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Sample records for carbonyl groups content

  1. New method to determine the total carbonyl functional group content in extractable particulate organic matter by tandem mass spectrometry.

    Science.gov (United States)

    Dron, J; Zheng, W; Marchand, N; Wortham, H

    2008-08-01

    A functional group analysis method was developed to determine the quantitative content of carbonyl functional groups in atmospheric particulate organic matter (POM) using constant neutral loss scanning-tandem mass spectrometry (CNLS-MS/MS). The neutral loss method consists in monitoring the loss of a neutral fragment produced by the fragmentation of a precursor ion in a collision cell. The only ions detected are the daughter ions resulting from the loss of the neutral fragment under study. Then, scanning the loss of a neutral fragment characteristic of a functional group enables the selective detection of the compounds bearing the chemical function under study within a complex mixture. The selective detection of carbonyl functional groups was achieved after derivatization with pentafluorophenylhydrazine (PFPH) by monitoring the neutral loss of C(6)F(5)N (181 amu), which was characteristic of a large panel of derivatized carbonyl compounds. The method was tested on 25 reference mixtures of different composition, all containing 24 carbonyl compounds at randomly determined concentrations. The repeatability and calibration tests were satisfying as they resulted in a relative standard deviation below 5% and a linear range between 0.01 and 0.65 mM with a calculated detection limit of 0.0035 mM. Also, the relative deviation induced by changing the composition of the mixture while keeping the total concentration of carbonyl functional groups constant was less than 20%. These reliability experiments demonstrate the high robustness of the developed procedure for accurate carbonyl functional group measurement, which was applied to atmospheric POM samples. Copyright (c) 2008 John Wiley & Sons, Ltd.

  2. Organocatalytic Hydrophosphonylation Reaction of Carbonyl Groups.

    Science.gov (United States)

    Herrera, Raquel P

    2017-09-01

    This revision is covering the limited examples reported for a pivotal strategy in the formation of C-P bonds such as the asymmetric organocatalytic hydrophosphonylation of carbonyl groups (Pudovik reaction). The scope and limitations, and the proposed mechanisms for the scarce different possibilities of asymmetric induction are also shown. The recent evolution and future trends of this undeveloped approach are commented. © 2017 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Ozone Effects on Protein Carbonyl Content in the Frontal ...

    Science.gov (United States)

    Oxidative stress (OS) plays an important role in susceptibility and disease in old age. Understanding age-related susceptibility is a critical part of community-based human health risk assessment of chemical exposures. There is growing concern over a common air pollutant, ozone (03), and adverse health effects including dysfunction of the pulmonary, cardiac, and nervous systems. The objective of this study was to test whether OS plays a role in the adverse effects caused by 03 exposure, and if so, if effects were age-dependent. We selected protein carbonyl as an indicator of OS because carbonyl content of cells is a useful indicator of oxidative protein damage and has been linked to chemical-induced adverse effects. Male Brown Norway rats (4, 12, and 24 months) were exposed to 03 (0,0.25 or 1 ppm) via inhalation for 6 h/day, 2 days per week for 13 weeks. Frontal cortex (FC) and cerebellum (CB) were dissected, quick frozen on dry ice, and stored at -80°C. Protein carbonyls were assayed using commercial kits. Hydrogen peroxide, a positive control, increased protein carbonyls in cortical tissue in vitro in a concentration-dependent manner. Significant effects of age on protein carbonyls in FC and a significant effect of age and 03 dose on protein carbonyls in CB were observed. In control rats, there was an age-dependent increase in protein carbonyls indicating increased OS in 12 and 24 month old rats compared to 4 month old rats. Although 03 increase

  4. Protein carbonyl content: a novel biomarker for aging in HIV/AIDS patients.

    Science.gov (United States)

    Kolgiri, Vaishali; Patil, Vinayak Wamanrao

    The major complications of "treated" Human Immunodeficiency Virus (HIV) infection are cardiovascular disease, malignancy, renal disease, liver disease, bone disease, and perhaps neurological complications, which are phenomena of the normal aging process occurring at an earlier age in the HIV-infected population. The present study is aimed to explore protein carbonyl content as a biomarker for detecting oxidative DNA damage induced ART toxicity and/or accelerated aging in HIV/AIDS patients. To investigate the potential of carbonyl content as a biomarker for detecting oxidative Deoxyribonucleic acid (DNA) damage induced Antiretroviral Theraphy (ART) toxicity and/or accelerated aging in HIV/AIDS patients. In this case-control study a total 600 subjects were included. All subjects were randomly selected and grouped as HIV-negative (control group) (n=300), HIV-infected ART naive (n=100), HIV-infected on first line ART (n=100), and HIV-infected on second line ART (n=100). Seronegative control subjects were age- and sex-matched with the ART naive patients and the two other groups. Carbonyl protein was determined by the method described in Levine et al. DNA damage marker 8-OH-dG was determined using 8-hydroxy-2-deoxy Guanosine StressXpress ELA Kit by StressMarq Biosciences. Protein carbonyl content levels and oxidative DNA damage were significantly higher (paging in HIV/AIDS patients. Larger studies are warranted to elucidate the role of carbonyl content as a biomarker for premature aging in HIV/AIDS patients. Copyright © 2016 Sociedade Brasileira de Infectologia. Published by Elsevier Editora Ltda. All rights reserved.

  5. Protein carbonyl content: a novel biomarker for aging in HIV/AIDS patients

    Directory of Open Access Journals (Sweden)

    Vaishali Kolgiri

    2017-01-01

    Conclusions: Carbonyl content may has a role as a biomarker for detecting oxidative DNA damage induced ART toxicity and/or accelerated aging in HIV/AIDS patients. Larger studies are warranted to elucidate the role of carbonyl content as a biomarker for premature aging in HIV/AIDS patients.

  6. Relationship between laparoscopic cholecystectomy operative time and carbonyl hemoglobin content

    Directory of Open Access Journals (Sweden)

    ZHANG Qi

    2013-06-01

    Full Text Available ObjectiveTo investigate whether operative time of laparoscopic cholecystectomy impacts the carbonyl hemoglobin (COHb concentration in peripheral blood. MethodsForty patients with gallstones and indications for laparoscopic cholecystectomy were enrolled in the study. Peripheral venous blood samples were collected at the beginning and end of the operative procedure. COHb concentration was measured by UV spectroscopy. The significance of changes in COHb concentration in relation to time of the operative procedure (rounded to the nearest minute was assessed by statistical correlation coefficient test. ResultsThe laparoscopic procedure was completed in 38 cases, and two patients required conversion to laparotomy. The content of COHb in peripheral venous blood had significantly increased during the laparoscopic operation (operation beginning: 11.07%±1.18% vs. operation end: 1.44%±0.26%, P<0.05. The change was positively correlated with operation time (r=0.85. ConclusionCarbon monoxide produced during the laparoscopic cholecystectomy procedure can lead to an increase in peripheral venous blood COHb. The longer the operation lasts, the greater the increase in COHb.

  7. Determination of Carbonyl Functional Groups in Bio-oils by Potentiometric Titration: The Faix Method.

    Science.gov (United States)

    Black, Stuart; Ferrell, Jack R

    2017-02-07

    Carbonyl compounds present in bio-oils are known to be responsible for bio-oil property changes upon storage and during upgrading. Specifically, carbonyls cause an increase in viscosity (often referred to as 'aging') during storage of bio-oils. As such, carbonyl content has previously been used as a method of tracking bio-oil aging and condensation reactions with less variability than viscosity measurements. Additionally, carbonyls are also responsible for coke formation in bio-oil upgrading processes. Given the importance of carbonyls in bio-oils, accurate analytical methods for their quantification are very important for the bio-oil community. Potentiometric titration methods based on carbonyl oximation have long been used for the determination of carbonyl content in pyrolysis bio-oils. Here, we present a modification of the traditional carbonyl oximation procedures that results in less reaction time, smaller sample size, higher precision, and more accurate carbonyl determinations. While traditional carbonyl oximation methods occur at room temperature, the Faix method presented here occurs at an elevated temperature of 80 °C.

  8. Catalytic hydrogenation of carbonyl group for deuterated compound production

    International Nuclear Information System (INIS)

    Gluhoi, C. Andreea; Marginean, P.; Lazar, Diana; Almasan, V.

    1999-01-01

    The total deuterated isopropyl alcohol can be produced starting from acetone. The developed technology comprises two steps: Deuteration of acetone by H/D isotopic exchange between acetone and heavy water in homogeneous catalysis. Reduction of the deuterated acetone with deuterium in presence of a metal/support catalyst. H/D isotopic exchange reaction of the H atoms from CH 3 groups is easy to occur because carbonyl group weakens C-H bond (ceto-enolyc tautomery). The big difference between boiling points of acetone and water permits an easy separation of acetone by distillation method. The reduction of acetone with deuterium was performed in a dynamic reactor by passing a deuterium flow saturated with acetone vapour through a supported nickel catalyst bed. The reaction products were analysed on-line using a flame ionisation detector. The supported nickel catalysts were checked for this reaction. By using nickel over different supports the selectivity for isopropyl alcohol was about 100%. The propane was detected only as traces. The catalytic activity depends strongly on the support nature: the Ni/SiO 2 is less active, while the Ni/TiO 2 presents the larger value for the intrinsic activity. (authors)

  9. Chemoselective Reduction and Alkylation of Carbonyl Functions Using Phosphonium Salts as an in Situ Protecting Groups.

    Science.gov (United States)

    Ohta, Reiya; Fujioka, Hiromichi

    2017-01-01

    Recent progress in the chemoselective reduction and alkylation of carbonyl functions using our in situ protection method is described. Methods that enable reversal or control of the reactivity of a carbonyl functional group are potentially useful. They open up new areas of synthetic organic chemistry and change the concept of retrosynthesis because they remove the need for complicated protection/deprotection sequences. In this account, we discuss the strategy and applications of our in situ protection method using phosphonium salts.

  10. Role of protein-bound carbonyl groups in the formation of advanced glycation endproducts.

    Science.gov (United States)

    Liggins, J; Furth, A J

    1997-08-22

    Several mechanisms have been postulated for the formation of advanced glycation endproducts (AGEs) from glycated proteins; they all feature protein-bound carbonyl intermediates. Using 2,4-dinitrophenylhydrazine (DNPH), we have detected these intermediates on bovine serum albumin, lysozyme and beta-lactoglobulin after in vitro glycation by glucose or fructose. Carbonyls were formed in parallel with AGE-fluorophores, via oxidative Maillard reactions. Neither Amadori nor Heyns products contributed to the DNPH reaction. Fluorophore and carbonyl yields were much enhanced in lipid-associated proteins, but both groups could also be detected in lipid-free proteins. When pre-glycated proteins were incubated in the absence of free sugar, carbonyl groups were rapidly lost in a first-order reaction, while fluorescence continued to develop beyond the 21 days of incubation. Another unexpected finding was that not all carbonyl groups were blocked by aminoguanidine, although there was complete inhibition of reactions leading to AGE-fluorescence. It is suggested that carbonyls acting as fluorophore precursors react readily with aminoguanidine, while others are resistant to this hydrazine, possibly because they are involved in ring closure. Factors influencing the relative rates of acyclisation and hydrazone formation are discussed, together with possible implications for antiglycation therapy.

  11. Separation of Trace Amount Zn (II Using Additional Carbonyl and Carboxyl Groups Functionalized-Nano Graphene

    Directory of Open Access Journals (Sweden)

    A. Moghimi

    2013-01-01

    Full Text Available A novel and selective method for the fast determination of trace amounts of Zn(IIions in water samples has been developed.  The first additional carbonyl and carboxyl functionalized-nano graphene (SPFNano graphene. The presence of additional carbonyl and carboxyl groups located at the edge of the sheets makes GO sheets strongly hydrophilic, allowing them to readily swell and disperse in water. Based on these oxygen functionalities, different model structures of GO were used as absorbent for extraction of Zn (II   ions by solid phase extraction method. The complexes were eluted with HNO3 (2M10% V.V-1 methanol in acetone and determined the analyte by flame atomic absorption spectrometry.  The procedure is based on the selective formation of Zn (II at optimum pH by elution with organic eluents and determination by flame atomic absorption spectrometry. The method is based on complex formation on the surface of the ENVI-18 DISKTM disks modified carbonyl and carboxyl functionalized-nano graphene oxide molecules covalently bonded together followed by stripping of the retained species by minimum amounts of appropriate organic solvents. The elution is efficient and quantitative. The effect of potential interfering ions, pH, SPFNano graphene, amount, stripping solvent, and sample flow rate were also investigated. Under the optimal experimental conditions, the break-through volume was found to about 1000mL providing a preconcentration factor of 500. The maximum capacity of the disks was found to be 456± 3 µg for Zn2+.The limit of detection of the proposed method is 5ng per 1000mL.The method was applied to the extraction and recovery of Zn in different water samples.

  12. Soil water content plays an important role in soil-atmosphere exchange of carbonyl sulfide (OCS)

    Science.gov (United States)

    Yi, Zhigang; Behrendt, Thomas; Bunk, Rüdiger; Wu, Dianming; Kesselmeier, Jürgen

    2016-04-01

    Carbonyl sulfide (OCS) is a quite stable gas in the troposphere and is transported up to the stratosphere, where it contributes to the sulfate aerosol layer (Crutzen 1976). The tropospheric concentration seems to be quite constant, indicating a balance between sinks and sources. Recent work by Sandoval-Soto et al. (2005) demonstrated the enormous strength of the vegetation sink and the urgent needs to understand the sinks and sources. The role of soils is a matter of discussion (Kesselmeier et al., 1999; Van Diest and Kesselmeier, 2008; Maseyk et al., 2014; Whelan et al., 2015). To better understand the influence of soil water content and OCS mixing ratio on OCS fluxes, we used an OCS analyzer (LGR COS/CO Analyzer 907-0028, Los Gatos, CA, USA) coupled with automated soil chamber system (Behrendt et al., 2014) to measure the OCS fluxes with a slow drying of four different types of soil (arable wheat soil in Mainz, blueberry soil in Waldstein, spruce soil in Waldstein and needle forest soil in Finland). Results showed that OCS fluxes as well as the optimum soil water content for OCS uptake varied significantly for different soils. The net production rates changed significantly with the soil drying out from 100% to about 5% water holding capacity (WHC), implying that soil water content play an important role in the uptake processes. The production and uptake processes were distinguished by the regression of OCS fluxes under different OCS mixing ratios. OCS compensation points (CP) were found to differ significantly for different soil types and water content, with the lowest CP at about 20% WHC, implying that when estimating the global budgets of OCS, especially for soils fluxes, soil water content should be taken into serious consideration. References Crutzen, P. J. 1976, Geophys. Res. Lett., 3, 73-76. Sandoval-Soto, L. et al., 2005, Biogeosciences, 2, 125-132. Kesselmeier, J. et al., 1999, J. Geophys. Res., 104, 11577-11584. Van Diest, H. and Kesselmeier, J. 2008

  13. Levels of protein hydroperoxides and carbonyl groups in guinea pigs native of high altitudes (Huancavelica, 3660 m)

    OpenAIRE

    Huayta, Roxana; Zúñiga, Haydée; Esquerre, Cynthia; Hernández, Luz; Carranza, Elizabeth

    2014-01-01

    The influence of hypobaric hypoxia on protein oxidation in lungs, heart, liver, kidneys and testicles of high altitude native guinea pigs (Huancavelica, 3660 m) in comparison to sea level (Lima, 150 m) native guinea pigs was evaluated. The concentration of protein hydroperoxides (POOH) and carbonyl groups (GC) as markers of protein oxidation, as well as total thiols (TT) concentration, powerful reducing agents that act as live antioxidants were determined. The results showed low concentration...

  14. Directionality of Cation/Molecule Bonding in Lewis Bases Containing the Carbonyl Group.

    Science.gov (United States)

    Valadbeigi, Younes; Gal, Jean-François

    2017-09-14

    Relationship between the C═O-X + (X = H, Li, Na, K, Al, Cu) angle and covalent characteristic of the X + -M (M = CH 2 O, CH 3 CHO, acetone, imidazol-2-one (C 2 H 2 N 2 O), cytosine, γ-butyrolactone) was investigated, theoretically. The calculated electron densities ρ at the bond critical points revealed that the covalency of the M-X + interaction depended on the nature of the cation and varied as H + > Cu + > Al + > Li + > Na + > K + . The alkali cations tended to participate in electrostatic interactions and aligned with the direction of the molecule dipole or local dipole of C═O group to form linear C═O-X geometries. Because of overlapping with lone-pair electrons of the sp 2 carbonyl oxygen, the H + and Cu + formed a bent C═O-X angle. Al + displayed an intermediate behavior; the C═O-Al angle was 180° in [CH 2 O/Al] + (mainly electrostatic), but when the angle was bent (146°) under the effect of local dipole of an adjacent imine group in cytosine, the covalency of the CO-Al + interaction increased. The C═O-X angles in M/X + adduct ions were scanned in different O-X bond lengths. It was found that the most favorable C═O-X angle depended on the O-X bond length. This dependency was attributed to variation of covalent and electrostatic contributions with O-X distance. In addition, the structures of [CH 2 S/X] + and [CH 2 Se/X] + were studied, and only bent C═S-X and C═Se-X angles were obtained for all cations, although the dipole vectors of CH 2 S and CH 2 Se coincide with the C═S and C═Se bonds. The bending of the C═S-X and C═Se-X angles was attributed to the covalent characteristic of S-X and Se-X interactions due to high polarizability of S and Se atoms.

  15. Conduction properties of KcsA measured using brownian dynamics with flexible carbonyl groups in the selectivity filter.

    Science.gov (United States)

    Chung, Shin-Ho; Corry, Ben

    2007-07-01

    In the narrow segment of an ion conducting pathway, it is likely that a permeating ion influences the positions of the nearby atoms that carry partial or full electronic charges. Here we introduce a method of incorporating the motion of charged atoms lining the pore into Brownian dynamics simulations of ion conduction. The movements of the carbonyl groups in the selectivity filter of the KcsA channel are calculated explicitly, allowing their bond lengths, bond angles, and dihedral angels to change in response to the forces acting upon them. By systematically changing the coefficients of bond stretching and of angle bending, the carbon and oxygen atoms can be made to fluctuate from their fixed positions by varying mean distances. We show that incorporating carbonyl motion in this way does not alter the mechanism of ion conduction and only has a small influence on the computed current. The slope conductance of the channel increases by approximately 25% when the root mean-square fluctuations of the carbonyl groups are increased from 0.01 to 0.61 A. The energy profiles and the number of resident ions in the channel remain unchanged. The method we utilized here can be extended to allow the movement of glutamate or aspartate side chains lining the selectivity filters of other ionic channels.

  16. Evaluation of ADMA, carbonyl groups, CAT and NKA in depressed patients with and without posttraumatic stress disorder.

    Science.gov (United States)

    Ogłodek, Ewa A

    2017-08-01

    It has been shown that asymmetric dimethylarginine (ADMA), carbonyl groups, catalase (CAT) and neurokinin A (NKA) are actively involved in neuronal processes such as depression and posttraumatic stress disorder (PTSD). One of their roles is to protect the body from oxidative damage. This is done by affecting neuronal growth, development and plasticity. The study aimed at assessing the concentrations of ADMA, carbonyl groups, CAT and NKA in patients with varying levels of depression severity, PTSD, and depression concurrent with PTSD. The study covered 460 people. Out of them, 120 suffered from different types of depression. The study groups comprised: 60 subjects with mild depression (MD), 60 subjects with moderate depression (MOD), 60 subjects with severe depression (SeD), 60 subjects with MD and PTSD (MD+PTSD), 60 subjects with MOD and PTSD (MOD+PTSD), 60 subjects with SeD and PTSD (SeD+PTSD), and 60 subjects with PTSD alone. Each group of 60 participants included 30 males and 30 females. The concentrations of all blood parameters were determined at 7 a.m. using the ELISA method. Depressive episodes became more severe as the concentration levels of studied markers increased. ADMA, carbonyl groups, CAT and NKA can be useful markers of chronic stress in both males and females with depression, PTSD, and depression concurrent with PTSD. They can be utilized when making an initial diagnosis and evaluating the severity of disease. Changes in their concentration levels may show a biological response to oxidative stress characteristic of depression. Copyright © 2017. Published by Elsevier Urban & Partner Sp. z o.o.

  17. Application of density functional theory to the nitric oxide heterogeneous reduction mechanism in the presence of hydroxyl and carbonyl groups

    International Nuclear Information System (INIS)

    Zhang, Hai; Jiang, Xiumin; Liu, Jiaxun; Shen, Jun

    2014-01-01

    Highlights: • The role of hydroxyl and carbonyl groups are studied on two modified zigzag models. • Energetics and kinetics for the proposed pathways are chiefly investigated. • New active sites are beneficial for NO adsorption and N-O bond dissociation. • The highly exothermicity of C(NCO) formation is helpful for CO 2 and N 2 elimination. - Abstract: Comprehensive theoretical calculations are carried out to investigate the nitric oxide (NO) heterogeneous reduction mechanism in the presence of hydroxyl (-OH) and carbonyl (>C=O) groups. Energetics (activation energy and thermochemistry data) and kinetics (thermal rate constant) for the proposed pathways are provided by density functional theory (DFT) and conventional transition state theory (TST), respectively. The role played by -OH and >C=O has been clarified. In the presence of -OH, four stepwise reactions with the highest energy barrier of 251.7 kJ/mol are found to produce new active sites. Subsequently, a number of elementary reactions with energy barrier below 116.1 kJ/mol take place to reduce NO. The role of > C=O is to yield NCO intermediate. The formation of NCO is highly exothermic with 709.4 kJ/mol, which contributes to the elimination of carbon dioxide (CO 2 ) and nitrogen (N 2 ). The discovered mechanism is consistent with previous experimental observation that NO heterogeneous reduction is enhanced due to the presence of oxygen

  18. Reciprocal carbonyl-carbonyl interactions in small molecules and proteins.

    Science.gov (United States)

    Rahim, Abdur; Saha, Pinaki; Jha, Kunal Kumar; Sukumar, Nagamani; Sarma, Bani Kanta

    2017-07-19

    Carbonyl-carbonyl n→π* interactions where a lone pair (n) of the oxygen atom of a carbonyl group is delocalized over the π* orbital of a nearby carbonyl group have attracted a lot of attention in recent years due to their ability to affect the 3D structure of small molecules, polyesters, peptides, and proteins. In this paper, we report the discovery of a "reciprocal" carbonyl-carbonyl interaction with substantial back and forth n→π* and π→π* electron delocalization between neighboring carbonyl groups. We have carried out experimental studies, analyses of crystallographic databases and theoretical calculations to show the presence of this interaction in both small molecules and proteins. In proteins, these interactions are primarily found in polyproline II (PPII) helices. As PPII are the most abundant secondary structures in unfolded proteins, we propose that these local interactions may have implications in protein folding.Carbonyl-carbonyl π* non covalent interactions affect the structure and stability of small molecules and proteins. Here, the authors carry out experimental studies, analyses of crystallographic databases and theoretical calculations to describe an additional type of carbonyl-carbonyl interaction.

  19. Validation of protein carbonyl measurement

    DEFF Research Database (Denmark)

    Augustyniak, Edyta; Adam, Aisha; Wojdyla, Katarzyna

    2015-01-01

    Protein carbonyls are widely analysed as a measure of protein oxidation. Several different methods exist for their determination. A previous study had described orders of magnitude variance that existed when protein carbonyls were analysed in a single laboratory by ELISA using different commercial...... protein carbonyl analysis across Europe. ELISA and Western blotting techniques detected an increase in protein carbonyl formation between 0 and 5min of UV irradiation irrespective of method used. After irradiation for 15min, less oxidation was detected by half of the laboratories than after 5min...... irradiation. Three of the four ELISA carbonyl results fell within 95% confidence intervals. Likely errors in calculating absolute carbonyl values may be attributed to differences in standardisation. Out of up to 88 proteins identified as containing carbonyl groups after tryptic cleavage of irradiated...

  20. Lack of FTSH4 Protease Affects Protein Carbonylation, Mitochondrial Morphology, and Phospholipid Content in Mitochondria of Arabidopsis: New Insights into a Complex Interplay.

    Science.gov (United States)

    Smakowska, Elwira; Skibior-Blaszczyk, Renata; Czarna, Malgorzata; Kolodziejczak, Marta; Kwasniak-Owczarek, Malgorzata; Parys, Katarzyna; Funk, Christiane; Janska, Hanna

    2016-08-01

    FTSH4 is one of the inner membrane-embedded ATP-dependent metalloproteases in mitochondria of Arabidopsis (Arabidopsis thaliana). In mutants impaired to express FTSH4, carbonylated proteins accumulated and leaf morphology was altered when grown under a short-day photoperiod, at 22°C, and a long-day photoperiod, at 30°C. To provide better insight into the function of FTSH4, we compared the mitochondrial proteomes and oxyproteomes of two ftsh4 mutants and wild-type plants grown under conditions inducing the phenotypic alterations. Numerous proteins from various submitochondrial compartments were observed to be carbonylated in the ftsh4 mutants, indicating a widespread oxidative stress. One of the reasons for the accumulation of carbonylated proteins in ftsh4 was the limited ATP-dependent proteolytic capacity of ftsh4 mitochondria, arising from insufficient ATP amount, probably as a result of an impaired oxidative phosphorylation (OXPHOS), especially complex V. In ftsh4, we further observed giant, spherical mitochondria coexisting among normal ones. Both effects, the increased number of abnormal mitochondria and the decreased stability/activity of the OXPHOS complexes, were probably caused by the lower amount of the mitochondrial membrane phospholipid cardiolipin. We postulate that the reduced cardiolipin content in ftsh4 mitochondria leads to perturbations within the OXPHOS complexes, generating more reactive oxygen species and less ATP, and to the deregulation of mitochondrial dynamics, causing in consequence the accumulation of oxidative damage. © 2016 American Society of Plant Biologists. All Rights Reserved.

  1. Effect of carbonyl group on the lifetimes of pentafluoroacetophenone and pentafluorobenzaldehyde radical anions in aqueous solution: a pulse radiolysis study

    International Nuclear Information System (INIS)

    Shoute, L.C.T.

    1996-01-01

    Hydrated electrons react with pentafluoroacetophenone (PFA) to form radical anion. Evidence for the formation of the radical anion was obtained from observation of intermolecular electron transfer from PFA .- to p-benzoquinone (Q) and methyl viologen (MV 2+ ) to form Q .- and MV .+ . The radical anion lose fluoride with a rate constant of 5x10 4 s -1 . The radical anion has a pK a =7.5. Radical anion of pentafluorobenzaldehyde (PFB) was observed on reduction PFB with hydrated electron. It has a pK a =7.2. It loses fluoride with a rate constant of 1.2x10 5 s -1 . The studies show that substitution of a carbonyl group in the aromatic ring of a perfluorinated compound led to dramatic increase in the lifetime of the radical anion formed on electron addition due to decrease in the rate of fluoride elimination. This led to the possibility of observing their reactions with other solute present in the solution. (author). 6 refs., 1 tab

  2. Ab initio and DFT studies of the interaction between carbonyl and thiocarbonyl groups: the role of S center dot center dot center dot O chalcogen bonds

    Czech Academy of Sciences Publication Activity Database

    Zierkiewicz, W.; Fanfrlík, Jindřich; Hobza, Pavel; Michalska, D.; Zeegers-Huyskens, T.

    2016-01-01

    Roč. 135, č. 9 (2016), č. článku 217. ISSN 1432-881X R&D Projects: GA ČR(CZ) GBP208/12/G016 Institutional support: RVO:61388963 Keywords : chalcogen bonds * carbonyl and thiocarbonyl groups * CCSD(T) * DFT Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.890, year: 2016 http://link.springer.com/article/10.1007%2Fs00214-016-1972-z

  3. Improved thermooxidation and sedimentation stability of covalently-coated carbonyl iron particles with cholesteryl groups and their influence on magnetorheology

    Czech Academy of Sciences Publication Activity Database

    Mrlík, M.; Ilčíková, M.; Pavlínek, V.; Mosnáček, J.; Peer, Petra; Filip, Petr

    2013-01-01

    Roč. 396, april (2013), s. 146-151 ISSN 0021-9797 R&D Projects: GA ČR GA202/09/1626 Grant - others:GA MŠk(CZ) ED2.1.00/03.0111 Institutional support: RVO:67985874 Keywords : covalent coating * carbonyl iron * cholesteryl chloroformate * thermooxidation * Magnetorheology Subject RIV: BK - Fluid Dynamics Impact factor: 3.552, year: 2013

  4. Dansyl labeling and bidimensional mass spectrometry to investigate protein carbonylation.

    Science.gov (United States)

    Palmese, Angelo; De Rosa, Chiara; Marino, Gennaro; Amoresano, Angela

    2011-01-15

    Carbonylation is a non-enzymatic irreversible post-translational modification. The adduction of carbonyl groups to proteins is due to the presence of excess of ROS in cells. Carbonylation of specific amino acid side chains is one of the most abundant consequences of oxidative stress; therefore, the determination of carbonyl groups content in proteins is regarded as a reliable way to estimate the cellular damage caused by oxidative stress. This paper reports a novel RIGhT (Reporter Ion Generating Tag) (A. Amoresano, G. Monti, C. Cirulli, G. Marino. Rapid Commun. Mass Spectrom. 2006, 20, 1400) approach for selective labeling of carbonyl groups in proteins using dansylhydrazide, coupled with selective analysis by bidimensional mass spectrometry. We first applied this approach to ribonuclease A and lysozyme as model proteins. According to the so-called 'gel-free procedures', the analysis is carried out at the level of peptides following tryptic digest of the whole protein mixture. Modified RNaseA was analyzed in combined MS(2) and MS(3) scan mode, to specifically select the dansylated species taking advantage of the dansyl-specific fragmentation pathways. This combination allowed us to obtain a significant increase in signal/noise ratio and a significant increase in sensitivity of analysis, due to the reduction of duty cycle of the mass spectrometer. The unique signal obtained was correlated to peptide 1-10 of RNaseA carbonylated and labeled by dansylhydrazide. This strategy represents the first method leading to the direct identification of the carbonylation sites in proteins, thus indicating the feasibility of this strategy to investigate protein carbonylation in a proteomic approach. Copyright © 2010 John Wiley & Sons, Ltd.

  5. Rhodium(I)-catalyzed cyclization of allenynes with a carbonyl group through unusual insertion of a C-O bond into a rhodacycle intermediate.

    Science.gov (United States)

    Oonishi, Yoshihiro; Yokoe, Takayuki; Hosotani, Akihito; Sato, Yoshihiro

    2014-01-20

    Rhodium(I)-catalyzed cyclization of allenynes with a tethered carbonyl group was investigated. An unusual insertion of a CO bond into the C(sp(2) )-rhodium bond of a rhodacycle intermediate occurs via a highly strained transition state. Direct reductive elimination from the obtained rhodacyle intermediate proceeds to give a tricyclic product containing an 8-oxabicyclo[3.2.1]octane skeleton, while β-hydride elimination from the same intermediate gives products that contain fused five- and seven-membered rings in high yields. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. THE METAL CARBONYLS.

    Science.gov (United States)

    Blanchard, A A

    1941-10-03

    When the metal carbonyls were first discovered, their properties were startling because they seemed to violate nearly all the previously recognized generalizations of chemistry. Even to-day the existence of the carbonyls is not particularly emphasized in elementary courses of chemistry because it is rather hard to reconcile them with the first presentations of the generalizations of chemistry. Nevertheless, as the student progresses deeper into the knowledge of chemistry it becomes desirable to include the knowledge of the carbonyls both because they become more comprehensible when viewed in the light of Werner's system of coordination and because they themselves contribute to the comprehension of the Werner theory. As long ago as 1931, Reiff in his discussion of cobalt nitrosyl carbonyl recognized the correlation between the effective atomic number and the volatility of carbonyls. A more recent study of charged Werner coordination complexes, that is, of complex ions, has shown a similar role of the effective atomic number. We are standing on fairly firm ground when we point out the correlation between E.A.N. and the volatility of the carbonyl complexes and the existence of complex ions. Be it noted that we have made no postulates as to the arrangement of the electrons in quantum levels. In the inert gases the outer principal quantum group is supposed always to contain eight electrons. In the carbonyls and other Werner complexes there is no compelling reason to suppose that the electrons in the coordinating layer, be this layer of eight, ten, twelve or sixteen electrons, are not all at the same energy level. Although we have confined our discussion almost exclusively to the property of volatility, the carbonyls are very interesting from the standpoint of several other properties, for example, magnetic susceptibility and dielectric constant. Enthusiasts in the interpretation of such properties try to draw conclusions as to the condition of the electrons, sometimes

  7. Swift heavy ion irradiation effects on carbonyl and trans-vinylene groups in high and low density polyethylene

    International Nuclear Information System (INIS)

    Grosso, M.F. del; Chappa, V.C.; Arbeitman, C.R.; Garcia Bermudez, G.; Behar, M.

    2009-01-01

    In this work, we have studied the effects of swift heavy ion irradiation on the creation of new functional groups in high and low density polyethylene (HDPE and LDPE). Polymers were irradiated with different ions (6.77 MeV He and 47 MeV Li) and fluences. The induced changes were analyzed by Fourier transform infrared (FTIR) spectroscopy. Creation and damage cross sections for some groups were compared for two different types of PE.

  8. Swift heavy ion irradiation effects on carbonyl and trans-vinylene groups in high and low density polyethylene

    Energy Technology Data Exchange (ETDEWEB)

    Grosso, M.F. del, E-mail: delgrosso@tandar.cnea.gov.a [Gerencia de Investigacion y Aplicaciones, TANDAR-CNEA (Argentina); Chappa, V.C. [Gerencia de Investigacion y Aplicaciones, TANDAR-CNEA (Argentina); CONICET (Argentina); Arbeitman, C.R. [Gerencia de Investigacion y Aplicaciones, TANDAR-CNEA (Argentina); Garcia Bermudez, G. [Gerencia de Investigacion y Aplicaciones, TANDAR-CNEA (Argentina); CONICET (Argentina); Escuela de Ciencia y Tecnologia, UNSAM (Argentina); Behar, M. [Instituto de Fisica, UFRGS, Porto Alegre (Brazil)

    2009-10-01

    In this work, we have studied the effects of swift heavy ion irradiation on the creation of new functional groups in high and low density polyethylene (HDPE and LDPE). Polymers were irradiated with different ions (6.77 MeV He and 47 MeV Li) and fluences. The induced changes were analyzed by Fourier transform infrared (FTIR) spectroscopy. Creation and damage cross sections for some groups were compared for two different types of PE.

  9. Protein carbonylation in plants

    DEFF Research Database (Denmark)

    Møller, Ian Max; Havelund, Jesper; Rogowska-Wrzesinska, Adelina

    2017-01-01

    This chapter provides an overview of the current knowledge on protein carbonylation in plants and its role in plant physiology. It starts with a brief outline of the turnover and production sites of reactive oxygen species (ROS) in plants and the causes of protein carbonylation. This is followed...... by a description of the methods used to study protein carbonylation in plants, which is also very brief as the methods are similar to those used in studies on animals. The chapter also focuses on protein carbonylation in plants in general and in mitochondria and in seeds in particular, as case stories where...... specific carbonylated proteins have been identified. Protein carbonylation appears to accumulate at all stages of seed development and germination investigated to date. In some cases, such as seed aging, it is probably simply an accumulation of oxidative damage. However, in other cases protein...

  10. Stereoselective synthesis of tricyclic compounds by intramolecular palladium-catalyzed addition of aryl iodides to carbonyl groups

    Directory of Open Access Journals (Sweden)

    Jakub Saadi

    2016-06-01

    Full Text Available Starting from γ-ketoesters with an o-iodobenzyl group we studied a palladium-catalyzed cyclization process that stereoselectively led to bi- and tricyclic compounds in moderate to excellent yields. Four X-ray crystal structure analyses unequivocally defined the structure of crucial cyclization products. The relative configuration of the precursor compounds is essentially transferred to that of the products and the formed hydroxy group in the newly generated cyclohexane ring is consistently in trans-arrangement with respect to the methoxycarbonyl group. A transition-state model is proposed to explain the observed stereochemical outcome. This palladium-catalyzed Barbier-type reaction requires a reduction of palladium(II back to palladium(0 which is apparently achieved by the present triethylamine.

  11. Acrolein with an alpha, beta-unsaturated Carbonyl Group Inhibits LPS-induced Homodimerization of Toll-like Receptor 4

    Science.gov (United States)

    Acrolein is a highly electrophilic a,ß-unsaturated aldehyde present in a number of environmental sources, especially cigarette smoke. It reacts strongly with the thiol groups of cysteine residues by Michael addition and has been reported to inhibit nuclear factor-kB (NF-kB) activation by lipopolysac...

  12. Beyond alkyl transfer: Synthesis of main group metal (Mg, Ca, Zn) silyl and tris(oxazolinyl)borato complexes and their stoichiometric and catalytic reactions with borane Lewis acids and carbonyls

    Energy Technology Data Exchange (ETDEWEB)

    Lampland, Nicole Lynn [Iowa State Univ., Ames, IA (United States)

    2015-05-09

    Recently, the fundamental knowledge of main group metal chemistry has grown. This progress is crucial for the further development of main group metal compounds in silicon chemistry and catalysis and for advancing their applications as green alternatives to many rare earth and transition metal compounds. This thesis focuses on reactivity beyond the welldocumented alkyl-transfer applications for main group metals, and it highlights examples of reactions with Lewis acids and the reduction of carbonyls.

  13. Examination of bariatric surgery Facebook support groups: a content analysis.

    Science.gov (United States)

    Koball, Afton M; Jester, Dylan J; Domoff, Sarah E; Kallies, Kara J; Grothe, Karen B; Kothari, Shanu N

    2017-08-01

    Support following bariatric surgery is vital to ensure long-term postoperative success. Many individuals undergoing bariatric surgery are turning to online modalities, especially the popular social media platform Facebook, to access support groups and pages. Despite evidence suggesting that the majority of patients considering bariatric surgery are utilizing online groups, little is known about the actual content of these groups. The purpose of the present study was to conduct a content analysis of bariatric surgery support groups and pages on Facebook. Online via Facebook, independent academic medical center, United States. Data from bariatric surgery-related Facebook support groups and pages were extracted over a 1-month period in 2016. Salient content themes (e.g., progress posts, depression content, eating behaviors) were coded reliably (all κ> .70). More than 6,800 posts and replies were coded. Results indicated that seeking recommendations (11%), providing information or recommendations (53%), commenting on changes since surgery (19%), and lending support to other members (32%) were the most common types of posts. Content surrounding anxiety, eating behaviors, depression, body image, weight bias, and alcohol was found less frequently. Online bariatric surgery groups can be used to receive support, celebrate physical and emotional accomplishments, provide anecdotal accounts of the "bariatric lifestyle" for preoperative patients, and comment on challenges with mental health and experiences of weight bias. Providers should become acquainted with the content commonly found in online groups and exercise caution in recommending these platforms to information-seeking patients. Copyright © 2017 American Society for Bariatric Surgery. Published by Elsevier Inc. All rights reserved.

  14. Group Counseling with United States Racial Minority Groups: A 25-Year Content Analysis

    Science.gov (United States)

    Stark-Rose, Rose M.; Livingston-Sacin, Tina M.; Merchant, Niloufer; Finley, Amanda C.

    2012-01-01

    A 25-year content analysis was conducted of published group work articles that focused on 5 racial groups (African American, Asian American/Pacific Islander, Latino/a, Native American, and Intercultural group). Articles were included if they described an intervention or conceptual model with 1 of the racial groups. The analysis revealed 15 content…

  15. 50Hz Extremely Low Frequency Electromagnetic Fields Enhance Protein Carbonyl Groups Content in Cancer Cells: Effects on Proteasomal Systems

    Directory of Open Access Journals (Sweden)

    A. M. Eleuteri

    2009-01-01

    Full Text Available Electromagnetic fields are an assessed cause of prolonging free radicals lifespan. This study was carried out to investigate the influence of extremely low frequency electromagnetic fields on protein oxidation and on the 20S proteasome functionality, the complex responsible for the degradation of oxidized proteins. Caco 2 cells were exposed, for 24–72 hours, to 1 mT, 50 Hz electromagnetic fields. The treatment induced a time-dependent increase both in cell growth and in protein oxidation, more evident in the presence of TPA, while no changes in cell viability were detected. Exposing the cells to 50 Hz electromagnetic fields caused a global activation of the 20S proteasome catalytic components, particularly evident at 72 hours exposure and in the presence of TPA. The finding that EGCG, a natural antioxidant compound, counteracted the field-related pro-oxidant effects demonstrates that the increased proteasome activity was due to an enhancement in intracellular free radicals.

  16. Focusing on Content: Discourse in L2 Peer Review Groups

    Science.gov (United States)

    Vorobel, Oksana; Kim, Deoksoon

    2014-01-01

    Recent studies on peer review groups in second language classes have focused on various topics, including collaboration (Carr, 2008) and the effect of peer review versus teacher feedback on students' writing (Zhang, 1995). One area that has received little attention is the content of students' speech during peer review. This longitudinal case…

  17. Has Group Work Education Lost Its Social Group Work Essence? A Content Analysis of MSW Course Syllabi in Search of Mutual Aid and Group Conflict Content

    Science.gov (United States)

    Sweifach, Jay Stephen

    2015-01-01

    This article presents the results of a content analysis of MSW group work course syllabi in an effort to better understand the extent to which mutual aid and group conflict, two important dimensions of social group work, are included and featured as prominent elements in MSW-level group work instruction.

  18. Content-Related Interactions in Self-initiated Study Groups

    Science.gov (United States)

    Christian, Karen; Talanquer, Vicente

    2012-09-01

    The central goal of the present exploratory study was to investigate the nature of the content-related interactions in study groups independently organized by college organic chemistry students. We were particularly interested in the identification of the different factors that affected the emergence of opportunities for students to co-construct understanding and engage in higher levels of cognitive processing. Our results are based on the analysis of in situ observations of 34 self-initiated study sessions involving over a 100 students in three academic semesters. The investigation revealed three major types of social regulation processes, teaching, tutoring, and co-construction in the observed study sessions. However, the extent to which students engaged in each of them varied widely from one session to another. This variability was mostly determined by the specific composition of the study groups and the nature of the study tasks in which they were engaged. Decisions about how to organize the study session, the relative content knowledge and conceptual understanding expressed by the participants, as well as the cognitive level of the problems that guided group work had a strong impact on the nature of student interactions. Nevertheless, group talk in the observed study groups was mostly focused on low-level cognitive processes. The results of our work provide insights on how to better support students' productive engagement in study groups.

  19. [Healthy eating support groups on Facebook: content and features].

    Science.gov (United States)

    Leis, Ángela; Mayer, Miguel Ángel; Torres Niño, Javier; Rodríguez-González, Alejandro; Suelves, Josep Maria; Armayones, Manuel

    2013-01-01

    To determine the features and use of groups related to healthy eating on Facebook. We carried out a cross-sectional study through the Internet. Using the API on Facebook, we included open groups related to healthy eating in the Spanish language. The variables studied were name, description, category, the number and gender of users, date of creation, number of posts, content of the first 20 posts, and the most recent update. We selected 281 open groups for inclusion in the study. Of these, 125 were excluded because the content was unrelated to healthy eating. Finally 156 groups were studied with 14,619 users (10,373 women [71%] and 3,919 men [26.8%]). Dietary products were promoted by 40% of the groups. Facebook is used as a means of communication and for sharing health information. Because many of these groups promote dietary products, their usefulness for health education is doubtful. Health organizations should participate in social media. Copyright © 2012 SESPAS. Published by Elsevier Espana. All rights reserved.

  20. Structure and content of competitive group compositions in sports aerobics

    Directory of Open Access Journals (Sweden)

    Tetiana Moshenska

    2017-02-01

    Full Text Available Purpose: to make the analysis of modern competitive group compositions in sports aerobics. Material & Methods: pedagogical, sociological and methods of mathematical statistics were used. 10 coaches took part in the experimental part; analysis of protocols and video records of competitions of the aged category of children of 9–11 years old, who perform in the nomination of triplets and quintuples (group exercises, is carried out. Results: the content of competitive compositions and the allocated indicators are studied which defined it. Conclusions: the basic structural elements, which characterize competitive compositions, are allocated. Their components, quantity and time of performance are defined. It is established that variety of aerobic contents, spaces, and means of registration, musical compliance and logicality of creation of the whole competitive composition at high quality of performance characterizes teams – winners.

  1. Validation of protein carbonyl measurement: A multi-centre study

    Directory of Open Access Journals (Sweden)

    Edyta Augustyniak

    2015-04-01

    Full Text Available Protein carbonyls are widely analysed as a measure of protein oxidation. Several different methods exist for their determination. A previous study had described orders of magnitude variance that existed when protein carbonyls were analysed in a single laboratory by ELISA using different commercial kits. We have further explored the potential causes of variance in carbonyl analysis in a ring study. A soluble protein fraction was prepared from rat liver and exposed to 0, 5 and 15 min of UV irradiation. Lyophilised preparations were distributed to six different laboratories that routinely undertook protein carbonyl analysis across Europe. ELISA and Western blotting techniques detected an increase in protein carbonyl formation between 0 and 5 min of UV irradiation irrespective of method used. After irradiation for 15 min, less oxidation was detected by half of the laboratories than after 5 min irradiation. Three of the four ELISA carbonyl results fell within 95% confidence intervals. Likely errors in calculating absolute carbonyl values may be attributed to differences in standardisation. Out of up to 88 proteins identified as containing carbonyl groups after tryptic cleavage of irradiated and control liver proteins, only seven were common in all three liver preparations. Lysine and arginine residues modified by carbonyls are likely to be resistant to tryptic proteolysis. Use of a cocktail of proteases may increase the recovery of oxidised peptides. In conclusion, standardisation is critical for carbonyl analysis and heavily oxidised proteins may not be effectively analysed by any existing technique.

  2. Content analysis of neurodegenerative and mental diseases social groups.

    Science.gov (United States)

    Martínez-Pérez, Borja; de la Torre-Díez, Isabel; Bargiela-Flórez, Beatriz; López-Coronado, Miguel; Rodrigues, Joel J P C

    2015-12-01

    This article aims to characterize the different types of Facebook and Twitter groups for different mental diseases, their purposes, and their functions. We focused the search on depressive disorders, dementia, and Alzheimer's and Parkinson's diseases and examined the Facebook (www.facebook.com) and Twitter (www.twitter.com) groups. We used four assessment criteria: (1) purpose, (2) type of creator, (3) telehealth content, and (4) free-text responses in surveys and interviews. We observed a total of 357 Parkinson groups, 325 dementia groups, 853 Alzheimer groups, and 1127 depression groups on Facebook and Twitter. Moreover, we analyze the responses provided by different users. The survey and interview responses showed that many people were interested in using social networks to support and help in the fight against these diseases. The results indicate that social networks are acceptable by users in terms of simplicity and utility. People use them for finding support, information, self-help, advocacy and awareness, and for collecting funds. © The Author(s) 2014.

  3. Bifunctional dendrons for multiple carbohydrate presentation via carbonyl chemistry

    Directory of Open Access Journals (Sweden)

    Davide Bini

    2014-07-01

    Full Text Available The synthesis of new dendrons of the generations 0, 1 and 2 with a double bond at the focal point and a carbonyl group at the termini has been carried out. The carbonyl group has been exploited for the multivalent conjugation to a sample saccharide by reductive amination and alkoxyamine conjugation.

  4. Carbonyl-Olefin Exchange Reaction: Present State and Outlook

    Science.gov (United States)

    Kalinova, Radostina; Jossifov, Christo

    The carbonyl-olefin exchange reaction (COER) is a new reaction between carbonyl group and olefin double bond, which has a formal similarity with the olefin metathesis (OM) - one carbon atom in the latter is replaced with an oxygen atom. Till now the new reaction is performed successfully only when the two functional groups (carbonyl group and olefin double bond) are in one molecule and are conjugated. The α, β-unsaturated carbonyl compounds (substituted propenones) are the compounds with such a structure. They polymerize giving substituted polyacetylenes. The chain propagation step of this polymerization is in fact the COER. The question arises: is it possible the COER to take place when the two functional groups are not in one molecule and are not conjugated, and could this reaction became an alternative of the existing carbonyl olefination reactions?

  5. Oxidative versus Non-oxidative Decarboxylation of Amino Acids: Conditions for the Preferential Formation of Either Strecker Aldehydes or Amines in Amino Acid/Lipid-Derived Reactive Carbonyl Model Systems.

    Science.gov (United States)

    Zamora, Rosario; León, M Mercedes; Hidalgo, Francisco J

    2015-09-16

    Comparative formation of both 2-phenylethylamine and phenylacetaldehyde as a consequence of phenylalanine degradation by carbonyl compounds was studied in an attempt to understand if the amine/aldehyde ratio can be changed as a function of reaction conditions. The assayed carbonyl compounds were selected because of the presence in the chain of both electron-donating and electron-withdrawing groups and included alkenals, alkadienals, epoxyalkenals, oxoalkenals, and hydroxyalkenals as well as lipid hydroperoxides. The obtained results showed that the 2-phenylethylamine/phenylacetaldehyde ratio depended upon both the carbonyls and the reaction conditions. Thus, it can be increased using electron-donating groups in the chain of the carbonyl compound, small amounts of carbonyl compound, low oxygen content, increasing the pH, or increasing the temperature at pH 6. Opposed conditions (use of electron-withdrawing groups in the chain of the carbonyl compound, large amounts of carbonyl compound, high oxygen contents, low pH values, and increasing temperatures at low pH values) would decrease the 2-phenylethylamine/phenylacetaldehyde ratio, and the formation of aldehydes over amines in amino acid degradations would be favored.

  6. Synthesis and characterization of rhodium(I) complexes with P-N donor ligands and their catalytic application in transfer hydrogenation of carbonyl group

    Energy Technology Data Exchange (ETDEWEB)

    Barah, Geetika; Sarmah, Podma Poliov; Boruah, Devajani [Dept. of Chemistry, Dibrugarh University, Dibrugarh (India)

    2015-04-15

    Three rhodium(I) complexes of the types [Rh(COE)Cl(η{sup 2}-L)] (1a,1b) and [RhCl(η{sup 2}-L) (η{sup 1}-L)] (1c), where L = P⁓N donor ligands 2-[2-(diphenylphosphino) ethyl]pyridine, (PPh{sub 2}Etpy) (a), 2-(diphenylphosphino)pyridine (PPh{sub 2}py) (b), and 3-(diphenylphosphino)-1-propylamine (PPh{sub 2}(CH{sub 2}){sub 3}NH{sub 2}) (c), have been synthesized by reacting [Rh(coe){sub 2}Cl]{sub 2} with the respective ligands in 1:2 molar ratio for 1a, 1b and 1:4 molar ratio for 1c in DCM under refluxing condition. The complexes were characterized using different analytical techniques such as FT-IR, ESI(+) mass spectrometry, {sup 1}H and {sup 31}P{"1H} NMR spectrometry, conductivity measurements, and melting point determination. The synthesized complexes were found to exhibit good catalytic activity for the transfer hydrogenation of carbonyl compounds to corresponding alcohols with high conversion rate.

  7. Degradation of carbonyl hydroperoxides in the atmosphere and in combustion

    KAUST Repository

    Xing, Lili; Bao, Junwei Lucas; Wang, Zhandong; Zhang, Feng; Truhlar, Donald G.

    2017-01-01

    Oxygenates with carbonyl and hydroperoxy functional groups are important intermediates that are generated during the autooxidation of organic compounds in the atmosphere and during the autoignition of transport fuels. In the troposphere

  8. Millimeter wave spectra of carbonyl cyanide ⋆

    Science.gov (United States)

    Bteich, S.B.; Tercero, B.; Cernicharo, J.; Motiyenko, R.A.; Margulès, L.; Guillemin, J.-C.

    2016-01-01

    Context More than 30 cyanide derivatives of simple organic molecules have been detected in the interstellar medium, but only one dicarbonitrile has been found and that very recently. There is still a lack of high-resolution spectroscopic data particularly for dinitriles derivatives. The carbonyl cyanide molecule is a new and interesting candidate for astrophysical detection. It could be formed by the reaction of CO and CN radicals, or by substitution of the hydrogen atom by a cyano group in cyanoformaldehyde, HC(=O)CN, that has already been detected in the interstellar medium. Aims The available data on the rotational spectrum of carbonyl cyanide is limited in terms of quantum number values and frequency range, and does not allow accurate extrapolation of the spectrum into the millimeter-wave range. To provide a firm basis for astrophysical detection of carbonyl cyanide we studied its millimeter-wave spectrum. Methods The rotational spectrum of carbonyl cyanide was measured in the frequency range 152 - 308 GHz and analyzed using Watson’s A- and S-reduction Hamiltonians. Results The ground and first excited state of v5 vibrational mode were assigned and analyzed. More than 1100 distinct frequency lines of the ground state were fitted to produce an accurate set of rotational and centrifugal distortion constants up to the eighth order. The frequency predictions based on these constants should be accurate enough for astrophysical searches in the frequency range up to 500 GHz and for transition involving energy levels with J ≤ 100 and Ka ≤ 42. Based on the results we searched for interstellar carbonyl cyanide in available observational data without success. Thus, we derived upper limits to its column density in different sources. PMID:27738349

  9. Content-Based Covert Group Detection in Social Networks

    Science.gov (United States)

    2017-09-06

    The students took courses in natural language processing, data mining in various multi-media data sets, text retrieval, text summarization and... mining in social media including: we performed work, on (a) diffusion in social networks, (b) influence maximization in signed social networks, (c...Learning, Information Retrieval, Data Mining and Database. There are 8,293 messages. Our method outperformed state of the art methods based on content

  10. Investigation of Clostridium botulinum group III's mobilome content

    NARCIS (Netherlands)

    Woudstra, Cédric; Maréchal, Le Caroline; Souillard, Rozenn; Anniballi, Fabrizio; Auricchio, Bruna; Bano, Luca; Bayon-Auboyer, Marie Hélène; Koene, Miriam; Mermoud, Isabelle; Brito, Roseane B.; Lobato, Francisco C.F.; Silva, Rodrigo O.S.; Dorner, Martin B.; Fach, Patrick

    2018-01-01

    Clostridium botulinum group III is mainly responsible for botulism in animals. It could lead to high animal mortality rates and, therefore, represents a major environmental and economic concern. Strains of this group harbor the botulinum toxin locus on an unstable bacteriophage. Since the release of

  11. Submicron aerosol organic functional groups, ions, and water content at the Centreville SEARCH site (Alabama), during SOAS campaign

    Science.gov (United States)

    Ruggeri, G.; Ergin, G.; Modini, R. L.; Takahama, S.

    2013-12-01

    The SOAS campaign was conducted from June 1 to July 15 of 2013 in order to understand the relationship between biogenic and anthropogenic emissions in the South East US1,2. In this study, the organic and inorganic composition of submicron aerosol in the Centreville SEARCH site was measured by Fourier Transform Infrared Spectroscopy (FTIR) and the Ambient Ion Monitor (AIM; URG Corporation), whereas the aerosol water content was measured with a Dry Ambient Aerosol Size Spectrometer (DAASS)3. Organic functional group analysis was performed on PM1 aerosol selected by cyclone and collected on teflon filters with a time resolution of 4-12 hours, using one inlet heated to 50 °C and the other operated either at ambient temperature or 70 °C 4. The AIM measured both condensed and gas phase composition with a time resolution of 1 hour, providing partitioning behavior of inorganic species such as NH3/NH4+, HNO3/NO3-. These measurements collectively permit calculation of pure-component vapor pressures of candidate organic compounds and activity coefficients of interacting components in the condensed phase, using models such as SIMPOL.15, E-AIM6, and AIOMFAC7. From these results, the water content of the aerosol is predicted, and a comparison between modeled and measured partitioning of inorganic compounds and water vapor are discussed, in addition to organic aerosol volatility prediction based on functional group analysis. [1]- Goldstein, A.H., et al., Biogenic carbon and anthropogenic pollutants combine to form a cooling haze over the southeastern United States. Proceedings of the National Academy of Sciences of the United States of America, 2009. 106(22), 8835-8840. [2]- Carlton, A.G., Turpin, B.J., 2013. Particle partitioning potential of organic compounds is highest in the Eastern US and driven by anthropogenic water. Atmospheric Chemistry and Physics Discussions 13, 12743-12770. [3]- Khlystov, A., Stanier, C.O., Takahama, S., Pandis, S.N., 2005. Water content of ambient

  12. Investigation of Clostridium botulinum group III's mobilome content.

    Science.gov (United States)

    Woudstra, Cédric; Le Maréchal, Caroline; Souillard, Rozenn; Anniballi, Fabrizio; Auricchio, Bruna; Bano, Luca; Bayon-Auboyer, Marie-Hélène; Koene, Miriam; Mermoud, Isabelle; Brito, Roseane B; Lobato, Francisco C F; Silva, Rodrigo O S; Dorner, Martin B; Fach, Patrick

    2018-02-01

    Clostridium botulinum group III is mainly responsible for botulism in animals. It could lead to high animal mortality rates and, therefore, represents a major environmental and economic concern. Strains of this group harbor the botulinum toxin locus on an unstable bacteriophage. Since the release of the first complete C. botulinum group III genome sequence (strain BKT015925), strains have been found to contain others mobile elements encoding for toxin components. In this study, seven assays targeting toxin genes present on the genetic mobile elements of C. botulinum group III were developed with the objective to better characterize C. botulinum group III strains. The investigation of 110 C. botulinum group III strains and 519 naturally contaminated samples collected during botulism outbreaks in Europe showed alpha-toxin and C2-I/C2-II markers to be systematically associated with type C/D bont-positive samples, which may indicate an important role of these elements in the pathogenicity mechanisms. On the contrary, bont type D/C strains and the related positive samples appeared to contain almost none of the markers tested. Interestingly, 31 bont-negative samples collected on farms after a botulism outbreak revealed to be positive for some of the genetic mobile elements tested. This suggests loss of the bont phage, either in farm environment after the outbreak or during laboratory handling. Copyright © 2017 Elsevier Ltd. All rights reserved.

  13. Phenolic carbonyls undergo rapid aqueous photodegradation to form low-volatility, light-absorbing products

    Science.gov (United States)

    Smith, Jeremy D.; Kinney, Haley; Anastasio, Cort

    2016-02-01

    We investigated the aqueous photochemistry of six phenolic carbonyls - vanillin, acetovanillone, guaiacyl acetone, syringaldehyde, acetosyringone, and coniferyl aldehyde - that are emitted from wood combustion. The phenolic carbonyls absorb significant amounts of solar radiation and decay rapidly via direct photodegradation, with lifetimes (τ) of 13-140 min under Davis, CA winter solstice sunlight at midday (solar zenith angle = 62°). The one exception is guaiacyl acetone, where the carbonyl group is not directly connected to the aromatic ring: This species absorbs very little sunlight and undergoes direct photodegradation very slowly (τ > 103 min). We also found that the triplet excited states (3C*) of the phenolic carbonyls rapidly oxidize syringol (a methoxyphenol without a carbonyl group), on timescales of 1-5 h for solutions containing 5 μM phenolic carbonyl. The direct photodegradation of the phenolic carbonyls, and the oxidation of syringol by 3C*, both efficiently produce low volatility products, with SOA mass yields ranging from 80 to 140%. Contrary to most aliphatic carbonyls, under typical fog conditions we find that the primary sink for the aromatic phenolic carbonyls is direct photodegradation in the aqueous phase. In areas of significant wood combustion, phenolic carbonyls appear to be small but significant sources of aqueous SOA: over the course of a few hours, nearly all of the phenolic carbonyls will be converted to SOA via direct photodegradation, enhancing the POA mass from wood combustion by approximately 3-5%.

  14. Binding cooperativity between a ligand carbonyl group and a hydrophobic side chain can be enhanced by additional H-bonds in a distance dependent manner: A case study with thrombin inhibitors.

    Science.gov (United States)

    Said, Ahmed M; Hangauer, David G

    2015-01-01

    One of the underappreciated non-covalent binding factors, which can significantly affect ligand-protein binding affinity, is the cooperativity between ligand functional groups. Using four different series of thrombin inhibitors, we reveal a strong positive cooperativity between an H-bond accepting carbonyl functionality and the adjacent P3 hydrophobic side chain. Adding an H-bond donating amine adjacent to the P3 hydrophobic side chain further increases this positive cooperativity thereby improving the Ki by as much as 546-fold. In contrast, adding an amidine multiple H-bond/salt bridge group in the distal S1 pocket does not affect this cooperativity. An analysis of the crystallographic B-factors of the ligand groups inside the binding site indicates that the strong cooperativity is mainly due to a significant mutual reduction in the residual mobility of the hydrophobic side chain and the H-bonding functionalities that is absent when the separation distance is large. This type of cooperativity is important to encode in binding affinity prediction software, and to consider in SAR studies. Copyright © 2015 Elsevier Masson SAS. All rights reserved.

  15. Theoretical predictions of properties and gas-phase chromatography behaviour of carbonyl complexes of group-6 elements Cr, Mo, W, and element 106, Sg.

    Science.gov (United States)

    Pershina, V; Anton, J

    2013-05-07

    Fully relativistic, four-component density functional theory electronic structure calculations were performed for M(CO)6 of group-6 elements Cr, Mo, W, and element 106, Sg, with an aim to predict their adsorption behaviour in the gas-phase chromatography experiments. It was shown that seaborgium hexacarbonyl has a longer M-CO bond, smaller ionization potential, and larger polarizability than the other group-6 molecules. This is explained by the increasing relativistic expansion and destabilization of the (n - 1)d AOs with increasing Z in the group. Using results of the calculations, adsorption enthalpies of the group-6 hexacarbonyls on a quartz surface were predicted via a model of physisorption. According to the results, -ΔHads should decrease from Mo to W, while it should be almost equal--within the experimental error bars--for W and Sg. Thus, we expect that in the future gas-phase chromatography experiments it will be almost impossible--what concerns ΔHads--to distinguish between the W and Sg hexacarbonyls by their deposition on quartz.

  16. Transactive memory in organizational groups: the effects of content, consensus, specialization, and accuracy on group performance.

    Science.gov (United States)

    Austin, John R

    2003-10-01

    Previous research on transactive memory has found a positive relationship between transactive memory system development and group performance in single project laboratory and ad hoc groups. Closely related research on shared mental models and expertise recognition supports these findings. In this study, the author examined the relationship between transactive memory systems and performance in mature, continuing groups. A group's transactive memory system, measured as a combination of knowledge stock, knowledge specialization, transactive memory consensus, and transactive memory accuracy, is positively related to group goal performance, external group evaluations, and internal group evaluations. The positive relationship with group performance was found to hold for both task and external relationship transactive memory systems.

  17. 40 CFR Table 6 to Subpart Vvvv of... - Default Organic HAP Contents of Petroleum Solvent Groups

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 12 2010-07-01 2010-07-01 true Default Organic HAP Contents of... Manufacturing Pt. 63, Subpt. VVVV, Table 6 Table 6 to Subpart VVVV of Part 63—Default Organic HAP Contents of Petroleum Solvent Groups As specified in § 63.5758(a)(6), when detailed organic HAP content data for solvent...

  18. Application of Focal Conflict Theory to Psychoeducational Groups: Implications for Process, Content, and Leadership

    Science.gov (United States)

    Champe, Julia; Rubel, Deborah J.

    2012-01-01

    Group psychoeducation is a common group type used for a range of purposes. The literature presents balancing content and process as a challenge for psychoeducational group leaders. While the significance of group psychoeducation is supported, practitioners are given little direction for addressing process in these groups. Focal Conflict Theory…

  19. The cysteine 34 residue of A1M/α1-microglobulin is essential for protection of irradiated cell cultures and reduction of carbonyl groups.

    Science.gov (United States)

    Rutardottir, S; Nilsson, E J C; Pallon, J; Gram, M; Åkerström, B

    2013-07-01

    α1-microglobulin (A1M) is a 26 kDa plasma and a tissue protein belonging to the lipocalin family. The reductase and free radical scavenger A1M has been shown to protect cells and extracellular matrix against oxidative and irradiation-induced damage. The reductase activity was previously shown to depend upon an unpaired cysteinyl side-chain, C34, and three lysyl side-chains, K92, 118, and 130, located around the open end of the lipocalin pocket. The aim of this work was to investigate whether the cell and matrix protection by A1M is a result of its reductase activity by using A1M-variants with site-directed mutations of the C34, K92, K118, and K130 positions. The results show that the C34 side-chain is an absolute requirement for protection of HepG2 cell cultures against alpha-particle irradiation-induced cell death, upregulation of stress response and cell cycle regulation genes. Mutation of C34 also resulted in loss of the reduction capacity toward heme- and hydrogen peroxide-oxidized collagen, and the radical species 2,2´-azino-bis (3-ethyl-benzo-thiazoline-6-sulphonic acid) (ABTS). Furthermore, mutation of C34 significantly suppressed the cell-uptake of A1M. The K92, K118, and K130 side-chains were of minor importance in cell protection and reduction of oxidized collagen but strongly influenced the reduction of the ABTS-radical. It is concluded that antioxidative protection of cells and collagen by A1M is totally dependent on its C34 amino acid residue. A model of the cell protection mechanism of A1M should be based on the redox activity of the free thiolyl group of the C34 side-chain and a regulatory role of the K92, K118, and K130 residues.

  20. Ruthenium(ii)-catalyzed olefination via carbonyl reductive cross-coupling.

    Science.gov (United States)

    Wei, Wei; Dai, Xi-Jie; Wang, Haining; Li, Chenchen; Yang, Xiaobo; Li, Chao-Jun

    2017-12-01

    Natural availability of carbonyl groups offers reductive carbonyl coupling tremendous synthetic potential for efficient olefin synthesis, yet the catalytic carbonyl cross-coupling remains largely elusive. We report herein such a reaction, mediated by hydrazine under ruthenium(ii) catalysis. This method enables facile and selective cross-couplings of two unsymmetrical carbonyl compounds in either an intermolecular or intramolecular fashion. Moreover, this chemistry accommodates a variety of substrates, proceeds under mild reaction conditions with good functional group tolerance, and generates stoichiometric benign byproducts. Importantly, the coexistence of KO t Bu and bidentate phosphine dmpe is vital to this transformation.

  1. Millimeter wave spectra of carbonyl cyanide

    Science.gov (United States)

    Bteich, S. B.; Tercero, B.; Cernicharo, J.; Motiyenko, R. A.; Margulès, L.; Guillemin, J.-C.

    2016-07-01

    Context. More than 30 cyanide derivatives of simple organic molecules have been detected in the interstellar medium, but only one dicarbonitrile has been found and that very recently. There is still a lack of high-resolution spectroscopic data particularly for dinitriles derivatives. The carbonyl cyanide molecule is a new and interesting candidate for astrophysical detection. It could be formed by the reaction of CO and CN radicals, or by substitution of the hydrogen atom by a cyano group in cyanoformaldehyde, HC(=O)CN, that has already been detected in the interstellar medium. Aims: The available data on the rotational spectrum of carbonyl cyanide is limited in terms of quantum number values and frequency range, and does not allow accurate extrapolation of the spectrum into the millimeter-wave range. To provide a firm basis for astrophysical detection of carbonyl cyanide we studied its millimeter-wave spectrum. Methods: The rotational spectrum of carbonyl cyanide was measured in the frequency range 152-308 GHz and analyzed using Watson's A- and S-reduction Hamiltonians. Results: The ground and first excited state of v5 vibrational mode were assigned and analyzed. More than 1100 distinct frequency lines of the ground state were fitted to produce an accurate set of rotational and centrifugal distortion constants up to the eighth order. The frequency predictions based on these constants should be accurate enough for astrophysical searches in the frequency range up to 500 GHz and for transition involving energy levels with J ≤ 100 and Ka ≤ 42. Based on the results we searched for interstellar carbonyl cyanide in available observational data without success. Thus, we derived upper limits to its column density in different sources. This paper makes use of the following ALMA data: ADS/JAO.ALMA#2011.0.00009.SV. ALMA is a partnership of ESO (representing its member states), NSF (USA), and NINS (Japan) with NRC (Canada), NSC, and ASIAA (Taiwan), and KASI (Republic of

  2. Radical carbonylations using a continuous microflow system

    Directory of Open Access Journals (Sweden)

    Takahide Fukuyama

    2009-07-01

    Full Text Available Radical-based carbonylation reactions of alkyl halides were conducted in a microflow reactor under pressurized carbon monoxide gas. Good to excellent yields of carbonylated products were obtained via radical formylation, carbonylative cyclization and three-component coupling reactions, using tributyltin hydride or TTMSS as a radical mediator.

  3. A prospective randomized trial of content expertise versus process expertise in small group teaching.

    Science.gov (United States)

    Peets, Adam D; Cooke, Lara; Wright, Bruce; Coderre, Sylvain; McLaughlin, Kevin

    2010-10-14

    Effective teaching requires an understanding of both what (content knowledge) and how (process knowledge) to teach. While previous studies involving medical students have compared preceptors with greater or lesser content knowledge, it is unclear whether process expertise can compensate for deficient content expertise. Therefore, the objective of our study was to compare the effect of preceptors with process expertise to those with content expertise on medical students' learning outcomes in a structured small group environment. One hundred and fifty-one first year medical students were randomized to 11 groups for the small group component of the Cardiovascular-Respiratory course at the University of Calgary. Each group was then block randomized to one of three streams for the entire course: tutoring exclusively by physicians with content expertise (n = 5), tutoring exclusively by physicians with process expertise (n = 3), and tutoring by content experts for 11 sessions and process experts for 10 sessions (n = 3). After each of the 21 small group sessions, students evaluated their preceptors' teaching with a standardized instrument. Students' knowledge acquisition was assessed by an end-of-course multiple choice (EOC-MCQ) examination. Students rated the process experts significantly higher on each of the instrument's 15 items, including the overall rating. Students' mean score (±SD) on the EOC-MCQ exam was 76.1% (8.1) for groups taught by content experts, 78.2% (7.8) for the combination group and 79.5% (9.2) for process expert groups (p = 0.11). By linear regression student performance was higher if they had been taught by process experts (regression coefficient 2.7 [0.1, 5.4], p teach first year medical students within a structured small group environment; preceptors with process expertise result in at least equivalent, if not superior, student outcomes in this setting.

  4. Thiophene-2-carbonyl azide

    Directory of Open Access Journals (Sweden)

    Michael Findlater

    2013-08-01

    Full Text Available The title compound, C5H3N3OS, is almost planar (r.m.s. deviation for the ten non-H atoms = 0.018 Å and forms an extended layer structure in the (100 plane, held together via hydrogen-bonding interactions between adjacent molecules. Of particular note is the occurrence of RC—H...N−=N+=NR interactions between an aromatic C—H group and an azide moiety which, in conjunction with a complementary C—H...O=C interaction, forms a nine-membered ring.

  5. Comparison of carbonyl compounds emissions from diesel engine fueled with biodiesel and diesel

    Science.gov (United States)

    He, Chao; Ge, Yunshan; Tan, Jianwei; You, Kewei; Han, Xunkun; Wang, Junfang; You, Qiuwen; Shah, Asad Naeem

    The characteristics of carbonyl compounds emissions were investigated on a direct injection, turbocharged diesel engine fueled with pure biodiesel derived from soybean oil. The gas-phase carbonyls were collected by 2,4-dinitrophenylhydrazine (DNPH)-coated silica cartridges from diluted exhaust and analyzed by HPLC with UV detector. A commercial standard mixture including 14 carbonyl compounds was used for quantitative analysis. The experimental results indicate that biodiesel-fueled engine almost has triple carbonyls emissions of diesel-fueled engine. The weighted carbonyls emission of 8-mode test cycle of biodiesel is 90.8 mg (kW h) -1 and that of diesel is 30.7 mg (kW h) -1. The formaldehyde is the most abundant compound of carbonyls for both biodiesel and diesel, taking part for 46.2% and 62.7% respectively. The next most significant compounds are acetaldehyde, acrolein and acetone for both fuels. The engine fueled with biodiesel emits a comparatively high content of propionaldehyde and methacrolein. Biodiesel, as an alternative fuel, has lower specific reactivity (SR) caused by carbonyls compared with diesel. When fueled with biodiesel, carbonyl compounds make more contribution to total hydrocarbon emission.

  6. Frustrated Lewis pairs-assisted reduction of carbonyl compounds

    DEFF Research Database (Denmark)

    Marek, Ales; Pedersen, Martin Holst Friborg

    2015-01-01

    An alternative and robust method for the reduction of carbonyl groups by frustrated Lewis pairs (FLPs) is reported in this paper. With its very mild reaction conditions, good to excellent yields, absolute regioselectivity and the non-metallic character of the reagent, it provides an excellent too...

  7. Fish proteins as targets of ferrous-catalyzed oxidation: identification of protein carbonyls by fluorescent labeling on two-dimensional gels and MALDI-TOF/TOF mass spectrometry.

    Science.gov (United States)

    Pazos, Manuel; da Rocha, Angela Pereira; Roepstorff, Peter; Rogowska-Wrzesinska, Adelina

    2011-07-27

    Protein oxidation in fish meat is considered to affect negatively the muscle texture. An important source of free radicals taking part in this process is Fenton's reaction dependent on ferrous ions present in the tissue. The aim of this study was to investigate the susceptibility of cod muscle proteins in sarcoplasmic and myofibril fractions to in vitro metal-catalyzed oxidation and to point out protein candidates that might play a major role in the deterioration of fish quality. Extracted control proteins and proteins subjected to free radicals generated by Fe(II)/ascorbate mixture were labeled with fluorescein-5-thiosemicarbazide (FTSC) to tag carbonyl groups and separated by two-dimensional gel electrophoresis. Consecutive visualization of protein carbonyl levels by capturing the FTSC signal and total protein levels by capturing the SyproRuby staining signal allowed us to quantify the relative change in protein carbonyl levels corrected for changes in protein content. Proteins were identified using MALDI-TOF/TOF mass spectrometry and homology-based searches. The results show that freshly extracted cod muscle proteins exhibit a detectable carbonylation background and that the incubation with Fe(II)/ascorbate triggers a further oxidation of both sarcoplasmic and myofibril proteins. Different proteins exhibited various degrees of sensitivity to oxidation processes. Glyceraldehyde 3-phosphate dehydrogenase (GAPDH), nucleoside diphosphate kinase B (NDK), triosephosphate isomerase, phosphoglycerate mutase, lactate dehydrogenase, creatine kinase, and enolase were the sarcoplasmic proteins most vulnerable to ferrous-catalyzed oxidation. Moreover, NDK, phosphoglycerate mutase, and GAPDH were identified in several spots differing by their pI, and those forms showed different susceptibilities to metal-catalyzed oxidation, indicating that post-translational modifications may change the resistance of proteins to oxidative damage. The Fe(II)/ascorbate treatment significantly

  8. Study on physico-chemical properties of dialdehyde yam starch with different aldehyde group contents

    International Nuclear Information System (INIS)

    Zhang, Liming; Liu, Peng; Wang, Yugao; Gao, Wenyuan

    2011-01-01

    Dialdehyde yam starches (DASs) are prepared and characterized. Compared with native starch, viscosity average molecular weight of DASs decreases, and the extent of degradation depends on content of the aldehyde groups. Fourier transform infrared (FT-IR) spectra confirm that the characteristic peak for C=O group at 1732 cm -1 is enhanced with the increasing of content of the aldehyde groups. Scanning electron microscopy (SEM) micrographs show that the surface of starch granules becomes wrinkled. X-ray diffraction (XRD) patterns clearly indicate that their crystallinity decreases with the increasing content of the aldehyde groups before they become amorphous at higher oxidation states. The experimental results of thermogravimetric analysis (TGA) show that DASs have poor stability as compared to native starch. With the increase in content of the aldehyde groups, the thermal stability of DAS declines gradually. According to the results of differential scanning calorimetry (DSC), gelatinization temperature (T o and T p ) of DASs are increased, whereas the gelatinization enthalpy decreased.

  9. Who we were and who we will be : The temporal context of women's in-group stereotype content

    NARCIS (Netherlands)

    Morton, Thomas A.; Rabinovich, Anna; Postmes, Tom

    Research has elaborated considerably on the dimensions of out-group stereotype content and on the origins and functions of different content combinations. Less attention has been given to the origins and functions of in-group stereotype content. We argue that in-group stereotypes are likely to serve

  10. Transition metal catalyzed carbonylation reactions carbonylative activation of C-X bonds

    CERN Document Server

    Beller, Matthias

    2014-01-01

    This book provides students and researchers in organic synthesis with a detailed discussion of carbonylation from the basics through to applications. It discusses the past, present and future of carbonylation reactions.

