WorldWideScience

Sample records for metal carbonyls

  1. Synthesis of main-chain metal carbonyl organometallic macromolecules (MCMCOMs).

    Science.gov (United States)

    Cao, Kai; Murshid, Nimer; Wang, Xiaosong

    2015-04-01

    Synthesis of main-chain metal carbonyl organometallic macromolecules (MCMCOMs) is difficult, mainly due to the instability of metal carbonyl complexes. Despite its challenge a number of MCMCOMs has been prepared by strategically using organometallic, organic, and polymer synthetic chemistry. Main contributions to this research field were reported by the groups of Tyler, Pannell, and Wang and are briefly summarized in this article. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Hydrogenation of coal liquid utilizing a metal carbonyl catalyst

    Science.gov (United States)

    Feder, Harold M.; Rathke, Jerome W.

    1979-01-01

    Coal liquid having a dissolved transition metal, catalyst as a carbonyl complex such as Co.sub.2 (CO.sub.8) is hydrogenated with hydrogen gas or a hydrogen donor. A dissociating solvent contacts the coal liquid during hydrogenation to form an immiscible liquid mixture at a high carbon monoxide pressure. The dissociating solvent, e.g. ethylene glycol, is of moderate coordinating ability, while sufficiently polar to solvate the transition metal as a complex cation along with a transition metal, carbonyl anion in solution at a decreased carbon monoxide pressure. The carbon monoxide pressure is reduced and the liquids are separated to recover the hydrogenated coal liquid as product. The dissociating solvent with the catalyst in ionized form is recycled to the hydrogenation step at the elevated carbon monoxide pressure for reforming the catalyst complex within fresh coal liquid.

  3. 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.

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

    DEFF Research Database (Denmark)

    Møller, Ian Max; Rogowska-Wrzesinska, Adelina; Rao, Shyama Prasad

    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...

  5. 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

  6. 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

  7. Metal Carbonyl-Hydrosilane Reactions and Hydrosilation Catalysis

    Energy Technology Data Exchange (ETDEWEB)

    Cutler, A. R.

    2001-04-14

    Manganese carbonyl complexes serve as hydrosilation precatalysts for selectively transforming a carbonyl group into a siloxy methylene or a fully reduced methylene group. Substrates of interest include (1) aldehydes, ketones, carboxylic acids, silyl esters, and esters, and (2) their organometallic acyl counterparts. Three relevant catalytic reactions are shown. Two types of manganese precatalysts have been reported: (a) alkyl and acyl complexes (L)(C0){sub 4}MnR [L = CO, PPh{sub 3}; R = COCH{sub 3}, COPh, CH{sub 3}] and (b) halides (CO){sub 5}MnX and [(CO){sub 4}MnX]{sub 2} (X = Br, I). The former promote hydrosilation and deoxygenation catalysis; the latter promote dehydrogenative silation of alcohols and carboxylic acids as well as hydrosilation and deoxygenation of some metallocarboxylic acid derivatives. In every case studied, these Mn precatalysts are far more reactive or selective than traditional Rh(I) precatalysts.

  8. Anisotropic thermal motion in transition-metal carbonyls from experiments and ab initio theory.

    Science.gov (United States)

    Deringer, Volker L; Wang, Ai; George, Janine; Dronskowski, Richard; Englert, Ulli

    2016-09-21

    The thermal motion of atoms in crystals is quantified by anisotropic displacement parameters (ADPs). Here we show that dispersion-corrected periodic density-functional theory can be used to compute accurate ADPs for transition metal carbonyls, which serve as model systems for crystalline organometallic and coordination compounds.

  9. Synthesis and Characterization of Group-6 Metal Carbonyl Complexes of Aroyl Hydrazone Derivatives

    OpenAIRE

    Saleem, Mohd; Sharma, Mohita; Mahajan, Simpy; Sheikh, H. N.; Kalsotra, B. L.

    2012-01-01

    Carbonyl complexes of Chromium, molybdenum and tungsten of composition, [M(CO)4L-L], (where M= Cr, Mo or W and L-L= benzoic acid[1-(Furan-2-yl)methylene]hydrazide (BFMH), benzoic acid[(thiophene-2-yl)methylene]hydrazide (BTMH), benzoic acid[1-(thiophene-2-yl)ethylidene] hydrazide (BTEH), benzoic acid (phenylmethylene)hydrazide (BPMH) and benzoic acid[1-(anisol-3-yl)methylene] hydrazide (BAMH) are reported. These have been prepared by refluxing metal carbonyls and the ligands in 1:1molar ratio...

  10. 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 ...

  11. Synthesis and Characterization of Group-6 Metal Carbonyl Complexes of Aroyl Hydrazone Derivatives

    Directory of Open Access Journals (Sweden)

    Mohd Saleem

    2012-01-01

    Full Text Available Carbonyl complexes of Chromium, molybdenum and tungsten of composition, [M(CO4L-L], (where M= Cr, Mo or W and L-L= benzoic acid[1-(Furan-2-ylmethylene]hydrazide (BFMH, benzoic acid[(thiophene-2-ylmethylene]hydrazide (BTMH, benzoic acid[1-(thiophene-2-ylethylidene] hydrazide (BTEH, benzoic acid (phenylmethylenehydrazide (BPMH and benzoic acid[1-(anisol-3-ylmethylene] hydrazide (BAMH are reported. These have been prepared by refluxing metal carbonyls and the ligands in 1:1molar ratio. The complexes were characterized by elemental analysis, IR spectra, UV-vis spectra, 1H NMR, TGA/DTA, conductivity and magnetic susceptibility measurements. The IR bands suggest that in all the complexes the ligands behave as neutral bidentate chelating type coordinating metal through carbonyl oxygen and azomethine nitrogen. The CO force constants and CO-CO interaction constants for these derivatives have been calculated using Cotton-Kraihanzel secular equations, which indicate poor π-bonding ability of the coordinated ligands.

  12. 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

  13. Homogeneity of Surface Sites in Supported Single-Site Metal Catalysts: Assessment with Band Widths of Metal Carbonyl Infrared Spectra.

    Science.gov (United States)

    Hoffman, Adam S; Fang, Chia-Yu; Gates, Bruce C

    2016-10-06

    Determining and controlling the uniformity of isolated metal sites on surfaces of supports are central goals in investigations of single-site catalysts because well-defined species provide opportunities for fundamental understanding of the surface sites. CO is a useful probe of surface metal sites, often reacting with them to form metal carbonyls, the infrared spectra of which provide insights into the nature of the sites and the metal-support interface. Metals bonded to various support surface sites give broad bands in the spectra, and when narrow bands are observed, they indicate a high degree of uniformity of the metal sites. Much recent work on single-site catalysts has been done with supports that are inherently nonuniform, giving supported metal species that are therefore nonuniform. Herein we summarize values of ν CO data characterizing supported iridium gem-dicarbonyls, showing that the most nearly uniform of them are those supported on zeolites and the least uniform are those supported on metal oxides. Guided by ν CO data of supported iridium gem-dicarbonyls, we have determined new, general synthesis methods to maximize the degree of uniformity of iridium species on zeolites and on MgO. We report results for a zeolite HY-supported iridium gem-dicarbonyl with full width at half-maximum values of only 4.6 and 5.2 cm -1 characterizing the symmetric and asymmetric CO stretches and implying that this is the most nearly uniform supported single-site metal catalyst.

  14. Determination of bond energies by mass spectrometry. Some transition metal carbonyls

    Energy Technology Data Exchange (ETDEWEB)

    Michels, G.D.

    1979-01-01

    Two groups of transition metal carbonyls have been studied, M(CO)/sub 6/ and M(CO)/sub 5/CS complexes of the Group VIB metals and M/sub 2/(CO)/sub 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)/sub 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)/sub 6/ to M(CO)/sub 5/CS weakens the remaining M--CO bonds by an average of 0.2 eV. Previously unreported MnTc(CO)/sub 10/ and TcRe(CO)/sub 10/ are prepared by halide substitution of Tc(CO)/sub 5/Br and Re(CO)/sub 5/Br with Mn(CO)/sub 5//sup -/ and Tc(CO)/sub 5//sup -/, respectively. In the positive ion, metal and mixed-metal decacarbonyls are considered as (CO)/sub 5/M/sup +/--M(CO)/sub 5/ complexes possessing five strong and five weak M--CO bonds. For Mn/sub 2/(CO)/sub 10/ and Re/sub 2/(CO)/sub 10/, M/sup +/--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)/sub 5//sup +/ and M(CO)/sub 5/.

  15. Catalytic Transfer Hydrogenation of Biomass-Derived Carbonyls over Hafnium-Based Metal-Organic Frameworks.

    Science.gov (United States)

    Rojas-Buzo, Sergio; García-García, Pilar; Corma, Avelino

    2018-01-23

    A series of highly crystalline, porous, hafnium-based metal-organic frameworks (Hf-MOFs) have been shown to catalyze the transfer hydrogenation reaction of levulinic ester to produce γ-valerolactone by using isopropanol as a hydrogen donor. The results are compared with their zirconium-based counterparts. The role of the metal center in Hf-MOFs has been identified and reaction parameters optimized. NMR studies using isotopically labeled isopropanol provide evidence that the transfer hydrogenation occurs through a direct intermolecular hydrogen transfer route. The catalyst, Hf-MOF-808, can be recycled several times with only a minor decrease in catalytic activity. The generality of the procedure has been demonstrated by accomplishing the transformation with aldehydes, ketones, and α,β-unsaturated carbonyl compounds. The combination of Hf-MOF-808 with the Brønsted-acidic Al-Beta zeolite gives the four-step one-pot transformation of furfural to γ-valerolactone in good yield of 75 %. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Three-step metal-promoted allene-based preparation of bis(heterocyclic) cyclophanes from carbonyl compounds.

    Science.gov (United States)

    Alcaide, Benito; Almendros, Pedro; Quirós, M Teresa; Lázaro, Carlos; Torres, M Rosario

    2014-07-03

    A straightforward metal-mediated method for the synthesis of bis(dihydrofuryl) cyclophane scaffolds from carbonyl compounds has been developed. The combination of the dihydrofuran moiety with different heterocycles such as β-lactams and sugars allows high levels of skeletal diversity. The process comprises indium-promoted one-pot carbonyl bis(allenylation) and gold- or palladium-catalyzed double cyclization in the resulting bis(allenols), followed by selective ruthenium-catalyzed macrocyclization. In some cases, the method has been successfully applied to the synthesis of the challenging Z-isomers. The E- versus Z-stereochemistry of the metathesis-formed double bonds could not be assigned taking into consideration the usual coupling constants criteria, but a diagnostic based on the chemical shifts of the two olefinic protons located at the macrocyclic double bond was established.

  17. 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

  18. Transition metal-free oxidation of benzylic alcohols to carbonyl compounds by hydrogen peroxide in the presence of acidic silica gel

    Directory of Open Access Journals (Sweden)

    Hossein Ghafuri

    2015-01-01

    Full Text Available Oxidation of alcohols to carbonyl compounds has become an important issue in the process industry as well as many other applications. In this method, various benzylic alcohols were successfully converted to corresponding aldehydes and ketones under transition metal-free condition using hydrogen peroxide in the presence of some amount of catalytic acidic silica gel. Silica gel is inexpensive and available. One of the most important features of this method is its short reaction time.

  19. 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.

  20. Metal carbonyl-hydrosilane reactions and hydrosilation catalysis. Final report for period May 1, 1995 - August 14, 1999

    Energy Technology Data Exchange (ETDEWEB)

    Cutler, Alan R.

    2001-04-14

    Manganese carbonyl complexes serve as hydrosilation precatalysts for selectively transforming a carbonyl group into a doxy methylene or a fully reduced methylene group. Substrates of interest include (1) aldehydes, ketones, carboxylic acids, silyl esters, and esters, and (2) their organometallic acyl counterparts. Two types of manganese precatalysts have been reported: (a) alkyl and acyl complexes (L)(CO){sub 4}MnR [L = CO, PPh{sub 3}; R = COCH{sub 3}, COPh, CH{sub 3}] and (b) halides (CO){sub 5}MnX and [(CO){sub 4}MnX]{sub 2} (X = Br, I). The former promote hydrosilation and deoxygenation catalysis; the latter promote dehydrogenative silation of alcohols and carboxylic acids as well as hydrosilation and deoxygenation of some metallocarboxylic acid derivatives. In every case studied, these Mn precatalysts are far more reactive or selective than traditional Rh(l) precatalysts. The reaction chemistry of the above and other Mn alkyl complexes with hydrosilanes was studied in order to probe catalysis mechanism(s). Thus, Mn(CO){sub 5} methyl, benzyl, acetyl, and benzoyl (4 p-substituents) complexes reacted with hydrosilines by four different mechanisms, which were established. A noteworthy development was that the methyl and benzoyl complexes gave moderate yields of a new ({eta}{sup 2}-Si-H) silane adduct (CO){sub 4}Mn(SiMe{sub 2}Ph)(H-SiMe{sub 2}Ph), which is stable in the presence of excess silane. This silane adduct promotes all three catalytic reactions; its extraordinary activity and potential selectivity are under study.

  1. Heterometallic metal-organic framework-templated synthesis of porous Co3O4/ZnO nanocage catalysts for the carbonylation of glycerol

    Science.gov (United States)

    Lü, Yinyun; Jiang, Yating; Zhou, Qi; Li, Yunmei; Chen, Luning; Kuang, Qin; Xie, Zhaoxiong; Zheng, Lansun

    2017-12-01

    The efficient synthesis of glycerol carbonate (GLC) has recently received great attention due to its significance in reducing excess glycerol in biodiesel production as well as its promising applications in several industrial fields. However, the achievement of high conversion and high selectivity of GLC from glycerol in heterogeneous catalytic processes remains a challenge due to the absence of high-performance solid catalysts. Herein, highly porous nanocage catalysts composed of well-mixed Co3O4 and ZnO nanocrystals were successfully fabricated via a facile heterometallic metal-organic framework (MOF)-templated synthetic route. Benefiting from a high porosity and the synergistic effect between Co3O4 and ZnO, the as-prepared composite catalysts exhibited a significantly enhanced production efficiency of GLC in the carbonylation reaction of glycerol with urea compared to the single-component counterparts. The yield of GLC over the Co50Zn50-350 catalyst reached 85.2%, with 93.3% conversion and near 91% GLC selectivity, and this catalytic performance was superior to that over most heterogeneous catalysts. More importantly, the proposed templated synthetic strategy of heterometallic MOFs facilitates the regulation of catalyst composition and surface structure and can therefore be potentially extended in the tailoring of other metal oxide composite catalysts.

  2. Structures, Interconversions, and Spectroscopy of Iron Carbonyl Clusters with an Interstitial Carbide: Localized Metal Center Reduction by Overall Cluster Oxidation.

    Science.gov (United States)

    Kuppuswamy, Subramaniam; Wofford, Joshua D; Joseph, Chris; Xie, Zhu-Lin; Ali, Azim K; Lynch, Vincent M; Lindahl, Paul A; Rose, Michael J

    2017-05-15

    The syntheses, interconversions, and spectroscopic properties of a set of iron carbonyl clusters containing an interstitial carbide are reported. This includes the low temperature X-ray structures of the six-iron clusters (Y) 2 [Fe 6 (μ 6 -C)(μ 2 -CO) 4 (CO) 12 ] (1a-c; where Y = NMe 4 , NEt 4 , PPh 4 ); the five-iron cluster [Fe 5 (μ 5 -C)(CO) 15 ] (3); and the novel formulation of the five-iron cluster (NMe 4 ) 2 [Fe 5 (μ 5 -C)(μ 2 -CO)(CO) 13 ] (4). Also included in this set is the novel charge-neutral cluster, [Fe 6 (μ 6 -C)(CO) 18 ] (2), for which we were unable to obtain a crystallographic structure. As synthetic proof for the identity of 2, we performed a closed loop of interconversions within a family of crystallographically defined species (1, 3, and 4): [Fe 6 ] 2- → [Fe 6 ] 0 → [Fe 5 ] 0 → [Fe 5 ] 2- → [Fe 6 ] 2- . The structural, spectroscopic, and electronic properties of this "missing link" cluster 2 were investigated by IR, Raman, XPS, and Mössbauer spectroscopies-as well as by DFT calculations. A single ν CO feature (1965 cm -1 ) in the IR spectrum of 2, as well as a prominent Raman feature (ν symm = 1550 cm -1 ), are consistent with the presence of terminal carbonyls and a {(μ 6 -C)Fe 6 } arrangement of iron centers around the central carbide. The XPS of 2 exhibits a higher energy Fe 2p 3/2 feature (707.4 eV) as compared to that of 1 (705.5 eV), consistent with the two-electron oxidation induced by treatment of 1 with two equivalents of [Fc](PF 6 ) under CO atmosphere (for the two added CO ligands). DFT calculations indicate two axial and four equatorial Fe sites in 1, all of which have the same or similar oxidation states, for example, two Fe(0) and four Fe(+0.5). These assignments are supported by Mössbauer spectra for 1, which exhibit two closely spaced quadrupole doublets with δ = 0.076 and 0.064 mm s -1 . The high-field Mössbauer spectrum of 2 (4.2 K) exhibits three prominent quadrupole doublets with δ = -0.18, -0.11, and

  3. The Hydrolysis of Carbonyl Sulfide at Low Temperature: A Review

    Science.gov (United States)

    Zhao, Shunzheng; Yi, Honghong; Tang, Xiaolong; Jiang, Shanxue; Gao, Fengyu; Zhang, Bowen; Zuo, Yanran; Wang, Zhixiang

    2013-01-01

    Catalytic hydrolysis technology of carbonyl sulfide (COS) at low temperature was reviewed, including the development of catalysts, reaction kinetics, and reaction mechanism of COS hydrolysis. It was indicated that the catalysts are mainly involved metal oxide and activated carbon. The active ingredients which can load on COS hydrolysis catalyst include alkali metal, alkaline earth metal, transition metal oxides, rare earth metal oxides, mixed metal oxides, and nanometal oxides. The catalytic hydrolysis of COS is a first-order reaction with respect to carbonyl sulfide, while the reaction order of water changes as the reaction conditions change. The controlling steps are also different because the reaction conditions such as concentration of carbonyl sulfide, reaction temperature, water-air ratio, and reaction atmosphere are different. The hydrolysis of carbonyl sulfide is base-catalyzed reaction, and the force of the base site has an important effect on the hydrolysis of carbonyl sulfide. PMID:23956697

  4. 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...

  5. Low frequency vapour phase infrared spectra of metal carbonyls, derivatives of the type xmn (CO)/sub 5/ (where X=Br, Cl, H, D, Ch/sub 3/, Cd/sub 3/ Cf/sub 3/)

    International Nuclear Information System (INIS)

    Mehmood, Z.

    2009-01-01

    Many vibrations which occur in the far-infrared region of spectrum are similar to the types of vibrations found in other regions of the spectrum. They fall in the far-infrared because the atomic masses are large and/or the forces resisting the deformation are small. Most of the vibrations of metal carbonyls fall into this category and hence they give a good example of what can be expected A number of metal carbonyls ego BrMn(CO)/sub 5/, CIMn(CO)/sub 5/, HMn(CO)/sub 5/, DMn(CO)/sub 5/, CH/sub 3/Mn(CO)/sub 5/, CD/sub 3/Mn(CO)/sub 5/ and CF/sub 3/Mn(CO)/sub 5/ have been studied in the vapour phase for first time and it is now possible to discuss the general nature of the vibration in this region. The metal- CO stretching frequencies are found between 350 and 475 cm/sup -1/ The metal-C-O bending frequencies are more scattered and fall between 275 and 650 cm/sup -1/ depending in part upon the phase of motion. The OC-M-CO bending modes occur between 50 and 150 cm/sup -1/. Other vibrations are founds in this region when one or more CO group are replaced by groups in which heavy atoms are attached to the metal. Factor which shifts the positions of the frequencies, such as mass or charge on the metal carbonyl moiety, will be discussed. (author)

  6. Hydrophosphorylation of 1,3-diphenyl-2-propen-1-one and 1-methyl-3-phenyl-2-propen-1-one in the coordination sphere of carbonyl complexes of group 6B metals

    International Nuclear Information System (INIS)

    Kuramshin, A.I.; Karpenko, E.A.; Cherkasov, R.A.

    2001-01-01

    Methods of synthesis of η 2 - and η 4 - complexes of chalcone and benzalacetone with hexacarbonyl mononuclear complexes of group 6B metals (M Cr, Mo, W) were developed and conditions of selective η 2 - or η 4 - coordination of π-heterodiene ligand were ascertained. By the method of IR and NMR spectroscopy it was shown that hydrophosphorylation of the complexes prepared occurs in the metal coordination sphere by the Abramov reaction scheme resulting in the relevant η 2 -coordinated α-hydroxyphosphonates. According to data of quantum-chemical calculations heterodienes lose planarity as a result of π-coordination with metal, which explains regioselectivity of phosphorylation by more electrophilic carbonyl group of coordinated enone [ru

  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. Carbonyl-Olefin Exchange Reaction and Related Chemistry

    Science.gov (United States)

    Jossifov, Christo; Kalinova, Radostina

    A new carbon—carbon double bond forming reaction (carbonyl olefin exchange reaction) mediated by transition metal catalytic systems has been discovered. The catalytic systems used (transition metal halides or oxohalides alone or in combination with Lewis acids) are active only in the case when the two reacting groups are in one molecules and are conjugated. In addition these systems accelerate other reactions which run simultaneously with the carbonyl olefin metathesis rendering a detailed investigation of the process very complicated.

  9. 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.

  10. Atomic alignment effect in the dissociative energy transfer reaction of metal carbonyls (Fe(CO)5, Ni(CO)4) with oriented Ar (3P2, M(J) = 2).

    Science.gov (United States)

    Ohoyama, H; Matsuura, Y

    2011-10-13

    The atomic alignment effect has been studied for the dissociative energy transfer reaction of metal carbonyls (Fe(CO)(5), Ni(CO)(4)) with the oriented Ar ((3)P(2), M(J) = 2). The emission intensity from the excited metal products (Fe*, Ni*) has been measured as a function of the atomic alignment in the collision frame. The selectivity of the atomic orbital alignment of Ar ((3)P(2), M(J) = 2) (rank 2 moment, a(2)) is found to be opposite for the two reaction systems; the Fe(CO)(5) reaction is favorable at the Π configuration (positive a(2)), while the Ni(CO)(4) reaction is favorable at the Σ configuration (negative a(2)). Moreover, a significant spin alignment effect (rank 4 moment, a(4)) is recognized only in the Ni(CO)(4) reaction. The atomic alignment effect turns out to be essentially different between the two reaction systems; the Fe(CO)(5) reaction is controlled by the configuration of the half-filled 3p atomic orbital of Ar ((3)P(2)) in the collision frame (L dependence), whereas the Ni(CO)(4) reaction is controlled by the configuration of the total angular moment J (including spin) of Ar ((3)P(2)) in the collision frame (J dependence). As the origin of J dependence observed only in the Ni(CO)(4) reaction, the correlation (and/or the interference) between two electron exchange processes via the electron rearrangements is proposed.

  11. Validation of protein carbonyl measurement

    DEFF Research Database (Denmark)

    Augustyniak, Edyta; Adam, Aisha; Wojdyla, Katarzyna

    2015-01-01

    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...

  12. Influence of heating time and metal ions on the amount of free fatty acids and formation rates of selected carbonyl compounds during the thermal oxidation of canola oil.

    Science.gov (United States)

    Bastos, Luciane Conceição Silva; Pereira, Pedro Afonso de Paula

    2010-12-22

    Canola oil was heated continuously for 8 h at a typical frying temperature (180 °C) in the presence of various concentrations of the metal ions Fe(III), Cu(II), and Al(III) (9.2, 27.5, and 46.0 μg L(-1) of oil) to evaluate changes occurring in the amount of free fatty acids, expressed as acidity index, and in the formation rates of aldehydes. The aldehydes were collected and derivatized in silica cartridges functionalized with C18 and impregnated with an acid solution of 2,4-dinitrophenylhydrazine, after which they were eluted with acetonitrile and analyzed by LC-DAD-MS. Among the substances emitted, the following were identified and quantified: formaldehyde, acetaldehyde, acrolein, propanal, butanal, hexanal, (E)-2-heptenal, and octanal. During heating of the oil, the compounds presenting the highest mean formation rates were acrolein, hexanal, and acetaldehyde. In the study of the metal ions, the addition of ions to the samples generally led to a corresponding increase in the formation rates of the eight substances. The compounds showing the highest relative increases in formation rates were formaldehyde, acetaldehyde, propanal, and heptenal. In terms of catalytic effect, copper proved to be the most efficient in promoting increased formation rates, followed by iron and aluminum.

  13. 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.

  14. 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.

  15. 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...

  16. Study of interaction products of chromium, molybdenum and tungsten carbonyls with ethanolamines

    Energy Technology Data Exchange (ETDEWEB)

    Mozgin, S.V.; Felin, M.G.; Subbotina, N.A.; Spitsyn, V.I. (Moskovskij Gosudarstvennyj Univ. (USSR))

    1982-11-01

    The interaction of the 6th group metal carbonyls with mono-, di-, and triethanolamines was investigated. It was established that chromium, molybdenum and tungsten carbonyls could react with ethanolamines. Complex compounds of the mentioned metals that had been separated after carrying out those reactions were characterized by chemical analysis data. Properties of the produced complexes were studied by methods of UV, visible and IR spectroscopy, thermomagnetic and thermal analyses and their structure is proposed.

  17. 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

  18. Iron(III)-catalysed carbonyl-olefin metathesis

    Science.gov (United States)

    Ludwig, Jacob R.; Zimmerman, Paul M.; Gianino, Joseph B.; Schindler, Corinna S.

    2016-05-01

    The olefin metathesis reaction of two unsaturated substrates is one of the most powerful carbon-carbon-bond-forming reactions in organic chemistry. Specifically, the catalytic olefin metathesis reaction has led to profound developments in the synthesis of molecules relevant to the petroleum, materials, agricultural and pharmaceutical industries. These reactions are characterized by their use of discrete metal alkylidene catalysts that operate via a well-established mechanism. While the corresponding carbonyl-olefin metathesis reaction can also be used to construct carbon-carbon bonds, currently available methods are scarce and severely hampered by either harsh reaction conditions or the required use of stoichiometric transition metals as reagents. To date, no general protocol for catalytic carbonyl-olefin metathesis has been reported. Here we demonstrate a catalytic carbonyl-olefin ring-closing metathesis reaction that uses iron, an Earth-abundant and environmentally benign transition metal, as a catalyst. This transformation accommodates a variety of substrates and is distinguished by its operational simplicity, mild reaction conditions, high functional-group tolerance, and amenability to gram-scale synthesis. We anticipate that these characteristics, coupled with the efficiency of this reaction, will allow for further advances in areas that have historically been enhanced by olefin metathesis.

  19. α-Regioselective Barbier Reaction of Carbonyl Compounds and Allyl Halides Mediated by Praseodymium.

    Science.gov (United States)

    Wu, San; Li, Ying; Zhang, Songlin

    2016-09-02

    The first utility of praseodymium as a mediating metal in the Barbier reaction of carbonyl compounds with allyl halides was reported in this paper. In contrast to the traditional metal-mediated or catalyzed Barbier reactions, exclusive α-adducts were obtained in this one-pot reaction with a broad scope of substrates and feasible reaction conditions.

  20. Enantioselective Iridium Catalyzed Carbonyl Allylation from the Alcohol Oxidation Level via Transfer Hydrogenation: Minimizing Pre-Activation for Synthetic Efficiency

    Science.gov (United States)

    Han, Soo Bong; Kim, In Su; Krische, Michael J.

    2010-01-01

    Existing methods for enantioselective carbonyl allylation, crotylation and tert-prenylation require stoichiometric generation of pre-metallated nucleophiles and often employ stoichiometric chiral modifiers. Under the conditions of transfer hydrogenation employing an ortho-cyclometallated iridium C,O-benzoate catalyst, enantioselective carbonyl allylations, crotylations and tert-prenylations are achieved in the absence of stoichiometric metallic reagents or stoichiometric chiral modifiers. Moreover, under transfer hydrogenation conditions, primary alcohols function dually as hydrogen donors and aldehyde precursors, enabling enantioselective carbonyl addition directly from the alcohol oxidation level. PMID:20024203

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

    African Journals Online (AJOL)

    Sodium borohydride (0.4–1.5 equivalents) in the presence of ammonium oxalate (0.2 equivalents) reduces varieties of organic carbonyl compounds such as aldehydes, ketones, acyloins, α-diketones and α,β-unsaturated carbonyl compounds to their corresponding alcohols. Reduction reactions were carried out in ...

