarbonylative amination reaction of aryl and heteroaryl esters has been achieved for the first time. The new amination protocol allows the direct interconversion of esters and amides into the corresponding amines and represents a good alternative to classical rearrangements as well as cross coupling reactions.

Intolerance to dietary biogenic amines: A review

NARCIS (Netherlands)

Jansen, S.C.; Dusseldorp, M. van; Bottema, K.C.; Dubois, A.E.J.

2003-01-01

Objective: To evaluate the scientific evidence for purported intolerance to dietary biogenic amines. Data Sources: MEDLINE was searched for articles in the English language published between January 1966 and August 2001. The keyword biogenic amin* was combined with hypersens*, allerg*, intoler*, and

Intolerance to dietary biogenic amines : a review

NARCIS (Netherlands)

Jansen, SC; van Dusseldorp, M; Bottema, KC; Dubois, AEJ

Objective: To evaluate the scientific evidence for purported intolerance to dietary biogenic amines. Data Sources: MEDLINE was searched for articles in the English language published between January 1966 and August 2001. The keyword biogenic amin* was combined with hypersens*, allergen intoler*, and

Analysis of a Buchwald-Hartwig amination: reaction for pharmaceutical production

DEFF Research Database (Denmark)

Christensen, Henrik

The Buchwald-Hartwig amination reaction is widely used in the production of N-arylated amines in the pharmaceutical industry. The reaction is betweenan aryl halogen and a primary or secondary amine in the presence of a base and a homogeneous catalyst giving the desired N-arylated amine. Due to mild...... is to increase the understanding of the chem­ical reaction mechanisms and kinetics for the Buchwald-Hartwig amination reaction. Also, to develop methods for application of these mechanisms and kinetics to optimize and scale up an organic synthesis to an industrial phar­maceutical production. The Buchwald...

Analysis of a Buckwald-Hartwig amination: reaction for pharmaceutical production

DEFF Research Database (Denmark)

Christensen, Henrik; Kiil, Søren; Dam-Johansen, Kim

The Buchwald-Hartwig amination reaction is widely used in the production of N-arylated amines in the pharmaceutical industry. The reaction is betweenan aryl halogen and a primary or secondary amine in the presence of a base and a homogeneous catalyst giving the desired N-arylated amine. Due to mild...... is to increase the understanding of the chem­ical reaction mechanisms and kinetics for the Buchwald-Hartwig amination reaction. Also, to develop methods for application of these mechanisms and kinetics to optimize and scale up an organic synthesis to an industrial phar­maceutical production. The Buchwald...

Solvent-free functionalization of carbon nanotube buckypaper with amines

International Nuclear Information System (INIS)

Basiuk, Elena V.; Ramírez-Calera, Itzel J.; Meza-Laguna, Victor; Abarca-Morales, Edgar; Pérez-Rey, Luis A.; Re, Marilena; Prete, Paola; Lovergine, Nico

2015-01-01

Graphical abstract: - Abstract: We demonstrate the possibility of fast and efficient solvent-free functionalization of buckypaper (BP) mats prefabricated from oxidized multiwalled carbon nanotubes (MWCNTs-ox), by using three representative amines of different structure: one monofunctional aliphatic amine, octadecylamine (ODA), one monofunctional aromatic amine, 1-aminopyrene (AP), and one aromatic diamine, 1,5-diaminonaphthalene (DAN). The functionalization procedure, which relies on the formation of amide bonds with carboxylic groups of MWCNTs-ox, is performed at 150–180 °C under reduced pressure and takes about 4 h including auxiliary degassing. The amine-treated BP samples (BP-ODA, BP-AP and BP-DAN, respectively) were characterized by means of a variety of analytical techniques such as Fourier-transform infrared and Raman spectroscopy, thermogravimetric and differential thermal analysis, scanning and transmission electron microscopy, scanning helium ion microscopy, and atomic force microscopy. The highest amine content was found for BP-ODA, and the lowest one was observed for BP-DAN, with a possible contribution of non-covalently bonded amine molecules in all three cases. Despite of some differences in spectral and morphological characteristics for amine-functionalized BP samples, they have in common a dramatically increased stability in water as compared to pristine BP and, on the other hand, a relatively invariable electrical conductivity.

Fluorinated Amine Stereotriads via Allene Amination.

Science.gov (United States)

Liu, Lu; Gerstner, Nels C; Oxtoby, Lucas J; Guzei, Ilia A; Schomaker, Jennifer M

2017-06-16

The incorporation of fluorine into organic scaffolds often improves the bioactivity of pharmaceutically relevant compounds. C-F/C-N/C-O stereotriad motifs are prevalent in antivirals, neuraminidase inhibitors, and modulators of androgen receptors, but are challenging to install. An oxidative allene amination strategy using Selectfluor rapidly delivers triply functionalized triads of the form C-F/C-N/C-O, exhibiting good scope and diastereoselectivity for all syn products. The resulting stereotriads are readily transformed into fluorinated pyrrolidines and protected α-, β-, and γ-amino acids.

Evaluation of amine inhibitors for suitability as crevice buffering agents

International Nuclear Information System (INIS)

Jayaweera, P.; Hettiarachchi, S.

1994-03-01

This report describes the results of a research effort to evaluate the suitability of some selected amines and amino acids as a crevice-buffering agents in pressurized water reactor (PWR) steam generators. The amines may be useful for buffering acid crevices, and the amino acids, because they contain both acidic and basic groups, may be useful for acidic and caustic crevices. Five commercially available amines and two amino acids were studied during this research. The study involved (1) the hydrolysis of these commercially available amines and amino acids, including measurement of their kinetics of decomposition, in simulated steam generator bulk water at 290 C, and (2) determination of their thermal stability in a simulated crevice environment. The study showed that, although the high-molecular-weight amines undergo hydrothermal decomposition, they have a better buffering capacity than their low-molecular-weight counterparts at 290 C. The amines provide effective crevice buffering by increasing the pH of the crevice solution by as much as 2.84 and to 4.24 units in the experimental setup used in this program. It was concluded that polyamines provide excellent buffering of the simulated crevice environment at 290 C and morpholine remains the best low-molecular-weight amine investigated. However, detailed volatility studies of the amines were not considered in this work. Such data would be needed before in-plant testing to ensure that the amines can concentrate in steam generator crevices to the levels assumed in this study

New potential of the reductive alkylation of amines

International Nuclear Information System (INIS)

Gusak, K N; Ignatovich, Zh V; Koroleva, E V

2015-01-01

Available data on the reductive alkylation of amines with carbonyl compounds — a key method for the preparation of secondary and tertiary amines — are described systematically. The review provides information on the relevant reducing agents and catalysts and on the use of chiral catalysts in stereo- and enantiocontrolled reactions of amine synthesis. The effect of the reactant and catalyst structures on the reaction rates and chemo- and stereo(enantio)selectivity is considered. The bibliography includes 156 references

Poly(Amido Amine)s Containing Agmatine and Butanol Side Chains as Efficient Gene Carriers.

Science.gov (United States)

Won, Young-Wook; Ankoné, Marc; Engbersen, Johan F J; Feijen, Jan; Kim, Sung Wan

2016-04-01

A new type of bioreducible poly(amido amine) copolymer is synthesized by the Michael addition polymerization of cystamine bisacrylamide (CBA) with 4-aminobutylguanidine (agmatine, AGM) and 4-aminobutanol (ABOL). Since the positively charged guanidinium groups of AGM and the hydroxybutyl groups of ABOL in the side chains have shown to improve the overall transfection efficiency of poly(amido amine)s, it is hypothesized that poly(CBA-ABOL/AGM) synthesized at the optimal ratio of both components would result in high transfection efficiency and minimal toxicity. In this study, a series of the poly(CBA-ABOL/AGM) copolymers is synthesized as gene carriers. The polymers are characterized and luciferase transfection efficiencies of the polymers in various cell lines are investigated to select the ideal ratio between AGM and ABOL. The poly(CBA-ABOL/AGM) containing 80% AGM and 20% ABOL has shown the best transfection efficiency with the lowest cytotoxicity, indicating that this polymer is very promising as a potent and nontoxic gene carrier. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fluorescence quenching of Rhodamine B base by two amines

Science.gov (United States)

Bakkialakshmi, S.; Selvarani, P.; Chenthamarai, S.

2013-03-01

Fluorescence quenching of Rhodamine B base (RhB) in DMF solution has been studied at different concentrations of the amine Triethyl amine (TEA) and n-butyl amine (NBA) at room temperature. It has been observed that the fluorescence intensity of RhB decrease with increase in the concentration of the TEA and NBA. It has been observed that the quenching due to amines proceeds via dynamic quenching process. The rate constants for the quenching process have been calculated using Stern-Volmer equation. Time resolved fluorescence study and 1H NMR spectral study have also been carried out and discussed.

Catalyst- and Reagent-free Electrochemical Azole C-H Amination.

Science.gov (United States)

Qiu, Youai; Struwe, Julia; Meyer, Tjark H; Oliveira, Joao Carlos Agostinho Carlos Agostinho; Ackermann, Lutz

2018-06-14

Catalyst-, and chemical oxidant-free electrochemical azole C-H aminations were accomplished via cross-dehydrogenative C-H/N-H functionalization. The catalyst-free electrochemical C-H amination proved feasible on azoles with high levels of efficacy and selectivity, avoiding the use of stoichiometric oxidants under ambient conditions. Likewise, the C(sp3)-H nitrogenation proved viable under otherwise identical conditions. The dehydrogenative C-H amination featured ample scope, including cyclic and acyclic aliphatic amines as well as anilines, and employed sustainable electricity as the sole oxidant. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

BIOGENIC AMINES CONTENT IN SELECTED WINES DURING WINEMAKING

Directory of Open Access Journals (Sweden)

Radka Flasarová

2012-02-01

Full Text Available The aim of this study was to describe the development of selected biogenic amines (histamine; tyramine; phenylethylamine; putrescine; agmatine; and cadaverine during the winemaking in 10 selected species grown in Central Europe in 2008. The analysis was performed using ion-exchange chromatography by the sodium-citrate buffers with the post-column ninhydrin derivatization and photometric detection. A comparison of the content of biogenic amines in red and wine varieties showed that red wines have higher concentrations of biogenic amines.

Biogenic amines in dry fermented sausages: a review.

Science.gov (United States)

Suzzi, Giovanna; Gardini, Fausto

2003-11-15

Biogenic amines are compounds commonly present in living organisms in which they are responsible for many essential functions. They can be naturally present in many foods such as fruits and vegetables, meat, fish, chocolate and milk, but they can also be produced in high amounts by microorganisms through the activity of amino acid decarboxylases. Excessive consumption of these amines can be of health concern because their not equilibrate assumption in human organism can generate different degrees of diseases determined by their action on nervous, gastric and intestinal systems and blood pressure. High microbial counts, which characterise fermented foods, often unavoidably lead to considerable accumulation of biogenic amines, especially tyramine, 2-phenylethylamine, tryptamine, cadaverine, putrescine and histamine. However, great fluctuations of amine content are reported in the same type of product. These differences depend on many variables: the quali-quantitative composition of microbial microflora, the chemico-physical variables, the hygienic procedure adopted during production, and the availability of precursors. Dry fermented sausages are worldwide diffused fermented meat products that can be a source of biogenic amines. Even in the absence of specific rules and regulations regarding the presence of these compounds in sausages and other fermented products, an increasing attention is given to biogenic amines, especially in relation to the higher number of consumers with enhanced sensitivity to biogenic amines determined by the inhibition of the action of amino oxidases, the enzymes involved in the detoxification of these substances. The aim of this paper is to give an overview on the presence of these compounds in dry fermented sausages and to discuss the most important factors influencing their accumulation. These include process and implicit factors as well as the role of starter and nonstarter microflora growing in the different steps of sausage production

Direct α-C-H bond functionalization of unprotected cyclic amines

Science.gov (United States)

Chen, Weijie; Ma, Longle; Paul, Anirudra; Seidel, Daniel

2018-02-01

Cyclic amines are ubiquitous core structures of bioactive natural products and pharmaceutical drugs. Although the site-selective abstraction of C-H bonds is an attractive strategy for preparing valuable functionalized amines from their readily available parent heterocycles, this approach has largely been limited to substrates that require protection of the amine nitrogen atom. In addition, most methods rely on transition metals and are incompatible with the presence of amine N-H bonds. Here we introduce a protecting-group-free approach for the α-functionalization of cyclic secondary amines. An operationally simple one-pot procedure generates products via a process that involves intermolecular hydride transfer to generate an imine intermediate that is subsequently captured by a nucleophile, such as an alkyl or aryl lithium compound. Reactions are regioselective and stereospecific and enable the rapid preparation of bioactive amines, as exemplified by the facile synthesis of anabasine and (-)-solenopsin A.

Sponges with covalently tethered amines for high-efficiency carbon capture

KAUST Repository

Qi, Genggeng

2014-12-12

© 2014 Macmillan Publishers Limited. All rights reserved. Adsorption using solid amine sorbents is an attractive emerging technology for energy-efficient carbon capture. Current syntheses for solid amine sorbents mainly based on physical impregnation or grafting-to methods (for example, aminosilane-grafting) lead to limited sorbent performance in terms of stability and working capacity, respectively. Here we report a family of solid amine sorbents using a grafting-from synthesis approach and synthesized by cationic polymerization of oxazolines on mesoporous silica. The sorbent with high amount of covalently tethered amines shows fast adsorption rate, high amine efficiency and sorbent capacity well exceeding the highest value reported to date for lowerature carbon dioxide sorbents under simulated flue gas conditions. The demonstrated efficiency of the new amine-immobilization chemistry may open up new avenues in the development of advanced carbon dioxide sorbents, as well as other nitrogen-functionalized systems.

Sequential metabolism of secondary alkyl amines to metabolic-intermediate complexes: opposing roles for the secondary hydroxylamine and primary amine metabolites of desipramine, (s)-fluoxetine, and N-desmethyldiltiazem.

Science.gov (United States)

Hanson, Kelsey L; VandenBrink, Brooke M; Babu, Kantipudi N; Allen, Kyle E; Nelson, Wendel L; Kunze, Kent L

2010-06-01

Three secondary amines desipramine (DES), (S)-fluoxetine [(S)-FLX], and N-desmethyldiltiazem (MA) undergo N-hydroxylation to the corresponding secondary hydroxylamines [N-hydroxydesipramine, (S)-N-hydroxyfluoxetine, and N-hydroxy-N-desmethyldiltiazem] by cytochromes P450 2C11, 2C19, and 3A4, respectively. The expected primary amine products, N-desmethyldesipramine, (S)-norfluoxetine, and N,N-didesmethyldiltiazem, are also observed. The formation of metabolic-intermediate (MI) complexes from these substrates and metabolites was examined. In each example, the initial rates of MI complex accumulation followed the order secondary hydroxylamine > secondary amine > primary amine, suggesting that the primary amine metabolites do not contribute to formation of MI complexes from these secondary amines. Furthermore, the primary amine metabolites, which accumulate in incubations of the secondary amines, inhibit MI complex formation. Mass balance studies provided estimates of the product ratios of N-dealkylation to N-hydroxylation. The ratios were 2.9 (DES-CYP2C11), 3.6 [(S)-FLX-CYP2C19], and 0.8 (MA-CYP3A4), indicating that secondary hydroxylamines are significant metabolites of the P450-mediated metabolism of secondary alkyl amines. Parallel studies with N-methyl-d(3)-desipramine and CYP2C11 demonstrated significant isotopically sensitive switching from N-demethylation to N-hydroxylation. These findings demonstrate that the major pathway to MI complex formation from these secondary amines arises from N-hydroxylation rather than N-dealkylation and that the primary amines are significant competitive inhibitors of MI complex formation.

Biogenic amines and radiosensitivity of solitary cells

International Nuclear Information System (INIS)

Goncharenko, E.N.

1978-01-01

Different stability of cells to ionizing radiation is considered from a position of the ''elevated biochemical radioresistance background'' concept. Experimental evidence presented indicates an important role of endogenic amines (serotonin and histamine) possessing radioprotector properties in the cell radioresistance formation. The concept about their effect as being solely a result of circulatory hypoxia is critically discussed. The experimental results favor the existence of a ''cellular'' component, along with the ''hypoxic'' one, in the mechanism of action of biogenic amines. These compounds can affect the initial stages of peroxide oxidation of lipids, thereby favoring a less intensive oxidation induced by radiation. Biogenic amines can also exert influence on the cyclic nucleotide system

Ni-Catalyzed Carbon-Carbon Bond-Forming Reductive Amination.

Science.gov (United States)

Heinz, Christoph; Lutz, J Patrick; Simmons, Eric M; Miller, Michael M; Ewing, William R; Doyle, Abigail G

2018-02-14

This report describes a three-component, Ni-catalyzed reductive coupling that enables the convergent synthesis of tertiary benzhydryl amines, which are challenging to access by traditional reductive amination methodologies. The reaction makes use of iminium ions generated in situ from the condensation of secondary N-trimethylsilyl amines with benzaldehydes, and these species undergo reaction with several distinct classes of organic electrophiles. The synthetic value of this process is demonstrated by a single-step synthesis of antimigraine drug flunarizine (Sibelium) and high yielding derivatization of paroxetine (Paxil) and metoprolol (Lopressor). Mechanistic investigations support a sequential oxidative addition mechanism rather than a pathway proceeding via α-amino radical formation. Accordingly, application of catalytic conditions to an intramolecular reductive coupling is demonstrated for the synthesis of endo- and exocyclic benzhydryl amines.

Potential occupational risk of amines in carbon capture for power generation.

Science.gov (United States)

Gentry, P Robinan; House-Knight, Tamara; Harris, Angela; Greene, Tracy; Campleman, Sharan

2014-08-01

While CO2 capture and storage (CCS) technology has been well studied in terms of its efficacy and cost of implementation, there is limited available data concerning the potential for occupational exposure to amines, mixtures of amines, or degradation of by-products from the CCS process. This paper is a critical review of the available data concerning the potential effects of amines and CCS-degradation by-products. A comprehensive review of the occupational health and safety issues associated with exposure to amines and amine by-products at CCS facilities was performed, along with a review of the regulatory status and guidelines of amines, by-products, and CCS process vapor mixtures. There are no specific guidelines or regulations regarding permissible levels of exposure via air for amines and degradation products that could form atmospheric oxidation of amines released from post-combustion CO2 capture plants. While there has been a worldwide effort to develop legal and regulatory frameworks for CCS, none are directly related to occupational exposures. By-products of alkanolamine degradation may pose the most significant health hazard to workers in CCS facilities, with several aldehydes, amides, nitramines, and nitrosamines classified as either known or potential/possible human carcinogens. The absence of large-scale CCS facilities; absence and unreliability of reported data in the literature from pilot facilities; and proprietary amine blends make it difficult to estimate potential amine exposures and predict formation and exposure to degradation products.

Scope and Mechanism of a True Organocatalytic Beckmann Rearrangement with a Boronic Acid/Perfluoropinacol System under Ambient Conditions.

Science.gov (United States)

Mo, Xiaobin; Morgan, Timothy D R; Ang, Hwee Ting; Hall, Dennis G

2018-04-18

Catalytic activation of hydroxyl functionalities is of great interest for the production of pharmaceuticals and commodity chemicals. Here, 2-alkoxycarbonyl- and 2-phenoxycarbonyl-phenylboronic acid were identified as efficient catalysts for the direct and chemoselective activation of oxime N-OH bonds in the Beckmann rearrangement. This classical organic reaction provides a unique approach to prepare functionalized amide products that may be difficult to access using traditional amide coupling between carboxylic acids and amines. Using only 5 mol % of boronic acid catalyst and perfluoropinacol as an additive in a polar solvent mixture, the operationally simple protocol features mild conditions, a broad substrate scope, and a high functional group tolerance. A wide variety of diaryl, aryl-alkyl, heteroaryl-alkyl, and dialkyl oximes react under ambient conditions to afford high yields of amide products. Free alcohols, amides, carboxyesters, and many other functionalities are compatible with the reaction conditions. Investigations of the catalytic cycle revealed a novel boron-induced oxime transesterification providing an acyl oxime intermediate involved in a fully catalytic nonself-propagating Beckmann rearrangement mechanism. The acyl oxime intermediate was prepared independently and was subjected to the reaction conditions. It was found to be self-sufficient; it reacts rapidly, unimolecularly without the need for free oxime. A series of control experiments and 18 O labeling studies support a true catalytic pathway involving an ionic transition structure with an active and essential role for the boronyl moiety in both steps of transesterification and rearrangement. According to 11 B NMR spectroscopic studies, the additive perfluoropinacol provides a transient, electrophilic boronic ester that is thought to serve as an internal Lewis acid to activate the ortho-carboxyester and accelerate the initial, rate-limiting step of transesterification between the precatalyst

The chemistry of amine radical cations produced by visible light photoredox catalysis

Directory of Open Access Journals (Sweden)

Jie Hu

2013-10-01

Full Text Available Amine radical cations are highly useful reactive intermediates in amine synthesis. They have displayed several modes of reactivity leading to some highly sought-after synthetic intermediates including iminium ions, α-amino radicals, and distonic ions. One appealing method to access amine radical cations is through one-electron oxidation of the corresponding amines under visible light photoredox conditions. This approach and subsequent chemistries are emerging as a powerful tool in amine synthesis. This article reviews synthetic applications of amine radical cations produced by visible light photocatalysis.

Application of ultraviolet, ozone, and advanced oxidation treatments to washwaters to destroy nitrosamines, nitramines, amines, and aldehydes formed during amine-based carbon capture.

Science.gov (United States)

Shah, Amisha D; Dai, Ning; Mitch, William A

2013-03-19

Although amine-based CO(2) absorption is a leading contender for full-scale postcombustion CO(2) capture at power plants, concerns have been raised about the potential release of carcinogenic N-nitrosamines and N-nitramines formed by reaction of exhaust gas NO(x) with the amines. Experiments with a laboratory-scale pilot unit suggested that washwater units meant to scrub contaminants from absorber unit exhaust could potentially serve as a source of N-nitrosamines via reactions of residual NO(x) with amines accumulating in the washwater. Dosage requirements for the continuous treatment of the washwater recycle line with ultraviolet (UV) light for destruction of N-nitrosamines and N-nitramines, and with ozone or hydroxyl radical-based advanced oxidation processes (AOPs) for destruction of amines and aldehydes, were evaluated. Although amine destruction. Ozone achieved 90% amine removal in washwaters at 5-12 molar excess of ozone, indicating transferred dosage levels of ∼100 mg/L for 90% removal in a first-stage washwater unit, but likely only ∼10 mg/L if applied to a second-stage washwater. Accurate dosage and cost estimates would require pilot testing to capture synergies between UV and ozone treatments.

Mesoporous amine-bridged polysilsesquioxane for CO2 capture

KAUST Repository

Qi, Genggeng; Fu, Liling; Duan, Xiaonan; Choi, Brian Hyun; Abraham, Michael; Giannelis, Emmanuel P.

2011-01-01

A novel class of amine-supported sorbents based on amine-bridged mesoporous polysilsesquioxane was developed via a simple one-pot sol-gel process. The new sorbent allows the incorporation of a large amount of active groups without sacrificing

Enantioselective catalytic syntheses of alpha-branched chiral amines

DEFF Research Database (Denmark)

Brase, S.; Baumann, T.; Dahmen, S.

2007-01-01

Chiral amines play a pivotal role in fine chemical and natural product syntheses and the design of novel materials.......Chiral amines play a pivotal role in fine chemical and natural product syntheses and the design of novel materials....

Effects of dietary amines on the gut and its vasculature.

Science.gov (United States)

Broadley, Kenneth J; Akhtar Anwar, M; Herbert, Amy A; Fehler, Martina; Jones, Elen M; Davies, Wyn E; Kidd, Emma J; Ford, William R

2009-06-01

Trace amines, including tyramine and beta-phenylethylamine (beta-PEA), are constituents of many foods including chocolate, cheeses and wines and are generated by so-called 'friendly' bacteria such as Lactobacillus, Lactococcus and Enterococcus species, which are found in probiotics. We therefore examined whether these dietary amines could exert pharmacological effects on the gut and its vasculature. In the present study we examined the effects of tyramine and beta-PEA on the contractile activity of guinea-pig and rat ileum and upon the isolated mesenteric vasculature and other blood vessels. Traditionally, these amines are regarded as sympathomimetic amines, exerting effects through the release of noradrenaline from sympathetic nerve endings, which should relax the gut. A secondary aim was therefore to confirm this mechanism of action. However, contractile effects were observed in the gut and these were independent of noradrenaline, acetylcholine, histamine and serotonin receptors. They were therefore probably due to the recently described trace amine-associated receptors. These amines relaxed the mesenteric vasculature. In contrast, the aorta and coronary arteries were constricted, a response that was also independent of a sympathomimetic action. From these results, we propose that after ingestion, trace amines could stimulate the gut and improve intestinal blood flow. Restriction of blood flow elsewhere diverts blood to the gut to aid digestion. Thus, trace amines in the diet may promote the digestive process through stimulation of the gut and improved gastrointestinal circulation.

The mysterious trace amines: protean neuromodulators of synaptic transmission in mammalian brain.

Science.gov (United States)

Burchett, Scott A; Hicks, T Philip

2006-08-01

The trace amines are a structurally related group of amines and their isomers synthesized in mammalian brain and peripheral nervous tissues. They are closely associated metabolically with the dopamine, noradrenaline and serotonin neurotransmitter systems in mammalian brain. Like dopamine, noradrenaline and serotonin the trace amines have been implicated in a vast array of human disorders of affect and cognition. The trace amines are unique as they are present in trace concentrations, exhibit high rates of metabolism and are distributed heterogeneously in mammalian brain. While some are synthesized in their parent amine neurotransmitter systems, there is also evidence to suggest other trace amines may comprise their own independent neurotransmitter systems. A substantial body of evidence suggests that the trace amines may play very significant roles in the coordination of biogenic amine-based synaptic physiology. At high concentrations, they have well-characterized presynaptic "amphetamine-like" effects on catecholamine and indolamine release, reuptake and biosynthesis; at lower concentrations, they possess postsynaptic modulatory effects that potentiate the activity of other neurotransmitters, particularly dopamine and serotonin. The trace amines also possess electrophysiological effects that are in opposition to these neurotransmitters, indicating to some researchers the existence of receptors specific for the trace amines. While binding sites or receptors for a few of the trace amines have been advanced, the absence of cloned receptor protein has impeded significant development of their detailed mechanistic roles in the coordination of catecholamine and indolamine synaptic physiology. The recent discovery and characterization of a family of mammalian G protein-coupled receptors responsive to trace amines such as beta-phenylethylamine, tyramine, and octopamine, including socially ingested psychotropic drugs such as amphetamine, 3,4-methylenedioxymethamphetamine, N

Carbon Dioxide-Mediated C(sp3)-H Arylation of Amine Substrates.

Science.gov (United States)

Kapoor, Mohit; Liu, Daniel; Young, Michael C

2018-05-25

Elaborating amines via C-H functionalization has been an important area of research over the past decade but has generally relied on an added directing group or sterically hindered amine approach. Since free-amine-directed C(sp 3 )-H activation is still primarily limited to cyclization reactions and to improve the sustainability and reaction scope of amine-based C-H activation, we present a strategy using CO 2 in the form of dry ice that facilitates intermolecular C-H arylation. This methodology has been used to enable an operationally simple procedure whereby 1° and 2° aliphatic amines can be arylated selectively at their γ-C-H positions. In addition to potentially serving as a directing group, CO 2 has also been demonstrated to curtail the oxidation of sensitive amine substrates.

Decomposition of some amines and amino acids in steam generator environments

International Nuclear Information System (INIS)

Jayaweera, P.; Hettiarachchi, S.; Millett, P.J.

1994-01-01

Hydrothermal decomposition rate constants and high temperature pH values of some selected high-molecular weight amines and amino acids were measured under simulated steam generator conditions. These amines and amino acids were evaluated as potential crevice buffering agents for steam generator applications in pressurized water reactors. The study showed that, although the high molecular weight amines undergo hydrothermal decomposition, they have a better buffer capacity than their low molecular weight counterparts at 290 C. The amines provide effective crevice buffering by increasing the pH of the simulated crevice solution by as much as 2.84 to 4.24 units. However, volatility data for the amines and amino acids are needed before in-plant testing to ensure that amines can concentrate sufficiently in steam generator crevices to provide effective buffering

Uranium diphosphonates templated by interlayer organic amines

International Nuclear Information System (INIS)

Nelson, Anna-Gay D.; Alekseev, Evgeny V.; Albrecht-Schmitt, Thomas E.; Ewing, Rodney C.

2013-01-01

The hydrothermal treatment of uranium trioxide and methylenediphosphonic acid with a variety of amines (2,2-dipyridyl, triethylenediamine, ethylenediamine, and 1,10-phenanthroline) at 200 °C results in the crystallization of a series of layered uranium diphosphonate compounds, [C 10 H 9 N 2 ]{UO 2 (H 2 O)[CH 2 (PO 3 )(PO 3 H)]} (Ubip2), [C 6 H 14 N 2 ]{(UO 2 ) 2 [CH 2 (PO 3 )(PO 3 H)] 2 ·2H 2 O} (UDAB), [C 2 H 10 N 2 ] 2 {(UO 2 ) 2 (H 2 O) 2 [CH 2 (PO 3 ) 2 ] 2 ·0.5H 2 O} (Uethyl), and [C 12 H 9 N 2 ]{UO 2 (H 2 O)[CH 2 (PO 3 )(PO 3 H)]} (Uphen). The crystal structures of the compounds are based on UO 7 units linked by methylenediphosphonate molecules to form two-dimensional anionic sheets in Ubip2 and UDAB, and one-dimensional anionic chains in Uethyl and Uphen, which are charge balanced by protonated amine molecules. Interaction of the amine molecules with phosphonate oxygens and water molecules results in extensive hydrogen bonding in the interlayer. These amine molecules serve both as structure-directing agents and charge-balancing cations for the anionic uranium phosphonate sheets and chains in the formation of the different coordination geometries and topologies of each structure. Reported herein are the syntheses, structural and spectroscopic characterization of the synthesized compounds. - Graphical abstract: The Raman spectra of the synthesized compounds and an illustration of the stacking of the layers with the diprotonated triethylenediamine molecules in [C 6 H 14 N 2 ]{(UO 2 ) 2 [CH 2 (PO 3 )(PO 3 H)] 2 ·2H 2 O} UDAB. Solvent water molecules are removed for clarity. The corresponding Raman spectra for the complexes synthesized is also shown. The structure is constructed from UO 7 pentagonal bipyramids (yellow), oxygen=red, phosphorus=magenta, carbon=black, and nitrogen=blue. Highlights: ► Organic amines act both as charge-balancing and as structure-directing agents. ► Extensive hydrogen bonding interactions with solvent water molecules and amines

Pyruvic Oxime Nitrification and Copper and Nickel Resistance by a Cupriavidus pauculus, an Active Heterotrophic Nitrifier-Denitrifier

OpenAIRE

Ramirez, Miguel; Obrzydowski, Jennifer; Ayers, Mary; Virparia, Sonia; Wang, Meijing; Stefan, Kurtis; Linchangco, Richard; Castignetti, Domenic

2014-01-01

Heterotrophic nitrifiers synthesize nitrogenous gasses when nitrifying ammonium ion. A Cupriavidus pauculus, previously thought an Alcaligenes sp. and noted as an active heterotrophic nitrifier-denitrifier, was examined for its ability to produce nitrogen gas (N2) and nitrous oxide (N2O) while heterotrophically nitrifying the organic substrate pyruvic oxime [CH3–C(NOH)–COOH]. Neither N2 nor N2O were produced. Nucleotide and phylogenetic analyses indicated that the organism is a member of a g...

Aqueous amine solution characterization for post-combustion CO_2 capture process

International Nuclear Information System (INIS)

El Hadri, Nabil; Quang, Dang Viet; Goetheer, Earl L.V.; Abu Zahra, Mohammad R.M.

2017-01-01

Highlights: • The CO_2 solubility of 30 aqueous amine solutions was measured at 30 wt% and 313.15 K. • The CO_2 loading of HMD is the highest, and that of TEA is the lowest. • 2DMAE, 3DMA1P, 1DMA2P, MDEA, TMPAD and 2EAE have a low heat of absorption with CO_2. • 2EAE can be used as an alternative to MEA in the CO_2 capture process. - Abstract: This article presents a thermodynamic and kinetic characterization of CO_2 absorption by 30 aqueous amine solutions. A solvent screening setup (S.S.S.) was used to find the CO_2 loading (α) for 30 different aqueous amine solutions (30 wt%) at a pressure of 1 bar with feed gas containing 15 vol% CO_2 and 85 vol% N_2 at 313.15 K to provide reliable absorber parameters. The structures of various amines (linear, non-linear, polyamines, sterically hindered, etc.) were tested and the S.S.S. results showed that hexamethylenediamine (HMD) has higher CO_2 loading at 1.35 moles of CO_2/mole of amine, and triethanolamine (TEA) has the lowest at 0.39 mole of CO_2/mole of amine. The heat of absorption indicates that MDEA has the lowest and HMD has the highest at −52.51 kJ/mole of CO_2 and −98.39 kJ/mole of CO_2, respectively. The combined data for the CO_2 loading and the absorption heat generated 6 amines that have good properties for the post-combustion CO_2 capture process in comparison with that of MEA. These amines are made up of one secondary amine (2-ethylaminoethanol, 2EAE) and 5 tertiary amines (N-methyldiethanolamine, MDEA, 1-dimethylamino-2-propanol, 1DMA2P, 2-dimethylaminoethanol, 2DMAE, 3-dimethylamino-1-propanol, 3DMA1P and N,N,N′,N′-tetramethyl-1,3-propanediamine, TMPDA). In comparison with the amine reference MEA (ΔH = −85.13 kJ/mole of CO_2 and α = 0.58 mole CO_2/mole of amine), the 6 amines have heats of absorption that are between −68.95 kJ/mole of CO_2 and −52.51 kJ/mole of CO_2, and their CO_2 loading is between 0.52 and 1.16 mole of CO_2/mole amine. The third important parameter, namely the

Amine Functionalized Porous Network

KAUST Repository

Eddaoudi, Mohamed; Guillerm, Vincent; Weselinski, Lukasz Jan; Alkordi, Mohamed H.; Mohideen, Mohamed Infas Haja; Belmabkhout, Youssef

2015-01-01

Amine groups can be introduced in porous materials by a direct (one pot) or post-synthetic modification (PSM) process on aldehyde groups, and the resulting porous materials have increased gas affinity.

Amine Functionalized Porous Network

KAUST Repository

Eddaoudi, Mohamed

2015-05-28

Amine groups can be introduced in porous materials by a direct (one pot) or post-synthetic modification (PSM) process on aldehyde groups, and the resulting porous materials have increased gas affinity.

Monomers for thermosetting and toughening epoxy resins. [glycidyl amine derivatives, propargyl-containing amines, and mutagenic testing of aromatic diamines

Science.gov (United States)

Pratt, J. R.

