Heavily doped GaAs:Te layers grown by MOVPE using diisopropyl telluride as a source

Energy Technology Data Exchange (ETDEWEB)

Daniltsev, V. M.; Demidov, E. V.; Drozdov, M. N.; Drozdov, Yu. N., E-mail: drozdyu@ipmras.ru; Kraev, S. A.; Surovegina, E. A.; Shashkin, V. I.; Yunin, P. A. [Russian Academy of Sciences, Institute for Physics of Microstructures (Russian Federation)

2016-11-15

The capabilities of GaAs epitaxial layers extremely heavily doped with tellurium by metal-organic vapor-phase epitaxy using diisopropyl telluride as a source are studied. It is shown that tellurium incorporation into GaAs occurs to an atomic concentration of 10{sup 21} cm{sup –3} without appreciable diffusion and segregation effects. Good carrier concentrations (2 × 10{sup 19} cm{sup –3}) and specific contact resistances of non-alloyed ohmic contacts (1.7 × 10{sup –6} Ω cm{sup 2}) give grounds to use such layers to create non-alloyed ohmic contacts in electronic devices. A sharp decrease in the electrical activity of Te atoms, a decrease in the electron mobility, and an increase in the contact resistance at atomic concentrations above 2 × 10{sup 20} cm{sup –3} are detected.

Integrated circuit microsensor for selectively detection nitrogen dioxide and diisopropyl methylphosphonate

Energy Technology Data Exchange (ETDEWEB)

Kolesar, E.S. Jr. (Air Force Inst. of Technology, Dept. of Electrical and Computer Engineering, Wright-Patterson Air Force Base, Dayton, OH (United States)); Brothers, C.P. Jr. (Air Force Inst. of Technology, Dept. of Electrical and Computer Engineering, Wright-Patterson Air Force Base, Dayton, OH (United States)); Howe, C.P. (Air Force Inst. of Technology, Dept. of Electrical and Computer Engineering, Wright-Patterson Air Force Base, Dayton, OH (United States)); Jenkins, T.J. (Air Force Inst. of Technology, Dept. of Electrical and Computer Engineering, Wright-Patterson Air Force Base, Dayton, OH (United States)); Moosey, A.T. (Air Force Inst. of Technology, Dept. of Electrical and Computer Engineering, Wright-Patterson Air Force Base, Dayton, OH (United States)); Shin, J.E. (Air Force Inst. of Technology, Dept. of Electrical and Computer Engineering, Wright-Patterson Air Force Base, Dayton, OH (United States)); Wiseman, J.M. (Air Force Inst. of Technology, Dept. of Electrical an

1992-11-20

A novel gas-sensitive microsensor, known as the interdigitated gate electrode field effect transistor (IGEFET), was realized by selectively depositing a chemically-active, electron-beam evaporated copper phthalocyanine (CuPc) thin film onto an integrated circuit (IC). When isothermally operated at 150 C, the microsensor can selectively and reversibly detect parts-per-billion concentration levels of nitrogen dioxide (NO[sub 2]) and diisopropyl methylphosphonate (DIMP). The selectivity feature of the microsensor was established by operating it with a 5 V peak amplitude, 2 [mu]s duration, 1000 Hz repetition frequency pulse, and then analyzing its time- and frequency-domain responses. The envelopes associated with the normalized-difference Fourier transform magnitude spectra, and their derivatives, reveal features which unambiguously distinguish the NO[sub 2] and DIMP challenge gas responses. Furthermore, the area beneath each response envelope may correspondingly be interpreted as the microsensor's sensitivity for a specific challenge gas concentration. Scanning electron microscopy (SEM) was used to characterize the morphology of the CuPc thin film. Additionally, infrared (IR) spectroscopy was employed to verify the [alpha]- and [beta]-phases of the sublimed CuPc thin films and to study the NO[sub 2]- and DIMP-CuPc interactions. (orig.)

Synthesis of 2,6-diisopropyl-phenylcarbamoylmethyl-iminodiacetic acid (DISIDA) and 4-n-p-butyl-phenylcarbamoylmethyl-iminodiacetic acid (BUTYL-IDA). Preparation of lyophilized kit to be used as 99(supm)Tc agent in hepatobiliary system

International Nuclear Information System (INIS)

Hamada, E.S.; Barbosa, M.F. de; Theodora, M.A.; Almeida, M. de; Colturato, M.T.; Muramoto, E.; Silva, C.P.G. da.

1987-08-01

The synthesis of 2,6 diisopropyl IDA (DISIDA) and 4-n-butyl IDA (BUTIL-IDA) is described. Their spectroscopic properties, radiopharmaceutical preparation and their use as 99 (sup m)Tc complex agent in hepatobiliary studies, are also reported. (Author) [pt

Regulation of apoptosis and priming of neutrophil oxidative burst by diisopropyl fluorophosphate

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Tsang Jennifer LY

2010-07-01

Full Text Available Abstract Background Diisopropyl fluorophosphate (DFP is a serine protease inhibitor that is widely used as an inhibitor of endogenous proteases in in vitro neutrophil studies. Its effects on neutrophil function are unclear. We sought to determine the biological effects of DFP on human neutrophil apoptosis and oxidative burst. Methods We isolated neutrophils from healthy volunteers, incubated them with DFP (2.5 mM, and evaluated neutrophil elastase (NE activity, neutrophil degranulation, apoptosis as reflected in hypodiploid DNA formation and exteriorization of phosphatidylserine (PS, processing and activity of caspases-3 and -8, oxidative burst activity and hydrogen peroxide release. Results Consistent with its activity as a serine protease inhibitor, DFP significantly inhibited NE activity but not the degranulation of azurophilic granules. DFP inhibited constitutive neutrophil apoptosis as reflected in DNA fragmentation, and the processing and activity of caspases-3 and -8. DFP also inhibited priming of neutrophils for oxidative burst activity and hydrogen peroxide release. However, DFP enhanced the exteriorization of PS in a dose-dependent manner. Conclusion We conclude that DFP exerts significant effects on neutrophil inflammatory function that may confound the interpretation of studies that use it for its antiprotease activity. We further conclude that endogenous proteases play a role in the biology of constitutive neutrophil apoptosis.

Role of morphine administration with 99m-technetium-labelled di-isopropyl iminodiacetic acid in the diagnosis of acute cholecystitis

International Nuclear Information System (INIS)

Louridas, G.; Botha, J.R.; Esser, J.D.; Savitch, I.; Vas, M.; Levin, J.; Myburgh, J.A.

1987-01-01

Patients presenting with a clinical diagnosis suggestive of acute cholecystitis had a 99m-technetium-labelled di-isopropyl iminodiacetic acid (DISIDA) scan. Two groups of patients were investigated. In group 1, 66 patients underwent cholescintigraphy and after 60 minutes morphine was given to all patients whose gallbladders had not filled. The accuracy rate of this procedure was 91%, sensitivity 83%, specificity 97%, positive predictive value 96,2% and negative predictive value 87,5%. In group 2, 97 patients had cholescintigraphy with morphine being administered at the beginning of the procedure. The accuracy rate of this investigation was 97,9%, sensitivity 100%, specificity 96,6%, positive predictive value 95% and negative predictive value 100%. We recommend the early use of morphine in all patients undergoing a DISIDA scan for acute cholecystitis

Hydrolase stabilization via entanglement in poly(propylene sulfide) nanoparticles: stability towards reactive oxygen species

International Nuclear Information System (INIS)

Allen, Brett L; Johnson, Jermaine D; Walker, Jeremy P

2012-01-01

In the advancement of green syntheses and sustainable reactions, enzymatic biocatalysis offers extremely high reaction rates and selectivity that goes far beyond the reach of chemical catalysts; however, these enzymes suffer from typical environmental constraints, e.g. operational temperature, pH and tolerance to oxidative environments. A common hydrolase enzyme, diisopropylfluorophosphatase (DFPase, EC 3.1.8.2), has demonstrated a pronounced efficacy for the hydrolysis of a variety of substrates for potential toxin remediation, but suffers from the aforementioned limitations. As a means to enhance DFPase’s stability in oxidative environments, enzymatic covalent immobilization within the polymeric matrix of poly(propylene sulfide) (PPS) nanoparticles was performed. By modifying the enzyme’s exposed lysine residues via thiolation, DFPase is utilized as a comonomer/crosslinker in a mild emulsion polymerization. The resultant polymeric polysulfide shell acts as a ‘sacrificial barrier’ by first oxidizing to polysulfoxides and polysulfones, rendering DFPase in an active state. DFPase–PPS nanoparticles thus retain activity upon exposure to as high as 50 parts per million (ppm) of hypochlorous acid (HOCl), while native DFPase is observed as inactive at 500 parts per billion (ppb). This trend is also confirmed by enzyme-generated (chloroperoxidase (CPO), EC 1.11.1.10) reactive oxygen species (ROS) including both HOCl (3 ppm) and ClO 2 (100 ppm). (paper)

[COMPARATIVE SENSITIVITY OF CHOLINESTERASES IN VERTEBRATES AND INVERTEBRATES TO HIGHLY SPECIFIC ORGANOPHOSPHORUS INHIBITORS DIISOPROPYL FLUOROPHOSPHATE (DFP) AND (2-ETHOXYMETHYL PHOSPHORYL THIOETHYL) ETHYL (METHYL) SULPHONIUM SULPHOMETHYLAT (GD-42)].

Science.gov (United States)

Basova, N E; Kormilitsyn, B N; Perchenok, A Yu; Rozengart, E V; Saakov, V S; Suvorov, A A

2015-01-01

The review presents data on comparative reactivity of 68 cholinesterase preparation from various organs and tissues in a number of vertebrates and invertebrates based on sensitivity to two highly specific and most studied organophosphorus inhibitors--diisopropyl fluorophosphates (DFP) and (2-ethoxymethyl phosphoryl thioethyl) ethyl (methyl) sulphonium sulphomethylat (GD-42). Analysis of these data suggests a great diversity in enzymologic characteristics of cholinesterase preparation in representatives of vertebrates and invertebrates, this variety observed even for closely related enzymes in animals of almost the same level of development.

Stability 'in vivo' and 'in vitro' of the diisopropyl-IDA sup(99m)Tc

International Nuclear Information System (INIS)

Verdera, E.S.; Leon, A.S.; Robles, A.M.; Correa, Angela; Oliver, Guillermo; Gamma, Santos; Lanzzeri, Stella; Mitta, A.E.A.

1982-01-01

The 'in vitro' and 'in vivo' stability of the diisopropyl (IDA-3) kit in solution and of the molecule labelled with sup(99m)Tc was studied. The following items were studied a) shelf life of the kit in solution b) 'in vitro' stability of the labelled molecule c) distribution and elimination kinetics d) identification and behaviour of the excretion products. Chromatographic control shows 95% yield of labelled product after 20 days storage at 4 deg C and 92% yield after 30 days in the same conditions; biological distribution was good in both cases. Regarding the 'in vitro' stability, no alteration was observed within the 4 hours after its preparation. The stability of the complex was determined by the reaction between sup(99m)TcIDA-3 and DTPA. Analysis by electrophoresis shows the complex to be stable even with DTPA concentrations 5 times higher. Kinetics of distribution and elimination of the labelled molecule, in animals, were afterwards confirmed by sequential scintigraphic images in humans. The excretion of unaltered sup(99m)Tc-IDA by biliary and urinary ways was confirmed by cromatographic and electrophoretic analysis of bladder and gall bladder content and by determination of its biological distribution. (author) [es

Synthesis, spectral and antimicrobial activity of [3-(4-chloro-phenoxy-2,4-diisopropyl-2,3,4,5-tetrahydro-1H-3l5-benzo[e][1,3,2]diazaphosphepin-3-ylidene]-alkyl-amine

Directory of Open Access Journals (Sweden)

R. Usha Nagalakshmi

2009-11-01

Full Text Available 3-(4-chlorophenoxy-2,4-diisopropyl-2,3,4,5-tetrahydro-1H-benzo[e][1,3,2]diaza-phosphepine was synthesized starting from 1,2-bis(bromomethylbenzene by reacting with 2 equimolar isopropyl amine, one equimolar PBr3 and then one equimolar 4-chlorophenol, respectively. The Staudinger reaction of the diazaphphosphine with a series of alkyl azides gave the corresponding iminophosphoranes. Antibacterial activities of the synthesized iminophosphoranes were screened

Isobaric (vapour + liquid + liquid) equilibrium data for (di-n-propyl ether + n-propyl alcohol + water) and (diisopropyl ether + isopropyl alcohol + water) systems at 100 kPa

International Nuclear Information System (INIS)

Lladosa, Estela; Monton, Juan B.; Burguet, MaCruz; Torre, Javier de la

2008-01-01

Isobaric (vapour + liquid + liquid) equilibria were measured for the (di-n-propyl ether + n-propyl alcohol + water) and (diisopropyl ether + isopropyl alcohol + water) system at 100 kPa. The apparatus used for the determination of (vapour + liquid + liquid) equilibrium data was an all-glass dynamic recirculating still with an ultrasonic homogenizer couple to the boiling flask. The experimental data demonstrated the existence of a heterogeneous ternary azeotrope for both ternary systems. The (vapour + liquid + liquid) equilibria data were found to be thermodynamically consistent for both systems. The experimental data were compared with the estimation using UNIQUAC and NRTL models and the prediction of UNIFAC model

High temperature shock tube experiments and kinetic modeling study of diisopropyl ketone ignition and pyrolysis

KAUST Repository

Barari, Ghazal; Pryor, Owen; Koroglu, Batikan; Sarathy, Mani; Masunov, Artë m E.; Vasu, Subith S.

2017-01-01

Diisopropyl ketone (DIPK) is a promising biofuel candidate, which is produced using endophytic fungal conversion. In this work, a high temperature detailed combustion kinetic model for DIPK was developed using the reaction class approach. DIPK ignition and pyrolysis experiments were performed using the UCF shock tube. The shock tube oxidation experiments were conducted between 1093K and 1630K for different reactant compositions, equivalence ratios (φ=0.5–2.0), and pressures (1–6atm). In addition, methane concentration time-histories were measured during 2% DIPK pyrolysis in argon using cw laser absorption near 3400nm at temperatures between 1300 and 1400K near 1atm. To the best of our knowledge, current ignition delay times (above 1050K) and methane time histories are the first such experiments performed in DIPK at high temperatures. Present data were used as validation targets for the new kinetic model and simulation results showed fair agreement compared to the experiments. The reaction rates corresponding to the main consumption pathways of DIPK were found to have high sensitivity in controlling the reactivity, so these were adjusted to attain better agreement between the simulation and experimental data. A correlation was developed based on the experimental data to predict the ignition delay times using the temperature, pressure, fuel concentration and oxygen concentration.

High temperature shock tube experiments and kinetic modeling study of diisopropyl ketone ignition and pyrolysis

KAUST Repository

Barari, Ghazal

2017-03-10

Diisopropyl ketone (DIPK) is a promising biofuel candidate, which is produced using endophytic fungal conversion. In this work, a high temperature detailed combustion kinetic model for DIPK was developed using the reaction class approach. DIPK ignition and pyrolysis experiments were performed using the UCF shock tube. The shock tube oxidation experiments were conducted between 1093K and 1630K for different reactant compositions, equivalence ratios (φ=0.5–2.0), and pressures (1–6atm). In addition, methane concentration time-histories were measured during 2% DIPK pyrolysis in argon using cw laser absorption near 3400nm at temperatures between 1300 and 1400K near 1atm. To the best of our knowledge, current ignition delay times (above 1050K) and methane time histories are the first such experiments performed in DIPK at high temperatures. Present data were used as validation targets for the new kinetic model and simulation results showed fair agreement compared to the experiments. The reaction rates corresponding to the main consumption pathways of DIPK were found to have high sensitivity in controlling the reactivity, so these were adjusted to attain better agreement between the simulation and experimental data. A correlation was developed based on the experimental data to predict the ignition delay times using the temperature, pressure, fuel concentration and oxygen concentration.

UV and γ-ray resistance of poly(N-methylmaleimide-alt-isobutene) and poly(diisopropyl fumarate) as transparent polymer films

Science.gov (United States)

Imaizumi, Ryota; Furuta, Masakazu; Okamura, Haruyuki; Matsumoto, Akikazu

2017-09-01

UV and γ-ray resistance of transparent polymers obtained by radical polymerization of maleic and fumaric acid derivatives, i.e., an alternating copolymer of N-methylmaleimide and isobutene (PMI) and poly(diisopropyl fumarate) (PDiPF), was investigated. Transmittance in UV and visible regions of these polymers were examined after UV irradiation and compared with the results for poly(methyl methacrylate) (PMMA) and polycarbonate (PC) as conventional transparent polymers. The order of stability toward UV irradiation was PMMA≈PDiPF>PMI>>PC, deduced from changes in the transmittance of 380 nm light. Tensile mechanical properties, such as elastic modulus, maximum strength, and elongation values of PMI, PDiPF, and PMMA were also investigated after UV and γ-radiation. UV irradiation induced the side chain scission of PMI and PDiPF via Norrish I type reaction as well as crosslinking by combination between formed polymer radicals, leading to deterioration in their optical and mechanical properties. γ-radiation induced significant changes in molecular weight and mechanical properties of the polymers. In conclusion, PMI exhibited unchanged mechanical properties and PDiPF maintained its high transparency under various irradiation conditions.

Deactivating Chemical Agents Using Enzyme-Coated Nanofibers Formed by Electrospinning

Science.gov (United States)

2016-01-01

7.3mM/mg). Key words Coaxial electrospinning, DFPase, Enzyme, chemical warfare , nanofiber, decontamination . Introduction Chemical warfare ...Krile, R.; Nishioka, M.; Taylor, M.; Riggs, K.; Stone, H. Decontamination of Toxic Industrial Chemicals and Chemical Warfare Agents On Building...298 (Rev. 8-98) Prescribed by ANSI Std. Z39.18 MATS COATINGS ELECTROSPINNING CHEMICAL WARFARE

Impaired recovery of brain muscarinic receptor sites following an adaptive down-regulation induced by repeated administration of diisopropyl fluorophosphate in aged rats

International Nuclear Information System (INIS)

Pintor, A.; Fortuna, S.; De Angelis, S.; Michalek, H.

1990-01-01

Potential age-related differences in the recovery rate of brain cholinesterase activity (ChE) and muscarinic acetylcholine receptor binding sites (mAChRs) following reduction induced by repeated treatment with diisopropyl fluorophosphate (DFP) were evaluated in Sprague-Dawley rats. Male 3- and 24-month old rats were s.c. injected with DFP on alternate days for 2 weeks and killed 48 hr and 7, 14, 21, 28 and 35 days after the last treatment. In the hippocampus and striatum, but not in the cerebral cortex, of control rats there as a significant age-related decline of ChE activity and maximal density of 3H-QNB binding sites (Bmax). The repeated administration of DFP during the first week caused a syndrome of cholinergic stimulation both in aged and young rats. The syndrome was more pronounced, in terms of intensity and duration in aged than in young animals resulting in 40 and 12% mortality, respectively; during the second week the syndrome attenuated in the two age-groups. The percentage inhibition of brain ChE at the end of DFP treatment did not differ between young and surviving aged rats. The down-regulation of mACRs was present in the three brain regions of both young and age rats (from 20 to 40%). Factorial analysis of variance showed significant differences for age, recovery rate, and significant interaction between age and recovery rate, both for ChE and mAChRs in young rats the three brain areas

Impaired recovery of brain muscarinic receptor sites following an adaptive down-regulation induced by repeated administration of diisopropyl fluorophosphate in aged rats

Energy Technology Data Exchange (ETDEWEB)

Pintor, A.; Fortuna, S.; De Angelis, S.; Michalek, H. (Istituto Superiore di Sanita, Rome (Italy))

1990-01-01

Potential age-related differences in the recovery rate of brain cholinesterase activity (ChE) and muscarinic acetylcholine receptor binding sites (mAChRs) following reduction induced by repeated treatment with diisopropyl fluorophosphate (DFP) were evaluated in Sprague-Dawley rats. Male 3- and 24-month old rats were s.c. injected with DFP on alternate days for 2 weeks and killed 48 hr and 7, 14, 21, 28 and 35 days after the last treatment. In the hippocampus and striatum, but not in the cerebral cortex, of control rats there as a significant age-related decline of ChE activity and maximal density of 3H-QNB binding sites (Bmax). The repeated administration of DFP during the first week caused a syndrome of cholinergic stimulation both in aged and young rats. The syndrome was more pronounced, in terms of intensity and duration in aged than in young animals resulting in 40 and 12% mortality, respectively; during the second week the syndrome attenuated in the two age-groups. The percentage inhibition of brain ChE at the end of DFP treatment did not differ between young and surviving aged rats. The down-regulation of mACRs was present in the three brain regions of both young and age rats (from 20 to 40%). Factorial analysis of variance showed significant differences for age, recovery rate, and significant interaction between age and recovery rate, both for ChE and mAChRs in young rats the three brain areas.

Comparative non-cholinergic neurotoxic effects of paraoxon and diisopropyl fluorophosphate (DFP) on human neuroblastoma and astrocytoma cell lines

International Nuclear Information System (INIS)

Qian Yongchang; Venkatraj, Jijayanagaram; Barhoumi, Rola; Pal, Ranadip; Datta, Aniruddha; Wild, James R.; Tiffany-Castiglioni, Evelyn

2007-01-01

The objective of this study was to evaluate the comparative non-cholinergic neurotoxic effects of paraoxon, which is acutely neurotoxic, and diisopropyl fluorophosphate (DFP), which induces OPIDN, in the human neuroblastoma SY5Y and the human astrocytoma cell line CCF-STTG1. SY5Y cells have been studied extensively as a model for OP-induced neurotoxicity, but CCF cells have not previously been studied. We conducted a preliminary human gene array assay of OP-treated SY5Y cells in order to assess at the gene level whether these cells can distinguish between OP compounds that do and do not cause OPIDN. Paraoxon and DFP induced dramatically different profiles of gene expression. Two genes were upregulated and 13 downregulated by at least 2-fold in paraoxon-treated cells. In contrast, one gene was upregulated by DFP and none was downregulated at the 2-fold threshold. This finding is consistent with current and previous observations that SY5Y cells can distinguish between OPs that do or do not induce OPIDN. We also examined gene array results for possible novel target proteins or metabolic pathways for OP neurotoxicity. Protein levels of glucose regulated protein 78 (GRP78) revealed that paraoxon exposure at 3 μM for 24 h significantly reduced GRP78 levels by 30% in neuroblastoma cells, whereas DFP treatment had no effect. In comparison with SY5Y neuroblastoma cells, paraoxon and DFP (3 μM for 24 h) each significantly increased GRP78 levels by 23-24% in CCF astrocytoma cells. As we have previously evaluated intracellular changes in Ca 2+ levels in SY5Y cells, we investigated the effects of paraoxon and DFP on cellular Ca 2+ homeostasis in CCF by studying cytosolic and mitochondrial basal calcium levels. A significant decrease in the ratio of mitochondrial to cytosolic Ca 2+ fluorescence was detected in CCF cultures treated for either 1 or 3 days with 1, 3, 10, or 30 μM paraoxon. In contrast, treatment with DFP for 1 day had no significant effect on the ratio of

Proteinases of human epidermis; a possible mechanism for polymorphonuclear leukocyte chemotaxis

Energy Technology Data Exchange (ETDEWEB)

Levine, N; Hatcher, V B; Lazarus, G S [Albert Einstein Coll. of Medicine, Bronx, N.Y. (USA); Montefiore Hospital, New York (USA); Duke Univ., Durham, N.C. (USA))

1976-12-08

Three neutral proteinases (EC 3.4.-,-) and cathepsin D have been identified in human epidermis utilizing a highly sensitive radioactive method. The proteinases were extracted in 1.0 M KCl and 0.1% Triton X-100 and separated by Sephadex G-75 chromatography. The neutral proteinase peaks were all inhibited by diisopropyl fluorophosphate and thus were serine proteinases. Incubation of the enzyme fractions with (/sup 3/H)diisopropyl fluorophosphate followed by sodium dodecyl sulfate polyacrylamide gel electrophoresis demonstrated that the two larger molecular weight proteinases were enzyme mixtures. The small molecular weight (/sup 3/H)diisopropyl fluorophosphate proteinase migrated as a single band. Injection of the small molecular weight neutral proteinase into rabbit skin produced a polymorphonuclear leukocyte infiltration and edema. The reaction was not observed with the diisopropul fluorophosphate-inhibited enzyme fraction. The release of neutral proteinases may be one of the signal events in the epidermal inflammatory response.

Host-Guest Inclusion Complexes between Amlodipine Enantiomers in the Biphasic Recognition Chiral Extraction System using Tartaric Acid and β-Cyclodextrin Derivatives as Positive Confirmation by using their Enantioselective Extraction.

Science.gov (United States)

Al Azzam, Khaldun M; Abdallah, Hassan H; Halim, Hairul N Abdul; Ahmad, Maizatul Akmam; Shaibah, Hassan

2015-01-01

The current work reports an extended theoretical study from our previous experimental work for the enantioselective extraction of amlodipine enantiomers in a biphasic recognition chiral extraction system (BRCES) consisting of hydrophobic D-diisopropyl tartrate dissolved in organic phase (n-decanol) and hydrophilic hydroxypropyl-β-cyclodextrin (HP-β-CD) in aqueous phase (acetate buffer) which preferentially recognize the R-enantiomer and S-enantiomer, respectively. The calculations were simulated using a semi-empirical PM3 method as a part of the Gaussian09 software package and were used to optimize the structures of the hosts, guests, and host-guest complexes in the gas phase without any restrictions. It was found that HP-β-CD has the strongest recognition ability among the three β-CD derivatives studied, namely HP-β-CD, hydroxyethyl-β-cyclodextrin (HE-β-CD), and methylated-β-cyclodextrin (Me-β-CD), due to the large interaction energies (Ecomp = -14.3025 kcal/ mol), while D-diisopropyl tartrate has the strongest ability among the four tartaric acid derivatives studied namely; L-diisopropyl tartrate, D-diisopropyl tartrate, L-diethyl tartrate, and D-diethyl tartrate (Ecomp = -5.9964 kcal/ mol). The computational calculations for the enantioselective partitioning of amlodipine enantiomers rationalized the reasons for the different behaviors for this extraction. The present theoretical results may be informative to scientists who are devoting themselves to developing models for their experimental parts or for enhancing the hydrophobic drug solubility in drug delivery systems.

Host-Guest Inclusion Complexes between Amlodipine Enantiomers in the Biphasic Recognition Chiral Extraction System using Tartaric Acid and β-Cyclodextrin Derivatives as Positive Confirmation by using their Enantioselective Extraction

Science.gov (United States)

Al Azzam, Khaldun M.; Abdallah, Hassan H.; Halim, Hairul N. Abdul; Ahmad, Maizatul Akmam; Shaibah, Hassan

2015-01-01

The current work reports an extended theoretical study from our previous experimental work for the enantioselective extraction of amlodipine enantiomers in a biphasic recognition chiral extraction system (BRCES) consisting of hydrophobic D-diisopropyl tartrate dissolved in organic phase (n-decanol) and hydrophilic hydroxypropyl-β-cyclodextrin (HP-β-CD) in aqueous phase (acetate buffer) which preferentially recognize the R-enantiomer and S-enantiomer, respectively. The calculations were simulated using a semi-empirical PM3 method as a part of the Gaussian09 software package and were used to optimize the structures of the hosts, guests, and host-guest complexes in the gas phase without any restrictions. It was found that HP-β-CD has the strongest recognition ability among the three β-CD derivatives studied, namely HP-β-CD, hydroxyethyl-β-cyclodextrin (HE-β-CD), and methylated-β-cyclodextrin (Me-β-CD), due to the large interaction energies (Ecomp = −14.3025 kcal/ mol), while D-diisopropyl tartrate has the strongest ability among the four tartaric acid derivatives studied namely; L-diisopropyl tartrate, D-diisopropyl tartrate, L-diethyl tartrate, and D-diethyl tartrate (Ecomp = −5.9964 kcal/ mol). The computational calculations for the enantioselective partitioning of amlodipine enantiomers rationalized the reasons for the different behaviors for this extraction. The present theoretical results may be informative to scientists who are devoting themselves to developing models for their experimental parts or for enhancing the hydrophobic drug solubility in drug delivery systems. PMID:26839848

Observation of a re-entrant phase transition in the molecular complex tris(μ2-3,5-diisopropyl-1,2,4-triazolato-κ2N1:N2trigold(I under high pressure

Directory of Open Access Journals (Sweden)

Christopher H. Woodall

2016-09-01

Full Text Available We report a molecular crystal that exhibits four successive phase transitions under hydrostatic pressure, driven by aurophilic interactions, with the ground-state structure re-emerging at high pressure. The effect of pressure on two polytypes of tris(μ2-3,5-diisopropyl-1,2,4-triazolato-κ2N1:N2trigold(I (denoted Form-I and Form-II has been analysed using luminescence spectroscopy, single-crystal X-ray diffraction and first-principles computation. A unique phase behaviour was observed in Form-I, with a complex sequence of phase transitions between 1 and 3.5 GPa. The ambient C2/c mother cell transforms to a P21/n phase above 1 GPa, followed by a P21/a phase above 2 GPa and a large-volume C2/c supercell at 2.70 GPa, with the previously observed P21/n phase then reappearing at higher pressure. The observation of crystallographically identical low- and high-pressure P21/n phases makes this a rare example of a re-entrant phase transformation. The phase behaviour has been characterized using detailed crystallographic theory and modelling, and rationalized in terms of molecular structural distortions. The dramatic changes in conformation are correlated with shifts of the luminescence maxima, from a band maximum at 14040 cm−1 at 2.40 GPa, decreasing steeply to 13550 cm−1 at 3 GPa. A similar study of Form-II displays more conventional crystallographic behaviour, indicating that the complex behaviour observed in Form-I is likely to be a direct consequence of the differences in crystal packing between the two polytypes.

Synthesis and characterization of novel triptycene dianhydrides and polyimides of intrinsic microporosity based on 3,3ʹ-dimethylnaphthidine

KAUST Repository

Ghanem, Bader; Alghunaimi, Fahd; Ma, Xiaohua; Alaslai, Nasser Y.; Pinnau, Ingo

2016-01-01

Two intrinsically microporous polyimides were obtained by high-temperature, one-pot poly-condensation reaction of novel triptycene-based dianhydrides containing dimethyl- or diisopropyl-bridgehead groups with a commercially available highly

Recovery of carrier-free gold-195

International Nuclear Information System (INIS)

Iofa, B.Z.; Ivanova, N.A.

1995-01-01

It is known that gold(III) is readily extracted from nitric acid solutions with ethers. The authors have studied extraction of trace amounts of gold(III) from nitric acid solutions with diethyl and diisopropyl ethers in the presence of significant excess of Pt(IV). Distribution coefficients of gold(III) were measured radiometrically using carrier-free gold-195 or spectrophotometrically in the presence of platinum(IV). Very high coefficients of gold separation from platinum may be achieved. Preliminary experiments have shown that zinc-65 was not extracted with ethers from nitric acid solutions. As an extraction system, the authors have chosen the system 10 M HNO 3 -diisopropyl ether. After model experiments, the authors have performed recovery of carrier-free gold-195 from a real platinum target irradiated with protons in a cyclotron

Synthesis and characterization of oxovanadium (IV) dithiocarbamates with pyridine

Energy Technology Data Exchange (ETDEWEB)

Doadrio, Antonio L.; Sotelo, Jose; Fernandez-Ruano, Ana [Universidad Complutense, Madrid (Spain). Facultad de Farmacia. Dept. de Quimica Inorganica y Bioinorganica]. E-mail: antoniov@farm.ucm.es

2002-07-01

We report the synthesis and study of a new series of oxovanadium (IV) dithiocarbamate adducts and derivatives with pyridine and cyclohexyl, di-iso-butyl, di-n-propyl, aniline, morpholine, piperidine and di-iso-propyl amines. The complexes have been characterized by analytical, magneto chemical, IR, visible-UV spectral and thermal studies, and are assigned the formulas [VO(L){sub 2}].py, where L=cyclohexyl, di-iso-butyl, di-n-propyl, aniline dithiocarbamate and [VO(OH)(L)(py){sub 2}] OH.H{sub 2}O (L=morpholine, piperidine and di-iso-propyl dithiocarbamate). The effect of the adduct formation on the p{sub V=0} bound is discussed in terms of the IR (V=O, V-S and V-N stretching frequencies) and electronic spectra (d-d transitions). (author)

The human receptor for urokinase plasminogen activator. NH2-terminal amino acid sequence and glycosylation variants

DEFF Research Database (Denmark)

Behrendt, N; Rønne, E; Ploug, M

1990-01-01

The receptor for human urokinase-type plasminogen activator (u-PA) was purified from phorbol 12-myristate 13-acetate-stimulated U937 cells by temperature-induced phase separation of detergent extracts, followed by affinity chromatography with immobilized diisopropyl fluorophosphate-treated u...

Localization of urokinase-type plasminogen activator receptor on U937 cells

DEFF Research Database (Denmark)

Hansen, S H; Behrendt, N; Danø, K

1990-01-01

The binding of human urokinase-type plasminogen activator (u-PA) to the surface of the human monocytic cell line U937 was studied by immunological detection of bound u-PA or binding of biotinylated diisopropyl fluorophosphate-inactivated human u-PA visualized by light or electron microscopy...

A novel esterase from Saccharomyces carlsbergensis, a possible function for the yeast TIP1 gene

DEFF Research Database (Denmark)

Horsted, M W; Dey, E S; Holmberg, S

1998-01-01

An extracellular esterase was isolated from the brewer's yeast, Saccharomyces carlsbergensis. Inhibition by diisopropyl fluorophosphate shows that the enzyme has a serine active site. By mass spectrometry, the molecular weight of the enzyme was 16.9 kDa. The optimal pH for activity was in the range...

Regio- and stereoselective hydrosilylation of immobilized terminal alkynes

DEFF Research Database (Denmark)

Pedersen, Palle Jacob; Henriksen, Jonas; Gotfredsen, Charlotte Held

2008-01-01

Regio- and stereoselective hydrosilylation of terminal alkynes on solid support using diisopropyl hydrosilanes yielding b-(E)-vinyl silanes with excellent selectivity is reported. The hydrosilylation is catalyzed by Pt(DVDS)/P(iBuNCH2CH2)3N (DVDS = 1,3-divinyl-1,1,3,3-tetramethyl-disiloxane), in ...

Facile one-pot synthesis of functionalized organophosphonate ...

Indian Academy of Sciences (India)

WINTEC

The reaction of phosphorus trichloride with 2,6-diisopropyl phenol in the presence of LiCl under reflux ... on a Perkin Elmer Spectrum One FT–IR spectrometer. Microanalyses were performed on a Thermo Finni- gan (FLASH EA .... 3.1 Synthesis and characterization .... and no other signals corresponding to the formation.