  11. Content-related interactions and methods of reasoning within self-initiated organic chemistry study groups

    Science.gov (United States)

    Christian, Karen Jeanne

    2011-12-01

    Students often use study groups to prepare for class or exams; yet to date, we know very little about how these groups actually function. This study looked at the ways in which undergraduate organic chemistry students prepared for exams through self-initiated study groups. We sought to characterize the methods of social regulation, levels of content processing, and types of reasoning processes used by students within their groups. Our analysis showed that groups engaged in predominantly three types of interactions when discussing chemistry content: co-construction, teaching, and tutoring. Although each group engaged in each of these types of interactions at some point, their prevalence varied between groups and group members. Our analysis suggests that the types of interactions that were most common depended on the relative content knowledge of the group members as well as on the difficulty of the tasks in which they were engaged. Additionally, we were interested in characterizing the reasoning methods used by students within their study groups. We found that students used a combination of three content-relevant methods of reasoning: model-based reasoning, case-based reasoning, or rule-based reasoning, in conjunction with one chemically-irrelevant method of reasoning: symbol-based reasoning. The most common way for groups to reason was to use rules, whereas the least common way was for students to work from a model. In general, student reasoning correlated strongly to the subject matter to which students were paying attention, and was only weakly related to student interactions. Overall, results from this study may help instructors to construct appropriate tasks to guide what and how students study outside of the classroom. We found that students had a decidedly strategic approach in their study groups, relying heavily on material provided by their instructors, and using the reasoning strategies that resulted in the lowest levels of content processing. We suggest

  12. Degree and content of negative meaning in four different age groups in Germany

    NARCIS (Netherlands)

    Read, S.; Westerhof, G.J.; Dittmann-Kohli, F.

    2005-01-01

    The aim of this study was to investigate the degree and content of negative meaning (i.e., negative evaluations, motivations, feelings) in four different age groups of men and women in East- and West-Germany. A sample was drawn from 290 cities in Germany which was stratified according to four age

  13. Evidence for the social role theory of stereotype content: observations of groups' roles shape stereotypes.

    Science.gov (United States)

    Koenig, Anne M; Eagly, Alice H

    2014-09-01

    In applying social role theory to account for the content of a wide range of stereotypes, this research tests the proposition that observations of groups' roles determine stereotype content (Eagly & Wood, 2012). In a novel test of how stereotypes can develop from observations, preliminary research collected participants' beliefs about the occupational roles (e.g., lawyer, teacher, fast food worker, chief executive officer, store clerk, manager) in which members of social groups (e.g., Black women, Hispanics, White men, the rich, senior citizens, high school dropouts) are overrepresented relative to their numbers in the general population. These beliefs about groups' typical occupational roles proved to be generally accurate when evaluated in relation to data from the Bureau of Labor Statistics. Then, correlational studies predicted participants' stereotypes of social groups from the attributes ascribed to group members' typical occupational roles (Studies 1a, 1b, and 1c), the behaviors associated with those roles (Study 2), and the occupational interest profile of the roles (Study 3). As predicted by social role theory, beliefs about the attributes of groups' typical roles were strongly related to group stereotypes on both communion and agency/competence. In addition, an experimental study (Study 4) demonstrated that when social groups were described with changes to their typical social roles in the future, their projected stereotypes were more influenced by these future roles than by their current group stereotypes, thus supporting social role theory's predictions about stereotype change. Discussion considers the implications of these findings for stereotype change and the relation of social role theory to other theories of stereotype content. 2014 APA, all rights reserved

  14. Using the Stereotype Content Model to examine group depictions in Fascism: An Archival Approach.

    Science.gov (United States)

    Durante, Federica; Volpato, Chiara; Fiske, Susan T

    2010-04-01

    The Stereotype Content Model (SCM) suggests potentially universal intergroup depictions. If universal, they should apply across history in archival data. Bridging this gap, we examined social groups descriptions during Italy's Fascist era. In Study 1, articles published in a Fascist magazine- La Difesa della Razza -were content analyzed, and results submitted to correspondence analysis. Admiration prejudice depicted ingroups; envious and contemptuous prejudices depicted specific outgroups, generally in line with SCM predictions. No paternalistic prejudice appeared; historical reasons might explain this finding. Results also fit the recently developed BIAS Map of behavioral consequences. In Study 2, ninety-six undergraduates rated the content-analysis traits on warmth and competence, without knowing their origin. They corroborated SCM's interpretations of the archival data.

  15. Advanced Oxidation Protein Products and Carbonylated Proteins as Biomarkers of Oxidative Stress in Selected Atherosclerosis-Mediated Diseases

    Directory of Open Access Journals (Sweden)

    Bogna Gryszczyńska

    2017-01-01

    Full Text Available Objectives. The main question of this study was to evaluate the intensity of oxidative protein modification shown as advanced oxidation protein products (AOPP and carbonylated proteins, expressed as protein carbonyl content (C=O in abdominal aortic aneurysms (AAA, aortoiliac occlusive disease (AIOD, and chronic kidney disease (CKD. Design and Methods. The study was carried out in a group of 35 AAA patients and 13 AIOD patients. However, CKD patients were divided into two groups: predialysis (PRE included 50 patients or hemodialysis (HD consisted of 34 patients. AOPP and C=O were measured using colorimetric assay kit, while C-reactive protein concentration was measured by high-sensitivity assay (hsCRP. Results. The concentration of AOPP in both AAA and AIOD groups was higher than in PRE and HD groups according to descending order: AAA~AIOD > HD > PRE. The content of C=O was higher in the PRE group in comparison to AIOD and AAA according to the descending order: PRE~HD > AAA~AIOD. Conclusions. AAA, AIOD, and CKD-related atherosclerosis (PRE and HD contribute to the changes in the formation of AOPP and C=O. They may promote modification of proteins in a different way, probably due to the various factors that influence oxidative stress here.

  16. Content

    DEFF Research Database (Denmark)

    Keiding, Tina Bering

    secondary levels. In subject matter didactics, the question of content is more developed, but it is still mostly confined to teaching on lower levels. As for higher education didactics, discussions on selection of content are almost non-existent on the programmatic level. Nevertheless, teachers are forced...... curriculum, in higher education, and to generate analytical categories and criteria for selection of content, which can be used for systematic didactical reflection. The larger project also concerns reflection on and clarification of the concept of content, including the relation between content at the level......Aim, content and methods are fundamental categories of both theoretical and practical general didactics. A quick glance in recent pedagogical literature on higher education, however, reveals a strong preoccupation with methods, i.e. how teaching should be organized socially (Biggs & Tang, 2007...

  17. Degradation of carbonyl hydroperoxides in the atmosphere and in combustion

    KAUST Repository

    Xing, Lili

    2017-10-12

    Oxygenates with carbonyl and hydroperoxy functional groups are important intermediates that are generated during the autooxidation of organic compounds in the atmosphere and during the autoignition of transport fuels. In the troposphere, the degradation of carbonyl hydroperoxides leads to low-vapor-pressure polyfunctional species that be taken into in cloud and fog droplets or to the formation of secondary organic aerosols (SOAs). In combustion, the fate of carbonyl hydroperoxides is important for the performance of advanced combustion engines, especially for autoignition. A key fate of the carbonyl hydroperoxides is reac-tion with OH radicals, for which kinetics data are experimentally unavailable. Here, we study 4-hydroperoxy-2-pentanone (CH3C(=O)CH2CH(OOH)CH3) as a model compound to clarify the kinetics of OH reactions with carbonyl hydroperoxides, in par-ticular H-atom abstraction and OH addition reactions. With a combination of electronic structure calculations, we determine previ-ously missing thermochemical data, and with multipath variational transition state theory (MP-VTST), a multidimensional tunnel-ing (MT) approximation, multiple-structure anharmonicity, and torsional potential anharmonicity we obtained much more accurate rate constants than the ones that can computed by conventional single-structure harmonic transition state theory (TST) and than the empirically estimated rate constants that are currently used in atmospheric and combustion modeling. The roles of various factors in determining the rates are elucidated. The pressure-dependent rate constants for the addition reaction are computed using system-specific quantum RRK theory. The calculated temperature range is 298-2400 K, and the pressure range is 0.01–100 atm. The accu-rate thermodynamic and kinetics data determined in this work are indispensable in the global modeling of SOAs in atmospheric science and in the detailed understanding and prediction of ignition properties of hydrocarbons

  18. Comparison of sampling methods for radiocarbon dating of carbonyls in air samples via accelerator mass spectrometry

    Science.gov (United States)

    Schindler, Matthias; Kretschmer, Wolfgang; Scharf, Andreas; Tschekalinskij, Alexander

    2016-05-01

    Three new methods to sample and prepare various carbonyl compounds for radiocarbon measurements were developed and tested. Two of these procedures utilized the Strecker synthetic method to form amino acids from carbonyl compounds with either sodium cyanide or trimethylsilyl cyanide. The third procedure used semicarbazide to form crystalline carbazones with the carbonyl compounds. The resulting amino acids and semicarbazones were then separated and purified using thin layer chromatography. The separated compounds were then combusted to CO2 and reduced to graphite to determine 14C content by accelerator mass spectrometry (AMS). All of these methods were also compared with the standard carbonyl compound sampling method wherein a compound is derivatized with 2,4-dinitrophenylhydrazine and then separated by high-performance liquid chromatography (HPLC).

  19. Comparison of sampling methods for radiocarbon dating of carbonyls in air samples via accelerator mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Schindler, Matthias, E-mail: matthias.schindler@physik.uni-erlangen.de; Kretschmer, Wolfgang; Scharf, Andreas; Tschekalinskij, Alexander

    2016-05-15

    Three new methods to sample and prepare various carbonyl compounds for radiocarbon measurements were developed and tested. Two of these procedures utilized the Strecker synthetic method to form amino acids from carbonyl compounds with either sodium cyanide or trimethylsilyl cyanide. The third procedure used semicarbazide to form crystalline carbazones with the carbonyl compounds. The resulting amino acids and semicarbazones were then separated and purified using thin layer chromatography. The separated compounds were then combusted to CO{sub 2} and reduced to graphite to determine {sup 14}C content by accelerator mass spectrometry (AMS). All of these methods were also compared with the standard carbonyl compound sampling method wherein a compound is derivatized with 2,4-dinitrophenylhydrazine and then separated by high-performance liquid chromatography (HPLC).

  20. Mechanistic differences between methanol and dimethyl ether carbonylation in side pockets and large channels of mordenite.

    Science.gov (United States)

    Boronat, Mercedes; Martínez, Cristina; Corma, Avelino

    2011-02-21

    The activity and selectivity towards carbonylation presented by Brønsted acid sites located inside the 8MR pockets or in the main 12MR channels of mordenite is studied by means of quantum-chemical calculations, and the mechanistic differences between methanol and DME carbonylation are investigated. The selectivity towards carbonylation is higher inside the 8MR pockets, where the competitive formation of DME and hydrocarbons that finally leads to catalyst deactivation is sterically impeded. Moreover, inclusion of dispersion interactions in the calculations leads to agreement between the calculated activation barriers for the rate determining step and the experimentally observed higher reactivity of methoxy groups located inside the 8MR channels.

  1. Qualitative evaluation of mobile cancer apps with particular attention to the target group, content, and advertising.

    Science.gov (United States)

    Böhme, Cathleen; von Osthoff, Marc Baron; Frey, Katrin; Hübner, Jutta

    2018-01-01

    Medical apps are gaining importance rapidly. Also in the field of cancer care, apps are offered. Yet, so far little is known with respect to their quality. In a pilot phase we developed a rating tool based on formal and content-related criteria for the assessment of cancer apps. We used this instrument on cancer apps available in the App Store (iOS) concerning breast, prostate and colorectal cancer. The results were stratified according to target group, content and advertising. We assessed 41 mobile cancer apps. Six apps (14.63%) scored very high, fifteen apps (36.59%) high, seventeen apps (41.46%) were deficient, and three apps (7.32%) were insufficient. The largest group of apps represents those apps with the "deficient" rating. The very good to good apps had reliable sources, a concrete intent/ purpose in their app description, and a strict distinction of scientific content and advertisement. Apps with the predicates "deficient" or "insufficient" had particularly poor ratings, e.g. in the subscales "information on sources" and "data protection". Almost half of the tested apps were deficient or insufficient. In order to improve safety of patients using apps, some regulation seems mandatory. Putting apps under the legislation for medical products might be one way to better regulate and control quality. Second, efforts should focus on the development of checklists that make it easier for patients to search for suitable cancer apps.

  2. The use of "vertical integration groups" to help define and update course/clerkship content.

    Science.gov (United States)

    Nierenberg, D W

    1998-10-01

    Faculty at many medical schools are working hard to improve the quality of their curricula. While the world "curriculum" means different things to different people, curricular change often includes improving the structure of the teaching/learning environment (e.g., seminars or problem-based learning groups vs lectures), the content of courses and clerkships (the core set of knowledge, skills, and attitudes that should be learned), and the manner in which student learning of knowledge and skills is evaluated (the sense that evaluation can help "drive" the curriculum). The author describes how "vertical integration groups" have been used over four years at Dartmouth Medical School to improve and modernize the content of courses and clerkships. In this approach, students and faculty work together to address and improve content areas that normally are not associated with traditional, discipline-centered courses or clerkships. The author discusses the advantages of this approach, the challenges encountered during implementation, and examples of how the approach has been put into action.

  3. Accumulation of carbonyls accelerates the formation of pentosidine, an advanced glycation end product: carbonyl stress in uremia.

    Science.gov (United States)

    Miyata, T; Ueda, Y; Yamada, Y; Izuhara, Y; Wada, T; Jadoul, M; Saito, A; Kurokawa, K; van Ypersele de Strihou, C

    1998-12-01

    Advanced glycation end product (AGE) formation is related to hyperglycemia in diabetes but not in uremia, because plasma AGE levels do not differ between diabetic and nondiabetic hemodialysis patients. The mechanism of this phenomenon remains elusive. Previously, it was suggested that elevation of AGE levels in uremia might result from the accumulation of unknown AGE precursors. The present study evaluates the in vitro generation of pentosidine, a well identified AGE structure. Plasma samples from healthy subjects and nondiabetic hemodialysis patients were incubated under air for several weeks. Pentosidine levels were determined at intervals by HPLC assay. Pentosidine rose to a much larger extent in uremic than in control plasma. Pentosidine yield, i.e., the change in pentosidine level between 0 and 4 wk divided by 28 d, averaged 0.172 nmol/ml per d in uremic versus 0.072 nmol/ml per d in control plasma (P aminoguanidine and OPB-9195, which inhibit the Maillard reaction, lowered pentosidine yield in both uremic and control plasma. When ultrafiltrated plasma was exposed to 2,4-dinitrophenylhydrazine, the yield of hydrazones, formed by interaction with carbonyl groups, was markedly higher in uremic than in control plasma. These observations strongly suggest that the pentosidine precursors accumulated in uremic plasma are carbonyl compounds. These precursors are unrelated to glucose or ascorbic acid, whose concentration is either normal or lowered in uremic plasma. They are also unrelated to 3-deoxyglucosone, a glucose-derived dicarbonyl compound whose level is raised in uremic plasma: Its addition to normal plasma fails to increase pentosidine yield. This study reports an elevated level of reactive carbonyl compounds ("carbonyl stress") in uremic plasma. Most have a lower than 5000 Da molecular weight and are thus partly removed by hemodialysis. Their effect on pentosidine generation can be inhibited by aminoguanidine or OPB-9195. Carbonyl stress might contribute to

  4. The use of biodiesel blends on a non-road generator and its impacts on ozone formation potentials based on carbonyl emissions

    International Nuclear Information System (INIS)

    Chai, Ming; Lu, Mingming; Liang, Fuyan; Tzillah, Aisha; Dendramis, Nancy; Watson, Libya

    2013-01-01

    In this study, emissions of carbonyl compounds from the use B50 and B100 were measured with a non-road diesel generator. A total of 25 carbonyl compounds were identified in the exhaust, including 10 with laboratory-synthesized standards. Formaldehyde, acetaldehyde, and acrolein were found as the most abundant carbonyl compounds emitted for both diesel and biodiesel. The sulphur content of diesel fuels and the source of biodiesel fuels were not found to have a significant impact on the emission of carbonyl compounds. The overall maximum incremental reactivity (MIR) was the highest at 0 kW and slightly increased from 25 to 75 kW. The MIR of B100 was the highest, followed by diesel and B50, which is consistent with the emission rates of total carbonyl compounds. This suggests that the use of biodiesel blends may be more beneficial to the environment than using pure biodiesel. -- Highlights: •Carbonyl compound emission from biodiesel blends combustion on a non-road generator. •25 compounds were identified, including 10 by laboratory-synthesized standards. •Sources of biodiesel have insignificant impacts on carbonyl compounds emission. •Sulphur contents have insignificant impacts on carbonyl compounds emission. •MIR of emitted carbonyls decreases in the following order: B100, diesel, B50. -- The study found that B50 resulted in lower total carbonyl emission rates and ozone formation potential resultant from these compounds, whereas both increased with B100

  5. Determination of carbonyl compounds (acetaldehyde and formaldehyde in polyethylene terephthalate containers designated for water conservation

    Directory of Open Access Journals (Sweden)

    Redžepović Azra S.

    2012-01-01

    Full Text Available Polyethylene terephthalate (PET has in the last several years become the main packaging material for many food products, particularly carbonated beverages and bottled water, as well as for products of chemical industry (packaging of various hygiene maintenance agents, pesticides, solvents, etc.. The strength and permeability properties of PET are very good for packaging of beverages, its resistance to chemicals is high and it has a high degree of transparency. Acetaldehyde and formaldehyde are formed during the thermoforming of PET containers. After cooling, acetaldehyde and formaldehyde remain trapped in the walls of a PET bottle and may migrate into the water after filling and storage. Since there are no migration tests in Serbia prescribed for the determination of acetaldehyde and formaldehyde, the purpose of the paper is to test the quantitative contents of carbonyl compounds (acetaldehyde and formaldehyde in PET containers of different volumes, made by various manufacturers of bottled mineral carbonated and noncarbonated water, and exposed to different temperatures. In this study, the migration of acetaldehyde and formaldehyde from PET bottles into mineral carbonated and noncarbonated water was determined by high performance liquid chromatography. Taking into consideration that formaldehyde and acetaldehyde have no UV active or fluorescent group, the chromatography shall be preceded by derivatization in a closed system (due to a low boiling point of acetaldehyde and formaldehyde, which shall transform carbonyl compounds into UV active compounds.

  6. Seeking support on facebook: a content analysis of breast cancer groups.

    Science.gov (United States)

    Bender, Jacqueline L; Jimenez-Marroquin, Maria-Carolina; Jadad, Alejandro R

    2011-02-04

    Social network sites have been growing in popularity across broad segments of Internet users, and are a convenient means to exchange information and support. Research on their use for health-related purposes is limited. This study aimed to characterize the purpose, use, and creators of Facebook groups related to breast cancer. We searched Facebook (www.Facebook.com) using the term breast cancer. We restricted our analysis to groups that were related to breast cancer, operated in English, and were publicly available. Two of us independently extracted information on the administrator and purpose of the group, as well as the number of user-generated contributions. We developed a coding scheme to guide content analysis. We found 620 breast cancer groups on Facebook containing a total of 1,090,397 members. The groups were created for fundraising (277/620, 44.7%), awareness (236, 38.1%), product or service promotion related to fundraising or awareness (61, 9%), or patient/caregiver support (46, 7%). The awareness groups as a whole contained by far the most members (n = 957,289). The majority of groups (532, 85.8%) had 25 wall posts or fewer. The support oriented groups, 47% (27/57) of which were established by high school or college students, were associated with the greatest number of user-generated contributions. Facebook groups have become a popular tool for awareness-raising, fundraising, and support-seeking related to breast cancer attracting over one million users. Given their popularity and reach, further research is warranted to explore the implications of social network sites as a health resource across various health conditions, cultures, ages, and socioeconomic groups.

  7. Psychosocial experiences of the internet in a group of adolescents: A qualitative content analysis.

    Science.gov (United States)

    Mahdizadeh, Mehrsadat; Solhi, Mahnaz; Ebadifard Azar, Farbod; Taghipour, Ali; Asgharnejad Farid, Aliasghar

    2017-01-01

    Background: Social networking has a dramatically increasing trend among adolescents. By creating novel models of content production, distribution, and reception, this space has introduced opportunities and threats for adolescents, which must be understood in relation with their health status. This study was conducted with the aim of describing the psychosocial experiences of Iranian adolescents in the Internet's virtual space. Methods: The present qualitative formal content analysis was conducted in Mashhad a city Iran. The participants included 32 adolescents of 13-18 years of age. Data were collected through 32 semi-structured individual and group interviews with maximum variation. The data were recorded, transcribed, and then analyzed via MAXQ 10 software. Results: In this study, 2 main themes of "moving towards constructiveness" and "perceiving social and psychological tensions" were formed. Accordingly, 9 subcategories were formulated including: increasing the social capital, a good feeling in life, escaping loneliness, being seen in the social network, intelligent selection of content, perceived threats, temptation, decline of behavioral values and principles, and emotional and social helplessness. Conclusion: Adolescents' positive and negative experiences in the Internet form based on personal and environmental factors. These experiences affect the mental and social dimensions of their health. These factors call for the attention of scholars and policymakers for developing enabling strategies for adolescents, and their families and for experts for promoting adolescents' health.

  8. Practicable group testing method to evaluate weight/weight GMO content in maize grains.

    Science.gov (United States)

    Mano, Junichi; Yanaka, Yuka; Ikezu, Yoko; Onishi, Mari; Futo, Satoshi; Minegishi, Yasutaka; Ninomiya, Kenji; Yotsuyanagi, Yuichi; Spiegelhalter, Frank; Akiyama, Hiroshi; Teshima, Reiko; Hino, Akihiro; Naito, Shigehiro; Koiwa, Tomohiro; Takabatake, Reona; Furui, Satoshi; Kitta, Kazumi

    2011-07-13

    Because of the increasing use of maize hybrids with genetically modified (GM) stacked events, the established and commonly used bulk sample methods for PCR quantification of GM maize in non-GM maize are prone to overestimate the GM organism (GMO) content, compared to the actual weight/weight percentage of GM maize in the grain sample. As an alternative method, we designed and assessed a group testing strategy in which the GMO content is statistically evaluated based on qualitative analyses of multiple small pools, consisting of 20 maize kernels each. This approach enables the GMO content evaluation on a weight/weight basis, irrespective of the presence of stacked-event kernels. To enhance the method's user-friendliness in routine application, we devised an easy-to-use PCR-based qualitative analytical method comprising a sample preparation step in which 20 maize kernels are ground in a lysis buffer and a subsequent PCR assay in which the lysate is directly used as a DNA template. This method was validated in a multilaboratory collaborative trial.

  9. Kinetics of carbonyl reductase from human brain.

    OpenAIRE

    Bohren, K M; von Wartburg, J P; Wermuth, B

    1987-01-01

    Initial-rate analysis of the carbonyl reductase-catalysed reduction of menadione by NADPH gave families of straight lines in double-reciprocal plots consistent with a sequential mechanism being obeyed. The fluorescence of NADPH was increased up to 7-fold with a concomitant shift of the emission maximum towards lower wavelength in the presence of carbonyl reductase, and both NADPH and NADP+ caused quenching of the enzyme fluorescence, indicating formation of a binary enzyme-coenzyme complex. D...

  10. Protein Carbonylation and Adipocyte Mitochondrial Function*

    Science.gov (United States)

    Curtis, Jessica M.; Hahn, Wendy S.; Stone, Matthew D.; Inda, Jacob J.; Droullard, David J.; Kuzmicic, Jovan P.; Donoghue, Margaret A.; Long, Eric K.; Armien, Anibal G.; Lavandero, Sergio; Arriaga, Edgar; Griffin, Timothy J.; Bernlohr, David A.

    2012-01-01

    Carbonylation is the covalent, non-reversible modification of the side chains of cysteine, histidine, and lysine residues by lipid peroxidation end products such as 4-hydroxy- and 4-oxononenal. In adipose tissue the effects of such modifications are associated with increased oxidative stress and metabolic dysregulation centered on mitochondrial energy metabolism. To address the role of protein carbonylation in the pathogenesis of mitochondrial dysfunction, quantitative proteomics was employed to identify specific targets of carbonylation in GSTA4-silenced or overexpressing 3T3-L1 adipocytes. GSTA4-silenced adipocytes displayed elevated carbonylation of several key mitochondrial proteins including the phosphate carrier protein, NADH dehydrogenase 1α subcomplexes 2 and 3, translocase of inner mitochondrial membrane 50, and valyl-tRNA synthetase. Elevated protein carbonylation is accompanied by diminished complex I activity, impaired respiration, increased superoxide production, and a reduction in membrane potential without changes in mitochondrial number, area, or density. Silencing of the phosphate carrier or NADH dehydrogenase 1α subcomplexes 2 or 3 in 3T3-L1 cells results in decreased basal and maximal respiration. These results suggest that protein carbonylation plays a major instigating role in cytokine-dependent mitochondrial dysfunction and may be linked to the development of insulin resistance in the adipocyte. PMID:22822087

  11. Protein carbonylation and adipocyte mitochondrial function.

    Science.gov (United States)

    Curtis, Jessica M; Hahn, Wendy S; Stone, Matthew D; Inda, Jacob J; Droullard, David J; Kuzmicic, Jovan P; Donoghue, Margaret A; Long, Eric K; Armien, Anibal G; Lavandero, Sergio; Arriaga, Edgar; Griffin, Timothy J; Bernlohr, David A

    2012-09-21

    Carbonylation is the covalent, non-reversible modification of the side chains of cysteine, histidine, and lysine residues by lipid peroxidation end products such as 4-hydroxy- and 4-oxononenal. In adipose tissue the effects of such modifications are associated with increased oxidative stress and metabolic dysregulation centered on mitochondrial energy metabolism. To address the role of protein carbonylation in the pathogenesis of mitochondrial dysfunction, quantitative proteomics was employed to identify specific targets of carbonylation in GSTA4-silenced or overexpressing 3T3-L1 adipocytes. GSTA4-silenced adipocytes displayed elevated carbonylation of several key mitochondrial proteins including the phosphate carrier protein, NADH dehydrogenase 1α subcomplexes 2 and 3, translocase of inner mitochondrial membrane 50, and valyl-tRNA synthetase. Elevated protein carbonylation is accompanied by diminished complex I activity, impaired respiration, increased superoxide production, and a reduction in membrane potential without changes in mitochondrial number, area, or density. Silencing of the phosphate carrier or NADH dehydrogenase 1α subcomplexes 2 or 3 in 3T3-L1 cells results in decreased basal and maximal respiration. These results suggest that protein carbonylation plays a major instigating role in cytokine-dependent mitochondrial dysfunction and may be linked to the development of insulin resistance in the adipocyte.

  12. Anchoring selenido-carbonyl ruthenium clusters to functionalized silica xerogels

    International Nuclear Information System (INIS)

    Cauzzi, Daniele; Graiff, Claudia; Pattacini, Roberto; Predieri, Giovanni; Tiripicchio, Antonio

    2003-01-01

    Silica Xerogels containing carbonyl Ru 3 Se 2 nido clusters were prepared in three different ways. The simple dispersion of [Ru 3 (μ 3 -Se) 2 (CO) 7 (PPh 3 ) 2 ] via sol gel process produces an inhomogeneous material; by contrast, homogeneous xerogels were obtained by reaction of [Ru 3 (μ 3 -Se) 2 (CO) 8 (PPh 3 )] with functionalized xerogels containing grafted diphenylphosphine moieties and by reaction of [Ru 3 (CO) 12 ] with a xerogel containing grafted phosphine-selenide groups. The reaction between [Ru 3 (CO) 12 ] and dodecyl diphenylphosphine selenide led to the formation of four selenido carbonyl clusters, which are soluble in hydrocarbon solvents and can be deposited as thin films from their solution by slow evaporation. (author)

  13. Deuterium enrichment by selective photo-induced dissociation of an organic carbonyl compound

    International Nuclear Information System (INIS)

    Marling, J.B.

    1981-01-01

    A deuterium-enriched material is produced by selective photoinduced dissociation of a gas phase organic carbonyl compound containing at least one hydrogen atom bonded to an atom adjacent to a carbonyl group. Alkyl carbonyl compounds such as acetone, acetaldehyde, trifluoroacetic acid, cyclobutanone, cyclopentanone, methyl acetate, 3,3-dimethyl-2-butanone, 2,4-pentanedione, and 4-methyl-2-pentanone are preferred. The carbonyl compound is subjected to intense infrared radiation from one laser, or two lasers operating at different frequencies, to selectively dissociate the deuterated molecules into stable products. The undissociated compound may be redeuterated by direct aqueous liquid phase H/D exchange, or by indirect liquid phase exchange using an alkanol in an intermediate step

  14. Glucosinolates and isothiocyanates from broccoliseed extractsuppressproteinglycationand carbonylation

    Directory of Open Access Journals (Sweden)

    Marina Hirano,

    2018-01-01

    Full Text Available Background: Glucosinolates from brassica plants are hydrolyzed by internal or salivary myrosinase to produce isothiocyanates. Glucoraphanin, a major glucosinolate in broccoli, is hydrolyzed to sulforaphane (SFN, which exhibits antitumor and detoxification activities. Regarding the influence of broccoli and its constituents on the skin, a few studies have reported anti-inflammatory and antioxidant effects. Recently, advanced glycation end products (AGEs and carbonyl proteins have been reported to accelerate skin aging. Objective: We evaluated the effects of broccoli seed extract (BSE and glucosinolates on protein glycation and carbonylation in vitro. Methods: To evaluate the effects of BSE and its constituents, protein glycation and carbonylation were induced by mixing fructose with bovine serum albumin (BSA and then measuring production of AGEs, fructosamine, and carbonyl proteins (CP. Production of CP after mixing fatty acids with BSA was also assessed. Furthermore, the effect of BSE and its constituents on CP production by human fibroblasts (TIG103 was examined. Results: BSE suppressed the production of AGEs, fructosamine, and CP after mixing fructose and BSA. BSE also suppressed production of CP when oxidized linoleic acid was mixed with BSA. Isothiocyanates, including SFN and iberin, suppressed fructose-based CP production, but SFN had no effect on CP production stimulated by oxidized linoleic acid. In contrast, glucosinolates from BSE did not suppress fructose-based CP production, but suppressed CP production due to oxidized linoleic acid. Among the glucosinolates in BSE, glucoberteroin showed the strongest suppression of CP production. CP production in fibroblasts was also suppressed by glucosinolates, including glucoiberin and glucoberteroin. Conclusions: BSE demonstrated anti-glycation and anti-carbonylation effects on protein reactions with fructose and oxidized fatty acids. Isothiocyanates suppressed protein carbonylation induced by

  15. COMPARATIVE STUDY OF EFFICACY OF FERROUS SULPHATE AND CARBONYL IRON IN ANEMIA OF ANTENATAL WOMEN

    Directory of Open Access Journals (Sweden)

    Radhika

    2015-03-01

    Full Text Available Iron deficiency anemia is the most common and important public health problem all over the world in the risk group of antenatal women. Research is going on to improve the iron status of the pregnant women with different forms of iron available. In this regard, Carbonyl Iron is showing promising results in improving the red cell mass with better compliance. 120 antenatal women were recruited in this study. The study comprised of 6weeks for each patient. They were given Carbonyl Iron 100 mg/day and FeS04 100gm/day . Before and after treatment all the baseline and specific investigations were one. Results were tabulated, comparison and significance were tested by unpaired student ’s’ test and their 'p' value was calculated. Results were shown graphically also. Carbonyl Iron showed improvement in hemoglobin, PCV and better than ferrous Sulphate (P <0.001. Incidence of side effects were less with Carbonyl Iron than Ferrous Sulphate, better compliance was seen with Carbonyl Iron. In conclusion, the present study s howed that Carbonyl Iron had better efficacy and safety in the management of Iron deficiency anemia in antenatal women than ferrous Sulphate

  16. Advocates, interest groups and Australian news coverage of alcohol advertising restrictions: content and framing analysis.

    Science.gov (United States)

    Fogarty, Andrea S; Chapman, Simon

    2012-08-31

    Legislating restrictions on alcohol advertising is a cost-effective measure to reduce consumption of alcohol. Yet Australia relies upon industry self-regulation through voluntary codes of practice regarding the content, timing and placement of alcohol advertising. Ending industry self-regulation was recommended by the National Preventative Health Taskforce; a suggestion contested by the drinks industry. Debates about emerging alcohol-control policies regularly play out in the news media, with various groups seeking to influence the discussion. This paper examines news coverage of recommendations to restrict alcohol advertising to see how supporters and opponents frame the debate, with a view to providing some suggestions for policy advocates to advance the discussion. We used content and framing analyses to examine 329 Australian newspaper items mentioning alcohol advertising restrictions over 24 months. All items were coded for mentions of specific types of advertising and types of advertising restrictions, the presence of news frames that opposed or endorsed advertising restrictions, statements made within each frame and the news-actors who appeared. Restrictions were the main focus in only 36% of 329 items. Alcohol advertising was conceived of as television (47%) and sport-related (56%). Restrictions were mentioned in non-specific terms (45%), or specified as restrictions on timing and placement (49%), or content (22%). Public health professionals (47%) appeared more frequently than drinks industry representatives (18%). Five supportive news frames suggested the policy is a sensible public health response, essential to protect children, needed to combat the drinks industry, required to stop pervasive branding, or as only an issue in sport. Four unsupportive frames positioned restrictions as unnecessary for a responsible industry, an attack on legitimate commercial activities, ineffective and 'nannyist', or inessential to government policy. Support varied among

  17. Advocates, interest groups and Australian news coverage of alcohol advertising restrictions: content and framing analysis

    Science.gov (United States)

    2012-01-01

    Background Legislating restrictions on alcohol advertising is a cost-effective measure to reduce consumption of alcohol. Yet Australia relies upon industry self-regulation through voluntary codes of practice regarding the content, timing and placement of alcohol advertising. Ending industry self-regulation was recommended by the National Preventative Health Taskforce; a suggestion contested by the drinks industry. Debates about emerging alcohol-control policies regularly play out in the news media, with various groups seeking to influence the discussion. This paper examines news coverage of recommendations to restrict alcohol advertising to see how supporters and opponents frame the debate, with a view to providing some suggestions for policy advocates to advance the discussion. Methods We used content and framing analyses to examine 329 Australian newspaper items mentioning alcohol advertising restrictions over 24 months. All items were coded for mentions of specific types of advertising and types of advertising restrictions, the presence of news frames that opposed or endorsed advertising restrictions, statements made within each frame and the news-actors who appeared. Results Restrictions were the main focus in only 36% of 329 items. Alcohol advertising was conceived of as television (47%) and sport-related (56%). Restrictions were mentioned in non-specific terms (45%), or specified as restrictions on timing and placement (49%), or content (22%). Public health professionals (47%) appeared more frequently than drinks industry representatives (18%). Five supportive news frames suggested the policy is a sensible public health response, essential to protect children, needed to combat the drinks industry, required to stop pervasive branding, or as only an issue in sport. Four unsupportive frames positioned restrictions as unnecessary for a responsible industry, an attack on legitimate commercial activities, ineffective and ‘nannyist’, or inessential to government

  18. Advocates, interest groups and Australian news coverage of alcohol advertising restrictions: content and framing analysis

    Directory of Open Access Journals (Sweden)

    Fogarty Andrea S

    2012-08-01

    Full Text Available Abstract Background Legislating restrictions on alcohol advertising is a cost-effective measure to reduce consumption of alcohol. Yet Australia relies upon industry self-regulation through voluntary codes of practice regarding the content, timing and placement of alcohol advertising. Ending industry self-regulation was recommended by the National Preventative Health Taskforce; a suggestion contested by the drinks industry. Debates about emerging alcohol-control policies regularly play out in the news media, with various groups seeking to influence the discussion. This paper examines news coverage of recommendations to restrict alcohol advertising to see how supporters and opponents frame the debate, with a view to providing some suggestions for policy advocates to advance the discussion. Methods We used content and framing analyses to examine 329 Australian newspaper items mentioning alcohol advertising restrictions over 24 months. All items were coded for mentions of specific types of advertising and types of advertising restrictions, the presence of news frames that opposed or endorsed advertising restrictions, statements made within each frame and the news-actors who appeared. Results Restrictions were the main focus in only 36% of 329 items. Alcohol advertising was conceived of as television (47% and sport-related (56%. Restrictions were mentioned in non-specific terms (45%, or specified as restrictions on timing and placement (49%, or content (22%. Public health professionals (47% appeared more frequently than drinks industry representatives (18%. Five supportive news frames suggested the policy is a sensible public health response, essential to protect children, needed to combat the drinks industry, required to stop pervasive branding, or as only an issue in sport. Four unsupportive frames positioned restrictions as unnecessary for a responsible industry, an attack on legitimate commercial activities, ineffective and ‘nannyist’, or

  19. Spatiotemporal distribution of carbonyl compounds in China

    International Nuclear Information System (INIS)

    Ho, K.F.; Ho, Steven Sai Hang; Huang, R.-J.; Dai, W.T.; Cao, J.J.; Tian, Linwei; Deng, W.J.

    2015-01-01

    A sampling campaign was carried out at nine Chinese cities in 2010/2011. Fifteen monocarbonyls (C#= 1–9) were quantified. Temperature is the rate-determining factor of the summertime carbonyl levels. The carbonyl emissions in winter are mainly driven by the primary anthropogenic sources like automobile. A molar ratio of propionaldehyde to nonaldehyde is a barometer of the impact of atmospheric vegetation emission which suggesting that strong vegetation emissions exist in summer and high propionaldehyde abundance is caused by fossil fuel combustion in winter. Potential health risk assessment of formaldehyde and acetaldehyde was conducted and the highest cumulative risks were observed at Chengdu in summer and Wuhan in winter. Because of the strong photochemical reaction and large amount of anthropogenic emissions, high concentrations of carbonyl compounds were observed in Chengdu. The use of ethanol-blended gasoline in Wuhan is the key reason of acetaldehyde emission and action should be taken to avoid potential health risks. - Highlights: • A national wide survey of ambient carbonyl compounds were conducted in China. • Using ethanol-blended gasoline can lead to higher cancer risks. • High concentrations of HMW carbonyls (C6, C7, C8 and C9) were observed in all cities. • HMW carbonyls (C6–C9) species show a very consistent seasonal variation. • C 3 /C 9 acts as an indicator for the impact of vegetation emission in the atmosphere. - Capsule abstract: Strong vegetation emission occurs in summer atmosphere and high acetaldehyde emission due to ethanol-blended gasoline consumption in 9 Chinese cities is discouraged

  20. Who we were and who we will be: the temporal context of women's in-group stereotype content.

    Science.gov (United States)

    Morton, Thomas A; Rabinovich, Anna; Postmes, Tom

    2012-06-01

    Research has elaborated considerably on the dimensions of out-group stereotype content and on the origins and functions of different content combinations. Less attention has been given to the origins and functions of in-group stereotype content. We argue that in-group stereotypes are likely to serve different social identity functions, and thus attract different content, dependent on individual differences in in-group identification and on the temporal perspective of the perceiver. Two studies (Ns = 43 and 93) found that women's in-group stereotype content varied as a function of gender group identification and temporal perspective. When the past was primed, highly identified women generated stereotypes that emphasized the warmth (but not competence) of their group. When the future was primed, highly identified women generated stereotypes that emphasized the competence (as well as warmth) of their group. These results are discussed in terms of the use of stereotypes for social creativity versus social change. © 2012 The British Psychological Society.

  1. Contents

    Directory of Open Access Journals (Sweden)

    Editor IJRED

    2012-11-01

    Full Text Available International Journal of Renewable Energy Development www.ijred.com Volume 1             Number 3            October 2012                ISSN 2252- 4940   CONTENTS OF ARTICLES page Design and Economic Analysis of a Photovoltaic System: A Case Study 65-73 C.O.C. Oko , E.O. Diemuodeke, N.F. Omunakwe, and E. Nnamdi     Development of Formaldehyde Adsorption using Modified Activated Carbon – A Review 75-80 W.D.P Rengga , M. Sudibandriyo and M. Nasikin     Process Optimization for Ethyl Ester Production in Fixed Bed Reactor Using Calcium Oxide Impregnated Palm Shell Activated Carbon (CaO/PSAC 81-86 A. Buasri , B. Ksapabutr, M. Panapoy and N. Chaiyut     Wind Resource Assessment in Abadan Airport in Iran 87-97 Mojtaba Nedaei       The Energy Processing by Power Electronics and its Impact on Power Quality 99-105 J. E. Rocha and B. W. D. C. Sanchez       First Aspect of Conventional Power System Assessment for High Wind Power Plants Penetration 107-113 A. Merzic , M. Music, and M. Rascic   Experimental Study on the Production of Karanja Oil Methyl Ester and Its Effect on Diesel Engine 115-122 N. Shrivastava,  , S.N. Varma and M. Pandey  

  2. Highly enantioselective rhodium(I)-catalyzed carbonyl carboacylations initiated by C-C bond activation.

    Science.gov (United States)

    Souillart, Laetitia; Cramer, Nicolai

    2014-09-01

    The lactone motif is ubiquitous in natural products and pharmaceuticals. The Tishchenko disproportionation of two aldehydes, a carbonyl hydroacylation, is an efficient and atom-economic access to lactones. However, these reaction types are limited to the transfer of a hydride to the accepting carbonyl group. The transfer of alkyl groups enabling the formation of CC bonds during the ester formation would be of significant interest. Reported herein is such asymmetric carbonyl carboacylation of aldehydes and ketones, thus affording complex bicyclic lactones in excellent enantioselectivities. The rhodium(I)-catalyzed transformation is induced by an enantiotopic CC bond activation of a cyclobutanone and the formed rhodacyclic intermediate reacts with aldehyde or ketone groups to give highly functionalized lactones. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Convenient Reduction of Carbonyl Compounds to their ...

    African Journals Online (AJOL)

    NICO

    Alcohols and their derivatives occupy an important position in organic synthesis. ... review also reveals that the reduction of carbonyl compounds ..... 1 H.B. Ji and Y.B. She, Green Oxidation and Reduction, China Petrochemi- cal Press, Beijing ...

  4. Protein Carbonylation in Patients with Myelodysplastic Syndromes

    Czech Academy of Sciences Publication Activity Database

    Hlaváčková, A.; Štikarová, J.; Kotlín, R.; Chrastinová, L.; Šácha, Pavel; Májek, P.; Čermák, J.; Suttnar, J.; Dyr, J. E.

    2015-01-01

    Roč. 126, č. 23 (2015), s. 5232 ISSN 0006-4971. [Annual Meeting and Exposition of the American Society of Hematology /55./. 07.12.2013-10.12.2013, New Orleans] Institutional support: RVO:61388963 Keywords : protein carbonylation * myelodysplastic syndromes Subject RIV: CE - Biochemistry

  5. What Really Happens in Quantitative Group Research? Results of a Content Analysis of Recent Quantitative Research in "JSGW"

    Science.gov (United States)

    Boyle, Lauren H.; Whittaker, Tiffany A.; Eyal, Maytal; McCarthy, Christopher J.

    2017-01-01

    The authors conducted a content analysis on quantitative studies published in "The Journal for Specialists in Group Work" ("JSGW") between 2012 and 2015. This brief report provides a general overview of the current practices of quantitative group research in counseling. The following study characteristics are reported and…

  6. Method for conversion of .beta.-hydroxy carbonyl compounds

    Science.gov (United States)

    Lilga, Michael A.; White, James F.; Holladay, Johnathan E.; Zacher, Alan H.; Muzatko, Danielle S.; Orth, Rick J.

    2010-03-30

    A process is disclosed for conversion of salts of .beta.-hydroxy carbonyl compounds forming useful conversion products including, e.g., .alpha.,.beta.-unsaturated carbonyl compounds and/or salts of .alpha.,.beta.-unsaturated carbonyl compounds. Conversion products find use, e.g., as feedstock and/or end-use chemicals.

  7. Expression, purification, crystallization and preliminary X-ray diffraction analysis of carbonyl reductase from Candida parapsilosis ATCC 7330

    International Nuclear Information System (INIS)

    Aggarwal, Nidhi; Mandal, P. K.; Gautham, Namasivayam; Chadha, Anju

    2013-01-01

    The expression, purification, crystallization, preliminary X-ray diffraction and molecular-replacement studies on C. parapsilosis carbonyl reductase are reported. The NAD(P)H-dependent carbonyl reductase from Candida parapsilosis ATCC 7330 catalyses the asymmetric reduction of ethyl 4-phenyl-2-oxobutanoate to ethyl (R)-4-phenyl-2-hydroxybutanoate, a precursor of angiotensin-converting enzyme inhibitors such as Cilazapril and Benazepril. The carbonyl reductase was expressed in Escherichia coli and purified by GST-affinity and size-exclusion chromatography. Crystals were obtained by the hanging-drop vapour-diffusion method and diffracted to 1.86 Å resolution. The asymmetric unit contained two molecules of carbonyl reductase, with a solvent content of 48%. The structure was solved by molecular replacement using cinnamyl alcohol dehydrogenase from Saccharomyces cerevisiae as a search model

  8. Reaction of acid esters of methylenebis(phosphonous acid) with carbonyl compounds

    International Nuclear Information System (INIS)

    Novikova, Z.S.; Odinets, I.L.; Lutsenko, I.F.

    1987-01-01

    The reaction of methylenebis(phosphonites) containing two hydrophosphoryl groupings with aliphatic and aromatic aldehydes and ketones in the presence of alkali metal fluorides leads to methylenebis(α-hydroxyalkylphosphinates). The reaction of methylenebis(phosphonites) containing one hydrophosphoryl groupings with carbonyl compounds in the presence of alkali metal fluorides proceeds with the formation of a new type of heterocyclic phosphorus compound, viz., 1,2λ 3 ,4λ 5 -oxadiphospholanes. The reaction of acid esters of methylenebis(phosphonous) acid with carbonyl compounds in the presence of alkali metal alkoxides or a tertiary amine is accompanied by phosphinate-phosphonate rearrangement of the intermediately formed α-hydroxylalkylphosphinates

  9. Let another praise you? The effects of source and attributional content on responses to group-directed praise.

    Science.gov (United States)

    Rabinovich, Anna; Morton, Thomas A; Crook, Michael; Travers, Claire

    2012-12-01

    Not all types of praise may be equally stimulating. Instead, positive feedback carries different meaning depending on the source that delivers it and the attributions for success that it contains. In the present study, source (in-group vs. out-group) of praise and its content (attributing success to internal vs. external causes) were experimentally manipulated. The results revealed that there was a significant interaction between source and content of praise on performance in a praise-related task. As predicted, participants exposed to out-group praise were motivated by external attributions for success rather than by internal attributions. Conversely, when praise originated from an in-group source, the attributional content of praise did not affect performance. This effect of source and content of praise on relevant behaviour was mediated by willingness to protect group image. Thus, responses to praise are contingent on what it implies about group success--corresponding to patterns demonstrated in previous work on group-directed criticism. ©2012 The British Psychological Society.

  10. The dynamic evolution of social ties and user-generated content: a case study on a Douban group

    Science.gov (United States)

    Shan, Siqing; Ren, Jie; Li, Cangyan

    2017-11-01

    As platforms based on user-generated content (UGC), social media platforms emphasise the social ties between users and user participation, which promote the communication and propagation of ideas and help to build and maintain relationships. However, many researchers have studied only predefined social networks, such as academic social networks. We believe that there are certain characteristics associated with the network's UGC worth evaluating. We conducted research in communities in which content attracts discussion and new members and examined the evolution patterns of social and content networks in a topic-oriented Douban group. Datasets of user and content information in communities of interest were collected through web crawler software. Networks based on social and content ties were constructed and analysed. We chose scale, density, centrality, average path length and cluster coefficient as measures for exploring the evolution and correlation of both types of networks. These findings are valuable for social media marketing and helpful in directing and controlling public opinion.

  11. Molecular Engineering with Organic Carbonyl Electrode Materials for Advanced Stationary and Redox Flow Rechargeable Batteries.

    Science.gov (United States)

    Zhao, Qing; Zhu, Zhiqiang; Chen, Jun

    2017-12-01

    Organic carbonyl electrode materials that have the advantages of high capacity, low cost and being environmentally friendly, are regarded as powerful candidates for next-generation stationary and redox flow rechargeable batteries (RFBs). However, low carbonyl utilization, poor electronic conductivity and undesired dissolution in electrolyte are urgent issues to be solved. Here, we summarize a molecular engineering approach for tuning the capacity, working potential, concentration of active species, kinetics, and stability of stationary and redox flow batteries, which well resolves the problems of organic carbonyl electrode materials. As an example, in stationary batteries, 9,10-anthraquinone (AQ) with two carbonyls delivers a capacity of 257 mAh g -1 (2.27 V vs Li + /Li), while increasing the number of carbonyls to four with the formation of 5,7,12,14-pentacenetetrone results in a higher capacity of 317 mAh g -1 (2.60 V vs Li + /Li). In RFBs, AQ, which is less soluble in aqueous electrolyte, reaches 1 M by grafting -SO 3 H with the formation of 9,10-anthraquinone-2,7-disulphonic acid, resulting in a power density exceeding 0.6 W cm -2 with long cycling life. Therefore, through regulating substituent groups, conjugated structures, Coulomb interactions, and the molecular weight, the electrochemical performance of carbonyl electrode materials can be rationally optimized. This review offers fundamental principles and insight into designing advanced carbonyl materials for the electrodes of next-generation rechargeable batteries. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Evolution of Functional Groups during Pyrolysis Oil Upgrading

    Energy Technology Data Exchange (ETDEWEB)

    Stankovikj, Filip [Department; Tran, Chi-Cong [Department; Kaliaguine, Serge [Department; Olarte, Mariefel V. [Pacific Northwest National Laboratory, Richland, Washington 99354, United States; Garcia-Perez, Manuel [Department

    2017-07-14

    In this paper, we examine the evolution of functional groups (carbonyl, carboxyl, phenol, and hydroxyl) during stabilization at 100–200 °C of two typical wood derived pyrolysis oils from BTG and Amaron in a batch reactor over Ru/C catalyst for 4h. An aqueous and an oily phase were obtained. The content of functional groups in both phases were analyzed by GC/MS, 31P-NMR, 1H-NMR, elemental analysis, KF titration, carbonyl groups by Faix, Folin – Ciocalteu method and UV-Fluorescence. The consumption of hydrogen was between 0.007 and 0.016 g/g oil, and 0.001-0.020 g of CH4/g of oil, 0.005-0.016 g of CO2/g oil and 0.03-0.10 g H2O/g oil were formed. The content of carbonyl, hydroxyl, and carboxyl groups in the volatile GC-MS detectable fraction decreased (80, 65, and ~70% respectively), while their behavior in the total oil and hence in the non-volatile fraction was more complex. The carbonyl groups initially decreased having minimum at ~125-150°C and then increased, while the hydroxyl groups had reversed trend. This might be explained by initial hydrogenation of the carbonyl groups to form hydroxyls, followed by continued dehydration reactions at higher temperatures that may increase their content. The 31P-NMR was on the limit of its sensitivity for the carboxylic groups to precisely detect changes in the non-volatile fraction, however the more precise titration method showed that the concentration of carboxylic groups in the non-volatile fraction remains constant with increased stabilization temperature. The UV-Fluorescence results show that repolymerization increases with temperature. ATR-FTIR method coupled with deconvolution of the region between 1490 and 1850 cm-1 showed to be a good tool for following the changes in carbonyl groups and phenols of the stabilized pyrolysis oils. The deconvolution of the IR bands around 1050 and 1260 cm-1 correlated very well with the changes in the 31P-NMR silent O groups (likely ethers). Most of the H2O formation could be

  13. Nicotine, aerosol particles, carbonyls and volatile organic compounds in tobacco- and menthol-flavored e-cigarettes.

    Science.gov (United States)

    Lee, Mi-Sun; LeBouf, Ryan F; Son, Youn-Suk; Koutrakis, Petros; Christiani, David C

    2017-04-27

    We aimed to assess the content of electronic cigarette (EC) emissions for five groups of potentially toxic compounds that are known to be present in tobacco smoke: nicotine, particles, carbonyls, volatile organic compounds (VOCs), and trace elements by flavor and puffing time. We used ECs containing a common nicotine strength (1.8%) and the most popular flavors, tobacco and menthol. An automatic multiple smoking machine was used to generate EC aerosols under controlled conditions. Using a dilution chamber, we targeted nicotine concentrations similar to that of exposure in a general indoor environment. The selected toxic compounds were extracted from EC aerosols into a solid or liquid phase and analyzed with chromatographic and spectroscopic methods. We found that EC aerosols contained toxic compounds including nicotine, fine and nanoparticles, carbonyls, and some toxic VOCs such as benzene and toluene. Higher mass and number concentrations of aerosol particles were generated from tobacco-flavored ECs than from menthol-flavored ECs. We found that diluted machine-generated EC aerosols contain some pollutants. These findings are limited by the small number of ECs tested and the conditions of testing. More comprehensive research on EC exposure extending to more brands and flavor compounds is warranted.

  14. Nicotine and Carbonyl Emissions From Popular Electronic Cigarette Products: Correlation to Liquid Composition and Design Characteristics.

    Science.gov (United States)

    El-Hellani, Ahmad; Salman, Rola; El-Hage, Rachel; Talih, Soha; Malek, Nathalie; Baalbaki, Rima; Karaoghlanian, Nareg; Nakkash, Rima; Shihadeh, Alan; Saliba, Najat A

    2018-01-05

    Available in hundreds of device designs and thousands of flavors, electronic cigarette (ECIG) may have differing toxicant emission characteristics. This study assesses nicotine and carbonyl yields in the most popular brands in the U.S. market. These products included disposable, prefilled cartridge, and tank-based ECIGs. Twenty-seven ECIG products of 10 brands were procured and their power outputs were measured. The e-liquids were characterized for pH, nicotine concentration, propylene glycol/vegetable glycerin (PG/VG) ratio, and water content. Aerosols were generated using a puffing machine and nicotine and carbonyls were, respectively, quantified using gas chromatograph and high-performance liquid chromatography. A multiregression model was used to interpret the data. Nicotine yields varied from 0.27 to 2.91 mg/15 puffs, a range corresponding to the nicotine yield of less than 1 to more than 3 combustible cigarettes. Nicotine yield was highly correlated with ECIG type and brand, liquid nicotine concentration, and PG/VG ratio, and to a lower significance with electrical power, but not with pH and water content. Carbonyls, including the carcinogen formaldehyde, were detected in all ECIG aerosols, with total carbonyl concentrations ranging from 3.72 to 48.85 µg/15 puffs. Unlike nicotine, carbonyl concentrations were mainly correlated with power. In 15 puffs, some ECIG devices emit nicotine quantities that exceed those of tobacco cigarettes. Nicotine emissions vary widely across products but carbonyl emissions showed little variations. In spite of that ECIG users are exposed to toxicologically significant levels of carbonyl compounds, especially formaldehyde. Regression analysis showed the importance of design and e-liquid characteristics as determinants of nicotine and carbonyl emissions. Periodic surveying of characteristics of ECIG products available in the marketplace is valuable for understanding population-wide changes in ECIG use patterns over time. © The

  15. New and extended parameterization of the thermodynamic model AIOMFAC: calculation of activity coefficients for organic-inorganic mixtures containing carboxyl, hydroxyl, carbonyl, ether, ester, alkenyl, alkyl, and aromatic functional groups

    Directory of Open Access Journals (Sweden)

    A. Zuend

    2011-09-01

    Full Text Available We present a new and considerably extended parameterization of the thermodynamic activity coefficient model AIOMFAC (Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients at room temperature. AIOMFAC combines a Pitzer-like electrolyte solution model with a UNIFAC-based group-contribution approach and explicitly accounts for interactions between organic functional groups and inorganic ions. Such interactions constitute the salt-effect, may cause liquid-liquid phase separation, and affect the gas-particle partitioning of aerosols. The previous AIOMFAC version was parameterized for alkyl and hydroxyl functional groups of alcohols and polyols. With the goal to describe a wide variety of organic compounds found in atmospheric aerosols, we extend here the parameterization of AIOMFAC to include the functional groups carboxyl, hydroxyl, ketone, aldehyde, ether, ester, alkenyl, alkyl, aromatic carbon-alcohol, and aromatic hydrocarbon. Thermodynamic equilibrium data of organic-inorganic systems from the literature are critically assessed and complemented with new measurements to establish a comprehensive database. The database is used to determine simultaneously the AIOMFAC parameters describing interactions of organic functional groups with the ions H+, Li+, Na+, K+, NH4+, Mg2+, Ca2+, Cl, Br, NO3, HSO4, and SO42−. Detailed descriptions of different types of thermodynamic data, such as vapor-liquid, solid-liquid, and liquid-liquid equilibria, and their use for the model parameterization are provided. Issues regarding deficiencies of the database, types and uncertainties of experimental data, and limitations of the model, are discussed. The challenging parameter optimization problem is solved with a novel combination of powerful global minimization

  16. Spatiotemporal distribution of carbonyl compounds in China.

    Science.gov (United States)

    Ho, K F; Ho, Steven Sai Hang; Huang, R-J; Dai, W T; Cao, J J; Tian, Linwei; Deng, W J

    2015-02-01

    A sampling campaign was carried out at nine Chinese cities in 2010/2011. Fifteen monocarbonyls (C# = 1-9) were quantified. Temperature is the rate-determining factor of the summertime carbonyl levels. The carbonyl emissions in winter are mainly driven by the primary anthropogenic sources like automobile. A molar ratio of propionaldehyde to nonaldehyde is a barometer of the impact of atmospheric vegetation emission which suggesting that strong vegetation emissions exist in summer and high propionaldehyde abundance is caused by fossil fuel combustion in winter. Potential health risk assessment of formaldehyde and acetaldehyde was conducted and the highest cumulative risks were observed at Chengdu in summer and Wuhan in winter. Because of the strong photochemical reaction and large amount of anthropogenic emissions, high concentrations of carbonyl compounds were observed in Chengdu. The use of ethanol-blended gasoline in Wuhan is the key reason of acetaldehyde emission and action should be taken to avoid potential health risks. Copyright © 2014 Elsevier Ltd. All rights reserved.

  17. Carbonyl Compounds Generated from Electronic Cigarettes

    Directory of Open Access Journals (Sweden)

    Kanae Bekki

    2014-10-01

    Full Text Available Electronic cigarettes (e-cigarettes are advertised as being safer than tobacco cigarettes products as the chemical compounds inhaled from e-cigarettes are believed to be fewer and less toxic than those from tobacco cigarettes. Therefore, continuous careful monitoring and risk management of e-cigarettes should be implemented, with the aim of protecting and promoting public health worldwide. Moreover, basic scientific data are required for the regulation of e-cigarette. To date, there have been reports of many hazardous chemical compounds generated from e-cigarettes, particularly carbonyl compounds such as formaldehyde, acetaldehyde, acrolein, and glyoxal, which are often found in e-cigarette aerosols. These carbonyl compounds are incidentally generated by the oxidation of e-liquid (liquid in e-cigarette; glycerol and glycols when the liquid comes in contact with the heated nichrome wire. The compositions and concentrations of these compounds vary depending on the type of e-liquid and the battery voltage. In some cases, extremely high concentrations of these carbonyl compounds are generated, and may contribute to various health effects. Suppliers, risk management organizations, and users of e-cigarettes should be aware of this phenomenon.

  18. Exploring Peer-to-Peer Library Content and Engagement on a Student-Run Facebook Group

    Science.gov (United States)

    van Beynen, Kaya; Swenson, Camielle

    2016-01-01

    Student-run Facebook groups offer librarians a new means of interacting with students in their native digital domain. Facebook groups, a service launched in 2010 enables university students to create a virtual forum to discuss their concerns, issues, and promote events. While still a relatively new feature, these groups are increasingly being…

  19. A note on the potassium contents of a group of 154 people in normal health

    Energy Technology Data Exchange (ETDEWEB)

    Speight, R G [Radiological and Safety Division, Atomic Energy Establishment, Winfrith, Dorchester, Dorset (United Kingdom)

    1964-02-15

    During routine operation of the Winfrith Whole Body Monitor, estimates are made of the potassium contents of subjects measured. The results for the period October, 1961 to June, 1963, together with a brief analysis and correlation with sex, age, weight and height of the subjects are presented in this memorandum. (author)

  20. Perceived social structural relations and group stereotypes : A test of the Stereotype Content Model in Malaysia

    NARCIS (Netherlands)

    Janssens, Heleen; Verkuijten, Maykel; Khan, Aqeel

    2015-01-01

    Using data from two studies, the current research tests the Stereotype Content Model (SCM) within a Malaysian context using Chinese and ethnic Malay participants. The aim of the research is to examine the theoretical underpinnings of the SCM in a new context by investigating the role of aspects of

  1. Carbonyl emission and toxicity profile of diesel blends with an animal-fat biodiesel and a tire pyrolysis liquid fuel.

    Science.gov (United States)

    Ballesteros, R; Guillén-Flores, J; Martínez, J D

    2014-02-01

    In this paper, two diesel fuels, an animal-fat biodiesel and two diesel blends with the animal-fat biodiesel (50vol.%) and with a tire pyrolysis liquid (TPL) fuel (5vol.%) have been tested in a 4-cylinder, 4-stroke, turbocharged, intercooled, 2.0L Nissan diesel automotive engine (model M1D) with common-rail injection system and diesel oxidation catalyst (DOC). Carbonyl emissions have been analyzed both before and after DOC and specific reactivity of carbonyl profile has been calculated. Carbonyl sampling was carried out by means of a heated line, trapping the gas in 2,4-DNPH cartridges. The eluted content was then analyzed in an HPLC system, with UV-VIS detection. Results showed, on the one hand, an increase in carbonyl emissions with the biodiesel fraction in the fuel. On the other hand, the addition of TPL to diesel also increased carbonyl emissions. These trends were occasionally different if the emissions were studied after the DOC, as it seems to be selectivity during the oxidation process. The specific reactivity was also studied, finding a decrease with the oxygen content within the fuel molecule, although the equivalent ozone emissions slightly increased with the oxygen content. Finally, the emissions toxicity was also studied, comparing them to different parameters defined by different organizations. Depending on the point of study, emissions were above or below the established limits, although acrolein exceeded them as it has the least permissive values. Copyright © 2013 Elsevier Ltd. All rights reserved.

  2. Carbonyl Emissions from Gasoline and Diesel Motor Vehicles

    Energy Technology Data Exchange (ETDEWEB)

    Destaillats, Hugo; Jakober, Chris A.; Robert, Michael A.; Riddle, Sarah G.; Destaillats, Hugo; Charles, M. Judith; Green, Peter G.; Kleeman, Michael J.

    2007-12-01

    Carbonyls from gasoline powered light-duty vehicles (LDVs) and heavy-duty diesel powered vehicles (HDDVs) operated on chassis dynamometers were measured using an annular denuder-quartz filter-polyurethane foam sampler with O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine derivatization and chromatography-mass spectrometry analyses. Two internal standards were utilized based on carbonyl recovery, 4-fluorobenzaldehyde forcarbonyls and 6-fluoro-4-chromanone for>_C8 compounds. Gas- and particle-phase emissions for 39 aliphatic and 20 aromatic carbonyls ranged from 0.1 ? 2000 ?g/L fuel for LDVs and 1.8 - 27000 mu g/L fuel for HDDVs. Gas-phase species accounted for 81-95percent of the total carbonyls from LDVs and 86-88percent from HDDVs. Particulate carbonyls emitted from a HDDV under realistic driving conditions were similar to concentrations measured in a diesel particulate matter (PM) standard reference material. Carbonyls accounted for 19percent of particulate organic carbon (POC) emissions from low-emission LDVs and 37percent of POC emissions from three-way catalyst equipped LDVs. This identifies carbonyls as one of the largest classes of compounds in LDV PM emissions. The carbonyl fraction of HDDV POC was lower, 3.3-3.9percent depending upon operational conditions. Partitioning analysis indicates the carbonyls had not achieved equilibrium between the gas- and particle-phase under the dilution factors of 126-584 used in the current study.

  3. Advocates, interest groups and Australian news coverage of alcohol advertising restrictions: content and framing analysis

    OpenAIRE

    Fogarty Andrea S; Chapman Simon

    2012-01-01

    Abstract Background Legislating restrictions on alcohol advertising is a cost-effective measure to reduce consumption of alcohol. Yet Australia relies upon industry self-regulation through voluntary codes of practice regarding the content, timing and placement of alcohol advertising. Ending industry self-regulation was recommended by the National Preventative Health Taskforce; a suggestion contested by the drinks industry. Debates about emerging alcohol-control policies regularly play out in ...

  4. Weak carbonyl-methyl intermolecular interactions in acetone clusters explored by IR plus VUV spectroscopy

    International Nuclear Information System (INIS)

    Guan, Jiwen; Hu, Yongjun; Xie, Min; Bernstein, Elliot R.

    2012-01-01

    Highlights: ► The carbonyl overtone of acetone clusters is observed by IR-VUV spectroscopy. ► Acetone molecules in the dimer are stacked with an antiparallel way. ► The structure of the acetone trimer and the tetramer are the cyclic structures. ► The carbonyl groups would interact with the methyl groups in acetone clusters. ► These weak interactions are further confirmed by H/D substitution experiment. -- Abstract: Size-selected IR–VUV spectroscopy is employed to detect vibrational characteristics in the region 2850 ∼ 3550 cm −1 of neutral acetone and its clusters (CH 3 COCH 3 ) n (n = 1–4). Features around 3440 cm −1 in the spectra of acetone monomer and its clusters are assigned to the carbonyl stretch (CO) overtone. These features red-shift from 3455 to 3433 cm −1 as the size of the clusters increases from the monomer to the tetramer. Based on calculations, the experimental IR spectra in the C=O overtone region suggest that the dominant structures for the acetone trimer and tetramer should be cyclic in the supersonic expansion sample. This study also suggests that the carbonyl groups interact with the methyl groups in the acetone clusters. These weak interactions are further confirmed by the use of deuterium substitution.

  5. On the Reaction of Carbonyl Diphosphonic Acid with Hydroxylamine and O-alkylhydroxylamines: Unexpected Degradation of P-C-P Bridge.

    Science.gov (United States)

    Khomich, Olga A; Yanvarev, Dmitry V; Novikov, Roman A; Kornev, Alexey B; Puljulla, Elina; Vepsäläinen, Jouko; Khomutov, Alex R; Kochetkov, Sergey N

    2017-06-23

    Derivatives of methylenediphosphonic acid possess wide spectra of biological activities and are used in enzymology as research tools as well as in practical medicine. Carbonyl diphosphonic acid is a promising starting building block for synthesis of functionally substituted methylenediphosphonates. Investigation of the interaction of carbonyl diphosphonic acid with hydroxylamine clearly demonstrates that it is impossible to isolate oxime within the pH range 2-12, while only cyanophosphonic and phosphoric acids are the products of the fast proceeding Beckmann-like fragmentation. In the case of O -alkylhydroxylamines, corresponding alcohols are found in the reaction mixtures in addition to cyanophosphonic and phosphoric acids. Therefore, two residues of phosphonic acid being attached to a carbonyl group provide new properties to this carbonyl group, making its oximes very unstable. This principally differs carbonyl diphosphonic acid from structurally related phosphonoglyoxalic acid and other α-ketophosphonates.

  6. Palladium-catalyzed Reppe carbonylation.

    Science.gov (United States)

    Kiss, G

    2001-11-01

    PdX2L2/L/HA (A = weakly coordinating anion, L = phosphine) complexes are active catalysts in the hydroesterification of alkenes, alkynes, and conjugated dienes. Shell, the only major corporate player in the field, recently developed two very active catalyst systems tailored to the hydroesterification of either alkenes or alkynes. The hydroesterification of propyne with their Pd(OAc)2/PN/HA (PN = (2-pyridyl)diphenylphosphine, HA = strong acid with weakly coordinating anion, like methanesulfonic acid) catalyst has been declared commercially ready. However, despite the significant progress in the activity of Pd-hydroesterification catalysts, further improvements are warranted. Thus, for example, activity maintenance still seems to be an issue. Homogeneous Pd catalysts are prone to a number of deactivation reactions. Activity and stability promoters are often corrosive and add to the complexity of the system, making it less attractive. Nonetheless, the versatility of the process and its tolerance toward the functional groups of substrates should appeal especially to the makers of specialty products. Although hydroesterification yields esters from alkenes, alkynes, and dienes in fewer steps than hydroformylation does, the latter has some advantages at the current state of the art. (1) Hydroformylation catalysts, particularly some recently published phosphine-modified Rh systems, can achieve very high regioselectivity for the linear product that hydroesterification catalysts cannot match yet. By analogy with hydroformylation, bulkier ligands ought to be tested in hydroesterification to increase normal-ester selectivity. (2) Hydroformylation is proven, commercial. Hydroesterification can only replace it if it can provide significant economic incentives. Similar or just marginally better performance could not justify the cost of development of a new technology. (3) Hydroesterification requires pure CO while hydroformylation uses syngas, a mixture of CO and H2. The latter

  7. A content analysis of chronic diseases social groups on Facebook and Twitter.

    Science.gov (United States)

    De la Torre-Díez, Isabel; Díaz-Pernas, Francisco Javier; Antón-Rodríguez, Míriam

    2012-01-01

    Research on the use of social networks for health-related purposes is limited. This study aims to characterize the purpose and use of Facebook and Twitter groups concerning colorectal cancer, breast cancer, and diabetes. We searched in Facebook ( www.facebook.com ) and Twitter ( www.twitter.com ) using the terms "colorectal cancer," "breast cancer," and "diabetes." Each important group has been analyzed by extracting its network name, number of members, interests, and Web site URL. We found 216 breast cancer groups, 171 colorectal cancer groups, and 527 diabetes groups on Facebook and Twitter. The largest percentage of the colorectal cancer groups (25.58%) addresses prevention, similarly to breast cancer, whereas diabetes groups are mainly focused on research issues (25.09%). There are more social groups about breast cancer and diabetes on Facebook (around 82%) than on Twitter (around 18%). Regarding colorectal cancer, the difference is less: Facebook had 62.23%, and Twitter 31.76%. Social networks are a useful tool for supporting patients suffering from these three diseases. Regarding the use of these social networks for disease support purposes, Facebook shows a higher usage rate than Twitter, perhaps because Twitter is newer than Facebook, and its use is not so generalized.

  8. Dormancy alleviation by NO or HCN leading to decline of protein carbonylation levels in apple (Malus domestica Borkh.) embryos.

    Science.gov (United States)

    Krasuska, Urszula; Ciacka, Katarzyna; Dębska, Karolina; Bogatek, Renata; Gniazdowska, Agnieszka

    2014-08-15

    Deep dormancy of apple (Malus domestica Borkh.) embryos can be overcome by short-term pre-treatment with nitric oxide (NO) or hydrogen cyanide (HCN). Dormancy alleviation of embryos modulated by NO or HCN and the first step of germination depend on temporary increased production of reactive oxygen species (ROS). Direct oxidative attack on some amino acid residues or secondary reactions via reactive carbohydrates and lipids can lead to the formation of protein carbonyl derivatives. Protein carbonylation is a widely accepted covalent and irreversible modification resulting in inhibition or alteration of enzyme/protein activities. It also increases the susceptibility of proteins to proteolytic degradation. The aim of this work was to investigate protein carbonylation in germinating apple embryos, the dormancy of which was removed by pre-treatment with NO or HCN donors. It was performed using a quantitative spectrophotometric method, while patterns of carbonylated protein in embryo axes were analyzed by immunochemical techniques. The highest concentration of protein carbonyl groups was observed in dormant embryos. It declined in germinating embryos pre-treated with NO or HCN, suggesting elevated degradation of modified proteins during seedling formation. A decrease in the concentration of carbonylated proteins was accompanied by modification in proteolytic activity in germinating apple embryos. A strict correlation between the level of protein carbonyl groups and cotyledon growth and greening was detected. Moreover, direct in vitro carbonylation of BSA treated with NO or HCN donors was analyzed, showing action of both signaling molecules as protein oxidation agents. Copyright © 2014 Elsevier GmbH. All rights reserved.

  9. The acidic functional groups of humic acid

    Energy Technology Data Exchange (ETDEWEB)

    Shanxiang, Li; Shuhe, Sun; Zhai Zongxi, Wu Qihu

    1983-09-01

    The acidic functional groups content, pK value, DELTAH and DELTAS of humic acid (HA) and nitro-humic acid (NHA) were determined by potentiometry, conductometry and calorimetric titration. The thermodynamic parameters of carboxylic groups and phenolic hydroxyl groups of humic acid are similar to that of simple hydroxy-benzoic acid. The configuration sites of acidic functional groups in humic acid from different coals are different. The carbonyl groups on aromatic rings are probably ortho to phenolic -OH for HA and NHA extracted from Huangxian's brown coal and Japanese lignite, while those from Lingshi's weathered coal are not. The weak -COOH groups of the latter possess higher chemical activity. The -COOH content in HA increases, phenolic -OH group decreases and the chemical acidity of acidic functional groups increases when HA is oxidized by nitric acid. (14 refs.)

  10. Reactions of rhodium(I) carbonyl chloride with olefins

    International Nuclear Information System (INIS)

    Varshavskii, Yu.S.; Kiseleva, N.V.; Cherkasova, T.G.; Buzina, N.A.; Bresler, L.S.

    1987-01-01

    The reactions of [Rh(CO) 2 Cl] 2 (Y 0 ) with cyclooctene and several other olefins (1-heptene, 1-hexene, ethylene, and cyclohexene) have been studied by IR and 13 C NMR spectroscopy. The main reaction products are the binuclear complexes Rh 2 L(CO) 3 Cl 2 (Y 1 ) and [RhL(CO)Cl] 2 (Y 2 ), where L denotes the olefin. The extent of replacement of the carbonyl groups depends on the nature of the olefin and the conditions under which the reaction is carried out (the L:Rh ratio and the removal of CO from the reaction sphere). The liquid olefins form the following series according to their ability to replace the carbonyl groups: C 8 H 14 > C 7 H 14 , C 6 H 12 > C 6 H 10 . In the presence of an excess of C 8 H 14 , Y 2 disproportionates with the formation of a dicarbonyl product, which presumably corresponds to the formula Rh(C 8 H 14 ) 2 (CO) 2 Cl (a pentacoordinate complex with a trigonal-bipyramidal structure). The 13 C signal in the NMR spectrum of a solution of Y 2 in C 8 H 14 is a singlet with σ( 13 C) 180.3 ppm, which is an indication of the rapid exchange of the carbonyl groups. Rapid exchange of the CO ligands is also observed in solutions of Y 0 in the olefins (with the exception of C 6 H 10 ). For example, the 13 C signal in the spectrum of a solution of Y 0 in C 8 H 14 is a singlet with σ( 13 C) 179.8 ppm. The spectrum of Y 0 in C 6 H 10 is a doublet with σ( 13 C) = 178.5 ppm and 1 J(CRh) = 76.3 Hz. A scheme for the interaction of Y 0 with olefins based on the conception of the trans antagonism of π-acceptor ligands has been proposed

  11. E-learning for Critical Thinking: Using Nominal Focus Group Method to Inform Software Content and Design

    Science.gov (United States)

    Parker, Steve; Mayner, Lidia; Michael Gillham, David

    2015-01-01

    Background: Undergraduate nursing students are often confused by multiple understandings of critical thinking. In response to this situation, the Critiique for critical thinking (CCT) project was implemented to provide consistent structured guidance about critical thinking. Objectives: This paper introduces Critiique software, describes initial validation of the content of this critical thinking tool and explores wider applications of the Critiique software. Materials and Methods: Critiique is flexible, authorable software that guides students step-by-step through critical appraisal of research papers. The spelling of Critiique was deliberate, so as to acquire a unique web domain name and associated logo. The CCT project involved implementation of a modified nominal focus group process with academic staff working together to establish common understandings of critical thinking. Previous work established a consensus about critical thinking in nursing and provided a starting point for the focus groups. The study was conducted at an Australian university campus with the focus group guided by open ended questions. Results: Focus group data established categories of content that academic staff identified as important for teaching critical thinking. This emerging focus group data was then used to inform modification of Critiique software so that students had access to consistent and structured guidance in relation to critical thinking and critical appraisal. Conclusions: The project succeeded in using focus group data from academics to inform software development while at the same time retaining the benefits of broader philosophical dimensions of critical thinking. PMID:26835469

  12. "Anonymous Meltdown": Content Themes Emerging in a Nonfacilitated, Peer-only, Unstructured, Asynchronous Online Support Group for Family Caregivers.

    Science.gov (United States)

    Diefenbeck, Cynthia A; Klemm, Paula R; Hayes, Evelyn R

    2017-12-01

    By providing care for loved ones in the home, family caregivers save millions of dollars for our overtaxed healthcare system. Support groups can lighten the psychological burden of caregiving. Nonprofessionally facilitated (or peer) online caregiver support groups can help meet a critical need in healthcare as a low-cost resource for caregivers. Online caregiver peer support groups can promote the health and well-being of family caregivers and, by extension, the patients themselves, resulting in cost-savings for society. A better understanding of these types of groups is of critical importance, given the unrelenting pace of demographic shift in the United States. The purpose of this study was to examine content themes emerging from an unstructured, asynchronous online peer support group for family caregivers of people with chronic illness. Qualitative content analysis was used, yielding six themes: "experiencing the emotional toll," "need for catharsis/venting," "finding the silver linings," "seeking specific advice/problem solving," "realizing home is no longer a haven," and "adapting to the caregiver role." The themes reflect what emerged organically in an online support group that was not professionally facilitated or structured in any way. Heterogeneity in the relationship between caregivers and care recipients may negatively affect outcomes and requires further study.