1981-01-01

Eight glycidyl amines were prepared by alkylating the parent amine with epichlorohydrin to form chlorohydrin, followed by cyclization with aqueous NaOH. Three of these compounds contained propargyl groups with postcuring studies. A procedure for quantitatively estimating the epoxy content of these glycidyl amines was employed for purity determination. Two diamond carbonates and several model propargly compounds were prepared. The synthesis of three new diamines, two which contain propargyloxy groups, and another with a sec-butyl group is in progress. These materials are at the dinitro stage ready for the final hydrogenation step. Four aromatic diamines were synthesized for mutagenic testing purposes. One of these compounds rapidly decomposes on exposure to air.

Nitrile-functionalized tertiary amines as highly efficient and reversible SO2 absorbents

International Nuclear Information System (INIS)

Hong, Sung Yun; Kim, Heehwan; Kim, Young Jin; Jeong, Junkyo; Cheong, Minserk; Lee, Hyunjoo; Kim, Hoon Sik; Lee, Je Seung

2014-01-01

Highlights: • Nitrile-functionalized tertiary amines physically and reversibly absorb SO 2 . • Tertiary alkanolamines chemically and irreversibly absorb SO 2 through OH group. • SO 2 absorption modes were studied by spectroscopy and computational calculations. -- Abstract: Three different types of nitrile-functionalized amines, including 3-(N,N-diethylamino)propionitrile (DEAPN), 3-(N,N-dibutylamino)propionitrile (DBAPN), and N-methyl-N,N-dipropionitrile amine (MADPN) were synthesized, and their SO 2 absorption performances were evaluated and compared with those of hydroxy-functionalized amines such as N,N-diethyl-N-ethanol amine (DEEA), N,N-dibutyl-N-ethanol amine (DBEA), and N-methyl-N,N-diethanol amine (MDEA). Absorption–desorption cycle experiments clearly demonstrate that the nitrile-functionalized amines are more efficient than the hydroxy-functionalized amines in terms of absorption rate and regenerability. Computational calculations with DBEA and DBAPN revealed that DBEA bearing a hydroxyethyl group chemically interacts with SO 2 through oxygen atom, forming an ionic compound with a covalently bound -OSO 2 − group. On the contrary, DBAPN bearing a nitrile group physically interacts with SO 2 through the nitrogen and the hydrogen atoms of the two methylene groups adjacent to the amino and nitrile functionalities

Production of biogenic amines in "Salamini italiani alla cacciatora PDO".

Science.gov (United States)

Coı X0308 Sson, Jean Daniel; Cerutti, Caterina; Travaglia, Fabiano; Arlorio, Marco

2004-06-01

Various fermented and seasoned foods such as cheese, sauerkraut, wine, beer and meat products may contain biogenic amines. The aim of this paper was to describe the presence of some biogenic amines (histamine, tyramine, tryptamine, 2-phenylethylamine) in "Salamini italiani alla cacciatora PDO", a typical fermented-ripened dry sausage widely consumed in Italy. Total level of biogenic amines in commercial samples ranged from 71 to 586 mg kg(-1). The amine recovered in higher concentrations was tyramine (372 mg kg(-1)) followed by histamine (165 mg kg(-1)). The second aim of this work was the quality control of the production in order to determine the parameters influencing the presence of biogenic amines in ripened salami. Sausages sampled for analysis during production, manipulation and ripening showed the presence of tyramine (64.4 mg kg(-1)) only after 15 days of fermentation. All investigated biogenic amines were detected in "Salamini" after 21 days of fermentation. We suggest the control of biogenic as important tool to establish the better condition of preservation of "Salamini italiani alla cacciatore PDO" during their shelf-life.

Thermodynamic study of (heptane + amine) mixtures. III: Excess and partial molar volumes in mixtures with secondary, tertiary, and cyclic amines at 298.15 K

International Nuclear Information System (INIS)

Lepori, Luciano; Gianni, Paolo; Spanedda, Andrea; Matteoli, Enrico

2011-01-01

Graphical abstract: Highlights: → Excess volumes of (sec., tert., or cyclic amines + heptane) mixtures. → Excess volumes are positive for small size amines and decrease as the size increases. → Group contributions to predict the partial molar volumes of amines in heptane. → The void volume is larger for sec. and tert. than for linear amines in heptane. → The void volume is much smaller for cyclic than for linear amines in heptane. - Abstract: Excess molar volumes V E at 298.15 K were determined by means of a vibrating tube densimeter for binary mixtures of {heptane + open chain secondary (diethyl to dibutyl) and tertiary (triethyl to tripentyl) amines} as well as for cyclic imines (C 2 , C 3 , C 4 , C 6 , and C 7 ) and primary cycloalkylamines (C 5 , C 6 , C 7 , and C 12 ). The V E values were found positive for mixtures involving small size amines, with V E decreasing as the size increases. Negative V E 's were found for tributyl- and tripentylamine, heptamethylenimine, and cyclododecylamine. Mixtures of heptane with cycloheptylamine showed an s-shaped curve. Partial molar volumes V 0 of amines at infinite dilution in heptane were obtained from V E and compared with V 0 of hydrocarbons and other classes of organic compounds taken from literature. An additivity scheme, based on the intrinsic volume approach, was applied to estimate group (CH 3 , CH 2 , CH, C, NH 2 , NH, N, OH, O, CO, and COO) contributions to V 0 . These contributions, the effect of cyclization on V 0 , and the limiting slope of the apparent excess molar volumes were discussed in terms of solute-solvent and solute-solute interactions.

New insights into controlling tube-bundle fouling using alternative amines

International Nuclear Information System (INIS)

Turner, C.W.; Klimas, S.J.; Guzonas, D.A.; Frattini, P.L.; Fruzzetti, K.

2002-01-01

A volatile amine is added to the secondary heat-transport system of a nuclear power plant to reduce the rate of corrosion and corrosion product transport in the feedwater and to protect steam generator (SG) crevices and materials exposed to steam condensate. Volatility and base strength of the amine at the SG operating temperature are two important considerations when choosing the optimum amine (or mixture of amines) for corrosion control in the steam cycle. Atomic Energy of Canada Limited (AECL) and Electric Power Research Institute (EPRI) have been collaborating in an extensive investigation of the effectiveness of amines at controlling the rate of tube-bundle fouling under SG operating conditions. Tests have been performed using a radiotracing technique in a high-temperature fouling loop facility at Chalk River Laboratories operated by AECL. This investigation has provided new insights into the role played by the amine in determining the rate of tube-bundle fouling in the SG. These insights are being used by AECL and EPRI to develop criteria for the selection of an amine that has optimum properties for both corrosion control and deposit control in the secondary heat transport system. The investigation has found that the rate of tube-bundle fouling is strongly dependent upon the surface chemistry of the corrosion products. For example, the fouling rates of fully oxidized iron oxides, such as hematite and lepidocrocite, are at least an order of magnitude greater than the fouling rate of magnetite under identical operating conditions. The difference is related to the sign of the surface charge on the corrosion products at temperature. The choice of amine for pH-control also influences the fouling rate. This was originally thought to be a surface-charge effect as well, but recent tests have suggested that it is related to the role that the amine plays in governing the rate of deposit consolidation on the heat-transfer surface. Amines that promote a high rate of

Production of Primary Amines by Reductive Amination of Biomass-Derived Aldehydes/Ketones.

Science.gov (United States)

Liang, Guanfeng; Wang, Aiqin; Li, Lin; Xu, Gang; Yan, Ning; Zhang, Tao

2017-03-06

Transformation of biomass into valuable nitrogen-containing compounds is highly desired, yet limited success has been achieved. Here we report an efficient catalyst system, partially reduced Ru/ZrO 2 , which could catalyze the reductive amination of a variety of biomass-derived aldehydes/ketones in aqueous ammonia. With this approach, a spectrum of renewable primary amines was produced in good to excellent yields. Moreover, we have demonstrated a two-step approach for production of ethanolamine, a large-market nitrogen-containing chemical, from lignocellulose in an overall yield of 10 %. Extensive characterizations showed that Ru/ZrO 2 -containing multivalence Ru association species worked as a bifunctional catalyst, with RuO 2 as acidic promoter to facilitate the activation of carbonyl groups and Ru as active sites for the subsequent imine hydrogenation. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Extraction separation studies of uranium(VI) by amine oxides

International Nuclear Information System (INIS)

Ejaz, M.

1975-01-01

The extraction of uranium(VI) by two amine oxides, 4-(5-nonyl)pyridine oxide and trioctylamine oxide has been studied. The extraction behavior of these two N-oxides is compared. The dependence of extraction on the type of amine oxide and acid, nature of organic diluent, and amine oxide concentration has been investigated. The influence of the concentration of the metal and salting-out agents is described. The possible mechanism of extraction is discussed in the light of the results of extraction isotherms, loading radiodata, and log-log plots of amine oxide concentration vs distribution ratio. The separation factors for a number of metal ions are reported, and the separation of uranium from some fission elements has also been achieved

Effect of donor orientation on ultrafast intermolecular electron transfer in coumarin-amine systems

International Nuclear Information System (INIS)

Singh, P. K.; Nath, S.; Bhasikuttan, A. C.; Kumbhakar, M.; Mohanty, J.; Sarkar, S. K.; Mukherjee, T.; Pal, H.

2008-01-01

Effect of donor amine orientation on nondiffusive ultrafast intermolecular electron transfer (ET) reactions in coumarin-amine systems has been investigated using femtosecond fluorescence upconversion measurements. Intermolecular ET from different aromatic and aliphatic amines used as donor solvents to the excited coumarin-151 (C151) acceptor occurs with ultrafast rates such that the shortest fluorescence lifetime component (τ 1 ) is the measure of the fastest ET rate (τ 1 =τ ET fast =(k ET fast ) -1 ), assigned to the C151-amine contact pairs in which amine donors are properly oriented with respect to C151 to maximize the acceptor-donor electronic coupling (V el ). It is interestingly observed that as the amine solvents are diluted by suitable diluents (either keeping solvent dielectric constant similar or with increasing dielectric constant), the τ 1 remains almost in the similar range as long as the amine dilution does not cross a certain critical limit, which in terms of the amine mole fraction (x A ) is found to be ∼0.4 for aromatic amines and ∼0.8 for aliphatic amines. Beyond these dilutions in the two respective cases of the amine systems, the τ 1 values are seen to increase very sharply. The large difference in the critical x A values involving aromatic and aliphatic amine donors has been rationalized in terms of the largely different orientational restrictions for the ET reactions as imposed by the aliphatic (n-type) and aromatic (π-type) nature of the amine donors [A. K. Satpati et al., J. Mol. Struct. 878, 84 (2008)]. Since the highest occupied molecular orbital (HOMO) of the n-type aliphatic amines is mostly centralized at the amino nitrogen, only some specific orientations of these amines with respect to the close-contact acceptor dye [also of π-character; A. K. Satpati et al., J. Mol. Struct. 878, 84 (2008) and E. W. Castner et al., J. Phys. Chem. A 104, 2869 (2000)] can give suitable V el and thus ultrafast ET reaction. In contrary, the

Surface Modification of Zinc with an Oxime for Corrosion Protection in Chloride Medium

Directory of Open Access Journals (Sweden)

Ganesha Achary

2013-01-01

Full Text Available The surface treatment of zinc was done with different concentrations of an oxime (2E-2-(hydroxylamino-1,2-diphenylethanol molecule by the immersion method. The electrochemical corrosion studies of surface-treated zinc specimens were performed in aqueous sodium chloride solution (1 M, pH 5.0 at different temperatures in order to study the corrosion mechanism. The recorded electrochemical data indicated a basic modification of the cathodic corrosion behavior of the treated zinc resulting in a decrease of the electron transfer rate. The zinc samples treated by immersion in the inhibiting organic solution presented good corrosion resistance. Using scanning electron microscopy (SEM, it was found that a protective film was formed on the surface of zinc.

Nitrile-functionalized tertiary amines as highly efficient and reversible SO2 absorbents.

Science.gov (United States)

Hong, Sung Yun; Kim, Heehwan; Kim, Young Jin; Jeong, Junkyo; Cheong, Minserk; Lee, Hyunjoo; Kim, Hoon Sik; Lee, Je Seung

2014-01-15

Three different types of nitrile-functionalized amines, including 3-(N,N-diethylamino)propionitrile (DEAPN), 3-(N,N-dibutylamino)propionitrile (DBAPN), and N-methyl-N,N-dipropionitrile amine (MADPN) were synthesized, and their SO2 absorption performances were evaluated and compared with those of hydroxy-functionalized amines such as N,N-diethyl-N-ethanol amine (DEEA), N,N-dibutyl-N-ethanol amine (DBEA), and N-methyl-N,N-diethanol amine (MDEA). Absorption-desorption cycle experiments clearly demonstrate that the nitrile-functionalized amines are more efficient than the hydroxy-functionalized amines in terms of absorption rate and regenerability. Computational calculations with DBEA and DBAPN revealed that DBEA bearing a hydroxyethyl group chemically interacts with SO2 through oxygen atom, forming an ionic compound with a covalently bound OSO2(-) group. On the contrary, DBAPN bearing a nitrile group physically interacts with SO2 through the nitrogen and the hydrogen atoms of the two methylene groups adjacent to the amino and nitrile functionalities. Copyright © 2013 Elsevier B.V. All rights reserved.

Detection of homing-in of stem cells labeled with technetium-99m hexamethylpropyleneamine oxime in infarcted myocardium after intracoronary injection

International Nuclear Information System (INIS)

Patel, Chetan D; Agarwal, Snehlata; Seth, Sandeep; Mohanty, Sujata; Aggarwal, Himesh; Gupta, Namit

2014-01-01

Bone marrow stem cells having myogenic potential are promising candidates for various cell-based therapies for myocardial disease. We present here images showing homing of technetium-99m (Tc-99m) hexamethylpropyleneamine oxime (HMPAO) labeled stem cells in the infarcted myocardium from a pilot study conducted to radio-label part of the stem cells in patients enrolled in a stem cell clinical trial for recent myocardial infarction

Metal-Mediated Couplings of Primary Alcohols with Amines and Carbohydrates

DEFF Research Database (Denmark)

Maggi, Agnese; Madsen, Robert

. The reaction is proposed to proceed by initial dehydrogenation of the alcohol to the aldehyde, which stays coordinated to the ruthenium centre. Then, nucleophilic attack of the amine affords the hemiaminal, which is released from ruthenium and converted into the imine. Project 2: Tin-mediated regioselective 6...... from alcohols and amines catalyzed by a ruthenium N-heterocyclic carbene complex. The successful method development and application of a convenient and direct (one step) synthesis of imines from alcohols and amines is described. The developed method provides quick andextended access to structurally...... and amines have been coupled in the presence of the catalyst to afford the corresponding imines in moderate to good yields. Optically pure amines gave the corresponding imines without any sign of racemization. Moreover, the one-pot diastereoselective addition of different organometallic reagents to the imine...

Chromosomal localization of the human vesicular amine transporter genes

Energy Technology Data Exchange (ETDEWEB)

Peter, D.; Finn, P.; Liu, Y.; Roghani, A.; Edwards, R.H.; Klisak, I.; Kojis, T.; Heinzmann, C.; Sparkes, R.S. (UCLA School of Medicine, Los Angeles, CA (United States))

1993-12-01

The physiologic and behavioral effects of pharmacologic agents that interfere with the transport of monoamine neurotransmitters into vesicles suggest that vesicular amine transport may contribute to human neuropsychiatric disease. To determine whether an alteration in the genes that encode vesicular amine transport contributes to the inherited component of these disorders, the authors have isolated a human cDNA for the brain transporter and localized the human vesciular amine transporter genes. The human brain synaptic vesicle amine transporter (SVAT) shows unexpected conservation with rat SVAT in the regions that diverge extensively between rat SVAT and the rat adrenal chromaffin granule amine transporter (CGAT). Using the cloned sequences with a panel of mouse-human hybrids and in situ hybridization for regional localization, the adrenal CGAT gene (or VAT1) maps to human chromosome 8p21.3 and the brain SVAT gene (or VAT2) maps to chromosome 10q25. Both of these sites occur very close to if not within previously described deletions that produce severe but viable phenotypes. 26 refs., 3 figs., 1 tab.

Ozone Promotes Chloropicrin Formation by Oxidizing Amines to Nitro Compounds.

Science.gov (United States)

McCurry, Daniel L; Quay, Amanda N; Mitch, William A

2016-02-02

Chloropicrin formation has been associated with ozonation followed by chlorination, but the reaction pathway and precursors have been poorly characterized. Experiments with methylamine demonstrated that ozonation converts methylamine to nitromethane at ∼100% yield. Subsequent chlorination converts nitromethane to chloropicrin at ∼50% yield under the conditions evaluated. Similarly high yields from other primary amines were limited to those with functional groups on the β-carbon (e.g., the carboxylic acid in glycine) that facilitate carbon-carbon bond cleavage to release nitromethyl anion. Secondary amines featuring these reactive primary amines as functional groups (e.g., secondary N-methylamines) formed chloropicrin at high yields, likely by facile dealkylation to release the primary nitro compound. Chloropicrin yields from tertiary amines were low. Natural water experiments, including derivatization to transform primary and secondary amines to less reactive carbamate functional groups, indicated that primary and secondary amines were the dominant chloropicrin precursors during ozonation/chlorination. Ozonation followed by chlorination of the primary amine side chain of lysine demonstrated low yields (∼0.2%) of chloropicrin, but high yields (∼17%) of dichloronitrolysine, a halonitroalkane structural analogue to chloropicrin. However, chloropicrin yields increased and dichloronitrolysine yields decreased in the absence of hydroxyl radical scavengers, suggesting that future research should characterize the potential occurrence of such halonitroalkane analogues relative to natural radical scavenger (e.g., carbonate) concentrations.

Characterization of particulate amines

International Nuclear Information System (INIS)

Gundel, L.A.; Chang, S.G.; Clemenson, M.S.; Markowitz, S.S.; Novakov, T.

1979-01-01

The reduced nitrogen compounds associated with ambient particulate matter are chemically characterized by means of ESCA and proton activation analysis. Ambient particulate samples collected on silver filters in Berkeley, California were washed with water and organic solvents, and ESCA and proton activation analysis were performed in order to determine the composition of various nitrogen compounds and the total nitrogen content. It is found that 85% of the amines originally present in ambient particulate matter can be removed by water extraction, whereas the ammonium and nitrate are completely removed. An observed increase in ammonium ion in the extract, compared with its concentration in the original sample, coupled with the commensurate decrease in amine concentration, is attributed to the hydrolysis of amide groups, which may cause analytical methods based on extraction to yield erroneous results

The ozonolysis of primary aliphatic amines in fine particles

Science.gov (United States)

Zahardis, J.; Geddes, S.; Petrucci, G. A.

2008-02-01

The oxidative processing by ozone of the particulate amines octadecylamine (ODA) and hexadecylamine (HDA) is reported. Ozonolysis of these amines resulted in strong NO2- and NO3- ion signals that increased with ozone exposure as monitored by photoelectron resonance capture ionization aerosol mass spectrometry. These products suggest a mechanism of progressive oxidation of the particulate amines to nitroalkanes. Additionally, a strong ion signal at 125 m/z is assigned to the ion NO3- (HNO3). For ozonized mixed particles containing ODA or HDA + oleic acid (OL), with pO3≥3×10-7 atm, imine, secondary amide, and tertiary amide products were measured. These products most likely arise from reactions of amines with aldehydes (for imines) and stabilized Criegee intermediates (SCI) or secondary ozonides (for amides) from the fatty acid. The routes to amides via SCI and/or secondary ozonides were shown to be more important than comparable amide forming reactions between amines and organic acids, using azelaic acid as a test compound. Finally, direct evidence is provided for the formation of a surface barrier in the ODA + OL reaction system that resulted in the retention of OL at high ozone exposures (up to 10-3 atm for 17 s). This effect was not observed in HDA + OL or single component OL particles, suggesting that it may be a species-specific surfactant effect from an in situ generated amide or imine. Implications to tropospheric chemistry, including particle bound amines as sources of oxidized gas phase nitrogen species (e.g.~NO2, NO3), formation of nitrogen enriched HULIS via ozonolysis of amines and source apportionment are discussed.

Amine-selective bioconjugation using arene diazonium salts.

Science.gov (United States)

Diethelm, Stefan; Schafroth, Michael A; Carreira, Erick M

2014-08-01

A novel bioconjugation strategy is presented that relies on the coupling of diazonium terephthalates with amines in proteins. The diazonium captures the amine while the vicinal ester locks it through cyclization, ensuring no reversibility. The reaction is highly efficient and proceeds under mild conditions and short reaction times. Densely functionalized, complex natural products were directly coupled to proteins using low concentrations of coupling partners.

Construction of New Potential Reactivators of Phosphonylated Acetylcholinesterase. Substitution of F for H in the Nucleus of Pyridinecarboxaldehyde Oximes.

Science.gov (United States)

1983-11-01

essential to the content of the re- port and in all cases NMR data subjected to interpretation in this report have been entered in typography to...compared. In the Second Quarter reactions in the synthetic pathway to 3-F-2-PAM were scaled-up. Low yields were encountered for the specific nitration...oxime was synthetically achieved by way of the Markovac-Stevens-Ash-Hackley reaction , and the compound was characterized by its mass spectrum, NMR

STUDIES ON VINYL POLYMERIZATION WITH INITIATION SYSTEM CONTAINING AMINE DERIVATIVES

Institute of Scientific and Technical Information of China (English)

QIU Kunyuan; ZHANG Jingyi; FENG Xinde(S. T. Voong)

1983-01-01

Two main types of amine-containing initiation systems were studied in this work. In the case of MMA polymerization initiated by BPO-amine (DMT, DHET, DMA) redox systems, it was found that the polymerization rate and colour stability of the polymer for different amine systems were in the following order: DMT≈DHET＞DMA. Accordingly, BPO-DMT and BPO-DHET are effective initiators. In the case of MEMA polymerization by amine (DMT, DHET, DMA) alone, it was found that the polymerization rate and the percentage of conversion for these different amine systems were in the following order: DMT≥DHET＞DMA. The polymerization rate and the percentage of conversion also increased with the increase of DMT concentration. From the kinetic investigation the rate equation of Rp=K [DMT]1/2 [MEMA]3/2 was obtained, and the overall activation energy of polymerization was calculated to be 34.3 KJ/mol (8.2 Kcal/mol). Moreover, the polymerization of MEMA in the presence of DMT was strongly inhibited by hydroquinone, indicating the polymerization being free radical in nature. From these results, the mechanism of MEMA polymerization initiated by amine was proposed.

Redox self-sufficient whole cell biotransformation for amination of alcohols.

Science.gov (United States)

Klatte, Stephanie; Wendisch, Volker F

2014-10-15

Whole cell biotransformation is an upcoming tool to replace common chemical routes for functionalization and modification of desired molecules. In the approach presented here the production of various non-natural (di)amines was realized using the designed whole cell biocatalyst Escherichia coli W3110/pTrc99A-ald-adh-ta with plasmid-borne overexpression of genes for an l-alanine dehydrogenase, an alcohol dehydrogenase and a transaminase. Cascading alcohol oxidation with l-alanine dependent transamination and l-alanine dehydrogenase allowed for redox self-sufficient conversion of alcohols to the corresponding amines. The supplementation of the corresponding (di)alcohol precursors as well as amino group donor l-alanine and ammonium chloride were sufficient for amination and redox cofactor recycling in a resting buffer system. The addition of the transaminase cofactor pyridoxal-phosphate and the alcohol dehydrogenase cofactor NAD(+) was not necessary to obtain complete conversion. Secondary and cyclic alcohols, for example, 2-hexanol and cyclohexanol were not aminated. However, efficient redox self-sufficient amination of aliphatic and aromatic (di)alcohols in vivo was achieved with 1-hexanol, 1,10-decanediol and benzylalcohol being aminated best. Copyright © 2014 Elsevier Ltd. All rights reserved.

Base metal dehydrogenation of amine-boranes

Science.gov (United States)

Blacquiere, Johanna Marie [Ottawa, CA; Keaton, Richard Jeffrey [Pearland, TX; Baker, Ralph Thomas [Los Alamos, NM

2009-06-09

A method of dehydrogenating an amine-borane having the formula R.sup.1H.sub.2N--BH.sub.2R.sup.2 using base metal catalyst. The method generates hydrogen and produces at least one of a [R.sup.1HN--BHR.sup.2].sub.m oligomer and a [R.sup.1N--BR.sup.2].sub.n oligomer. The method of dehydrogenating amine-boranes may be used to generate H.sub.2 for portable power sources, such as, but not limited to, fuel cells.

Systems of cerium(3) nitrate-dimethyl amine nitrate-water and cerium(3) nitrate-dimethyl amine nitrate-water

International Nuclear Information System (INIS)

Mininkov, N.E.; Zhuravlev, E.F.

1976-01-01

Solubility of solid phases in the systems cerium(3)nitrate-water-dimethyl amine nitrate and cerium(3)nitrate-water-dimethyl amine nitrate has been st ed by the method of isothermal sections at 25 and 50 deo. C. It has been shown that one anhydrous compound is formed in each system with a ratio of cerium(3) nitrate to amine nitrate 1:5. The compounds formed in the systems have been separated from the corresponding solutions and studied by microcrystalloscopic, X-ray phase, thermal and infrared spectroscopic methods. On the basis of spectroscopic studies the following formula has been assigned to the compound: [(CH 3 ) 2 NH 2 + ] 5 x[Ce(NO 3 ) 8 ]. The thermal analysis of the compound has shown that its melting point is 106 deg C. The solubility isotherms in the system Ce(NO 3 ) 3 -H 2 O-(C 2 H 5 ) 2 NHxHNO 3 consist of three branches which intersect in two eutonic points

Extraction of some acids using aliphatic amines

International Nuclear Information System (INIS)

Matutano, L.

1964-06-01

Hydrochloric, nitric, sulphuric, perchloric, phosphoric, acetic and formic acids in aqueous solution (0.05 to 10 M) are extracted by amberlite LA2 and trilaurylamine in solution, 5 per cent by volume, in kerosene and xylene respectively. The extraction process consists of: neutralization of the amine salt; a 'molecular extraction', i.e. an extraction using an excess of acid with respect to the stoichiometry of the amine salt. According to the behaviour of the acid during the extraction, three groups may be distinguished: completely dissociated acids, carboxylic acids, phosphoric acid. This classification is also valid for the extraction of the water which occurs simultaneously with that of the acid. An extraction mechanism is put forward for formic acid and the formation constant of its amine salt is calculated. (author) [fr

40 CFR 721.3620 - Fatty acid amine condensate, polycarboxylic acid salts.

Science.gov (United States)

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Fatty acid amine condensate... Specific Chemical Substances § 721.3620 Fatty acid amine condensate, polycarboxylic acid salts. (a... a fatty acid amine condensate, polycarboxylic acid salts. (PMN P-92-445) is subject to reporting...

Purity of antidotal oxime HI-6 DMS as an active pharmaceutical ingredient for auto-injectors and infusions.

Science.gov (United States)

Bogan, Reinhard; Koller, Marianne; Klaubert, Bernd

2012-01-01

As reactivators of inhibited acetylcholinesterase, oximes are essential antidotes in poisoning by organophosphorus compounds. Due to its superior efficacy in cases of soman, cyclosarin, and sarin poisoning, the oxime HI-6 represents a promising option for an active pharmaceutical ingredient (API) in the further development of antidote therapy for nerve agent poisoning. Developmental lots of HI-6 DMS (dimethanesulfonate) provided by different manufacturers were examined with respect to their content and purity with a view to their future use as an API. There are distinct differences in the HI-6 content from three manufacturers. With respect to purity, gradual differences arise with the known synthetic by-products as well as with unknown accompanying compounds. It became apparent that in the case of a modified synthesis using protective groups, the proportion of some synthesis by-products decreases considerably. With one exception, they are thus below the reporting threshold for API in accordance with pertinent regulatory guidelines. In HI-6, an unknown impurity always occurs, whose percentage necessitates identification due to regulations. This unknown impurity, which has not been described so far, could be identified as an isomer. These findings supply data required for the description of pharmaceutical quality in accordance with module 3 of a Common Technical Document (CTD). They thus contribute to the marketing authorization of this substance as an API for auto-injectors and infusions. Copyright © 2012 John Wiley & Sons, Ltd.

Boron-Catalyzed N-Alkylation of Amines using Carboxylic Acids.

Science.gov (United States)

Fu, Ming-Chen; Shang, Rui; Cheng, Wan-Min; Fu, Yao

2015-07-27

A boron-based catalyst was found to catalyze the straightforward alkylation of amines with readily available carboxylic acids in the presence of silane as the reducing agent. Various types of primary and secondary amines can be smoothly alkylated with good selectivity and good functional-group compatibility. This metal-free amine alkylation was successfully applied to the synthesis of three commercial medicinal compounds, Butenafine, Cinacalcet. and Piribedil, in a one-pot manner without using any metal catalysts. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Development of lyophilized kit of Tin-Glucoheptonate for in vitro labeling of leucocytes with {sup 99m}Tc; Desenvolvimento de reagente liofilizado de glucoheptonato-estanho para marcacao de leucocitos com Tecnecio-99m in vitro

Energy Technology Data Exchange (ETDEWEB)

Nascimento, Rosemeire Fagundes

2007-07-01

The study and localization of inflammatory and infection process in Nuclear Medicine represents a relevant tool in diagnostic procedures. In same cases, the diagnostic is easy and based on anamnesis and clinical observation; in other cases, the patients are asymptomatic or present non specific symptoms that difficult the diagnostic. The early diagnostic of inflammatory or infectious process allow the early introduction of therapy and prevents complications. Farther, the differentiation between inflammation and infection is of extreme importance as well as the localization of the focus. The use of labeled leucocytes, studied and applied in much pathologies, is the method of choice for the visualization of inflammation and infection. The scintigraphy using labeled leucocytes was introduced at 1976 by McAffe and Thakur and since of this is used in the diagnostic of different pathologies related to leucocyte infiltration like intestinal inflammatory disease, bone or prosthetic-vascular infections. The in vitro labeling of leucocytes with {sup 111}In was performed using oxime or tropolone as ligand and with {sup 99m}Tc using hexamethylpropylene amine oxime (HMPAO) as ligand, resulting in a lipophilic complex. The {sup 99m}Tc-HMPAG complex was preferably employed in many indications and countries do to the ideal physical properties of {sup 99m}Tc that results in low dose to the patient. However, the labeling employing the HMPAO complex results in some disadvantages like the low stability of the complex, and some requirements related to the {sup 99m}Tc elution (like the time pos elution), beyond the high cost of the compound that is imported. The aim of this work was the development of a tin-glucoheptonate lyophilized kit for in vitro leucocytes labeling with {sup 99m}Tc using the pre-stannization method. The optimization of the labeling technique was developed using leucocytes isolated from total blood and employing different volumes of the tinglucoheptonate reagent and

Conversion of alcohols to enantiopure amines through dual-enzyme hydrogen-borrowing cascades.

Science.gov (United States)

Mutti, Francesco G; Knaus, Tanja; Scrutton, Nigel S; Breuer, Michael; Turner, Nicholas J

2015-09-25

α-Chiral amines are key intermediates for the synthesis of a plethora of chemical compounds at industrial scale. We present a biocatalytic hydrogen-borrowing amination of primary and secondary alcohols that allows for the efficient and environmentally benign production of enantiopure amines. The method relies on a combination of two enzymes: an alcohol dehydrogenase (from Aromatoleum sp., Lactobacillus sp., or Bacillus sp.) operating in tandem with an amine dehydrogenase (engineered from Bacillus sp.) to aminate a structurally diverse range of aromatic and aliphatic alcohols, yielding up to 96% conversion and 99% enantiomeric excess. Primary alcohols were aminated with high conversion (up to 99%). This redox self-sufficient cascade possesses high atom efficiency, sourcing nitrogen from ammonium and generating water as the sole by-product. Copyright © 2015, American Association for the Advancement of Science.

Detection of cometary amines in samples returned by Stardust

Science.gov (United States)

Glavin, D. P.; Dworkin, J. P.; Sandford, S. A.

2008-02-01

The abundances of amino acids and amines, as well as their enantiomeric compositions, were measured in samples of Stardust comet-exposed aerogel and foil using liquid chromatography with UV fluorescence detection and time of flight mass spectrometry (LC-FD/ToF-MS). A suite of amino acids and amines including glycine, L-alanine, β-alanine (BALA), γ-amino-n-butyric acid (GABA), ɛ-amino-n-caproic acid (EACA), ethanolamine (MEA), methylamine (MA), and ethylamine (EA) were identified in acid-hydrolyzed, hot-water extracts of these Stardust materials above background levels. With the exception of MA and EA, all other primary amines detected in cometexposed aerogel fragments C2054,4 and C2086,1 were also present in the flight aerogel witness tile that was not exposed to the comet, indicating that most amines are terrestrial in origin. The enhanced relative abundances of MA and EA in comet-exposed aerogel compared to controls, coupled with MA to EA ratios (C2054,4: 1.0 ± 0.2; C2086,1: 1.8 ± 0.2) that are distinct from preflight aerogels (E243-13C and E243-13F: 7 ± 3), suggest that these volatile amines were captured from comet Wild 2. MA and EA were present predominantly in an acid-hydrolyzable bound form in the aerogel, rather than as free primary amines, which is consistent with laboratory analyses of cometary ice analog materials. It is possible that Wild 2 MA and EA were formed on energetically processed icy grains containing ammonia and approximately equal abundances of methane and ethane. The presence of cometary amines in Stardust material supports the hypothesis that comets were an important source of prebiotic organic carbon and nitrogen on the early Earth.

The ozonolysis of primary aliphatic amines in fine particles

Directory of Open Access Journals (Sweden)

J. Zahardis

2008-02-01

Full Text Available The oxidative processing by ozone of the particulate amines octadecylamine (ODA and hexadecylamine (HDA is reported. Ozonolysis of these amines resulted in strong NO₂^– and NO₃^– ion signals that increased with ozone exposure as monitored by photoelectron resonance capture ionization aerosol mass spectrometry. These products suggest a mechanism of progressive oxidation of the particulate amines to nitroalkanes. Additionally, a strong ion signal at 125 m/z is assigned to the ion NO₃^– (HNO₃. For ozonized mixed particles containing ODA or HDA + oleic acid (OL, with p_O3≥3×10^–7 atm, imine, secondary amide, and tertiary amide products were measured. These products most likely arise from reactions of amines with aldehydes (for imines and stabilized Criegee intermediates (SCI or secondary ozonides (for amides from the fatty acid. The routes to amides via SCI and/or secondary ozonides were shown to be more important than comparable amide forming reactions between amines and organic acids, using azelaic acid as a test compound. Finally, direct evidence is provided for the formation of a surface barrier in the ODA + OL reaction system that resulted in the retention of OL at high ozone exposures (up to 10⁻³ atm for 17 s. This effect was not observed in HDA + OL or single component OL particles, suggesting that it may be a species-specific surfactant effect from an in situ generated amide or imine. Implications to tropospheric chemistry, including particle bound amines as sources of oxidized gas phase nitrogen species (e.g.~NO₂, NO₃, formation of nitrogen enriched HULIS via ozonolysis of amines and source apportionment are discussed.