  2. Design and Synthesis of 11C-Labelled Compound Libraries for the Molecular Imaging of EGFr, VEGFr-2, AT1 and AT2 Receptors: Transition-Metal Mediated Carbonylations Using [11C]Carbon Monoxide

    International Nuclear Information System (INIS)

    Aaberg, Ola

    2009-01-01

    This work deals with radiochemistry and new approaches to develop novel PET tracers labelled with the radionuclide 11 C. Two methods for the synthesis of 11 C-labelled acrylamides have been explored. First, [1- 11 C]-acrylic acid was obtained from a palladium(0)-mediated 11 C-carboxylation of acetylene with [ 11 C]carbon monoxide; this could be converted to the corresponding acyl chloride and then combined with benzylamine to form N-benzyl[carbonyl- 11 C]acrylamide. In the second method, the palladium(0)-mediated carbonylation of vinyl halides with [ 11 C]carbon monoxide was explored. This latter method, yielded labelled acrylamides in a single step with retention of configuration at the C=C double bond, and required less amine compared to the acetylene method. The vinyl halide method was used to synthesize a library of 11 C-labelled EGFr-inhibitors in 7-61% decay corrected radiochemical yield via a combinatorial approach. The compounds were designed to target either the active or the inactive form of EGFr, following computational docking studies. The rhodium(I)-mediated carbonylative cross-coupling of an azide and an amine was shown to be a very general reaction and was used to synthesize a library of dual VEGFr-2/PDGFrβ inhibitors that were 11 C-labelled at the urea position in 38-78% dc rcy. The angiotensin II AT 1 receptor antagonist eprosartan was 11 C-labelled at one of the carboxyl groups in one step using a palladium(0)-mediated carboxylation. Autoradiography shows specific binding in rat kidney, lung and adrenal cortex, and organ distribution shows a high accumulation in the intestines, kidneys and liver. Specific binding in frozen sections of human adrenal incidentalomas warrants further investigations of this tracer. Three angiotensin II AT 2 ligands were 11 C-labelled at the amide group in a palladium(0)-mediated aminocarbonylation in 16-36% dc rcy. One of the compounds was evaluated using in vitro using autoradiography, and in vivo using organ

  3. 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

  4. 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.

  5. [pi] Backbonding in Carbonyl Complexes and Carbon-Oxygen Stretching Frequencies: A Molecular Modeling Exercise

    Science.gov (United States)

    Montgomery, Craig D.

    2007-01-01

    An exercise is described that has illustrated the effect of various factors on [pi] backbonding to carbonyl ligands, where the students can view the molecular orbitals corresponding to the M-CO [pi] interaction as well as the competing interaction between the metal and co-ligands. The visual and hands-on nature of the modeling exercise has helped…

  6. Polycyclic Aromatic Hydrocarbons via Iron(III)-Catalyzed Carbonyl-Olefin Metathesis.

    Science.gov (United States)

    McAtee, Christopher C; Riehl, Paul S; Schindler, Corinna S

    2017-03-01

    Polycyclic aromatic hydrocarbons are important structural motifs in organic chemistry, pharmaceutical chemistry, and materials science. The development of a new synthetic strategy toward these compounds is described based on the design principle of iron(III)-catalyzed carbonyl-olefin metathesis reactions. This approach is characterized by its operational simplicity, high functional group compatibility, and regioselectivity while relying on FeCl 3 as an environmentally benign, earth-abundant metal catalyst. Experimental evidence for oxetanes as reactive intermediates in the catalytic carbonyl-olefin ring-closing metathesis has been obtained.

  7. Enamine/enolate-mediated organocatalytic azide-carbonyl [3+2] cycloaddition reactions for the synthesis of densely functionalized 1,2,3-triazoles.

    Science.gov (United States)

    Ramasastry, Sripada S V

    2014-12-22

    Organocatalytic click! Recent advances in the metal-free enamine/enolate-mediated azide-carbonyl [3+2] cycloaddition reaction are discussed. These approaches require neither a metal catalyst nor alkyne substrates. Owing to the ready availability of carbonyl compounds, these methods thus offer excellent alternatives for the synthesis of 1,4-/1,5-disubstituted and 1,4,5-trisubstituted 1,2,3-triazoles. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Carbonated soft drinks and carbonyl stress burden.

    Science.gov (United States)

    Nakayama, Keisuke; Nakayama, Masaaki; Terawaki, Hiroyuki; Murata, Yaeko; Sato, Toshinobu; Kohno, Masahiro; Ito, Sadayoshi

    2009-12-01

    Carbonated soft drinks reportedly contain methylglyoxal (MG), which is strongly associated with human carbonyl stress. We sought to evaluate the effects of carbonated drink intake on human carbonyl stress. We measured MG levels in 4 commercial beverage brands, and evaluated the changes in plasma MG in healthy subjects following the intake of carbonated drinks. By 30 min after intake of samples containing high glucose and high MG, the levels of plasma MG, glucose, insulin and uric acid had increased significantly, and then returned to basal levels by 120 min. After intake of the low-calorie carbonated samples containing little MG, there were no increases in plasma MG. Our results suggest that glucose-containing carbonated soft drinks are associated with increases in not only glucose but also carbonyl burden.

  9. Benzyllithiums bearing aldehyde carbonyl groups. A flash chemistry approach.

    Science.gov (United States)

    Nagaki, Aiichiro; Tsuchihashi, Yuta; Haraki, Suguru; Yoshida, Jun-ichi

    2015-07-14

    Reductive lithiation of benzyl halides bearing aldehyde carbonyl groups followed by reaction with subsequently added electrophiles was successfully accomplished without affecting the carbonyl groups by taking advantage of short residence times in flow microreactors.

  10. 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

  11. Polymethylhydrosiloxane reduction of carbonyl function catalysed by ...

    African Journals Online (AJOL)

    However, in the reduction of the substrate with two methoxy groups in close proximity (1,2-positions), the reaction necessitated a larger amount of the titanium catalyst and a longer reaction time to complete the reduction of the carbonyl function due to a likely complex formation of titanium tetrachloride with the methoxy ...

  12. Cyclometallated ruthenium (II) carbonyl complexes with 1 ...

    Indian Academy of Sciences (India)

    A facile method for the synthesis of a series of cyclometallated ruthenium(II) carbonyl complexes with 1-pyrenaldehyde 4-R-3-thiosemicarbazones (H2Ln where the two H's represent the dissociable thioamide and pyrenyl protons; R = H, Me and Ph) has been described. The characterization of the complexes having the ...

  13. 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.

  14. Vapor-phase carbonylation of dimethoxymethane over H-Faujasite.

    Science.gov (United States)

    Celik, Fuat E; Kim, Tae-Jin; Bell, Alexis T

    2009-01-01

    Carbonylation gets a phase lift: The usual liquid-phase, high-pressure processes for carbonylating formaldehydes are avoided in a novel vapor-phase reaction. Using an acid zeolite (Faujasite) at near-atmospheric pressure dimethoxymethane (DMM; the dimethyl acetal of formaldehyde; see scheme) is carbonylated to produce methyl methoxyacetate (MMAc). This approach provides a new route to ethylene glycol under mild conditions.

  15. 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.)

  16. Oxidation of Reduced Sulfur Species: Carbonyl Sulfide

    DEFF Research Database (Denmark)

    Glarborg, Peter; Marshall, Paul

    2013-01-01

    A detailed chemical kinetic model for oxidation of carbonyl sulfide (OCS) has been developed, based on a critical evaluation of data from the literature. The mechanism has been validated against experimental results from batch reactors, flow reactors, and shock tubes. The model predicts satisfact......A detailed chemical kinetic model for oxidation of carbonyl sulfide (OCS) has been developed, based on a critical evaluation of data from the literature. The mechanism has been validated against experimental results from batch reactors, flow reactors, and shock tubes. The model predicts...... satisfactorily oxidation of OCS over a wide range of stoichiometric air–fuel ratios (0.5 ≤λ≤7.3), temperatures (450–1700 K), and pressures (0.02–3.0 atm) under dry conditions. The governing reaction mechanisms are outlined based on calculations with the kinetic model. The oxidation rate of OCS is controlled...

  17. 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.

  18. 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....

  19. 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.

  20. Enantioselective gamma- and delta-Borylation of Unsaturated Carbonyl Derivatives: Synthesis, Mechanistic Insights, and Applications

    Science.gov (United States)

    Hoang, Gia L.

    Chiral boronic esters are valuable synthetic intermediates widely used in a variety of stereospecific transformations. Transition metal-catalyzed asymmetric hydroboration (CAHB) of alkenes is among the most popular methods for their preparation. Enantioselective hydroboration of activated alkenes (i.e., vinyl arene derivatives or conjugated carbonyl compounds) have been extensively studied by many research groups. We, on the other hand, are interested in enantioselective hydroboration of unactivated alkenes utilizing coordinating functional groups (e.g., carbonyl derivatives) to give functionalized, chiral boronic esters. While conjugate addition and C-H activation methodologies provide efficient alternatives to CAHB for enantioselective beta-borylation of carbonyl compounds, direct gamma- and delta-borylations were essentially unknown prior to our wok on CAHB. The gamma-borylated products were used for understanding stereochemical aspects of Suzuki-Miyaura cross-coupling reactions resulting in stereoretention and in contrast to similar beta-borylated carbonyl derivatives reported in literature. Some other selected transformations were carried out to construct a number of biologically relevant structural motifs, such as lignan precursors, 1,4-amino alcohols, gamma-amino acid derivatives, 5-substitued-gamma-lactone and lactam ring systems. In addition, collaborative experimental and computational studies of the enantioselective desymmetrization via CAHB gain a better understanding of the mechanistic pathways.

  1. 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.

  2. 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.

  3. 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.

  4. 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).

  5. 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.

  6. 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.

  7. Carbonyl emissions in diesel and biodiesel exhaust

    Science.gov (United States)

    Machado Corrêa, Sérgio; Arbilla, Graciela

    With the use of biodiesel in clear growth, it is important to quantify any potential emission benefits or liabilities of this fuel. Several researches are available concerning the regulated emissions of biodiesel/diesel blends, but there is a lack of information about non-regulated emissions. In a previous paper [Corrêa, S.M., Arbilla, G., 2006. Emissões de formaldeído e acetaldeído de misturas biodiesel/diesel. Periódico Tchê Química, 3, 54-68], the emissions of aromatic hydrocarbons were reported. In this work, seven carbonyl emissions (formaldehyde, acetaldehyde, acrolein, acetone, propionaldehyde, butyraldehyde, and benzaldehyde) were evaluated by a heavy-duty diesel engine fueled with pure diesel (D) and biodiesel blends (v/v) of 2% (B2), 5% (B5), 10% (B10), and 20% (B20). The tests were conducted using a six cylinder heavy-duty engine, typical of the Brazilian fleet of urban buses, in a steady-state condition under 1000, 1500, and 2000 rpm. The exhaust gases were diluted nearly 20 times and the carbonyls were sampled with SiO 2-C18 cartridges, impregnated with acid solution of 2,4-dinitrophenylhydrazine. The chemical analyses were performed by high performance liquid chromatography using UV detection. Using average values for the three modes of operation (1000, 1500, and 2000 rpm) benzaldehyde showed a reduction on the emission (-3.4% for B2, -5.3% for B5, -5.7% for B10, and -6.9% for B20) and all other carbonyls showed a significative increase: 2.6, 7.3, 17.6, and 35.5% for formaldehyde; 1.4, 2.5, 5.4, and 15.8% for acetaldehyde; 2.1, 5.4, 11.1, and 22.0% for acrolein+acetone; 0.8, 2.7, 4.6, and 10.0% for propionaldehyde; 3.3, 7.8, 16.0, and 26.0% for butyraldehyde.

  8. 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?

  9. 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.

  10. 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.

  11. 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.

  12. 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

  13. Positive trends in Southern Hemisphere carbonyl sulfide

    Science.gov (United States)

    Kremser, Stefanie; Jones, Nicholas B.; Palm, Mathias; Lejeune, Bernard; Wang, Yuting; Smale, Dan; Deutscher, Nicholas M.

    2015-11-01

    Transport of carbonyl sulfide (OCS) from the troposphere to the stratosphere contributes sulfur to the stratospheric aerosol layer, which reflects incoming short-wave solar radiation, cooling the climate system. Previous analyses of OCS observations have shown no significant trend, suggesting that OCS is unlikely to be a major contributor to the reported increases in stratospheric aerosol loading and indicating a balanced OCS budget. Here we present analyses of ground-based Fourier transform spectrometer measurements of OCS at three Southern Hemisphere sites spanning 34.45°S to 77.80°S. At all three sites statistically significant positive trends are seen from 2001 to 2014 with an observed overall trend in total column OCS at Wollongong of 0.73 ± 0.03%/yr, at Lauder of 0.43 ± 0.02%/yr, and at Arrival Heights of 0.45 ± 0.05%/yr. These observed trends in OCS imply that the OCS budget is not balanced and could contribute to constraints on current estimates of sources and sinks.

  14. 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...

  15. 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...

  16. Efficiency of Carbonyl Iron in Prevention of Anaemia in Piglets

    Directory of Open Access Journals (Sweden)

    M. Svoboda

    2007-01-01

    Full Text Available The aim of this study was to evaluate efficiency of elemental iron preparation in the form of carbonyl iron in prevention of iron deficiency in piglets. The piglets in group I (n = 14 were given 210 mg of carbonyl iron orally at the age of 3 days. The piglets in group II (n = 15 received 210 mg of carbonyl iron orally on days 3 and 9. In group III (n = 14 the piglets were injected i.m. with 200 mg Fe3+ as iron dextran. Fourteen days after birth, haemoglobin concentration in group I started to decrease and the piglets developed anaemia. In group II, at the age of 28 days, Hb dropped below 80 g/l and the piglets developed anaemia. Under conditions of this trial, the oral administration of carbonyl iron did not prevent development of iron deficiency in piglets.

  17. Targeting Reactive Carbonyl Species with Natural Sequestering Agents

    Directory of Open Access Journals (Sweden)

    Sung Won Hwang

    2016-02-01

    Full Text Available Reactive carbonyl species generated by the oxidation of polyunsaturated fatty acids and sugars are highly reactive due to their electrophilic nature, and are able to easily react with the nucleophilic sites of proteins as well as DNA causing cellular dysfunction. Levels of reactive carbonyl species and their reaction products have been reported to be elevated in various chronic diseases, including metabolic disorders and neurodegenerative diseases. In an effort to identify sequestering agents for reactive carbonyl species, various analytical techniques such as spectrophotometry, high performance liquid chromatography, western blot, and mass spectrometry have been utilized. In particular, recent advances using a novel high resolution mass spectrometry approach allows screening of complex mixtures such as natural products for their sequestering ability of reactive carbonyl species. To overcome the limited bioavailability and bioefficacy of natural products, new techniques using nanoparticles and nanocarriers may offer a new attractive strategy for increased in vivo utilization and targeted delivery of bioactives.

  18. Aerobic Oxidation of Alcohols to Carbonyl Compounds Catalyzed by ...

    Indian Academy of Sciences (India)

    hydroxyphthalimide. 1. Introduction. The selective oxidation of alcohols to the corresponding carbonyl compounds is one of the most important reac- tions in organic synthesis and fine chemical industries.1. Numerous methods have been developed for the ...

  19. Carbonyl species characteristics during the evaporation of essential oils

    Science.gov (United States)

    Chiang, Hsiu-Mei; Chiu, Hua-Hsien; Lai, Yen-Ming; Chen, Ching-Yen; Chiang, Hung-Lung

    2010-06-01

    Carbonyls emitted from essential oils can affect the air quality when they are used in indoors, especially under poor ventilation conditions. Lavender, lemon, rose, rosemary, and tea tree oils were selected as typical and popular essential oils to investigate in terms of composition, thermal characteristics and fifteen carbonyl constituents. Based on thermogravimetric (TG) analysis, the activation energy was 7.6-8.3 kcal mol -1, the reaction order was in the range of 0.6-0.7 and the frequency factor was 360-2838 min -1. Formaldehyde, acetaldehyde, acetone, and propionaldehyde were the dominant carbonyl compounds, and their concentrations were 0.034-0.170 ppm. The emission factors of carbonyl compounds were 2.10-3.70 mg g -1, and acetone, propionaldehyde, acetaldehyde, and formaldehyde accounted for a high portion of the emission factor of carbonyl compounds in essential oil exhaust. Some unhealthy carbonyl species such as formaldehyde and valeraldehyde, were measured at low-temperature during the vaporization of essential oils, indicating a potential effect on indoor air quality and human health.

  20. Nickel and iron pincer complexes as catalysts for the reduction of carbonyl compounds.

    Science.gov (United States)

    Chakraborty, Sumit; Bhattacharya, Papri; Dai, Huiguang; Guan, Hairong

    2015-07-21

    The reductions of aldehydes, ketones, and esters to alcohols are important processes for the synthesis of chemicals that are vital to our daily life, and the reduction of CO2 to methanol is expected to provide key technology for carbon management and energy storage in our future. Catalysts that affect the reduction of carbonyl compounds often contain ruthenium, osmium, or other precious metals. The high and fluctuating price, and the limited availability of these metals, calls for efforts to develop catalysts based on more abundant and less expensive first-row transition metals, such as nickel and iron. The challenge, however, is to identify ligand systems that can increase the thermal stability of the catalysts, enhance their reactivity, and bypass the one-electron pathways that are commonly observed for first-row transition metal complexes. Although many other strategies exist, this Account describes how we have utilized pincer ligands along with other ancillary ligands to accomplish these goals. The bis(phosphinite)-based pincer ligands (also known as POCOP-pincer ligands) create well-defined nickel hydride complexes as efficient catalysts for the hydrosilylation of aldehydes and ketones and the hydroboration of CO2 to methanol derivatives. The hydride ligands in these complexes are substantially nucleophilic, largely due to the enhancement by the strongly trans-influencing aryl groups. Under the same principle, the pincer-ligated nickel cyanomethyl complexes exhibit remarkably high activity (turnover numbers up to 82,000) for catalytically activating acetonitrile and the addition of H-CH2CN across the C═O bonds of aldehydes without requiring a base additive. Cyclometalation of bis(phosphinite)-based pincer ligands with low-valent iron species "Fe(PR3)4" results in diamagnetic Fe(II) hydride complexes, which are active catalysts for the hydrosilylation of aldehydes and ketones. Mechanistic investigation suggests that the hydride ligand is not delivered to the

  1. 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

  2. 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

  3. 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

  4. Magnetorheological Fluids with Carbonyl and Water Atomized Iron Powders

    Science.gov (United States)

    Bombard, Antonio J. F.; Teodoro, João Victor R.

    Our aim in this work was to propose the use of a ternary blend of two carbonyl iron powder CIP, mixed with water atomized iron powder (WAIP), to reduce the off-state viscosity, without prejudice of MRF performance in terms of yield stress and torque output. The idea of mix water atomized iron powder with carbonyl iron powder is not new. The US Pat. # 5,900,184 by Weiss et al. (1999) describes that a binary blend, half-to-half, can reduces the viscosity of MRF in the absence of magnetic field, and increase the torque output under field.

  5. One-pot desymmetrizing hydroformylation/carbonyl ene cyclization process: straightforward access to highly functionalized cyclohexanols.

    Science.gov (United States)

    Bigot, Aurélien; Breuninger, Daniel; Breit, Bernhard

    2008-12-04

    Rapid access to highly functionalized alkylidene cyclohexanols through a one-pot desymmetrizing hydroformylation/carbonyl ene cyclization starting from simple bisalkenylcarbinols is reported. Mechanistic insight into the carbonyl ene reaction is given, highlighting the importance of hyperconjugative substituent effects.

  6. Deactivation mechanism of the simultaneous removal of carbonyl ...

    Indian Academy of Sciences (India)

    KAI LI

    2017-11-10

    Nov 10, 2017 ... REGULAR ARTICLE. Deactivation mechanism of the simultaneous removal of carbonyl sulphide and carbon disulphide over Fe–Cu–Ni/MCSAC catalysts. KAI LIa, XIN SONGa, CHI WANGb, YI MEIb, XIN SUNa and PING NINGa,∗. aFaculty of Environmental Science and Engineering, Kunming University of ...

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

    Indian Academy of Sciences (India)

    Administrator

    Abstract. The complex permittivity, permeability and microwave-absorbing properties of rubber composites filled with carbonyl iron are measured at frequencies from 2–18 GHz. The results indicate that the reflection loss peak shifts towards low frequency region with increasing layer thickness or increasing weight concentra-.

  8. CARBONYL SULFIDE INHALATION PRODUCES BRAIN LESIONS IN F344 RATS.

    Science.gov (United States)

    Carbonyl sulfide (COS) is an intermediate in the production of pesticides and herbicides, and is a metabolite of the neurotoxicant carbon disulfide. The potential neurotoxicity of inhaled COS was investigated in F344 rats. Male rats were exposed to 0, 75, 150, 300, or 600 ppm COS...

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

    Indian Academy of Sciences (India)

    Home; Journals; Bulletin of Materials Science; Volume 33; Issue 5. Electromagnetic properties of carbonyl iron and their microwave absorbing characterization as filler in silicone rubber. Yuping Duan ... These results show that the composites possess good microwave absorbing ability in both low- and highfrequency bands.

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

    Indian Academy of Sciences (India)

    Abstract. Regioselectivity of the photochemical [2 + 2] cyclo-addition of triplet carbonyl compounds with a series of ground state electron-rich and electron-poor alkenes, the Paterno-Büchi reaction, is studied. Activation barriers for the first step of the triplet reaction are computed in the case of the O-attack. Next, the observed ...

  11. Sampling And Analysis Of Carbonyl In Laboratory Atmospheres ...

    African Journals Online (AJOL)

    A sampling and analytical method has been developed for carbonyl concentrations in different laboratory atmospheres at the faculty of Science Bayero University; Kano, Nigeria using cold oximation followed by titrimetric finish. The analysis was carried out between 008 and 1800 hrs from from October 2002 to June 2003.

  12. Hyperfine coupling constants in muonium adducts of the carbonyl bond

    International Nuclear Information System (INIS)

    Cox, S.F.J.; Scott, C.A.; Geeson, D.A.; Rhodes, C.J.; Symons, M.C.R.; Roduner, E.

    1986-01-01

    A representative series is studied of organic radicals formed by the effective addition of muonium to the carbonyl oxygen atom of aldehydes, ketones, esters and amides. Low values of the muon-electron hyperfine coupling are measured which are particularly sensitive to radical structure and dynamics. The systematics of these values are discussed in terms of the opposing contributions of conjugation and hyperconjugation. (orig.)

  13. 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...

  14. 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

  15. Cesium Carbonate-Catalyzed α-Phenylchalcogenation of Carbonyl Compounds with Diphenyl Dichalcogenide

    Directory of Open Access Journals (Sweden)

    Yutaka Nishiyama

    2009-09-01

    Full Text Available It was found that cesium carbonate has a unique catalytic ability on the reaction of carbonyl compounds with diphenyl diselenide to give the corresponding α-phenylseleno carbonyl compounds in moderate to good yields. Similarly, the α-phenylthiolation of carbonyl compounds with diphenyl disulfide was promoted by the cesium carbonate catalyst.

  16. 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 ...

  17. 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

  18. Recent advances in efficient and selective synthesis of di-, tri-, and tetrasubstituted alkenes via Pd-catalyzed alkenylation-carbonyl olefination synergy.

    Science.gov (United States)

    Negishi, Ei-ichi; Huang, Zhihong; Wang, Guangwei; Mohan, Swathi; Wang, Chao; Hattori, Hatsuhiko

    2008-11-18

    Although generally considered competitive, the alkenylation and carbonyl olefination routes to alkenes are also complementary. In this Account, we focus on these approaches for the synthesis of regio- and stereodefined di- and trisubstituted alkenes and a few examples of tetrasubstituted alkenes. We also discuss the subset of regio- and stereodefined dienes and oligoenes that are conjugated. Pd-catalyzed cross-coupling using alkenyl metals containing Zn, Al, Zr, and B (Negishi coupling and Suzuki coupling) or alkenyl halides and related alkenyl electrophiles provides a method of alkenylation with the widest applicability and predictability, with high stereo- and regioselectivity. The requisite alkenyl metals or alkenyl electrophiles are most commonly prepared through highly selective alkyne addition reactions including (i) conventional polar additions, (ii) hydrometalation, (iii) carbometalation, (iv) halometalation, and (v) other heteroatom-metal additions. Although much more limited in applicability, the Heck alkenylation offers an operationally simpler, viable alternative when it is highly selective and satisfactory. A wide variety of carbonyl olefination reactions, especially the Wittig olefination and its modifications represented by the E-selective HWE olefination and the Z-selective Still-Gennari olefination, collectively offer the major alternative to the Pd-catalyzed alkenylation. However, the carbonyl olefination method fundamentally suffers from more limited stereochemical options and generally lower stereoselectivity levels than the Pd-catalyzed alkenylation. In a number of cases, however, very high (>98%) stereoselectivity levels have been attained in the syntheses of both E and Z isomers. The complementarity of the alkenylation and carbonyl olefination routes provide synthetic chemists with valuable options. While the alkenylation involves formation of a C-C single bond to a CC bond, the carbonyl olefination converts a CO bond to a CC bond. When a

  19. One-pot Reductive Amination of carbonyl Compounds with Nitro Compounds by Transfer Hydrogenation over Co-Nxas catalyst.

    Science.gov (United States)

    Zhou, Peng; Zhang, Zehui

    2017-05-09

    A new method was developed for the synthesis of secondary amines through the one-pot reductive amination of carbonyl compounds with nitro compounds using formic acid as the hydrogen donor over a heterogeneous non-noble-metal catalyst (Co-N x /C-800-AT, generated by the pyrolysis of the cobalt phthalocyanine/silica composite at 800°C under a N 2 atmosphere and subsequent etching by HF). Both nitrogen and cobalt were of considerable importance in the transfer hydrogenation reactions with formic acid. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. 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%.

  1. 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)

  2. Role of Carbonyl Modifications on Aging-Associated Protein Aggregation

    Science.gov (United States)

    Tanase, Maya; Urbanska, Aleksandra M.; Zolla, Valerio; Clement, Cristina C.; Huang, Liling; Morozova, Kateryna; Follo, Carlo; Goldberg, Michael; Roda, Barbara; Reschiglian, Pierluigi; Santambrogio, Laura

    2016-01-01

    Protein aggregation is a common biological phenomenon, observed in different physiological and pathological conditions. Decreased protein solubility and a tendency to aggregate is also observed during physiological aging but the causes are currently unknown. Herein we performed a biophysical separation of aging-related high molecular weight aggregates, isolated from the bone marrow and splenic cells of aging mice and followed by biochemical and mass spectrometric analysis. The analysis indicated that compared to younger mice an increase in protein post-translational carbonylation was observed. The causative role of these modifications in inducing protein misfolding and aggregation was determined by inducing carbonyl stress in young mice, which recapitulated the increased protein aggregation observed in old mice. Altogether our analysis indicates that oxidative stress-related post-translational modifications accumulate in the aging proteome and are responsible for increased protein aggregation and altered cell proteostasis.

  3. Carbonyl Sulfides as Possible Intermediates in the Photolysis of Oxathiiranes

    DEFF Research Database (Denmark)

    Carlsen, Lars; Snyder, J. P.; Holm, A.

    1981-01-01

    Diphenyl oxathiirane, formed by irradiation of thiobenzophenone S-oxide at 77 K, is photochemically converted into a blue, thermally unstable compound which decomposes at ca 100–110 K (λmax 550 nm, (ϵ ca 11,000). Lack of change in magnetic susceptibility during the light induced conversion...... of sulfine to ketone via the oxathiirane and the subsequent blue intermediate implies the absence of triplet and biradical singlet transients. The unknown carbonyl sulfide functionality, R2C&z.dbnd;O&z.dbnd;S, thereby emerges as a strong candidate for producing the visible absorption. Comparison of the wave...... functions for CH2&z.dbnd;S&z.dbnd;O and CH2&z.dbnd;O&z.dbnd;S arising from MNDO limited CI geometry optimizations leads to the conclusion that the carbonyl sulfide structure is best described as a zwitterion rather than as a singlet biradical. The failure to observe cycloaddition products between the blue...

  4. 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.

  5. 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.