  13. E-learning for Critical Thinking: Using Nominal Focus Group Method to Inform Software Content and Design.

    Science.gov (United States)

    Parker, Steve; Mayner, Lidia; Michael Gillham, David

    2015-12-01

    Undergraduate nursing students are often confused by multiple understandings of critical thinking. In response to this situation, the Critiique for critical thinking (CCT) project was implemented to provide consistent structured guidance about critical thinking. This paper introduces Critiique software, describes initial validation of the content of this critical thinking tool and explores wider applications of the Critiique software. Critiique is flexible, authorable software that guides students step-by-step through critical appraisal of research papers. The spelling of Critiique was deliberate, so as to acquire a unique web domain name and associated logo. The CCT project involved implementation of a modified nominal focus group process with academic staff working together to establish common understandings of critical thinking. Previous work established a consensus about critical thinking in nursing and provided a starting point for the focus groups. The study was conducted at an Australian university campus with the focus group guided by open ended questions. Focus group data established categories of content that academic staff identified as important for teaching critical thinking. This emerging focus group data was then used to inform modification of Critiique software so that students had access to consistent and structured guidance in relation to critical thinking and critical appraisal. The project succeeded in using focus group data from academics to inform software development while at the same time retaining the benefits of broader philosophical dimensions of critical thinking.

  14. Framing student dialogue and argumentation: Content knowledge development and procedural knowing in SSI inquiry group work

    Directory of Open Access Journals (Sweden)

    Anne Kristine Byhring

    2014-10-01

    Full Text Available In this article, we discuss the negotiation of the situated common ground in classroom conversations. Decision making on socioscientific issues (SSI includes norms of diverse funds of knowledge and interests. Arguments and justification may include warrants that cannot necessarily be weighed on the same scale. We discuss Roberts’ Visions 1 and 2 of scientific literacy as framing the common ground of classroom discussions. Two teacher–student dialogue sequences with 11th grade students from the Norwegian research project ElevForsk exemplify the negotiation of the situated common ground and the students’ deliberations. Our analysis examines what goes on in the thematic content, as well as at the interpersonal level of language use. Further, we suggest that different framings may complement each other and provide a space for the students’ emerging scientific conceptual development as well as for deliberation as a form of emerging procedural knowing.

  15. Acute inhalation toxicity of carbonyl sulfide

    Energy Technology Data Exchange (ETDEWEB)

    Benson, J.M.; Hahn, F.F.; Barr, E.B. [and others

    1995-12-01

    Carbonyl sulfide (COS), a colorless gas, is a side product of industrial procedures sure as coal hydrogenation and gasification. It is structurally related to and is a metabolite of carbon disulfide. COS is metabolized in the body by carbonic anhydrase to hydrogen sulfide (H{sub 2}S), which is thought to be responsible for COS toxicity. No threshold limit value for COS has been established. Results of these studies indicate COS (with an LC{sub 50} of 590 ppm) is slightly less acutely toxic than H{sub 2}S (LC{sub 50} of 440 ppm).

  16. The DIALOGUE project. Report of the Gaming group on the structure and content of the project

    International Nuclear Information System (INIS)

    Andersson, Johan; Hallencreutz, M.; Andersson, Kjell; Wene, C.O.; Westerlund, S.

    1993-11-01

    The DIALOGUE project has been conducted by the Swedish Nuclear Power Inspectorate (SKI) since 1990. The aim of the project was to stimulate a dialogue between different interest groups within Sweden. The purpose of this dialogue was to establish a licensing process, prior to a future licensing of a repository for spent nuclear waste, in which several of the parties involved are reasonably confident. The DIALOGUE project was carried out with the participation of other government agencies, municipalities and environmental groups and was headed by the former chairman of the National Licensing Board for Environmental Protection

  17. Pattern of occurrence and occupancy of carbonylation sites in proteins

    DEFF Research Database (Denmark)

    Rao, R Shyama Prasad; Møller, Ian Max

    2011-01-01

    sites. Comparison of metal-catalyzed oxidation of two closely related proteins indicates that this type of carbonylation might not be very specific in proteins. Interestingly, carbonylated sites show a very strong tendency to cluster together in the protein primary sequence hinting at some sort......Proteins are targets for modification by reactive oxygen species, and carbonylation is an important irreversible modification that increases during oxidative stress. While information on protein carbonylation is accumulating, its pattern is not yet understood. We have made a meta...

  18. AEL Career Decision-Making Program. Worker Trait Group File Content Notebook.

    Science.gov (United States)

    Appalachia Educational Lab., Charleston, WV.

    The Career Information System File is utilized in the organization and management procedures of the Career Information System (CIS) component of the Career Decision-Making (CDM) Program developed by Appalachia Educational Laboratory. (See CE 019 229 for an overview of the total CDM Program.) The twelve career areas and worker trait groups used to…

  19. EVOLUTION IN THE H I GAS CONTENT OF GALAXY GROUPS: PRE-PROCESSING AND MASS ASSEMBLY IN THE CURRENT EPOCH

    Energy Technology Data Exchange (ETDEWEB)

    Hess, Kelley M. [Astrophysics, Cosmology and Gravity Centre (ACGC), Department of Astronomy, University of Cape Town, Rondebosch 7701 (South Africa); Wilcots, Eric M., E-mail: hess@ast.uct.ac.za, E-mail: ewilcots@astro.wisc.edu [Department of Astronomy, University of Wisconsin-Madison, Madison, WI 53706 (United States)

    2013-11-01

    We present an analysis of the neutral hydrogen (H I) content and distribution of galaxies in groups as a function of their parent dark matter halo mass. The Arecibo Legacy Fast ALFA survey α.40 data release allows us, for the first time, to study the H I properties of over 740 galaxy groups in the volume of sky common to the Sloan Digital Sky Survey (SDSS) and ALFALFA surveys. We assigned ALFALFA H I detections a group membership based on an existing magnitude/volume-limited SDSS Data Release 7 group/cluster catalog. Additionally, we assigned group ''proximity' membership to H I detected objects whose optical counterpart falls below the limiting optical magnitude—thereby not contributing substantially to the estimate of the group stellar mass, but significantly to the total group H I mass. We find that only 25% of the H I detected galaxies reside in groups or clusters, in contrast to approximately half of all optically detected galaxies. Further, we plot the relative positions of optical and H I detections in groups as a function of parent dark matter halo mass to reveal strong evidence that H I is being processed in galaxies as a result of the group environment: as optical membership increases, groups become increasingly deficient of H I rich galaxies at their center and the H I distribution of galaxies in the most massive groups starts to resemble the distribution observed in comparatively more extreme cluster environments. We find that the lowest H I mass objects lose their gas first as they are processed in the group environment, and it is evident that the infall of gas rich objects is important to the continuing growth of large scale structure at the present epoch, replenishing the neutral gas supply of groups. Finally, we compare our results to those of cosmological simulations and find that current models cannot simultaneously predict the H I selected halo occupation distribution for both low and high mass halos.

  20. Oxidation of an activated carbon commercial and characterization of the content of superficial acid groups

    International Nuclear Information System (INIS)

    Cortes, Juan Carlos; Giraldo Liliana; Garcia, Andres A; Garcia, Cesar; Moreno, Juan C

    2008-01-01

    The changes of the surface acid groups of an activated commercial carbon after placing it under oxidation treatment with nitric acid are studied. The time used was in the range 1.5 and 9 hours, the concentrations range was from 4 to 7 molL -1 . The study included the determination of immersion enthalpy. Boehm's type titrations, FTIR, and pH at the point of zero charge, pH p zc. It was found that total acid groups are in a range from 0.207 mmolg -1 to 1.247 mmolg -1 , and that they are proportional to the immersion enthalpy in NaOH that are between 40 and 54Jg -1 . The pH p zc decreases with the oxidation treatment and have values between 8.3 and 4.3

  1. Sulfhydryl group content of chicken progesterone receptor: effect of oxidation on DNA binding activity

    International Nuclear Information System (INIS)

    Peleg, S.; Schrader, W.T.; O'Malley, B.W.

    1988-01-01

    DNA binding activity of chicken progesterone receptor B form (PRB) and A form (PRA) has been examined. This activity is strongly dependent upon the presence of thiols in the buffer. Stability studies showed that PRB was more sensitive to oxidation that was PRA. Receptor preparations were fractionated by DNA-cellulose chromatography to DNA-positive and DNA-negative subpopulations, and sulfhydryl groups were quantified on immunopurified receptor by labeling with [ 3 H]-N-ethylmaleimide. Labeling of DNA-negative receptors with [ 3 H]-N-ethylmaleimide showed 21-23 sulfhydryl groups on either PRA or PRB form when the proteins were reduced and denatured. A similar number was seen without reduction if denatured DNA-positive receptor species were tested. In contrast, the DNA-negative PRB had only 10-12 sulfhydryl groups detectable without reduction. A similar number (12-13 sulfhydryl groups) was found for PRA species that lost DNA binding activity after exposure to a nonreducing environment in vitro. The authors conclude that the naturally occurring receptor forms unable to bind to DNA, as well as receptor forms that have lost DNA binding activity due to exposure to nonreducing environment in vitro, contain 10-12 oxidized cysteine residues, likely present as disulfide bonds. Since they were unable to reduce the disulfide bonds when the native DNA-negative receptor proteins were treated with dithiothreitol (DTT), they speculate that irreversible loss of DNA binding activity of receptor in vitro is due to oxidation of cysteine residues that are not accessible to DTT in the native state

  2. Catalytic performance of heterogeneous Rh/C3N4 for the carbonylation of methanol

    Science.gov (United States)

    Budiman, Anatta Wahyu; Choi, Myoung Jae; Nur, Adrian

    2018-02-01

    The excess of water in homogeneous the carbonylation of methanol system could increase the amount of by-products formed through water-gas shift reaction and could accelerate the rusting of equipment. Many scientists tried to decrease the content of water in the carbonylation of methanol system by using lithium and iodide promoter that results a moderate catalytic activity in the water content at 2wt%. The heterogenized catalyst offers several distinct advantages such as it was enables increased catalyst concentration in the reaction mixture, which is directly proportional to acetic acid production rate, without the addition of an alkali iodide salt promoter. The heterogeneous catalyst also results in reduced by-product formation. This study is aimed to produce a novel catalyst (Rh/C3N4) with a high selectivity of acetic acid in a relatively lower water and halide content. This novel catalyst performs high conversion and selectivity of acetic acid as the result of the strong ionic bonding of melamine and rhodium complex species that was caused by the presence of methyl iodide species. The CO2 in feed gas significantly decreases the catalytic activity of Rh-melamine because of its inert characteristics. The kinetic test was performed as that the first order kinetic equation. The kinetic tests revealed the reaction route of the the carbonylation of methanol in this system was performed trough the methyl acetate.

  3. Ruthenium(ii)-catalyzed olefination via carbonyl reductive cross-coupling† †Electronic supplementary information (ESI) available: Experimental details. See DOI: 10.1039/c7sc04207h

    Science.gov (United States)

    Wei, Wei; Dai, Xi-Jie; Wang, Haining; Li, Chenchen; Yang, Xiaobo

    2017-01-01

    Natural availability of carbonyl groups offers reductive carbonyl coupling tremendous synthetic potential for efficient olefin synthesis, yet the catalytic carbonyl cross-coupling remains largely elusive. We report herein such a reaction, mediated by hydrazine under ruthenium(ii) catalysis. This method enables facile and selective cross-couplings of two unsymmetrical carbonyl compounds in either an intermolecular or intramolecular fashion. Moreover, this chemistry accommodates a variety of substrates, proceeds under mild reaction conditions with good functional group tolerance, and generates stoichiometric benign byproducts. Importantly, the coexistence of KOtBu and bidentate phosphine dmpe is vital to this transformation. PMID:29568466

  4. Content Analysis and User Characteristics of a Smartphone-Based Online Support Group for People Living with HIV.

    Science.gov (United States)

    Flickinger, Tabor E; DeBolt, Claire; Wispelwey, Erin; Laurence, Colleen; Plews-Ogan, Erin; Waldman, Ava Lena; Reynolds, George; Cohn, Wendy F; Beach, Mary Catherine; Ingersoll, Karen; Dillingham, Rebecca

    2016-09-01

    Although there is growing interest in mobile applications and online support groups to enhance chronic disease self-management, little is known about their potential impact for people living with HIV (PLWH). We developed an innovative online support group delivered through a community message board (CMB) within a clinic-affiliated smartphone application Positive Links (PL). We analyzed characteristics of posters and nonposters to the CMB and evaluated content posted to the CMB. For this study, 38 HIV-infected patients received cell phones with the PL application that included the opportunity to interact with other users on a CMB. Logistic regressions investigated associations between participant characteristics and posting. CMB messages were downloaded and analyzed qualitatively. 24 participants posted to the CMB; 14 did not. Participants had lower odds of posting if they were white (p = 0.028) and had private insurance (p = 0.003). Participants had higher odds of posting if they had unsuppressed viral loads (p = 0.034). Of the 840 CMB messages over 8 months, 62% had psychosocial content, followed by community chat (29%), and biomedical content (10%). Psychosocial content was most prevalent on this CMB, in contrast to other online forums dominated by informational content. Participants who posted expressed support for each other, appreciation for the community, and a perception that the app played a positive role in their HIV self-management. This CMB on a clinic-affiliated mobile application may reach vulnerable populations, including racial/ethnic minorities and those of lower socioeconomic status, and provide psychosocial support to PLWH.

  5. Microscopic mechanism of amino silicone oil modification and modification effect with different amino group contents based on molecular dynamics simulation

    Science.gov (United States)

    He, Liping; Li, Wenjun; Chen, Dachuan; Yuan, Jianmin; Lu, Gang; Zhou, Dianwu

    2018-05-01

    The microscopic mechanism of amino silicone oil (ASO) modification of natural fiber was investigated for the first time using molecular dynamics (MD) simulation at the atomic and molecular levels. The MD simulation results indicated that the ASO molecular interacted with the cellulose molecular within the natural fiber, mainly by intermolecular forces of Nsbnd Hsbnd O and Osbnd Hsbnd N hydrogen bonds and the molecular chain of ASO absorbed onto the natural fiber in a selective orientation, i.e., the hydrophobic alkyl groups (sbnd CnH2n+1) project outward and the polar amino groups (sbnd NH2) point to the surface of natural fiber. Consequently, the ASO modification changed the surface characteristic of natural fiber from hydrophilic to hydrophobic. Furthermore, the modification effects of the ASO modification layer with different amino group contents (m:n ratio) were also evaluated in this study by calculating the binding energy between the ASO modifier and natural fiber, and the cohesive energy density and free volume of the ASO modification layer. The results showed that the binding energy reached a maximum when the m:n ratio of ASO was of 8:4, suggesting that a good bonding strength was achieved at this m:n ratio. It was also found that the cohesive energy density enhanced with the increase in the amino group content, and the higher the cohesive energy density, the easier the formation of the ASO modification layer. However, the fraction free volume decreased with the increase in the amino group content. This is good for improving the water-proof property of natural fiber. The present work can provide an effective method for predicting the modification effects and designing the optimized m:n ratio of ASO modification.

  6. Real life experimental determination of platinum group metals content in automotive catalytic converters

    Science.gov (United States)

    Yakoumis, I.; Moschovi, A. M.; Giannopoulou, I.; Panias, D.

    2018-03-01

    The real life experimental protocol for the preparation of spent automobile catalyst samples for elemental analysis is thoroughly described in the following study. Collection, sorting and dismantling, homogenization and sample preparation for X-Ray fluorescence spectroscopy and Atomic Adsorption Spectroscopy combined with Inductive coupled plasma mass spectrometry are discussed in detail for both ceramic and metallic spent catalysts. The concentrations of Platinum Group Metals (PGMs) in spent catalytic converters are presented based on typical consignments of recycled converters (more than 45,000 pieces) from the Greek Market. The conclusions clearly denoted commercial metallic catalytic foil contains higher PGMs loading than ceramic honeycombs. On the other hand, the total PGMs loading in spent ceramic catalytic converters has been found higher than the corresponding value for the metallic ones.

  7. Essential element contents in food groups from the second Brazilian total diet study

    International Nuclear Information System (INIS)

    Ambrogi, J.B.; Avegliano, R.P.; Maihara, V.A.

    2016-01-01

    Total diet study (TDS) has been considered as one of the most appropriate approaches to estimate dietary exposure of essential elements. This paper presents preliminary results of concentrations and average dietary daily intakes of Ca, Co, Cr, Fe, K, Na, Se and Zn from the 2nd Brazilian TDS. Nineteen groups from a Food List which represents the daily intake of the population from the Brazilian southeastern region were analyzed by instrumental neutron activation analysis. The dietary daily intake values for Ca (641 mg), Fe (19.6 mg), K (2738 mg), Na (2466 mg), Se (56.4 μg), and Zn (15.3 mg) were higher than the 1st Brazilian TDS. (author)

  8. Polydiphenylacetylene with Schiff Base End Groups: Synthesis and Characterization

    Science.gov (United States)

    Kalinova, Radostina; Jossifov, Christo

    The carbonyl-olefin exchange reaction is a new reaction between carbonyl group and olefin double bond, which has a formal similarity with the olefin metathesis - one carbon atom in the latter is replaced with an oxygen atom. Till now the new reaction is performed successfully only when the two functional groups (carbonyl group and olefin double bond) are in one molecule and are conjugated. The α, β-unsaturated carbonyl compounds (substituted propenones) are the compounds with such a structure. They polymerize giving substituted polyacetylenes. The chain propagation step of this polymerization is in fact the carbonyl-olefin exchange reaction. The question arises: is it possible the carbonyl-olefin exchange reaction to take place when the two functional groups are not in one molecule and are not conjugated, and could this reaction become an alternative of the existing carbonyl olefination reactions?

  9. Electromagnetic properties of carbonyl iron and their microwave ...

    Indian Academy of Sciences (India)

    Administrator

    The aim of this paper is to develop a novel thin micro- wave absorber with good absorbing performance in wide bandwidth and lightweight. So we investigated the micro- wave absorbing characterization of silicone rubber using carbonyl iron as filler. Carbonyl iron can be widely used in the field of electromagnetic shielding ...

  10. Synthesis of Cyclohexane-Fused Isocoumarins via Cationic Palladium(II)-Catalyzed Cascade Cyclization Reaction of Alkyne-Tethered Carbonyl Compounds Initiated by Intramolecular Oxypalladation of Ester-Substituted Aryl Alkynes.

    Science.gov (United States)

    Zhang, Jianbo; Han, Xiuling; Lu, Xiyan

    2016-04-15

    A cationic Pd(II)-catalyzed cascade cyclization reaction of alkyne-tethered carbonyl compounds was developed. This reaction is initiated by intramolecular oxypalladation of alkynes with an ester group followed by 1,2-addition of the formed C-Pd(II) bond to the carbonyl group, providing a highly efficient method for the synthesis of cyclohexane-fused isocoumarins.

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

    International Nuclear Information System (INIS)

    Pourali, Ali Reza; Goli, Arezou

    2006-01-01

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

  12. Proteomic and carbonylation profile analysis of rat skeletal muscles following acute swimming exercise.

    Directory of Open Access Journals (Sweden)

    Francesca Magherini

    Full Text Available Previous studies by us and other groups characterized protein expression variation following long-term moderate training, whereas the effects of single bursts of exercise are less known. Making use of a proteomic approach, we investigated the effects of acute swimming exercise (ASE on protein expression and carbonylation patterns in two hind limb muscles: the Extensor Digitorum Longus (EDL and the Soleus, mostly composed of fast-twitch and slow-twitch fibres, respectively. Carbonylation is one of the most common oxidative modifications of proteins and a marker of oxidative stress. In fact, several studies suggest that physical activity and the consequent increase in oxygen consumption can lead to increase in reactive oxygen and nitrogen species (RONS production, hence the interest in examining the impact of RONS on skeletal muscle proteins following ASE. Results indicate that protein expression is unaffected by ASE in both muscle types. Unexpectedly, the protein carbonylation level was reduced following ASE. In particular, the analysis found 31 and 5 spots, in Soleus and EDL muscles respectively, whose carbonylation is reduced after ASE. Lipid peroxidation levels in Soleus were markedly reduced as well. Most of the decarbonylated proteins are involved either in the regulation of muscle contractions or in the regulation of energy metabolism. A number of hypotheses may be advanced to account for such results, which will be addressed in future studies.

  13. Repair Effect of Seaweed Polysaccharides with Different Contents of Sulfate Group and Molecular Weights on Damaged HK-2 Cells

    Directory of Open Access Journals (Sweden)

    Poonam Bhadja

    2016-05-01

    Full Text Available The structure–activity relationships and repair mechanism of six low-molecular-weight seaweed polysaccharides (SPSs on oxalate-induced damaged human kidney proximal tubular epithelial cells (HK-2 were investigated. These SPSs included Laminaria japonica polysaccharide, degraded Porphyra yezoensis polysaccharide, degraded Gracilaria lemaneiformis polysaccharide, degraded Sargassum fusiforme polysaccharide, Eucheuma gelatinae polysaccharide, and degraded Undaria pinnatifida polysaccharide. These SPSs have a narrow difference of molecular weight (from 1968 to 4020 Da after degradation by controlling H2O2 concentration. The sulfate group (–SO3H content of the six SPSs was 21.7%, 17.9%, 13.3%, 8.2%, 7.0%, and 5.5%, respectively, and the –COOH contents varied between 1.0% to 1.7%. After degradation, no significant difference was observed in the contents of characteristic –SO3H and –COOH groups of polysaccharides. The repair effect of polysaccharides was determined using cell-viability test by CCK-8 assay and cell-morphology test by hematoxylin-eosin staining. The results revealed that these SPSs within 0.1–100 μg/mL did not express cytotoxicity in HK-2 cells, and each polysaccharide had a repair effect on oxalate-induced damaged HK-2 cells. Simultaneously, the content of polysaccharide –SO3H was positively correlated with repair ability. Furthermore, the low-molecular-weight degraded polysaccharides showed better repair activity on damaged HK-2 cells than their undegraded counterpart. Our results can provide reference for inhibiting the formation of kidney stones and for developing original anti-stone polysaccharide drugs.

  14. Complex permeability and permittivity variation of carbonyl iron rubber in the frequency range of 2 to 18 GHz

    Directory of Open Access Journals (Sweden)

    Adriana Medeiros Gama

    2010-04-01

    Full Text Available The complex dielectric permittivity (e and magnetic permeability (m of Radar Absorbing Materials (RAM based on metallic magnetic particles (carbonyl iron particles embedded in a dielectric matrix (silicon rubber have been studied in the frequency range of 2 to 18 GHz. The relative permeability and permittivity of carbonyl iron-silicon composites for various mass fractions are measured by the transmission/reflection method using a vector network analyzer. The concentration dependence of permittivity and permeability on the frequency is analyzed. In a general way, the results show that e´ parameter shows a more significant variation among the evaluated parameters (e”, m”, m’. The comparison of dielectric and magnetic loss tangents (e”/e” and m”/m’, respectively shows more clearly the variation of both parameters (e and m according to the frequency. It is also observed that higher carbonyl iron content fractions favor both dielectric and magnetic loss tangents.

  15. Optimized biotin-hydrazide enrichment and mass spectrometry analysis of peptide carbonyls

    DEFF Research Database (Denmark)

    Havelund, Jesper F.; Wojdyla, K; Jensen, O. N.

    Irreversible cell damage through protein carbonylation is the result of reaction with reactive oxygen species (ROS) and has been coupled to many diseases. The precise molecular consequences of protein carbonylation, however, are still not clear. The localization of the carbonylated amino acid is ...... modifications are isobaric to carbonylation and it is often challenging to detect the weaker signal from carbonylated peptides necessitating enrichment step. We here present an optimized method for the enrichment of carbonylated peptides....

  16. Catalyst Initiation in the Oscillatory Carbonylation Reaction

    Directory of Open Access Journals (Sweden)

    Katarina Novakovic

    2011-01-01

    Full Text Available Palladium(II iodide is used as a catalyst in the phenylacetylene oxidative carbonylation reaction that has demonstrated oscillatory behaviour in both pH and heat of reaction. In an attempt to extract the reaction network responsible for the oscillatory nature of this reaction, the system was divided into smaller parts and they were studied. This paper focuses on understanding the reaction network responsible for the initial reactions of palladium(II iodide within this oscillatory reaction. The species researched include methanol, palladium(II iodide, potassium iodide, and carbon monoxide. Several chemical reactions were considered and applied in a modelling study. The study revealed the significant role played by traces of water contained in the standard HPLC grade methanol used.

  17. The Ash Content of the Main Muscle Groups and Edible Offal Collected From Hares (Lepus europaeus Pallas

    Directory of Open Access Journals (Sweden)

    Gabriela Tărnăuceanu Frunză

    2016-03-01

    Full Text Available Abstract. The availability of hares (Lepus europaeus Pallas, unlike that of domestic rabbits, is restricted by hunting seasons. Rabbit meat, according to research from Spain, is a rich source of K, P, Fe and Mg, but poor in Na, being recommended for people with hypertension. The largest quantity of macro minerals studied in rabbit meat was determined for K and P, and the most abundant micro minerals were Zn, Fe, Cu and Mn. In hare meat, ash content is not sufficiently studied. The current low level of knowledge motivated the present study. The aim of this study was to establish the ash content for major muscle groups and edible offal of hares. The biological material used was collected from 49 hares with an average weight of 5.6 kg, at the age of reproductive maturity (adults: 11-12 months. Different muscle groups (the muscles Cervicalis, Intercostalis, Longissimus Dorsi, Psoas major, Triceps Brachi, Biceps femoris, Semimembranosus and the main edible offal (heart, liver, kidney were sampled. The ash was determined by calcination (in Supertherm C311 oven calcination at 5500C. The results obtained were interpreted statistically (arithmetic mean (X, standard deviation (s, variance (s2 and coefficient of variation (V% and the statistical significance of differences was tested using the ANOVA Single Factor algorithm (p>0.05; p<0.01; p<0.001. Ash content for the main muscle groups analysed varied from the lowest average values of 1.095% for the Intercostalis muscles, to the highest average values of 1.256%, for Triceps brachii muscles.

  18. Carbonyl complexes of rhodium with N-donor ligands: factors determining the formation of terminal versus bridging carbonyls

    NARCIS (Netherlands)

    Dzik, W.I.; Creusen, C.; de Gelder, R.; Peters, T.P.J.; Smits, J.M.M.; de Bruin, B.

    2010-01-01

    Cationic rhodium carbonyl complexes supported by a series of different N-3- and N-4-donor ligands were prepared, and their ability to form carbonyl-bridged species was evaluated. Complex [Rh(K3-bpa)(cod)r (1(+)) (bpa = bis(2-picolyBamine, cod = cis,cis-1,5-cyclooctadiene) reacts with I bar of CO to

  19. Presence and potential significance of aromatic-ketone groups in aquatic humic substances

    Science.gov (United States)

    Leenheer, J.A.; Wilson, M.A.; Malcolm, R.L.

    1987-01-01

    Aquatic humic- and fulvic-acid standards of the International Humic Substances Society were characterized, with emphasis on carbonyl-group nature and content, by carbon-13 nuclear-magnetic-resonance spectroscopy, proton nuclear-magnetic-resonance spectroscopy, and infrared spectroscopy. After comparing spectral results of underivatized humic and fulvic acids with spectral results of chemically modified derivatives, that allow improved observation of the carbonyl group, the data clearly indicated that aromatic ketone groups comprised the majority of the carbonyl-group content. About one ketone group per monocyclic aromatic ring was determined for both humic and fulvic acids. Aromatic-ketone groups were hypothesized to form by photolytic rearrangements and oxidation of phenolic ester and hydrocarbon precursors; these groups have potential significance regarding haloform formation in water, reactivity resulting from active hydrogen of the methyl and methylene adjacent to the ketone groups, and formation of hemiketal and lactol structures. Aromatic-ketone groups also may be the point of attachment between aliphatic and aromatic moieties of aquatic humic-substance structure. ?? 1987.

  20. #CleftProud: A Content Analysis and Online Survey of 2 Cleft Lip and Palate Facebook Groups.

    Science.gov (United States)

    Stock, Nicola Marie; Martindale, Anna; Cunniffe, Claire

    2018-01-01

    More than 2 billion people worldwide now use social networking sites, with an increasing number of users accessing these sites to obtain health information and engage in emotional support. Yet, investigation of social networking sites in the context of cleft lip and/or palate (CL/P) has been scarce. Real-time data posted during 2 weeks in April 2017 were collected from 2 existing private Facebook groups (hosted by the Cleft Lip and Palate Association United Kingdom) using video screen capture software. The number of posts, comments, unique contributors, and post "likes" was recorded, as well as the type and theme of each post. Data relating to the benefits and challenges of participation in the 2 groups were also collected via an online survey. A content analysis of real-time data identified perioperative care, associated syndromes, and dental health to be particular areas of concern for parents/caregivers. Expectations, experiences, and outcomes of further treatment were key topics of discussion for adults with CL/P. Common benefits of the groups included the ability to connect with others, learn about local events, give and receive emotional support, and obtain quick responses to queries in a semi-anonymous environment. Disadvantages of the groups included a reliance upon opinion rather than medical fact and the frequent use of inappropriate terminology. Social networking sites appear to be a helpful source of health-related information and peer support for the CL/P population, yet closer monitoring of these groups may be required.

  1. Water content differences have stronger effects than plant functional groups on soil bacteria in a steppe ecosystem.

    Directory of Open Access Journals (Sweden)

    Ximei Zhang

    Full Text Available Many investigations across natural and artificial plant diversity gradients have reported that both soil physicochemical factors and plant community composition affect soil microbial communities. To test the effect of plant diversity loss on soil bacterial communities, we conducted a five-year plant functional group removal experiment in a steppe ecosystem in Inner Mongolia (China. We found that the number and composition type of plant functional groups had no effect on bacterial diversity and community composition, or on the relative abundance of major taxa. In contrast, bacterial community patterns were significantly structured by soil water content differences among plots. Our results support researches that suggest that water availability is the key factor structuring soil bacterial communities in this semi-arid ecosystem.

  2. Emission, absorption and group delay of microwaves in the atmosphere in relation to water vapour content over the Indian subcontinent

    Science.gov (United States)

    Sen, A. K.; Gupta, A. K. D.; Karmakar, P. K.; Barman, S. D.; Bhattacharya, A. B.; Purkait, N.; Gupta, M. K. D.; Sehra, J. S.

    1985-01-01

    The advent of satellite communication for global coverage has apparently indicated a renewed interest in the studies of radio wave propagation through the atmosphere, in the VHF, UHF and microwave bands. The extensive measurements of atmosphere constituents, dynamics and radio meterological parameters during the Middle Atmosphere Program (MAP) have opened up further the possibilities of studying tropospheric radio wave propagation parameters, relevant to Earth/space link design. The three basic parameters of significance to radio propagation are thermal emission, absorption and group delay of the atmosphere, all of which are controlled largely by the water vapor content in the atmosphere, particular at microwave bands. As good emitters are also good absorbers, the atmospheric emission as well as the absorption attains a maximum at the frequency of 22.235 GHz, which is the peak of the water vapor line. The group delay is practically independent of frequency in the VHF, UHF and microwave bands. However, all three parameters exhibit a similar seasonal dependence originating presumably from the seasonal dependence of the water vapor content. Some of the interesting results obtained from analyses of radiosonde data over the Indian subcontinent collected by the India Meteorological Department is presented.

  3. Protein conjugated with aldehydes derived from lipid peroxidation as an independent parameter of the carbonyl stress in the kidney damage

    Directory of Open Access Journals (Sweden)

    Medina-Navarro Rafael

    2011-11-01

    Full Text Available Abstract Background One of the well-defined and characterized protein modifications usually produced by oxidation is carbonylation, an irreversible non-enzymatic modification of proteins. However, carbonyl groups can be introduced into proteins by non-oxidative mechanisms. Reactive carbonyl compounds have been observed to have increased in patients with renal failure. In the present work we have described a procedure designed as aldehyde capture to calculate the protein carbonyl stress derived solely from lipid peroxidation. Methods Acrolein-albumin adduct was prepared as standard at alkaline pH. Rat liver microsomal membranes and serum samples from patients with diabetic nephropathy were subjected to the aldehyde capture procedure and aldol-protein formation. Before alkalinization and incubation, samples were precipitated and redisolved in 6M guanidine. The absorbances of the samples were read with a spectrophotometer at 266 nm against a blank of guanidine. Results Evidence showed abundance of unsaturated aldehydes derived from lipid peroxidation in rat liver microsomal membranes and in the serum of diabetic patients with advanced chronic kidney disease. Carbonyl protein and aldol-proteins resulted higher in the diabetic nephropathy patients (p Conclusion The aldehyde-protein adduct represents a non oxidative component of carbonyl stress, independent of the direct amino acid oxidation and could constitute a practical and novelty strategy to measure the carbonyl stress derived solely from lipid peroxidation and particularly in diabetic nephropathy patients. In addition, we are in a position to propose an alternative explanation of why alkalinization of urine attenuates rhabdomyolysis-induced renal dysfunction.

  4. High throughput assay for evaluation of reactive carbonyl scavenging capacity.

    Science.gov (United States)

    Vidal, N; Cavaille, J P; Graziani, F; Robin, M; Ouari, O; Pietri, S; Stocker, P

    2014-01-01

    Many carbonyl species from either lipid peroxidation or glycoxidation are extremely reactive and can disrupt the function of proteins and enzymes. 4-hydroxynonenal and methylglyoxal are the most abundant and toxic lipid-derived reactive carbonyl species. The presence of these toxics leads to carbonyl stress and cause a significant amount of macromolecular damages in several diseases. Much evidence indicates trapping of reactive carbonyl intermediates may be a useful strategy for inhibiting or decreasing carbonyl stress-associated pathologies. There is no rapid and convenient analytical method available for the assessment of direct carbonyl scavenging capacity, and a very limited number of carbonyl scavengers have been identified to date, their therapeutic potential being highlighted only recently. In this context, we have developed a new and rapid sensitive fluorimetric method for the assessment of reactive carbonyl scavengers without involvement glycoxidation systems. Efficacy of various thiol- and non-thiol-carbonyl scavenger pharmacophores was tested both using this screening assay adapted to 96-well microplates and in cultured cells. The scavenging effects on the formation of Advanced Glycation End-product of Bovine Serum Albumin formed with methylglyoxal, 4-hydroxynonenal and glucose-glycated as molecular models were also examined. Low molecular mass thiols with an α-amino-β-mercaptoethane structure showed the highest degree of inhibitory activity toward both α,β-unsaturated aldehydes and dicarbonyls. Cysteine and cysteamine have the best scavenging ability toward methylglyoxal. WR-1065 which is currently approved for clinical use as a protective agent against radiation and renal toxicity was identified as the best inhibitor of 4-hydroxynonenal.

  5. High throughput assay for evaluation of reactive carbonyl scavenging capacity

    Directory of Open Access Journals (Sweden)

    N. Vidal

    2014-01-01

    Full Text Available Many carbonyl species from either lipid peroxidation or glycoxidation are extremely reactive and can disrupt the function of proteins and enzymes. 4-hydroxynonenal and methylglyoxal are the most abundant and toxic lipid-derived reactive carbonyl species. The presence of these toxics leads to carbonyl stress and cause a significant amount of macromolecular damages in several diseases. Much evidence indicates trapping of reactive carbonyl intermediates may be a useful strategy for inhibiting or decreasing carbonyl stress-associated pathologies. There is no rapid and convenient analytical method available for the assessment of direct carbonyl scavenging capacity, and a very limited number of carbonyl scavengers have been identified to date, their therapeutic potential being highlighted only recently. In this context, we have developed a new and rapid sensitive fluorimetric method for the assessment of reactive carbonyl scavengers without involvement glycoxidation systems. Efficacy of various thiol- and non-thiol-carbonyl scavenger pharmacophores was tested both using this screening assay adapted to 96-well microplates and in cultured cells. The scavenging effects on the formation of Advanced Glycation End-product of Bovine Serum Albumin formed with methylglyoxal, 4-hydroxynonenal and glucose-glycated as molecular models were also examined. Low molecular mass thiols with an α-amino-β-mercaptoethane structure showed the highest degree of inhibitory activity toward both α,β-unsaturated aldehydes and dicarbonyls. Cysteine and cysteamine have the best scavenging ability toward methylglyoxal. WR-1065 which is currently approved for clinical use as a protective agent against radiation and renal toxicity was identified as the best inhibitor of 4-hydroxynonenal.

  6. 16th Carbonyl Metabolism Meeting: from enzymology to genomics

    Directory of Open Access Journals (Sweden)

    Maser Edmund

    2012-12-01

    Full Text Available Abstract The 16th International Meeting on the Enzymology and Molecular Biology of Carbonyl Metabolism, Castle of Ploen (Schleswig-Holstein, Germany, July 10–15, 2012, covered all aspects of NAD(P-dependent oxido-reductases that are involved in the general metabolism of xenobiotic and physiological carbonyl compounds. Starting 30 years ago with enzyme purification, structure elucidation and enzyme kinetics, the Carbonyl Society members have meanwhile established internationally recognized enzyme nomenclature systems and now consider aspects of enzyme genomics and enzyme evolution along with their roles in diseases. The 16th international meeting included lectures from international speakers from all over the world.

  7. Role of Protein Carbonylation in Skeletal Muscle Mass Loss Associated with Chronic Conditions

    Directory of Open Access Journals (Sweden)

    Esther Barreiro

    2016-05-01

    Full Text Available Muscle dysfunction, characterized by a reductive remodeling of muscle fibers, is a common systemic manifestation in highly prevalent conditions such as chronic heart failure (CHF, chronic obstructive pulmonary disease (COPD, cancer cachexia, and critically ill patients. Skeletal muscle dysfunction and impaired muscle mass may predict morbidity and mortality in patients with chronic diseases, regardless of the underlying condition. High levels of oxidants may alter function and structure of key cellular molecules such as proteins, DNA, and lipids, leading to cellular injury and death. Protein oxidation including protein carbonylation was demonstrated to modify enzyme activity and DNA binding of transcription factors, while also rendering proteins more prone to proteolytic degradation. Given the relevance of protein oxidation in the pathophysiology of many chronic conditions and their comorbidities, the current review focuses on the analysis of different studies in which the biological and clinical significance of the modifications induced by reactive carbonyls on proteins have been explored so far in skeletal muscles of patients and animal models of chronic conditions such as COPD, disuse muscle atrophy, cancer cachexia, sepsis, and physiological aging. Future research will elucidate the specific impact and sites of reactive carbonyls on muscle protein content and function in human conditions.

  8. Instrument for Airborne Measurement of Carbonyl Sulfide, Phase I

    Data.gov (United States)

    National Aeronautics and Space Administration — Southwest Sciences proposes to develop small, low power instrumentation for the real-time direct measurement of carbonyl sulfide (OCS) in the atmosphere, especially...

  9. Instrument for Airborne Measurement of Carbonyl Sulfide, Phase II

    Data.gov (United States)

    National Aeronautics and Space Administration — In this Phase II SBIR program, Southwest Sciences will continue the development of small, low power instrumentation for real-time direct measurement of carbonyl...

  10. DNA damage by carbonyl stress in human skin cells

    International Nuclear Information System (INIS)

    Roberts, Michael J.; Wondrak, Georg T.; Laurean, Daniel Cervantes; Jacobson, Myron K.; Jacobson, Elaine L.

    2003-01-01

    Reactive carbonyl species (RCS) are potent mediators of cellular carbonyl stress originating from endogenous chemical processes such as lipid peroxidation and glycation. Skin deterioration as observed in photoaging and diabetes has been linked to accumulative protein damage from glycation, but the effects of carbonyl stress on skin cell genomic integrity are ill defined. In this study, the genotoxic effects of acute carbonyl stress on HaCaT keratinocytes and CF3 fibroblasts were assessed. Administration of the α-dicarbonyl compounds glyoxal and methylglyoxal as physiologically relevant RCS inhibited skin cell proliferation, led to intra-cellular protein glycation as evidenced by the accumulation of N ε -(carboxymethyl)-L-lysine (CML) in histones, and caused extensive DNA strand cleavage as assessed by the comet assay. These effects were prevented by treatment with the carbonyl scavenger D-penicillamine. Both glyoxal and methylglyoxal damaged DNA in intact cells. Glyoxal caused DNA strand breaks while methylglyoxal produced extensive DNA-protein cross-linking as evidenced by pronounced nuclear condensation and total suppression of comet formation. Glycation by glyoxal and methylglyoxal resulted in histone cross-linking in vitro and induced oxygen-dependent cleavage of plasmid DNA, which was partly suppressed by the hydroxyl scavenger mannitol. We suggest that a chemical mechanism of cellular DNA damage by carbonyl stress occurs in which histone glycoxidation is followed by reactive oxygen induced DNA stand breaks. The genotoxic potential of RCS in cultured skin cells and its suppression by a carbonyl scavenger as described in this study have implications for skin damage and carcinogenesis and its prevention by agents selective for carbonyl stress

  11. DNA damage by carbonyl stress in human skin cells

    Energy Technology Data Exchange (ETDEWEB)

    Roberts, Michael J.; Wondrak, Georg T.; Laurean, Daniel Cervantes; Jacobson, Myron K.; Jacobson, Elaine L

    2003-01-28

    Reactive carbonyl species (RCS) are potent mediators of cellular carbonyl stress originating from endogenous chemical processes such as lipid peroxidation and glycation. Skin deterioration as observed in photoaging and diabetes has been linked to accumulative protein damage from glycation, but the effects of carbonyl stress on skin cell genomic integrity are ill defined. In this study, the genotoxic effects of acute carbonyl stress on HaCaT keratinocytes and CF3 fibroblasts were assessed. Administration of the {alpha}-dicarbonyl compounds glyoxal and methylglyoxal as physiologically relevant RCS inhibited skin cell proliferation, led to intra-cellular protein glycation as evidenced by the accumulation of N{sup {epsilon}}-(carboxymethyl)-L-lysine (CML) in histones, and caused extensive DNA strand cleavage as assessed by the comet assay. These effects were prevented by treatment with the carbonyl scavenger D-penicillamine. Both glyoxal and methylglyoxal damaged DNA in intact cells. Glyoxal caused DNA strand breaks while methylglyoxal produced extensive DNA-protein cross-linking as evidenced by pronounced nuclear condensation and total suppression of comet formation. Glycation by glyoxal and methylglyoxal resulted in histone cross-linking in vitro and induced oxygen-dependent cleavage of plasmid DNA, which was partly suppressed by the hydroxyl scavenger mannitol. We suggest that a chemical mechanism of cellular DNA damage by carbonyl stress occurs in which histone glycoxidation is followed by reactive oxygen induced DNA stand breaks. The genotoxic potential of RCS in cultured skin cells and its suppression by a carbonyl scavenger as described in this study have implications for skin damage and carcinogenesis and its prevention by agents selective for carbonyl stress.

  12. Propheromones that release pheromonal carbonyl compounds in light.

    Science.gov (United States)

    Liu, X; Macaulay, E D; Pickett, J A

    1984-05-01

    Pheromonal carbonyl compounds; (Z)-11-hexadecanal, (E)-citral, and 2-heptanone were treated with six alcohols to give acetals or ketals, some of which acted as propheromones by releasing the pheromonal carbonyl compounds in ultraviolet or simulated sunlight. Highest yields of pheromone were obtained from adducts prepared witho-nitrobenzyl alcohol ando-nitrophenylethane-1,2-diol. Adducts from (Z)-11-hexadecenal and these two alcohols were employed in lures to catch diamondback moths,Plutella xylostella (L.).

  13. The Emergence of Manganese-Based Carbonyl Hydrosilylation Catalysts.

    Science.gov (United States)

    Trovitch, Ryan J

    2017-11-21

    In recent years, interest in homogeneous manganese catalyst development has intensified because of the earth-abundant and nontoxic nature of this metal. Although compounds of Mn have largely been utilized for epoxidation reactions, recent efforts have revealed that Mn catalysts can mediate a broad range of reductive transformations. Low-valent Mn compounds have proven to be particularly effective for the hydrosilylation of carbonyl- and carboxylate-containing substrates, and this Account aims to highlight my research group's contributions to this field. In our initial 2014 communication, we reported that the bis(imino)pyridine-supported compound ( Ph2PPr PDI)Mn mediates ketone hydrosilylation with exceptional activity under solvent-free conditions. Silanes including Ph 2 SiH 2 , (EtO) 3 SiH, (EtO) 2 MeSiH, and (EtO)Me 2 SiH were found to partially reduce cyclohexanone in the presence of ( Ph2PPr PDI)Mn, while turnover frequencies of up to 1280 min -1 were observed using PhSiH 3 . This led us to evaluate the hydrosilylation of 11 additional ketones and allowed for the atom-efficient preparation of tertiary and quaternary silanes. At that time, it was also discovered that ( Ph2PPr PDI)Mn catalyzes the dihydrosilylation of esters (by way of acyl C-O bond hydrosilylation) to yield a mixture of silyl ethers with modest activity. Earlier this year, the scope of these transformations was extended to aldehydes and formates, and the observed hydrosilylation activities are among the highest obtained for any transition-metal catalyst. The effectiveness of three related catalysts has also been evaluated: ( Ph2PPr PDI)MnH, ( PyEt PDEA)Mn, and [( Ph2PEt PDI)Mn] 2 . To our surprise, ( Ph2PPr PDI)MnH was found to exhibit higher carboxylate dihydrosilylation activity than ( Ph2PPr PDI)Mn, while ( PyEt PDEA)Mn demonstrated remarkable carbonyl hydrosilylation activity considering that it lacks a redox-active supporting ligand. The evaluation of [( Ph2PEt PDI)Mn] 2 revealed

  14. Contribution to radiation-chemically catalyzed hydroformylation of butenes in the presence of metal carbonyls

    International Nuclear Information System (INIS)

    Joosten, L.

    1976-01-01

    In this paper a study is presented of the influence of gamma-radiation on the catalytic hydroformylation of olefines. As model olefines buten-1 and buten-2 as well as their mixtures have been used together with the catalysts di-cobalt octacarbonyle and rhodium (I) tristri phenyl-phosphine carbonyle hydride. In addition the catalytic activity of the VI. side group carbonyles Cr(CO) 6 , Mo(CO) 6 and W(CO) 6 has been studied under radiation chemical conditions. For this purpose a mixture of olefine, solvent (cyclo hexane) and calalyst has been pressurized and processed in a mixing autoklave together with a Co and H 2 (1:1) mixture, variing the reaction variables within certain limits. (orig.) [de

  15. Prediction of intramuscular fat content and major fatty acid groups of lamb M. longissimus lumborum using Raman spectroscopy.

    Science.gov (United States)

    Fowler, Stephanie M; Ponnampalam, Eric N; Schmidt, Heinar; Wynn, Peter; Hopkins, David L

    2015-12-01

    A hand held Raman spectroscopic device was used to predict intramuscular fat (IMF) levels and the major fatty acid (FA) groups of fresh intact ovine M. longissimus lumborum (LL). IMF levels were determined using the Soxhlet method, while FA analysis was conducted using a rapid (KOH in water, methanol and sulphuric acid in water) extraction procedure. IMF levels and FA values were regressed against Raman spectra using partial least squares regression and against each other using linear regression. The results indicate that there is potential to predict PUFA (R(2)=0.93) and MUFA (R(2)=0.54) as well as SFA values that had been adjusted for IMF content (R(2)=0.54). However, this potential was significantly reduced when correlations between predicted and observed values were determined by cross validation (R(2)cv=0.21-0.00). Overall, the prediction of major FA groups using Raman spectra was more precise (relative reductions in error of 0.3-40.8%) compared to the null models. Copyright © 2015 Elsevier Ltd. All rights reserved.

  16. The magnetorheological fluid of carbonyl iron suspension blended with grafted MWCNT or graphene

    Science.gov (United States)

    Rwei, Syang-Peng; Ranganathan, Palraj; Chiang, Whe-Yi; Wang, Tza-Yi

    2017-12-01

    In this work, the magnetorheological (MR) fluids containing MWCNT/CI (carbonyl iron) complex and graphene/CI complex were prepared and have the better dispersity in silicone oil than CI powders alone. 1, 4-Aminobenzoic acid (PABA) was used as a grafting agent to modify CI powders to have NH2-end-group so that such nanoparticles can adsorb to acid-treated MWCNT or graphene via attraction of NH2 and COOH groups. The MWCNT/CI complex and graphene/CI complex have a structure of carbonyl iron nanoparticles adsorbed to MWCNT and graphene by self assembly, respectively. Because the carbonyl iron particles possessing magnetic permeability in nanometer scale adsorb to MWCNT or graphene which usually has a nanometer-scaled diameter and a micrometer-scaled length in this work, the dispersity of MWCNT/CI or graphene/CI complex in silicone oil is superior than the previous report [15] that the micrometer-scaled carbonyl iron microspheres were coated with multiwalled carbon nanotubes. Among CI (unmodified), MWCNT/CI and graphene/CI, graphene/CI has the best dispersity while MWCNT/CI still has the better dispersity than unmodified CI. At the temperature T = 300 K, the saturation magnetizations of CI, MWCNT/CI, graphene/CI are 208, 211 emu/g, and 204 emu/g, respectively, indicating that MWCNT/CI complex and graphene/CI complex still maintain the saturation magnetization as high as CI without being interfered by the blended MWCNT or graphene. A wide dynamic range of the yield stress adjusted through varying the electric current can be achieved by the MR fluids containing 69 wt% MWCNT/CI and graphene/CI which is useful in a shock absorber or damper. The result of the yield stress indicates the suspended MWCNT/CI particles are oriented more easily toward the direction perpendicular to the flow direction to block the flow stream lines.

  17. Ligand-Enabled γ-C–H Olefination and Carbonylation: Construction of β-Quaternary Carbon Centers

    Science.gov (United States)

    2015-01-01

    Monoselective γ-C–H olefination and carbonylation of aliphatic acids has been accomplished by using a combination of a quinoline-based ligand and a weakly coordinating amide directing group. The reaction provides a new route for constructing richly functionalized all-carbon quaternary carbon centers at the β-position of aliphatic acids. PMID:24666182

  18. 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.

  19. Informational and emotional elements in online support groups: a Bayesian approach to large-scale content analysis.

    Science.gov (United States)

    Deetjen, Ulrike; Powell, John A

    2016-05-01

    This research examines the extent to which informational and emotional elements are employed in online support forums for 14 purposively sampled chronic medical conditions and the factors that influence whether posts are of a more informational or emotional nature. Large-scale qualitative data were obtained from Dailystrength.org. Based on a hand-coded training dataset, all posts were classified into informational or emotional using a Bayesian classification algorithm to generalize the findings. Posts that could not be classified with a probability of at least 75% were excluded. The overall tendency toward emotional posts differs by condition: mental health (depression, schizophrenia) and Alzheimer's disease consist of more emotional posts, while informational posts relate more to nonterminal physical conditions (irritable bowel syndrome, diabetes, asthma). There is no gender difference across conditions, although prostate cancer forums are oriented toward informational support, whereas breast cancer forums rather feature emotional support. Across diseases, the best predictors for emotional content are lower age and a higher number of overall posts by the support group member. The results are in line with previous empirical research and unify empirical findings from single/2-condition research. Limitations include the analytical restriction to predefined categories (informational, emotional) through the chosen machine-learning approach. Our findings provide an empirical foundation for building theory on informational versus emotional support across conditions, give insights for practitioners to better understand the role of online support groups for different patients, and show the usefulness of machine-learning approaches to analyze large-scale qualitative health data from online settings. © The Author 2016. Published by Oxford University Press on behalf of the American Medical Informatics Association. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

  20. Effects of learning content in context on knowledge acquisition and recall: a pretest-posttest control group design.

    Science.gov (United States)

    Bergman, Esther M; de Bruin, Anique B H; Vorstenbosch, Marc A T M; Kooloos, Jan G M; Puts, Ghita C W M; Leppink, Jimmie; Scherpbier, Albert J J A; van der Vleuten, Cees P M

    2015-08-15

    It is generally assumed that learning in context increases performance. This study investigates the relationship between the characteristics of a paper-patient context (relevance and familiarity), the mechanisms through which the cognitive dimension of context could improve learning (activation of prior knowledge, elaboration and increasing retrieval cues), and test performance. A total of 145 medical students completed a pretest of 40 questions, of which half were with a patient vignette. One week later, they studied musculoskeletal anatomy in the dissection room without a paper-patient context (control group) or with (ir)relevant-(un)familiar context (experimental groups), and completed a cognitive load scale. Following a short delay, the students completed a posttest. Surprisingly, our results show that students who studied in context did not perform better than students who studied without context. This finding may be explained by an interaction of the participants' expertise level, the nature of anatomical knowledge and students' approaches to learning. A relevant-familiar context only reduced the negative effect of learning the content in context. Our results suggest discouraging the introduction of an uncommon disease to illustrate a basic science concept. Higher self-perceived learning scores predict higher performance. Interestingly, students performed significantly better on the questions with context in both tests, possibly due to a 'framing effect'. Since studies focusing on the physical and affective dimensions of context have also failed to find a positive influence of learning in a clinically relevant context, further research seems necessary to refine our theories around the role of context in learning.

  1. An evaluation of multimedia and online support groups (OSG) contents and application of information by infertile patients: Mixed method study

    Science.gov (United States)

    Wiweko, Budi; Narasati, Shabrina; Agung, Prince Gusti; Zesario, Aulia; Wibawa, Yohanes Satrya; Maidarti, Mila; Harzif, Achmad Kemal; Pratama, Gita; Sumapradja, Kanadi; Muharam, Raden; Hestiantoro, Andon

    2018-02-01

    Background: The presence of Online Support Groups (OSG) is expected to empower patients with infertility, thus allowing patients to be the focus of healthcare services. This study will evaluate multimedia content, OSG, and utilization of information for decision-making by patients using infertility services. This study is a mixed method study conducted from January - June 2016 at Yasmin IVF Clinic, Dr. Cipto Mangunkusumo General Hospital; and SMART IVF Clinic, Jakarta. The subjects are patients with infertility who sought treatment at the clinics. Data was collected through a structured interview in the form of a questionnaire. Informed consent was obtained from all individual participants included in the study. All procedures that performed in studies were by the ethical standards of the institutional. The result from 72 respondents showed quantitative analysis did not reveal any association between multimedia and OSG information sources with patient knowledge regarding infertility management. However, qualitative analysis highlighted three issues: the information regarding infertility services in the available multimedia and the OSG; use of the available information by patients when deciding to use infertility services. The level of awareness of respondents on searching information regarding infertility on the clinic website is still limited. It happened because most of the patients in the clinic are unaware of clinic website existence which provided the infertility information. Therefore, the clinic website needs to be promoted so the usage of this website will increase in the future.

  2. Fermentable oligosaccharide, disaccharide, monosaccharide and polyol content of foods commonly consumed by ethnic minority groups in the United Kingdom.

    Science.gov (United States)

    Prichard, Rebeca; Rossi, Megan; Muir, Jane; Yao, Ck; Whelan, Kevin; Lomer, Miranda

    2016-06-01

    Dietary restriction of fermentable oligosaccharides, disaccharides, monosaccharides and polyols (FODMAPs) is an effective management approach for functional bowel disorders; however, its application is limited by the paucity of food composition data available for ethnic minority groups. The aim was to identify and measure the FODMAP content of these commonly consumed foods. According to their perceived importance to clinical practise, the top 20 ranked foods underwent FODMAP analysis using validated analytical techniques (total fructans, Megazyme hexokinase (HK) assay; all others, high-performance liquid chromatography (HPLC) with evaporative light scattering detectors). Of the 20 foods analysed, five were identified as significant sources of at least one FODMAP. Fructans and galacto-oligosaccharides were the major FODMAPs in these foods, including channa dal (0.13 g/100 g; 0.36 g/100 g), fenugreek seeds (1.11 g/100 g; 1.27 g/100 g), guava (0.41 g/100 g; not detected), karela (not detected; 1.12 g/100 g) and tamarind (2.35 g/100 g; 0.02 g/100 g). Broadening the availability of FODMAP composition data will increase the cultural application of low FODMAP dietary advice.

  3. Excited state characterization of carbonyl containing carotenoids: a comparison between single and multireference descriptions

    Science.gov (United States)

    Spezia, Riccardo; Knecht, Stefan; Mennucci, Benedetta

    Carotenoids can play multiple roles in biological photoreceptors thanks to their rich photophysics. In the present work, we have investigated six of the most common carbonyl containing carotenoids: Echinenone, Canthaxanthin, Astaxanthin, Fucoxanthin, Capsanthin and Capsorubin. Their excitation properties are investigated by means of a hybrid density functional theory (DFT) and multireference configuration interaction (MRCI) approach to elucidate the role of the carbonyl group: the bright transition is of {\\pi}{\\pi}* character, as expected, but the presence of a C=O moiety reduces the energy of n{\\pi}* transitions which may become closer to the {\\pi}{\\pi}* transition, in particular as the conjugation chain decreases. This can be related to the presence of a low-lying charge transfer state typical of short carbonyl- containing carotenoids. The DFT/MRCI results are finally used to benchmark single- reference time-dependent DFT-based methods: among the investigated functionals, the meta- GGA (and in particular M11L and MN12L) functionals show to perform the best for all six investigated systems.

  4. Characterization of Carbonyl Compounds in the Ambient Air of an Industrial City in Korea

    Directory of Open Access Journals (Sweden)

    Sung-Ok Baek

    2011-01-01

    Full Text Available The purpose of this study was to characterize spatial and temporal variations of carbonyl compounds in Gumi city, where a number of large electronic-industrial complexes are located. Carbonyl samples were collected at five sites in the Gumi area: three industrial, one commercial, and one residential area. Sampling was carried out throughout a year from December 2003 to November 2004. At one industrial site, samples were taken every six days, while those of the other sites were for seven consecutive days in every season. Each sample was collected for 150 minutes and at intervals of three times a day (morning, afternoon, and evening. A total of 476 samples were analyzed to determine 15 carbonyl compounds by the USEPA TO-11A (DNPH-cartridge/HPLC method. In general, acetaldehyde appeared to be the most abundant compound, followed by formaldehyde, and acetone+acrolein. Mean concentrations of acetaldehyde were two to three times higher in the industrial sites than in the other sites, with its maximum of 77.7 ppb. In contrast, ambient levels of formaldehyde did not show any significant difference between the industrial and non-industrial groups. Its concentrations peaked in summer probably due to the enhanced volatilization and photochemical reactivity. These results indicate significant emission sources of acetaldehyde in the Gumi industrial complexes. Mean concentrations of organic solvents (such as acetone+acrolein and methyl ethyl ketone were also significantly high in industrial areas. In conclusion, major sources of carbonyl compounds, including acetaldehyde, are strongly associated with industrial activities in the Gumi city area.

  5. Determination of Carbonyl Compounds in Exhaled Cigarette Smoke

    Directory of Open Access Journals (Sweden)

    Moldoveanu S

    2014-12-01

    Full Text Available This paper presents the findings on a quantitative evaluation of carbonyl levels in exhaled cigarette smoke from human subjects. The cigarettes evaluated include products with 5.0 mg ‘tar’, 10.6 mg ‘tar’ and 16.2 mg ‘tar’, where ‘tar’ is defined as the weight of total wet particulate matter (TPM minus the weight of nicotine and water, and the cigarettes are smoked following U.S. Federal Trade Commission (FTC recommendations. The measured levels of carbonyls in the exhaled smoke were compared with calculated yields of carbonyls in the inhaled smoke and a retention efficiency was obtained. The number of human subjects included a total of ten smokers for the 10.6 mg ‘tar’, five for the 16.2 mg ‘tar’, and five for the 5.0 mg ‘tar’ product, each subject smoking three cigarettes. The analyzed carbonyl compounds included several aldehydes (formaldehyde, acetaldehyde, acrolein, propionaldehyde, crotonaldehyde and n-butyraldehyde, and two ketones (acetone and 2-butanone. The smoke collection from the human subjects was vacuum assisted. Exhaled smoke was collected on Cambridge pads pretreated with a solution of dinitrophenylhydrazine (DNPH followed by high performance liquid chromatography (HPLC analysis of the dinitrophenylhydrazones of the carbonyl compounds. The cigarette butts from the smokers were collected and analyzed for nicotine. The nicotine levels for the cigarette butts from the smokers were used to calculate the level of carbonyls in the inhaled smoke, based on calibration curves. These were generated separately by analyzing the carbonyls in smoke and the nicotine in the cigarette butts obtained by machine smoking under different puffing regimes. The comparison of the level of carbonyl compounds in exhaled smoke with that from the inhaled smoke showed high retention of all the carbonyls. The retention of aldehydes was above 95% for all three different ‘tar’ levels cigarettes. The ketones were retained with a

  6. Emissions of carbonyl compounds from various cookstoves in China

    International Nuclear Information System (INIS)

    Zhang, J.; Smith, K.R.; Univ. of California, Berkeley, CA

    1999-01-01

    This paper presents a new database of carbonyl emission factors for commonly used cookstoves in China. The emission factors, reported both on a fuel-mass basis (mg/kg) and on a defined cooking-task basis (mg/task), were determined using a carbon balance approach for 22 types of fuel/stove combinations. These include various stoves using different species of crop residues and wood, kerosene, and several types of coals and gases. The results show that all the tested cookstoves produced formaldehyde and acetaldehyde and that the vast majority of the biomass stoves produced additional carbonyl compounds such as acetone, acrolein, propionaldehyde, crotonaldehyde, 2-butanone, isobutyraldehyde, butyraldehyde, isovaleraldehyde, valeraldehyde, hexaldehyde, benzaldehyde, o-tolualdehyde, m,p-tolualdehyde, and 2,4-dimethylbenzaldehyde. Carbonyls other than formaldehyde and acetaldehyde, however, were rarely generated by burning coal, coal gas, and natural gas. Kerosene and LPG stoves generated more carbonyl compounds than coal, coal gas, and natural gas stoves, but less than biomass stoves. Indoor levels of carbonyl compounds for typical village houses during cooking hours, estimated using a mass balance model and the measured emission factors, can be high enough to cause acute health effects documented for formaldehyde exposure, depending upon house parameters and individuals' susceptibility

  7. Observations and Explicit Modeling of Summertime Carbonyl Formation in Beijing: Identification of Key Precursor Species and Their Impact on Atmospheric Oxidation Chemistry

    Science.gov (United States)

    Yang, Xue; Xue, Likun; Wang, Tao; Wang, Xinfeng; Gao, Jian; Lee, Shuncheng; Blake, Donald R.; Chai, Fahe; Wang, Wenxing

    2018-01-01

    Carbonyls are an important group of volatile organic compounds (VOCs) that play critical roles in tropospheric chemistry. To better understand the formation mechanisms of carbonyl compounds, extensive measurements of carbonyls and related parameters were conducted in Beijing in summer 2008. Formaldehyde (11.17 ± 5.32 ppbv), acetone (6.98 ± 3.01 ppbv), and acetaldehyde (5.27 ± 2.24 ppbv) were the most abundant carbonyl species. Two dicarbonyls, glyoxal (0.68 ± 0.26 ppbv) and methylglyoxal (MGLY; 1.10 ± 0.44 ppbv), were also present in relatively high concentrations. An observation-based chemical box model was used to simulate the in situ production of formaldehyde, acetaldehyde, glyoxal, and MGLY and quantify their contributions to ozone formation and ROx budget. All four carbonyls showed similar formation mechanisms but exhibited different precursor distributions. Alkenes (mainly isoprene and ethene) were the dominant precursors of formaldehyde, while both alkenes (e.g., propene, i-butene, and cis-2-pentene) and alkanes (mainly i-pentane) were major precursors of acetaldehyde. For dicarbonyls, both isoprene and aromatic VOCs were the dominant parent hydrocarbons of glyoxal and MGLY. Photolysis of oxygenated VOCs was the dominant source of ROx radicals (approximately >80% for HO2 and approximately >70% for RO2) in Beijing. Ozone production occurred under a mixed-control regime with carbonyls being the key VOC species. Overall, this study provides some new insights into the formation mechanisms of carbonyls, especially their parent hydrocarbon species, and underlines the important role of carbonyls in radical chemistry and ozone pollution in Beijing. Reducing the emissions of alkenes and aromatics would be an effective way to mitigate photochemical pollution in Beijing.

  8. Estimation of glandular content rate and statistical analysis of the influence of age group and compressed breast thickness on the estimated value

    International Nuclear Information System (INIS)

    Ohmori, Naoki; Ashida, Kenji; Fujita, Osamu

    2003-01-01

    Because the glandular content rate is an important factor in evaluating breast cancer detection and average glandular dose, it is important in mammography research to estimate and analyze this rate. The purpose of this study was to obtain a formula for statistical estimation of the glandular content rate, to clarify statistically the influence of age group and compressed breast thickness (CBT) on estimating the glandular content rate, and to show statistically the general relation between glandular content rate and the factors of age and CBT. The subjects were 740 Japanese women aged 20-91 years (mean±SD: 48.3±12.8 years) who had undergone mammography. In our study, the glandular content rate was statistically estimated from age group, mAs-value, and CBT when subjects underwent mammography, from a phantom simulation, and from MR images of the breast. In addition, multivariate analysis was carried to examine statistically the influence of age group and CBT on glandular content rate. The mean glandular content rate as estimated by age group was as follows: 35.6% for those in their 20s, 33.4% in the 30s, 27.5% in the 40s, 23.8% in the 50s, and 21.8% in those 60 and over. The rate for the subjects as a whole was 27.1%. This study indicated that overestimation occurred if the estimated value of the glandular content rate was not corrected in the 3D-measurement by MRI. In addition, this study showed that the statistical influence on glandular content rate was significantly larger for CBT than age. (author)

  9. First results from the IllustrisTNG simulations: the stellar mass content of groups and clusters of galaxies

    Science.gov (United States)

    Pillepich, Annalisa; Nelson, Dylan; Hernquist, Lars; Springel, Volker; Pakmor, Rüdiger; Torrey, Paul; Weinberger, Rainer; Genel, Shy; Naiman, Jill P.; Marinacci, Federico; Vogelsberger, Mark

    2018-03-01

    The IllustrisTNG project is a new suite of cosmological magnetohydrodynamical simulations of galaxy formation performed with the AREPO code and updated models for feedback physics. Here, we introduce the first two simulations of the series, TNG100 and TNG300, and quantify the stellar mass content of about 4000 massive galaxy groups and clusters (1013 ≤ M200c/M⊙ ≤ 1015) at recent times (z ≤ 1). The richest clusters have half of their total stellar mass bound to satellite galaxies, with the other half being associated with the central galaxy and the diffuse intracluster light. Haloes more massive than about 5 × 1014 M⊙ have more diffuse stellar mass outside 100 kpc than within 100 kpc, with power-law slopes of the radial mass density distribution as shallow as the dark matter's ( - 3.5 ≲ α3D ≲ -3). Total halo mass is a very good predictor of stellar mass, and vice versa: at z = 0, the 3D stellar mass measured within 30 kpc scales as ∝(M500c)0.49 with a ˜0.12 dex scatter. This is possibly too steep in comparison to the available observational constraints, even though the abundance of The Next Generation less-massive galaxies ( ≲ 1011 M⊙ in stars) is in good agreement with the measured galaxy stellar mass functions at recent epochs. The 3D sizes of massive galaxies fall too on a tight (˜0.16 dex scatter) power-law relation with halo mass, with r^stars_0.5 ∝ (M_200c)^{0.53}. Even more fundamentally, halo mass alone is a good predictor for the whole stellar mass profiles beyond the inner few kiloparsecs, and we show how on average these can be precisely recovered given a single-mass measurement of the galaxy or its halo.

  10. Catalytic production of metal carbonyls from metal oxides

    Science.gov (United States)

    Sapienza, Richard S.; Slegeir, William A.; Foran, Michael T.

    1984-01-01

    This invention relates to the formation of metal carbonyls from metal oxides and specially the formation of molybdenum carbonyl and iron carbonyl from their respective oxides. Copper is used here in admixed form or used in chemically combined form as copper molybdate. The copper/metal oxide combination or combined copper is utilized with a solvent, such as toluene and subjected to carbon monoxide pressure of 25 atmospheres or greater at about 150.degree.-260.degree. C. The reducing metal copper is employed in catalytic concentrations or combined concentrations as CuMoO.sub.4 and both hydrogen and water present serve as promoters. It has been found that the yields by this process have been salutary and that additionally the catalytic metal may be reused in the process to good effect.

  11. [Evaluation of influence of diet content and its supplementation with chosen group of B vitamins on lipids and lipoprtoteins concentration in female rat serum].

    Science.gov (United States)

    Friedrich, Mariola; Goluch-Koniuszy, Zuzanna

    2009-01-01

    The influence of diet content and its supplementation with chosen group of B vitamins on the intake of feeding stuff increase, changes of body mass, accumulation of fat tissue, lipids and lipoproteins concentration in the blood of female rats were under research. The animals, aged 5 months, were divided into three groups (8 persons each) and fed ad libitum with granulated Labofeed B type mix. Group I with the basic mix containing among other things whole grain, Group II with a modified mix, where whole grain was replaced by wheat flour and saccharose and Group III with modified mix supplemented in excess with chosen vitamins of B group. This experiment took 6 weeks during which the amount of consumed feed was currently evaluated, and the body mass was controlled weekly. After finishing the experiment in the obtained serum the concentration of triacylglycerols, complete cholesterol with enzyme method and the content of cholesterol fractions with electrophoretic separation method were determined. Analysis of fat content in muscles and livers was conducted and the amount of round the bodily organ fat was determined. It was ascertained that change of the content of the feed and its supplementation with the chosen B group vitamins did not influence in a substantial way its intake and the increase of body mass, however it had influenced substantially, in animals fed with the modified feed the accumulation of round the organ fat and in supplemented the intramuscular fat. Analysis of the results enabled the ascertainment that the diet supplementation with chosen ingredients of the B group vitamins corrects the negative effect of accumulation of the visceral fat tissue as a result of the change of its contents, caused substantial increase in the concentration of triacylglycerols, complete cholesterol and its fractions VLDL- and LDL- with simultaneous decrease of the concentration of cholesterol HDL- fractions.

  12. The Effect of Functional Roles on Group Efficiency : Using Multilevel Modeling and Content Analysis to Investigate Computer-Supported Collaboration in Small Groups

    NARCIS (Netherlands)

    Strijbos, J.W.; Martens, R.L.; Jochems, W.M.G.; Broers, N.J.

    2004-01-01

    The usefulness of roles to support small group performance can often be read; however, their effect is rarely empirically assessed. This article reports the effects of functional roles on group performance, efficiency, and collaboration during computer-supported collaborative learning. A comparison

  13. Plasma protein carbonyl responses to anaerobic exercise in female cyclists

    Directory of Open Access Journals (Sweden)

    M.E Afzalpour

    2016-03-01

    Full Text Available Single bouts of aerobic exercise may leads to oxidative stress due to the use of oxygen for metabolism and the generation of reactive oxygen. In athletes, oxidative stress can lead to several deleterious performance effects, such as muscular oxidative damage, muscle soreness, loss of skeletal muscle force production and/or inflammation. However, little is known regarding the severity and duration of oxidative stress arising from intensive anaerobic modes of exercise in aerobically-trained athletes. The purpose of this study was to investigate the effect of a single bout of intensive anaerobic exercise on plasma protein carbonyl (PC in aerobically-trained women. Aerobically-trained, provincial female cyclists [n = 18, age: 24.2±2.7 years; stature: 163.6±4.6 cm; body mass: 53.4±4.2 kg] were randomly assigned into either a non-exercising control (CON; n = 9 or experimental (EXP; n = 9 group that underwent a 30-second anaerobic (Wingate cycle ergometer exercise session. Blood sampling took place before exercise, immediately after the exercise (IE, and 24 hours following the exercise (24HR bout. In the EXP, results indicated significant (P ≤ 0.05 differences in PC levels between the pre-test and IE (0.010±0.0124 to 0.0149±0.0420 mmol/milt; P = 0.010, and IE and 24HR (0.0149±0.0420 to 0.0111±0.0183 mmol/milt; P = 0.013. No significant differences were observed between pre-test and 24HR (0.010±0.0124 to 0.0111±0.0183 mmol/milt; P = 0.371. These results indicate that oxidative protein damage, as indicated by PC levels, rises immediately with the onset of anaerobic exercise, but returns to resting levels within 24 hours following exercise in aerobically-trained women.

  14. Effects of gasoline aromatic content on emissions of volatile organic compounds and aldehydes from a four-stroke motorcycle.

    Science.gov (United States)

    Yao, Yung-Chen; Tsai, Jiun-Horng

    2013-01-01

    A new four-stroke carburettor motorcycle engine without any engine adjustments was used to study the impact of fuel aromatic content on the exhaust emissions of organic air pollutants (volatile organic compounds and carbonyls). Three levels of aromatic content, i.e. 15, 25, and 50% (vol.) aromatics mixed with gasoline were tested. The emissions of aromatic fuel were compared with those of commercial unleaded gasoline. The results indicated that the A 15 (15 vol% aromatics in gasoline) fuel exhibited the greatest total organic emission improvement among these three aromatic fuels as compared with commercial gasoline, reaching 59%. The highest emission factors of alkanes, alkenes, and carbonyl groups appeared in the reference fuel (RF) among all of the test fuels. A 15 showed the highest emission reduction in alkanes (73%), aromatics (36%), and carbonyls (28%), as compared to those of the RF. The highest emission reduction ofalkenes was observed when using A25 as fuel. A reduction in fuel aromatic content from 50 to 25 and 15 vol% in gasoline decreased benzene and toluene emissions, but increased the aldehyde emissions. In general, the results showed that the highest emission reductions for the most of measured organic pollutants appeared when using A 15 as the fuel.

  15. Metal-Diazo Radicals of α-Carbonyl Diazomethanes

    Science.gov (United States)

    Li, Feifei; Xiao, Longqiang; Liu, Lijian

    2016-03-01

    Metal-diazo radicals of α-carbonyl diazomethanes are new members of the radical family and are precursors to metal-carbene radicals. Herein, using electron paramagnetic resonance spectroscopy with spin-trapping, we detect diazo radicals of α-carbonyl diazomethanes, induced by [RhICl(cod)]2, [CoII(por)] and PdCl2, at room temperature. The unique quintet signal of the Rh-diazo radical was observed in measurements of α-carbonyl diazomethane adducts of [RhICl(cod)]2 in the presence of 5,5-dimethyl-pyrroline-1-N-oxide (DMPO). DFT calculations indicated that 97.2% of spin density is localized on the diazo moiety. Co- and Pd-diazo radicals are EPR silent but were captured by DMPO to form spin adducts of DMPO-N• (triplet-of-sextets signal). The spin-trapping also provides a powerful tool for detection of metal-carbene radicals, as evidenced by the DMPO-trapped carbene radicals (DMPO-C•, sextet signal) and 2-methyl-2-nitrosopropane-carbene adducts (MNP-C•, doublet-of-triplets signal). The transformation of α-carbonyl diazomethanes to metal-carbene radicals was confirmed to be a two-step process via metal-diazo radicals.

  16. Carbonyl atmospheric reaction products of aromatic hydrocarbons in ambient air

    Science.gov (United States)

    Obermeyer, Genevieve; Aschmann, Sara M.; Atkinson, Roger; Arey, Janet

    To convert gaseous carbonyls to oximes during sampling, an XAD-4 resin denuder system pre-coated with O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine and followed by analysis with methane positive chemical ionization gas chromatography/mass spectrometry was used to measure carbonyls in ambient air samples in Riverside, CA. In conjunction with similar analyses of environmental chamber OH radical-initiated reactions of o- and p-xylene, 1,2,4-trimethylbenzene, ethylbenzene, 4-hydroxy-2-butanone and 1,4-butanediol, we identified benzaldehyde, o-, m- and p-tolualdehyde and acetophenone and the dicarbonyls glyoxal, methylglyoxal, biacetyl, ethylglyoxal, 1,4-butenedial, 3-hexene-2,5-dione, 3-oxo-butanal, 1,4-butanedial and malonaldehyde in the ambient air samples. As discussed, these carbonyls and dicarbonyls can be formed from the OH radical-initiated reactions of aromatic hydrocarbons and other volatile organic compounds emitted into the atmosphere, and we conclude that in situ atmospheric formation is a major source of these carbonyls in our Riverside, CA, ambient air samples.

  17. Plasma protein carbonyl levels and breast cancer risk

    Czech Academy of Sciences Publication Activity Database

    Rössner ml., Pavel; Terry, M. B.; Gammon, M. D.; Agrawal, M.; Zhang, F. F.; Ferris, J.S.; Teitelbaum, S. L.; Eng, S. M.; Gaudet, M. M.; Neugut, A. I.; Santella, R. M.

    2007-01-01

    Roč. 11, č. 5 (2007), s. 1138-1148 ISSN 1582-1838 Institutional research plan: CEZ:AV0Z50390512 Keywords : oxidative stress * protein carbonyl * breast cancer Subject RIV: DN - Health Impact of the Environment Quality Impact factor: 6.807, year: 2007

  18. Selective Oxidative Carbonylation of Aniline to Diphenylurea with Ionic Liquids

    DEFF Research Database (Denmark)

    Zahrtmann, Nanette; Claver, Carmen; Godard, Cyril

    2018-01-01

    A catalytic system for the selective oxidative carbonylation of aniline to diphenylurea based on Pd complexes in combination with imidazolium ionic liquids is presented. Both oxidants, Pd complexes and ionic liquids affect the activity of the reaction while the choice of oxidant determines...

  19. cyclo-addition reaction of triplet carbonyl compounds to substituted ...

    Indian Academy of Sciences (India)

    Unknown

    cited state energy of the olefin must be higher than that of the ketone so that ... the first singlet and triplet1,3 (n, π*) excited state of the carbonyl compounds.3,4 ... of the oxetane via carbon–carbon and carbon–oxygen attacks. They found the ...