Cell-surface acceleration of urokinase-catalyzed receptor cleavage

DEFF Research Database (Denmark)

Høyer-Hansen, G; Ploug, M; Behrendt, N

1997-01-01

by a prior incubation of the cells with uPA inactivated by diisopropyl fluorophosphate, demonstrating a requirement for specific receptor binding of the active uPA to obtain the high-efficiency cleavage of cell-bound uPAR. Furthermore, amino-terminal sequence analysis revealed that uPAR(2+3), purified from U...

Ultra-microporous triptycene-based polyimide membranes for high-performance gas separation

KAUST Repository

Ghanem, Bader

2014-03-11

A highly permeable and highly selective polyimide of intrinsic microporosity is prepared using a 9,10-diisopropyl-triptycene contortion center. The three-dimensionality and shape-persistence of triptycene afford exceptional sieving-based gas separation performance transcending the latest permeability/selectivity trade-offs for industrial gas separations involving oxygen and hydrogen. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ultra-microporous triptycene-based polyimide membranes for high-performance gas separation

KAUST Repository

Ghanem, Bader; Swaidan, Raja; Litwiller, Eric; Pinnau, Ingo

2014-01-01

A highly permeable and highly selective polyimide of intrinsic microporosity is prepared using a 9,10-diisopropyl-triptycene contortion center. The three-dimensionality and shape-persistence of triptycene afford exceptional sieving-based gas separation performance transcending the latest permeability/selectivity trade-offs for industrial gas separations involving oxygen and hydrogen. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Identification and characterization of dimeric oxidation products of p-cymene-2,3-diol isolated from Thymus vulgaris L.

Science.gov (United States)

Rainis, Guido; Ternes, Waldemar

2014-01-08

The aim of this study was to investigate the oxidation products of p-cymene-2,3-diol, a major antioxidative constituent of thyme (Thymus vulgaris L.). Although a dimeric form of p-cymene-2,3-diol and some derivative substances exhibiting valuable food technological and health-promoting properties have been reported in earlier publications, no obvious correlation has been shown between these substances. A modified HPLC-ESI-MS method made it possible to prove that two dimers, 3,4,3',4'-tetrahydroxy-5,5'-diisopropyl-2,2'-dimethylbiphenyl (1) and the newly identified 3',4'-dihydroxy-5,5'-diisopropyl-2,2'-dimethylbiphenyl-3,4-dione (2), are oxidation products of p-cymene-2,3-diol. 2 was characterized by the fragmentation pattern determined by multiple mass spectrometry, (1)H NMR, (13)C NMR, H-H COSY, HSQC, and HMBC. Both biphenyls were also quantitated in freeze-dried thyme as well as in a food matrix spiked with thyme extract. Model experiments using raw and cooked minced pork meat as matrix and sodium nitrite as oxidizing and reduction agent with and without ascorbic acid as protective reagent showed the correlation between food processing and dimer generation.

Host-Guest Inclusion Complexes between Amlodipine Enantiomers in Biphasic Recognition Chiral Extraction System using Tartaric Acid and β-Cyclodextrin Derivatives as Positive Confirmation Using of their Enantioselective Extraction

OpenAIRE

AZZAM, Khaldun; ABDALLAH, Hassan; HALIM, Hairul; AHMAD, Maizatul; SHAIBAH, Hassan

2015-01-01

The current work reports an extended theoretical study from our previous experimental work for the enantioselective extraction of amlodipine enantiomers in a biphasic recognition chiral extraction system (BRCES) consisting of hydrophobic D-diisopropyl tartrate dissolved in organic phase (n-decanol) and hydrophilic hydroxypropyl-?-cyclodextrin (HP-?-CD) in aqueous phase (acetate buffer) which preferentially recognize the R-enantiomer and S-enantiomer, respectively. The calculations were simula...

Synthesis and biological activity of allosteric modulators of GABAB receptors part 3. 3-(2,6-bis-iso-propyl-4-hydroxyphenyl)propanols

International Nuclear Information System (INIS)

Kerr, David I.B.; Ong, Jennifer; Khalafy, Jabbar; Rimaz, Mehdi; Prager, Rolf H.

2007-01-01

A series of six 2,2-disubstituted 3-[3,5-di-iso-propyl-4-hydroxyphenyl]propan-1-ol derivatives have been prepared for evaluation as allosteric modulators of GABA B receptors. The activity (EC 50 30 μM) was greatest for the dimethyl analogue, but the isopropylphenyl compounds were generally weaker than the corresponding t-butyl compounds. Methylation of the phenolic group led to loss of activity. (author)

[3 + 2]-Cycloadditions of nitrile ylides after photoactivation of vinyl azides under flow conditions

Directory of Open Access Journals (Sweden)

Stephan Cludius-Brandt

2013-08-01

Full Text Available The photodenitrogenation of vinyl azides to 2H-azirines by using a photoflow reactor is reported and compared with thermal formation of 2H-azirines. Photochemically, the ring of the 2H-azirines was opened to yield the nitrile ylides, which underwent a [3 + 2]-cycloaddition with 1,3-dipolarophiles. When diisopropyl azodicarboxylate serves as the dipolarophile, 1,3,4-triazoles become directly accessible starting from the corresponding vinyl azide.

Health assessment of gasoline and fuel oxygenate vapors: Neurotoxicity evaluation

OpenAIRE

O?Callaghan, James P.; Daughtrey, Wayne C.; Clark, Charles R.; Schreiner, Ceinwen A.; White, Russell

2014-01-01

Sprague?Dawley rats were exposed via inhalation to vapor condensates of either gasoline or gasoline combined with various fuel oxygenates to assess potential neurotoxicity of evaporative emissions. Test articles included vapor condensates prepared from ?baseline gasoline? (BGVC), or gasoline combined with methyl tertiary butyl ether (G/MTBE), ethyl t-butyl ether (G/ETBE), t-amyl methyl ether (G/TAME), diisopropyl ether (G/DIPE), ethanol (G/EtOH), or t-butyl alcohol (G/TBA). Target concentrati...

Experimental and clinical trials of new /sub 99m/Tc-labeled hepatobiliary agents

International Nuclear Information System (INIS)

Wistow, B.W.; Subramanian, G.; Gagne, G.M.; Henderson, R.W.; McAfee, J.G.; Hall, R.C.; Grossman, Z.D.

1978-01-01

Several new derivatives of lidocaine were synthesized and used to examine the intra- and extrahepatic bile ducts and gallbladder. Diisopropyl-IDA exhibited approximately twice the bile concentration of 131 I-rose bengal during the first hour after injection. P-butyl-IDA also concentrates moderately well in the bile and has the added advantage of very low excretion into the urine (2%). It seems more effective than the other IDA derivatives at high bilirubin levels

Determination of Fluorine in Fluoro-Organic Compounds in Low Concentrations in Air

Science.gov (United States)

1944-06-27

Analysis of 2-Fluoroethanol in Air ..... SUMMARY BIBLIOGRAPHY 15 APPENDIX , 16 FIGURE 1 Apparatus PLATE 1 CDS Scrubber SECRET ) SECRET...liter, and 68$ at 1 - 2 mg. per liter. By using two scrubbers in series, 90$ of di-isopropyl fluorophosphate was recovered at a concentration of 1 to 2...chromic acid and detection of HP by etching of the glass container ; (5) scrub- bing the gas with ammonia and decomposing the fluoro-organic compound4

Drinking Water Criteria for the Groundwater Pollutant Diisopropyl Methylphosphonate (DIMP).

Science.gov (United States)

1987-07-01

methylphosphonate, phosphoric acid , isopropyl alcohol, and S--propylene. DIMP forms a number of metal complexes in the absence of moisture. 1 7-19 For a...triisopropyl phosphite .7𔄂 Other methods are mentioned in the patent literature.9-11 The solubility limit of DIMP in water has not been determined. In studies...of DIMP hydrolysis in acidic and basic solutions, 12 0.12 N or higher DIMP was used at temperatures above 800 C, indicating solubilities of above 11 g

A cytotoxic serine proteinase isolated from mouse submandibular gland.

Science.gov (United States)

Shimamura, T; Nagumo, N; Ikigai, H; Murakami, K; Okubo, S; Toda, M; Ohnishi, R; Tomita, M

1989-08-01

We have isolated a novel cytotoxic factor from the submandibular glands of male BALB/c mice by Sephadex G-50 gel filtration chromatography and reverse-phase HPLC. The cytotoxic factor is a serine proteinase, which belongs to the mouse glandular kallikrein (mGK) family, with an Mr of approximately 27,000. The purified serine proteinase showed cytotoxic activity against mouse thymocytes in a dose-dependent manner, and a serine proteinase inhibitor, diisopropyl fluorophosphate, blocked its cytotoxic activity.

Synthesis and characterization of novel triptycene dianhydrides and polyimides of intrinsic microporosity based on 3,3ʹ-dimethylnaphthidine

KAUST Repository

Ghanem, Bader

2016-08-29

Two intrinsically microporous polyimides were obtained by high-temperature, one-pot poly-condensation reaction of novel triptycene-based dianhydrides containing dimethyl- or diisopropyl-bridgehead groups with a commercially available highly sterically hindered 3,3 \\'-dimethylnaphthidine (DMN) diamine monomer. The dimethyl bridgehead groups in the triptycene building block provided the DMN-based polyimide (TDA1-DMN) with larger surface area (760 m(2) g(-1)) than the diisopropyl-based polyimide (TDA1-DMN) (680 m(2) g(-1)), greater fraction of ultramicroporosity, as observed from N-2 and CO2 NLDFT adsorption analysis, and higher gas permeability and selectivity. Wide-angle X-ray diffraction (WAXD) measurements demonstrated that TDA1-DMN and TDAi3-DMN exhibited a bimodal pore size distribution, where TDA1-DMN showed smaller d-spacing values and broader intensity peaks. Both TDADMN-based polyimides showed very high gas permeabilities with moderate selectivities. For example, fresh TDA1-DMN exhibited an O-2 permeability of 783 Barrer coupled with an O-2/N-2 selectivity of 4.3 and H-2 permeability of 3050 Barrer with H-2/N-2 selectivity of 16.7, values that surpassed the 2008 Robeson permeability/selectivity upper bounds. Physical aging of the TDA-DMN polyimide films over a period of 250 days showed relatively small changes in permeability (similar to 20%) and selectivity (similar to 5%). (C) 2016 Elsevier Ltd. All rights reserved.

Escherichia coli contains a soluble ATP-dependent protease (Ti) distinct from protease La

Energy Technology Data Exchange (ETDEWEB)

Hwang, B.J.; Park, W.J.; Chung, C.H.; Goldberg, A.L.

1987-08-01

The energy requirement for protein breakdown in Escherichia coli has generally been attributed to the ATP-dependence of protease La, the lon gene product. The authors have partially purified another ATP-dependent protease from lon/sup -/ cells that lack protease La (as shown by immunoblotting). This enzyme hydrolyzes (/sup 3/H)methyl-casein to acid-soluble products in the presence of ATP and Mg/sup 2 +/. ATP hydrolysis appears necessary for proteolytic activity. Since this enzyme is inhibited by diisopropyl fluorophosphate, it appears to be a serine protease, but it also contains essential thiol residues. They propose to name this enzyme protease Ti. It differs from protease La in nucleotide specificity, inhibitor sensitivity, and subunit composition. On gel filtration, protease Ti has an apparent molecular weight of 370,000. It can be fractionated by phosphocellulose chromatography or by DEAE chromatography into two components with apparent molecular weights of 260,000 and 140,000. When separated, they do not show preteolytic activity. One of these components, by itself, has ATPase activity and is labile in the absence of ATP. The other contains the diisopropyl fluorophosphate-sensitive proteolytic site. These results and the similar findings of Katayama-Fujimura et al. indicate that E. coli contains two ATP-hydrolyzing proteases, which differ in many biochemical features and probably in their physiological roles.

Escherichia coli contains a soluble ATP-dependent protease (Ti) distinct from protease La

International Nuclear Information System (INIS)

Hwang, B.J.; Park, W.J.; Chung, C.H.; Goldberg, A.L.

1987-01-01

The energy requirement for protein breakdown in Escherichia coli has generally been attributed to the ATP-dependence of protease La, the lon gene product. The authors have partially purified another ATP-dependent protease from lon - cells that lack protease La (as shown by immunoblotting). This enzyme hydrolyzes [ 3 H]methyl-casein to acid-soluble products in the presence of ATP and Mg 2+ . ATP hydrolysis appears necessary for proteolytic activity. Since this enzyme is inhibited by diisopropyl fluorophosphate, it appears to be a serine protease, but it also contains essential thiol residues. They propose to name this enzyme protease Ti. It differs from protease La in nucleotide specificity, inhibitor sensitivity, and subunit composition. On gel filtration, protease Ti has an apparent molecular weight of 370,000. It can be fractionated by phosphocellulose chromatography or by DEAE chromatography into two components with apparent molecular weights of 260,000 and 140,000. When separated, they do not show preteolytic activity. One of these components, by itself, has ATPase activity and is labile in the absence of ATP. The other contains the diisopropyl fluorophosphate-sensitive proteolytic site. These results and the similar findings of Katayama-Fujimura et al. indicate that E. coli contains two ATP-hydrolyzing proteases, which differ in many biochemical features and probably in their physiological roles

The distribution of n-caprylic acid between organic solvents and aqueous sodium sulfate solution

International Nuclear Information System (INIS)

Gloe, K.; Muehl, P.; Kholkin, A.I.; Gindin, L.M.

1981-01-01

The distribution of 14 C-labelled n-caprylic acid between n-decane, benzene, isoamyl acetate, diisopropyl ketone, isoamyl alcohol and an aqueous 0.6 molar sodium sulfate solution was studied. The distribution constants and the dimerisation constants were determined for the reactions HRsub((w)) reversible HRsub((org)) and 2 HRsub((org)) reversible (HR)sub(2(org)), respectively. Both the effect of the solvent on the acid distribution and the importance of such studies for the interpretation of liquid-liquid extraction equilibria are discussed. (author)

Modified Ta/MCM-41 catalysts for enantioselective oxidation of thioanisole

OpenAIRE

Fadhli, Marwa; Khedher, Ilyes; Fraile, José M.

2015-01-01

Ta-MCM41 catalysts have been prepared by grafting of Ta(OEt)5 on MCM41, pre-calcined at three different temperatures (550, 650 and 750 °C). These solids have been modified with two chiral ligands: R-(+)-diethyl l-tartrate (DET) and R-(+)-diisopropyl l-tartrate (DIPT). The formation of the chiral tantalum species and their influence on the structure of MCM41 have been studied by several characterization techniques, such as XRD, FTIR, N2 adsorption isotherms and MAS NMR. The grafted tantalum sp...

Synthesis of highly reactive polyisobutylene catalyzed by EtAlCl 2/Bis(2-chloroethyl) ether soluble complex in hexanes

KAUST Repository

Kumar, Rajeev Ananda; Zheng, Bin; Huang, Kuo-Wei; Emert, Jack I.; Faust, Rudolf

2014-01-01

The polymerization of isobutylene (IB) to yield highly reactive polyisobutylene (HR PIB) with high exo-olefin content using GaCl3 or FeCl3·diisopropyl ether complexes has been previously reported.1 In an effort to further improve polymerization rates and exo-olefin content, we have studied ethylaluminum dichloride (EADC) complexes with diisopropyl ether, 2-chloroethyl ethyl ether (CEEE), and bis(2-chloroethyl) ether (CEE) as catalysts in conjunction with tert-butyl chloride as initiator in hexanes at different temperatures. All three complexes were readily soluble in hexanes. Polymerization, however, was only observed with CEE. At 0 °C polymerization was complete in 5 min at [t-BuCl] = [EADC·CEE] = 10 mM and resulted in PIB with ∼70% exo-olefin content. Studies on complexation using ATR FTIR and 1H NMR spectroscopy revealed that at 1:1 stoichiometry a small amount of EADC remains uncomplexed. By employing an excess of CEE, exo-olefin contents increased up to 90%, while polymerization rates decreased only slightly. With decreasing temperature, polymerization rates decreased while molecular weights as well as exo-olefin contents increased, suggesting that isomerization has a higher activation energy than β-proton abstraction. Density functional theory (DFT) studies on the Lewis acid·ether binding energies indicated a trend consistent with the polymerization results. The polymerization mechanism proposed previously for Lewis acid·ether complexes1 adequately explains all the findings. © 2014 American Chemical Society.

Acute ecological toxicity and environmental persistence of simulants

Energy Technology Data Exchange (ETDEWEB)

Cataldo, D.A.; Ligotke, M.W.; McVeety, B.D.; Fellows, R.J.; Bolton, H. Jr.; Li, S.W.; Van Voris, P.; Wentsel, R.S.

1988-06-01

The objectives of these studies are to establish the comparative environmental behavior and chemical fate of chemical simulants. Laboratory studies were undertaken to establish: (1) deposition efficiency (deposition velocities, Vd) for receptor surfaces including plant foliage and soils; (2) dose/response relationships for important environmental components including plants and soil microflora; and (3) the environmental persistence of the simulants. Chemical agent simulants are employed for a range of testing and training activities where use of chemical agents is less than suitable from a safety and environmental standpoint. A variety of chemical simulant materials are used to simulate either nerve agents or blister agents. The following research describes the environmental effects and persistence of four simulants. These are the nerve agent stimulants diisopropyl methylphosphonate (DIMP), diisopropyl fluorophosphate (DFP), and bis (2-ethylhexyl) phosphonate (BIS), and the mustard stimulant 2-chloroethyl ethyl sulfide (CEES). The vapor pressures for DIMP, DFP, and CEES are relatively high, reported to be 0.17, 0.58 and 3.4 mm Hg, respectively; while that of BIS is substantially less at 5.8 /times/ 10/sup /minus/5/ mm Hg at 25/degree/C. The chemical characteristics of DFP and CEES are very similar to G/VX-agents and mustard, respectively, and are employed for materials evaluation under controlled conditions. However, their toxicity precludes their use in the environment. DIMP and BIS are currently used for testing in the open air. 3 figs., 3 tabs.

Synthesis of highly reactive polyisobutylene catalyzed by EtAlCl 2/Bis(2-chloroethyl) ether soluble complex in hexanes

KAUST Repository

Kumar, Rajeev Ananda

2014-03-25

The polymerization of isobutylene (IB) to yield highly reactive polyisobutylene (HR PIB) with high exo-olefin content using GaCl3 or FeCl3·diisopropyl ether complexes has been previously reported.1 In an effort to further improve polymerization rates and exo-olefin content, we have studied ethylaluminum dichloride (EADC) complexes with diisopropyl ether, 2-chloroethyl ethyl ether (CEEE), and bis(2-chloroethyl) ether (CEE) as catalysts in conjunction with tert-butyl chloride as initiator in hexanes at different temperatures. All three complexes were readily soluble in hexanes. Polymerization, however, was only observed with CEE. At 0 °C polymerization was complete in 5 min at [t-BuCl] = [EADC·CEE] = 10 mM and resulted in PIB with ∼70% exo-olefin content. Studies on complexation using ATR FTIR and 1H NMR spectroscopy revealed that at 1:1 stoichiometry a small amount of EADC remains uncomplexed. By employing an excess of CEE, exo-olefin contents increased up to 90%, while polymerization rates decreased only slightly. With decreasing temperature, polymerization rates decreased while molecular weights as well as exo-olefin contents increased, suggesting that isomerization has a higher activation energy than β-proton abstraction. Density functional theory (DFT) studies on the Lewis acid·ether binding energies indicated a trend consistent with the polymerization results. The polymerization mechanism proposed previously for Lewis acid·ether complexes1 adequately explains all the findings. © 2014 American Chemical Society.

Understanding Chemistry and Unique NMR Characters of Novel Amide and Ester Leflunomide Analogues

Directory of Open Access Journals (Sweden)

Morkos A. Henen

2017-12-01

Full Text Available A series of diverse substituted 5-methyl-isoxazole-4-carboxylic acid amides, imide and esters in which the benzene ring is mono or disubstituted was prepared. Spectroscopic and conformational examination was investigated and a new insight involving steric interference and interesting downfield deviation due to additional diamagnetic anisotropic effect of the amidic carbonyl group and the methine protons in 2,6-diisopropyl-aryl derivative (2 as conformationaly restricted analogues Leflunomide was discussed. Individual substituent electronic effects through π resonance of p-substituents and most stable conformation of compound (2 are discussed.

Enhancement of lymphocyte proliferation by mouse glandular kallikrein.

Science.gov (United States)

Hu, Z Q; Murakami, K; Ikigai, H; Shimamura, T

1992-03-01

Mouse glandular kallikrein (mGK) strongly enhanced the spontaneous and mitogen-induced proliferation of lymphocytes. Both blast formation and 3H-TdR incorporation were dose-dependently enhanced at the same time many cells were killed. The enhancing activity was independent of EGF, because EGF-binding proteins (mGK-9 in mGK-6,9 mixture and mGK-13), renal kallikrein (mGK-6) and human kallikrein all displayed the same enhancement. A serine proteinase inhibitor, diisopropyl fluorophosphate, could block the enhancement by mGK. The new function suggests that mGK is important in the immune system as a regulatory molecule.

The extraction of some trivalent elements with Aliquat-336

Energy Technology Data Exchange (ETDEWEB)

FLandgren, A.; Liljenzin, J.O.; Skalberg, M. [Chalmers Univ. of Technology, Goeteborg (Sweden)

1995-10-01

The extraction behaviour of some trivalent elements in the Aliquate-336-1,3-diisopropyl genzene-nitric acid system has been investigated. For most of the elements a maximum in the distribution ratio occur at about 2 molar nitric acid. At 0.20 molar Aliquate-336 lanthanum attained the highest distribution ratio, about 0.05, of all investigated elements. It was found that nitric acid to a large extent influences the distribution ratio of trivalent elements since it competes with metal nitrate complexes for the extractant molecules. A first approach to a model describing the extraction system is derived.

(E-N,N-Diethyl-2,6-diisopropyl-4-[2-(4-nitrophenylethenyl]aniline

Directory of Open Access Journals (Sweden)

Heiner Detert

2013-12-01

Full Text Available The title compound, C24H32N2O2, was prepared by Horner olefination of 4-diethylamino-3,5-diisopropylbenzaldehyde and diethyl p-nitrobenzylphosphonate. There are two independent molecules (A and B in the asymmetric unit. Their main axes, defined by the line connecting the N atoms of the nitro and amino groups, open an angle of 79.42 (3°. Steric hindrance around the amino group is reflected in a long aryl C—N bond [1.434 (3 Å for molecule A and 1.440 (3 Å for molecule B], a pyramidal geometry [angle sum = 350.0 (2° for molecule A and 349.6 (2° for molecule B], and dihedral angles between the phenylene group and the plane defined by the CH2—N—CH2 unit of 86.9 (3° for molecule A and 88.3 (3° for molecule B. This gives structural support for the electronic decoupling of the amino group from the nearly planar nitrostilbene moiety (r.m.s. deviation for C, N and O atoms = 0.097 for molecule A and 0.107 Å for molecule B.

A novel fibrinolytic enzyme (nattokinase) in the vegetable cheese Natto; a typical and popular soybean food in the Japanese diet.

Science.gov (United States)

Sumi, H; Hamada, H; Tsushima, H; Mihara, H; Muraki, H

1987-10-15

A strong fibrinolytic activity was demonstrated in the vegetable cheese Natto, which is a typical soybean food eaten in Japan. The average activity was calculated at about 40 CU (plasmin units)/g wet weight. This novel fibrinolytic enzyme, named nattokinase, was easily extracted with saline. The mol. wt and pI were about 20,000 and 8.6, respectively. Nattokinase not only digested fibrin but also the plasmin substrate H-D-Val-Leu-Lys-pNA (S-2251), which was more sensitive to the enzyme than other substrates tried. Diisopropyl fluorophosphate and 2,2,2-trichloro-1-hydroxyethyl-o,o-dimethylphosphate strongly inhibited this fibrinolytic enzyme.

In vitro determination of skin decontamination efficacy using a water shower

International Nuclear Information System (INIS)

Reifenrath, W.G.

1990-01-01

The ability of a water shower to remove radioactivity from excised pig skin exposed to radiolabeled diisopropyl fluorophosphate and n-butyl 2-chloroethyl sulfide was determined. Skin samples were decontaminated 15 minutes after chemical exposures (1 mg/cm 2 ) and the distribution of radioactivity was determined 1 hour after decontamination. Compared to controls (no decontamination), shower decontamination reduced the evaporative loss of radioactivity from the skin surface after decontamination or reduced radioactive residues on the skin surface. Shower decontamination of skin at 15 minutes could not prevent penetration of radiolabel into the viable layers of skin or into fluid bathing the dermal surface of the skin, but was beneficial in reducing skin surface concentrations, which may lead to further exposure or contamination

Update on radionuclide imaging in hepatobiliary disease

International Nuclear Information System (INIS)

Rosenthall, L.

1981-01-01

The recent introduction of technetium Tc 99m-labeled acetanilide iminodiacetic acid (/sup 99m/Tc-IDA) analogues has facilitated the clincal study of the bile flow pathways. A variety of /sup 99m/Tc-IDA derivaties are under investigation. Basically all are metabolized by the hepatocyte and immediately thereafter excreted unconjugated into the biliary tract. Of the various derivatives tested, e.g., dimethyl (lidofenin), diethyl, paraisopropyl (iprofenin), parabutyl (butilfenin), and diisopropyl (disofenin), the last named is the best universal agent at this time. By serial liver imaging the patency of the cystic duct and the integrity of altered cholangiointestinal anatomy can be assessed, leakage of bile and gastric reflux can be disclosed, and medical and surgical jaundice can be distinguished

Bovine nucleus caudatus acetylcholinesterase: active site determination and investigation of a dimeric form obtained by selective proteolysis

Energy Technology Data Exchange (ETDEWEB)

Landauer, P.; Ruess, K.P.; Lieflaender, M.

1984-09-01

The number of catalytic subunits of purified bovine nucleus caudatus acetylcholinesterase (E.C. 3.1.1.7) has been determined by active site labelling with (3H)diisopropyl fluorophosphate ((3H)DFP). The 10.5 S, 16 S, and 20 S forms were estimated to contain two, four, and six active sites, respectively, per molecule. A 4.8 S form, which showed a weak amphiphile-dependent activity behavior, was obtained by selective proteolytic digestion with pronase. The inability of the purified 4.8 S form to aggregate after detergent removal, and the molecular mass in the range of 130-165 kD under nondenaturating conditions, indicate that this form is a dimeric form, lacking those hydrophobic regions responsible for aggregation.

Tritium activity in milk by liquid scintillation counting

International Nuclear Information System (INIS)

Zheng Huang

1993-01-01

This paper estimates the total tritium content of both the organic and aqueous fractions simultaneously. To fulfill these conditions, the chosen scintillator should be able to accept large sample loadings and display the same counting efficiency for the organic as well as aqueous fractions of the whole milk. In an attempt to establish this method, samples from four different brands of milk were analysed using the pseudocumence based Picofluor 30 (Canberra Packard) and the di-isopropyl naphthalene based Aquasafe 500 (Zinser Analytic) scintillator solution. Glass vials were used thus enabling visual observation to be made. The tritium activities of four different brands of milks were estimated to be very low and at, or near, the detection level of the system

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

Science.gov (United States)

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

2009-02-01

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

Synthesis of highly reactive polyisobutylene with FeCl3/ether complexes in hexane; kinetic and mechanistic studies

KAUST Repository

Kumar, Rajeev Ananda; De, Priyadarsi; Zheng, Bin; Huang, Kuo-Wei; Emert, Jack I.; Faust, Rudolf

2015-01-01

The kinetics and mechanism of the polymerization of isobutylene catalyzed by FeCl3·ether complexes in hexane at 0°C were investigated. The polymerization rates increased in the diisopropyl ether< 2-chloroethyl ethyl ether < bis(2-chloroethyl) ether order, attributed to electronic effects. The polymerization rates increased with increasing initiator and catalyst concentrations. The first order plots, however, deviated from the linear suggesting that the cation concentration decreases with time. The previously proposed mechanism is inadequate to explain this finding. The decrease in the polymerization rate with time is explained by the low solubility of the H+ROR′FeCl4 - complexes that precipitate during polymerization. Based on mechanistic studies the revised mechanism now also includes the equilibrium H+ROR′FeCl4 - ⇋ HCl + FeCl3·ROR′.

γ-Diimine palladium(II based complexes mediated polymerization of methyl methacrylate

Directory of Open Access Journals (Sweden)

Mahmoud Sunjuk

2017-02-01

Full Text Available The synthesis of new palladium(II complexes of the type [Pd(A–NC–ph–CN–ACl2] (4a–e (A = cyclohexyl (a, 2-isoprpropyl (b, pyrenyl (c, naphthyl (d, and 2,6-diisopropyl (e is described. The isolated γ-diimine ligands and their corresponding palladium(II complexes were characterized by their physical properties, elemental analysis, 1H NMR-, 13C NMR, and infrared spectroscopy. The palladium(II complexes (4a–e were employed successfully as catalysts for atom transfer radical polymerization (ATRP of methyl methacrylate (MMA in the presence of ethyl-2-bromoisobutyrate (EBIB as initiator at 90 °C. Polymerization with these catalyst systems afforded polymers with low molecular weight distribution (Mw/Mn and syndio-rich atactic poly (MMA with relatively higher [rr] diads.

Identification of alkylated phosphates by gas chromatography-mass spectrometric investigations with different ionization principles of a thermally aged commercial lithium ion battery electrolyte.

Science.gov (United States)

Weber, Waldemar; Kraft, Vadim; Grützke, Martin; Wagner, Ralf; Winter, Martin; Nowak, Sascha

2015-05-15

The thermal aging process of a commercial LiPF6 based lithium ion battery electrolyte has been investigated in view of the formation of volatile phosphorus-containing degradation products. Aging products were analyzed by GC-MS. Structure determination of the products was performed by support of chemical ionization MS in positive and negative modes. A fraction of the discovered compounds belongs to the group of fluorophosphates (phosphorofluoridates) which are in suspect of potential toxicity. This is well known for relative derivatives, e.g. diisopropyl fluorophosphate. Another fraction of the identified compounds belongs to the group of trialkyl phosphates. These compounds may provide a positive impact on the thermal and electrochemical performance of Li-based batteries as repeatedly described in the literature. Copyright © 2015 Elsevier B.V. All rights reserved.

Potentiating action of propofol at GABAA receptors of retinal bipolar cells

DEFF Research Database (Denmark)

Yue, Lan; Xie, An; Bruzik, Karol S

2011-01-01

Purpose. Propofol (2,6-diisopropyl phenol), a widely used systemic anesthetic, is known to potentiate GABA(A) receptor activity in a number of CNS neurons and to produce changes in electroretinographically recorded responses of the retina. However, little is known about propofol's effects...... on specific retinal neurons. The authors investigated the action of propofol on GABA-elicited membrane current responses of retinal bipolar cells, which have both GABA(A) and GABA(C) receptors. Methods. Single, enzymatically dissociated bipolar cells obtained from rat retina were treated with propofol...... + propofol) led to a progressive increase in peak response amplitude and, at higher propofol concentrations, additional changes that included a prolonged time course of response recovery. Pre-exposure of the cell to perfusing propofol typically enhanced the rate of development of potentiation produced...

Synthesis and structural characterization of CdS nanoparticles using nitrogen adducts of mixed diisopropylthiourea and dithiolate derivatives of Cd(II) complexes

Science.gov (United States)

Osuntokun, Jejenija; Ajibade, Peter A.

2015-07-01

[Cd(diptu)2(ced)], [Cd(diptu)2(ced)(bpy)], [Cd(diptu)2(ced)(phen)], (where diptu = diisopropyl thiourea; ced = 1-cyano-1-carboethoxylethylene-2,2‧-dithiolate; bpy = 2,2‧-bipyridine and phen = 1,10-phenanthroline) have been prepared and used as single source precursors for the preparation of hexadecylamine capped CdS nanoparticles. The precursor complexes were characterized by elemental analysis, FTIR and TGA. The structural properties of the nanoparticles were investigated using powder X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy techniques (SEM). The optical properties of the nanoparticles were studied using UV-Visible and photoluminescence spectroscopy. The XRD analysis showed that the nanoparticles were indexed to the hexagonal phase of CdS and the TEM results showed CdS nanoparticles with average crystallite sizes of 4.00-8.80 nm.

Alpha-Bungarotoxin labeling and acetylcholinesterase localization at the Mauthner fiber giant synapse in the hatchetfish

International Nuclear Information System (INIS)

Day, J.W.; Hall, D.H.; Hall, L.M.; Bennett, M.V.

1983-01-01

Autoradiographic and histochemical techniques have been used to characterize further the pharmacology of transmission at the Mauthner fiber giant synapse of the South American hatchetfish. [ 125 I]alpha-Bungarotoxin was applied to hatchetfish medullae and a standard autoradiographic procedure was carried out on 3- to 4-microns sections of glutaraldehyde-fixed tissue. All Mauthner fiber giant synapses, as identified by light microscopic criteria, had closely associated silver grains. Labeling was blocked by d-tubocurarine. Glutaraldehyde-fixed slices of hatchetfish medulla were stained histochemically for acetylcholinesterase; all giant synapses that could be identified in the light microscope showed heavy deposits of reaction product. Staining was blocked by diisopropyl-fluorophosphate, which inhibits both pseudocholinesterase and acetylcholinesterase, but was not blocked by tetraisopropylpyrophosphoramide, a specific pseudocholinesterase inhibitor. This evidence strongly supports the suggestion that the Mauthner fiber giant synapse is nicotinic cholinergic

alpha-Bungarotoxin labeling and acetylcholinesterase localization at the Mauthner fiber giant synapse in the hatchetfish

International Nuclear Information System (INIS)

Day, J.W.; Hall, D.H.; Hall, L.M.; Bennett, M.V.

1983-01-01

Autoradiographic and histochemical techniques have been used to characterize further the pharmacology of transmission at the Mauthner fiber giant synapse of the South American hatchetfish. [ 125 I]alpha-Bungarotoxin was applied to hatchetfish medullae and a standard autoradiographic procedure was carried out on 3- to 4-microns sections of glutaraldehyde-fixed tissue. All Mauthner fiber giant synapses, as identified by light microscopic criteria, had closely associated silver grains. Labeling was blocked by d-tubocurarine. Glutaraldehyde-fixed slices of hatchetfish medulla were stained histochemically for acetylcholinesterase; all giant synapses that could be identified in the light microscope showed heavy deposits of reaction product. Staining was blocked by diisopropyl-fluorophosphate, which inhibits both pseudocholinesterase and acetylcholinesterase, but was not blocked by tetraisopropylpyrophosphoramide, a specific pseudocholinesterase inhibitor. This evidence strongly supports the suggestion that the Mauthner fiber giant synapse is nicotinic cholinergic

Alpha-Bungarotoxin labeling and acetylcholinesterase localization at the Mauthner fiber giant synapse in the hatchetfish

Energy Technology Data Exchange (ETDEWEB)

Day, J.W.; Hall, D.H.; Hall, L.M.; Bennett, M.V.