  6. The reaction of sulfhydryl groups with carbonyl compounds.

    Science.gov (United States)

    Włodek, L

    1988-01-01

    The sulfhydryl groups of L-cysteine and reduced glutathione (GSH) react nonenzymatically with formaldehyde (F), acrolein (Al), acetaldehyde (AA), malondialdehyde (DAM), pyruvate (P), oxoglutarate (oxo-G) and glucose (G) to form thiazolidine derivatives. These reactions show different velocities and the adducts formed show different stabilities. The equilibrium constants K, as well as the rate constants kr for the reverse reaction, show considerable variation. The carbonyls reveal higher reactivity with sulfhydryl group of L-Cys than with those of GSH, and the stability of the adducts is higher than that of GSH. Al, F and AA react more rapidly with both thiol compounds than the other carbonyls, but the adducts are less stable. The sulfhydryl groups level of bovine serum albumin as well as those of high- and low-molecular thiols of human plasma is reduced in the presence of Al, F or DAM.

  7. 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

  8. 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 ...

  9. Three-component coupling of acylphosphonates and two carbonyl compounds promoted by low-valent samariums: one-Pot synthesis of beta-hydroxyphosphonates

    Science.gov (United States)

    Takaki; Itono; Nagafuji; Naito; Shishido; Takehira; Makioka; Taniguchi; Fujiwara

    2000-01-28

    Three-component coupling of acylphosphonates and two carbonyl compounds leading to beta-hydroxyphosphonates has been achieved with low-valent samariums. Thus, acylphosphonates reacted with aldehydes in the presence of semicatalytic amounts of samarium metal or SmI(2) to give acyloxyphosphonates in good yields. The second coupling reaction of the acyloxyphosphonates with aldehydes or ketones promoted by SmI(2) afforded beta-hydroxyphosphonates instead of olefins. Moreover, these two reactions could be carried out in one pot.

  10. 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

  11. 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

  12. Interresidue carbonyl-carbonyl polarization transfer experiments in uniformly 13C, 15N-labeled peptides and proteins

    Science.gov (United States)

    Janik, Rafal; Ritz, Emily; Gravelle, Andrew; Shi, Lichi; Peng, Xiaohu; Ladizhansky, Vladimir

    2010-03-01

    In this work, we demonstrate that Homonuclear Rotary Resonance Recoupling (HORROR) can be used to reintroduce carbonyl-carbonyl interresidue dipolar interactions and to achieve efficient polarization transfer between carbonyl atoms in uniformly 13C, 15N-labeled peptides and proteins. We show that the HORROR condition is anisotropically broadened and overall shifted to higher radio frequency intensities because of the CSA effects. These effects are analyzed theoretically using Average Hamiltonian Theory. At spinning frequencies used in this study, 22 kHz, this broadening is experimentally found to be on the order of a kilohertz at a proton field of 600 MHz. To match HORROR condition over all powder orientations, variable amplitude radio frequency (RF) fields are required, and efficient direct transfers on the order of 20-30% can be straightforwardly established. Two- and three-dimensional chemical shift correlation experiments establishing long-range interresidue connectivities (e.g., (N[i]-CO[i - 2])) are demonstrated on the model peptide N-acetyl-valine-leucine, and on the third immunoglobulin binding domain of protein G. Possible future developments are discussed.

  13. 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.

  14. 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.

  15. Formation of amorphous metal alloys by chemical vapor deposition

    Science.gov (United States)

    Mullendore, Arthur W.

    1990-01-01

    Amorphous alloys are deposited by a process of thermal dissociation of mixtures or organometallic compounds and metalloid hydrides, e.g., transition metal carbonyl such as nickel carbonyl, and diborane. Various sizes and shapes of deposits can be achieved, including near-net-shape free standing articles, multilayer deposits, and the like. Manipulation or absence of a magnetic field affects the nature and the structure of the deposit.

  16. 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.

  17. 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.

  18. Preparation and magnetorheological characteristics of polymer coated carbonyl iron suspensions

    International Nuclear Information System (INIS)

    Choi, J.S.; Park, B.J.; Cho, M.S.; Choi, H.J.

    2006-01-01

    Core-shell structured magnetic carbonyl iron (CI)-poly(methyl methacrylate) (PMMA) particles were fabricated via CI-seeded dispersion polymerization method, in order to enhance dispersion stability of their magnetorheological (MR) fluid when dispersed in mineral oil. The rheological properties of MR fluid with core-shell structured magnetic particles were then measured via a rotational rheometer with a magnetic field generator. It was found that the synthesized core-shell structured encapsulated CI particles possess better dispersion stability in suspending oil than bare CI particle suspension, due to the density reduction of the particles

  19. 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

  20. 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

  1. Carbonylated plasma proteins as potential biomarkers of obesity induced type 2 diabetes mellitus.

    Science.gov (United States)

    Bollineni, Ravi Chand; Fedorova, Maria; Blüher, Matthias; Hoffmann, Ralf

    2014-11-07

    Protein carbonylation is a common nonenzymatic oxidative post-translational modification, which is often considered as biomarker of oxidative stress. Recent evidence links protein carbonylation also to obesity and type 2 diabetes mellitus (T2DM), though the protein targets of carbonylation in human plasma have not been identified. In this study, we profiled carbonylated proteins in plasma samples obtained from lean individuals and obese patients with or without T2DM. The plasma samples were digested with trypsin, carbonyl groups were derivatized with O-(biotinylcarbazoylmethyl)hydroxylamine, enriched by avidin affinity chromatography, and analyzed by RPC-MS/MS. Signals of potentially modified peptides were targeted in a second LC-MS/MS analysis to retrieve the peptide sequence and the modified residues. A total of 158 unique carbonylated proteins were identified, of which 52 were detected in plasma samples of all three groups. Interestingly, 36 carbonylated proteins were detected only in obese patients with T2DM, whereas 18 were detected in both nondiabetic groups. The carbonylated proteins originated mostly from liver, plasma, platelet, and endothelium. Functionally, they were mainly involved in cell adhesion, signaling, angiogenesis, and cytoskeletal remodeling. Among the identified carbonylated proteins were several candidates, such as VEGFR-2, MMP-1, argin, MKK4, and compliment C5, already connected before to diabetes, obesity and metabolic diseases.

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

    DEFF Research Database (Denmark)

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

    2017-01-01

    preparation and chromatography. For the first time MS/MS data analysis utilising diagnostic biotin fragment ions is used to pinpoint sites of biotin labelling and improve the confidence of carbonyl peptide assignments. We identified a total of 125 carbonylated residues in bovine serum albumin after extensive...... at the protein level and help to understand how carbonylation affects protein structure and function. The challenge for future research is to identify the type and nature of oxidised residues to gain a deeper understanding of the mechanism(s) governing carbonylation in cells and organisms and assess their role...

  3. 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.

  4. trans-Di-μ-carbonyl-bis{carbonyl[η5-2,3,4,5-tetramethyl-1-(5-methyl-2-furylcyclopentadienyl]ruthenium(I}(Ru—Ru

    Directory of Open Access Journals (Sweden)

    Jin Lin

    2009-08-01

    Full Text Available In the crystal structure of the title compound, [Ru2(C14H17O2(CO4], each RuI atom is connected to one end-on and two bridging carbonyl groups and one cyclopentadienyl ring. The two Ru atoms are connected into binuclear complexes via two bridging carbonyl groups, forming four-membered rings which are located on centres of inversion. The Ru—Ru distance of 2.7483 (11 Å corresponds to a single bond. The two carbonyl groups in these binuclear complexes are trans-oriented.

  5. Carbothermic reduction of refractory metals

    International Nuclear Information System (INIS)

    Anderson, R.N.; Parlee, N.A.D.

    1976-01-01

    The reduction of stable refractory metal oxides by carbon is generally unacceptable since the product is usually contaminated with carbides. The carbide formation may be avoided by selecting a solvent metal to dissolve the reactive metal as it is produced and reduce its chemical activity below that required for carbide formation. This approach has been successfully applied to the oxides of Si, Zr, Ti, Al, Mg, and U. In the case where a volatile suboxide, a carbonyl reaction, or a volatile metal occur, the use of the solvent metal appears satisfactory to limit the loss of material at low pressures. In several solute--solvent systems, vacuum evaporation is used to strip the solvent metal from the alloy to give the pure metal

  6. Catalytic olefin polymerization with early transition metal compounds

    NARCIS (Netherlands)

    Eshuis, Johan Jan Willem

    1991-01-01

    The catalysis of organic reactions by soluble metal complexes has become a major tool in synthesis, both in the laboratory and in the chemical industry. Processes catalyzed by transition metal complexes include carbonylation, olefin polymerization, olefin addition, olefin oxidation and alkane and

  7. 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

  8. Quantification of airborne fossil and biomass carbonylic carbon by combined radiocarbon and liquid chromatography mass spectrometry

    Science.gov (United States)

    Larsen, B. R.; Tudos, A.; Slanina, J.; Van der Borg, K.; Kotzias, D.

    Airborne carbonyl compounds have been sampled at three European semi-remote to semi-urban test sites for radiocarbon ( 14C) analysis. The used methodology included collection on 2,4-dinitrophenylhydrazine coated silica gel cartridges, chromatographic isolation of the formed hydrazones, combustion into CO 2, reduction into graphite followed by accelerator mass spectrometry. In combination with this, liquid chromatography coupled to atmospheric pressure chemical ionisation mass spectrometry was used for chemical speciation of the collected carbonyls. At all sites the carbonyls were found to be of a mixed biogenic/anthropogenic origin. The determining factor for the proportion of fossil (anthropogenic) carbon in the samples was the vicinity of urban sources for carbonyls and their photochemical precursors. At meteorological conditions, which gave the test sites semi-rural/semi-remote characteristics the samples contained an average of 24% (range: 10-34%) of fossil carbonylic carbon. When air masses were transported from urban areas to the test-sites significantly higher proportions of fossil carbonylic carbon were determined with a maximum of 61%. Principal component analysis on this limited data set indicated that a low fossil proportion of carbonylic carbon is associated with high proportions of acetaldehyde, acetone, pentanone and acrolein. Until further radicarbon studies are carried out the conclusion remains that for the carbonyl compounds measured European background levels are of a predominant biogenic origin.

  9. Iron(III)-Catalyzed Ring-Closing Carbonyl-Olefin Metathesis.

    Science.gov (United States)

    Saá, Carlos

    2016-09-05

    Recent developments in catalytic carbonyl-olefin metathesis are summarized in this Highlight. Schindler and co-workers have reported that the environmentally benign FeCl3 catalyst promotes ring-closing carbonyl-olefin metathesis (RCCOM) in high yield under very mild conditions. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. 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.

  11. 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.

  12. One-pot Reductive Amination of Carbonyl Compounds with NaBH4 ...

    Indian Academy of Sciences (India)

    product. Another problem during reductive amination of carbonyl compounds with primary amines is over- alkylation and direct reduction of carbonyl compound to the corresponding alcohol. In these cases, formation and isolation of the imines which followed by reduction can avoid the problem, but the need to isolate imines.

  13. PROCESS OF COATING WITH NICKEL BY THE DECOMPOSITION OF NICKEL CARBONYL

    Science.gov (United States)

    Hoover, T.B.

    1959-04-01

    An improved process is presented for the deposition of nickel coatings by the thermal decomposition of nickel carbonyl vapor. The improvement consists in incorporating a small amount of hydrogen sulfide gas in the nickel carbonyl plating gas. It is postulated that the hydrogen sulfide functions as a catalyst. i

  14. 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

  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. 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.

  17. 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 (trees, i.e., camphor tree (Cinnamomum camphora), sweet olive (Osmanthus fragrans), cedar (Cedrus deodara), and dawn redwood (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.

  18. Anti-Amoebic Properties of Carbonyl Thiourea Derivatives

    Directory of Open Access Journals (Sweden)

    Maizatul Akma Ibrahim

    2014-04-01

    Full Text Available Thiourea derivatives display a broad spectrum of applications in chemistry, various industries, medicines and various other fields. Recently, different thiourea derivatives have been synthesized and explored for their anti-microbial properties. In this study, four carbonyl thiourea derivatives were synthesized and characterized, and then further tested for their anti-amoebic properties on two potential pathogenic species of Acanthamoeba, namely A. castellanii (CCAP 1501/2A and A. polyphaga (CCAP 1501/3A. The results indicate that these newly-synthesized thiourea derivatives are active against both Acanthamoeba species. The IC50 values obtained were in the range of 2.39–8.77 µg·mL‑1 (9.47–30.46 µM for A. castellanii and 3.74–9.30 µg·mL‑1 (14.84–31.91 µM for A. polyphaga. Observations on the amoeba morphology indicated that the compounds caused the reduction of the amoeba size, shortening of their acanthopodia structures, and gave no distinct vacuolar and nuclear structures in the amoeba cells. Meanwhile, fluorescence microscopic observation using acridine orange and propidium iodide (AOPI staining revealed that the synthesized compounds induced compromised-membrane in the amoeba cells. The results of this study proved that these new carbonyl thiourea derivatives, especially compounds M1 and M2 provide potent cytotoxic properties toward pathogenic Acanthamoeba to suggest that they can be developed as new anti-amoebic agents for the treatment of Acanthamoeba keratitis.

  19. Oxidative carbonylation of phenol to diphenyl carbonate by Pd/MFe2O4 magnetic catalyst

    Directory of Open Access Journals (Sweden)

    Zhang Linfeng

    2015-01-01

    Full Text Available In order to screen one suitable catalyst for magnetically stabilized fluidized bed (MSFB reactor in the process of oxidative carbonylation of phenol to diphenyl carbonate (DPC, Pd/MFe2O4 catalysts were chosen, then prepared and characterized by XRD, H2-TPR, XPS and VSM (Vibrating Sample Magnetometer. Compared to the other metal ion doped spinel ferrite catalysts, the catalytic activity of Pd/MnFe2O4 was much higher, which the single pass yield of DPC reached 33.12% with selectivity above 99%, and TOF (turnover frequency reached 70.56molDPC•(molPd•h-1.The result showed that the formation of the ferrite oxygen-deficient and ion transference in the ferrites was in favor of the catalytic activity. When the support MnFe2O4 was calcinated at 500ºC, the saturation magnetization of the obtained catalyst Pd/MnFe2O4 came up to 43.1 A•m2•kg-1. With good magnetic property and brilliant catalytic activity the catalyst Pd/MnFe2O4 may suite for industrial experiments in MSFB reactor in future.

  20. [XIm][FeI(CO)3(SnI3)2] (XIm: EMIm, EHIm, PMIm) containing a barbell-shaped FeSn2-carbonyl complex.

    Science.gov (United States)

    Wolf, Silke; Winter, Florian; Pöttgen, Rainer; Middendorf, Nils; Klopper, Wim; Feldmann, Claus

    2012-09-21

    By reacting Fe(CO)(5) and SnI(4) in the ionic liquids [XIm][NTf(2)] (XIm: 1-ethyl-3-methylimidazolium/EMIm, 1-ethyl-imidazolium/EHIm, 1-propyl-3-methylimidazolium/PMIm; NTf(2): bistrifluoridomethansulfonimide), the compounds [XIm][FeI(CO)(3)(SnI(3))(2)] are obtained as transparent, dark red crystals. According to single-crystal structure analysis, the title compounds crystallize monoclinically and contain the anionic carbonyl complex [FeI(CO)(3)(SnI(3))(2)](-) as well as [EMIm](+), [EHIm](+) or [PMIm](+) cations. The anionic carbonyl is composed of a Sn-Fe-Sn barbell-shaped building unit with Fe-Sn distances of 252.0(1) pm. Herein, tin is coordinated distorted tetrahedrally by iodine; iron is coordinated pseudo-octahedrally by three carbonyl ligands, one iodine atom and two tin atoms. Bonding situation and valence state are investigated in detail for [EMIm][FeI(CO)(3)(SnI(3))(2)] based on bond-lengths considerations, infrared spectroscopy, Mössbauer spectroscopy, density functional theory and DFT-based Mulliken population analysis. Hence, the formal oxidation state of the metal atoms can be concluded to Fe(±0) and Sn(3+).

  1. 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.

  2. Paraquat exposure and Sod2 knockdown have dissimilar impacts on the Drosophila melanogaster carbonylated protein proteome

    Science.gov (United States)

    Narayanasamy, Suresh K.; Simpson, David C.; Martin, Ian; Grotewiel, Mike; Gronert, Scott

    2014-01-01

    Exposure to Paraquat and RNA interference knockdown of Mn or mitochondrial superoxide dismutase (Sod2) are known to result in significant lifespan reduction, locomotor dysfunction, and mitochondrial degeneration in Drosophila melanogaster. Both perturbations increase the flux of the progenitor ROS, superoxide, but the molecular underpinnings of the resulting phenotypes are poorly understood. Improved understanding of such processes could lead to advances in the treatment of numerous age-related disorders. Superoxide toxicity can act through protein carbonylation. Analysis of carbonylated proteins is attractive since carbonyl groups are not present in the twenty canonical amino acids and are amenable to labeling and enrichment strategies. Here, carbonylated proteins were labeled with biotin hydrazide and enriched on streptavidin beads. On-bead digestion was used to release carbonylated protein peptides, with relative abundance ratios versus controls obtained using the iTRAQ MS-based proteomics approach. Western blotting and biotin quantitation assay approaches were also investigated. By both western blotting and proteomics, Paraquat exposure, but not Sod2 knockdown, resulted in increased carbonylated protein relative abundance. For Paraquat exposure versus control, the median carbonylated protein relative abundance ratio (1.53) determined using MS-based proteomics was in good agreement with that obtained using a commercial biotin quantitation kit (1.36). PMID:25091824

  3. Supported Single-Site Ti(IV) on a Metal–Organic Framework for the Hydroboration of Carbonyl Compounds

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Zhiyuan [College; amp, Molecular Sciences, Institute of Advanced Studies, Wuhan University, Wuhan 430072, PR China; Chemical; amp, Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States; Liu, Dong [College; amp, Molecular Sciences, Institute of Advanced Studies, Wuhan University, Wuhan 430072, PR China; Chemical; amp, Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States; Camacho-Bunquin, Jeffrey [Chemical; amp, Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States; Zhang, Guanghui [Department; Yang, Dali [College; amp, Molecular Sciences, Institute of Advanced Studies, Wuhan University, Wuhan 430072, PR China; Chemical; amp, Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States; López-Encarnación, Juan M. [Chemical; amp, Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States; Department; Xu, Yunjie [Department; Ferrandon, Magali S. [Chemical; amp, Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States; Niklas, Jens [Chemical; amp, Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States; Poluektov, Oleg G. [Chemical; amp, Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States; Jellinek, Julius [Chemical; amp, Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States; Lei, Aiwen [College; amp, Molecular Sciences, Institute of Advanced Studies, Wuhan University, Wuhan 430072, PR China; Chemical; amp, Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States; Bunel, Emilio E. [Chemical; amp, Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States; Delferro, Massimiliano [Chemical; amp, Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States

    2017-10-10

    ABSTRACT: A stable and structurally well-defined titanium alkoxide catalyst supported on a metal-organic-framework (MOF) of UiO-67 topology (ANL1-Ti(OiPr)2) was synthesized and fully characterized by a variety of analytical and spectroscopic techniques, including BET, TGA, PXRD, XAS, DRIFT, SEM, and DFT computations. The Ti-functionalized MOF was demonstrated active for the catalytic hydroboration of a wide range of aldehydes and ketones with HBpin as the boron source. Compared to traditional homogeneous and supported hydroboration catalysts, ANL1-Ti(OiPr)2 is completely recyclable and reusable, making it a promising hydroboration catalyst alternative for green and sustainable chemical synthesis. DFT calculations suggest that the catalytic hydroboration proceeds via a (1) hydride transfer between the active Ti-hydride species and a carbonyl moiety (rate determining step), and (2) alkoxide transfer (intramolecular σ-bond metathesis) to generate the boronate ester product.

  4. Characteristics of carbonyls: Concentrations and source strengths for indoor and outdoor residential microenvironments in China

    Science.gov (United States)

    Wang, B.; Lee, S. C.; Ho, K. F.

    Indoor and outdoor carbonyl concentrations were measured simultaneously in 12 urban dwellings in Beijing, Shanghai, Guangzhou, and Xi'an, China in summer (from July to September in 2004) and winter (from December 2004 to February 2005). Formaldehyde was the most abundant indoor carbonyls species, while formaldehyde, acetaldehyde and acetone were found to be the most abundant outdoor carbonyls species. The average formaldehyde concentrations in summer indoor air varied widely between cities, ranging from a low of 19.3 μg m -3 in Xi'an to a high of 92.8 μg m -3 in Beijing. The results showed that the dwellings with tobacco smoke, incense burning or poor ventilation had significantly higher indoor concentrations of certain carbonyls. It was noticed that although one half of the dwellings in this study installed with low emission building materials or furniture, the carbonyls levels were still significantly high. It was also noted that in winter both the indoor and outdoor acetone concentrations in two dwellings in Guangzhou were significantly high, which were mainly caused by the usage of acetone as industrial solvent in many paint manufacturing and other industries located around Guangzhou and relatively longer lifetime of acetone for removal by photolysis and OH reaction than other carbonyls species. The indoor carbonyls levels in Chinese dwellings were higher than that in dwellings in the other countries. The levels of indoor and ambient carbonyls showed great seasonal differences. Six carbonyls species were carried out the estimation of indoor source strengths. Formaldehyde had the largest indoor source strength, with an average of 5.25 mg h -1 in summer and 1.98 mg h -1 in winter, respectively. However, propionaldehyde, crotonaldehyde and benzaldehyde had the weakest indoor sources.

  5. Millimeter-Wave Transmittance and Reflectance Measurement on Pure and Diluted Carbonyl Iron

    Science.gov (United States)

    Korolev, Konstantin; Chen, Shu; Li, Zijing; Afsar, Mohammed

    2010-03-01

    Transmittance and reflectance measurements on highly absorbing carbonyl iron materials over a broad millimeter-wave frequency range have been performed. Frequency dependence of the complex dielectric permittivity of carbonyl iron diluted composite and pure powdered materials have been determined in the millimeter waves for the first time. The measurements have been employed using a free-space quasi-optical millimeter-wave spectrometer equipped with a set of high power backward wave oscillators as sources of coherent radiation, tunable in the range from 30 -- 120 GHz. Significant transmission zone of the millimeter-wave radiation at frequency around 60 GHz has been observed in transmittance spectra for the carbonyl iron materials.

  6. FeCl3 -Catalyzed Ring-Closing Carbonyl-Olefin Metathesis.

    Science.gov (United States)

    Ma, Lina; Li, Wenjuan; Xi, Hui; Bai, Xiaohui; Ma, Enlu; Yan, Xiaoyu; Li, Zhiping

    2016-08-22

    Exploiting catalytic carbonyl-olefin metathesis is an ongoing challenge in organic synthesis. Reported herein is an FeCl3 -catalyzed ring-closing carbonyl-olefin metathesis. The protocol allows access to a range of carbo-/heterocyclic alkenes with good efficiency and excellent trans diastereoselectivity. The methodology presents one of the rare examples of catalytic ring-closing carbonyl-olefin metathesis. This process is proposed to take place by FeCl3 -catalyzed oxetane formation followed by retro-ring-opening to deliver metathesis products. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Visible Light-Induced Carbonylation Reactions with Organic Dyes as the Photosensitizers.

    Science.gov (United States)

    Peng, Jin-Bao; Qi, Xinxin; Wu, Xiao-Feng

    2016-09-08

    Dyes can CO do it: Organic dyes and pigments are usually applied in textile dyeing, which can be dated back to the Neolithic period. Interestingly, the possibility to use organic dyes as photoredox catalysts has also been noticed by organic chemists and applied in organic synthesis. Carbonylation reactions as a powerful procedure in carbonyl-containing compound preparation have also been studied. In this manuscript, the recent achievements in using organic dyes as visible-light sensitizers in carbonylation chemistry are summarized and discussed. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Reaction between carbonyl compound and ammonia on the bimetallic catalyst the Eu, Yb system; Eu, Yb kei baimetarikku shokubaijo deno karuboniru kagobutsu to anmonia tono hanno

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1999-09-01

    Ln-Cu/Al{sub 2}O{sub 3}, Ln-Fe/SiO{sub 2}, Ln-Ni/SiO{sub 2}, Ln-Co/SiO{sub 2} bimetallic catalyst are obtained Cu/Al{sub 2}O{sub 3}, Fe/SiO{sub 2} and Ni/SiO{sub 2} and Co/SiO{sub 2}, when it reacted with the rare metal which dissolved in the liquid ammonia. Using it, the reaction between carbonyl compound and ammonia was examined at 473-523K reaction temperature. In the reaction between carbonyl compound and ammonia, these bimetallic catalysts can be developed to amination and reductive alkylation, those relation reactions and in order to show the activity for hydrogenation, dehydrogenation and conversion hydrogenation, which made the ammonia to be the hydrogen source. The catalysis greatly changed with the rare earth metal composition in the catalyst. Especially, the Ln-Cu/Al{sub 2}O{sub 3} catalyst showed the activity for the reaction between methyl acetate and ammonia. By adding the rare earth metal at Cu/Al{sub 2}O{sub 3}, the Eu-Cu/Al{sub 2}O{sub 3} catalyst was more activated, and the acetonitrile was given. Eu-Cu /Al{sub 2}O{sub 3}, since it has the high activity for the conversion hydrogenation from the ammonia, the reductive amination progressed acetone ammonia hydrogen, and isopropylamine was formed. (translated by NEDO)

  9. 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.

  10. Tropical sources and sinks of carbonyl sulfide observed from space

    Science.gov (United States)

    Glatthor, Norbert; Höpfner, Michael; Baker, Ian T.; Berry, Joe; Campbell, Elliott; Kawa, Stephan R.; Krysztofiak, Gisele; Sinnhuber, Björn-Martin; Stiller, Gabriele; Stinecipher, Jim; von Clarmann, Thomas

    2016-04-01

    According to current budget estimations the seasonal variation of carbonyl sulfide (COS) is governed by oceanic release and vegetation uptake. Its assimilation by plants is assumed to be similar to the photosynthetic uptake of CO2 but, contrary to the latter process, to be irreversible. Therefore COS has been suggested as co-tracer of the carbon cycle. Observations of COS, however, are sparse, especially in tropical regions. We use the comprehensive data set of spaceborne measurements of the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) to analyze its global distribution. Two major features are observed in the tropical upper troposphere around 250 hPa: enhanced amounts over the western Pacific and the Maritime Continent, peaking around 550 pptv in boreal summer, and a seasonally varying depletion of COS extending from tropical South America to Africa. The large-scale COS depletion, which in austral summer amounts up to -40 pptv as compared to the rest of the respective latitude band, has not been observed before and reveals the seasonality of COS uptake through tropical vegetation. The observations can only be reproduced by global models, when a large vegetation uptake and a corresponding increase in oceanic emissions as proposed in several recent publications is assumed.

  11. 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.

  12. Assessing canopy performance using carbonyl sulfide (COS) measurements.

    Science.gov (United States)

    Yang, Fulin; Qubaja, Rafat; Tatarinov, Fyodor; Rotenberg, Eyal; Yakir, Dan

    2018-03-25

    Carbonyl sulfide (COS) is a tracer of ecosystem photosynthesis that can advance carbon cycle research from leaf to global scales; however, a range of newly reported caveats related to sink/source strength of various ecosystem components hinder its application. Using comprehensive eddy-covariance and chamber measurements, we systematically measure ecosystem contributions from leaf, stem, soil and litter and were able to close the ecosystem COS budget. The relative contributions of non-photosynthetic components to the overall canopy-scale flux are relatively small (~4% during peak activity season) and can be independently estimated based on their responses to temperature and humidity. Converting COS to photosynthetic CO 2 fluxes based on the leaf relative uptake of COS/CO 2 , faces challenges due to observed daily and seasonal changes. Yet, this ratio converges around a constant value (~1.6), and the variations, dominated by light intensity, were found unimportant on a flux-weighted daily time-scale, indicating a mean ratio of daytime gross-to-net primary productivity of ~2 in our ecosystem. The seasonal changes in the leaf relative uptake ratio may indicate a reduction in mesophyll conductance in winter, and COS-derived canopy conductance permitted canopy temperature estimate consistent with radiative skin temperature. These results support the feasibility of using COS as a powerful and much-needed means of assessing ecosystem function and its response to change. This article is protected by copyright. All rights reserved. This article is protected by copyright. All rights reserved.