Increased rCBF in gray matter heterotopias detected by SPECT using 99mTc hexamethyl-propylenamine oxime

International Nuclear Information System (INIS)

Henkes, H.; Klinikum Rudolf Virchow, Berlin; Hosten, N.; Cordes, M.; Neumann, K.; Hansen, M.L.

1991-01-01

Imaging findings of morphology and regional cerebral blood flow in two patients suffering from epileptic seizures are presented. CT and MRI revealed heterotopic gray matter as a probable structural correlate, causing the seizure disorder. 99m Tc hexamethyl-propylenamine oxime (HM-PAO) SPECT demonstrated focally increased regional cerebral blood flow in both patients in the areas of their heterotopic lesions. Heterotopic and orthotopic gray matter seem to have similar features in terms of regional perfusion. A focally increased brain perfusion in interictal epileptic patients may indicate an underlying migration anomaly. (orig.)

Catalyst for hydrogen-amine D exchange

International Nuclear Information System (INIS)

Holtslander, W.J.; Johnson, R.E.

1976-01-01

A process is claimed for deuterium isotopic enrichment (suitable for use in heavy water production) by amine-hydrogen exchange in which the exchange catalyst comprises a mixture of alkyl amides of two metals selected from the group consisting of the alkali metals. Catalyst mixtures comprising at least one of the alkali amides of lithium and potassium are preferred. At least one of the following benefits are obtained: decreased hydride formation, decreased thermal decomposition of alkyl amide, increased catalyst solubility in the amine phase, and increased exchange efficiency. 11 claims

Influence of amine structure on the post-cured photo-yellowing of novel amine diacrylate terminated ultraviolet and electron beam cured coatings

International Nuclear Information System (INIS)

Allen, N.S.; Lo, D.

1990-01-01

The post ultraviolet (UV) and electron beam (EB) cured photo-yellowing of nine novel amine terminated diacrylate monomers has been compared with that of standard commercial diethylamine diacrylate monomer using second order derivative UV absorption spectroscopy. Whilst all the UV cured monomers exhibited an initial rapid growth in UV absorption followed by a rapid photo-bleaching, the EB cured monomers exhibited a very slow growth in absorption followed by a plateau and subsequent slow photo-bleaching. In the former case the residual benzophenone photo-initiator is sensitising the photo-yellowing reaction and its subsequent photo-bleaching. Differences in the rates may be determined by the nature of the exciplex between the terminal amine groups and the benzophenone initiator. With regard to the nature of the amine structure all the simple alkylamines exhibit the greatest degree of photo-yellowing whilst hydroxyl containing amines are generally lower. In the former case methylene hydrogen atoms alpha to the nitrogen atom are important for abstraction. Dicyclohexylamine provides the most stable monomer toward photo-yellowing due to the stability of the alpha methylene hydrogen atoms and steric hindrance by the two bulky cyclohexane rings towards the formation of conjugated chromophores. For the EB cured monomers the degree of photo-yellowing increases with increasing alkyl chain length of the amine group due to the increased possibility of the formation of conjugated chromophores. (author)

Structure and activity of Aspergillus nidulans copper amine oxidase

DEFF Research Database (Denmark)

McGrath, Aaron P; Mithieux, Suzanne M; Collyer, Charles A

2011-01-01

Aspergillus nidulans amine oxidase (ANAO) has the unusual ability among the family of copper and trihydroxyphenylalanine quinone-containing amine oxidases of being able to oxidize the amine side chains of lysine residues in large peptides and proteins. We show here that in common with the related...... enzyme from the yeast Pichia pastoris, ANAO can promote the cross-linking of tropoelastin and oxidize the lysine residues in α-casein proteins and tropoelastin. The crystal structure of ANAO, the first for a fungal enzyme in this family, has been determined to a resolution of 2.4 Å. The enzyme is a dimer...... with the archetypal fold of a copper-containing amine oxidase. The active site is the most open of any of those of the structurally characterized enzymes in the family and provides a ready explanation for its lysine oxidase-like activity....

Dynamic SPECT of the brain using a lipophilic technetium-99m complex, PnAO

DEFF Research Database (Denmark)

Holm, S; Andersen, A R; Vorstrup, S

1985-01-01

m PnAO was injected i.v. as a bolus of 15 to 25 mCi. The distribution was followed over 10-sec intervals using a highly sensitive, rapidly rotating SPECT (Tomomatic 64) and compared to 133Xe flow maps. Upon arrival of the PnAO bolus to the brain, a high uptake was found in brain tissue with high......The lipophilic 99mTc-labeled oxime propylene amine oxime (PnAO) should, according to recent reports behave like 133Xe in the human brain. This study compares SPECT images of the two tracers in six subjects: four stroke cases, one transitory ischemic attack case and one normal subject. Technetium-99......AO has a high yet incomplete brain extraction yielding a flow dominated initial distribution with limitations mentioned....

Yb(OTf){sub 3}-catalyzed one-pot three component synthesis for tertiary amines

Energy Technology Data Exchange (ETDEWEB)

Lee, Bum Seok; Kim, Ji Hye; Nam, Tae Kyu; Jang, Doo Ok [Dept. of Chemistry, Yonsei University, Wonju (Korea, Republic of)

2015-07-15

Tertiary amine functionality is found in many natural bioactive products such as alkaloids, amino acids, nucleic acids, pharmaceuticals, and agrochemicals. Tertiary amines have also been used as building blocks for nitrogen-containing organic compounds and synthetic polymers. A one-pot method for direct reductive amination of aldehydes has been developed to synthesize tertiary amines using HMDS as a nitrogen source in the presence of Yb(OTf ){sub 3}. With a stoichiometric amount of HMDS, the reaction afforded the desired tertiary amines without competitive reduction of the parent carbonyl compounds. This reaction offers a convenient and efficient protocol for synthesizing aromatic and aliphatic tertiary amines under mild reaction conditions.

SEDIMENT-ASSOCIATED REACTIONS OF AROMATIC AMINES. 2. QSAR DEVELOPMENT

Science.gov (United States)

The fate of aromatic amines in soils and sediments is dominated by irreversible binding through nucleophilic addition and oxidative radical coupling. Despite the common occurrence of the aromatic amine functional group in organic chemicals, the molecular properties useful for pr...

A method for the preparation of lipophilic macrocyclic technetium-99m complexes

International Nuclear Information System (INIS)

Troutner, D.E.; Volkert, W.A.

1991-01-01

A procedure for the preparation of technetium complexes applicable as diagnostic radiopharmaceuticals is suggested and documented with 27 examples. Technetium-99m is reacted with a suitable complexant selected from the class of alkylenamine oximes containing 2 or 3 carbon atoms in the alkylene group. The lipophilic macrocyclic complexes possess an amine, amide, carboxy, carboxy ester, hydroxy or alkoxy group or a suitable electron acceptor group. (M.D.). 7 tabs

Manganese-catalysed benzylic C(sp3)-H amination for late-stage functionalization.

Science.gov (United States)

Clark, Joseph R; Feng, Kaibo; Sookezian, Anasheh; White, M Christina

2018-06-01

Reactions that directly install nitrogen into C-H bonds of complex molecules are significant because of their potential to change the chemical and biological properties of a given compound. Although selective intramolecular C-H amination reactions are known, achieving high levels of reactivity while maintaining excellent site selectivity and functional-group tolerance remains a challenge for intermolecular C-H amination. Here, we report a manganese perchlorophthalocyanine catalyst [MnIII(ClPc)] for intermolecular benzylic C-H amination of bioactive molecules and natural products that proceeds with unprecedented levels of reactivity and site selectivity. In the presence of a Brønsted or Lewis acid, the [MnIII(ClPc)]-catalysed C-H amination demonstrates unique tolerance for tertiary amine, pyridine and benzimidazole functionalities. Mechanistic studies suggest that C-H amination likely proceeds through an electrophilic metallonitrene intermediate via a stepwise pathway where C-H cleavage is the rate-determining step of the reaction. Collectively, these mechanistic features contrast with previous base-metal-catalysed C-H aminations and provide new opportunities for tunable selectivities.

Highly efficient and diastereoselective gold(I)-catalyzed synthesis of tertiary amines from secondary amines and alkynes: substrate scope and mechanistic insights.

Science.gov (United States)

Liu, Xin-Yuan; Guo, Zhen; Dong, Sijia S; Li, Xiao-Hua; Che, Chi-Ming

2011-11-11

An efficient method for the synthesis of tertiary amines through a gold(I)-catalyzed tandem reaction of alkynes with secondary amines has been developed. In the presence of ethyl Hantzsch ester and [{(tBu)(2)(o-biphenyl)P}AuCl]/AgBF(4) (2 mol %), a variety of secondary amines bearing electron-deficient and electron-rich substituents and a wide range of alkynes, including terminal and internal aryl alkynes, aliphatic alkynes, and electron-deficient alkynes, underwent a tandem reaction to afford the corresponding tertiary amines in up to 99 % yield. For indolines bearing a preexisting chiral center, their reactions with alkynes in the presence of ethyl Hantzsch ester catalyzed by [{(tBu)(2)(o-biphenyl)P}AuCl]/AgBF(4) (2 mol %) afforded tertiary amines in excellent yields and with good to excellent diastereoselectivity. All of these organic transformations can be conducted as a one-pot reaction from simple and readily available starting materials without the need of isolation of air/moisture-sensitive enamine intermediates, and under mild reaction conditions (mostly room temperature and mild reducing agents). Mechanistic studies by NMR spectroscopy, ESI-MS, isotope labeling studies, and DFT calculations on this gold(I)-catalyzed tandem reaction reveal that the first step involving a monomeric cationic gold(I)-alkyne intermediate is more likely than a gold(I)-amine intermediate, a three-coordinate gold(I) intermediate, or a dinuclear gold(I)-alkyne intermediate. These studies also support the proposed reaction pathway, which involves a gold(I)-coordinated enamine complex as a key intermediate for the subsequent transfer hydrogenation with a hydride source, and reveal the intrinsic stereospecific nature of these transformations observed in the experiments. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dicationic and zwitterionic catalysts for the amine-initiated, immortal ring-opening polymerisation of rac-lactide: facile synthesis of amine-terminated, highly heterotactic PLA

NARCIS (Netherlands)

Clark, L.; Cushion, M.G.; Dyer, H.E.; Schwarz, A.D.; Duchateau, R.; Mountford, P.

2010-01-01

Dicationic, zwitterionic and conventional yttrium compounds act as catalysts for the primary or secondary amine-initiated immortal ROP of rac-lactide; amine-terminated, highly heterotactic poly(rac-lactides) with narrow polydispersities and well-controlled molecular weights are prepared in this

Astramol polypropyleneimine dendrimers as Norrish Type II amine synergists

NARCIS (Netherlands)

Jansen, J.F.G.A.; Dias, A.A.; Hartwig, H.; Janssen, R.A.J.

2000-01-01

UV-curable coatings for various applications . In most of these applications they serve a dual role ie as initiator and as oxygen scavenger. Dimethylethanolamine is one of the more frequently employed aliphatic amines. However, this amine is a highly volatile . AstramolTM polypropyleneimine

Thermal properties of wood reacted with a phosphorus pentoxide–amine system

Science.gov (United States)

Hong-Lin Lee; George C. Chen; Roger M. Rowell

2004-01-01

The objective of this research was to improve the fire-retardant properties of wood in one treatment using a phosphorus pentoxide–amine system. Phosphorus pentoxide and 16 amines including alkyl, halophenyl, and phenyl amines were compounded in N,N-dimethylformamide and the resulting solutions containing phosphoramides were reacted with wood. The characteristics of...

Analysis of carbonyl compounds via headspace solid-phase microextraction with on-fiber derivatization and gas chromatographic-ion trap tandem mass spectrometric determination of their O-(2,3,4,5,6-pentafluorobenzyl)oxime derivatives

Energy Technology Data Exchange (ETDEWEB)

Schmarr, Hans-Georg [Dienstleistungszentrum Laendlicher Raum (DLR) Rheinpfalz, Breitenweg 71, D-67435 Neustadt an der Weinstrasse (Germany)], E-mail: hans-georg.schmarr@dlr.rlp.de; Potouridis, Theodoros; Ganss, Sebastian; Sang, Wei; Koepp, Benedikt; Bokuz, Ursula; Fischer, Ulrich [Dienstleistungszentrum Laendlicher Raum (DLR) Rheinpfalz, Breitenweg 71, D-67435 Neustadt an der Weinstrasse (Germany)

2008-06-09

An improved method for the analysis of carbonyls is described utilizing a headspace solid-phase microextraction (HS-SPME) step and on-fiber derivatization with O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine (PFBHA) hydrochloride. Thermal desorption of the oxime derivatives formed on the fiber is followed by gas chromatographic separation coupled to an ion trap tandem mass spectrometer (GC-ITMS). Selecting specific fragment ions within the electron ionization (EI{sup +}) mass spectra of these oxime derivatives as precursor ions for MS-MS fragmentation provides a suitable method for the target analysis of individual carbonyl classes, such as alkanals, (E)-2-alkenals, (E,E)-2,4-alkadienals, and others. Retention indices on polar as well as on apolar stationary phases along with EI{sup +} mass spectra patterns are presented for a large set of oxime derivatives, giving valuable information needed for unambiguous assignment of substances in complex sample matrices. The fast sample preparation and derivatization step via HS-SPME can be automated and is applicable to a variety of biological samples and foodstuffs, allowing rapid and sensitive screening analyses of important aldehydic biomarkers and aroma active compounds.

Bioinspired organocatalytic aerobic C-H oxidation of amines with an ortho-quinone catalyst.

Science.gov (United States)

Qin, Yan; Zhang, Long; Lv, Jian; Luo, Sanzhong; Cheng, Jin-Pei

2015-03-20

A simple bioinspired ortho-quinone catalyst for the aerobic oxidative dehydrogenation of amines to imines is reported. Without any metal cocatalysts, the identified optimal ortho-quinone catalyst enables the oxidations of α-branched primary amines and cyclic secondary amines. Mechanistic studies have disclosed the origins of different performances of ortho-quinone vs para-quinone in biomimetic amine oxidations.

Nitrile-functionalized tertiary amines as highly efficient and reversible SO{sub 2} absorbents

Energy Technology Data Exchange (ETDEWEB)

Hong, Sung Yun; Kim, Heehwan; Kim, Young Jin; Jeong, Junkyo; Cheong, Minserk [Department of Chemistry and Research Institute of Basic Sciences, Kyung Hee University, 1 Hoegi-dong, Dongdaemun-gu, Seoul 130-701 (Korea, Republic of); Lee, Hyunjoo [Clean Energy Center, Korea Institute of Science and Technology, Seoul 136-791 (Korea, Republic of); Kim, Hoon Sik, E-mail: khs2004@khu.ac.kr [Department of Chemistry and Research Institute of Basic Sciences, Kyung Hee University, 1 Hoegi-dong, Dongdaemun-gu, Seoul 130-701 (Korea, Republic of); Lee, Je Seung, E-mail: leejs70@khu.ac.kr [Department of Chemistry and Research Institute of Basic Sciences, Kyung Hee University, 1 Hoegi-dong, Dongdaemun-gu, Seoul 130-701 (Korea, Republic of)

2014-01-15

Highlights: • Nitrile-functionalized tertiary amines physically and reversibly absorb SO{sub 2}. • Tertiary alkanolamines chemically and irreversibly absorb SO{sub 2} through OH group. • SO{sub 2} absorption modes were studied by spectroscopy and computational calculations. -- Abstract: Three different types of nitrile-functionalized amines, including 3-(N,N-diethylamino)propionitrile (DEAPN), 3-(N,N-dibutylamino)propionitrile (DBAPN), and N-methyl-N,N-dipropionitrile amine (MADPN) were synthesized, and their SO{sub 2} absorption performances were evaluated and compared with those of hydroxy-functionalized amines such as N,N-diethyl-N-ethanol amine (DEEA), N,N-dibutyl-N-ethanol amine (DBEA), and N-methyl-N,N-diethanol amine (MDEA). Absorption–desorption cycle experiments clearly demonstrate that the nitrile-functionalized amines are more efficient than the hydroxy-functionalized amines in terms of absorption rate and regenerability. Computational calculations with DBEA and DBAPN revealed that DBEA bearing a hydroxyethyl group chemically interacts with SO{sub 2} through oxygen atom, forming an ionic compound with a covalently bound -OSO{sub 2}{sup −} group. On the contrary, DBAPN bearing a nitrile group physically interacts with SO{sub 2} through the nitrogen and the hydrogen atoms of the two methylene groups adjacent to the amino and nitrile functionalities.

Impact of thiol and amine functionalization on photoluminescence properties of ZnO films

International Nuclear Information System (INIS)

Jayalakshmi, G.; Saravanan, K.; Balasubramanian, T.

2013-01-01

In the present study, we have investigated surface functionalization of ZnO films with dodecanethiol (Thiol) and trioctylamine (amine) by X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), contact angle (CA) and photoluminescence (PL) measurements. The chemical bondings of thiol and amine with ZnO have been confirmed via the formation of Zn–S and Zn–N bonds by XPS measurements. AFM measurements on ZnO films before and after surface functionalization with thiol and amine provide evidence for the successful functionalization of thiol and amine on ZnO surfaces without any island formation. The CA measurements on ZnO films before and after surface functionalization with thiol and amine show the hydrophobic nature. PL measurements of thiol and amine functionalized ZnO show enhancements of UV emission and quenching of visible emission. The enhanced UV emissions in thiol and amine functionalized ZnO films suggest that the surface defects such as oxygen vacancies are passivated by thiol and amine functionalization. -- Highlights: ► Surface functionalization is a new approach to reduce surface dependent non-radiative process. ► Oxygen vacancies are passivated on surface functionalization. ► Thiol and amine functionalized ZnO show enhancements of UV emission

Study on synthesis, application and mechanism of benzophenone/amine initiator

International Nuclear Information System (INIS)

Xiong Wei; Liu Jinshui; Wen Yinjun; Wan Qizhong; Zhou Xianyan; Xiao Hanling; Yang Jianwen

1999-01-01

Through Michael addition reaction of trimethylolpropane triacrylate (TMPTA) with diethylamine (DEA), a new kind of tertiary amine derivative was synthesized and its structure was identified by 'H-NMR. When used in combination with benzophenone, this amine presented excellent curing speed and could be a substitute for initiator Darocur R 1173, which is effective but expensive. If so, the cost of UV-curable coatings can descend apparently. The functioning mechanism of benzophenone/amine bimolecular initiator was studied

2-Hydro-4-n-But oxypropiophenone Oxime as a spectrophotometric reagent for Fe (III)

International Nuclear Information System (INIS)

Purohit, K.; Desai, K.K.

2006-01-01

2-Hydro-4-n-But oxypropiophenone Oxime [Hipbone] has been synthesized and used for the spectrophotometric determination of Fe (III). The reagent gives purple coloured complex with Fe (III) in 50% alcoholic medium in pH range of 2.5-4.5. Beer's law is obeyed up to 23.1 ppm of Fe (III). Molar absorptivity and sandell's sensitivity at 500 nm of complex were found to be 7.062x 10 power2 lit.mol.cm and 0.079 ug of Fe (III)/cm respectively. Composition and stability constant have been determined. The reagent is successfully used for determination of Fe (III) in dolomite and in pharmaceutical sample. It is also used for the indirect determination of fluoride in tap water sample. (author)

Contribution of direct actions of the oxime HI-6 in reversing soman-induced muscle weakness in the rat diaphragm

Energy Technology Data Exchange (ETDEWEB)

Alder, M.; Maxwell, D.M.; Filbert, M.G.; Deshpande, S.S.

1994-12-31

The actions of the bispyridinium oxime HI-6 ((4-AMINOCARBONYL) PYRIDINO-methoxymethyl- 2-(HYDROXYIMINO)METHYL- pyridinium dichloride) were investigated in vitro on rat phrenic nerve-hemidiaphragm preparations. Isometric twitch and tetanic tensions were elicited at 37 deg C with supramaximal nerve stimulation at frequencies of 20 and 50 Hz. To approximate normal respiration patterns, trials consisting of 30 successive 0.55 5 trains were alternated with 1.25 5 rest periods. Under control conditions, the above stimulation pattern generated tensions that were well maintained at both frequencies. In contrast, a marked depression of muscle tension was observed in diaphragms removed from rats administered 339 ug/kg soman (3 LD50) and tested in vitro. Addition of HI-6, 4 h after soman exposure, led to a nearly complete recovery of muscle tension at 20 Hz. At 50 Hz, muscle tensions still declined especially when trains were elicited at 1.25 and 3 5 intervals. The recovery by HI-6 observed in this study appears to be mediated by mechanisms unrelated to acetylcholinesterase reactivation since no increase of enzymatic activity was detected and the effect was reversed by a brief washout in oxime-free physiological solution. The results suggest that the direct action of HI-6 may play a role in restoring soman-induced diaphragmatic failure but this effect would be significant primarily under low use conditions.

Intolerance to dietary biogenic amines: a review.

Science.gov (United States)

Jansen, Sophia C; van Dusseldorp, Marijke; Bottema, Kathelijne C; Dubois, Anthony E J

2003-09-01

To evaluate the scientific evidence for purported intolerance to dietary biogenic amines. MEDLINE was searched for articles in the English language published between January 1966 and August 2001. The keyword biogenic amin* was combined with hypersens*, allerg*, intoler*, and adverse. Additionally, the keywords histamine, tyramine, and phenylethylamine were combined with headache, migraine, urticaria, oral challenge, and oral provocation. Articles were also selected from references in relevant literature. Only oral challenge studies in susceptible patients were considered. Studies with positive results (ie, studies in which an effect was reported) were only eligible when a randomized, double-blind, placebo-controlled design was used. Eligible positive result studies were further evaluated according to a number of scientific criteria. Studies with negative results (ie, studies in which no effect was reported) were examined for factors in their design or methods that could be responsible for a false-negative outcome. Results of methodologically weak or flawed studies were considered inconclusive. A total of 13 oral challenge studies (5 with positive results and 8 with negative results) were found. Three of them (all with positive results) were considered ineligible. By further evaluation of the 10 eligible studies, 6 were considered inconclusive. The 4 conclusive studies all reported negative results. One conclusive study showed no relation between biogenic amines in red wine and wine intolerance. Two conclusive studies found no effect of tyramine on migraine. One conclusive study demonstrated no relation between the amount of phenylethylamine in chocolate and headache attacks in individuals with headache. The current scientific literature shows no relation between the oral ingestion of biogenic amines and food intolerance reactions. There is therefore no scientific basis for dietary recommendations concerning biogenic amines in such patients.

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

Science.gov (United States)

Li, Chenghong

2013-09-05

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

Composition of amino acids and bioactive amines in common wines of Brazil

Directory of Open Access Journals (Sweden)

Bruna Carla Agustini

2014-10-01

Full Text Available Since most consumed wines in Brazil are common wines and since their representativeness is not accounted for in scientific research, current study quantifies bioactive amines and their precursors in Brazilian sweet and dry common wines, correlates the formation of amines with physical and chemical parameters and clusters studied areas by their amine and amino acid contents. Forty-seven wine samples varying in type, color and origin were analyzed simultaneously for seventeen amino acids, ammonium ion and five bioactive amines by reversed-phase high performance liquid chromatography and ultraviolet detection after the derivation phase. Physical and chemical analyses comprised titratable acidity, pH, organic acids, sugar and alcohol contents. Sweet wines had lower concentrations of amino acids and bioactive amines. Dry white wines had higher amino acid contents when compared to those in dry red wines. Since multivariate data analysis confirmed similarities between the studied regions, their unity as potential viniculture area was reinforced. Amine levels in Brazilian common wines were reported for the first time and results reinforced the importance of bioactive amines quantification and the use of suitable vinification practices to reduce their formation.

Conditions allowing the formation of biogenic amines in cheese

NARCIS (Netherlands)

Joosten, H.M.L.J.

1988-01-01

A study was undertaken to reveal the conditions that allow the formation of biogenic amines in cheese.

The starters most commonly used in the Dutch cheese industry do not have decarboxylative properties. Only if the milk or curd is contaminated with non-starter bacteria, amine

Indirubin Derivative 7-Bromoindirubin-3-Oxime (7Bio Attenuates Aβ Oligomer-Induced Cognitive Impairments in Mice

Directory of Open Access Journals (Sweden)

Liping Chen

2017-11-01

Full Text Available Indirubins are natural occurring alkaloids extracted from indigo dye-containing plants. Indirubins could inhibit various kinases, and might be used to treat chronic myelocytic leukemia, cancer and neurodegenerative disorders. 7-bromoindirubin-3-oxime (7Bio, an indirubin derivative derived from indirubin-3-oxime, possesses inhibitory effects against cyclin-dependent kinase-5 (CDK5 and glycogen synthase kinase-3β (GSK3β, two pharmacological targets of Alzheimer's disease (AD. In this study, we have discovered that 2.3–23.3 μg/kg 7Bio effectively prevented β-amyloid (Aβ oligomer-induced impairments of spatial cognition and recognition without affecting bodyweight and motor functions in mice. Moreover, 7Bio potently inhibited Aβ oligomer-induced expression of interleukin-6 (IL-6 and tumor necrosis factor-α (TNF-α. Furthermore, 7Bio significantly prevented the decreased expression of synapsin-1 and PSD-95, biomarkers of pre-synaptic and post-synaptic proteins in Aβ oligomer-treated mice. The mean optical density (OD with hyper-phosphorylated tau (pTau, glial fibrillary acidic protein (GFAP and CD45 positive staining in the hippocampus of 7Bio-treated mice were significantly decreased compared to those of Aβ oligomer-treated mice. In addition, Western blotting analysis showed that 7Bio attenuated Aβ oligomer-decreased expression of pSer9-GSK3β. Those results suggested that 7Bio could potently inhibit Aβ oligomer-induced neuroinflammation, synaptic impairments, tau hyper-phosphorylation, and activation of astrocytes and microglia, which may contribute to the neuroprotective effects of 7Bio. Based on these findings, we expected that 7Bio might be developed as a novel anti-AD lead compound.

Blue Chitin columns for the extraction of heterocyclic amines from urine samples

DEFF Research Database (Denmark)

Bang, J.; Frandsen, Henrik Lauritz; Skog, K.

2004-01-01

During normal cooking of meat, a class of mutagenic/carcinogenic compounds called heterocyclic amines is formed. Heterocyclic amines are rapidly absorbed and metabolised in the human body, and for estimation of the intake of heterocyclic amines, it is useful to determinate their levels in the uri...

Analysis of Biogenic Amines by GC/FID and GC/MS

OpenAIRE

Nakovich, Laura

2003-01-01

Low levels of biogenic amines occur naturally, but high levels (FDA sets 50 ppm of histamine in fish as the maximum allowable level) can lead to scombroid poisoning. Amines in general are difficult to analyze by Gas Chromatography (GC) due to their lack of volatility and their interaction with the GC column, often leading to significant tailing and poor reproducibility. Biogenic amines need to be derivatized before both GC and HPLC analyses. The objective of this research was to devel...

Identification of amines in wintertime ambient particulate material using high resolution aerosol mass spectrometry

Science.gov (United States)

Bottenus, Courtney L. H.; Massoli, Paola; Sueper, Donna; Canagaratna, Manjula R.; VanderSchelden, Graham; Jobson, B. Thomas; VanReken, Timothy M.

2018-05-01

Significant amounts of amines were detected in fine particulate matter (PM) during ambient wintertime conditions in Yakima, WA, using a high resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). Positive matrix factorization (PMF) of the organic aerosol (OA) signal resulted in a six-factor solution that included two previously unreported amine OA factors. The contributions of the amine factors were strongly episodic, but the concentration of the combined amine factors was as high as 10-15 μg m-3 (2-min average) during those episodes. In one occasion, the Amine-II component was 45% of total OA signal. The Amine-I factor was dominated by spectral peaks at m/z 86 (C5H12N+) and m/z 100 (C6H14N+), while the Amine-II factor was dominated by spectral peaks at m/z 58 (C3H8N+ and C2H6N2+) and m/z 72 (C4H10N+ and C3H8N2+). The ions dominating each amine factor showed distinct time traces, suggesting different sources or formation processes. Investigation into the chemistry of the amine factors suggests a correlation with inorganic anions for Amine-I, but no evidence that the Amine-II was being neutralized by the same inorganic ions. We also excluded the presence of organonitrates (ON) in the OA. The presence of C2H4O2+ at m/z 60 (a levoglucosan fragment) in the Amine-I spectrum suggests some influence of biomass burning emissions (more specifically residential wood combustion) in this PMF factor, but wind direction suggested that the most likely sources of these amines were agricultural activities and feedlots to the S-SW of the site.

Regional cerebral blood flow as assessed by principal component analysis and 99mTc-HMPAO SPET in healthy subjects at rest: normal distribution and effect of age and gender

International Nuclear Information System (INIS)

Pagani, M.; Salmaso, D.; Jonsson, C.; Hatherly, R.; Larsson, S.A.; Jacobsson, H.; Waegner, A.

2002-01-01

The increasing implementation of standardisation techniques in brain research and clinical diagnosis has highlighted the importance of reliable baseline data from normal control subjects for inter-subject analysis. In this context, knowledge of the regional cerebral blood flow (rCBF) distribution in normal ageing is a factor of the utmost importance. In the present study, rCBF was investigated in 50 healthy volunteers (25 men, 25 women), aged 31-78 years, who were examined at rest by means of single-photon emission tomography (SPET) using technetium-99m d,l-hexamethylpropylene amine oxime (HMPAO). After normalising the CBF data, 27 left and 27 right volumes of interest (VOIs) were selected and automatically outlined by standardisation software (computerised brain atlas). The heavy load of flow data thus obtained was reduced in number and grouped in factors by means of principal component analysis (PCA). PCA extracted 12 components explaining 81% of the variance and including the vast majority of cortical and subcortical regions. Analysis of variance and regression analyses were performed for rCBF, age and gender before PCA was applied and subsequently for each single extracted factor. There was a significantly higher CBF on the right side than on the left side (P<0.001). In the overall analysis, a significant decrease was found in CBF (P=0.05) with increasing age, and this decrease was particularly evident in the left hemisphere (P=0.006). When gender was specifically analysed, CBF was found to decrease significantly with increasing age in females (P=0.037) but not in males. Furthermore, a significant decrease in rCBF with increasing age was found in the brain vertex (P=0.05), left frontotemporal cortex (P=0.012) and temporocingulate cortex (P=0.003). By contrast, relative rCBF in central structures increased with age (P=0.001). The ability of standardisation software and PCA to identify functionally connected brain regions might contribute to a better

Automatic determination of brain perfusion index for measurement of cerebral blood flow using spectral analysis and {sup 99m}Tc-HMPAO

Energy Technology Data Exchange (ETDEWEB)

Takasawa, Masashi [Division of Strokology, Department of Internal Medicine and Therapeutics, Osaka University Graduate School of Medicine, 2-2, Yamadaoka, Suita City, Osaka, 565-0871 (Japan); Department of Nuclear Medicine, Osaka University Graduate School of Medicine, Osaka (Japan); Murase, Kenya; Kawamata, Minoru [Department of Allied Health Sciences, Osaka University Graduate School of Medicine, Osaka (Japan); Oku, Naohiko; Imaizumi, Masao; Osaki, Yasuhiro; Paul, Asit K. [Department of Nuclear Medicine, Osaka University Graduate School of Medicine, Osaka (Japan); Yoshikawa, Takuya; Kitagawa, Kazuo; Matsumoto, Masayasu; Hori, Masatsugu [Division of Strokology, Department of Internal Medicine and Therapeutics, Osaka University Graduate School of Medicine, 2-2, Yamadaoka, Suita City, Osaka, 565-0871 (Japan)

2002-11-01

Cerebral blood flow (CBF) can be non-invasively quantified using the brain perfusion index (BPI), determined from radionuclide angiographic data generated by technetium-99m hexamethylpropylene amine oxime ({sup 99m}Tc-HMPAO). We previously reported the use of a spectral analysis (SA) method using {sup 99m}Tc-HMPAO to calculate the BPI. In this report, we demonstrate an automatic method for determining the optimal BPI value and compare the optimal BPI values with the absolute CBF values measured using H{sub 2}{sup 15}O positron emission tomography (PET). Bilateral cerebral hemispheres of 11 patients with various brain diseases were examined using {sup 99m}Tc-HMPAO. In the automatic SA procedure, the radioactivity curve for the aortic arch (C{sub a}) was shifted by 0-10 s. The radioactivity curve for the brain (C{sub b}) was estimated using the shifted C{sub a}, and the error value between the actually measured and the estimated C{sub b} (Err) was calculated. When the Err was at a minimum, the BPI value was defined as optimal BPI. The difference in BPI from the optimal BPI was calculated as vertical stroke BPI - optimal BPI vertical stroke / optimal BPI x 100 (%). In all participants, an H{sub 2}{sup 15}O PET examination was also performed, and the BPI values were compared with the absolute CBF values measured using H{sub 2}{sup 15}O PET (mCBF{sup PET}). The difference between BPI and the optimal BPI increased significantly from 4.87%{+-}1.69% to 18.38%{+-}3.93% (mean{+-}SD) when the Err value increased. The optimal BPI value (y) was well correlated with the mCBF{sup PET} value (x) (y=0.21x-0.0075, r=0.800). Our results suggest that this automatic SA method provides an accurate estimate of BPI that can be used for the quantification of CBF using {sup 99m}Tc-HMPAO SA. (orig.)

Regional cerebral blood flow in patients with sickle cell disease: study with single photon emission computed tomography

International Nuclear Information System (INIS)

Al-Kandari, F.A.; Owunwanne, A.; Syed, G.M.; Elgazzar, A.H.; Rizui, A.M.; Al-Ajmi, J.A.; Mohammed, A.M.; Ar Marouf, R.; Shiekh, M.