1983-02-01

Autoradiographic and histochemical techniques have been used to characterize further the pharmacology of transmission at the Mauthner fiber giant synapse of the South American hatchetfish. (/sup 125/I)alpha-Bungarotoxin was applied to hatchetfish medullae and a standard autoradiographic procedure was carried out on 3- to 4-microns sections of glutaraldehyde-fixed tissue. All Mauthner fiber giant synapses, as identified by light microscopic criteria, had closely associated silver grains. Labeling was blocked by d-tubocurarine. Glutaraldehyde-fixed slices of hatchetfish medulla were stained histochemically for acetylcholinesterase; all giant synapses that could be identified in the light microscope showed heavy deposits of reaction product. Staining was blocked by diisopropyl-fluorophosphate, which inhibits both pseudocholinesterase and acetylcholinesterase, but was not blocked by tetraisopropylpyrophosphoramide, a specific pseudocholinesterase inhibitor. This evidence strongly supports the suggestion that the Mauthner fiber giant synapse is nicotinic cholinergic.

alpha-Bungarotoxin labeling and acetylcholinesterase localization at the Mauthner fiber giant synapse in the hatchetfish

Energy Technology Data Exchange (ETDEWEB)

Day, J.W.; Hall, D.H.; Hall, L.M.; Bennett, M.V.

1983-02-01

Autoradiographic and histochemical techniques have been used to characterize further the pharmacology of transmission at the Mauthner fiber giant synapse of the South American hatchetfish. (/sup 125/I)alpha-Bungarotoxin was applied to hatchetfish medullae and a standard autoradiographic procedure was carried out on 3- to 4-microns sections of glutaraldehyde-fixed tissue. All Mauthner fiber giant synapses, as identified by light microscopic criteria, had closely associated silver grains. Labeling was blocked by d-tubocurarine. Glutaraldehyde-fixed slices of hatchetfish medulla were stained histochemically for acetylcholinesterase; all giant synapses that could be identified in the light microscope showed heavy deposits of reaction product. Staining was blocked by diisopropyl-fluorophosphate, which inhibits both pseudocholinesterase and acetylcholinesterase, but was not blocked by tetraisopropylpyrophosphoramide, a specific pseudocholinesterase inhibitor. This evidence strongly supports the suggestion that the Mauthner fiber giant synapse is nicotinic cholinergic.

An efficient protocol for the palladium-catalysed Suzuki-Miyaura cross-coupling

KAUST Repository

Marziale, Alexander N.; Jantke, Dominik; Faul, Stefan Holger; Reiner, Thomas; Herdtweck, Eberhardt; Eppinger, Jö rg

2011-01-01

The palladacyclic catalyst precursor received by ortho-palladation of ([1,1′-biphenyl]-2-yloxy)diisopropyl-phosphine represents a highly active system for Suzuki-Miyaura cross-coupling reactions when used in neat water. An efficient, broadly applicable and sustainable aqueous protocol was developed using 2.5 eq. of Na2CO3 as base, allowing the reaction to be performed under air and at ambient temperature with Pd loadings of 0.04 mol%. Coupling products are obtained in high yields and excellent purity by simple filtration with no organic solvents needed throughout the whole reaction. A broad variety of functional groups are tolerated and a large number of substrates can be applied with this protocol. The crystal structure of the palladacyclic catalyst precursor is presented as well as investigations targeting the nature of catalyst activation and the active catalytic species. © 2011 The Royal Society of Chemistry.

E3 protein of bovine coronavirus is a receptor-destroying enzyme with acetylesterase activity

International Nuclear Information System (INIS)

Vlasak, R.; Luytjes, W.; Leider, J.; Spaan, W.; Palese, P.

1988-01-01

In addition to members of the Orthomyxoviridae and Paramyxoviridae, several coronaviruses have been shown to possess receptor-destroying activities. Purified bovine coronavirus (BCV) preparations have an esterase activity which inactivates O-acetylsialic acid-containing receptors on erythrocytes. Diisopropyl fluorophosphate (DFP) completely inhibits this receptor-destroying activity of BCV, suggesting that the viral enzyme is a serine esterase. Treatment of purified BCV with [ 3 H]DFP and subsequent sodium dodecyl sulfate-polyacrylamide gel electrophoresis of the proteins revealed that the esterase/receptor-destroying activity of BCV is associated with the E3 protein was specifically phosphorylated. This finding suggests that the esterase/receptor-destroying activity of BCV is associated with the E3 protein. Furthermore, treatment of BCV with DFP dramatically reduced its infectivity in a plaque assay. It is assumed that the esterase activity of BCV is required in an early step of virus replication, possible during virus entry or uncoating

Synthesis and Characterization of New Silver (I N-Heterocyclic Ccarbene Ccomplex Dderived from Imidazol-2-ylidene salt

Directory of Open Access Journals (Sweden)

Mohammedl Mujbe Hasson

2018-04-01

Full Text Available A new N, N'-imidazolium salt 1-(2,6-diisopropylphenyl-3- (4,6-dimorpholino -1,3,5-traizine-2-yl-1H-imidazol-3-ium chloride as a precursor of N - heterocyclic carbene ligand was prepared via the reaction of 1 - (2, 6 - diisopropyl phenyl - 1H - imidazole with 1, 3, 5 - triazine derivative bearing morpholine substituent (2, 6 -dimorpholine - 6- chloro-1, 3, 5-triaziazine. Linear coordi-nated Ag (І NHC complex was synthesised via deprotonation of the imidazolium salt and reac-tion with Ag2O in darkness at room temperature by in situ method. The complex was synthesised for using as transfer agent to prepare another transition metals complexes by transmetallation method in the future. The imidazolium salt and their silver complex have been characterized by 1 H and 13C NMR spectroscopy as well as mass spectrometry.

An extraovarian protein accumulated in mosquito oocytes is a carboxypeptidase activated in embryos

Energy Technology Data Exchange (ETDEWEB)

Wenlong Cho; Deitsch, K.W.; Raikhel, A.S. (Michigan State Univ., East Lansing (United States))

1991-12-01

The authors report a phenomenon previously unknown for oviparous animals; in Aedes aegypti mosquitoes a serine carboxypeptidase is synthesized extraovarially and then internalized by oocytes. The cDNA encoding mosquito vitellogenic carboxypeptidase (VCP) was cloned and sequenced. The VCP cDNA hybridizes to a 1.5-kilobase mRNA present only in the fat body of vitellogenic females. The deduced amino acid sequence of VCP shares significant homology with members of the serine carboxypeptidase family. Binding assays using a serine protease inhibitor, ({sup 3}H)diisopropyl fluorophosphate, showed that VCP is activated in eggs at the onset of embryonic development. Activation of VCP is associated with the reduction in its size from 53 kDa (inactive proenzyme) to 48 kDa (active enzyme). The active, 48-kDa, form of VCP is maximally present at the middle of embryonic development and disappears by the end.

Thrombocytin, a serine protease from Bothrops atrox venom. 1. Purification and characterization of the enzyme

Energy Technology Data Exchange (ETDEWEB)

Kirby, E.P. (Temple Univ. Health Sciences Center, Philadelphia, PA); Niewiarowski, S.; Stocker, K.; Kettner, C.; Shaw, E.; Brudzynsi, T.M.

1979-08-07

Thrombocytin, a platelet-activating enzyme from Bothrops atrox venom, has been purified to homogeneity by precipitation with sodium salicylate and chromatography on heparin-agarose. Thrombocytin is a single-chain glycoprotein with a molecular weight of 36,000 which contains 5.6% carbohydrate. It causes platelet aggregation, release of platelet serotonin, and activation of factor XIII. The most sensitive substrate for the amidolytic activity of thrombocytin was Tos-Gly-Pro-Arg-p-nitroanilide hydrochloride. The activity of thrombocytin on this substrate and on platelets was inhibited by diisopropyl fluorophosphate (DFP), soybean trypsin inhibitor, and several arginine chloromethyl ketones. Active site titration with nitrophenyl guanidinobenzoate demonstrated that approximately 86% of the preparation was in the active form. These experiments demonstrate the presence of serine and histidine in the active site of thrombocytin and suggest that thrombocytin is a classical serine protease with a platelet-activating activity similar to thrombin.

Muscarinic receptor plasticity in the brain of senescent rats: down-regulation after repeated administration of diisopropyl fluorophosphate

International Nuclear Information System (INIS)

Pintor, A.; Fortuna, S.; Volpe, M.T.; Michalek, H.

1988-01-01

Potential age-related differences in the response of Fischer 344 rats to subchronic treatment with diisopropylfluorophosphate (DFP) were evaluated in terms of brain cholinesterase (ChE) inhibition and muscarinic receptor sites. Male 3- and 24-month old rats were sc injected with sublethal doses of DFP for 2 weeks and killed 48 hrs after the last treatment. In the cerebral cortex, hippocampus and striatum of control rats a significant age-related reduction of ChE and of maximum number of 3 H-QNB binding sites (Bmax) was observed. The administration of DFP to senescent rats resulted in more pronounced and longer lasting syndrome of cholinergic stimulation, with marked body weight loss and 60% mortality. The percentage inhibition of brain ChE induced by DFP did not differ between young and senescent rats. As expected, in young rats DFP caused a significant decrease of Bmax, which in the cerebral cortex reached about 40%. In the surviving senescent rats, the percentage decrease of Bmax due to DFP with respect to age-matched controls was very similar to that of young animals, especially in the cerebral cortex. Thus there is great variability in the response of aged rats to DFP treatment, from total failure of adaptive mechanisms resulting in death to considerable muscarinic receptor plasticity

Muscarinic receptor plasticity in the brain of senescent rats: down-regulation after repeated administration of diisopropyl fluorophosphate

Energy Technology Data Exchange (ETDEWEB)

Pintor, A.; Fortuna, S.; Volpe, M.T.; Michalek, H.

1988-01-01

Potential age-related differences in the response of Fischer 344 rats to subchronic treatment with diisopropylfluorophosphate (DFP) were evaluated in terms of brain cholinesterase (ChE) inhibition and muscarinic receptor sites. Male 3- and 24-month old rats were sc injected with sublethal doses of DFP for 2 weeks and killed 48 hrs after the last treatment. In the cerebral cortex, hippocampus and striatum of control rats a significant age-related reduction of ChE and of maximum number of /sup 3/H-QNB binding sites (Bmax) was observed. The administration of DFP to senescent rats resulted in more pronounced and longer lasting syndrome of cholinergic stimulation, with marked body weight loss and 60% mortality. The percentage inhibition of brain ChE induced by DFP did not differ between young and senescent rats. As expected, in young rats DFP caused a significant decrease of Bmax, which in the cerebral cortex reached about 40%. In the surviving senescent rats, the percentage decrease of Bmax due to DFP with respect to age-matched controls was very similar to that of young animals, especially in the cerebral cortex. Thus there is great variability in the response of aged rats to DFP treatment, from total failure of adaptive mechanisms resulting in death to considerable muscarinic receptor plasticity.

Research and development for solar thermal energy system. Research on advanced solar component; Taiyonetsu energy system no kenkyu kaihatsu. Kiki no kenkyu

Energy Technology Data Exchange (ETDEWEB)

Tanaka, T; Doi, T; Takashima, T; Ando, Y; Masuda, T; Fujii, T [Electrotechnical Laboratory, Tsukuba (Japan)

1994-12-01

Described herein are the results of the FY1994 research program for research on advanced solar components as part of research and development of solar thermal energy. The catalyst for liquid-film reactions is prepared, and the flask tests are conducted as the preliminary experiments for development of the reactor in which 2-propanol is fallen in liquid film over the catalyst dispersed to accelerate its decomposition. It is decomposable when fallen in liquid film even in the presence of 35% of acetone. The catalyst of ruthenium carried by activated coal is used to produce 2-propanol under an exothermic condition from acetone and hydrogen. Diisopropyl ether and 4-methyl-2-pentanone are produced as by-products, when the reactor tube is kept at 140 to 200{degree}C at the external wall, diminishing as temperature is increased. There is a temperature differential of 20 to 30{degree}C in the reactor tube between the center axis and external wall. 3 figs.

Acetylation/deacetylation reactions of T-2, acetyl T-2, HT-2, and acetyl HT-2 toxins in bovine rumen fluid in vitro

International Nuclear Information System (INIS)

Munger, C.E.; Ivie, G.W.; Christopher, R.J.; Hammock, B.D.; Phillips, T.D.

1987-01-01

A tritiated preparation of the trichothecene mycotoxin, T-2 toxin, underwent both acetylation and deacetylation reactions when incubated with bovine rumen fluid in vitro. Products from incubations of T-2 in rumen fluid included acetyl T-2, HT-2, and acetyl HT-2. Direct studies with tritiated samples of each of these metabolites confirmed their relatively facile interconversion in the rumen. Studies with [ 3 H]HT-2 under conditions of inhibited esterase activity (added diisopropyl fluorophosphate) showed that acetylation is preferred at C-3 vs. C-4. Studies with [ 3 H]acetyl T-2 indicated that deacetylation similarly occurs with greater rapidity at C-3. There were no indications that ester hydrolysis of these trichothecenes occurred at C-8 or C-15 or that they were subjected to epoxide reduction reactions. These data suggest that acetylation of T-2 and other trichothecenes in the rumen in situ may ultimately result in the absorption of more lipophilic metabolites whose toxicological and residual properties are at present unknown

Radiation chemistry of alternative fuel oxygenates - substituted ethers

International Nuclear Information System (INIS)

Mezyk, S. P.; Cooper, W. J.; Bartels, D. M.; Tobien, T.; O'Shea, K. E.

1999-01-01

The electron beam process, an advanced oxidation and reduction technology, is based in the field of radiation chemistry. Fundamental to the development of treatment processes is an understanding of the underlying chemistry. The authors have previously evaluated the bimolecular rate constants for the reactions of methyl tert-butyl ether (MTBE) and with this study have extended their studies to include ethyl tert-butyl ether (ETBE), di-isopropyl ether (DIPE) and tert-amyl methyl ether (TAME) with the hydroxyl radical, hydrogen atom and solvated electron using pulse radiolysis. For all of the oxygenates the reaction with the hydroxyl radical appears to be of primary interest in the destruction of the compounds in water. The rates with the solvated electron are limiting values as the rates appear to be relatively low. The hydrogen atom rate constants are relatively low, coupled with the low yield in radiolysis, they concluded that these are of little significance in the destruction of the alternative fuel oxygenates (and MTBE)

Liquid-Liquid Extraction and Determination of Trace Elements in Iron Minerals by Atomic Absorption Spectrometry

International Nuclear Information System (INIS)

Taseska, Milena; Stafilov, Trajche; Makreski, Petre; Jacimovic, Radojko; Jovanovski, Gligor

2006-01-01

Various trace elements (cadmium, chromium, cobalt, nickel, manganese) in some iron minerals were determined by flame (FAAS) and electrothermal atomic absorption spectrometry (ETAAS). The studied minerals were chalcopyrite (CuFeS 2 ), hematite (Fe 2 O 3 ) and pyrite (FeS 2 ). To avoid the interference of iron, a method for liquid-liquid extraction of iron and determination of investigated elements in the inorganic phase was proposed. Iron was extracted by diisopropyl ether in hydrochloride acid solution and the extraction method was optimized. Some parameters were obtained to be significantly important: Fe mass in the sample should not exceed 0.3 g, the optimal concentration of HCI should be 7.8 mol 1 -1 and ratio of the inorganic and organic phase should be 1: 1. The procedure was verified by the method of standard additions and by its applications to reference standard samples. The investigated minerals originate from various mines in the Republic of Macedonia. (Author)

cDNA cloning of porcine brain prolyl endopeptidase and identification of the active-site seryl residue

Energy Technology Data Exchange (ETDEWEB)

Rennex, D.; Hemmings, B.A.; Hofsteenge, J.; Stone, S.R. (Friedrich Miescher-Institut, Basel (Switzerland))

1991-02-26

Prolyl endopeptidase is a cytoplasmic serine protease. The enzyme was purified from porcine kidney, and oligonucleotides based on peptide sequences from this protein were used to isolate a cDNA clone from a porcine brain library. This clone contained the complete coding sequence of prolyl endopeptidase and encoded a polypeptide with a molecular mass of 80751 Da. The deduced amino acid sequence of prolyl endopeptidase showed no sequence homology with other known serine proteases. ({sup 3}H)Diisopropyl fluorophosphate was used to identify the active-site serine of prolyl endopeptidase. One labeled peptide was isolated and sequenced. The sequence surrounding the active-site serine was Asn-Gly-Gly-Ser-Asn-Gly-Gly. This sequence is different from the active-site sequences of other known serine proteases. This difference and the lack of overall homology with the known families of serine proteases suggest that prolyl endopeptidase represents a new type of serine protease.

E3 protein of bovine coronavirus is a receptor-destroying enzyme with acetylesterase activity

Energy Technology Data Exchange (ETDEWEB)

Vlasak, R.; Luytjes, W.; Leider, J.; Spaan, W.; Palese, P.

1988-12-01

In addition to members of the Orthomyxoviridae and Paramyxoviridae, several coronaviruses have been shown to possess receptor-destroying activities. Purified bovine coronavirus (BCV) preparations have an esterase activity which inactivates O-acetylsialic acid-containing receptors on erythrocytes. Diisopropyl fluorophosphate (DFP) completely inhibits this receptor-destroying activity of BCV, suggesting that the viral enzyme is a serine esterase. Treatment of purified BCV with (/sup 3/H)DFP and subsequent sodium dodecyl sulfate-polyacrylamide gel electrophoresis of the proteins revealed that the esterase/receptor-destroying activity of BCV is associated with the E3 protein was specifically phosphorylated. This finding suggests that the esterase/receptor-destroying activity of BCV is associated with the E3 protein. Furthermore, treatment of BCV with DFP dramatically reduced its infectivity in a plaque assay. It is assumed that the esterase activity of BCV is required in an early step of virus replication, possible during virus entry or uncoating.

Adenovirus type 2 endopeptidase: an unusual phosphoprotein enzyme matured by autocatalysis

Energy Technology Data Exchange (ETDEWEB)

Chatterjee, P.K.; Flint, S.J.

1987-02-01

A 19-kDa protein, present in low copy number in purified adenovirus type 2, has been characterized. Several criteria were used to establish that this protein is neither a degradation product of the known structural proteins of the virion nor a minor, unusually modified, form of protein VII. This 19-kDa protein, unlike other virion proteins, possesses alkali-resistant phosphoamino acids. Analysis by partial proteolysis indicated that it is related to a 23-kDa phosphoprotein present in H2ts-1 virions assembled in infected cells maintained at 39/sup 0/C. Affinity labeling with (/sup 3/H)diisopropyl fluorophosphate showed that the 19-kDa protein contains the active site for a serine protease. The authors, therefore, conclude that the 19-kDa protein is the active form of the adenovirus-encoded endopeptidase, defined by the H2ts-1 mutation, and is synthesized as a 23-kDa precursor that appears to mature by autocatalysis.

Hydrosilylation induced by N→Si intramolecular coordination: spontaneous transformation of organosilanes into 1-aza-silole-type molecules in the absence of a catalyst.

Science.gov (United States)

Novák, Miroslav; Dostál, Libor; Alonso, Mercedes; De Proft, Frank; Růžička, Aleš; Lyčka, Antonín; Jambor, Roman

2014-02-24

Our attempts to synthesize the N→Si intramolecularly coordinated organosilanes Ph2 L(1) SiH (1 a), PhL(1) SiH2 (2 a), Ph2 L(2) SiH (3 a), and PhL(2) SiH2 (4 a) containing a CH=N imine group (in which L(1) is the C,N-chelating ligand {2-[CH=N(C6 H3 -2,6-iPr2)]C6 H4}(-) and L(2) is {2-[CH=N(tBu)]C6 H4}(-)) yielded 1-[2,6-bis(diisopropyl)phenyl]-2,2-diphenyl-1-aza-silole (1), 1-[2,6-bis(diisopropyl)phenyl]-2-phenyl-2-hydrido-1-aza-silole (2), 1-tert-butyl-2,2-diphenyl-1-aza-silole (3), and 1-tert-butyl-2-phenyl-2-hydrido-1-aza-silole (4), respectively. Isolated organosilicon amides 1-4 are an outcome of the spontaneous hydrosilylation of the CH=N imine moiety induced by N→Si intramolecular coordination. Compounds 1-4 were characterized by NMR spectroscopy and X-ray diffraction analysis. The geometries of organosilanes 1 a-4 a and their corresponding hydrosilylated products 1-4 were optimized and fully characterized at the B3LYP/6-31++G(d,p) level of theory. The molecular structure determination of 1-3 suggested the presence of a Si-N double bond. Natural bond orbital (NBO) analysis, however, shows a very strong donor-acceptor interaction between the lone pair of the nitrogen atom and the formal empty p orbital on the silicon and therefore, the calculations show that the Si-N bond is highly polarized pointing to a predominantly zwitterionic Si(+) N(-) bond in 1-4. Since compounds 1-4 are hydrosilylated products of 1 a-4 a, the free energies (ΔG298), enthalpies (ΔH298), and entropies (ΔH298) were computed for the hydrosilylation reaction of 1 a-4 a with both B3LYP and B3LYP-D methods. On the basis of the very negative ΔG298 values, the hydrosilylation reaction is highly exergonic and compounds 1 a-4 a are spontaneously transformed into 1-4 in the absence of a catalyst. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Corticosterone primes the neuroinflammatory response to DFP in mice: potential animal model of Gulf War Illness.

Science.gov (United States)

O'Callaghan, James P; Kelly, Kimberly A; Locker, Alicia R; Miller, Diane B; Lasley, Steve M

2015-06-01

Gulf War Illness (GWI) is a multi-symptom disorder with features characteristic of persistent sickness behavior. Among conditions encountered in the Gulf War (GW) theater were physiological stressors (e.g., heat/cold/physical activity/sleep deprivation), prophylactic treatment with the reversible AChE inhibitor, pyridostigmine bromide (PB), the insect repellent, N,N-diethyl-meta-toluamide (DEET), and potentially the nerve agent, sarin. Prior exposure to the anti-inflammatory glucocorticoid, corticosterone (CORT), at levels associated with high physiological stress, can paradoxically prime the CNS to produce a robust proinflammatory response to neurotoxicants and systemic inflammation; such neuroinflammatory effects can be associated with sickness behavior. Here, we examined whether CORT primed the CNS to mount neuroinflammatory responses to GW exposures as a potential model of GWI. Male C57BL/6 mice were treated with chronic (14 days) PB/ DEET, subchronic (7-14 days) CORT, and acute exposure (day 15) to diisopropyl fluorophosphate (DFP), a sarin surrogate and irreversible AChE inhibitor. DFP alone caused marked brain-wide neuroinflammation assessed by qPCR of tumor necrosis factor-α, IL6, chemokine (C-C motif) ligand 2, IL-1β, leukemia inhibitory factor, and oncostatin M. Pre-treatment with high physiological levels of CORT greatly augmented (up to 300-fold) the neuroinflammatory responses to DFP. Anti-inflammatory pre-treatment with minocycline suppressed many proinflammatory responses to CORT+DFP. Our findings are suggestive of a possible critical, yet unrecognized interaction between the stressor/environment of the GW theater and agent exposure(s) unique to this war. Such exposures may in fact prime the CNS to amplify future neuroinflammatory responses to pathogens, injury, or toxicity. Such occurrences could potentially result in the prolonged episodes of sickness behavior observed in GWI. Gulf War (GW) veterans were exposed to stressors, prophylactic

[1,2-Bis(diisopropyl-phosphan-yl)ethane-κ(2) P,P'](carbonato-κ(2) O,O')nickel(II).

Science.gov (United States)

Morales-Becerril, Illan; Flores-Alamo, Marcos; Garcia, Juventino J

2013-04-01

In the crystal of the title compound, [Ni(CO3)(C14H32P2)], the metal center in each of three independent mol-ecules shows slight tetra-hedral distortion from ideal square-planar coordination geometry, with angles between the normals to the planes defined by the cis-P-Ni-P and cis-O-Ni-O fragments of 3.92 (17), 0.70 (16) and 2.17 (14)° in the three mol-ecules. In the crystal, there are inter-molecular C-H⋯O hydrogen bonds that show a laminar growth in the ab plane.

Thermodynamic modeling of ternary and quaternary (liquid + liquid) systems containing water, FeCl3, HCl and diisopropyl ether

International Nuclear Information System (INIS)

Milosevic, Miran; Hendriks, Ilse; Smits, Ralph E.R.; Schuur, Boelo; Haan, André B. de

2013-01-01

Highlights: • Literature data from various sources was validated experimentally. • Ternary and quaternary (liquid + liquid) systems were successfully described with the NRTL model. • Some deflection at higher HCl concentrations between model and data. • Additional data verification proved correctness of the literature data. -- Abstract: Liquid–liquid extraction using ethers as solvents is a potentially energy saving alternative for the concentration of aqueous ferric chloride solutions. Adequate thermodynamic models that describe the behavior of the resulting quaternary systems (FeCl 3 , ether, acid and water) are not available in the literature. In this paper, the development of an equilibrium description applying the NRTL-model is presented, including experimental validation and fitting of the NRTL-parameters on the validated data. Equilibrium experiments were performed for the ternary systems (water + HCl + DiPE) and (water + FeCl 3 + DiPE) and the obtained data is in good agreement with the results from Maljkovic et al.[37] and Cambell et al.[39]. Experimental data of the quaternary system is taken from Maljkovic et al.[37]. The obtained binary interaction parameters to describe the (liquid + liquid) quaternary system (water + FeCl 3 + HCl + DiPE) and the constituting ternaries by the NRTL model are presented. Model predictions are in good agreement with the experimental data

Thermodynamic modeling of ternary and quaternary (liquid + liquid) systems containing water, FeCl3, HCl and diisopropyl ether

NARCIS (Netherlands)

Milosevic, M.; Hendriks, I.; Smits, R.E.R.; Schuur, B.; Haan, de A.B.

2013-01-01

Liquid–liquid extraction using ethers as solvents is a potentially energy saving alternative for the concentration of aqueous ferric chloride solutions. Adequate thermodynamic models that describe the behavior of the resulting quaternary systems (FeCl3, ether, acid and water) are not available in

Cooperative study with sup(99m)Tc diisopropil-IDA on biliary tract diseases

International Nuclear Information System (INIS)

Mitta, A.E.A.; Mollerach, F; Almeida, C.A.

1982-01-01

The results of a cooperative study on the investigation of the biliary tract with sup(99m)Tc diisopropyl-IDA are presented. 15 normal volunteers and 75 patients with acute cholecystitis (AC), chronic cholecystitis (CC), hepatocellular jaundice (HCJ), incomplete extrahepatic biliary obstruction (IEBO) and complete extrahepatic biliary obstruction (CEBO) were studied. The biological behaviour of the radiopharmaceutical in the two groups was determined through the measurement of the uptake times and of the times of arrival in the hepatic parenchyma, in the intra and extrahepatic bile ducts, in the gallbladder, in the duodenum and in the kidneys. The pathophysiologic features found in the AC, CC, HCJ, IEBO and CEBO are described. It is concluded that the procedure has a selective indication in the AC, that its value is limited in the CC, and that in jaundice, except in very special situations, the method gives very little information of clinic value. The possibility of performing cooperative scientific studies between Latin-American Departments, increasing their efficiency, is emphasized. (author) [es

Development of a new analytical tool for assessing the mutagen 2-methyl-1,4-dinitro-pyrrole in meat products by LC-ESI-MS/MS.

Science.gov (United States)

Molognoni, Luciano; Daguer, Heitor; de Sá Ploêncio, Leandro Antunes; Yotsuyanagi, Suzana Eri; da Silva Correa Lemos, Ana Lucia; Joussef, Antonio Carlos; De Dea Lindner, Juliano

2018-08-01

The use of sorbate and nitrite in meat processing may lead to the formation of 2-methyl-1,4-dinitro-pyrrole (DNMP), a mutagenic compound. This work was aimed at developing and validating an analytical method for the quantitation of DNMP by liquid chromatography-tandem mass spectrometry. Full validation was performed in accordance to Commission Decision 2002/657/EC and method applicability was checked in several samples of meat products. A simple procedure, with low temperature partitioning solid-liquid extraction, was developed. The nitrosation during the extraction was monitored by the N-nitroso-DL-pipecolic acid content. Chromatographic separation was achieved in 8 min with di-isopropyl-3-aminopropyl silane bound to hydroxylated silica as stationary phase. Samples of bacon and cooked sausage yielded the highest concentrations of DNMP (68 ± 3 and 50 ± 3 μg kg -1 , respectively). The developed method proved to be a reliable, selective, and sensitive tool for DNMP measurements in meat products. Copyright © 2018 Elsevier B.V. All rights reserved.

The role of the gamma camera in the study of gastric function

International Nuclear Information System (INIS)

Esser, J.D.; Mannell, A.; Hinder, R.A.

1984-01-01

With the gamma camera food labelled with radioactive tracers can be visualized as it enters and leaves the stomach. Radiopharmaceuticals such as technetium-99m di-isopropyl iminodiacetic acid simulate the bile pathway and can be used to demonstrate duodenogastric reflux. Duodenogastric reflux and gastric emptying of solid or liquid meals can be quantitated when the gamma camera is linked to a microprocessor. The test meal used at the Johannesburg and Hillbrow Hospitals consists of a 99 (sup m)Tc-labelled chicken liver weighing 30 g mixed with 70 g cooked ground beef. These studies are valuable for investigating symptomatic postgastrectomy patients and patients who have neurogenic or metabolic diseases which result in abnormal gastric function. The efficacy of drugs given to relieve these symptoms can also be assessed. In this paper we discuss the nuclear medicine techniques used to study gastric function. Examples are given of abnormalities which may not be diagnosed on gastroscopy or barium meal examination but which can be clearly identified by gamma camera techniques

Molecular and crystal structure of gossypol tetramethyl ether with an unknown solvate

Directory of Open Access Journals (Sweden)

Muhabbat Honkeldieva

2015-02-01

Full Text Available The title compound, C34H38O8 (systematic name: 5,5′-diisopropyl-2,2′,3,3′-tetramethoxy-7,7′-dimethyl-2H,2′H-8,8′-bi[naphtho[1,8-bc]furan]-4,4′-diol, has been obtained from a gossypol solution in a mixture of dimethyl sulfate and methanol. The molecule is situated on a twofold rotation axis, so the asymmetric unit contains one half-molecule. In the molecule, the hydroxy groups are involved in intramolecular O—H...O hydrogen bonds, and the two naphthyl fragments are inclined each to other by 83.8 (1°. In the crystal, weak C—H...O and C—H...π interactions consolidate the packing, which exhibits channels with an approximate diameter of 6 Å extending along the c-axis direction. These channels are filled with highly disordered solvent molecules, so their estimated scattering contribution was subtracted from the observed diffraction data using the SQUEEZE option in PLATON [Spek, A. L. (2015. Acta Cryst. C71, 9–18].

Characterization of an alkaline protease associated with a granulosis virus of Plodia interpunctella.

Science.gov (United States)

Tweeten, K A; Bulla, L A; Consigli, R A

1978-06-01

An alkaline protease was found to be associated with the granulosis virus of the Indian meal moth. Plodia interpunctella. The protease was located within the protein matrix of the occluded virus and hydrolyzed the major constituent of this matrix, a 28,000-dalton protein (granulin), to a mixture of polypeptides ranging in molecular weight from 10,000 to 27,000. A rapid, sensitive assay for the protease was developed using radioactively labeled granulosis virus as substrate. With this assay, the proteolytic activity could be detected by measuring the release of acid-soluble peptides from the labeled virus. The protease had a pH optimum of 10.5 and a temperature optimum of 40 degrees C and was inhibited by diisopropyl phosphorofluoridate, phenylmethylsulfonyl fluoride, and L-(1-tosylamido-2-phenyl) ethyl chloromethyl ketone. Purification of the protease from matrix protein was achieved by anion-exchange and gel permeation chromatography. The molecular weight of the isolated protease, determined by sodium dodecyl sulfate-polyacrylamide gel electrophoresis and gel filtration, was approximately 14,000.

Atomic layer deposition of GeO{sub 2} thin films on Si(100) using Ge(N,N'-R,R-en)(NMe{sub 2}){sub 2} (where R = Isopropyl and t-Butyl) precursors

Energy Technology Data Exchange (ETDEWEB)

Kim, Dae Hyun; Shin, Jin Ho [Soulbrain Sigma-Aldrich Co., Ltd., Gongju (Korea, Republic of); Jung, Jae Sun; Kang, Jun Gill [Chungnam National University, Daejeon (Korea, Republic of)

2015-08-15

In this study, we introduced bis(dimethylamino)(N,N'-diisopropyl-ethylenediamine) germanium (1) and bis (dimethyl-amino)(N,N'-di-tert-butyl-ethylenediamine) germanium (2) as novel ALD precursors and analyzed the ALD growth characteristics to obtain the best possible film properties. A 5-L three-neck flask was charged with 2.5 L of toluene, GeCl{sub 4} (60 g, 0.28 mol) was added and then cooled to -15 to -20 .deg. C. the two precursors produced good-quality GeO{sub 2} thin films via the ALD process. The ALD windows of bis(dimethylamino)(N,N'-di-isopropyl-ethylenediamine) germanium and bis(dimethylamino)(N,N'-di-tert -butyl-ethylene-diamine) germanium were established at 200–330 .deg. C with a growth rate of about 0.40 and 0.31 Å/cycle, respectively. ALD-type growth mode was verified by increasing the precursor pulsing time. Growth rate was saturated from 3.0 s. These films have considerable potential for industrial applications.

Demonstration of spread-on peel-off consumer products for sampling surfaces contaminated with pesticides and chemical warfare agent signatures.

Science.gov (United States)

Behringer, Deborah L; Smith, Deborah L; Katona, Vanessa R; Lewis, Alan T; Hernon-Kenny, Laura A; Crenshaw, Michael D

2014-08-01

A terrorist attack using toxic chemicals is an international concern. The utility of rubber cement and latex body paint as spray-on/spread-on peel-off collection media for signatures attributable to pesticides and chemical warfare agents from interior building and public transportation surfaces two weeks post-deposition is demonstrated. The efficacy of these media to sample escalator handrail, stainless steel, vinyl upholstery fabric, and wood flooring is demonstrated for two pesticides and eight chemicals related to chemical warfare agents. The chemicals tested are nicotine, parathion, atropine, diisopropyl methylphosphonate, dimethyl methylphosphonate, dipinacolyl methylphosphonate, ethyl methylphosphonic acid, isopropyl methylphosphonic acid, methylphosphonic acid, and thiodiglycol. Amounts of each chemical found are generally greatest when latex body paint is used. Analytes with low volatility and containing an alkaline nitrogen or a sulfur atom (e.g., nicotine and parathion) usually are recovered to a greater extent than the neutral phosphonate diesters and acidic phosphonic acids (e.g., dimethyl methylphosphonate and ethyl methylphosphonic acid). Copyright © 2014 Elsevier Ireland Ltd. All rights reserved.