  20. Olefination of carbonyl compounds: modern and classical methods

    Energy Technology Data Exchange (ETDEWEB)

    Korotchenko, V N; Nenajdenko, Valentine G; Balenkova, Elizabeth S [Department of Chemistry, M.V. Lomonosov Moscow State University, Moscow (Russian Federation); Shastin, Aleksey V [Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Moscow Region (Russian Federation)

    2004-10-31

    The published data on the methods for alkene synthesis by olefination of carbonyl compounds are generalised and systematised. The main attention is given to the use of transition metals and organoelement compounds. The review covers the data on both classical and newly developed methods that are little known to chemists at large.

  1. Olefination of carbonyl compounds: modern and classical methods

    Science.gov (United States)

    Korotchenko, V. N.; Nenajdenko, Valentine G.; Balenkova, Elizabeth S.; Shastin, Aleksey V.

    2004-10-01

    The published data on the methods for alkene synthesis by olefination of carbonyl compounds are generalised and systematised. The main attention is given to the use of transition metals and organoelement compounds. The review covers the data on both classical and newly developed methods that are little known to chemists at large.

  2. Chemical reactions in organic monomolecular layers. Condensation of hydrazine on carbonyl functions

    International Nuclear Information System (INIS)

    Rosilio, Charles; Ruaudel-Teixier, Annie.

    1976-01-01

    Evidence is given for chemical reactions of hydrazine (NH 2 -NH 2 ) with different carbonyl functional groups of organic molecules in the solid state, in monomolecular layer structures. The condensation of hydrazine with these molecules leads to conjugated systems by bridging the N-N links, to cyclizations, and also to polycondensations. The reactions investigated were followed up by infrared spectrophotometry, by transmission and metallic reflection. These chemical reactions revealed in the solid phase constitute a polycondensation procedure which is valuable in obtaining organized polymers in monomolecular layers [fr

  3. Contribution of carbonyl photochemistry to aging of atmospheric secondary organic aerosol

    DEFF Research Database (Denmark)

    Mang, Stephen A.; Henricksen, Dana K.; Bateman, Adam P.

    2008-01-01

    of freshly prepared SOA was estimated to be on the order of' 15 L mol(-1) cm(-1) at 300 rim, implying one carbonyl group in every SOA constituent. The absorption by the SOA material slowly increased in the visible and near-UV during storage of SOA in open air in the dark, presumably as a result......The photodegradation of secondary organic aerosol (SOA) material by actinic UV radiation was investigated. SOA was generated via the dark reaction of ozone and d-limonene, collected onto quartz-fiber filters, and exposed to wavelength-tunable radiation. Photochemical production of CO was monitored...

  4. Copper-catalyzed 1,2-addition of α-carbonyl iodides to alkynes.

    Science.gov (United States)

    Xu, Tao; Hu, Xile

    2015-01-19

    β,γ-Unsaturated ketones are an important class of organic molecules. Herein, copper catalysis has been developed for the synthesis of β-γ-unsaturated ketones through 1,2-addition of α-carbonyl iodides to alkynes. The reactions exhibit wide substrate scope and high functional group tolerance. The reaction products are versatile synthetic intermediates to complex small molecules. The method was applied for the formal synthesis of (±)-trichostatin A, a histone deacetylase inhibitor. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Characterization of Coal Quality Based On Ash Content From M2 Coal-Seam Group, Muara Enim Formation, South Sumatra Basin

    Directory of Open Access Journals (Sweden)

    Frillia Putri Nasution

    2017-09-01

    Full Text Available Muara Enim Formation is well known as coal-bearing formation in South Sumatra Basin. As coal-bearing formation, this formation was subjects of many integrated study. Muara Enim Formation can be divided into four coal-seam group, M1, M2, M3, and M4. The M2 group comprising of Petai (C, Suban (B, Lower Mangus (A2, and Upper Mangus (A1. Depositional environments of Group M2 is transitional lower delta plain with sub-depositional are crevasse splay and distributary channel. The differentiation of both sub-depositional environments can be caused the quality of coal deposit. One of quality aspects is ash content. This research conducted hopefully can give better understanding of relationship between depositional environments to ash content. Group M2 on research area were found only Seam C, Seam B, and Seam A2, that has distribution from north to central so long as 1400 m. Coal-seam thickness C ranged between 3.25-9.25 m, Seam B range 7.54-13.43 m, and Seam C range 1.53-8.37 m, where all of coal-seams thickening on the central part and thinning-splitting to northern part and southern part. The ash content is formed from burning coal residue material. Ash contents on coal seam caused by organic and inorganic compound which resulted from mixing modified material on surrounded when transportation, sedimentation, and coalification process. There are 27 sample, consists of 9 sample from Seam C, 8 sample from Seam B, and 10 sample from Seam A2. Space grid of sampling is 100-150 m. Ash content influenced by many factors, but in research area, main factor is existence of inorganic parting. Average ash content of Seam C is 6,04%, Seam B is 5,05%, and Seam A2 is 3,8%. Low ash content influenced by settle environment with minor detrital material. High ash content caused by oxidation and erosional process when coalification process. Ash content on coal in research area originated from detritus material carried by channel system into brackish area or originated

  6. ImageGrouper: a group-oriented user interface for content-based image retrieval and digital image arrangement

    NARCIS (Netherlands)

    Nakazato, Munehiro; Manola, L.; Huang, Thomas S.

    In content-based image retrieval (CBIR), experimental (trial-and-error) query with relevance feedback is essential for successful retrieval. Unfortunately, the traditional user interfaces are not suitable for trying different combinations of query examples. This is because first, these systems

  7. Low pressure carbonylation of benzyl chloride = Die carbonylierung von benzylchlorid bei niedrigen drücken

    NARCIS (Netherlands)

    Luggenhorst, H.J.; Westerterp, K.R.

    1986-01-01

    For carbonylations, metal carbonyls, particularly cobalt and iron carbonyls, are often used as catalysts. These reactions take place under rather drastic reaction conditions, e.g. 200–300 °C and 60–100 MPa. In some patents it is stated that similar reactions using the same catalysts can also be

  8. The subjective content of historical memory in autobiographical narratives of representatives of titular ethnic group and national diaspora (based on the example of the Volga Germans

    Directory of Open Access Journals (Sweden)

    Rakhmatulina D.V.

    2017-07-01

    Full Text Available the article contains a justification of the research approach to the detection of subjective content of historical memory among groups of respondents from different ethnic background; presents the results of a study of two groups of respondents, who are descendants of the Volga Germans and the representatives of the titular nation (Russian; establishes the main cultural and historical events of life of the peoples that make up the historical memory.

  9. Effect of Content of Sulfate Groups in Seaweed Polysaccharides on Antioxidant Activity and Repair Effect of Subcellular Organelles in Injured HK-2 Cells

    Directory of Open Access Journals (Sweden)

    Xiao-Tao Ma

    2017-01-01

    Full Text Available This study aims to investigate the repair effect of subcellular structure injuries of the HK-2 cells of four degraded seaweed polysaccharides (DSPs, namely, the degraded Porphyra yezoensis, Gracilaria lemaneiformis, Sargassum fusiform, and Undaria pinnatifida polysaccharides. The four DSPs have similar molecular weight, but with different content of sulfate groups (i.e., 17.9%, 13.3%, 8.2%, and 5.5%, resp.. The damaged model was established using 2.8 mmol/L oxalate to injure HK-2 cells, and 60 μg/mL of various DSPs was used to repair the damaged cells. With the increase of sulfate group content in DSPs, the scavenging activity of radicals and their reducing power were all improved. Four kinds of DSPs have repair effect on the subcellular organelles of damaged HK-2 cells. After being repaired by DSPs, the release amount of lactate dehydrogenase was decreased, the integrity of cell membrane and lysosome increased, the Δψm increased, the cell of G1 phase arrest was inhibited, the proportion of S phase increased, and cell apoptotic and necrosis rates were significantly reduced. The greater the content of sulfate group is, the stronger is the repair ability of the polysaccharide. These DSPs, particularly the polysaccharide with higher sulfate group content, may be a potential drug for the prevention and cure of kidney stones.

  10. Radioactive cesium content in selected food products. Pt. 2. Radioactive cesium in daily food rations of selected population groups

    International Nuclear Information System (INIS)

    Skibniewska, K.; Smoczynski, S.S.; Wisniewska, I.

    1993-01-01

    The content of radioactive cesium isotopes emitting beta radiation was studied in daily food rations analysed in diets of working-class and non-working-class families from food products from the regions of Olsztyn, Poznan, Lublin, Warsaw and Wroclaw in 1987 and 1988. In 1987 the highest level of radioactive cesium was found in the food rations in Olsztyn, and lowest in the rations in Poznan (3.32 and 0.65 Bq/kg respectively). In 1988 higher radiocesium content was found in rations composed according to the data on the diet consumed daily in non-working-class families. In that case the highest content was in the daily food rations composed in Warsaw - 2.35 Bq/kg and lowest in Poznan - 1.19 Bq/kg in the daily food rations of working-class families about one half of that value was found. The calculated means values of both analysed rations were: 1.35 for Olsztyn, 0.89 for Poznan, and 1.86 Bq/kg for Warsaw. The calculated mean value of the contamination with radioactive cesium was in 1988 0.93 Bq/kg for the rations in working-class families (in 1987 it was 1.80 Bq/kg). (author). 15 refs, 1 tab

  11. Brightest group galaxies - II: the relative contribution of BGGs to the total baryon content of groups at z < 1.3

    Science.gov (United States)

    Gozaliasl, Ghassem; Finoguenov, Alexis; Khosroshahi, Habib G.; Henriques, Bruno M. B.; Tanaka, Masayuki; Ilbert, Olivier; Wuyts, Stijn; McCracken, Henry J.; Montanari, Francesco

    2018-04-01

    We performed a detailed study of the evolution of the star formation rate (SFR) and stellar mass of the brightest group galaxies (BGGs) and their relative contribution to the total baryon budget within R200 (f^{BGG}_{b,200}). The sample comprises 407 BGGs selected from X-ray groups (M200 = 1012.8-1014 M⊙) out to z ˜ 1.3 identified in the Cosmic Evolution Survey (COSMOS), XMM Large-Scale Structure survey (XMM-LSS), and the All-Wavelength Extended Groth strip International Survey (AEGIS) fields. We find that BGGs constitute two distinct populations of quiescent and star-forming galaxies and their mean SFR is ˜2 dex higher than the median SFR at z 2 dex. We take into account the halo mass growth of groups in selecting the sample of BGGs and find that the mean (median) stellar mass of BGGs has grown by 0.3 dex since z = 1.3 to the present day. We show that up to ˜ 45 per cent of the stellar mass growth in a star-forming BGG can be due to its star formation activity. With respect to f^{BGG}_{b,200}, we find it to increase with decreasing redshift by ˜0.35 dex, while decreasing with halo mass in a redshift-dependent manner. We show that the slope of the relation between f^{BGG}_{b,200} and halo mass increases negatively with decreasing redshift. This trend is driven by an insufficient star formation in BGGs, compared to the halo growth rate. We separately show the BGGs with the 20 per cent highest f^{BGG}_{b,200} are generally non-star-forming galaxies and grow in mass by processes not related to star formation (e.g. dry mergers and tidal striping). We present the M⋆-Mh and M⋆/Mh-Mh relations and compare them with semi-analytic model predictions and a number of results from the literature. We quantify the intrinsic scatter in stellar mass of BGGs at fixed halo mass (σ _{log M_{\\star}}) and find that σ _{{log }M_{\\star}} increases from 0.3 dex at z ˜ 0.2-0.5 dex at z ˜ 1.0 due to the bimodal distribution of stellar mass.

  12. Toward Green Acylation of (Heteroarenes: Palladium-Catalyzed Carbonylation of Olefins to Ketones

    Directory of Open Access Journals (Sweden)

    Jie Liu

    2017-11-01

    Full Text Available Green Friedel–Crafts acylation reactions belong to the most desired transformations in organic chemistry. The resulting ketones constitute important intermediates, building blocks, and functional molecules in organic synthesis as well as for the chemical industry. Over the past 60 years, advances in this topic have focused on how to make this reaction more economically and environmentally friendly by using green acylating conditions, such as stoichiometric acylations and catalytic homogeneous and heterogeneous acylations. However, currently well-established methodologies for their synthesis either produce significant amounts of waste or proceed under harsh conditions, limiting applications. Here, we present a new protocol for the straightforward and selective introduction of acyl groups into (hetero­arenes without directing groups by using available olefins with inexpensive CO. In the presence of commercial palladium catalysts, inter- and intramolecular carbonylative C–H functionalizations take place with good regio- and chemoselectivity. Compared to classical Friedel–Crafts chemistry, this novel methodology proceeds under mild reaction conditions. The general applicability of this methodology is demonstrated by the direct carbonylation of industrial feedstocks (ethylene and diisobutene as well as of natural products (eugenol and safrole. Furthermore, synthetic applications to drug molecules are showcased.

  13. Penicitroamide, an Antimicrobial Metabolite with High Carbonylization from the Endophytic Fungus Penicillium sp. (NO. 24).

    Science.gov (United States)

    Feng, Zi-Wei; Lv, Meng-Meng; Li, Xue-Shuang; Zhang, Liang; Liu, Cheng-Xiong; Guo, Zhi-Yong; Deng, Zhang-Shuang; Zou, Kun; Proksch, Peter

    2016-10-28

    Penicitroamide ( 1 ), a new metabolite with a new framework, was isolated from the ethyl acetate extract of the PDB (Potato Dextrose Broth) medium of Penicillium sp. (NO. 24). The endophytic fungus Penicillium sp. (NO. 24) was obtained from the healthy leaves of Tapiscia sinensis Oliv. The structure of penicitroamide ( 1 ) features a bicyclo[3.2.1]octane core unit with a high degree of carbonylization (four carbonyl groups and one enol group). The chemical structure of penicitroamide ( 1 ) was elucidated by analysis of 1D-, 2D-NMR and MS data. In bioassays, penicitroamide ( 1 ) displayed antibacterial potency against two plant pathogens, Erwinia carotovora subsp. Carotovora (Jones) Bersey, et al. and Sclerotium rolfsii Sacc. with MIC 50 at 45 and 50 μg/mL. Compound 1 also showed 60% lethality against brine shrimp at 10 μg/mL. Penicitroamide ( 1 ) exhibited no significant activity against A549, Caski, HepG2 and MCF-7 cells with IC 50 > 50 μg/mL. Finally, the possible biosynthetic pathway of penicitroamide ( 1 ) was discussed.

  14. Registered nurses' thoughts on blended learning in a postgraduate course in cancer care--content analyses of web surveys and a focus group interview.

    Science.gov (United States)

    Arving, Cecilia; Wadensten, Barbro; Johansson, Birgitta

    2014-06-01

    Purpose of the research was to describe registered nurses' (RNs) (n = 53) thoughts on the blended learning format in a 'specialist nursing programme in cancer care'. The study was conducted in autumn 2007 and 2008. A content analysis of answers to open-ended questions in a web-based questionnaire and a focus group interview were carried out. The analysis revealed that the RNs appreciated blended learning. The web lectures facilitated learning and gave RNs access to the education at any time. However, according to the RNs, knowledge is gained through interaction between RNs and teachers, and this aspect needed to be improved. The RNs also thought that the content of the seminars on campus should focus on evidence-based nursing knowledge and practical skills, not just taught as stable facts and procedures. The result from the present study could help to improve the design and content of advanced nursing courses using a blended learning format.

  15. Measurement of total electron content of midlatitude ionosphere and protonosphere via Faraday rotation and group relay techniques using transmission from geostationary satellites ATS-3 and ATS-6

    Science.gov (United States)

    Paul, M. P.

    1982-01-01

    Measurement of integrated columnar electron content and total electron content for the local ionosphere and the overlying protonosphere via Faraday rotation and group delay techniques has proven very useful. A field station was established having the geographic location of 31.5 deg N latitude and 91.06 deg W longitude to accomplish these objectives. A polarimeter receiving system was set up in the beginning to measure the Faraday rotation of 137.35 MHz radio signal from geostationary satellite ATS 3 to yield the integrated columnar electron content of the local ionosphere. The measurement was continued regularly, and the analysis of the data thus collected provided a synopsis of the statistical variation of the ionosphere along with the transient variations that occurred during the periods of geomagnetic and other disturbances.

  16. Thio-phene-2-carbonyl azide.

    Science.gov (United States)

    Hsu, Gene C; Singer, Laci M; Cordes, David B; Findlater, Michael

    2013-01-01

    The title compound, C5H3N3OS, is almost planar (r.m.s. deviation for the ten non-H atoms = 0.018 Å) and forms an extended layer structure in the (100) plane, held together via hydrogen-bonding inter-actions between adjacent mol-ecules. Of particular note is the occurrence of RC-H⋯N(-)=N(+)=NR inter-actions between an aromatic C-H group and an azide moiety which, in conjunction with a complementary C-H⋯O=C inter-action, forms a nine-membered ring.

  17. [Effects of acupuncture stimulation of different acupoint groups on sleeping latency, serum and hippocampal TNF-α and IL-25 contents in rats with gastric mucosal injury].

    Science.gov (United States)

    Huang, Ying-Hua; Li, Qian; Yang, Ping; Yan, Ya-Nan; Ma, Hui-Fang

    2015-04-01

    To observe the effect of acupuncture intervention on gastric ulcer (GU) and sleeping quality from the viewpoint of brain-gut axis which plays an important role in the regulation of many vital functions in the body. Forty male Wistar rats were randomized into normal control, GU model, acupuncture of "Zhongwan"(CV 12)-"Zusanli"(ST 36, gastric function regulating acupoints), acupuncture of "Shenmai" (BL 62)-"Zhaohai" (KI 6, sleep-promotion acupoints), and acupuncture of CV 12-ST 36+ BL 62-KI 6 (combined treatment) groups, with 8 rats in each group. GU model was established by intragastric perfusion of dehydrated alcohol (1 mL/rat), and sleep model established by intraperitoneal injection of pentobarbital sodium (40 mg/kg) after the last treatment. The abovementioned acupoints were punctured with filiform needles and stimulated by manipulating the needle for about 30 s, once every 5 min during 20 min of needle retention. The treatment was conducted once daily for five days. The contents of tumor necrosis factor-alpha (TNF-α) and interleukin-25(IL-25) in the serum and hippocampal tissues were detected by ELISA. Compared with the normal control group, the gastric ulcer index score, barbiturate-induced sleeping time, and TNF-α and IL-25 contents in both serum and hippocampus were significantly increased in the model group (P sleeping time, and TNF-α and IL-25 contents in both serum and hippocampus were significantly down-regulated in the CV 12-ST 36, BL 62-KI 6 and combined treatment groups (P sleeping time (P sleeping time in gastric ulcer rats, which may be related to its effects in reducing TNF-α and IL-25 contents in the serum and hippocampus tissues, suggesting a correlation between the gastrointestinal disorder and sleeping.

  18. Measurements of carbonyls in a 13-story building.

    Science.gov (United States)

    Báez, Armando P; Padilla, Hugo G; García, Rocío M; Belmont, Raúl D; Torres, Maria del Carmen B

    2004-01-01

    Formaldehyde and acetaldehyde are emitted by many mobile and stationary sources and secondary aldehydes are intermediates in the photo-oxidation of organic compounds in the atmosphere. These aldehydes are emitted indoors by many materials such as furniture, carpets, heating and cooling systems, an by smoking. Carbonyls, mainly formaldehyde and acetaldehyde, have been studied because of their adverse health effects. In addition, formaldehyde is a suspected carcinogen. Therefore, the concentrations of formaldehyde and acetaldehyde were determined to assess the inhalation exposure doses to carbonyls for people who work in a 13-story building and in order to evaluate the cancer hazard. Carbonyl compounds in indoor and outdoor air were measured at a 13-story building located in Mexico City. The mezzanine, fifth and tenth floors, and the third level-parking garage were selected for sampling. Samples were collected in two sampling periods, the first from April 20 to 29, 1998 and the second from December 1 to 20, 1998. Carbonyls were sampled by means of DNHP-coated cartridges at a flow rate of 1 l min(-1) from 9:00 to 19:00 hours, during 2-hour time intervals and analyzed by HPLC with hours, during 2-hour time intervals and analyzed by HPLC with UV/VIS detection. Mean carbonyl concentrations were highest in the 3rd level-parking garage, with the formaldehyde concentration being the highest ranging from 108 to 418 microg m(-3). In working areas, the highest carbonyl arithmetic mean concentrations (AM) were observed on the 5th floor. Acetone and formaldehyde concentrations were highest in April ranging from 161 to 348 microg m(-3) (AM = 226) and from 157 to 270 microg m(-3) (AM = 221), respectively. Propionaldehyde and butyraldehyde were present in smaller concentrations ranging from 2 to 25 and 1 to 28 microg m(-3), respectively, considering all the samples. Mean indoor/outdoor ratios of carbonyls ranged from 1.8 to 9.6. A reduction of inhalation exposure doses of 41% and

  19. Reactions of α-phosphorylated carbonyl compounds with amino alcohols

    International Nuclear Information System (INIS)

    Moskva, V.V.; Sitdikova, T.Sh.; Zykova, T.V.; Alparova, M.V.; Shagvaleev, F.Sh.

    1986-01-01

    2-Aminoethanol reacts with carbonyl compounds with the formation, depending on the structure of the latter, either of a mixture of azomethines and oxazolidines, or of only azomethines. In the development of investigations on the reactivity of α-phosphorylated carbonyl compounds the authors studied the reactions of a number of amino alcohols with phosphorylated acetaldehyde and acetone. In both cases they observed the formation of compounds of enamine structure, oxazolidines and azomethines were not observed. By means of NMR spectroscopy they established clearly the formation of the E-isomeric products. The 1 H, 31 P, and 13 C NMR spectra were recorded on a WP-80 spectrometer. Chemical shifts of protons and 13 C nuclei are given relative to TMS, and phosphorus nuclei relative to orthophosphoric acid

  20. Synthetic and mechanistic aspects of titanium-mediated carbonyl olefinations

    Energy Technology Data Exchange (ETDEWEB)

    Petasis, N.A.; Staszewski, J.P.; Hu, Yong-Han; Lu, Shao-Po [Univ. of Southern California, Los Angeles, CA (United States)

    1995-12-31

    A new method for the olefination of carbonyl compounds with dimethyl titanocene, and other related bishydrocarbyl titanocene derivatives has been recently developed in the author`s laboratories. This process is experimentally convenient and works with various types of carbonyl compounds, including aldehydes, ketones, esters, lactones, carbonates, anhydrides, amides, imides, lactams, thioesters, selenoesters, and acylsilanes. More recent studies have focused on the scope and utility of this reaction, including mechanistic studies and synthetic applications. In addition to varying the reaction conditions, the authors have examined several mixed titanocene derivatives and have found ways for carrying out this type of olefination at room temperature, such as the use of tris(trimethylsilyl) titanacyclobutene. The authors have also employed this reaction in the modification of carbohydrates and cyclobutenediones. This olefination was also followed-up with subsequent transformations to produce carbocycles and heterocycles, including tetrahydrofurans and tetrahydropyrans.

  1. A three-membered ring approach to carbonyl olefination.

    Science.gov (United States)

    Niyomchon, Supaporn; Oppedisano, Alberto; Aillard, Paul; Maulide, Nuno

    2017-10-23

    The carbon-carbon double bond, with its diverse and multifaceted reactivity, occupies a prominent position in organic synthesis. Although a variety of simple alkenes are readily available, the mild and chemoselective introduction of a unit of unsaturation into a functionalized organic molecule remains an ongoing area of research, and the olefination of carbonyl compounds is a cornerstone of such approaches. Here we show the direct olefination of hydrazones via the intermediacy of three-membered ring species generated by addition of sulfoxonium ylides, departing from the general dogma of alkenes synthesis from carbonyls. Moreover, the mild reaction conditions and operational simplicity of the transformation render the methodology appealing from a practical point of view.

  2. Emissions of Toxic Carbonyls in an Electronic Cigarette

    Directory of Open Access Journals (Sweden)

    Guthery William

    2016-01-01

    Full Text Available Electronic cigarettes (e-cigs provide a smoke-free alternative for inhalation of nicotine without the vast array of toxic and carcinogenic combustion products produced by tobacco smoke. Elevated levels of toxic carbonyls may be generated during vaporisation; however, it is unclear whether that is indicative of a fault with the device or is due to the applied conditions of the test. A device, designed and built at this facility, was tested to determine the levels of selected toxic carbonyls. The reservoir was filled with approximately 960 mg of an e-liquid formulation containing 1.8% (w/v nicotine. Devices were puffed 200 times in blocks of 40 using a standardised regime consisting of a 55 mL puff volume; 3 s puff duration; 30 s puff interval; square wave puff profile. Confirmatory testing for nicotine and total aerosol delivery resulted in mean (n = 8 values of 10 mg (RSD 12.3% and 716 mg (RSD 11.2%, respectively. Emissions of toxic carbonyls were highly variable yet were between < 0.1% and 22.9% of expected levels from a Kentucky Reference Cigarette (K3R4F puffed 200 times under Health Canada Intense smoking conditions. It has been shown that a device built to a high specification with relatively consistent nicotine and aerosol delivery emits inconsistent levels of carbonyls. The exposure is greatly reduced when compared with lit tobacco products. However, it was observed that as the reservoirs neared depletion then emission levels were significantly higher

  3. Nucleophilic tetrafluoroethylation of carbonyl compounds with fluorinated sulfones

    Czech Academy of Sciences Publication Activity Database

    Václavík, Jiří; Chernykh, Yana; Jurásek, Bronislav; Beier, Petr

    2015-01-01

    Roč. 169, Jan (2015), s. 24-31 ISSN 0022-1139 R&D Projects: GA ČR GAP207/11/0421 Grant - others:GA MŠk(CZ) ED3.2.00/08.0144; GA MŠk(CZ) LM2010005 Institutional support: RVO:61388963 Keywords : fluorine * tetrafluoroethylation * sulfones * nucleophilic addition * carbonyl compounds Subject RIV: CC - Organic Chemistry Impact factor: 2.213, year: 2015

  4. Magnetophoretic manipulation in microsystem using carbonyl iron-polydimethylsiloxane microstructures

    OpenAIRE

    Faivre, Magalie; Gelszinnis, Renaud; Degouttes, Jérôme; Terrier, Nicolas; Rivière, Charlotte; Ferrigno, Rosaria; Deman, Anne-Laure

    2014-01-01

    This paper reports the use of a recent composite material, noted hereafter i-PDMS, made of carbonyl iron microparticles mixed in a PolyDiMethylSiloxane (PDMS) matrix, for magnetophoretic functions such as capture and separation of magnetic species. We demonstrated that this composite which combine the advantages of both components, can locally generate high gradients of magnetic field when placed between two permanent magnets. After evaluating the magnetic susceptibility of the material as a ...

  5. Photosynthetic capacities of mature tropical forest trees in Rwanda are linked to successional group identity rather than to leaf nutrient content

    Science.gov (United States)

    Dusenge, Mirindi Eric; Wallin, Göran; Gårdesten, Johanna; Adolfsson, Lisa; Niyonzima, Felix; Nsabimana, Donat; Uddling, Johan

    2014-05-01

    Tropical forests are crucial in the global carbon balance, yet information required to estimate how much carbon that enter these ecosystems through photosynthesis is very limited, in particular for Africa and for tropical montane forests. In order to increases the knowledge of natural variability of photosynthetic capacities in tropical tree species in tropical Africa, measurements of leaf traits and gas exchange were conducted on sun and shade leaves of ten tree species growing in two tropical forests in Rwanda in central Africa. Seven species were studied in Ruhande Arboretum, a forest plantation at mid altitude (1700 m), and six species in Nyungwe National Park, a cooler and higher altitude (at 2500 m) montane rainforest. Three species were common to both sites. At Nyungwe, three species each belonged to the successional groups pioneer and climax species. Climax species had considerably lower maximum rates of photosynthetic carboxylation (Vcmax) and electron transport (Jmax) than pioneer species. This difference was not related to leaf nutrient content, but rather seemed to be caused by differences in within-leaf N allocation between the two successional groups. With respect to N, leaves of climax species invested less N into photosynthetic enzymes (as judged by lower Vcmax and Jmax values) and more N into chlorophyll (as judged by higher SPAD values). Photosynthetic capacities, (i.e., Jmax and Vcmax), Jmax to Vcmax ratio and P content were significantly higher in Nyungwe than in Arboretum. Sun leaves had higher photosynthetic capacities and nutrient content than shade leaves. Across the entire dataset, variation in photosynthetic capacities among species was not related to leaf nutrient content, although significant relationships were found within individual species. This study contributes critical tropical data for global carbon models and suggests that, for montane rainforest trees of different functional types, successional group identity is a better

  6. Strontium 90 and cesium 137 content in the daily diet of two groups of people in Plovdiv

    International Nuclear Information System (INIS)

    Babakova, I.; Trendafilov, I.; Todorov, D.

    1975-01-01

    The contents of strontium 90 and cesium 137 in the daily diet of children, 7-11 years old, and teenagers, 14-18 years old, living under boarding house conditions is determined. The daily strontium 90 intake in the organism of children and teenagers amounts to 9,78 pCi, respectively 17,96 pCi and the daily intake of cesium 137 - to 13,21 pCi, respectively 21,33 pCi. The bigger part of the strontium 90 and cesium 137 intake comes from the bread, accounting for 4,85 pCi stroncium 90 and 5,08 to 7,0 pCi cesium 137. (author)

  7. The effect of zinc on the growth, content of the photosynthetic pigments, and thiol groups of the freshwater alga Pseudokirchneriella subcapitata (Korshikov) Hindak

    International Nuclear Information System (INIS)

    Filova, A.; Molnarova, M.

    2015-01-01

    In these experiments were studied the effects of zinc chloride (Zn 2+ ) on the alga Pseudokirchneriella subcapitata (Korshikov) Hindak. The changes in the growth stimulation/inhibition, content of the photosynthetic pigments, and thiol groups were the aim of the article. The zinc concentration 0.036 mg.l -1 supported the algal growth. The first toxic effect of Zn on the growth was observed at the zinc concentration 0.072 mg.l -1 . However, the significant inhibitory effect on the growth was showed in the algal suspensions with 0.360 and 4.320 mg Zn.l -1 . Inhibition of the algal growth was in the range 65 - 70% compared to control (0% inhibition). The content of chlorophyll a was significant inhibited at the zinc concentration 0.0240 mg.l -1 , but at the higher used concentration was inhibited with the extremely significations. With increased zinc content in the algal medium the thiol (-SH) groups content increased and in the highest zinc concentrations (2.160 and 4.320 mg.l -1 ) overreached control three times. (authors)

  8. Predicting methionine and lysine contents in soybean meal and fish meal using a group method of data handling-type neural network

    Energy Technology Data Exchange (ETDEWEB)

    Mottaghitalab, M.; Nikkhah, N.; Darmani-Kuhi, H.; López, S.; France, J.

    2015-07-01

    Artificial neural network models offer an alternative to linear regression analysis for predicting the amino acid content of feeds from their chemical composition. A group method of data handling-type neural network (GMDH-type NN), with an evolutionary method of genetic algorithm, was used to predict methionine (Met) and lysine (Lys) contents of soybean meal (SBM) and fish meal (FM) from their proximate analyses (i.e. crude protein, crude fat, crude fibre, ash and moisture). A data set with 119 data lines for Met and 116 lines for Lys was used to develop GMDH-type NN models with two hidden layers. The data lines were divided into two groups to produce training and validation sets. The data sets were imported into the GEvoM software for training the networks. The predictive capability of the constructed models was evaluated by their abilities to estimate the validation data sets accurately. A quantitative examination of goodness of fit for the predictive models was made using a number of precision, concordance and bias statistics. The statistical performance of the models developed revealed close agreement between observed and predicted Met and Lys contents for SBM and FM. The results of this study clearly illustrate the validity of GMDH-type NN models to estimate accurately the amino acid content of poultry feed ingredients from their chemical composition . (Author)

  9. Synthesis of enantiomerically enriched drug precursors and an insect pheromone via reduction of ketones using commercially available carbonyl reductase screening kit "Chiralscreen® OH".

    Science.gov (United States)

    Nagai, Toshiya; Sakurai, Saki; Natori, Naoki; Hataoka, Manaka; Kinoshita, Takako; Inoue, Hiroyoshi; Hanaya, Kengo; Shoji, Mitsuru; Sugai, Takeshi

    2018-04-01

    Commercially available "Chiralscreen® OH" starter kit containing five types of carbonyl reductases (E001, E007, E031, E039, and E078) was used for the reduction of several aromatic and aliphatic ketones to obtain enantiomerically enriched drug precursors and an insect pheromone. Almost stereochemically pure secondary alcohols, used in the synthesis of drugs such as (R)-rasagiline mesylate, (S)-rivastigmine, (R)-chlorphenesin carbamate, and (R)-mexiletine, and the insect pheromone (4S,5R)-sitophilure, were conveniently obtained. The enzymes worked well with ketones containing at least one non-bulky substituent at the carbonyl group. The diverse stereochemical preference of the above five carbonyl reductases was clarified. Copyright © 2017 Elsevier Ltd. All rights reserved.

  10. Magnetomechanical properties of composites and fibers made from thermoplastic elastomers (TPE) and carbonyl iron powder (CIP)

    Science.gov (United States)

    Schrödner, Mario; Pflug, Günther

    2018-05-01

    Magnetoactive elastomers (MAE) made from composites of five thermoplastic elastomers (TPE) of different stiffness with carbonyl iron powder (CIP) as magnetic component were investigated. The composites were produced by melt blending of the magnetic particles with the TPEs in a twin-screw extruder. The resulting materials were characterized by ac permeability testing, stress-strain measurements with and without external magnetic field and magnetically controlled bending of long cylindrical rods in a homogenous magnetic field. The magnetic field necessary for deflection of the rods decreases with decreasing modulus and increasing iron particle content. This effect can be used e.g. for magnetically controlled actuation. Some highly filled MAE show a magnetic field induced increase of Young's modulus. Filaments could be spun from some of the composites.

  11. Capturing public opinion on public health topics: a comparison of experiences from a systematic review, focus group study, and analysis of online, user-generated content

    Directory of Open Access Journals (Sweden)

    Emma Louise Giles

    2015-08-01

    Full Text Available BackgroundCapturing public opinion towards public health topics is important to ensure that services, policy and research are aligned with the beliefs and priorities of the general public. A number of approaches can be used to capture public opinion. MethodsWe are conducting a programme of work on the effectiveness and acceptability of health promoting financial incentive interventions. We have captured public opinion on financial incentive interventions using three methods: a systematic review, focus group study, and analysis of online user-generated comments to news media reports. In this short, editorial-style, piece we compare and contrast our experiences with these three methods.ResultsEach of these methods had their advantages and disadvantages. Advantages include tailoring of the research question for systematic reviews, probing of answers during focus groups, and the ability to aggregate a large data set using online user-generated content. However, disadvantages include needing to update systematic reviews, participants conforming to a dominant perspective in focus groups, and being unable to collect respondent characteristics during analysis of user-generated online content. That said, analysis of user-generated online content offers additional time and resource advantages, and we found it elicited similar findings to those obtained via more traditional methods, such as systematic reviews and focus groups. ConclusionsA number of methods for capturing public opinions on public health topics are available. Public health researchers, policy makers and practitioners should choose methods appropriate to their aims. Analysis user-generated online content, especially in the context of news media reports, may be a quicker and cheaper alternative to more traditional methods, without compromising on the breadth of opinions captured.

  12. Capturing Public Opinion on Public Health Topics: A Comparison of Experiences from a Systematic Review, Focus Group Study, and Analysis of Online, User-Generated Content.

    Science.gov (United States)

    Giles, Emma Louise; Adams, Jean M

    2015-01-01

    Capturing public opinion toward public health topics is important to ensure that services, policy, and research are aligned with the beliefs and priorities of the general public. A number of approaches can be used to capture public opinion. We are conducting a program of work on the effectiveness and acceptability of health promoting financial incentive interventions. We have captured public opinion on financial incentive interventions using three methods: a systematic review, focus group study, and analysis of online user-generated comments to news media reports. In this short editorial-style piece, we compare and contrast our experiences with these three methods. Each of these methods had their advantages and disadvantages. Advantages include tailoring of the research question for systematic reviews, probing of answers during focus groups, and the ability to aggregate a large data set using online user-generated content. However, disadvantages include needing to update systematic reviews, participants conforming to a dominant perspective in focus groups, and being unable to collect respondent characteristics during analysis of user-generated online content. That said, analysis of user-generated online content offers additional time and resource advantages, and we found it elicited similar findings to those obtained via more traditional methods, such as systematic reviews and focus groups. A number of methods for capturing public opinions on public health topics are available. Public health researchers, policy makers, and practitioners should choose methods appropriate to their aims. Analysis of user-generated online content, especially in the context of news media reports, may be a quicker and cheaper alternative to more traditional methods, without compromising on the breadth of opinions captured.

  13. Influence of warmth and competence on the promotion of safe in-group selection: Stereotype content model and social categorization of faces.

    Science.gov (United States)

    Ponsi, G; Panasiti, M S; Scandola, M; Aglioti, S M

    2016-01-01

    Categorizing an individual as a friend or foe plays a pivotal role in navigating the social world. According to the stereotype content model (SCM), social perception relies on two fundamental dimensions, warmth and competence, which allow us to process the intentions of others and their ability to enact those intentions, respectively. Social cognition research indicates that, in categorization tasks, people tend to classify other individuals as more likely to belong to the out-group than the in-group (in-group overexclusion effect, IOE) when lacking diagnostic information, probably with the aim of protecting in-group integrity. Here, we explored the role of warmth and competence in group-membership decisions by testing 62 participants in a social-categorization task consisting of 150 neutral faces. We assessed whether (a) warmth and competence ratings could predict the in-group/out-group categorization, and (b) the reliance on these two dimensions differed in low-IOE versus high-IOE participants. Data showed that high ratings of warmth and competence were necessary to categorize a face as in-group. Moreover, while low-IOE participants relied on warmth, high-IOE participants relied on competence. This finding suggests that the proneness to include/exclude unknown identities in/from one's own in-group is related to individual differences in the reliance on SCM social dimensions. Furthermore, the primacy of the warmth effect seems not to represent a universal phenomenon adopted in the context of social evaluation.

  14. [Effects of acupuncture stimulation of different acupoint groups on sleeping duration and serum and striatal dopamine contents in rats with gastric mucosal injury].

    Science.gov (United States)

    Yang, Ping; Peng, Lei; Li, Jie-Ting; Ma, Hui-Fang

    2014-02-01

    To observe the effect of acupuncture intervention on gastric ulcer (GU) and sleeping quality from the viewpoint of brain-gut axis which plays an important role in the regulation of many vital functions in health and disease. Forty male Wistar rats were randomized into normal control, GU model, acupuncture of "Zhongwan" (CV 12)-"Zusanli" (ST 36, gastric treatment acupoints), acupuncture of "Shenmai" (BL 62)-"Zhaohai" (KI 6, sleep-promotion acupoints), and acupuncture of CV 12-ST 36-BL 62-KI 6 (combined treatment) groups, with 8 rats in each group. GU model was established by intragastric perfusion of dehydrated alcohol (1 mL/rat), and sleep model established by intraperitoneal injection of pentobarbital sodium (40 mg/kg) after the last treatment. The abovementioned acupoints were punctured with filiform needles and stimulated by manipulating the needle for about 30 s, once every 5 mm during 20 mm of needle retention. The treatment was conducted once daily for five days. Gastric mucosal lesion index was assessed by Guth's method, and the mucosal pathological changes were observed under microscope after H. E. staining. The contents of dopamine (DA) in the serum and striatal tissues were detected by ELISA kit. Compared with the normal control group, the rats' sleeping duration, and serum DA content were markedly decreased and the gastric mucosal lesion index, and the striatal DA content remarkably increased in the model group (P sleeping duration, and serum DA content were significantly increased, and the gastric mucosal lesion index, and the striatal DA content remarkably down-regulated in the CV 12-ST 36 (gastric treatment acupoints), BL 62-KI 6 (sleep-promotion acupoints) and CV 12-ST 36-BL 62-KI 6 (combined treatment) groups (P sleep promotion acupoints group in reducing mucosal lesion index and in increasing serum DA level (P sleeping duration in gastric lesion rats, which may be related to its effects in increasing blood DA and lowering striatal DA level

  15. Carbonyl compounds in gas and particle phases of mainstream cigarette smoke

    Energy Technology Data Exchange (ETDEWEB)

    Pang, Xiaobing, E-mail: pangxbyuanj@gmail.com [Department of Chemistry, University of York, Heslington, York, YO10 5DD (United Kingdom); Lewis, Alastair C., E-mail: ally.lewis@york.ac.uk [National Centre for Atmospheric Science, University of York, Heslington, York, YO10 5DD (United Kingdom)

    2011-11-01

    Carbonyl compounds (carbonyls) are important constituents of cigarette smoke and some are toxic and may be carcinogenic or mutagenic to humans. In this study carbonyl emissions in the gas and particle phases of mainstream cigarette smoke were assessed by GC-MS with pentafluorophenyl hydrazine (PFPH) derivatization. Seven brands of cigarettes and one brand of cigar common in the UK market and having differing nicotine, tar and carbon monoxide yields were investigated. Sixteen carbonyl components were identified in gaseous emissions and twenty in the particle phase. In the gaseous emissions, acetaldehyde presented as the predominant species, followed by formaldehyde, 2-propenal, and pentanal. In the particulate emissions, 1-hydroxy-2-propanone was the most abundant followed by formaldehyde, benzaldehyde, and 2,5-dimethylbenzaldehyde. Significant differences were found in carbonyl emissions among the brands of cigarettes. The gaseous carbonyl emissions varied in the range of 216-405 {mu}g cigarette{sup -1} ({mu}g cig{sup -1}) and the particulate carbonyl emissions varied in the range of 23-127 {mu}g cig{sup -1}. Positive correlations were found between the total emission of carbonyls, tar yield and carbon monoxide yield. Similar gas/particle (G/P) partitioning ratios of carbonyls were found among all cigarettes, which implies that G/P partitions of carbonyls in smoke mainly depend on the physical properties of the carbonyls. The gaseous carbonyl emissions were enhanced by 40% to 130% when some of the water, accounting for 8-12% of cigarettes in mass, was removed from the tobacco. Non-filtered cigarettes showed significantly higher carbonyl emissions compared to their filtered equivalents. Carbonyl particulate accounted for 11-19% by mass of total particulate matter from tobacco smoke. The cigar generated 806 {mu}g cig{sup -1} gaseous and 141 {mu}g cig{sup -1} particulate carbonyls, which is 2-4 times greater than the cigarettes. - Highlights: {yields} Carbonyl

  16. Carbonyl compounds in gas and particle phases of mainstream cigarette smoke

    International Nuclear Information System (INIS)

    Pang, Xiaobing; Lewis, Alastair C.

    2011-01-01

    Carbonyl compounds (carbonyls) are important constituents of cigarette smoke and some are toxic and may be carcinogenic or mutagenic to humans. In this study carbonyl emissions in the gas and particle phases of mainstream cigarette smoke were assessed by GC-MS with pentafluorophenyl hydrazine (PFPH) derivatization. Seven brands of cigarettes and one brand of cigar common in the UK market and having differing nicotine, tar and carbon monoxide yields were investigated. Sixteen carbonyl components were identified in gaseous emissions and twenty in the particle phase. In the gaseous emissions, acetaldehyde presented as the predominant species, followed by formaldehyde, 2-propenal, and pentanal. In the particulate emissions, 1-hydroxy-2-propanone was the most abundant followed by formaldehyde, benzaldehyde, and 2,5-dimethylbenzaldehyde. Significant differences were found in carbonyl emissions among the brands of cigarettes. The gaseous carbonyl emissions varied in the range of 216-405 μg cigarette -1 (μg cig -1 ) and the particulate carbonyl emissions varied in the range of 23-127 μg cig -1 . Positive correlations were found between the total emission of carbonyls, tar yield and carbon monoxide yield. Similar gas/particle (G/P) partitioning ratios of carbonyls were found among all cigarettes, which implies that G/P partitions of carbonyls in smoke mainly depend on the physical properties of the carbonyls. The gaseous carbonyl emissions were enhanced by 40% to 130% when some of the water, accounting for 8-12% of cigarettes in mass, was removed from the tobacco. Non-filtered cigarettes showed significantly higher carbonyl emissions compared to their filtered equivalents. Carbonyl particulate accounted for 11-19% by mass of total particulate matter from tobacco smoke. The cigar generated 806 μg cig -1 gaseous and 141 μg cig -1 particulate carbonyls, which is 2-4 times greater than the cigarettes. - Highlights: → Carbonyl emission factors in both gas (16 species) and

  17. Diverse roles of hydrogen in rhenium carbonyl chemistry: hydrides, dihydrogen complexes, and a formyl derivative.

    Science.gov (United States)

    Li, Nan; Xie, Yaoming; King, R Bruce; Schaefer, Henry F

    2010-11-04

    Rhenium carbonyl hydride chemistry dates back to the 1959 synthesis of HRe(CO)₅ by Hieber and Braun. The binuclear H₂Re₂(CO)₈ was subsequently synthesized as a stable compound with a central Re₂(μ-H)₂ unit analogous to the B₂(μ-H)₂ unit in diborane. The complete series of HRe(CO)(n) (n = 5, 4, 3) and H₂Re₂(CO)(n) (n = 9, 8, 7, 6) derivatives have now been investigated by density functional theory. In contrast to the corresponding manganese derivatives, all of the triplet rhenium structures are found to lie at relatively high energies compared with the corresponding singlet structures consistent with the higher ligand field splitting of rhenium relative to manganese. The lowest energy HRe(CO)₅ structure is the expected octahedral structure. Low-energy structures for HRe(CO)(n) (n = 4, 3) are singlet structures derived from the octahedral HRe(CO)₅ structure by removal of one or two carbonyl groups. For H₂Re₂(CO)₉ a structure HRe₂(CO)₉(μ-H), with one terminal and one bridging hydrogen atom, lies within 3 kcal/mol of the structure Re₂(CO)₉(η²-H₂), similar to that of Re₂(CO)₁₀. For H₂Re₂(CO)(n) (n = 8, 7, 6) the only low-energy structures are doubly bridged singlet Re₂(μ-H)₂(CO)(n) structures. Higher energy dihydrogen complex structures are also found.

  18. Ambient levels of carbonyl compounds and their sources in Guangzhou, China

    Science.gov (United States)

    Feng, Yanli; Wen, Sheng; Chen, Yingjun; Wang, Xinming; Lü, Huixiong; Bi, Xinhui; Sheng, Guoying; Fu, Jiamo

    Ambient levels of carbonyl compounds and their possible sources, vehicular exhaust and cooking exhaust, were studied at seven places in Guangzhou, including five districts (a residential area, an industrial area, a botanical garden, a downtown area and a semi-rural area), a bus station and a restaurant during the period of June-September 2003. Nineteen carbonyl compounds were identified in the ambient air, of which acetone was the most abundant carbonyl, followed by formaldehyde and acetaldehyde. Only little changes were found in carbonyl concentration levels in the five different districts because of their dispersion and mixture in the atmosphere in summer. The lower correlations between the carbonyls' concentrations might result from the mixture of carbonyls derived from different sources, including strong photochemical reactions at noon in summer. Formaldehyde and acetaldehyde were the main carbonyls in bus station, while straight-chain carbonyls were comparatively abundant in cooking exhaust. Besides vehicular exhaust, cooking might be another major source of carbonyl compounds in Guangzhou City, especially for high molecular weight carbonyls.

  19. A method of detecting carbonyl compounds in tree leaves in China.

    Science.gov (United States)

    Huang, Juan; Feng, Yanli; Fu, Jiamo; Sheng, Guoying

    2010-06-01

    Carbonyl compounds have been paid more and more attention because some carbonyl species have been proven to be carcinogenic or a risk for human health. Plant leaves are both an important emission source and an important sink of carbonyl compounds. But the research on carbonyl compounds from plant leaves is very scarce. In order to make an approach to the emission mechanism of plant leaves, a new method was established to extract carbonyl compounds from fresh plant leaves. The procedure combining derivatization with ultrasonication was developed for the fast extraction of carbonyl compounds from tree leaves. Fresh leaves (Metasequoia glyptostroboides), were selected and extracted by this method. Seven carbonyl compounds, including formaldehyde, acetaldehyde, acetone, acrolein, p-tolualdehyde, m/o-tolualdehyde, and hexaldehyde were determined and quantified. The most common carbonyl species of the four tree leaves were formaldehyde, acrolein, and m/o-tolualdehyde. They accounted for 67.3% in cedar, 50.8% in sweet olive, 45.8% in dawn redwood, and 44.6% in camphor tree, respectively. Camphor tree had the highest leaf level of m/o-tolualdehyde with 15.0 +/- 3.4 microg g(-1)(fresh leaf weight), which indicated that camphor tree may be a bioindicator of the level of tolualdehyde or xylene in the atmosphere. By analyzing carbonyl compounds from different tree leaves, it is not only helpful for further studying the relationship between sink and emission of carbonyls from plants, but also helpful for exploring optimum plant population in urban greening.

  20. Reduction of titanocene dichloride with dysprosium: access to a stable titanocene(ii) equivalent for phosphite-free Takeda carbonyl olefination.

    Science.gov (United States)

    Bousrez, G; Déchamps, I; Vasse, J-L; Jaroschik, F

    2015-05-28

    The reduction of titanocene dichloride with dysprosium yields a new titanocene(ii) equivalent without the need for further stabilising ligands. This reagent can be employed in combination with dithioacetals for the olefination of different carbonyl groups and allows for a simplified all-in-one procedure.

  1. Platinum-group element contents of Karelian kimberlites: Implications for the PGE budget of the sub-continental lithospheric mantle

    Science.gov (United States)

    Maier, W. D.; O'Brien, H.; Peltonen, P.; Barnes, Sarah-Jane

    2017-11-01

    We present high-precision isotope dilution data for Os, Ir, Ru, Pt, Pd and Re in Group I and Group II kimberlites from the Karelian craton, as well as 2 samples of the Premier Group I kimberlite pipe from the Kaapvaal craton. The samples have, on average, 1.38 ppb Pt and 1.33 ppb Pd, with Pt/Pd around unity. These PGE levels are markedly lower, by as much as 80%, than those reported previously for kimberlites from South Africa, Brazil and India, but overlap with PGE results reported recently from Canadian kimberlites. Primitive-mantle-normalised chalcophile element patterns are relatively flat from Os to Pt, but Cu, Ni and, somewhat less so, Au are enriched relative to the PGE (e.g., Cu/Pd > 25.000). Pd/Ir ratios are 3,6 on average, lower than in most other mantle melts. The PGE systematics can be largely explained by two components, (i) harzburgite/lherzolite detritus of the SCLM with relatively high IPGE (Os-Ir-Ru)/PPGE (Rh-Pt-Pd) ratios, and (ii) a melt component that has high PPGE/IPGE ratios. By using the concentrations of iridium in the kimberlites as a proxy for the proportion of mantle detritus in the magma, we estimate that the analysed kimberlites contain 3-27% entrained and partially dissolved detritus from the sub-continental lithospheric mantle, consistent with previous estimates of kimberlites elsewhere (Tappe S. et al., 2016, Chem. Geol. 10.1016/j.chemgeo.2016.08.019).

  2. The content of conjugated linoleic acid (CLA) isomer groups in milk of two Polish sheep breeds determined by silver ion liquid chromatography (Ag(+)-HPLC).

    Science.gov (United States)

    Rozbicka-Wieczorek, Agnieszka; Radzik-Rant, Aurelia; Rant, Witold; Czauderna, Marian

    2013-01-01

    Sheep milk is rich in CLA isomers which are biologically active components influencing human health. There are four geometric CLA isomer pairs: cis, trans; trans, cis; trans, trans and cis, cis. The aim of the present study was the analysis of CLA isomer groups content by Ag+-HPLC in milk fat of Zelazneńska (ZS) and Wrzosówka (WS) sheep breeds. The ewes of both breeds were kept under the same environmental and nutritional conditions. Milk samples were collected from 60 suckling ewes (30 from each breed), at the age of 3-4 years and in their 4th week of lactation. A higher total amount of all CLA isomer groups was obtained in milk of ZS ewes, however, this result was statistically insignificant. The percentage of the main c9, t11 isomer in total CLA was higher in Wrzosówka milk (68% vs. 74%). The content of the trans, trans isomer group in milk fat of the studied breeds was similar. The percentage of this group in total CLA in milk of WS and ZS constitutes 7.2% and 7.7%, respectively. The amount of cis,cis isomers in milk fat of ZS was higher thanWS (P < or = 0.01).

  3. Serum levels of carbonylated and nitrosylated proteins in mobbing victims with workplace adjustment disorders.

    Science.gov (United States)

    Di Rosa, A E; Gangemi, S; Cristani, M; Fenga, C; Saitta, S; Abenavoli, E; Imbesi, S; Speciale, A; Minciullo, P L; Spatari, G; Abbate, S; Saija, A; Cimino, F

    2009-12-01

    Today the most important problem in the work place is psychological abuse, which may affect the health because of high levels of stress and anxiety. There is evidence that most psychiatric disorders are associated with increased oxidative stress but nothing is reported about the presence of oxidative stress in mobbing victims. This study has been carried out in a group of 19 patients affected by workplace mobbing-due adjustment disorders, in comparison with 38 healthy subjects, to evaluate whether oxidative stress may be induced by mobbing. Serum levels of protein carbonyl groups and of nitrosylated proteins, biological markers of oxidative stress conditions, were higher than those measured in healthy subjects. These findings may contribute to a better understanding of the redox homeostasis dysregulation occurring in victims of workplace mobbing.

  4. Flavonoid content in ethanolic extracts of selected raw and traditionally processed indigenous foods consumed by vulnerable groups of Kenya: antioxidant and type II diabetes-related functional properties.

    Science.gov (United States)

    Kunyanga, Catherine N; Imungi, Jasper K; Okoth, Michael W; Biesalski, Hans K; Vadivel, Vellingiri

    2011-08-01

    The present study evaluated the flavonoid content, antioxidant as well as type II diabetes-related enzyme inhibition activities of ethanolic extract of certain raw and traditionally processed indigenous food ingredients including cereals, legumes, oil seeds, tubers, vegetables and leafy vegetables, which are commonly consumed by vulnerable groups in Kenya. The vegetables exhibited higher flavonoid content (50-703 mg/100 g) when compared with the grains (47-343 mg/100 g). The ethanolic extract of presently studied food ingredients revealed 33-93% DPPH radical scavenging capacity, 486-6,389 mmol Fe(II)/g reducing power, 19-43% α-amylase inhibition activity and 14-68% α-glucosidase inhibition activity. Among the different food-stuffs, the drumstick and amaranth leaves exhibited significantly higher flavonoid content with excellent functional properties. Roasting of grains and cooking of vegetables were found to be suitable processing methods in preserving the functional properties. Hence, such viable processing techniques for respective food samples will be considered in the formulation of functional supplementary foods for vulnerable groups in Kenya.

  5. Gender and age groups interactions in the quantification of bone marrow fat content in lumbar spine using 3T MR spectroscopy: A multivariate analysis of covariance (Mancova)

    International Nuclear Information System (INIS)

    Roldan-Valadez, Ernesto; Piña-Jimenez, Carlos; Favila, Rafael; Rios, Camilo

    2013-01-01

    Introduction: There is an age-related conversion of red to yellow bone marrow in the axial skeleton, with a gender-related difference less well established. Our purpose was to clarify the variability of bone marrow fat fraction (FF) in the lumbar spine due to the interaction of gender and age groups. Methods: 44 healthy volunteers (20 males, 30–65 years old and 24 females, 30–69 years old) underwent 3T magnetic resonance spectroscopy (MRS) and conventional MRI examination of the lumbar spine; single-voxel spectrum was acquired for each vertebral body (VB). After controlling body mass index (BMI), a two-way between-groups multivariate analysis of covariance (MANCOVA) assessed the gender and age group differences in FF quantification for each lumbar VB. Results: There was a significant interaction between gender and age group, p = .017, with a large effect size (partial η 2 = .330). However the interaction explained only 33% of the observed variance. Main effects were not statistically significant. BMI was non-significantly related to FF quantification. Conclusions: Young males showed a high FF content, which declined in the 4th decade, then increased the next 3 decades to reach a FF content just below the initial FF means. Females’ FF were low in the 3rd decade, depicted an accelerated increase in the 4th decade, then a gradual increase the next 3 decades to reach a FF content similar to males’ values. Our findings suggest that quantification of bone marrow FF using MRS might be used as a surrogate biomarker of bone marrow activity in clinical settings

  6. Gender and age groups interactions in the quantification of bone marrow fat content in lumbar spine using 3T MR spectroscopy: A multivariate analysis of covariance (Mancova)

    Energy Technology Data Exchange (ETDEWEB)

    Roldan-Valadez, Ernesto, E-mail: ernest.roldan@usa.net [Magnetic Resonance Unit, Medica Sur Clinic and Foundation, Mexico City (Mexico); Piña-Jimenez, Carlos [Magnetic Resonance Unit, Medica Sur Clinic and Foundation, Mexico City (Mexico); Favila, Rafael [GE Healthcare, Mexico City (Mexico); Rios, Camilo [Neurochemistry Department, Mexican National Institute of Neurology and Neurosurgery, Mexico City (Mexico)

    2013-11-01

    Introduction: There is an age-related conversion of red to yellow bone marrow in the axial skeleton, with a gender-related difference less well established. Our purpose was to clarify the variability of bone marrow fat fraction (FF) in the lumbar spine due to the interaction of gender and age groups. Methods: 44 healthy volunteers (20 males, 30–65 years old and 24 females, 30–69 years old) underwent 3T magnetic resonance spectroscopy (MRS) and conventional MRI examination of the lumbar spine; single-voxel spectrum was acquired for each vertebral body (VB). After controlling body mass index (BMI), a two-way between-groups multivariate analysis of covariance (MANCOVA) assessed the gender and age group differences in FF quantification for each lumbar VB. Results: There was a significant interaction between gender and age group, p = .017, with a large effect size (partial η{sup 2} = .330). However the interaction explained only 33% of the observed variance. Main effects were not statistically significant. BMI was non-significantly related to FF quantification. Conclusions: Young males showed a high FF content, which declined in the 4th decade, then increased the next 3 decades to reach a FF content just below the initial FF means. Females’ FF were low in the 3rd decade, depicted an accelerated increase in the 4th decade, then a gradual increase the next 3 decades to reach a FF content similar to males’ values. Our findings suggest that quantification of bone marrow FF using MRS might be used as a surrogate biomarker of bone marrow activity in clinical settings.

  7. Rapid Determination of Six Low Molecular Carbonyl Compounds in Tobacco Smoke by the APCI-MS/MS Coupled to Data Mining

    Directory of Open Access Journals (Sweden)

    Wuduo Zhao

    2017-01-01

    Full Text Available A simple method was established for the rapid determination of low molecular carbonyl compounds by the combination of atmospheric pressure chemical ionization tandem mass spectrometry (APCI-MS/MS and data mining. The ionization was carried out in positive mode, and six low molecular carbonyl compounds of acrolein, acetone, propionaldehyde, crotonaldehyde, butanone, and butyraldehyde were analyzed by both full scan mode and daughter scan mode. To overcome the quantitative difficulties from isomer of acetone/propionaldehyde and butanone/butyraldehyde, the quantitation procedure was performed with the characteristic ion of [CH3O]+ under CID energy of 5 and 15 eV. Subsequently, the established method was successfully applied to analysis of six low molecular carbonyl compounds in tobacco smoke with analytical period less than four minutes. The contents of acrolein, acetone, propionaldehyde, crotonaldehyde, butanone, and butyraldehyde for a cigarette were about 63±5.8, 325±82, 55±9.7, 11±1.4, 67±5.9, and 12±1.8 μg/cig, respectively. The experimental results indicated that the established method had the potential application in rapid determination of low molecular carbonyl compounds.

  8. Online Social Support for the Prevention of Smoking Relapse: A Content Analysis of the WhatsApp and Facebook Social Groups.

    Science.gov (United States)

    Cheung, Yee Tak Derek; Chan, Ching Han Helen; Wang, Man Ping; Li, Ho Cheung William; Lam, Tai-Hing

    2017-06-01

    Online social groups have been increasingly used for smoking cessation intervention. This study aimed to explore the social support components of the online discussion through WhatsApp and Facebook, how these components addressed the need of relapse prevention, and how the participants evaluated this intervention. We coded and analyzed the posts (N = 467) by the 82 recent quitters in WhatsApp and Facebook social groups, who were recruited from the eight smoking cessation clinics in Hong Kong to participate in a pragmatic randomized trial of relapse prevention. Participants' postintervention feedback was collected from the 13 qualitative interviews after the intervention. The WhatsApp social groups had more participants' posts than the Facebook counterparts. The participants' posts in the online social groups could be classified as sharing views and experiences (55.5%), encouragement (28.7%), and knowledge and information (15.8%). About half of the participants' posts (52.9%) addressed the themes listed in the U.S. Clinical Practice Guideline for preventing smoking relapse. The participants perceived the posts as useful reminders for smoking cessation, but avoidance of reporting relapse, inactive discussions, and uninteresting content were barriers to the success of the intervention. Online social groups provided a useful platform for the delivery of cessation support and encouragement of reporting abstinence, which support relapse prevention. The effectiveness of such intervention can be improved by encouraging more self-report of relapse, active discussions, sharing of interesting content, and using an appropriate discussion platform. Quitters who participate in the online social groups can benefit from peer support and information sharing, and hence prevent smoking relapse.

  9. Carbonyl Compounds Produced by Vaporizing Cannabis Oil Thinning Agents.

    Science.gov (United States)

    Troutt, William D; DiDonato, Matthew D

    2017-11-01

    Cannabis use has increased in the United States, particularly the use of vaporized cannabis oil, which is often mixed with thinning agents for use in vaporizing devices. E-cigarette research shows that heated thinning agents produce potentially harmful carbonyls; however, similar studies have not been conducted (1) with agents that are commonly used in the cannabis industry and (2) at temperatures that are appropriate for cannabis oil vaporization. The goal of this study was to determine whether thinning agents used in the cannabis industry produce potentially harmful carbonyls when heated to a temperature that is appropriate for cannabis oil vaporization. Four thinning agents (propylene glycol [PG], vegetable glycerin [VG], polyethylene glycol 400 [PEG 400], and medium chain triglycerides [MCT]) were heated to 230°C and the resulting vapors were tested for acetaldehyde, acrolein, and formaldehyde. Each agent was tested three times. Testing was conducted in a smoking laboratory. Carbonyl levels were measured in micrograms per puff block. Analyses showed that PEG 400 produced significantly higher levels of acetaldehyde and formaldehyde than PG, MCT, and VG. Formaldehyde production was also significantly greater in PG compared with MCT and VG. Acrolein production did not differ significantly across the agents. PG and PEG 400 produced high levels of acetaldehyde and formaldehyde when heated to 230°C. Formaldehyde production from PEG 400 isolate was particularly high, with one inhalation accounting for 1.12% of the daily exposure limit, nearly the same exposure as smoking one cigarette. Because PG and PEG 400 are often mixed with cannabis oil, individuals who vaporize cannabis oil products may risk exposure to harmful formaldehyde levels. Although more research is needed, consumers and policy makers should consider these potential health effects before use and when drafting cannabis-related legislation.

  10. Determination of Carbonyl Compounds in Cigarette Mainstream Smoke. The CORESTA 2010 Collaborative Study and Recommended Method

    Directory of Open Access Journals (Sweden)

    Intorp M

    2014-12-01

    Full Text Available A recommended method has been developed and published by CORESTA, applicable to the quantification of selected carbonyl compounds (acetaldehyde, formaldehyde, acetone, acrolein, methyl ethyl ketone, crotonaldehyde, propionaldehyde and butyraldehyde in cigarette mainstream smoke. The method involved smoke collection in impinger traps, derivatisation of carbonyls with 2,4-dinitrophenylhydrazine (DNPH, separation of carbonyl hydrazones by reversed phase high performance liquid chromatography and detection by ultra violet or diode array.

  11. Determination of carbonyl compounds in air by HPLC

    International Nuclear Information System (INIS)

    Garcia, S.; Perez, R.M.; Campos, A.; Gonzalez, D.

    1995-09-01

    A method for the determination of seven carbonyl compounds in air is presented. The procedure involve sampling of air by a Sep-Pak cartridge impregnated with 2,4-dinitrophenylhydrazine. Elution was done with 3 mL of acetonitrile and the eluate was diluted to 5 mL. The analysis was done by HPLC with UV detection and external standard method quantification. It has been achieved relative standard deviations about 5% and detection limits of 80 ng/cartridge for formaldehyde, acetaldehyde and acetone+acrolein. Three different types of samples (rural, urban, petrol emission) were successfully analyzed

  12. Determination of carbonyl compounds in air by HPLC

    International Nuclear Information System (INIS)

    Garcia, S.; Perez, R.M.; Campos, A.; Gonzalez, D.

    1995-01-01

    A method for the determination of seven carbonyl compounds in air is presented. The procedure involve sampling of air by a Sep-Pak Cartridge impregnated with 2,4-dinitrophenylhydrazine. Elution was done with 3 mL of acetonitrile and the eluate was diluted to 5 mL. The analysis was done by HPLC with UV detection and external standard method quantification. It has been achieved relative standard deviations about 5% and detection limits of 80 ng/cartridge for formaldehyde, acetaldehyde and acetoacetonitrile. Three different types of samples (rural, urban, petrol emission) were successfully analyzed. (Author) 12 refs

  13. Magnetic properties of carbonyl iron particles in magnetorheological fluids

    International Nuclear Information System (INIS)

    Gorodkin, S R; James, R O; Kordonski, W I

    2009-01-01

    Knowledge of the magnetic properties of dispersed magnetic particles is a prerequisite to the design an MR fluid with desired performance. A term specific susceptibility is introduced for characterization of particle susceptibility. The study was performed with the Bartington MS2B magnetic susceptibility system on small samples volume. Specific magnetic susceptibility of iron particles was found to be a linear function of median particle size. Structural change in the fluid, including particle organization, led to susceptibility drift and may affect fluid performance. It was shown that susceptibility data can be used for evaluation of the concentration of carbonyl iron particles in MR fluids.

  14. Selective transformation of carbonyl ligands to organic molecules

    Energy Technology Data Exchange (ETDEWEB)

    Cutler, A.R.

    1992-05-12

    Studies on the carbonylation of ({eta}{sup 5}-indenyl)(L)(CO)Ru-R complexes (L = CO, PPh{sub 3}; R = CH{sub 2}OMe, CH{sub 3}) have been completed. Particularly noteworthy is that the methoxymethyl complexes readily transform to their acyl derivatives under mild conditions that leave their iron congeners inert towards CO. Surprisingly, even ({eta}{sup 5}-indenyl)(PPh{sub 3}){sub 2}Ru-CH{sub 3} carbonylates and gives ({eta}{sup 5}-indenyl)(PPh{sub 3})(CO)Ru-C(O)CH{sub 3}. Mechanistic studies on the non catalyzed'' hydrosilation of the manganese acyls (CO){sub 5}Mn-C(O)CH{sub 2}R (R = H, OCH{sub 3}, CH{sub 3}) with Et{sub 3}SiH and of cobalt acetyls (CO){sub 3}(PR{sub 3})CoC(O)CH{sub 3} with several monohydrosilanes have been completed. The cobalt acetyls cleanly give ethoxysilanes (not acetaldehyde), and the manganese acyls provide {alpha}-siloxyvinyl complexes Z-(CO){sub 5}Mn-C(OSiEt{sub 3})=CHR (R = H, CH{sub 3}, OCH{sub 3}). Carbonylation and protolytic cleavage of the latter generate pyruvoyl complexes (CO){sub 5}Mn-COCOR (R = CH{sub 3}, CH{sub 2}CH{sub 3}), formally the products of net double carbonylation'' sequences. Studies in progress are concerned with how manganese complexes as diverse as (CO){sub 5}Mn-Y (Y = C(O)R, R, BR - but not SiMe{sub 3} or Mn(CO){sub 5}) and ({eta}{sup 3}-C{sub 3}H{sub 5})Mn(CO){sub 2}L (but not CpMn(CO){sub 3} or CpMn(CO){sub 2}({eta}{sup 2}HSiR{sub 3})) function as efficient hydrosilation catalysts towards Cp(CO){sub 2}FeC(O)CH{sub 3}, for example. These reactions cleanly afford fully characterized {alpha}-siloxyethyl complexes Fp-CH(OSiR{sub 3})CH{sub 3} under conditions where typically Rh(1) hydrosilation catalysts are inactive. Several of these manganese complexes also catalytically hydrosilate organic esters, including lactones, to their ethers R-CH{sub 2}OR; these novel ester reductions occur quantitatively at room temperature and appear to be general in scope.

  15. High-performance supercapacitors of carboxylate-modified hollow carbon nanospheres coated on flexible carbon fibre paper: Effects of oxygen-containing group contents, electrolytes and operating temperature

    International Nuclear Information System (INIS)

    Phattharasupakun, Nutthaphon; Wutthiprom, Juthaporn; Suktha, Phansiri; Iamprasertkun, Pawin; Chanlek, Narong; Shepherd, Celine; Hadzifejzovic, Emina; Moloney, Mark G.; Foord, John S.; Sawangphruk, Montree

    2017-01-01

    Although functionalized carbon-based materials have been widely used as the supercapacitor electrodes, the optimum contents of the functional groups, the charge storage mechanisms, and the effects of electrolytes and operating temperature have not yet been clearly investigated. In this work, carboxylate-modified hollow carbon nanospheres (c-HCN) with different functional group contents synthesized by an oxidation process of carbon nanospheres with nitric acid were coated on flexible carbon fibre paper and used as the supercapacitor electrodes. An as-fabricated supercapacitor of the c-HCN with a finely tuned 6.2 atomic % of oxygen of the oxygen-containing groups in an ionic liquid electrolyte exhibits a specific capacitance of 390 F g"−"1, a specific energy of 115 Wh kg"−"1, and a maximum specific power of 13548 W kg"−"1 at 70 °C. The charge storage mechanism investigated is based on the chemical adsorption of the ionic liquid electrolyte on the c-HCN electrode. This process is highly reversible leading to high capacity retention. The supercapacitor in this work may be practically used in many high energy and power applications.

  16. A biotin enrichment strategy identifies novel carbonylated amino acids in proteins from human plasma

    DEFF Research Database (Denmark)

    Havelund, Jesper F; Wojdyla, Katarzyna; Davies, Michael J

    2017-01-01

    Protein carbonylation is an irreversible protein oxidation correlated with oxidative stress, various diseases and ageing. Here we describe a peptide-centric approach for identification and characterisation of up to 14 different types of carbonylated amino acids in proteins. The modified residues...... in vitro metal ion-catalysed oxidation. Furthermore, we assigned 133 carbonylated sites in 36 proteins in native human plasma protein samples. The optimised workflow enabled detection of 10 hitherto undetected types of carbonylated amino acids in proteins: aldehyde and ketone modifications of leucine...

  17. Project management plan for Waste Area Grouping 5 Old Hydrofracture Facility tanks content removal at Oak Ridge National Laboratory, Oak Ridge, Tennessee

    International Nuclear Information System (INIS)

    1996-07-01

    The purpose of the Old Hydrofracture Facility (OHF) tanks content removal project is to transfer inventory from the five OHF tanks located in Waste Area Grouping (WAG) 5 at Oak Ridge National Laboratory (ORNL) to the Melton Valley Storage Tanks (MVST) liquid low-level (radioactive) waste (LLLW) storage facility, and remediate the remaining OHF tank shells. The major activities involved are identified in this document along with the organizations that will perform the required actions and their roles and responsibilities for managing the project

  18. Carbonyl[4-(2,3-dimethylphenylaminopent-3-en-2-onato-κ2N,O](triphenylphosphine-κPrhodium(I

    Directory of Open Access Journals (Sweden)

    Gertruida J. S. Venter

    2009-11-01

    Full Text Available In the title compound, [Rh(C13H16NO(C18H15P(CO], the coordination geometry of the RhI atom is square-planar, formed by the coordinating N and O atoms of the bidentate enaminoketonate ligand, one C atom from the carbonyl group and a P atom from triphenylphosphine. The complex displays a 0.591 (3:0.409 (3 ratio disorder of the phenyl unit of the monoanionic N,O-bidentate ligand. Intramolecular hydrogen bonding is observed between a C—H group of the triphenylphosphine unit and the O atom of the enaminoketonate ligand.

  19. Cationic Copolymerization of 3,3-Bis(hydroxymethyl)oxetane and Glycidol: Biocompatible Hyperbranched Polyether Polyols with High Content of Primary Hydroxyl Groups.

    Science.gov (United States)

    Christ, Eva-Maria; Hobernik, Dominika; Bros, Matthias; Wagner, Manfred; Frey, Holger

    2015-10-12

    The cationic ring-opening copolymerization of 3,3-bis(hydroxymethyl)oxetane (BHMO) with glycidol using different comonomer ratios (BHMO content from 25 to 90%) and BF3OEt2 as an initiator has been studied. Apparent molecular weights of the resulting hyperbranched polyether copolymers ranged from 1400 to 3300 g mol(-1) (PDI: 1.21-1.48; method: SEC, linear PEG standards). Incorporation of both comonomers is evidenced by MALDI-TOF mass spectroscopy. All hyperbranched polyether polyols with high content of primary hydroxyl groups portray good solubility in water, which correlates with an increasing content of glycerol units. Detailed NMR characterization was employed to elucidate the copolymer microstructures. Kinetic studies via FTIR demonstrated a weak gradient-type character of the copolymers. MTT assays of the copolymers (up to 100 μg mL(-1)) on HEK and fibroblast cell lines (3T3, L929, WEHI) as well as viability tests on the fibroblast cells were carried out to assess the biocompatibility of the materials, confirming excellent biocompatibility. Transfection efficiency characterization by flow cytometry and confocal laser microscopy demonstrated cellular uptake of the copolymers. Antiadhesive properties of the materials on surfaces were assessed by adhesion assays with fibroblast cells.

  20. User Preferences for Content, Features, and Style for an App to Reduce Harmful Drinking in Young Adults: Analysis of User Feedback in App Stores and Focus Group Interviews.

    Science.gov (United States)

    Milward, Joanna; Khadjesari, Zarnie; Fincham-Campbell, Stephanie; Deluca, Paolo; Watson, Rod; Drummond, Colin

    2016-05-24

    Electronic screening and brief intervention (eSBI) is effective in reducing weekly alcohol consumption when delivered by a computer. Mobile phone apps demonstrate promise in delivering eSBI; however, few have been designed with an evidence-based and user-informed approach. This study aims to explore from a user perspective, preferences for content, appearance, and operational features to inform the design of a mobile phone app for reducing quantity and frequency of drinking in young adults engaged in harmful drinking (18-30 year olds). Phase 1 included a review of user reviews of available mobile phone apps that support a reduction in alcohol consumption. Apps were identified on iTunes and Google Play and were categorized into alcohol reduction support, entertainment, blood alcohol content measurement (BAC), or other. eSBI apps with ≥18 user reviews were subject to a content analysis, which coded praise, criticism, and recommendations for app content, functionality, and esthetics. Phase 2 included four focus groups with young adults drinking at harmful levels and residing in South London to explore their views on existing eSBI apps and preferences for future content, functionality, and appearance. Detailed thematic analysis of the data was undertaken. In Phase 1, of the 1584 apps extracted, 201 were categorized as alcohol reduction, 154 as BAC calculators, 509 as entertainment, and 720 as other. We classified 32 apps as eSBI apps. Four apps had ≥18 user reviews: Change for Life Drinks Tracker, Drinksmeter, Drinkaware, and Alcohol Units Calculator. The highest proportion of content praises were for information and feedback provided in the apps (12/27, 44%), followed by praise for the monitoring features (5/27, 19%). Many (8/12, 67%) criticisms were for the drinking diary; all of these were related to difficulty entering drinks. Over half (18/32, 56%) of functionality criticisms were descriptions of software bugs, and over half of those (10/18, 56%) were for app

  1. Composition of amino acid using carbon monoxide. Amide carbonylation reaction

    Energy Technology Data Exchange (ETDEWEB)

    Izawa, Kunisuke (Ajinomoto Co., Inc., Tokyo (Japan))

    1989-02-01

    Amide carbonylation reaction is a method to compose N-acyl-{alpha}-amino acid from aldehyde, carboxylic acid amide, and carbon monoxide in a phase and with high yield. Unlike the conventional Strecker reaction, this method does not use HCN which is in question on public pollution and does not require hydrolysis. This amide carbonylation reaction was discovered by Wakamatsu and others of Ajinomoto Co.,Ltd. Present application examples of this method are the composition of N-acetyl amino acid from the aldehyde class, the composition of N-Acyl amino acid from olefin, the composition of N-acyl or acetyl amino acid from the raw material of alcohol and the halide class, the composition of N-acyl or acetyl amino acid via the isomerization of epoxide and allyl alcohol, the composition of amino dicarboxylic acid, applying deoxidation of ring acid anhydride, the composition of N-acyl amino acid from the raw material of the amine class, the stereoselective composition of -substitution ring-{alpha}-amino acid, and the composition of amino aldehyde. 24 refs., 2 figs., 2 tabs.