  13. Carbonyl Sulfide for Tracing Carbon Fluxes Field Campaign Report

    Energy Technology Data Exchange (ETDEWEB)

    Campbell, J. Elliott [Univ. of California, Merced, CA (United States); Berry, Joseph A. [Carnegie Inst. of Science, Stanford, CA (United States); Billesbach, Dave [Univ. of Nebraska, Lincoln, NE (United States); Torn, Margaret S [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Zahniser, Mark [Aerodyne Research, Inc., Billerica, MA (United States); Seibt, Ulrike [Univ. of California, Los Angeles, CA (United States); Maseyk, Kadmiel [Pierre and Marie Curie Univ., Paris (France)

    2016-04-01

    The April-June 2012 campaign was located at the U.S. Department of Energy (DOE)’s Atmospheric Radiation Measurement (ARM) Climate Research Facility Southern Great Plains (SGP) site Central Facility and had three purposes. One goal was to demonstrate the ability of current instrumentation to correctly measure fluxes of atmospheric carbonyl sulfide (COS). The approach has been describe previously as a critical approach to advancing carbon cycle science1,2, but requires further investigation at the canopy scale to resolve ecosystem processes. Previous canopy-scale efforts were limited to data rates of 1Hz. While 1 Hz measurements may work in a few ecosystems, it is widely accepted that data rates of 10 to 20 Hz are needed to fully capture the exchange of traces gases between the atmosphere and vegetative canopy. A second goal of this campaign was to determine if canopy observations could provide information to help interpret the seasonal double peak in airborne observations at SGP of CO2 and COS mixing ratios. A third goal was to detect potential sources and sinks of COS that must be resolved before using COS as a tracer of gross primary productivity (GPP).

  14. Photodecomposition of Molybdenum andTungsten Carbonyl Complexes

    Directory of Open Access Journals (Sweden)

    Thamer A. Alwani

    2009-01-01

    Full Text Available The photodecomposition of four different colored organometallic molybdenum and tungsten carbonyl complexes, i.e. [Mo(CO52LA] (complex I, [(Mo(CO3(bipy2LB] (complex II, [(W(CO3(tmen2LB] (complex III and [Mo(CO2LC]2 (complex I V where LA 2-phenyl-1,3-indandionebis(2-methyl anilines, LB 2-phenyl-1,3-indandione bis (4-hydroxy anilines and LCbis (2-hydroxo-benzalydine benzidine ion have been performed at 365 nm in chloroform at 25 °C under oxygen atmosphere. The absorbance spectrum of these complexes has been recorded with the time of irradiation in order to examine the kinetics of photodecomposition. The rate of the photodecomposition process was investigated and the relative values of the rate constants of dissociation (Kd for the first-order reaction are tabulated. The apparent rate constant of photodecomposition was found to be (8.33-11.50 × 10-5 s-1.

  15. Fluorescent hydrazides for the high-performance liquid chromatographic determination of biological carbonyls.

    Science.gov (United States)

    Anderson, J M

    1986-01-01

    Methods for the determination of carbonyl compounds of biological origin by high-performance liquid chromatography were improved by the use of new fluorescent derivatizing agents. Eight fluorescent hydrazides were either synthesized or obtained commercially and compared to dansyl hydrazine (1-dimethylaminonaphthalene-5-sulfonylohydrazide). Four of the compounds yielded carbonyl hydrazones with a higher relative fluorescence quantum yield than dansyl hydrazine in acetonitrile:water mixtures. Darpsyl hydrazide [(3-phenylpyrazoline-1-yl)-4-phenylsulfonylohydrazide] and apmayl hydrazide [N-(2-aminophenyl-6-methylbenzthiazole)-acetylohydrazide] both yielded an increase of greater than 20-fold in sensitivity over dansyl hydrazine in determinations of abscisic acid and jasmonic acid from plant tissues. Different hydrazides and derivatizing conditions were found to be optimum for the determination of different carbonyl compounds. Also, a simple method for precolumn purification of the hydrazones of acidic carbonyls was developed to remove contaminants arising during derivatization and from the tissue source.

  16. Magnetic carbonyl iron suspension with organoclay additive and its magnetorheological properties

    CSIR Research Space (South Africa)

    Hato, MJ

    2011-02-01

    Full Text Available Soft magnetic carbonyl iron (CI) based magnetorheological (MR) fluids containing three different loadings of submicron-sized organoclay were prepared. The MR characteristics were measured via rotational and oscillatory tests, in which the flow...

  17. Protective mechanisms of Cucumis sativus in diabetes-related models of oxidative stress and carbonyl stress

    Directory of Open Access Journals (Sweden)

    Himan Heidari

    2016-03-01

    Conclusion: It can be concluded that C. sativus has protective effects in diabetes complications and can be considered a safe and suitable candidate for decreasing the oxidative stress and carbonyl stress that is typically observed in diabetes mellitus.

  18. 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).

  19. 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).

  20. Reaction or organomagnesium compounds of the adamantane series with carbonyl compounds

    International Nuclear Information System (INIS)

    Yurchenko, A.G.; Fedorenko, T.V.

    1987-01-01

    In the transformations of organomagnesium compounds of the adamantane series involving aldehydes, ketones, esters, and acid chlorides the nature of the reaction products and their yields are determined by the steric hindrances at the reaction centers of the organomagnesium and carbonyl compounds and by the ease of homolysis of the C-H bonds of the carbonyl reagent. The retardation of the faster addition of the Grignard reagent at the carbonyl group as a result of steric hindrances permits homolytic removal of a hydrogen atom from the carbonyl compound by the adamantyl radical. The PMR spectra were measured on a Tesla BS-487C spectrometer at 80 MHz in carbon tetrachloride with the substances at concentrations of 5-20% and with TMS as internal standard. The IR spectra were obtained in carbon tetrachloride on a UR-10 spectrophotometer

  1. 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.

  2. 1,2,3-Triazoles from carbonyl azides and alkynes: filling the gap.

    Science.gov (United States)

    Haldón, Estela; Álvarez, Eleuterio; Nicasio, M Carmen; Pérez, Pedro J

    2014-08-18

    Electron deficient azides are challenging substrates in CuAAC reactions. Particularly, when N-carbonyl azides are applied the formation of N-carbonyl triazoles has not yet been observed. We report herein the first example of this class of reaction, with a copper-based system that efficiently enables the synthesis of N-carbamoyl 1,2,3-triazoles by [3+2] cycloaddition of N-carbamoyl azides and alkynes.

  3. 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.

  4. Functionalization of 6-Nitrobenzo[1,3]dioxole with Carbonyl Compounds via TDAE methodology

    Directory of Open Access Journals (Sweden)

    Patrice Vanelle

    2005-05-01

    Full Text Available We report herein the synthesis of substituted 2-(6-nitrobenzo[1,3]dioxol-5-yl-1- aryl ethanols and 2-(6-nitrobenzo[1,3]dioxol-5-yl-propionic acid ethyl esters from the reaction of 5-chloromethyl-6-nitrobenzo[1,3]dioxole with various aromatic carbonyl and α- carbonyl ester derivatives using the tetrakis(dimethylaminoethylene (TDAE methodology.

  5. Diastereo- and Enantioselective Iridium Catalyzed Carbonyl (α-Cyclopropyl)allylation via Transfer Hydrogenation.

    Science.gov (United States)

    Tsutsumi, Ryosuke; Hong, Suckchang; Krische, Michael J

    2015-09-07

    The first examples of diastereo- and enantioselective carbonyl α-(cyclopropyl)allylation are reported. Under the conditions of iridium catalyzed transfer hydrogenation using the chiral precatalyst (R)-Ir-I modified by SEGPHOS, carbonyl α-(cyclopropyl)allylation may be achieved with equal facility from alcohol or aldehyde oxidation levels. This methodology provides a conduit to hitherto inaccessible inaccessible enantiomerically enriched cyclopropane-containing architectures. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. 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.

  7. 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.

  8. Selective Palladium(II)-Catalyzed Carbonylation of Methylene β-C-H Bonds in Aliphatic Amines.

    Science.gov (United States)

    Cabrera-Pardo, Jaime R; Trowbridge, Aaron; Nappi, Manuel; Ozaki, Kyohei; Gaunt, Matthew J

    2017-09-18

    Palladium(II)-catalyzed C-H carbonylation reactions of methylene C-H bonds in secondary aliphatic amines lead to the formation of trans-disubstituted β-lactams in excellent yields and selectivities. The generality of the C-H carbonylation process is aided by the action of xantphos-based ligands and is important in securing good yields for the β-lactam products. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. 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...

  10. Oxidative Stress and Carbonyl Lesions in Ulcerative Colitis and Associated Colorectal Cancer

    Directory of Open Access Journals (Sweden)

    Zhiqi Wang

    2016-01-01

    Full Text Available Oxidative stress has long been known as a pathogenic factor of ulcerative colitis (UC and colitis-associated colorectal cancer (CAC, but the effects of secondary carbonyl lesions receive less emphasis. In inflammatory conditions, reactive oxygen species (ROS, such as superoxide anion free radical (O2∙-, hydrogen peroxide (H2O2, and hydroxyl radical (HO∙, are produced at high levels and accumulated to cause oxidative stress (OS. In oxidative status, accumulated ROS can cause protein dysfunction and DNA damage, leading to gene mutations and cell death. Accumulated ROS could also act as chemical messengers to activate signaling pathways, such as NF-κB and p38 MAPK, to affect cell proliferation, differentiation, and apoptosis. More importantly, electrophilic carbonyl compounds produced by lipid peroxidation may function as secondary pathogenic factors, causing further protein and membrane lesions. This may in turn exaggerate oxidative stress, forming a vicious cycle. Electrophilic carbonyls could also cause DNA mutations and breaks, driving malignant progression of UC. The secondary lesions caused by carbonyl compounds may be exceptionally important in the case of host carbonyl defensive system deficit, such as aldo-keto reductase 1B10 deficiency. This review article updates the current understanding of oxidative stress and carbonyl lesions in the development and progression of UC and CAC.

  11. A study of photochemical and physical processes affecting carbonyl compounds in the Arctic atmospheric boundary layer

    Energy Technology Data Exchange (ETDEWEB)

    Grannas, A.M.; Shepson, P.B.; Guimbaud, C. [Purdue Univ., West Lafayette, IN (US). Dept. of Earth and Atmospheric Sciences] [and others

    2002-06-01

    Experiments were conducted during the ALERT 2000 field campaign aimed at understanding the role of air-snow interactions in carbonyl compound chemistry and the associated ozone depletion in the atmospheric boundary layer. Under sunlit conditions, we find that formaldehyde, acetaldehyde and acetone exhibit a significant diel cycle with average ambient air concentrations of 166, 53 and 385 ppt, respectively. A box model of Arctic surface layer chemistry was used to understand the diel behavior of carbonyl compound concentrations at Alert, Nunavut, Canada, with a focus on the chemical and physical processes that affect carbonyl compounds. Results of the study showed that the measured carbonyl compound concentrations can only be simulated when a radiation-dependent snowpack source term (possibly photochemistry) and a temperature-dependent sink (physical uptake on snow grains) of carbonyl compounds were added to the model. We are able to simulate the concentration and amplitude of the observed diel cycle, but not the phase of the cycle. These results help confirm the importance of snowpack chemistry and physical processes with respect to carbonyl compound concentrations in the Arctic surface boundary layer, and reveal weakness in the details of our understanding. (Author)

  12. 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.

  13. 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.

  14. 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

  15. 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.

  16. A new agent for derivatizing carbonyl species used to investigate limonene ozonolysis

    Science.gov (United States)

    Wells, J. R.; Ham, Jason E.

    2014-12-01

    A new method for derivatizing carbonyl compounds is presented. The conversion of a series of dicarbonyls to oximes in aqueous solution and from gas-phase sampling was achieved using O-tert-butylhydroxylamine hydrochloride (TBOX). Some advantages of using this derivatization agent include: aqueous reactions, lower molecular weight oximes, and shortened oxime-formation reaction time. Additionally, the TBOX derivatization technique was used to investigate the carbonyl reaction products from limonene ozonolysis. With ozone (O3) as the limiting reagent, four carbonyl compounds were detected: 7-hydroxy-6-oxo-3-(prop-1-en-2-yl)heptanal; 3-Isopropenyl-6-oxoheptanal (IPOH), 3-acetyl-6-oxoheptanal (3A6O) and one carbonyl of unknown structure. Using cyclohexane as a hydroxyl (OHrad) radical scavenger, the relative yields (peak area) of the unknown carbonyl, IPOH, and 3A6O were reduced indicating the influence secondary OH radicals have on limonene ozonolysis products. The relative yield of the hydroxy-dicarbonyl based on the chromatogram was unchanged suggesting it is only made by the limonene + O3 reaction. The detection of 3A6O using TBOX highlights the advantages of a smaller molecular weight derivatization agent for the detection of multi-carbonyl compounds. The use of TBOX derivatization if combined with other derivatization agents may address a recurring need to simply and accurately detect multi-functional oxygenated species in air.

  17. 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

  18. 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.

  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. Benchmarking of protein carbonylation analysis in Caenorhabditis elegans: specific considerations and general advice.

    Science.gov (United States)

    Pyr Dit Ruys, S; Bonzom, J-M; Frelon, S

    2016-10-01

    Oxidative stress has been extensively studied due to its correlation with cellular disorders and aging. In proteins, one biomarker of oxidative stress is the presence of carbonyl groups, such as aldehyde and ketone, in specific amino acid side chains such as lysine, proline, arginine and threonine, so-called protein carbonylation (PC). PC study is now a growing field in general and medical science since PC accumulation is associated with various pathologies and disorders. At present, enzyme-linked immunosorbent assays (ELISA) seem to be the most robust method of quantifying the presence of carbonyl groups in proteins, despite having some recognised caveats. In parallel, gel-based approaches present cross-comparison difficulties, along with other technical problems. As generic PC analyses still suffer from poor homogeneity, leading to cross-data analysis difficulties and poor results overlap, the need for harmonisation in the field of carbonyl detection is now widely accepted. This study aims to highlight some of the technical challenges in proteomic gel-based multiplexing experiments when dealing with PC in difficult samples like those from Caenorhabditis elegans, from protein extraction to carbonyl detection. We demonstrate that some critical technical parameters, such as labelling time, probe concentration, and total and carbonylated protein recovery rates, should be re-addressed in a sample-specific way. We also defined a procedure to cost-effectively adapt CyDye™-hydrazide-based protocols to specific samples, especially when the experimental interest is focused on studying differences between stimulating conditions with a maximised signal-to-noise ratio. Moreover, we have improved an already-existing powerful solubilisation buffer, making it potentially useful for hard-to-solubilise protein pellets. Lastly, the depicted methodology exemplifies a simple way of normalising carbonyl-related signal to total protein in SDS-PAGE multiplexing experiments. Within

  1. Excited State Evolution towards ligand loss and ligand chelation at group 6 metal carbonyl centres

    NARCIS (Netherlands)

    Manton, J.C.; Amirjalayer, S.; Coleman, A.C.; McMahon, S.; Harvey, E.C.; Greetham, G.M.; Clark, I.P.; Buma, W.J.; Woutersen, S.; Pryce, M.T.; Long, C.

    2014-01-01

    The photochem. and photophysics of three model "half-​sandwich" complexes (η6-​benzophenone)​Cr(CO)​3, (η6-​styrene)​Cr(CO)​3, and (η6-​allylbenzene)​Cr(CO)​3 were investigated using pico-​second time-​resolved IR spectroscopy and time-​dependent d. functional theory methods. The

  2. 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

  3. 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.

  4. Synthesis, characterization and applications of polymer-metal ...

    Indian Academy of Sciences (India)

    vibrations. The ester carbonyl is identified through the appearance of a strong absorption band at 1732 cm ... tate fashion. The IR spectrum of functionalized copoly- mer shows intense band at 1651 cm. −1 due to C=O stretching in hydrazone and its downward shift in Fe(II) complex suggest coordination of metal ion through.

  5. Rh(I)-catalyzed CO gas-free carbonylative cyclization reactions of alkynes with 2-bromophenylboronic acids using formaldehyde.

    Science.gov (United States)

    Morimoto, Tsumoru; Yamasaki, Kae; Hirano, Akihisa; Tsutsumi, Ken; Kagawa, Natsuko; Kakiuchi, Kiyomi; Harada, Yasuyuki; Fukumoto, Yoshiya; Chatani, Naoto; Nishioka, Takanori

    2009-04-16

    The rhodium(I)-catalyzed reaction of alkynes with 2-bromophenylboronic acids in the presence of paraformaldehyde resulted in a CO gas-free carbonylative cyclization, yielding indenone derivatives. [RhCl(BINAP)](2) and [RhCl(cod)](2) were responsible for the decarbonylation of formaldehyde and the subsequent carbonylation of alkynes with 2-haloboronic acids, respectively, leading to efficient whole carbonylation. Sterically bulky and electron-withdrawing groups on unsymmetrically substituted alkynes favored the alpha-position of indenones.

  6. Positive trends in Southern Hemisphere observations of carbonyl sulfide

    Science.gov (United States)

    Kremser, Stefanie; Jones, Nicholas; Smale, Dan; Palm, Mathias; Lejeune, Bernard; Wang, Yuting; Deutscher, Nicholas

    2016-04-01

    Carbonyl sulfide (OCS; lifetime of about 5.7 years) is the longest lived reduced sulfur-containing gas in the atmosphere. The primary source of OCS is the ocean, which is both a direct source (through OCS emission) and an indirect source (due to oxidation of carbon disulfide, CS2, and dimethyl sulfide). Other natural sources of OCS include volcanic outgassing and direct fluxes from wetland regions. The removal of OCS from the atmosphere is dominated by soil and vegetation uptake, with minor contributions from reactions with the hydroxyl radical. Small anthropogenic sources of OCS are coal combustion, biomass burning, and aluminum production. A dominant indirect source results from CS2 emissions from the rayon industry. Transport of tropospheric OCS to the stratosphere during volcanically quiescent periods has been suggested to contribute sulfur to the stratospheric aerosol layer which affects atmospheric radiative balance. If, however, production of stratospheric aerosols from OCS oxidation is smaller than typical estimates, this OCS contribution would be overestimated. The magnitude of the OCS flux to the stratosphere is currently not well quantified as is the relative contribution of OCS to background aerosol loading. While earlier model simulations indicate OCS fluxes into the atmosphere exceeding removal, past total column observations of OCS show no significant trend. Analysis of tropospheric OCS columns at Arrival Heights (Antarctica) and Lauder (New Zealand) show strong positive trends from 2001-2008 followed by weaker trends to 2015, with unexpected temporal coherence. Since trends in ocean and land sources/sinks at these two sites, respectively, are unlikely to be similar, the coherence in trend structure likely results from changes in transport of OCS from the tropics to middle and high latitudes. Potential causes for OCS increases are (i) increases in tropical lower stratospheric OCS and/or (ii) strengthening of the large-scale circulation which

  7. Multiple-sulfur isotope effects during photolysis of carbonyl sulfide

    Directory of Open Access Journals (Sweden)

    Y. Lin

    2011-10-01

    Full Text Available Laboratory experiments were carried out to determine sulfur isotope effects during ultraviolet photolysis of carbonyl sulfide (OCS to carbon monoxide (CO and elemental sulfur (S0. The OCS gas at 3.7 to 501 mbar was irradiated with or without a N2 bath gas using a 150 W Xe arc lamp. Sulfur isotope ratios for the product S0 and residual OCS were analyzed by an isotope ratio mass-spectrometer with SF6 as the analyte gas. The isotope fractionation after correction for the reservoir effects is −6.8‰ for the ratio 34S/32S, where product S0 is depleted in heavy isotopes. The magnitude of the overall isotope effect is not sensitive to the addition of N2 but increases to −9.5‰ when radiation of λ > 285 nm is used. The measured isotope effect reflects that of photolysis as well as the subsequent sulfur abstraction (from OCS reaction. The magnitude of isotope effects for the abstraction reaction is estimated by transition state theory to be between −18.9 and −3.1‰ for 34S which gives the photolysis isotope effect as −10.5 to +5.3‰. The observed triple isotope coefficients are ln(δ34S + 1/ln(δ34S + 1 = 0.534 ± 0.005 and ln(δ36S + 1/ln(δ34S + 1 = 1.980 ± 0.021. These values differ from canonical values for mass-dependent fractionation of 0.515 and 1.90, respectively. The result demonstrates that the OCS photolysis does not produce large isotope effects of more than about 10‰ for 34S/32S, and can be the major source of background stratospheric sulfate aerosol (SSA during volcanic quiescence.

  8. Ambient gas-particle partitioning of atmospheric carbonyl at an urban site in Beijing

    Science.gov (United States)

    Shen, H.; Chen, Z.

    2017-12-01

    Carbonyls are important oxidation intermediates of hydrocarbons and major carcinogenic and genotoxic compounds in urban areas. While their health and climate impacts are primarily associated with their gas-particle conversion such as oligomers and brown carbon formation in particle phase, however, observations of their actual ambient gas-particle partitioning are sparse. In this study, the Sep-Pak DNPH-Silica Gel Cartridges and a four-channel particle sampler were used to collect carbonyls in gaseous and particle (PM2.5) phases simultaneously. Six carbonyls (formaldehyde, acetaldehyde, acetone, propionaldehyde and two dicarbonyls, glyoxal and methylglyoxal) of the ten observed in gas phase (plus butyraldehyde, methacrolein, methyl vinyl ketone, benzaldehyde) were detected in ambient particles. The measured gas/particle (G/P) partitioning coefficients (Kp,field) of the six carbonyls were calculated and compared to their predicted G/P partitioning coefficients (Kp,theor) based on the absorptive partitioning theory. The values of Kp,field are 105-106 times higher than Kp,theor and the Kp,field of the measured total carbonyls were determined to be as high as (0.3-11)×10-4 m3 µg-1, indicating that small carbonyls were much easier to enter the particle phase than previously expected and their distribution between gas and particles varied greatly with environmental conditions. The measured Kp,CHOCHO > Kp,CH3COCHO > Kp,CH3CH3CHO > Kp,CH3CHO ≈ Kp,HCHO > Kp,CH3COCH3, suggesting that the aldehyde group, to some extent, is more likely to promote the carbonyl compounds into particle phase than ketone group and methyl group. The variation trends of the measured G/P partitioning coefficients were very consistent and significantly correlated, and did not reflect the different salting effect for glyoxal and methylglyoxal ("salting-in" for glyoxal and "salting-out" for methylglyoxal), which indicated that the factors affecting the gas-particle partitioning of carbonyls in the

  9. Cyclometallated ruthenium(II) carbonyl complexes with 1 ...

    Indian Academy of Sciences (India)

    robust and less sensitive to air and moisture.15,16. We have reported some cyclometallated platinum group metal ion complexes with pincer-like CNO- ..... by condensation reactions of equimolar amounts of. 1-pyrenecarboxaldehyde with the corresponding sub- stituted thiosemicarbazides in acidic ethanol by fol- lowing a ...

  10. 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.

  11. The effect of humidity on peak value of HEMA carbonyl absorbance band

    Directory of Open Access Journals (Sweden)

    Adioro Soetojo

    2006-09-01

    Full Text Available Bond strength between 2-Hydroxyethyl methacrylate HEMA-based dentin bonding agent and dentin collagen had proved by presence of the chemical interaction. This union involved the carbonyl group on HEMA resin with amino group on dentin collagen following produce an amide chain. However, this bond strength influence by humidity condition of dentin collagen and HEMA resin. The aim of this study is to measure the effect of humidity on peak value of the HEMA carbonyl absorbance band. The bond strength between by HEMA bonding agent and dentine collagen was analyzed in different humidity, e.g. in 60%, 70%, 80%, and 90% humidity. Control experiment was done in ambient room humidity that is 65%. Chemical bond that formed between HEMA and dentine collagen was carried out by mixing pure HEMA with bovine type-I collagen which had been stored in different humidity. The esther carbonyl group of HEMA will react with the amino group of collagen, produced an amide bonding, which is observed by measuring the IR spectrum absorbance of the esther carbonyl group of HEMA in KBr method. The decrease of the carbonyl group absorbance indicates the more chemical bonds formed. By measuring the absorbance of C=O esther in different humidity, it showed that the greatest number of chemical bonds resulted when the experiment was done in 70% humidity condition.

  12. 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.

  13. 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.

  14. Formation of carbonyl groups on cellulose during ozone treatment of pulp: consequences for pulp bleaching.

    Science.gov (United States)

    Pouyet, Frédéric; Chirat, Christine; Potthast, Antje; Lachenal, Dominique

    2014-08-30

    The formation of carbonyl groups during the ozone treatment (Z) of eucalyptus (Eucalyptus grandis and Eucalyptus urophylla hybrid) kraft pulps and their behaviors during subsequent alkaline stages were investigated by the CCOA method with carbazole-9-carboxylic acid [2-(2-aminooxethoxy)-ethoxy] amide (CCOA) as the carbonyl-selective fluorescence label. Several pulp samples with or without lignin and hexenuronic acids (hexA) were used to elucidate the effects of these components when present in unbleached kraft pulp. Both hexA and lignin increased the formation of carbonyl groups on cellulose and hemicellulose during ozonation. It was concluded that radicals are likely formed when ozone reacts with either lignin or hexA. These carbonyl groups were involved in cellulose depolymerization during subsequent alkaline extraction stages with sodium hydroxide (E) and alkaline hydrogen peroxide (P, in ZEP or ZP). Their numbers decreased after E but increased during P when H2O2 was not stabilized enough. Several ways to minimize the occurrence of carbonyl group formation are suggested. Copyright © 2014. Published by Elsevier Ltd.

  15. Brand variation in oxidant production in mainstream cigarette smoke: Carbonyls and free radicals.

    Science.gov (United States)

    Reilly, Samantha M; Goel, Reema; Trushin, Neil; Elias, Ryan J; Foulds, Jonathan; Muscat, Joshua; Liao, Jason; Richie, John P

    2017-08-01

    Oxidative stress/damage resulting from exposure to cigarette smoke plays a critical role in the development of tobacco-caused diseases. Carbonyls and free radicals are two major classes of oxidants in tobacco smoke. There is little information on the combined delivery of these oxidants across different cigarette brands; thus, we set out to measure and compare their levels in mainstream smoke from popular US cigarettes. Mainstream smoke from 28 different cigarette brands produced by smoking (FTC protocol) was analyzed for five important, abundant carbonyls, and levels were compared to previously determined free radical for the same brands. Overall, there were large variations (3- to 6-fold) in carbonyl levels across brands with total carbonyl levels ranging from 275 to 804 μg/cigarette, which persisted even after adjusting for ventilation. Individual carbonyl levels were highly correlated with each other (r 2 : 0.40-0.95, P brand and the resulting difference in oxidant burden could potentially lead to differences in disease risk. Copyright © 2017 Elsevier Ltd. All rights reserved.

  16. 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.

  17. Measurements of ambient hydrocarbons and carbonyls in the Pearl River Delta (PRD), China

    Science.gov (United States)

    Yuan, Bin; Chen, Wentai; Shao, Min; Wang, Ming; Lu, Sihua; Wang, Bin; Liu, Ying; Chang, Chih-Chung; Wang, Boguang

    2012-10-01

    Measurements of 47 hydrocarbons and 3 carbonyls were performed at six sites in July 2006 and in October-November 2008 in Pearl River Delta (PRD), China. The distribution of volatile organic compound (VOC) concentrations and compositions at different sites revealed photochemical losses of hydrocarbons and secondary formation of carbonyls. Carbonyls were shown to be an important contributor to OH loss rates and ozone formation potentials. Correlations between VOCs were used to identify the sources of VOC species. Liquefied petroleum gas (LPG) is an important contributor in Guangzhou. Vehicle emissions were the dominant sources of C4-C5 alkenes (except isoprene), whereas industrial and/or solvent use accounted for a significant fraction of aromatic concentrations. Ethylbenzene/m, p-xylene ratios accurately described ozone formation at all sites except a site located upwind of Guangzhou in 2008.

  18. 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.

  19. 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.

  20. 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

    .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......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...... the carbonyl compounds also correlated with SO2 and the levels of carbonyl compounds were mainly controlled by meteorological parameters. The highest concentration levels were coincident with episodes of long-range transport from central Europe. A pronounced diurnal profile similar to those observed for PAN...

  1. Ruthenium(II carbonyl compounds with the 4′-chloro-2,2′:6′,2′′-terpyridine ligand

    Directory of Open Access Journals (Sweden)

    Rajendhraprasad Tatikonda

    2017-04-01

    Full Text Available Two ruthenium carbonyl complexes with the 4′-chloro-2,2′:6′,2′′-terpyridine ligand (tpy-Cl, C15H10ClN3, i.e. [RuCl(tpy-Cl(CO2][RuCl3(CO3] (I [systematic name: cis-dicarbonylchlorido(4′-chloro-2,2′:6′,2′′-terpyridine-κ3Nruthenium(II fac-tricarbonyltrichloridoruthenate(II], and [RuCl2(tpy-Cl(CO2] (II [cis-dicarbonyl-trans-dichlorido(4′-chloro-2,2′:6′,2′′-terpyridine-κ2N1,N1′ruthenium(II], were synthesized and characterized by single-crystal X-ray diffraction. The RuII atoms in both centrosymmetric structures (I and (II display similar, slightly distorted octahedral 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 octahedral [Ru(CO3Cl3]− 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 RuII atom is completed by two carbonyl and two chlorido ligands. In the crystal structures of both (I and (II, weak C—H...Cl interactions are observed.