2007-01-01

Neurological complications have been reported in patients with sickle-cell disease (SCD) using positron emission tomography (PET), magnetic resonance imaging (MRI), and computed tomography (CT), but not with single photon emission computed tomography (SPECT). The objective of this study was to investigate brain perfusion in the patients with SCD using SPECT after technetium-99m hexamethylpropylene amine oxime ( 99m Tc-HMPAO), was administered and compare the findings with those of demography, physical examination, MRI and hematological profile. The study involved 21 patients (12 males, 9 females, age at study 8-45 years) who were known to be having SCD for a duration of at least 5 years. The patients were not in acute crisis and had normal neurological assessments with no known history of stroke or transient ischemic episode or previous abnormal CT or MRI brain scan, and were right-handed. The brain SPECT was performed after intravenous injection of 740 MBq (20 mCi) 99m Tc-HMPAO in adults or an appropriate dose in pediatric patients. The scans were visually interpreted by two nuclear medicine physicians and a decision was reached by consensus. An MRI done 3 months later was interpreted by a radiologist. The demographic data and hematological profile were obtained from the medical records of the patients. Of the 21 patients, 7 (age 11-22 years) had brain perfusion deficit mostly in the frontal lobe either alone or in combination with temporal and/or parietal lobe. The MRI was abnormal in 2 patients. The brain perfusion deficit was not associated with the demographic data of the patients or hematological profiles. The findings show that SPECT was useful in detecting brain perfusion deficit in SCD patients, and such an early detection may be clinically useful in the subsequent follow-up of such patients, since it is known that cerebral perfusion deficit can lead to silent infarct and/or overt stroke, and affect cognitive skills. (author)

Principal component and volume of interest analyses in depressed patients imaged by {sup 99m}Tc-HMPAO SPET: a methodological comparison

Energy Technology Data Exchange (ETDEWEB)

Pagani, Marco [Institute of Cognitive Sciences and Technologies, CNR, Rome (Italy); Section of Nuclear Medicine, Department of Hospital Physics, Karolinska Hospital, Stockholm (Sweden); Gardner, Ann; Haellstroem, Tore [NEUROTEC, Division of Psychiatry, Karolinska Institutet, Huddinge University Hospital, Stockholm (Sweden); Salmaso, Dario [Institute of Cognitive Sciences and Technologies, CNR, Rome (Italy); Sanchez Crespo, Alejandro; Jonsson, Cathrine; Larsson, Stig A. [Section of Nuclear Medicine, Department of Hospital Physics, Karolinska Hospital, Stockholm (Sweden); Jacobsson, Hans [Department of Radiology, Karolinska Hospital, Stockholm (Sweden); Lindberg, Greger [Department of Medicine, Division of Gastroenterology and Hepatology, Karolinska Institutet, Huddinge University Hospital, Stockholm (Sweden); Waegner, Anna [Department of Clinical Neuroscience, Division of Neurology, Karolinska Hospital, Stockholm (Sweden)

2004-07-01

Previous regional cerebral blood flow (rCBF) studies on patients with unipolar major depressive disorder (MDD) have analysed clusters of voxels or single regions and yielded conflicting results, showing either higher or lower rCBF in MDD as compared to normal controls (CTR). The aim of this study was to assess rCBF distribution changes in 68 MDD patients, investigating the data set with both volume of interest (VOI) analysis and principal component analysis (PCA). The rCBF distribution in 68 MDD and 66 CTR, at rest, was compared. Technetium-99m d,l-hexamethylpropylene amine oxime single-photon emission tomography was performed and the uptake in 27 VOIs, bilaterally, was assessed using a standardising brain atlas. Data were then grouped into factors by means of PCA performed on rCBF of all 134 subjects and based on all 54 VOIs. VOI analysis showed a significant group x VOI x hemisphere interaction (P<0.001). rCBF in eight VOIs (in the prefrontal, temporal, occipital and central structures) differed significantly between groups at the P<0.05 level. PCA identified 11 anatomo-functional regions that interacted with groups (P<0.001). As compared to CTR, MDD rCBF was relatively higher in right associative temporo-parietal-occipital cortex (P<0.01) and bilaterally in prefrontal (P<0.005) and frontal cortex (P<0.025), anterior temporal cortex and central structures (P<0.05 and P<0.001 respectively). Higher rCBF in a selected group of MDD as compared to CTR at rest was found using PCA in five clusters of regions sharing close anatomical and functional relationships. At the single VOI level, all eight regions showing group differences were included in such clusters. PCA is a data-driven method for recasting VOIs to be used for group evaluation and comparison. The appearance of significant differences absent at the VOI level emphasises the value of analysing the relationships among brain regions for the investigation of psychiatric disease. (orig.)

The role of FDG-PET, HMPAO-SPET and MRI in the detection of brain involvement in patients with systemic lupus erythematosus

Energy Technology Data Exchange (ETDEWEB)

Kao Chiahung [Department of Nuclear Medicine, Taichung Veterans General Hospital, Taichung (Taiwan, Province of China); Lan Jungliang [Division of Rheumatology, Taichung Veterans General Hospital, Taichung (Taiwan, Province of China); ChangLai Shengping [Department of Nuclear Medicine, Chung-Shan Medical and Dental College, Taichung (Taiwan, Province of China); Liao Kokaung [Electron Microscopic Laboratory, Chung-Shan Medical and Dental College, Taichung (Taiwan, Province of China); Yen Rouhfang; Chieng Poonung [Department of Nuclear Medicine, National Taiwan University Hospital, Taipei (Taiwan, Province of China)

1999-02-01

Involvement of the brain is one of the most important complications of systemic lupus erythematosus (SLE); however, its diagnosis is difficult due to the lack of effective imaging methods. We combined three brain imaging modalities - positron emission tomography with fluorine-18 2-fluoro-2-deoxy-d-glucose (FDG-PET), single-photon emission computed tomography with technetium-99m hexamethylpropylene amine oxime (HMPAO-SPET) and magnetic resonance imaging (MRI) - in order to detect brain involvement in SLE. Thirty-seven SLE patients, aged 22-45 years, were divided into three groups. Group 1 (G1) consisted of ten patients with major neuropsychiatric manifestations; group 2 (G2) consisted of 15 patients with minor manifestations; and group 3 (G3) consisted of 12 patients without manifestations. FDG-PET findings were abnormal in 51% of patients: 90% of G1, 67% of G2 and 0% of G3 patients respectively. HMPAO-SPET findings were abnormal in 62% of patients: 100% of G1, 73% of G2 and 17% of G3 patients respectively. MRI findings were abnormal in 35% of patients: 70% of G1, 40% of G2 and 0% of G3 patients respectively. Grey matter was more commonly involved than white matter; 62% of patients presented with lesions in the cerebral cortex, 27% with lesions in the basal ganglion, 5% with lesions in the cerebellum, and 19% with lesions in white matter. No white matter lesions were found on FDG-PET or HMPAO-SPET. However, in 19% of patients, MRI demonstrated abnormally high signal lesions in white matter. Forty-three percent of cases had positive serum anticardiolipin antibodies (ACA). However, ACA was not related to FDG-PET, HMPAO-SPET or MRI findings. It may be concluding that HMPAO-SPET is a more sensitive tool for detecting brain involvement in SLE patients when compared with FDG-PET or MRI. However, MRI is necessary for detecting lesions in white matter. (orig.) With 3 figs., 2 tabs., 46 refs.

Regional cerebral blood flow as assessed by principal component analysis and {sup 99m}Tc-HMPAO SPET in healthy subjects at rest: normal distribution and effect of age and gender

Energy Technology Data Exchange (ETDEWEB)

Pagani, M. [Inst. of Neurobiology and Molecular Medicine, CNR, Rome (Italy); Dept. of Hospital Physics, Karolinska Hospital, Stockholm (Sweden); Salmaso, D. [Inst. of Psychology, CNR, Rome (Italy); Jonsson, C.; Hatherly, R.; Larsson, S.A. [Dept. of Hospital Physics, Karolinska Hospital, Stockholm (Sweden); Jacobsson, H. [Dept. of Diagnostic Radiology, Karolinska Hospital, Stockholm (Sweden); Waegner, A. [Dept. of Clinical Neuroscience, Karolinska Institutet, Stockholm (Sweden); Dept. of Clinical Neuroscience, Karolinska Hospital, Stockholm (Sweden)

2002-01-01

The increasing implementation of standardisation techniques in brain research and clinical diagnosis has highlighted the importance of reliable baseline data from normal control subjects for inter-subject analysis. In this context, knowledge of the regional cerebral blood flow (rCBF) distribution in normal ageing is a factor of the utmost importance. In the present study, rCBF was investigated in 50 healthy volunteers (25 men, 25 women), aged 31-78 years, who were examined at rest by means of single-photon emission tomography (SPET) using technetium-99m d,l-hexamethylpropylene amine oxime (HMPAO). After normalising the CBF data, 27 left and 27 right volumes of interest (VOIs) were selected and automatically outlined by standardisation software (computerised brain atlas). The heavy load of flow data thus obtained was reduced in number and grouped in factors by means of principal component analysis (PCA). PCA extracted 12 components explaining 81% of the variance and including the vast majority of cortical and subcortical regions. Analysis of variance and regression analyses were performed for rCBF, age and gender before PCA was applied and subsequently for each single extracted factor. There was a significantly higher CBF on the right side than on the left side (P<0.001). In the overall analysis, a significant decrease was found in CBF (P=0.05) with increasing age, and this decrease was particularly evident in the left hemisphere (P=0.006). When gender was specifically analysed, CBF was found to decrease significantly with increasing age in females (P=0.037) but not in males. Furthermore, a significant decrease in rCBF with increasing age was found in the brain vertex (P=0.05), left frontotemporal cortex (P=0.012) and temporocingulate cortex (P=0.003). By contrast, relative rCBF in central structures increased with age (P=0.001). The ability of standardisation software and PCA to identify functionally connected brain regions might contribute to a better

Different uptake of 99mTc-ECD adn 99mTc-HMPAO in the same brains: analysis by statistical parametric mapping.

Science.gov (United States)

Hyun, Y; Lee, J S; Rha, J H; Lee, I K; Ha, C K; Lee, D S

2001-02-01

The purpose of this study was to investigate the differences between technetium-99m ethyl cysteinate dimer (99mTc-ECD) and technetium-99m hexamethylpropylene amine oxime (99mTc-HMPAO) uptake in the same brains by means of statistical parametric mapping (SPM) analysis. We examined 20 patients (9 male, 11 female, mean age 62+/-12 years) using 99mTc-ECD and 99mTc-HMPAO single-photon emission tomography (SPET) and magnetic resonance imaging (MRI) of the brain less than 7 days after onset of stroke. MRI showed no cortical infarctions. Infarctions in the pons (6 patients) and medulla (1), ischaemic periventricular white matter lesions (13) and lacunar infarction (7) were found on MRI. Split-dose and sequential SPET techniques were used for 99mTc-ECD and 99mTc-HMPAO brain SPET, without repositioning of the patient. All of the SPET images were spatially transformed to standard space, smoothed and globally normalized. The differences between the 99mTc-ECD and 99mTc-HMPAO SPET images were statistically analysed using statistical parametric mapping (SPM) 96 software. The difference between two groups was considered significant at a threshold of uncorrected P values less than 0.01. Visual analysis showed no hypoperfused areas on either 99mTc-ECD or 99mTc-HMPAO SPET images. SPM analysis revealed significantly different uptake of 99mTc-ECD and 99mTc-HMPAO in the same brains. On the 99mTc-ECD SPET images, relatively higher uptake was observed in the frontal, parietal and occipital lobes, in the left superior temporal lobe and in the superior region of the cerebellum. On the 99mTc-HMPAO SPET images, relatively higher uptake was observed in the medial temporal lobes, thalami, periventricular white matter and brain stem. These differences in uptake of the two tracers in the same brains on SPM analysis suggest that interpretation of cerebral perfusion is possible using SPET with 99mTc-ECD and 99mTc-HMPAO.

Advances in regional cerebral blood flow measurement and patho-physiological analysis by SPECT

Energy Technology Data Exchange (ETDEWEB)

Odano, Ikuo [Niigata Univ. (Japan). School of Medicine

1994-04-01

Recently, two kinds of radiopharmaceuticals have been developed to represent the biodistribution of regional blood flow, which are N-isopropyl-p-[[sup 123]I]iodoamphetamine (IMP) and [sup 99m]Tc-hexamethylpropylene-amine-oxime (HMPAO). The charachteristics, clinical usage and imitation of these two radiolabeled agents are discussed. The advantage of [sup 123]I-IMP is that it has high first-pass extraction and long retention in brain tissue, hence it can be used to measure the absolute values of regional cerebral blood flow (rCBF). When the kinetics of [sup 123]I-IMP is assumed to be freely diffusible in the brain, its behavior is considered by 2-compartment model, especially which is assumed by the microsphere model in the early period after the i.v. injection of [sup 123]I-IMP. Comparing the rCBF measured by [sup 123]I-IMP with that by [sup 133]Xe inhalation SPECT method, we have to consider PaCO[sub 2] when both SPECT studies are performed, because PaCO[sub 2] is one of the big factors which make effects on the alteration of rCBF. [sup 123]I-IMP has an interesting character of the redistribution phenomenon which represrent the degree of ischemia in the cerebrovascular diseases. Distribution volume an important datum obtained by the SPECT study with [sup 123]I-IMP, which represent the degree of retention, i.e. binding potential of [sup 123]I-IMP in the brain tissue. I introduced the usage of the distribution volume of [sup 123]I-IMP, which was constructed in the rate constant square method, in the differential diagnosis of Parkinson's disease and progressive supranuclear palsy (PSP). The clinical usage of [sup 99m] Tc-HMPAT was mentioned, the advantage of which is the rapid fixation in the brain tissue and the distribution does not change for long time after the i.v. injection. Hence [sup 99m]Tc-HMPAO is used for the diagnosis of epileptic foci and certain loading tests such as balloon occlusion test, postural test and acetazolamide loading test. (author).

Regional differences between {sup 99m}Tc-ECD and {sup 99m}Tc-HMPAO SPET in perfusion changes with age and gender in healthy adults

Energy Technology Data Exchange (ETDEWEB)

Inoue, Kentaro; Nakagawa, Manabu; Goto, Ryoi; Kinomura, Shigeo; Sato, Tachio; Sato, Kazunori; Fukuda, Hiroshi [Department of Nuclear Medicine and Radiology, Institute of Development, Aging and Cancer, Tohoku University, 4-1 Seiryomachi Aoba-ku, 980-8575, Sendai (Japan)

2003-11-01

A number of studies using single-photon emission tomography (SPET) have shown perfusion changes with age in several cortical and subcortical areas, which might distort the results of perfusion imaging studies of neuropsychiatric disorders. Technetium-99m labelled ethyl cysteinate dimer (ECD) and hexamethylpropylene amine oxime (HMPAO) are both used as markers of cerebral perfusion, but have different pharmacokinetics and retention patterns. The aim of this study was to determine whether age and gender effects on perfusion SPET differ depending on whether {sup 99m}Tc-HMPAO or {sup 99m}Tc-ECD is used. Forty-five subjects (20 male and 25 female, mean age 52.8{+-}6.6 years) were assigned to {sup 99m}Tc-HMPAO SPET (HMPAO group), and 39 subjects (24 male and 15 female, mean age 52.6{+-}6.7 years) to {sup 99m}Tc-ECD SPET (ECD group). SPET images were obtained about 10 min after intravenous injection of approximately 800 MBq {sup 99m}Tc-HMPAO or {sup 99m}Tc-ECD using the same SPET scanner. Three-dimensional volumetric magnetic resonance imaging was performed to as7sess morphological changes in the grey matter. All image processing and statistical analyses were performed using SPM99 software. An area in the right anterior frontal lobe showed an increase in perfusion with age only in the HMPAO group, whereas areas in the bilateral retrosplenial cortex showed decreases in perfusion with age only in the ECD group; neither group showed corresponding changes in the grey matter. The present study shows that different effects of age on perfusion are observed depending on whether {sup 99m}Tc-HMPAO and {sup 99m}Tc-ECD is used. This suggests that the results of perfusion SPET are differently confounded depending on the tracer used, and that perfusion SPET with these tracers has limitations when used in research on subtle perfusion changes. (orig.)

Electrochemical degradation of aromatic amines on BDD electrodes

International Nuclear Information System (INIS)

Pacheco, M.J.; Santos, V.; Ciriaco, L.; Lopes, A.

2011-01-01

The electrochemical oxidation of four aromatic amines, with different substituent groups, 3-amino-4-hydroxy-5-nitrobenzenesulfonic acid (A1), 5-amino-2-methoxybenzenesulfonic acid (A2), 2,4-dihydroxyaniline hydrochloride (A3) and benzene-1,4-diamine (A4), was performed using as anode a boron-doped diamond electrode, commercially available at Adamant Technologies. Tests were run at room temperature with model solutions of the different amines, with concentrations of 200 ppm, using as electrolyte 0.035 M Na 2 SO 4 aqueous solutions, in a batch cell with recirculation, at different current densities (200 and 300 A m -2 ). The following analyses were performed with the samples collected during the assays: UV-Vis spectrophotometry, chemical oxygen demand (COD), total organic carbon (TOC), total Kjeldahl nitrogen, ammonia nitrogen, nitrates and HPLC. Results have shown a good electrodegradation of all the amines tested, with COD removals, after 6 h assays, higher than 90% and TOC removals between 60 and 80%. Combustion efficiency (η C ), which measures the tendency to convert organic carbon to CO 2 , was also determined for all the amines, being η CA1 CA2 CA3 CA4 = 0.99.

Control of Biogenic Amines in Fermented Sausages: Role of Starter Cultures

Science.gov (United States)

Latorre-Moratalla, M.L.; Bover-Cid, Sara; Veciana-Nogués, M.T.; Vidal-Carou, M.C.

2012-01-01

Biogenic amines show biological activity and exert undesirable physiological effects when absorbed at high concentrations. Biogenic amines are mainly formed by microbial decarboxylation of amino acids and thus are usually present in a wide range of foods, fermented sausages being one of the major biogenic amine sources. The use of selected starter cultures is one of the best technological measures to control aminogenesis during meat fermentation. Although with variable effectiveness, several works show the ability of some starters to render biogenic amine-free sausages. In this paper, the effect of different starter culture is reviewed and the factors determining their performance discussed. PMID:22586423

Control of biogenic amines in fermented sausages: role of starter cultures

Directory of Open Access Journals (Sweden)

Mariluz eLatorre-Moratalla

2012-05-01

Full Text Available Biogenic amines show biological activity and exert undesirable physiological effects when absorbed at high concentrations. Biogenic amines are mainly formed by microbial decarboxylation of amino acids and thus are usually present in a wide range of foods, fermented sausages being one of the major biogenic amine sources. The use of selected starter cultures is one of the best technological measures to control aminogenesis during meat fermentation. Although with variable effectiveness, several works show the ability of some starters to render biogenic amine-free sausages. In this paper, the effect of different starter culture is reviewed and the factors determining their performance discussed.

Amine oxidases as important agents of pathological processes of rhabdomyolysis in rats.

Science.gov (United States)

Gudkova, O O; Latyshko, N V; Shandrenko, S G

2016-01-01

In this study we have tested an idea on the important role of amine oxidases (semicarbazide-sensitive amine oxidase, diamine oxidase, polyamine oxidase) as an additional source of oxidative/carbonyl stress under glycerol-induced rhabdomyolysis, since the enhanced formation of reactive oxygen species and reactive carbonyl species in a variety of tissues is linked to various diseases. In our experiments we used the sensitive fluorescent method devised for estimation of amine oxidases activity in the rat kidney and thymus as targeted organs under rhabdomyolysis. We have found in vivo the multiple rises in activity of semicarbazide-sensitive amine oxidase, diamine oxidase, polyamine oxidase (2-4.5 times) in the corresponding cell fractions, whole cells or their lysates at the 3-6th day after glycerol injection. Aberrant antioxidant activities depended on rhabdomyolysis stage and had organ specificity. Additional treatment of animals with metal chelator ‘Unithiol’ adjusted only the activity of antioxidant enzymes but not amine oxidases in both organs. Furthermore the in vitro experiment showed that Fenton reaction (hydrogen peroxide in the presence of iron) products alone had no effect on semicarbazide-sensitive amine oxidase activity in rat liver cell fraction whereas supplementation with methylglyoxal resulted in its significant 2.5-fold enhancement. Combined action of the both agents had additive effect on semicarbazide-sensitive amine oxidase activity. We can assume that biogenic amine and polyamine catabolism by amine oxidases is upregulated by oxidative and carbonyl stress factors directly under rhabdomyolysis progression, and the increase in catabolic products concentration contributes to tissue damage in glycerol-induced acute renal failure and apoptosis stimulation in thymus.

Enrichment Mechanism of Semiconducting Single-walled Carbon Nanotubes by Surfactant Amines

Science.gov (United States)

Ju, Sang-Yong; Utz, Marcel; Papadimitrakopoulos, Fotios

2009-01-01

Utilization of single-walled carbon nanotubes (SWNTs) in high-end applications hinges on separating metallic (met-) from semiconducting (sem-) SWNTs. Surfactant amines, like octadecylamine (ODA) have proven instrumental for the selective extraction of sem-SWNTs from tetrahydrofuran (THF) nanotube suspensions. The chemical shift differences along the tail of an asymmetric, diacetylenic surfactant amine were used to probe the molecular dynamics in the presence and absence of nanotubes via NMR. The results suggest that the surfactant amine head is firmly immobilized onto the nanotube surface together with acidic water, while the aliphatic tail progressively gains larger mobility as it gets farther from the SWNT. X-ray and high-resolution TEM studies indicate that the sem-enriched sample is populated mainly by small nanotube bundles containing ca. three SWNTs. Molecular simulations in conjunction with previously determined HNO3/H2SO4 oxidation depths for met- and sem-SWNTs indicate that the strong pinning of the amine surfactants on the sem-enriched SWNTs bundles is a result of a well-ordered arrangement of nitrate/amine salts separated with a monomolecular layer of H2O. Such continuous 2D arrangement of nitrate/amine salts shields the local environment adjacent to sem-enriched SWNTs bundles and maintains an acidic pH that preserves nanotube oxidation (i.e. SWNTn+). This, in turn, results in strong interactions with charge-balancing NO3- counter ions that through their association with neutralized surfactant amines provide effective THF dispersion and consequent sem-enrichment. PMID:19397291

Long-chain amine-templated synthesis of gallium sulfide and gallium selenide nanotubes

Science.gov (United States)

Seral-Ascaso, A.; Metel, S.; Pokle, A.; Backes, C.; Zhang, C. J.; Nerl, H. C.; Rode, K.; Berner, N. C.; Downing, C.; McEvoy, N.; Muñoz, E.; Harvey, A.; Gholamvand, Z.; Duesberg, G. S.; Coleman, J. N.; Nicolosi, V.

2016-06-01

We describe the soft chemistry synthesis of amine-templated gallium chalcogenide nanotubes through the reaction of gallium(iii) acetylacetonate and the chalcogen (sulfur, selenium) using a mixture of long-chain amines (hexadecylamine and dodecylamine) as a solvent. Beyond their role as solvent, the amines also act as a template, directing the growth of discrete units with a one-dimensional multilayer tubular nanostructure. These new materials, which broaden the family of amine-stabilized gallium chalcogenides, can be tentatively classified as direct large band gap semiconductors. Their preliminary performance as active material for electrodes in lithium ion batteries has also been tested, demonstrating great potential in energy storage field even without optimization.We describe the soft chemistry synthesis of amine-templated gallium chalcogenide nanotubes through the reaction of gallium(iii) acetylacetonate and the chalcogen (sulfur, selenium) using a mixture of long-chain amines (hexadecylamine and dodecylamine) as a solvent. Beyond their role as solvent, the amines also act as a template, directing the growth of discrete units with a one-dimensional multilayer tubular nanostructure. These new materials, which broaden the family of amine-stabilized gallium chalcogenides, can be tentatively classified as direct large band gap semiconductors. Their preliminary performance as active material for electrodes in lithium ion batteries has also been tested, demonstrating great potential in energy storage field even without optimization. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr01663d

Bifunctional (cyclopentadienone)iron-tricarbonyl complexes: Synthesis, computational studies and application in reductive amination

KAUST Repository

Moulin, Solenne; Dentel, Hé lè ne; Pagnoux-Ozherelyeva, Anastassiya; Gaillard, Sylvain; Poater, Albert; Cavallo, Luigi; Lohier, Jean Franç ois; Renaud, Jean Luc

2013-01-01

. Festival of amination: Two series of modified Knölker's complexes were synthesised and applied in the reductive amination of various carbonyl derivatives with primary or secondary amines (see scheme, TIPS = triisopropylsilyl). For a mechanistic insight

Tris{2-[(2-aminobenzylideneamino]ethyl}amine

Directory of Open Access Journals (Sweden)

Perla Elizondo Martínez

2010-12-01

Full Text Available The title Schiff base, C27H33N7, is a tripodal amine displaying C3 symmetry, with the central tertiary N atom lying on the threefold crystallographic axis. The N—CH2—CH2—N conformation of the pendant arms is gauche [torsion angle = 76.1 (3°], which results in a claw-like molecule, with the terminal aniline groups wrapped around the symmetry axis. The lone pair of the apical N atom is clearly oriented inwards towards the cavity, and should thus be chemically inactive. The amine NH2 substituents lie in the plane of the benzene ring to which they are bonded. With such an arrangement, one amine H atom forms an S(6 motif through a weak N—H...N hydrogen bond with the imine N atom, while the other is engaged in an intermolecular N—H...π contact involving the benzene ring of a neighbouring molecule related by inversion. The benzene rings also participate in an intramolecular C—H...π contact of similar strength. In the crystal structure, molecules are separated by empty voids (ca 5% of the crystal volume, although the crystal seems to be unsolvated.

Clustering of amines and hydrazines in atmospheric nucleation

Science.gov (United States)

Li, Siyang; Qu, Kun; Zhao, Hailiang; Ding, Lei; Du, Lin

2016-06-01

It has been proved that the presence of amines in the atmosphere can enhance aerosol formation. Hydrazine (HD) and its substituted derivatives, monomethylhydrazine (MMH) and unsymmetrical dimethylhydrazine (UDMH), which are organic derivatives of amine and ammonia, are common trace atmospheric species that may contribute to the growth of nucleation clusters. The structures of the hydrazine and amine clusters containing one or two common nucleation molecules (ammonia, water, methanol and sulfuric acid) have been optimized using density functional theory (DFT) methods. The clusters growth mechanism has been explored from the thermochemistry by calculating the Gibbs free energies of adding an ammonia, water, methanol or sulfuric acid molecule step by step at room temperature, respectively. The results show that hydrazine and its derivatives could enhance heteromolecular homogeneous nucleation in the earth's atmosphere.

Devulcanization of Waste Tire Rubber Using Amine Based Solvents and Ultrasonic Energy

Directory of Open Access Journals (Sweden)

Walvekar Rashmi

2018-01-01

Full Text Available This research project focuses on an alternative pathway of devulcanizing waste tire rubber by using amine based chemicals. Waste tire rubbers are known to be as toxic, non-degradable material due to their vulcanized crosslink carbon structure, and disposing of such waste could impose hazardous impacts on the environment. The current rubber recycling methods that are practiced today are rather uneconomical, non-environmentally friendly, and also producing recycled rubber with low quality due to the alteration in the main polymeric chains of waste rubber. This project aims to answer the question of whether the usage of amine can produce high quality rubber, where the properties of recycled rubber is almost the same as new/virgin rubber. With known potential of amine, it is a challenge for the chemical to selectively cleave the sulfur bonds without affecting the main carbon backbone chain in the rubber structure and diminishing much of the rubber properties. To study this research, amine-treated rubber must undergo devulcanisation process by applying heat and sonication energy. Then, the properties of the amine-treated rubber were determined through a set of characterization tests and analysis which are: gel content test to determine the weight of rubber before and after devulcanization, the thermogravimetric analysis (TGA to determine the thermal degradation and stability of rubber, and Fourier Transform Infrared Spectroscopy (FTIR to determine any structural change of the rubber. In this research so far, the first two preliminary analysis tests have been performed. The gel content test has shown that tertiary amine samples possessed a lower gel content (% of (77 – 63 %, compared to primary amine samples (falls within the range of 80%, as well as the TGA test in which tertiary amine samples degrade faster than primary amine samples (suggesting a higher degree of rubber structure breakdown. For each type of amine, the concertation of amine did

Uranium diphosphonates templated by interlayer organic amines

Energy Technology Data Exchange (ETDEWEB)

Nelson, Anna-Gay D., E-mail: nelsoa@umich.edu [Department of Civil Engineering and Geological Sciences, University of Notre Dame, IN 46556 (United States); Department of Earth and Environmental Sciences, University of Michigan, Ann Arbor, MI 48109-1005 (United States); Alekseev, Evgeny V. [Institute of Energy and Climate Research (IEK-6), Forschungszentrum Juelich Wilhelm-Johnen-Strasse, 52428 Juelich (Germany); Institut fuer Kristallographie, RWTH Aachen University, D-52066 Aachen (Germany); Albrecht-Schmitt, Thomas E. [Department of Civil Engineering and Geological Sciences, University of Notre Dame, IN 46556 (United States); Department of Chemistry and Biochemistry, University of Notre Dame, IN 46556 (United States); Ewing, Rodney C. [Department of Earth and Environmental Sciences, University of Michigan, Ann Arbor, MI 48109-1005 (United States)

2013-02-15

The hydrothermal treatment of uranium trioxide and methylenediphosphonic acid with a variety of amines (2,2-dipyridyl, triethylenediamine, ethylenediamine, and 1,10-phenanthroline) at 200 Degree-Sign C results in the crystallization of a series of layered uranium diphosphonate compounds, [C{sub 10}H{sub 9}N{sub 2}]{l_brace}UO{sub 2}(H{sub 2}O)[CH{sub 2}(PO{sub 3})(PO{sub 3}H)]{r_brace} (Ubip2), [C{sub 6}H{sub 14}N{sub 2}]{l_brace}(UO{sub 2}){sub 2}[CH{sub 2}(PO{sub 3})(PO{sub 3}H)]{sub 2}{center_dot}2H{sub 2}O{r_brace} (UDAB), [C{sub 2}H{sub 10}N{sub 2}]{sub 2}{l_brace}(UO{sub 2}){sub 2}(H{sub 2}O){sub 2}[CH{sub 2}(PO{sub 3}){sub 2}]{sub 2}{center_dot}0.5H{sub 2}O{r_brace} (Uethyl), and [C{sub 12}H{sub 9}N{sub 2}]{l_brace}UO{sub 2}(H{sub 2}O)[CH{sub 2}(PO{sub 3})(PO{sub 3}H)]{r_brace} (Uphen). The crystal structures of the compounds are based on UO{sub 7} units linked by methylenediphosphonate molecules to form two-dimensional anionic sheets in Ubip2 and UDAB, and one-dimensional anionic chains in Uethyl and Uphen, which are charge balanced by protonated amine molecules. Interaction of the amine molecules with phosphonate oxygens and water molecules results in extensive hydrogen bonding in the interlayer. These amine molecules serve both as structure-directing agents and charge-balancing cations for the anionic uranium phosphonate sheets and chains in the formation of the different coordination geometries and topologies of each structure. Reported herein are the syntheses, structural and spectroscopic characterization of the synthesized compounds. - Graphical abstract: The Raman spectra of the synthesized compounds and an illustration of the stacking of the layers with the diprotonated triethylenediamine molecules in [C{sub 6}H{sub 14}N{sub 2}]{l_brace}(UO{sub 2}){sub 2}[CH{sub 2}(PO{sub 3})(PO{sub 3}H)]{sub 2}{center_dot}2H{sub 2}O{r_brace} UDAB. Solvent water molecules are removed for clarity. The corresponding Raman spectra for the complexes synthesized is also

Factors influencing the regioselectivity of the oxidation of asymmetric secondary amines with singlet oxygen.

Science.gov (United States)

Ushakov, Dmitry B; Plutschack, Matthew B; Gilmore, Kerry; Seeberger, Peter H

2015-04-20

Aerobic amine oxidation is an attractive and elegant process for the α functionalization of amines. However, there are still several mechanistic uncertainties, particularly the factors governing the regioselectivity of the oxidation of asymmetric secondary amines and the oxidation rates of mixed primary amines. Herein, it is reported that singlet-oxygen-mediated oxidation of 1° and 2° amines is sensitive to the strength of the α-C-H bond and steric factors. Estimation of the relative bond dissociation energy by natural bond order analysis or by means of one-bond C-H coupling constants allowed the regioselectivity of secondary amine oxidations to be explained and predicted. In addition, the findings were utilized to synthesize highly regioselective substrates and perform selective amine cross-couplings to produce imines. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chemical and Molecular Descriptors for the Reactivity of Amines with CO{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Lee, Anita S.; Kitchin, John R.

2012-10-24

Amine-based solvents are likely to play an important role in CO{sub 2} capture applications in the future, and the identification of amines with superior performance will facilitate their use in CO{sub 2} capture. While some improvements in performance will be achieved through process modifications, modifying the CO{sub 2} capture performance of an amine also implies in part an ability to modify the reactions between the amine and CO{sub 2} through development of new functionalized amines. We present a computational study of trends in the reactions between CO{sub 2} and functionalized amines with a focus on identifying molecular descriptors that determine trends in reactivity. We examine the formation of bicarbonate and carbamate species on three classes of functionalized amines: alkylamines, alkanolamines, and fluorinated alkylamines including primary, secondary and tertiary amines in each class. These functional groups span electron-withdrawing to donating behavior, hydrogen-bonding, extent of functionalization, and proximity effects of the functional groups. Electron withdrawing groups tend to destabilize CO{sub 2} reaction products, whereas electron-donating groups tend to stabilize CO{sub 2} reaction products. Hydrogen bonding stabilizes CO{sub 2} reaction products. Electronic structure descriptors based on electronegativity were found to describe trends in the bicarbonate formation energy. A chemical correlation was observed between the carbamate formation energy and the carbamic acid formation energy. The local softness on the reacting N in the amine was found to partially explain trends carbamic acid formation energy.

Analysis of amines by pH-Metrie in organic media

International Nuclear Information System (INIS)

Hamidi, A.; Elias, Abdelhamid; Achache, M.; Didi, M.

1999-01-01

Amines with long hydro carbonic strength and principally Trioclkylamines, are characterised by an important complexation mechanism for certain metals. This is the case for trioctylamine (TOA) which is very used in purification and uranium recovery from certain ores (1,2). This substance is generally found mixed with mono and di-octyl amines in commercial products and in synthesis mixtures. The purpose of this work is to develop a pH titration method in an organic media for a mixture consisted of mono, di and tri octyl amines (MOA, DOA et TOA). Adequate operating analysis condition have been proposed, based on intrinsic chemical properties for each precipitated substances (3,4). The obtained results show that this technique is recommended for qualitative and quantitative analysis of precipitated amines mixtures. The method is reproducible and the detection limit can reach 0,0001 molar

Selective fluorescence quenching of nitrogen-containing polycyclic aromatic hydrocarbons by aliphatic amines

International Nuclear Information System (INIS)

Li Xiaoping; McGuffin, Victoria L.