  2. Synthesis of dimethyl carbonate by oxidative carbonylation of methanol

    Energy Technology Data Exchange (ETDEWEB)

    Lee, B.G.; Han, M.S.; Kim, H.S.; Ahn, B.S.; Park, K.Y.

    1999-07-01

    Dimethyl carbonate (DMC) synthesis reaction by oxidative carbonylation of methanol has been studied using vapor phase flow reaction system in the presence of Cu-based catalysts. A series of Cu-based catalysts were prepared by the conventional impregnation method using activated carbon (AC) as support. The effect of various promoters and reaction conditions on the catalytic reactivities was intensively evaluated in terms of methanol conversion and DMC selectivity. The morphological change of catalysts during the reaction was also compared by X-ray diffraction and SEM analysis. Regardless of catalyst compositions, the optimal reaction temperature for oxidative carbonylation of methanol was found to be around 120--130 C. The reaction rate was too slow below 100 C, while too many by-products were produced above 150 C. Among the various catalysts employed, CuCl{sub 2}/NaOH/AC catalyst with the mole ratio of OH/Cu = 0.5--1.0 has shown the best catalytic performance, which appears to have a strong relationship with the formation of intermediate species, Cu{sub 2}(OH){sub 3}Cl.

  3. Protonation Sites, Tandem Mass Spectrometry and Computational Calculations of o-Carbonyl Carbazolequinone Derivatives.

    Science.gov (United States)

    Martínez-Cifuentes, Maximiliano; Clavijo-Allancan, Graciela; Zuñiga-Hormazabal, Pamela; Aranda, Braulio; Barriga, Andrés; Weiss-López, Boris; Araya-Maturana, Ramiro

    2016-07-05

    A series of a new type of tetracyclic carbazolequinones incorporating a carbonyl group at the ortho position relative to the quinone moiety was synthesized and analyzed by tandem electrospray ionization mass spectrometry (ESI/MS-MS), using Collision-Induced Dissociation (CID) to dissociate the protonated species. Theoretical parameters such as molecular electrostatic potential (MEP), local Fukui functions and local Parr function for electrophilic attack as well as proton affinity (PA) and gas phase basicity (GB), were used to explain the preferred protonation sites. Transition states of some main fragmentation routes were obtained and the energies calculated at density functional theory (DFT) B3LYP level were compared with the obtained by ab initio quadratic configuration interaction with single and double excitation (QCISD). The results are in accordance with the observed distribution of ions. The nature of the substituents in the aromatic ring has a notable impact on the fragmentation routes of the molecules.

  4. Solution-Processable Balanced Ambipolar Field-Effect Transistors Based on Carbonyl-Regulated Copolymers.

    Science.gov (United States)

    Yang, Chengdong; Fang, Renren; Yang, Xiongfa; Chen, Ru; Gao, Jianhua; Fan, Hanghong; Li, Hongxiang; Hu, Wenping

    2018-04-04

    It is very important to develop ambipolar field effect transistors to construct complementary circuits. To obtain balanced hole- and electron-transport properties, one of the key issues is to regulate the energy levels of the frontier orbitals of the semiconductor materials by structural tailoring, so that they match well with the electrode Fermi levels. Five conjugated copolymers were synthesized and exhibited low LUMO energy levels and narrow bandgaps on account of the strong electron-withdrawing effect of the carbonyl groups. Polymer thin film transistors were prepared by using a solution method and exhibited high and balanced hole and electron mobility of up to 0.46 cm 2  V -1  s -1 , which suggested that these copolymers are promising ambipolar semiconductor materials. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Effect of sulfite treatment on total antioxidant capacity, total oxidant status, lipid hydroperoxide, and total free sulfydryl groups contents in normal and sulfite oxidase-deficient rat plasma.

    Science.gov (United States)

    Herken, Emine Nur; Kocamaz, Erdogan; Erel, Ozcan; Celik, Hakim; Kucukatay, Vural

    2009-08-01

    Sulfites, which are commonly used as preservatives, are continuously formed in the body during the metabolism of sulfur-containing amino acids. Sulfite oxidase (SOX) is an essential enzyme in the pathway of the oxidative degradation of sulfite to sulfate protecting cells from sulfite toxicity. This article investigated the effect of sulfite on total antioxidant capacity (TAC), total oxidant status, lipid hydroperoxide (LOOH), and total free sulfydryl groups (-SH) levels in normal and SOX-deficient male albino rat plasma. For this purpose, rats were divided into four groups: control, sulfite-treated, SOX-deficient, and sulfite-treated SOX-deficient groups. SOX deficiency was established by feeding rats a low molybdenum diet and adding to their drinking water 200 ppm tungsten. Sulfite (70 mg/kg) was administered to the animals via their drinking water. SOX deficiency together with sulfite treatment caused a significant increase in the plasma LOOH and total oxidant status levels. -SH content of rat plasma significantly decreased by both sulfite treatment and SOX deficiency compared to the control. There was also a significant decrease in plasma TAC level by sulfite treatment. In conclusion, sulfite treatment affects the antioxidant/oxidant balance of the plasma cells of the rats toward oxidants in SOX-deficient groups.

  6. Carbonyl[4-(2,6-dimethylphenylaminopent-3-en-2-onato-κ2N,O](triphenylphosphine-κPrhodium(I acetone hemisolvate

    Directory of Open Access Journals (Sweden)

    Andreas Roodt

    2009-12-01

    Full Text Available In the title compound, [Rh(C13H16NO(C18H15P(CO]·0.5C3H6O, the Rh atom exhibits a square-planar coordination geometry, being coordinated by the N and O atoms of the bidentate β-diketonato ligand, a P atom from the triphenylphosphine unit and a C atom from the carbonyl group. The asymmetric unit also contains a disordered half-molecule, lying about an inversion center, of the acetone solvate. Intermolecular C—H...O hydrogen bonds are observed between a C—H group of the triphenylphosphine unit and a carbonyl O atom and between the methyl group of the enaminoketonato backbone and the solvent O atom. In addition, an intramolecular interaction is observed between a C—H group of the triphenylphosphine unit and the O atom of the enaminoketonato ligand.

  7. EVA reactive blending with Si–H terminated polysiloxane by carbonyl hydrosilylation reaction: From compatibilised blends to crosslinking networks

    International Nuclear Information System (INIS)

    Bonnet, J.; Bounor-Legaré, V.; Alcouffe, P.; Cassagnau, P.

    2012-01-01

    A new and original method based on carbonyl hydrosilylation was developed to prepare ethylene-vinyl acetate (EVA)/polysiloxane polymer blends. This focused on the addition of hydrogenosilane groups (SiH) from polysiloxane to the carbonyl groups of EVA. The influence of the nature of the polysiloxane on blend properties was investigated by rheology and scanning electron microscopy. Mixing of a low viscosity polysiloxane with a high viscosity EVA matrix produced a two-phase morphology. The occurrence of the hydrosilylation reaction at the EVA/polysiloxane interface promoted a homogenisation of the blend depending on the molar ratio SiH/vinyl acetate groups, [SiH]/[VA], and the viscosity ratio of the blend. Two distinct behaviours were observed. The formation of a crosslinked network under shear was obtained for a low viscosity ratio between polysiloxane and EVA (λ polysiloxane/EVA = 4.0 × 10 −6 ) with a high concentration of SiH groups ([SiH]/[VA] = 0.5), while the formation of a compatibilised blend was observed for high molar mass polysiloxanes (Mn > 15,000 g mol −1 ) with a low concentration of SiH ([SiH]/[VA] −3 ). -- Highlights: ► Carbonyl hydrosilylation reaction was found to enhance EVA/polysiloxane immiscible blends. ► EVA crosslinking was obtained with a low molar mass polysiloxane. ► EVA compatibilisation was obtained with a high molar mass polysiloxane. ► Shear rate was found to improve the hydrosilylation reaction at the interface. ► A two-phase morphology of the blends was observed after reaction with fine polysiloxane nodules.

  8. Rh(I) -Catalyzed Intramolecular Carbonylative C-H/C-I Coupling of 2-Iodobiphenyls Using Furfural as a Carbonyl Source.

    Science.gov (United States)

    Furusawa, Takuma; Morimoto, Tsumoru; Nishiyama, Yasuhiro; Tanimoto, Hiroki; Kakiuchi, Kiyomi

    2016-08-19

    Synthesis of fluoren-9-ones by a Rh-catalyzed intramolecular C-H/C-I carbonylative coupling of 2-iodobiphenyls using furfural as a carbonyl source is presented. The findings indicate that the rate-determining step is not a C-H bond cleavage but, rather, the oxidative addition of the C-I bond to a Rh(I) center. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Preparation and microwave shielding property of silver-coated carbonyl iron powder

    International Nuclear Information System (INIS)

    Cao, Xiao Guo; Ren, Hao; Zhang, Hai Yan

    2015-01-01

    Highlights: • The silver-coated carbonyl iron powder is prepared by the electroless plating process. • The silver-coated carbonyl iron powder is a new kind of conductive filler. • The reflection and absorption dominate the shielding mechanism of the prepared powder. • Increasing the thickness of electroconductive adhesive will increase the SE. - Abstract: Electroless silver coating of carbonyl iron powder is demonstrated in the present investigation. The carbonyl iron powders are characterized by scanning electron microscope (SEM), energy dispersive X-ray spectroscopy (EDX), and X-ray diffraction analysis (XRD) before and after the coating process. The relatively uniform and continuous silver coating is obtained under the given coating conditions. In this paper, the electromagnetic interference (EMI) shielding mechanism of the silver-coated carbonyl iron powder is suggested. The reflection of silver coating and absorption of carbonyl iron powder dominate the shielding mechanism of the silver-coated carbonyl iron powder. The silver-coated carbonyl iron powders are used as conductive filler in electroconductive adhesive for electromagnetic interference shielding applications. The effect of the thickness of electroconductive adhesive on the shielding effectiveness (SE) is investigated. The results indicate that the SE increases obviously with the increase of the thickness of electroconductive adhesive. The SE of the electroconductive adhesive with 0.35 mm thickness is above 38 dB across the tested frequency range

  10. Reactions of ruthenium and osmium cluster carbonyls with heteroatom-substituted and functionalized alkynes

    International Nuclear Information System (INIS)

    Koridze, A.A.

    2000-01-01

    The results of studies of the reactions of ruthenium and osmium cluster carbonyls with metal (M = Re, Mn, Fe) alkynes, silylalkynes, propargyl alcohols and their derivatives, diynes, enynes, and ferrocenylacetylene are summarized. Intramolecular rearrangements in the cluster complexes including migrations of carbonyl, hydride, and hydrocarbon ligands and the metal core reorganization are considered [ru

  11. Design and fabrication of microfluidic mixer from carbonyl iron–PDMS composite membrane

    KAUST Repository

    Li, Jiaxing; Zhang, Mengying; Wang, Limu; Li, Weihua; Sheng, Ping; Wen, Weijia

    2010-01-01

    This paper introduces a carbonyl iron-PDMS (CI-PDMS) composite magnetic elastomer in which carbonyl iron (CI) particles are uniformly distributed in a PDMS matrix. The CI particles and the PDMS were mixed at different weight ratios and tested

  12. Metal-atom fluorescence from the quenching of metastable rare gases by metal carbonyls

    International Nuclear Information System (INIS)

    Hollingsworth, W.E.

    1982-11-01

    A flowing afterglow apparatus was used to study the metal fluorescence resulting from the quenching of metastable rare-gas states by metal carbonyls. The data from the quenching or argon, neon, and helium by iron and nickel carbonyl agreed well with a restricted degree of freedom model indicating a concerted bond-breaking dissociation

  13. Defects in tor regulatory complexes retard aging and carbonyl/oxidative stress development in yeast Sассharomyces cerevisiae

    Directory of Open Access Journals (Sweden)

    B. V. Homza

    2014-02-01

    Full Text Available TOR signaling pathway first described in yeast S. сerevisiae is the highly conserved regulator of eukaryotic cell growth, aging and stress resistance. The effect of nitrogen sources, in particular amino acids, on the activity of TOR signaling pathway is well studied, however its relation to carbohydrates is poor understood. The aim of the present study is expanding of our understanding of potential role of TOR regulatory complexes in development of carbonyl/oxidative stress that can result from yeast cultivation on glucose and fructose. It has been shown that the level of α-dicarbonyl compounds and protein carbonyl groups increased with time of yeast cultivation and was higher in cells grown on fructose that demonstrated their accelerated aging and carbonyl/oxidative stress development as compared with cells grown on glucose. The strains defective in TOR proteins cultivated in the presence of glucose as well as fructose demonstrated lower markers of the stress and aging than parental strain. Thus these data confirmed the previous conclusion on fructose more potent ability to cause carbonyl/oxidative stress and accelerated aging in S. cerevisiae as compared with glucose. However, defects in TOR regulatory complexes retard aging and development of the stress in yeast independent on the type of carbohydrate in the cultivation medium.

  14. Protein carbonylation and metal-catalyzed protein oxidation in a cellular perspective

    DEFF Research Database (Denmark)

    Møller, Ian Max; Rogowska-Wrzesinska, Adelina; Rao, R S P

    2011-01-01

    Proteins can become oxidatively modified in many different ways, either by direct oxidation of amino acid side chains and protein backbone or indirectly by conjugation with oxidation products of polyunsaturated fatty acids and carbohydrates. While reversible oxidative modifications are thought...... to be relevant in physiological processes, irreversible oxidative modifications are known to contribute to cellular damage and disease. The most well-studied irreversible protein oxidation is carbonylation. In this work we first examine how protein carbonylation occurs via metal-catalyzed oxidation (MCO) in vivo...... and in vitro with an emphasis on cellular metal ion homeostasis and metal binding. We then review proteomic methods currently used for identifying carbonylated proteins and their sites of modification. Finally, we discuss the identified carbonylated proteins and the pattern of carbonylation sites in relation...

  15. Development of an automatic sampling device for the continuous measurement of atmospheric carbonyls compounds

    International Nuclear Information System (INIS)

    Perraud, V.

    2007-12-01

    Two sampling strategies were studied to develop an automatic instrument for the continuous measurement of atmospheric carbonyl compounds. Because of its specificity towards carbonyls compounds, sampling by using a transfer of gaseous phase in a liquid phase associated with a simultaneous chemical derivatization of the trapped compounds was first studied. However, this method do not allow a quantitative sampling of all studied carbonyl compounds, nor a continuous measurement in the field. To overcome the difficulties, a second strategy was investigated: the cryogenic adsorption onto solid adsorbent followed by thermodesorption and a direct analysis by GC/MS. Collection efficiency using different solid adsorbents was found greater than 95% for carbonyl compounds consisting of 1 to 7 carbons. This work is a successful first step towards the realization of the automatic sampling device for a continuous measurement of atmospheric carbonyls compounds. (author)

  16. Impact of HVAC filter on indoor air quality in terms of ozone removal and carbonyls generation

    Science.gov (United States)

    Lin, Chi-Chi; Chen, Hsuan-Yu

    2014-06-01

    This study aims at detecting ozone removal rates and corresponding carbonyls generated by ozone reaction with HVAC filters from various building, i.e., shopping mall, school, and office building. Studies were conducted in a small-scale environmental chamber. By examining dust properties including organic carbon proportion and specific surface area of dusts adsorbed on filters along with ozone removal rates and carbonyls generation rate, the relationship among dust properties, ozone removal rates, and carbonyls generation was identified. The results indicate a well-defined positive correlation between ozone removal efficiency and carbonyls generation on filters, as well as a positive correlation among the mass of organic carbon on filters, ozone removal efficiency and carbonyls generations.

  17. Perceived needs and experiences with healthcare services of women with spinal cord injury during pregnancy and childbirth - a qualitative content analysis of focus groups and individual interviews.

    Science.gov (United States)

    Bertschy, Sue; Geyh, Szilvia; Pannek, Jürgen; Meyer, Thorsten

    2015-06-16

    Women after a spinal cord injury (SCI), who decide to get pregnant and to become mothers, have special health care service needs. This study aims to identify the perceived service needs of woman with SCI during pregnancy and childbirth in Switzerland and to reconstruct their experiences of healthcare service utilization based on their accounts. A qualitative content analysis based on focus groups and individual interviews was conducted. 17 mothers with SCI who had given birth following SCI within the past 15 years participated. The data were transcribed verbatim before content analyses were carried out. Primary data was collected from August 2012 to September 2013 at the Swiss Paraplegic Research Centre, Nottwil; the University of Lausanne and at the homes of the participants. Mothers reported a broad spectrum of medical needs, including the need for access to improved integrated care. They also reported difficulties finding providers with knowledge of both paraplegiology (i.e. spinal cord medicine) and gynaecology. Mothers preferred using local health care services and regular birth hospitals, and reported receiving no additional benefit from the services of specialised SCI centres during pregnancy. A pre-existing provider-patient relationship was helpful for optimizing care processes. This study showed that pregnant women with SCI have various perceived healthcare needs and health care service use. Effective programs to improve these women's access to integrated care during pregnancy and childbirth and policies requiring the provision of specific pregnancy information and pre-birth services are necessary.

  18. Activation of heterogenised rhodium carbonylation catalyst infrared spectroscopic study

    Energy Technology Data Exchange (ETDEWEB)

    Scurrell, M S

    1977-01-01

    In a study related to heterogeneous versions of homogeneous catalysts active in carbonylation of methanol to acetic acid, the catalyst consisted of 1Vertical Bar3< rhodium as rhodium trichloride supported on 13X zeolite and evacuated at 437/sup 0/K. Contacting the catalyst with carbon monoxide caused two bands, at 2025 and 2095 cm/sup -1/, to appear. Contact with a mixture of carbon monoxide and methyl iodide (the usual promoter) caused bands at 2085, 1710, 1440, and 1370 cm/sup -1/ to appear; the first two correspond to the bands at 2062 and 1711 cm/sup -1/ in homogeneous catalysts attributed to the formation of Rh(CH/sup 3/CO)(CO)X/sup 2/I/sup -/. Spectra.

  19. SILP catalysis in gas-phase hydroformylation and carbonylation

    Energy Technology Data Exchange (ETDEWEB)

    Riisager, A.; Fehrmann, R. [Technical Univ. of Denmark, Lyngby (Denmark). Dept. of Chemistry; Haumann, M.; Wasserscheid, P. [Univ. Erlangen-Nuernberg (Germany). Lehrstuhl fuer Chemische Reaktionstechnik

    2006-07-01

    Supported ionic liquid phase (SILP) catalysts are new materials consisting of an ionic liquid-metal catalyst solution highly dispersed on a porous support. The use of a non-volatile, ionic liquid catalyst phase in SILP catalysts results in a stable heterogeneous-type material with selectivity and efficiency like homogeneous catalysts. The silica-supported SILP Rh-bisphosphine hydroformylation catalyst exhibited good activities and excellent selectivities in gas phase hydroformylation with stability exceeding 700 hours time-on-stream. Spectroscopic and kinetic data confirmed the homogeneous nature of the catalyst. In the Rh- SILP catalysed carbonylation of methanol the formation of undesired by-products could be suppressed by variation of residence time and gas pressure. (orig.)

  20. Core Content for Undergraduate Medical Education in Spain: Recommendations of the Instructors' Group of the Spanish Academy of Dermatology and Venereology (AEDV).

    Science.gov (United States)

    Casanova, J M; Pujol, R M; Ferrándiz, C; Betlloch, I; Bosch, R J; Fernández, V; Martí, R M; Requena, L; Moreno, J C; Alegre, V; Vilata, J J; Vilar, N; Jaén, P; Bielsa, I; Querol, I; Azón, T; Borrego, L; Mascaró, J M; Alsina, M; Díaz, R M; Suarez, R; García-Bustinduy, M; García-Patos, V; Estrach, T

    2016-03-01

    Skin problems are among the most frequent reasons for seeking medical attention in primary care. In recent years, as a result of the process of adapting medical curricula to the requirements of the European Higher Education Area, the amount of time students spend learning the concepts of dermatology has been reduced in many universities. In order to reach a consensus on core content for undergraduate education in dermatology, we sent a survey to the 57 members of the instructors' group of the Spanish Academy of Dermatology and Venereology (AEDV), asking their opinions on what objectives should be set for a dermatology course in Spain. A total of 131 previously selected objectives were listed. We then applied the Delphi method to achieve consensus on which ones the respondents considered important or very important (score≥4 on a Likert scale). Nineteen responses (33%) were received. On the second round of the Delphi process, 68 objectives achieved average scores of at least 4. The respondents emphasized that graduates should understand the structure and functions of the skin and know about bacterial, viral, and fungal skin infections, the most common sexually transmitted diseases (STDs), and the 4 main inflammatory dermatoses. Students should also learn about common complaints, such as itching and bald patches; the management of dermatologic emergencies; purpura and erythema nodosum as signs of internal disease; and the prevention of STDs and skin cancer. During clinical clerkships students should acquire the communication skills they will need to interview patients, write up a patient's medical history, and refer the patient to a specialist. The AEDV's group of instructors have defined their recommendations on the core content that medical faculties should adopt for the undergraduate subject of dermatology in Spain. Copyright © 2014. Published by Elsevier España, S.L.U.

  1. Acid-Group-Content-Dependent Proton Conductivity Mechanisms at the Interlayer of Poly(N-dodecylacrylamide-co-acrylic acid) Copolymer Multilayer Nanosheet Films.

    Science.gov (United States)

    Sato, Takuma; Tsukamoto, Mayu; Yamamoto, Shunsuke; Mitsuishi, Masaya; Miyashita, Tokuji; Nagano, Shusaku; Matsui, Jun

    2017-11-14

    The effect of the content of acid groups on the proton conductivity at the interlayer of polymer-nanosheet assemblies was investigated. For that purpose, amphiphilic poly(N-dodecylacrylamide-co-acrylic acid) copolymers [p(DDA/AA)] with varying contents of AA were synthesized by free radical polymerization. Surface pressure (π)-area (A) isotherms of these copolymers indicated that stable polymer monolayers are formed at the air/water interface for AA mole fraction (n) ≤ 0.49. In all cases, a uniform dispersion of the AA groups in the polymer monolayer was observed. Subsequently, polymer monolayers were transferred onto solid substrates using the Langmuir-Blodgett (LB) technique. X-ray diffraction (XRD) analyses of the multilayer films showed strong Bragg diffraction peaks, suggesting a highly uniform lamellar structure for the multilayer films. The proton conductivity of the multilayer films parallel to the direction of the layer planes were measured by impedance spectroscopy, which revealed that the conductivity increased with increasing values of n. Activation energies for proton conduction of ∼0.3 and 0.42 eV were observed for n ≥ 0.32 and n = 0.07, respectively. Interestingly, the proton conductivity of a multilayer film with n = 0.19 did not follow the Arrhenius equation. These results were interpreted in terms of the average distance between the AA groups (l AA ), and it was concluded that, for n ≥ 0.32, an advanced 2D hydrogen bonding network was formed, while for n = 0.07, l AA is too long to form such hydrogen bonding networks. The l AA for n = 0.19 is intermediate to these extremes, resulting in the formation of hydrogen bonding networks at low temperatures, and disruption of these networks at high temperatures due to thermally induced motion. These results indicate that a high proton conductivity with low activation energy can be achieved, even under weakly acidic conditions, by arranging the acid groups at an optimal distance.

  2. Hydrogeology of the Dakota Group aquifer with emphasis on the radium-226 content of its contained ground water, Canon City Embayment, Fremont and Pueblo Counties, Colorado

    International Nuclear Information System (INIS)

    Vinckier, T.A.

    1982-01-01

    The Dakota Group aquifer of the Canon City embayment comprises two primary water-bearing units, the Lytle Sandstone Member at the base and the Dakota Sandstone at the top, separated by the semiconfining, arenaceous Glencairn Shale Member. The ground water in this area probably represents a mixture of some or all of the following genetic types: (1) ground water connate to the Dakota Group; (2) ground water, connate or otherwise, entering the aquifer as leakage from adjacent semiconfining strata; (3) deeply circulated meteoric ground water; and (4) hydrothermal fluids (magmatic or metamorphic ground water) purged from the crystalline basement complex underlying the embayment. The contents of the radium-226 in ground water from 117 wells completed in part or all of the Dakota Group were determined by the dissolved radon-222 emanation method. Sixty-seven percent of the ground water samples have radium-226 activities greater than 5.0 picocuries per liter of water (5.0 pCi/1), the recommended maximum permissible concentration of radium-226 in drinking water established by the Environmental Protection Agency in 1973. Inspection of gamma-ray logs of about 20 wells revealed the presence of moderate to extremely high gamma radiation in strata of the Dakota Group, the Morrison Formation, the Fountain Formation, and in the crystalline basement rocks. High levels of radium-226 in drinking water supplies pose potentially serious health hazards to the users. Owners of wells producing such water supplies are advised to (1) install, at the homesite, ion exchange (filtering units) capable of removing 226 Ra 2 + ions and other aqueous radium species from the water or (2) effectively case out those stratigraphic intervals in the bore hole showing high gamma radiation preventing possible radium-rich ground water within these intervals from entering the well

  3. Personal exposure and health risk assessment of carbonyls in family cars and public transports-a comparative study in Nanjing, China.

    Science.gov (United States)

    Xu, Huaizhou; Zhang, Qin; Song, Ninghui; Guo, Min; Zhang, Shenghu; Ji, Guixiang; Shi, Lili

    2017-11-01

    To evaluate passenger health risks associated with inhalation exposure to carbonyl compounds mainly emitted from decoration materials of vehicles, we tested the carbonyl concentrations in interior air of 20 family cars, 6 metro lines, and 5 buses in the city of Nanjing. To assess non-carcinogenic health risks, we compared the data to the health guidelines of China, US Environmental Protection Agency (EPA), and Office of Environmental Health Hazard Assessment (OEHHA), respectively. To assess carcinogenic risks, we followed a standard approach proposed by the OEHHA to calculate lifetime cancer risks (LCR) of formaldehyde and acetaldehyde for various age groups. The results showed that there are formaldehyde, acetaldehyde, and acrolein concentrations in 40, 35, and 50% of family car samples exceeded the reference concentrations (RfCs) provided by Chinese guidelines (GB/T 27630-2011 and GB/T 18883-2002). Whereas, in the tested public transports, concentrations of the three carbonyls were all below the Chinese RfCs. Fifty and 90% of family cars had formaldehyde and acrolein concentrations exceeding the guidelines of OEHHA. Only one public transport sample (one bus) possesses formaldehyde and acetaldehyde concentrations above the chronic inhalation reference exposure limits (RELs). Furthermore, the assessments of carcinogenic risk of formaldehyde and acetaldehyde showed that lifetime cancer risks were higher than the limits of EPA for some family cars and public transports. In the study, buses and metros appear to be relatively clean environments, with total carbonyl concentrations that do not exceed 126 μg/m 3 . In family cars, carbonyl levels showed significant variations from 6.1 to 811 μg/m 3 that was greatly influenced by direct emissions from materials inside the vehicles. Public transports seemed to be the first choice for resident trips as compared to family cars. Graphical abstract ᅟ.

  4. Purification and characterization of akr1b10 from human liver: role in carbonyl reduction of xenobiotics.

    Science.gov (United States)

    Martin, Hans-Jörg; Breyer-Pfaff, Ursula; Wsol, Vladimir; Venz, Simone; Block, Simone; Maser, Edmund

    2006-03-01

    Members of the aldo-keto reductase (AKR) superfamily have a broad substrate specificity in catalyzing the reduction of carbonyl group-containing xenobiotics. In the present investigation, a member of the aldose reductase subfamily, AKR1B10, was purified from human liver cytosol. This is the first time AKR1B10 has been purified in its native form. AKR1B10 showed a molecular mass of 35 kDa upon gel filtration and SDS-polyacrylamide gel electrophoresis. Kinetic parameters for the NADPH-dependent reduction of the antiemetic 5-HT3 receptor antagonist dolasetron, the antitumor drugs daunorubicin and oracin, and the carcinogen 4-methylnitrosamino-1-(3-pyridyl)-1-butanone (NNK) to the corresponding alcohols have been determined by HPLC. Km values ranged between 0.06 mM for dolasetron and 1.1 mM for daunorubicin. Enzymatic efficiencies calculated as kcat/Km were more than 100 mM-1 min-1 for dolasetron and 1.3, 0.43, and 0.47 mM-1 min-1 for daunorubicin, oracin, and NNK, respectively. Thus, AKR1B10 is one of the most significant reductases in the activation of dolasetron. In addition to its reducing activity, AKR1B10 catalyzed the NADP+-dependent oxidation of the secondary alcohol (S)-1-indanol to 1-indanone with high enzymatic efficiency (kcat/Km=112 mM-1 min-1). The gene encoding AKR1B10 was cloned from a human liver cDNA library and the recombinant enzyme was purified. Kinetic studies revealed lower activity of the recombinant compared with the native form. Immunoblot studies indicated large interindividual variations in the expression of AKR1B10 in human liver. Since carbonyl reduction of xenobiotics often leads to their inactivation, AKR1B10 may play a role in the occurrence of chemoresistance of tumors toward carbonyl group-bearing cytostatic drugs.

  5. Soil atmosphere exchange of carbonyl sulfide (COS regulated by diffusivity depending on water-filled pore space

    Directory of Open Access Journals (Sweden)

    H. Van Diest

    2008-04-01

    Full Text Available The exchange of carbonyl sulfide (COS between soil and the atmosphere was investigated for three arable soils from Germany, China and Finland and one forest soil from Siberia for parameterization in the relation to ambient carbonyl sulfide (COS concentration, soil water content (WC and air temperature. All investigated soils acted as sinks for COS. A clear and distinct uptake optimum was found for the German, Chinese, Finnish and Siberian soils at 11.5%, 9%, 11.5%, and 9% soil WC, respectively, indicating that the soil WC acts as an important biological and physical parameter for characterizing the exchange of COS between soils and the atmosphere. Different optima of deposition velocities (Vd as observed for the Chinese, Finnish and Siberian boreal soil types in relation to their soil WC, aligned at 19% in relation to the water-filled pore space (WFPS, indicating the dominating role of gas diffusion. This interpretation was supported by the linear correlation between Vd and bulk density. We suggest that the uptake of COS depends on the diffusivity dominated by WFPS, a parameter depending on soil WC, soil structure and porosity of the soil.

  6. Aluminium, carbonyls and cytokines in human nipple aspirate fluids: Possible relationship between inflammation, oxidative stress and breast cancer microenvironment.

    Science.gov (United States)

    Mannello, F; Ligi, D; Canale, M

    2013-11-01

    The human breast is likely exposed to Al (aluminium) from many sources including diet and personal care products. Underarm applications of aluminium salt-based antiperspirant provide a possible long-term source of exposure, especially after underarm applications to shaved and abraded skin. Al research in breast fluids likely reflects the intraductal microenvironment. We found increased levels of aluminium in noninvasively collected nipple aspirate fluids (NAF) from 19 breast cancer patients compared with 16 healthy control subjects (268 vs 131 μg/l, respectively; p Aluminium content and carbonyl levels showed a significant positive linear correlation (r(2) 0.6628, p aluminium salts) we also found a significantly increased levels of pro-inflammatory cytokines (IL-1β, IL-6, IL-12 p70, and TNF-α) and chemoattractant CC and CXC chemokines (IL-8, MIP-1α and MCP-1). In 12 invasive cancer NAF samples we found a significant positive linear correlation among aluminium, carbonyls and pro-inflammatory IL-6 cytokine (Y = 64.79x-39.63, r(2) 0.8192, p aluminium ions in oxidative and inflammatory status perturbations of breast cancer microenvironment, suggesting aluminium accumulation in breast microenvironment as a possible risk factor for oxidative/inflammatory phenotype of breast cells. © 2013.

  7. Active control of methanol carbonylation selectivity over Au/carbon anode by electrochemical potential.

    Science.gov (United States)

    Funakawa, Akiyasu; Yamanaka, Ichiro; Otsuka, Kiyoshi

    2005-05-12

    Electrochemical oxidative carbonylation of methanol was studied over Au supported carbon anode in CO. The major carbonylation products were dimethyl oxalate (DMO) and dimethyl carbonate (DMC). The minor oxidation products were dimethoxy methane (DMM) and methyl formate (MF) from methanol and CO(2). Influences of various reaction conditions were studied on carbonylation activities and selectivities. The selectivities to DMO and DMC can be controlled by the electrochemical potential. Electrocatalysis of Au/carbon anode was studied by cyclic voltammetry (CV), stoichiometric reactions among Au(3+), methanol, and CO, and UV-vis spectra. The Au/carbon anode was characterized by XRD, SEM, and BE images before and after the carbonylation. These experimental facts strongly suggest that transition of oxidation states of Au affects changing of the carbonylation selectivities to DMO and DMC. Au(0) is the active species for the selective DMO formation by direct electrochemical carbonylation at low potentials (selective DMC formation by indirect electrochemical carbonylation through Au(3+)/Au(+) redox at high potentials (>+1.3 V).

  8. Protein carbonylation sites in bovine raw milk and processed milk products.

    Science.gov (United States)

    Milkovska-Stamenova, Sanja; Mnatsakanyan, Ruzanna; Hoffmann, Ralf

    2017-08-15

    During thermal treatment of milk, proteins are oxidized, which may reduce the nutritional value of milk, abolish protein functions supporting human health, especially important for newborns, and yield potentially harmful products. The side chains of several amino acids can be oxidized to reactive carbonyls, which are often used to monitor oxidative stress in organisms. Here we mapped protein carbonylation sites in raw milk and different brands of pasteurized, ultra high temperature (UHT) treated milk, and infant formulas (IFs) after digesting the precipitated proteins with trypsin. Reactive carbonyls were derivatized with O-(biotinylcarbazoylmethyl)hydroxylamine to enrich the modified peptides by avidin-biotin affinity chromatography and analyze them by nanoRP-UPLC-ESI-MS. Overall, 53 unique carbonylated peptides (37 carbonylation sites, 15 proteins) were identified. Most carbonyls were derived from dicarbonyls (mainly glyoxal). The number of carbonylation sites increased with the harsher processing from raw milk (4) to pasteurized (16) and UHT milk (16) and to IF (24). Copyright © 2017 Elsevier Ltd. All rights reserved.

  9. Low pressure carbonylation of benzyl chloride = Die carbonylierung von benzylchlorid bei niedrigen drücken

    OpenAIRE

    Luggenhorst, H.J.; Westerterp, K.R.

    1986-01-01

    For carbonylations, metal carbonyls, particularly cobalt and iron carbonyls, are often used as catalysts. These reactions take place under rather drastic reaction conditions, e.g. 200–300 °C and 60–100 MPa. In some patents it is stated that similar reactions using the same catalysts can also be carried out under rather mild reaction conditions, such as 0–100 °C and 0–2.5 MPa. We studied the conversion of benzyl chloride to phenyl acetic methyl ester in a semi-batch reactor in which one of the...

  10. Formation of neutral and charged gold carbonyls on highly facetted gold nanostructures

    Science.gov (United States)

    Chau, Thoi-Dai; Visart de Bocarmé, Thierry; Kruse, Norbert; Wang, Richard L. C.; Kreuzer, Hans Jürgen

    2003-12-01

    We show that gold mono- and di-carbonyls are formed on gold field emitter tips during interaction with carbon monoxide gas at room temperature and in the presence of high electrostatic fields. The experiments are done in a time-of-flight atom probe to obtain mass spectra. The yield of monocarbonyl cations is about twice that of di-carbonyl ions. Density functional theory calculations are reported that explain the field stabilization of adsorbed carbonyls and the desorption yield of their cations.

  11. Carbonylation of 1-hexene in the presence of palladium-anion-exchange resin catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Lapidus, A.L.; Pirozhkov, S.D.; Buiya, M.A.; Lunin, A.F.; Karapetyan, L.P.; Saldadze, K.M.

    1986-06-20

    Activated charcoal, silica gel, and zeolites containing palladium are active in the carbonylation of lower olefins by carbon monoxide. In the present work, they studied the carbonylation of 1-hexene in the presence of a series of palladium catalysts containing An-221, An-251, and AN-511 anion-exchange catalysts produced in the USSR as the supports. A catalyst obtained by the deposition of palladium(II) on weakly basic anion-exchange resins displays high efficiency in the carbonylation of 1-hexene with the formation of a nixture of enanthoic and 2-methylcaproic acids.

  12. Effect of the carbonyl iron particles on acoustic absorption properties of magnetic polyurethane foam

    Science.gov (United States)

    Geng, Jialu; Wang, Caiping; Zhu, Honglang; Wang, Xiaojie

    2018-03-01

    Elastomeric matrix embedded with magnetic micro-sized particles has magnetically controllable properties, which has been investigated extensively in the last decades. In this study we develop a new magnetically controllable elastomeric material for acoustic applications at lower frequencies. The soft polyurethane foam is used as matrix material due to its extraordinary elastic and acoustic absorption properties. One-step method is used to synthesize polyurethane foam, in which all components including polyether polyols 330N, MDI, deionized water, silicone oil, carbonyl iron particle (CIP) and catalyst are put into one container for curing. Changing any component can induce the change of polyurethane foam's properties, such as physical and acoustic properties. The effect of the content of MDI on acoustic absorption is studied. The CIPs are aligned under extra magnetic field during the foaming process. And the property of polyurethane foam with aligned CIPs is also investigated. Scanning electron microscope (SEM) is used to observe the structure of pore and particle-chain. The two-microphone impedance tube and the transfer function method are used to test acoustic absorption property of the magnetic foams.

  13. Maternal aging affects oocyte resilience to carbonyl cyanide-m-chlorophenylhydrazone -induced mitochondrial dysfunction in cows.

    Directory of Open Access Journals (Sweden)

    Kazuki Kansaku

    Full Text Available Mitochondrial quality control is important for maintaining cellular and oocyte viability. In addition, aging affects mitochondrial quality in many cell types. In the present study, we examined how aging affects oocyte mitochondrial biogenesis and degeneration in response to induced mitochondrial dysfunction. Cumulus oocyte complexes were harvested from the ovaries of young (21‒45 months and aged (≥120 months cows and treated for 2 hours with 10 μM carbonyl cyanide-m- chlorophenylhydrazone (CCCP, or a vehicle control, after which cumulus oocyte complexes were subjected to in vitro fertilization and culture. CCCP treatment reduced ATP content and increased reactive oxygen species (ROS levels in the oocytes of both young and aged cows. When CCCP-treated cumulus oocyte complexes were subsequently cultured for 19 hours and/or subjected to fertilization, high ROS levels in oocytes and a low rate of blastocyst development was observed in oocytes derived from aged cows. In addition, we observed differential responses in mitochondrial biogenesis to CCCP treatment between young and aged cows. CCCP treatment enhanced mitochondrial biogenesis concomitant with upregulation of SIRT1 expression in oocytes of young, but not aged, cows. In conclusion, aging affects mitochondrial quality control and recuperation of oocytes following CCCP-induced mitochondrial dysfunction.

  14. Language of motivation and emotion in an internet support group for smoking cessation: explorative use of automated content analysis to measure regulatory focus.

    Science.gov (United States)

    Johnsen, Jan-Are K; Vambheim, Sara M; Wynn, Rolf; Wangberg, Silje C

    2014-01-01

    The present study describes a novel approach to the identification of the motivational processes in text data extracted from an Internet support group (ISG) for smoking cessation. Based on the previous findings that a "prevention" focus might be more relevant for maintaining behavior change, it was hypothesized that 1) language use (ie, the use of emotional words) signaling a "promotion" focus would be dominant in the initiating stages of the ISG, and 2) that the proportion of words signaling a prevention focus would increase over time. The data were collected from the ISG site, spanning 4 years of forum activity. The data were analyzed using the Linguistic Inquiry and Word Count application. The first hypothesis - of promotion focus dominance in the initiating stages - was not supported during year 1. However, for all the other years measured, the data showed that a prevention failure was more dominant compared with a promotion failure. The results indicate that content analysis could be used to investigate motivational and language-driven processes in ISGs. Understanding the interplay between self-regulation, lifestyle change, and modern communication channels could be of vital importance in providing the public with better health care services and interventions.

  15. Thermal characterization of magnetically aligned carbonyl iron/agar composites.

    Science.gov (United States)

    Diaz-Bleis, D; Vales-Pinzón, C; Freile-Pelegrín, Y; Alvarado-Gil, J J

    2014-01-01

    Composites of magnetic particles into polymeric matrices have received increasing research interest due to their capacity to respond to external magnetic or electromagnetic fields. In this study, agar from Gelidium robustum has been chosen as natural biocompatible polymer to build the matrix of the magnetic carbonyl iron particles (CIP) for their uses in biomedical fields. Heat transfer behavior of the CIP-agar composites containing different concentrations (5, 10, 15, 20, 25 and 30% w/w) of magnetically aligned and non-aligned CIP in the agar matrix was studied using photothermal radiometry (PTR) in the back-propagation emission configuration. The morphology of the CIP-agar composites with aligned and non-aligned CIP under magnetic field was also evaluated by scanning electron microscopy (SEM). The results revealed a dominant effect of CIP concentration over the alignment patterns induced by the magnetic field, which agrees with the behavior of the thermal diffusivity and thermal conductivity. Agar served as a perfect matrix to be used with CIP, and CIP-agar composites magnetically aligned at 20% CIP concentration can be considered as promising 'smart' material for hyperthermia treatments in the biomedical field. Copyright © 2013 Elsevier Ltd. All rights reserved.

  16. The oceanic cycle and global atmospheric budget of carbonyl sulfide

    Energy Technology Data Exchange (ETDEWEB)

    Weiss, P.S.

    1994-12-31

    A significant portion of stratospheric air chemistry is influenced by the existence of carbonyl sulfide (COS). This ubiquitous sulfur gas represents a major source of sulfur to the stratosphere where it is converted to sulfuric acid aerosol particles. Stratospheric aerosols are climatically important because they scatter incoming solar radiation back to space and are able to increase the catalytic destruction of ozone through gas phase reactions on particle surfaces. COS is primarily formed at the surface of the earth, in both marine and terrestrial environments, and is strongly linked to natural biological processes. However, many gaps in the understanding of the global COS cycle still exist, which has led to a global atmospheric budget that is out of balance by a factor of two or more, and a lack of understanding of how human activity has affected the cycling of this gas. The goal of this study was to focus on COS in the marine environment by investigating production/destruction mechanisms and recalculating the ocean-atmosphere flux.

  17. Plant Uptake of Atmospheric Carbonyl Sulfide in Coast Redwood Forests

    Science.gov (United States)

    Campbell, J. E.; Whelan, M. E.; Berry, J. A.; Hilton, T. W.; Zumkehr, A.; Stinecipher, J.; Lu, Y.; Kornfeld, A.; Seibt, U.; Dawson, T. E.; Montzka, S. A.; Baker, I. T.; Kulkarni, S.; Wang, Y.; Herndon, S. C.; Zahniser, M. S.; Commane, R.; Loik, M. E.

    2017-12-01

    The future resilience of coast redwoods (Sequoia sempervirens) is now of critical concern due to the detection of a 33% decline in California coastal fog over the 20th century. However, ecosystem-scale measurements of photosynthesis and stomatal conductance are challenging in coast redwood forests, making it difficult to anticipate the impacts of future changes in fog. To address this methodological problem, we explore coastal variations in atmospheric carbonyl sulfide (COS or OCS), which could potentially be used as a tracer of these ecosystem processes. We conducted atmospheric flask campaigns in coast redwood sites, sampling at surface heights and in the canopy ( 70 m), at the University of California Landels-Hill Big Creek Reserve and Big Basin State Park. We simulated COS atmosphere-biosphere exchange with a high-resolution 3-D model to interpret these data. Flask measurements indicated a persistent daytime drawdown between the coast and the downwind forest (45 ± 6 ppt COS) that is consistent with the expected relationship between COS plant uptake, stomatal conductance, and gross primary production. Other sources and sinks of COS that could introduce noise to the COS tracer technique (soils, anthropogenic activity, nocturnal plant uptake, and surface hydrolysis on leaves) are likely to be small relative to daytime COS plant uptake. These results suggest that COS measurements may be useful for making ecosystem-scale estimates of carbon, water, and energy exchange in coast redwood forests.

  18. Global gridded anthropogenic emissions inventory of carbonyl sulfide

    Science.gov (United States)

    Zumkehr, Andrew; Hilton, Tim W.; Whelan, Mary; Smith, Steve; Kuai, Le; Worden, John; Campbell, J. Elliott

    2018-06-01

    Atmospheric carbonyl sulfide (COS or OCS) is the most abundant sulfur containing gas in the troposphere and is an atmospheric tracer for the carbon cycle. Gridded inventories of global anthropogenic COS are used for interpreting global COS measurements. However, previous gridded anthropogenic data are a climatological estimate based on input data that is over three decades old and are not representative of current conditions. Here we develop a new gridded data set of global anthropogenic COS sources that includes more source sectors than previously available and uses the most current emissions factors and industry activity data as input. Additionally, the inventory is provided as annually varying estimates from years 1980-2012 and employs a source specific spatial scaling procedure. We estimate a global source in year 2012 of 406 Gg S y-1 (range of 223-586 Gg S y-1), which is highly concentrated in China and is twice as large as the previous gridded inventory. Our large upward revision in the bottom-up estimate of the source is consistent with a recent top-down estimate based on air-monitoring and Antarctic firn data. Furthermore, our inventory time trends, including a decline in the 1990's and growth after the year 2000, are qualitatively consistent with trends in atmospheric data. Finally, similarities between the spatial distribution in this inventory and remote sensing data suggest that the anthropogenic source could potentially play a role in explaining a missing source in the global COS budget.

  19. Efficient and selective α-bromination of carbonyl compounds with N-bromosuccinimide under microwave

    KAUST Repository

    Guan, Xiao-Yu; Al-Misba'a, Zahra; Huang, Kuo-Wei

    2014-01-01

    A highly efficient method for the synthesis of α-halocarbonyl compounds has been achieved via selective monobromination of aromatic and aliphatic carbonyl compounds with N-bromosuccinimide catalyzed by p-toluenesulfonic acid under microwave irradiation within 30 min.

  20. Structure and Bonding in Binuclear Metal Carbonyls. Classical Paradigms vs. Insights from Modern Theoretical Calculations

    Czech Academy of Sciences Publication Activity Database

    Ponec, Robert

    2015-01-01

    Roč. 1053, SI (2015), s. 195-213 ISSN 2210-271X Institutional support: RVO:67985858 Keywords : binuclear metal carbonyls * DAFH analysis * 18-electron rule Subject RIV: CC - Organic Chemistry Impact factor: 1.403, year: 2015

  1. Nanostructured palladium tailored via carbonyl chemical route towards oxygen reduction reaction

    International Nuclear Information System (INIS)

    Luo, Y.; Mora-Hernández, J.M.; Estudillo-Wong, L.A.; Arce-Estrada, E.M.; Alonso-Vante, N.

    2015-01-01

    Graphical Abstract: Mass-depending morphologies of nanostructured Palladium obtained via the carbonyl chemical route. Display Omitted -- Highlights: •Mass-depending morphology was observed in nanostructured palladium supported on carbon prepared by the carbonyl chemical route. •The Morphological effect of carbon supported Pd was investigated towards ORR. -- Abstract: Carbon supported palladium nanostructures were synthesized via the carbonyl chemical route. Compared with nanostructured platinum, prepared via carbonyl chemical route, Pd nanomaterials showed mass-loading morphology, whereas particle size and morphology of Pt nanostructures was constant. The oxygen reduction reaction (ORR) on nanostructured Pd, with different morphology in both acid and alkaline medium was investigated. A relationship, based on X-ray diffraction structural analysis pattern, transmission electron microscope, with the Pd morphological effect on ORR activity was identified

  2. Efficient and selective α-bromination of carbonyl compounds with N-bromosuccinimide under microwave

    KAUST Repository

    Guan, Xiao-Yu

    2014-02-07

    A highly efficient method for the synthesis of α-halocarbonyl compounds has been achieved via selective monobromination of aromatic and aliphatic carbonyl compounds with N-bromosuccinimide catalyzed by p-toluenesulfonic acid under microwave irradiation within 30 min.

  3. Synthesis and Characterization of Tc(I) Carbonyl Nitrosyl Species Relevant to the Hanford Tank Waste: FY 2016 Status Report

    Energy Technology Data Exchange (ETDEWEB)

    Hall, Gabriel B. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Chatterjee, Sayandev [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Levitskaia, Tatiana G. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Martin, Thibaut J. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Wall, Nathalie [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Walter, Eric D. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

    2015-11-24

    Among long-lived radioactive constituents in the Hanford tank waste, Tc presents a unique challenge in that it exists predominantly in the liquid phase, generally in the anionic form of pertechnetate, TcO4-, which is highly volatile at low-activity waste (LAW) vitrification melter temperatures and mobile in the Hanford site’s subsurface environment. The complex behavior of Tc under storage, treatment, and immobilization conditions significantly affects its management options, which to-date remain uncertain. In strongly alkaline environments, Tc exists as pertechnetate, TcO4- (oxidation state +7), and in the reduced forms (oxidation state < +7) collectively known as non-pertechnetate species. Pertechnetate is a well-characterized, anionic Tc species that can be removed from LAW by anion exchange or solvent extraction methods. There is no definitive information on the origin of the non-pertechnetate Tc species, nor is there a comprehensive description of their composition and behavior. It has been recently proposed that the non-pertechnetate species can comprise Tc(I) metal center and carbonyl or mixed carbonyl nitrosyl ligands stabilizing low-valent Tc. Recent work by our group has significantly expanded this previous work, generating a series of Tc(I) carbonyl compounds and demonstrating that they can be generated from reduction of TcO4- in the simulated Hanford tank waste in presence of CO at elevated temperature (Levitskaia et al. 2014). These results are consistent with the previous proposal that [Tc(CO)3]+ species can be present in the Hanford tank waste and suggest that the low Tc(I) oxidation state is stabilized by the π-accepting ability of the CO ligands. The continuation work has been initiated to develop model Tc carbonyl nitrosyl compounds and investigate their potential presence in the Hanford tank wastes. This report summarizes our to-date results.

  4. Functional group composition of ambient and source organic aerosols determined by tandem mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Dron, J.; El Haddad, I.; Temime-Roussel, B.; Wortham, H.; Marchand, N. [Univ Aix Marseille, CNRS, Lab Chim Provence, Equipe Instrumentat and React Atmospher, UMR 6264, F-13331 Marseille 3 (France); Jaffrezo, J.L. [Univ Grenoble 1, CNRS, UMR 5183, Lab Glaciol and Geophys Environm, F-38402 St Martin Dheres (France)

    2010-07-01

    The functional group composition of various organic aerosols (OA) is investigated using a recently developed analytical approach based on atmospheric pressure chemical ionisation-tandem mass spectrometry (APCIMS/MS). The determinations of three functional groups contents are performed quantitatively by neutral loss (carboxylic and carbonyl groups, R-COOH and R-CO-R' respectively) and precursor ion (nitro groups, R-NO{sub 2}) scanning modes of a tandem mass spectrometer. Major organic aerosol sources are studied: vehicular emission and wood combustion for primary aerosol sources; and a secondary organic aerosol (SOA) produced through photooxidation of o-xylene. The results reveal significant differences in the functional group contents of these source aerosols. The laboratory generated SOA is dominated by carbonyls while carboxylics are preponderate in the wood combustion particles. On the other hand, vehicular emissions are characterised by a strong nitro content. The total amount of the three functional groups accounts for 1.7% (vehicular) to 13.5% (o-xylene photooxidation) of the organic carbon. Diagnostic functional group ratios are then used to tentatively discriminate sources of particles collected in an urban background environment located in an Alpine valley (Chamonix, France) during a strong winter pollution event. The three functional groups under study account for a total functionalization rate of 2.2 to 3.8% of the organic carbon in this ambient aerosol, which is also dominated by carboxylic moieties. In this particular case study of a deep alpine valley during winter, we show that the nitro- and carbonyl-to-carboxylic diagnostic ratios can be a useful tool to discriminate sources. In these conditions, the total OA concentrations are highly dominated by wood combustion OA. This result is confirmed by an organic markers source apportionment approach which assess a wood burning organic carbon contribution of about 60%. Finally, examples of functional

  5. Functional group composition of ambient and source organic aerosols determined by tandem mass spectrometry

    Directory of Open Access Journals (Sweden)

    J. Dron

    2010-08-01

    Full Text Available The functional group composition of various organic aerosols (OA is investigated using a recently developed analytical approach based on atmospheric pressure chemical ionisation-tandem mass spectrometry (APCI-MS/MS. The determinations of three functional groups contents are performed quantitatively by neutral loss (carboxylic and carbonyl groups, R-COOH and R-CO-R´ respectively and precursor ion (nitro groups, R-NO2 scanning modes of a tandem mass spectrometer. Major organic aerosol sources are studied: vehicular emission and wood combustion for primary aerosol sources; and a secondary organic aerosol (SOA produced through photooxidation of o-xylene. The results reveal significant differences in the functional group contents of these source aerosols. The laboratory generated SOA is dominated by carbonyls while carboxylics are preponderate in the wood combustion particles. On the other hand, vehicular emissions are characterised by a strong nitro content. The total amount of the three functional groups accounts for 1.7% (vehicular to 13.5% (o-xylene photooxidation of the organic carbon. Diagnostic functional group ratios are then used to tentatively discriminate sources of particles collected in an urban background environment located in an Alpine valley (Chamonix, France during a strong winter pollution event. The three functional groups under study account for a total functionalisation rate of 2.2 to 3.8% of the organic carbon in this ambient aerosol, which is also dominated by carboxylic moieties. In this particular case study of a deep alpine valley during winter, we show that the nitro- and carbonyl-to-carboxylic diagnostic ratios can be a useful tool to discriminate sources. In these conditions, the total OA concentrations are highly dominated by wood combustion OA. This result is confirmed by an organic markers source apportionment approach which assess a wood burning organic carbon contribution of about 60

  6. Fluoride-Mediated Dephosphonylation of α-Diazo-β-carbonyl Phosphonates.

    Science.gov (United States)

    Phatake, Ravindra S; Mullapudi, Venkannababu; Wakchaure, Vivek C; Ramana, Chepuri V

    2017-01-20

    The possibility of fluoride-mediated selective dephosphonylation of α-diazo-β-carbonyl phosphonates such as the Ohira-Bestmann reagent has been proposed and executed. The resulting α-diazocarbonyl intermediates undergo a (3 + 2)-cycloaddition at room temperature with conjugated olefins and benzynes. Interestingly, under the current conditions, the resulting cycloaddition products underwent either N-acylation (with excess α-diazo-β-carbonyl phosphonates) or Michael addition (with conjugated olefins).

  7. Structure and Reactivity of Zeolite- and Carbon-Supported Catalysts for the Oxidative Carbonylation of Alcohols

    OpenAIRE

    Briggs, Daniel Neal

    2010-01-01

    AbstractStructure and Reactivity of Zeolite- and Carbon-Supported Catalysts for the Oxidative Carbonylation of AlcoholsbyDaniel Neal BriggsDoctor of Philosophy in Chemical EngineeringUniversity of California, BerkeleyProfessor Alexis T. Bell, Chair The oxidative carbonylation of alcohols to produce dialkyl carbonates is a process that takes place commercially in a slurry of cuprous chloride in the appropriate alcohol. While this process is chemically efficient, it incurs costs in terms of ene...

  8. Cytoprotective Effects of Pumpkin (Cucurbita Moschata) Fruit Extract against Oxidative Stress and Carbonyl Stress.

    Science.gov (United States)

    Shayesteh, Reyhaneh; Kamalinejad, Mohammad; Adiban, Hasan; Kardan, Azin; Keyhanfar, Fariborz; Eskandari, Mohammad Reza

    2017-10-01

    Background Diabetes mellitus is a chronic endocrine disorder that is associated with significant mortality and morbidity due to microvascular and macrovascular complications. Diabetes complications accompanied with oxidative stress and carbonyl stress in different organs of human body because of the increased generation of free radicals and impaired antioxidant defense systems. In the meantime, reactive oxygen species (ROS) and reactive carbonyl species (RCS) have key mediatory roles in the development and progression of diabetes complications. Therapeutic strategies have recently focused on preventing such diabetes-related abnormalities using different natural and chemical compounds. Pumpkin ( Cucurbita moschata ) is one of the most important vegetables in the world with a broad-range of pharmacological activities such as antihyperglycemic effect. Methods In the present study, the cytoprotective effects of aqueous extract of C. moschata fruit on hepatocyte cytotoxicity induced by cumene hydroperoxide (oxidative stress model) or glyoxal (carbonylation model) were investigated using freshly isolated rat hepatocytes. Results The extract of C. moschata (50 μg/ml) excellently prevented oxidative and carbonyl stress markers, including hepatocyte lysis, ROS production, lipid peroxidation, glutathione depletion, mitochondrial membrane potential collapse, lysosomal damage, and cellular proteolysis. In addition, protein carbonylation was prevented by C. moschata in glyoxal-induced carbonyl stress. Conclusion It can be concluded that C. moschata has cytoprotective effects in oxidative stress and carbonyl stress models and this valuable vegetable can be considered as a suitable herbal product for the prevention of toxic subsequent of oxidative stress and carbonyl stress seen in chronic hyperglycemia. © Georg Thieme Verlag KG Stuttgart · New York.

  9. Organocatalyzed α-Sulfenylation of carbonyl compounds using N-formly/Acyl Sulfenmides

    International Nuclear Information System (INIS)

    Noh, Hyeon Wan; Lee, Chan; Jang, Hye Young

    2017-01-01

    α-Sulfenylation of aldehydes and ketones using N-formyl and N-acyl sulfenamides, prepared by Cu-catalyzed aerobic coupling of amides and thiols, was achieved in the presence of cyclic secondary amine⋅HCl catalysts. To obtain various sulfur-functionalized carbonyl compounds, sulfenamides containing aromatic and aliphatic organosulfur were investigated. As carbonyl compounds, cyclic and acyclic ketones, 1,3-dicarbonyl compounds, and aldehydes were investigated, affording the desired α-sulfenylation products in good yields

  10. Organocatalyzed α-Sulfenylation of carbonyl compounds using N-formly/Acyl Sulfenmides

    Energy Technology Data Exchange (ETDEWEB)

    Noh, Hyeon Wan; Lee, Chan; Jang, Hye Young [Dept. of Energy Systems Research, Ajou University, Suwon (Korea, Republic of)

    2017-03-15

    α-Sulfenylation of aldehydes and ketones using N-formyl and N-acyl sulfenamides, prepared by Cu-catalyzed aerobic coupling of amides and thiols, was achieved in the presence of cyclic secondary amine⋅HCl catalysts. To obtain various sulfur-functionalized carbonyl compounds, sulfenamides containing aromatic and aliphatic organosulfur were investigated. As carbonyl compounds, cyclic and acyclic ketones, 1,3-dicarbonyl compounds, and aldehydes were investigated, affording the desired α-sulfenylation products in good yields.

  11. Ammonia synthesis in the presence of rhodium-ruthenium-iridium carbonyl clusters

    International Nuclear Information System (INIS)

    Fedoseev, I.V.; Solov'ev, N.V.

    2007-01-01

    Researches in the field of platinum metal coordination compounds, where nitrogen enters as a ligand in coordination sphere of metal, are discussed. Results of experiments on the ammonia synthesis during the CO+N 2 mixture passing through alkali solution containing mixture of carbonyl clusters of rhodium, ruthenium and iridium at atmospheric pressure are given. Technique of the experiment and steps of assumed reactions of nitrogen fixation by Rh, Ir and Ru carbonyl clusters are demonstrated [ru

  12. Plasma-treated carbonyl iron particles as a dispersed phase in magnetorheological fluids

    OpenAIRE

    Sedlačík, M.; Pavlínek, V.; Lehocký, M.; Mráček, A.; Grulich, O.; Švrčinová, P. (Petra); Filip, P. (Petr); Vesel, A.

    2011-01-01

    The aim of this paper is to document suitability of plasma-treated carbonyl iron particles as a dispersed phase in magnetorheological fluids. Surface-modified carbonyl iron particles were prepared via their exposure to 50% argon and 50% octafluorocyclobutane plasma. The X-ray photoelectron spectroscopy was used for analysis of chemical bonding states in the surface layer. Plasma-treated particles were adopted for a dispersed phase in magnetorheological (MR) fluids, and the MR behaviour was in...

  13. Carbonyl Emissions in E-cigarette Aerosol: A Systematic Review and Methodological Considerations

    Directory of Open Access Journals (Sweden)

    Konstantinos E. Farsalinos

    2018-01-01

    Full Text Available Carbonyl emissions from tobacco cigarettes represent a substantial health risk contributing to smoking-related morbidity and mortality. As expected, this is an important research topic for tobacco harm reduction products, in an attempt to compare the relative risk of these products compared to tobacco cigarettes. In this study, a systematic review of the literature available on PubMed was performed analyzing the studies evaluating carbonyl emissions from e-cigarettes. A total of 32 studies were identified and presented. We identified a large diversity of methodologies, with substantial discrepancies in puffing patterns, aerosol collection and analytical methods as well as reported units of measurements. Such discrepancies make comparisons difficult, and in some cases the accuracy of the findings cannot be determined. Importantly, control for the generation of dry puffs was not performed in the vast majority of studies, particularly in studies using variable power devices, which could result in testing conditions and reported carbonyl levels that have no clinical relevance or context. Some studies have been replicated, verifying the presence of dry puff conditions. Whenever realistic use conditions were ensured, carbonyl emissions from e-cigarettes were substantially lower than tobacco cigarette smoke, while newer generation (bottom-coil, cotton wick atomizers appeared to emit minimal levels of carbonyls with questionable clinical significance in terms of health risk. However, extremely high levels of carbonyl emissions were reported in some studies, and all these studies need to be replicated because of potentially important health implications.

  14. Predicting personal exposure to airborne carbonyls using residential measurements and time/activity data

    Science.gov (United States)

    Liu, Weili; Zhang, Junfeng (Jim); Korn, Leo R.; Zhang, Lin; Weisel, Clifford P.; Turpin, Barbara; Morandi, Maria; Stock, Tom; Colome, Steve

    As a part of the Relationships of Indoor, Outdoor, and Personal Air (RIOPA) study, 48 h integrated residential indoor, outdoor, and personal exposure concentrations of 10 carbonyls were simultaneously measured in 234 homes selected from three US cities using the Passive Aldehydes and Ketones Samplers (PAKS). In this paper, we examine the feasibility of using residential indoor concentrations to predict personal exposures to carbonyls. Based on paired t-tests, the means of indoor concentrations were not different from those of personal exposure concentrations for eight out of the 10 measured carbonyls, indicating indoor carbonyls concentrations, in general, well predicted the central tendency of personal exposure concentrations. In a linear regression model, indoor concentrations explained 47%, 55%, and 65% of personal exposure variance for formaldehyde, acetaldehyde, and hexaldehyde, respectively. The predictability of indoor concentrations on cross-individual variability in personal exposure for the other carbonyls was poorer, explainingexposure concentrations. It was found that activities related to driving a vehicle and performing yard work had significant impacts on personal exposures to a few carbonyls.

  15. Protein carbonylation associated to high-fat, high-sucrose diet and its metabolic effects.

    Science.gov (United States)

    Méndez, Lucía; Pazos, Manuel; Molinar-Toribio, Eunice; Sánchez-Martos, Vanesa; Gallardo, José M; Rosa Nogués, M; Torres, Josep L; Medina, Isabel

    2014-12-01

    The present research draws a map of the characteristic carbonylation of proteins in rats fed high-caloric diets with the aim of providing a new insight of the pathogenesis of metabolic diseases derived from the high consumption of fat and refined carbohydrates. Protein carbonylation was analyzed in plasma, liver and skeletal muscle of Sprague-Dawley rats fed a high-fat, high-sucrose (HFHS) diet by a proteomics approach based on carbonyl-specific fluorescence-labeling, gel electrophoresis and mass spectrometry. Oxidized proteins along with specific sites of oxidative damage were identified and discussed to illustrate the consequences of protein oxidation. The results indicated that long-term HFHS consumption increased protein oxidation in plasma and liver; meanwhile, protein carbonyls from skeletal muscle did not change. The increment of carbonylation by HFHS diet was singularly selective on specific target proteins: albumin from plasma and liver, and hepatic proteins such as mitochondrial carbamoyl-phosphate synthase (ammonia), mitochondrial aldehyde dehydrogenase, argininosuccinate synthetase, regucalcin, mitochondrial adenosine triphosphate synthase subunit beta, actin cytoplasmic 1 and mitochondrial glutamate dehydrogenase 1. The possible consequences that these specific protein carbonylations have on the excessive weight gain, insulin resistance and nonalcoholic fatty liver disease resulting from HFHS diet consumption are discussed. Copyright © 2014 Elsevier Inc. All rights reserved.

  16. Line profile analyses of rhodium metal obtained by decomposition of rhodium carbonyl

    International Nuclear Information System (INIS)

    Chandra, D.; Mandalia, H.; Garner, M.L.; Blakely, M.K.; Lau, K.H.

    1995-01-01

    Metal carbonyls are important for chemical vapor deposition (CVD) of metals and alloys and formation of high surface area metallic particles which have potential applications as catalysts. Rhodium carbonyl [Rh 6 (CO) 16 ] produces high surface area metallic particles whose structure has been reported as monoclinic (I2/a) with lattice dimensions, a=17.00(±0.03)Angstrom, b=9.78(±0.02)Angstrom, c=17.53(±0.03)Angstrom and Β=121 degrees 45' ± 30' at room temperature. Generally, metal carbonyl crystals dissociate under vacuum as carbonyl gas and decompose to metallic crystals and carbon monoxide at higher temperatures. However, the behavior of rhodium carbonyl crystals is different; they decompose directly to metallic rhodium without the formation of rhodium carbonyl gas in vacuum. Several residual fine grains of rhodium metal are found after the decomposition in vacuum at relatively low temperatures. The metallic samples of rhodium were obtained from vapor pressure experiments using torsion Knudsen-effusion apparatus. X-ray diffraction analyses performed on these gains showed severely broadened Bragg reflections indicative of small particle size and/or lattice microgram. In this study, a comparison of lattice strains and domain sizes obtained by integral breadth and Fourier methods has been made. In addition a comparison of the lattice strains and domain sizes has been made between the Cauchy, Gaussian, Cauchy-Gaussian and Aqua integral breadth methods

  17. Characteristics of carbonyl compounds in public vehicles of Beijing city: Concentrations, sources, and personal exposures

    Science.gov (United States)

    Pang, Xiaobing; Mu, Yujing

    The characteristics of carbonyl compounds (carbonyls) including concentrations, major sources, and personal exposure were investigated for 29 vehicles including taxi, bus and subway in Beijing. It was found that the taxis (Xiali, TA) and buses (Huanghe, BA) fueled by gasoline with longer service years had the higher indoor carbonyl levels (178±42.7 and 188±31.6 μg m -3) while subways energized by electricity without exhaust and the jingwa buses (BB) driven in the suburb had the lower levels with total concentrations of 98.5±26.3 and 92.1±20.3 μg m -3, respectively. Outdoor carbonyls of taxi cars and buses were nearly at the same level with their total concentrations varying from 80 to 110 μg m -3. The level of outdoor subways carbonyls was equal with the ambient air levels. Exhaust leakage, indoor material emissions, photochemical formation, and infiltration of outdoor air were considered to be the major sources to in-vehicle carbonyls. Personal exposures and cancer risk to formaldehyde and acetaldehyde were calculated for professional bus and taxi drivers, respectively. Taxi drivers had the highest cancer risk with personal exposure to formaldehyde and acetaldehyde of 212 and 243 μg day -1, respectively. The public concern should pay considerable attention to professional drivers' health.

  18. Expression, purification, crystallization and preliminary X-ray analysis of NAD(P)H-dependent carbonyl reductase specifically expressed in thyroidectomized chicken fatty liver

    International Nuclear Information System (INIS)

    Yoneda, Kazunari; Fukuda, Yudai; Shibata, Takeshi; Araki, Tomohiro; Nikki, Takahiro; Sakuraba, Haruhiko; Ohshima, Toshihisa

    2012-01-01

    An NAD(P)H-dependent carbonyl reductase specifically expressed in thyroidectomized chicken fatty liver was successfully isolated and crystallized. An NAD(P)H-dependent carbonyl reductase specifically expressed in thyroidectomized chicken fatty liver was crystallized using the sitting-drop vapour-diffusion method with polyethylene glycol 300 as the precipitant. The crystals belonged to the monoclinic space group C2, with unit-cell parameters a = 104.26, b = 81.32, c = 77.27 Å, β = 119.43°, and diffracted to 1.86 Å resolution on beamline NE3A at the Photon Factory. The overall R merge was 5.4% and the data completeness was 99.4%

  19. Protein carbonylation, protein aggregation and neuronal cell death in a murine model of multiple sclerosis

    Science.gov (United States)

    Dasgupta, Anushka

    Many studies have suggested that oxidative stress plays an important role in the pathophysiology of both multiple sclerosis (MS) and its animal model experimental autoimmune encephalomyelitis (EAE). Yet, the mechanism by which oxidative stress leads to tissue damage in these disorders is unclear. Recent work from our laboratory has revealed that protein carbonylation, a major oxidative modification caused by severe and/or chronic oxidative stress conditions, is elevated in MS and EAE. Furthermore, protein carbonylation has been shown to alter protein structure leading to misfolding/aggregation. These findings prompted me to hypothesize that carbonylated proteins, formed as a consequence of oxidative stress and/or decreased proteasomal activity, promote protein aggregation to mediate neuronal apoptosis in vitro and in EAE. To test this novel hypothesis, I first characterized protein carbonylation, protein aggregation and apoptosis along the spinal cord during the course of myelin-oligodendrocyte glycoprotein (MOG)35-55 peptide-induced EAE in C57BL/6 mice [Chapter 2]. The results show that carbonylated proteins accumulate throughout the course of the disease, albeit by different mechanisms: increased oxidative stress in acute EAE and decreased proteasomal activity in chronic EAE. I discovered not only that there is a temporal correlation between protein carbonylation and apoptosis but also that carbonyl levels are significantly higher in apoptotic cells. A high number of juxta-nuclear and cytoplasmic protein aggregates containing the majority of the oxidized proteins are also present during the course of EAE, which seems to be due to reduced autophagy. In chapter 3, I show that when gluthathione levels are reduced to those in EAE spinal cord, both neuron-like PC12 (nPC12) cells and primary neuronal cultures accumulate carbonylated proteins and undergo cell death (both by necrosis and apoptosis). Immunocytochemical and biochemical studies also revealed a temporal

  20. Language of motivation and emotion in an Internet support group for smoking cessation: explorative use of automated content analysis to measure regulatory focus

    Directory of Open Access Journals (Sweden)

    Johnsen JAK

    2014-01-01

    Full Text Available Jan-Are K Johnsen,1 Sara M Vambheim,2 Rolf Wynn,3,4 Silje C Wangberg3,51Department of Clinical Dentistry, University of Tromsø, 2Department of Psychology, University of Tromsø, 3Division of Addiction and Specialized Psychiatry, University Hospital of North-Norway, 4Department of Clinical Medicine, University of Tromsø, Tromsø, 5Narvik University College, Narvik, NorwayAbstract: The present study describes a novel approach to the identification of the motivational processes in text data extracted from an Internet support group (ISG for smoking cessation. Based on the previous findings that a “prevention” focus might be more relevant for maintaining behavior change, it was hypothesized that 1 language use (ie, the use of emotional words signaling a “promotion” focus would be dominant in the initiating stages of the ISG, and 2 that the proportion of words signaling a prevention focus would increase over time. The data were collected from the ISG site, spanning 4 years of forum activity. The data were analyzed using the Linguistic Inquiry and Word Count application. The first hypothesis – of promotion focus dominance in the initiating stages – was not supported during year 1. However, for all the other years measured, the data showed that a prevention failure was more dominant compared with a promotion failure. The results indicate that content analysis could be used to investigate motivational and language-driven processes in ISGs. Understanding the interplay between self-regulation, lifestyle change, and modern communication channels could be of vital importance in providing the public with better health care services and interventions.Keywords: self-regulation, behavior change, emotion, prevention

  1. Validity test of the IPD-Work consortium approach for creating comparable job strain groups between Job Content Questionnaire and Demand-Control Questionnaire

    Directory of Open Access Journals (Sweden)

    Bongkyoo Choi

    2015-04-01

    Full Text Available Objectives: This study aims to test the validity of the IPD-Work Consortium approach for creating comparable job strain groups between the Job Content Questionnaire (JCQ and the Demand-Control Questionnaire (DCQ. Material and Methods: A random population sample (N = 682 of all middle-aged Malmö males and females was given a questionnaire with the 14-item JCQ and 11-item DCQ for the job control and job demands. The JCQ job control and job demands scores were calculated in 3 different ways: using the 14-item JCQ standard scale formulas (method 1; dropping 3 job control items and using the 11-item JCQ standard scale formulas with additional scale weights (method 2; and the approach of the IPD Group (method 3, dropping 3 job control items, but using the simple 11-item summation-based scale formulas. The high job strain was defined as a combination of high demands and low control. Results: Between the 2 questionnaires, false negatives for the high job strain were much greater than false positives (37–49% vs. 7–13%. When the method 3 was applied, the sensitivity of the JCQ for the high job strain against the DCQ was lowest (0.51 vs. 0.60–0.63 when the methods 1 and 2 were applied, although the specificity was highest (0.93 vs. 0.87–0.89 when the methods 1 and 2 were applied. The prevalence of the high job strain with the JCQ (the method 3 was applied was considerably lower (4–7% than with the JCQ (the methods 1 and 2 were applied and the DCQ. The number of congruent cases for the high job strain between the 2 questionnaires was smallest when the method 3 was applied. Conclusions: The IPD-Work Consortium approach showed 2 major weaknesses to be used for epidemiological studies on the high job strain and health outcomes as compared to the standard JCQ methods: the greater misclassification of the high job strain and lower prevalence of the high job strain.

  2. Validity test of the IPD-Work consortium approach for creating comparable job strain groups between Job Content Questionnaire and Demand-Control Questionnaire.

    Science.gov (United States)

    Choi, Bongkyoo; Ko, Sangbaek; Ostergren, Per-Olof

    2015-01-01

    This study aims to test the validity of the IPD-Work Consortium approach for creating comparable job strain groups between the Job Content Questionnaire (JCQ) and the Demand-Control Questionnaire (DCQ). A random population sample (N = 682) of all middle-aged Malmö males and females was given a questionnaire with the 14-item JCQ and 11-item DCQ for the job control and job demands. The JCQ job control and job demands scores were calculated in 3 different ways: using the 14-item JCQ standard scale formulas (method 1); dropping 3 job control items and using the 11-item JCQ standard scale formulas with additional scale weights (method 2); and the approach of the IPD Group (method 3), dropping 3 job control items, but using the simple 11-item summation-based scale formulas. The high job strain was defined as a combination of high demands and low control. Between the 2 questionnaires, false negatives for the high job strain were much greater than false positives (37-49% vs. 7-13%). When the method 3 was applied, the sensitivity of the JCQ for the high job strain against the DCQ was lowest (0.51 vs. 0.60-0.63 when the methods 1 and 2 were applied), although the specificity was highest (0.93 vs. 0.87-0.89 when the methods 1 and 2 were applied). The prevalence of the high job strain with the JCQ (the method 3 was applied) was considerably lower (4-7%) than with the JCQ (the methods 1 and 2 were applied) and the DCQ. The number of congruent cases for the high job strain between the 2 questionnaires was smallest when the method 3 was applied. The IPD-Work Consortium approach showed 2 major weaknesses to be used for epidemiological studies on the high job strain and health outcomes as compared to the standard JCQ methods: the greater misclassification of the high job strain and lower prevalence of the high job strain. This work is available in Open Access model and licensed under a CC BY-NC 3.0 PL license.

  3. Fast retrievals of tropospheric carbonyl sulfide with IASI

    Science.gov (United States)

    Vincent, R. Anthony; Dudhia, Anu

    2017-02-01

    Iterative retrievals of trace gases, such as carbonyl sulfide (OCS), from satellites can be exceedingly slow. The algorithm may even fail to keep pace with data acquisition such that analysis is limited to local events of special interest and short time spans. With this in mind, a linear retrieval scheme was developed to estimate total column amounts of OCS at a rate roughly 104 times faster than a typical iterative retrieval. This scheme incorporates two concepts not utilized in previously published linear estimates. First, all physical parameters affecting the signal are included in the state vector and accounted for jointly, rather than treated as effective noise. Second, the initialization point is determined from an ensemble of atmospheres based on comparing the model spectra to the observations, thus improving the linearity of the problem. All of the 2014 data from the Infrared Atmospheric Sounding Interferometer (IASI), instruments A and B, were analysed and showed spatial features of OCS total columns, including depletions over tropical rainforests, seasonal enhancements over the oceans, and distinct OCS features over land. Error due to assuming linearity was found to be on the order of 11 % globally for OCS. However, systematic errors from effects such as varying surface emissivity and extinction due to aerosols have yet to be robustly characterized. Comparisons to surface volume mixing ratio in situ samples taken by NOAA show seasonal correlations greater than 0.7 for five out of seven sites across the globe. Furthermore, this linear scheme was applied to OCS, but may also be used as a rapid estimator of any detectable trace gas using IASI or similar nadir-viewing instruments.