  2. Cryopreservation of bull semen is associated with carbonylation of sperm proteins.

    Science.gov (United States)

    Mostek, Agnieszka; Dietrich, Mariola Aleksandra; Słowińska, Mariola; Ciereszko, Andrzej

    2017-04-01

    Artificial insemination with cryopreserved semen enables affordable, large-scale dissemination of gametes with superior genetics. However, cryopreservation can cause functional and structural damage to spermatozoa that is associated with reactive oxygen species (ROS) production, impairment of sperm motility and decreased fertilizing potential, but little attention has been paid to protein changes. The goal of this study was to investigate the oxidative modifications (measured as carbonylation level changes) of bull spermatozoa proteins triggered by the cryopreservation process. Flow cytometry and computer-assisted sperm analysis were used to evaluate changes in viability, ROS level and motility of spermatozoa. Western blotting, in conjunction with two-dimensional electrophoresis (2D-oxyblot) and matrix-assisted laser desorption/ionization time-of-flight/time-of-flight spectrometry, was employed to identify and quantify the specifically carbonylated spermatozoa proteins. Cryopreservation decreased motility and viability but increased the number of ROS-positive cells. We identified 11 proteins (ropporin-1, outer dense fiber protein 2, glutathione S-transferase, triosephosphate isomerase, capping protein beta 3 isoform, actin-related protein M1, actin-related protein T2, NADH dehydrogenase, isocitrate dehydrogenase, cilia- and flagella-associated protein 161, phosphatidylethanolamine-binding protein 4) showing differences in protein carbonylation in response to cryopreservation. The identified proteins are associated with cytoskeleton and flagella organization, detoxification and energy metabolism. Moreover, almost all of the identified carbonylated proteins are involved in capacitation. Our results indicate for the first time that cryopreservation induces oxidation of selected sperm proteins via carbonylation. We suggest that carbonylation of sperm proteins could be a direct result of oxidative stress and potentially lead to disturbances of capacitation

  3. 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....

  4. 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

    dismutase, or catalase dependent, suggesting that inhibition is not radical mediated. These effects are suggested to be due to direct adduction of the free- or protein-bound carbonyls with the target enzyme. Such an interpretation is supported by the detection of the loss of thiol groups on GAPDH...... and the detection of cross-linked materials on protein gels. Though direct comparison of the extent of inhibition induced by free versus protein-bound carbonyls was not possible, the significantly higher concentrations of the latter materials over the former in diabetic plasma and cells lead us to suggest...

  5. 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.

  6. 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.

  7. Selective Palladium(II)-Catalyzed Carbonylation of Methylene β-C-H Bonds in Aliphatic Amines.

    OpenAIRE

    Cabrera-Pardo, Jaime R; Trowbridge, Aaron; Nappi, Manuel; Ozaki, Kyohei; Gaunt, Matthew James

    2017-01-01

    Pd(II)-catalyzed C–H carbonylation of methylene C–H bonds in secondary aliphatic amines leads to the formation trans-disubstituted β-lactams in excellent yields and selectivities. The generality of the C–H carbonylation process is aided by the action of xantphos-based ligands and is important in securing good yields of the β-lactam products. EPSRC (EP/100548X/1), ERC (ERC-STG-259711), Royal Society (Wolfson Award), Marie Curie Foundation and Herchel Smith Foundation.

  8. Modernized low pressure carbonylation methods in batch and flow employing common acids as a CO source.

    Science.gov (United States)

    Brancour, Célia; Fukuyama, Takahide; Mukai, Yu; Skrydstrup, Troels; Ryu, Ilhyong

    2013-06-07

    Carbonylation reactions, such as Heck, Sonogashira, and radical carbonylations, were successfully carried out in a "two-chamber reactor" where carbon monoxide was produced ex situ by the Morgan reaction (dehydration of formic acid by sulfuric acid). By a subsequent application in a microflow system using a "tube-in-tube" reactor where gas-permeable Teflon AF2400 was used as the inner tube, it is demonstrated that formic acid/sulfuric acid can be employed concomitantly with an amine base such as triethylamine in the Heck aminocarbonylation of aryl iodide.

  9. Aqueous Catalytic Pauson-Khand-Type Reactions of Enynes with Formaldehyde: Transfer Carbonylation Involving an Aqueous Decarbonylation and a Micellar Carbonylation

    OpenAIRE

    Fuji, Koji; Morimoto, Tsumoru; Tsutsumi, Ken; Kakiuchi, Kiyomi

    2003-01-01

    One rhodium(I) complex catalyzes two processes in an overall Pauson-Khand-type reaction of enynes such as 1 with formaldehyde in an aqueous medium to give bicyclic cyclopentenones such as 2 in excellent yields. The use of a water-soluble phosphane ligand in conjunction with a hydrophobic phosphane ligand in the presence of a surfactant promotes the decarbonylation of formaldehyde in the aqueous phase and the carbonylation of enynes in the micellar phase.

  10. In situ visualization of carbonylation and its co-localization with proteins, lipids, DNA and RNA in Caenorhabditis elegans.

    Science.gov (United States)

    Kuzmic, Mira; Javot, Hélène; Bonzom, Jean-Marc; Lecomte-Pradines, Catherine; Radman, Miroslav; Garnier-Laplace, Jacqueline; Frelon, Sandrine

    2016-12-01

    All key biological macromolecules are susceptible to carbonylation - an irreparable oxidative damage with deleterious biological consequences. Carbonyls in proteins, lipids and DNA from cell extracts have been used as a biomarker of oxidative stress and aging, but formation of insoluble aggregates by carbonylated proteins precludes quantification. Since carbonylated proteins correlate with and become a suspected cause of morbidity and mortality in some organisms, there is a need for their accurate quantification and localization. Using appropriate fluorescent probes, we have developed an in situ detection of total proteins, DNA, RNA, lipids and carbonyl groups at the level of the whole organism. In C. elegans, we found that after UV irradiation carbonylation co-localizes mainly with proteins and, to a lesser degree, with DNA, RNA and lipids. The method efficiency was illustrated by carbonylation induction assessment over 5 different UV doses. The procedure enables the monitoring of carbonylation in the nematode C. elegans during stress, aging and disease along its life cycle including the egg stage. Copyright © 2016 Elsevier Inc. All rights reserved.

  11. Synthesis of the [beta]-D-glucosyl ester of [carbonyl-[sup 13]C]-indole-3-acetic acid

    Energy Technology Data Exchange (ETDEWEB)

    Jakas, A.; Magnus, V. (Rudjer Boskovic Inst., Zagreb (Croatia)); Horvat, S.; Sandberg, G. (Swedish Univ. of Agricultural Sciences, Uppsala (Sweden))

    1993-10-01

    An efficient, operationally simple synthetic approach to 1-O-([carbonyl-[sup 13]C]-indole-3'-ylacetyl)-[beta]-D-glucopyranose is described. The synthesis was carried out by fusing a fully benzylated 1-O-glucosylpseudourea intermediate with [carbonyl-[sup 13]C]-indole-3-acetic acid, followed by hydrogenolytic removal of the protective groups. (Author).

  12. 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

  13. The Potential of Carbonyl Sulfide as a Proxy for Gross Primary Production at Flux Tower Sites

    Science.gov (United States)

    Regional and continental scale studies of the seasonal dynamics of atmospheric carbonyl sulfide (OCS) mole fractions and leaf-level studies of plant OCS exchange have shown a close relationship with those for CO2. CO2 has sinks and sources within terrestrial ecosystems, but the primary terrestrial e...

  14. 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.

  15. Additive role of attapulgite nanoclay on carbonyl iron-based magnetorheological suspension

    CSIR Research Space (South Africa)

    Chae, HS

    2014-09-01

    Full Text Available Attapulgite (ATP), a fibrous nanoclay mineral, was adopted as an additive in this study to improve the sedimentation problem of soft magnetic carbonyl iron (CI)-based magnetorheological (MR) fluids caused by the density mismatch between the CI...

  16. 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.

  17. Ion solvation by channel carbonyls characterized by 17O solid-state NMR at 21 T.

    Science.gov (United States)

    Hu, Jun; Chekmenev, Eduard Y; Gan, Zhehong; Gor'kov, Peter L; Saha, Saikat; Brey, William W; Cross, Timothy A

    2005-08-31

    Recently available ultrahigh magnetic fields offer new opportunities for studies of quadrupole nuclei in biological solids because of the dramatic enhancement in sensitivity and resolution associated with the reduction of second-order quadrupole interactions. Here, we present a new approach for understanding the function and energetics of ion solvation in channels using solid-state 17O NMR spectroscopy of single-site 17O-labeled gramicidin A. The chemical shift and quadrupole coupling parameters obtained in powder samples of lyophilized material are similar to those shown in the literature for carbonyl oxygens. In lipid bilayers, it is found that the carbonyl 17O anisotropic chemical shift of Leu10, one of the three carbonyl oxygens contributing to the ion binding site in gramicidin A, is altered by 40 ppm when K+ ion binds to the channel, demonstrating a high sensitivity to such interactions. Moreover, considering the large breadth of the carbonyl 17O chemical shift (>500 ppm), the recording of anisotropic 17O chemical shifts in bilayers aligned with respect to magnetic field B0 offers high-quality structural restraints similar to 15N and 13C anisotropic chemical shifts.

  18. Canopy uptake dominates nighttime carbonyl sulfide fluxes in a boreal forest

    NARCIS (Netherlands)

    Kooijmans, Linda MJ; Maseyk, Kadmiel; Seibt, Ulli; Sun, Wu; Vesala, Timo; Mammarella, Ivan; Kolari, Pasi; Aalto, Juho; Franchin, Alessandro; Vecchi, Roberta; Valli, Gianluigi; Chen, Huilin

    2017-01-01

    Nighttime vegetative uptake of carbonyl sulfide (COS) can exist due to the incomplete closure of stomata and the light independence of the enzyme carbonic anhydrase, which complicates the use of COS as a tracer for gross primary productivity (GPP). In this study we derived night-time COS fluxes in a

  19. Enantioselective α-Arylation of Carbonyls via Cu(I)-Bisoxazoline Catalysis

    Science.gov (United States)

    Harvey, James S.; Simonovich, Scott P.; Jamison, Christopher R.; MacMillan, David W. C.

    2011-01-01

    The enantioselective α-arylation of both lactones and acyl oxazolidones has been accomplished using a combination of diaryliodonium salts and copper catalysis. These mild catalytic conditions provide a new strategy for the enantioselective construction and retention of enolizable α-carbonyl benzylic stereocenters, a valuable synthon for the production of medicinal agents. PMID:21848265

  20. 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...

  1. 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...

  2. Magnetic Silica-Supported Ruthenium Nanoparticles: An Efficient Catalyst for Transfer Hydrogenation of Carbonyl Compounds

    Science.gov (United States)

    One-pot synthesis of ruthenium nanoparticles on magnetic silica is described which involve the in situ generation of magnetic silica (Fe3O4@ SiO2) and ruthenium nano particles immobilization; the hydration of nitriles and transfer hydrogenation of carbonyl compounds occurs in hi...

  3. HYDROGENATION OF UNSATURATED CARBONYLS IN SCCO2 AS REACTION MEDIUM OVER NI-SUPPORTED CATALYSTS

    Science.gov (United States)

    Selective hydrogenation of a, a unsaturated carbonyls where molecules containing C=C and C=O double bonds has both practical importance for fine chemicals industry and theoretical significance. Various studies are reported to enhance the selective hydrogenation of C=O over group...

  4. One-pot Reductive Amination of Carbonyl Compounds with NaBH₄ ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 129; Issue 1. One-pot Reductive Amination of Carbonyl Compounds with NaBH₄-B(OSO₃H)₃/SiO₂ in Acetonitrile and in Solvent-free Condition. HOSEIN HAMADI SAMIRA JAVADI. Regular Article Volume 129 Issue 1 January 2017 pp 75-80 ...

  5. Analysis of selected carbonyl oxidation products in wine by liquid chromatography with diode array detection.

    Science.gov (United States)

    Elias, Ryan J; Laurie, V Felipe; Ebeler, Susan E; Wong, Jon W; Waterhouse, Andrew L

    2008-09-19

    A high performance liquid chromatography (HPLC) method for the detection and quantitation of acetaldehyde, glyceraldehyde, pyruvic acid, 2-ketoglutaric acid, and formaldehyde in wine, based on the formation of the 2,4-dinitrophenylhydrazones, is presented. These carbonyl compounds often result from the chemical oxidation of major wine components, and are known to affect flavor and color stability. Their analysis in wine is complicated due to their instability and their tendency to react reversibly with bisulfite to form alpha-hydroxysulfonates. Published methods that break down the sulfonates for the quantitation of total carbonyls in wine involve alkaline hydrolysis of sulfite-bound carbonyls, but we show, for the first time, that this alkaline treatment step significantly increases the concentration of carbonyls during analysis. A solution based on oxygen exclusion is described. The technique offers good specificity, reproducibility (%RSD 0.45-10.6), and limits of detection (1.29-7.53microgL(-1)). The method was successfully used to monitor concentration changes of these compounds in both white and red wines.

  6. Modular Approach for Novel Nanostructered Polycondensates Enabled by the Unique Selectivity of Carbonyl Biscaprolactam

    NARCIS (Netherlands)

    Loontjens, Ton

    2003-01-01

    New enabling chemistries have been developed to produce novel well-defined polymeric materials through the additions of small amounts of reactive functional compounds to standard polymers during regular processing steps. We found that carbonyl biscaprolactam and its derivatives couple polymer chains

  7. Cobalt-catalysed C-H carbonylative cyclisation of aliphatic amides.

    Science.gov (United States)

    Williamson, Patrick; Galván, Alicia; Gaunt, Matthew J

    2017-04-01

    A cobalt-catalysed C-H carbonylation of aliphatic carboxamide derivatives is described, employing commercially available Co(ii)-salts in the presence of a silver oxidant. This operationally simple process utilises an atmospheric pressure of CO and generates a range of substituted succinimide products bearing diverse functional groups that can be successfully accessed via this methodology.

  8. NMR Studies of Structure-Reactivity Relationships in Carbonyl Reduction: A Collaborative Advanced Laboratory Experiment

    Science.gov (United States)

    Marincean, Simona; Smith, Sheila R.; Fritz, Michael; Lee, Byung Joo; Rizk, Zeinab

    2012-01-01

    An upper-division laboratory project has been developed as a collaborative investigation of a reaction routinely taught in organic chemistry courses: the reduction of carbonyl compounds by borohydride reagents. Determination of several trends regarding structure-activity relationship was possible because each student contributed his or her results…

  9. Direct photolysis of carbonyl compounds dissolved in cloud and fog~droplets

    Directory of Open Access Journals (Sweden)

    S. A. Epstein

    2013-09-01

    Full Text Available Gas-phase photolysis is an important tropospheric sink for many carbonyl compounds; however the significance of direct photolysis of these compounds dissolved in cloud and fog droplets is uncertain. We develop a theoretical approach to assess the importance of aqueous photolysis for a series of carbonyls that possess carboxyl and hydroxyl functional groups by comparison with rates of other atmospheric processes. We use computationally and experimentally derived effective Henry's law constants, hydration equilibrium parameters, aqueous hydroxyl radical (OH rate constants, and optical extinction coefficients to identify types of compounds that will (or will not have competitive aqueous photolysis rates. We also present molecular dynamics simulations designed to estimate gas- and aqueous-phase extinction coefficients of unstudied atmospherically relevant compounds found in d-limonene and isoprene secondary organic aerosol. In addition, experiments designed to measure the photolysis rate of glyceraldehyde, an atmospherically relevant water-soluble organic compound, reveal that aqueous quantum yields are highly molecule-specific and cannot be extrapolated from measurements of structurally similar compounds. We find that only two out of the 92 carbonyl compounds investigated, pyruvic acid and acetoacetic acid, may have aqueous photolysis rates that exceed the rate of oxidation by dissolved OH. For almost all carbonyl compounds lacking α,β-conjugation that were investigated, atmospheric removal by direct photolysis in cloud and fog droplets can be neglected under typical atmospheric conditions.

  10. 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

  11. Study on microwave absorbing properties of carbonyl-iron composite coating based on PVC and Al sheet

    Energy Technology Data Exchange (ETDEWEB)

    Duan Yuping, E-mail: duanyp@dlut.edu.cn [School of Material and Engineering, Dalian University of Technology, Dalian 116085 (China); Wu Guangli; Gu Shuchao [School of Material and Engineering, Dalian University of Technology, Dalian 116085 (China); Li Shuqing [School of Material and Engineering, Dalian University of Technology, Dalian 116085 (China); Beijing Aeronautical Manufacturing Technology Research Institute, Beijing 100024 (China); Ma Guojia [Beijing Aeronautical Manufacturing Technology Research Institute, Beijing 100024 (China)

    2012-05-15

    To suppress the increasingly terrible electromagnetic pollution, microwave absorption coatings based on polyvinyl chloride (PVC) sheet have been fabricated, employing polyurethane varnish (PU) as matrix and carbonyl-iron particle (CIP) as absorbent. The morphology, static magnetic and microwave absorption properties of CIP were characterized by scanning electron microscope (SEM), vibrating sample magnetometer (VSM) and vector network analyzer (VNA), respectively. Bruggeman's equation was introduced to calculate the electromagnetic parameters of materials in the frequency range of 2-18 GHz and the loss mechanisms were discussed. Furthermore, the microwave absorption properties of composite coatings with different component content and thickness were investigated. The results show that the electromagnetic properties of the composite heavily depended on the particle loadings. The minimum reflection peaks of the coatings shift towards the lower frequency region with the increase of CIP content or coating thickness. PVC-based coatings with a component content of 1:7 (PU:CIP mass ratio) in CIP/PU layer, exhibit a minimum reflection loss value of -29 dB at 4 GHz and a permissible reflection loss (RL {<=} -10 dB) frequency band of 2-6 GHz, which is much better than the performance of the common metal-based coatings in the lower frequency.

  12. Circulating Protein Carbonyls, Antioxidant Enzymes and Related Trace Minerals among Preterms with Respiratory Distress Syndrome.

    Science.gov (United States)

    Ahmed, Ahmed El-Abd; Abd-Elmawgood, Eman Ahmed; Hassan, Mohammed H

    2017-07-01

    Information about oxidative stress in preterms with Respiratory Distress Syndrome (RDS) is defective, so various researches in this area are required, which may open new roads in understanding the pathogenesis of the disease, hence provide additional helpful therapeutic approaches. To assess and compare the plasma level of protein carbonyls as a marker for oxidant status and the antioxidant enzymes; Superoxide Dismutase (SOD) and Glutathione Peroxidase (GPx) and the related trace minerals in the form of Copper (Cu), Zinc (Zn) and Selenium (Se) as markers for antioxidant status, in preterms with and without RDS. A hospital-based case-control study was conducted on fifty-seven preterm neonates (37 preterms with RDS and 20 preterms without RDS) admitted to neonatal intensive care unit of Qena University Hospitals after approval of the University Hospital Ethical Committee. Plasma protein carbonyls assay was done using commercially available ELISA assay kit. Plasma Cu, Zn, Se, erythrocyte SOD and GPx activities assays were done using commercially available colorimetric assay kits. Significant higher plasma levels of protein carbonyls and oxidant/antioxidants ratio (protein carbonyls/{SOD+GPx}) with significant lower plasma levels of Zn, Cu, Se, erythrocyte SOD and GPx activities were found in the preterms with RDS when compared with the preterms without RDS (p<0.001 for all measured markers for both groups). In terms of birth weights and gestational ages, they were negatively correlated with both plasma protein carbonyls and oxidant/antioxidants ratio and positively correlated with plasma copper, zinc, selenium, erythrocyte SOD and GPx activities in a statistically significant manner. Non-significant correlations were found between the measured oxidative stress markers and the severity of RDS. Oxidative stress may have a contributory role in the development of RDS among preterms. Lower birth weight and prematurity may increase the susceptibity to oxidative stress among

  13. Chaperone heat shock protein 90 mobilization and hydralazine cytoprotection against acrolein-induced carbonyl stress.

    Science.gov (United States)

    Burcham, Philip C; Raso, Albert; Kaminskas, Lisa M

    2012-11-01

    Toxic carbonyls such as acrolein participate in many degenerative diseases. Although the nucleophilic vasodilatory drug hydralazine readily traps such species under "test-tube" conditions, whether these reactions adequately explain its efficacy in animal models of carbonyl-mediated disease is uncertain. We have previously shown that hydralazine attacks carbonyl-adducted proteins in an "adduct-trapping" reaction that appears to take precedence over direct "carbonyl-sequestering" reactions, but how this reaction conferred cytoprotection was unclear. This study explored the possibility that by increasing the bulkiness of acrolein-adducted proteins, adduct-trapping might alter the redistribution of chaperones to damaged cytoskeletal proteins that are known targets for acrolein. Using A549 lung adenocarcinoma cells, the levels of chaperones heat shock protein (Hsp) 40, Hsp70, Hsp90, and Hsp110 were measured in intermediate filament extracts prepared after a 3-h exposure to acrolein. Exposure to acrolein alone modestly increased the levels of all four chaperones. Coexposure to hydralazine (10-100 μM) strongly suppressed cell ATP loss while producing strong adduct-trapping in intermediate filaments. Most strikingly, hydralazine selectively boosted the levels of cytoskeletal-associated Hsp90, including a high-mass species that was sensitive to the Hsp90 inhibitor 17-N-allylamino-17-demethoxygeldanamycin. Biochemical fractionation of acrolein- and hydralazine-treated cells revealed that hydralazine likely promoted Hsp90 migration from cytosol into other subcellular compartments. A role for Hsp90 mobilization in cytoprotection was confirmed by the finding that brief heat shock treatment suppressed acute acrolein toxicity in A549 cells. Taken together, these findings suggest that by increasing the steric bulk of carbonyl-adducted proteins, adduct-trapping drugs trigger the intracellular mobilization of the key molecular chaperone Hsp90.

  14. 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.

  15. Surface functionalization of carbonyl iron with aluminum phosphate coating toward enhanced anti-oxidative ability and microwave absorption properties

    Science.gov (United States)

    Duan, Wenju; Li, Xuandong; Wang, Ying; Qiang, Rong; Tian, Chunhua; Wang, Na; Han, Xijiang; Du, Yunchen

    2018-01-01

    Fe@AlPO4 core-shell composites with tunable AlPO4 content have been successfully prepared through in situ deposition of AlPO4 on the surface of carbonyl iron. The presence of the AlPO4 layer improves the anti-oxidative ability of the internal carbonyl iron, so that surface oxidation and magnetic degradation in these composites are significantly suppressed when compared with naked carbonyl iron. It is worth noting that the AlPO4 layer can affect the electromagnetic parameters of carbonyl iron, resulting in well-matched characteristic impedance. By optimizing the AlPO4 layer content, the Fe@AlPO4 composite can display excellent reflection loss characteristics, and qualified absorption in a very broad frequency range (2.4-18.0 GHz over -10 dB) can be achieved. The microwave absorption performance of the Fe@AlPO4 composite is indeed superior to pure carbonyl iron as well as many previously reported carbonyl iron-based composites. More importantly, the Fe@AlPO4 composite can maintain good microwave absorption properties after treatment at high temperature for long time periods. These results provide new insight into the fabrication of carbonyl iron-based composites with good microwave absorption and anti-oxidative properties that meet the requirements in practical applications.

  16. Auto-Tandem Catalysis in Ionic Liquids: Synthesis of 2-Oxazolidinones by Palladium-Catalyzed Oxidative Carbonylation of Propargylic Amines in EmimEtSO₄.

    Science.gov (United States)

    Mancuso, Raffaella; Maner, Asif; Ziccarelli, Ida; Pomelli, Christian; Chiappe, Cinzia; Della Ca', Nicola; Veltri, Lucia; Gabriele, Bartolo

    2016-07-08

    A convenient carbonylative approach to 2-oxazolidinone derivatives carried out using an ionic liquid (1-ethyl-3-methylimidazolium ethyl sulfate, EmimEtSO₄) as the solvent is presented. It is based on the sequential concatenation of two catalytic cycles, both catalyzed by the same metal species (auto-tandem catalysis): the first cycle corresponds to the oxidative monoaminocarbonylation of the triple bond of propargylic amines to give the corresponding 2-ynamide intermediates, while the second one involves the cyclocarbonylation of the latter to yield 2-(2-oxooxazolidin-5-ylidene)-acetamides. Reactions are carried out using a simple catalytic system consisting of PdI₂ in conjunction with an excess of KI, and the catalyst/solvent system could be recycled several times without appreciable loss of activity after extraction of the organic product with Et₂O.

  17. Separation of Metal Binding and Electron Transfer Sites as a Strategy To Stabilize the Ligand-Reduced and Metal-Oxidized Form of [Mo(CO)4L

    Czech Academy of Sciences Publication Activity Database

    Bulak, E.; Varnali, T.; Schwederski, B.; Bubrin, D.; Fiedler, Jan; Kaim, W.

    2011-01-01

    Roč. 30, č. 23 (2011), s. 6441-6445 ISSN 0276-7333 R&D Projects: GA ČR GA203/09/0705 Institutional research plan: CEZ:AV0Z40400503 Keywords : Electron Transfer Sites * [Mo(CO)4L] * metal carbonyl complexes Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.963, year: 2011

  18. 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.

  19. 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.

  20. 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

    dismutase, or catalase dependent, suggesting that inhibition is not radical mediated. These effects are suggested to be due to direct adduction of the free- or protein-bound carbonyls with the target enzyme. Such an interpretation is supported by the detection of the loss of thiol groups on GAPDH...... 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...

  1. 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.

  2. 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....

  3. 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....

  4. 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.

  5. Proteome oxidative carbonylation during oxidative stress-induced premature senescence of WI-38 human fibroblasts

    DEFF Research Database (Denmark)

    Le Boulch, Marine; Ahmed, Emad K; Rogowska-Wrzesinska, Adelina

    2018-01-01

    Accumulation of oxidatively damaged proteins is a hallmark of cellular and organismal ageing, and is also a phenotypic feature shared by both replicative senescence and stress-induced premature senescence of human fibroblasts. Moreover, proteins that are building up as oxidized (i.e. the "Oxi......-proteome") during ageing and age-related diseases represent a restricted set of cellular proteins, indicating that certain proteins are more prone to oxidative carbonylation and subsequent intracellular accumulation. The occurrence of specific carbonylated proteins upon oxidative stress induced premature senescence...... of WI-38 human fibroblasts and their follow-up identification have been addressed in this study. Indeed, it was expected that the identification of these proteins would give insights into the mechanisms by which oxidatively damaged proteins could affect cellular function. Among these proteins, some...

  6. Energy transfer and photochemistry on a metal surface: Mo(CO)6 on Rh(100)

    International Nuclear Information System (INIS)

    Germer, T.A.; Ho, W.

    1989-01-01

    The occurrence of photoinduced reactions on solid surfaces depends on the relative rates between the excited-state decomposition and the energy transfer to the surface. In this study, the photodecomposition of Mo(CO) 6 on Rh(100) at 90 K by 325-nm UV irradiation has been studied as a function of coverage and surface preparation using thermal desorption spectroscopy, electron energy-loss spectroscopy, and photoinduced desorption spectroscopy. It is found that Mo(CO) 6 adsorbs dissociatively on Rh(100) into carbonyl fragments and CO in the first monolayer and molecularly in multilayers. Photoinduced desorption of CO is observed for the multilayers adsorbed onto the dissociated first layer via a nonthermal electronic excitation of adsorbed metal carbonyls. The presence of the metal surface prevents complete decarbonylation as in the gas phase; deexcitation of electronically excited carbonyls is not sufficiently fast to quench all the observed photochemistry. It is also found that Mo(CO) 6 adsorbs molecularly on a presaturated CO ordered overlayer on Rh(100) and undergoes photodissociation to a greater degree than on the dissociated and disordered surface of carbonyl fragments. The ordered CO layer effectively screens the interaction between the molecular carbonyls and the Rh(100) layer surface

  7. 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.

  8. 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...