Acetylation/deacetylation reactions of T-2, acetyl T-2, HT-2, and acetyl HT-2 toxins in bovine rumen fluid in vitro

Energy Technology Data Exchange (ETDEWEB)

Munger, C.E.; Ivie, G.W.; Christopher, R.J.; Hammock, B.D.; Phillips, T.D.

A tritiated preparation of the trichothecene mycotoxin, T-2 toxin, underwent both acetylation and deacetylation reactions when incubated with bovine rumen fluid in vitro. Products from incubations of T-2 in rumen fluid included acetyl T-2, HT-2, and acetyl HT-2. Direct studies with tritiated samples of each of these metabolites confirmed their relatively facile interconversion in the rumen. Studies with (/sup 3/H)HT-2 under conditions of inhibited esterase activity (added diisopropyl fluorophosphate) showed that acetylation is preferred at C-3 vs. C-4. Studies with (/sup 3/H)acetyl T-2 indicated that deacetylation similarly occurs with greater rapidity at C-3. There were no indications that ester hydrolysis of these trichothecenes occurred at C-8 or C-15 or that they were subjected to epoxide reduction reactions. These data suggest that acetylation of T-2 and other trichothecenes in the rumen in situ may ultimately result in the absorption of more lipophilic metabolites whose toxicological and residual properties are at present unknown.

Capillary gas chromatographic analysis of nerve agents using large volume injections. Final report

Energy Technology Data Exchange (ETDEWEB)

Deinum, T.; Nieuwenhuy, C.

1994-11-01

The procedure developed at TNO-Prins Maurits Laboratory (TNO-PML) for the verification of intact organophosphorus chemical warfare agents in water samples was improved. The last step in this procedure, the laborious and non-reproducible transfer of an ethyl acetate extract onto a Tenax-adsorption tube followed by thermal desorption of the Tenax-tube, was replaced by large volume injection of the extract onto a capillary gas chromatographic system. The parameters controlling the injection of a large volume of an extract (200 ul) were investigated and optimized. As ethyl acetate caused severe problems, potential new solvents were evaluated. With the improved procedure, the nerve agents sarin, tabun, soman, diisopropyl fluorophosphate (DFP) and VX could be determined in freshly prepared water samples at pg/ml (ppt) levels. The fate of the nerve agents under study in water at two pH`s (4.8 and 6) was investigated. For VX, the pH should be adjusted before extraction. Moreover, it is worthwhile to acidify water samples to diminish hydrolysis.

Endotoxin induction of an inhibitor of plasminogen activator in bovine pulmonary artery endothelial cells

Energy Technology Data Exchange (ETDEWEB)

1986-01-05

The effects of bacterial lipopolysaccharide (endotoxin) on the fibrinolytic activity of bovine pulmonary artery endothelial cells were examined. Endotoxin suppressed the net fibrinolytic activity of cell extracts and conditioned media in a dose-dependent manner. The effects of endotoxin required at least 6 h for expression. Cell extracts and conditioned media contained a 44-kDa urokinase-like plasminogen activator. Media also contained multiple plasminogen activators with molecular masses of 65-75 and 80-100 kDa. Plasminogen activators in extracts and media were unchanged by treatment of cells with endotoxin. Diisopropyl fluorophosphate (DFP)-abolished fibrinolytic activity of extracts and conditioned media. DFP-treated samples from endotoxin-treated but not untreated cells inhibited urokinase and tissue plasminogen activator, but not plasmin. Inhibitory activity was lost by incubation at pH 3 or heating to 56/sup 0/C for 10 min. These treatments did not affect inhibitory activity of fetal bovine serum. Incubation of /sup 125/I-urokinase with DFP-treated medium from endotoxin-treated cells produced an inactive complex with an apparent molecular mass of 80-85 kDa.

[1,2-Bis(diisopropyl­phosphan­yl)ethane-κ2 P,P′](carbonato-κ2 O,O′)nickel(II)

Science.gov (United States)

Morales-Becerril, Illan; Flores-Alamo, Marcos; Garcia, Juventino J.

2013-01-01

In the crystal of the title compound, [Ni(CO3)(C14H32P2)], the metal center in each of three independent mol­ecules shows slight tetra­hedral distortion from ideal square-planar coordination geometry, with angles between the normals to the planes defined by the cis-P—Ni—P and cis-O—Ni—O fragments of 3.92 (17), 0.70 (16) and 2.17 (14)° in the three mol­ecules. In the crystal, there are inter­molecular C—H⋯O hydrogen bonds that show a laminar growth in the ab plane. PMID:23633999

Structural Diversity in Alkali Metal and Alkali Metal Magnesiate Chemistry of the Bulky 2,6-Diisopropyl-N-(trimethylsilyl)anilino Ligand.

Science.gov (United States)

Fuentes, M Ángeles; Zabala, Andoni; Kennedy, Alan R; Mulvey, Robert E

2016-10-10

Bulky amido ligands are precious in s-block chemistry, since they can implant complementary strong basic and weak nucleophilic properties within compounds. Recent work has shown the pivotal importance of the base structure with enhancement of basicity and extraordinary regioselectivities possible for cyclic alkali metal magnesiates containing mixed n-butyl/amido ligand sets. This work advances alkali metal and alkali metal magnesiate chemistry of the bulky arylsilyl amido ligand [N(SiMe 3 )(Dipp)] - (Dipp=2,6-iPr 2 -C 6 H 3 ). Infinite chain structures of the parent sodium and potassium amides are disclosed, adding to the few known crystallographically characterised unsolvated s-block metal amides. Solvation by N,N,N',N'',N''-pentamethyldiethylenetriamine (PMDETA) or N,N,N',N'-tetramethylethylenediamine (TMEDA) gives molecular variants of the lithium and sodium amides; whereas for potassium, PMDETA gives a molecular structure, TMEDA affords a novel, hemi-solvated infinite chain. Crystal structures of the first magnesiate examples of this amide in [MMg{N(SiMe 3 )(Dipp)} 2 (μ-nBu)] ∞ (M=Na or K) are also revealed, though these breakdown to their homometallic components in donor solvents as revealed through NMR and DOSY studies. © 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Study of the nature of the binding of phosphate residues in the phosphorylated form of succinyl-CoA synthetase from pigeon breast muscle

International Nuclear Information System (INIS)

Valiulina, D.S.; Skalbe, T.A.; Matveeva, L.N.

1987-01-01

The hydrolytic stability of the phosphorylated protein was investigated within a wide pH range. It was shown that the bond of the phosphate residue to protein in complex I is hydrolyzed at alkaline pH values (11.0 and 13.0). At acid pH values this bond is 50% hydrolyzed. The bond of the phosphate residue to protein in complex II is hydrolyzed at acid pH values and is stable at alkaline pH values of the medium. The phosphorylation reaction of the enzyme I, both with hydroxylamine and with diisopropyl fluorophosphate, led to 50% dephosphorylation of the protein. An analysis of an alkaline hydrolysate (3 N NaOH, 3 h, 100 0 C) of the radioactive phosphorylated enzyme II by ion exchange chromatography showed that the radioactive label of the protein is distributed in the fractions of 1-N- and 3-N-phosphohistidine, as well as 1,3-N-diphosphohistidine. The data obtained suggested that phosphate in the phosphorylated enzyme I is bound to protein, with the formation of acyl phosphate and phosphoester bonds. Phosphate in the phosphorylated enzyme II is bound to protein with the formation of a phosphoamide bond

Sensitive multiresidue method by HS-SPME/GC-MS for 10 volatile organic compounds in urine matrix: a new tool for biomonitoring studies on children.

Science.gov (United States)

Antonucci, Arianna; Vitali, Matteo; Avino, Pasquale; Manigrasso, Maurizio; Protano, Carmela

2016-08-01

A HS-SPME method coupled with GC-MS analysis has been developed for simultaneously measuring the concentration of 10 volatile organic compounds (VOCs) (benzene, toluene, ethylbenzene, o-, m-, and p-xylene, methyl tert-butyl ether, ethyl tert-butyl ether, 2-methyl-2-butyl methyl ether, and diisopropyl ether) in urine matrix as a biomonitoring tool for populations at low levels of exposure to such VOCs. These compounds, potentially toxic for human health, are common contaminants of both outdoor and indoor air, as they are released by autovehicular traffic; some of them are also present in environmental tobacco smoke (ETS). Thus, the exposure to these pollutants cannot be neglected and should be assessed. The low limits of detection and quantification (LODs and LOQs <6.5 and 7.5 ng L(-1), respectively) and the high reproducibility (CVs <4 %) make the developed method suited for biomonitoring populations exposed at low levels such as children. Further, the method is cost-effective and low in time-consumption; therefore, it is useful for investigating large populations. It has been applied to children exposed to traffic pollution and/or ETS; the relevant results are reported, and the relevant implications are discussed.

Deuterium isotope fractionation between ortho-alkyl substituted phenols and t-butylthiol in oxygen bases

International Nuclear Information System (INIS)

Wawer, A.; Jelenska-Kazimierczuk, M.; Szydlowski, J.

1998-01-01

Equilibrium isotope effect in the exchange reaction of deuterium between phenol(P), 2-isopropyl phenol (IPP), 2,6-diisopropyl phenol (DIPP), 2,6-diterbutyl phenol (DTBP) and tertbutylthiol (TBT) has been studied in 296 K. The fractionation factors (α) have been measured in cyclohexane and carbon tetrachloride solutions and in a few oxygen bases: acetone, 1,4-dioxane, ethyl formate, ethyl ether, tetrahydrofurane, N,N-dimethylformamide, dimethylsulfoxide and hexamethylphosphoramide. Using chemical shifts of phenol OH protons, the thermodynamic parameters of complex formation with the oxygen bases have been determined. The experimental data show that lnα correlates with the formation enthalpy of the phenol-oxygen base complex in DIPP-TBT-base system but there is no simple correlation in IPP-TBT-base system. Furthermore, it was found that in DTBT-TBT-base system lnα depends linearly on the basicity of the solvent (DN parameters). On the other hand, lnα correlates with acidic parameters of the solvents (AN) in IPP-TBT-base and P-TBT-base systems. All above correlations are explained by taking into account two competition processes: self association of phenol molecules and their solvation by oxygen bases. (author)

Efficient photochemical generation of peroxycarboxylic nitric anhydrides with ultraviolet light-emitting diodes

Science.gov (United States)

Rider, N. D.; Taha, Y. M.; Odame-Ankrah, C. A.; Huo, J. A.; Tokarek, T. W.; Cairns, E.; Moussa, S. G.; Liggio, J.; Osthoff, H. D.

2015-07-01

Photochemical sources of peroxycarboxylic nitric anhydrides (PANs) are utilized in many atmospheric measurement techniques for calibration or to deliver an internal standard. Conventionally, such sources rely on phosphor-coated low-pressure mercury (Hg) lamps to generate the UV light necessary to photo-dissociate a dialkyl ketone (usually acetone) in the presence of a calibrated amount of nitric oxide (NO) and oxygen (O2). In this manuscript, a photochemical PAN source in which the Hg lamp has been replaced by arrays of ultraviolet light-emitting diodes (UV-LEDs) is described. The output of the UV-LED source was analyzed by gas chromatography (PAN-GC) and thermal dissociation cavity ring-down spectroscopy (TD-CRDS). Using acetone, diethyl ketone (DIEK), diisopropyl ketone (DIPK), or di-n-propyl ketone (DNPK), respectively, the source produces peroxyacetic (PAN), peroxypropionic (PPN), peroxyisobutanoic (PiBN), or peroxy-n-butanoic nitric anhydride (PnBN) from NO in high yield (> 90 %). Box model simulations with a subset of the Master Chemical Mechanism (MCM) were carried out to rationalize product yields and to identify side products. The present work demonstrates that UV-LED arrays are a viable alternative to current Hg lamp setups.

Preparation of high purification and food grade phosphoric acid from technical grade phosphoric acid by liquid-liquid detraction method

International Nuclear Information System (INIS)

Alimoradi, M.; Borji, F.; Kishani, A.

2002-01-01

Pay attention to increasing consumption of high purification and food grade phosphoric acid in various industries and food industries and on in on hand and lack of preparation between production and distribution of this products its purification is so vital. In this article of liquid-liquid extraction method with normal hexane-mixture of ammonia and acetone-diisopropyl alcohol and normal butanol solvents and these determination of distribution coefficient each one with ph-me try titration we can evaluate effectiveness and sufficiency each one. Because of proper coefficient distribution and its local production of normal butanol solvent and low price is the best solvent. To phosphoric acid modifying coefficient distribution for extraction of phosphoric acid we can add a little value sulfuric acid to the mixture and to remove flouride impurity we add a little Na 2 O. After extraction stage extracted phosphoric acid in the normal strips by evaluating with distilled water and then by passing the carbon active bed and following passes of cationic resine column and concentrated with vacuum distillation. Conclusion of this article is produce of phosphoric acid 85% w/w and food grade from impure phosphoric acid 52% w/w with technical grade

Removal of lindane from an aqueous solution by using aminopropyl silica gel-immobilized calix[6]arene.

Science.gov (United States)

Tor, Ali; Aydin, Mehmet Emin; Aydin, Senar; Tabakci, Mustafa; Beduk, Fatma

2013-11-15

An aminopropyl silica gel-immobilized calix[6]arene (C[6]APS) has been used for the removal of lindane from an aqueous solution in batch sorption technique. The C[6]APS was synthesized with p-tert-butylcalix[6]arene hexacarboxylate derivative and aminopropyl silica gel in the presence of N,N'-diisopropyl carbodiimide coupling reagent. The sorption study was carried out as functions of solution pH, contact time, initial lindane concentration, C[6]APS dosage and ionic strength of solution. The matrix effect of natural water samples on the sorption efficiency of C[6]APS was also investigated. Maximum lindane removal was obtained at a wide pH range of 2-8 and sorption equilibrium was achieved in 2h. The isotherm analysis indicated that the sorption data can be represented by both Langmuir and Freundlich isotherm models. Increasing ionic strength of the solutions increased the sorption efficiency and matrix of natural water samples had no effect on the sorption of lindane. By using multilinear regression model, regression equation was also developed to explain the effects of the experimental variables. Copyright © 2013 Elsevier B.V. All rights reserved.

Simultaneous initiation of degranulation and inhibition of leukotriene release by soman in human basophils

Energy Technology Data Exchange (ETDEWEB)

Meier, H.L.; Warner, J.; MacGlashan, D.W.

1995-12-31

Previous studies noted that the serine esterase inhibitor, soman, could induce histamine release from human basophils. To investigate the mechanisms by which soman causes histamine release (a preformed mediator), we also examined its ability to induce leukotriene release (a newly synthesized mediator) from basophils. We found that no leukotriene release followed activation with soman, while histamine release was usually greater than 70%. In addition, soman and diisopropyl-fluorophosphate were found actively to suppress low level spontaneous leukotriene release as well as ongoing leukotriene release induced by anti-IgE antibody. Soman (0.3 mM) was able to stop leukotriene release as rapidly as the calcium chelator, EDTA. In a series of control experiments, it was noted that soman did not influence the metabolism of LTC4 to LTD4 or LTE4 (for which little metabolism occurred), eliminating the possibility that reduced LTC4 release could have resulted from its enhanced metabolism. Therefore, using one compound (soman), basophils could be simultaneously activated to degranulate while having the pathway leading to leukotriene release actively suppressed. These results provide further evidence that histamine and leukotriene release are independent pathways resulting from the activation of basophils.

Specificity of carboxylesterase protection against the toxicity of organophosphorus compounds. (Reannouncement with new availability information)

Energy Technology Data Exchange (ETDEWEB)

Maxwell, D.M.

1992-12-31

The ability of endogenous carboxylesterase (CaE) to protect against the lethal effects of a variety of organophosphorus (OP) compounds was examined in rats. The in vivo protection provided by endogenous CaE was measured by the difference in the LD50 values of OP compounds in controlrats and rats whose CaE activity had been inhibited by sc injection with2 mg/kg of 2-(O cresyl)-4H-1,3,2-benzodi oxaphosphorin-2-oxide. Endogenous CaE provided significant protection against the in vivo toxicity of soman, sarin, tabun, and paraoxon, but not against dichlorvos, diisopropyl fluorophosphate, or ethoxymethyl-S-2- (DIISOPROPYLAMINO)ETHYL THIOPHOSPHONATE (VX). The relationship between the in vivo CaE protection against OP compounds and their relative reactivities with CaE and acetylcholinesterase (AChE) was evaluated by measuring the in vitro bimolecular rate constants (ki) for inhibition of plasma CaE and brain AChE. Except for VX, ki values for CaE inhibition varied <10-fold while ki values for AChE inhibition varied 105-fold. Chemical warfare agents, Nerve agents, Organophosphoruscompound soman, VX, Carboxylesterase, Protection, Pretreatment.

Active site of tripeptidyl peptidase II from human erythrocytes is of the subtilisin type

Energy Technology Data Exchange (ETDEWEB)

Tomkinson, B.; Wernstedt, C.; Hellman, U.; Zetterqvist, Oe.

1987-11-01

The present report presents evidence that the amino acid sequence around the serine of the active site of human tripeptidyl peptidase II is of the subtilisin type. The enzyme from human erythrocytes was covalently labeled at its active site with (/sup 3/H)diisopropyl fluorophosphate, and the protein was subsequently reduced, alkylated, and digested with trypsin. The labeled tryptic peptides were purified by gel filtration and repeated reversed-phase HPLC, and their amino-terminal sequences were determined. Residue 9 contained the radioactive label and was, therefore, considered to be the active serine residue. The primary structure of the part of the active site (residues 1-10) containing this residue was concluded to be Xaa-Thr-Gln-Leu-Met-Asx-Gly-Thr-Ser-Met. This amino acid sequence is homologous to the sequence surrounding the active serine of the microbial peptidases subtilisin and thermitase. These data demonstrate that human tripeptidyl peptidase II represents a potentially distinct class of human peptidases and raise the question of an evolutionary relationship between the active site of a mammalian peptidase and that of the subtilisin family of serine peptidases.

Study of the nature of the binding of phosphate residues in the phosphorylated form of succinyl-CoA synthetase from pigeon breast muscle

Energy Technology Data Exchange (ETDEWEB)

Valiulina, D.S.; Skalbe, T.A.; Matveeva, L.N.

1987-01-10

The hydrolytic stability of the phosphorylated protein was investigated within a wide pH range. It was shown that the bond of the phosphate residue to protein in complex I is hydrolyzed at alkaline pH values (11.0 and 13.0). At acid pH values this bond is 50% hydrolyzed. The bond of the phosphate residue to protein in complex II is hydrolyzed at acid pH values and is stable at alkaline pH values of the medium. The phosphorylation reaction of the enzyme I, both with hydroxylamine and with diisopropyl fluorophosphate, led to 50% dephosphorylation of the protein. An analysis of an alkaline hydrolysate (3 N NaOH, 3 h, 100/sup 0/C) of the radioactive phosphorylated enzyme II by ion exchange chromatography showed that the radioactive label of the protein is distributed in the fractions of 1-N- and 3-N-phosphohistidine, as well as 1,3-N-diphosphohistidine. The data obtained suggested that phosphate in the phosphorylated enzyme I is bound to protein, with the formation of acyl phosphate and phosphoester bonds. Phosphate in the phosphorylated enzyme II is bound to protein with the formation of a phosphoamide bond.

Isothermal Vapour-Liquid Equilibria in the Binary and Ternary Systems Composed of 2-Propanol, Diisopropyl Ether and 4-Methyl-2-Pentanone

Czech Academy of Sciences Publication Activity Database

Psutka, Štěpán; Wichterle, Ivan

2005-01-01

Roč. 235, č. 1 (2005), s. 58-63 ISSN 0378-3812 R&D Projects: GA ČR(CZ) GA104/03/1555; GA AV ČR(CZ) KSK4040110 Institutional research plan: CEZ:AV0Z40720504 Keywords : VLE experimental data * prediction Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.478, year: 2005

Isothermal Vapour-Liquid Equilibria in the Binary and Ternary Systems Composed of 2-Propanol, Diisopropyl Ether and 1-Methoxy-2-Propanol

Czech Academy of Sciences Publication Activity Database

Psutka, Štěpán; Wichterle, Ivan

2004-01-01

Roč. 220, č. 2 (2004), s. 161-165 ISSN 0378-3812 R&D Projects: GA ČR GA104/03/1555 Institutional research plan: CEZ:AV0Z4072921 Keywords : alcohol * ether * alkoxyalcohol Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.356, year: 2004

Bioaccumulation of Stentorin, the Probable Causative Agent for Discolored ("Purple") Eggs and Ovaries in Blue Catfish (Ictalurus furcatus) from Eufaula Lake, Oklahoma, USA.

Science.gov (United States)

Gale, Robert W; Papoulias, Diana M; Schmitt, Christopher J

2015-08-18

Observations of reddish to "purple" discolored eggs in the ovaries of adult female blue catfish (Ictalurus furcatus) from the northern arm of Eufaula Lake, a eutrophic multiuse impoundment in east-central Oklahoma, were first reported in 2006. Blue catfish eggs are normally cream to light yellow. Reports peaked in 2007-2008 and declined through 2009-2010; purple eggs have not been reported between 2010 and 2014. In the laboratory, all tissues and fluids of affected fish were strongly orange-red fluorescent under UV illumination, with the fluorescence most apparent in the lipid-rich ovaries and eggs. The causative agent was isolated chromatographically and confirmed by mass spectrometry as stentorin (1,3,4,6,8,10,11,13-octahydroxy-2,5-diisopropyl-phenanthro[1,10,9,8,o,p,q,r,a]perylene-7,14-dione), the fluorescent, lipophilic pigment associated with the photoreceptor protein of the ciliated protozoan Stentor coeruleus (Heterotrichea; Stentoridae). Larval medaka (Orizias latipes) readily consumed S. coeruleus in the laboratory and were observed to fluoresce in the same manner as the affected blue catfish. Potential deleterious effects of stentorin bioaccumulation remain to be determined, as do the geographic extent and the identities of other fluorescent compounds isolated from catfish eggs and ovaries.

Bioaccumulation of stentorin, the probable causative agent for discolored (“purple”) eggs and ovaries in blue catfish (Ictalurus furcatus) from Eufaula Lake, Oklahoma, USA

Science.gov (United States)

Gale, Robert W.; Papoulias, Diana M.; Schmitt, Christopher J.

2015-01-01

Observations of reddish to “purple” discolored eggs in the ovaries of adult female blue catfish (Ictalurus furcatus) from the northern arm of Eufaula Lake, a eutrophic multiuse impoundment in east-central Oklahoma, were first reported in 2006. Blue catfish eggs are normally cream to light yellow. Reports peaked in 2007–2008 and declined through 2009–2010; purple eggs have not been reported between 2010 and 2014. In the laboratory, all tissues and fluids of affected fish were strongly orange-red fluorescent under UV illumination, with the fluorescence most apparent in the lipid-rich ovaries and eggs. The causative agent was isolated chromatographically and confirmed by mass spectrometry as stentorin (1,3,4,6,8,10,11,13-octahydroxy-2,5-diisopropyl-phenanthro[1,10,9,8,o,p,q,r,a]perylene-7,14-dione), the fluorescent, lipophilic pigment associated with the photoreceptor protein of the ciliated protozoan Stentor coeruleus (Heterotrichea; Stentoridae). Larval medaka (Orizias latipes) readily consumed S. coeruleus in the laboratory and were observed to fluoresce in the same manner as the affected blue catfish. Potential deleterious effects of stentorin bioaccumulation remain to be determined, as do the geographic extent and the identities of other fluorescent compounds isolated from catfish eggs and ovaries.

Efficient photochemical generation of peroxycarboxylic nitric anhydrides with ultraviolet light emitting diodes

Science.gov (United States)

Rider, N. D.; Taha, Y. M.; Odame-Ankrah, C. A.; Huo, J. A.; Tokarek, T. W.; Cairns, E.; Moussa, S. G.; Liggio, J.; Osthoff, H. D.

2015-01-01

Photochemical sources of peroxycarboxylic nitric anhydrides (PANs) are utilized in many atmospheric measurement techniques for calibration or to deliver an internal standard. Conventionally, such sources rely on phosphor-coated low-pressure mercury (Hg) lamps to generate the UV light necessary to photo-dissociate a dialkyl ketone (usually acetone) in the presence of a calibrated amount of nitric oxide (NO) and oxygen (O2). In this manuscript, a photochemical PAN source in which the Hg lamp has been replaced by arrays of ultraviolet light-emitting diodes (UV-LEDs) is described. The output of the UV-LED source was analyzed by gas chromatography (PAN-GC) and thermal dissociation cavity ring-down spectroscopy (TD-CRDS). Using acetone, diethyl ketone (DIEK), diisopropyl ketone (DIPK), or di-n-propyl ketone (DNPK), respectively, the source produces peroxyacetic (PAN), peroxypropionic (PPN), peroxyisobutanoic (PiBN), or peroxy-n-butanoic nitric anhydride (PnBN) from NO in high yield (> 90%). Box model simulations with a subset of the Master Chemical Mechanism (MCM) were carried out to rationalize products yields and to identify side products. The use of UV-LED arrays offers many advantages over conventional Hg lamp setups, including greater light output over a narrower wavelength range, lower power consumption, and minimal generation of heat.

Adaptive processes of the central and autonomic cholinergic neurotransmitter system: Age-related differences

International Nuclear Information System (INIS)

Fortuna, S.; Pintor, A.; Michalek, H.

1991-01-01

Potential age-related differences in the response of the ileum strip longitudinal and circular muscle to repeated treatment with diisopropyl fluorophosphate (DFP) were evaluated in Sprague-Dawley rats. The response was measured in terms of both biochemical parameters (acetylcholinesterase-AChE inhibition, muscarinic acetylcholine receptor binding sites-mAChRs, choline acetyltransferase-ChAT) and functional responsiveness (contractility of the isolated ileum stimulated by cholinergic agonists). The biochemical data were compared with those obtained for the cerebral cortex. In the ileum strip of control rats there was a significant age-related decline of AChE, maximal density of 3 H-QNB binding sites (Bmax) and ChAT. During the first week of DFP treatment the cholinergic syndrome was more pronounced in aged than in young rats, resulting in 35% and 10% mortality, respectively; subsequently the syndrome attenuated. At the end of DFP treatment ileal AChE were inhibited by about 30%; the down-regulation of mAChRs was about 50% in young and 35% in aged rats. No significant differences in the recovery rate of AChE were noted between young and aged rats. On the contrary, mAChRs normalized within 5 weeks in young and 3 weeks in aged rats

Radiopharmacology of iminodiacetic acid N-derivatives analysis in biological models and comparison to human beings

International Nuclear Information System (INIS)

Canellas, C.O.; Arguelles, M.G.; Mitta, A.E.A.

1987-01-01

It was studied the influence of chemical structures and molecular weight in the distribution of several iminodiacetic acid N-derivatives and to determine the potential use of these radiopharmaceuticals in humans. The study was performed with the following derivatives: N-(2,6 dimetyphenylcarbamoylmethy) iminodiacetic acid, N(2.6 dietylphenyl-carbamoylmethy) iminodiacetic acid, N-(2,6 diisopropylphenylcarbamoylmethy) iminodiacetic acid and the previously unknown N-derivative N-(2,6 diisopropyl, phenylcarbamoylethyl) iminodiacetic aced. These were sinthesized by a modified procedure by MITTA et al. and controlled by NMR, mass spectrometry, elemental composition and also toxicity pirogens, lethal dose and the chelate's radiochemical dose were determined. Liver gallbladder, intestinal and renal kinetics were studied in mice. In order to evaluate the metabolic pathways of the radiopharmaceuticals, the content of gallbladder and the urine were reinjected. Plasma kinetics and the plasmatic half life was determined by extracorporeal circulation in Wistar rats. For the use in human beings, test were carried out in different branches of nuclear medicine, in normal volunteers and carriers of different pathologic disorders. The patients were divided into four groups: acute and chronic cholecystitis, cirrhosis and jaundice. It was obtained the liver/heart activity ratio and estimated the appearance times of the intrahepatic ducts, gallbladder, duodenum and renal persistence. (M.E.L.) [es

Disposition in male volunteers of a subanaesthetic intravenous dose of an oil in water emulsion of 14C-propofol.

Science.gov (United States)

Simons, P J; Cockshott, I D; Douglas, E J; Gordon, E A; Hopkins, K; Rowland, M

1988-04-01

1. An intravenous dose of 14C-propofol (0.47 mg/kg) administered to six male volunteers was rapidly eliminated with 88% recovered in the urine in 5 days and less than 2% in faeces. 2. The dose was cleared by metabolism with less than 0.3% excreted unchanged. The major metabolites were the glucuronic acid conjugate of propofol and the glucuronic acid and sulphate conjugates of its hydroxylated derivative, 2,6-diisopropyl-1,4-quinol. Propofol glucuronide accounted for about 53% of the urinary radioactivity and was the major metabolite in plasma from 30 min post dose. 3. The blood concentration of propofol declined in a biphasic manner from a maximum mean value of 0.44 microgram/ml, 2 min after injection. The half-lives of the first and second exponential phases, mean values 5 min and 97 min respectively, varied widely among subjects. A proportion of the dose was cleared slowly, probably due to slow release from less well perfused tissues. Propofol accounted for 94% of the total blood radioactivity at 2 min but only about 6% from 3 to 8 h post dose. 4. Propofol has a volume of distribution equivalent to about 3 to 4 times body weight, and a mean total body clearance of 2.2 1/min.

Some Investigations on Protease Enzyme Production Kinetics Using Bacillus licheniformis BBRC 100053 and Effects of Inhibitors on Protease Activity

Directory of Open Access Journals (Sweden)

Zahra Ghobadi Nejad

2014-01-01

Full Text Available Due to great commercial application of protease, it is necessary to study kinetic characterization of this enzyme in order to improve design of enzymatic reactors. In this study, mathematical modeling of protease enzyme production kinetics which is derived from Bacillus licheniformis BBRC 100053 was studied (at 37°C, pH 10 after 73 h in stationary phase, and 150 rpm. The aim of the present paper was to determine the best kinetic model and kinetic parameters for production of protease and calculating Ki (inhibition constant of different inhibitors to find the most effective one. The kinetic parameters Km (Michaelis-Menten constant and Vm (maximum rate were calculated 0.626 mM and 0.0523 mM/min. According to the experimental results, using DFP (diisopropyl fluorophosphate and PMSF (phenylmethanesulfonyl fluoride as inhibitors almost 50% of the enzyme activity could be inhibited when their concentrations were 0.525 and 0.541 mM, respectively. Ki for DFP and PMSF were 0.46 and 0.56 mM, respectively. Kinetic analysis showed that the Lineweaver-Burk model was the best fitting model for protease production kinetics DFP was more effective than PMSF and both of them should be covered in the group of noncompetitive inhibitors.

Adaptive processes of the central and autonomic cholinergic neurotransmitter system: Age-related differences

Energy Technology Data Exchange (ETDEWEB)

Fortuna, S.; Pintor, A.; Michalek, H. (Istituto Superiore di Sanita, Rome (Italy))

1991-01-01

Potential age-related differences in the response of the ileum strip longitudinal and circular muscle to repeated treatment with diisopropyl fluorophosphate (DFP) were evaluated in Sprague-Dawley rats. The response was measured in terms of both biochemical parameters (acetylcholinesterase-AChE inhibition, muscarinic acetylcholine receptor binding sites-mAChRs, choline acetyltransferase-ChAT) and functional responsiveness (contractility of the isolated ileum stimulated by cholinergic agonists). The biochemical data were compared with those obtained for the cerebral cortex. In the ileum strip of control rats there was a significant age-related decline of AChE, maximal density of {sup 3}H-QNB binding sites (Bmax) and ChAT. During the first week of DFP treatment the cholinergic syndrome was more pronounced in aged than in young rats, resulting in 35% and 10% mortality, respectively; subsequently the syndrome attenuated. At the end of DFP treatment ileal AChE were inhibited by about 30%; the down-regulation of mAChRs was about 50% in young and 35% in aged rats. No significant differences in the recovery rate of AChE were noted between young and aged rats. On the contrary, mAChRs normalized within 5 weeks in young and 3 weeks in aged rats.

''In vitro'' and ''in vivo'' studies 2,6 - diisopropyl-fenil-carboilmethyl iminodiacetic acid labeled with99mTc (Disida -99mTc)

International Nuclear Information System (INIS)

Martinez, D.Y.F.; Barbosa, M.R.F.F. de; Muramoto, E.; Achando, S.S.; Silva, C.P.G. da.

1988-07-01

The ''in vivo'' and ''in vitro'' studies on DISIDA - 99m Tc at the hepatobiliary level were made. The binding of DISIDA - 99m Tc to plasmatic proteins and the fraction at which this binding occurs were determined. The distribution coefficient in n-octanol/saline solution was 0.41 showing the lipophilicity of the compound. The images in rats show the biological distribution as well as the hepatobiliary clearance of the radiopharmaceutical under its unmetabolized form. (author) [pt

CCDC 813378: Experimental Crystal Structure Determination : trans-bis(1,3-Di-isopropyl-2,3-dihydro-1H-benzimidazol-2-ylidene)-bis(thiocyanato)-nickel

KAUST Repository

Jothibasu, R.; Huang, Kuo-Wei; Huynh, Han Vinh

2011-01-01

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

Study On The Synthesis Of Disida Derivatives For Labeling With 99mTc

International Nuclear Information System (INIS)

Pham Ngoc Dien; Duong Van Dong; Nguyen Thi Thu; Bui Van Cuong; Mai Phuoc Tho; Vo Cam Hoa

2007-01-01

This study describes the synthesis method and characterization of 2,6-Diisopropyl acetanilide iminodiacetic acid (DISIDA). DISIDA is synthesized by replacement reaction of two Clo atoms in chloroacetyl chloride molecule. The synthesis process has two steps. Step1: The synthesis of 2,6-diisopropylacetanilide; Step 2: The synthesis of DISIDA. The good result obtained in the step 1 reaction, it was carried out in the low pH i.e acid medium. The synthesis reaction achieved high performance at room temperature for 2 hours. The product was crystallized completely while adding in mixture reaction amount sodium acetate by drop wise and stir slowly. The step 2 reaction was carried out in medium of alkali (pH = 10-12), reaction temperature was 50 o C - 60 o C, reaction time during 8 hours. After that EtOH was evaporated by vacuum and compound was crystallized with pH = 2-3, in cool medium ( o C ). Raw material was recrystallized many time by cool EtOH. Pure product (DISIDA ) was characterized by IR, LC/MS, HPLC spectroscopy, melting point, crystal picture. Synthesized DISIDA, when tagged with diagnostic radionuclides such as 99m Tc are quite good, 99m Tc-DISIDA Complexes with RC purity and labeling efficiency >98% and above could be prepared by ordinary reaction condition, that reason can apply for valuation of possibility and reality on different purposes. (author)

Reduction of the Work Function of Gold by N-Heterocyclic Carbenes

KAUST Repository

Kim, Hye Kyung

2017-04-12

N-Heterocyclic carbenes (NHCs) bind strongly to gold and other metals. This work experimentally probes the effect of NHCs on the work function (WF) of gold for the first time, theoretically analyzes the origin of this effect, and examines the effectiveness of NHC-modified gold as an electron-injecting electrode. UV photoelectron spectroscopy shows the WF of planar gold is reduced by nearly 2 eV to values of 3.3–3.5 eV. This effect is seen for NHCs with various heterocyclic cores, and with either small or large N,N′-substituents. DFT calculations indicate the WF reduction results from both the interface dipole formed between the NHC and the gold and from the NHC molecular dipole. For N,N′-diisopropyl-NHCs, an important contributor to the former is charge transfer associated with coordination of the carbene carbon atom to gold. In contrast, the carbene carbon of N,N′-2,6-diisopropylphenyl-NHCs is not covalently bound to gold, resulting in a lower interface dipole; however, a larger molecular dipole partially compensates for this. Single-layer C60 diodes with NHC-modified gold as the bottom electrode demonstrate high rectification ratios and show that these electrodes can act as effective electron-injecting contacts, suggesting they may be useful for a variety of materials applications.