2004-01-01

In this investigation, primary, secondary, and tertiary amines are evaluated for their efficiency and selectivity as fluorescence quenchers for polycyclic aromatic hydrocarbons (PAHs) and nitrogen-containing polycyclic aromatic hydrocarbons (N-PAHs). In general, the quenching efficiency tends to increase from primary to tertiary amine due to a greater number of alkyl groups that increase the electron-donating ability. However, the selectivity decreases from primary to tertiary amine. The effect of low concentrations of water is also examined. Because water can form hydrogen bonds with amines, the nonbonding electron pair is not available for interaction with the fluorophore, thus the quenching constant is decreased. These aliphatic amines are then applied to PAHs and N-PAHs and some interesting trends are observed. Whereas amino-PAHs remain virtually unquenched by different amines, aza-PAHs are all quenched well. The selectivity between aza-PAHs and amino-PAHs is as high as several hundred. This trend provides an easy and effective method to discriminate between these classes of N-PAHs. Moreover, the alternant aza-PAHs are quenched more than their corresponding alternant PAHs

Early Post-Irradiation Changes in the Metabolism of Biogenic Amines; Les Changements Precoces du Metabolisme des Amines Biogenes apres Irradiation

Energy Technology Data Exchange (ETDEWEB)

Deanovic, Z [Institut Rudjer Boskovic, Zagreb, Yugoslavia (Croatia)

1971-03-15

There is accumulating evidence for the radiation-induced release of biogenic amines from their body stores. Having in mind the high patho-physiological activity of these ''local'' hormones and ''neuro-hormones'', it is reasonable to assume that they play an important role in the pathogenesis of the acute radiation syndrome. Under these pathological conditions the possible synergic and antagonistic effects of biogenic amines due to their complex interactions must be taken into consideration. The extent and dose-dependence of post-irradiation changes in the metabolism of histamine, serotonin, catecholamines and acetylcholine will be examined regarding particularly the search for biochemical indicators of radiation injury. The determination of bio-amines and their metabolites in urine seems to be a suitable method for following up those metabolic changes which could be of a biodosimetrical and/or prognostical value. Data published on this subject, obtained in experimental animals as well as in man, have been reviewed and the applicability of these tests is discussed. (author) [French] Des preuves se sont accumulees, qui demontrent que les amines biogenes sont liberees de leurs depots sous l'effet des rayonnements ionisants. Etant donne la grande activite pathophysiologique de ces hormones 'locales' et 'neurohormones', il est raisonnable de considerer que ces substances biogenes jouent un role important dans la pathogenese du syndrome aigu d'irradiation. Dans ces conditions pathologiques il faut tenir compte des effets synergiques et antagonistes des bio-amines, lies a des interactions compliquees. Les changements metaboliques en fonction de la dose recue font l'objet d'un examen qui englobe les alterations quantitatives de .'histamine, de la serotonine, des catecholamines et de l'acetylcholine et dont l'objectif est la recherche sur des indicateurs biochimiques de la lesion provoquee par l'irradiation. L'analyse des bio-amines et de leurs metabolites dans les urines

Extraction of uranyl sulfate with primary amine

International Nuclear Information System (INIS)

Mrnka, M.; Bizek, V.; Nekovar, P.; Cizevska, S.; Schroetterova, D.

1984-01-01

PRIMENE JM-T was used for extraction. Its composition was found to approach the general formula C 21 H 43 NH 2 . It was found that the extraction of uranyl sulfate is lower in case of a higher steady-state concentration of sulfuric acid in the aqueous phase. Extraction is accompanied with coextraction of water. The results obtained showed that uranyl sulfate passes into the organic phase by two mechanisms: extraction with amine sulfate and extraction with free amine. A mathematical description of the process was made based on the obtained results. (E.S.)

Poly(Amido Amine)s containing agmatine and butanol side chains as efficient gene carriers

NARCIS (Netherlands)

Won, Young-Wook; Ankone, Martinus J.K.; Engbersen, Johannes F.J.; Feijen, Jan; Kim, S.W.

2016-01-01

A new type of bioreducible poly(amido amine) copolymer is synthesized by the Michael addition polymerization of cystamine bisacrylamide (CBA) with 4-aminobutylguanidine (agmatine, AGM) and 4-aminobutanol (ABOL). Since the positively charged guanidinium groups of AGM and the hydroxybutyl groups of

Multi-Objective Optimization for Solid Amine CO2 Removal Assembly in Manned Spacecraft

Directory of Open Access Journals (Sweden)

Rong A

2017-07-01

Full Text Available Carbon Dioxide Removal Assembly (CDRA is one of the most important systems in the Environmental Control and Life Support System (ECLSS for a manned spacecraft. With the development of adsorbent and CDRA technology, solid amine is increasingly paid attention due to its obvious advantages. However, a manned spacecraft is launched far from the Earth, and its resources and energy are restricted seriously. These limitations increase the design difficulty of solid amine CDRA. The purpose of this paper is to seek optimal design parameters for the solid amine CDRA. Based on a preliminary structure of solid amine CDRA, its heat and mass transfer models are built to reflect some features of the special solid amine adsorbent, Polyethylenepolyamine adsorbent. A multi-objective optimization for the design of solid amine CDRA is discussed further in this paper. In this study, the cabin CO2 concentration, system power consumption and entropy production are chosen as the optimization objectives. The optimization variables consist of adsorption cycle time, solid amine loading mass, adsorption bed length, power consumption and system entropy production. The Improved Non-dominated Sorting Genetic Algorithm (NSGA-II is used to solve this multi-objective optimization and to obtain optimal solution set. A design example of solid amine CDRA in a manned space station is used to show the optimal procedure. The optimal combinations of design parameters can be located on the Pareto Optimal Front (POF. Finally, Design 971 is selected as the best combination of design parameters. The optimal results indicate that the multi-objective optimization plays a significant role in the design of solid amine CDRA. The final optimal design parameters for the solid amine CDRA can guarantee the cabin CO2 concentration within the specified range, and also satisfy the requirements of lightweight and minimum energy consumption.

Effect of foamability index of short chain alkyl amines on flotation of quartz

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Szczerkowska Sabina

2016-01-01

Full Text Available Amines can be used for flotation of various minerals, especially quartz. The flotation efficiency of quartz depends on the amine type and dose. It was proved that the shorter alkyl amine, higher amine concentration has to be used to recover quartz at the same level. In flotation amines play a role of both collectors and frothers. The ability of a amine to collect particles can be expressed in the form of contact angle, while the foaming properties by different parameters including dynamic foamability index (DFI and critical coalescence concentration (CCC. Determination of DFI and CCC requires advanced techniques and methods. Therefore, in this paper a rapid and facile method for determination of foaming properties of amines and also other surfactants was used. It was based on measuring the initial foam and froth heights in a conventional flotation machine at different concentrations of surfactants. The foam height-concentration curve was described by utilizing an empirical equation which was based on one-adjustable parameter called the foamability index (FI. In this work the foamability index was determined for butylamine (ButNH2, hexylamine (HexNH2 and octylamine (OctNH2 as examples of short chain alkyl amines. The determined foamability indices were 92, 12 and 4 mg/dm3 for ButNH2, HexNH2 and OctNH2, respectively. It was shown that when the flotation results of quartz were presented in the form of recovery versus normalized amine concentration in relation to the foamability index (c/FI, all the experimental data points converged to one curve. It indicates that amines act similarly but at different concentrations expressed as FI. The foamability index seems to be a useful parameter for characterizing any flotation frother.

Therapeutic efficacy of milbemycin oxime/praziquantel oral formulation (Milbemax® against Thelazia callipaeda in naturally infested dogs and cats

Directory of Open Access Journals (Sweden)

Motta Bruna

2012-05-01

Full Text Available Abstract Background Over the last few decades, canine and feline thelaziosis caused by Thelazia callipaeda eye worms has gained the attention of the veterinary community due to the spread of this ocular infestation in geographical areas previously regarded as non endemic. The therapeutic efficacy of milbemycin oxime/praziquantel tablets (Milbemax® against T. callipaeda was tested in naturally infested dogs and cats. Methods From January 2009 to July 2011 a placebo controlled and randomized field study was conducted in T. callipaeda endemic areas of Switzerland (CH and Italy (ITA involving client-owned animals. Dogs (n = 56 and cats (n = 31 were physically examined at enrolment Day 0 (D0 and twice afterwards (D7 and D14. Infested animals were orally treated with Milbemax® or with placebo tablets on D0 and, if an animal was found still infested with T. callipaeda, also on D7. On D14 nematodes were flushed from the conjunctiva, identified and counted. Results Out of 56 dogs, 43 were included in the statistical analysis, whereas 13 were excluded because the products under investigation were not administered with food, as required by the label. On D7 and D14, 72.7% and 90.9% of treated dogs were eye worm free, whereas in the placebo group 95.2% and 76.2% still harbored nematodes, resulting in a mean percentage worm count reduction for the Milbemax® group of 86.1% and 96.8%, respectively. Both results were significantly higher (p = 0.0001 than the placebo group. Out of the 31 cats included in the study at D7 and D14, 53.3% and 73.3% treated with Milbemax® were free of T. callipaeda, while 81.3% and 73.3 in the placebo group were still harbouring eye worms, resulting in a mean percentage worm count reduction for the treated group of 62.2% and 80.0%, respectively. Both results were significantly higher (p = 0.0106 and p = 0.0043 than the placebo group. Conclusions The commercial formulation of milbemycin oxime at the minimal dose

Platinum-Catalyzed, Terminal-Selective C(sp(3))-H Oxidation of Aliphatic Amines.

Science.gov (United States)

Lee, Melissa; Sanford, Melanie S

2015-10-14

This Communication describes the terminal-selective, Pt-catalyzed C(sp(3))-H oxidation of aliphatic amines without the requirement for directing groups. CuCl2 is employed as a stoichiometric oxidant, and the reactions proceed in high yield at Pt loadings as low as 1 mol%. These transformations are conducted in the presence of sulfuric acid, which reacts with the amine substrates in situ to form ammonium salts. We propose that protonation of the amine serves at least three important roles: (i) it renders the substrates soluble in the aqueous reaction medium; (ii) it limits binding of the amine nitrogen to Pt or Cu; and (iii) it electronically deactivates the C-H bonds proximal to the nitrogen center. We demonstrate that this strategy is effective for the terminal-selective C(sp(3))-H oxidation of a variety of primary, secondary, and tertiary amines.

Factors influencing phase-disengagement rates in solvent-extraction systems employing tertiary amine extractants

International Nuclear Information System (INIS)

Moyer, B.A.; McDowell, W.J.

1981-01-01

The primary purpose of the present investigation was to examine the effects of amine size and structure on phase disengagement. Nine commercial tertiary amines were tested together with four laboratory-quality amines for uranium extraction and both organic-continuous (OC) and aqueous-continuous (AC) phase disengagement under Amex-type conditions. Synthetic acid sulfate solutions with and without added colloidal silica and actual ore leach solutions were used as the aqueous phases. Phase disengagement results were correlated with amine size and branching and solution wetting behavior on a silicate (glass) surface. The results suggest that the performance of some Amex systems may be improved by using branched chain tertiary amine extractants of higher molecular weight than are now normally used

Facile and Green Synthesis of Saturated Cyclic Amines

Directory of Open Access Journals (Sweden)

Arruje Hameed

2017-10-01

Full Text Available Single-nitrogen containing saturated cyclic amines are an important part of both natural and synthetic bioactive compounds. A number of methodologies have been developed for the synthesis of aziridines, azetidines, pyrrolidines, piperidines, azepanes and azocanes. This review highlights some facile and green synthetic routes for the synthesis of unsubstituted, multisubstituted and highly functionalized saturated cyclic amines including one-pot, microwave assisted, metal-free, solvent-free and in aqueous media.

Calcium(ii)-catalyzed enantioselective conjugate additions of amines.

Science.gov (United States)

Uno, Brice E; Dicken, Rachel D; Redfern, Louis R; Stern, Charlotte M; Krzywicki, Greg G; Scheidt, Karl A

2018-02-14

The direct enantioselective chiral calcium(ii)·phosphate complex (Ca[CPA] 2 )-catalyzed conjugate addition of unprotected alkyl amines to maleimides was developed. This mild catalytic system represents a significant advance towards the general convergent asymmetric amination of α,β-unsaturated electrophiles, providing medicinally relevant chiral aminosuccinimide products in high yields and enantioselectivities. Furthermore, the catalyst can be reused directly from a previously chromatographed reaction and still maintain both high yield and selectivity.

Amine terminated SAMs: Investigating why oxygen is present in these films

International Nuclear Information System (INIS)

Baio, J.E.; Weidner, T.; Brison, J.; Graham, D.J.; Gamble, Lara J.; Castner, David G.

2009-01-01

Self-assembled monolayers (SAMs) on gold prepared from amine-terminated alkanethiols have long been employed as model positively charged surfaces. Yet in previous studies significant amounts of unexpected oxygen containing species are always detected in amine terminated SAMs. Thus, the goal of this investigation was to determine the source of these oxygen species and minimize their presence in the SAM. The surface composition, structure, and order of amine-terminated SAMs on Au were characterized by X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectroscopy (ToF-SIMS), sum frequency generation (SFG) and near edge X-ray absorption fine structure (NEXAFS) spectroscopy. XPS determined compositions of amine-terminated SAMs in the current study exhibited oxygen concentrations of 2.4 ± 0.4 atomic %, a substantially lower amount of oxygen than reported in previously published studies. High-resolution XPS results from the S 2p , C 1s and N 1s regions did not detect any oxidized species. Angle-resolved XPS indicated that the small amount of oxygen detected was located at or near the amine head group. Small amounts of oxidized nitrogen, carbon and sulfur secondary ions, as well as ions attributed to water, were detected in the ToF-SIMS data due to the higher sensitivity of ToF-SIMS. The lack of N-O, S-O, and C-O stretches in the SFG spectra are consistent with the XPS and ToF-SIMS results and together show that oxidation of the amine-terminated thiols alone can only account for, at most, a small fraction of the oxygen detected by XPS. Both the SFG and angle-dependent NEXAFS indicated the presence of gauche defects in the amine SAMs. However, the SFG spectral features near 2865 cm -1 , assigned to the stretch of the methylene group next to the terminal amine unit, demonstrate the SAM is reasonably ordered. The SFG results also show another broad feature near 3200 cm -1 related to hydrogen-bonded water. From this multi-technique investigation it is

Biogenic Amines in Insect Antennae

Directory of Open Access Journals (Sweden)

Marianna I. Zhukovskaya

2017-06-01

Full Text Available Insect antenna is a multisensory organ, each modality of which can be modulated by biogenic amines. Octopamine (OA and its metabolic precursor tyramine (TA affect activity of antennal olfactory receptor neurons. There is some evidence that dopamine (DA modulates gustatory neurons. Serotonin can serve as a neurotransmitter in some afferent mechanosensory neurons and both as a neurotransmitter and neurohormone in efferent fibers targeted at the antennal vessel and mechanosensory organs. As a neurohormone, serotonin affects the generation of the transepithelial potential by sensillar accessory cells. Other possible targets of biogenic amines in insect antennae are hygro- and thermosensory neurons and epithelial cells. We suggest that the insect antenna is partially autonomous in the sense that biologically active substances entering its hemolymph may exert their effects and be cleared from this compartment without affecting other body parts.

Role of amine structure on carbon dioxide adsorption from ultradilute gas streams such as ambient air.

Science.gov (United States)

Didas, Stephanie A; Kulkarni, Ambarish R; Sholl, David S; Jones, Christopher W

2012-10-01

A fundamental study on the adsorption properties of primary, secondary, and tertiary amine materials is used to evaluate what amine type(s) are best suited for ultradilute CO(2) capture applications. A series of comparable materials comprised of primary, secondary, or tertiary amines ligated to a mesoporous silica support via a propyl linker are used to systematically assess the role of amine type. Both CO(2) and water adsorption isotherms are presented for these materials in the range relevant to CO(2) capture from ambient air and it is demonstrated that primary amines are the best candidates for CO(2) capture from air. Primary amines possess both the highest amine efficiency for CO(2) adsorption as well as enhanced water affinity compared to other amine types or the bare silica support. The results suggest that the rational design of amine adsorbents for the extraction of CO(2) from ambient air should focus on adsorbents rich in primary amines. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Copper(II)-catalyzed electrophilic amination of quinoline N-oxides with O-benzoyl hydroxylamines.

Science.gov (United States)

Li, Gang; Jia, Chunqi; Sun, Kai; Lv, Yunhe; Zhao, Feng; Zhou, Kexiao; Wu, Hankui

2015-03-21

Copper acetate-catalyzed C-H bond functionalization amination of quinoline N-oxides was achieved using O-benzoyl hydroxylamine as an electrophilic amination reagent, thereby affording the desired products in moderate to excellent yields. Electrophilic amination can also be performed in good yield on a gram scale.

Activation of human IK and SK Ca2+ -activated K+ channels by NS309 (6,7-dichloro-1H-indole-2,3-dione 3-oxime)

DEFF Research Database (Denmark)

Strøbaek, Dorte; Teuber, Lene; Jørgensen, Tino D

2004-01-01

We have identified and characterized the compound NS309 (6,7-dichloro-1H-indole-2,3-dione 3-oxime) as a potent activator of human Ca2+ -activated K+ channels of SK and IK types, whereas it is devoid of effect on BK type channels. IK- and SK-channels have previously been reported to be activated...

Catalyst Deactivation Reactions : The Role of Tertiary Amines Revisited

NARCIS (Netherlands)

Novarino, Elena; Rios, Itzel Guerrero; van der Veer, Siebe; Meetsma, Auke; Hessen, Bart; Bouwkamp, Marco W.

2011-01-01

Decamethylzirconocene cation [Cp*2ZrMe](+) (2) decomposes in bromobenzene-d(5) solution to generate sigma-aryl species [Cp*Zr-2(2-C6H4Br-kappa Br,C)][B(C6F5)(4)] (3). This a-bond metathesis reaction is catalyzed by tertiary amines via a two-step mechanism, in which the amine acts as a proton relay.

Functional expression of amine oxidase from Aspergillus niger (AO-I) in Saccharomyces cerevisiae.

Science.gov (United States)

Kolaríková, Katerina; Galuszka, Petr; Sedlárová, Iva; Sebela, Marek; Frébort, Ivo

2009-01-01

The aim of this work was to prepare recombinant amine oxidase from Aspergillus niger after overexpressing in yeast. The yeast expression vector pDR197 that includes a constitutive PMA1 promoter was used for the expression in Saccharomyces cerevisiae. Recombinant amine oxidase was extracted from the growth medium of the yeast, purified to homogeneity and identified by activity assay and MALDI-TOF peptide mass fingerprinting. Similarity search in the newly published A. niger genome identified six genes coding for copper amine oxidase, two of them corresponding to the previously described enzymes AO-I a methylamine oxidase and three other genes coding for FAD amine oxidases. Thus, A. niger possesses an enormous metabolic gear to grow on amine compounds and thus support its saprophytic lifestyle.

Evaluation and Computational Characterization of the Faciliated Transport of Glc Carbon C-1 Oxime Reactivators Across a Blood Brain Barrier Model

Science.gov (United States)

2013-01-01

blood brain barrier (BBB) to reactivate inhibited brain acetylcholinesterase (AChE). We selected glucose (Glc) transporters (GLUT) for this purpose as...Eur. J. Pharm. 332 (1997) 43–52. [4] N.J. Abbott , L. Ronnback, E. Hansson, Astrocyte-endothelial interactions at the blood –brain barrier, Nat. Rev...5a. CONTRACT NUMBER oxime reactivators across a blood brain barrier model 5b. GRANT NUMBER 1.E005.08.WR 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S

Enzymatic network for production of ether amines from alcohols

DEFF Research Database (Denmark)

Palacio, Cyntia M.; Crismaru, Ciprian G.; Bartsch, Sebastian

2016-01-01

We constructed an enzymatic network composed of three different enzymes for the synthesis of valuable ether amines. The enzymatic reactions are interconnected to catalyze the oxidation and subsequent transamination of the substrate and to provide cofactor recycling. This allows production...... of the desired ether amines from the corresponding ether alcohols with inorganic ammonium as the only additional substrate. To examine conversion, individual and overall reaction equilibria were established. Using these data, it was found that the experimentally observed conversions of up to 60% observed...... for reactions containing 10mM alcohol and up to 280mM ammonia corresponded well to predicted conversions. The results indicate that efficient amination can be driven by high concentrations of ammonia and may require improving enzyme robustness for scale-up....

Ultrafast relaxation dynamics of amine-substituted bipyridyl ruthenium(II) complexes

Science.gov (United States)

Song, Hongwei; Wang, Xian; Yang, WenWen; He, Guiying; Kuang, Zhuoran; Li, Yang; Xia, Andong; Zhong, Yu-Wu; Kong, Fan'ao

2017-09-01

The excited state properties of a series of ruthenium(II) amine-substituted bipyridyl complexes, [Ru(bpy)n(NNbpy)3-n]2+, were investigated by steady-state and transient absorption spectroscopy, as well as quantum chemical calculations. The steady-state absorption spectra of these complexes in CH3CN show a distinct red-shift of the 1MLCT absorption with increasing numbers of amine substituent, whereas the emission spectra indicate an energy gap order of [Ru(bpy)3]2+ > [Ru(bpy)2(NNbpy)]2+ > [Ru(NNbpy)3]2+ > [Ru(bpy)(NNbpy)2]2+. Nanosecond, femtosecond transient absorption and electrochemical measurements suggest that NNbpy ligand has a strong influence on the electronic and emission properties of these complexes, due to electron-rich amine substituent. We illustrate how the numbers of amine substituent modulate the spectroscopic properties of transition metal complexes, which is related to the design of new electro-active systems with novel photoelectrochemical properties.

Nano ZnO/amine composites antimicrobial additives to acrylic paints

Directory of Open Access Journals (Sweden)

H.B. Kamal

2015-12-01

Full Text Available Nano ZnO has been widely used as an antimicrobial agent not only for food packaging purposes but also in many coating processes. The present work is meant to enhance such functions through the preparation of sustainable and safe conduct of nano ZnO composites with amine derivatives that are characterized by their antimicrobial and anti-fouling functional activities. The results obtained revealed a more comprehensive approach to the antimicrobial function based on the reported active oxide species role. The oxide/amine composites and the acrylic emulsion paint were characterized chemically and structurally through FT-IR, TGA and TEM supported by biological assessment of each ZnO/amine composite action. Results of the study concluded that equilibrium between the nano ZnO particles size, their dispersion form, and amine ability to stabilize the actively produced oxygen species responsible for the antimicrobial function, should all be accounted for when persistence of antimicrobial agent efficiency is regarded.

Alkylselenite-catalyzed Oxidative Carbonylation of Amines: Density Functional Theory Study

Energy Technology Data Exchange (ETDEWEB)

Hwang, Sun; Kim, Hoon Sik; Cheong, Minserk [Kyung Hee Univ., Seoul (Korea, Republic of)

2012-11-15

Ureas and carbamates have been conventionally produced by the reaction of amines with phosgene. However, phosgenation processes raise severe environmental concerns, which are attributed to the toxicity of phosgene and the formation of corrosive hydrogen chloride as a co-product. The considerable industrial interest in replacing current phosgene-based processes prompted several methods using non-phosgene routes including carbonylation of amines or nitro compounds and carbomethoxylation of amines with dialkylcarbonates. Among these, catalytic oxidative carbonylation of an amine in the presence of alcohol has been studied most extensively. Catalytic systems based on precious metals such as Rh and Pd are commonly used for this purpose, but most of these catalytic systems suffer from either low reactivity or severe reaction conditions such as high temperature and pressures. In conclusion, the facile change of selenium oxidation state by CO and O{sub 2} might be the main reason for the activity of the selenium catalyst for this reaction.

Alkylselenite-catalyzed Oxidative Carbonylation of Amines: Density Functional Theory Study

International Nuclear Information System (INIS)

Hwang, Sun; Kim, Hoon Sik; Cheong, Minserk

2012-01-01

Ureas and carbamates have been conventionally produced by the reaction of amines with phosgene. However, phosgenation processes raise severe environmental concerns, which are attributed to the toxicity of phosgene and the formation of corrosive hydrogen chloride as a co-product. The considerable industrial interest in replacing current phosgene-based processes prompted several methods using non-phosgene routes including carbonylation of amines or nitro compounds and carbomethoxylation of amines with dialkylcarbonates. Among these, catalytic oxidative carbonylation of an amine in the presence of alcohol has been studied most extensively. Catalytic systems based on precious metals such as Rh and Pd are commonly used for this purpose, but most of these catalytic systems suffer from either low reactivity or severe reaction conditions such as high temperature and pressures. In conclusion, the facile change of selenium oxidation state by CO and O 2 might be the main reason for the activity of the selenium catalyst for this reaction

From caffeine to fish waste: amine compounds present in food and drugs and their interactions with primary amine oxidase.

LENUS (Irish Health Repository)

Olivieri, Aldo

2011-07-01

Tissue bound primary amine oxidase (PrAO) and its circulating plasma-soluble form are involved, through their catalytic activity, in important cellular roles, including the adhesion of lymphocytes to endothelial cells during various inflammatory conditions, the regulation of cell growth and maturation, extracellular matrix deposition and maturation and glucose transport. PrAO catalyses the oxidative deamination of several xenobiotics and has been linked to vascular toxicity, due to the generation of cytotoxic aldehydes. In this study, a series of amines and aldehydes contained in food and drugs were tested via a high-throughput assay as potential substrates or inhibitors of bovine plasma PrAO. Although none of the compounds analyzed were found to be substrates for the enzyme, a series of molecules, including caffeine, the antidiabetics phenformin and tolbutamide and the antimicrobial pentamidine, were identified as PrAO inhibitors. Although the inhibition observed was in the millimolar and micromolar range, these data show that further work will be necessary to elucidate whether the interaction of ingested biogenic or xenobiotic amines with PrAO might adversely affect its biological roles.

Metal Monolithic Amine-grafted Zeolite for CO{sub 2} Capture

Energy Technology Data Exchange (ETDEWEB)

Chuang, Steven

2011-03-31

The solid amine sorbent for CO{sub 2} capture process has advantages of simplicity and low operating cost compared to the MEA (monoethanolamine) process. Solid amine sorbents reported so far suffered from either low CO{sub 2} capture capacity or low stability. The solid amine sorbent developed in this project exhibited more than 3.2 mmol/g and degraded less than 10% even after 500 cycles of heating and cooling in absence of steam. The presence of steam further enhanced CO{sub 2} capture capacity. The cost of the sorbent is estimated to be less than $7.00/lb. This sorbent was developed using the results of in situ infrared spectroscopic study. Infrared results showed that CO{sub 2} adsorbs on TEPA (tetraethylenepentamine)/PEG (polyethylene glycol) as carbamates and bicarbonates. The CO{sub 2} adsorption capacity and oxidation resistance of the amine sorbent can be enhanced by the interactions between NH{sub 2} of TEPA molecules with the OH group of PEG molecules. PEG was also found to be effectively disperse and immobilize the aromatic amines for SO{sub 2} adsorption. The infrared study also showed that SiO{sub 2} is a significantly better support than zeolites due to its proper hydrophobicity. The results of this study led to the development of a high performance solid amine sorbent under simulated gas flow condition in a fixed bed, a fluidized bed, and a metal monolith unit. This study showed heat transfer could become a major technical issue in scaling up a fixed bed adsorber. The use of the fluidized bed and metal monoliths can alleviate the heat transfer issue. The metal monolith could be suitable for small scale applications due to the high cost of manufacturing; the fluidized bed mode would be most suitable for large scale applications. Preliminary economic analysis suggested that the Akron solid amine process would cost 45% less than that of MEA process.

Concentration, size distribution and dry deposition of amines in atmospheric particles of urban Guangzhou, China

Science.gov (United States)

Liu, Fengxian; Bi, Xinhui; Zhang, Guohua; Peng, Long; Lian, Xiufeng; Lu, Huiying; Fu, Yuzhen; Wang, Xinming; Peng, Ping'an; Sheng, Guoying

2017-12-01

Size-segregated PM10 samples were collected in Guangzhou, China during autumn of 2014. Nine amines, including seven aliphatic amines and two heterocyclic amines, were detected using a gas chromatography-mass spectrometer after derivatization by benzenesulfonyl chloride. The total concentration of the nine amines (Ʃamines) was 79.6-140.9 ng m-3 in PM10. The most abundant species was methylamine (MA), which had a concentration of 29.2-70.1 ng m-3. MA, dimethylamine (DMA), diethylamine (DEA) and dibutylamine (DBA) were the predominant amines in the samples and accounted for approximately 80% of Ʃamines in each size segment. Two heterocyclic amines, pyrrolidine (PYR) and morpholine (MOR), were detected in all samples and had average concentrations of 1.14 ± 0.37 and 1.89 ± 0.64 ng m-3, respectively, in particles with aerodynamic diameters ammonium ranged from 0.0068 to 0.0107 in particles with diameters <1.5 μm, and the maximum ratio occurred in the smallest particles (diameter< 0.49 μm). The average dry deposition flux and velocity of Ʃamines in PM10 were 7.9 ± 1.6 μg m-2 d-1 and 0.084 ± 0.0021 cm s-1, respectively. The results of this study provide essential information on the contribution of amines to secondary organic aerosols and dry removal mechanisms in urban areas.

Purification and characterization of the amine dehydrogenase from a facultative methylotroph.

Science.gov (United States)

Coleman, J P; Perry, J J

1984-01-01

Strain RA-6 is a pink-pigmented organism which can grow on a variety of substrates including methylamine. It can utilize methylamine as sole source of carbon via an isocitrate lyase negative serine pathway. Methylamine grown cells contain an inducible primary amine dehydrogenase [primary amine: (acceptor) oxidoreductase (deaminating)] which is not present in succinate grown cells. The amine dehydrogenase was purified to over 90% homogeneity. It is an acidic protein (isoelectric point of 5.37) with a molecular weight of 118,000 containing subunits with approximate molecular weights of 16,500 and 46,000. It is active on an array of primary terminal amines and is strongly inhibited by carbonyl reagents. Cytochrome c or artificial electron acceptors are required for activity; neither NAD nor NADP can serve as primary electron acceptor.

Nucleophilic addition of amines to the activated ethylene bond in non-aqueous media

International Nuclear Information System (INIS)

Perepichka, Igor F.; Popov, Anatolii F.

1995-01-01

The kinetics of addition of a number of primary and secondary aliphatic amines to trans-(2-furyl) nitro ethylene (1) has been studied in solvents of various polarities (from acetonitrile, ε 37.5, to heptane, ε 1.89). It has been shown that the reaction is catalysed both by the amine reagent and by tertiary amines. On the basis of analyzing the observed kinetic regularities a stepwise reaction mechanism has been proposed which involves formation of zwitterionic intermediate (3) at the first equilibrium step (k 1 , K 1 ) which is then converted into the reaction product by means of proton transfer in parallel routes, the non-catalytic one (k 2 ) and that catalysed by the initial (K 3 ) or tertiary (K 4 ) amine. The observed high values of the deuterium isotope effects in the reaction (K H /K D ∼ 2.3 - 8.9) confirm that proton transfer occurs in the rate-limiting step of the reaction (primary kinetic isotope effect). The third order by amine kinetic route is observed in low polar media which is due to participation of amine dimers (R 2 NH HNR 2 ) in the reaction. The observed kinetic regularities are compared with those for the nucleophilic aromatic substitution reactions in low-polar media, and the conclusion has been made that the reaction route of the third order by amine proceeds as reversible nucleophilic attack by amine dimer and following base-catalysed transformation of the intermediate into the product. (author)

Corrosion inhibition of brass by aliphatic amines

International Nuclear Information System (INIS)

Taha, K. K.; Sheshadri, B. S; Ahmed, M. F.

2005-01-01

Aliphatic amines hexylamine (HCA), octylamine (OCA) and decylamine (DCA) have been used as corrosion inhibitors for (70/30) brass in 0.I M HCIO 4 . The inhibitor efficiency (%P) calculated using weight loss, Tafel extrapolation, linear polarization and impedance methods was found to be in the order DCA> OCA> HCA. These adsorb on brass surface following bockris-swinkels' isotherm. DCA, OCA and HCA displaced 4, 3 and 2 molecules of water from interface respectively. Displacement of water molecules brought a great reorganization of double layer at the interface. These amines during corrosion form complexes with dissolved zinc and copper ions.(Author)

A one-pot chemoselective synthesis of secondary amines by using a biomimetic electrocatalytic system

International Nuclear Information System (INIS)

Largeron, Martine

2009-01-01

A one-pot electrochemically induced oxidation-imine formation-reduction route to secondary amines is described in detail. The key step of the process consists of the o-iminoquinone-mediated chemoselective catalytic oxidation of a primary aliphatic amine substrate, in the presence of a second amine used as the alkylating agent. Through the examination of the scope of the reaction by systematically varying both amine substrate and amine alkylating agent, it can be shown that this reaction sequence, leaving ammonia as the sole by-product, allows the rapid synthesis of various secondary amines in moderate to good yields. This process, that highlights the pre-eminent green advantages of electrochemical synthesis, especially the utilization of electricity as energy instead of chemical reagents, high atom economy as well as ambient temperature and pressure, could be a mild alternative to already reported synthetic methods.

A one-pot chemoselective synthesis of secondary amines by using a biomimetic electrocatalytic system

Energy Technology Data Exchange (ETDEWEB)

Largeron, Martine [UMR CNRS 8638, Synthese et Structure de Molecules d' nteret Pharmacologique, Universite Paris Descartes, Faculte des Sciences Pharmaceutiques et Biologiques, 4 Avenue de l' Observatoire, 75270 Paris Cedex 06 (France)], E-mail: martine.largeron@parisdescartes.fr

2009-09-01

A one-pot electrochemically induced oxidation-imine formation-reduction route to secondary amines is described in detail. The key step of the process consists of the o-iminoquinone-mediated chemoselective catalytic oxidation of a primary aliphatic amine substrate, in the presence of a second amine used as the alkylating agent. Through the examination of the scope of the reaction by systematically varying both amine substrate and amine alkylating agent, it can be shown that this reaction sequence, leaving ammonia as the sole by-product, allows the rapid synthesis of various secondary amines in moderate to good yields. This process, that highlights the pre-eminent green advantages of electrochemical synthesis, especially the utilization of electricity as energy instead of chemical reagents, high atom economy as well as ambient temperature and pressure, could be a mild alternative to already reported synthetic methods.

In Situ Preparation of Polyether Amine Functionalized MWCNT Nanofiller as Reinforcing Agents

Directory of Open Access Journals (Sweden)

Ayber Yıldrım

2014-01-01

Full Text Available In situ preparation of polyether amine functionalized cross-linked multiwalled carbon nanotube (MWCNT nanofillers may improve the thermal and mechanical properties of the composites in which they are used as reinforcing agents. The reduction and functionalization of MWCNT using ethylenediamine in the presence of polyether amine produced stitched MWCNT's due to the presence of two amine (–NH2 functionalities on both sides of the polymer. Polyether amine was chosen to polymerize the carboxylated MWCNT due to its potential to form bonds with the amino groups and carboxyl groups of MWCNT which produces a resin used as polymeric matrix for nanocomposite materials. The attachment of the polyether amine (Jeffamine groups was verified by TGA, FT-IR, XRD, SEM, and Raman spectroscopy. The temperature at which the curing enthalpy is maximum, observed by DSC, was shifted to higher values by adding functionalized MWCNT. SEM images show the polymer formation between MWCNT sheets.

A practical and catalyst-free trifluoroethylation reaction of amines using trifluoroacetic acid

Science.gov (United States)

Andrews, Keith G.; Faizova, Radmila; Denton, Ross M.

2017-06-01

Amines are a fundamentally important class of biologically active compounds and the ability to manipulate their physicochemical properties through the introduction of fluorine is of paramount importance in medicinal chemistry. Current synthesis methods for the construction of fluorinated amines rely on air and moisture sensitive reagents that require special handling or harsh reductants that limit functionality. Here we report practical, catalyst-free, reductive trifluoroethylation reactions of free amines exhibiting remarkable functional group tolerance. The reactions proceed in conventional glassware without rigorous exclusion of either moisture or oxygen, and use trifluoroacetic acid as a stable and inexpensive fluorine source. The new methods provide access to a wide range of medicinally relevant functionalized tertiary β-fluoroalkylamine cores, either through direct trifluoroethylation of secondary amines or via a three-component coupling of primary amines, aldehydes and trifluoroacetic acid. A reduction of in situ-generated silyl ester species is proposed to account for the reductive selectivity observed.