  9. Identification of carbonylated lipids from different phospholipid classes by shotgun and LC-MS lipidomics.

    Science.gov (United States)

    Ni, Zhixu; Milic, Ivana; Fedorova, Maria

    2015-07-01

    Oxidized lipids play a significant role in the pathogenesis of numerous oxidative stress-related human disorders, such as atherosclerosis, obesity, inflammation, and autoimmune diseases. Lipid peroxidation, induced by reactive oxygen and nitrogen species, yields a high variety of modified lipids. Among them, carbonylated lipid peroxidation products (oxoLPP), formed by oxidation of the fatty acid moiety yielding aldehydes or ketones (carbonyl groups), are electrophilic compounds that are able to modify nucleophilic substrates like proteins, nucleic acid, and aminophospholipids. Some carbonylated phosphatidylcholines possess even pro-inflammatory activities. However, little is known about oxoLPP derived from other phospholipid (PL) classes. Here, we present a new analytical strategy based on the mass spectrometry (MS) of PL-oxoLPP derivatized with 7-(diethylamino)coumarin-3-carbohydrazide (CHH). Shotgun MS revealed many oxoLPP derived from in vitro oxidized glycerophosphatidylglycerols (PG, 31), glycerophosphatidylcholine (PC, 23), glycerophosphatidylethanolamine (PE, 34), glycerophosphatidylserines (PS, 7), glycerophosphatidic acids (PA, 17), and phosphatidylinositiolphosphates (PIP, 6) vesicles. This data were used to optimize LipidXplorer-assisted identification, and a python-based post-processing script was developed to increase both throughput and accuracy. When applied to full lipid extracts from rat primary cardiomyocytes treated with peroxynitrite donor SIN-1, ten PL-bound oxoLPP were unambiguously identified by LC-MS, including two PC-, two PE-, one PG-, two PS-, and three PA-derived species. Some of the well-known carbonylated PC were detected, while most PL-oxoLPP were shown for the first time.

  10. 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

  11. Yttrium (III chloride catalyzed Mannich reaction: An efficient procedure for the synthesis of β-amino carbonyl compounds

    Directory of Open Access Journals (Sweden)

    Venkateswarlu Yekkirala

    2014-12-01

    Full Text Available Yttrium (III chloride catalyzed Mannich reaction of aldehydes with ketones and amines in acetonitrile at reflux temperature to give various β-amino carbonyl compounds in very good yields.

  12. Use of carbonyl group addition--elimination reactions for synthesis of nucleic acid conjugates.

    Science.gov (United States)

    Zatsepin, Timofei S; Stetsenko, Dmitry A; Gait, Michael J; Oretskaya, Tatiana S

    2005-01-01

    This review outlines the synthesis of covalent conjugates of oligonucleotides and their analogues that are obtained by reactions of carbonyl compounds with various nucleophiles such as primary amines, N-alkoxyamines, hydrazines, and hydrazides. The products linked by imino, oxime, hydrazone, or thiazolidine groups are shown to be useful intermediates for a wide range of chemical biology applications. Methods for their preparation, isolation, purification, and analysis are highlighted, and the comparative stabilities of the respective linkages are evaluated. The relative merits of incorporation of a carbonyl group, particularly an aldehyde group, into either the oligonucleotide or the ligand parts are considered. Examples of harnessing of aldehyde-nucleophile coupling for the labeling of nucleic acids are given, as well as their conjugation to various biomolecules (e.g. peptides and small molecule ligands), site-specific cross-linking of oligonucleotides to nucleic acid-binding proteins, assembly of multibranched supramolecular structures, and immobilization on functionalized surfaces. Future perspectives of bioconjugation and complex molecular engineering via carbonyl group addition-elimination reactions in nucleic acids chemistry are discussed.

  13. Excessive caloric intake acutely causes oxidative stress, GLUT4 carbonylation, and insulin resistance in healthy men.

    Science.gov (United States)

    Boden, Guenther; Homko, Carol; Barrero, Carlos A; Stein, T Peter; Chen, Xinhua; Cheung, Peter; Fecchio, Chiara; Koller, Sarah; Merali, Salim

    2015-09-09

    Obesity-linked insulin resistance greatly increases the risk for type 2 diabetes, hypertension, dyslipidemia, and non-alcoholic fatty liver disease, together known as the metabolic or insulin resistance syndrome. How obesity promotes insulin resistance remains incompletely understood. Plasma concentrations of free fatty acids and proinflammatory cytokines, endoplasmic reticulum ( ER) stress, and oxidative stress are all elevated in obesity and have been shown to induce insulin resistance. However, they may be late events that only develop after chronic excessive nutrient intake. The nature of the initial event that produces insulin resistance at the beginning of excess caloric intake and weight gain remains unknown. We show that feeding healthy men with ~6000 kcal/day of the common U.S. diet [~50% carbohydrate (CHO), ~ 35% fat, and ~15% protein] for 1 week produced a rapid weight gain of 3.5 kg and the rapid onset (after 2 to 3 days) of systemic and adipose tissue insulin resistance and oxidative stress but no inflammatory or ER stress. In adipose tissue, the oxidative stress resulted in extensive oxidation and carbonylation of numerous proteins, including carbonylation of GLUT4 near the glucose transport channel, which likely resulted in loss of GLUT4 activity. These results suggest that the initial event caused by overnutrition may be oxidative stress, which produces insulin resistance, at least in part, via carbonylation and oxidation-induced inactivation of GLUT4. Copyright © 2015, American Association for the Advancement of Science.

  14. 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.

  15. Emissions of isoprene, monoterpene and short-chained carbonyl compounds from Eucalyptus spp. in southern Australia

    Science.gov (United States)

    Winters, Anthony J.; Adams, Mark A.; Bleby, Tim M.; Rennenberg, Heinz; Steigner, Dominik; Steinbrecher, Rainer; Kreuzwieser, Jürgen

    Eucalypts are among the highest emitters of biogenic volatile organic compounds, yet there is relatively little data available from field studies of this genus. Emissions of isoprene, monoterpenes and the short-chained carbonyls formaldehyde, acetaldehyde and acetone were determined from four species ( Eucalyptus camaldulensis, Eucalyptus globulus, Eucalyptus grandis, and Eucalytpus viminalis) in Australia. A smaller comparative study was conducted on E. camaldulensis in south-eastern Australia. Carbonyl emissions, reported here for the first time from eucalypts, were generally comparable with rates reported for other species, with diurnal emissions peaking at about 4, 75 and 34 nmol m -2 min -1 for acetone, formaldehyde and acetaldehyde respectively. There was wide variation in diurnal isoprene and monoterpene emissions between species, but under standard conditions, isoprene emissions were much lower than previous reports. Conversely, standard emission rates of monoterpenes were as much as six times greater than previous reports for some species. Emission of each carbonyl was correlated with its ambient concentration across different species, but more weakly related to temperature. Acetaldehyde emission in particular was significantly correlated with transpiration, but not with sap flow or with ethanol concentrations in xylem sap, suggesting fermentation within the leaf and stomatal conductance are primary controlling processes. Differences in acetaldehyde exchange velocities between sites, in addition to transpiration differences, suggest stomata may indeed exert long term emission regulation, in contrast to compounds for which no biological sink exists.

  16. Effect of carbonyl inhibitors and their H₂O₂ detoxification on lactic acid fermentation.

    Science.gov (United States)

    Li, Jing; Zhu, Caiqing; Tu, Maobing; Han, Pingping; Wu, Yonnie

    2015-04-01

    Biomass degradation compounds significantly inhibit biochemical conversion of biomass prehydrolysates to biofuels and chemicals, such as lactic acid. To characterize the structure-activity relationship of carbonyl inhibition on lactic acid fermentation, we examined effects of eight carbonyl compounds (furfural, 5-hydroxymethyl furfural, vanillin, syringaldehyde, 4-hydroxybenzaldehyde, phthalaldehyde, benzoic acid, and pyrogallol aldehyde) and creosol on lactic acid production by Lactobacillus delbrueckii. Pyrogallol aldehyde reduced the cell growth rate by 35 % at 1.0 mM and inhibited lactic acid production completely at 2.0 mM. By correlating the molecular descriptors to the inhibition constants in lactic acid fermentation, we found a good relationship between the hydrophobicity (Log P) of aldehydes and their inhibition constants in fermentation. The inhibitory effect of carbonyl inhibitors appeared to correlate with their thiol reactivity as well. In addition, we found that H2O2 detoxified pyrogallol aldehyde and phthalaldehyde inhibitory activity. H2O2 detoxification was applied to real biomass prehydrolysates in lactic acid fermentation.

  17. 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

  18. 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.

  19. Brown carbon formation by aqueous-phase carbonyl compound reactions with amines and ammonium sulfate.

    Science.gov (United States)

    Powelson, Michelle H; Espelien, Brenna M; Hawkins, Lelia N; Galloway, Melissa M; De Haan, David O

    2014-01-21

    Reactions between small water-soluble carbonyl compounds, ammonium sulfate (AS), and/or amines were evaluated for their ability to form light-absorbing species in aqueous aerosol. Aerosol chemistry was simulated with bulk phase reactions at pH 4, 275 K, initial concentrations of 0.05 to 0.25 M, and UV-vis and fluorescence spectroscopy monitoring. Glycolaldehyde-glycine mixtures produced the most intense absorbance. In carbonyl compound reactions with AS, methylamine, or AS/glycine mixtures, product absorbance followed the order methylglyoxal > glyoxal > glycolaldehyde > hydroxyacetone. Absorbance extended into the visible, with a wavelength dependence fit by absorption Ångstrom coefficients (Å(abs)) of 2 to 11, overlapping the Å(abs) range of atmospheric, water-soluble brown carbon. Many reaction products absorbing between 300 and 400 nm were strongly fluorescent. On a per mole basis, amines are much more effective than AS at producing brown carbon. In addition, methylglyoxal and glyoxal produced more light-absorbing products in reactions with a 5:1 AS-glycine mixture than with AS or glycine alone, illustrating the importance of both organic and inorganic nitrogen in brown carbon formation. Through comparison to biomass burning aerosol, we place an upper limit on the contribution of these aqueous carbonyl-AS-amine reactions of ≤ 10% of global light absorption by brown carbon.

  20. 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.

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

    Science.gov (United States)

    Barreiro, Esther

    2016-05-06

    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.

  2. Synthesis, structural and vibrational properties of 1-(adamantane-1-carbonyl)-3-halophenyl thioureas

    Science.gov (United States)

    Saeed, Aamer; Erben, Mauricio F.; Bolte, Michael

    2013-02-01

    1-(Adamantane-1-carbonyl)-3-(2,4-dichlorophenyl)thiourea (1) and 1-(adamantane-1-carbonyl)-3-(2-bromo-4,6-difluorophenyl)thiourea (2) were synthesized by the reaction of adamantane-1-carbonyl chloride with ammonium thiocyanate to afford the adamantane-1-carbonylisothiocyanate in situ followed by treatment with suitable halogenated anilines. The structures of the products were established by elemental analyses, Fourier transform infrared spectroscopy (FTIR), 1H, 13C nuclear magnetic resonance (NMR), mass spectroscopy and single crystal X-ray diffraction study. Bond lengths and angles show the usual values. All of three condensed cyclohexane rings of the adamantane residues adopt the usual chair conformation. The molecular conformation of 1 and 2 is stabilized by an intramolecular (Nsbnd H⋯Odbnd C) hydrogen bond which forms a pseudo-six-membered ring. Structural features have been complemented with the joint analysis of the FTIR and FT-Raman spectra along with quantum chemical calculations at the B3LYP/6-311++G** level.

  3. 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.

  4. Diurnal and seasonal variations of carbonyls and their effect on ozone concentrations in the atmosphere of Monterrey, Mexico.

    Science.gov (United States)

    Menchaca-Torre, H Lizette; Mercado-Hernández, Roberto; Rodríguez-Rodríguez, José; Mendoza-Domínguez, Alberto

    2015-04-01

    Few studies have been made regarding carbonyl concentrations in Monterrey, México. The Monterrey Metropolitan Area (MMA) has the third largest population in the country and has increasing pollution issues. The concentrations of 10 aldehydes and two ketones were measured in the MMA, in the spring and fall of 2011 and 2012. Formaldehyde (16-42 ppbv) was the most abundant carbonyl, followed by acetaldehyde (5-15 ppbv) and acetone (7-15 ppbv). The concentrations showed marked diurnal trends with maximum values between 10:00 a.m. and 2:00 p.m., when photochemical activity is intense. Thus, secondary production of carbonyls is statistically significant in the city. Biogenic production of several carbonyls, such as 2-butanone, was supported by their mid correlation with solar radiation and low correlation with propionaldehyde, which is mainly emitted by anthropogenic sources. The seasonal variability of the concentrations was observed in the first three samplings, with the highest levels reached in the fall. The rainy conditions during the fourth sampling did not allow comparison. Carbonyl-NOx-O3 analysis was made. Results indicated a carbonyl-sensitive atmosphere, especially during the midday samplings of 10:00 a. m. to 2:00 p.m. and 2:00 p.m. and 6:00 p.m. because of the intense solar radiation during these periods. Monitoring of carbonyls in Monterrey, Mexico, was performed to quantify the pollutant concentration in the city's atmosphere. Although primary emission is significantly important, the secondary production of the pollutants, along with ozone production being carbonyl sensitive, indicates that air pollution controls must address the direct sources and the precursors of the pollutants to achieve air quality.

  5. 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

  6. Ba/Cd/Zn metal salts carboxylate and dibasic lead stearate

    African Journals Online (AJOL)

    Revue Synthèse N° 20, Juin 2009. S.F. Chabira et M. Sebaa. 94. Effect of thermal stabilizers. (Ba/Cd/Zn metal salts carboxylate and dibasic lead stearate) on the kinetic of carbonyls formation of PVC films. Salem Fouad Chabira et Mohamed Sebaa. Department of Mechanics, Laghouat University,. BP 37 G, Laghouat 03000, ...

  7. Synthesis of 2-substituted tetraphenylenes via transition-metal-catalyzed derivatization of tetraphenylene

    Directory of Open Access Journals (Sweden)

    Shulei Pan

    2016-06-01

    Full Text Available A new strategy for the synthesis of 2-substituted tetraphenylenes through a transition-metal-catalyzed derivatization has been developed. Three types of functionalities, including OAc, X (Cl, Br, I and carbonyl, were introduced onto tetraphenylene, which allows the easy access to a variety of monosubstituted tetraphenylenes. These reactions could accelerate research on the properties and application of tetraphenylene derivatives.

  8. Sensing of polymeric sensor-based rhodamine B derivative for metal ...

    Indian Academy of Sciences (India)

    ity after complexes with metal ions by activating a carbonyl group in a spirolactone or a spirolactam moiety [27–30]. The mechanism is based on the switch off/on of the spirocyclic moiety mediated by guests. In general, spirolactam formation of rhodamine derivatives is non-fluorescent, whereas its ring-opened amide system ...

  9. Human microsomal carbonyl reducing enzymes in the metabolism of xenobiotics: well-known and promising members of the SDR superfamily.

    Science.gov (United States)

    Skarydová, Lucie; Wsól, Vladimír

    2012-05-01

    The best known, most widely studied enzyme system in phase I biotransformation is cytochrome P450 (CYP), which participates in the metabolism of roughly 9 of 10 drugs in use today. The main biotransformation isoforms of CYP are associated with the membrane of the endoplasmatic reticulum (ER). Other enzymes that are also active in phase I biotransformation are carbonyl reducing enzymes. Much is known about the role of cytosolic forms of carbonyl reducing enzymes in the metabolism of xenobiotics, but their microsomal forms have been mostly poorly studied. The only well-known microsomal carbonyl reducing enzyme taking part in the biotransformation of xenobiotics is 11β-hydroxysteroid dehydrogenase 1, a member of the short-chain dehydrogenase/reductase superfamily. Physiological roles of microsomal carbonyl reducing enzymes are better known than their participation in the metabolism of xenobiotics. This review is a summary of the fragmentary information known about the roles of the microsomal forms. Besides 11β-hydroxysteroid dehydrogenase 1, it has been reported, so far, that retinol dehydrogenase 12 participates only in the detoxification of unsaturated aldehydes formed upon oxidative stress. Another promising group of microsomal biotransformation carbonyl reducing enzymes are some members of 17β-hydroxysteroid dehydrogenases. Generally, it is clear that this area is, overall, quite unexplored, but carbonyl reducing enzymes located in the ER have proven very interesting. The study of these enzymes could shed new light on the metabolism of several clinically used drugs or they could become an important target in connection with some diseases.

  10. 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.

  11. Gas phase carbonyl compounds in ship emissions: Differences between diesel fuel and heavy fuel oil operation

    Science.gov (United States)

    Reda, Ahmed A.; Schnelle-Kreis, J.; Orasche, J.; Abbaszade, G.; Lintelmann, J.; Arteaga-Salas, J. M.; Stengel, B.; Rabe, R.; Harndorf, H.; Sippula, O.; Streibel, T.; Zimmermann, R.

    2014-09-01

    Gas phase emission samples of carbonyl compounds (CCs) were collected from a research ship diesel engine at Rostock University, Germany. The ship engine was operated using two different types of fuels, heavy fuel oil (HFO) and diesel fuel (DF). Sampling of CCs was performed from diluted exhaust using cartridges and impingers. Both sampling methods involved the derivatization of CCs with 2,4-Dinitrophenylhydrazine (DNPH). The CCs-hydrazone derivatives were analyzed by two analytical techniques: High Performance Liquid Chromatography-Diode Array Detector (HPLC-DAD) and Gas Chromatography-Selective Ion Monitoring-Mass Spectrometry (GC-SIM-MS). Analysis of DNPH cartridges by GC-SIM-MS method has resulted in the identification of 19 CCs in both fuel operations. These CCs include ten aliphatic aldehydes (formaldehyde, acetaldehyde, propanal, isobutanal, butanal, isopentanal, pentanal, hexanal, octanal, nonanal), three unsaturated aldehydes (acrolein, methacrolein, crotonaldehyde), three aromatic aldehyde (benzaldehyde, p-tolualdehyde, m,o-molualdehyde), two ketones (acetone, butanone) and one heterocyclic aldehyde (furfural). In general, all CCs under investigation were detected with higher emission factors in HFO than DF. The total carbonyl emission factor was determined and found to be 6050 and 2300 μg MJ-1 for the operation with HFO and DF respectively. Formaldehyde and acetaldehyde were found to be the dominant carbonyls in the gas phase of ship engine emission. Formaldehyde emissions factor varied from 3500 μg MJ-1 in HFO operation to 1540 μg MJ-1 in DF operation, which is 4-30 times higher than those of other carbonyls. Emission profile contribution of CCs showed also a different pattern between HFO and DF operation. The contribution of formaldehyde was found to be 58% of the emission profile of HFO and about 67% of the emission profile of DF. Acetaldehyde showed opposite behavior with higher contribution of 16% in HFO compared to 11% for DF. Heavier carbonyls

  12. 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

  13. Lipid Peroxide-Derived Short-Chain Carbonyls Mediate Hydrogen Peroxide-Induced and Salt-Induced Programmed Cell Death in Plants1[OPEN

    Science.gov (United States)

    Biswas, Md. Sanaullah; Mano, Jun’ichi

    2015-01-01

    Lipid peroxide-derived toxic carbonyl compounds (oxylipin carbonyls), produced downstream of reactive oxygen species (ROS), were recently revealed to mediate abiotic stress-induced damage of plants. Here, we investigated how oxylipin carbonyls cause cell death. When tobacco (Nicotiana tabacum) Bright Yellow-2 (BY-2) cells were exposed to hydrogen peroxide, several species of short-chain oxylipin carbonyls [i.e. 4-hydroxy-(E)-2-nonenal and acrolein] accumulated and the cells underwent programmed cell death (PCD), as judged based on DNA fragmentation, an increase in terminal deoxynucleotidyl transferase dUTP nick end labeling-positive nuclei, and cytoplasm retraction. These oxylipin carbonyls caused PCD in BY-2 cells and roots of tobacco and Arabidopsis (Arabidopsis thaliana). To test the possibility that oxylipin carbonyls mediate an oxidative signal to cause PCD, we performed pharmacological and genetic experiments. Carnosine and hydralazine, having distinct chemistry for scavenging carbonyls, significantly suppressed the increase in oxylipin carbonyls and blocked PCD in BY-2 cells and Arabidopsis roots, but they did not affect the levels of ROS and lipid peroxides. A transgenic tobacco line that overproduces 2-alkenal reductase, an Arabidopsis enzyme to detoxify α,β-unsaturated carbonyls, suffered less PCD in root epidermis after hydrogen peroxide or salt treatment than did the wild type, whereas the ROS level increases due to the stress treatments were not different between the lines. From these results, we conclude that oxylipin carbonyls are involved in the PCD process in oxidatively stressed cells. Our comparison of the ability of distinct carbonyls to induce PCD in BY-2 cells revealed that acrolein and 4-hydroxy-(E)-2-nonenal are the most potent carbonyls. The physiological relevance and possible mechanisms of the carbonyl-induced PCD are discussed. PMID:26025050

  14. Lipid Peroxide-Derived Short-Chain Carbonyls Mediate Hydrogen Peroxide-Induced and Salt-Induced Programmed Cell Death in Plants.

    Science.gov (United States)

    Biswas, Md Sanaullah; Mano, Jun'ichi

    2015-07-01

    Lipid peroxide-derived toxic carbonyl compounds (oxylipin carbonyls), produced downstream of reactive oxygen species (ROS), were recently revealed to mediate abiotic stress-induced damage of plants. Here, we investigated how oxylipin carbonyls cause cell death. When tobacco (Nicotiana tabacum) Bright Yellow-2 (BY-2) cells were exposed to hydrogen peroxide, several species of short-chain oxylipin carbonyls [i.e. 4-hydroxy-(E)-2-nonenal and acrolein] accumulated and the cells underwent programmed cell death (PCD), as judged based on DNA fragmentation, an increase in terminal deoxynucleotidyl transferase dUTP nick end labeling-positive nuclei, and cytoplasm retraction. These oxylipin carbonyls caused PCD in BY-2 cells and roots of tobacco and Arabidopsis (Arabidopsis thaliana). To test the possibility that oxylipin carbonyls mediate an oxidative signal to cause PCD, we performed pharmacological and genetic experiments. Carnosine and hydralazine, having distinct chemistry for scavenging carbonyls, significantly suppressed the increase in oxylipin carbonyls and blocked PCD in BY-2 cells and Arabidopsis roots, but they did not affect the levels of ROS and lipid peroxides. A transgenic tobacco line that overproduces 2-alkenal reductase, an Arabidopsis enzyme to detoxify α,β-unsaturated carbonyls, suffered less PCD in root epidermis after hydrogen peroxide or salt treatment than did the wild type, whereas the ROS level increases due to the stress treatments were not different between the lines. From these results, we conclude that oxylipin carbonyls are involved in the PCD process in oxidatively stressed cells. Our comparison of the ability of distinct carbonyls to induce PCD in BY-2 cells revealed that acrolein and 4-hydroxy-(E)-2-nonenal are the most potent carbonyls. The physiological relevance and possible mechanisms of the carbonyl-induced PCD are discussed. © 2015 American Society of Plant Biologists. All Rights Reserved.

  15. Carbon monoxide and carbon dioxide hydrogenation catalyzed by supported ruthenium carbonyl clusters: a novel procedure for encapsulating Ru3(Co)12 within the pores of Na-Y zeolite. Technical report No. 1, 1986-1987

    Energy Technology Data Exchange (ETDEWEB)

    Hastings, W.R.; Cameron, C.J.; Thomas, M.J.; Baird, M.C.

    1988-01-01

    Zeolite-supported ruthenium catalysts for the hydrogenation of carbon monoxide and carbon dioxide were prepared by sorbing Ru(CO)5 (molecular diameter 6.3 A) onto Na-Y zeolite and Linde 5A molecular sieve. Although the metal carbonyl is not absorbed into the pores of the molecular sieve (diameter 4.2 A), it is readily absorbed into the pores (diameter 7.4 A) and supercages (diameter 13 A) of the Na-Y zeolite. The Ru(CO)5 in Na-Y coverts in the absence of carbon monoxide to the much larger Ru3(CO)12 (diameter 9.2 A), which remains on the surface of the molecular sieve but is trapped within the supercages of the Na-Y zeolite because it cannot pass through the smaller pores. Slow, temperature-programmed heating of the Ru3(CO)12 in Na-Y to 350 C under a flow of hydrogen results in decarbonylation and formation of a CO hydrogenation catalyst that produces a very atypical (for ruthenium) hydrocarbon distribution truncated at about C10. The unusual product distribution presumably arises because the catalyst sites are situated within the zeolite supercages. Thus the metal is highly dispersed and or the growing hydrocarbon chains are subject to geometrical limitations on their growth. Consistent with this prothesis, ruthenium carbonyl clusters immobilized on the external surfaces of Na-Y zeolite, Linde 5A molecular sieve, and gamma alumina all exhibit typical, nonselective hydrocarbon-product distributions.

  16. 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.

  17. 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.

  18. Carbonyl compounds in dining areas, kitchens and exhaust streams in restaurants with varying cooking methods in Kaohsiung, Taiwan.

    Science.gov (United States)

    Cheng, Jen-Hsuan; Lee, Yi-Shiun; Chen, Kang-Shin

    2016-03-01

    Eighteen carbonyl species in C1-C10 were measured in the dining areas, kitchens and exhaust streams of six different restaurant types in Kaohsiung, southern Taiwan. Measured results in the dining areas show that Japanese barbecue (45.06ppb) had the highest total carbonyl concentrations (sum of 18 compounds), followed by Chinese hotpot (38.21ppb), Chinese stir-frying (8.99ppb), Western fast-food (8.22ppb), Chinese-Western mixed style (7.38ppb), and Chinese buffet (3.08ppb), due to their different arrangements for dining and cooking spaces and different cooking methods. On average, low carbon-containing species (C1-C4), e.g., formaldehyde, acetaldehyde, acetone and butyraldehyde were dominant and contributed 55.01%-94.52% of total carbonyls in the dining areas of all restaurants. Meanwhile, Chinese-Western mixed restaurants (45.48ppb) had high total carbonyl concentrations in kitchens mainly because of its small kitchen and poor ventilation. However, high carbon-containing species (C5-C10) such as hexaldehyde, heptaldehyde and nonanaldehyde (16.62%-77.00% of total carbonyls) contributed comparatively with low carbon-containing compounds (23.01%-83.39% of total carbonyls) in kitchens. Furthermore, Chinese stir-frying (132.10ppb), Japanese barbecue (125.62ppb), Western fast-food (122.67ppb), and Chinese buffet (119.96ppb) were the four restaurant types with the highest total carbonyl concentrations in exhaust streams, indicating that stir-frying and grilling are inclined to produce polluted gases. Health risk assessments indicate that Chinese hotpot and Japanese barbecue exceeded the limits of cancer risk (10(-6)) and hazard index (=1), mainly due to high concentrations of formaldehyde. The other four restaurants were below both limits. Copyright © 2015. Published by Elsevier B.V.

  19. 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

  20. Design of supramolecular metal complex catalytic systems for organic and petrochemical synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Karakhanov, Eduard A; Maksimov, Anton L; Runova, Elena A [Department of Chemistry, M.V. Lomonosov Moscow State University, Moscow (Russian Federation)

    2005-01-31

    The state-of-the-art in investigations into the supramolecular catalysis by metal complexes using macrocyclic receptor molecules is surveyed. The emphasis is placed on issues related to the design of novel metal complex catalysts capable of molecular recognition and to their applications in organic synthesis, in particular, in such reactions as hydrogenation, hydroformylation, carbonylation, hydroxylation, Wacker oxidation, biomimetic oxidation, and some others. The factors affecting the activity, stability and selectivity of such catalytic systems are discussed.

  1. Metal-metal-hofteproteser

    DEFF Research Database (Denmark)

    Ulrich, Michael; Overgaard, Søren; Penny, Jeannette

    2014-01-01

    In Denmark 4,456 metal-on-metal (MoM) hip prostheses have been implanted. Evidence demonstrates that some patients develope adverse biological reactions causing failures of MoM hip arthroplasty. Some reactions might be systemic. Failure rates are associated with the type and the design of the Mo...

  2. 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

  3. 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

  4. Redox Proteomic Profiling of Specifically Carbonylated Proteins in the Serum of Triple Transgenic Alzheimer's Disease Mice.