  4. New Ir Bis-Carbonyl Precursor for Water Oxidation Catalysis

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Daria L. [Department of Chemistry, Yale University, 225; Beltrán-Suito, Rodrigo [Department of Chemistry, Yale University, 225; Thomsen, Julianne M. [Department of Chemistry, Yale University, 225; Hashmi, Sara M. [Department of Chemical and Environmental; Materna, Kelly L. [Department of Chemistry, Yale University, 225; Sheehan, Stafford W. [Catalytic Innovations LLC, 70 Crandall; Mercado, Brandon Q. [Department of Chemistry, Yale University, 225; Brudvig, Gary W. [Department of Chemistry, Yale University, 225; Crabtree, Robert H. [Department of Chemistry, Yale University, 225

    2016-02-05

    This paper introduces IrI(CO)2(pyalc) (pyalc = (2-pyridyl)-2-propanoate) as an atom-efficient precursor for Ir-based homogeneous oxidation catalysis. This compound was chosen to simplify analysis of the water oxidation catalyst species formed by the previously reported Cp*IrIII(pyalc)OH water oxidation precatalyst. Here, we present a comparative study on the chemical and catalytic properties of these two precursors. Previous studies show that oxidative activation of Cp*Ir-based precursors with NaIO4 results in formation of a blue IrIV species. This activation is concomitant with the loss of the placeholder Cp* ligand which oxidatively degrades to form acetic acid, iodate, and other obligatory byproducts. The activation process requires substantial amounts of primary oxidant, and the degradation products complicate analysis of the resulting IrIV species. The species formed from oxidation of the Ir(CO)2(pyalc) precursor, on the other hand, lacks these degradation products (the CO ligands are easily lost upon oxidation) which allows for more detailed examination of the resulting Ir(pyalc) active species both catalytically and spectroscopically, although complete structural analysis is still elusive. Once Ir(CO)2(pyalc) is activated, the system requires acetic acid or acetate to prevent the formation of nanoparticles. Investigation of the activated bis-carbonyl complex also suggests several Ir(pyalc) isomers may exist in solution. By 1H NMR, activated Ir(CO)2(pyalc) has fewer isomers than activated Cp*Ir complexes, allowing for advanced characterization. Future research in this direction is expected to contribute to a better structural understanding of the active species. A diol crystallization agent was needed for the structure determination of 3.

  5. Photoinduced intramolecular substitution reaction of aryl halide with carbonyl oxygen of amide group

    CERN Document Server

    Park, Y T; Kim, M S; Kwon, J H

    2002-01-01

    Photoreaction of N-(o-halophenyl)acetamide in basic acetonitrile produces an intramolecular substituted product, 2-methylbenzoxazole in addition to reduced product, acetanilide, whereas photoreaction of N-(o-halobenzyl)acetamide affords a reduced product, N-benzylacetamide only. On the basis of preparative reaction, kinetics, and UV/vis absorption behavior, an electrophilic aromatic substitution of aryl halide with oxygen of its amide bond are proposed.

  6. Photoinduced intramolecular substitution reaction of aryl halide with carbonyl oxygen of amide group

    Energy Technology Data Exchange (ETDEWEB)

    Park, Yong Tae; Song, Myong Geun; Kim, Moon Sub; Kwon, Jeong Hee [Kyungpook National Univ., Daegu (Korea, Republic of)

    2002-09-01

    Photoreaction of N-(o-halophenyl)acetamide in basic acetonitrile produces an intramolecular substituted product, 2-methylbenzoxazole in addition to reduced product, acetanilide, whereas photoreaction of N-(o-halobenzyl)acetamide affords a reduced product, N-benzylacetamide only. On the basis of preparative reaction, kinetics, and UV/vis absorption behavior, an electrophilic aromatic substitution of aryl halide with oxygen of its amide bond are proposed.

  7. Photoinduced intramolecular substitution reaction of aryl halide with carbonyl oxygen of amide group

    International Nuclear Information System (INIS)

    Park, Yong Tae; Song, Myong Geun; Kim, Moon Sub; Kwon, Jeong Hee

    2002-01-01

    Photoreaction of N-(o-halophenyl)acetamide in basic acetonitrile produces an intramolecular substituted product, 2-methylbenzoxazole in addition to reduced product, acetanilide, whereas photoreaction of N-(o-halobenzyl)acetamide affords a reduced product, N-benzylacetamide only. On the basis of preparative reaction, kinetics, and UV/vis absorption behavior, an electrophilic aromatic substitution of aryl halide with oxygen of its amide bond are proposed

  8. Metal Organic Frameworks as Solid Catalysts in Condensation Reactions of Carbonyl Groups

    Czech Academy of Sciences Publication Activity Database

    Dhakshinamoorthy, A.; Opanasenko, Maksym; Čejka, Jiří; Garcia, H.

    2013-01-01

    Roč. 355, 2-3 (2013), s. 247-268 ISSN 1615-4150 R&D Projects: GA ČR GBP106/12/G015 Grant - others:European Commission(XE) FP7/2007-2013, contract 228862 Institutional support: RVO:61388955 Keywords : alcohol condensation * green chemistry * Henry reaction Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 5.542, year: 2013

  9. Organometallic and Bioorganometallic Chemistry - Ferrocene and Metal Carbonyls

    Directory of Open Access Journals (Sweden)

    Čakić Semenčić, M.

    2011-02-01

    Full Text Available Organometallic chemistry deals with compounds containing metal-carbon bonds. Basic organometallics derived from the s- and p-block metals (containing solely σ-bonds were understood earlier, while organometallic chemistry of the d- and f-block has developed much more recently. These compounds are characterized by three types of M-C bonds (σ, π and δand their structures are impossible to deduce by chemical means alone; fundamental advances had to await the development of X-ray diffraction, as well as IR- and NMR-spectroscopy. On the other hand, elucidation of the structure of e. g. vitamin B12 and ferrocene (discovered in 1951 contributed to progress in these instrumental analytical methods, influencing further phenomenal success of transition-metal organometallic chemistry in the second half of the twentieth century. The most thoroughly explored fields of application of organometallics were in the area of catalysis, asymmetric synthesis, olefin metathesis, as well as organic synthesis and access to new materials and polymers.The most usual ligands bound to d- and f-metals are carbon monoxide, phosphines, alkyls, carbenes and arenes, and in this review the bonding patterns in the metal carbonyls and ferrocene are elaborated. The common characteristics of these two classes are two-component bonds. The CO-M bonds include (i donation from ligand HOMO to vacant M d-orbitals (σ-bond, and (ii back-donation from the filled M d-orbitals in the ligand LUMO (π-bond. Similar (but much more complicated ferrocene contains delocalized bonds consisting of electron donation from Cp to Fe (σ-bonds- and π-bonding and δ-back-bonding from metal to Cp. In such a way ferrocene, i. e. (η5-Cp2Fe contains 18 bonding electrons giving to this compound "superaromatic" properties in the sense of stability and electrophilic substitution. In contrast to benzenoid aromatic compounds reactions in two Cp-rings can occur giving homo- and heteroannularly mono-, two-… per

  10. Reaction of phosphorus ylides with carbonyl compounds in supercritical carbon dioxide

    International Nuclear Information System (INIS)

    Jeong, Kyung Il; Kim, Hak Do; Shim, Jae Jin; Ra, Choon Sup

    2004-01-01

    The condensation reaction of (benzylene)triphenylphosphoranes with carbonyl compounds in supercritical carbon dioxide was examined. Reactions of (benzylene)phosphoranes (ca. 1 mmol) with several benzaldehydes in a supercritical carbon dioxide (80 .deg. C, 2,000 psi) containing THF entrainer (5%) in a 24 mL reactor proceed smoothly to yield olefination products in fairly good to excellent yields but slower, compared to reactions in a conventional THF solvent. Generally, phosphoranes that are not substituted with a nitro group show more (Z)-selective reactions with aromatic aldehydes under scCO 2 condition than in THF. The reaction of (benzylene)triphenylphosphosphoranes with 4-t-butylcyclohexanone gave the corresponding olefin compounds with a low conversion under both the supercritical carbon dioxide and the organic THF solvent. Our preliminary study showed the Wittig reaction carries out smoothly in supercritical carbon dioxide medium and also a possible tunability of this reaction pathway by adding a entrainer. The results would be useful for devising a novel process for the environmentally friendly Wittig reaction

  11. Reaction of phosphorus ylides with carbonyl compounds in supercritical carbon dioxide

    Energy Technology Data Exchange (ETDEWEB)

    Jeong, Kyung Il; Kim, Hak Do; Shim, Jae Jin; Ra, Choon Sup [Yeungnam Univ., Gyongsan (Korea, Republic of)

    2004-02-15

    The condensation reaction of (benzylene)triphenylphosphoranes with carbonyl compounds in supercritical carbon dioxide was examined. Reactions of (benzylene)phosphoranes (ca. 1 mmol) with several benzaldehydes in a supercritical carbon dioxide (80 .deg. C, 2,000 psi) containing THF entrainer (5%) in a 24 mL reactor proceed smoothly to yield olefination products in fairly good to excellent yields but slower, compared to reactions in a conventional THF solvent. Generally, phosphoranes that are not substituted with a nitro group show more (Z)-selective reactions with aromatic aldehydes under scCO{sub 2} condition than in THF. The reaction of (benzylene)triphenylphosphosphoranes with 4-t-butylcyclohexanone gave the corresponding olefin compounds with a low conversion under both the supercritical carbon dioxide and the organic THF solvent. Our preliminary study showed the Wittig reaction carries out smoothly in supercritical carbon dioxide medium and also a possible tunability of this reaction pathway by adding a entrainer. The results would be useful for devising a novel process for the environmentally friendly Wittig reaction.

  12. Proteomic identification of carbonylated proteins in F344 rat hippocampus after 1-bromopropane exposure

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Zhenlie [Department of Occupational and Environmental Health, Nagoya University Graduate School of Medicine, Nagoya 466‐8550 (Japan); Department of Toxicology, Guangdong Prevention and Treatment Center for Occupational Diseases, Guangzhou 510‐300 (China); Ichihara, Sahoko [Graduate School of Regional Innovation Studies, Mie University, Tsu 514‐8507 (Japan); Oikawa, Shinji [Department of Environmental and Molecular Medicine, Mie University Graduate School of Medicine, Mie 514‐8507 (Japan); Chang, Jie; Zhang, Lingyi; Subramanian, Kaviarasan; Mohideen, Sahabudeen Sheik [Department of Occupational and Environmental Health, Nagoya University Graduate School of Medicine, Nagoya 466‐8550 (Japan); Ichihara, Gaku, E-mail: gak@med.nagoya-u.ac.jp [Department of Occupational and Environmental Health, Nagoya University Graduate School of Medicine, Nagoya 466‐8550 (Japan)

    2012-08-15

    1-Bromopropane (1-BP) is neurotoxic in both experimental animals and humans. Previous proteomic analysis of rat hippocampus implicated alteration of protein expression in oxidative stress, suggesting that oxidative stress plays a role in 1-BP-induced neurotoxicity. To understand this role at the protein level, we exposed male F344 rats to 1-BP at 0, 400, or 1000 ppm for 8 h/day for 1 week or 4 weeks by inhalation and quantitated changes in hippocampal protein carbonyl using a protein carbonyl assay, two-dimensional gel electrophoresis (2-DE), immunoblotting, and matrix-assisted laser-desorption ionization time-of-flight mass spectrometry (MALDI-TOF-TOF/MS). Hippocampal reactive oxygen species and protein carbonyl were significantly increased, demonstrating 1-BP-associated induction of oxidative stress and protein damage. MALDI-TOF-TOF/MS identified 10 individual proteins with increased carbonyl modification (p < 0.05; fold-change ≥ 1.5). The identified proteins were involved in diverse biological processes including glycolysis, ATP production, tyrosine catabolism, GTP binding, guanine degradation, and neuronal metabolism of dopamine. Hippocampal triosephosphate isomerase (TPI) activity was significantly reduced and negatively correlated with TPI carbonylation (p < 0.001; r = 0.83). Advanced glycation end-product (AGE) levels were significantly elevated both in the hippocampus and plasma, and hippocampal AGEs correlated negatively with TPI activity (p < 0.001; r = 0.71). In conclusion, 1-BP-induced neurotoxicity in the rat hippocampus seems to involve oxidative damage of cellular proteins, decreased TPI activity, and elevated AGEs. -- Highlights: ► 1-BP increases hippocampal ROS levels and hippocampal and plasma protein carbonyls. ► 1-BP increases TPI carbonylation and decreases TPI activity in the hippocampus. ► 1-BP increases hippocampal and plasma AGE levels.

  13. Enzyme-like specificity in zeolites: a unique site position in mordenite for selective carbonylation of methanol and dimethyl ether with CO.

    Science.gov (United States)

    Boronat, Mercedes; Martínez-Sánchez, Cristina; Law, David; Corma, Avelino

    2008-12-03

    The mechanism of methanol carbonylation at different positions of zeolite MOR is investigated by quantum-chemical methods in order to discover which are the active sites that can selectively catalyze the desired reaction. It is shown that when methanol carbonylation competes with hydrocarbon formation, the first reaction occurs preferentially within 8MR channels. However, the unique selectivity for the carbonylation of methanol and dimethyl ether in mordenite is not only due to the size of the 8MR channel: neither process occurs equally at the two T3-O31 and T3-O33 positions. We show that only the T3-O33 positions are selective and that this selectivity is due to the unusual orientation of the methoxy group in relation to the 8MR channel (parallel to the cylinder axis). Only in this situation does the transition state for the attack of CO fit perfectly in the 8MR channel, while the reaction with methanol or DME is sterically impeded. This result explains why T3-O31, while also located in the 8MR channel of mordenite, is not as selective as the T3-O33 position and why ferrierite, although it contains 8MR channels, is less selective than mordenite. The competing effect of water is explained at the molecular level, and the molecular microkinetic reaction model has been established.

  14. Simultaneous detection of low and high molecular weight carbonylated compounds derived from lipid peroxidation by electrospray ionization-tandem mass spectrometry.

    Science.gov (United States)

    Milic, Ivana; Hoffmann, Ralf; Fedorova, Maria

    2013-01-02

    Reactive oxygen species (ROS) and other oxidative agents such as free radicals can oxidize polyunsaturated fatty acids (PUFA) as well as PUFA in lipids. The oxidation products can undergo consecutive reactions including oxidative cleavages to yield a chemically diverse group of products, such as lipid peroxidation products (LPP). Among them are aldehydes and ketones ("reactive carbonyls") that are strong electrophiles and thus can readily react with nucleophilic side chains of proteins, which can alter the protein structure, function, cellular distribution, and antigenicity. Here, we report a novel technique to specifically derivatize both low molecular and high molecular weight carbonylated LPP with 7-(diethylamino)coumarin-3-carbohydrazide (CHH) and analyze all compounds by electrospray ionization-mass spectrometry (ESI-MS) in positive ion mode. CHH-derivatized compounds were identified by specific neutral losses or fragment ions. The fragment ion spectra displayed additional signals that allowed unambiguous identification of the lipid, fatty acids, cleavage sites, and oxidative modifications. Oxidation of docosahexaenoic (DHA, 22:6), arachidonic (AA, 20:4), linoleic (LA, 18:2), and oleic acids (OA, 18:1) yielded 69 aliphatic carbonyls, whose structures were all deduced from the tandem mass spectra. When four phosphatidylcholine (PC) vesicles containing the aforementioned unsaturated fatty acids were oxidized, we were able to deduce the structures of 122 carbonylated compounds from the tandem mass spectra of a single shotgun analysis acquired within 15 min. The high sensitivity (LOD ∼ 1 nmol/L for 4-hydroxy-2-nonenal, HNE) and a linear range of more than 3 orders of magnitude (10 nmol/L to 10 μmol/L for HNE) will allow further studies on complex biological samples including plasma.

  15. Determination of bond energies by mass spectrometry. Some transition metal carbonyls

    International Nuclear Information System (INIS)

    Michels, G.D.

    1979-01-01

    Two groups of transition metal carbonyls have been studied, M(CO) 6 and M(CO) 5 CS complexes of the Group VIB metals and M 2 (CO) 10 complexes of the Group VIIB metals. Results for the hexacarbonyl complexes indicate that the measured fragmentation energies are in error by 0.25 +- 0.02 eV per CO produced. This is attributed to excitation of CO to the first vibrational state. Least-squares dissociation energies calculated from corrected data for M(CO) 5 CS complexes indicate that the M--CS bond is 3 to 4 times stronger than the M--CO bonds. Substitution of CS for CO in going from M(CO) 6 to M(CO) 5 CS weakens the remaining M--CO bonds by an average of 0.2 eV. Previously unreported MnTc(CO) 10 and TcRe(CO) 10 are prepared by halide substitution of Tc(CO) 5 Br and Re(CO) 5 Br with Mn(CO) 5 - and Tc(CO) 5 - , respectively. In the positive ion, metal and mixed-metal decacarbonyls are considered as (CO) 5 M + --M(CO) 5 complexes possessing five strong and five weak M--CO bonds. For Mn 2 (CO) 10 and Re 2 (CO) 10 , M + --M dissociation energies are 3.0 +- 0.1 and 4.0 +- 0.3 eV, respectively. These energies are 2.5 times greater than those reported for homolytic cleavage to M(CO) 5 + and M(CO) 5

  16. Observations of the uptake of carbonyl sulfide (COS by trees under elevated atmospheric carbon dioxide concentrations

    Directory of Open Access Journals (Sweden)

    L. Sandoval-Soto

    2012-08-01

    Full Text Available Global change forces ecosystems to adapt to elevated atmospheric concentrations of carbon dioxide (CO2. We understand that carbonyl sulfide (COS, a trace gas which is involved in building up the stratospheric sulfate aerosol layer, is taken up by vegetation with the same triad of the enzymes which are metabolizing CO2, i.e. ribulose-1,5-bisphosphate carboxylase/oxygenase (Rubisco, phosphoenolpyruvate carboxylase (PEP-Co and carbonic anhydrase (CA. Therefore, we discuss a physiological/biochemical acclimation of these enzymes affecting the sink strength of vegetation for COS. We investigated the acclimation of two European tree species, Fagus sylvatica and Quercus ilex, grown inside chambers under elevated CO2, and determined the exchange characteristics and the content of CA after a 1–2 yr period of acclimation from 350 ppm to 800 ppm CO2. We demonstrate that a compensation point, by definition, does not exist. Instead, we propose to discuss a point of uptake affinity (PUA. The results indicate that such a PUA, the CA activity and the deposition velocities may change and may cause a decrease of the COS uptake by plant ecosystems, at least as long as the enzyme acclimation to CO2 is not surpassed by an increase of atmospheric COS. As a consequence, the atmospheric COS level may rise causing an increase of the radiative forcing in the troposphere. However, this increase is counterbalanced by the stronger input of this trace gas into the stratosphere causing a stronger energy reflection by the stratospheric sulfur aerosol into space (Brühl et al., 2012. These data are very preliminary but may trigger a discussion on COS uptake acclimation to foster measurements with modern analytical instruments.

  17. Microwave absorption properties of a wave-absorbing coating employing carbonyl-iron powder and carbon black

    International Nuclear Information System (INIS)

    Liu Lidong; Duan Yuping; Ma Lixin; Liu Shunhua; Yu Zhen

    2010-01-01

    To prevent serious electromagnetic interference, a single-layer wave-absorbing coating employing complex absorbents composed of carbonyl-iron powder (CIP) and carbon black (CB) with epoxy resin as matrix was prepared. The morphologies of CIP and CB were characterized by scanning electron microscope (SEM) and transmission electron microscope (TEM), respectively. The electromagnetic parameters of CIP and CB were measured in the frequency range of 2-18 GHz by transmission/reflection technology, and the electromagnetic loss mechanisms of the two particles were discussed, respectively. The microwave absorption properties of the coatings were investigated by measuring reflection loss (RL) using arch method. The effects of CIP ratio, CB content and thickness on the microwave absorption properties were discussed, respectively. The results showed that the higher thickness, CIP or CB content could make the absorption band shift towards the lower frequency range. Significantly, the wave-absorbing coating could be applied in different frequency ranges according to actual demand by controlling the content of CIP or CB in composites.

  18. Microwave absorption properties of a wave-absorbing coating employing carbonyl-iron powder and carbon black

    Science.gov (United States)

    Liu, Lidong; Duan, Yuping; Ma, Lixin; Liu, Shunhua; Yu, Zhen

    2010-11-01

    To prevent serious electromagnetic interference, a single-layer wave-absorbing coating employing complex absorbents composed of carbonyl-iron powder (CIP) and carbon black (CB) with epoxy resin as matrix was prepared. The morphologies of CIP and CB were characterized by scanning electron microscope (SEM) and transmission electron microscope (TEM), respectively. The electromagnetic parameters of CIP and CB were measured in the frequency range of 2-18 GHz by transmission/reflection technology, and the electromagnetic loss mechanisms of the two particles were discussed, respectively. The microwave absorption properties of the coatings were investigated by measuring reflection loss (RL) using arch method. The effects of CIP ratio, CB content and thickness on the microwave absorption properties were discussed, respectively. The results showed that the higher thickness, CIP or CB content could make the absorption band shift towards the lower frequency range. Significantly, the wave-absorbing coating could be applied in different frequency ranges according to actual demand by controlling the content of CIP or CB in composites.

  19. Enhanced microwave absorption in ZnO/carbonyl iron nano-composites by coating dielectric material

    Energy Technology Data Exchange (ETDEWEB)

    Zhou Chang [School of Physics and Material Science, Anhui University, Hefei 230036 (China); Key Laboratory of Opto-electronic Information Acquisition and Manipulation Ministry of Education, Anhui University, Hefei 230039 (China); Fang Qingqing, E-mail: physfangqq@126.com [School of Physics and Material Science, Anhui University, Hefei 230036 (China) and Key Laboratory of Opto-electronic Information Acquisition and Manipulation Ministry of Education, Anhui University, Hefei 230039 (China); Yan Fangliang; Wang Weina; Wu Keyue; Liu Yanmei; Lv Qingrong; Zhang Hanming; Zhang Qiping; Li Jinguang; Ding Qiongqiong [School of Physics and Material Science, Anhui University, Hefei 230036 (China); Key Laboratory of Opto-electronic Information Acquisition and Manipulation Ministry of Education, Anhui University, Hefei 230039 (China)

    2012-05-15

    The microwave absorption properties of zinc oxide/carbonyl iron composite nanoparticles fabricated by high energy ball milling were studied at 0-20 GHz. Experiments showed that ZnO as a kind of dielectric material coating carbonyl iron particles made the bandwidth of reflection loss (RL)<-5 dB expanding to the low frequency, and enhanced absorption effect obviously. For a 3 mm thickness absorber of ZnO/carbonyl iron after 30 h milling, the values of RL<-5 dB and RL<-8 dB were obtained in the frequency range from 7.0 GHz to 17.8 GHz and from 9.8 dB to 14.9 dB, respectively, and its strongest RL peak was -29.34 dB at 13.59 GHz. The magnetic loss of carbonyl iron particles and the dielectric loss of ZnO particles were the main mechanisms of microwave absorption for the composites. - Highlights: Black-Right-Pointing-Pointer We fabricated zinc oxide/carbonyl iron composites by high energy ball milling. Black-Right-Pointing-Pointer ZnO dielectric property increased absorption effect and absorption bandwidth. Black-Right-Pointing-Pointer Absorbing frequence of composites is expanding to low frequency direction. Black-Right-Pointing-Pointer The craft of high energy ball milling is easy to realize commerce production.

  20. Enhanced microwave absorption in ZnO/carbonyl iron nano-composites by coating dielectric material

    International Nuclear Information System (INIS)

    Zhou Chang; Fang Qingqing; Yan Fangliang; Wang Weina; Wu Keyue; Liu Yanmei; Lv Qingrong; Zhang Hanming; Zhang Qiping; Li Jinguang; Ding Qiongqiong

    2012-01-01

    The microwave absorption properties of zinc oxide/carbonyl iron composite nanoparticles fabricated by high energy ball milling were studied at 0–20 GHz. Experiments showed that ZnO as a kind of dielectric material coating carbonyl iron particles made the bandwidth of reflection loss (RL)<−5 dB expanding to the low frequency, and enhanced absorption effect obviously. For a 3 mm thickness absorber of ZnO/carbonyl iron after 30 h milling, the values of RL<−5 dB and RL<−8 dB were obtained in the frequency range from 7.0 GHz to 17.8 GHz and from 9.8 dB to 14.9 dB, respectively, and its strongest RL peak was −29.34 dB at 13.59 GHz. The magnetic loss of carbonyl iron particles and the dielectric loss of ZnO particles were the main mechanisms of microwave absorption for the composites. - Highlights: ► We fabricated zinc oxide/carbonyl iron composites by high energy ball milling. ► ZnO dielectric property increased absorption effect and absorption bandwidth. ► Absorbing frequence of composites is expanding to low frequency direction. ► The craft of high energy ball milling is easy to realize commerce production.

  1. Catalytic reactions of synthesis gas. Part 2. Methanol carbonylation and homologation

    Energy Technology Data Exchange (ETDEWEB)

    Niemelae, M.

    1993-01-01

    The aim of the review is to evaluate the applicability of methanol hydrocarbonylation as a second test reaction to study the nondissociative activation of CO by heterogeneous rhodium and cobalt catalysts. The main emphasis in methanol (hydro)carbonylation chemistry has been on homogeneous reactions. These systems have been seen advantageous in selectivity, activity and ease of modification. The heterogenization attempts have been carried out to obtain easier separation of the catalyst and the product. The activity of cobalt, rhodium and other metals supported on different materials have been studied in heterogeneous methanol (hydro)carbonylation. The observed activities have been considerably influenced by the support. The most effective catalyst support has been activated carbon. Good carbonylation activities and selectivities have also been observed in conjunction with zeolite supports. The literature study indicates that the typical experimental conditions of methanol (hydro)carbonylation do not exceed the constructional and operational limits of the available reactor system, i.e. 500 C and 50 bar. The reaction is suitable for testing Co and Rh precursors, since both cobalt and rhodium compounds have shown carbonylation activity.

  2. Enhanced antioxidation and microwave absorbing properties of SiO2-coated flaky carbonyl iron particles

    Science.gov (United States)

    Zhou, Yingying; Xie, Hui; Zhou, Wancheng; Ren, Zhaowen

    2018-01-01

    SiO2 was successfully coated on the surface of flaky carbonyl iron particles using a chemical bath deposition method in the presence of 3-aminopropyl triethoxysilane (APTES). The morphologies, composition, valence states of elements, as well as antioxidation and electromagnetic properties of the samples were characterized by scanning electron microscope (SEM), energy dispersive spectrometer (EDS), X-ray photoelectron spectroscopy (XPS), thermogravimetric (TG) and microwave network analyzer. TG curve shows the obvious weight gain of carbonyl iron was deferred to 360 °C after SiO2-coated, which can be ascribed to the exits of SiO2 overlayer. Compared with the raw carbonyl iron, SiO2-coated sample shows good wave absorption performance due to its impedance matching. The electromagnetic properties of raw and SiO2-coated carbonyl iron particles were characterized in X band before and after heat treatment at 250 °C for 10 h. It was established that SiO2-coated carbonyl iron demonstrate good thermal stability, indicating SiO2-coating is useful in the usage of microwave absorbers operating at temperature up to 250 °C.

  3. Proteomic evaluation of myofibrillar carbonylation in chilled fish mince and its inhibition by catechin.

    Science.gov (United States)

    Pazos, Manuel; Maestre, Rodrigo; Gallardo, José M; Medina, Isabel

    2013-01-01

    The present study investigates the susceptibility of individual myofibrillar proteins from mackerel (Scomber scombrus) mince to undergo carbonylation reactions during chilled storage, and the antioxidant capacity of (+)-catechin to prevent oxidative processes of proteins. The carbonylation of each particular protein was quantified by combining the labelling of protein carbonyls by fluorescein-5-thiosemicarbazide (FTSC) with 1-D or 2-D gel electrophoresis. Alpha skeletal actin, glycogen phosphorylase, unnamed protein product (UNP) similar to enolase, pyruvate kinase, isoforms of creatine kinase, aldolase A and an isoform of glyceraldehyde 3-phosphate dehydrogenase (G3PDH) showed elevated oxidation in chilled non-supplemented mince. Myosin heavy chain (MHC) was not carbonylated in chilled muscle, but an extensive MHC degradation was observed in those samples. The supplementation of catechin reduced protein oxidation and lipid oxidation in a concentration-dependent manner: control>25>100≈200ppm. Therefore, the highest catechin concentrations (100 and 200ppm) exhibited the strongest antioxidant activity. Catechin (200ppm) reduced significantly carbonylation of protein spots identified as glycogen phosphorylase, pyruvate kinase muscle isozyme, isoforms of creatine kinase. Conversely, catechin was ineffective to inhibit the oxidation of actin and UNP similar to enolase. These results draw attention to the inefficiency of catechin to prevent actin oxidation, in contrast to the extremely high efficiency of catechin in inhibiting oxidation of lipids and other proteins. Copyright © 2012 Elsevier Ltd. All rights reserved.

  4. Optical chemical sensors for atmospheric pollutants based on nano porous materials: application to the formaldehyde and the other carbonyl compounds

    International Nuclear Information System (INIS)

    Paolacci, H.

    2006-12-01

    Formaldehyde, a well-identified indoor pollutant, was recently classified as carcinogenic. New regulations for the air quality are expected and therefore there is a need for low-cost sensors, sensitive and selective with a fast response time for the detection of formaldehyde at ppb level. In the present work, we had developed a chemical sensor based on nano-porous matrices doped with Fluoral-P and optical methods of detection. The nano-porous matrices, elaborated via the Sol-Gel process, display nano-pores whose cavity is tailored for the trapping of the targeted pollutant. They provide a first selectivity with the discrimination of the pollutants by their size. A second selectivity is obtained with a molecular probe, Fluoral-P, which reacts specifically with formaldehyde leading to the 3,5- di-acetyl-1,4-dihydro-lutidine (DDL). The kinetics of formation of DDL was studied as function of many parameters such as the concentration of Fluoral-P in the matrix, the pollutant content in gas mixture, the flow rate, the relative humidity of the gas mixtures and interference with other carbonylated compounds. The present chemical sensor can detect, via absorbance measurements, 2 ppb of formaldehyde within 30 min over a O to 60% relative humidity range. Moreover, to detect the total carbonylated compounds, we also explored the potentiality of a chemical sensor using, as a probe molecule, the 2'4-dinitro-phenyl-hydrazine which forms with these compounds the corresponding hydrazones derivatives. A patent was deposited for these two sensors. We have also developed a semi-miniaturized prototype for demonstration, using a flow cell, a miniaturized spectrophotometer, a light source and a lap-top. (author)

  5. Project management plan for Waste Area Grouping 5 Old Hydrofracture Facility tanks contents removal at Oak Ridge National Laboratory, Oak Ridge, Tennessee

    International Nuclear Information System (INIS)

    1998-02-01

    This revision (Rev. 1) updates the schedule and designation of responsibilities for the Old Hydrofracture Facility (OHF) tanks contents removal project. Ongoing and planned future activities include: cold testing of the sluicing and pumping system; readiness assessment; equipment relocation and assembly; isotopic dilution of fissile radionuclides; sluicing and transfer of the tanks contents; and preparation of the Removal Action Completion Report. The most significant change is that the sluicing and pumping system has been configured by and will be operated by CDM Federal Programs Corporation. In addition, a new technical lead and a new project analyst have been designated within Lockheed Martin Energy Systems, Inc. and Lockheed Martin Energy Research Corp. The schedule for tanks contents removal has been accelerated, with transfer of the final batch of tank slurry now scheduled for March 31, 1998 (instead of November 10, 1998). The OHF sluicing and pumping project is proceeding as a non-time-critical removal action under the Comprehensive Environmental Response, Compensation, and Liability Act. The purpose of the project is to remove the contents from five inactive underground storage tanks, designated T-1, T-2, T-3, T-4, and T-9. The tanks contain an estimated 52,700 gal of liquid and sludge, together comprising a radioactive inventory of approximately 30,000 Ci

  6. Identifying and Exploring Future Trends Impacting on Academic Libraries: A Mixed Methodology Using Journal Content Analysis, Focus Groups, and Trend Reports

    Science.gov (United States)

    Gwyer, Roisin

    2015-01-01

    This article compares three sources of information about academic libraries to consider what the future could hold and the skills needed to deliver effective services within that future. The starting point is the contents of "New Review of Academic Librarianship" (formerly "British Journal of Academic Librarianship") from 1986,…

  7. Influence of the Dielectric Medium on the Carbonyl Infrared Absorption Peak of Acetylferrocene

    Directory of Open Access Journals (Sweden)

    F. López-Linares

    2005-02-01

    Full Text Available The solvent effect on the position of the carbonyl vibrational stretching ofacetylferrocene in aprotic media was studied in this work. The solvent-induced shifts in thisorganometallic compound were interpreted in terms of the alternative reaction field model(SCRF-MO proposed by Kolling. In contrast to the established trends for carbonyl groupsin organic systems, the results suggest that the continuum models for the reaction field arenot adequate and that the influence of dipolarity-polarizability described by aninhomogeneous coupling function θ (ε L(n 2 that assumes optical dielectric saturation isresponsible for the carbonyl band shift and, there is empirical evidence that the effect offield-induced intermolecular interaction on band shift, interpreted in terms of the van derWaals forces from the solvent, have a important contribution to this phenomena.

  8. Coal and biomass-based chemicals via carbonylation, hydroformylation and homologation reactions

    Energy Technology Data Exchange (ETDEWEB)

    Sunavala, P.D.; Raghunath, B.

    The paper emphasizes the importance of carbonylation, hydroformylation and homologation reactions in the manufacture of organic chemicals (such as acetic acid, acetic anhydride, cellulose acetate, vinyl acetate monomer, aliphatic amines, isocyanates, methanol, ethanol, n-butanol, ethylene glycol, acrylic acid, etc.) from coal and biomass feedstocks. Topics covered are: synthesis of acetic acid; manufacture of acetic anhydride; synthesis of vinyl acetate monomer by carbonylation; synthesis of aliphatic amines by hydroformylation; synthesis of organic diisocyanates; ethanol synthesis by homologation of methanol; synthesis of ethylene glycol via hydroformylation of formaldehyde; synthesis of n- butanol and n-butyraldehyde by propylene formylation; synthesis of acrylic acid; homologation reaction of carboxylic acid esters with ruthenium catalysts; and synthesis of phenyl isocyanate from nitrobenzene by reductive carbonylation. 26 refs.

  9. Effect of carbonyl iron particles composition on the physical characteristics of MR grease

    Energy Technology Data Exchange (ETDEWEB)

    Mohamad, Norzilawati, E-mail: mnorzilawati@gmail.com; Mazlan, Saiful Amri, E-mail: amri.kl@utm.my [Vehicle System Engineering, Malaysia – Japan International Institute of Technology, Universiti Teknologi Malaysia, Jalan Sultan Yahya Petra (Jalan Semarak), Kuala Lumpur, 54000 (Malaysia); Ubaidillah, E-mail: ubaidillah@uns.ac.id [Vehicle System Engineering, Malaysia – Japan International Institute of Technology, Universiti Teknologi Malaysia, Jalan Sultan Yahya Petra (Jalan Semarak), Kuala Lumpur, 54000 (Malaysia); Mechanical Engineering Department, Faculty of Engineering, Universitas Sebelas Maret, Jl. Ir. Sutami 36A, Kentingan, Surakarta, 57126, Central Java, Surakarta (Indonesia)

    2016-03-29

    Magnetorheological (MR) grease is an extension of the study of magnetorheological materials. The MR grease can help to reduce the particles sedimentation problem occurred in the MR fluids. Within this study, an effort has been taken to investigate the effect of different weight compositions of carbonyl iron particles on the physical and chemical characteristics of the MR grease under off-state condition (no magnetic field). The MR grease is prepared by mixing carbonyl iron particles having a size range of 1 to 10 µm with commercial NPC Highrex HD-3 grease. Characterizations of MR grease are investigated using Vibrating Sample Magnetometer (VSM), Environmental Scanning Electron Microscopy (ESEM), Differential Scanning Calorimeter (DSC) and rheometer. The dependency of carbonyl iron particles weight towards the magnetic properties of MR grease and other characterizations are investigated.

  10. Stereoselective Carbonyl Olefination with Fluorosulfoximines: Facile Access to Z or E Terminal Monofluoroalkenes.

    Science.gov (United States)

    Liu, Qinghe; Shen, Xiao; Ni, Chuanfa; Hu, Jinbo

    2017-01-09

    Terminal monofluoroalkenes are important structural motifs in the design of bioactive compounds, such as homeostasis regulators and mechanism-based enzyme inhibitors. However, it is difficult to control the stereoselectivity of known carbonyl olefination reactions, and olefin metathesis is limited to disubstituted terminal monofluoroalkenes. Although sulfoximines have been used extensively in organic synthesis, reports on their use in carbonyl olefination reactions have not appeared to date. Herein, we report highly stereoselective carbonyl monofluoroolefination with a fluorosulfoximine reagent. The potential of this method is demonstrated by the synthesis of MDL 72161 and by the late-stage monofluoromethylenation of complex molecules, such as haloperidol and steroid derivatives. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. First application of supported ionic liquid phase (SILP) catalysis for continuous methanol carbonylation

    DEFF Research Database (Denmark)

    Riisager, Anders; Jørgensen, Betina; Wasserscheid, Peter

    2006-01-01

    A solid, silica-supported ionic liquid phase (SILP) rhodium iodide Monsanto-type catalyst system, [BMIM][Rh(CO)(2)I-2]-[BMIM]I -SiO2, exhibits excellent activity and selectivity towards acetyl products in fixed-bed, continuous gas-phase methanol carbonylation.......A solid, silica-supported ionic liquid phase (SILP) rhodium iodide Monsanto-type catalyst system, [BMIM][Rh(CO)(2)I-2]-[BMIM]I -SiO2, exhibits excellent activity and selectivity towards acetyl products in fixed-bed, continuous gas-phase methanol carbonylation....

  12. Reductive coupling of carbon monoxide in a rhenium carbonyl complex with pendant Lewis acids.

    Science.gov (United States)

    Miller, Alexander J M; Labinger, Jay A; Bercaw, John E

    2008-09-10

    Phosphinoborane ligands impart unique reactivity to a rhenium carbonyl cation relative to simple phosphine complexes. Addition of either triethylborohydride or a platinum hydride (that can be formed from H2) forms a rhenium boroxycarbene. This carbene, which crystallizes as a dimer, disproportionates over a period of days to afford the starting cation and a structurally unprecedented boroxy(boroxymethyl)carbene, in which a new C-C bond has been formed between two reduced CO ligands. This product of C-C bond formation can be independently synthesized by addition of 2 equiv of hydride to the rhenium carbonyl cation.

  13. Impaired cardiac SIRT1 activity by carbonyl stress contributes to aging-related ischemic intolerance.

    Directory of Open Access Journals (Sweden)

    Chunhu Gu

    Full Text Available Reactive aldehydes can initiate protein oxidative damage which may contribute to heart senescence. Sirtuin 1 (SIRT1 is considered to be a potential interventional target for I/R injury management in the elderly. We hypothesized that aldehyde mediated carbonyl stress increases susceptibility of aged hearts to ischemia/reperfusion (I/R injury, and elucidate the underlying mechanisms with a focus on SIRT1. Male C57BL/6 young (4-6 mo and aged (22-24 mo mice were subjected to myocardial I/R. Cardiac aldehyde dehydrogenase (ALDH2, SIRT1 activity and protein carbonyls were assessed. Our data revealed that aged heart exhibited increased endogenous aldehyde/carbonyl stress due to impaired ALDH2 activity concomitant with blunted SIRT1 activity (P<0.05. Exogenous toxic aldehydes (4-HNE exposure in isolated cardiomyocyte verified that aldehyde-induced carbonyl modification on SIRT1 impaired SIRT1 activity leading to worse hypoxia/reoxygenation (H/R injury, which could all be rescued by Alda-1 (ALDH2 activator (all P<0.05. However, SIRT1 inhibitor blocked the protective effect of Alda-1 on H/R cardiomyocyte. Interestingly, myocardial I/R leads to higher carbonylation but lower activity of SIRT1 in aged hearts than that seen in young hearts (P<0.05. The application of Alda-1 significantly reduced the carbonylation on SIRT1 and markedly improved the tolerance to in vivo I/R injury in aged hearts, but failed to protect Sirt1(+/- knockout mice against myocardial I/R injury. This was verified by Alda-1 treatment improved postischemic contractile function recovery in ex vivo perfused aged but not in Sirt1(+/- hearts. Thus, aldehyde/carbonyl stress is accelerated in aging heart. These results provide a new insight that impaired cardiac SIRT1 activity by carbonyl stress plays a critical role in the increased susceptibility of aged heart to I/R injury. ALDH2 activation can restore this aging-related myocardial ischemic intolerance.

  14. Dithioacetals as an Entry to Titanium-Alkylidene Chemistry: A New and Efficient Carbonyl Olefination.

    Science.gov (United States)

    Breit, Bernhard

    1998-03-02

    Wittig, Horner-Wadsworth-Emmons, Julia-Lythgoe, Tebbe, Grubbs, and Petasis-when it comes to carbonyl olefinations, these names are familiar to all chemistry students. In the future, the name Takeda will probably have to be added to this list. His recent work on the formation of titanium-alkylidene species from dithioacetals has provided organic chemists with a remarkable method for carbonyl olefination that is generally applicable under neutral to Lewis acidic conditions. © 1998 WILEY-VCH Verlag GmbH, Weinheim, Fed. Rep. of Germany.

  15. Influence of age and splanchnic nerve on the action of melatonin in the adrenomedullary catecholamine content and blood glucose level in the avian group.

    Science.gov (United States)

    Mahata, S K; Mandal, A; Ghosh, A

    1988-01-01

    A single intraperitoneal (IP) melatonin injection (0.5 mg/100 g body wt.) caused an increase in norepinephrine (NE) fluorescence and elevation of NE content in newly-hatched pigeons (Columba livia), but a reduction of NE fluorescence and depletion of NE content in the adrenal medulla of newly-hatched crows (Corvus splendens) after 0.5 h of treatment. In contrast, in adults melatonin caused increase in NE fluorescence and elevation of NE content only in the parakeet (Psittacula krameri). Half an hour of IP melatonin treatment (0.5 mg/100 g body wt.) induced release of epinephrine (E) from the adrenal medulla of newly-hatched pigeon and parakeet. In contrast, in the adults melatonin caused more than a two-fold increase in E in the pigeon, and a significant increase in the crow. Single IP melatonin injection (0.5 mg/100 g body wt.) caused hypoglycemia in the newly-hatched parakeet and adult pigeon, and hyperglycemia in newly-hatched pigeon after 0.5 h of treatment. Melatonin failed to regulate glucose homoeostasis in newly-hatched and adult crow. Splanchnic denervation of the left adrenal gland was performed in the adult pigeon. The right adrenal served as the innervated gland. Melatonin-induced modulation of catecholamines following a single IP injection (0.5 mg/100 g body wt.) revealed significant increases in NE fluorescence and NE content at 4 and 12 h after treatment in the denervated gland only, which gradually approached normal levels 9 days after treatment.(ABSTRACT TRUNCATED AT 250 WORDS)

  16. Soil emission and uptake of carbonyl sulfide at a temperate mountain grassland

    Science.gov (United States)

    Kitz, Florian; Hammerle, Albin; Laterza, Tamara; Spielmann, Felix M.; Wohlfahrt, Georg

    2016-04-01

    Flux partitioning, i.e. inferring gross primary productivity (GPP) and ecosystem respiration from the measured net ecosystem carbon dioxide (CO2) exchange, is one uncertainty in modelling the carbon cycle and in times where robust models are needed to assess future global changes a persistent problem. A promising new approach is to derive GPP by measuring carbonyl sulfide (COS), the most abundant sulfur-containing trace gas in the atmosphere, with a mean concentration of about 500 pptv in the troposphere. This is possible because COS and CO2 enter the leaf via a similar pathway and are processed by the same enzyme (carbonic anhydrase). A prerequisite to use COS as a proxy for canopy photosynthesis is a robust estimation of COS sources and sinks in an ecosystem. Past studies described soils either as a sink or source, depending on properties like soil temperature and soil water content. The main aim of this study was to quantify the soil COS exchange and its drivers of a temperate mountain grassland in order to aid the use of COS as tracer for canopy CO2 and water vapor exchange. We conducted a field campaign with a Quantum cascade laser at a temperate mountain grassland to estimate the soil COS fluxes under ambient conditions and while simulating a drought. We used self-built fused silica (i.e. light-transparent) soil chambers to avoid COS emissions from built-in materials and to assess the impact of radiation. Vegetation was removed within the chambers, therefor more radiation reached the soil surface compared to natural conditions. This might be the reason for highly positive fluxes during daytime more similar to agricultural study sites. To further investigate this large soil COS source we conducted within canopy concentration measurements near the soil surface and still recorded fluxes confirming the soil as a COS source during daytime. Results from the drought experiment suggested a strong impact of incoming radiation on soil COS fluxes followed by soil

  17. Probing the Carbonyl Functionality of a Petroleum Resin and Asphaltene through Oximation and Schiff Base Formation in Conjunction with N-15 NMR.

    Directory of Open Access Journals (Sweden)

    Kevin A Thorn

    Full Text Available Despite recent advances in spectroscopic techniques, there is uncertainty regarding the nature of the carbonyl groups in the asphaltene and resin fractions of crude oil, information necessary for an understanding of the physical properties and environmental fate of these materials. Carbonyl and hydroxyl group functionalities are not observed in natural abundance 13C nuclear magnetic resonance (NMR spectra of asphaltenes and resins and therefore require spin labeling techniques for detection. In this study, the carbonyl functionalities of the resin and asphaltene fractions from a light aliphatic crude oil that is the source of groundwater contamination at the long term USGS study site near Bemidji, Minnesota, have been examined through reaction with 15N-labeled hydroxylamine and aniline in conjunction with analysis by solid and liquid state 15N NMR. Ketone groups were revealed through 15N NMR detection of their oxime and Schiff base derivatives, and esters through their hydroxamic acid derivatives. Anilinohydroquinone adducts provided evidence for quinones. Some possible configurations of the ketone groups in the resin and asphaltene fractions can be inferred from a consideration of the likely reactions that lead to heterocyclic condensation products with aniline and to the Beckmann reaction products from the initially formed oximes. These include aromatic ketones and ketones adjacent to quaternary carbon centers, β-hydroxyketones, β-diketones, and β-ketoesters. In a solid state cross polarization/magic angle spinning (CP/MAS 15N NMR spectrum recorded on the underivatized asphaltene as a control, carbazole and pyrrole-like nitrogens were the major naturally abundant nitrogens detected.

  18. Probing the carbonyl functionality of a petroleum resin and asphaltene through oximation and schiff base formation in conjunction with N-15 NMR

    Science.gov (United States)

    Thorn, Kevin A.; Cox, Larry G.

    2015-01-01

    Despite recent advances in spectroscopic techniques, there is uncertainty regarding the nature of the carbonyl groups in the asphaltene and resin fractions of crude oil, information necessary for an understanding of the physical properties and environmental fate of these materials. Carbonyl and hydroxyl group functionalities are not observed in natural abundance 13C nuclear magnetic resonance (NMR) spectra of asphaltenes and resins and therefore require spin labeling techniques for detection. In this study, the carbonyl functionalities of the resin and asphaltene fractions from a light aliphatic crude oil that is the source of groundwater contamination at the long term USGS study site near Bemidji, Minnesota, have been examined through reaction with 15N-labeled hydroxylamine and aniline in conjunction with analysis by solid and liquid state 15N NMR. Ketone groups were revealed through 15N NMR detection of their oxime and Schiff base derivatives, and esters through their hydroxamic acid derivatives. Anilinohydroquinone adducts provided evidence for quinones. Some possible configurations of the ketone groups in the resin and asphaltene fractions can be inferred from a consideration of the likely reactions that lead to heterocyclic condensation products with aniline and to the Beckmann reaction products from the initially formed oximes. These include aromatic ketones and ketones adjacent to quaternary carbon centers, β-hydroxyketones, β-diketones, and β-ketoesters. In a solid state cross polarization/magic angle spinning (CP/MAS) 15N NMR spectrum recorded on the underivatized asphaltene as a control, carbazole and pyrrole-like nitrogens were the major naturally abundant nitrogens detected.

  19. Short Intramolecular N–H⋯C(carbonyl Interactions in Mixed-Ligand Molybdenum Hexacarbonyl Derivatives

    Directory of Open Access Journals (Sweden)

    Matthew G. Budge

    2011-06-01

    Full Text Available The syntheses and single-crystal structures of Mo(CO3(phen(dipy (1, Mo(CO3(biquin(dipy (2 and Mo(CO3(dpme(dipy (3, (phen = 1,10-phenanthroline, C12H8N2; dipy = 2,2'-dipyridylamine, C10H9N3; biquin = 2,2'-biquinoline, C18H12N2; dpme = 2,2'-dipyridylmethane, C11H10N2 are described. In each case, distorted fac-MoC3N3 octahedral coordination geometries arise for the metal atoms. Short intramolecular N–H…C interactions from the dipy N–H group to a carbonyl carbon atom occur in each structure. Crystal data: 1 (C25H17MoN5O3, Mr = 531.38, monoclinic, P21/n (No. 14, Z = 4, a = 11.0965 (5 Å, b = 13.0586 (6 Å, c = 16.6138 (8 Å, b = 108.324 (1°, V = 2285.31 (18 Å3, R(F = 0.035, wR(F2 = 0.070. 2 (C31H21MoN5O3, Mr = 607.47, monoclinic, P21/n (No. 14, Z = 4, a = 11.4788 (6 Å, b = 19.073 (1 Å, c = 11.9881 (6 Å, b = 95.179 (1°, V = 2613.9 (2 Å3, R(F = 0.030, wR(F2 = 0.076. 3 (C24H19MoN5O3, Mr = 521.38, monoclinic, P21/n (No. 14, Z = 4, a = 8.4222 (3 Å, b = 21.5966 (9 Å, c = 12.5011 (5 Å, b = 94.065 (1°, V = 2268.12 (15 Å3, R(F = 0.025, wR(F2 = 0.065.

  20. Ketene as a Reaction Intermediate in the Carbonylation of Dimethyl Ether to Methyl Acetate over Mordenite

    DEFF Research Database (Denmark)

    Rasmussen, Dominik Bjørn; Christensen, Jakob Munkholt; Temel, Burcin

    2015-01-01

    Unprecedented insight into the carbonylation of dimethyl ether over Mordenite is provided through the identification of ketene (CH2CO) as a reaction intermediate. The formation of ketene is predicted by detailed DFT calculations and verified experimentally by the observation of doubly deuterated ...

  1. Determination of protein carbonyls in plasma, cell extracts, tissue homogenates, isolated proteins

    DEFF Research Database (Denmark)

    Weber, Daniela; Davies, Michael J.; Grune, Tilman

    2015-01-01

    Protein oxidation is involved in regulatory physiological events as well as in damage to tissues and is thought to play a key role in the pathophysiology of diseases and in the aging process. Protein-bound carbonyls represent a marker of global protein oxidation, as they are generated by multiple...

  2. Femtosecond Fluorescence and Intersystem Crossing in Rhenium(I) Carbonyl-Bipyridine Complexes

    Czech Academy of Sciences Publication Activity Database

    Cannizzo, A.; Blanco-Rodríguez, A. M.; Nahhas, A. E.; Šebera, Jakub; Záliš, Stanislav; Vlček, Antonín; Chergui, M.

    2008-01-01

    Roč. 130, č. 28 (2008), s. 8967-8974 ISSN 0002-7863 R&D Projects: GA MŠk 1P05OC068 Institutional research plan: CEZ:AV0Z40400503 Keywords : rhenium(I) * carbonyl-bipyridine * intersystem crossing Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 8.091, year: 2008

  3. Formation and emissions of carbonyls during and following gas-phase ozonation of indoor materials

    DEFF Research Database (Denmark)

    Poppendieck, D.G.; Hubbard, H.F.; Weschler, Charles J.

    2007-01-01

    at concentrations of 1000 ppm in the inlet stream of experimental chambers. Fifteen target carbonyls were selected and measured as building ozonation by-products (BOBPs). During the 36 h that include the 16 h ozonation and 20 h persistence phase, the total BOBP mass released from flooring and wall coverings ranged...

  4. First application of supported ionic liquid phase (SILP) catalysis for continuous methanol carbonylation.

    Science.gov (United States)

    Riisager, Anders; Jørgensen, Betina; Wasserscheid, Peter; Fehrmann, Rasmus

    2006-03-07

    A solid, silica-supported ionic liquid phase (SILP) rhodium iodide Monsanto-type catalyst system, [BMIM][Rh(CO)2I2]-[BMIM]I-SiO2, exhibits excellent activity and selectivity towards acetyl products in fixed-bed, continuous gas-phase methanol carbonylation.

  5. Unsuitability of using the DNPH-coated solid sorbent cartridge for determination of airborne unsaturated carbonyls

    Science.gov (United States)

    Ho, Steven Sai Hang; Ho, K. F.; Liu, W. D.; Lee, S. C.; Dai, W. T.; Cao, J. J.; Ip, H. S. S.

    2011-01-01

    Measurements of aldehydes and ketones are typically conducted by derivatization using sorbent cartridges coated with 2,4-dinitrophenylhydrazine (DNPH). The collected samples are eluted with acetonitrile and analyzed by high-pressure liquid chromatography coupled with an ultra-violet detector (HPLC/UV). This paper intends to examine artifacts about its suitability in identification of unsaturated carbonyls. Kinetic tests for acrolein, crotonaldehyde, methacrolein and methyl vinyl ketone (MVK) showed formations of carbonyl-DNP-hydrazone during sampling, which could further react with DNPH, resulting in undesired UV absorption products [e.g., carbonyl-DNP-hydrazone-DNPH (dimer) and 2(carbonyl-DNP-hydrazone)-DNPH (trimer)]. The dimerization and trimerization occurred for acrolein and MVK whereas only dimerization for crotonaldehyde and methacrolein. The polymerization products undoubtedly affect the integrity of the chromatogram, leading to misidentification and inaccurate quantification. Whether precautions taken during sampling and/or sample treatment could avoid or minimize this artifact has not been thoughtfully investigated. More often, such artifacts are usually overlooked by scientists when the data are reported.

  6. Antioxidative potential of Perna viridis and its protective role against ROS induced lipidperoxidation and protein carbonyl

    Digital Repository Service at National Institute of Oceanography (India)

    Jena, K.B.; Jagtap, T.G.; Verlecar, X.N.

    ) such as hydrogen peroxide (H2O2) and hydroxyl radical (OH•), and inhibition of lipid peroxidation (LPX) and protein carbonyl (PC). The scavenging activity of DPPH radical, H sub(2) O sub(2) and OH• radicals increased in dose dependent manner. The reducing power...

  7. Magnetically Recoverable Supported Ruthenium Catalyst for Hydrogenation of Alkynes and Transfer Hydrogenation of Carbonyl Compounds

    Science.gov (United States)

    A ruthenium (Ru) catalyst supported on magnetic nanoparticles (NiFe2O4) has been successfully synthesized and used for hydrogenation of alkynes at room temperature as well as transfer hydrogenation of a number of carbonyl compounds under microwave irradiation conditions. The cata...

  8. [1,3-Bis(diphenyl-phosphino)pentane-κP,P']tetra-carbonyl-chromium(0).

    Science.gov (United States)

    Shawkataly, Omar Bin; Thangadurai, Daniel T; Pankhi, Mohd Aslam A; Shahinoor Dulal Islam, S M; Fun, Hoong-Kun

    2009-02-04

    In the title compound, [Cr(C(29)H(30)P(2))(CO)(4)], the Cr atom is octa-hedrally coordinated by four carbonyl ligands and one bidentate phosphine ligand, which is bounded as a chelate in a cis position. The average Cr-P and Cr-C bond lengths are 2.377 and 1.865 Å, respectively.

  9. Mechanism of stimulation of endogenous fermentation in yeast by carbonyl cyanide m-chlorophenylhydrazone

    NARCIS (Netherlands)

    Noshiro, A.; Purwin, C.; Laux, M.; Nicolaij, K.; Scheffers, W.A.; Holzer, H.

    1987-01-01

    Addition of the uncoupler and protonophore carbonyl cyanide m-chlorophenylhydrazone (CCCP) to starved yeast cells starts endogenous alcoholic fermentation lasting about 20 min. Hexose 6-phosphates, fructose 2,6-bisphosphate, and pyruvate accumulate in less than 2 min after addition of CCCP from

  10. Iron Dextran treatment does not induce serum protein carbonyls in the newborn pig

    Science.gov (United States)

    Oxidation of serum proteins can lead to carbonyl formation which alters their function and is often associated with stress-related diseases. Since it is recommended that all pigs reared in modern production facilities be given supplemental iron at birth to prevent anemia, and metals can catalyze th...

  11. Effect of carotenoid structure on excited-state dynamics of carbonyl carotenoids

    Czech Academy of Sciences Publication Activity Database

    Chábera, P.; Fuciman, M.; Hříbek, P.; Polívka, Tomáš

    2009-01-01

    Roč. 11, - (2009), s. 8795-8703 ISSN 1463-9076 R&D Projects: GA AV ČR IAA608170604 Institutional research plan: CEZ:AV0Z50510513 Keywords : excited-state dynamics * carbonyl carotenoids * femtosecond spectroscopy Subject RIV: BO - Biophysics Impact factor: 4.116, year: 2009

  12. Ruthenium(II) carbonyl compounds with the 4'-chloro-2,2':6',2''-terpyridine ligand.

    Science.gov (United States)

    Tatikonda, Rajendhraprasad; Haukka, Matti

    2017-04-01

    Two ruthenium carbonyl complexes with the 4'-chloro-2,2':6',2''-terpyridine ligand (tpy-Cl, C 15 H 10 ClN 3 ), i.e. [RuCl(tpy-Cl)(CO) 2 ][RuCl 3 (CO) 3 ] (I) [systematic name: cis -di-carbonyl-chlorido(4'-chloro-2,2':6',2''-terpyridine-κ 3 N )ruthenium(II) fac -tricarbonyltri-chlorido-ruthenate(II)], and [RuCl 2 (tpy-Cl)(CO) 2 ] (II) [ cis -dicarbonyl- trans -di-chlorido(4'-chloro-2,2':6',2''-terpyridine-κ 2 N 1 , N 1' )ruthenium(II)], were synthesized and characterized by single-crystal X-ray diffraction. The Ru II atoms in both centrosymmetric structures (I) and (II) display similar, slightly distorted octa-hedral coordination spheres. The coordination sphere in the complex cation in compound (I) is defined by three N atoms of the tridentate tpy-Cl ligand, two carbonyl carbon atoms and one chlorido ligand; the charge is balanced by an octa-hedral [Ru(CO) 3 Cl 3 ] - counter-anion. In the neutral compound (II), the tpy-Cl ligand coordinates to the metal only through two of its N atoms. The coordination sphere of the Ru II atom is completed by two carbonyl and two chlorido ligands. In the crystal structures of both (I) and (II), weak C-H⋯Cl inter-actions are observed.

  13. [Association between carbonyl proteins and tumor necrosis factor alpha with muscle strength in young and older women: exploratory study].

    Science.gov (United States)

    Martínez Huenchullán, Sergio Francisco; Mancilla Solorza, Eladio Bernabé

    2015-01-01

    It has recently been proposed that there is a close relationship between oxidative stress and low-grade chronic inflammation. Both processes have been related separately to muscle function in older adults (OA). Nevertheless, it still has not been determined if this relationship is present particularly in OA. The objective of this study was to determine the relationship between the plasma levels of TNF-α and carbonyl proteins (CP) and muscle strength in a group of young and older women. An exploratory study was conducted on 13 older and 8 young women, in whom the plasma levels of CP and TNF-α were measured. Muscle strength was measured by handgrip test, quadriceps voluntary maximal isometric strength, arm curl, and the 30 second sit to stand test. There were no differences in the plasma levels of CP and TNF-α between the groups, but there was relationship between the biomarkers only in the OA group. A non-linear relationship was observed between CP and quadriceps voluntary maximal isometric strength only in the OA group (R(2)=36.2; P=.038). For TNF-α there were no significant association with any of the applied tests. There is an association between CP and quadriceps voluntary maximal isometric strength only in the OA group, which could indicate a deleterious action of oxidative stress on muscle function, particularly in aging. Copyright © 2015 SEGG. Published by Elsevier Espana. All rights reserved.

  14. Project management plan for Waste Area Grouping 5 Old Hydrofracture Facility tanks contents removal at Oak Ridge National Laboratory, Oak Ridge, Tennessee

    International Nuclear Information System (INIS)

    1998-06-01

    On January 1, 1992, the US Department of Energy (DOE), the US Environmental Protection Agency (EPA) Region IV, and the Tennessee Department of Environment and Conservation (TDEC) signed a Federal Facility Agreement (FFA) concerning the Oak Ridge Reservation. The FFA requires that inactive liquid low-level (radioactive) waste (LLLW) tanks at Oak Ridge National Laboratory (ORNL) be remediated in accordance with requirements of the Comprehensive Environmental Response, Compensation, and Liability Act (CERCLA). This revision is to update the schedule and designation of responsibilities for the Old Hydrofracture Facility (OHF) tanks contents removal project. The scope of this project is to transfer inventory from the five inactive LLLW tanks at the OHF into the active LLLW system

  15. Preliminary engineering report waste area grouping 5, Old Hydrofracture Facility Tanks content removal project, Oak Ridge National Laboratory, Oak Ridge, Tennessee

    International Nuclear Information System (INIS)

    1996-06-01

    The Superfund Amendments and Reauthorization Act of the Comprehensive Environmental Response, Compensation, and Liability Act (CERCLA) requires a Federal Facilities Agreement (FFA) for federal facilities placed on the National Priorities List. The Oak Ridge Reservation was placed on that list on December 21, 1989, and the agreement was signed in November 1991 by the U.S. Department of Energy (DOE) Oak Ridge Operations Office, the U.S. Environmental Protection Agency (EPA) Region IV, and the Tennessee Department of Environment and Conservation (TDEC). The effective date of the FFA is January 1, 1992. One objective of the FFA is to ensure that liquid low-level waste (LLLW) tanks that are removed from service are evaluated and remediated through the CERCLA process. Five inactive LLLW tanks, designated T-1, T-2, T-3, T-4, and T-9, located at the Old Hydrofracture (OHF) Facility in the Melton Valley area of Oak Ridge National Laboratory (ORNL) have been evaluated and are now entering the remediation phase. As a precursor to final remediation, this project will remove the current liquid and sludge contents of each of the five tanks (System Requirements Document, Appendix A). It was concluded in the Engineering Evaluation/Cost Analysis [EE/CA] for the Old Hydrofracture Facility Tanks (DOE 1996) that sluicing and pumping the contaminated liquid and sludge from the five OHF tanks was the preferred removal action. Evaluation indicated that this alternative meets the removal action objective and can be effective, implementable, and cost-effective. Sluicing and removing the tank contents was selected because this action uses (1) applicable experience, (2) the latest information about technologies and techniques for removing the wastes from the tanks, and (3) activities that are currently acceptable for storage of transuranic (TRU) mixed waste

  16. Gas-phase chemistry of Mo, Ru, W, and Os metal carbonyl complexes

    International Nuclear Information System (INIS)

    Wang, Y.; Qin, Z.; Fan, F.L.

    2014-01-01

    Metal carbonyl complexes were used for studying the gas-phase chemical behavior of Mo, Ru, W and Os isotopes with an on-line low temperature isothermal gas chromatography apparatus. Short-lived Mo and Ru isotopes were produced by a 252 Cf spontaneous fission source. Short-lived nuclides of W and Os were produced using the heavy ion reactions 19 F + 159 Tb and 165 Ho, respectively. Short-lived products were thermalized in a recoil chamber filled with a gas mixture of helium and carbon monoxide. The carbonyls formed were then transported through capillaries to an isothermal chromatography column for study of the adsorption behavior as a function of temperature. On-line isothermal chromatography (IC) experiments on Teflon (PTFE) and quartz surfaces showed that short-lived isotopes of the listed elements can form carbonyl complexes which are very volatile and interact most likely in physical sorption processes. Deduced adsorption enthalpies of Mo and Ru carbonyls were -38 ± 2 kJ/mol and -36 ± 2 kJ/mol, respectively. These values are in good agreement with literature data, partly obtained with different chromatographic techniques. A validation of the applied Monte Carlo model to deduce adsorption enthalpies with Mo isotopes of different half-lives proved the validity of the underlying adsorption model. The investigations using a gas-jet system coupled to a heavy ion accelerator without any preseparator clearly showed the limitations of the approach. The He and CO gas mixture, which was directly added into the chamber, will result in decomposition of CO gas and produce some aerosol particles. After the experiment of 173 W and 179 Os in the heavy ion experiments, the Teflon column was covered by a yellowish deposit; the adsorption enthalpy of W and Os carbonyls could therefore not be properly deduced using Monte Carlo simulations. (orig.)

  17. Boys to Men: Entertainment Media. Messages about Masculinity: A National Poll of Children, Focus Groups, and Content Analysis of Entertainment Media.

    Science.gov (United States)

    Heintz-Knowles, Katharine; Li-Vollmer, Meredith; Chen, Perry; Harris, Tarana; Haufler, Adrienne; Lapp, Joan; Miller, Patti

    Boys are especially active users of media, and researchers have suggested that the cumulative impact of media, such as television, movies, and music videos, may make them some of the most influential forces in boys' lives. This report presents the findings of a national poll of 1,200 young people (ages 10 to 17) and focus groups in which boys…

  18. Characterisation of the appearance of radioactive metabolites in monkey and human plasma from the 5-HT1A receptor radioligand, [carbonyl-11C]WAY-100635 - explanation of high signal contrast in PET and an aid to biomathematical modelling

    International Nuclear Information System (INIS)

    Osman, Safiye; Lundkvist, Camilla; Pike, Victor W.; Halldin, Christer; McCarron, Julie A.; Swahn, Carl-Gunnar; Farde, Lars; Ginovart, Nathalie; Luthra, Sajinder K.; Gunn, Roger N.; Bench, Christopher J.; Sargent, Peter A.; Grasby, Paul M.

    1998-01-01

    N-(2-(4-(2-Methoxy-phenyl)-1-piperazin-1-yl)ethyl)-N-(2-pyridyl) cyclohexanecarboxamide (WAY-100635), labelled in its amido carbonyl group with 11 C (t 1/2 = 20.4 min), is a promising radioligand for the study of brain 5-HT 1A receptors with positron emission tomography (PET). Thus, in PET experiments in six cynomolgus monkeys and seven healthy male volunteers, [carbonyl- 11 C]WAY-100635 was taken up avidly by brain. Radioactivity was retained in regions rich in 5-HT 1A receptors, such as occipital cortex, temporal cortex and raphe nuclei, but cleared rapidly from cerebellum, a region almost devoid of 5-HT 1A receptors. [Carbonyl- 11 C]WAY-100635 provides about 3- and 10-fold higher signal contrast (receptor-specific to nonspecific binding) than [O-methyl- 11 C]WAY-100635 in receptor-rich areas of monkey and human brain, respectively. To elucidate the effect of label position on radioligand behaviour and to aid in the future biomathematical interpretation of the kinetics of regional cerebral radioactivity uptake in terms of receptor-binding parameters, HPLC was used to measure [carbonyl- 11 C]WAY-100635 and its radioactive metabolites in plasma at various times after intravenous injection. Radioactivity cleared rapidly from monkey and human plasma. Parent radioligand represented 19% of the radioactivity in monkey plasma at 47 min and 8% of the radioactivity in human plasma at 40 min. [Carbonyl- 11 C]desmethyl-WAY-100635 was below detectable limits in monkey plasma and at most a very minor radioactive metabolite in human plasma. [ 11 C]Cyclohexanecarboxylic acid was identified as a significant radioactive metabolite. In human plasma this maximally represented 21% of the radioactivity at 10 min after radioligand injection. All other major radioactive metabolites in monkey and human plasma were even more polar. No-carrier-added [carbonyl- 11 C]cyclohexanecarboxylic acid was prepared in the laboratory and after intravenous administration into cynomolgus monkey was

  19. Two-step milling on the carbonyl iron particles and optimizing on the composite absorption

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Yonggang, E-mail: xuyonggang221@163.com [Science and Technology on Electromagnetic Scattering Laboratory, Shanghai 200438 (China); Yuan, Liming; Wang, Xiaobing [Science and Technology on Electromagnetic Scattering Laboratory, Shanghai 200438 (China); Zhang, Deyuan [Bionic and Micro/Nano/Bio Manufacturing Technology Research Center, School of Mechanical Engineering and Automation, Beihang University, Beijing 100191 (China)

    2016-08-15

    The flaky carbonyl iron particles (CIPs) were prepared using a two-step milling process. The surface morphology was characterized by the scanning electron microscopy, the static magnetic property was evaluated on a vibrating sample magnetometer and X-ray diffraction (XRD) patterns were done to analyze the particle crystal grain structure. The complex permittivity and permeability were measured using a vector network analyzer in the frequency range of 2–18 GHz. Then Hermite interpolation based on the calculated scattering parameters of the tested composite was used to derive the permittivity and permeability of the composite with random volume content. The results showed that the saturation magnetization value of the flaky CIPs decreased as the CIPs was changed to the flakes by high and low speeding milling. The diffraction peaks of the single α-Fe existed in the XRD pattern of CIPs, and the characteristic peaks was broad and the intensity of the diffraction pattern was lower as the high-speeding milling time increased. The sample H2L20 had the largest particle size, the average diameter was 8.64 μm, the thickness was 0.59 μm according to the fitted aspect ratio 14.65. The derived permittivity and permeability using the Hermite interpolation was accurate compared with the tested result, the deviation was about 0.39 + j0.45 and 2.5 + j0.51. Finally, the genetic algorithm was used to optimize the thickness of the CIPs composite of a wide absorbing band of 8–18 GHz. The optimized reflection loss (RL) result showed that the absorbing composites with thickness 1.47 mm had an excellent absorbing property (RL < −10 dB) in 8–18 GHz. - Graphical abstract: The property of absorber added two speeding milling CIPs could be enhanced using the genetic algorithm. - Highlights: • Flaky CIPs were prepared using a two-step milling process. • The permeability increased during the low speeding milling. • The aspect ratio of flaky CIPs increased in the optimized process

  20. 50 Hz electric field effects on protein carbonyl (PCO), heme oxygenase-1 (HO-1) and hydroxyproline levels

    International Nuclear Information System (INIS)

    Ozgur, Elcin; Goknur, Guler; Seyhan, Nesrin

    2008-01-01

    Full text: Non-ionizing electromagnetic field (EMF) radiation sources, such as power lines and other Extremely Low Frequency (ELF) sources have become one of the most ubiquitous components of the spectrum of the human environment, and the possibility that they may have hazardous effects on human health is a major a public concern. Although it is well documented that EMFs have biological effects, the degree to which these exposures constitute a human health hazard is not clear yet. Today relation between production of oxidative stress resulted by reactive oxygen species and electrical stimulus, also the protective effects of antioxidant treatments are mentioned in many researches. In this study, it was aimed to determine both oxidation of proteins and protein collagen levels under 50 Hz 12 kV/m vertical Electric (E) Field exposure and the N-Acetylcysteine (NAC) administration which is a well-known antioxidant. To this end, protein carbonyl levels (PCO) as bio-markers of oxidative stress and Heme oxygenase-1 (HO-1), an enzyme that catalyzes the degradation of heme analyzed to figure out the protein oxidation. Hydroxyproline level, a major component of the protein collagen was measured in order to express the level of collagen in lung tissue. Guinea pigs, weighted 250-300 g, were used in the study. A total forty male guinea pigs were randomly divided into four groups which are composed of 10 guinea pigs each for groups: 1) Group I (Sham); 2) Group II (NAC-administrated group); 3) Group III (E Field Exposure group); 4) Group IV (NAC administrated + E Field exposed group). One week exposure period for 8 hours per daily was conducted for each exposure groups (Group III, Group IV ). The electric field exposure period was from 9 a.m. to 5 p.m. After the last exposure day, the guinea pigs were anesthetized by the injection of ketamine and xylazine. The guinea pigs were killed by decapitation. Statistical analyses were carried out using SPSS software (SPSS 11.5 for windows

  1. Utilization in rats of 14C-L-lysine-labeled casein browned by amino-carbonyl reaction

    International Nuclear Information System (INIS)

    Mori, Bunpei; Nakatsuji, Hirotaka.

    1977-01-01

    The investigation was carried out in order to elucidate the reason for the reduction in nutritive value of browned protein, by using labeled casein as a model protein. Goat casein preparation in which lysine residues had been labeled with 14 C was browned by amino-carbonyl reaction with glucose at 37 0 C. Browned or non-browned casein was ingested by growing rats by spaced feeding. When the rats ingested the browned casein the experimental group, higher radioactivity was found in TCA-soluble fraction in the small intestine as compared with that in the control group, while radioactivity was scarecely found in feces for 22 hr. Along with absorption delay, considerably high radioactivity was found in urine. The recovery of radioactivity in expired air of rats fed the labeled casein (browned and non-browned) was measured. In the experimental group, expired 14 CO 2 came out slower than the control group. From these results, it is suggested that the main reason for the reduction in nutritive value by browning reaction may be the formation of a lysine derivative in a protein, which remains in the small intestinal lumen as an absorption-delayed material and is finally excreted in urine. (auth.)

  2. Protein carbonyl: An oxidative stress marker in gingival crevicular fluid in healthy, gingivitis, and chronic periodontitis subjects

    Directory of Open Access Journals (Sweden)

    Avani R Pradeep

    2013-01-01

    Full Text Available Background: A defined role for reactive oxygen species (ROS in the tissue destruction that characterizes periodontitis has been described. Protein carbonyl (PC is the most widely used biomarker for oxidative damage to proteins, and reflects cellular damage induced by multiple forms of ROS. The purpose of this study is to determine the presence of PC in gingival crevicular fluid (GCF in healthy, gingivitis, and chronic periodontitis (CP subjects and to find an association, if any. Materials and Methods: A total number of 75 subjects (38 males and 37 females were selected based on their clinical parameters into three groups: Group 1 (25 healthy subjects, Group 2 (25 gingivitis subjects, and Group 3 (25 CP subjects. GCF samples were collected to estimate the levels of PC. Results: The PC concentration in GCF was highest in subjects with CP as compared to gingivitis and healthy subjects and a significant association was observed between GCF PC levels and all periodontal parameters. Conclusion: There was an increase in PC levels in GCF as the disease process progressed from healthy to gingivitis and CP, suggesting a role for increased oxidative stress in CP.

  3. Immunological characterisation of groups of people exposed to beryllium as a result of burning coal with high contents of this toxin

    International Nuclear Information System (INIS)

    Bencko, V.; Vasilieva, E.V.; Tichy, V.; Konopikova, L.; Horecka, J.; Symon, K.

    1990-01-01

    An epidemological study was made of persons occupationally (39) and non-occupationally (34) exposed to relatively low concentrations of beryllium in air as a result of coal combustion. Beryllium concentrations in the workplace were between 30 and 800x10 -5 mg.m -3 , and in the town of Sokolov 1.68-0.39x10 -5 mg.m -3 . Radial immunodiffusion was used to determine main immunoglobulin classes, and the passive haemagglutination reaction used to determine antibodies (lungs, heart, liver, spleen, thyroid) and antibodies to nuclear (ANA) and mitochondrial (AMA) antigens in intact rat lungs and rats with experimental berylliosis. In both exposed groups significant increase in IgG and IgA and autoantibodies was found compared with controls (60). Specific AMA and ANA were found in exposed groups (higher values in women). (UK)

  4. A promising method for identifying cross-cultural differences in patient perspective: the use of Internet-based focus groups for content validation of new patient reported outcome assessments.