High-performance intrinsically microporous dihydroxyl-functionalized triptycene-based polyimide for natural gas separation

KAUST Repository

Alaslai, Nasser Y.; Ghanem, Bader; Alghunaimi, Fahd; Pinnau, Ingo

2016-01-01

A novel polyimide of intrinsic microporosity (PIM-PI) was synthesized from a 9,10-diisopropyl-triptycene-based dianhydride (TPDA) and dihydroxyl-functionalized 4,6-diaminoresorcinol (DAR). The unfunctionalized TPDA-m-phenylenediamine (mPDA) polyimide derivative was made as a reference material to evaluate the effect of the OH group in TPDA-DAR on its gas transport properties. Pure-gas permeability coefficients of He, H2, N2, O2, CH4, and CO2 were measured at 35 °C and 2 atm. The BET surface area based on nitrogen adsorption of dihydroxyl-functionalized TPDA-DAR (308 m2g-1) was 45% lower than that of TPDA-mPDA (565 m2g-1). TPDA-mPDA had a pure-gas CO2 permeability of 349 Barrer and CO2/CH4 selectivity of 32. The dihydroxyl-functionalized TPDA-DAR polyimide exhibited enhanced pure-gas CO2/CH4 selectivity of 46 with a moderate decrease in CO2 permeability to 215 Barrer. The CO2 permeability of TPDA-DAR was ∼30-fold higher than that of a commercial cellulose triacetate membrane coupled with 39% higher pure-gas CO2/CH4 selectivity. The TPDA-based dihydroxyl-containing polyimide showed good plasticization resistance and maintained high mixed-gas selectivity of 38 when tested at a typical CO2 natural gas wellhead CO2 partial pressure of 10 atm.

Health assessment of gasoline and fuel oxygenate vapors: neurotoxicity evaluation.

Science.gov (United States)

O'Callaghan, James P; Daughtrey, Wayne C; Clark, Charles R; Schreiner, Ceinwen A; White, Russell

2014-11-01

Sprague-Dawley rats were exposed via inhalation to vapor condensates of either gasoline or gasoline combined with various fuel oxygenates to assess potential neurotoxicity of evaporative emissions. Test articles included vapor condensates prepared from "baseline gasoline" (BGVC), or gasoline combined with methyl tertiary butyl ether (G/MTBE), ethyl t-butyl ether (G/ETBE), t-amyl methyl ether (G/TAME), diisopropyl ether (G/DIPE), ethanol (G/EtOH), or t-butyl alcohol (G/TBA). Target concentrations were 0, 2000, 10,000 or 20,000mg/mg(3) and exposures were for 6h/day, 5days/week for 13weeks. The functional observation battery (FOB) with the addition of motor activity (MA) testing, hematoxylin and eosin staining of brain tissue sections, and brain regional analysis of glial fibrillary acidic protein (GFAP) were used to assess behavioral changes, traditional neuropathology and astrogliosis, respectively. FOB and MA data for all agents, except G/TBA, were negative. G/TBA behavioral effects resolved during recovery. Neuropathology was negative for all groups. Analyses of GFAP revealed increases in multiplebrain regions largely limited to males of the G/EtOH group, findings indicative of minor gliosis, most significantly in the cerebellum. Small changes (both increases and decreases) in GFAP were observed for other test agents but effects were not consistent across sex, brain region or exposure concentration. Copyright © 2014 Elsevier Inc. All rights reserved.

Efficient modulation of γ-aminobutyric acid type A receptors by piperine derivatives.

Science.gov (United States)

Schöffmann, Angela; Wimmer, Laurin; Goldmann, Daria; Khom, Sophia; Hintersteiner, Juliane; Baburin, Igor; Schwarz, Thomas; Hintersteininger, Michael; Pakfeifer, Peter; Oufir, Mouhssin; Hamburger, Matthias; Erker, Thomas; Ecker, Gerhard F; Mihovilovic, Marko D; Hering, Steffen

2014-07-10

Piperine activates TRPV1 (transient receptor potential vanilloid type 1 receptor) receptors and modulates γ-aminobutyric acid type A receptors (GABAAR). We have synthesized a library of 76 piperine analogues and analyzed their effects on GABAAR by means of a two-microelectrode voltage-clamp technique. GABAAR were expressed in Xenopus laevis oocytes. Structure-activity relationships (SARs) were established to identify structural elements essential for efficiency and potency. Efficiency of piperine derivatives was significantly increased by exchanging the piperidine moiety with either N,N-dipropyl, N,N-diisopropyl, N,N-dibutyl, p-methylpiperidine, or N,N-bis(trifluoroethyl) groups. Potency was enhanced by replacing the piperidine moiety by N,N-dibutyl, N,N-diisobutyl, or N,N-bistrifluoroethyl groups. Linker modifications did not substantially enhance the effect on GABAAR. Compound 23 [(2E,4E)-5-(1,3-benzodioxol-5-yl)-N,N-dipropyl-2,4-pentadienamide] induced the strongest modulation of GABAA (maximal GABA-induced chloride current modulation (IGABA-max = 1673% ± 146%, EC50 = 51.7 ± 9.5 μM), while 25 [(2E,4E)-5-(1,3-benzodioxol-5-yl)-N,N-dibutyl-2,4-pentadienamide] displayed the highest potency (EC50 = 13.8 ± 1.8 μM, IGABA-max = 760% ± 47%). Compound 23 induced significantly stronger anxiolysis in mice than piperine and thus may serve as a starting point for developing novel GABAAR modulators.

A Colorimetric Sensor for Qualitative Discrimination and Quantitative Detection of Volatile Amines

Directory of Open Access Journals (Sweden)

Zhonglin Tang

2010-06-01

Full Text Available We have developed a novel colorimetric sensor based on a digital camera and white LED illumination. Colorimetric sensor arrays (CSAs were made from a set of six chemically responsive dyes impregnated on an inert substrate plate by solution casting. Six common amine aqueous solutions, including dimethylamine, triethylamine, diisopropyl-amine, aniline, cyclohexylamine, and pyridine vaporized at 25 °C and six health-related trimethylamine (TMA concentrations including 170 ppm, 51 ppm, 8 ppm, 2 ppm, 125 ppb and 50 ppb were analyzed by the sensor to test its ability for the qualitative discrimination and quantitative detection of volatile amines. We extracted the feature vectors of the CSA's response to the analytes from a fusional color space, which was obtained by conducting a joint search algorithm of sequential forward selection and sequential backward selection (SFS&SBS based on the linear discriminant criteria (LDC in a mixed color space composed of six common color spaces. The principle component analysis (PCA followed by the hierarchical cluser analysis (HCA were utilized to discriminate 12 analytes. Results showed that the colorimetric sensor grouped the six amine vapors and five TMA concentrations correctly, while TMA concentrations of 125 ppb and 50 ppb were indiscriminable from each other. The limitation of detection (LOD of the sensor for TMA was found to be lower than 50 ppb. The CSAs were reusable for TMA concentrations below 8 ppm.

Human leukocyte and porcine pancreatic elastase: X-ray crystal structures, mechanism, substrate specificity, and mechanism-based inhibitors

International Nuclear Information System (INIS)

Bode, W.; Meyer, E. Jr.; Powers, J.C.

1989-01-01

The serine protease family of enzymes is one of the most widely studied group of enzymes, as evidenced by the fact that more crystal structures are available for individuals of this superfamily than for any other homologous group of enzymes. These enzymes contain a conserved triad of catalytic residues including Ser-195, His-57, and Asp-102. The active-site serine is very nucleophilic, and serine proteases are inhibited by specific serine protease reagents such as diisopropyl phosphorofluoridate (DFP), phenylmethanesulfonyl fluoride, and 3,4-dichloroisocoumarin. Elastases are a group of proteases that possess the ability to cleave the important connective tissue protein elastin. Elastin has the unique property of elastic recoil, is widely distributed in vertebrate tissue, and is particularly abundant in the lungs, arteries, skin, and ligaments. Human neutrophil elastase and pancreatic elastase are two major serine proteases that cleave elastin. Neutrophil elastase is found in the dense granules of polymorphonuclear leukycytes and is essential for phagocytosis and defense against infection by invading microorganisms. Pancreatic elastase is stored as an inactive zymogen in the pancreas and is secreted into the intestines where it becomes activated by trypsin and then participates in digestion. Both elastases cleave substrates at peptide bonds where the P 1 residue is an amino acid residue with a small alkyl side chain

High-performance intrinsically microporous dihydroxyl-functionalized triptycene-based polyimide for natural gas separation

KAUST Repository

Alaslai, Nasser Y.

2016-03-22

A novel polyimide of intrinsic microporosity (PIM-PI) was synthesized from a 9,10-diisopropyl-triptycene-based dianhydride (TPDA) and dihydroxyl-functionalized 4,6-diaminoresorcinol (DAR). The unfunctionalized TPDA-m-phenylenediamine (mPDA) polyimide derivative was made as a reference material to evaluate the effect of the OH group in TPDA-DAR on its gas transport properties. Pure-gas permeability coefficients of He, H2, N2, O2, CH4, and CO2 were measured at 35 °C and 2 atm. The BET surface area based on nitrogen adsorption of dihydroxyl-functionalized TPDA-DAR (308 m2g-1) was 45% lower than that of TPDA-mPDA (565 m2g-1). TPDA-mPDA had a pure-gas CO2 permeability of 349 Barrer and CO2/CH4 selectivity of 32. The dihydroxyl-functionalized TPDA-DAR polyimide exhibited enhanced pure-gas CO2/CH4 selectivity of 46 with a moderate decrease in CO2 permeability to 215 Barrer. The CO2 permeability of TPDA-DAR was ∼30-fold higher than that of a commercial cellulose triacetate membrane coupled with 39% higher pure-gas CO2/CH4 selectivity. The TPDA-based dihydroxyl-containing polyimide showed good plasticization resistance and maintained high mixed-gas selectivity of 38 when tested at a typical CO2 natural gas wellhead CO2 partial pressure of 10 atm.

Evaluation of bile reflux in HIDA images based on fluid mechanics.

Science.gov (United States)

Lo, Rong-Chin; Huang, Wen-Lin; Fan, Yu-Ming

2015-05-01

We propose a new method to help physicians assess, using a hepatobiliary iminodiacetic acid scan image, whether or not there is bile reflux into the stomach. The degree of bile reflux is an important index for clinical diagnosis of stomach diseases. The proposed method applies image-processing technology combined with a hydrodynamic model to determine the extent of bile reflux or whether the duodenum is also folded above the stomach. This condition in 2D dynamic images suggests that bile refluxes into the stomach, when endoscopy shows no bile reflux. In this study, we used optical flow to analyze images from Tc99m-diisopropyl iminodiacetic acid cholescintigraphy (Tc99m-DISIDA) to ascertain the direction and velocity of bile passing through the pylorus. In clinical diagnoses, single photon emission computed tomography (SPECT) is the main clinical tool for evaluating functional images of hepatobiliary metabolism. Computed tomography (CT) shows anatomical images of the external contours of the stomach, liver, and biliary extent. By exploiting the functional fusion of the two kinds of medical image, physicians can obtain a more accurate diagnosis. We accordingly reconstructed 3D images from SPECT and CT to help physicians choose which cross sections to fuse with software and to help them more accurately diagnose the extent and quantity of bile reflux. Copyright © 2015 Elsevier Ltd. All rights reserved.

ANALYSIS AND IDENTIFICATION SPIKING CHEMICAL COMPOUNDS RELATED TO CHEMICAL WEAPON CONVENTION IN UNKNOWN WATER SAMPLES USING GAS CHROMATOGRAPHY AND GAS CHROMATOGRAPHY ELECTRON IONIZATION MASS SPECTROMETRY

Directory of Open Access Journals (Sweden)

Harry Budiman

2010-06-01

Full Text Available The identification and analysis of chemical warfare agents and their degradation products is one of important component for the implementation of the convention. Nowadays, the analytical method for determination chemical warfare agent and their degradation products has been developing and improving. In order to get the sufficient analytical data as recommended by OPCW especially in Proficiency Testing, the spiking chemical compounds related to Chemical Weapon Convention in unknown water sample were determined using two different techniques such as gas chromatography and gas chromatography electron-impact ionization mass spectrometry. Neutral organic extraction, pH 11 organic extraction, cation exchanged-methylation, triethylamine/methanol-silylation were performed to extract the chemical warfare agents from the sample, before analyzing with gas chromatography. The identification of chemical warfare agents was carried out by comparing the mass spectrum of chemicals with mass spectrum reference from the OPCW Central Analytical Database (OCAD library while the retention indices calculation obtained from gas chromatography analysis was used to get the confirmation and supported data of  the chemical warfare agents. Diisopropyl methylphosphonate, 2,2-diphenyl-2-hydroacetic acid and 3-quinuclidinol were found in unknown water sample. Those chemicals were classified in schedule 2 as precursor or reactant of chemical weapons compound in schedule list of Chemical Weapon Convention.   Keywords: gas chromatography, mass spectrometry, retention indices, OCAD library, chemical warfare agents

Reduction of the Work Function of Gold by N-Heterocyclic Carbenes

KAUST Repository

Kim, Hye Kyung; Hyla, Alexander; Winget, Paul; Li, Hong; Wyss, Chelsea M.; Jordan, Abraham J.; Larrain, Felipe A.; Sadighi, Joseph P.; Fuentes-Hernandez, Canek; Kippelen, Bernard; Bredas, Jean-Luc; Barlow, Stephen; Marder, Seth R.

2017-01-01

N-Heterocyclic carbenes (NHCs) bind strongly to gold and other metals. This work experimentally probes the effect of NHCs on the work function (WF) of gold for the first time, theoretically analyzes the origin of this effect, and examines the effectiveness of NHC-modified gold as an electron-injecting electrode. UV photoelectron spectroscopy shows the WF of planar gold is reduced by nearly 2 eV to values of 3.3–3.5 eV. This effect is seen for NHCs with various heterocyclic cores, and with either small or large N,N′-substituents. DFT calculations indicate the WF reduction results from both the interface dipole formed between the NHC and the gold and from the NHC molecular dipole. For N,N′-diisopropyl-NHCs, an important contributor to the former is charge transfer associated with coordination of the carbene carbon atom to gold. In contrast, the carbene carbon of N,N′-2,6-diisopropylphenyl-NHCs is not covalently bound to gold, resulting in a lower interface dipole; however, a larger molecular dipole partially compensates for this. Single-layer C60 diodes with NHC-modified gold as the bottom electrode demonstrate high rectification ratios and show that these electrodes can act as effective electron-injecting contacts, suggesting they may be useful for a variety of materials applications.

Improved hepatocyte function of future liver remnant of cirrhotic rats after portal vein ligation: a bonus other than volume shifting.

Science.gov (United States)

Lin, Kun-Ju; Liao, Chien-Hung; Hsiao, Ing-Tsung; Yen, Tzu-Chen; Chen, Tse-Ching; Jan, Yi-Yin; Chen, Miin-Fu; Yeh, Ta-Sen

2009-02-01

Preoperative portal vein embolization is increasingly employed for those with hepatocellular carcinoma and cirrhosis to gain a volume-shifting effect. However, the alterations of histologic architecture and hepatocyte function of future liver remnant (FLR) remain unexplored. Portal vein ligation (PVL) was performed in cirrhotic and noncirrhotic rats. Regeneration indices that include the DNA synthesis index, restituted liver mass, and the redistributed volume ratio were measured. The indocyanine green 15' retention test (ICG-R15), histologic changes, total Knodell score, and activated hepatic stellate cells (HSCs) were measured before and after PVL. Tc-99m sulfur-colloid liver single photon emission computed tomography (SPECT) and diisopropyl iminoacetic acid (DISIDA) SPECT were conducted. The redistributed volume ratio of cirrhotic rats was less than noncirrhotic rats (63% vs 80%, P baseline (6.0 +/- 4.1% vs 15.8 +/- 4.6%, P baseline. The redistributed volume ratio of noncirrhotic and cirrhotic rats based on 99mTc sulfur-colloid SPECT were 79% and 64%, respectively. The clearance T(1/2) of FLR in cirrhotic rats based on DISIDA SPECT was decreased compared with baseline (5.2 +/- 1.9 min vs 8.6 +/- 3.1 min). The regenerated functional liver mass of cirrhotic rats after PVL is less than noncirrhotic rats, whereas the hepatocyte function of FLR in cirrhotic rats is improved relevant to tissue remodeling.

Purification and characterization of protease Re, a cytoplasmic endoprotease in Escherichia coli

Energy Technology Data Exchange (ETDEWEB)

Park, J.H.; Lee, Y.S.; Chung, C.H.; Goldberg, A.L.

1988-02-01

Protease Re, a new cytoplasmic endoprotease in Escherichia coli, was purified to homogeneity by conventional procedures, using (/sup 3/H) casein as the substrate. The enzyme consists of a single polypeptide of 82,000 molecular weight. It is maximally active between pH 7 and 8.5 and is independent of ATP. It has a pI of 6.8 and a K/sub m/ of 10.8 ..mu..M for casein. Since diisopropyl fluorophosphate and phenylmethylsulfonyl fluoride inhibited this enzyme, it appears to be a serine protease. Protease Re was sensitive to inhibition by L-1-tosylamido-2-phenylethylchloromethylketone but not to that by 1-chloro-3-tosylamido-7-aminoheptanone, thiol-blocking reagents, chelating agents, or various peptide aldehydes. Re also degraded (/sup 125/I) globin, (/sup 125/I) glucagon, and /sup 125/I-labeled denatured bovine serum albumin to acid-soluble products (generally oligopeptides of > 1500 daltons), but it showed no activity against serum albumin, growth hormone, insulin, or a variety of fluorometric peptide substrates. It also hydrolyzed oxidatively inactivated glutamine synthetase (generated by ascorbate, oxygen, and iron) four- to fivefold more rapidly than the native protein. Protease Re appears to be identical to the proteolytic enzyme isolated by Roseman and Levine by its ability to degrade selectively oxidatively damaged glutamine synthetase in vivo. Its role in intracellular protein breakdown is uncertain.

Characterization of acetylcholinesterase-inhibition by itopride.

Science.gov (United States)

Iwanaga, Y; Kimura, T; Miyashita, N; Morikawa, K; Nagata, O; Itoh, Z; Kondo, Y

1994-11-01

Itopride is a gastroprokinetic benzamide derivative. This agent inhibited both electric eel acetylcholinesterase (AChE) and horse serum butyrylcholinesterase (BuChE). The IC50 of itopride with AChE (2.04 +/- 0.27 microM) was, however, 100-fold less than that with BuChE, whereas in the case of neostigmine with AChE (11.3 +/- 3.4 nM), it was 10-fold less. The recovery of AChE activity inhibited by 10(-7) M neostigmine was partial, but that inhibited by up to 3 x 10(-5) M itopride was complete when the reaction mixture was subjected to ultrafiltration. Double reciprocal plots of the experimental data showed that both Km and Vmax were affected by itopride, suggesting that the inhibition is a "mixed" type, although primarily being an uncompetitive one. The inhibitory effect of itopride on cholinesterase (ChE) activity in guinea pig gastrointestine was much weaker than that on pure AChE. However, in the presence of a low dose of diisopropyl fluorophosphate, just enough to inhibit BuChE but not AChE, the IC50s of itopride against ChE activities were found to be about 0.5 microM. In conclusion, itopride exerts reversible and a "mixed" type of inhibition preferably against AChE. The IC50 of itopride for electric eel and guinea pig gastrointestinal AChE inhibition was 200 times and 50 times as large as that of neostigmine, respectively.

In vitro comparison of rat and chicken brain neurotoxic esterase

International Nuclear Information System (INIS)

Novak, R.; Padilla, S.

1986-01-01

A systematic comparison was undertaken to characterize neurotoxic esterase (NTE) from rat and chicken brain in terms of inhibitor sensitivities, pH optima, and molecular weights. Paraoxon titration of phenyl valerate (PV)-hydrolyzing carboxylesterases showed that rat esterases were more sensitive than chicken to paraoxon inhibition at concentrations less than or equal to microM and superimposable with chicken esterases at concentrations of 2.5-1000 microM. Mipafox titration of the paraoxon-resistant esterases at a fixed paraoxon concentration of 100 microM (mipafox concentration: 0-1000 microM) resulted in a mipafox I50 of 7.3 microM for chicken brain NTE and 11.6 microM for rat brain NTE. NTE (i.e., paraoxon-resistant, mipafox-sensitive esterase activity) comprised 80% of chicken and 60% of rat brain paraoxon-resistant activity with the specific activity of chicken brain NTE approximately twice that of rat brain NTE. The pH maxima for NTE from both species was similar showing broad, slightly alkaline optima from pH 7.9 to 8.6. [ 3 H]Diisopropyl phosphorofluoridate (DFP)-labeled NTE from the brains of both species had an apparent mol wt of 160,000 measured by sodium dodecyl sulfate polyacrylamide gel electrophoresis. In conclusion, NTE from both species was very similar, with the mipafox I50 for rat NTE within the range of reported values for chicken and human NTE, and the inhibitor parameters of the chicken NTE assay were applicable for the rat NTE assay

Health assessment of gasoline and fuel oxygenate vapors: reproductive toxicity assessment.

Science.gov (United States)

Gray, Thomas M; Steup, David; Roberts, Linda G; O'Callaghan, James P; Hoffman, Gary; Schreiner, Ceinwen A; Clark, Charles R

2014-11-01

Vapor condensates of baseline gasoline (BGVC), or gasoline-blended with methyl tertiary butyl ether (G/MTBE), ethyl t-butyl ether (G/ETBE), t-amyl methyl ether (G/TAME), diisopropyl ether (G/DIPE), ethanol (G/EtOH), or t-butyl alcohol (G/TBA) were evaluated for reproductive toxicity in rats at target concentrations of 2000, 10,000, or 20,000mg/m(3), 6h/day, 7days/week. BGVC and G/MTBE were assessed over two generations, the others for one generation. BGVC and G/MTBE F1 offspring were evaluated for neuropathology and changes in regional brain glial fibrillary acidic protein content. No neurotoxicity was observed. Male kidney weight was increased consistent with light hydrocarbon nephropathy. In adult rats, decreased body weight gain and increased liver weight were seen. Spleen weight decreased in adults and pups exposed to G/TBA. No pathological changes to reproductive organs occurred in any study. Decreased food consumption was seen in G/TAME lactating females. Transient decreases in G/TAME offspring weights were observed during lactation. Except for a minor increase in time to mating in G/TBA which did not affect other reproductive parameters, there were no adverse reproductive findings. The NOAEL for reproductive and offspring parameters was 20,000mg/m(3) for all vapor condensates except for lower offspring NOAELs of 10,000mg/m(3) for G/TBA and 2000mg/m(3) for G/TAME. Copyright © 2014 Elsevier Inc. All rights reserved.

Health assessment of gasoline and fuel oxygenate vapors: micronucleus and sister chromatid exchange evaluations.

Science.gov (United States)

Schreiner, Ceinwen A; Hoffman, Gary M; Gudi, Ramadevi; Clark, Charles R

2014-11-01

Micronucleus and sister chromatid exchange (SCE) tests were performed for vapor condensate of baseline gasoline (BGVC), or gasoline with oxygenates, methyl tert-butyl ether (G/MTBE), ethyl tert butyl ether (G/ETBE), t-amyl methyl ether (G/TAME), diisopropyl ether (G/DIPE), t-butyl alcohol (TBA), or ethanol (G/EtOH). Sprague Dawley rats (the same 5/sex/group for both endpoints) were exposed to 0, 2000, 10,000, or 20,000mg/m(3) of each condensate, 6h/day, 5days/week over 4weeks. Positive controls (5/sex/test) were given cyclophosphamide IP, 24h prior to sacrifice at 5mg/kg (SCE test) and 40mg/kg (micronucleus test). Blood was collected from the abdominal aorta for the SCE test and femurs removed for the micronucleus test. Blood cell cultures were treated with 5μg/ml bromodeoxyuridine (BrdU) for SCE evaluation. No significant increases in micronucleated immature erythrocytes were observed for any test material. Statistically significant increases in SCE were observed in rats given BGVC alone or in female rats given G/MTBE. G/TAME induced increased SCE in both sexes at the highest dose only. Although DNA perturbation was observed for several samples, DNA damage was not expressed as increased micronuclei in bone marrow cells. Inclusion of oxygenates in gasoline did not increase the effects of gasoline alone or produce a cytogenetic hazard. Copyright © 2014 Elsevier Inc. All rights reserved.

Purification of lysosomal phospholipase A and demonstration of proteins that inhibit phospholipase A in a lysosomal fraction from rat kidney cortex

International Nuclear Information System (INIS)

Hostetler, K.Y.; Gardner, M.F.; Giordano, J.R.

1986-01-01

Phospholipase A has been isolated from a crude lysosomal fraction from rat kidney cortex and purified 7600-fold with a recovery of 9.8% of the starting activity. The purified enzyme is a glycoprotein having an isoelectric point of pH 5.4 and an apparent molecular weight of 30,000 by high-pressure liquid chromatography gel permeation. Naturally occurring inhibitors of lysosomal phospholipase A are present in two of the lysosomal-soluble protein fractions obtained in the purification. They inhibit hydrolysis of 1,2-di[1- 14 C]oleoylphosphatidylcholine by purified phospholipase A 1 with IC 50 values of 7-11 μg. The inhibition is abolished by preincubation with trypsin at 37 0 C, but preincubation with trypsin at 4 0 C has no effect, providing evidence that the inhibitors are proteins. The results suggest that the activity of lysosomal phospholipase A may be regulated in part by inhibitory proteins. Lysosomal phospholipase A from rat kidney hydrolyzes the sn-1 acyl group of phosphatidylcholine, does not require divalent cations for full activity, and is not inhibited by ethylenediaminetetraacetic acid. It has an acid pH optimum of 3.6-3.8. Neither rho-bromophenacyl bromide, diisopropyl fluorophosphate, nor mercuric ion inhibits phospholipase A 1 . In contrast to rat liver, which has two major isoenzymes of acid phospholipase A 1 , kidney cortex has only one isoenzyme of lysosomal phospholipase A 1

Health assessment of gasoline and fuel oxygenate vapors: subchronic inhalation toxicity.

Science.gov (United States)

Clark, Charles R; Schreiner, Ceinwen A; Parker, Craig M; Gray, Thomas M; Hoffman, Gary M

2014-11-01

Sprague Dawley rats were exposed via inhalation to vapor condensates of either gasoline or gasoline combined with various fuel oxygenates to assess whether their use in gasoline influences the hazard of evaporative emissions. Test substances included vapor condensates prepared from an EPA described "baseline gasoline" (BGVC), or gasoline combined with methyl tertiary butyl ether (G/MTBE), ethyl t-butyl ether (G/ETBE), t-amyl methyl ether (G/TAME), diisopropyl ether (G/DIPE), ethanol (G/EtOH), or t-butyl alcohol (G/TBA). Target concentrations were 0, 2000, 10,000 or 20,000mg/m(3) and exposures were for 6h/day, 5days/week for 13weeks. A portion of the animals were maintained for a four week recovery period to determine the reversibility of potential adverse effects. Increased kidney weight and light hydrocarbon nephropathy (LHN) were observed in treated male rats in all studies which were reversible or nearly reversible after 4weeks recovery. LHN is unique to male rats and is not relevant to human toxicity. The no observed effect level (NOAEL) in all studies was 10,000mg/m(3), except for G/MTBE (<2000) and G/TBA (2000). The results provide evidence that use of the studied oxygenates are unlikely to increase the hazard of evaporative emissions during refueling, compared to those from gasoline alone. Copyright © 2014 The Authors. Published by Elsevier Inc. All rights reserved.

Health assessment of gasoline and fuel oxygenate vapors: developmental toxicity in rats.

Science.gov (United States)

Roberts, Linda G; Gray, Thomas M; Trimmer, Gary W; Parker, Robert M; Murray, F Jay; Schreiner, Ceinwen A; Clark, Charles R

2014-11-01

Gasoline-vapor condensate (BGVC) or condensed vapors from gasoline blended with methyl t-butyl ether (G/MTBE), ethyl t-butyl ether (G/ETBE), t-amyl methyl ether (G/TAME) diisopropyl ether (G/DIPE), ethanol (G/EtOH), or t-butyl alcohol (G/TBA) were evaluated for developmental toxicity in Sprague-Dawley rats exposed via inhalation on gestation days (GD) 5-20 for 6h/day at levels of 0 (control filtered air), 2000, 10,000, and 20,000mg/m(3). These exposure durations and levels substantially exceed typical consumer exposure during refueling (<1-7mg/m(3), 5min). Dose responsive maternal effects were reduced maternal body weight and/or weight change, and/or reduced food consumption. No significant malformations were seen in any study. Developmental effects occurred at 20,000mg/m(3) of G/TAME (reduced fetal body weight, increased incidence of stunted fetuses), G/TBA (reduced fetal body weight, increased skeletal variants) and G/DIPE (reduced fetal weight) resulting in developmental NOAEL of 10,000mg/m(3) for these materials. Developmental NOAELs for other materials were 20,000mg/m(3) as no developmental toxicity was induced in those studies. Developmental NOAELs were equal to or greater than the concurrent maternal NOAELs which ranged from 2000 to 20,000mg/m(3). There were no clear cut differences in developmental toxicity between vapors of gasoline and gasoline blended with the ether or alcohol oxygenates. Copyright © 2014 Elsevier Inc. All rights reserved.

Accessibility of receptor-bound urokinase to type-1 plasminogen activator inhibitor

Energy Technology Data Exchange (ETDEWEB)

Cubellis, M.V.; Andreasen, P.; Ragno, P.; Mayer, M.; Dano, K.; Blasi, F. (Univ. of Copenhagen (Denmark))

1989-07-01

Urokinase plasminogen activator (uPA) interacts with a surface receptor and with specific inhibitors, such as plasminogen activator inhibitor type 1 (PAI-1). These interactions are mediated by two functionally independent domains of the molecule: the catalytic domain (at the carboxyl terminus) and the growth factor domain (at the amino terminus). The authors have now investigated whether PAI-1 can bind and inhibit receptor-bound uPA. Binding of {sup 125}I-labeled ATF (amino-terminal fragment of uPA) to human U937 monocyte-like cells can be competed for by uPA-PAI-1 complexes, but not by PAI-1 alone. Preformed {sup 125}I-labeled uPA-PAI-1 complexes can bind to uPA receptor with the same binding specificity as uPA. PAI-1 also binds to, and inhibits the activity of, receptor-bound uPA in U937 cells, as shown in U937 cells by a caseinolytic plaque assay. Plasminogen activator activity of these cells is dependent on exogenous uPA, is competed for by receptor-binding diisopropyl fluorophosphate-treated uPA, and is inhibited by the addition of PAI-1. In conclusion, in U937 cells the binding to the receptor does not shield uPA from the action of PAI-1. The possibility that in adherent cells a different localization of PAI-1 and uPA leads to protection of uPA from PAI-1 is to be considered.

Purification of lysosomal phospholipase A and demonstration of proteins that inhibit phospholipase A in a lysosomal fraction from rat kidney cortex

Energy Technology Data Exchange (ETDEWEB)

Hostetler, K.Y.; Gardner, M.F.; Giordano, J.R.

1986-10-21

Phospholipase A has been isolated from a crude lysosomal fraction from rat kidney cortex and purified 7600-fold with a recovery of 9.8% of the starting activity. The purified enzyme is a glycoprotein having an isoelectric point of pH 5.4 and an apparent molecular weight of 30,000 by high-pressure liquid chromatography gel permeation. Naturally occurring inhibitors of lysosomal phospholipase A are present in two of the lysosomal-soluble protein fractions obtained in the purification. They inhibit hydrolysis of 1,2-di(1-/sup 14/C)oleoylphosphatidylcholine by purified phospholipase A/sub 1/ with IC/sub 50/ values of 7-11 ..mu..g. The inhibition is abolished by preincubation with trypsin at 37/sup 0/C, but preincubation with trypsin at 4/sup 0/C has no effect, providing evidence that the inhibitors are proteins. The results suggest that the activity of lysosomal phospholipase A may be regulated in part by inhibitory proteins. Lysosomal phospholipase A from rat kidney hydrolyzes the sn-1 acyl group of phosphatidylcholine, does not require divalent cations for full activity, and is not inhibited by ethylenediaminetetraacetic acid. It has an acid pH optimum of 3.6-3.8. Neither rho-bromophenacyl bromide, diisopropyl fluorophosphate, nor mercuric ion inhibits phospholipase A/sub 1/. In contrast to rat liver, which has two major isoenzymes of acid phospholipase A/sub 1/, kidney cortex has only one isoenzyme of lysosomal phospholipase A/sub 1/.