    Science.gov (United States)

    Shen, Liming; Chen, Youjiao; Yang, Aochu; Chen, Cheng; Liao, Liping; Li, Shuiming; Ying, Ming; Tian, Jing; Liu, Qiong; Ni, Jiazuan

    2016-04-12

    Oxidative stress is a key event in the onset and progression of neurodegenerative diseases, including Alzheimer's disease (AD). To investigate the role of oxidative stress in AD and to search for potential biomarkers in peripheral blood, serums were collected in this study from the 3-, 6-, and 12-month-old triple transgenic AD mice (3×Tg-AD mice) and the age- and sex-matched non-transgenic (non-Tg) littermates. The serum oxidized proteins were quantified by slot-blot analysis and enzyme-linked immunosorbent assay (ELISA) to investigate the total levels of serum protein carbonyl groups. Western blotting, in conjunction with two-dimensional gel electrophoresis (2D-Oxyblot), was employed to identify and quantify the specifically-carbonylated proteins in the serum of 3×Tg-AD mice. The results showed that the levels of serum protein carbonyls were increased in the three month old 3×Tg-AD mice compared with the non-Tg control mice, whereas no significant differences were observed in the six and 12 months old AD mice, suggesting that oxidative stress is an early event in AD progression. With the application of 2D-Oxyblot analysis, (immunoglobin) Ig gamma-2B chain C region (IGH-3), Ig lambda-2 chain C region (IGLC2), Ig kappa chain C region (IGKC), and Ig kappa chain V-V region HP R16.7 were identified as significantly oxidized proteins compared with the control. Among them IGH-3 and IGKC were validated via immunoprecipitation and Western blot analysis. Identification of oxidized proteins in the serums of 3×Tg-AD mice can not only reveal potential roles of those proteins in the pathogenesis of AD but also provide potential biomarkers of AD at the early stage.

  5. Formation and emissions of carbonyls during and following gas-phase ozonation of indoor materials

    Science.gov (United States)

    Poppendieck, D. G.; Hubbard, H. F.; Weschler, C. J.; Corsi, R. L.

    Ozone concentrations that are several orders of magnitude greater than typical urban ambient concentrations are necessary for gas-phase ozonation of buildings, either for deodorization or for disinfection of biological agents. However, there is currently no published literature on the interaction of building materials and ozone under such extreme conditions. It would be useful to understand, for example in the case of building re-occupation planning, what types and amounts of reaction products may form and persist in a building after ozonation. In this study, 24 materials were exposed to ozone 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 from 1 to 20 mg m -2, with most of the carbonyls being of lower molecular weight (C 1-C 4). In contrast, total BOBP mass released from wood-based products ranged from 20 to 100 mg m -2, with a greater fraction of the BOBPs being heavier carbonyls (C 5-C 9). The total BOBP mass released during an ozonation event is a function of both the total surface area of the material and the BOBP emission rate per unit area of material. Ceiling tile, carpet, office partition, and gypsum wallboard with flat latex paint often have large surface areas in commercial buildings and these same materials exhibited relatively high BOBP releases. The greatest overall BOBP mass releases were observed for three materials that building occupants might have significant contact with: paper, office partition, and medium density fiberboard, e.g., often used in office furniture. These materials also exhibited extended BOBP persistence following ozonation; some BOBPs (e.g., nonanal) persist for months or more at emission rates large enough to result in indoor concentrations that exceed their odor

  6. 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.

  7. Pd/C Catalyzed Carbonylation of Azides in the Presence of Amines.

    Science.gov (United States)

    Zhao, Jin; Li, Zongyang; Yan, Shuaihu; Xu, Shiyang; Wang, Ming-An; Fu, Bin; Zhang, Zhenhua

    2016-04-15

    A facile and efficient Pd/C-catalyzed carbonylation of both aliphatic and aromatic azides in the presence of amines is reported. Serving as the widely existed fragments in an array of biological pharmaceuticals, functionalized unsymmetrical ureas were straightforwardly synthesized by using readily available and cheap azides with amines under CO atmosphere, with the extrusion of N2 as the only byproduct. It was found that not only aryl azides but also benzyl and alkyl azides were suited for this methodology. Another feature of this procedure was the employment of a highly efficient palladium charcoal catalytic system.

  8. 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.

  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. A Device-Independent Evaluation of Carbonyl Emissions from Heated Electronic Cigarette Solvents.

    Science.gov (United States)

    Wang, Ping; Chen, Wenhao; Liao, Jiawen; Matsuo, Toshiki; Ito, Kazuhide; Fowles, Jeff; Shusterman, Dennis; Mendell, Mark; Kumagai, Kazukiyo

    2017-01-01

    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.

  11. 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.

  12. 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......; 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...

  13. Mechanistic Investigations of the Iron(III)-Catalyzed Carbonyl-Olefin Metathesis Reaction.

    Science.gov (United States)

    Ludwig, Jacob R; Phan, Susan; McAtee, Christopher C; Zimmerman, Paul M; Devery, James J; Schindler, Corinna S

    2017-08-09

    Iron(III)-catalyzed carbonyl-olefin ring-closing metathesis represents a new approach toward the assembly of molecules traditionally generated by olefin-olefin metathesis or olefination. Herein, we report detailed synthetic, spectroscopic, kinetic, and computational studies to determine the mechanistic features imparted by iron(III), substrate, and temperature to the catalytic cycle. These data are consistent with an iron(III)-mediated asynchronous, concerted [2+2]-cycloaddition to form an intermediate oxetane as the turnover-limiting step. Fragmentation of the oxetane via Lewis acid-activation results in the formation of five- and six-membered unsaturated carbocycles.

  14. Sensitivity of Saccharomyces cerevisiae defective in TOR signaling pathway to carbonyl/oxidative stress

    Directory of Open Access Journals (Sweden)

    Valishkevych B. V.

    2014-09-01

    Full Text Available Aim. To investigate the influence of carbonyl/oxidative stress induced by glyoxal, methylglyoxal and hydrogen peroxide on the survival of Saccharomyces cerevisiae, defective for different parts of TOR- signaling pathway, grown on glucose or fructose. Methods. The assessment of number of colony-forming units to determine the yeast reproductive ability. Results. It was shown that at certain concentrations the mentioned above toxicants caused an increase in yeast survival, indicating the hormetic effect. Conclusions. The TOR signaling pathway is involved in the hormetic effect, but it is specific for each strain and depends on the type of carbohydrate in the incubation medium.

  15. Metallated metal-organic frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Bury, Wojciech; Farha, Omar K.; Hupp, Joseph T.; Mondloch, Joseph E.

    2017-02-07

    Porous metal-organic frameworks (MOFs) and metallated porous MOFs are provided. Also provided are methods of metallating porous MOFs using atomic layer deposition and methods of using the metallated MOFs as catalysts and in remediation applications.

  16. Metallated metal-organic frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Bury, Wojciech; Farha, Omar K.; Hupp, Joseph T.; Mondloch, Joseph E.

    2017-08-22

    Porous metal-organic frameworks (MOFs) and metallated porous MOFs are provided. Also provided are methods of metallating porous MOFs using atomic layer deposition and methods of using the metallated MOFs as catalysts and in remediation applications.

  17. Engineered Trx2p industrial yeast strain protects glycolysis and fermentation proteins from oxidative carbonylation during biomass propagation

    Directory of Open Access Journals (Sweden)

    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.

  18. Wafer-scale laser lithography. I. Pyrolytic deposition of metal microstructures

    International Nuclear Information System (INIS)

    Herman, I.P.; Hyde, R.A.; McWilliams, B.M.; Weisberg, A.H.; Wood, L.L.

    1982-01-01

    Mechanisms for laser-driven pyrolytic deposition of micron-scale metal structures on crystalline silicon have been studied. Models have been developed to predict temporal and spatial propeties of laser-induced pyrolytic deposition processes. An argon ion laser-based apparatus has been used to deposit metal by pyrolytic decomposition of metal alkyl and carbonyl compounds, in order to evaluate the models. These results of these studies are discussed, along with their implications for the high-speed creation of micron-scale metal structures in ultra-large scale integrated circuit systems. 4 figures

  19. 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.

  20. 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.

  1. Enhanced microwave absorbing properties and heat resistance of carbonyl iron by electroless plating Co

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Hongyu, E-mail: wanghongyu07010310@163.com; Zhu, Dongmei; Zhou, Wancheng; Luo, Fa

    2015-11-01

    Co coated carbonyl iron particles (Co (CI)) are fabricated through electroless plating method, and the electromagnetic microwave absorbing properties are investigated in the frequencies during 8.2–12.4 GHz. The complex permittivity of CI particles after electroless plating Co is higher than that of raw CI particles due to improvment of the polarization process. Furthermore, according to the XRD and TG results, the Co layer can enhance the heat resistance of CI particles. The bandwidth below −10 dB can reach 3.9 GHz for the Co(CI) absorbent. The results indicate that the electroless plating Co not only enhances the absorbing properties but also improves the heat resistance of CI. - Highlights: • The Co-coated carbonyl iron Co(CI) particles were prepared by electroless plating. • The electromagnetic wave absorbing properties of Co(CI) particles were studied. • The heat treatment on the absorbing property of Co(CI) particles was studied. • The Co(CI) particles have good absorbing property when compared with CI.

  2. Permeability measurements in cobalt ferrite and carbonyl iron powders and suspensions

    International Nuclear Information System (INIS)

    Vicente, J. de; Bossis, G.; Lacis, S.; Guyot, M.

    2002-01-01

    Magnetic permeability data of cobalt ferrite and carbonyl iron suspensions are discussed. Using an induction method, the relative differential permeability, μ r,dif , was measured as a function of the internal magnetic field for different volume fractions of the solid phase. In the case of cobalt ferrite suspensions, the μ r,dif -H curve was obtained for a first increasing ramp of magnetic field (data series ''1''), a decreasing ramp (data series ''2''), and the second increasing one (data series ''3''). Series ''1'' showed a maximum in the μ r,dif -H trend that did not appear in series ''2'' and ''3''. Furthermore, the data in series ''2'' and ''3'' are always below those in series ''1''. The latter behavior could be ascribed to the presence of hysteresis, and in fact it was not observed in carbonyl iron suspensions, where hysteresis is absent. The presence of the maximum in permeability is common for both types of suspensions. It is found that it only disappears if the particle motions are restricted by dispersing them in a rigid (epoxy) matrix, or if the suspensions are previously structured by applying a magnetic field to a sample prepared in an elastomer matrix. We conclude that the maxima in μ r,dif -H curves are associated to the motion or orientation of the dispersed particles during application of the first field ramp. The comparison with predictions of models allows to deduce some quantitative information on the structures formed by the particles

  3. 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).

  4. Gel-free proteomic methodologies to study reversible cysteine oxidation and irreversible protein carbonyl formation.

    Science.gov (United States)

    Boronat, S; García-Santamarina, S; Hidalgo, E

    2015-05-01

    Oxidative modifications in proteins have been traditionally considered as hallmarks of damage by oxidative stress and aging. However, oxidants can generate a huge variety of reversible and irreversible modifications in amino acid side chains as well as in the protein backbones, and these post-translational modifications can contribute to the activation of signal transduction pathways, and also mediate the toxicity of oxidants. Among the reversible modifications, the most relevant ones are those arising from cysteine oxidation. Thus, formation of sulfenic acid or disulfide bonds is known to occur in many enzymes as part of their catalytic cycles, and it also participates in the activation of signaling cascades. Furthermore, these reversible modifications have been usually attributed with a protective role, since they may prevent the formation of irreversible damage by scavenging reactive oxygen species. Among irreversible modifications, protein carbonyl formation has been linked to damage and death, since it cannot be repaired and can lead to protein loss-of-function and to the formation of protein aggregates. This review is aimed at researchers interested on the biological consequences of oxidative stress, both at the level of signaling and toxicity. Here we are providing a concise overview on current mass-spectrometry-based methodologies to detect reversible cysteine oxidation and irreversible protein carbonyl formation in proteomes. We do not pretend to impose any of the different methodologies, but rather to provide an objective catwalk on published gel-free approaches to detect those two types of modifications, from a biologist's point of view.

  5. 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.

  6. Behavior of VOCs and Carbonyl Compounds Emission from Different Types of Wallpapers in Korea

    Directory of Open Access Journals (Sweden)

    Jungyun Lim

    2014-04-01

    Full Text Available Emissions of volatile organic compounds (VOCs and carbonyls from three types of commercially available wallpapers (i.e., PVC-coated, paper-backed, natural material-coated in Korea were evaluated using a 20 L small chamber. A total of 332 products were tested for emission factors, frequencies of occurrence and composition ratios. Toluene and formaldehyde concentrations were below Korean standard values for all products; however, the total VOC (TVOC concentrations exceeded current standards (4.0 mg/m2·h for 30 products. The TVOC emission factor for PVC-coated wallpapers, for which polymer materials are used in the manufacturing process, was seven and 16 times higher than those of paper-backed and natural material-coated wallpapers, respectively. The detection frequencies for toluene and formaldehyde were the highest (82.5% and fourth highest (79.5%, respectively among the 50 target chemical species. The composition ratios for BTEX ranged from 0.3% to 5.1% and unidentified VOCs, which were not qualitatively analyzed using standard gas methods, ranged from 90.2% to 94.8%. Among six carbonyl compounds (acrolein was not detected in any type of wallpaper, acetone had the highest concentrations in PVC-coated (44.6% and paper-backed (66.6% wallpapers. Formaldehyde emissions were highest (64.6% for natural material-coated wallpapers, a result of the formaldehyde-based resin used in the manufacturing process for these products.

  7. Behavior of VOCs and carbonyl compounds emission from different types of wallpapers in Korea.

    Science.gov (United States)

    Lim, Jungyun; Kim, Suejin; Kim, Arong; Lee, Wooseok; Han, Jinseok; Cha, Jun-Seok

    2014-04-17

    Emissions of volatile organic compounds (VOCs) and carbonyls from three types of commercially available wallpapers (i.e., PVC-coated, paper-backed, natural material-coated) in Korea were evaluated using a 20 L small chamber. A total of 332 products were tested for emission factors, frequencies of occurrence and composition ratios. Toluene and formaldehyde concentrations were below Korean standard values for all products; however, the total VOC (TVOC) concentrations exceeded current standards (4.0 mg/m²·h) for 30 products. The TVOC emission factor for PVC-coated wallpapers, for which polymer materials are used in the manufacturing process, was seven and 16 times higher than those of paper-backed and natural material-coated wallpapers, respectively. The detection frequencies for toluene and formaldehyde were the highest (82.5%) and fourth highest (79.5%), respectively among the 50 target chemical species. The composition ratios for BTEX ranged from 0.3% to 5.1% and unidentified VOCs, which were not qualitatively analyzed using standard gas methods, ranged from 90.2% to 94.8%. Among six carbonyl compounds (acrolein was not detected in any type of wallpaper), acetone had the highest concentrations in PVC-coated (44.6%) and paper-backed (66.6%) wallpapers. Formaldehyde emissions were highest (64.6%) for natural material-coated wallpapers, a result of the formaldehyde-based resin used in the manufacturing process for these products.

  8. 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.

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

    Directory of Open Access Journals (Sweden)

    Zi-Wei Feng

    2016-10-01

    Full Text Available 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 MIC50 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 IC50 > 50 μg/mL. Finally, the possible biosynthetic pathway of penicitroamide (1 was discussed.

  10. Brønsted Acid-Catalyzed Carbonyl-Olefin Metathesis inside a Self-Assembled Supramolecular Host.

    Science.gov (United States)

    Catti, Lorenzo; Tiefenbacher, Konrad

    2017-12-20

    Carbonyl-olefin metathesis represents a powerful yet underdeveloped method for the formation of carbon-carbon bonds. So far, no Brønsted acid based method for the catalytic carbonyl-olefin metathesis has been described. Herein, a cocatalytic system based on a simple Brønsted acid (HCl) and a self-assembled supramolecular host is presented. The developed system compares well with the current benchmark catalyst for carbonyl-olefin metathesis in terms of substrate scope and yield of isolated product. Control experiments provide strong evidence that the reaction proceeds inside the cavity of the supramolecular host. A mechanistic probe indicates that a stepwise reaction mechanism is likely. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. 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

  12. Metal-metal-hofteproteser

    DEFF Research Database (Denmark)

    Ulrich, Michael; Overgaard, Søren; Penny, Jeannette

    2014-01-01

    In Denmark 4,456 metal-on-metal (MoM) hip prostheses have been implanted. Evidence demonstrates that some patients develope adverse biological reactions causing failures of MoM hip arthroplasty. Some reactions might be systemic. Failure rates are associated with the type and the design of the Mo......M hip implant. A Danish surveillance programme has been initiated addressing these problems....

  13. The structural, magnetic and microwave properties of spherical and flake shaped carbonyl iron particles as thin multilayer microwave absorbers

    Energy Technology Data Exchange (ETDEWEB)

    Khani, Omid, E-mail: omidkhani@mut-es.ac.ir [Department of Physics, Shahid Chamran University of Ahvaz, Ahvaz, Islamic Republic of Iran (Iran, Islamic Republic of); Shoushtari, Morteza Zargar [Department of Physics, Shahid Chamran University of Ahvaz, Ahvaz, Islamic Republic of Iran (Iran, Islamic Republic of); Ackland, Karl; Stamenov, Plamen [School of Physics and CRANN, Trinity College, Dublin 2 (Ireland)

    2017-04-15

    An increase in microwave permeability is a prerequisite for reducing the thickness of radar absorber coatings. The aim of this paper is to increase the magnetic loss of commercial carbonyl iron particles for fabricating wideband microwave absorbers with a multilayer structure. For this purpose, carbonyl iron particles were milled and their static and dynamic magnetic properties were studied before and after milling. A distinct morphological change from spherical to flake-like particles is measured with increased milling time, whereas no distinct changes in magnetic properties are measured with increased milling time. The imaginary part of the permeability (µ'') of the milled carbonyl iron particles increased from 1.23 to 1.88 and showed a very broad peak over the entire frequency range 1–18 GHz. The experimental results were modeled using the Rousselle effective medium theory (EMT) in the Neo formulation. The theoretical predictions showed good agreement with the experimental results. Two layer absorbers were designed according to the measured microwave parameters and the multilayer design. The results revealed that a thin multilayer with a thickness of 1.75 mm can effectively absorb microwaves in both the entire X and Ku frequency bands. The results suggest that microwave absorbers with excellent absorption properties could be mass-produced, using commercial carbonyl iron particles. - Highlights: • The microwave properties of carbonyl iron particles can be controlled effectively by particles shape. • Milling process transforms the carbonyl iron particle morphology from spherical to flake-like. • No appreciable differences in the magnetic and chemical local environments were detected by means of Mossbauer spectroscopy. • The two layer design showed appropriate absorptions in a rather wide frequency range.

  14. 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.

  15. 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.

  16. Protein hydroperoxides and carbonyl groups generated by porphyrin-induced photo-oxidation of bovine serum albumin

    DEFF Research Database (Denmark)

    Silvester, J A; Timmins, G S; Davies, Michael Jonathan

    1998-01-01

    Porphyrin-sensitized photo-oxidation of bovine serum albumin results in oxidation at specific sites to produce protein radical species: at the Cys-34 residue (to give a thiyl radical) and at one or both tryptophan residues (Trp-134 and Trp-214) to give tertiary carbon-centered radicals and cause...... disruption of the indole ring system. This study shows that these photo-oxidation processes also consume oxygen and give rise to hydrogen peroxide, protein hydroperoxides, and carbonyl functions. The yield of hydrogen peroxide, protein hydroperoxides, and carbonyl functions is shown to be dependent...

  17. 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.

  18. 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.

  19. Metal-free carbon-carbon bond-forming reductive coupling between boronic acids and tosylhydrazones.

    Science.gov (United States)

    Barluenga, José; Tomás-Gamasa, María; Aznar, Fernando; Valdés, Carlos

    2009-09-01

    The formation of carbon-carbon bonds is a fundamental transformation in organic synthesis. In spite of the myriad methods available, advantageous methodologies in terms of selectivity, availability of starting materials, operational simplicity, functional-group tolerance, environmental sustainability and economy are in constant demand. In this context, the development of new cross-coupling reactions that use catalysts based on inexpensive and non-toxic metals is attracting increasing attention. Similarly, efficient processes that do not require a metal catalyst are of extraordinary interest. Here, we report a new and efficient metal-free carbon-carbon bond-forming coupling between tosylhydrazones and boronic acids. This reaction is very general and functional-group tolerant. As the required tosylhydrazones are easily generated from carbonyl compounds, it can be seen as a reductive coupling of carbonyls, a process of high synthetic relevance that requires several steps using other methodologies.

  20. Analysis of biogenic carbonyl compounds in rainwater by stir bar sorptive extraction technique with chemical derivatization and gas chromatography-mass spectrometry.

    Science.gov (United States)

    Pang, Xiaobing; Lewis, Alastair C; Shaw, Marvin D

    2017-02-01

    Stir bar sorptive extraction is a powerful technique for the extraction and analysis of organic compounds in aqueous matrices. Carbonyl compounds are ubiquitous components in rainwater, however, it is a major challenge to accurately identify and sensitively quantify carbonyls from rainwater due to the complex matrix. A stir bar sorptive extraction technique was developed to efficiently extract carbonyls from aqueous samples following chemical derivatization by O-(2,3,4,5,6-pentafluorobenzyl) hydroxylamine hydrochloride. Several commercial stir bars in two sizes were used to simultaneously measure 29 carbonyls in aqueous samples with detection by gas chromatography with mass spectrometry. A 100 mL aqueous sample was extracted by stir bars and the analytes on stir bars were desorbed into a 2 mL solvent solution in an ultrasonic bath. The preconcentration Coefficient for different carbonyls varied between 30 and 45 times. The limits of detection of stir bar sorptive extraction with gas chromatography mass spectrometry for carbonyls (10-30 ng/L) were improved by ten times compared with other methods such as gas chromatography with electron capture detection and stir bar sorptive extraction with high-performance liquid chromatography and mass spectrometry. The technique was used to determine carbonyls in rainwater samples collected in York, UK, and 20 carbonyl species were quantified including glyoxal, methylglyoxal, isobutenal, 2-hydroxy ethanal. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Brake performance of core–shell structured carbonyl iron/silica based magnetorheological suspension

    International Nuclear Information System (INIS)

    Nguyen, Phuong-Bac; Do, Xuan-Phu; Jeon, Juncheol; Choi, Seung-Bok; Liu, Ying Dan; Choi, Hyoung Jin

    2014-01-01

    Chemically stable core–shell structured magnetic particles were synthesized by coating soft-magnetic carbonyl iron (CI) microspheres with silica through a sol–gel reaction, and applied as magnetorheological (MR) materials for a specially designed small-sized MR brake. The dynamic yield stress of the MR suspension containing the synthesized particles was also measured using a rotational rheometer under an applied magnetic field. The performance characteristics of the MR brake, including field dependent torque, hysteresis, time and torque tracking control responses were examined. The results showed that with the exception of the settling time, the other response times were faster than those of the pristine CI based MR fluid. - Highlights: • Silica coated magnetic particle was fabricated as magnetorheological (MR) material. • Small-sized MR brake of disc-type was specially designed. • MR fluid based on silica coated particles exhibited improved tracking accuracy

  2. 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 molecular electric dipole moment. These findings are explained by a tunneling model invoking the laser-induced Stark shifts associated with the dipoles and polarizabilities of the molecule and its unrelaxed cation. The focus of the present article is to understand the strong-field ionization of one......-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...

  3. The long underestimated carbonyl function of carbohydrates – an organocatalyzed shot into carbohydrate chemistry.

    Science.gov (United States)

    Mahrwald, R

    2015-09-21

    The aggressive and strong development of organocatalysis provides several protocols for the convenient utilization of the carbonyl function of unprotected carbohydrates in C-C-bond formation processes. These amine-catalyzed mechanisms enable multiple cascade-protocols for the synthesis of a wide range of carbohydrate-derived compound classes. Several, only slightly different protocols, have been developed for the application of 1,3-dicarbonyl compounds in the stereoselective chain-elongation of unprotected carbohydrates and the synthesis of highly functionalized C-glycosides of defined configuration. In addition, C-glycosides can also be accessed by amine-catalyzed reactions with methyl ketones. By a one-pot cascade reaction of isocyanides with unprotected aldoses and amino acids access to defined configured glycopeptide mimetics is achieved. Depending on the reaction conditions different origins to control the installation of configuration during the bond-formation process were observed.

  4. 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.

  5. Reaction mechanism of dimethyl ether carbonylation to methyl acetate over mordenite

    DEFF Research Database (Denmark)

    Rasmussen, Dominik Bjørn; Christensen, Jakob Munkholt; Temel, B.

    2017-01-01

    concentrations in CO between 0.2 and 2.0%, and at a temperature of 438 K. The theoretical study showed that the reaction of CO with surface methyl groups, the rate-limiting step, is faster in the eight-membered side pockets than in the twelve-membered main channel of the zeolite; the subsequent reaction......The reaction mechanism of dimethyl ether carbonylation to methyl acetate over mordenite was studied theoretically with periodic density functional theory calculations including dispersion forces and experimentally in a fixed bed flow reactor at pressures between 10 and 100 bar, dimethyl ether...... of dimethyl ether with surface acetyl to form methyl acetate was demonstrated to occur with low energy barriers in both the side pockets and in the main channel. The present analysis has thus identified a path, where the entire reaction occurs favourably on a single site within the side pocket, in good...

  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. Ligand additivity in the valence photoelectron spectroscopy of phosphine-substituted molybdenum carbonyls

    International Nuclear Information System (INIS)

    Bursten, B.E.; Darensbourg, D.J.; Kellogg, G.E.; Lichtenberger, D.L.

    1984-01-01

    The He I valence photoelectron spectra in the 6-9-eV ionization region are reported for seven phosphine-substituted molybdenum carbonyls. The observation of vibrational structure due to excitation of a CO stretching mode in several of the spectra aids band assignment. These data are used to test the validity of the model of ligand additivity for determining the energetics of the dπ electrons in octahedral d 6 complexes. It is shown that the model successfully correlates the positions, intensities, and number of the ionization bands for the molybdenum compounds. A comparison of the results for the complexes of different phosphine ligands indicates that the trimethyl (PMe 3 ), triethyl (PEt 3 ), and tri-n-butyl (P-n-Bu 3 ) phosphines are comparable π-acceptors, but that the sigma-donor strength increases as PMe 3 3 3

  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. Comparative inhibition of tetrameric carbonyl reductase activity in pig heart cytosol by alkyl 4-pyridyl ketones.

    Science.gov (United States)

    Shimada, Hideaki; Tanigawa, Takahiro; Matayoshi, Kazunori; Katakura, Kazufumi; Babazono, Ken; Takayama, Hiroyuki; Murahashi, Tsuyoshi; Akita, Hiroyuki; Higuchi, Toshiyuki; Eto, Masashi; Imamura, Yorishige

    2014-06-01

    The present study is to elucidate the comparative inhibition of tetrameric carbonyl reductase (TCBR) activity by alkyl 4-pyridyl ketones, and to characterize its substrate-binding domain. The inhibitory effects of alkyl 4-pyridyl ketones on the stereoselective reduction of 4-benzoylpyridine (4-BP) catalyzed by TCBR were examined in the cytosolic fraction of pig heart. Of alkyl 4-pyridyl ketones, 4-hexanoylpyridine, which has a straight-chain alkyl group of five carbon atoms, inhibited most potently TCBR activity and was a competitive inhibitor. Furthermore, cyclohexyl pentyl ketone, which is substituted by cyclohexyl group instead of phenyl group of hexanophenone, had much lower ability to be reduced than hexanophenone. These results suggest that in addition to a hydrophobic cleft corresponding to a straight-chain alkyl group of five carbon atoms, a hydrophobic pocket with affinity for an aromatic group is located in the substrate-binding domain of TCBR.

  10. 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.

  11. The hydrogen bond stabilizing effect in enammonium salts of captodative aminoalkenes containing a carbonyl group

    Science.gov (United States)

    Fedorov, S. V.; Rulev, A. Yu; Chipanina, N. N.; Sherstyannikova, L. V.; Turchaninov, V. K.

    2004-03-01

    Enhanced stability of enammonium salts of captodative carbonyl-containing aminoalkenes as compared to the salts of simple enamines is discussed on the basis of 1H and 13C NMR, IR, UV spectroscopy and the results quantum chemical calculations. Stabilization of the N-protonated form of captodative aminoalkenes is due to either intramolecular (NH +⋯OC) or intermolecular (NH +⋯Solv or NH +⋯X -) hydrogen bonding, whereas the C-protonated form is destabilized due to umpolung of the carbon-carbon double bond. The formation of bifurcated (three-centered) hydrogen bond between the enammonium cation and the solvent is demonstrated. The three-centered solvate complex is characterized by nonclassical dependence of the chemical shift of the bridging hydrogen atom from the proton-acceptor power of the solvent.