    Science.gov (United States)

    Atkinson, Mark J; Lohs, Jan; Kuhagen, Ilka; Kaufman, Julie; Bhaidani, Shamsu

    2006-09-22

    This proof of concept (POC) study was designed to evaluate the use of an Internet-based bulletin board technology to aid parallel cross-cultural development of thematic content for a new set of patient-reported outcome measures (PROs). The POC study, conducted in Germany and the United States, utilized Internet Focus Groups (IFGs) to assure the validity of new PRO items across the two cultures--all items were designed to assess the impact of excess facial oil on individuals' lives. The on-line IFG activities were modeled after traditional face-to-face focus groups and organized by a common 'Topic' Guide designed with input from thought leaders in dermatology and health outcomes research. The two sets of IFGs were professionally moderated in the native language of each country. IFG moderators coded the thematic content of transcripts, and a frequency analysis of code endorsement was used to identify areas of content similarity and difference between the two countries. Based on this information, draft PRO items were designed and a majority (80%) of the original participants returned to rate the relative importance of the newly designed questions. The use of parallel cross-cultural content analysis of IFG transcripts permitted identification of the major content themes in each country as well as exploration of the possible reasons for any observed differences between the countries. Results from coded frequency counts and transcript reviews informed the design and wording of the test questions for the future PRO instrument(s). Subsequent ratings of item importance also deepened our understanding of potential areas of cross-cultural difference, differences that would be explored over the course of future validation studies involving these PROs. The use of IFGs for cross-cultural content development received positive reviews from participants and was found to be both cost and time effective. The novel thematic coding methodology provided an empirical platform on which to

  5. Characterization of hydrocarbons, halocarbons and carbonyls in the atmosphere of Hong Kong.

    Science.gov (United States)

    Guo, H; Lee, S C; Louie, P K K; Ho, K F

    2004-12-01

    Ambient air quality measurements of 156 species including 39 alkanes, 32 alkenes, 2 alkynes, 24 aromatic hydrocarbons, 43 halocarbons and 16 carbonyls, were carried out for 120 air samples collected at two sampling stations (CW and TW) in 2001 throughout Hong Kong. Spatial variations of volatile organic compounds (VOCs) in the atmosphere were investigated. Levels of most alkanes and alkenes at TW site were higher than that at the CW site, while the BTEX concentrations at the two sites were close. The BTEX ratios at CW and TW were 1.6:10.1:1.0:1.6 and 2.1:10.8:1.0:2.0, respectively. For major halogenated hydrocarbons, the mean concentrations of chloromethane, CFCs 12 and 22 did not show spatial variations at the two sites. However, site-specific differences were observed for trichloroethene and tetrachloroethene. Furthermore, there were no significant differences for carbonyls such as formaldehyde, acetaldehyde and acetone between the two sites. The levels of selected hydrocarbons in winter were 1-5 times that in summer. There were no common seasonal trends for carbonyls in Hong Kong. The ambient level of formaldehyde, the most abundant carbonyl, was higher in summer. However, levels of acetaldehyde, acetone and benzaldehyde in winter were 1.6-3.8 times that in summer. The levels of CFCs 11 and 12, and chloromethane in summer were higher than that in winter. Strong correlation of most hydrocarbons with propene and n-butane suggested that the primary contributors of hydrocarbons were vehicular emissions in Hong Kong. In addition, gasoline evaporation, use of solvents, leakage of liquefied petroleum gas (LPG), natural gas leakage and other industrial emissions, and even biogenic emissions affected the ambient levels of hydrocarbons. The sources of halocarbons were mainly materials used in industrial processes and as solvents. Correlation analysis suggested that photochemical reactions made significant contributions to the ambient levels of carbonyls in summer whereas

  6. Interaction between alkaline earth cations and oxo-ligands. DFT study of the affinity of the Ca2+ cation for carbonyl ligands.

    Science.gov (United States)

    da Costa, Leonardo Moreira; Carneiro, José Walkimar de Mesquita; Romeiro, Gilberto Alves; Paes, Lilian Weitzel Coelho

    2011-02-01

    The affinity of the Ca(2+) ion for a set of substituted carbonyl ligands was analyzed with both the DFT (B3LYP/6-31+G(d)) and semi-empirical (PM6) methods. Two types of ligands were studied: a set of monosubstituted [O=CH(R)] and a set of disubstituted ligands [O=C(R)(2)] (R=H, F, Cl, Br, OH, OCH(3), CH(3), CN, NH(2) and NO(2)), with R either directly bound to the carbonyl carbon atom or to the para position of a phenyl ring. The interaction energy was calculated to quantify the affinity of the Ca(2+) cation for the ligands. Geometric and electronic parameters were correlated with the intensity of the metal-ligand interaction. The electronic nature of the substituent is the main parameter that determines the interaction energy. Donor groups make the interaction energy more negative (stabilizing the complex formed), while acceptor groups make the interaction energy less negative (destabilizing the complex formed).

  7. Ionization of oriented carbonyl sulfide molecules by intense circularly polarized laser pulses

    DEFF Research Database (Denmark)

    Dimitrovski, Darko; Abu-Samha, Mahmoud; Madsen, Lars Bojer

    2011-01-01

    We present combined experimental and theoretical results on strong-field ionization of oriented carbonyl sulfide molecules by circularly polarized laser pulses. The obtained molecular frame photoelectron angular distributions show pronounced asymmetries perpendicular to the direction of the molec......We present combined experimental and theoretical results on strong-field ionization of oriented carbonyl sulfide molecules by circularly polarized laser pulses. The obtained molecular frame photoelectron angular distributions show pronounced asymmetries perpendicular to the direction......-dimensionally-oriented polar molecules, in particular asymmetries in the emission direction of the photoelectrons. In the following article [Phys. Rev. A 83, 023406 (2011)] the focus is to understand strong-field ionization from three-dimensionally-oriented asymmetric top molecules, in particular the suppression of electron...

  8. Molecular Active Sites in Heterogeneous Ir-La/C-Catalyzed Carbonylation of Methanol to Acetates.

    Science.gov (United States)

    Kwak, Ja Hun; Dagle, Robert; Tustin, Gerald C; Zoeller, Joseph R; Allard, Lawrence F; Wang, Yong

    2014-02-06

    We report that when Ir and La halides are deposited on carbon, exposure to CO spontaneously generates a discrete molecular heterobimetallic structure, containing an Ir-La covalent bond that acts as a highly active, selective, and stable heterogeneous catalyst for the carbonylation of methanol to produce acetic acid. This catalyst exhibits a very high productivity of ∼1.5 mol acetyl/mol Ir·s with >99% selectivity to acetyl (acetic acid and methyl acetate) without detectable loss in activity or selectivity for more than 1 month of continuous operation. The enhanced activity can be mechanistically rationalized by the presence of La within the ligand sphere of the discrete molecular Ir-La heterobimetallic structure, which acts as a Lewis acid to accelerate the normally rate-limiting CO insertion in Ir-catalyzed carbonylation. Similar approaches may provide opportunities for attaining molecular (single site) behavior similar to homogeneous catalysis on heterogeneous surfaces for other industrial applications.

  9. Influence of gamma radiation reaction on the hydroesterification of butenes catalyzed by metal carbonyls

    International Nuclear Information System (INIS)

    Velde, J. van der.

    1976-01-01

    In the hydro carboxylation reaction, which first has been studied by Reppe, olefine and acetylene compounds are processed with carbon monoxide and water at high pressures and high temperatures in the presence of metal carbonyls. This reaction can be enhanced considerably by application of ionizing radiation. Lower pressures and in particular lower temperatures can be used if gamma irradiation is performed during carboxylation. For the experiments a mixture of buten-1 and buten-2 as well as pure buten-1 and pure buten-2 has been used to study the behaviour of these olefines with respect to the isomerization of the reaction products and to the olefines not transformed in the reaction process. Replacing water, methanol has been used as a reaction component, thus obtaining directly the respective carbonyl acid esters, which can be analysed quantitatively and qualitatively with respect to their isomeric composition by gaschromatography. (orig./HK) [de

  10. Spectroscopic and theoretical studies on the aromaticity of pyrrol-2-yl-carbonyl conformers

    Science.gov (United States)

    Dubis, Alina T.; Wojtulewski, Sławomir; Filipkowski, Karol

    2013-06-01

    The aromaticity of s-cis and s-trans pyrrol-2-yl carbonyl conformers was studied by FT-IR, 1H NMR spectroscopy and DFT calculations at the B3LYP/6-311++G(d,p) level of theory. The Harmonic Oscillator Model of Aromaticity (HOMA) and Nucleus Independent Chemical Shift (NICS) indices were calculated to estimate π-electron delocalization in the pyrrole ring. The usefulness of infrared spectroscopy in the evaluation of the aromaticity of the homogeneous set of pyrroles is discussed. The influence of 2-substitution on different aspects of aromaticity and stability of the pyrrol-2-yl carbonyl conformers is also discussed. It is concluded that the substitution effect of the title pyrrole derivatives can be explained on the basis of theoretical and experimental measurements of π-electron delocalization, including IR data.

  11. Age-related carbonylation of fibrocartilage structural proteins drives tissue degenerative modification.

    Science.gov (United States)

    Scharf, Brian; Clement, Cristina C; Yodmuang, Supansa; Urbanska, Aleksandra M; Suadicani, Sylvia O; Aphkhazava, David; Thi, Mia M; Perino, Giorgio; Hardin, John A; Cobelli, Neil; Vunjak-Novakovic, Gordana; Santambrogio, Laura

    2013-07-25

    Aging-related oxidative stress has been linked to degenerative modifications in different organs and tissues. Using redox proteomic analysis and illustrative tandem mass spectrometry mapping, we demonstrate oxidative posttranslational modifications in structural proteins of intervertebral discs (IVDs) isolated from aging mice. Increased protein carbonylation was associated with protein fragmentation and aggregation. Complementing these findings, a significant loss of elasticity and increased stiffness was measured in fibrocartilage from aging mice. Studies using circular dichroism and intrinsic tryptophan fluorescence revealed a significant loss of secondary and tertiary structures of purified collagens following oxidation. Collagen unfolding and oxidation promoted both nonenzymatic and enzymatic degradation. Importantly, induction of oxidative modification in healthy fibrocartilage recapitulated the biochemical and biophysical modifications observed in the aging IVD. Together, these results suggest that protein carbonylation, glycation, and lipoxidation could be early events in promoting IVD degenerative changes. Copyright © 2013 Elsevier Ltd. All rights reserved.

  12. Design and fabrication of microfluidic mixer from carbonyl iron–PDMS composite membrane

    KAUST Repository

    Li, Jiaxing

    2010-10-12

    This paper introduces a carbonyl iron-PDMS (CI-PDMS) composite magnetic elastomer in which carbonyl iron (CI) particles are uniformly distributed in a PDMS matrix. The CI particles and the PDMS were mixed at different weight ratios and tested to determine the influence of CI concentration. The magnetic and mechanical properties of the magnetic elastomers were characterized, respectively, by vibrating-sample magnetometer and by tensile testing using a mechanical analyzer. The elastomer was found to exhibit high magnetization and good mechanical flexibility. The morphology and deformation of the CI-PDMS membrane also were observed. A magnetically actuated microfluidic mixer (that is, a micromixer) integrated with CI-PDMS elastomer membranes was successfully designed and fabricated. The high efficiency and quality of the mixing makes possible the impressive potential applications of this unique CI-PDMS material in microfluidic systems. © Springer-Verlag 2010.

  13. Alkylselenite-catalyzed Oxidative Carbonylation of Amines: Density Functional Theory Study

    Energy Technology Data Exchange (ETDEWEB)

    Hwang, Sun; Kim, Hoon Sik; Cheong, Minserk [Kyung Hee Univ., Seoul (Korea, Republic of)

    2012-11-15

    Ureas and carbamates have been conventionally produced by the reaction of amines with phosgene. However, phosgenation processes raise severe environmental concerns, which are attributed to the toxicity of phosgene and the formation of corrosive hydrogen chloride as a co-product. The considerable industrial interest in replacing current phosgene-based processes prompted several methods using non-phosgene routes including carbonylation of amines or nitro compounds and carbomethoxylation of amines with dialkylcarbonates. Among these, catalytic oxidative carbonylation of an amine in the presence of alcohol has been studied most extensively. Catalytic systems based on precious metals such as Rh and Pd are commonly used for this purpose, but most of these catalytic systems suffer from either low reactivity or severe reaction conditions such as high temperature and pressures. In conclusion, the facile change of selenium oxidation state by CO and O{sub 2} might be the main reason for the activity of the selenium catalyst for this reaction.

  14. Alkylselenite-catalyzed Oxidative Carbonylation of Amines: Density Functional Theory Study

    International Nuclear Information System (INIS)

    Hwang, Sun; Kim, Hoon Sik; Cheong, Minserk

    2012-01-01

    Ureas and carbamates have been conventionally produced by the reaction of amines with phosgene. However, phosgenation processes raise severe environmental concerns, which are attributed to the toxicity of phosgene and the formation of corrosive hydrogen chloride as a co-product. The considerable industrial interest in replacing current phosgene-based processes prompted several methods using non-phosgene routes including carbonylation of amines or nitro compounds and carbomethoxylation of amines with dialkylcarbonates. Among these, catalytic oxidative carbonylation of an amine in the presence of alcohol has been studied most extensively. Catalytic systems based on precious metals such as Rh and Pd are commonly used for this purpose, but most of these catalytic systems suffer from either low reactivity or severe reaction conditions such as high temperature and pressures. In conclusion, the facile change of selenium oxidation state by CO and O 2 might be the main reason for the activity of the selenium catalyst for this reaction

  15. Deoxygenative gem-difluoroolefination of carbonyl compounds with (chlorodifluoromethyltrimethylsilane and triphenylphosphine

    Directory of Open Access Journals (Sweden)

    Fei Wang

    2014-02-01

    Full Text Available Background: 1,1-Difluoroalkenes cannot only be used as valuable precursors for organic synthesis, but also act as bioisosteres for enzyme inhibitors. Among various methods for their preparation, the carbonyl olefination with difluoromethylene phosphonium ylide represents one of the most straightforward methods.Results: The combination of (chlorodifluoromethyltrimethylsilane (TMSCF2Cl and triphenylphosphine (PPh3 can be used for the synthesis of gem-difluoroolefins from carbonyl compounds. Comparative experiments demonstrate that TMSCF2Cl is superior to (bromodifluoromethyltrimethylsilane (TMSCF2Br and (trifluoromethyltrimethylsilane (TMSCF3 in this reaction.Conclusion: Similar to many other Wittig-type gem-difluoroolefination reactions in the presence of PPh3, the reaction of TMSCF2Cl with aldehydes and activated ketones is effective.

  16. Criegee Intermediates: What Direct Production and Detection Can Teach Us About Reactions of Carbonyl Oxides

    Science.gov (United States)

    Taatjes, Craig A.

    2017-05-01

    The carbonyl oxide intermediates in the ozonolysis of alkenes, often known as Criegee intermediates, are potentially important reactants in Earth's atmosphere. For decades, careful analysis of ozonolysis systems was employed to derive an understanding of the formation and reactions of these species. Recently it has proved possible to synthesize at least some of these intermediates separately from ozonolysis, and hence to measure their reaction kinetics directly. Direct measurements have allowed new or more detailed understanding of each type of gas-phase reaction that carbonyl oxides undergo, often acting as a complement to highly detailed ozonolysis experiments. Moreover, the use of direct characterization methods to validate increasingly accurate theoretical investigations can enhance their impact well beyond the set of specific reactions that have been measured. Reactions that initiate particles or fuel their growth could be a new frontier for direct measurements of Criegee intermediate chemistry.

  17. Analysis of protein carbonylation - pitfalls and promise in commonly used methods

    DEFF Research Database (Denmark)

    Rogowska-Wrzesinska, A.; Wojdyla, K.; Nedic, O.

    2014-01-01

    that research scientists are becoming more eager to be able to measure accurately the level of oxidized protein in biological materials, and to determine the precise site of the oxidative attack on the protein, in order to get insights into the molecular mechanisms involved in the progression of diseases....... Several methods for measuring protein carbonylation have been implemented in different laboratories around the world. However, to date no methods prevail as the most accurate, reliable, and robust. The present paper aims at giving an overview of the common methods used to determine protein carbonylation...... in biological material as well as to highlight the limitations and the potential. The ultimate goal is to give quick tips for a rapid decision making when a method has to be selected and taking into consideration the advantage and drawback of the methods....

  18. Analysis of protein carbonylation-pitfalls and promise in commonly used methods

    DEFF Research Database (Denmark)

    Rogowska-Wrzesinska, Adelina; Wojdyla, K; Nedić, O

    2014-01-01

    that research scientists are becoming more eager to be able to measure accurately the level of oxidized protein in biological materials, and to determine the precise site of the oxidative attack on the protein, in order to get insights into the molecular mechanisms involved in the progression of diseases....... Several methods for measuring protein carbonylation have been implemented in different laboratories around the world. However, to date no methods prevail as the most accurate, reliable, and robust. The present paper aims at giving an overview of the common methods used to determine protein carbonylation...... in biological material as well as to highlight the limitations and the potential. The ultimate goal is to give quick tips for a rapid decision making when a method has to be selected and taking into consideration the advantage and drawback of the methods....

  19. Novel Routes to Ethylene Glycol Synthesis via Acid-Catalyzed Carbonylation of Formaldehyde and Dimethoxymethane

    OpenAIRE

    Celik, Fuat Emin

    2010-01-01

    Carbon-carbon bond forming carbonylation reactions were investigated as candidates to replace ethene epoxidation as the major source of ethylene glycol production. This work was motivated by the potentially lower cost of carbon derived from synthesis gas as compared to ethylene. Synthesis gas can be produced from relatively abundant and cheap natural gas, coal, and biomass resources whereas ethylene is derived from increasingly scarce and expensive crude oil. From synthesis gas, a range of...

  20. Carbonylative Heck Reactions Using CO Generated ex Situ in a Two-Chamber System

    DEFF Research Database (Denmark)

    Hermange, Philippe; Gøgsig, Thomas; Lindhardt, Anders Thyboe

    2011-01-01

    A carbonylative Heck reaction of aryl iodides and styrene derivatives employing a two-chamber system using a stable, crystalline, and nontransition metal based carbon monoxide source is reported. By applying near-stoichiometric amounts of the carbon monoxide precursor, an effective exploitation o...... of the hazardous CO gas is obtained affording chalcone derivatives in good yields. Application to isotope labeling, incorporating 13CO, was further established....

  1. Reductive Coupling of Carbon Monoxide in a Rhenium Carbonyl Complex with Pendant Lewis Acids

    OpenAIRE

    Miller, Alexander J. M.; Labinger, Jay A.; Bercaw, John E.

    2008-01-01

    Phosphinoborane ligands impart unique reactivity to a rhenium carbonyl cation relative to simple phosphine complexes. Addition of either triethylborohydride or a platinum hydride (that can be formed from H2) forms a rhenium boroxycarbene. This carbene, which crystallizes as a dimer, disproportionates over a period of days to afford the starting cation and a structurally unprecedented boroxy(boroxymethyl)carbene, in which a new C−C bond has been formed between two reduced CO ligands. This prod...

  2. Organocatalyzed Asymmetric α-Oxidation, α-Aminoxylation and α-Amination of Carbonyl Compounds

    OpenAIRE

    Worawan Bhanthumnavin; Tirayut Vilaivan

    2010-01-01

    Organocatalytic asymmetric α-oxidation and amination reactions of carbonyl compounds are highly useful synthetic methodologies, especially in generating chiral building blocks that previously have not been easily accessible by traditional methods. The concept is relatively new and therefore the list of new catalysts, oxidizing and aminating reagents, as well as new substrates, are expanding at an amazing rate. The scope of this review includes new reactions and catalysts, mechanistic aspects ...

  3. The interaction of metal carbonyl compounds with organic polymers and monomers

    OpenAIRE

    Lyons, Michael P.

    1993-01-01

    The photochemistry of W(CO)6, Mo(CO)6, and Cr(CO)6 in the presence of monomeric and polymeric triphenylphosphine ligands was investigated in toluene solution, using laser flash photolysis with 355nm excitation. The mechanism and kinetics of interaction of the primary photoproducts M(CO)5(toluene) (M = W, Mo, or Cr) with the various monomeric ligands were investigated. Interaction of the metal carbonyl photofragments with various homopolymers is also discussed. The polymerisation methods used ...

  4. Plasma-treated carbonyl iron particles as a dispersed phase in magnetorheological fluids

    Czech Academy of Sciences Publication Activity Database

    Sedlačík, M.; Pavlínek, V.; Lehocký, M.; Mráček, A.; Grulich, O.; Švrčinová, Petra; Filip, Petr; Vesel, A.

    2011-01-01

    Roč. 387, 1-3 (2011), s. 99-103 ISSN 0927-7757 Grant - others:GA ČR(CZ) GD104/09/H080; OP VaVpI(XE) CZ.1.05/2.1.00/03.0111 Program:GD Institutional research plan: CEZ:AV0Z20600510 Keywords : carbonyl iron * magnetorheological fluid * plasma * viscoelasticity Subject RIV: BK - Fluid Dynamics Impact factor: 2.236, year: 2011

  5. Hydroxylamine-induced oxidation of ferrous carbonylated truncated hemoglobins from Mycobacterium tuberculosis and Campylobacter jejuni is limited by carbon monoxide dissociation.

    Science.gov (United States)

    Ascenzi, Paolo; Ciaccio, Chiara; Gasperi, Tecla; Pesce, Alessandra; Caporaso, Lucia; Coletta, Massimo

    2017-08-01

    Hydroxylamine (HA) is an oxidant of ferrous globins and its action has been reported to be inhibited by CO, even though this mechanism has not been clarified. Here, kinetics of the HA-mediated oxidation of ferrous carbonylated Mycobacterium tuberculosis truncated hemoglobin N and O (Mt-trHbN(II)-CO and Mt-trHbO(II)-CO, respectively) and Campylobacter jejuni truncated hemoglobin P (Cj-trHbP(II)-CO), at pH 7.2 and 20.0 °C, are reported. Mixing Mt-trHbN(II)-CO, Mt-trHbO(II)-CO, and Cj-trHbP(II)-CO solution with the HA solution brings about absorption spectral changes reflecting the disappearance of the ferrous carbonylated derivatives with the concomitant formation of the ferric species. HA oxidizes irreversibly Mt-trHbN(II)-CO, Mt-trHbO(II)-CO, and Cj-trHbP(II)-CO with the 1:2 stoichiometry. The dissociation of CO turns out to be the rate-limiting step for the oxidation of Mt-trHbN(II)-CO, Mt-trHbO(II)-CO, and Cj-trHbP(II)-CO by HA. Values of the second-order rate constant for HA-mediated oxidation of Mt-trHbN(II)-CO, Mt-trHbO(II)-CO, and Cj-trHbP(II)-CO range between 8.8 × 10 4 and 8.6 × 10 7 M -1 s -1 , reflecting different structural features of the heme distal pocket. This study (1) demonstrates that the inhibitory effect of CO is linked to the dissociation of this ligand, giving a functional basis to previous studies, (2) represents the first comparative investigation of the oxidation of ferrous carbonylated bacterial 2/2 globins belonging to the N, O, and P groups by HA, (3) casts light on the correlation between kinetics of HA-mediated oxidation and carbonylation of globins, and (4) focuses on structural determinants modulating the HA-induced oxidation process.

  6. Selectivity of a heterogeneous rhodium catalyst for the carbonylation of monohydric alcohols

    Energy Technology Data Exchange (ETDEWEB)

    Christensen, B; Scurrell, M S

    1977-01-01

    Selectivity of a heterogeneous rhodium catalyst for the carbonylation of monohydric alcohols with carbon monoxide in the presence of the corresponding alkyl iodides as promotors was studied in a glass reactor at approx. 0.05:1 alcohol/carbon monoxide ratio. The 1% by wt rhodium-zeolite catalyst was prepared by immersing a Linde molecular sieve zeolite Type 13X in rhodium trichloride at 80/sup 0/C for 15 hr. Methanol was converted to methyl acetate at 433/sup 0/-513/sup 0/K with selectivites > 90% even at the highest temperatures, and dimethyl ether was by-produced. In the absence of methyl iodide, the carbonylation rate decreased drastically but the dehydration was virtually unaffected. The selectivity for ethanol carbonylation decreased from 99% at 383/sup 0/K to 6% at 523/sup 0/K due to the formation of ethylene (predominant at > 470/sup 0/K) and diethyl ether. The only product of the reaction with propan-2-ol studied at 433/sup 0/ or 473/sup 0/K was propene with 100% conversion at 473/sup 0/K. These results are consistent with the relative ease of reactant dehydration on polar catalysts. Table and 13 references.

  7. Vapor phase carbonylation of dimethyl ether and methyl acetate with supported transition metal catalysts

    International Nuclear Information System (INIS)

    Shikada, T.; Fujimoto, K.; Tominaga, H.O.

    1986-01-01

    The synthesis of acetic acid (AcOH) from methanol (MeOH) and carbon monoxide has been performed industrially in the liquid phase using a rhodium complex catalyst and an iodide promoter. The selectivity to AcOH is more than 99% under mild conditions (175 0 C, 28 atm). The homogeneous rhodium catalyst has been also effective for the synthesis of acetic anhydride (Ac 2 O) by carbonylation of dimethyl ether (DME) or methyl acetate (AcOMe). However, rhodium is one of the most expensive metals and its proved reserves are quite limited. It is highly desired, therefore, to develop a new catalyst as a substitute for rhodium. The authors have already reported that nickel supported on active carbon exhibits an excellent activity for the vapor phase carbonylation of MeOh in the presence of iodide promoter and under moderately pressurized conditions. In addition, corrosive attack on reactors by iodide compounds is expected to be negligible in the vapor phase system. In the present work, vapor phase carbonylation of DME and AcOMe on nickel-active carbon (Ni/A.C.) and molybdenum-active carbon (Mo/A.C.) catalysts was studied

  8. Gas chromatographic analysis of reactive carbonyl compounds formed from lipids upon UV-irradiation

    International Nuclear Information System (INIS)

    Dennis, K.J.; Shibamoto, T.

    1990-01-01

    Peroxidation of lipids produces carbonyl compounds; some of these, e.g., malonaldehyde and 4-hydroxynonenal, are genotoxic because of their reactivity with biological nucleophiles. Analysis of the reactive carbonyl compounds is often difficult. The methylhydrazine method developed for malonaldehyde analysis was applied to simultaneously measure the products formed from linoleic acid, linolenic acid, arachidonic acid, and squalene upon ultraviolet-irradiation (UV-irradiation). The photoreaction products, saturated monocarbonyl, alpha,beta-unsaturated carbonyls, and beta-dicarbonyls, were derivatized with methylhydrazine to give hydrazones, pyrazolines, and pyrazoles, respectively. The derivatives were analyzed by gas chromatography and gas chromatography-mass spectrometry. Lipid peroxidation products identified included formaldehyde, acetaldehyde, acrolein, malonaldehyde, n-hexanal, and 4-hydroxy-2-nonenal. Malonaldehyde levels formed upon 4 hr of irradiation were 0.06 micrograms/mg from squalene, 2.4 micrograms/mg from linolenic acid, and 5.7 micrograms/mg from arachidonic acid. Significant levels of acrolein (2.5 micrograms/mg) and 4-hydroxy-2-nonenal (0.17 micrograms/mg) were also produced from arachidonic acid upon 4 hr irradiation

  9. A carnosine intervention study in overweight human volunteers: bioavailability and reactive carbonyl species sequestering effect

    Science.gov (United States)

    Regazzoni, Luca; de Courten, Barbora; Garzon, Davide; Altomare, Alessandra; Marinello, Cristina; Jakubova, Michaela; Vallova, Silvia; Krumpolec, Patrik; Carini, Marina; Ukropec, Jozef; Ukropcova, Barbara; Aldini, Giancarlo

    2016-06-01

    Carnosine is a natural dipeptide able to react with reactive carbonyl species, which have been recently associated with the onset and progression of several human diseases. Herein, we report an intervention study in overweight individuals. Carnosine (2 g/day) was orally administered for twelve weeks in order to evaluate its bioavailability and metabolic fate. Two carnosine adducts were detected in the urine samples of all subjects. Such adducts are generated from a reaction with acrolein, which is one of the most toxic and reactive compounds among reactive carbonyl species. However, neither carnosine nor adducts have been detected in plasma. Urinary excretion of adducts and carnosine showed a positive correlation although a high variability of individual response to carnosine supplementation was observed. Interestingly, treated subjects showed a significant decrease in the percentage of excreted adducts in reduced form, accompanied by a significant increase of the urinary excretion of both carnosine and carnosine-acrolein adducts. Altogether, data suggest that acrolein is entrapped in vivo by carnosine although the response to its supplementation is possibly influenced by individual diversities in terms of carnosine dietary intake, metabolism and basal production of reactive carbonyl species.

  10. Nitrite promotes protein carbonylation and Strecker aldehyde formation in experimental fermented sausages: are both events connected?

    Science.gov (United States)

    Villaverde, A; Ventanas, J; Estévez, M

    2014-12-01

    The role played by curing agents (nitrite, ascorbate) on protein oxidation and Strecker aldehyde formation is studied. To fulfill this objective, increasing concentrations of nitrite (0, 75 and 150ppm) and ascorbate (0, 250 and 500ppm) were added to sausages subjected to a 54day drying process. The concurrence of intense proteolysis, protein carbonylation and formation of Strecker aldehydes during processing of sausages suggests that α-aminoadipic semialdehyde (AAS) and γ-glutamic semialdehyde (GGS) may be implicated in the formation of Strecker aldehydes. The fact that nitrite (150ppm, ingoing amount) significantly promoted the formation of protein carbonyls at early stages of processing and the subsequent formation of Strecker aldehydes provides strength to this hypothesis. Ascorbate (125 and 250ppm) controlled the overall extent of protein carbonylation in sausages without declining the formation of Strecker aldehydes. These results may contribute to understanding the chemistry fundamentals of the positive influence of nitrite on the flavor and overall acceptability of cured muscle foods. Copyright © 2014 Elsevier Ltd. All rights reserved.

  11. Seasonal behavior of carbonyls and source characterization of formaldehyde (HCHO) in ambient air

    Science.gov (United States)

    Lui, K. H.; Ho, Steven Sai Hang; Louie, Peter K. K.; Chan, C. S.; Lee, S. C.; Hu, Di; Chan, P. W.; Lee, Jeffrey Chi Wai; Ho, K. F.

    2017-03-01

    Gas-phase formaldehyde (HCHO) is an intermediate and a sensitive indicator for volatile organic compounds (VOCs) oxidation, which drives tropospheric ozone production. Effective photochemical pollution control strategies demand a thorough understanding of photochemical oxidation precursors, making differentiation between sources of primary and secondary generated HCHO inevitable. Spatial and seasonal variations of airborne carbonyls based on two years of measurements (2012-2013), coupled with a correlation-based HCHO source apportionment analysis, were determined for three sampling locations in Hong Kong (denoted HT, TC, and YL). Formaldehyde and acetaldehyde were the two most abundant compounds of the total quantified carbonyls. Pearson's correlation analysis (r > 0.7) implies that formaldehyde and acetaldehyde possibly share similar sources. The total carbonyl concentration trends (HT rural). A regression analysis further quantifies the relative primary HCHO source contributions at HT (∼13%), TC (∼21%), and YL (∼40%), showing more direct vehicular emissions in urban than rural areas. Relative secondary source contributions at YL (∼36%) and TC (∼31%) resemble each other, implying similar urban source contributions. Relative background source contributions at TC could be due to a closed structure microenvironment that favors the trapping of HCHO. Comparable seasonal differences are observed at all stations. The results of this study will aid in the development of a new regional ozone (O3) control policy, as ambient HCHO can enhance O3 production and also be produced from atmospheric VOCs oxidation (secondary HCHO).

  12. Carbonyl compounds and PAH emissions from CNG heavy-duty engine

    International Nuclear Information System (INIS)

    Gambino, M.; Cericola, R.; Corbo, P.; Iannaccone, S.

    1993-01-01

    Previous works carried out in Istituto Motori laboratories have shown that natural gas is a suitable fuel for general means of transportation. This is because of its favorable effects on engine performance and pollutant emissions. The natural gas fueled engine provided the same performance as the diesel engine, met R49 emission standards, and showed very low smoke levels. On the other hand, it is well known that internal combustion engines emit some components that are harmful for human health, such as carbonyl compounds and polycyclic aromatic hydrocarbons (PAH). This paper shows the results of carbonyl compounds and PAH emissions analysis for a heavy-duty Otto cycle engine fueled with natural gas. The engine was tested using the R49 cycle that is used to measure the regulated emissions. The test analysis has been compared with an analysis of a diesel engine, tested under the same conditions. Total PAH emissions from the CNG engine were about three orders of magnitude lower than from the diesel engine. Formaldehyde emission from the CNG engine was about ten times as much as from the diesel engine, while emissions of other carbonyl compounds were comparable

  13. Effect of fiber material on ozone removal and carbonyl production from carpets

    Science.gov (United States)

    Abbass, Omed A.; Sailor, David J.; Gall, Elliott T.

    2017-01-01

    Indoor air quality is affected by indoor materials such as carpets that may act as sources and/or sinks of gas-phase air pollutants. Heterogeneous reactions of ozone with carpets may result in potentially harmful products. In this study, indoor residential carpets of varying fiber types were tested to evaluate their ability to remove ozone, and to assess their role in the production of carbonyls when exposed to elevated levels of ozone. Tests were conducted with six types of new unused carpets. Two sets of experiments were conducted, the first measured ozone removal and ozone deposition velocities, and the second measured primary carbonyl production and secondary production as a result of exposure to ozone. The tests were conducted using glass chambers with volume of 52 L each. Air exchange rates for all tests were 3 h-1. The ozone removal tests show that, for the conditions tested, the polyester carpet sample had the lowest ozone removal (40%), while wool carpet had the greatest ozone removal (65%). Most carpet samples showed higher secondary than primary carbonyl emissions, with carpets containing polypropylene fibers being a notable exception. Carpets with polyester fibers had both the highest primary and secondary emissions of formaldehyde among all samples tested. While it is difficult to make blanket conclusions about the relative air quality merits of various carpet fiber options, it is clear that ozone removal percentages and emissions of volatile organic compounds can vary drastically as a function of fiber type.

  14. Spatial distributions of and diurnal variations in low molecular weight carbonyl compounds in coastal seawater, and the controlling factors

    Energy Technology Data Exchange (ETDEWEB)

    Takeda, Kazuhiko, E-mail: takedaq@hiroshima-u.ac.jp [Graduate School of Biosphere Science, Hiroshima University, 1-7-1 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8521 (Japan); Katoh, Shinya; Mitsui, Yumi; Nakano, Shinichi [Graduate School of Biosphere Science, Hiroshima University, 1-7-1 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8521 (Japan); Nakatani, Nobutake [Graduate School of Biosphere Science, Hiroshima University, 1-7-1 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8521 (Japan); Department of Environmental and Symbiotic Sciences, Rakuno Gakuen University, 582 Bunkyodai-Midorimachi, Ebetsu, Hokkaido 069-8501 (Japan); Sakugawa, Hiroshi [Graduate School of Biosphere Science, Hiroshima University, 1-7-1 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8521 (Japan)

    2014-09-15

    We studied the spatial distributions of and the diurnal variations in four low molecular weight (LMW) carbonyl compounds, formaldehyde, acetaldehyde, propionaldehyde, and glyoxal, in coastal seawater. The samples were taken from the coastal areas of Hiroshima Bay, the Iyo Nada, and the Bungo Channel, western Japan. The formaldehyde, acetaldehyde, and glyoxal concentrations were higher in the northern part of Hiroshima Bay than at offshore sampling points in the Iyo Nada and the Bungo Channel. These three compounds were found at much higher concentrations in the surface water than in deeper water layers in Hiroshima Bay. It is noteworthy that propionaldehyde was not detected in any of the seawater samples, the concentrations present being lower than the detection limit (1 nanomole per liter (nM)) of the high performance liquid chromatography (HPLC) system we used. Photochemical and biological experiments were performed in the laboratory to help understand the characteristic distributions and fates of the LMW carbonyl compounds. The primary process controlling their fate in the coastal environment appears to be their biological consumption. The direct photo degradation of propionaldehyde, initiated by ultraviolet (UV) absorption, was observed, although formaldehyde and acetaldehyde were not degraded by UV irradiation. Our results suggest that the degradation of the LMW carbonyl compounds by photochemically formed hydroxyl radicals is relatively insignificant in the study area. Atmospheric deposition is a possible source of soluble carbonyl compounds in coastal surface seawater, but it may not influence the carbonyl concentrations in offshore waters. - Highlights: • Low molecular weight (LMW) carbonyl compounds in coastal seawater were determined. • Photochemical productions of LMW carbonyl compounds in seawater were observed. • LMW carbonyl compounds were largely consumed biologically. • Photochemical degradation was relatively insignificant in the study area.

  15. Spatial distributions of and diurnal variations in low molecular weight carbonyl compounds in coastal seawater, and the controlling factors

    International Nuclear Information System (INIS)

    Takeda, Kazuhiko; Katoh, Shinya; Mitsui, Yumi; Nakano, Shinichi; Nakatani, Nobutake; Sakugawa, Hiroshi

    2014-01-01

    We studied the spatial distributions of and the diurnal variations in four low molecular weight (LMW) carbonyl compounds, formaldehyde, acetaldehyde, propionaldehyde, and glyoxal, in coastal seawater. The samples were taken from the coastal areas of Hiroshima Bay, the Iyo Nada, and the Bungo Channel, western Japan. The formaldehyde, acetaldehyde, and glyoxal concentrations were higher in the northern part of Hiroshima Bay than at offshore sampling points in the Iyo Nada and the Bungo Channel. These three compounds were found at much higher concentrations in the surface water than in deeper water layers in Hiroshima Bay. It is noteworthy that propionaldehyde was not detected in any of the seawater samples, the concentrations present being lower than the detection limit (1 nanomole per liter (nM)) of the high performance liquid chromatography (HPLC) system we used. Photochemical and biological experiments were performed in the laboratory to help understand the characteristic distributions and fates of the LMW carbonyl compounds. The primary process controlling their fate in the coastal environment appears to be their biological consumption. The direct photo degradation of propionaldehyde, initiated by ultraviolet (UV) absorption, was observed, although formaldehyde and acetaldehyde were not degraded by UV irradiation. Our results suggest that the degradation of the LMW carbonyl compounds by photochemically formed hydroxyl radicals is relatively insignificant in the study area. Atmospheric deposition is a possible source of soluble carbonyl compounds in coastal surface seawater, but it may not influence the carbonyl concentrations in offshore waters. - Highlights: • Low molecular weight (LMW) carbonyl compounds in coastal seawater were determined. • Photochemical productions of LMW carbonyl compounds in seawater were observed. • LMW carbonyl compounds were largely consumed biologically. • Photochemical degradation was relatively insignificant in the study area

  16. Time and dose effects of cigarette smoke and acrolein on protein carbonyl formation in HaCaT keratinocytes.

    Science.gov (United States)

    Avezov, K; Reznick, A Z; Aizenbud, D

    2015-01-01

    Cigarette smoke (CS) is an important environmental source of human exposure to a highly toxic and chemically active α,β-unsaturated aldehyde: acrolein. It is capable of causing protein carbonylation and dysfunction, especially in oral tissues of smokers, constantly exposed to CS toxic constituents. The foremost damage is considered to be cumulative, but even a short exposure can be potentially harmful. The objectives of the current study were to examine the short time and dose effects of direct CS and acrolein exposure on intracellular protein carbonylation in epithelial cells. HaCaT-keratinocytes were exposed to different doses of acrolein and whole phase CS using a unique smoking simulator apparatus that mimics the exposure in smokers. The rate of intracellular protein carbonyl modification was examined 10-60 min after the exposure by Western blot. In addition, the effect of pre-incubation with a thiol scavenger N-acetylcysteine (NAC) was also assessed. We found that intracellular protein carbonyls increased as fast as 10 min after CS exposure and their concentration doubled after 20 min, with a slight elevation afterwards. Also, carbonyl levels increased gradually as CS and acrolein doses were elevated. Addition of 1 mM NAC neutralized part of the damage. We conclude that CS and acrolein intracellular protein carbonylation is dose- and time- dependent. Even a short time exposure to CS and its aldehydic constituents can be potentially harmful.

  17. Spectral characterization of superficial coal groups

    International Nuclear Information System (INIS)

    Ahmad, I.; Khan, M.A.; Ishaq, M.; Shakirullah; Bahadur, A.

    2004-01-01

    Spectral characterization of superficial coal groups was performed in KBr pellets. KBr Pellets were prepared for virgin and variously pretreated coal samples. Spectra of satisfactory resolution were obtained in wave number range-4000-400 cm /sup -1/. Presence of broad absorption bands corresponds to hydroxyl, carbonyl, carboxyl and phenolic functionalities in the spectra clearly define their presence in all samples understudy. Forced oxidation proved effective for oxidation of both aliphatic and aromatic configurations, which can be revealed from the respective spectra. (author)

  18. Local Content

    CSIR Research Space (South Africa)

    Gibberd, Jeremy

    2016-10-01

    Full Text Available Local content refers to materials and products made in a country as opposed those that are imported. There is an increasing interest in the concept of local content as a means of supporting local economies and providing jobs (Belderbos & Sleuwaegen...

  19. Ischemia-reperfusion rat model of acute pancreatitis: protein carbonyl as a putative early biomarker of pancreatic injury.

    Science.gov (United States)

    Schanaider, Alberto; de Carvalho, Thales Penna; de Oliveira Coelho, Simone; Renteria, Juan Miguel; Eleuthério, Elis Cristina Araújo; Castelo-Branco, Morgana Teixeira Lima; Madi, Kalil; Baetas-da-Cruz, Wagner; de Souza, Heitor Siffert Pereira

    2015-08-01

    Acute pancreatitis (AP) is an inflammatory disorder that can affect adjacent and/or remote organs. Some evidence indicates that the production of reactive oxygen species is able to induce AP. Protein carbonyl (PC) derivatives, which can also be generated through oxidative cleavage mechanisms, have been implicated in several diseases, but there is little or no information on this biomarker in AP. We investigated the association between some inflammatory mediators and PC, with the severity of ischemia-reperfusion AP. Wistar rats (n = 56) were randomly assigned in the following groups : control; sham, 15- or 180-min clamping of splenic artery, with 24 or 72 h of follow-up. The relationships between serum level of PC and thiobarbituric acid reactive species (TBARS) to myeloperoxidase (MPO) activity in tissue homogenates and to cytokines in culture supernatants of pancreatic samples were analyzed. MPO activity was related to the histology scores and increased in all clamping groups. Tumor necrosis factor-alpha (TNF-α), interleukin 1 beta (IL-1β), and interleukin-6 were higher in the 180-min groups. Significant correlations were found between MPO activity and the concentrations of TNF-α and IL-1β. PC levels increased in the 15-min to 24-h group. TBARS levels were not altered substantially. MPO activity and TNF-α and IL-1β concentrations in pancreatic tissue are correlated with AP severity. Serum levels of PC appear to begin to rise early in the course of the ischemia-reperfusion AP and are no longer detected at later stages in the absence of severe pancreatitis. These data suggest that PC can be an efficient tool for the diagnosis of early stages of AP.

  20. Microwave spectrum, dipole moment, and internal dynamics of the methyl fluoride-carbonyl sulfide weakly bound complex.

    Science.gov (United States)

    Serafin, Michal M; Peebles, Sean A

    2008-02-21

    Rotational spectra for the normal and four isotopically substituted species of the 1:1 complex between methyl fluoride (H3CF) and carbonyl sulfide (OCS) have been measured using Fourier-transform microwave spectroscopy in the 5-16 GHz frequency region. The observed spectra fit well to a semirigid Watson Hamiltonian, and an analysis of the rotational constants has allowed a structure to be determined for this complex. The dipole moment vectors of the H3CF and OCS monomers are aligned approximately antiparallel with a C...C separation of 3.75(3) A and with an ab plane of symmetry. The values of the Pcc planar moments were found to be considerably different from the expected rigid values for all isotopologues. An estimate of approximately 14.5(50) cm-1 for the internal rotation barrier of the CH3 group with respect to the framework of the complex has been made using the Pcc values for the H3CF-OCS and D3CF-OCS isotopic species. Two structures, very close in energy and approximately related by a 60 degrees rotation about the C3 axis of the methyl fluoride, were identified by ab initio calculations at the MP2/6-311++G(2d,2p) level and provide reasonable agreement with the experimental rotational constants and dipole moment components.

  1. Identification of the urinary metabolites of 4-bromoaniline and 4-bromo-[carbonyl-13C]-acetanilide in rat.

    Science.gov (United States)

    Scarfe, G B; Nicholson, J K; Lindon, J C; Wilson, I D; Taylor, S; Clayton, E; Wright, B

    2002-04-01

    1. The urinary excretion of 4-bromoaniline and its [carbonyl-(13)C]-labelled N-acetanilide, together with their corresponding metabolites, have been investigated in the rat following i.p. administration at 50 mg kg(-1). 2. Metabolite profiling was performed by reversed-phase HPLC with UV detection, whilst identification was performed using a combination of enzymic hydrolysis and directly coupled HPLC-NMR-MS analysis. The urinary metabolite profile was quantitatively and qualitatively similar for both compounds with little of either excreted unchanged. 3. The major metabolite present in urine was 2-amino-5-bromophenylsulphate, but, in addition, a number of metabolites with modification of the N-acetyl moiety were identified (from both the [(13)C]-acetanilide or produced following acetylation of the free bromoaniline). 4. For 4-bromoacetanilide, N-deacetylation was a major route of metabolism, but despite the detection of the acetanilide following the administration of the free aniline, there was no evidence of reacetylation (futile deacetylation). 5. Metabolites resulting from the oxidation of the acetyl group included a novel glucuronide of an N-glycolanilide, an unusual N-oxanilic acid and a novel N-acetyl cysteine conjugate.

  2. Characterisation and optimisation of a method for the detection and quantification of atmospherically relevant carbonyl compounds in aqueous medium

    Science.gov (United States)

    Rodigast, M.; Mutzel, A.; Iinuma, Y.; Haferkorn, S.; Herrmann, H.

    2015-01-01

    Carbonyl compounds are ubiquitous in the atmosphere and either emitted primarily from anthropogenic and biogenic sources or they are produced secondarily from the oxidation of volatile organic compounds (VOC). Despite a number of studies about the quantification of carbonyl compounds a comprehensive description of optimised methods is scarce for the quantification of atmospherically relevant carbonyl compounds. Thus a method was systematically characterised and improved to quantify carbonyl compounds. Quantification with the present method can be carried out for each carbonyl compound sampled in the aqueous phase regardless of their source. The method optimisation was conducted for seven atmospherically relevant carbonyl compounds including acrolein, benzaldehyde, glyoxal, methyl glyoxal, methacrolein, methyl vinyl ketone and 2,3-butanedione. O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine hydrochloride (PFBHA) was used as derivatisation reagent and the formed oximes were detected by gas chromatography/mass spectrometry (GC/MS). The main advantage of the improved method presented in this study is the low detection limit in the range of 0.01 and 0.17 μmol L-1 depending on carbonyl compounds. Furthermore best results were found for extraction with dichloromethane for 30 min followed by derivatisation with PFBHA for 24 h with 0.43 mg mL-1 PFBHA at a pH value of 3. The optimised method was evaluated in the present study by the OH radical initiated oxidation of 3-methylbutanone in the aqueous phase. Methyl glyoxal and 2,3-butanedione were found to be oxidation products in the samples with a yield of 2% for methyl glyoxal and 14% for 2,3-butanedione.

  3. Cross-talk between lipid and protein carbonylation in a dynamic cardiomyocyte model of mild nitroxidative stress

    Directory of Open Access Journals (Sweden)

    Eva Griesser

    2017-04-01

    Full Text Available Reactive oxygen and nitrogen species (ROS/RNS play an important role in the regulation of cardiac function. Increase in ROS/RNS concentration results in lipid and protein oxidation and is often associated with onset and/or progression of many cardiovascular disorders. However, interplay between lipid and protein modifications has not been simultaneously studied in detail so far. Biomolecule carbonylation is one of the most common biomarkers of oxidative stress. Using a dynamic model of nitroxidative stress we demonstrated rapid changes in biomolecule carbonylation in rat cardiomyocytes. Levels of carbonylated species increased as early as 15 min upon treatment with the peroxynitrite donor, 3-morpholinosydnonimine (SIN-1, and decreased to values close to control after 16 h. Total (lipids+proteins vs. protein-specific carbonylation showed different dynamics, with a significant increase in protein-bound carbonyls at later time points. Treatment with SIN-1 in combination with inhibitors of proteasomal and autophagy/lysosomal degradation pathways allowed confirmation of a significant role of the proteasome in the degradation of carbonylated proteins, whereas lipid carbonylation increased in the presence of autophagy/lysosomal inhibitors. Electrophilic aldehydes and ketones formed by lipid peroxidation were identified and relatively quantified using LC-MS/MS. Molecular identity of reactive species was used for data-driven analysis of their protein targets. Combination of different enrichment strategies with LC-MS/MS analysis allowed identification of more than 167 unique proteins with 332 sites modified by electrophilic lipid peroxidation products. Gene ontology analysis of modified proteins demonstrated enrichment of several functional categories including proteins involved in cytoskeleton, extracellular matrix, ion channels and their regulation. Using calcium mobilization assays, the effect of nitroxidative stress on the activity of several ion

  4. Hydrothermal synthesis of carbonyl iron-carbon nanocomposite: Characterization and electromagnetic performance

    Directory of Open Access Journals (Sweden)

    Hakimeh Pourabdollahi

    Full Text Available In this research, the electromagnetic absorption properties of the carbonyl iron-carbon (CI/C nanocomposite prepared via hydrothermal reaction using glucose as carbon precursor was studied in the range of 8.2–12.4 GHz. In hydrothermal reaction, glucose solution containing CI particles, placed in autoclave for 4 h under 453 K. Using surface coating technology is a method that prevents Cl oxidation and improves CI electromagnetic absorption. The structure, morphology and magnetic performances of the prepared nanocomposites were characterized by X-ray diffraction (XRD, energy dispersive spectrometry (EDS, transmission electron microscopy (TEM and vibrating sample magnetometer (VSM. The electromagnetic properties including complex permittivity (εr, the permeability (µr, dielectric loss, magnetic loss, reflection loss, and attenuation constant were investigated using a vector network analyzer. For The CI/C nanocomposite, the bandwidth of −10 dB and −20 dB were obtained in the frequency range of 9.8–12.4 and 11.0–11.8 GHz, respectively. As well as, the reflection loss was −46.69 dB at the matching frequency of 11.5 GHz, when the matching thickness was 1.3 mm. While for CI particles the reflection loss for 4.4 mm thickness was −16.86 dB at the matching frequency of 12.3 GHz. The results indicate that the existence layer of carbon on carbonyl iron enhance the electromagnetic absorbing properties. Therefore, this nanocomposite can be suitable for in the radar absorbing coatings. Keywords: Hydrothermal synthesis, Carbonyl iron-carbon nanocomposite, Microwave absorption, Reflection loss

  5. The Drosophila carbonyl reductase sniffer is an efficient 4-oxonon-2-enal (4ONE) reductase.

    Science.gov (United States)

    Martin, Hans-Jörg; Ziemba, Marta; Kisiela, Michael; Botella, José A; Schneuwly, Stephan; Maser, Edmund

    2011-05-30

    Studies with the fruit-fly Drosophila melanogaster demonstrated that the enzyme sniffer prevented oxidative stress-induced neurodegeneration. Mutant flies overexpressing sniffer had significantly extended life spans in a 99.5% oxygen atmosphere compared to wild-type flies. However, the molecular mechanism of this protection remained unclear. Sequence analysis and database searches identified sniffer as a member of the short-chain dehydrogenase/reductase superfamily with a 27.4% identity to the human enzyme carbonyl reductase type I (CBR1). As CBR1 catalyzes the reduction of the lipid peroxidation products 4HNE and 4ONE, we tested whether sniffer is able to metabolize these lipid derived aldehydes by carbonyl reduction. To produce recombinant enzyme, the coding sequence of sniffer was amplified from a cDNA-library, cloned into a bacterial expression vector and the His-tagged protein was purified by Ni-chelate chromatography. We found that sniffer catalyzed the NADPH-dependent carbonyl reduction of 4ONE (K(m)=24±2 μM, k(cat)=500±10 min(-1), k(cat)/K(m)=350 s(-1) mM(-1)) but not that of 4HNE. The reaction product of 4ONE reduction by sniffer was mainly 4HNE as shown by HPLC- and GC/MS analysis. Since 4HNE, though still a potent electrophile, is less neurotoxic and protein reactive than 4ONE, one mechanism by which sniffer exerts its neuroprotective effects in Drosophila after oxidative stress may be enzymatic reduction of 4ONE. Copyright © 2010 Elsevier Ireland Ltd. All rights reserved.

  6. Carbonyl Stress and Microinflammation-Related Molecules as Potential Biomarkers in Schizophrenia

    Directory of Open Access Journals (Sweden)

    Tohru Ohnuma

    2018-03-01

    Full Text Available This literature review primarily aims to summarize our research, comprising both cross-sectional and longitudinal studies, and discuss the possibility of using microinflammation-related biomarkers as peripheral biomarkers in the diagnosis and monitoring of patients with schizophrenia. To date, several studies have been conducted on peripheral biomarkers to recognize the potential markers for the diagnosis of schizophrenia and to determine the state and effects of therapy in patients with schizophrenia. Research has established a correlation between carbonyl stress, an environmental factor, and the pathophysiology of neuropsychiatric diseases, including schizophrenia. In addition, studies on biomarkers related to these stresses have achieved results that are either replicable or exhibit consistent increases or decreases in patients with schizophrenia. For instance, pentosidine, an advanced glycation end product (AGE, is considerably elevated in patients with schizophrenia; however, low levels of vitamin B6 [a detoxifier of reactive carbonyl compounds (RCOs] have also been reported in some patients with schizophrenia. Another study on peripheral markers of carbonyl stress in patients with schizophrenia revealed a correlation of higher levels of glyceraldehyde-derived AGEs with higher neurotoxicity and lower levels of soluble receptors capable of diminishing the effects of AGEs. Furthermore, studies on evoked microinflammation-related biomarkers (e.g., soluble tumor necrosis factor receptor 1 have reported relatively consistent results, suggesting the involvement of microinflammation in the pathophysiology of schizophrenia. We believe that our cross-sectional and longitudinal studies as well as various previous inflammation marker studies that could be interpreted from several perspectives, such as mild localized encephalitis and microvascular disturbance, highlighted the importance of early intervention as prevention and distinguished the possible

  7. A Simple Catalytic Mechanism for the Direct Coupling of α-Carbonyls with Functionalized Amines: A One-Step Synthesis of Plavix

    OpenAIRE

    Evans, Ryan W.; Zbieg, Jason R.; Zhu, Shaolin; Li, Wei; MacMillan, David W. C.

    2013-01-01

    The direct α-amination of ketones, esters, and aldehydes has been accomplished via copper catalysis. In the presence of catalytic copper(II) bromide, a diverse range of carbonyl and amine substrates undergo fragment coupling to produce synthetically useful α-amino substituted motifs. The transformation is proposed to proceed via a catalytically generated α-bromo carbonyl species; nucleophilic displacement of the bromide by the amine then delivers the α-amino carbonyl adduct while the catalyst...

  8. A green synthesis of α,β-unsaturated carbonyl compounds from glyceraldehyde acetonide

    Directory of Open Access Journals (Sweden)

    Cláudia O. Veloso

    2011-01-01

    Full Text Available The catalytic behavior of Cs-exchanged and Cs-impregnated zeolites (X and Y was studied using the Knoevenagel condensation between glyceraldehyde acetonide and ethyl acetoacetate in order to produce the corresponding α,β-unsaturated carbonyl compound that is an important intermediate for fine chemicals. The influence of reaction temperature, type of zeolite, and basicity of the sites on the catalytic behavior of the samples was evaluated. All zeolites were active for the studied reaction. The formation of the main condensation product was favored at lower reaction temperatures. Products of further condensations were also observed especially for samples that were only dried before catalytic test.

  9. Determination of carbonyl compounds in air by HPLC; Determinacion de compuestos carbonilicos en aire por HPLC

    Energy Technology Data Exchange (ETDEWEB)

    Garcia, S; Perez, R M; Campos, A; Gonzalez, D

    1995-07-01

    A method for the determination of seven carbonyl compounds in air is presented. The procedure involve sampling of air by a Sep-Pak Cartridge impregnated with 2,4-dinitrophenylhydrazine. Elution was done with 3 mL of acetonitrile and the eluate was diluted to 5 mL. The analysis was done by HPLC with UV detection and external standard method quantification. It has been achieved relative standard deviations about 5% and detection limits of 80 ng/cartridge for formaldehyde, acetaldehyde and acetoacetonitrile. Three different types of samples (rural, urban, petrol emission) were successfully analyzed. (Author) 12 refs.

  10. 13C NMR investigation of the structure of cationic carbonyls in transition metal zeolites

    International Nuclear Information System (INIS)

    Ben Taarit, Y.

    1979-01-01

    13 C NMR spectroscopy was used to investigate the nature of carbon monoxide adsorbed on transition metal ions hosted in a synthetic faujastite type zeolite. The adsorbed CO species was characterised by a highly shielded carbon nucleus. Using the Pople approximation for the paramagnetic shielding term, the observed chemical shift was rationalised assuming the formation of a cationic carbonyl species with an appreciable electronic transfer from the carbon lone pair to the transition metal ion and negligible π back-bonding if at all. (Auth.)

  11. Electrochemical synthesis of transition element complexes with carboxyl- and carbonyl-containing ligands

    International Nuclear Information System (INIS)

    Frolov, V.Yu.; Bolotin, S.N.; Panyushkin, V.T.

    2005-01-01

    Complexes of d- and f-elements (E = Cu, Ni, Zn, Nd, Tb, Pr, Gd, Er) with carboxyl- and carbonyl-containing ligands were synthesized by the electrochemical method. The products were characterized by elemental analysis, thermal gravimetric analysis and IR spectra. The influence exerted by a number of factors on the process course was studied. The dependence of the electro synthesis parameters on the composition of the forming compounds was established. A new method for anodic synthesis of these compounds was developed [ru

  12. Organocatalyzed Asymmetric α-Oxidation, α-Aminoxylation and α-Amination of Carbonyl Compounds

    Directory of Open Access Journals (Sweden)

    Worawan Bhanthumnavin

    2010-02-01

    Full Text Available Organocatalytic asymmetric α-oxidation and amination reactions of carbonyl compounds are highly useful synthetic methodologies, especially in generating chiral building blocks that previously have not been easily accessible by traditional methods. The concept is relatively new and therefore the list of new catalysts, oxidizing and aminating reagents, as well as new substrates, are expanding at an amazing rate. The scope of this review includes new reactions and catalysts, mechanistic aspects and synthetic applications of α-oxidation, hydroxylation, aminoxylation, amination, hydrazination, hydroxyamination and related α-heteroatom functionalization of aldehydes, ketones and related active methylene compounds published during 2005–2009.

  13. Elevated Levels of Carbonyl Compounds in the Atmosphere of Eastern Himalaya in India

    Science.gov (United States)

    Sarkar, C.; Chatterjee, A.; Majumdar, D.; Raha, S.; Ghosh, S. K.; Srivastava, A.

    2015-12-01

    A first ever study on atmospheric carbonyl compounds (CC) were made over eastern Himalaya in India. Samples were collected over a high altitude hill station, Darjeeling (27.01°N, 88.15°E, 2200 masl) during 2011-2012. It is well known that CC have toxic and carcinogenic properties as well as they have important effects on regional climate. Therefore their presence in the environment is of great concern especially for the Himalayan region because of the ecological and geographical importance of the area. The average annual concentration of total CCs was 293.3 ± 463.9 μgm-3 with maximum during post monsoon (1104.8 ± 568.0 μgm-3) and minimum during winter season (72.2 ± 42.9 μgm-3). Darjeeling experiences huge emissions of carbonaceous pollutants from massive influx of tourists during premonsoon and postmonsoon seasons. Though the emission strength could be comparable, the loss of carbonyls from the atmosphere could be due to photochemical degradation under high solar insolation during premonsoon. Acetone was most abundant species with an annual average concentration of 200.8±352.9 μgm-3 with 70 % contribution to the total CCs measured. Interestingly, acetone over Darjeeling was found to be much higher than most of the metropolitan cities in the world. The average formaldehyde to acetaldehyde ratio (1.64 ± 1.43) over Darjeeling is a good representation of a typical urban atmosphere at this high altitude over this part of Himalaya. High carbonyl concentration over eastern Himalaya compared to other megacities across the globe could be attributed to uncontrolled activities related to development in tourism, high population density and moreover it's unique orography and land use pattern with narrow roads, unplanned township etc. The unscientific treatment of human and animal and other domestic waste is another major concern which significantly contribute to carbonyl and other carbonaceous pollutants over this part of Himalaya.

  14. Selective transformation of carbonyl ligands to organic molecules. Progress report, September 1, 1989--November 14, 1992

    Energy Technology Data Exchange (ETDEWEB)

    Cutler, A.R.

    1992-05-12

    Studies on the carbonylation of ({eta}{sup 5}-indenyl)(L)(CO)Ru-R complexes (L = CO, PPh{sub 3}; R = CH{sub 2}OMe, CH{sub 3}) have been completed. Particularly noteworthy is that the methoxymethyl complexes readily transform to their acyl derivatives under mild conditions that leave their iron congeners inert towards CO. Surprisingly, even ({eta}{sup 5}-indenyl)(PPh{sub 3}){sub 2}Ru-CH{sub 3} carbonylates and gives ({eta}{sup 5}-indenyl)(PPh{sub 3})(CO)Ru-C(O)CH{sub 3}. Mechanistic studies on the ``non catalyzed`` hydrosilation of the manganese acyls (CO){sub 5}Mn-C(O)CH{sub 2}R (R = H, OCH{sub 3}, CH{sub 3}) with Et{sub 3}SiH and of cobalt acetyls (CO){sub 3}(PR{sub 3})CoC(O)CH{sub 3} with several monohydrosilanes have been completed. The cobalt acetyls cleanly give ethoxysilanes (not acetaldehyde), and the manganese acyls provide {alpha}-siloxyvinyl complexes Z-(CO){sub 5}Mn-C(OSiEt{sub 3})=CHR (R = H, CH{sub 3}, OCH{sub 3}). Carbonylation and protolytic cleavage of the latter generate pyruvoyl complexes (CO){sub 5}Mn-COCOR (R = CH{sub 3}, CH{sub 2}CH{sub 3}), formally the products of net ``double carbonylation`` sequences. Studies in progress are concerned with how manganese complexes as diverse as (CO){sub 5}Mn-Y [Y = C(O)R, R, BR - but not SiMe{sub 3} or Mn(CO){sub 5}] and ({eta}{sup 3}-C{sub 3}H{sub 5})Mn(CO){sub 2}L [but not CpMn(CO){sub 3} or CpMn(CO){sub 2}({eta}{sup 2}HSiR{sub 3})] function as efficient hydrosilation catalysts towards Cp(CO){sub 2}FeC(O)CH{sub 3}, for example. These reactions cleanly afford fully characterized {alpha}-siloxyethyl complexes Fp-CH(OSiR{sub 3})CH{sub 3} under conditions where typically Rh(1) hydrosilation catalysts are inactive. Several of these manganese complexes also catalytically hydrosilate organic esters, including lactones, to their ethers R-CH{sub 2}OR; these novel ester reductions occur quantitatively at room temperature and appear to be general in scope.

  15. A Device-Independent Evaluation of Carbonyl Emissions from Heated Electronic Cigarette Solvents.

    Directory of Open Access Journals (Sweden)

    Ping Wang

    Full Text Available To investigate how the two main electronic (e- cigarette solvents-propylene glycol (PG and glycerol (GL-modulate the formation of toxic volatile carbonyl compounds under precisely controlled temperatures in the absence of nicotine and flavor additives.PG, GL, PG:GL = 1:1 (wt/wt mixture, and two commercial e-cigarette liquids were vaporized in a stainless steel, tubular reactor in flowing air ranging up to 318°C to simulate e-cigarette vaping. Aerosols were collected and analyzed to quantify the amount of volatile carbonyls produced with each of the five e-liquids.Significant amounts of formaldehyde and acetaldehyde were detected at reactor temperatures ≥215°C for both PG and GL. Acrolein was observed only in e-liquids containing GL when reactor temperatures exceeded 270°C. At 318°C, 2.03±0.80 μg of formaldehyde, 2.35±0.87 μg of acetaldehyde, and a trace amount of acetone were generated per milligram of PG; at the same temperature, 21.1±3.80 μg of formaldehyde, 2.40±0.99 μg of acetaldehyde, and 0.80±0.50 μg of acrolein were detected per milligram of GL.We developed a device-independent test method to investigate carbonyl emissions from different e-cigarette liquids under precisely controlled temperatures. PG and GL were identified to be the main sources of toxic carbonyl compounds from e-cigarette use. GL produced much more formaldehyde than PG. Besides formaldehyde and acetaldehyde, measurable amounts of acrolein were also detected at ≥270°C but only when GL was present in the e-liquid. At 215°C, the estimated daily exposure to formaldehyde from e-cigarettes, exceeded United States Environmental Protection Agency (USEPA and California Office of Environmental Health Hazard Assessment (OEHHA acceptable limits, which emphasized the need to further examine the potential cancer and non-cancer health risks associated with e-cigarette use.

  16. High glucose, glucose fluctuation and carbonyl stress enhance brain microvascular endothelial barrier dysfunction: Implications for diabetic cerebral microvasculature.

    Science.gov (United States)

    Li, Wei; Maloney, Ronald E; Aw, Tak Yee

    2015-08-01

    We previously demonstrated that in normal glucose (5mM), methylglyoxal (MG, a model of carbonyl stress) induced brain microvascular endothelial cell (IHEC) dysfunction that was associated with occludin glycation and prevented by N-acetylcysteine (NAC). Herein, we investigated the impact of high glucose and low GSH, conditions that mimicked the diabetic state, on MG-induced IHEC dysfunction. MG-induced loss of transendothelial electrical resistance (TEER) was potentiated in IHECs cultured for 7 or 12 days in 25 mM glucose (hyperglycemia); moreover, barrier function remained disrupted 6h after cell transfer to normal glucose media (acute glycemic fluctuation). Notably, basal occludin glycation was elevated under these glycemic states. TEER loss was exaggerated by inhibition of glutathione (GSH) synthesis and abrogated by NAC, which corresponded to GSH decreases and increases, respectively. Significantly, glyoxalase II activity was attenuated in hyperglycemic cells. Moreover, hyperglycemia and GSH inhibition increased MG accumulation, consistent with a compromised capacity for MG elimination. α-Oxoaldehydes (MG plus glyoxal) levels were elevated in streptozotocin-induced diabetic rat plasma. Immunohistochemistry revealed a prevalence of MG-positive, but fewer occludin-positive microvessels in the diabetic brain in vivo, and Western analysis confirmed an increase in MG-occludin adducts. These results provide the first evidence that hyperglycemia and acute glucose fluctuation promote MG-occludin formation and exacerbate brain microvascular endothelial dysfunction. Low occludin expression and high glycated-occludin contents in diabetic brain in vivo are factors that would contribute to the dysfunction of the cerebral microvasculature during diabetes. Copyright © 2015 The Authors. Published by Elsevier B.V. All rights reserved.

  17. High glucose, glucose fluctuation and carbonyl stress enhance brain microvascular endothelial barrier dysfunction: Implications for diabetic cerebral microvasculature

    Directory of Open Access Journals (Sweden)

    Wei Li

    2015-08-01

    Full Text Available We previously demonstrated that in normal glucose (5 mM, methylglyoxal (MG, a model of carbonyl stress induced brain microvascular endothelial cell (IHEC dysfunction that was associated with occludin glycation and prevented by N-acetylcysteine (NAC. Herein, we investigated the impact of high glucose and low GSH, conditions that mimicked the diabetic state, on MG-induced IHEC dysfunction. MG-induced loss of transendothelial electrical resistance (TEER was potentiated in IHECs cultured for 7 or 12 days in 25 mM glucose (hyperglycemia; moreover, barrier function remained disrupted 6 h after cell transfer to normal glucose media (acute glycemic fluctuation. Notably, basal occludin glycation was elevated under these glycemic states. TEER loss was exaggerated by inhibition of glutathione (GSH synthesis and abrogated by NAC, which corresponded to GSH decreases and increases, respectively. Significantly, glyoxalase II activity was attenuated in hyperglycemic cells. Moreover, hyperglycemia and GSH inhibition increased MG accumulation, consistent with a compromised capacity for MG elimination. α-Oxoaldehydes (MG plus glyoxal levels were elevated in streptozotocin-induced diabetic rat plasma. Immunohistochemistry revealed a prevalence of MG-positive, but fewer occludin-positive microvessels in the diabetic brain in vivo, and Western analysis confirmed an increase in MG–occludin adducts. These results provide the first evidence that hyperglycemia and acute glucose fluctuation promote MG–occludin formation and exacerbate brain microvascular endothelial dysfunction. Low occludin expression and high glycated-occludin contents in diabetic brain in vivo are factors that would contribute to the dysfunction of the cerebral microvasculature during diabetes.

  18. Engineered Trx2p industrial yeast strain protects glycolysis and fermentation proteins from oxidative carbonylation during biomass propagation

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    Gómez-Pastor Rocío

    2012-01-01

    Full Text Available Abstract Background In the yeast biomass production process, protein carbonylation has severe adverse effects since it diminishes biomass yield and profitability of industrial production plants. However, this significant detriment of yeast performance can be alleviated by increasing thioredoxins levels. Thioredoxins are important antioxidant defenses implicated in many functions in cells, and their primordial functions include scavenging of reactive oxygen species that produce dramatic and irreversible alterations such as protein carbonylation. Results In this work we have found several proteins specifically protected by yeast Thioredoxin 2 (Trx2p. Bidimensional electrophoresis and carbonylated protein identification from TRX-deficient and TRX-overexpressing cells revealed that glycolysis and fermentation-related proteins are specific targets of Trx2p protection. Indeed, the TRX2 overexpressing strain presented increased activity of the central carbon metabolism enzymes. Interestingly, Trx2p specifically preserved alcohol dehydrogenase I (Adh1p from carbonylation, decreased oligomer aggregates and increased its enzymatic activity. Conclusions The identified proteins suggest that the fermentative capacity detriment observed under industrial conditions in T73 wine commercial strain results from the oxidative carbonylation of specific glycolytic and fermentation enzymes. Indeed, increased thioredoxin levels enhance the performance of key fermentation enzymes such as Adh1p, which consequently increases fermentative capacity.

  19. Characterization of selected volatile organic compounds, polycyclic aromatic hydrocarbons and carbonyl compounds at a roadside monitoring station

    Science.gov (United States)

    Ho, K. F.; Lee, S. C.; Chiu, Gloria M. Y.

    Volatile organic compounds (VOCs), PAHs and carbonyl compounds are the major toxic components in Hong Kong. Emissions from motor vehicles have been one of the primary pollution sources in the metropolitan areas throughout Hong Kong for a long time. A 1-yr monitoring program for VOCs, PAHs and carbonyl compounds had been performed at a roadside urban station at Hong Kong Polytechnic University in order to determine the variations and correlations of each selected species (VOCs, PAHs and carbonyl compounds). This study is aimed to analyze toxic volatile organic compounds (benzene, toluene, ethylbenzene and xylene), two carbonyl compounds (formaldehyde, acetaldehyde), and selective polycyclic aromatic hydrocarbons. The monitoring program started from 16 April 1999 to 30 March 2000. Ambient VOC concentrations, many of which originate from the same sources as particulate PAHs and carbonyls compounds, show significant quantities of benzene, toluene and xylenes. Correlations and multivariate analysis of selected gaseous and particulate phase organic pollutants were performed. Source identification by principle component analysis and hierarchical cluster analysis allowed the identification of four sources (factors) for the roadside monitoring station. Factor 1 represents the effect of diesel vehicle exhaust. Factor 2 shows the contribution of aromatic compounds. Factor 3 explains photochemical products—formaldehyde and acetaldehyde. Factor 4 explains the effect of gasoline vehicle exhaust.

  20. Sulfur isotopic fractionation of carbonyl sulfide during degradation by soil bacteria and enzyme

    Science.gov (United States)

    Kamezaki, Kazuki; Hattori, Shohei; Ogawa, Takahiro; Toyoda, Sakae; Kato, Hiromi; Katayama, Yoko; Yoshida, Naohiro

    2017-04-01

    Carbonyl sulfide (COS) is an atmospheric trace gas that possess great potential for tracer of carbon cycle (Campbell et al., 2008). COS is taken up by vegetation during photosynthesis like absorption of carbon dioxide but COS can not emit by respiration of vegetation, suggesting possible tracer for gross primary production. However, some studies show the COS-derived GPP is larger than the estimates by using carbon dioxide flux because COS flux by photolysis and soil flux are not distinguished (e.g. Asaf et al., 2013). Isotope analysis is a useful tool to trace sources and transformations of trace gases. Recently our group developed a promising new analytical method for measuring the stable sulfur isotopic compositions of COS using nanomole level samples: the direct isotopic analytical technique of on-line gas chromatography-isotope ratio mass spectrometry (GC-IRMS) using fragmentation ions S+ enabling us to easily analyze sulfur isotopes in COS (Hattori et al., 2015). Soil is thought to be important as both a source and a sink of COS in the troposphere. In particular, soil has been reported as a large environmental sink for atmospheric COS. Bacteria isolated from various soils actively degrade COS, with various enzymes such as carbonic anhydrase and COSase (Ogawa et al., 2013) involved in COS degradation. However, the mechanism and the magnitude of bacterial contribution in terms of a sink for atmospheric COS is still uncertain. Therefore, it is important to quantitatively evaluate this contribution using COS sulfur isotope analysis. We present isotopic fractionation constants for COS by laboratory incubation experiments during degradation by soil bacteria and COSase. Incubation experiments were conducted using strains belonging to the genera Mycobacterium, Williamsia, Cupriavidus, and Thiobacillus, isolated from natural soil or activated sludge and enzyme purified from a bacteria. As a result, the isotopic compositions of OCS were increased during degradation of

  1. A dietary supplement improves facial photoaging and skin sebum, hydration and tonicity modulating serum fibronectin, neutrophil elastase 2, hyaluronic acid and carbonylated proteins.

    Science.gov (United States)

    Di Cerbo, Alessandro; Laurino, Carmen; Palmieri, Beniamino; Iannitti, Tommaso

    2015-03-01

    Excessive exposure to the sun can cause severe photoaging as early as the second decade of life resulting in a loss of physiological elastic fiber functions. We designed a first study to assess differences in facial skin pH, sebum, elasticity, hydration and tonicity and serum levels of fibronectin, elastin, neutrophil elastase 2, hyaluronic acid and carbonylated proteins between patients affected by facial photoaging and healthy controls. In a second study we tested the hypothesis that a dietary supplement would improve facial photoaging, also promoting changes in the above mentioned skin and serum parameters. In the first study we enrolled 30 women [age: 47.5 ± 1.6 years (mean ± standard error of the mean)] affected by moderate facial photoaging (4 cm ≤ Visual Analogue Scale (VAS)Skin Tester was used to analyze differences in facial skin parameters between patients affected by facial photoaging and healthy controls. Skin Tester was also used to assess the effect of VISCODERM Pearls on facial skin parameters and compared with placebo 2 weeks after the end of treatment. Serum levels of fibronectin, elastin, neutrophil elastase 2, hyaluronic acid and carbonylated proteins were measured by enzyme-linked immunosorbent assay in the first cohort of patients affected by facial photoaging and healthy controls and, at baseline and 2 weeks after the end of treatment, in the second cohort of patients who underwent treatment with VISCODERM Pearls and placebo. VAS photoaging score was higher in patients affected by photoaging, if compared with healthy controls (p hydration and tonicity were decreased in patients affected by photoaging, if compared with healthy controls (all p hydration and tonicity were increased in the active treatment group vs. placebo (p skin hydration, tonicity and elasticity and increased skin pH and sebum. Treatment with the dietary supplement VISCODERM Pearls significantly improved VAS photoaging score and skin hydration, sebum and tonicity 2 weeks

  2. Carbonylation Modification Regulates Na/K-ATPase Signaling and Salt Sensitivity: A Review and a Hypothesis.

    Science.gov (United States)

    Shah, Preeya T; Martin, Rebecca; Yan, Yanling; Shapiro, Joseph I; Liu, Jiang

    2016-01-01

    Na/K-ATPase signaling has been implicated in different physiological and pathophysiological conditions. Accumulating evidence indicates that oxidative stress not only regulates the Na/K-ATPase enzymatic activity, but also regulates its signaling and other functions. While cardiotonic steroids (CTS)-induced increase in reactive oxygen species (ROS) generation is an intermediate step in CTS-mediated Na/K-ATPase signaling, increase in ROS alone also stimulates Na/K-ATPase signaling. Based on literature and our observations, we hypothesize that ROS have biphasic effects on Na/K-ATPase signaling, transcellular sodium transport, and urinary sodium excretion. Oxidative modulation, in particular site specific carbonylation of the Na/K-ATPase α1 subunit, is a critical step in proximal tubular Na/K-ATPase signaling and decreased transcellular sodium transport leading to increases in urinary sodium excretion. However, once this system is overstimulated, the signaling, and associated changes in sodium excretion are blunted. This review aims to evaluate ROS-mediated carbonylation of the Na/K-ATPase, and its potential role in the regulation of pump signaling and sodium reabsorption in the renal proximal tubule (RPT).

  3. Structural insights into the neuroprotective-acting carbonyl reductase Sniffer of Drosophila melanogaster.

    Science.gov (United States)

    Sgraja, Tanja; Ulschmid, Julia; Becker, Katja; Schneuwly, Stephan; Klebe, Gerhard; Reuter, Klaus; Heine, Andreas

    2004-10-01

    In vivo studies with the fruit-fly Drosophila melanogaster have shown that the Sniffer protein prevents age-dependent and oxidative stress-induced neurodegenerative processes. Sniffer is a NADPH-dependent carbonyl reductase belonging to the enzyme family of short-chain dehydrogenases/reductases (SDRs). The crystal structure of the homodimeric Sniffer protein from Drosophila melanogaster in complex with NADP+ has been determined by multiple-wavelength anomalous dispersion and refined to a resolution of 1.75 A. The observed fold represents a typical dinucleotide-binding domain as detected for other SDRs. With respect to the cofactor-binding site and the region referred to as substrate-binding loop, the Sniffer protein shows a striking similarity to the porcine carbonyl reductase (PTCR). This loop, in both Sniffer and PTCR, is substantially shortened compared to other SDRs. In most enzymes of the SDR family this loop adopts a well-defined conformation only after substrate binding and remains disordered in the absence of any bound ligands or even if only the dinucleotide cofactor is bound. In the structure of the Sniffer protein, however, the conformation of this loop is well defined, although no substrate is present. Molecular modeling studies provide an idea of how binding of substrate molecules to Sniffer could possibly occur.