New procedure of selected biogenic amines determination in wine samples by HPLC

Energy Technology Data Exchange (ETDEWEB)

Piasta, Anna M.; Jastrzębska, Aneta, E-mail: aj@chem.uni.torun.pl; Krzemiński, Marek P.; Muzioł, Tadeusz M.; Szłyk, Edward

2014-06-27

Highlights: • We proposed new procedure for derivatization of biogenic amines. • The NMR and XRD analysis confirmed the purity and uniqueness of derivatives. • Concentration of biogenic amines in wine samples were analyzed by RP-HPLC. • Sample contamination and derivatization reactions interferences were minimized. - Abstract: A new procedure for determination of biogenic amines (BA): histamine, phenethylamine, tyramine and tryptamine, based on the derivatization reaction with 2-chloro-1,3-dinitro-5-(trifluoromethyl)-benzene (CNBF), is proposed. The amines derivatives with CNBF were isolated and characterized by X-ray crystallography and {sup 1}H, {sup 13}C, {sup 19}F NMR spectroscopy in solution. The novelty of the procedure is based on the pure and well-characterized products of the amines derivatization reaction. The method was applied for the simultaneous analysis of the above mentioned biogenic amines in wine samples by the reversed phase-high performance liquid chromatography. The procedure revealed correlation coefficients (R{sup 2}) between 0.9997 and 0.9999, and linear range: 0.10–9.00 mg L{sup −1} (histamine); 0.10–9.36 mg L{sup -1} (tyramine); 0.09–8.64 mg L{sup −1} (tryptamine) and 0.10–8.64 mg L{sup −1} (phenethylamine), whereas accuracy was 97%–102% (recovery test). Detection limit of biogenic amines in wine samples was 0.02–0.03 mg L{sup −1}, whereas quantification limit ranged 0.05–0.10 mg L{sup −1}. The variation coefficients for the analyzed amines ranged between 0.49% and 3.92%. Obtained BA derivatives enhanced separation the analytes on chromatograms due to the inhibition of hydrolysis reaction and the reduction of by-products formation.

Amine functionalized nanodiamond promotes cellular adhesion, proliferation and neurite outgrowth

International Nuclear Information System (INIS)

Hopper, A P; Dugan, J M; Gill, A A; Haycock, J W; Claeyssens, F; Fox, O J L; May, P W

2014-01-01

In this study, we report the production of amine functionalized nanodiamond. The amine functionalized nanodiamond forms a conformal monolayer on a negatively charged surface produced via plasma polymerization of acrylic acid. Nanodiamond terminated surfaces were studied as substrates for neuronal cell culture. NG108-15 neuroblastoma-glyoma hybrid cells were successfully cultured upon amine functionalized nanodiamond coated surfaces for between 1 and 7 d. Additionally, primary dorsal root ganglion (DRG) neurons and Schwann cells isolated from Wistar rats were also successfully cultured over a period of 21 d illustrating the potential of the coating for applications in the treatment of peripheral nerve injury. (paper)

Amine oxidase from lentil seedlings: energetic domains and effect of temperature on activity.

Science.gov (United States)

Moosavi-Nejad, S Z; Rezaei-Tavirani, M; Padiglia, A; Floris, G; Moosavi-Movahedi, A A

2001-07-01

Copper/TPQ amine oxidases from mammalian and plant sources have shown many differences in substrate specificity and molecular properties. In this work the activity of lentil seedling amine oxidase was followed at various temperatures in 100 mM potassium phosphate buffer, pH 7, using benzylamine as substrate. The discontinuous Arrhenius plot of lentil amine oxidase showed two distinct phases with a jump between them. Thermal denaturation of the enzyme, using differential scanning calorimetry under the same experimental conditions, showed a transition at the same temperature ranges in the absence of substrate, indicating the occurrence of conformational changes, with an enthalpy change of about 175.9 kJ/mole. The temperature-induced changes of the activity of lentil amine oxidase are compared with those of bovine serum amine oxidase (taken from the literature).

Deuterium exchange between hydrofluorocarbons and amines

International Nuclear Information System (INIS)

Hammond, W.B.; Bigeleisen, J.; Tuccio, S.A.

1983-01-01

The invention consists of a process for obtaining a compound enriched in deuterium which comprises the known method of exposing a gaseous hydrofluorocarbon to infrared laser radiation of a predetermined frequency to selectively cause a chemical reaction involving hydrofluorocarbon molecules containing deuterium without substantially affecting hydrofluorocarbon molecules not containing deuterium, thereby producing, as reaction products, a compound enriched in deuterium and hydrofluorocarbon depleted in deuterium; combined with a new method, which comprises enriching the deuterium content of the depleted hydrofluorocarbon by contacting the depleted hydrofluorocarbon with an alkali metal amide and an amine having a concentration of deuterium at least that which will yield an increase in deuterium concentration of the hydrofluorocarbon upon equilibration, whereby the amine becomes depleted in deuterium

A Bioinspired Organocatalytic Cascade for the Selective Oxidation of Amines under Air.

Science.gov (United States)

Largeron, Martine; Fleury, Maurice-Bernard

2017-05-17

A bioinspired organocatalytic cascade reaction for the selective aerobic oxidative cross-coupling of primary amines to imines is described. This approach takes advantages of commercially available pyrogallol monomeric precursor to deliver low loadings of natural purpurogallin in situ, under air. This is further engaged in a catalytic process with the amine substrate affording, under single turnover, the active biomimetic quinonoid organocatalyst and the homocoupled imine intermediate, which is then converted into cross-coupled imine after dynamic transimination. This organocatalytic cascade inspired by both purpurogallin biosynthesis and copper amine oxidases allows the aerobic oxidation of non-activated primary amines that non-enzymatic organocatalysts were not able to accomplish alone. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A rapid detection method for policy-sensitive amines real-time supervision.

Science.gov (United States)

Zhang, Haixu; Shu, Jinian; Yang, Bo; Zhang, Peng; Ma, Pengkun

2018-02-01

Many organic amines that comprise a benzene ring are policy-sensitive because of their toxicity and links to social harm. However, to date, detection of such compounds mainly relies on offline methods. This study proposes an online pptv (parts per trillion by volume) level of detection method for amines, using the recently-built vacuum ultraviolet photoionization mass spectrometer (VUV-PIMS) combined with a new doping technique. Thus, the dichloromethane doping-assisted photoionization mass spectra of aniline, benzylamine, phenethylamine, amphetamine, and their structural isomers were recorded. The dominant characteristic mass peaks for all amines are those afforded by protonated amines and the amino radical-loss. The signal intensities of the amines were enhanced by 60-130 times compared to those recorded without doping assistance. Under 10s detection time, the sensitivities of aniline and benzylamine in the gas phase were determined as 4.0 and 2.7 countspptv -1 , with limits of detection (LODs) of 36 and 22 pptv, respectively. Notably, the detection efficiency of this method can be tenfold better in future applications since the ion transmission efficiency of the mass spectrometer was intentionally reduced to ~ 10% in this study. Therefore, dichloromethane doping-assisted photoionization mass spectrometry has proven to be a highly promising on-line approach to amine detection in environmental and judicial supervision and shows great potential for application in the biological field. Copyright © 2017 Elsevier B.V. All rights reserved.

Dynamics of CO 2 Adsorption on Amine Adsorbents. 2. Insights Into Adsorbent Design

KAUST Repository

Bollini, Praveen

2012-11-21

Packed bed breakthrough experiments are reported for commercial zeolite 13X and 3-aminopropyl-functionalized SBA-15 silica materials with three different amine loadings. Mass and heat transfer dynamics for all four materials are modeled successfully. Amine adsorbents with open pores are found to exhibit faster mass diffusion rates compared to zeolite 13X. When amine loading is increased by coupling aminopropyl groups, premature breakthrough combined with a long tail is observed. Contrary to conventional physisorbants, finite heat losses to the column wall do not explain the long breakthrough tail. A rate model that accounts for heterogeneity in diffusion was found to accurately capture the breakthrough shape of the high loading material. Batch uptake measurements support the hypothesis that slow diffusion through the polymer phase is what hampers adsorption kinetics in the high amine loading adsorbent. The results emphasize the importance of designing materials that are not overloaded with amine sites, as excessive amine loadings can lead to depressed adsorption kinetics and premature column breakthrough. © 2012 American Chemical Society.

Reducing the energy penalty costs of postcombustion CCS systems with amine-storage.

Science.gov (United States)

Patiño-Echeverri, Dalia; Hoppock, David C

2012-01-17

Carbon capture and storage (CCS) can significantly reduce the amount of CO(2) emitted from coal-fired power plants but its operation significantly reduces the plant's net electrical output and decreases profits, especially during times of high electricity prices. An amine-based CCS system can be modified adding amine-storage to allow postponing 92% of all its energy consumption to times of lower electricity prices, and in this way has the potential to effectively reduce the cost of CO(2) capture by reducing the costs of the forgone electricity sales. However adding amine-storage to a CCS system implies a significant capital cost that will be outweighed by the price-arbitrage revenue only if the difference between low and high electricity prices is substantial. In this paper we find a threshold for the variability in electricity prices that make the benefits from electricity price arbitrage outweigh the capital costs of amine-storage. We then look at wholesale electricity markets in the Eastern Interconnect of the United States to determine profitability of amine-storage systems in this region. Using hourly electricity price data from years 2007 and 2008 we find that amine storage may be cost-effective in areas with high price variability.

Tertiary-amine-containing thermo- and pH-sensitive hydrophilic ABA triblock copolymers: effect of different tertiary amines on thermally induced sol-gel transitions.

Science.gov (United States)

Henn, Daniel M; Wright, Roger A E; Woodcock, Jeremiah W; Hu, Bin; Zhao, Bin

2014-03-11

This Article reports on the synthesis of a series of well-defined, tertiary-amine-containing ABA triblock copolymers, composed of a poly(ethylene oxide) (PEO) central block and thermo- and pH-sensitive outer blocks, and the study of the effect of different tertiary amines on thermally induced sol-gel transition temperatures (T(sol-gel)) of their 10 wt % aqueous solutions. The doubly responsive ABA triblock copolymers were prepared from a difunctional PEO macroinitiator by atom transfer radical polymerization of methoxydi(ethylene glycol) methacrylate and ethoxydi(ethylene glycol) methacrylate at a feed molar ratio of 30:70 with ∼5 mol % of either N,N-diethylaminoethyl methacrylate (DEAEMA), N,N-diisopropylaminoethyl methacrylate, or N,N-di(n-butyl)aminoethyl methacrylate. The chain lengths of thermosensitive outer blocks and the molar contents of tertiary amines were very similar for all copolymers. Using rheological measurements, we determined the pH dependences of T(sol-gel) of 10 wt % aqueous solutions of these copolymers in a phosphate buffer. The T(sol-gel) versus pH curves of all polymers exhibited a sigmoidal shape. The T(sol-gel) increased with decreasing pH; the changes were small on both high and low pH sides. At a specific pH, the T(sol-gel) decreased with increasing the hydrophobicity of the tertiary amine, and upon decreasing pH the onset pH value for the T(sol-gel) to begin to increase noticeably was lower for the more hydrophobic tertiary amine-containing copolymer. In addition, we studied the effect of different tertiary amines on the release behavior of FITC-dextran from 10 wt % micellar gels in an acidic medium at 37 and 27 °C. The release profiles for three studied hydrogels at 37 °C were essentially the same, suggesting that the release was dominated by the diffusion of FITC-dextran. At 27 °C, the release was significantly faster for the DEAEMA-containing copolymer, indicating that both diffusion and gel dissolution contributed to the

Mesoporous amine-bridged polysilsesquioxane for CO2 capture

KAUST Repository

Qi, Genggeng

2011-01-01

A novel class of amine-supported sorbents based on amine-bridged mesoporous polysilsesquioxane was developed via a simple one-pot sol-gel process. The new sorbent allows the incorporation of a large amount of active groups without sacrificing surface area or pore volume available for CO2 capture, leading to a CO2 capture capacity of 3.2 mmol g−1 under simulated flue gas conditions. The sorbent is readily regenerated at 100°C and exhibits good stability over repetitive adsorption-desorption cycling.

Biogenic Amines as Quality Marker in Organic and Fair-Trade Cocoa-Based Products

Directory of Open Access Journals (Sweden)

Donatella Restuccia

2016-08-01

Full Text Available In this study, the quantitative determination of eight biogenic amines (cadaverine, serotonin, histamine, spermidine, spermine, tyramine, putrescine and β-phenylethylamine by an liquid chromatography method with evaporative light scattering detection was performed. The analysis of several samples of conventional, organic and fair trade cocoa-derivatives showed that organic and fair trade samples always contain much lower amine concentrations in comparison with their conventional counterparts, supporting the idea that biogenic amines can be regarded as cocoa quality markers. Irrespective of the kind of sample, results also showed that the most abundant amines were histamine, tyramine, spermidine, putrescine and spermine while β-phenylethylamine, cadaverine and serotonine have been found more rarely, all the amines never reaching dangerous amounts for consumer health. With the aim to confirm the experimental results, clustering analysis was performed on samples and instrumental results using principal component analysis.

Molecular Evolution and Functional Divergence of Trace Amine-Associated Receptors.

Directory of Open Access Journals (Sweden)

Seong-Il Eyun

Full Text Available Trace amine-associated receptors (TAARs are a member of the G-protein-coupled receptor superfamily and are known to be expressed in olfactory sensory neurons. A limited number of molecular evolutionary studies have been done for TAARs so far. To elucidate how lineage-specific evolution contributed to their functional divergence, we examined 30 metazoan genomes. In total, 493 TAAR gene candidates (including 84 pseudogenes were identified from 26 vertebrate genomes. TAARs were not identified from non-vertebrate genomes. An ancestral-type TAAR-like gene appeared to have emerged in lamprey. We found four therian-specific TAAR subfamilies (one eutherian-specific and three metatherian-specific in addition to previously known nine subfamilies. Many species-specific TAAR gene duplications and losses contributed to a large variation of TAAR gene numbers among mammals, ranging from 0 in dolphin to 26 in flying fox. TAARs are classified into two groups based on binding preferences for primary or tertiary amines as well as their sequence similarities. Primary amine-detecting TAARs (TAAR1-4 have emerged earlier, generally have single-copy orthologs (very few duplication or loss, and have evolved under strong functional constraints. In contrast, tertiary amine-detecting TAARs (TAAR5-9 have emerged more recently and the majority of them experienced higher rates of gene duplications. Protein members that belong to the tertiary amine-detecting TAAR group also showed the patterns of positive selection especially in the area surrounding the ligand-binding pocket, which could have affected ligand-binding activities and specificities. Expansions of the tertiary amine-detecting TAAR gene family may have played important roles in terrestrial adaptations of therian mammals. Molecular evolution of the TAAR gene family appears to be governed by a complex, species-specific, interplay between environmental and evolutionary factors.

The distribution and adsorption behavior of aliphatic amines in marine and lacustrine sediments

Science.gov (United States)

Wang, Xu-chen; Lee, Cindy

1990-10-01

The methylated amines—monomethyl-, dimethyl-, and trimethyl amine (MMA, DMA, TMA)—are commonly found in aquatic environments, apparently as a result of decomposition processes. Adsorption of these amines to clay minerals and organic matter significantly influences their distribution in sediments. Laboratory measurements using 14C-radiolabelled amines and application of a linear partitioning model resulted in calculated adsorption coefficients of 2.4-4.7 (MMA), 3.3 (DMA), and 3.3-4.1 (TMA). Further studies showed that adsorption of amines is influenced by salinity of the porewaters, and clay mineral and organic matter content of the sediment solid phase. Concentrations of monomethyl- and dimethyl amine were measured in the porewaters and the solid phase of sediment samples collected from Flax Pond and Lake Ronkonkoma (NY), Long Island Sound, and the coastal Peru upwelling area. These two amines were present in all sediments investigated. A clear seasonal increase in the solid-phase concentration of MMA and DMA in Flax Pond sediments was likely related to the annual senescence of salt marsh grasses, either directly as a source of these compounds or indirectly by providing additional exchange capacity to the sediments. The distribution of amines in the solid and dissolved phases observed in all sediments investigated suggests that the distribution of these compounds results from a balance among production, decomposition, and adsorption processes.

A protocol for amide bond formation with electron deficient amines and sterically hindered substrates

DEFF Research Database (Denmark)

Due-Hansen, Maria E; Pandey, Sunil K; Christiansen, Elisabeth

2016-01-01

A protocol for amide coupling by in situ formation of acyl fluorides and reaction with amines at elevated temperature has been developed and found to be efficient for coupling of sterically hindered substrates and electron deficient amines where standard methods failed.......A protocol for amide coupling by in situ formation of acyl fluorides and reaction with amines at elevated temperature has been developed and found to be efficient for coupling of sterically hindered substrates and electron deficient amines where standard methods failed....

Amine metabolism in the human brain : evaluation of the probenecid test

NARCIS (Netherlands)

Korf, Jacob

1971-01-01

There are indirect indications, that biogenic amines in the brain are concerned with pathological states such as depression (serotonin, 5HT and noradrenaline, NA) and Parkonsonism (dopamine, DA). These indications were obtained from measurements of amines and their metabolites in pe - ripheral

CO_2 capture by amine-functionalized nanoporous materials: A review

International Nuclear Information System (INIS)

Chen, Chao; Kim, Jun; Ahn, Wha-Seung

2014-01-01

Amine-functionalized nanoporous materials can be prepared by the incorporation of diverse organic amine moieties into the pore structures of a range of support materials, such as mesoporous silica and alumina, zeolite, carbon and metal organic frameworks (MOFs), either by direct functionalization or post-synthesis through physical impregnation or grafting. These hybrid materials have great potential for practical applications, such as dry adsorbents for postcombustion CO_2 capture, owing to their high CO_2 capture capacity, high capture selectivity towards CO_2 compared to other gases, and excellent stability. This paper summarizes the preparation methods and CO_2 capture performance based on the equilibrium CO_2 uptake of a range of amine-functionalized nanoporous materials

Vapour pressure and enthalpy of vaporization of aliphatic poly-amines

International Nuclear Information System (INIS)

Efimova, Anastasia A.; Emel'yanenko, Vladimir N.; Verevkin, Sergey P.; Chernyak, Yury

2010-01-01

Molar enthalpies of vaporization of aliphatic poly-amines: 1,4-dimethylpiperazine [106-58-1], 1-(2-aminoethyl)-piperazine, [140-31-8], 1-(2-aminoethyl)-4-methyl-piperazine [934-98-5], and triethylenetetramine [112-24-3] were obtained from the temperature dependence of the vapour pressure measured by the transpiration method. A large number of the primary experimental results on temperature dependences of vapour pressures of the parent compounds have been collected from the literature and have been treated uniformly in order to derive vaporization enthalpies of poly-amines at the reference temperature 298.15 K. An internal consistency check was performed on enthalpy of vaporization values for poly-amines studied in this work.

Effect of immobilized amine density on cadmium(II) adsorption capacities for ethanediamine-modified magnetic poly-(glycidyl methacrylate) microspheres

Energy Technology Data Exchange (ETDEWEB)

Dong, Tingting [Key Laboratory of Green Process and Engineering, State Key Laboratory of Biochemical Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Yang, Liangrong, E-mail: lryang@ipe.ac.cn [Key Laboratory of Green Process and Engineering, State Key Laboratory of Biochemical Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190 (China); Pan, Feng; Xing, Huifang; Wang, Li; Yu, Jiemiao [Key Laboratory of Green Process and Engineering, State Key Laboratory of Biochemical Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190 (China); Qu, Hongnan [Key Laboratory of Green Process and Engineering, State Key Laboratory of Biochemical Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao 266101 (China); Rong, Meng [Key Laboratory of Green Process and Engineering, State Key Laboratory of Biochemical Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Liu, Huizhou, E-mail: hzliu@ipe.ac.cn [Key Laboratory of Green Process and Engineering, State Key Laboratory of Biochemical Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190 (China)

2017-04-01

A series of ethanediamine (EDA) – modified magnetic poly-(glycidyl methacrylate) (m-PGMA-EDA)microspheres with different amine density were synthesized and their cadmium saturation adsorption capacities were examined. The results showed that the cadmium saturation adsorption capacity increased with the immobilized amine density. However, they did not show strong positive linear correlation in the whole range of amine density examined. The molar ratio of amine groups to the adsorbed cadmium decreased with the increase of amine density and eventually reached a minimum value about 4. It suggested that low immobilized amine density led to low coordination efficiency of the amine. It is hypothesized that the immobilized amine groups needed to be physically close enough to form stable amine-metal complex. When the amine density reached to a critical value 1.25 m mol m{sup −2}, stable amine-cadmium complex (4:1 N/Cd) was proposed to form. To illustrate the coordination mechanism (structure and number) of amine and Cd, FT-IR spectra of m-PGMA-EDA and m-PGMA-EDA-Cd , and X-ray photoelectron spectroscopy (XPS) of PGMA–EDA and PGMA-EDA-Cd were examined and analyzed. - Highlights: • A series of magnetic poly-(glycidyl methacrylate) (m-PGMA-EDA)microspheres with different amine density were synthesized and their cadmium saturation adsorption capacities were examined. • The molar ratio of amine groups to adsorbed cadmium decreased with the increase of amine density and eventually reached a minimum value about 4. • when the amine density reached high enough, 4:1 N/Cd complex was proposed to form, and the hydroxyl also participated in the chelating with Cd.

Homologation of methanol catalyzed by transition metal complexes in the presence of tertiary amines

Energy Technology Data Exchange (ETDEWEB)

Tanaka, Masato; Ogata, Ikuei

1987-12-18

This paper describes the homologation of methanol by transition metal carbonyl catalysts in the presence of tertiary amines. Methanol was reacted with amine using a catalyst at 180/sup 0/C under 100 atm in the atmosphere of CO and H/sub 2/ mixed at the ratio of 4 in an autoclave. The reaction activities and selectivities of ethanol using iron carbonyl and Co carbonyl catalysts are superior. Only the iron catalyst was used hereafter because phosphine is required for the latter catalyst. N-methyl- piperidine, a cyclic amine, is superior to the other amines. The selectivity of ethanol is higher under higher partial pressure of H/sub 2/ and lower partial pressure of CO. The conversion rate is optimum at 180/sup 0/ and it goes down with increasing the temperature from it. Since the selectivity is markedly decreased with increasing amine, the reaction activity must be balanced with the amount of amine. The presence of solvent affects it. (3 figs, 6 tabs, 15 refs)

Electrodeposition of amine-terminatedpoly(ethylene glycol) to titanium surface

International Nuclear Information System (INIS)

Tanaka, Yuta; Doi, Hisashi; Iwasaki, Yasuhiko; Hiromoto, Sachiko; Yoneyama, Takayuki; Asami, Katsuhiko; Imai, Hachiro; Hanawa, Takao

2007-01-01

The immobilization of poly(ethylene glycol), PEG, to a solid surface is useful to functionalize the surface, e.g., to prevent the adsorption of proteins. No successful one-stage technique for the immobilization of PEG to base metals has ever been developed. In this study, PEG in which both terminals or one terminal had been modified with amine bases was immobilized onto a titanium surface using electrodeposition. PEG was dissolved in a NaCl solution, and electrodeposition was carried out at 310 K with - 5 V for 300 min. The thickness of the deposited PEG layer was evaluated using ellipsometry, and the bonding manner of PEG to the titanium surface was characterized using X-ray photoelectron spectroscopy after electrodeposition. The results indicated that a certain amount of PEG was adsorbed on titanium through both electrodeposition and immersion when PEG was terminated by amine. However, terminated amines existed at the surface of titanium and were combined with titanium oxide as N-HO by electrodeposition, while amines randomly existed in the molecule and showed an ionic bond with titanium oxide by immersion. The electrodeposition of PEG was effective for the inhibition of albumin adsorption. This process is useful for materials that have electroconductivity and a complex morphology

Inhibitory Effects of Spices on Biogenic Amine Accumulation during Fish Sauce Fermentation.

Science.gov (United States)

Zhou, Xuxia; Qiu, Mengting; Zhao, Dandan; Lu, Fei; Ding, Yuting

2016-04-01

The presence of high levels of biogenic amines is detrimental to the quality and safety of fish sauce. This study investigated the effects of ethanol extracts of spices, including garlic, ginger, cinnamon, and star anise extracts, in reducing the accumulation of biogenic amines during fish sauce fermentation. The concentrations of biogenic amines, which include histamine, putrescine, tyramine, and spermidine, all increased during fish sauce fermentation. When compared with the samples without spices, the garlic and star anise extracts significantly reduced these increases. The greatest inhibitory effect was observed for the garlic ethanolic extracts. When compared with controls, the histamine, putrescine, tyramine, and spermidine contents and the overall biogenic amine levels of the garlic extract-treated samples were reduced by 30.49%, 17.65%, 26.03%, 37.20%, and 27.17%, respectively. The garlic, cinnamon, and star anise extracts showed significant inhibitory effects on aerobic bacteria counts. Furthermore, the garlic and star anise extracts showed antimicrobial activity against amine producers. These findings may be helpful for enhancing the safety of fish sauce. © 2016 Institute of Food Technologists®

Environmentally friendly chemoselective oxidation of primary aliphatic amines by using a biomimetic electrocatalytic system.

Science.gov (United States)

Largeron, Martine; Chiaroni, Angèle; Fleury, Maurice-Bernard

2008-01-01

Environmentally friendly oxidation of primary aliphatic amines to imines has been successfully achieved, under metal-free conditions, by the use of diverse electrogenerated o-azaquinone mediators. High catalytic performance, together with high chemoselectivity, were observed with electron-poor o-azaquinone catalysts generated from 2-aminoresorcinol derivatives. Similar to copper amine oxidase enzymes, these mediators exhibited lower reactivity toward alpha-branched primary amines and no reactivity toward secondary amines. In the case of 3,4-aminophenol derivatives lacking a 2-hydroxy group, the generated o-azaquinone species failed to catalyze the oxidation of the amine to the corresponding imine. Further mechanistic considerations allowed a rationalization of the crucial role of the 2-hydroxy group in converting a catalytically inert species into a highly effective biomimetic catalyst.

Platinum-Catalyzed Terminal-Selective C(sp3)–H Oxidation of Aliphatic Amines

Science.gov (United States)

Lee, Melissa; Sanford, Melanie S.

2016-01-01

This paper describes the terminal-selective Pt-catalyzed C(sp3)–H oxidation of aliphatic amines without the requirement for directing groups. CuCl2 is employed as a stoichiometric oxidant, and the reactions proceed in high yield at Pt loadings as low as 1 mol %. These transformations are conducted in the presence of sulfuric acid, which reacts with the amine substrates in situ to form ammonium salts. We propose that protonation of the amine serves at least three important roles: (i) it renders the substrates soluble in the aqueous reaction medium; (ii) it limits binding of the amine nitrogen to Pt or Cu; and (ii) it electronically deactivates the C–H bonds proximal to the nitrogen center. We demonstrate that this strategy is effective for the terminal-selective C(sp3)–H oxidation of a variety of primary, secondary and tertiary amines. PMID:26439251

Structure-Activity Relationships for Rates of Aromatic Amine Oxidation by Manganese Dioxide.

Science.gov (United States)

Salter-Blanc, Alexandra J; Bylaska, Eric J; Lyon, Molly A; Ness, Stuart C; Tratnyek, Paul G

2016-05-17

New energetic compounds are designed to minimize their potential environmental impacts, which includes their transformation and the fate and effects of their transformation products. The nitro groups of energetic compounds are readily reduced to amines, and the resulting aromatic amines are subject to oxidation and coupling reactions. Manganese dioxide (MnO2) is a common environmental oxidant and model system for kinetic studies of aromatic amine oxidation. In this study, a training set of new and previously reported kinetic data for the oxidation of model and energetic-derived aromatic amines was assembled and subjected to correlation analysis against descriptor variables that ranged from general purpose [Hammett σ constants (σ(-)), pKas of the amines, and energies of the highest occupied molecular orbital (EHOMO)] to specific for the likely rate-limiting step [one-electron oxidation potentials (Eox)]. The selection of calculated descriptors (pKa, EHOMO, and Eox) was based on validation with experimental data. All of the correlations gave satisfactory quantitative structure-activity relationships (QSARs), but they improved with the specificity of the descriptor. The scope of correlation analysis was extended beyond MnO2 to include literature data on aromatic amine oxidation by other environmentally relevant oxidants (ozone, chlorine dioxide, and phosphate and carbonate radicals) by correlating relative rate constants (normalized to 4-chloroaniline) to EHOMO (calculated with a modest level of theory).

Iridium‐Catalyzed Condensation of Amines and Vicinal Diols to Substituted Piperazines

DEFF Research Database (Denmark)

Lorentz-Petersen, Linda Luise Reeh; Nordstrøm, Lars Ulrik Rubæk; Madsen, Robert

2012-01-01

is believed to involve dehydrogenation of the 1,2‐diol to the α‐hydroxy aldehyde, which condenses with the amine to form the α‐hydroxy imine. The latter rearranges to the corresponding α‐amino carbonyl compound, which then reacts with another amine followed by reduction of the resulting imine.......A straightforward procedure is described for the synthesis of piperazines from amines and 1,2‐diols. The heterocyclization is catalyzed by [Cp*IrCl2]2 and sodium hydrogen carbonate and can be achieved with either toluene or water as solvent. The transformation does not require any stoichiometric...

Mechanistic insights into the oxidative dehydrogenation of amines to nitriles in continuous flow

DEFF Research Database (Denmark)

Corker, Emily C.; Ruiz-Martínez, Javier; Riisager, Anders

2015-01-01

The oxidative dehydrogenation of various aliphatic amines to their corresponding nitrile compounds using RuO2/Al2O3 catalysts in air was successfully applied to a continuous flow reaction. Conversions of amines (up to >99%) and yields of nitriles (up to 77%) varied depending on reaction conditions...... and the amine utilised. The presence of water was found to be important for the activity and stability of the RuO2/Al2O3 catalyst. The Hammett relationship and in situ infrared spectroscopy were applied to divulge details about the catalytic mechanism of the oxidative dehydrogenation of amines over RuO2/Al2O3...

Amines as extracting agents for the quantitative determinations of actinides in biological samples

International Nuclear Information System (INIS)

Singh, N.P.

1987-01-01

The use of amines (primary, secondary and tertiary chains and quaternary ammonium salts) as extracting agents for the quantitative determination of actinides in biological samples is reviewed. Among the primary amines, only Primene JM-T is used to determine Pu in urine and bone. No one has investigated the possibility of using secondary amines to quantitatively extract actinides from biological samples. Among the tertiary amines, tri-n-octylamine, tri-iso-octylamine, tyricaprylamine (Alamine) and trilaurylamine (tridodecylamine) are used extensively to extract and separate the actinides from biological samples. Only one quaternary ammonium salt, methyltricapryl ammonium chloride (Aliquat-336), is used to extract Pu from biological samples. (author) 28 refs

Solid amine which is marked as a carbon dioxide absorbing and desorbing agent. Tansan gas no kyudacchakuzai to shite chumoku sareru kotai amin

Energy Technology Data Exchange (ETDEWEB)

Otsubo, Koji

1990-01-01

These days, phenomenon of the global warming due to the increase of carbon dioxide has become a great problem. Also in a space craft, in order to maintain human lives a system to get rid of carbon dioxide which is increased in the living sphere is required. As an agent to get rid of carbon dioxide in space, gas or liquid are hard to use, and moreover the agent must be highly reliable, energy conservative, of light weight and compact. Taking above conditions into consideration, trade-off was carried out on present technologies which might be of use. As a result, it was concluded that use of solid amine which has high selective absorbing capacity of carbon dioxide is most probable. In a system using solid amine; in order to make the area which touches air maximum, solid amine is made into small balls of 50 - 500 micro m diameters, and two pairs of canisters which make it possible to maintain solid amine and make adsorption and desorption easy are applied. And in the system alternative adsorption and desorption of carbon dioxide continues. Carbon dioxide recovered is to be used for a plant growing system in a space craft. Long term characteristic tests of the system are being carried out. 4 figs.

Solid amine sorbents for CO2 capture by chemical adsorption: A review

Directory of Open Access Journals (Sweden)

Elif Erdal Ünveren

2017-03-01

Full Text Available Amines are well-known for their reversible reactions with CO2, which make them ideal for CO2 capture from several gas streams, including flue gas. In this respect, selective CO2 absorption by aqueous alkanolamines is the most mature technology but the process is energy intensive and has also corrosion problems. Both disadvantages can be diminished to a certain extent by chemical adsorption of CO2 selectively. The most important element of the chemical adsorption of CO2 involves the design and development of a suitable adsorbent which consist of a porous support onto which an amine is attached or immobilized. Such an adsorbent is often called as solid amine sorbent. This review covers solid amine-based studies which are developed and published in recent years. First, the review examines several different types of porous support materials, namely, three mesoporous silica (MCM-41, SBA-15 and KIT-6 and two polymeric supports (PMMA and PS for CO2 adsorption. Emphasis is given to the synthesis, modifications and characterizations -such as BET and PXRD data-of them. Amination of these supports to obtain a solid amine sorbent through impregnation or grafting is reviewed comparatively. Focus is given to the adsorption mechanisms, material characteristics, and synthesis methods which are discussed in detail. Significant amount of original data are also presented which makes this review unique. Finally, relevant CO2 adsorption (or equilibrium capacity data, and cyclic adsorption/desorption performance and stability of important classes of solid amine sorbents are critically reviewed. These include severa PEI or TEPA impregnated adsorbents and APTES-grafted systems.

The ozonolysis of primary aliphatic amines in single and multicomponent fine particles

Science.gov (United States)

Zahardis, J.; Geddes, S.; Petrucci, G. A.

2007-10-01

The oxidative processing by ozone of the particulate amines octadecylamine (ODA) and hexadecylamine (HDA) is reported. Ozonolysis of these amines resulted in strong NO2- and NO3- ion signals that increased with ozone exposure as monitored by photoelectron resonance capture ionization aerosol mass spectrometry. These products suggest a mechanism of progressive oxidation of the particulate amines to nitro alkanes. Additionally, a strong ion signal at 125 m/z is assigned to the ion NO3-(HNO3). For ozonized mixed particles containing ODA or HDA + oleic acid (OL), with pO3≥3×10-7 atm, imine, secondary amide, and tertiary amide products were measured. These products most likely arise from reactions of amines with aldehydes (for imines) and stabilized Criegee intermediates (SCI) or secondary ozonides (for amides) from the fatty acid. The routes to amides via SCI and/or secondary ozonides was shown to be more important than comparable amide forming reactions between amines and organic acids, using azelaic acid as a test compound. Finally, direct evidence is provided for the formation of a surface barrier in the ODA + OL reaction system that resulted in the retention of OL at high ozone exposures (up to 10-3 atm for 17 s). This effect was not observed in HDA + OL or single component OL particles, suggesting that it may be a species-specific surfactant effect from an in situ generated amide or imine. Implications to tropospheric chemistry, including particle bound amines as sources of oxidized gas phase nitrogen species (e.g. NO2, NO3), formation of nitrogen enriched HULIS via ozonolysis of amines and source apportionment are discussed.

Synthesis of propargylic and allenic carbamates via the C-H amination of alkynes.