Substitution of valine for glycine-558 in the congenital dysthrombin thrombin Quick II alters primary substrate specificity

Energy Technology Data Exchange (ETDEWEB)

Henriksen, R.A.; Mann, K.G. (Univ. of Vermont, Burlington (USA))

1989-03-07

Thrombin Quick II is one of two dysfunctional forms of thrombin derived from the previously described congenital dysprothrombin prothrombin Quick. Thrombin Quick II does not clot fibrinogen, hydrolyze p-nitroanilide substrates of thrombin, or bind N{sup 2}-(5-(dimethylamino)naphthalene-1-sulfonyl)arginine N,N-(3-ethyl-1,5-pentanediyl)amide, a high-affinity competitive inhibitor of thrombin. To determine the structural alteration in thrombin Quick II, the reduced, carboxymethylated protein was hydrolyzed by a lysyl endopeptidase. A peptide not present in a parallel thrombin hydrolysate was identified by reverse-phase chromatography. This Gly residue, which is highly conserved in the chymotrypsin family of serine proteases, forms part of the substrate binding pocket for bulky aromatic and basic side chains in chymotrypsin and trypsin, respectively. However, in porcine elastase 1, the corresponding residue is threonine. Consistent with the identified structural alteration, thrombin Quick II incorporates ({sup 3}H)diisopropyl fluorophosphate stoichiometrically and hydrolyzes the elastase substrate succinyl-Ala-Ala-Pro-Leu-p-nitroanilide with a relative k{sub cat}/K{sub M} of 0.14 when compared to thrombin. This results from a 3-fold increase in K{sub M} and a 2.5-fold decrease in k{sub cat} for thrombin Quick II when compared to thrombin acting on the same substrate. These results and those of other investigators studying mutant trypsins support the conclusion that the catalytic activity of serine proteases is very sensitive to structural alterations in the primary substrate binding pocket.

A novel monocyclic triterpenoid and a norsesquaterpenol from the aerial parts of Suaeda monoica Forssk. ex J.F. Gmel with cell proliferative potential

Directory of Open Access Journals (Sweden)

Mansour S. Al-Said

2017-11-01

Full Text Available Suaeda monoica Forssk. ex J.F. Gmel (Chenopodiaceae, a mangrove herb, is distributed in tropical Africa, Arabian Peninsula, India, Pakistan, Palestine and Jordan. The plant parts are used to treat sore throat, hepatitis, wounds, rheumatism, paralysis, asthma, snakebites, skin disease and ulcer. Two new phytoconstituents characterized as 13,17-octahydropentalene-4,4,10,23-tetramethyl-17,21-diisopropyl-tetradecahydrocyclo-[a]-phenanthrene-(14, 20(23, 21(30-trien-5α-ol (SMC-3 and [1,4,4-trimethyl-cyclopent-1(5-enyl]-9,10,17,21-tetramethyl-9α-ol-16α (17α-epoxy heptadecan-6,10-dione (SMC-4 belong to the class norsesquaterpenol and monocyclic triterpenoid, respectively, along with two known compounds 3-epi-lupeol (SMC-1 and 4-cyclopentylpyrocatechol (SMC-2 have been isolated from the ethanol extract of aerial parts of S. monoica using normal and reverse phase column as well as planar chromatography. The spectroscopic studies including 1D, 2D NMR (DEPT, COSY, HMBC and HSQC aided by EIMS mass and IR spectra were used to establish their structures. All the four compounds were tested for cytotoxicity on cultured HepG2 cells and for cell proliferation activities. The results revealed no cytotoxicity even at highest (6.25–50 μg/ml dose of all the four compounds. The compound SMC-1 showed prominent cell proliferative activity as compared to other SMC compounds.

CCDC 849284: Experimental Crystal Structure Determination : Dichloro-(2,6-diisopropyl-N-(1-(6-(1H-pyrazol-1-yl)pyridin-2-yl)ethylidene)aniline)-cobalt(ii)

KAUST Repository

Gong, Dirong; Jia, Weiguo; Chen, Tao; Huang, Kuo-Wei

2013-01-01

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from

CCDC 849284: Experimental Crystal Structure Determination : Dichloro-(2,6-diisopropyl-N-(1-(6-(1H-pyrazol-1-yl)pyridin-2-yl)ethylidene)aniline)-cobalt(ii)

KAUST Repository

Gong, Dirong

2013-01-01

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

A multi-purpose tool for food inspection: Simultaneous determination of various classes of preservatives and biogenic amines in meat and fish products by LC-MS.

Science.gov (United States)

Molognoni, Luciano; Daguer, Heitor; de Sá Ploêncio, Leandro Antunes; De Dea Lindner, Juliano

2018-02-01

This paper describes an innovative fast and multipurpose method for the chemical inspection of meat and fish products by liquid chromatography-tandem mass spectrometry. Solid-liquid extraction and low temperature partitioning were applied to 17 analytes, which included large bacteriocins (3.5kDa) and small molecules (organic acids, heterocyclic compounds, polyene macrolides, alkyl esters of the p-hydroxybenzoic acid, aromatic, and aliphatic biogenic amines and polyamines). Chromatographic separation was achieved in 10min, using stationary phase of di-isopropyl-3-aminopropyl silane bound to hydroxylated silica. Method validation was in accordance to Commission Decision 657/2002/CE. Linear ranges were among 1.25-10.0mgkg -1 (natamycin and parabens), 2.50-10.0mgkg -1 (sorbate and nisin), 25.0-200mgkg -1 (biogenic amines, hexamethylenetetramine, benzoic and lactic acids), and 50.0-400mgkg -1 (citric acid). Expanded measurement uncertainty (U) was estimated by single laboratory validation combined to modeling in two calculation approaches: internal (U = 5%) and external standardization (U = 24%). Method applicability was checked on 89 real samples among raw, cooked, dry fermented and cured products, yielding acceptable recoveries. Many regulatory issues were revealed, corroborating the need for enhancement of the current analytical methods. This simple execution method dispenses the use of additional procedures of extraction and, therefore, reduces costs over time. It is suitable for routine analysis as a screening or confirmatory tool for both qualitative and quantitative results, replacing many time consuming analytical procedures. Copyright © 2017 Elsevier B.V. All rights reserved.

Health assessment of gasoline and fuel oxygenate vapors: immunotoxicity evaluation.

Science.gov (United States)

White, Kimber L; Peachee, Vanessa L; Armstrong, Sarah R; Twerdok, Lorraine E; Clark, Charles R; Schreiner, Ceinwen A

2014-11-01

Female Sprague Dawley rats were exposed via inhalation to vapor condensates of either gasoline or gasoline combined with various fuel oxygenates to assess potential immunotoxicity of evaporative emissions. Test articles included vapor condensates prepared from "baseline gasoline" (BGVC), or gasoline combined with methyl tertiary butyl ether (G/MTBE), ethyl t-butyl ether (G/ETBE), t-amyl methyl ether (G/TAME), diisopropyl ether (G/DIPE), ethanol (G/EtOH), or t-butyl alcohol (G/TBA). Target concentrations were 0, 2000, 10,000 or 20,000mg/mg(3) administered for 6h/day, 5days/week for 4weeks. The antibody-forming cell (AFC) response to the T-dependent antigen, sheep erythrocyte (sRBC), was used to determine the effects of the gasoline vapor condensates on the humoral components of the immune system. Exposure to BGVC, G/MTBE, G/TAME, and G/TBA did not result in significant changes in the IgM AFC response to sRBC, when evaluated as either specific activity (AFC/10(6) spleen cells) or as total spleen activity (AFC/spleen). Exposure to G/EtOH and G/DIPE resulted in a dose-dependent decrease in the AFC response, reaching the level of statistical significance only at the high 20,000mg/m(3) level. Exposure to G/ETBE resulted in a statistically significant decrease in the AFC response at the middle (10,000mg/m(3)) and high (20,000mg/m(3)) exposure concentrations. Copyright © 2014 Elsevier Inc. All rights reserved.

Measurement and prediction of aromatic solute distribution coefficients for aqueous-organic solvent systems. Final report

Energy Technology Data Exchange (ETDEWEB)

Campbell, J.R.; Luthy, R.G.

1984-06-01

Experimental and modeling activities were performed to assess techniques for measurement and prediction of distribution coefficients for aromatic solutes between water and immiscible organic solvents. Experiments were performed to measure distribution coefficients in both clean water and wastewater systems, and to assess treatment of a wastewater by solvent extraction. The theoretical portions of this investigation were directed towards development of techniques for prediction of solute-solvent/water distribution coefficients. Experiments were performed to assess treatment of a phenolic-laden coal conversion wastewater by solvent extraction. The results showed that solvent extraction for recovery of phenolic material offered several wastewater processing advantages. Distribution coefficients were measured in clean water and wastewater systems for aromatic solutes of varying functionality with different solvent types. It was found that distribution coefficients for these compounds in clean water systems were not statistically different from distribution coefficients determined in a complex coal conversion process wastewater. These and other aromatic solute distribution coefficient data were employed for evaluation of modeling techniques for prediction of solute-solvent/water distribution coefficients. Eight solvents were selected in order to represent various chemical classes: toluene and benzene (aromatics), hexane and heptane (alkanes), n-octanol (alcohols), n-butyl acetate (esters), diisopropyl ether (ethers), and methylisobutyl ketone (ketones). The aromatic solutes included: nonpolar compounds such as benzene, toluene and naphthalene, phenolic compounds such as phenol, cresol and catechol, nitrogenous aromatics such as aniline, pyridine and aminonaphthalene, and other aromatic solutes such as naphthol, quinolinol and halogenated compounds. 100 references, 20 figures, 34 tables.

Synthesis and physico-chemical characterization of CeO2/ZrO2-SO42- mixed oxides

International Nuclear Information System (INIS)

Hernandez E, J. M.; Silva R, R.; Garcia A, R.; Garcia S, L. A.; Handy, B. E.; Cardenas G, G.; Cueto H, A.

2012-01-01

Environmentally friendly solid-acid catalysts CeO 2 /ZrO 2 -SO 4 2- were prepared by the sol gel method varying CeO 2 content (10, 20 and 30 wt %) and using sulfation in situ, maintaining the sulfate ions amount present in the materials at 20 wt %. ZrO 2 and ZrO 2 -SO 4 2- were also prepared for comparison proposes using the same synthesis method. The materials were characterized by X-ray diffraction, nitrogen physisorption, potentiometric titration with n-butylamine, decomposition of 2-propanol and n-pentane isomerization. The specific surface area of ZrO 2 -SO 4 2- was high (160 m 2 /g) compared with the unmodified ZrO 2 (80 m 2 /g), however this area decreased with increasing the CeO 2 content (37-100 m 2 /g). There was no significant effect of CeO 2 on the tetragonal structure of ZrO 2 -SO 4 2- . The variation of acid sites amount runs parallel to the change of specific surface area. The acid sites amount decreased with increasing cerium oxide content. The decomposition of 2-propanol results fundamentally in the formation of dehydration products such as propylene and diisopropyl ether, both involving acid sites. In addition, a good performance during the n-pentane isomerization was observed for these materials. The selectivity towards isopentane reaches 84% when the Pt/CeO 2 /ZrO 2 -SO 4 2- catalyst with the highest CeO 2 content was used. (Author)

Redetermined structure of gossypol (P3 polymorph

Directory of Open Access Journals (Sweden)

Muhabbat Honkeldieva

2015-07-01

Full Text Available An improved crystal structure of the title compound, C30H30O8 (systematic name: 1,1′,6,6′,7,7′-hexahydroxy-5,5′-diisopropyl-3,3′-dimethyl[2,2′-binaphthalene]-8,8′-dicarbaldehyde, was determined based on modern CCD data. Compared to the previous structure [Talipov et al. (1985. Khim. Prirod. Soedin. (Chem. Nat. Prod., 6, 20–24], geometrical precision has been improved (typical C—C bond-distance s.u. = 0.002 Å in the present structure compared to 0.005 Å in the previous structure and the locations of several H atoms have been corrected. The gossypol molecules are in the aldehyde tautomeric form and the dihedral angle between the naphthyl fragments is 80.42 (4°. Four intramolecular O—H...O hydrogen bonds are formed. In the crystal, inversion dimers with graph-set motif R22(20 are formed by pairs of O—H...O hydrogen bonds; another pair of O—H...O hydrogen bonds with the same graph-set motif links the dimers into [001] chains. The packing of such chains in the crystal leads to the formation of channels (diameter = 5–8 Å propagating in the [101] direction. The channels presumably contain highly disordered solvent molecules; their contribution to the scattering was removed with the SQUEEZE [Spek (2015. Acta Cryst. C71, 9–18] routine in PLATON and the stated molecular mass, density etc., do not take them into account.

Flexible carbon nanotube sensors for nerve agent simulants

Energy Technology Data Exchange (ETDEWEB)

Cattanach, Kyle; Kulkarni, Rashmi D; Kozlov, Mikhail; Manohar, Sanjeev K [Alan G MacDiarmid Center for Innovation, Department of Chemistry, University of Texas at Dallas, Richardson 75083-0688 (United States)

2006-08-28

Chemiresistor-based vapour sensors made from network films of single-walled carbon nanotube (SWNT) bundles on flexible plastic substrates (polyethylene terephthalate, PET) can be used to detect chemical warfare agent simulants for the nerve agents Sarin (diisopropyl methylphosphonate, DIMP) and Soman (dimethyl methylphosphonate, DMMP). Large, reproducible resistance changes (75-150%), are observed upon exposure to DIMP or DMMP vapours, and concentrations as low as 25 ppm can be detected. Robust sensor response to simulant vapours is observed even in the presence of large equilibrium concentrations of interferent vapours commonly found in battle-space environments, such as hexane, xylene and water (10 000 ppm each), suggesting that both DIMP and DMMP vapours are capable of selectively displacing other vapours from the walls of the SWNTs. Response to these interferent vapours can be effectively filtered out by using a 2 {mu}m thick barrier film of the chemoselective polymer polyisobutylene (PIB) on the SWNT surface. These network films are composed of a 1-2 {mu}m thick non-woven mesh of SWNT bundles (15-30 nm diameter), whose sensor response is qualitatively and quantitatively different from previous studies on individual SWNTs, or a network of individual SWNTs, suggesting that vapour sorption at interbundle sites could be playing an important role. This study also shows that the line patterning method used in device fabrication to obtain any desired pattern of films of SWNTs on flexible substrates can be used to rapidly screen simulants at high concentrations before developing more complicated sensor systems.

Rapid degradation of D- and L-succinimide-containing peptides by a post-proline endopeptidase from human erythrocytes

Energy Technology Data Exchange (ETDEWEB)

Momand, J.; Clarke, S.

1987-12-01

The authors have been interested in the metabolic fate of proteins containing aspartyl succinimide (Asu) residues. These residues can be derived from the spontaneous rearrangement of Asp and Asn residues and from the spontaneous demethylation of enzymatically methylated L-isoAsp and D-Asp residues. Incubation of the synthetic hexapeptide N-Ac-Val-Tyr-Pro-Asu-Gly-Ala with the cytosolic fraction of human erythrocytes resulted in rapid cleavage of the prolyl-aspartyl succinimide bond producing the tripeptide N-Ac-Val-Try-Pro. The rate of this reaction is equal for both L- and D-Asu-containing peptides and is 10-fold greater that the rate of cleavage of a corresponding peptide containing a normal Pro-Asp linkage. When the aspartyl succinimide ring was replaced with an isoaspartyl residue, the cleavage rate was about 5 times that of the normal Pro-Asp peptide. The tripeptide-producing activity copurified on DEAE-cellulose chromatography with an activity that cleaves N-carbobenzoxy-Gly-Pro-4-methylcoumarin-7-amide, a post-proline endopeptidase substrate. These two activities were both inhibited by an antiserum to rat brain post-proline endopeptidase, and it appears that they are catalyzed by the same enzyme. This enzyme has a molecular weight of approximately 80,000 and is covalently labeled and inhibited by (/sup 3/H) diisopropyl fluorophosphate. The facile cleavage of the succinimide- and isoaspartyl-containing peptides by this post-proline endopeptidase suggests that it may play a role in the metabolism of peptides containing altered aspartyl residues.

Labeling of peripheral blood polymorphonuclear leukocytes with indium-111: a new method for the quantitation of in-vivo accumulation of PMNLs in rabbit skin

Energy Technology Data Exchange (ETDEWEB)

Wahba, A.V.; Barnes, B.; Lazarus, G.S.

1984-02-01

A precise method for quantitation of polymorphonuclear leukocyte (PMNL) accumulation in skin in vivo, has been developed so that the proinflammatory effects of various agents can be compared. This method can also be used to evaluate the effect of therapeutic agents on PMNL accumulation in vivo. Rabbit PMNLs were purified from heparinized blood by dextran sedimentation, hypotonic lysis, and separation on Ficoll-Hypaque. The PMNLs were labeled with 3-5 microCi per 10(6) cells of /sup 111/In oxine and reinfused coincidentally with different concentrations of different chemotactic and proinflammatory materials injected intradermally into the back. In some experiments, varying concentrations of acetic acid were applied topically. Four to 18 hours later, the rabbits were sacrificed. Eight-millimeter punch biopsies were obtained from the injection sites and counted in a gamma counter. The number of PMNLs infiltrating the dermis was also quantitated in histologic sections. A significant correlation was found between the percent increase in radioactivity and the percent increase in PMNL accumulation morphologically. Dose-response curves were generated using such proinflammatory materials as formyl-methionyl-leucyl-phenylalanine, lipopolysaccharide, activated serum, trypsin, glycogen, and acetic acid. These curves were highly reproducible from animal to animal. Using this assay, we found that as little as 1 microgram of trypsin induced detectable PMNL accumulation. This is 2-3 logs more sensitive than injecting mice intraperitoneally with trypsin. Diisopropyl fluorophosphate-inactivation of trypsin inhibited PMNL accumulation. This sensitive and quantitative bioassay of PMNL accumulation permits evaluation of multiple agents in the same animal, which decreases animal to animal variation.

Characterization of sodium dodecyl sulfate-resistant proteolytic activity in the hyperthermophilic archaebacterium Pyrococcus furiosus

Energy Technology Data Exchange (ETDEWEB)

Blumentals, I.I.; Robinson, A.S.; Kelly, R.M. (Johns Hopkins Univ., Baltimore, MD (USA))

1990-07-01

Cell extracts from Pyrococcus furiosus were found to contain five proteases, two of which (S66 and S102) are resistant to sodium dodecyl sulfate (SDS) denaturation. Cell extracts incubated at 98{degree}C in the presence of 1% SDS for 24 h exhibited substantial cellular proteolysis such that only four proteins could be visualized by amido black-Coomassie brilliant blue staining of SDS-polyacrylamide gels. The SDS-treated extract retained 19% of the initial proteolytic activity as represented by two proteases, S66 (66 kilodaltons (kDa)) and S102 (102 kDa). Immunoblot analysis with guinea pig sera containing antibodies against protease S66 indicated that S66 is related neither to S102 nor to the other proteases. The results of this analysis also suggest that S66 might be the hydrolysis product of a 200-kDa precursor which does not have proteolytic activity. The 24-h SDS-treated extract showed unusually thermostable proteolytic activity; the measured half-life at 98{degree}C was found to be 33 h. Proteases S66 and S102 were also resistant to denaturation by 8 M urea, 80 mM dithiothreitol, and 5% {beta}-mercaptoethanol. Purified protease S66 was inhibited by phenylmethylsulfonyl fluoride and diisopropyl fluorophosphate but not by EDTA, ethylene glycol-bis({beta}-aminoethyl ether)-N,N,N{prime},N{prime}-tetraacetic acid, or iodoacetic acid. These results indicate that S66 is a serine protease. Amino acid ester hydrolysis studies showed that protease S66 was hydrolytically active towards N-benzoyl-L-arginine ethyl ester.

Migration kinetics of mineral oil hydrocarbons from recycled paperboard to dry food: monitoring of two real cases.

Science.gov (United States)

Lorenzini, R; Biedermann, M; Grob, K; Garbini, D; Barbanera, M; Braschi, I

2013-01-01

Mineral oil hydrocarbons present in printing inks and recycled paper migrate from paper-based food packaging to foods primarily through the gas phase. Migration from two commercial products packed in recycled paperboard, i.e. muesli and egg pasta, was monitored up to the end of their shelf life (1 year) to study the influence of time, storage conditions, food packaging structure and temperature. Mineral oil saturated and aromatic hydrocarbons (MOSH and MOAH, respectively), and diisopropyl naphthalenes (DIPN) were monitored using online HPLC-GC/FID. Storage conditions were: free standing, shelved, and packed in transport boxes of corrugated board, to represent domestic, supermarket and warehouse storage, respectively. Migration to food whose packs were kept in transport boxes was the highest, especially after prolonged storage, followed by shelved and free-standing packs. Tested temperatures were representative of refrigeration, room temperature, storage in summer months and accelerated migration testing. Migration was strongly influenced by temperature: for egg pasta directly packed in paperboard, around 30 mg kg⁻¹ of MOSH migrated in 8 months at 20°C, but in only 1 week at 40°C. Muesli was contained into an internal polyethylene bag, which firstly adsorbed hydrocarbons and later released them partly towards the food. Differently, the external polypropylene bag, containing pasta and recycled paper tray, strongly limited the migration towards the atmosphere and gave rise to the highest level of food contamination. Tests at increased temperatures not only accelerated migration, but also widened the migration of hydrocarbons to higher molecular masses, highlighting thus a difficult interpretation of data from accelerated simulation.

Synthesis and physico-chemical characterization of CeO{sub 2}/ZrO{sub 2}-SO{sub 4}{sup 2-} mixed oxides

Energy Technology Data Exchange (ETDEWEB)

Hernandez E, J. M.; Silva R, R.; Garcia A, R. [Instituto Tecnologico de Ciudad Madero, Div. de Estudios de Posgrado e Investigacion, Juventino Rosas y Jesus Urueta s/n, Col. Los Mangos, 89440 Ciudad Madero, Tamaulipas (Mexico); Garcia S, L. A. [IPN, Centro Interdisciplinario de Investigaciones y de Estudios sobre Medio Ambiente y Desarrollo, 30 de Junio No. 1520, Barrio La Laguna Ticoman, 07340 Mexico D. F. (Mexico); Handy, B. E.; Cardenas G, G. [Universidad Autonoma de San Luis Potosi, CIEP, Facultad de Ciencias Quimicas, Av. Dr. Manuel Nava No. 6, Zona Universitaria, 78210 SLP, San Luis Potosi (Mexico); Cueto H, A. [Universidad Autonoma Metropolitana, Unidad Azcapotzalco, Av. San Pablo No. 180, Col. Reynosa Tamaulipas, 02200 Mexico D. F. (Mexico)

2012-07-01

Environmentally friendly solid-acid catalysts CeO{sub 2}/ZrO{sub 2}-SO{sub 4}{sup 2-} were prepared by the sol gel method varying CeO{sub 2} content (10, 20 and 30 wt %) and using sulfation in situ, maintaining the sulfate ions amount present in the materials at 20 wt %. ZrO{sub 2} and ZrO{sub 2}-SO{sub 4}{sup 2-} were also prepared for comparison proposes using the same synthesis method. The materials were characterized by X-ray diffraction, nitrogen physisorption, potentiometric titration with n-butylamine, decomposition of 2-propanol and n-pentane isomerization. The specific surface area of ZrO{sub 2}-SO{sub 4}{sup 2-} was high (160 m{sup 2}/g) compared with the unmodified ZrO{sub 2} (80 m{sup 2}/g), however this area decreased with increasing the CeO{sub 2} content (37-100 m{sup 2}/g). There was no significant effect of CeO{sub 2} on the tetragonal structure of ZrO{sub 2}-SO{sub 4}{sup 2-}. The variation of acid sites amount runs parallel to the change of specific surface area. The acid sites amount decreased with increasing cerium oxide content. The decomposition of 2-propanol results fundamentally in the formation of dehydration products such as propylene and diisopropyl ether, both involving acid sites. In addition, a good performance during the n-pentane isomerization was observed for these materials. The selectivity towards isopentane reaches 84% when the Pt/CeO{sub 2}/ZrO{sub 2}-SO{sub 4}{sup 2-} catalyst with the highest CeO{sub 2} content was used. (Author)

Effects of hydroxyl-functionalization and sub-Tg thermal annealing on high pressure pure- and mixed-gas CO2/CH4 separation by polyimide membranes based on 6FDA and triptycene-containing dianhydrides

KAUST Repository

Swaidan, Raja

2015-02-01

A sub-Tg thermally-annealed (250°C, 24h) ultra-microporous PIM-polyimide bearing a 9,10-diisopropyl-triptycene contortion center and hydroxyl-functionalized diamine (2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane, APAF) exhibited plasticization resistance up to 50bar for a 1:1 CO2/CH4 feed mixture, with a 9-fold higher CO2 permeability (30Barrer) and 2-fold increase in CO2/CH4 permselectivity (~50) over conventional dense cellulose acetate membranes at 10bar CO2 partial pressure. Interestingly, mixed-gas CO2/CH4 permselectivities were 10-20% higher than those evaluated under pure-gas conditions due to reduction of mixed-gas CH4 permeability by co-permeation of CO2. Gas transport, physisorption and fluorescence studies indicated a sieving pore-structure engaged in inter-chain charge transfer complexes (CTCs), similar to that of low-free-volume 6FDA-APAF polyimide. The isosteric heat of adsorption of CO2 as well as CO2/CH4 solubility selectivities varied negligibly upon replacement of OH with CH3 but CTC formation was hindered, CO2 sorption increased, CO2 permeability increased ~3-fold, CO2/CH4 permselectivity dropped to ~30 and CH4 mixed-gas co-permeation increased. These results suggest that hydroxyl-functionalization did not cause preferential polymer-gas interactions but primarily elicited diffusion-dominated changes owing to a tightened microstructure more resistant to CO2-induced dilations. Solution-processable hydroxyl-functionalized PIM-type polyimides provide a new platform of advanced materials that unites the high selectivities of low-free-volume polymers with the high permeabilities of PIM-type materials particularly for natural gas sweetening applications.

Dipeptidyl peptidase 4 - An important digestive peptidase in Tenebrio molitor larvae.

Science.gov (United States)

Tereshchenkova, Valeriia F; Goptar, Irina A; Kulemzina, Irina A; Zhuzhikov, Dmitry P; Serebryakova, Marina V; Belozersky, Mikhail A; Dunaevsky, Yakov E; Oppert, Brenda; Filippova, Irina Yu; Elpidina, Elena N

2016-09-01

Dipeptidyl peptidase 4 (DPP 4) is a proline specific serine peptidase that plays an important role in different regulatory processes in mammals. In this report, we isolated and characterized a unique secreted digestive DPP 4 from the anterior midgut of a stored product pest, Tenebrio molitor larvae (TmDPP 4), with a biological function different than that of the well-studied mammalian DPP 4. The sequence of the purified enzyme was confirmed by mass-spectrometry, and was identical to the translated RNA sequence found in a gut EST database. The purified peptidase was characterized according to its localization in the midgut, and substrate specificity and inhibitor sensitivity were compared with those of human recombinant DPP 4 (rhDPP 4). The T. molitor enzyme was localized mainly in the anterior midgut of the larvae, and 81% of the activity was found in the fraction of soluble gut contents, while human DPP 4 is a membrane enzyme. TmDPP 4 was stable in the pH range 5.0-9.0, with an optimum activity at pH 7.9, similar to human DPP 4. Only specific inhibitors of serine peptidases, diisopropyl fluorophosphate and phenylmethylsulfonyl fluoride, suppressed TmDPP 4 activity, and the specific dipeptidyl peptidase inhibitor vildagliptin was most potent. The highest rate of TmDPP 4 hydrolysis was found for the synthetic substrate Arg-Pro-pNA, while Ala-Pro-pNA was a better substrate for rhDPP 4. Related to its function in the insect midgut, TmDPP 4 efficiently hydrolyzed the wheat storage proteins gliadins, which are major dietary proteins of T. molitor. Published by Elsevier Ltd.

The neuroinflammatory phenotype in a mouse model of Gulf War Illness is unrelated to brain regional levels of acetylcholine as measured by quantitative HILIC-UPLC-MS/MS.

Science.gov (United States)

Miller, Julie V; LeBouf, Ryan F; Kelly, Kimberly A; Michalovicz, Lindsay T; Ranpara, Anand; Locker, Alicia R; Miller, Diane B; O'Callaghan, James P

2018-05-28

Many veterans of the 1991 Persian Gulf War (GW) returned with a chronic multisymptom illness that has been termed Gulf War Illness (GWI). Previous GWI studies have suggested that exposure to acetylcholinesterase inhibitors (AChEIs) in theater, such as sarin and/or pesticides, may have contributed to the symptomatology of GWI. Additionally, concomitant high physiological stress experienced during the war may have contributed to the initiation of the GWI phenotype. While inhibition of AChE leading to accumulation of acetylcholine (ACh) will activate the cholinergic anti-inflammatory pathway, the signature symptomatology of GWI has been shown to be associated with neuroinflammation. To investigate the relationship between ACh and neuroinflammation in discrete brain regions, we used our previously established mouse model of GWI, which combines an exposure to a high physiological stress mimic, corticosterone (CORT), with GW-relevant AChEIs. The AChEIs used in this study were diisopropyl fluorophosphate (DFP), chlorpyrifos oxon (CPO), and physostigmine (PHY). After AChEI exposure, ACh concentrations for cortex (CTX), hippocampus (HIP), and striatum (STR) were determined using hydrophilic interaction liquid chromatography (HILIC) with ultra-performance liquid chromatography (UPLC)-tandem-mass spectrometry (MS/MS). CORT pretreatment ameliorated the DFP-induced ACh increase in HIP and STR, but not CTX. CORT pretreatment did not significantly alter ACh levels for CPO and PHY. Further analysis of STR neuroinflammatory biomarkers revealed an exacerbated CORT+AChEI response, which does not correspond to measured brain ACh. By utilizing this new analytical method for discrete brain region analysis of ACh, this work suggests the exacerbated neuroinflammatory effects in our mouse model of GWI are not driven by the accumulation of brain region-specific ACh.

Decontamination Strategy for Large Area and/or Equipment Contaminated with Chemical and Biological Agents using a High Energy Arc Lamp (HEAL)

Energy Technology Data Exchange (ETDEWEB)

Schoske, Richard [ORNL; Kennedy, Patrick [ORNL; Duty, Chad E [ORNL; Smith, Rob R [ORNL; Huxford, Theodore J [ORNL; Bonavita, Angelo M [ORNL; Engleman, Greg [ORNL; Vass, Arpad Alexander [ORNL; Griest, Wayne H [ORNL; Ilgner, Ralph H [ORNL; Brown, Gilbert M [ORNL

2009-04-01

A strategy for the decontamination of large areas and or equipment contaminated with Biological Warfare Agents (BWAs) and Chemical Warfare Agents (CWAs) was demonstrated using a High Energy Arc Lamp (HEAL) photolysis system. This strategy offers an alternative that is potentially quicker, less hazardous, generates far less waste, and is easier to deploy than those currently fielded by the Department of Defense (DoD). For example, for large frame aircraft the United States Air Force still relies on the combination of weathering (stand alone in environment), air washing (fly aircraft) and finally washing the aircraft with Hot Soapy Water (HSW) in an attempt to remove any remaining contamination. This method is laborious, time consuming (upwards of 12+ hours not including decontamination site preparation), and requires large amounts of water (e.g., 1,600+ gallons for a single large frame aircraft), and generates large amounts of hazardous waste requiring disposal. The efficacy of the HEAL system was demonstrated using diisopropyl methyl phosphonate (DIMP) a G series CWA simulant, and Bacillus globigii (BG) a simulant of Bacillus anthracis. Experiments were designed to simulate the energy flux of a field deployable lamp system that could stand-off 17 meters from a 12m2 target area and uniformly expose a surface at 1360 W/m2. The HEAL system in the absence of a catalyst reduced the amount of B. globigii by five orders of magnitude at a starting concentration of 1.63 x 107 spores. In the case of CWA simulants, the HEAL system in the presence of the catalyst TiO2 effectively degraded DIMP sprayed onto a 100mm diameter Petri dish in 5 minutes.

Comparison of various molecular forms of bovine trypsin: Correlation of infrared spectra with X-ray crystal structures

Energy Technology Data Exchange (ETDEWEB)

Prestrelski, S.J. (Mount Sinai School of Medicine of the City Univ. of New York (USA)); Byler, D.M. (U.S. Department of Agriculture, Philadelphia, PA (USA)); Liebman, M.N. (AMOCO Technology Corporation, Naperville, IL (USA))

1991-01-01

Fourier-transform infrared spectroscopy is a valuable method for the study of protein conformation in solution primarily because of the sensitivity to conformation of the amide I band (1700-1620 cm{sup {minus}1}) which arises from the backbone C{double bond}O stretching vibration. Combined with resolution-enhancement techniques such as derivative spectroscopy and self-deconvolution, plus the application of iterative curve-fitting techniques, this method provides a wealth of information concerning protein secondary structure. Further extraction of conformational information from the amide I band is dependent upon discerning the correlations between specific conformation types and component bands in the amide I region. In this paper the authors report spectra-structure correlations derived from conformational perturbations in bovine trypsin which arise from autolytic processing, zymogen activation, and active-site inhibition. IR spectra were collected for the single-chain ({beta}-trypsin) and once-cleaved, double-chain ({alpha}-trypsin) forms as well as at various times during the course of autolysis and also for zymogen, trypsinogen, and {beta}-trypsin inhibited with diisopropyl fluorophosphate. Spectral differences among the various molecular forms were interpreted in light of previous biochemical studies of autolysis and the known three-dimensional structures of the zymogen, the active enzyme, and the DIP-inhibited form. The spectroscopic results from these proteins in D{sub 2}O imply that certain loop structures may absorb in the region of 1655 cm{sup {minus}1}. They estimate that this approach to data analysis and interpretation is sensitive to changes of 0.01 unit or less in the relative integrated intensities of component bands in spectra whose peaks are well resolved.

Dimerization-Induced Allosteric Changes of the Oxyanion-Hole Loop Activate the Pseudorabies Virus Assemblin pUL26N, a Herpesvirus Serine Protease.

Directory of Open Access Journals (Sweden)

Martin Zühlsdorf

2015-07-01

Full Text Available Herpesviruses encode a characteristic serine protease with a unique fold and an active site that comprises the unusual triad Ser-His-His. The protease is essential for viral replication and as such constitutes a promising drug target. In solution, a dynamic equilibrium exists between an inactive monomeric and an active dimeric form of the enzyme, which is believed to play a key regulatory role in the orchestration of proteolysis and capsid assembly. Currently available crystal structures of herpesvirus proteases correspond either to the dimeric state or to complexes with peptide mimetics that alter the dimerization interface. In contrast, the structure of the native monomeric state has remained elusive. Here, we present the three-dimensional structures of native monomeric, active dimeric, and diisopropyl fluorophosphate-inhibited dimeric protease derived from pseudorabies virus, an alphaherpesvirus of swine. These structures, solved by X-ray crystallography to respective resolutions of 2.05, 2.10 and 2.03 Å, allow a direct comparison of the main conformational states of the protease. In the dimeric form, a functional oxyanion hole is formed by a loop of 10 amino-acid residues encompassing two consecutive arginine residues (Arg136 and Arg137; both are strictly conserved throughout the herpesviruses. In the monomeric form, the top of the loop is shifted by approximately 11 Å, resulting in a complete disruption of the oxyanion hole and loss of activity. The dimerization-induced allosteric changes described here form the physical basis for the concentration-dependent activation of the protease, which is essential for proper virus replication. Small-angle X-ray scattering experiments confirmed a concentration-dependent equilibrium of monomeric and dimeric protease in solution.