  4. Carbonylation as a key reaction in anaerobic acetone activation by Desulfococcus biacutus.

    Science.gov (United States)

    Gutiérrez Acosta, Olga B; Hardt, Norman; Schink, Bernhard

    2013-10-01

    Acetone is activated by aerobic and nitrate-reducing bacteria via an ATP-dependent carboxylation reaction to form acetoacetate as the first reaction product. In the activation of acetone by sulfate-reducing bacteria, acetoacetate has not been found to be an intermediate. Here, we present evidence of a carbonylation reaction as the initial step in the activation of acetone by the strictly anaerobic sulfate reducer Desulfococcus biacutus. In cell suspension experiments, CO was found to be a far better cosubstrate for acetone activation than CO2. The hypothetical reaction product, acetoacetaldehyde, is extremely reactive and could not be identified as a free intermediate. However, acetoacetaldehyde dinitrophenylhydrazone was detected by mass spectrometry in cell extract experiments as a reaction product of acetone, CO, and dinitrophenylhydrazine. In a similar assay, 2-amino-4-methylpyrimidine was formed as the product of a reaction between acetoacetaldehyde and guanidine. The reaction depended on ATP as a cosubstrate. Moreover, the specific activity of aldehyde dehydrogenase (coenzyme A [CoA] acylating) tested with the putative physiological substrate was found to be 153 ± 36 mU mg(-1) protein, and its activity was specifically induced in extracts of acetone-grown cells. Moreover, acetoacetyl-CoA was detected (by mass spectrometry) after the carbonylation reaction as the subsequent intermediate after acetoacetaldehyde was formed. These results together provide evidence that acetoacetaldehyde is an intermediate in the activation of acetone by sulfate-reducing bacteria.

  5. Comparative Proteomic Analysis of Carbonylated Proteins from the Striatum and Cortex of Pesticide-Treated Mice

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    Christina Coughlan

    2015-01-01

    Full Text Available Epidemiological studies indicate exposures to the herbicide paraquat (PQ and fungicide maneb (MB are associated with increased risk of Parkinson’s disease (PD. Oxidative stress appears to be a premier mechanism that underlies damage to the nigrostriatal dopamine system in PD and pesticide exposure. Enhanced oxidative stress leads to lipid peroxidation and production of reactive aldehydes; therefore, we conducted proteomic analyses to identify carbonylated proteins in the striatum and cortex of pesticide-treated mice in order to elucidate possible mechanisms of toxicity. Male C57BL/6J mice were treated biweekly for 6 weeks with saline, PQ (10 mg/kg, MB (30 mg/kg, or the combination of PQ and MB (PQMB. Treatments resulted in significant behavioral alterations in all treated mice and depleted striatal dopamine in PQMB mice. Distinct differences in 4-hydroxynonenal-modified proteins were observed in the striatum and cortex. Proteomic analyses identified carbonylated proteins and peptides from the cortex and striatum, and pathway analyses revealed significant enrichment in a variety of KEGG pathways. Further analysis showed enrichment in proteins of the actin cytoskeleton in treated samples, but not in saline controls. These data indicate that treatment-related effects on cytoskeletal proteins could alter proper synaptic function, thereby resulting in impaired neuronal function and even neurodegeneration.

  6. Efficient light-harvesting using non-carbonyl carotenoids: Energy transfer dynamics in the VCP complex from Nannochloropsis oceanica.

    Science.gov (United States)

    Keşan, Gürkan; Litvín, Radek; Bína, David; Durchan, Milan; Šlouf, Václav; Polívka, Tomáš

    2016-04-01

    Violaxanthin-chlorophyll a protein (VCP) from Nannochloropsis oceanica is a Chl a-only member of the LHC family of light-harvesting proteins. VCP binds carotenoids violaxanthin (Vio), vaucheriaxanthin (Vau), and vaucheriaxanthin-ester (Vau-ester). Here we report on energy transfer pathways in the VCP complex. The overall carotenoid-to-Chla energy transfer has efficiency over 90%. Based on their energy transfer properties, the carotenoids in VCP can be divided into two groups; blue carotenoids with the lowest energy absorption band around 480nm and red carotenoids with absorption extended up to 530nm. Both carotenoid groups transfer energy efficiently from their S2 states, reaching efficiencies of ~70% (blue) and ~60% (red). The S1 pathway, however, is efficient only for the red carotenoid pool for which two S1 routes characterized by 0.33 and 2.4ps time constants were identified. For the blue carotenoids the S1-mediated pathway is represented only by a minor route likely involving a hot S1 state. The relaxed S1 state of blue carotenoids decays to the ground state within 21ps. Presence of a fraction of non-transferring red carotenoids with the S1 lifetime of 13ps indicates some specific carotenoid-protein interaction that must shorten the intrinsic S1 lifetime of Vio and/or Vau whose S1 lifetimes in methanol are 26 and 29ps, respectively. The VCP complex from N. oceanica is the first example of a light-harvesting complex binding only non-carbonyl carotenoids with carotenoid-to-chlorophyll energy transfer efficiency over 90%. Copyright © 2015 Elsevier B.V. All rights reserved.

  7. Sulfur isotopic analysis of carbonyl sulfide and its application for biogeochemical cycles

    Science.gov (United States)

    Hattori, Shohei; Kamezaki, Kazuki; Ogawa, Takahiro; Toyoda, Sakae; Katayama, Yoko; Yoshida, Naohiro

    2016-04-01

    Carbonyl sulfide (OCS or COS) is the most abundant gas containing sulfur in the atmosphere, with an average mixing ratio of 500 p.p.t.v. in the troposphere. OCS is suggested as a sulfur source of the stratospheric sulfate aerosols (SSA) which plays an important role in Earth's radiation budget and ozone depletion. Therefore, OCS budget should be validated for prediction of climate change, but the global OCS budget is imbalance. Recently we developed a promising new analytical method for measuring the stable sulfur isotopic compositions of OCS using nanomole level samples: the direct isotopic analytical technique of on-line gas chromatography-isotope ratio mass spectrometry (GC-IRMS) using fragmentation ions S+ (Hattori et al., 2015). The first measurement of the δ34S value for atmospheric OCS coupled with isotopic fractionation for OCS sink reactions in the stratosphere (Hattori et al., 2011; Schmidt et al., 2012; Hattori et al., 2012) explains the reported δ34S value for background stratospheric sulfate, suggesting that OCS is a potentially important source for background (nonepisodic or nonvolcanic) stratospheric sulfate aerosols. This new method measuring δ34S values of OCS can be used to investigate OCS sources and sinks in the troposphere to better understand its cycle. It is known that some microorganisms in soil can degrade OCS, but the mechanism and the contribution to the OCS in the air are still uncertain. In order to determine sulfur isotopic enrichment factor of OCS during degradation via microorganisms, incubation experiments were conducted using strains belonging to the genera Mycobacterium, Williamsia and Cupriavidus, isolated from natural soil environments (Kato et al., 2008). As a result, sulfur isotope ratios of OCS were increased during degradation of OCS, indicating that reaction for OC32S is faster than that for OC33S and OC34S. OCS degradation via microorganisms is not mass-independent fractionation (MIF) process, suggesting that this

  8. Tandem pseudopericyclic reactions: [1,5]-X sigmatropic shift/6pi-electrocyclic ring closure converting N-(2-X-carbonyl)phenyl ketenimines into 2-X-quinolin-4(3H)-ones.

    Science.gov (United States)

    Alajarín, Mateo; Ortín, María-Mar; Sanchez-Andrada, Pilar; Vidal, Angel

    2006-10-13

    N-(2-X-Carbonyl)phenyl ketenimines undergo, under mild thermal conditions, [1,5]-migration of the X group from the carbonyl carbon to the electron-deficient central carbon atom of the ketenimine fragment, followed by a 6pi-electrocyclic ring closure of the resulting ketene to provide 2-X-substituted quinolin-4(3H)-ones in a sequential one-pot manner. The X groups tested are electron-donor groups, such as alkylthio, arylthio, arylseleno, aryloxy, and amino. When involving alkylthio, arylthio, and arylseleno groups, the complete transformation takes place in refluxing toluene, whereas for aryloxy and amino groups the starting ketenimines must be heated at 230 degrees C in a sealed tube in the absence of solvent. The mechanism for the conversion of these ketenimines into quinolin-4(3H)-ones has been studied by ab initio and DFT calculations, using as model compounds N-(2-X-carbonyl)vinyl ketenimines bearing different X groups (X = F, Cl, OH, SH, NH(2), and PH(2)) converting into 4(3H)-pyridones. This computational study afforded two general reaction pathways for the first step of the sequence, the [1,5]-X shift, depending on the nature of X. When X is F, Cl, OH, or SH, the migration occurs in a concerted mode, whereas when X is NH(2) or PH(2), it involves a two-step sequence. The order of migratory aptitudes of the X substituents at the acyl group is predicted to be PH(2) > Cl > SH > NH(2) > F> OH. The second step of the full transformation, the 6pi-electrocyclic ring closure, is calculated to be concerted and with low energy barriers in all the cases. We have included in the calculations an alternative mode of cyclization of the N-(2-X-carbonyl)vinyl ketenimines, the 6pi-electrocyclic ring closure leading to 1,3-oxazines that involves its 1-oxo-5-aza-1,3,5-hexatrienic system. Additionally, the pseudopericyclic topology of the transition states for some of the [1,5]-X migrations (X = F, Cl, OH, SH), for the 6pi-electrocyclization of the ketene intermediates to the 4

  9. Gas/particle partitioning of carbonyls in the photooxidation of isoprene and 1,3,5-trimethylbenzene

    Directory of Open Access Journals (Sweden)

    R. M. Healy

    2008-06-01

    Full Text Available A new denuder-filter sampling technique has been used to investigate the gas/particle partitioning behaviour of the carbonyl products from the photooxidation of isoprene and 1,3,5-trimethylbenzene. A series of experiments was performed in two atmospheric simulation chambers at atmospheric pressure and ambient temperature in the presence of NOx and at a relative humidity of approximately 50%. The denuder and filter were both coated with the derivatizing agent O-(2,3,4,5,6-pentafluorobenzyl-hydroxylamine (PFBHA to enable the efficient collection of gas- and particle-phase carbonyls respectively. The tubes and filters were extracted and carbonyls identified as their oxime derivatives by GC-MS. The carbonyl products identified in the experiments accounted for around 5% and 10% of the mass of secondary organic aerosol formed from the photooxidation of isoprene and 1,3,5-trimethylbenzene respectively.

    Experimental gas/particle partitioning coefficients were determined for a wide range of carbonyl products formed from the photooxidation of isoprene and 1,3,5-trimethylbenzene and compared with the theoretical values based on standard absorptive partitioning theory. Photooxidation products with a single carbonyl moiety were not observed in the particle phase, but dicarbonyls, and in particular, glyoxal and methylglyoxal, exhibited gas/particle partitioning coefficients several orders of magnitude higher than expected theoretically. These findings support the importance of heterogeneous and particle-phase chemical reactions for SOA formation and growth during the atmospheric degradation of anthropogenic and biogenic hydrocarbons.

  10. Investigation of carbonyl compound sources at a rural site in the Yangtze River Delta region of China.

    Science.gov (United States)

    Wang, Ming; Chen, Wentai; Shao, Min; Lu, Sihua; Zeng, Limin; Hu, Min

    2015-02-01

    Carbonyl compounds are important intermediates in atmospheric photochemistry, but their primary sources are still not understood well. In this work, carbonyls, hydrocarbons, and alkyl nitrates were continuously measured during November 2011 at a rural site in the Yangtze River Delta region of China. Mixing ratios of carbonyls and hydrocarbons showed large fluctuations during the entire measurement. The average level for total measured volatile organic compounds during the pollution episode from 25th to 27th November, 2011 was 91.6 ppb, about 7 times the value for the clean period of 7th-8th, November, 2011. To preliminarily identify toluene sources at this site, the emission ratio of toluene to benzene (T/B) during the pollution episode was determined based on photochemical ages derived from the relationship of alkyl nitrates to their parent alkanes. The calculated T/B was 5.8 ppb/ppb, significantly higher than the values of 0.2-1.7 ppb/ppb for vehicular exhaust and other combustion sources, indicating the dominant influence of industrial emissions on ambient toluene. The contributions of industrial sources to ambient carbonyls were then calculated using a multiple linear regression fit model that used toluene and alkyl nitrates as respective tracers for industrial emission and secondary production. During the pollution episode, 18.5%, 69.0%, and 52.9% of measured formaldehyde, acetaldehyde, and acetone were considered to be attributable to industrial emissions. The emission ratios relative to toluene for formaldehyde, acetaldehyde, and acetone were determined to be 0.10, 0.20 and 0.40 ppb/ppb, respectively. More research on industrial carbonyl emission characteristics is needed to understand carbonyl sources better. Copyright © 2014. Published by Elsevier B.V.

  11. Application of vanadium incorporated phosphomolybdate supported on the modified kaolinin synthesis of diphenyl carbonate by oxidative carbonylation with phenol

    Directory of Open Access Journals (Sweden)

    Peng Meng

    2017-01-01

    Full Text Available Keggin-type molybdophosphoric acid, molybdophosphoric salt and vanadium incorporated molybdophosphoric salt supported on the modified kaolin (MK were investigated as redox co-catalysts for the oxidative carbonylation of phenol to diphenyl carbonate (DPC in the absence of solvent. The 20 wt.% of MnAMPV5 (one kind of vanadium incorporated molybdophosphoric salt loaded on MK showed the highest catalytic activity with the yield of 24.68% and a TON of 306, while the selectivity amounts to nearly 100% in all the carbonylation reactions. The catalysts were characterized by XRD, BET, XPS and H2-TPR. The reusability study showed that the catalysts were stable and active.

  12. Determination of gaseous and particulate carbonyls (glycolaldehyde, hydroxyacetone, glyoxal, methylglyoxal, nonanal and decanal in the atmosphere at Mt. Tai

    Directory of Open Access Journals (Sweden)

    K. Kawamura

    2013-05-01

    Full Text Available Gaseous and particulate semi-volatile carbonyl compounds were determined every three hours in the atmosphere of Mount Tai (elevation, 1534 m in the North China Plain during 2–5, 23–24 and 25 June 2006 under clear sky conditions. Using a two-step filter cartridge in a series, particulate carbonyls were first collected on a quartz filter and then gaseous carbonyls were collected on a quartz filter impregnated with O-benzylhydroxylamine (BHA. After the two-step derivatization with BHA and N,O-Bis(trimethylsilyltrifluoroacetamide (BSTFA, carbonyl derivatives were measured using a gas chromatography. The gaseous concentrations were obtained as follow: glycolaldehyde (range 0–826 ng m−3, average 303 ng m−3, hydroxyacetone (0–579 ng m−3, 126 ng m−3, glyoxal (46–1200 ng m−3, 487 ng m−3, methylglyoxal (88–2690 ng m−3, 967 ng m−3, n-nonanal (0–500 ng m−3, 89 ng m−3, and n-decanal (0–230 ng m−3, 39 ng m−3. These concentrations are among the highest ever reported in the urban and forest atmosphere. We found that gaseous α-dicarbonyls (glyoxal and methylglyoxal are more than 20 times more abundant than particulate carbonyls and that glycolaldehyde is one order of magnitude more abundant than in aerosol phase. In contrast, hydroxyacetone and normal aldehydes (nonanal and decanal are equally present in both phases. Time-resolved variations of carbonyls did not show any a clear diurnal pattern, except for hydroxyacetone. We found that glyoxal, methylglyoxal and glycolaldehyde positively correlated with levoglucosan (a tracer of biomass burning, suggesting that a contribution from field burning of agricultural wastes (wheat crops is significant for the bifunctional carbonyls in the atmosphere of Mt. Tai. Upward transport of the pollutants to the mountaintop from the low lands in the North China Plain is a major process to control the distributions of carbonyls in the upper atmosphere over Mt. Tai.

  13. Reactions of carbonyl compounds with α,β-unsaturated nitriles as a convenient pathway to carbo- and heterocycles

    International Nuclear Information System (INIS)

    Sharanin, Yu A; Goncharenko, M P; Litvinov, Victor P

    1998-01-01

    Published data on the methods for synthesis of carbo- and heterocyclic compounds based on reactions of α,β-unsaturated nitriles with carbonyl compounds and activated phenols are surveyed. It is demonstrated that all these reactions occur via nucleophilic addition of the carbanion generated from a carbonyl compound to the double bond of an unsaturated nitrile (the Michael reaction). The main routes of transformation of the adducts into carbo- and heterocyclic compounds are considered. The methods for regioselective preparation of fused 4H-pyrans or 1,4-dihydropyridines by varying conditions of cyclisation of Michael adducts are discussed. The bibliography includes 249 references.

  14. Microwave electromagnetic properties of carbonyl iron particles and Si/C/N nano-powder filled epoxy-silicone coating

    International Nuclear Information System (INIS)

    Qing Yuchang; Zhou Wancheng; Luo Fa; Zhu Dongmei

    2010-01-01

    The electromagnetic characteristics of carbonyl iron particles and Si/C/N nano-powder filled epoxy-silicone coatings were studied. The reflection loss of the coatings exceeds -10 dB at 8-18 GHz and -9 dB at 2-18 GHz when the coating thickness is 1 and 3 mm, respectively. The dielectric and magnetic absorbers filled coatings possess excellent microwave absorption, which could be attributed to the proper incorporate of the multi-polarization mechanisms as well as strong natural resonance. It is feasible to develop the thin and wideband microwave absorbing coatings using carbonyl iron particles and Si/C/N nano-powder.

  15. Microwave electromagnetic properties of carbonyl iron particles and Si/C/N nano-powder filled epoxy-silicone coating

    Science.gov (United States)

    Qing, Yuchang; Zhou, Wancheng; Luo, Fa; Zhu, Dongmei

    2010-02-01

    The electromagnetic characteristics of carbonyl iron particles and Si/C/N nano-powder filled epoxy-silicone coatings were studied. The reflection loss of the coatings exceeds -10 dB at 8-18 GHz and -9 dB at 2-18 GHz when the coating thickness is 1 and 3 mm, respectively. The dielectric and magnetic absorbers filled coatings possess excellent microwave absorption, which could be attributed to the proper incorporate of the multi-polarization mechanisms as well as strong natural resonance. It is feasible to develop the thin and wideband microwave absorbing coatings using carbonyl iron particles and Si/C/N nano-powder.

  16. Composition tunable cobalt–nickel and cobalt–iron alloy nanoparticles below 10 nm synthesized using acetonated cobalt carbonyl

    International Nuclear Information System (INIS)

    Schooneveld, Matti M. van; Campos-Cuerva, Carlos; Pet, Jeroen; Meeldijk, Johannes D.; Rijssel, Jos van; Meijerink, Andries; Erné, Ben H.; Groot, Frank M. F. de

    2012-01-01

    A general organometallic route has been developed to synthesize Co x Ni 1−x and Co x Fe 1−x alloy nanoparticles with a fully tunable composition and a size of 4–10 nm with high yield. In contrast to previously reported synthesis methods using dicobalt octacarbonyl (Co 2 (CO) 8 ), here the cobalt–cobalt bond in the carbonyl complex is first broken with anhydrous acetone. The acetonated compound, in the presence of iron carbonyl or nickel acetylacetonate, is necessary to obtain small composition tunable alloys. This new route and insights will provide guidelines for the wet-chemical synthesis of yet unmade bimetallic alloy nanoparticles.

  17. Combining in situ and laboratory measurements of soil-atmosphere carbonyl sulfide fluxes from four different biomes across Europe

    Science.gov (United States)

    Kitz, Florian; Gomez-Brandon, Maria; Hammerle, Albin; Spielmann, Felix M.; Insam, Heribert; Ibrom, Andreas; Migliavacca, Mirco; Moreno, Gerardo; Noe, Steffen M.; Wohlfahrt, Georg

    2017-04-01

    Flux partitioning, the quantification of photosynthesis and respiration, is a major uncertainty in modelling the carbon cycle and in times when robust models are needed to assess future global changes a persistent problem. A promising new approach is to derive gross primary production (GPP) from measurements of the carbonyl sulfide (COS) flux, the most abundant sulfur-containing trace gas in the atmosphere, with a mean concentration of about 500 pptv in the troposphere. This is possible because COS and CO2 enter the leaf via a similar pathway and are processed by the same enzyme (carbonic anhydrase). A prerequisite for using COS as a proxy for photosynthesis is a robust estimation of all non-leaf sources and sinks in an ecosystem. Past studies described soils either as a sink or source, depending on their properties like soil temperature and soil water content. In 2016 we conducted field campaigns in Austria (managed temperate mountain grassland), Spain (savannah), Denmark (temperate beech forest) and Estonia (hemiboreal forest) to estimate the soil-atmosphere COS fluxes under ambient conditions in different biomes. We used self-built fused silica soil chambers to avoid COS emissions from built-in materials and to assess the impact of radiation. At the grassland sites (Austria, Spain) vegetation was removed below the chambers, therefor more radiation reached the soil surface compared to natural conditions. The grassland sites were characterized by highly positive COS fluxes during daytime and COS fluxes around zero during nighttime. In contrast, the soils at the forest sites (Denmark, Estonia), characterized by less radiation on the soil surface, acted as a sink for COS. The impact of other abiotic factors, like soil water content and soil temperature, varied between the ecosystems. In addition to the field measurements soil and litter samples were taken at the study sites and used to measure COS fluxes under controlled conditions in the lab. Results from the

  18. The unusually strong hydrogen bond between the carbonyl of Q(A) and His M219 in the Rhodobacter sphaeroides reaction center is not essential for efficient electron transfer from Q(A)(-) to Q(B).

    Science.gov (United States)

    Breton, Jacques; Lavergne, Jérôme; Wakeham, Marion C; Nabedryk, Eliane; Jones, Michael R

    2007-06-05

    In native reaction centers (RCs) from photosynthetic purple bacteria the primary quinone (QA) and the secondary quinone (QB) are interconnected via a specific His-Fe-His bridge. In Rhodobacter sphaeroides RCs the C4=O carbonyl of QA forms a very strong hydrogen bond with the protonated Npi of His M219, and the Ntau of this residue is in turn coordinated to the non-heme iron atom. The second carbonyl of QA is engaged in a much weaker hydrogen bond with the backbone N-H of Ala M260. In previous work, a Trp side chain was introduced by site-directed mutagenesis at the M260 position in the RC of Rb. sphaeroides, resulting in a complex that is completely devoid of QA and therefore nonfunctional. A photochemically competent derivative of the AM260W mutant was isolated that contains a Cys side chain at the M260 position (denoted AM260(W-->C)). In the present work, the interactions between the carbonyl groups of QA and the protein in the AM260(W-->C) suppressor mutant have been characterized by light-induced FTIR difference spectroscopy of the photoreduction of QA. The QA-/QA difference spectrum demonstrates that the strong interaction between the C4=O carbonyl of QA and His M219 is lost in the mutant, and the coupled CO and CC modes of the QA- semiquinone are also strongly perturbed. In parallel, a band assigned to the perturbation of the C5-Ntau mode of His M219 upon QA- formation in the native RC is lacking in the spectrum of the mutant. Furthermore, a positive band between 2900 and 2400 cm-1 that is related to protons fluctuating within a network of highly polarizable hydrogen bonds in the native RC is reduced in amplitude in the mutant. On the other hand, the QB-/QB FTIR difference spectrum is essentially the same as for the native RC. The kinetics of electron transfer from QA- to QB were measured by the flash-induced absorption changes at 780 nm. Compared to native RCs the absorption transients are slowed by a factor of about 2 for both the slow phase (in the

  19. Copper-catalyzed oxidative desulfurization-oxygenation of thiocarbonyl compounds using molecular oxygen: an efficient method for the preparation of oxygen isotopically labeled carbonyl compounds.

    Science.gov (United States)

    Shibahara, Fumitoshi; Suenami, Aiko; Yoshida, Atsunori; Murai, Toshiaki

    2007-06-21

    A novel copper-catalyzed oxidative desulfurization reaction of thiocarbonyl compounds, using molecular oxygen as an oxidant and leading to formation of carbonyl compounds, has been developed, and the utility of the process is demonstrated by its application to the preparation of a carbonyl-18O labeled sialic acid derivative.

  20. Soil fluxes of carbonyl sulfide (COS), carbon monoxide, and carbon dioxide in a boreal forest in southern Finland

    Science.gov (United States)

    Sun, Wu; Kooijmans, Linda M. J.; Maseyk, Kadmiel; Chen, Huilin; Mammarella, Ivan; Vesala, Timo; Levula, Janne; Keskinen, Helmi; Seibt, Ulli

    2018-02-01

    Soil is a major contributor to the biosphere-atmosphere exchange of carbonyl sulfide (COS) and carbon monoxide (CO). COS is a tracer with which to quantify terrestrial photosynthesis based on the coupled leaf uptake of COS and CO2, but such use requires separating soil COS flux, which is unrelated to photosynthesis, from ecosystem COS uptake. For CO, soil is a significant natural sink that influences the tropospheric CO budget. In the boreal forest, magnitudes and variabilities of soil COS and CO fluxes remain poorly understood. We measured hourly soil fluxes of COS, CO, and CO2 over the 2015 late growing season (July to November) in a Scots pine forest in Hyytiälä, Finland. The soil acted as a net sink of COS and CO, with average uptake rates around 3 pmol m-2 s-1 for COS and 1 nmol m-2 s-1 for CO. Soil respiration showed seasonal dynamics controlled by soil temperature, peaking at around 4 µmol m-2 s-1 in late August and September and dropping to 1-2 µmol m-2 s-1 in October. In contrast, seasonal variations of COS and CO fluxes were weak and mainly driven by soil moisture changes through diffusion limitation. COS and CO fluxes did not appear to respond to temperature variation, although they both correlated well with soil respiration in specific temperature bins. However, COS : CO2 and CO : CO2 flux ratios increased with temperature, suggesting possible shifts in active COS- and CO-consuming microbial groups. Our results show that soil COS and CO fluxes do not have strong variations over the late growing season in this boreal forest and can be represented with the fluxes during the photosynthetically most active period. Well-characterized and relatively invariant soil COS fluxes strengthen the case for using COS as a photosynthetic tracer in boreal forests.

  1. Advertising Content

    OpenAIRE

    Simon P. Anderson; Régis Renault

    2002-01-01

    Empirical evidence suggests that most advertisements contain little direct informa- tion. Many do not mention prices. We analyze a firm'ss choice of advertising content and the information disclosed to consumers. A firm advertises only product informa- tion, price information, or both; and prefers to convey only limited product information if possible. Extending the "persuasion" game, we show that quality information takes precedence over price information and horizontal product information.T...

  2. Evaluation of Polyphenol Anthocyanin-Enriched Extracts of Blackberry, Black Raspberry, Blueberry, Cranberry, Red Raspberry, and Strawberry for Free Radical Scavenging, Reactive Carbonyl Species Trapping, Anti-Glycation, Anti-β-Amyloid Aggregation, and Microglial Neuroprotective Effects

    Directory of Open Access Journals (Sweden)

    Hang Ma

    2018-02-01

    Full Text Available Glycation is associated with several neurodegenerative disorders, including Alzheimer’s disease (AD, where it potentiates the aggregation and toxicity of proteins such as β-amyloid (Aβ. Published studies support the anti-glycation and neuroprotective effects of several polyphenol-rich fruits, including berries, which are rich in anthocyanins. Herein, blackberry, black raspberry, blueberry, cranberry, red raspberry, and strawberry extracts were evaluated for: (1 total phenolic and anthocyanins contents, (2 free radical (DPPH scavenging and reactive carbonyl species (methylglyoxal; MGO trapping, (3 anti-glycation (using BSA-fructose and BSA-MGO models, (4 anti-Aβ aggregation (using thermal- and MGO-induced fibrillation models, and, (5 murine microglia (BV-2 neuroprotective properties. Berry crude extracts (CE were fractionated to yield anthocyanins-free (ACF and anthocyanins-enriched (ACE extracts. The berry ACEs (at 100 μg/mL showed superior free radical scavenging, reactive carbonyl species trapping, and anti-glycation effects compared to their respective ACFs. The berry ACEs (at 100 μg/mL inhibited both thermal- and MGO-induced Aβ fibrillation. In addition, the berry ACEs (at 20 μg/mL reduced H2O2-induced reactive oxygen species production, and lipopolysaccharide-induced nitric oxide species in BV-2 microglia as well as decreased H2O2-induced cytotoxicity and caspase-3/7 activity in BV-2 microglia. The free radical scavenging, reactive carbonyl trapping, anti-glycation, anti-Aβ fibrillation, and microglial neuroprotective effects of these berry extracts warrant further in vivo studies to evaluate their potential neuroprotective effects against AD.

  3. Identification of the non-pertechnetate species in Hanford waste tanks, Tc(I) carbonyl complexes

    Energy Technology Data Exchange (ETDEWEB)

    Lukens, Wayne W.; Shuh, David K.; Schroeder, Norman C.; Ashley, Kenneth R.

    2003-10-16

    Immobilization of the high-level nuclear waste stored at the Hanford Reservation has been complicated by the presence of soluble, lower-valent technetium species. Previous work by Schroeder and Blanchard has shown that these species cannot be removed by ion-exchange and are difficult to oxidize. The Tc-K edge XANES spectra of the species in Tanks SY-101 and SY-103 were reported by Blanchard, but they could not be assigned to any known technetium complex. We report that the XANES spectra are most likely those of Tc(I) carbonyl species, especially fac-Tc(CO){sub 3}(gluconate){sup 2-}. This is further supported by EXAFS and {sup 99}Tc-NMR studies in nonradioactive simulants of these tank wastes.

  4. Catalytic synthesis of aromatic diisocyanates by means of carbonylation of nitrocompounds with carbon monoxide

    Energy Technology Data Exchange (ETDEWEB)

    Nefedov, B K; Manov-Yuvenskii, V I; Khoshdurdev, Kh O; Novikov, S S [AN SSSR, Moscow. Inst. Organicheskoj Khimii

    1977-02-11

    The development of an active and selective heterogeneous catalyst for synthesis of aromatic diisocyanates has been studied. The catalytic ability of the catalyst PdO-MoO/sub 3/-Fe/sub 2/O/sub 3/ deposited on ..gamma..-Al/sub 2/O/sub 3/ has been investigated in the reactions of carbonylation of aromatic dinitrocompounds with carbon oxide. The effect of the catalyst composition, method of catalyst production, reaction temperature and pressure on the catalytic ability have been studied. It has been established that the catalyst PdO-MoO/sub 3/-Fe/sub 2/O/sub 3/(2-6:1:1) deposited on ..gamma..-Al/sub 2/O/sub 3/ is highly active and selective in the reactions of carbonilation of aromatic dinitrocompounds at 210 deg and 300 atm. It has been used for synthesis of aromatic diisocyanates in yield 32-75%.

  5. Synthesis and Characterization of Low Solubility Poly Carbonyl Urea as a Slow Release Fertilizer

    International Nuclear Information System (INIS)

    Liu, Y.; Sun, X.

    2016-01-01

    Low solubility poly carbonyl urea has been successfully synthesized by the reaction of urea with methyl carbamate (MC) under the conditions of potassium carbonate as an initiator. It was characterized by FT-IR, /sup 13/C-NMR, and elemental analyser. In addition, the influences of the quantity of initiator, reaction temperature, reaction time and the molar ratio of starting materials on the conversion are discussed in detail. All those observations suggest that when initiator as 10 wt percent of urea, the reaction temperature 160 Degree C, 6 h, and n(urea):n(MC)=1:10, the reaction conversion rate can reach 78.4 percent. Moreover, the novel procedure is reported for the first time and has a significant N slow release properties, the N release in soil was 80 percent over 30 days. (author)

  6. Rotational spectrum and structure of the carbonyl sulfide-trifluoromethane weakly bound dimer.

    Science.gov (United States)

    Serafin, Michal M; Peebles, Sean A

    2006-11-02

    Pure rotational spectra of five isotopomers of the 1:1 weakly bound complex formed between carbonyl sulfide and trifluoromethane (TFM) have been measured using Fourier transform microwave spectroscopy. The experimental rotational constants and dipole moment components are consistent with a structure of C(s) symmetry in which the dipole moment vectors of OCS and HCF(3) are aligned antiparallel and at an angle of about 40 degrees and with a center of mass separation of 3.965(26) A. The derived H...O distance is 2.90(5) A, which is up to 0.6 A longer than is seen in other similar TFM complexes exhibiting C-H...O interactions. Ab initio calculations at the MP2/6-311++G(2d,2p) level give a structure with rotational constants that are in reasonable agreement with those of the normal isotopic species.

  7. A Moessbauer effect study of the bonding in several organoiron carbonyl clusters

    International Nuclear Information System (INIS)

    Long, G.J.; O'Brien, J.F.

    1988-01-01

    After a brief review of the applications of the Moessbauer effect to cyclopentadienyl containing compounds, the chemistry and spectral properties of the various iron carbonyl complexes are described. The electronic properties of a series of trinuclear and tetranuclear organoiron clusters have been investigated through Fenske-Hall self-consistent field molecular orbital calculations, and the results are compared with the Moessbauer effect isomer shifts. A linear correlation is found between the Slater effective nuclear charge, as calculated from the Fenske-Hall partial orbital occupancy factors, and the isomer shift. In these compounds the 4s orbital populations are rather constant. However, the cis and trans isomers of [CpFe(CO) 2 ] 2 have a significantly lower 4s orbital populations. In this case, the reduced 4s population must be accounted for by adding it to the effective nuclear charge to obtain a good correlation with the isomer shift. (orig.)

  8. Microbial carbonylation and hydroxylation of 20(R)-panaxadiol by Aspergillus niger.

    Science.gov (United States)

    Yan, Bin; Chen, Zhihua; Zhai, Xuguang; Yin, Guibo; Ai, Yafei; Chen, Guangtong

    2018-04-01

    20(R)-panaxadiol (PD) was metabolised by the fungus Aspergillus niger AS 3.3926 to its C-3 carbonylated metabolite and five other hydroxylated metabolites (1-6). Their structures were elucidated as 3-oxo-20(R)-panaxadiol (1), 3-oxo-7β-hydroxyl- 20(R)-panaxadiol (2), 3-oxo-7β,23α-dihydroxyl-20(R)-panaxadiol (3), 3,12-dioxo- 7β,23β-dihydroxyl-20(R)-panaxadiol (4), 3-oxo-1α,7β-dihydroxyl-20(R)-panaxadiol (5) and 3-oxo-7β,15β-dihydroxyl-20(R)-panaxadiol (6) by spectroscopic analysis. Among them, compounds 2-6 were new compounds. Pharmacological studies revealed that compound 6 exhibited significant anti-hepatic fibrosis activity.

  9. Magnetoelectric behavior of carbonyl iron mixed Mn oxide-coated ferrite nanoparticles

    Science.gov (United States)

    Ahad, Faris B. Abdul; Lee, Shang-Fan; Hung, Dung-Shing; Yao, Yeong-Der; Yang, Ruey-Bin; Lin, Chung-Kwei; Tsay, Chien-Yie

    2010-05-01

    The dielectric and magnetic properties of manganese oxide-coated Fe3O4 nanoparticles (NPs) were measured by the cavity perturbation method at x-band microwave frequencies ranging from 7-12.5 GHz with controlled external magnetic field up to 2.2 kOe at room temperature. Different ratios (5%, 10%, and 20% by weight) of coated NPs were prepared by sol-gel method then mixed with carbonyl iron powder in epoxy matrix. The saturation magnetization is inversely proportional to the NPs ratio in the mixture between 150 and 180 emu/g. The real part of the permittivity decreased with increasing NPs concentration, but the permittivity change by magnetic field increased. The tunability behavior is explained by insulator-ferromagnetic interface magnetoelectricity and the large surface volume ratio for the NPs.

  10. Electromagnetic and Microwave Absorption Properties of Carbonyl Tetrapod-Shaped Zno Nanostructures Composite Coatings

    Science.gov (United States)

    Yu, Haibo; Qin, Hui; Huang, Yunhua

    2012-08-01

    CIP/T-ZnO/EP composite coatings with carbonyl iron powders (CIP) and tetrapodshaped ZnO (T-ZnO) nanostructures as absorbers, and epoxy resin (EP) as matrix were prepared. The complex permittivity, permeability and microwave absorption properties of the coatings were investigated in the frequency range of 2-18 GHz. The effects of the weight ratio (CIP/T-ZnO/EP), the thickness and the solidification temperature on microwave absorption properties were discussed. When the weight ratio (CIP/TZnO/ EP), the thickness and the solidification temperature is 28:2:22, 1.8 mm, and 10°C, respectively, the optimal wave absorption with the minimum reflection loss (RL) value of -22.38 dB at 15.67 GHz and the bandwidth (RLcoatings may have a promising application in Ku-band (12-18 GHz).

  11. Temporal variation of carbonyl compound concentrations at a semi-rural site in Denmark

    DEFF Research Database (Denmark)

    Christensen, C.S.; Skov, H.; Nielsen, T.

    2000-01-01

    The atmospheric concentrations of formaldehyde, acetaldehyde and acetone were measured by the DNPH-technique at the semi-rural site Lille Valby, Denmark (55 degrees N) between May-July 1995, The average concentrations were observed to be 1.2 ppbv for formaldehyde, 0.8 ppbv for acetaldehyde and 1.......9 ppbv for acetone, For the set of carbonyl compounds, concentrations were found to be highly correlated, though only during daytime, The weak correlations observed during nighttime are believed to be caused by the dry deposition of especially formaldehyde, During periods with low photochemical activity...... of hydrocarbons during long-range transport. Especially, the concentration levels of acetone showed a pronounced seasonal-variation with the highest levels observed during summertime and lowest in winter and spring. The seasonal variation in the concentration levels of formaldehyde and acetaldehyde were small...

  12. Inactivation of cellular enzymes by carbonyls and protein-bound glycation/glycoxidation products

    DEFF Research Database (Denmark)

    Morgan, Philip E; Dean, Roger T; Davies, Michael Jonathan

    2002-01-01

    products. In this study, we have examined the effect of glucose and carbonyl compounds (methylglyoxal, glyoxal, glycolaldehyde, and hydroxyacetone), and glycation products arising from reaction of these materials with model proteins, on the activity of three key cellular enzymes: glyceraldehyde-3-phosphate...... dehydrogenase (GAPDH), glutathione reductase, and lactate dehydrogenase, both in isolation and in cell lysates. In contrast to glucose (1M, both fresh and aged for 8 weeks), which had no effect, marked inhibition of all three enzymes was observed with methylglyoxal and glyoxal. GAPDH was also inhibited...... by glycolaldehyde and hydroxyacetone. Incubation of these enzymes with proteins that had been preglycated with methylglyoxal, but not glucose, also resulted in significant time- and concentration-dependent inhibition with both isolated enzymes and cell lysates. This inhibition was not metal ion, oxygen, superoxide...

  13. Selectivity control of carbonylation of methanol to dimethyl oxalate and dimethyl carbonate over gold anode by electrochemical potential.

    Science.gov (United States)

    Funakawa, Akiyasu; Yamanaka, Ichiro; Takenaka, Sakae; Otsuka, Kiyoshi

    2004-05-05

    New and unique electrocatalysis of gold for the carbonylation of methanol to dimethyl oxalate (DMO) and dimethyl carbonate (DMC) was found. The selectivity to DMO and DMC could be controlled over gold anode by electrochemical potential, as you like. Drastic changes of gold electrocatalysis was due to changes of the oxidation state of gold, Au0 or Au3+.

  14. Palladium-catalyzed domino C,N-coupling/carbonylation/Suzuki coupling reaction: an efficient synthesis of 2-aroyl-/heteroaroylindoles.

    Science.gov (United States)

    Arthuis, Martin; Pontikis, Renée; Florent, Jean-Claude

    2009-10-15

    A convenient one-pot synthesis of 2-aroylindoles using a domino palladium-catalyzed C,N-coupling/carbonylation/C,C-coupling sequence is described. The reaction involved easily prepared 2-gem-dibromovinylanilines and boronic acids under carbon monoxide. Optimized reaction conditions allowed the construction of a wide variety of highly functionalized 2-aroyl-/heteroaroylindoles in satisfactory yields.

  15. Metal carbonyl vapor generation coupled with dielectric barrier discharge to avoid plasma quench for optical emission spectrometry.

    Science.gov (United States)

    Cai, Yi; Li, Shao-Hua; Dou, Shuai; Yu, Yong-Liang; Wang, Jian-Hua

    2015-01-20

    The scope of dielectric barrier discharge (DBD) microplasma as a radiation source for optical emission spectrometry (OES) is extended by nickel carbonyl vapor generation. We proved that metal carbonyl completely avoids the extinguishing of plasma, and it is much more suitable for matching the DBD excitation and OES detection with respect to significant DBD quenching by concomitant hydrogen when hydride generation is used. A concentric quartz UV reactor allows sample solution to flow through the central channel wherein to efficiently receive the uniformly distributed UV irradiation in the confined cylindrical space between the concentric tubes, which facilitates effective carbonyl generation in a nickel solution. The carbonyl is transferred into the DBD excitation chamber by an argon stream for nickel excitation, and the characteristic emission of nickel at 232.0 nm is detected by a charge-coupled device (CCD) spectrometer. A 1.0 mL sample solution results in a linear range of 5-100 μg L(-1) along with a detection limit of 1.3 μg L(-1) and a precision of 2.4% RSD at 50 μg L(-1). The present DBD-OES system is validated by nickel in certified reference materials.

  16. Iodine-catalyzed addition of 2-mercaptoethanol to chalcone derivatives: Synthesis of the novel β-mercapto carbonyl compounds

    Directory of Open Access Journals (Sweden)

    Gürkan Yerli

    2012-01-01

    Full Text Available In this study, a series of novel β-mercapto carbonyl derivatives (3-(2-hydroxyethylthio-1,3-diarylpropan-1-one (5a-i were prepared by addition of 2-mercaptoethanol (4 to chalcones (3a-i in the presence of catalytic amount of iodine (10 mol % in CH 2Cl 2.

  17. Ruthenium supported on magnetic nanoparticles: An efficient and recoverable catalyst for hydrogenation of alkynes and transfer hydrogenation of carbonyl compounds

    Science.gov (United States)

    Ruthenium supported on surface modified magnetic nanoparticles (NiFe2O4) has been successfully synthesized and applied for hydrogenation of alkynes at room temperature as well as transfer hydrogenation of a number of carbonyl compounds under microwave irradiation conditions. The ...

  18. The influence of chirality in the amide side chain on the carbonyl orientation in rotational isomers of 3-carbamoylpyridinium halides

    NARCIS (Netherlands)

    Bastiaansen, L.A.M.; Vermeulen, T.J.M.; Buck, H.M.; Smeets, W.J.J.; Kanters, J.A.

    1988-01-01

    The direction of the carbonyl orientation in solid amide rotamers of 3-(N-methyl-N-a-methylbenzylcarbamoyl)-1,2,4-trimethylpyridinium iodide is governed by the (R)- or (S)-chirality in the amide side chain; X-ray structures and c.d. spectra are correlated.

  19. Characteristics and personal exposures of carbonyl compounds in the subway stations and in-subway trains of Shanghai, China.

    Science.gov (United States)

    Feng, Yanli; Mu, Cuicui; Zhai, Jinqing; Li, Jian; Zou, Ting

    2010-11-15

    Carbonyl compounds including their concentrations, potential sources, diurnal variations and personal exposure were investigated in six subway stations and in-subway trains in Shanghai in June 2008. The carbonyls were collected onto solid sorbent (Tenax TA) coated with pentafluorophenyl hydrazine (PFPH), followed by solvent extraction and gas chromatography (GC)/mass spectrometry (MS) analysis of the PFPH derivatives. The total carbonyl concentrations of in-subway train were about 1.4-2.5 times lower than in-subway stations. A significant correlation (R>0.5, psubway stations. The diurnal variations in both the subway station and in-subway train showed that the concentrations of most carbonyls were much higher in the morning rush hour than in other sampling periods. Additionally, pronounced diurnal variations of acetaldehyde concentration before and after the evening peak hour in the subway train suggested that passengers contributed to high acetaldehyde levels. The personal exposure showed that the underground subway stations were important microenvironment for exposure to formaldehyde and acetaldehyde. Copyright © 2010 Elsevier B.V. All rights reserved.

  20. Highly efficient energy transfer from a carbonyl carotenoid to chlorophyll a in the main light harvesting complex of Chromera velia

    Czech Academy of Sciences Publication Activity Database

    Durchan, Milan; Kesan, G.; Šlouf, M.; Fuciman, M.; Staleva, H.; Tichý, Josef; Litvín, Radek; Bína, David; Vácha, František; Polívka, Tomáš

    2014-01-01

    Roč. 1837, č. 10 (2014), s. 1748-1755 ISSN 0005-2728 R&D Projects: GA ČR(CZ) GAP205/11/1164; GA ČR GBP501/12/G055 Institutional support: RVO:60077344 Keywords : Energy transfer * Light-harvesting * Carbonyl carotenoids Subject RIV: BO - Biophysics Impact factor: 5.353, year: 2014

  1. Reactive carbonyl compounds impair wound healing by vimentin collapse and loss of the primary cilium.

    Science.gov (United States)

    Rodríguez-Ribera, Lara; Slattery, Craig; Mc Morrow, Tara; Marcos, Ricard; Pastor, Susana

    2017-10-01

    In renal pathologies tubulo-interstitial fibrosis results from an aberrant wound-healing ability where the normal epithelial tissue is substituted for scar tissue caused by accumulation of extracellular matrix proteins (ECM). During the wound-healing process, epithelial cells may undergo epithelial-mesenchymal transition (EMT) acquiring a mesenchymal-like phenotype that allows cells to migrate and re-epithelialize the wound site. It has been reported that chronic inflammation and uremic milieu are involved in wound-healing and enhanced kidney damage in chronic kidney disease (CKD) patients. In this study we evaluated reactive carbonyl compounds (RCC) effects on renal wound healing. The compounds resulting from carbonyl stress evaluated in this study were glyoxal (GO), methylglyoxal (MGO), malondialdehyde (MDA) and 4-hydroxy-hexenal (HHE). Wound repair ability was evaluated by the wound healing assay using HK-2 cells. EMT was evaluated by morphological, protein and transcriptional changes using microscopy, western blot, zymography and RT-qPCR. Changes in the vimentin network and primary cilia were assessed by immunofluorescence. Our data demonstrated that MDA and GO delay wound closure mediated by vimentin disruption, which caused collagen I mRNA decrease, and deciliation. In contrast, HHE treatment (and MGO to a minor degree) induced morphological changes and increased mesenchymal marker expression and gelatinase activity in HK-2 cells. In this study, we have demonstrated for the first time that exposure to RCC differentially affects wound healing in proximal tubular epithelia. A better comprehension of effects of uremic toxins on wound healing and fibrosis and migration is necessary to seek mechanisms to slow down renal fibrosis. Copyright © 2017 Elsevier Ltd. All rights reserved.

  2. Neurotoxicity of carbonyl sulfide in F344 rats following inhalation exposure for up to 12 weeks

    International Nuclear Information System (INIS)

    Morgan, Daniel L.; Little, Peter B.; Herr, David W.; Moser, Virginia C.; Collins, Bradley; Herbert, Ronald; Johnson, G. Allan; Maronpot, Robert R.; Harry, G. Jean; Sills, Robert C.

    2004-01-01

    Carbonyl sulfide (COS), a high-priority Clean Air Act chemical, was evaluated for neurotoxicity in short-term studies. F344 rats were exposed to 75-600 ppm COS 6 h per day, 5 days per week for up to 12 weeks. In rats exposed to 500 or 600 ppm for up to 4 days, malacia and microgliosis were detected in numerous neuroanatomical regions of the brain by conventional optical microscopy and magnetic resonance microscopy (MRM). After a 2-week exposure to 400 ppm, rats were evaluated using a functional observational battery. Slight gait abnormality was detected in 50% of the rats and hypotonia was present in all rats exposed to COS. Decreases in motor activity, and forelimb and hindlimb grip strength were also detected. In rats exposed to 400 ppm for 12 weeks, predominant lesions were in the parietal cortex area 1 (necrosis) and posterior colliculus (neuronal loss, microgliosis, hemorrhage), and occasional necrosis was present in the putamen, thalamus, and anterior olivary nucleus. Carbonyl sulfide specifically targeted the auditory system including the olivary nucleus, nucleus of the lateral lemniscus, and posterior colliculus. Consistent with these findings were alterations in the amplitude of the brainstem auditory evoked responses (BAER) for peaks N 3 , P 4 , N 4 , and N 5 that represented changes in auditory transmission between the anterior olivary nucleus to the medial geniculate nucleus in animals after exposure for 2 weeks to 400 ppm COS. A concentration-related decrease in cytochrome oxidase activity was detected in the posterior colliculus and parietal cortex of exposed rats as early as 3 weeks. Cytochrome oxidase activity was significantly decreased at COS concentrations that did not cause detectable lesions, suggesting that disruption of the mitochondrial respiratory chain may precede these brain lesions. Our studies demonstrate that this environmental air contaminant has the potential to cause a wide spectrum of brain lesions that are dependent on the degree

  3. Chitosan Prevents Gentamicin-Induced Nephrotoxicity via a Carbonyl Stress-Dependent Pathway

    Directory of Open Access Journals (Sweden)

    Chu-Kung Chou

    2015-01-01

    Full Text Available Aminoglycosides are widely used to treat infections; however, their applications are limited by nephrotoxicity. With the increase of antibiotic resistance, the use of aminoglycosides is inevitable. Low-molecular-weight chitosan (LMWC has shown renal protective effects in dialysis patients. However, no study has evaluated LMWC for preventing aminoglycoside-induced nephrotoxicity or determined the mechanisms underlying the renal protective effects. In this study, LMWC (165 or 825 mg/kg/day or metformin (100 mg/kg/day was orally administered for 13 days to rats with nephropathy induced by gentamicin (GM, a kind of aminoglycoside (150 mg/kg/day i.p. for 6 days. Both LMCW doses improved renal function. Serum creatinine levels improved in rats treated with 165 and 825 mg/kg/day LMWC (from 2.14 ± 0.74 mg/dL to 1.26 ± 0.46 mg/dL and 0.69 ± 0.12 mg/dL, resp., P < 0.05. Blood urea nitrogen levels were also improved in these rats (from 73.73 ± 21.13 mg/dL to 58.70 ± 22.71 mg/dL and 28.82 ± 3.84 mg/dL, resp., P < 0.05. Additionally, renal tissue morphology improved after LMWC treatment, and accumulation of renal methylglyoxal, a damage factor associated with carbonyl stress, was reversed. These results show that LMWC prevents GM-induced renal toxicity via a carbonyl stress-dependent pathway.

  4. Synthesis and preclinical evaluation of [11C-carbonyl]PF-04457845 for neuroimaging of fatty acid amide hydrolase

    International Nuclear Information System (INIS)

    Hicks, Justin W.; Parkes, Jun; Sadovski, Oleg; Tong, Junchao; Houle, Sylvain; Vasdev, Neil; Wilson, Alan A.

    2013-01-01

    Introduction: Fatty acid amide hydrolase (FAAH) has a significant role in regulating endocannabinoid signaling in the central nervous system. As such, FAAH inhibitors are being actively sought for pain, addiction, and other indications. This has led to the recent pursuit of positron emission tomography (PET) radiotracers targeting FAAH. We report herein the preparation and preclinical evaluation of [ 11 C-carbonyl]PF-04457845, an isotopologue of the potent irreversible FAAH inhibitor. Methods: PF-04457845 was radiolabeled at the carbonyl position via automated [ 11 C]CO 2 -fixation. Ex vivo brain biodistribution of [ 11 C-carbonyl]PF-04457845 was carried out in conscious rats. Specificity was determined by pre-administration of PF-04457845 or URB597 prior to [ 11 C-carbonyl]PF-04457845. In a separate experiment, rats injected with the title radiotracer had whole brains excised, homogenized and extracted to examine irreversible binding to brain parenchyma. Results: The title compound was prepared in 5 ± 1% (n = 4) isolated radiochemical yield based on starting [ 11 C]CO 2 (decay uncorrected) within 25 min from end-of-bombardment in > 98% radiochemical purity and a specific activity of 73.5 ± 8.2 GBq/μmol at end-of-synthesis. Uptake of [ 11 C-carbonyl]PF-04457845 into the rat brain was high (range of 1.2–4.4 SUV), heterogeneous, and in accordance with reported FAAH distribution. Saturable binding was demonstrated by a dose-dependent reduction in brain radioactivity uptake following pre-treatment with PF-04457845. Pre-treatment with the prototypical FAAH inhibitor, URB597, reduced the brain radiotracer uptake in all regions by 71–81%, demonstrating specificity for FAAH. The binding of [ 11 C-carbonyl]PF-04457845 to FAAH at 40 min post injection was irreversible as 98% of the radioactivity in the brain could not be extracted. Conclusions: [ 11 C-carbonyl]PF-04457845 was rapidly synthesized via an automated radiosynthesis. Ex vivo biodistribution studies in

  5. Carbonyl compound emissions from a heavy-duty diesel engine fueled with diesel fuel and ethanol-diesel blend.

    Science.gov (United States)

    Song, Chonglin; Zhao, Zhuang; Lv, Gang; Song, Jinou; Liu, Lidong; Zhao, Ruifen

    2010-05-01

    This paper presents an investigation of the carbonyl emissions from a direct injection heavy-duty diesel engine fueled with pure diesel fuel (DF) and blended fuel containing 15% by volume of ethanol (E/DF). The tests have been conducted under steady-state operating conditions at 1200, 1800, 2600 rpm and idle speed. The experimental results show that acetaldehyde is the most predominant carbonyl, followed by formaldehyde, acrolein, acetone, propionaldehyde and crotonaldehyde, produced from both fuels. The emission factors of total carbonyls vary in the range 13.8-295.9 mg(kWh)(-1) for DF and 17.8-380.2mg(kWh)(-1) for E/DF, respectively. The introduction of ethanol into diesel fuel results in a decrease in acrolein emissions, while the other carbonyls show general increases: at low engine speed (1200 rpm), 0-55% for formaldehyde, 4-44% for acetaldehyde, 38-224% for acetone, and 5-52% for crotonaldehyde; at medium engine speed (1800 rpm), 106-413% for formaldehyde, 4-143% for acetaldehyde, 74-113% for acetone, 114-1216% for propionaldehyde, and 15-163% for crotonaldehyde; at high engine speed (2600 rpm), 36-431% for formaldehyde, 18-61% for acetaldehyde, 22-241% for acetone, and 6-61% for propionaldehyde. A gradual reduction in the brake specific emissions of each carbonyl compound from both fuels is observed with increase in engine load. Among three levels of engine speed employed, both DF and E/DF emit most CBC emissions at high engine speed. On the whole, the presence of ethanol in diesel fuel leads to an increase in aldehyde emissions. Copyright (c) 2010 Elsevier Ltd. All rights reserved.

  6. A top-down approach of surface carbonyl sulfide exchange by a Mediterranean oak forest ecosystem in southern France

    Science.gov (United States)

    Belviso, Sauveur; Reiter, Ilja Marco; Loubet, Benjamin; Gros, Valérie; Lathière, Juliette; Montagne, David; Delmotte, Marc; Ramonet, Michel; Kalogridis, Cerise; Lebegue, Benjamin; Bonnaire, Nicolas; Kazan, Victor; Gauquelin, Thierry; Fernandez, Catherine; Genty, Bernard

    2016-12-01

    The role that soil, foliage, and atmospheric dynamics have on surface carbonyl sulfide (OCS) exchange in a Mediterranean forest ecosystem in southern France (the Oak Observatory at the Observatoire de Haute Provence, O3HP) was investigated in June of 2012 and 2013 with essentially a top-down approach. Atmospheric data suggest that the site is appropriate for estimating gross primary production (GPP) directly from eddy covariance measurements of OCS fluxes, but it is less adequate for scaling net ecosystem exchange (NEE) to GPP from observations of vertical gradients of OCS relative to CO2 during the daytime. Firstly, OCS and carbon dioxide (CO2) diurnal variations and vertical gradients show no net exchange of OCS at night when the carbon fluxes are dominated by ecosystem respiration. This contrasts with other oak woodland ecosystems of a Mediterranean climate, where nocturnal uptake of OCS by soil and/or vegetation has been observed. Since temperature, water, and organic carbon content of soil at the O3HP should favor the uptake of OCS, the lack of nocturnal net uptake would indicate that its gross consumption in soil is compensated for by emission processes that remain to be characterized. Secondly, the uptake of OCS during the photosynthetic period was characterized in two different ways. We measured ozone (O3) deposition velocities and estimated the partitioning of O3 deposition between stomatal and non-stomatal pathways before the start of a joint survey of OCS and O3 surface concentrations. We observed an increasing trend in the relative importance of the stomatal pathway during the morning hours and synchronous steep drops of mixing ratios of OCS (amplitude in the range of 60-100 ppt) and O3 (amplitude in the range of 15-30 ppb) after sunrise and before the break up of the nocturnal boundary layer. The uptake of OCS by plants was also characterized from vertical profiles. However, the time window for calculation of the ecosystem relative uptake (ERU) of OCS

  7. Determination of protein-carbonyls and ubiquitin-mediated proteolysis as biomarkers of oxidative-stress in bivalvia and anthozoa

    International Nuclear Information System (INIS)

    Walker, Stephen Thomas

    2002-01-01

    This study describes the investigation of biomarkers of oxidative-stress in the bivalves Mytilus edulis and Dosinia lupinus, together with host and symbiont tissues of the scleractinian Anthozoa Agaricia agaricites. The biomarkers used were assay of total (via spectrophotometry) and individual (via Western blotting; Oxyblot kit) protein-carbonyls (PC=Os) and content of ubiquitin protein conjugates (UPC) via Western blotting (Bivalvia and Anthozoa) and immunohistochemistry (Anthozoa only). Additional assays for Bivalvia were Trolox equivalent antioxidant capacity (TEAC); and post γ-irradiation survival rates. Experimental stressors for Bivalvia were increased seawater temperature, H 2 O 2 and 60 Co γ-radiation (latter two were used in vivo and in vitro). Comparisons of clean and polluted marine sites are included. Stressors used for Anthozoa were increased solar irradiation concomitant with elevated seawater temperature. Results and conclusions were as follows: individual samples showed considerable variation, pooling of samples improved consistency. Controls for both biomarkers had detectable background levels in each phylum, against which relatively small differences were assessed. In M. edulis, no measurable differences in PC=Os could be determined when elevated seawater temperature or dilute H 2 O 2 ( 2 O 2 (30% v/v) produced a small difference. 60 Co γ-radiation produced clearer differences via Oxyblot and spectrophotometric assays. Comparison of four different tissues from the two bivalves found considerable species-specific and tissue-specific differences. Post-irradiation mortality between species was significantly different (<0.001), D. lupinus was more susceptible than M. edulis. TEAC values generally showed a decrease following irradiation (except for digestive gland). UPCs were clearly different between tissues and between species. PC=Os can be detected by DNPH-reactivity/Western blotting assay in host A. agaricites. UPCs can be assayed via Western

  8. Determination of protein-carbonyls and ubiquitin-mediated proteolysis as biomarkers of oxidative-stress in bivalvia and anthozoa

    Energy Technology Data Exchange (ETDEWEB)

    Walker, Stephen Thomas

    2002-07-01

    This study describes the investigation of biomarkers of oxidative-stress in the bivalves Mytilus edulis and Dosinia lupinus, together with host and symbiont tissues of the scleractinian Anthozoa Agaricia agaricites. The biomarkers used were assay of total (via spectrophotometry) and individual (via Western blotting; Oxyblot kit) protein-carbonyls (PC=Os) and content of ubiquitin protein conjugates (UPC) via Western blotting (Bivalvia and Anthozoa) and immunohistochemistry (Anthozoa only). Additional assays for Bivalvia were Trolox equivalent antioxidant capacity (TEAC); and post {gamma}-irradiation survival rates. Experimental stressors for Bivalvia were increased seawater temperature, H{sub 2}O{sub 2} and {sup 60}Co {gamma}-radiation (latter two were used in vivo and in vitro). Comparisons of clean and polluted marine sites are included. Stressors used for Anthozoa were increased solar irradiation concomitant with elevated seawater temperature. Results and conclusions were as follows: individual samples showed considerable variation, pooling of samples improved consistency. Controls for both biomarkers had detectable background levels in each phylum, against which relatively small differences were assessed. In M. edulis, no measurable differences in PC=Os could be determined when elevated seawater temperature or dilute H{sub 2}O{sub 2} (<30% v/v) stressors were used, nor with between-site comparisons. Concentrated H{sub 2}O{sub 2} (30% v/v) produced a small difference. {sup 60}Co {gamma}-radiation produced clearer differences via Oxyblot and spectrophotometric assays. Comparison of four different tissues from the two bivalves found considerable species-specific and tissue-specific differences. Post-irradiation mortality between species was significantly different (<0.001), D. lupinus was more susceptible than M. edulis. TEAC values generally showed a decrease following irradiation (except for digestive gland). UPCs were clearly different between tissues and

  9. Infrared spectroscopy of flavones and flavonols. Reexamination of the hydroxyl and carbonyl vibrations in relation to the interactions of flavonoids with membrane lipids

    Science.gov (United States)

    Baranović, Goran; Šegota, Suzana

    2018-03-01

    Detailed vibrational assignments for twelve flavonoids (seven flavones (flavone, 3- and 5-hydroxyflavone, chrysin, apigenin, fisetin and luteolin) and five flavonols (galangin, kaempferol, quercetin, morin and myricetin)) have been made based on own and reported experimental data and calculations at the B3LYP/6-31 + G(d,p) level of theory. All the molecules are treated in a uniform way by using the same set of redundancy-free set of internal coordinates. A generalized harmonic mode mixing is used to corroborate the vibrational characteristics of this important class of molecules. Each flavonoid molecule can be treated from the vibrational point of view as made of relatively weakly coupled chromone and phenyl part. It has been shown that the strongest band around 1600 cm- 1 need not be attributable to the Cdbnd O stretching. The way the vibrations of any of the hydroxyl groups are mixed with ring vibrations and vibrations of other neighboring hydroxyl groups is rather involved. This imposes severe limitations on any attempt to describe normal modes of a flavonol in terms of hydroxyl or carbonyl group vibrations. The role of water molecules in the appearance of flavonoid IR spectra is emphasized. Knowing for the great affinity of phosphate groups in lipids towards water, the immediate consequence is a reasonable assumption that flavonoid lipid interactions is mediated by water.

  10. Evaluation of the Nutritive Value of Carbonyl-amino Urea%羰氨缩合尿素的营养价值评价

    Institute of Scientific and Technical Information of China (English)

    李兴伟; 薛白; 王之盛; 徐世晓; 王基恒; 李占锋

    2011-01-01

    This experiment was conducted to evaluate the nutritive value of carbonyl-amino urea for ruminants. The slow release characteristic of carbonyl-amino urea was evaluated in vitro with the change of ammonia N concentration. After that, an experiment with a 3 ×3 Latin Square design was carried out to study the effect of carbonyl-amino urea (CAU) on ruminal fluid pH, ammonia N concentration, microbial protein production and blood indices in Tibetan sheep. The results in vitro showed that; ammonia N concentration in CAU group was significantly lower than that in urea phosphate (UP) group and greater than that in soybean meal ( SBM) group before 8 h, and it reached the maximum value of 42. 76 mg/dL at the 8th h in artificial rumen fermentation , which was 11.27% lower than that in UP group and 44. 08% higher than that in SBM group. The results in vivo showed that: ruminal fluid pH in all groups increased firstly, then decreased; it reached the minimum value at the 6th h after feeding and there was no difference (P >0.05) between SBM and CAU groups at the 6th h; after 14 h, there were no significant differences among the three groups. The ammonia N concentration in CAU group was lower than that in UP group, and there was on difference between SBM and CAU groups at the 2nd h after feeding( P >0. 05) ; at the 8th h, ammonia N concentrations in SBM and UP groups reached the minimum values, and there were on differences at other times. The average concentration of microbial crude protein was 17. 25 mg/dL, which was 3. 01% higher than that in UP group and 30. 45% higher than that in SBM group. Serum biochemical indices, such as BUN, TP, ALB, GOT and GPT, were all in normal physiological range and there were no significant differences among the three groups(P >0. 05). Collectively, the CAU supplementation could control the release speed of ammonia nitrogen and improve the fermentation in rumen, and promote microbial protein production by improving the BUN availability for

  11. Determination of Carbonyl Compounds in Cork Agglomerates by GDME-HPLC-UV: Identification of the Extracted Compounds by HPLC-MS/MS.

    Science.gov (United States)

    Brandão, Pedro Francisco; Ramos, Rui Miguel; Almeida, Paulo Joaquim; Rodrigues, José António

    2017-02-08

    A new approach is proposed for the extraction and determination of carbonyl compounds in solid samples, such as wood or cork materials. Cork products are used as building materials due to their singular characteristics; however, little is known about its aldehyde emission potential and content. Sample preparation was done by using a gas-diffusion microextraction (GDME) device for the direct extraction of volatile aldehydes and derivatization with 2,4-dinitrophenylhydrazine. Analytical determination of the extracts was done by HPLC-UV, with detection at 360 nm. The developed methodology proved to be a reliable tool for aldehyde determination in cork agglomerate samples with suitable method features. Mass spectrometry studies were performed for each sample, which enabled the identification, in the extracts, of the derivatization products of a total of 13 aldehydes (formaldehyde, acetaldehyde, furfural, propanal, 5-methylfurfural, butanal, benzaldehyde, pentanal, hexanal, trans-2-heptenal, heptanal, octanal, and trans-2-nonenal) and 4 ketones (3-hydroxy-2-butanone, acetone, cyclohexanone, and acetophenone). This new analytical methodology simultaneously proved to be consistent for the identification and determination of aldehydes in cork agglomerates and a very simple and straightforward procedure.

  12. Contribution to the study of the sintering of ex-carbonyl iron in the α and γ phases using the micro-fractographic technique

    International Nuclear Information System (INIS)

    Oxley Gaborit de Montjou, M.Th.

    1966-01-01

    The micro-fractographic study of the sintering of ex-carbonyl iron has shown or confirmed a number of phenomena of which the principal are as followed: Sintering in the a phase: -) existence of two stages of sintering differentiated by the type of rupture (inter or trans-crystalline); -) marked influence of the content of oxygen in the atmosphere and in the initial compressed sample on the speed of sintering; -) formation of striations on the grain-boundary surfaces and on the inner surface of pores caused by the presence of oxygen. Sintering in the γ phase: -) a pronounced decrease in the speed of sintering: the grains in the initial powder remain in the granular state within the final α crystal in the iron sintered in the lower γ range even after several hours of sintering; -) this granular structure can be eliminated by intermediate compression thus enabling the sintering process to proceed. A considerable decrease in the speed of sintering if the A 3 point is passed one or more times in the α range sintering. A high speed sintering if the treatment in the γ range is carried out at or above 1300 C. The results of this study agree with micrographic investigation as well as with dilatometric measurements and known auto-diffusion coefficients. (author) [fr

  13. COMMUNICATIONS GROUP

    CERN Multimedia

    L. Taylor

    2011-01-01

    Communications Infrastructure The 55 CMS Centres worldwide are well used by physicists working on remote CMS shifts, Computing operations, data quality monitoring, data analysis and outreach. The CMS Centre@CERN in Meyrin is particularly busy at the moment, hosting about 50 physicists taking part in the heavy-ion data-taking and analysis. Three new CMS meeting room will be equipped for videoconferencing in early 2012: 40/5B-08, 42/R-031, and 28/S-029. The CMS-TV service showing LHC Page 1, CMS Page 1, etc. (http://cmsdoc.cern.ch/cmscc/projector/index.jsp) is now also available for mobile devices: http://cern.ch/mcmstv. Figure 12: Screenshots of CMS-TV for mobile devices Information Systems CMS has a new web site: (http://cern.ch/cms) using a modern web Content Management System to ensure content and links are managed and updated easily and coherently. It covers all CMS sub-projects and groups, replacing the iCMS internal pages. It also incorporates the existing CMS public web site (http:/...

  14. Recent Developments in Carbonylation Chemistry Using [13 C]CO, [11 C]CO and [14 C]CO.

    Science.gov (United States)

    Nielsen, Dennis U; Neumann, Karoline T; Lindhardt, Anders T; Skrydstrup, Troels

    2018-06-01

    Carbon monoxide represents the most important C1-building block for the chemical industry, both for the production of bulk and fine chemicals, but also for synthetic fuels. Yet, its toxicity and subsequently its cautious handling has limited its applications in medicinal chemistry research and in particular for the synthesis of pharmaceutically relevant molecules. Recent years have nevertheless witnessed a considerable headway on the development of carbon monoxide surrogates and reactor systems, which provide an ideal setting for performing carbonylation chemistry with stoichiometric and sub-stoichiometric carbon monoxide. Such set-ups are particularly ideal for the introduction of isotope labels such as carbon-11, carbon-13 and carbon-14 into bioactive compounds. This review summarizes this growing field and examines the large number of carbonylation reactions that can be exploited for the introduction of a carbon isotope. This article is protected by copyright. All rights reserved.

  15. Magnetically tunable elasticity for magnetic hydrogels consisting of carrageenan and carbonyl iron particles.

    Science.gov (United States)

    Mitsumata, Tetsu; Honda, Atomu; Kanazawa, Hiroki; Kawai, Mika

    2012-10-11

    A new class of magnetoelastic gel that demonstrates drastic and reversible changes in storage modulus without using strong magnetic fields was obtained. The magnetic gel consists of carrageenan and carbonyl iron particles. The magnetic gel with a volume fraction of magnetic particles of 0.30 exhibited a reversible increase by a factor of 1400 of the storage modulus upon a magnetic field of 500 mT, which is the highest value in the past for magnetorheological soft materials. It is considered that the giant magnetoelastic behavior is caused by both high dispersibility and high mobility of magnetic particles in the carrageenan gel. The off-field storage modulus of the magnetic gel at volume fractions below 0.30 obeyed the Krieger-Dougherty equation, indicating random dispersion of magnetic particles. At 500 mT, the storage modulus was higher than 4.0 MPa, which is equal to that of magnetic fluids, indicating that the magnetic particles move and form a chain structure by magnetic fields. Morphological study revealed the evidence that the magnetic particles embedded in the gel were aligned in the direction of magnetic fields, accompanied by stretching of the gel network. We conclude that the giant magnetoelastic phenomenon originates from the chain structure consisting of magnetic particles similar to magnetic fluids.

  16. Isotope effect in the carbonyl sulfide reaction with O(3P)

    DEFF Research Database (Denmark)

    Hattori, Shohei; Schmidt, Johan Albrecht; Mahler, Denise W.

    2012-01-01

    The sulfur kinetic isotope effect (KIE) in the reaction of carbonyl sulfide (OCS) with O((3)P) was studied in relative rate experiments at 298 ± 2 K and 955 ± 10 mbar. The reaction was carried out in a photochemical reactor using long path FTIR detection, and data were analyzed using a nonlinear...... least-squares spectral fitting procedure with line parameters from the HITRAN database. The ratio of the rate of the reaction of OC(34)S relative to OC(32)S was found to be 0.9783 ± 0.0062 ((34)e = (-21.7 ± 6.2)‰). The KIE was also calculated using quantum chemistry and classical transition state theory......; at 300 K, the isotopic fractionation was found to be (34)e = -14.8‰. The OCS sink reaction with O((3)P) cannot explain the large fractionation in (34)S, over +73‰, indicated by remote sensing data. In addition, (34)e in OCS photolysis and OH oxidation are not larger than 10‰, indicating that...

  17. The influence of oscillations on product selectivity during the palladium-catalysed phenylacetylene oxidative carbonylation reaction.

    Science.gov (United States)

    Novakovic, Katarina; Grosjean, Christophe; Scott, Stephen K; Whiting, Andrew; Willis, Mark J; Wright, Allen R

    2008-02-07

    This paper reports on the influence of oscillations on product selectivity as well as the dynamics of product formation during the palladium-catalysed phenylacetylene oxidative carbonylation reaction in a catalytic system (PdI2, KI, Air, NaOAc in methanol). The occurrence of the pH oscillations is related to PdI2 granularity and the initial pH drop after phenylacetylene addition. To achieve pH and reaction exotherm oscillations regulation of the amount of PdI2 is required, ensuring that the initial pH does not fall significantly below 1 after phenylacetylene addition. Experiments in both oscillatory and non-oscillatory pH regimes were performed in an HEL SIMULAR reaction calorimeter with the concentration-time profiles measured using a GC-MS. It is demonstrated that when operating in an oscillatory pH regime product formation may be suppressed until oscillations occur after which there is a steep increase in the formation of Z-2-phenyl-but-2-enedioic acid dimethyl ester. When operating in non-oscillatory pH mode the products are formed steadily over time with the main products being Z-2-phenyl-but-2-enedioic acid dimethyl ester, 2-phenyl-acrylic acid methyl ester and E-3-phenyl-acrylic acid methyl ester.

  18. Carbonylation of aryl bromides with palladium polyphthalocyanine/active carbon catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Ohkatsu, Y.; Nakazawa, K.; Osa, T.

    1979-11-01

    The reaction of bromobenzene with carbon monoxide over carbon-supported 1.7Vertical Bar3< palladium polyphthalocyanine yielded carbonylated products in the presence of water or methanol and only benzene and dibromobenzene in their absence. At 300/sup 0/C and 1 sec contact time, e.g., the reaction of a 1:2.6:1 mole ratio feed of bromobenzene/methanol/carbon monoxide yielded benzoic acid with 61.7Vertical Bar3< selectivity at 83.2Vertical Bar3< conversion, a 1:0.8:3 feed gave benzoic acid with 84.4Vertical Bar3< selectivity at 40.7Vertical Bar3< conversion. The addition of water instead of methanol gave higher conversions, e.g., a feed of 1:3:1 bromobenzene/water/carbon monoxide yielded benzoic acid with 69.2Vertical Bar3< selectivity at 90.9Vertical Bar3< conversion. Analyses of product distributions obtained in these and autoclaved experiments at 10-50 kg/sq cm carbon monoxide pressure suggested a free radical mechanism.

  19. Comparison of extraction techniques and mass spectrometric ionization modes in the analysis of wine volatile carbonyls

    Energy Technology Data Exchange (ETDEWEB)

    Zapata, Julian; Mateo-Vivaracho, Laura; Cacho, Juan [Laboratory for Flavor Analysis and Enology, Institute of Engineering of Aragon, I3A, Department of Analytical Chemistry, Faculty of Sciences, University of Zaragoza, 50009 Zaragoza (Spain); Ferreira, Vicente, E-mail: vferre@unizar.es [Laboratory for Flavor Analysis and Enology, Institute of Engineering of Aragon, I3A, Department of Analytical Chemistry, Faculty of Sciences, University of Zaragoza, 50009 Zaragoza (Spain)

    2010-02-15

    This work presents a comparative study of the analytical characteristics of two methods for the analysis of carbonyl compounds in wine, both based on the derivatization with O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine hydrochloride (PFBHA). In the first method derivatives are formed in the solid phase extraction (SPE) cartridge in which the analytes have been previously isolated, while in the second method derivatives are formed in a solid phase microextraction (SPME) fibre saturated with vapors of the reagent and exposed to the sample headspace. In both cases detection has been carried out by electron impact (EI) or negative chemical ionization (NCI) mass spectrometry. The possibility of determining haloanisols simultaneously has been also considered. The method based on SPE presents, in general, better analytical properties than the SPME one. Although linearity was satisfactory for both methods (R{sup 2} > 0.99), repeatability of the SPE method (RSD < 10%) was better than that obtained with SPME (9% < RSD < 20%). Detection limits obtained with EI are better for the SPE method except for trihaloanisols, while with NCI detection limits for both strategies are comparable, although the SPME strategy presents worse results for ketones and methional. Detection limits are always lower with NCI, being the improvement most notable for SPME. Recovery experiments show that in the case of SPE, uncertainties are lower than 12% in all cases, while with the SPME method the imprecision plus the existence of matrix effects make the global uncertainty to be higher than 15%.

  20. Dimers of fluorinated methanes with carbonyl sulfide: the rotational spectrum and structure of difluoromethane-OCS.

    Science.gov (United States)

    Serafin, Michal M; Peebles, Sean A

    2008-12-11

    The pure rotational spectra of four isotopologues of the difluoromethane-carbonyl sulfide dimer have been measured in the 5-15 GHz region with use of pulsed-nozzle Fourier-transform microwave spectroscopy. The complex was determined to possess an ab plane of symmetry with a center of mass separation of 3.41(2) A and dipole moment components mu(a) = 1.1386(18) D, mu(b) = 0.4840(63) D, mu(total) = 1.2372(41) D. Experimental planar moments indicate that the two fluorine atoms straddle the symmetry plane while one of the C-H bonds of the difluoromethane monomer is aligned to interact with the oxygen atom of the OCS molecule. The assignment of the rotational spectrum for this dimer completes the experimental studies of the series of dimers involving fluorinated methanes (HCF(3), H(2)CF(2), and H(3)CF) complexed with OCS and makes possible a comparison of properties within this series.