Science.gov (United States)

Grigg, R David; Rigoli, Jared W; Pearce, Simon D; Schomaker, Jennifer M

2012-01-06

Propargylic amines are important intermediates for the synthesis of nitrogen-containing heterocycles. The insertion of a nitrene into a propargylic C-H bond has not been explored, despite the attention directed toward the Rh-catalyzed amination of other types of C-H bonds. In this communication, the conversion of a series of homopropargylic carbamates to propargylic carbamates and aminated allenes is described. © 2011 American Chemical Society

Degree of conversion and monomer elution of CQ/amine and TPO adhesives.

Science.gov (United States)

Pongprueksa, Pong; Miletic, Vesna; Janssens, Henriette; Van Landuyt, Kirsten L; De Munck, Jan; Godderis, Lode; Van Meerbeek, Bart

2014-06-01

To evaluate the effect of photo-initiator on the degree of conversion (DC) and elution of Bis-GMA and HEMA for 8 one-step adhesive formulations. We used Scotchbond Universal ('SBU-CQ/amine_4.0', 3M ESPE), containing about 2wt% camphorquinone (CQ) and 2wt% ethyl-4-dimethylamino benzoate (EDMAB), an experimental 'SBU-TPO_2.1' version, containing 2.1wt% diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO), and 6 experimental LUB adhesives (Kuraray Noritake), namely 'LUB-CQ/amine_0.7', 'LUB-CQ/amine_1.4', 'LUB-CQ/amine_4.0', 'LUB-TPO_0.35', 'LUB-TPO_0.7' and 'LUB-TPO_2.0', respectively containing 0.35wt% CQ and 0.35wt% EDMAB, 0.7wt% CQ and 0.7wt% EDMAB, 2.0wt% CQ and 2.0wt% EDMAB, 0.35wt% TPO, 0.7wt% TPO, and 2.0wt% TPO. DC was measured using micro-Raman spectroscopy. Additional specimens were immersed in ethanol for 24h to determine the elution of Bis-GMA and HEMA using HPLC. DC of the respective SBU and LUB adhesives was alike at high photo-initiator concentration. At low concentration, TPO was significantly more efficient than CQ/amine (LUB adhesives only). A statistically significant positive photo-initiator concentration effect on DC was noted for both CQ/amine and TPO (LUB adhesives only). A statistically significant inverse photo-initiator concentration effect on HEMA elution was noted for both the CQ/amine- and TPO-containing LUB adhesives. A significantly strong correlation was found between DC and Bis-GMA elution (R(2)=0.744, p=0.026), and between DC and HEMA elution (R(2)=0.913, p=0.002) for the LUB adhesives. The photo-initiator kind and concentration affect DC and the Bis-GMA/HEMA elution. TPO can be used as an alternative photo-initiator for CQ/amine. Copyright © 2014 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Hemoglobin binding of aromatic amines: molecular dosimetry and quantitative structure-activity relationships for N-oxidation.

Science.gov (United States)

Sabbioni, G

1993-01-01

Aromatic amines are important intermediates in industrial manufacturing. N-Oxidation to N-hydroxyarylamines is a key step in determining the genotoxic properties of aromatic amines. N-Hydroxyarylamines can form adducts with DNA, with tissue proteins, and with the blood proteins albumin and hemoglobin in a dose-dependent manner. The determination of hemoglobin adducts is a useful tool for biomonitoring exposed populations. We have established the hemoglobin binding index (HBI) [(mmole compound/mole hemoglobin)/(mmole compound/kg body weight)] of several aromatic amines in female Wistar rats. Including the values from other researchers obtained in the same rat strain, the logarithm of hemoglobin binding (logHBI) was plotted against the following parameters: the sum of the Hammett constants(sigma sigma = sigma p + sigma m), pKa, logP (octanol/water), the half-wave oxidation potential (E1/2), and the electronic descriptors of the amines and their corresponding nitrenium ions obtained by semi-empirical calculations (MNDO, AMI, and PM3), such as atomic charge densities, energies of the highest occupied molecular orbit and lowest occupied molecular orbit and their coefficients, the bond order of C-N, the dipole moments, and the reaction enthalpy [MNDOHF, AM1HF or PM3HF = Hf(nitrenium) - Hf(amine)]. The correlation coefficients were determined from the plots of all parameters against log HBI for all amines by means of linear regression analysis. The amines were classified in three groups: group 1, all parasubstituted amines (maximum, n = 9); group 2, all amines with halogens (maximun, n = 11); and group 3, all amines with alkyl groups (maximum, n = 13).(ABSTRACT TRUNCATED AT 250 WORDS) PMID:8319626

Interaction of aromatic amines with iron oxides: implications for prebiotic chemistry.

Science.gov (United States)

Shanker, Uma; Singh, Gurinder; Kamaluddin

2013-06-01

The interaction of aromatic amines (aniline, p-chloroaniline, p-toludine and p-anisidine) with iron oxides (goethite, akaganeite and hematite) has been studied. Maximum uptake of amines was observed around pH 7. The adsorption data obtained at neutral pH were found to follow Langmuir adsorption. Anisidine was found to be a better adsorbate probably due to its higher basicity. In alkaline medium (pH > 8), amines reacted on goethite and akaganeite to give colored products. Analysis of the products by GC-MS showed benzoquinone and azobenzene as the reaction products of aniline while p-anisidine afforded a dimer. IR analysis of the amine-iron oxide hydroxide adduct suggests that the surface acidity of iron oxide hydroxides is responsible for the interaction. The present study suggests that iron oxide hydroxides might have played a role in the stabilization of organic molecules through their surface activity and in prebiotic condensation reactions.

Bis[μ-(E-N-(pyridin-3-ylmethylidenehydroxyamine]-κ2N1:N3;κ2N3:N1-bis{[(E-N-(pyridin-3-ylmethylidene-κNhydroxyamine]silver(I} dinitrate

Directory of Open Access Journals (Sweden)

Shan Gao

2012-12-01

Full Text Available In the centrosymmetric dinuclear title AgI compound, [Ag2(C6H6N2O4](NO32, the aromatic amine-coordinated AgI atom is further bridged by two hydroxylamine molecules that use aromatic and oxime N atoms for bridging, and it exists in a distorted trigonal-planar geometry. In the crystal, the nitrate anions link to the dinuclear compound molecules via O—H...O hydrogen bonds, generating a chain running along the a-axis direction.

/sup 13/C-/sup 13/C spin-spin coupling constants in structural investigations. I. New method of determining the configuration of oximes and their derivatives

Energy Technology Data Exchange (ETDEWEB)

Krivdin, L.B.; Shcherbakov, V.V.; Kalabin, G.A.

1986-07-10

It was shown that the direct /sup 13/C-/sup 13/C spin-spin coupling constants can be used for the unambiguous identification of the configurational isomers of oximes and their derivatives. The stereospecificity of the constants is explained by the additional contribution from the unshared electron pair of the nitrogen atom to the spin-spin coupling constant between the adjacent carbon nuclei in the cis position.

Application of oxime-diversification to optimize ligand interactions within a cryptic pocket of the polo-like kinase 1 polo-box domain | Center for Cancer Research

Science.gov (United States)

By a process involving initial screening of a set of 87 aldehydes using an oxime ligation-based strategy, we were able to achieve a several-fold affinity enhancement over one of the most potent previously known polo-like kinase 1 (Plk1) polo-box domain (PBD) binding inhibitors. This improved binding may result by accessing a newly identified auxiliary region proximal to a key

Amine Chemistry at Aqueous Interfaces: The Study of Organic Amines in Neutralizing Acidic Gases at an Air/Water Surface Using Vibrational Sum Frequency Spectroscopy

Science.gov (United States)

McWilliams, L.; Wren, S. N.; Valley, N. A.; Richmond, G.

2014-12-01

Small organic bases have been measured in atmospheric samples, with their sources ranging from industrial processing to animal husbandry. These small organic amines are often highly soluble, being found in atmospheric condensed phases such as fogwater and rainwater. Additionally, they display acid-neutralization ability often greater than ammonia, yet little is known regarding their kinetic and thermodynamic properties. This presentation will describe the molecular level details of a model amine system at the vapor/liquid interface in the presence of acidic gas. We find that this amine system shows very unique properties in terms of its bonding, structure, and orientation at aqueous surfaces. The results of our studies using a combination of computation, vibrational sum frequency spectroscopy, and surface tension will report the properties inherent to these atmospherically relevant species at aqueous surfaces.

pH-sensitive diamond field-effect transistors (FETs) with directly aminated channel surface

International Nuclear Information System (INIS)

Song, Kwang-Soup; Nakamura, Yusuke; Sasaki, Yuichi; Degawa, Munenori; Yang, Jung-Hoon; Kawarada, Hiroshi

2006-01-01

We have introduced pH sensors fabricated on diamond thin films through modification of the surface-terminated atom. We directly modified the diamond surface from hydrogen to amine or oxygen with ultraviolet (UV) irradiation under ammonia gas. The quantified amine site based on the spectra obtained by X-ray photoelectron spectroscopy (XPS) is 26% (2.6 x 10 14 cm -2 ) with UV irradiation for 8 h and its coverage is dependent on the UV irradiation time. This directly aminated diamond surface is stable with long-term exposure in air and electrolyte solution. We fabricated diamond solution-gate field-effect transistors (SGFETs) without insulating layers on the channel surface. These diamond SGFETs with amine modified by direct amination are sensitive to pH (45 mV/pH) over a wide range from pH 2 to 12 and their sensitivity is dependent on the density of binding sites corresponding to UV irradiation time on the channel surface

Preparation of aminated chitosan/alginate scaffold containing halloysite nanotubes with improved cell attachment.

Science.gov (United States)

Amir Afshar, Hamideh; Ghaee, Azadeh

2016-10-20

The chemical nature of biomaterials play important role in cell attachment, proliferation and migration in tissue engineering. Chitosan and alginate are biodegradable and biocompatible polymers used as scaffolds for various medical and clinical applications. Amine groups of chitosan scaffolds play an important role in cell attachment and water adsorption but also associate with alginate carboxyl groups via electrostatic interactions and hydrogen bonding, consequently the activity of amine groups in the scaffold decreases. In this study, chitosan/alginate/halloysite nanotube (HNTs) composite scaffolds were prepared using a freeze-drying method. Amine treatment on the scaffold occurred through chemical methods, which in turn caused the hydroxyl groups to be replaced with carboxyl groups in chitosan and alginate, after which a reaction between ethylenediamine, 1-ethyl-3,(3-dimethylaminopropyl) carbodiimide (EDC) and scaffold triggered the amine groups to connect to the carboxyl groups of chitosan and alginate. The chemical structure, morphology and mechanical properties of the composite scaffolds were investigated by FTIR, CHNS, SEM/EDS and compression tests. The electrostatic attraction and hydrogen bonding between chitosan, alginate and halloysite was confirmed by FTIR spectroscopy. Chitosan/alginate/halloysite scaffolds exhibit significant enhancement in compressive strength compared with chitosan/alginate scaffolds. CHNS and EDS perfectly illustrate that amine groups were effectively introduced in the aminated scaffold. The growth and cell attachment of L929 cells as well as the cytotoxicity of the scaffolds were investigated by SEM and Alamar Blue (AB). The results indicated that the aminated chitosan/alginate/halloysite scaffold has better cell growth and cell adherence in comparison to that of chitosan/alginate/halloysite samples. Aminated chitosan/alginate/halloysite composite scaffolds exhibit great potential for applications in tissue engineering, ideally in

Mechanistic investigation of the iridium-catalysed alkylation of amines with alcohols

DEFF Research Database (Denmark)

Fristrup, Peter; Tursky, Matyas; Madsen, Robert

2012-01-01

where the intermediate aldehyde stays coordinated to the iridium catalyst and reacts with the amine to give a hemiaminal which is also bound to the catalyst. Dehydration to the imine and reduction to the product amine also takes place without breaking the coordination to the catalyst. The fact...

Reliability and Maintainability Analysis for the Amine Swingbed Carbon Dioxide Removal System

Science.gov (United States)

Dunbar, Tyler

2016-01-01

I have performed a reliability & maintainability analysis for the Amine Swingbed payload system. The Amine Swingbed is a carbon dioxide removal technology that has gone through 2,400 hours of International Space Station on-orbit use between 2013 and 2016. While the Amine Swingbed is currently an experimental payload system, the Amine Swingbed may be converted to system hardware. If the Amine Swingbed becomes system hardware, it will supplement the Carbon Dioxide Removal Assembly (CDRA) as the primary CO2 removal technology on the International Space Station. NASA is also considering using the Amine Swingbed as the primary carbon dioxide removal technology for future extravehicular mobility units and for the Orion, which will be used for the Asteroid Redirect and Journey to Mars missions. The qualitative component of the reliability and maintainability analysis is a Failure Modes and Effects Analysis (FMEA). In the FMEA, I have investigated how individual components in the Amine Swingbed may fail, and what the worst case scenario is should a failure occur. The significant failure effects are the loss of ability to remove carbon dioxide, the formation of ammonia due to chemical degradation of the amine, and loss of atmosphere because the Amine Swingbed uses the vacuum of space to regenerate the Amine Swingbed. In the quantitative component of the reliability and maintainability analysis, I have assumed a constant failure rate for both electronic and nonelectronic parts. Using this data, I have created a Poisson distribution to predict the failure rate of the Amine Swingbed as a whole. I have determined a mean time to failure for the Amine Swingbed to be approximately 1,400 hours. The observed mean time to failure for the system is between 600 and 1,200 hours. This range includes initial testing of the Amine Swingbed, as well as software faults that are understood to be non-critical. If many of the commercial parts were switched to military-grade parts, the expected

Quantification of amine functional groups and their influence on OM/OC in the IMPROVE network

Science.gov (United States)

Kamruzzaman, Mohammed; Takahama, Satoshi; Dillner, Ann M.

2018-01-01

Recently, we developed a method using FT-IR spectroscopy coupled with partial least squares (PLS) regression to measure the four most abundant organic functional groups, aliphatic C-H, alcohol OH, carboxylic acid OH and carbonyl C=O, in atmospheric particulate matter. These functional groups are summed to estimate organic matter (OM) while the carbon from the functional groups is summed to estimate organic carbon (OC). With this method, OM and OM/OC can be estimated for each sample rather than relying on one assumed value to convert OC measurements to OM. This study continues the development of the FT-IR and PLS method for estimating OM and OM/OC by including the amine functional group. Amines are ubiquitous in the atmosphere and come from motor vehicle exhaust, animal husbandry, biomass burning, and vegetation among other sources. In this study, calibration standards for amines are produced by aerosolizing individual amine compounds and collecting them on PTFE filters using an IMPROVE sampler, thereby mimicking the filter media and collection geometry of ambient standards. The moles of amine functional group on each standard and a narrow range of amine-specific wavenumbers in the FT-IR spectra (wavenumber range 1 550-1 500 cm-1) are used to develop a PLS calibration model. The PLS model is validated using three methods: prediction of a set of laboratory standards not included in the model, a peak height analysis and a PLS model with a broader wavenumber range. The model is then applied to the ambient samples collected throughout 2013 from 16 IMPROVE sites in the USA. Urban sites have higher amine concentrations than most rural sites, but amine functional groups account for a lower fraction of OM at urban sites. Amine concentrations, contributions to OM and seasonality vary by site and sample. Amine has a small impact on the annual average OM/OC for urban sites, but for some rural sites including amine in the OM/OC calculations increased OM/OC by 0.1 or more.

Atmospheric chemistry and environmental impact of the use of amines in carbon capture and storage (CCS).

Science.gov (United States)

Nielsen, Claus J; Herrmann, Hartmut; Weller, Christian

2012-10-07

This critical review addresses the atmospheric gas phase and aqueous phase amine chemistry that is relevant to potential emissions from amine-based carbon capture and storage (CCS). The focus is on amine, nitrosamine and nitramine degradation, and nitrosamine and nitramine formation processes. A comparison between the relative importance of the various atmospheric sinks for amines, nitrosamines and nitramines is presented.

Characterization of molybdenum interfacial crud in a uranium mill that employs tertiary-amine solvent extraction

International Nuclear Information System (INIS)

Moyer, B.; McDowell, W.J.

1983-01-01

In the present work, samples of a molybdenum-caused green gummy interfacial crud from an operating western US uranium mill have been physically and chemically examined. Formaton of cruds of this description has been a long-standing problem in the use of tertiary amine solvent extraction for the recovery of uranium from low-grade ores (Amex Process). The crud is essentially an organic-continuous dispersion containing about 10 wt % aqueous droplets and about 37 wt % greenish-yellow crystalline solids suspended in kerosene-amine process solvent. The greenish-yellow crystals were found to be a previously unknown double salt of tertiary amine molybdophosphate with three tertiary amine chlorides having the empirical formula (R 3 NH) 3 [PMo 12 O 40 ].3(R 3 NH)Cl. To confirm the identification of the compound, a pure trioctylamine (TOA) analog was synthesized. In laboratory extraction experiments, it was demonstrated that organic-soluble amine molydophosphate forms slowly upon contact of TOA solvent with dilute sulfuric acid solutions containing low concentrations of molybdate and phosphate. If the organic solutions of amine molybdophosphate were then contacted with aqueous NaCl solutions, a greenish-yellow precipitate of (TOAH) 3 [PMo 12 O 40 ].3(TOAH)Cl formed at the interface. The proposed mechanism for the formation of the crud under process conditions involves build up of molybdenum in the solvent, followed by reaction with extracted phosphate to give dissolved amine molybdophosphate. The amine molybdophosphate then co-crystallizes with amine chloride, formed during the stripping cycle, to give the insoluble double salt, which precipitates as a layer of small particles at the interface. The proposed solution to the problem is the use of branched-chain, instead of straight-chain, tertiary amine extractants under the expectation that branching would increase the solubility of the double salt. 2 figures, 5 tables

Dimethylzinc-Initiated Radical Coupling of β-Bromostyrenes with Ethers and Amines

DEFF Research Database (Denmark)

Sølvhøj, Amanda Birgitte; Ahlburg, Andreas; Madsen, Robert

2015-01-01

A new coupling reaction has been developed in which β-bromostyrenes react with ethers and tertiary amines to introduce the styryl group in the α-position. The transformation is mediated by Me2Zn/O2 with 10 % MnCl2 and is believed to proceed by a radical addition-elimination mechanism. The ether...... and the amine are employed as solvent and the coupling takes place through the most stable α radical for unsymmetrical substrates. The products are obtained in moderate to good yields as the pure E isomers. The coupling can be achieved with a range of smaller cyclic and acyclic ethers/amines as well as various...

Electron beam induced electronic transport in alkyl amine-intercalated VOx nanotubes

International Nuclear Information System (INIS)

O'Dwyer, C.; Lavayen, V.; Clavijo-Cedeno, C.; Torres, C.M.S.

2008-01-01

The electron beam induced electronic transport in primary alkyl amine-intercalated V 2 O 5 nanotubes is investigated where the organic amine molecules are employed as molecular conductive wires to an aminosilanized substrate surface and contacted to Au interdigitated electrode contacts. The results demonstrate that the high conductivity of the nanotubes is related to the non-resonant tunnelling through the amine molecules and a reduced polaron hopping conduction through the vanadium oxide itself. Both nanotube networks and individual nanotubes exhibit similarly high conductivities where the minority carrier transport is bias dependent and nanotube diameter invariant. (copyright 2008 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

Cheminformatics Modeling of Amine Solutions for Assessing their CO2 Absorption Properties.

Science.gov (United States)

Kuenemann, Melaine A; Fourches, Denis

2017-07-01

As stricter regulations on CO 2 emissions are adopted worldwide, identifying efficient chemical processes to capture and recycle CO 2 is of critical importance for industry. The most common process known as amine scrubbing suffers from the lack of available amine solutions capable of capturing CO 2 efficiently. Tertiary amines characterized by low heats of reaction are considered good candidates but their absorption properties can significantly differ from one analogue to another despite high structural similarity. Herein, after collecting and curating experimental data from the literature, we have built a modeling set of 41 amine structures with their absorption properties. Then we analyzed their chemical composition using molecular descriptors and non-supervised clustering. Furthermore, we developed a series of quantitative structure-property relationships (QSPR) to assess amines' CO 2 absorption properties from their structural characteristics. These models afforded reasonable prediction performances (e. g., Q 2 LOO =0.63 for CO 2 absorption amount) even though they are solely based on 2D chemical descriptors and individual machine learning techniques (random forest and neural network). Overall, we believe the chemical analysis and the series of QSPR models presented in this proof-of-concept study represent new knowledge and innovative tools that could be very useful for screening and prioritizing hypothetical amines to be synthesized and tested experimentally for their CO 2 absorption properties. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Using Amines and Alkanes as Thermal-Runaway Retardants for Lithium-Ion Battery

Science.gov (United States)

Shi, Yang

Thermal runaway imposes major challenges to large-scale lithium-ion batteries (LIBs). The working temperature of a LIB is usually around room temperature. However, upon mechanical abuse such as an impact or nail penetration, LIB cell components may fail and internal short circuits could be formed. As a result, a series of exothermic electrochemical reactions and decompositions would take place and the local temperature can rapidly increase. In this thesis, a few novel techniques are investigated to mitigate thermal runaway of LIBs. Mechanically triggered approach has been employed. Thermal-runaway retardant (TRR) is encapsulated in mechanically responsive packages made of materials inert to the battery environment, and upon external mechanical loadings the packages can be broken apart and release the TRR. This mechanism allows for the use of aggressive chemicals to suppress the short circuit discharge and reduce the subsequent exothermic phenomena, immediately after the battery is damaged even before temperature increase begins. The best TRR candidates are identified to be amines and alkanes. Among amines, secondary amines and tertiary amines perform better than primary amines. The reduction in electrolyte ionic conductivity and the displacement of electrolyte are the thermal-runaway-mitigation mechanisms of the secondary and the tertiary amines, respectively. Pentadecane is the best candidate among the alkanes under investigation, with the major working mechanism being electrolyte displacement. Impact tests on large pouch cells and high-energy battery chemistry were also performed; the results were quite encouraging.

Structure-Activity Relationships for Rates of Aromatic Amine Oxidation by Manganese Dioxide

International Nuclear Information System (INIS)

Salter-Blanc, Alexandra J.; Lyon, Molly A.; Science University, Portland, OR; Ness, Stuart C.; Science University, Portland, OR; Tratnyek, Paul G.; Science University, Portland, OR

2016-01-01

New energetic compounds are designed to minimize their potential environmental impacts, which includes their transformation and the fate and effects of their transformation products. The nitro groups of energetic compounds are readily reduced to amines, and the resulting aromatic amines are subject to oxidation and coupling reactions. Manganese dioxide (MnO 2 ) is a common environmental oxidant and model system for kinetic studies of aromatic amine oxidation. Here in this study, a training set of new and previously reported kinetic data for the oxidation of model and energetic-derived aromatic amines was assembled and subjected to correlation analysis against descriptor variables that ranged from general purpose [Hammett σ constants (σ − ), pK a s of the amines, and energies of the highest occupied molecular orbital (E HOMO )] to specific for the likely rate-limiting step [one-electron oxidation potentials (E ox )]. The selection of calculated descriptors (pK a ), E HOMO , and E ox ) was based on validation with experimental data. All of the correlations gave satisfactory quantitative structure-activity relationships (QSARs), but they improved with the specificity of the descriptor. The scope of correlation analysis was extended beyond MnO 2 to include literature data on aromatic amine oxidation by other environmentally relevant oxidants (ozone, chlorine dioxide, and phosphate and carbonate radicals) by correlating relative rate constants (normalized to 4-chloroaniline) to E HOMO (calculated with a modest level of theory).

Industrial Process Design for the Production of Aniline by Direct Amination

NARCIS (Netherlands)

Driessen, Rick T.; Kamphuis, Peter; Mathijssen, Lydwien; Zhang, Ruo; van der Ham, Louis G.J.; van den Berg, Henk; Zeeuw, Arend Jan

2017-01-01

The objective is to design a plant from raw material to product for the production of aniline by direct amination of benzene. The process design is started on a conceptual level and ended on a basic engineering level as well as a techno-economical evaluation. The amination of benzene by

Solvent extraction of cerium (III) with high molecular weight amines

International Nuclear Information System (INIS)

Chatterjee, A.; Basu, S.

1992-01-01

The use of high molecular weight amines in the extraction of cerium (III) as EDTA complex from neutral aqueous medium is reported. The extraction condition was optimised from the study of effects of several variables like concentration of amine and EDTA pH nature of diluents etc. The method has been applied for the determination of cerium in few mineral samples. (author). 7 refs., 5 tabs

Mechanism of the N-Hydroxylation of Primary and Secondary Amines by Cytochrome P450

DEFF Research Database (Denmark)

Seger, Signe T.; Rydberg, Patrik; Olsen, Lars

2015-01-01

Cytochrome P450 enzymes (CYPs) metabolize alkyl- and arylamines, generating several different products. For the primary and secondary amines, some of these reactions result in hydroxylated amines, which may be toxic. Thus, when designing new drugs containing amine groups, it is important to be able...... to predict if a given compound will be a substrate for CYPs, in order to avoid toxic metabolites, and hence to understand the mechanism that is utilized by CYPs. Two possible mechanisms, for the N-hydroxylation of primary and secondary amines mediated by CYPs, are studied by density functional theory (DFT...

Ligand-Enabled γ-C(sp(3))-H Olefination of Amines: En Route to Pyrrolidines.

Science.gov (United States)

Jiang, Heng; He, Jian; Liu, Tao; Yu, Jin-Quan

2016-02-17

Pd(II)-catalyzed olefination of γ-C(sp(3))-H bonds of triflyl (Tf) and 4-nitrobenzenesulfonyl (Ns) protected amines is achieved. Subsequent aza-Wacker oxidative cyclization or conjugate addition of the olefinated intermediates provides a variety of C-2 alkylated pyrrolidines. Three pyridine- and quinoline-based ligands are developed to match different classes of amine substrates, demonstrating a rare example of ligand-enabled C(sp(3))-H olefination reactions. The use of Ns protecting group to direct C(sp(3))-H activation of alkyl amines is also a significant step toward practical C-H functionalizations of alkyl amines.

Thermodynamics of protonation of amines in aqueous solutions at elevated temperatures

Energy Technology Data Exchange (ETDEWEB)

Kim, Inna, E-mail: inna.kim@sintef.no [SINTEF Materials and Chemistry, N-7465 Trondheim (Norway); Jens, Christian M., E-mail: chrijens@stud.ntnu.no [Norwegian University of Science and Technology (NTNU), N-7491 Trondheim (Norway); Grimstvedt, Andreas, E-mail: andreas.grimstvedt@sintef.no [SINTEF Materials and Chemistry, N-7465 Trondheim (Norway); Svendsen, Hallvard F., E-mail: hallvard.svendsen@chemeng.ntnu.no [Norwegian University of Science and Technology (NTNU), N-7491 Trondheim (Norway)

2011-11-15

Highlights: > Effect of ionic strength and temperature on dissociation constants of amines. > Effect of ionic strength of temperature on enthalpies of protonation of amines. > Measured dissociation constants and enthalpies of protonation used for fitting. > Coefficients for thermodynamically consistent correlations given for 5 amines. - Abstract: The dissociation constants, pK{sub a}, of monoethanolamine (MEA), N-methyldiethanolamine (MDEA), 2-amino-2-methyl-1-propanol (AMP), 2(2-aminoethyl)etanolamine (AEEA), and piperazine (Pz) were measured by potentiometric titration over the temperature range (298.15 to 363.15) K. Enthalpies of protonation, {Delta}H{sub p}, were measured calorimetrically at temperatures from (298.15 to 393.15) K for MEA, MDEA, and AMP, and from (298.15 to 353.15) K for AEEA and Pz. In addition, the effect of the ionic strength of the solutions on the protonation of MDEA was studied using NaCl as background salt {l_brace}(0 to 5.5) mol/kg-H{sub 2}O){r_brace}. Correlations for the reaction equilibrium constants for proton dissociation are proposed for the studied amines based on the experimental data from literature and from this work. Both experimental enthalpy data and dissociation constants were used for fitting. The results from this work may be used for thermodynamic modeling of CO{sub 2} capture processes using amines.

Bioinspired aerobic oxidation of secondary amines and nitrogen heterocycles with a bifunctional quinone catalyst.

Science.gov (United States)

Wendlandt, Alison E; Stahl, Shannon S

2014-01-08

Copper amine oxidases are a family of enzymes with quinone cofactors that oxidize primary amines to aldehydes. The native mechanism proceeds via an iminoquinone intermediate that promotes high selectivity for reactions with primary amines, thereby constraining the scope of potential biomimetic synthetic applications. Here we report a novel bioinspired quinone catalyst system consisting of 1,10-phenanthroline-5,6-dione/ZnI2 that bypasses these constraints via an abiological pathway involving a hemiaminal intermediate. Efficient aerobic dehydrogenation of non-native secondary amine substrates, including pharmaceutically relevant nitrogen heterocycles, is demonstrated. The ZnI2 cocatalyst activates the quinone toward amine oxidation and provides a source of iodide, which plays an important redox-mediator role to promote aerobic catalytic turnover. These findings provide a valuable foundation for broader development of aerobic oxidation reactions employing quinone-based catalysts.

Application of oxime-diversification to optimize ligand interactions within a cryptic pocket of the polo-like kinase 1 polo-box domain.

Science.gov (United States)

Zhao, Xue Zhi; Hymel, David; Burke, Terrence R

2016-10-15

By a process involving initial screening of a set of 87 aldehydes using an oxime ligation-based strategy, we were able to achieve a several-fold affinity enhancement over one of the most potent previously known polo-like kinase 1 (Plk1) polo-box domain (PBD) binding inhibitors. This improved binding may result by accessing a newly identified auxiliary region proximal to a key hydrophobic cryptic pocket on the surface of the protein. Our findings could have general applicability to the design of PBD-binding antagonists. Published by Elsevier Ltd.

Elaboration and characterisation of acids catalyst for the obtention of amines

International Nuclear Information System (INIS)

Khemaissia, S.; Zaoui, B.; Nibou, D.

1997-04-01

The nuclear energy has shown the interest of aminated substances as solvents for removal and purification. These extractants are generally used in uranium ores treatment processes and several technology fields, specially, in organic and pharmaceutical industries. The present work deals with elaboration and characterization of acidic solid catalyst used in aminated extractants obtaining

Detection of amines with extended distyrylbenzenes by strip assays.

Science.gov (United States)

Kumpf, Jan; Freudenberg, Jan; Fletcher, Katharyn; Dreuw, Andreas; Bunz, Uwe H F

2014-07-18

We herein describe the synthesis and property evaluation of three novel aldehyde-substituted pentameric phenylenevinylenes carrying branched oligo(ethylene glycol) (swallowtail, Sw) substituents. The targets were synthesized by a combination of Heck coupling and Wittig or Horner reactions of suitable precursor modules. If the pentameric phenylenevinylene carries only two of these Sw substituents, it is no longer water-soluble. When six of the Sw substituents are attached, regardless of their position, the pentameric phenylenevinylenes are well water-soluble. The dialdehydes were investigated with respect to their amine-sensing capabilities both in water as well as in the solid state, sprayed onto thin layer chromatography (TLC) plates (alox, silica gel, reversed phase silica gel). The recognition of amine vapors using the sprayed-on phenylenevinylene dialdehydes is superb and allows the identification of different amines on regular silica TLC plates via color changes, analyzed by a statistical tool, the multivariate analysis of variance (MANOVA) protocol.

Enhanced reactivities toward amines by introducing an imine arm to the pincer ligand: Direct coupling of two amines to form an imine without oxidant

KAUST Repository

He, Lipeng

2012-07-23

Dehydrogenative homocoupling of primary alcohols to form esters and coupling of amines to form imines was accomplished using a class of novel pincer ruthenium complexes. The reactivities of the ruthenium pincer complexes for the direct coupling of amines to form imines were enhanced by introducing an imine arm to the pincer ligand. Selective oxidation of benzylamines to imines was achieved using aniline derivatives as the substrate and solvent. © 2012 American Chemical Society.

Enhanced reactivities toward amines by introducing an imine arm to the pincer ligand: Direct coupling of two amines to form an imine without oxidant

KAUST Repository

He, Lipeng; Chen, Tao; Gong, Dirong; Lai, Zhiping; Huang, Kuo-Wei

2012-01-01

Dehydrogenative homocoupling of primary alcohols to form esters and coupling of amines to form imines was accomplished using a class of novel pincer ruthenium complexes. The reactivities of the ruthenium pincer complexes for the direct coupling of amines to form imines were enhanced by introducing an imine arm to the pincer ligand. Selective oxidation of benzylamines to imines was achieved using aniline derivatives as the substrate and solvent. © 2012 American Chemical Society.

Interaction of biogenic amines with ethanol.

Science.gov (United States)

Smith, A A

1975-01-01

Ethanol through its primary catabolite, acetaldehyde, competitively inhibits oxidation of aldehyde dehydrogenase substrates. As a consequence biogenic amines form increased quantities of alcohols rather than the corresponding acids. During this biotransformation, condensation reactions between deaminated and intact amines may occur which can yield tetrahydropapaverolines. These compounds are closely related to precursors of opioids which is cause to link ethanol abuse to morphine addiction. There is, however, no pharmacological or clinical evidence suggesting similarities between ethanol dependence or opiod addiction. Acetaldehyde plays an additional role in alkaloidal formation in vitro. Biogenic amines may react with acetaldehyde to form isoquinoline or carboline compounds. Some of these substances have significant pharmacological activity. Furthermore, they may enter neural stores and displace the natural neurotransmitter. Thus, they can act as false neurotransmitters. Some investigators believe that chronic ethanol ingestion leads to significant formation of such aberrant compounds which may then upset autonomic nervous system balance. This disturbance may explain the abnormal sympathetic activity seen in withdrawal. While these ideas about the etiology of alcohol abuse have a definite appeal, they are naturally based on in vitro preliminary work. Much study of the quantitative pharmacology of these compounds in animals is required before judgement can be made as to the merits of the proposed hypotheses. In the meantime, pharmacological studies on the ability of ethanol to depress respiration in the mouse has revealed that unlike opioids or barbituates, respiratory depression induced by ethanol requires the presence in brain of serotonin. This neurotransmitter also mediates the respiratory effects of several other alcohols but curiously, not chloral hydrate, yet this compound is purported to alter biogenic amine metabolism much like ethanol. Thus, the response

Amine chemistry. Update on impact on resin

International Nuclear Information System (INIS)

Bachman, Gregory; Kellogg, Douglas; Wilkes, Marty

2012-01-01

Impurity removal in the steam cycle and the associated prevention of corrosion and/or fouling of system components are the goals of ion exchange resins. However, in many instances (such as a switch to amine chemistry or a change in product specifications), resins do not remove, and, in fact, contribute impurities to the steam cycle. This paper reviews recent data compiled to determine the direct and indirect effects of amines on ion exchange resins used in the power industry. Water chemistries have improved in recent years, in large part due to changes in chemistry and resins, but it is necessary to continue to develop products, processes and techniques to reduce impurities and improve overall water chemistry in power plant systems. (orig.)