CCDC 1431673: Experimental Crystal Structure Determination : dibromo-(P,P-di-t-butyl-N-(6-(3,5-diisopropyl-1H-pyrazol-1-yl)pyridin-2-yl)phosphinous amide)-cobalt

KAUST Repository

Gong, Dirong

2016-01-01

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

Kinetics and Mechanism of the Gas-Phase Reaction of Selected Carbonyls with Cl Atoms between 250 and 340 K

Science.gov (United States)

Hasson, A. S.; Algrim, L.; Abdelhamid, A.; Tyndall, G. S.; Orlando, J. J.

2013-12-01

Carbonyls are important products from the gas phase degradation of most volatile organic compounds. Their atmospheric reactions therefore have a significant impact on atmospheric composition, particularly in aged air masses. While the reactions of short-chain linear carbonyls are well understood, the chemistry of larger (> C6) and branched carbonyl is more uncertain. To provide insight into these reactions, the reactions of three carbonyls (methyl isopropyl ketone, MIK; di-isopropyl ketone, DIK; and diethyl ketone, DEK) with chlorine atoms were investigated between 250 and 340 K and 1 atm in the presence and absence of NOx and an HO2 source (methanol). Experiments were performed in a photochemical reactor using a combination of long-path Fourier transform infra-red spectroscopy, proton transfer reaction mass spectrometry and gas chromatography with flame ionization detection. The kinetics were studied using the relative rate technique with butanone and isopropanol as the reference compounds. The Arrhenius expression for the three rate coefficients was determined to be k(DEK+Cl) = 3.87 x 10-11e(2 × 7 kJ/mol)/RT cm3 molecules-1 s-1 , k(MIPK+Cl) = 7.20 x 10-11e(0.2× 8 kJ/mol)/RT cm3 molecules-1 s-1 , and k(DIPK+Cl) = 3.33 x 10-10e(-3× 8 kJ/mol)/RT cm3 molecules-1 s-1 . Measured reaction products accounted for 38-72 % of the reacted carbon and were consistent with strong deactivation of the carbon atom adjacent to the carbonyl group with respect to H-atom abstraction by Cl atoms. The product distributions also provide insight into radical recycling from the organic peroxy + HO2 reaction, and the relative rates of isomerization, fragmentation and reaction with O2 for carbonyl-containing alkoxy radicals. Implications of these results will be discussed.

Group 13 ligand supported heavy-metal complexes: first structural evidence for gallium-lead and gallium-mercury bonds.

Science.gov (United States)

Prabusankar, Ganesan; Gemel, Christian; Winter, Manuela; Seidel, Rüdiger W; Fischer, Roland A

2010-05-25

Heavy-metal complexes of lead and mercury stabilized by Group 13 ligands were derived from the oxidative addition of Ga(ddp) (ddp=HC(CMeNC(6)H(3)-2,6-iPr(2))(2), 2-diisopropylphenylamino-4-diisopropyl phenylimino-2-pentene) with corresponding metal precursors. The reaction of Me(3)PbCl and Ga(ddp) afforded compound [{(ddp)Ga(Cl)}PbMe(3)] (1) composed of Ga-Pb(IV) bonds. In addition, the monomeric plumbylene-type compound [{(ddp)Ga(OSO(2)CF(3))}(2)Pb(thf)] (2a) with an unsupported Ga-Pb(II)-Ga linkage was obtained by the reaction of [Pb(OSO(2)CF(3))(3)] with Ga(ddp) (2 equiv). Compound 2a falls under the rare example of a discrete plumbylene-type compound supported by a nonclassical ligand. Interesting structural changes were observed when [Pb(OSO(2)CF(3))(3)]2.H(2)O was treated with Ga(ddp) in a 1:2 ratio to yield [{(ddp)Ga(mu-OSO(2)CF(3))}(2)(OH(2))Pb] (2b) at below -10 degrees C. Compound 2b consists of a bent Ga-Pb-Ga backbone with a bridging triflate group between the Ga-Pb bond and a weakly interacting water molecule at the gallium center. Similarly, the reaction of mercury thiolate Hg(SC(6)F(5)) with Ga(ddp) (2 equiv) produced the bimetallic homoleptic compounds anti-[{(ddp)Ga(SC(6)F(5))}(2)Hg] (3a) and gauche-[{(ddp)Ga(SC(6)F(5))}(2)Hg] (3b), respectively, with a linear Ga-Hg-Ga linkage. Compounds 1-3 were structurally characterized and these are the first examples of compounds comprised of Ga-Pb(II), Ga-Pb(IV), and Ga-Hg bonds.

Hydrolysis of VX on concrete: rate of degradation by direct surface interrogation using an ion trap secondary ion mass spectrometer.

Science.gov (United States)

Groenewold, Gary S; Williams, John M; Appelhans, Anthony D; Gresham, Garold L; Olson, John E; Jeffery, Mark T; Rowland, Brad

2002-11-15

The nerve agent VX (O-ethyl S-2-diisopropylaminoethyl methylphosphonothiolate) is lethal at very low levels of exposure, which can occur by dermal contact with contaminated surfaces. Hence, behavior of VX in contact with common urban or industrial surfaces is a subject of acute interest. In the present study, VX was found to undergo complete degradation when in contact with concrete surfaces. The degradation was directly interrogated at submonolayer concentrations by periodically performing secondary ion mass spectrometry (SIMS) analyses after exposure of the concrete to VX. The abundance of the [VX + H]+ ion in the SIMS spectra was observed to decrease in an exponential fashion, consistent with first-order or pseudo-first-order behavior. This phenomenon enabled the rate constant to be determined at 0.005 min(-1) at 25 degrees C, which corresponds to a half-life of about 3 h on the concrete surface. The decrease in [VX + H]+ was accompanied by an increase in the abundance of the principal degradation product diisopropylaminoethanethiol (DESH), which arises by cleavage of the P-S bond. Degradation to form DESH is accompanied by the formation of ethyl methylphosphonic acid, which is observable only in the negative ion spectrum. A second degradation product was also implicated, which corresponded to a diisopropylvinylamine isomer (perhaps N,N-diisopropyl aziridinium) that arose via cleavage of the S-C bond. No evidence was observed for the formation of the toxic S-2-diisopropylaminoethyl methylphosphonothioic acid. The degradation rate constants were measured at four different temperatures (24-50 degrees C), which resulted in a linear Arrhenius relationship and an activation energy of 52 kJ mol(-1). This value agrees with previous values observed for VX hydrolysis in alkaline solutions, which suggests that the degradation of submonolayer VX is dominated by alkaline hydrolysis within the adventitious water film on the concrete surface.

The search of the target of promotion: Phenylbenzoate esterase activities in hen peripheral nerve

International Nuclear Information System (INIS)

Moretto, A.; Nicolli, A.; Lotti, M.

2007-01-01

Certain esterase inhibitors, such as carbamates, phosphinates and sulfonyl halides, do not cause neuropathy as some organophosphates, but they may exacerbate chemical or traumatic insults to axons. This phenomenon is called promotion of axonopathies. Given the biochemical and toxicological characteristics of these compounds, the hypothesis was made that the target of promotion is a phenyl valerate (PV) esterase similar to neuropathy target esterase (NTE), the target of organophosphate induced delayed polyneuropathy. However, attempts to identify a PV esterase in hen peripheral nerve have been, so far, unsuccessful. We tested several esters, other than PV, as substrates of esterases from crude homogenate of the hen peripheral nerve. The ideal substrate should be poorly hydrolysed by NTE but extensively by enzyme(s) that are insensitive to non-promoters, such as mipafox, and sensitive to promoters, such as phenyl methane sulfonyl fluoride (PMSF). When phenyl benzoate (PB) was used as substrate, about 65% of total activity was resistant to the non-promoter mipafox (up to 0.5 mM, 20 min, pH 8.0), that inhibits NTE and other esterases. More than 90% of this resistant activity was sensitive to the classical promoter PMSF (1 mM, 20 min, pH 8.0) with an IC 50 of about 0.08 mM (20 min, pH 8.0). On the contrary, the non-promoter p-toluene sulfonyl fluoride caused only about 10% inhibition at 0.5 mM. Several esterase inhibitors including, paraoxon, phenyl benzyl carbamate, di-n-butyl dichlorovinyl phosphate and di-isopropyl fluorophosphate, were tested both in vitro and in vivo for inhibition of this PB activity. Mipafox-resistant PMSF-sensitive PB esterase activity(ies) was inhibited by promoters but not by non promoters and neuropathic compounds

Spectroscopic investigation of the structures of dialkyl tartrates and their cyclodextrin complexes.

Science.gov (United States)

Zhang, Peng; Polavarapu, Prasad L

2007-02-08

Structures of three dialkyl tartrates, namely, dimethyl tartrate, diethyl tartrate, and diisopropyl tartrate, in CCl4, dimethyl sulfoxide (DMSO)/DMSO-d6, and H2O/D2O solvents have been investigated using vibrational absorption (VA), vibrational circular dichroism (VCD), and optical rotatory dispersion (ORD). VA, VCD, and ORD spectra are found to be dependent on the solvent used. Density functional theory (DFT) calculations are used to interpret the experimental data in CCl4 and DMSO. The trans-COOR conformer with hydrogen bonding between the OH group and the C=O group attached to the same chiral carbon is dominant for dialkyl tartrates both in vacuum and in CCl4. The experimental VA, VCD, and ORD data of dialkyl-D-tartrates in CCl4 correlated well with those predicted for dimethyl-(S,S)-tartrate molecule as both isolated and solvated in CCl4. In DMSO solvent, dialkyl tartrate molecules favor formation of intermolecular hydrogen bonding with DMSO molecules. Clusters of dimethyl-(S,S)-tartrate, with one molecule of dimethyl-(S,S)-tartrate hydrogen bonded to two DMSO molecules, are used for the DFT calculations. A trans-COOR cluster and a trans-H cluster are needed to obtain a reasonable agreement between the predicted and experimental data of dimethyl tartrate in DMSO solvent. VA, VCD, and optical rotations are also measured for dialkyl tartrate-cyclodextrin complexes. It is noted that these properties are barely affected by complexation of dialkyl tartrates with cyclodextrins, indicating weak interaction between tartrates and cyclodextrin. Binding constants of alpha-CD and beta-CD with diethyl L-tartrate in both H2O and DMSO have been determined using isothermal titration calorimetry technique. The smaller binding constants (less than 100) confirmed the weak interaction between tartrates and cyclodextrin in the solution state.

Study of sorption of two sulfonylurea type of herbicides and their additives on soils and soil components.

Science.gov (United States)

Földényi, Rita; Tóth, Zoltán; Samu, Gyöngyi; Érsek, Csaba

2013-01-01

The sorption of two sulfonylurea type herbicides (chlorsulfuron: (1-(2-chlorophenylsulfonyl)-3-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)urea; tribenuron methyl: (methyl-2-[N-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-3-(methyl-ureido)-sulfonyl]-benzoate) was studied on sand and chernozem soil adsorbents. Experimental results for solutions prepared from the pure ingredients were compared to those prepared from the appropriate formulated commercial products. At small concentrations, the extent of adsorption of the active ingredient was higher than from the formulation containing solutions. Environmental fate and effects of the forming agents are less investigated because they rarely have concentration limits recommended by authorities. In addition to the adsorption of active ingredients, therefore, the sorption behavior of a widely used additive Supragil WP (sodium diisopropyl naphthalene sulphonate) was also studied. This dispersant is an anionic forming agent applied in a lot of pesticide formulations. Using three different soils (sand, brown forest, chernozem) as adsorbents two-step isotherms were obtained. The role of the soil organic matter (OM) was significant in the adsorption mechanism because the adsorbed amounts of the dispersant correlated with the specific surface area as well as with the total organic carbon (TOC) content of the soils. The sorption behavior indicates the operation of hydrophobic interaction mechanism between the soil OM and the dispersant. These results are supported by our further sorption experiments on clays, too. Zeta potential measurements seem to be promising for the interpretation of multi-step isotherms. The application of this technique proved that higher concentrations of the anionic forming agent assisted the peptization of soil organic matter (SOM) resulting in stable colloidal solution dominated by negative charges. Since the pesticides investigated are also anionic at the studied pH (7 and 8.3) the dissolved organics lead to the

The sources, fate, and toxicity of chemical warfare agent degradation products.

Science.gov (United States)

Munro, N B; Talmage, S S; Griffin, G D; Waters, L C; Watson, A P; King, J F; Hauschild, V

1999-01-01

We include in this review an assessment of the formation, environmental fate, and mammalian and ecotoxicity of CW agent degradation products relevant to environmental and occupational health. These parent CW agents include several vesicants: sulfur mustards [undistilled sulfur mustard (H), sulfur mustard (HD), and an HD/agent T mixture (HT)]; nitrogen mustards [ethylbis(2-chloroethyl)amine (HN1), methylbis(2-chloroethyl)amine (HN2), tris(2-chloroethyl)amine (HN3)], and Lewisite; four nerve agents (O-ethyl S-[2-(diisopropylamino)ethyl] methylphosphonothioate (VX), tabun (GA), sarin (GB), and soman (GD)); and the blood agent cyanogen chloride. The degradation processes considered here include hydrolysis, microbial degradation, oxidation, and photolysis. We also briefly address decontamination but not combustion processes. Because CW agents are generally not considered very persistent, certain degradation products of significant persistence, even those that are not particularly toxic, may indicate previous CW agent presence or that degradation has occurred. Of those products for which there are data on both environmental fate and toxicity, only a few are both environmentally persistent and highly toxic. Major degradation products estimated to be of significant persistence (weeks to years) include thiodiglycol for HD; Lewisite oxide for Lewisite; and ethyl methyl phosphonic acid, methyl phosphonic acid, and possibly S-(2-diisopropylaminoethyl) methylphosphonothioic acid (EA 2192) for VX. Methyl phosphonic acid is also the ultimate hydrolysis product of both GB and GD. The GB product, isopropyl methylphosphonic acid, and a closely related contaminant of GB, diisopropyl methylphosphonate, are also persistent. Of all of these compounds, only Lewisite oxide and EA 2192 possess high mammalian toxicity. Unlike other CW agents, sulfur mustard agents (e.g., HD) are somewhat persistent; therefore, sites or conditions involving potential HD contamination should include an

Profiling and functional classification of esterases in olive (Olea europaea) pollen during germination.

Science.gov (United States)

Rejón, Juan D; Zienkiewicz, Agnieszka; Rodríguez-García, María Isabel; Castro, Antonio J

2012-10-01

A pollen grain contains a number of esterases, many of which are released upon contact with the stigma surface. However, the identity and function of most of these esterases remain unknown. In this work, esterases from olive pollen during its germination were identifided and functionally characterized. The esterolytic capacity of olive (Olea europaea) pollen was examined using in vitro and in-gel enzymatic assays with different enzyme substrates. The functional analysis of pollen esterases was achieved by inhibition assays by using specific inhibitors. The cellular localization of esterase activities was performed using histochemical methods. Olive pollen showed high levels of non-specific esterase activity, which remained steady after hydration and germination. Up to 20 esterolytic bands were identified on polyacrylamide gels. All the inhibitors decreased pollen germinability, but only diisopropyl fluorophosphate (DIFP) hampered pollen tube growth. Non-specific esterase activity is localized on the surface of oil bodies (OBs) and small vesicles, in the pollen intine and in the callose layer of the pollen tube wall. Acetylcholinesterase (AChE) activity was mostly observed in the apertures, exine and pollen coat, and attached to the pollen tube wall surface and to small cytoplasmic vesicles. In this work, for the first time a systematic functional characterization of esterase enzymes in pollen from a plant species with wet stigma has been carried out. Olive pollen esterases belong to four different functional groups: carboxylesterases, acetylesterases, AChEs and lipases. The cellular localization of esterase activity indicates that the intine is a putative storage site for esterolytic enzymes in olive pollen. Based on inhibition assays and cellular localization of enzymatic activities, it can be concluded that these enzymes are likely to be involved in pollen germination, and pollen tube growth and penetration of the stigma.

Active site-dependent initiation at 1/sup 0/C by Chymase (CHY) of rat serosal mast cell (RSMC) exocytosis

Energy Technology Data Exchange (ETDEWEB)

Schick, B.; Austen, K.F.

1986-03-01

Exposure of RSMC (> 95% purity) to isolated CHY (0.5-1.5 U/ml), the major secretory granule protease, at 37/sup 0/C results in exocytosis, determined by the release of a soluble secretory granule enzyme, ..beta..-hexosaminidase. CHY-mediated RSMC exocytosis does not occur at 1/sup 0/C. Exposure of RSMC to CHY or ..cap alpha..-chymotrypsin (CT) at 1/sup 0/C, removal of buffer and resuspension of RSMC in buffer alone at 37/sup 0/C, yields the same exocytosis as direct exposure of RSMC to those chymotryptic enzymes at 37/sup 0/C. Differences in the interaction of CHY and CT with RSMC at 1/sup 0/C and 37/sup 0/C are dose-dependent, not qualitative. Binding to (< 0.5% of input) and dissociation of /sup 125/I-labeled CT (3-8 x 10/sup 8/ cpm/mg) from RSMC, as determined by spinning through oil, was time independent and saturation of specific binding was not achieved, indicating that the observed binding is nonspecific. Diisopropyl fluorophosphate (DFP) and lima bean trypsin inhibitor (LBTI) prevent subsequent exocytosis at 37/sup 0/C only if added within the first 10 min of the interaction of RSMC and CHY at 1/sup 0/C. Maximal CHY-mediated RSMC activation at 1/sup 0/C is achieved within 10 min and addition of DFP and LBTI after this period does not affect subsequent exocytosis. The dose- and time-dependent inhibition by DFP and LBTI at 1/sup 0/C of CHY initiation of RSMC exocytosis suggest that an enzymatic action of CHY on RSMC at 1/sup 0/C, not a binding reaction, commits RSMC to exocytosis at 37/sup 0/C.

Design and characterization of hirulogs: A novel class of bivalent peptide inhibitors of thrombin

Energy Technology Data Exchange (ETDEWEB)

Maraganore, J.M.; Bourdon, P.; Jablonski, J.; Ramachandran, K.L. (Biogen, Inc., Cambridge, MA (USA)); Fenton, J.W. II (New York State Department of Health, Albany (USA))

1990-07-31

A novel class of synthetic peptides has been designed that inhibit the thrombin catalytic site and exhibit specificity for the anion-binding exosite (ABE) of {alpha}-thrombin. These peptides, called hirulogs, consist of (i) an active-site specificity sequence with a restricted Arg-Pro scissile bond, (ii) a polymeric linker of glycyl residues from 6 to 18 {angstrom} in length, and (iii) an ABE recognition sequence such as that in the hirudin C-terminus. Hirulog-1 ((D-Phe)-Pro-Arg-Pro-(Gly){sub 4}-Asn-Gly-Asp-Phe-Glu-Glu-Ile-Pro-Glu-Tyr-Leu) inhibits the thrombin-catalyzed hydrolysis of a tripeptide p-nitroanilide substrate with K{sub i} = 2.3 nM. In contrast, the synthetic C-terminal hirudin peptide S-Hir{sub 53-64}, which binds to the thrombin ABE, blocked the fibrinogen clotting activity of the enzyme with K{sub i} = 144 nM but failed to inhibit the hydrolysis of p-nitroanilide substrates at concentrations as high as 1 mM. Hirulog-1, but not S-Hir{sub 53-64}, was found to inhibit the incorporation of ({sup 14}C)diisopropyl fluorophosphate in thrombin. Hirulog-1 appears specific for thrombin as it lacks inhibitory activities toward human factor Xa, human plasmin, and bovine trypsin at inhibitor:enzyme concentrations 3 orders of magnitude higher than those required to inhibit thrombin. The optimal inhibitory activity of hirulog-1 depends upon all three components of its structure. Comparison of anticoagulant activities of hirulog-1, hirudin, and S-Hir{sub 53-64} showed that the synthetic hirulog-1 is 2-fold more potent than hirudin and 100-fold more active than S-Hir{sub 53-64} in increasing the activated partial thromboplastin time of normal human plasma.

High prevalence of quasi-legal psychoactive substance use among male patients in HIV care in Japan: a cross-sectional study.

Science.gov (United States)

Hayashi, Kanna; Wakabayashi, Chihiro; Ikushima, Yuzuru; Tarui, Masayoshi

2017-02-23

Syndemics of illicit drug use and HIV remain as significant public health issues around the world. There has been increasing concern regarding the rapidly growing market of new psychoactive substances, particularly in Asia. In response, the Japanese government has increasingly banned such substances in recent years. We sought to identify the prevalence and correlates of use of quasi-legal psychoactive substances among people living with HIV/AIDS (PLHIV) in Japan. Data were derived from a nationwide survey of PLHIV conducted at nine leading HIV/AIDS care hospitals between July and December 2013. The prevalence and correlates of the use of quasi-legal psychoactive substances (e.g., synthetic cannabinoids, cathinone derivatives, etc. that had not been prohibited from using at the time of survey) among male participants were examined using multivariate survey logistic regression. Among 963 study participants, the majority (95.3%) were male. The most commonly used drug among men was quasi-legal psychoactive substances (55.3% ever and 12.8% in the previous year). In multivariate analysis, the lifetime use of tryptamine-type derivatives (i.e., 5-MeO-DIPT or N,N-diisopropyl-5-methoxytryptamine) (adjusted odds ratio [AOR]: 2.42; 95% confidence interval [CI]: 1.36-4.28) and methamphetamine/amphetamine (AOR: 3.59; 95% CI: 2.13-6.04) were independently associated with recent quasi-legal psychoactive substance use. In our sample of male PLHIV in Japan, quasi-legal psychoactive substances were the most commonly used drugs. Individuals who had ever used tryptamine-type derivatives or methamphetamine/amphetamine were more likely to report recent quasi-legal psychoactive substance use, suggesting a potential shift in drug use patterns from regulated to unregulated substances among this population. These findings indicate a need for further research to examine implications for HIV care.

Oxidative degradation of alternative gasoline oxygenates in aqueous solution by ultrasonic irradiation: Mechanistic study

Energy Technology Data Exchange (ETDEWEB)

Kim, Duk Kyung, E-mail: dkim@aum.edu [Department of Physical Science, Auburn University Montgomery, Montgomery, AL 36117 (United States); O' Shea, Kevin E., E-mail: osheak@fiu.edu [Department of Chemistry and Biochemistry, Florida International University, University Park, Miami, FL 33199 (United States); Cooper, William J. [Department of Civil and Environmental Engineering, Urban Water Research Center, University of California Irvine, Irvine, CA 92697-2175 (United States)

2012-07-15

Widespread pollution has been associated with gasoline oxygenates of branched ethers methyl tert-butyl ether (MTBE), di-isopropyl ether (DIPE), ethyl tert-butyl ether (ETBE), and tert-amyl ether (TAME) which enter groundwater. The contaminated plume develops rapidly and treatment for the removal/destruction of these ethers is difficult when using conventional methods. Degradation of MTBE, with biological methods and advanced oxidation processes, are rather well known; however, fewer studies have been reported for degradation of alternative oxygenates. Degradation of alternative gasoline oxygenates (DIPE, ETBE, and TAME) by ultrasonic irradiation in aqueous oxygen saturation was investigated to elucidate degradation pathways. Detailed degradation mechanisms are proposed for each gasoline oxygenate. The common major degradation pathways are proposed to involve abstraction of {alpha}-hydrogen atoms by hydroxyl radicals generated during ultrasound cavitation and low temperature pyrolytic degradation of ETBE and TAME. Even some of the products from {beta}-H abstraction overlap with those from high temperature pyrolysis, the effect of {beta}-H abstraction was not shown clearly from product study because of possible 1,5 H-transfer inside cavitating bubbles. Formation of hydrogen peroxide and organic peroxides was also determined during sonolysis. These data provide a better understanding of the degradation pathways of gasoline oxygenates by sonolysis in aqueous solutions. The approach may also serve as a model for others interested in the details of sonolysis. - Highlights: Black-Right-Pointing-Pointer Gasoline oxygenates (ETBE, TAME, DIPE) were completely degraded after 6 hours under ultrasonic irradiation in O{sub 2} saturation. Black-Right-Pointing-Pointer The major degradation pathways were proposed to involve abstraction of {alpha}-hydrogen atoms by hydroxyl radicals and low temperature pyrolytic degradation. Black-Right-Pointing-Pointer The effect of {beta

Inhibition of the prostaglandin EP2 receptor is neuroprotective and accelerates functional recovery in a rat model of organophosphorus induced status epilepticus

Science.gov (United States)

Rojas, Asheebo; Ganesh, Thota; Lelutiu, Nadia; Gueorguieva, Paoula; Dingledine, Raymond

2015-01-01

Exposure to high levels of organophosphorus compounds (OP) can induce status epilepticus (SE) in humans and rodents via acute cholinergic toxicity, leading to neurodegeneration and brain inflammation. Currently there is no treatment to combat the neuropathologies associated with OP exposure. We recently demonstrated that inhibition of the EP2 receptor for PGE2 reduces neuronal injury in mice following pilocarpine-induced SE. Here, we investigated the therapeutic effects of an EP2 inhibitor (TG6-10-1) in a rat model of SE using diisopropyl fluorophosphate (DFP). We tested the hypothesis that EP2 receptor inhibition initiated well after the onset of DFP-induced SE reduces the associated neuropathologies. Adult male Sprague-Dawley rats were injected with pyridostigmine bromide (0.1 mg/kg, sc) and atropine methylbromide (20 mg/kg, sc) followed by DFP (9.5 mg/kg, ip) to induce SE. DFP administration resulted in prolonged upregulation of COX-2. The rats were administered TG6-10-1 or vehicle (ip) at various time points relative to DFP exposure. Treatment with TG6-10-1 or vehicle did not alter the observed behavioral seizures, however six doses of TG6-10-1 starting 80-150 min after the onset of DFP-induced SE significantly reduced neurodegeneration in the hippocampus, blunted the inflammatory cytokine burst, reduced microglial activation and decreased weight loss in the days after status epilepticus. By contrast, astrogliosis was unaffected by EP2 inhibition 4 d after DFP. Transient treatments with the EP2 antagonist 1 h before DFP, or beginning 4 h after DFP, were ineffective. Delayed mortality, which was low (10%) after DFP, was unaffected by TG6-10-1. Thus, selective inhibition of the EP2 receptor within a time window that coincides with the induction of cyclooxygenase-2 by DFP is neuroprotective and accelerates functional recovery of rats. PMID:25656476

Vapour–Liquid Equilibria in the Binary and Ternary Systems Composed of 2,3-Dimethylbutane, Diisopropyl Ether, and 3-Methyl-2-Butanone at 313.15, 323.15 and 313.15 K

Czech Academy of Sciences Publication Activity Database

Pavlíček, Jan; Andresová, Adéla; Bogdanić, Grozdana; Wichterle, Ivan

2013-01-01

Roč. 344, APR 25 (2013), s. 59-64 ISSN 0378-3812 Institutional support: RVO:67985858 Keywords : vapour-liquid equilibrium * prediction * experimental data Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.241, year: 2013

CCDC 999049: Experimental Crystal Structure Determination : (1,3-bis(2,6-Di-isopropyl-4-methoxyphenyl)imidazolidin-2-ylidene)-dichloro-(3-phenyl-1H-inden-1-ylidene)-triphenylphosphine-ruthenium n-pentane solvate

KAUST Repository

Manzini, Simone; Blanco, Cé sar A. Urbina; Nelson, David J.; Poater, Albert; Lebl, Tomas; Meiries, Sé bastien; Slawin, Alexandra M.Z.; Falivene, Laura; Cavallo, Luigi; Nolan, Steven P.

2015-01-01

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

Verification of propofol sulfate as a further human propofol metabolite using LC-ESI-QQQ-MS and LC-ESI-QTOF-MS analysis.

Science.gov (United States)

Maas, Alexandra; Maier, Christoph; Michel-Lauter, Beate; Broecker, Sebastian; Madea, Burkhard; Hess, Cornelius

2017-03-01

Propofol (2,6-diisopropylphenol) is a water-insoluble, intravenous anesthetic that is widely used for the induction and maintenance of anesthesia as well as for endoscopic and pediatric sedation. After admission, propofol undergoes extensive hepatic and extrahepatic metabolism, including direct conjugation to propofol glucuronide and hydroxylation to 2,6-diisopropyl-1,4-quinol. The latter substance subsequently undergoes phase II metabolism, resulting in the formation of further metabolites (1quinolglucuronide, 4quinolglucuronide and 4quinol-sulfate). Further minor phase I propofol metabolites (2-(ω-propanol)-6-isopropylphenol and 2-(ω-propanol)-6-isopropyl-1,4-quinol)) are also described. Due to its chemical structure with the phenolic hydroxyl group, propofol is also an appropriate substrate for sulfation by sulfotransferases. The existence of propofol sulfate was investigated by liquid chromatography electrospray ionization triple quadrupole mass spectrometry (LCESIQQQ-MS) and liquid chromatography electrospray ionization quadrupole time-of-flight mass spectrometry (LCESI-QTOF-MS). A propofol sulfate reference standard was used for identification and method development, yielding a precursor at m/z 257 (deprotonated propofol sulfate) and product ions at m/z 177 (deprotonated propofol) and m/z 80 ([SO3]-). Propofol sulfate - a further phase II metabolite of propofol - was verified in urine samples by LC-ESI-QQQ-MS and LC-ESI-QTOF-MS. Analyses of urine samples from five volunteers collected before and after propofol-induced sedation verified the presence of propofol sulfate in urine following propofol administration, whereas ascertained concentrations of this metabolite were significantly lower compared with detected propofol glucuronide concentrations. The existence of propofol sulfate as a further phase II propofol metabolite in humans could be verified by two different detection techniques (LCESIQQQ-MS and LC-ESI-QTOFMS) on the basis of a propofol sulfate

Evaluation of 99mTc-Mercaptoacetyltriglycine-Biocytin as a new hepatobiliary imaging agent in mice coinjected with bilirubin

International Nuclear Information System (INIS)

Kim, Meyoung-kon; Seidel, Juergen; Le Nhat; Kim, In-Sook; Yoo, Tae-Moo; Barker, Craig; Kobayashi, Hisataka; Green, Michael V.; Carrasquillo, Jorge A.; Paik, Chang H.

1999-01-01

We evaluated 99m Tc-labeled mercaptoacetyltriglycine ( 99m Tc-MAG3)-biocytin as a hepatobiliary imaging agent in the absence and presence of bilirubin in mice. We then compared its pharmacokinetic parameters; peak liver/heart activity ratio (r max ) and half clearance time (HCT) with those of 99m Tc-labeled diisopropyl-iminodiacetic acid ( 99m Tc-disofenin). Balb/c mice were injected intravenously with hepatobiliary agent ( 99m Tc-MAG3-biocytin or 99m Tc-disofenin) alone or in combination with bilirubin at two doses (7 and 14 mg/kg) dissolved in 5% human serum albumin. Images were acquired every 15 s for 30 min with a gamma-camera equipped with a pinhole collimator. Dynamic images showed rapid hepatic uptake of 99m Tc-MAG3-biocytin, with rapid clearance from the blood and rapid excretion via the biliary system. Its hepatic uptake was not affected by bilirubin coinjection, whereas 99m Tc-disofenin coinjected with bilirubin showed a higher blood background than 99m Tc-disofenin alone. These qualitative findings were reflected in pharmacokinetic parameters, r max and HCT. The r max was obtained from plots of time versus liver/heart activity ratios obtained in equal-area regions of interest over the heart and liver. The HCT was calculated from the hepatic clearance curve from plots of time versus liver activity. 99m Tc-MAG3-biocytin without bilirubin coinjection showed an r max of 8.9±1.3 and an HCT of 399±36 s. These values did not change even when 14 mg/kg of bilirubin were coinjected. By contrast, the parameters for 99m Tc-disofenin with bilirubin were significantly (p max was decreased from 7.9±2.5 to 1.4±0.2 and HCT was increased from 292±32 s to 782±133 s. 99m Tc-MAG3-biocytin hepatobiliary scintigraphy in mice is not affected by bilirubin coinjection, and this hepatobiliary agent appears to offer promise for estimating hepatic function in patients with high bilirubin levels

Properties Of A Midgut Trypanolysin From The Tsetse Fly Glossina Morsitans Morsitans

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Mahamat H.Abakar

2015-08-01

Full Text Available The properties of a bloodmeal-induced trypanolysin from the midgut of the tsetse G. m. morsitans was studied in vitro. The semi-purified trypanolysin from twice-fed tsetse had the highest trypanolysin activity against bloodstream trypanosomes followed by those once-fed and the unfed flies. Serum found to display trypanolysin activity. The trypanolysin had no trypsin activity nor even affected by the enzyme. In addition trypanolysin was not affected by protease inhibitors such as soy bean trypsin inhibitor STI N-a-p-Tosyl-L-lysine chromethyl ketone TLCK phenylmethyl sulphonyl fluoride PMSF diisopropyl fluoro-phosphate DFP and tosylamide-2-phenylethyl chloromethyl ketone TPCK. However the activity was completely inhibited by diethyl pyrocarbonate DEPC and partially by aprotinin. The induction of trypanolysin activity by bloodmeal increased gradually reaching a peak at 72-120 h after the bloodmeal and then decreased rapidly with only 25 of the peak activity remaining after 192 h. The trypanolysin was inactivated during storage at 27amp8451 and 4amp8451 after 15 and 32 days respectively. Similarly heating the midguts trypanolysin to 60 - 80amp8451 led to loss of activity. On the other hand 50amp8451 was found to be the optimum temperature for trypanolysin activity. The activity was also unstable by freeze-thaw at 80amp8451 -70amp8451 -20amp8451 and 0amp8451 after 33 41 55 and 63 days respectively. Trypanolysin caused lyses of bloodstream-form T. b. brucei while the procyclic trypanosomes were unaffected. The highest trypanolysin activity in different tsetse species was found with Glossina longipennis followed by Glossina pallidipes Glossina morsitans centralis Glossina fuscipes fuscipes and G. m. morsitans. When the midgut homogenate was separated by anion-exchange chromatography the trypanolysin activity was recovered in the bound fraction. These results suggest that the midgut trypanolysin plays an important role in the establishment of

Biosynthesis of plasmalogens by the microsomal fraction of Fischer R-3259 sarcoma. Influence of specific 2-acyl chains on the desaturation of 1-alkyl-2-acyl-sn-gycero-3-phosphoethanolamine

Energy Technology Data Exchange (ETDEWEB)

Wykle, R.L.; Schremmer, J.M.