Amine chemistry. Update on impact on resin

Energy Technology Data Exchange (ETDEWEB)

Bachman, Gregory; Kellogg, Douglas [Siemens Industry, Inc., Rockford, IL (United States). Technology and Lab Services; Wilkes, Marty [Siemens Industry, Inc., Rockford, IL (United States). Water Technologies Div.

2012-03-15

Impurity removal in the steam cycle and the associated prevention of corrosion and/or fouling of system components are the goals of ion exchange resins. However, in many instances (such as a switch to amine chemistry or a change in product specifications), resins do not remove, and, in fact, contribute impurities to the steam cycle. This paper reviews recent data compiled to determine the direct and indirect effects of amines on ion exchange resins used in the power industry. Water chemistries have improved in recent years, in large part due to changes in chemistry and resins, but it is necessary to continue to develop products, processes and techniques to reduce impurities and improve overall water chemistry in power plant systems. (orig.)

Synthesis of (19E)-3 beta,7 alpha-dihydroxy-17-oxoandrost-5-en-19-al 19-(O-carboxymethyl)oxime, a new hapten for 7 alpha-hydroxydehydroepiandrosterone (3 beta,7 alpha-dihydroxyandrost-5-en-17-one).

Science.gov (United States)

Pouzar, V; Slavíková, T; Cerńy, I

1998-09-01

The title compound was prepared in 11 steps from 17,17-ethylenedioxy-19-hydroxyandrost-5-en-3 beta-yl acetate. After tert-butyldimethylsilyl protection of the 19-hydroxyl group, a 7-oxo group was introduced by oxidation with 3,5-dimethylpyrazole-chromium trioxide complex, and then selectively reduced with L-Selectride to give a 7 alpha-hydroxy derivative. This partially protected triol was acetylated and desilylated to 3,7-diacetate. Subsequent oxidation with pyridine-chromium trioxide complex gave 19-aldehyde, which was transformed into the corresponding protected 19-(O-carboxymethyl)oxime. Successive ketal cleavage, deacetylation, and methyl ester splitting gave the final (19E)-3 beta,7 alpha-dihydroxy-17-oxoandrost-5-en-19-al 19-(O-carboxymethyl)oxime, designed as a hapten for 7 alpha-hydroxydehydroepiandrosterone immunoassays.

Biogenic amines degradation by malolactic bacteria: towards a potential application in wine

Directory of Open Access Journals (Sweden)

Vittorio eCapozzi

2012-04-01

Full Text Available Biogenic amines in wine represent a toxicological risk for the health of the consumer, with several trade implications. In this study 26 strains of Lactobacillus plantarum were analysed for their ability to degrade biogenic amines commonly found during wine fermentation. Two strains of L. plantarum were selected in reason of their ability to degrade putrescine and tyramine. The degradation was assessed in vitro, both in presence of the biogenic amines and in presence of the specific chemical precursor and of producer bacteria. The two L. plantarum biotypes were found capable to work synergically. In addition, the survival in wine-like medium and the aptitude to degrade malic acid after alcoholic fermentation of the selected L. plantarum strains was analysed. Our results suggest the potential application of wine L. plantarum strains to design malolactic starter cultures able to degrade biogenic amines in wine.

Bifunctional (cyclopentadienone)iron-tricarbonyl complexes: Synthesis, computational studies and application in reductive amination

KAUST Repository

Moulin, Solenne

2013-11-15

Reductive amination under hydrogen pressure is a valuable process in organic chemistry to access amine derivatives from aldehydes or ketones. Knölker\\'s complex has been shown to be an efficient iron catalyst in this reaction. To determine the influence of the substituents on the cyclopentadienone ancillary ligand, a series of modified Knölker\\'s complexes was synthesised and fully characterised. These complexes were also transformed into their analogous acetonitrile iron-dicarbonyl complexes. Catalytic activities of these complexes were evaluated and compared in a model reaction. The scope of this reaction is also reported. For mechanistic insights, deuterium-labelling experiments and DFT calculations were undertaken and are also presented. Festival of amination: Two series of modified Knölker\\'s complexes were synthesised and applied in the reductive amination of various carbonyl derivatives with primary or secondary amines (see scheme, TIPS = triisopropylsilyl). For a mechanistic insight, deuterium-labelling experiments and DFT calculations were undertaken and are also presented. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Determination of oxyfluorfen herbicide and oxyfluorfen amine residues in garbanzo beans by liquid chromatography.

Science.gov (United States)

Zhou, M; Miles, C J

1991-01-01

Oxyfluorfen and oxyfluorfen amine were determined by liquid chromatography (LC) with ultraviolet (UV) and photoconductivity detection (PCD). A simple extraction procedure acceptably recovered both analytes from garbanzo beans over a wide range of fortifications (0.05 to 20 ppm) (83 +/- 4 for oxyfluorfen; 85 +/- 4 for oxyfluorfen amine). Percent recoveries decreased slightly as the fortification level decreased. Both analytes could be determined simultaneously at a concentration greater than 0.2 ppm in garbanzo beans. Detection limits were 3 ng for oxyfluorfen and 100 ng for oxyfluorfen amine using LC/UV, and 12 ng for both oxyfluorfen and oxyfluorfen amine with LC/PCD. Different knitted reaction coils and photoreactors were evaluated. Photoproduct yields and identification were determined by ion chromatography. The LC/PCD method measures oxyfluorfen and oxyfluorfen amine separately and has a shorter analysis time, while the standard method using gas chromatography measures total residues and is more sensitive.

Excess molar enthalpies for binary mixtures of different amines with water

International Nuclear Information System (INIS)

Zhang, Ruilei; Chen, Jian; Mi, Jianguo

2015-01-01

Highlights: • Isothermal excess molar enthalpies for binary mixtures of different amines with water. • The Redlich–Kister equation and the NRTL model was used to fit the experimental data. • The excess molar enthalpies were discussed with different structures of amines. - Abstract: The isothermal excess molar enthalpies for binary mixtures of different amines with water were measured with a C-80 Setaram calorimeter. The experimental results indicate that the excess molar enthalpy is related to the molecular structure. The experimental excess molar enthalpies were satisfactorily fitted with the Redlich–Kister equation. They were also used to test the suitability of the NRTL model, and the deviations are a little larger than the R–K equation

Risk assessment related to biogenic amines occurrence in ready-to-eat baby foods.

Science.gov (United States)

Czajkowska-Mysłek, Anna; Leszczyńska, Joanna

2017-07-01

Potential adverse reactions among infants and young children could appear after consumption of food containing small amounts of bioactive amines. This study presents the first assessment of biogenic amines occurrence in ready-to-eat vegetable without/with fish, meat and fruit baby products intended for the youngest consumers. The biogenic amine profiles and quantities of 6 amines were evaluated in 68 commercial baby foods produced by 10 leading manufacturers available in Poland, using HPLC-APCI-MS method. The total amine contents in analyzed products were obtained in the range of 1283-101421 ng/g. The maximum level of histamine (2375 ng/g) was found in the sample with spinach, tyramine (1667 ng/g) in fruit sample with banana, and of di- and polyamines (1263-53416 ng/g) in samples containing green peas. The results of amine analysis in baby foods indicated the presence of food ingredients which may be necessary to remove (tuna, possibly spinach) or reduce the amount added (spinach, green peas), either reduce their use by infants under 12 months of age (beef). Special attention should also be given to control the consumption of fruit baby products containing banana (higher tyramine and putrescine level). On the basis of obtained results a potential %ARfD, and the BAI were also evaluated. Copyright © 2017 Elsevier Ltd. All rights reserved.

Extension of the cubic-plus-association (CPA) equation of state to amines

DEFF Research Database (Denmark)

Kaarsholm, Mads Kristian; Derawi, Samer; Michelsen, Michael Locht

2005-01-01

The cubic-plus-association (CPA) equation of state has been extended to modeling mixtures containing amines. Special focus was given to primary and secondary amines, which are known to self-associate, thus forming hydrogen bonds in mixtures with alkanes. Pure-compound parameters have been determi...

Effect of storage conditions on the biogenic amine content in wild boar meat

Directory of Open Access Journals (Sweden)

Zdeňka Hutařová

2014-01-01

Full Text Available Hygienic quality of game meat depends on many factors during and after hunting. Freshness of meat is connected with the concentration of biogenic amines which is related to meat spoilage. The aim of this study was to assess changes in concentration of biogenic amines in raw meat of wild boar (n = 20, mean age 1–2 years during storage at different temperatures. Carcases of wild boars hunted in winter 2012 in hunting districts of south Moravia were stored unskinned during 21 days at various temperatures (0, 7 and 15 °C. Concentrations of biogenic amines (putrescine, cadaverine, tyramine, tryptamine, phenylethylamine, histamine, spermine and spermidine were determined in the shoulder and leg muscles by high-performance liquid chromatography in combination with triple quadrupole tandem mass spectrometry. Good hygienic quality was maintained when wild boar carcasses were stored for a maximum of 14 days at 0 °C (content of biogenic amines in 3 meat samples exceed the limit of 5 mg/kg on day 21 of storage or a maximum of 7 days at 7 °C (content of biogenic amines in 4 meat samples exceed the limit of 5 mg/kg on day 14 of storage. The temperature of 15 °C should be considered as unsuitable storage temperature if good hygienic quality of game meat during storage is to be guaranteed (content of biogenic amines in 2 meat samples exceed the limit of 5 mg/kg already on day 7 of storage. The study brings new information about the biogenic amine content and its changes in wild boar meat during the storage period of 21 days.

Deposition of stable amine coating onto polycaprolactone nanofibers by low pressure cyclopropylamine plasma polymerization

Energy Technology Data Exchange (ETDEWEB)

Manakhov, Anton [Plasma Technologies, CEITEC — Central European Institute of Technology, Masaryk University, Kotlářská 2, Brno 61137 (Czech Republic); Nečas, David [Plasma Technologies, CEITEC — Central European Institute of Technology, Masaryk University, Kotlářská 2, Brno 61137 (Czech Republic); Department of Physical Electronics, Faculty of Science, Masaryk University, Kotlářská 2, Brno 61137 (Czech Republic); Čechal, Jan [CEITEC — Central European Institute of Technology, Brno University of Technology, Technická 3058/10, 616 00 Brno (Czech Republic); Pavliňák, David [Department of Physical Electronics, Faculty of Science, Masaryk University, Kotlářská 2, Brno 61137 (Czech Republic); Eliáš, Marek [Plasma Technologies, CEITEC — Central European Institute of Technology, Masaryk University, Kotlářská 2, Brno 61137 (Czech Republic); Department of Physical Electronics, Faculty of Science, Masaryk University, Kotlářská 2, Brno 61137 (Czech Republic); and others

2015-04-30

Amine-rich films are of high interest for the bio-applications including drug delivery and tissue engineering thanks to their high reactivity allowing the formation of the covalent linkages between biomolecules and a surface. However, the bio-applications of amine-rich films require their good stability in water which is often achieved at large expenses of the amine concentration. Recently, non-toxic cyclopropylamine (CPA) has been applied for the plasma polymerization of films bearing high NH{sub x} environment combined with the moderate thickness loss (20%) after water immersion for 48 h. In this work, the amine-rich film with the NH{sub x} concentration over 7 at.% was deposited on Si substrates and polycaprolactone nanofiber meshes by using CPA plasma polymerization (pulsed mode) in a vertically oriented stainless steel reactor. The substrates were placed at the radio frequency electrode and the ion bombardment caused by direct-current self-bias was suppressed by using high pressure of 50 Pa. Analysis of samples by scanning electron microscopy did not reveal any cracks in the deposited layer formed during a sample immersion in water. Fourier transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS) confirmed a slight oxidation of amine groups in water but the film still contained 5 at.% of NH{sub x} (according to the N1s XPS fitting) after the immersion. The rapid oxidation of amine groups was observed during the aging experiment carried out in air at room temperature because FTIR revealed an increase of amide peaks that increased progressively with aging time. However, this oxidation was significantly reduced if the plasma polymer was stored at − 20 °C. Since the films exhibit high amine concentration and very good water stability they have great potential for applications as biocompatible functional coatings. - Highlights: • Cyclopropylamine plasma polymers deposited on polycaprolactone nanofibers • Amine-rich films with high

Deposition of stable amine coating onto polycaprolactone nanofibers by low pressure cyclopropylamine plasma polymerization

International Nuclear Information System (INIS)

Manakhov, Anton; Nečas, David; Čechal, Jan; Pavliňák, David; Eliáš, Marek

2015-01-01

Amine-rich films are of high interest for the bio-applications including drug delivery and tissue engineering thanks to their high reactivity allowing the formation of the covalent linkages between biomolecules and a surface. However, the bio-applications of amine-rich films require their good stability in water which is often achieved at large expenses of the amine concentration. Recently, non-toxic cyclopropylamine (CPA) has been applied for the plasma polymerization of films bearing high NH x environment combined with the moderate thickness loss (20%) after water immersion for 48 h. In this work, the amine-rich film with the NH x concentration over 7 at.% was deposited on Si substrates and polycaprolactone nanofiber meshes by using CPA plasma polymerization (pulsed mode) in a vertically oriented stainless steel reactor. The substrates were placed at the radio frequency electrode and the ion bombardment caused by direct-current self-bias was suppressed by using high pressure of 50 Pa. Analysis of samples by scanning electron microscopy did not reveal any cracks in the deposited layer formed during a sample immersion in water. Fourier transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS) confirmed a slight oxidation of amine groups in water but the film still contained 5 at.% of NH x (according to the N1s XPS fitting) after the immersion. The rapid oxidation of amine groups was observed during the aging experiment carried out in air at room temperature because FTIR revealed an increase of amide peaks that increased progressively with aging time. However, this oxidation was significantly reduced if the plasma polymer was stored at − 20 °C. Since the films exhibit high amine concentration and very good water stability they have great potential for applications as biocompatible functional coatings. - Highlights: • Cyclopropylamine plasma polymers deposited on polycaprolactone nanofibers • Amine-rich films with high water stability �

Maillard reaction of lactose and fluoxetine hydrochloride, a secondary amine.

Science.gov (United States)

Wirth, D D; Baertschi, S W; Johnson, R A; Maple, S R; Miller, M S; Hallenbeck, D K; Gregg, S M

1998-01-01

Analysis of commercially available generic formulations of fluoxetine HCl revealed the presence of lactose as the most common excipient. We show that such formulations are inherently less stable than formulations with starch as the diluent due to the Maillard reaction between the drug, a secondary amine hydrochloride, and lactose. The Amadori rearrangement product was isolated and characterized; the characterization was aided by reduction with sodium borohydride and subsequent characterization of this reduced adduct. The lactose-fluoxetine HCl reaction was examined in aqueous ethanol and in the solid state, in which factors such as water content, lubricant concentration, and temperature were found to influence the degradation. N-Formylfluoxetine was identified as a major product of this Maillard reaction and it is proposed that N-formyl compounds be used as markers for this drug-excipient interaction since they are easy to prepare synthetically. Many characteristic volatile products of the Maillard reaction have been identified by GC/MS, including furaldehyde, maltol, and 2,3-dihydro-3,5-dihydroxy-6-methyl-4 H-pyran-4-one. Close similarity between the degradation products of simple mixtures and formulated generic products was found; however, at least one product decomposed at a rate nearly 10 times that predicted from the simple models. Maillard products have also been identified in unstressed capsules. The main conclusion is that drugs which are secondary amines (not just primary amines as sometimes reported) undergo the Maillard reaction with lactose under pharmaceutically relevant conditions. This finding should be considered during the selection of excipients and stability protocols for drugs which are secondary amines or their salts, just as it currently is for primary amines.

Simultaneous extraction and quantitation of several bioactive amines in cheese and chocolate.

Science.gov (United States)

Baker, G B; Wong, J T; Coutts, R T; Pasutto, F M

1987-04-17

A method is described for simultaneous extraction and quantitation of the amines 2-phenylethylamine, tele-methylhistamine, histamine, tryptamine, m- and p-tyramine, 3-methoxytyramine, 5-hydroxytryptamine, cadaverine, putrescine, spermidine and spermine. This method is based on extractive derivatization of the amines with a perfluoroacylating agent, pentafluorobenzoyl chloride, under basic aqueous conditions. Analysis was done on a gas chromatograph equipped with an electron-capture detector and a capillary column system. The procedure is relatively rapid and provides derivatives with good chromatographic properties. Its application to analysis of the above amines in cheese and chocolate products is described.

Organocatalyzed Asymmetric α-Oxidation, α-Aminoxylation and α-Amination of Carbonyl Compounds

Directory of Open Access Journals (Sweden)

Worawan Bhanthumnavin

2010-02-01

Full Text Available Organocatalytic asymmetric α-oxidation and amination reactions of carbonyl compounds are highly useful synthetic methodologies, especially in generating chiral building blocks that previously have not been easily accessible by traditional methods. The concept is relatively new and therefore the list of new catalysts, oxidizing and aminating reagents, as well as new substrates, are expanding at an amazing rate. The scope of this review includes new reactions and catalysts, mechanistic aspects and synthetic applications of α-oxidation, hydroxylation, aminoxylation, amination, hydrazination, hydroxyamination and related α-heteroatom functionalization of aldehydes, ketones and related active methylene compounds published during 2005–2009.

Readily Available Chiral Benzimidazoles-Derived Guanidines as Organocatalysts in the Asymmetric α-Amination of 1,3-Dicarbonyl Compounds.

Science.gov (United States)

Benavent, Llorenç; Puccetti, Francesco; Baeza, Alejandro; Gómez-Martínez, Melania

2017-08-11

The synthesis and the evaluation as organocatalysts of new chiral guanidines derived from benzimidazoles in the enantioselective α-amination of 1,3-dicarbonyl compounds using di- t -butylazodicarboxylate as aminating agent is herein disclosed. The catalysts are readily synthesized through the reaction of 2-chlorobezimidazole and a chiral amine in moderate-to-good yields. Among all of them, those derived from ( R )-1-phenylethan-1-amine ( 1 ) and ( S )-1-(2-naphthyl)ethan-1-amine ( 3 ) turned out to be the most efficient for such asymmetric transformation, rendering good-to-high yields and moderate-to-good enantioselectivities for the amination products.

Amine functionalized cubic mesoporous silica nanoparticles as an oral delivery system for curcumin bioavailability enhancement

Science.gov (United States)

Budi Hartono, Sandy; Hadisoewignyo, Lannie; Yang, Yanan; Meka, Anand Kumar; Antaresti; Yu, Chengzhong

2016-12-01

In the present work, a simple method was used to develop composite curcumin-amine functionalized mesoporous silica nanoparticles (MSN). The nanoparticles were used to improve the bioavailability of curcumin in mice through oral administration. We investigated the effect of particle size on the release profile, solubility and oral bioavailability of curcumin in mice, including amine functionalized mesoporous silica micron-sized-particles (MSM) and MSN (100-200 nm). Curcumin loaded within amine functionalized MSN (MSN-A-Cur) had a better release profile and a higher solubility compared to amine MSM (MSM-A-Cur). The bioavailability of MSN-A-Cur and MSM-A-Cur was considerably higher than that of ‘free curcumin’. These results indicate promising features of amine functionalized MSN as a carrier to deliver low solubility drugs with improved bioavailability via the oral route.

Investigation of the adsorption of polymer chains on amine-functionalized double-walled carbon nanotubes.

Science.gov (United States)

Ansari, R; Ajori, S; Rouhi, S

2015-12-01

Molecular dynamics (MD) simulations were used to study the adsorption of different polymer chains on functionalized double-walled carbon nanotubes (DWCNTs). The nanotubes were functionalized with two different amines: NH2 (a small amine) and CH2-NH2 (a large amine). Considering three different polymer chains, all with the same number of atoms, the effect of polymer type on the polymer-nanotube interaction was studied. In general, it was found that covalent functionalization considerably improved the polymer-DWCNT interaction. By comparing the results obtained with different polymer chains, it was observed that, unlike polyethylene and polyketone, poly(styrene sulfonate) only weakly interacts with the functionalized DWCNTs. Accordingly, the smallest radius of gyration was obtained with adsorbed poly(styrene sulfonate). It was also observed that the DWCNTs functionalized with the large amine presented more stable interactions with polyketone and poly(styrene sulfonate) than with polyethylene, whereas the DWCNTs functionalized with the small amine showed better interfacial noncovalent bonding with polyethylene.

Matrix-isolation FTIR, theoretical structural analysis and reactivity of amino-saccharins: N-(1,1-dioxo-1,2-benzisothiazol-3-yl)- N-methyl amine and - N,N-dimethyl amine

Science.gov (United States)

Almeida, R.; Gómez-Zavaglia, A.; Kaczor, A.; Ismael, A.; Cristiano, M. L. S.; Fausto, R.

2009-12-01

In this work, two novel amino-substituted derivatives of saccharin, N-(1,1-dioxo-1,2-benzisothiazol-3-yl)- N-methyl amine (MBAD) and N-(1,1-dioxo-1,2-benzisothiazol-3-yl)- N, N-dimethyl amine (DMBAD), were synthesized and characterized, and their molecular structure and vibrational properties were investigated by matrix-isolation FTIR spectroscopy and theoretical calculations undertaken using different levels of approximation. The calculations predicted the existence of two conformers of MBAD. The lowest energy form was predicted to be considerably more stable than the second conformer (Δ E > ca. 20 kJ mol -1) and was the sole form contributing to the infrared spectrum of the compound isolated in solid xenon. Both conformers have planar amine moieties. In the case of DMBAD, only one doubly-degenerated-by-symmetry conformer exists, with the amine nitrogen atom considerably pyramidalized. The effect of the electron-withdrawing saccharyl ring on the C-N bond lengths is discussed. The different structural preferences around the amine nitrogen atom in the two molecules were explained in terms of repulsive interactions involving the additional methyl group of DMBAD. Observed structural features are correlated with the reactivity exhibited by the two compounds towards nucleophiles. The experimentally obtained spectra of the matrix-isolated monomers of MBAD and DMBAD were fully assigned by comparison with the corresponding calculated spectra.

Transition metals in the amination of chloroarenes

Energy Technology Data Exchange (ETDEWEB)

Serdyuk, O V [Leibniz-Institut fuer Katalyse an der Universitaet Rostock (Germany); Abaev, Vladimir T [North-Ossetia State University, Vladikavkaz (Russian Federation)

2009-11-30

The review is devoted to the catalytic amination of chloroarenes and chlorohetarenes. Examples of the formation of the C-N bond in the presence of iron-, nickel- and copper-based catalytic systems are given.

Reaction of iminopropadienones with amines: mechanistic explanations of zwitterionic intermediate, ketene and ketenimine formation.

Science.gov (United States)

Koch, Rainer; Finnerty, Justin J; Bruhn, Torsten; Borget, Fabien; Wentrup, Curt

2008-09-25

The complex reaction of thermally generated iminopropadienones with amines in the gas phase and upon matrix deposition and its varying product composition is investigated using density functional theory. In the high energy gas phase addition a single amine molecule reacts readily with iminopropadienone with the decisive step being a 1,3-hydrogen shift and activation barriers of at least 100 kJ/mol. In accordance with the experiment, the formation of ketenes is favored. In the condensed phase of an amine matrix, the utilization of amine dimers both as reagents and as explicit solvents lowers the activation energy required to a feasible 20-30 kJ/mol and predicts ketenimines as the main products, as observed experimentally.

Copper-Catalyzed Electrophilic Amination of Organoaluminum Nucleophiles with O-Benzoyl Hydroxylamines.

Science.gov (United States)

Zhou, Shuangliu; Yang, Zhiyong; Chen, Xu; Li, Yimei; Zhang, Lijun; Fang, Hong; Wang, Wei; Zhu, Xiancui; Wang, Shaowu

2015-06-19

A copper-catalyzed electrophilic amination of aryl and heteroaryl aluminums with N,N-dialkyl-O-benzoyl hydroxylamines that affords the corresponding anilines in good yields has been developed. The catalytic reaction proceeds very smoothly under mild conditions and exhibits good substrate scope. Moreover, the developed catalytic system is also well suited for heteroaryl aluminum nucleophiles, providing facile access to heteroaryl amines.

A redox-assisted molecular assembly of molybdenum oxide amine composite nanobelts

International Nuclear Information System (INIS)

Luo Haiyan; Wei Mingdeng; Wei Kemei

2011-01-01

Research highlights: → Nanobelts of molybdenum oxide amine were first synthesized via a redox-assisted molecular assembly route. → These nanobelts are highly crystalline with a several tens of micrometers in length and 20-30 nm in thickness. - Abstract: In this paper, the nanobelts of molybdenum oxide amine composite were successfully synthesized via a redox-assisted molecular assembly route under the hydrothermal conditions. The synthesized nanobelts were characterized by XRD, SEM, TEM, TG and FT-IR measurements. The thickness of nanobelts is found to be ca. 20-30 nm and their lengths are up to several tens of micrometers. Based on a series of the experimental results, a possible model, redox-intercalation-exfoliation, was suggested for the formation of nanobelts of molybdenum oxide amine composite.

Palladium-catalyzed aryl amination-heck cyclization cascade: A one-flask approach to 3-substituted Indoles

DEFF Research Database (Denmark)

Jensen, Thomas; Pedersen, Henrik; Bang-Andersen, B.

2008-01-01

Two for the price of one: A Pd/dppf-based catalyst provides access to the title compounds from 1,2-dihalogenated aromatic compounds and allylic amines in a single reaction flask. The initial aryl amination step occurs with excellent selectivity for the aryl iodide to ensure the formation of a sin......Two for the price of one: A Pd/dppf-based catalyst provides access to the title compounds from 1,2-dihalogenated aromatic compounds and allylic amines in a single reaction flask. The initial aryl amination step occurs with excellent selectivity for the aryl iodide to ensure the formation...

Pyridoxylamine reactivity kinetics as an amine based nucleophile for screening electrophilic dermal sensitizers

Science.gov (United States)

Chipinda, Itai; Mbiya, Wilbes; Adigun, Risikat Ajibola; Morakinyo, Moshood K.; Law, Brandon F.; Simoyi, Reuben H.; Siegel, Paul D.

2015-01-01

Chemical allergens bind directly, or after metabolic or abiotic activation, to endogenous proteins to become allergenic. Assessment of this initial binding has been suggested as a target for development of assays to screen chemicals for their allergenic potential. Recently we reported a nitrobenzenethiol (NBT) based method for screening thiol reactive skin sensitizers, however, amine selective sensitizers are not detected by this assay. In the present study we describe an amine (pyridoxylamine (PDA)) based kinetic assay to complement the NBT assay for identification of amine-selective and non-selective skin sensitizers. UV-Vis spectrophotometry and fluorescence were used to measure PDA reactivity for 57 chemicals including anhydrides, aldehydes, and quinones where reaction rates ranged from 116 to 6.2 × 10−6 M−1 s−1 for extreme to weak sensitizers, respectively. No reactivity towards PDA was observed with the thiol-selective sensitizers, non-sensitizers and prohaptens. The PDA rate constants correlated significantly with their respective murine local lymph node assay (LLNA) threshold EC3 values (R2 = 0.76). The use of PDA serves as a simple, inexpensive amine based method that shows promise as a preliminary screening tool for electrophilic, amine-selective skin sensitizers. PMID:24333919

Effects of dietary amines on the gut and its vasculature

OpenAIRE

Broadley, Kenneth John; Anwar, Mohammad Akhtar; Herbert, Amy Angharad; Fehler, Martina; Jones, Elen M.; Davies, W. E.; Kidd, Emma Jane; Ford, William Richard

2009-01-01

Trace amines, including tyramine and β-phenylethylamine (β-PEA), are constituents of many foods including chocolate, cheeses and wines and are generated by so-called ‘friendly’ bacteria such as Lactobacillus, Lactococcus and Enterococcus species, which are found in probiotics. We therefore examined whether these dietary amines could exert pharmacological effects on the gut and its vasculature. In the present study we examined the effects of tyramine and β-PEA on the contractile activity of gu...

Efficacy of fenbendazole and milbemycin oxime for treating baboons (Papio cynocephalus anubis) infected with Trichuris trichiura.

Science.gov (United States)

Reichard, Mason V; Wolf, Roman F; Carey, David W; Garrett, Jennifer Jane; Briscoe, Heather A

2007-03-01

We evaluated the efficacy of fenbendazole (FBZ) and milbemycin oxime (MO) in the treatment of baboons (Papio cynocephalus anubis) with naturally acquired Trichuris trichiura infection by comparing fecal egg count reduction (FECR) tests. We assigned 7 baboons, each singly housed and confirmed infected with T. trichiura, to treatment groups of FBZ (n=3) or MO (n=3), or as a control (n=1). All (100%) baboons that received FBZ stopped shedding T. trichiura eggs within 6 d of treatment, and fecal egg counts remained negative at 65 d after treatment. Although the number of T. trichiura eggs shed per gram of feces from 2 (67%) baboons decreased significantly after the second treatment with MO, this regimen never totally eliminated eggs of T. trichiura. The results of our study indicate that FBZ was more effective for treating baboons with T. trichiura than was MO.

Enzyme-controlled nitrogen-atom transfer enables regiodivergent C-H amination.

Science.gov (United States)

Hyster, Todd K; Farwell, Christopher C; Buller, Andrew R; McIntosh, John A; Arnold, Frances H

2014-11-05

We recently demonstrated that variants of cytochrome P450BM3 (CYP102A1) catalyze the insertion of nitrogen species into benzylic C-H bonds to form new C-N bonds. An outstanding challenge in the field of C-H amination is catalyst-controlled regioselectivity. Here, we report two engineered variants of P450BM3 that provide divergent regioselectivity for C-H amination-one favoring amination of benzylic C-H bonds and the other favoring homo-benzylic C-H bonds. The two variants provide nearly identical kinetic isotope effect values (2.8-3.0), suggesting that C-H abstraction is rate-limiting. The 2.66-Å crystal structure of the most active enzyme suggests that the engineered active site can preorganize the substrate for reactivity. We hypothesize that the enzyme controls regioselectivity through localization of a single C-H bond close to the iron nitrenoid.

Dietary exposure to heterocyclic amines in high-temperature cooked meat and fish in Malaysia.

Science.gov (United States)

Jahurul, M H A; Jinap, S; Ang, S J; Abdul-Hamid, A; Hajeb, P; Lioe, H N; Zaidul, I S M

2010-08-01

The intake of heterocyclic amines is influenced by the amount and type of meat and fish ingested, frequency of consumption, cooking methods, cooking temperature, and duration of cooking. In this study, the dietary intake of heterocyclic amines in Malaysia and their main sources were investigated. Forty-two samples of meat and fish were analysed by high-performance liquid chromatography with photodiode array detector to determine the concentration of the six predominant heterocyclic amines, namely: 2-amino-3-methylimidazo[4,5-f] quinoline (IQ), 2-amino-3,4-dimethylimidazo[4,5-f] quinoline(MeIQ), 2-amino-3,8-dimethylimidazo[4,5-f] quinoxaline (MeIQx), 2-amino-3,4,8-trimethylimidazo[4,5-f] quinoxaline (4,8-DiMeIQx), 2-amino-3,7,8-trimethylimidazo[4,5-f] quinoxaline (7,8-DiMeIQx), and 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP). Dietary intake data were obtained using a food-frequency questionnaire when interviewing 600 Malaysian respondents. The level of total heterocyclic amines in food samples studies ranged from not detected to 38.7 ng g(-1). The average daily intake level of heterocyclic amine was 553.7 ng per capita day(-1). The intake of PhIP was the highest, followed by MeIQx and MeIQ. The results reveal that fried and grilled chicken were the major dietary source of heterocyclic amines in Malaysia. However, the heterocyclic amine intake by the Malaysian population was lower than those reported from other regions.

Amine-terminated silicon nanoparticles: synthesis, optical properties and their use in bioimaging

NARCIS (Netherlands)

Rosso-Vasic, M.; Spruijt, E.; Popovic, Z.; Overgaag, K.; Lagen, van B.; Grandidier, B.; Vanmaekelbergh, D.; Domínguez-Gutiérrez, D.; Cola, de L.; Zuilhof, H.

2009-01-01

Very stable and bright emitting amine-terminated Si nanoparticles (NPs) with different alkyl chain lengths between the Si core and amine end-group are synthesized. The obtained NPs have a spherical shape and homogeneous size distribution (1.57 ± 0.24 nm). Their emission can be tuned from the UV to

Metabolism and genotoxicity of aromatic amines in aquatic organisms

International Nuclear Information System (INIS)

Knezovich, J.P.; Krauter, P.W.; Lawton, M.P.; Harrison, F.L.

1987-01-01

Marine mussels (Mytilus edulis) and bullfrog tadpoles (Rana catesbeiana) were used to investigate the comparative metabolism and genotoxicity of aromatic amines in vivo. These organisms were selected because they possess distinctly different metabolic capabilities: mussels lack an active mixed-function-oxidase enzyme system that is present in most other organisms, including amphibians. Using 14 C-labeled chemical probes (o- and p-toluidine, 2-aminofluorene (2-AF), and 2-acetylaminofluorene (2-AAF)), mussels and tadpoles well dosed with individual compounds by direct immersion in aqueous solutions. The identities of metabolites were then determined by HPLC and GC/MS methods. Results indicate that the N-conjugating pathways used by mussels result primarily in the detoxification of aromatic amines by limiting the amount of primary amine available for activation. The tadpoles excreted a number of 2-AAF metabolites but did form DNA and protein adducts in the liver. Induction of micronuclei in the peripheral red blood cells was also demonstrated. The tadpole was shown to be a sensitive biological indicator of pollution in aquatic ecosystems

Regularities of synthesis and mechanism of polycondensation of aromatic amines

International Nuclear Information System (INIS)

Matnishyan, Hagob

2002-01-01

Full text.Aniline polymers and its derivatives are widely used in modern electronics, electrical engineering and manufacturing of various appliances. They are used for production of electrical power sources, probes and sensors, composite materials absorbing high frequency radiations, anticorrosion coatings, nonlinear optical devices-such as lasers, cathode ray tubes, photodiodes etc. Such a wide usage of aromatic amine polymers brings up new demands to their structure and properties, which is dependent on conditions of synthesis and forming of the hard phase. The presented article describes regularities and mechanisms of oxidative polycondensation of aromatic amines. Several types of polymers have been synthesized by chemical and electrochemical oxidation of aniline and its chlor-, brom-, iodo-, nitro-, p-substituted derivatives; diphenylamine, benzidine and phenylenediamines in nonwater media. On the basis of kinetic and electrochemical studies and literature analysis we suggested a mechanism of polycondensation of aromatic amines. According to it, oxidation of amines starts with the electron transfer with cation-radical formation on the first stage, which stabilizes in acid environments due to complex formation with initial amine. Dimer formation and further growth of chain takes place upon another electron transfer from formed complex, which results in forming of macromolecules. We also suggested a scheme for obtaining of structures defect in media assisting in deprotonizing of cation radicals and formation of arylamine radical centers. Those processes lead to formation of azo- and diphenyl fragments in the main chain of the polymer and predetermine the possibility of chain disruption. We also considered reactions leading to formation of branched polymers and cyclic structures, such as phenazine in particular. The peculiarity of electrochemical process lies in regulation of concentration of active centres on the positive electrode surface

Debromination of endo-(+)-3-bromocamphor with primary amines