1979-08-07

In the Fischer R-3259 sarcoma, ethanolamine plasmalogens are synthesized from 1-akyl-2-acyl-sn-glycero-3-phosphoethanolamine by a microsomal desaturase that inserts a ..delta../sup 1/ double bond in the alkyl chain. In the present study, a series of 1-(1-/sup 14/C)hexadecyl-2-acyl-GPE substrates containing specific acyl groups ranging from C/sub 2/ /sub 0/ to C/sub 20/ /sub 4/ at the 2 position were prepared and tested as substrates for the microsomal ..delta../sup 1/-alkyl desaturase. The microsomal preparations contained an acyl hydrolase that removed the C/sub 2/ /sub 0/, C/sub 4/ /sub 0/, and C/sub 7/ /sub 0/ acyl groups from the 2 position. By inhibiting the hydrolase with diisopropyl fluorophosphate, it was possible to test conversion of the unaltered substrates to plasmalogens. The alkyl desaturase exhibited little discrimination among the specific acyl derivatives tested. The highest rate of desaturation was obtained with 1-(1-/sup 14/C)-hexadecyl-2-acyl-GPE synthesized in situ in the microsomes via acylation of 1-(1-/sup 14/C)hexadecyl-GPE; this rate was threefold that observed with exogenously acylated substrates. The 1-(1-/sup 14/C)hexadecyl-2-acyl-GPE synthesized in situ contained highly unsaturated acyl groups; no selectivity of the desaturase for specific acyl chains was detected when the different molecular species of 1-(1-/sup 14/C)alkyl-2-acyl-GPE and 1-(1-/sup 14/C)alk-1'-eyl-2-acyl-GPE were compared. The short-chain substrates, being moe hydrophilic, mimicked the chromatographic behavior of 1-alkyl-GPE, yet they did not resemble the lyso compound in its higher conversion to plasmalogens. Thus, despite their similar R/sub f/ values, the packing of the short-chain acyl homologues in the membrane may be quite different from that of the lyso compound. Binding of 1-hexadecyl-2-acyl-GPE and 1-hexadecyl-GPE to microsomal membranes was similar.

Inflammation Scan Using {sup 99m}Tc-HMPAO Labelled Leukocytes

Energy Technology Data Exchange (ETDEWEB)

Yang, Woo Jin; Chung, Soo Kyo; Shinn, Kyung Sub; Bahk, Yong Whee; Kim, Hoon Kyo [Catholic University College of Medicine, Seoul (Korea, Republic of)

1989-07-15

Inflammation scan using radiolabelled leukocytes has high sensitivity and specificity. Several methods for labelling leukocytes have been evaluated using P-32 diisopropyl fluorophosphate (DFP -32), H-3 thymidine, Cr-51 chromate, Ga-67 citrate and {sup 99m}Tc-sulfur colloid. In-111-oxine has proved so far to be the most reliable agent for labelling leukocytes. In-111-oxine is, however, expensive, not easily available when needed, and its radiation dose to leukocytes is relatively high. Moreover, resolution of the resultant image is relatively poor. {sup 99m}Tc is still the agent of choice because of, as compared with the indium, its favorable physical characteristics, lower cost and availability. Now the technique for labelling the leukocytes with technetium is successfully obtained using the lipophilic HMPAO with higher efficiency for granulocytes than for other cells. With this technique it is possible to label leukocytes in plans to improve the viability of the leukocytes. Inflammation scan using {sup 99m}Tc-HMPAO has been evaluated in several laboratories, and difference in methods for separation and labelling accounts for difference in efficiency, viability and biodistribution of the labelled leukocytes. We performed inflammation scan using leukocytes labelled with {sup 99m}Tc-HMPAO in three dogs 24 hours after inoculation of live E. Coli and S. Aureus in their right abdominal wall. We separated mixed leukocytes by simple sedimentation using 6% hetastarch (HES) and labelled the leukocytes with {sup 99m}Tc-HMPAO in 20% cell free plasma diluted with phosphate buffer solution. Uptake was high in the liver and spleen but is was minimal in the lungs on whole body scan. Kidneys and intestine showed minimal activity although it was high in the urinary bladder. Uptake of labelled leukocytes in the inflammation site was definite on 2 hour-postinjection scan and abscess was clearly delineated on 24 hour-delayed scan with high target-to-nontarget ratio. 4). Inflammation

Gasoline ether oxygenate occurrence in Europe, and a review of their fate and transport characteristics in the environment

Energy Technology Data Exchange (ETDEWEB)

Stupp, D.; Gass, M.; Leiteritz, H. [Dr. Stupp Consulting DSC, Tauw, Bergisch Gladbach (Germany); Pijls, C. [TAUW, Apeldoorn (Netherlands); Thornton, S. [University of Sheffield, Sheffield (United Kingdom); Smith, J.; Dunk, M.; Grosjean, T.; Den Haan, K. [CONCAWE, Brussels (Belgium)

2012-06-15

Ether oxygenates are added to certain gasoline (petrol) formulations to improve combustion efficiency and to increase the octane rating. In this report the term gasoline ether oxygenates (GEO) refers collectively to methyl tertiary butyl ether (MTBE), ethyl tertiary butyl ether (ETBE), tertiary amyl methyl ether (TAME), diisopropyl ether (DIPE), tertiary amyl ethyl ether (TAEE), tertiary hexyl methyl ether (THxME), and tertiary hexyl ethyl ether (THxEE), as well as the associated tertiary butyl alcohol (TBA). This report presents newly collated data on the production capacities and use of MTBE, ETBE, TAME, DIPE and TBA in 30 countries (27 EU countries and Croatia, Norway and Switzerland) to inform continued and effective environmental management practices for GEO by CONCAWE members. The report comprises data on gasoline use in Europe that were provided by CONCAWE and obtained from the European Commission. Furthermore Societe Generale de Surveillance (SGS) provided detailed analytical data (more than 1,200 sampling campaigns) on the GEO composition of gasoline in European countries in the period 2000-2010. Another major aspect of this report is the investigation of GEO distribution in groundwater, drinking water, surface water, runoff water, precipitation (rain/snow) and air in the European environment. Apart from the general sources of literature for the study, local environmental authorities and institutes in the 30 European countries have been contacted for additional information. Finally, a review of the international literature on GEO natural attenuation processes was undertaken with a focus on international reports and peer-reviewed scientific publications to give an overview on the known fate, transport and degradation mechanisms of GEO in the subsurface, to inform risk-management strategies that may rely on natural attenuation processes. The literature reveals that all GEO compounds used in fuels are highly water soluble and weakly retarded by aquifer

Stable isotope N-phosphoryl amino acids labeling for quantitative profiling of amine-containing metabolites using liquid chromatography mass spectrometry.

Science.gov (United States)

Zhang, Shanshan; Shi, Jinwen; Shan, Changkai; Huang, Chengting; Wu, Yile; Ding, Rong; Xue, Yuhua; Liu, Wen; Zhou, Qiang; Zhao, Yufen; Xu, Pengxiang; Gao, Xiang

2017-07-25

Stable isotope chemical labeling liquid chromatography-mass spectrometry (LC-MS) is a powerful strategy for comprehensive metabolomics profiling, which can improve metabolites coverage and quantitative information for exploration of metabolic regulation in complex biological systems. In the current work, a novel stable isotope N-phosphoryl amino acids labeling strategy (SIPAL) has been successful developed for quantitative profiling of amine-containing metabolites in urine based on organic phosphorus chemistry. Two isotopic reagents, 16 O 2 - and 18 O 2 -N-diisopropyl phosphoryl l-alanine N-hydroxysuccinimide esters ( 16 O/ 18 O-DIPP-L-Ala-NHS), were firstly synthesized in high yields for labeling the amine-containing metabolites. The performance of SIPAL strategy was tested by analyzing standard samples including 20 l-amino acids, 10 d-amino acids and small peptides by using LC-MS. We observed highly efficient and selective labeling for SIPAL strategy within 15 min in a one-pot derivatization reaction under aqueous reaction conditions. The introduction of a neutral phosphate group at N-terminus can increase the proton affinity and overall hydrophobicity of targeted metabolites, leading to the better ionization efficiency in electrospray ionization processes and chromatographic separations of hydrophilic metabolites on reversed-phase column. Furthermore, the chiral metabolites, such as d-amino acids, could be converted to diastereomers after SIPAL and successfully separated on regular reversed-phase column. The chirality of labeled enantiomers can be determined by using different detection methods such as 31 P NMR, UV, and MS, demonstrating the potential application of SIPAL strategy. In addition, absolute quantification of chiral metabolites in biological samples can be easily achieved by using SIPAL strategy. For this purpose, urine samples collected from a healthy volunteer were analyzed by using LC-ESI-Orbitrap MS. Over 300 pairs of different amine

Analysis of phosphate esters in plant material. Extraction and purification.

Science.gov (United States)

Isherwood, F A; Barrett, F C

1967-09-01

1. A critical study was made of the quantitative extraction of nucleotide and sugar phosphates from plant tissue by either boiling aqueous ethanol or cold trichloroacetic acid. The effect of the extraction technique on the inactivation of the enzymes in the plant tissue and the possibility of adsorption of the phosphate esters on the cell wall were especially considered. 2. In the recommended method the plant tissue was frozen in liquid nitrogen, ground to a powder and then blended with cold aqueous trichloroacetic acid containing 8-hydroxyquinoline to prevent adsorption. 3. The extract contained large amounts of trichloroacetic acid, cations, chloride, sugars, amino acids, hydroxy organic acids, phytic acid, orthophosphoric acid and high-molecular-weight material including some phosphorus-containing compounds. All of these were removed as they were liable to interfere with the chromatographic or enzymic assay of the individual nucleotide or sugar phosphates. 4. The procedure was as follows: the last traces of trichloroacetic acid were extracted with ether after the solution had been passed through a column of Dowex AG 50 in the hydrogen form to remove all cations. High-molecular-weight compounds were removed by ultrafiltration and low-molecular-weight solutes by a two-stage chromatography on cellulose columns with organic solvents. In the first stage, sugars, amino acids, chloride and phytic acid were separated by using a basic solvent (propan-1-ol-water-aqueous ammonia) and, in the second stage, the organic acids and orthophosphoric acid were separated by using an acidic solvent (di-isopropyl ether-formic acid-2-methylpropan-2-ol-water). The final solution of nucleotide and sugar phosphates was substantially free from other solutes and was suitable for the detection of individual phosphate esters by either chromatography or enzymic assay. 5. The recovery of d-glucose 6-phosphate or adenosine 5'-triphosphate added to a trichloroacetic acid extract simulating that

Imidazenil, a non-sedating anticonvulsant benzodiazepine, is more potent than diazepam in protecting against DFP-induced seizures and neuronal damage

Energy Technology Data Exchange (ETDEWEB)

Kadriu, Bashkim; Guidotti, Alessandro; Costa, Erminio [Psychiatric Institute, Department of Psychiatry, College of Medicine, University of Illinois at Chicago, 1601 W. Taylor St., Chicago, IL 60612 (United States); Auta, James [Psychiatric Institute, Department of Psychiatry, College of Medicine, University of Illinois at Chicago, 1601 W. Taylor St., Chicago, IL 60612 (United States)

2009-02-27

Organophosphate (OP)-nerve agent poisoning may lead to prolonged epileptiform seizure activity, which can result in irreversible neuronal brain damage. A timely and effective control of seizures with pharmacological agents can minimize the secondary and long-term neuropathology that may result from this damage. Diazepam, the current anticonvulsant of choice in the management of OP poisoning, is associated with unwanted effects such as sedation, amnesia, cardio-respiratory depression, anticonvulsant tolerance, and dependence liabilities. In search for an efficacious and safer anticonvulsant benzodiazepine, we studied imidazenil, a potent anticonvulsant that is devoid of sedative action and has a low intrinsic efficacy at {alpha}1- but is a high efficacy positive allosteric modulator at {alpha}5-containing GABA{sub A} receptors. We compared the potency of a combination of 2 mg/kg, i.p. atropine with: (a) imidazenil 0.05-0.5 mg/kg i.p. or (b) equipotent anti-bicuculline doses of diazepam (0.5-5 mg/kg, i.p.), against diisopropyl fluorophosphate (DFP; 1.5 mg/kg, s.c.)-induced status epilepticus and its associated neuronal damage. The severity and frequency of seizure activities were determined by continuous radio telemetry recordings while the extent of neuronal damage and neuronal degeneration were assessed using the TUNEL-based cleaved DNA end-labeling technique or neuron-specific nuclear protein (NeuN)-immunolabeling and Fluoro-Jade B (FJB) staining, respectively. We report here that the combination of atropine and imidazenil is at least 10-fold more potent and longer lasting than the combination with diazepam at protecting rats from DFP-induced seizures and the associated neuronal damage or ongoing degeneration in the anterior cingulate cortex, CA1 hippocampus, and dentate gyrus. While 0.5 mg/kg imidazenil effectively attenuated DFP-induced neuronal damage and the ongoing neuronal degeneration in the anterior cingulate cortex, dentate gyrus, and CA1 hippocampus, 5

Imidazenil, a non-sedating anticonvulsant benzodiazepine, is more potent than diazepam in protecting against DFP-induced seizures and neuronal damage

International Nuclear Information System (INIS)

Kadriu, Bashkim; Guidotti, Alessandro; Costa, Erminio; Auta, James

2009-01-01

Organophosphate (OP)-nerve agent poisoning may lead to prolonged epileptiform seizure activity, which can result in irreversible neuronal brain damage. A timely and effective control of seizures with pharmacological agents can minimize the secondary and long-term neuropathology that may result from this damage. Diazepam, the current anticonvulsant of choice in the management of OP poisoning, is associated with unwanted effects such as sedation, amnesia, cardio-respiratory depression, anticonvulsant tolerance, and dependence liabilities. In search for an efficacious and safer anticonvulsant benzodiazepine, we studied imidazenil, a potent anticonvulsant that is devoid of sedative action and has a low intrinsic efficacy at α1- but is a high efficacy positive allosteric modulator at α5-containing GABA A receptors. We compared the potency of a combination of 2 mg/kg, i.p. atropine with: (a) imidazenil 0.05-0.5 mg/kg i.p. or (b) equipotent anti-bicuculline doses of diazepam (0.5-5 mg/kg, i.p.), against diisopropyl fluorophosphate (DFP; 1.5 mg/kg, s.c.)-induced status epilepticus and its associated neuronal damage. The severity and frequency of seizure activities were determined by continuous radio telemetry recordings while the extent of neuronal damage and neuronal degeneration were assessed using the TUNEL-based cleaved DNA end-labeling technique or neuron-specific nuclear protein (NeuN)-immunolabeling and Fluoro-Jade B (FJB) staining, respectively. We report here that the combination of atropine and imidazenil is at least 10-fold more potent and longer lasting than the combination with diazepam at protecting rats from DFP-induced seizures and the associated neuronal damage or ongoing degeneration in the anterior cingulate cortex, CA1 hippocampus, and dentate gyrus. While 0.5 mg/kg imidazenil effectively attenuated DFP-induced neuronal damage and the ongoing neuronal degeneration in the anterior cingulate cortex, dentate gyrus, and CA1 hippocampus, 5 mg/kg or a

Quantitative profiling of O-glycans by electrospray ionization- and matrix-assisted laser desorption ionization-time-of-flight-mass spectrometry after in-gel derivatization with isotope-coded 1-phenyl-3-methyl-5-pyrazolone

International Nuclear Information System (INIS)

Sić, Siniša; Maier, Norbert M.; Rizzi, Andreas M.

2016-01-01

The potential and benefits of isotope-coded labeling in the context of MS-based glycan profiling are evaluated focusing on the analysis of O-glycans. For this purpose, a derivatization strategy using d_0/d_5-1-phenyl-3-methyl-5-pyrazolone (PMP) is employed, allowing O-glycan release and derivatization to be achieved in one single step. The paper demonstrates that this release and derivatization reaction can be carried out also in-gel with only marginal loss in sensitivity compared to in-solution derivatization. Such an effective in-gel reaction allows one to extend this release/labeling method also to glycoprotein/glycoform samples pre-separated by gel-electrophoresis without the need of extracting the proteins/digested peptides from the gel. With highly O-glycosylated proteins (e.g. mucins) LODs in the range of 0.4 μg glycoprotein (100 fmol) loaded onto the electrophoresis gel can be attained, with minor glycosylated proteins (like IgAs, FVII, FIX) the LODs were in the range of 80–100 μg (250 pmol–1.5 nmol) glycoprotein loaded onto the gel. As second aspect, the potential of isotope coded labeling as internal standardization strategy for the reliable determination of quantitative glycan profiles via MALDI-MS is investigated. Towards this goal, a number of established and emerging MALDI matrices were tested for PMP-glycan quantitation, and their performance is compared with that of ESI-based measurements. The crystalline matrix 2,6-dihydroxyacetophenone (DHAP) and the ionic liquid matrix N,N-diisopropyl-ethyl-ammonium 2,4,6-trihydroxyacetophenone (DIEA-THAP) showed potential for MALDI-based quantitation of PMP-labeled O-glycans. We also provide a comprehensive overview on the performance of MS-based glycan quantitation approaches by comparing sensitivity, LOD, accuracy and repeatability data obtained with RP-HPLC-ESI-MS, stand-alone nano-ESI-MS with a spray-nozzle chip, and MALDI-MS. Finally, the suitability of the isotope-coded PMP labeling strategy for

Quantitative profiling of O-glycans by electrospray ionization- and matrix-assisted laser desorption ionization-time-of-flight-mass spectrometry after in-gel derivatization with isotope-coded 1-phenyl-3-methyl-5-pyrazolone

Energy Technology Data Exchange (ETDEWEB)

Sić, Siniša; Maier, Norbert M.; Rizzi, Andreas M., E-mail: Andreas.Rizzi@univie.ac.at

2016-09-07

The potential and benefits of isotope-coded labeling in the context of MS-based glycan profiling are evaluated focusing on the analysis of O-glycans. For this purpose, a derivatization strategy using d{sub 0}/d{sub 5}-1-phenyl-3-methyl-5-pyrazolone (PMP) is employed, allowing O-glycan release and derivatization to be achieved in one single step. The paper demonstrates that this release and derivatization reaction can be carried out also in-gel with only marginal loss in sensitivity compared to in-solution derivatization. Such an effective in-gel reaction allows one to extend this release/labeling method also to glycoprotein/glycoform samples pre-separated by gel-electrophoresis without the need of extracting the proteins/digested peptides from the gel. With highly O-glycosylated proteins (e.g. mucins) LODs in the range of 0.4 μg glycoprotein (100 fmol) loaded onto the electrophoresis gel can be attained, with minor glycosylated proteins (like IgAs, FVII, FIX) the LODs were in the range of 80–100 μg (250 pmol–1.5 nmol) glycoprotein loaded onto the gel. As second aspect, the potential of isotope coded labeling as internal standardization strategy for the reliable determination of quantitative glycan profiles via MALDI-MS is investigated. Towards this goal, a number of established and emerging MALDI matrices were tested for PMP-glycan quantitation, and their performance is compared with that of ESI-based measurements. The crystalline matrix 2,6-dihydroxyacetophenone (DHAP) and the ionic liquid matrix N,N-diisopropyl-ethyl-ammonium 2,4,6-trihydroxyacetophenone (DIEA-THAP) showed potential for MALDI-based quantitation of PMP-labeled O-glycans. We also provide a comprehensive overview on the performance of MS-based glycan quantitation approaches by comparing sensitivity, LOD, accuracy and repeatability data obtained with RP-HPLC-ESI-MS, stand-alone nano-ESI-MS with a spray-nozzle chip, and MALDI-MS. Finally, the suitability of the isotope-coded PMP labeling

Electronic and steric influences of pendant amine groups on the protonation of molybdenum bis (dinitrogen) complexes

Energy Technology Data Exchange (ETDEWEB)

Labios, Liezel A. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Heiden, Zachariah M. [Washington State Univ., Pullman, WA (United States); Mock, Michael T. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

2015-05-04

The synthesis of a series of P^EtP^NRR' (P^EtP^NRR' = Et₂PCH₂CH₂P(CH₂NRR')₂, R = H, R' = Ph or 2,4-difluorophenyl; R = R' = Ph or ⁱPr) diphosphine ligands containing mono- and disubstituted pendant amine groups, and the preparation of their corresponding molybdenum bis(dinitrogen) complexes trans-Mo(N₂)₂(PMePh₂)₂(P^EtP^NRR') is described. In situ IR and multinuclear NMR spectroscopic studies monitoring the stepwise addition of (HOTf) to trans-Mo(N₂)₂(PMePh₂)₂(P^EtP^NRR') complexes in THF at -40 °C show that the electronic and steric properties of the R and R' groups of the pendant amines influence whether the complexes are protonated at Mo, a pendant amine, a coordinated N2 ligand, or a combination of these sites. For example, complexes containing mono-aryl substituted pendant amines are protonated at Mo and pendant amine to generate mono- and dicationic Mo–H species. Protonation of the complex containing less basic diphenyl-substituted pendant amines exclusively generates a monocationic hydrazido (Mo(NNH₂)) product, indicating preferential protonation of an N₂ ligand. Addition of HOTf to the complex featuring more basic diisopropyl amines primarily produces a monocationic product protonated at a pendant amine site, as well as a trace amount of dicationic Mo(NNH₂) product that contain protonated pendant amines. In addition, trans-Mo(N₂)₂(PMePh₂)₂(depe) (depe = Et₂PCH₂CH₂PEt₂) without a pendant amine was synthesized and treated with HOTf, generating a monocationic Mo(NNH₂) product. Protonolysis experiments conducted on select complexes in the series afforded trace amounts of NH₄⁺. Computational analysis of the series of trans-Mo(N₂)₂(PMePh₂)₂(P^EtP^NRR') complexes provides further insight into the proton affinity values of the metal center, N�

Development of methods for the purification of 67Ga and 68Ga for biomolecules labeling

International Nuclear Information System (INIS)

Costa, Renata Ferreira

2012-01-01

For more than fifty years, the long-lived 68 Ge/ 68 Ga generators have been in development, obtaining 68 Ga without the need of having in house cyclotron, which is a considerable convenience for PET centers that have no nearby cyclotrons. 68 Ga decays 89% by positron emission and low photon emission (1077 keV) and the physical half life of 67.7 minutes is compatible with the pharmacokinetics of low biomolecular weight substances like peptides and antibody fragments. Moreover, its established metallic chemistry allows it to be stably bound to the carrier peptide sequence via a suitable bifunctional chelator, such as DOTA. All these reasons together with the technology of PET/CT allowed advances in molecular imaging, in particular in the diagnosis of neuroendocrine diseases. However, the eluate from the commercial 68 Ge/ 68 Ga generators still contains high levels of long lived 68 Ge, besides other metallic impurities, which competes with 68 Ga with a consequent reduction of the labeling yield of biomolecules, such as Fe 3+ and Zn 2+ . Thus, the lower the amount of impurities in the eluate, the competition between the radiolabeled and unlabeled peptide by the receptor will be smaller and the quality of imaging will be better, a subsequent purification step is needed after the generator elution. The aim of this work is to evaluate different purifications methods of 68 Ga to label biomolecules, with emphasis on the study of the chemical impurities contained in the eluate and to develop a new purification method. Several purification methods were studied. Many cationic resin were tested simulating the commercial process. 68 Ga is adsorbed in cationic resin, which is not commercial available and eluted in acid/acetone solution. The use of minor particles of cationic resin AG50W-X4 (200-400 mesh) showed the best results. An innovate method was the extraction chromatography, which is based on the absorption of diisopropyl ether in XAD 16 and 68 Ga recovery in deionized

Development of methods for the purification of {sup 67}Ga and {sup 68}Ga for biomolecules labeling; Desenvolvimento de metodos de purificacao do {sup 67}Ga e {sup 68}Ga para a marcacao de biomoleculas

Energy Technology Data Exchange (ETDEWEB)

Costa, Renata Ferreira

2012-07-01

diisopropyl ether in XAD 16 and {sup 68}Ga recovery in deionized water. Although the results regarding to {sup 68}Ga recovery and the radiochemical separation between {sup 68}Ga and {sup 65}Zn were excellent, there was no reproducibility on the purification of metals. The most promising and innovative method was the {sup 68}Ga purification performed by cationic resin in basic media, which presented the best results, especially regarding the Zn reduction (98 {+-} 2)%, the chemical contaminant found in great abundance in {sup 68}Ga eluate. The total impurities reduction was (95 {+-} 4)%. The peptides DOTATOC/DOTATATE were labeled {sup 68}Ga in three different forms: purified {sup 68}Ga in basic solution, through solvent extraction and no purified {sup 68}Ga. The best result was achieved with DOTATATE labeling with purified {sup 68}Ga in basic media, proving the purification process efficiency. (author)

Identification and quantification of the migration of chemicals from plastic baby bottles used as substitutes for polycarbonate.

Science.gov (United States)

Simoneau, C; Van den Eede, L; Valzacchi, S

2012-01-01

Community positive list, which means that those should not be found even in the first migration. Such substances included 2,6-di-isopropylnaphthalene (DIPN), found in 4% of the bottles at levels up to 25 µg kg⁻¹, 2,4-di-tert-butyl phenol (in 90% of the bottles at levels up 400 µg kg⁻¹). Moreover, bisphenol A (BPA) was detected and quantified in baby bottles made of PA, but limited to one brand and model specific (but labelled BPA free). Results for baby bottles made of silicone also indicated the presence of components, e.g. potentially coming from inks (benzophenone, diisopropyl naphtahalene - DIPN, which could come for example from the presence of instruction leaflets in the bottles). In the case of silicone, phthalates were also found in relevant concentrations, with levels for DiBP and DBP from the first migration test of 50-150 µg kg⁻¹ and DEHP at levels 25-50 µg kg⁻¹.

Bonding Properties of a Novel Inorganometallic Complex, Ru(SnPh(3))(2)(CO)(2)(iPr-DAB) (iPr-DAB = N,N'-Diisopropyl-1,4-diaza-1,3-butadiene), and its Stable Radical-Anion, Studied by UV-Vis, IR, and EPR Spectroscopy, (Spectro-) Electrochemistry, and Density Functional Calculations.

Science.gov (United States)

Aarnts, Maxim P.; Wilms, Maikel P.; Peelen, Karin; Fraanje, Jan; Goubitz, Kees; Hartl, Frantisek; Stufkens, Derk J.; Baerends, Evert Jan; Vlcek, Antonín

1996-09-11

Ru(SnPh(3))(2)(CO)(2)(iPr-DAB) was synthesized and characterized by UV-vis, IR, (1)H NMR, (13)C NMR, (119)Sn NMR, and mass (FAB(+)) spectroscopies and by single-crystal X-ray diffraction, which proved the presence of a nearly linear Sn-Ru-Sn unit. Crystals of Ru(SnPh(3))(2)(CO)(2)(iPr-DAB).3.5C(6)H(6) form in the triclinic space group P&onemacr; in a unit cell of dimensions a = 11.662(6) Å, b = 13.902(3) Å, c = 19.643(2) Å, alpha = 71.24(2) degrees, beta = 86.91(4) degrees, gamma = 77.89(3) degrees, and V = 2946(3) Å(3). One-electron reduction of Ru(SnPh(3))(2)(CO)(2)(iPr-DAB) produces the stable radical-anion [Ru(SnPh(3))(2)(CO)(2)(iPr-DAB)](*-) that was characterized by IR, and UV-vis spectroelectrochemistry. Its EPR spectrum shows a signal at g = 1.9960 with well resolved Sn, Ru, and iPr-DAB (H, N) hyperfine couplings. DFT-MO calculations on the model compound Ru(SnH(3))(2)(CO)(2)(H-DAB) reveal that the HOMO is mainly of sigma(Sn-Ru-Sn) character mixed strongly with the lowest pi orbital of the H-DAB ligand. The LUMO (SOMO in the reduced complex) should be viewed as predominantly pi(H-DAB) with an admixture of the sigma(Sn-Ru-Sn) orbital. Accordingly, the lowest-energy absorption band of the neutral species will mainly belong to the sigma(Sn-Ru-Sn)-->pi(iPr-DAB) charge transfer transition. The intrinsic strength of the Ru-Sn bond and the delocalized character of the three-center four-electron Sn-Ru-Sn sigma-bond account for the inherent stability of the radical anion.

(3R*,6R*,4′S*,8′R*,3′′R*,6′′R*-3,3′′-Diisopropyl-6,6′′-dimethyl-2′,6′-diphenyldispiro[cyclohexane-1,4′-(3,7-dioxa-2,6-diazabicyclo[3.3.0]octane-8′,1′′-cyclohexane]-2,2′′-dione

Directory of Open Access Journals (Sweden)

Abdeslam Ansari

2013-07-01

Full Text Available The two oxazolidine rings (A and B of the title compound, C34H44N2O4, display roughly half-chair conformations, which could be described as twisted on the C—O bond. Together, the fused oxazolidine rings have a butterfly shape, with the H atoms attached to the ring junction C atoms in a cis orientation. The cyclohexane rings of both p-menthone fragments display chair conformations. The absolute configuration could not be determined from the X-ray diffraction data, but the relative configuration of the stereocentres could be deduced.

Advanced Extraction Methods for Actinide/Lanthanide Separations

International Nuclear Information System (INIS)

Scott, M.J.

2005-01-01

high level liquid wastes and a general actinide clean-up procedure. The selectivity of the standard extractant for tetravalent actinides, (N,N-diisobutylcarbamoylmethyl) octylphenylphosphineoxide (CMPO), was markedly improved by the attachment of three CMPO-like functions onto a triphenoxymethane platform, and a ligand that is both highly selective and effective for An(IV) ions was isolated. A 10 fold excess of ligand will remove virtually all of the 4+ actinides from the acidic layer without extracting appreciable quantities of An(III) and Ln(III) unlike simple CMPO ligands. Inspired by the success of the DIAMEX industrial process for extractions, three new tripodal chelates bearing three diglycolamide and thiodiglycolamide units precisely arranged on a triphenoxymethane platform have been synthesized for an highly efficient extraction of trivalent f-element cations from nitric acid media. A single equivalent of ligand will remove 80% of the Ln(III) ion from the acidic layer since the ligand is perfectly suited to accommodate the tricapped trigonal prismatic geometry preferred by the metal center. The ligand is perhaps the most efficient binder available for the heavier lanthanides and due to this unique attribute, the extraction event can be easily followed by 1H NMR spectroscopy confirming the formation of a TPP complex. The most lipophilic di-n-butyl tris-diglycolamide was found to be a significantly weaker extractant in comparison to the di-isopropyl analogs. The tris-thiodiglycolamide derivative proved to be an ineffective chelate for f-elements and demonstrated the importance of the etheric oxygens in the metal binding. The results presented herein clearly demonstrate a cooperative action of these three ligating groups within a single molecule, confirmed by composition and structure of the extracted complexes, and since actinides prefer to have high coordination numbers, the ligands should be particularly adept at binding with three arms. The use of such an

Advanced Extraction Methods for Actinide/Lanthanide Separations

Energy Technology Data Exchange (ETDEWEB)

Scott, M.J.

2005-12-01

high level liquid wastes and a general actinide clean-up procedure. The selectivity of the standard extractant for tetravalent actinides, (N,N-diisobutylcarbamoylmethyl) octylphenylphosphineoxide (CMPO), was markedly improved by the attachment of three CMPO-like functions onto a triphenoxymethane platform, and a ligand that is both highly selective and effective for An(IV) ions was isolated. A 10 fold excess of ligand will remove virtually all of the 4+ actinides from the acidic layer without extracting appreciable quantities of An(III) and Ln(III) unlike simple CMPO ligands. Inspired by the success of the DIAMEX industrial process for extractions, three new tripodal chelates bearing three diglycolamide and thiodiglycolamide units precisely arranged on a triphenoxymethane platform have been synthesized for an highly efficient extraction of trivalent f-element cations from nitric acid media. A single equivalent of ligand will remove 80% of the Ln(III) ion from the acidic layer since the ligand is perfectly suited to accommodate the tricapped trigonal prismatic geometry preferred by the metal center. The ligand is perhaps the most efficient binder available for the heavier lanthanides and due to this unique attribute, the extraction event can be easily followed by 1H NMR spectroscopy confirming the formation of a TPP complex. The most lipophilic di-n-butyl tris-diglycolamide was found to be a significantly weaker extractant in comparison to the di-isopropyl analogs. The tris-thiodiglycolamide derivative proved to be an ineffective chelate for f-elements and demonstrated the importance of the etheric oxygens in the metal binding. The results presented herein clearly demonstrate a cooperative action of these three ligating groups within a single molecule, confirmed by composition and structure of the extracted complexes, and since actinides prefer to have high coordination numbers, the ligands should be particularly adept at binding with three arms. The use of such an

A Procedure for the Determination of Alpha-Emitting Plutonium in Urine Using a Solid-State Counter; Methode de Determination du Plutonium Emetteur Alpha Present dans l'Urine, au Moyen d'un Compteur a Semi-Conducteurs; Metod opredeleniya al'fa-izlucheniya plutoniya v moche s pomoshch'yu poluprovodnikovogo schetchika; Procedimiento para Determinar la Actividad Alfa del Plutonio en la Orina con Ayuda de un Contador de Estado Solido

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Sandalls, F. J.; Morgan, A. [Health Physics and Medical Division, Atomic Energy Research Establishment, Harwell (United Kingdom)

1964-10-15

A method for the routine determination of alpha-emitting plutonium in urine is described. In evolving this procedure various techniques for concentrating, purifying and electro depositing plutonium were compared, and these investigations are summarized. In the procedure finally adopted, urine is wet-ashed and the residue dissolved in hydrochloric acid. Plutonium (IV) is co-precipitated with iron cupferride from this solution and extracted into chloroform. After evaporation of the chloroform, the residue is oxidized, dissolved in hydrochloric acid and the iron extracted into di-isopropyl ether. The aqueous phase containing the plutonium is evaporated and dissolved in an acid ammonium sulphate solution from which the plutonium is electrodeposited onto stainless steel. Quantitative recoveries are obtained over the electrodeposition stage and on overall recovery of 84 {+-} 7%. The electrodeposited plutonium is counted with a solid-state (silicon junction diode) detector in a counter developed for this purpose. The low inherent background of this type of counter is effectively reduced still further by counting only those alpha particles with energy in the 4.2 - 5.4 MeV range. The good resolution which can be obtained with thin electrodeposited sources of plutonium enables this narrow channel to be used with only small losses in counting efficiency. By counting over this restricted energy range, the blank activity arising from reagents and incomplete removal of alpha-emitting contaminants in urine is also reduced by a factor of two, to just over 0.01 pc/24-h sample. The limit of detection with this method is about 0.025 pc of Pu{sup 239}. (author) [French] Les auteurs exposent une methode pour la determination courante du plutonium emetteur alpha present dans l'urine. Pour mettre au point cette methode, ils ont compare diverse procedes de concentration, de purification et de depot electrolytique du plutonium; les resultats de ces recherches sont resumes dans le memoire