  12. Simple and fully automated preparation of [carbonyl-{sup 11}C]WAY-100635

    Energy Technology Data Exchange (ETDEWEB)

    Wadsak, W.; Ettlinger, D.E; Dudczak, R.; Kletter, K. [Medical Univ. of Vienna (Austria). Dept. of Nuclear Medicine; Mien, L.K. [Medical Univ. of Vienna (Austria). Dept. of Nuclear Medicine; Medical Univ. of Vienna (Austria). Dept. of Psychiatry; Vienna Univ. (Austria). Dept. of Pharmaceutical Technology and Biopharmaceutics; Lanzenberger, R.R. [Medical Univ. of Vienna (Austria). Dept. of Psychiatry; Haeusler, D. [Medical Univ. of Vienna (Austria). Dept. of Nuclear Medicine; Vienna Univ. (Austria). Dept. of Pharmaceutical Technology and Biopharmaceutics; Mitterhauser, M. [Medical Univ. of Vienna (Austria). Dept. of Nuclear Medicine; Vienna Univ. (Austria). Dept. of Pharmaceutical Technology and Biopharmaceutics; General Hospital of Vienna (Austria). Hospital Pharmacy

    2007-07-01

    So far, [carbonyl-{sup 11}C]WAY-100635 is the PET-tracer of choice for 5HT{sub 1A}-receptor-imaging. Since the preparation is still a challenge, we aimed at (1) the evaluation of various essential parameters for the successful preparation, (2) the simplification of the radiosynthesis and (3) the establishment of a safe and fully automated system. The preparation is based on a commercial synthesizer and all chemicals are used without further processing. We found a low failure rate (7.7%), high average yield (4.0 {+-} 1.0 GBq) and a specific radioactivity of 292 {+-} 168 GBq/{mu}mol (both at the end of synthesis, EOS). (orig.)

  13. The enhancement of the oxidation resistance of carbonyl iron by polyaniline coating and consequent changes in electromagnetic properties

    Czech Academy of Sciences Publication Activity Database

    Abshinova, M.; Kazantseva, N. E.; Sáha, P.; Sapurina, I.; Kovářová, Jana; Stejskal, Jaroslav

    2008-01-01

    Roč. 93, č. 10 (2008), s. 1826-1831 ISSN 0141-3910 R&D Projects: GA MŠk ME 847 Institutional research plan: CEZ:AV0Z40500505 Keywords : carbonyl iron * polyaniline * conducting polymer Subject RIV: CD - Macromolecular Chemistry Impact factor: 2.320, year: 2008

  14. 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.

  15. [Defects in TOR regulatory complexes retard aging and carbonyl/oxidative stress development in yeast Saccharomyces cerevisiae].

    Science.gov (United States)

    Homza, B V; Vasyl'kovs'ka, R A; Semchyshyn, H M

    2014-01-01

    TOR signaling pathway first described in yeast S. cerevisiae 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 alpha-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.

  16. Soil fluxes of carbonyl sulfide (COS), carbon monoxide, and carbon dioxide in a boreal forest in southern Finland

    NARCIS (Netherlands)

    Sun, Wu; Kooijmans, Linda M. J.; Maseyk, Kadmiel; Chen, Huilin; Mammarella, Ivan; Vesala, Timo; Levula, Janne; Keskinen, Helmi; Seibt, Ulli

    2018-01-01

    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

  17. Noticeable facilitation of the bismuth-mediated Barbier-type allylation of aromatic carbonyl compounds under solvent-free conditions.

    Science.gov (United States)

    Wada, Shinobu; Hayashi, Nobuyuki; Suzuki, Hitomi

    2003-06-21

    When milled together with bismuth shot in the presence of allyl halide, aromatic aldehydes readily underwent a Barbier-type allylation to afford the corresponding homoallyl alcohols in good yield. In contrast to the failure in solution reaction, aromatic ketones also underwent allylic carbonyl addition under solvent-free conditions to give the expected tertiary homoallyl alcohols in moderate to good yield.

  18. 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 ...

  19. Double Conjugate Addition of Dithiols to Propargylic Carbonyl Systems To Generate Protected 1,3-Dicarbonyl Compounds

    NARCIS (Netherlands)

    Sneddon, Helen F.; Heuvel, Alexandra van den; Hirsch, Anna K.H.; Booth, Richard A.; Shaw, David M.; Gaunt, Matthew J.; Ley, Steven V.

    2006-01-01

    The work describes the efficient double conjugate addition of ethane and propane dithiols in the presence of sodium methoxide to a wide variety of propargylic carbonyl containing compounds. The products of these reactions are differentiated, 1,3-dicarbonyl systems useful for various synthesis

  20. 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

  1. Shipp-in-Bottle Synthesis of Pt-Rh Carbonyls in NaX and NaY: FTIR Study

    Czech Academy of Sciences Publication Activity Database

    Brabec, Libor

    2001-01-01

    Roč. 169, 1/2 (2001), s. 127-136 ISSN 1381-1169 R&D Projects: GA AV ČR IAA4040710 Institutional research plan: CEZ:AV0Z4040901 Keywords : Pt-Rh carbonyls * FTIR * zeolites Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.520, year: 2001

  2. 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

  3. Inhibitory activity of carbonyl compounds on alcoholic fermentation by Saccharomyces cerevisiae.

    Science.gov (United States)

    Cao, Dongxu; Tu, Maobing; Xie, Rui; Li, Jing; Wu, Yonnie; Adhikari, Sushil

    2014-01-29

    Aldehydes and acids play important roles in the fermentation inhibition of biomass hydrolysates. A series of carbonyl compounds (vanillin, syringaldehyde, 4-hydroxybenzaldehyde, pyrogallol aldehyde, and o-phthalaldehyde) were used to examine the quantitative structure-inhibitory activity relationship of carbonyl compounds on alcoholic fermentation, based on the glucose consumption rate and the final ethanol yield. It was observed that pyrogallol aldehyde and o-phthalaldehyde (5.0 mM) reduced the initial glucose consumption rate by 60 and 89%, respectively, and also decreased the final ethanol yield by 60 and 99%, respectively. Correlating the molecular descriptors to inhibition efficiency in yeast fermentation revealed a strong relationship between the energy of the lowest unoccupied molecular orbital (ELUMO) of aldehydes and their inhibitory efficiency in fermentation. On the other hand, vanillin, syringaldehyde, and 4-hydroxybenzaldehyde (5.0 mM) increased the final ethanol yields by 11, 4, and 1%, respectively. Addition of vanillin appeared to favor ethanol formation over glycerol formation and decreased the glycerol yield in yeast fermentation. Furthermore, alcohol dehydrogenase (ADH) activity dropped significantly from 3.85 to 2.72, 1.83, 0.46, and 0.11 U/mg at 6 h of fermentation at vanillin concentrations of 0, 2.5, 5.0, 10.0, and 25.0 mM correspondingly. In addition, fermentation inhibition by acetic acid and benzoic acid was pH-dependent. Addition of acetate, benzoate, and potassium chloride increased the glucose consumption rate, likely because the salts enhanced membrane permeability, thus increasing glucose consumption.

  4. Branching Ratios for the Reaction of Carbonyl-Containing Organic Peroxy Radicals with Hydroperoxy Radicals

    Science.gov (United States)

    Hasson, A.; Tyndall, G. S.; Hernandez, S.; Campbell, S.; Singh, S.; Ibarra, Y.; Orlando, J. J.

    2009-12-01

    An important chemical sink for organic peroxy radicals (RO2) in the troposphere is reaction with hydroperoxy radicals (HO2). While this reaction is typically assumed to form hydroperoxides as the major products (R1a), a small number of carbonyl-containing peroxy radicals have been shown to undergo other reactions (R1b and R1c) with substantial branching ratios RO2 + HO2 → ROOH + O2 R1a RO2 + HO2 → ROH + O3 R1b RO2 + HO2 → RO + OH + O2 R1c. In this work, branching ratios for R1a-c were measured for six organic peroxy radicals: C2H5C(O)O2, C3H7C(O)O2, CH3C(O)CH2O2, CH3C(O)CH(O2)CH3, CH2ClCH(O2)C(O)CH3 and CH2ClC(CH3)(O2)CHO. The temperature (248 - 298 K) and pressure (100 - 800 Torr) dependence of the branching ratios for acetyl peroxy and acetonyl peroxy radicals was also investigated. Product yields were determined using a combination of long path Fourier Transform infrared spectroscopy, High Performance Liquid Chromatography with fluorescence detection, Gas Chromatography with Flame Ionization Detection and Gas Chromatography-Mass Spectrometry. All of the carbonyl-containing peroxy radicals investigated have significant branching ratios for Reaction R1c. The branching ratios for both acetyl peroxy and acetonyl peroxy radicals are temperature dependent but pressure independent over the ranges investigated. The mechanistic and atmospheric implications of these results will be discussed.

  5. 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

  6. Experimental Study of MR Suspensions of Carbonyl Iron Powders with Different Particle Sizes

    Science.gov (United States)

    Bombard, A. J. F.; Alcântara, M. R.; Knobel, M.; Volpe, P. L. O.

    Magnetorheological suspensions (MRS) based on mixtures of two commercial carbonyl iron powders (BASF grades CL and SU) as magnetic phase and hydrocarbon oil as liquid phase were prepared. CL and SU are both soft magnetic powders, but CL is a coarse powder, while SU is a fine one. The total mass fraction of iron was 80% w/w each formulation. Hydrophilic fumed silica (5% w/w of Aerosil® 200) was used to reduce the settling. The mixing ratios were: CL 0%, CL 20%, CL 40%, CL 60%, CL 80% and CL 100%. A MRS, the mixture CL 80%, showed considerable reduction of the plastic viscosity without field, in the range of 100 - 500 s-1, when compared to the MRS with just one powder. The yield stress values under applied field H ~ 340 kA/m were: 18.1 kPa for the MRS CL 0%, 18.3 kPa for the MRS's CL 20% and CL 40%, 20.0 kPa for the MRS CL 60%, 22.3 kPa for the MRS CL 80% and 23.3 kPa for the MRS CL 100%, respectively. For comparison, a sample of commercial MRF-132LD (Lord Corp.) in the same conditions showed yield value of 21.2 ± 0.6 kPa. On the other hand, another MRS, CL 60%, showed an increment of ~ 33% on the normal force, with relation to the MRS prepared with just CL or just SU powders, above 150 kA/m. Therefore, mixing carbonyl iron powders with different particle sizes can improve the performance of MRS, decreasing the 'off' plastic viscosity, and increasing the MR effect.

  7. Measurements of atmospheric carboxylic acids and carbonyl compounds in São Paulo City, Brazil.

    Science.gov (United States)

    Montero, L; Vasconcellos, P C; Souza, S R; Pires, M A; Sanchez-Ccoyllo, O R; Andrade, M F; Carvalho, L R

    2001-08-01

    Winter atmospheric measurements of gaseous lower carbonyl and carboxylic acids were carried out simultaneously (in 1999) at two distinct urban sites located in the city of São Paulo, Brazil. The greater metropolitan area of São Paulo is the largest industrialized region of Latin America and has a highly polluted atmosphere. It has an unconventional mix of vehicle types in that a variety of gasoline blends, including oxygenated ones, are used. Mixing ratios of formic and acetic acids ranged, respectively, from 0.6 to 19.4 and from 0.1 to 10.6 ppbv in one of the sites studied and from 1.4 to 18.4 and from 0.4 to 6.7 ppbv in the other site. High values of formic to acetic ratios were found, especially in the latter site (average = 4.3), suggesting that photochemical production was the predominant source of the formic and acetic acid during the afternoon. Differing from the acids, levels of carbonyls were similar at both sites. Higher average mixing ratios of acetaldehyde and formaldehyde were found in the morning (18.9 and 17.2 ppbv) and gradually decreased from midday (9.5 and 11.8 ppbv) to evening (7.2 and 10.2 ppbv). In the morning, vehicular direct emission seemed to be the main primary source of formaldehyde and acetaldehyde, whereas at midday and evening these compounds appeared to be mainly formed by photochemistry. Secondary photochemical production of organic acids and aldehydes (rather than primary emissions from vehicles) was shown to be more important in São Paulo's atmosphere from midday to evening, particularly on days with strong solar radiation.

  8. 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

  9. Crystal structure of fac-tri-carbonyl-chlorido-bis-(4-hy-droxy-pyridine)-rhenium(I)-pyridin-4(1H)-one (1/1).

    Science.gov (United States)

    Argibay-Otero, Saray; Carballo, Rosa; Vázquez-López, Ezequiel M

    2017-10-01

    The asymmetric unit of the title compound, [ReCl(C 5 H 5 NO) 2 (CO) 3 ]·C 5 H 5 NO, contains one mol-ecule of the complex fac -[ReCl(4-pyOH) 2 (CO) 3 ] (where 4-pyOH represents 4-hy-droxy-pyridine) and one mol-ecule of pyridin-4(1 H )-one (4-HpyO). In the mol-ecule of the complex, the Re atom is coordinated to two N atoms of the two 4-pyOH ligands, three carbonyl C atoms, in a facial configuration, and the Cl atom. The resulting geometry is slightly distorted octa-hedral. In the crystal structure, both fragments are associated by hydrogen bonds; two 4-HpyO mol-ecules bridge between two mol-ecules of the complex using the O=C group as acceptor for two different HO- groups of coordinated 4-pyOH from two neighbouring metal complexes. The resulting square arrangements are extented into infinite chains by hydrogen bonds involving the N-H groups of the 4-HpyO mol-ecule and the chloride ligands. The chains are further stabilized by π-stacking inter-actions.

  10. 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.

  11. New metals

    International Nuclear Information System (INIS)

    Bergqvist, U.

    1983-12-01

    The aim of this report is to estimate the exposure to various metals and metal compounds and discuss the available information of the possible toxic effects of these metals and compounds. In the first section, some metals are defined as those with either a large or a fast increasing exposure to living organisms. The available information on toxicity is discussed in the second section. In the third section interesting metals are defined as compounds having a large exposure and an apparent insufficient knowledge of their possible toxic effects. Comments on each of these metals are also to be found in the third section. (G.B.)

  12. Measurements of biogenic hydrocarbons and carbonyl compounds emitted by trees from temperate warm Atlantic rainforest, Brazil.

    Science.gov (United States)

    Carvalho, Lilian R F; Vasconcellos, Perola C; Mantovani, Waldir; Pool, Cristina S; Pisani, Silvana O

    2005-05-01

    This study is part of a three-year project on biogenic volatile organic compound (VOC) emissions from trees of the temperate warm Atlantic rainforest found in the metropolitan area of Sao Paulo City (MASP). No study of VOC emission rates from plant species has been carried out in the temperate warm Atlantic rainforest of Brazil prior to this work. Eleven species were selected (Alchornea sidifolia, Cupania oblongifolia, Cecropia pachystachia, Syagrus romanzoffiana, Casearia sylvestris, Machaerium villosum, Trema micrantha, Croton floribundus, Myrcia rostrata, Solanum erianthum and Ficus insipida) and some of them were studied in urban, sub-urban and forest areas inside the MASP in order to evaluate biogenic VOC composition at sites characterized by different emission sources. Biogenic VOC emissions were determined by placing branches of plants in a dynamic enclosure system, an all-Teflon cuvette, and by sampling the compounds in the air leaving the cuvette. Pre-concentration using adsorbents to retain the VOC, followed by GC-MS after thermal desorption of the sample, was employed to determine the amount of biogenic hydrocarbons. The collection of carbonyl compounds on a 2,4-dinitrophenylhydrazine coated silica followed by HPLC-UV was used to analyze low molecular weight carbonyl compounds. Emission rates of isoprene, alpha-pinene, camphene and limonene ranged from 0.01 to 2.16 microg C h(-1) g(-1) and emission rates of aldehydes (C(2)-C(6)), acrolein, methacrolein and 2-butanone ranged from 1.5 x 10(-2) to 2.3 micro g C h(-1) g (-1). Ambient and leaf temperatures, relative humidity, light intensity, O(3) and NO(x) levels in the local atmosphere were monitored during experiments. It was possible to identify different biogenic VOCs emitted from typical plants of temperate warm Atlantic rainforest. The emission rates were reported as a function of the type of site investigated and were only provided for compounds for which quantification was feasible. Other biogenic

  13. Conversion du methanol en ethanol par carbonylation suivie d'hydrogenolyse

    Science.gov (United States)

    Gaucher, Melissa

    Ce projet de maîtrise s'inscrit dans le cadre des nouvelles filières énergétiques renouvelables et s'effectue au sein de la Chaire de recherche industrielle sur l'éthanol cellulosique créée par trois partenaires industriels (Enerkem, CRB et Ethanol Greenfield) et le gouvernement du Québec en collaboration avec l'Université de Sherbrooke. La stratégie d'un des partenaires, Enerkem, est de convertir par gazéification des résidus de biomasse non homogène en Syngas, ce gaz est ensuite converti en méthanol puis en éthanol. L'objectif principal de ce projet est la conversion catalytique de l'acétate en alcool. Un catalyseur commercial, composé de cuivre et de chrome, a permis l'obtention des conversions de plus de 95 % et une sélectivité pour l'éthanol de plus de 50 % avec l'acétate de méthyle, de 99 % avec l'acétate d'éthyle et de 50 % avec l'acétate de butyle. Les conditions optimales trouvées impliquent une température de 215 °C, une pression de 350 psig, une vitesse spatiale de 1800 h -1 H2 STP et un ratio H2 : Acétate de 7. Un catalyseur alternatif, à base de cuivre et de zinc, a aussi été testé. L'objectif secondaire est la carbonylation du méthanol en acétate. Cette étape a été réalisée en phase gazeuse où des rendements très élevés, soit plus de 2000 kg d'acétate de méthyle par kg de métal précieux à l'heure (kg AM/ kg métal précieux/h), ont été obtenus. Les conditions d'opérations testées impliquent une température variant entre 200-240 °C, une pression entre 250-600 psig, des ratios McOH : CO de 1 à 2,5. Mots clés: Carbonylation, Éthanol, Hydrogénolyse, Catalyse hétérogène.

  14. Investigação espectroscópica dos carbonilos heterobimetálicos cis-[Fe(CO4(HgX2], X = Cl, Br,I Spectroscopic studies of heterobimetallic carbonyls cis-[Fe(CO4(HgX2], X=Cl, Br, I

    Directory of Open Access Journals (Sweden)

    José Roberto Zamian

    1999-12-01

    Full Text Available The series of compounds cis-[Fe(CO4(HgX2], X=Cl,Br,I shows an octahedral geometry around the iron atom with the two HgX groups cis to each other. In this paper the assignment for the carbonyl stretching modes and the calculation of their force constants were performed on the basis of the Cotton-Krainhanzel model. Taking into account all the data from the IR, 199Hg NMR and UV-vis spectra it is possible to verify the influence of X on the electronic densities at the metallic centers.

  15. Metal lagging

    International Nuclear Information System (INIS)

    Lemercier, Guy.

    1974-01-01

    The metal lagging described is characterized by the fact that it is formed of closed sacks composed of an elastic metal mass, compressed in an outer envelope made of a fine mesh metal fabric. The metal mass is composed of stainless steel wool stuffed into the envelope. This lagging is particularly intended for the thermal protection of the end slab of LMFBR type reactors [fr

  16. Atmospheric measurements of carbonyl sulfide, dimethyl sulfide, and carbon disulfide using the electron capture sulfur detector

    Science.gov (United States)

    Johnson, James E.; Bates, Timothy S.

    1993-01-01

    Measurements of atmospheric dimethyl sulfide (DMS), carbonyl sulfide (COS), and carbon disulfide (CS2) were conducted over the Atlantic Ocean on board the NASA Electra aircraft during the Chemical Instrumentation Test and Evaluation (CITE 3) project using the electron capture sulfur detector (ECD-S). The system employed cryogenic preconcentration of air samples, gas chromatographic separation, catalytic fluorination, and electron capture detection. Samples collected for DMS analysis were scrubbed of oxidants with NaOH impregnated glass fiber filters to preconcentration. The detection limits (DL) of the system for COS, DMS, and CS2 were 5, 5, and 2 ppt, respectively. COS concentrations ranged from 404 to 603 ppt with a mean of 489 ppt for measurements over the North Atlantic Ocean (31 deg N to 41 deg N), and from 395 to 437 ppt with a mean of 419 ppt for measurements over the Tropical Atlantic Ocean (11 deg S to 2 deg N). DMS concentrations in the lower marine boundary layer, below 600-m altitude, ranged from below DL to 150 ppt from flights over the North Atlantic, and from 9 to 104 ppt over the Tropical Atlantic. CS2 concentrations ranged from below DL to 29 ppt over the North Atlantic. Almost all CS2 measurements over the Tropical Atlantic were below DL.

  17. Human carbonyl reductase 4 is a mitochondrial NADPH-dependent quinone reductase.

    Science.gov (United States)

    Endo, Satoshi; Matsunaga, Toshiyuki; Kitade, Yukio; Ohno, Satoshi; Tajima, Kazuo; El-Kabbani, Ossama; Hara, Akira

    2008-12-26

    A protein encoded in the gene Cbr4 on human chromosome 4q32.3 belongs to the short-chain dehydrogenase/reductase family. Contrary to the functional annotation as carbonyl reductase 4 (CBR4), we show that the recombinant tetrameric protein, composed of 25-kDa subunits, exhibits NADPH-dependent reductase activity for o- and p-quinones, but not for other aldehydes and ketones. The enzyme was insensitive to dicumarol and quercetin, potent inhibitors of cytosolic quinone reductases. The 25-kDa CBR4 was detected in human liver, kidney and cell lines on Western blotting using anti-CBR4 antibodies. The overexpression of CBR4 in bovine endothelial cells reveals that the enzyme has a non-cleavable mitochondrial targeting signal. We further demonstrate that the in vitro quinone reduction by CBR4 generates superoxide through the redox cycling, and suggest that the enzyme may be involved in the induction of apoptosis by cytotoxic 9,10-phenanthrenequinone.

  18. Reactions of Cyclopropanone Acetals with Alkyl Azides: Carbonyl Addition versus Ring-Opening Pathways

    Science.gov (United States)

    Grecian, Scott; Desai, Pankaj; Mossman, Craig; Poutsma, Jennifer L.; Aubé, Jeffrey

    2008-01-01

    The Lewis acid-mediated reactions of substituted cyclopropanone acetals with alkyl azides were found to strongly depend on the structure of the ketone component. When cyclopropanone acetal was treated with alkyl azides, N-substituted 2-azetidinones and ethyl carbamate products were obtained, arising from azide addition to the carbonyl, followed by ring expansion or rearrangement, respectively. When 2,2-dimethylcyclopropanone acetals were reacted with azides in the presence of BF3•OEt2, the products obtained were α-amino-α′-diazomethyl ketones, which arose from C2–C3 bond cleavage of the corresponding cyclopropanone, giving oxyallyl cations, that were captured by azides. Aryl-substituted cyclopropanone acetals, when subjected to these conditions, afforded [1,2,3]oxaborazoles exclusively, which were also the result of C2–C3 bond rupture, azide capture and then loss of nitrogen. In the reactions of n-hexyl-substituted cyclopropanone acetals with alkyl azides, a mixture of 2-azetidinones and regioisomeric [1,2,3]oxaborazoles were obtained. The reasons for the different behavior of the various systems is discussed. PMID:17985920

  19. Direct 13C-detection for carbonyl relaxation studies of protein dynamics.

    Science.gov (United States)

    Pasat, Gabriela; Zintsmaster, John S; Peng, Jeffrey W

    2008-08-01

    We describe a method that uses direct 13C-detection for measuring rotating-frame carbonyl (13CO) relaxation rates to describe protein functional dynamics. Key advantages of method include the following: (i) unique access to 13CO groups that lack a scalar-coupled 15N-1H group; (ii) insensitivity to 15N/1H exchange-broadening that can derail 1H-detected 15N and HNCO methods; (iii) avoidance of artifacts caused by incomplete water suppression. We demonstrate the approach for both backbone and side-chain 13CO groups. Accuracy of the 13C-detected results is supported by their agreement with those obtained from established HNCO-based approaches. Critically, we show that the 13C-detection approach provides access to the 13CO groups of functionally important residues that are invisible via 1H-detected HNCO methods because of exchange-broadening. Hence, the 13C-based method fills gaps inherent in canonical 1H-detected relaxation experiments, and thus provides a novel complementary tool for NMR studies of biomolecular flexibility.

  20. Microwave absorbing property of silicone rubber composites with added carbonyl iron particles and graphite platelet

    International Nuclear Information System (INIS)

    Xu, Yonggang; Zhang, Deyuan; Cai, Jun; Yuan, Liming; Zhang, Wenqiang

    2013-01-01

    Silicone rubber composites filled with carbonyl iron particles (CIPs) and graphite platelet (GP) were prepared using non-coating or coating processes. The complex permittivity and permeability of the composites were measured using a vector network analyzer in the frequency range of 1–18 GHz and dc electric conductivity was measured by the standard four-point contact method. The results showed that CIPs/GP composites fabricated in the coating process had the highest permittivity and permeability due to the particle orientation and interactions between the two absorbents. The coating process resulted in a decreased effective eccentricity of the absorbents, and the dc conductivity increased according to Neelakanta's equations. The reflection loss (RL) value showed that the composites had an excellent absorbing property in the L-band, minimum −11.85 dB at 1.5 mm and −15.02 dB at 2 mm. Thus, GP could be an effective additive in preparing thin absorbing composites in the L-band. - Highlights: ► The added GP increased the permittivity and permeability of composites filled with CIPs. ► The enhancement was owing to interactions of the two absorbents and the fabrication process. ► The coating process decreased the effective eccentricity of the particles, and increased the conductivity of the composites. ► The composites to which CIPs/GP were added in coating process had excellent absorbing properties in the L-band.

  1. Quantification of A Tropical Missing Source From Ocean For The Carbonyl Sulfide Global Budget

    Science.gov (United States)

    Kuai, Le; Worden, John; Campbell, Elliott; Kulawik, Susan; Lee, Meemong; Montzka, Stephen; Berry, Joe; Baker, Ian; Denning, Scott; Kawa, Randy; Bian, Huisheng; Yung, Yuk

    2015-04-01

    Quantifying the carbonyl sulfide (OCS) surface fluxes contributes to the understanding of both sulfur cycle and carbon cycle. Although the major sources and sinks of OCS are well recognized, the uncertainties of individual types of the fluxes remain large. With the understanding of a large underestimate of ecosystem uptake, it suggests a large missing ocean source over tropical region to compensate the increased sink. However before AURA Tropospheric Emissions Spectrometer (TES) OCS data is released, no direct measurements have been taken to test this hypothesis. In this study, we performed a flux inversion to update the fluxes from TES OCS. Then we compared three experimental GEOS-Chem forward model runs driven by different fluxes based on TES inversion to HIPPO aircraft estimates in free troposphere and also to NOAA near surface observations. The TES data supports the hypothesis that a large source from tropical ocean is missing in the current OCS global budget and suggests that the source is even larger than that proposed in Berry et al., (2013). Consequently, it leads to a larger land uptake and increase the estimates of GPP. TES data also suggests the missing oceanic source is not symmetric about equator. It is strong and distributed further north of the equator (to 40°N) but weak and narrow south of the equator (to 20°S).

  2. Review of the toxicology of carbonyl sulfide, a new grain fumigant.

    Science.gov (United States)

    Bartholomaeus, Andrew R; Haritos, Victoria S

    2005-12-01

    Carbonyl sulfide (COS) is a new grain fumigant which has been developed to replace methyl bromide, being phased out due to its ozone depletion properties, and to supplement phosphine gas which is experiencing increased insect resistance. Treatment of commodities with COS, a highly effective fumigant, results in residues that are near or indistinguishable to natural background levels of this compound. COS is a naturally occurring gas, being the predominant sulfur moiety in the atmosphere, occurs naturally in food and is a normal by-product of mammalian aerobic metabolism. COS has low acute inhalational toxicity but with a steep dose response curve; COS is neither genotoxic nor a developmental toxicant but does reversibly impair male fertility. Prolonged, repeated exposure to COS is likely to present similar neurotoxicity hazards to that of the structurally and toxicologically related compound carbon disulfide. Although the occupational risks presented by COS as a fumigant of bulk grain are significant, these are, as they have been for a considerable time for phosphine and methyl bromide, manageable by good occupational safety practices. Consideration may need to be given to scrubbing of ventilated COS and its breakdown product hydrogen sulfide, at the completion of fumigation to minimise worker and bystander exposure. In terms of classical regulatory toxicology studies, the available database for COS is deficient in many aspects and registration in most jurisdictions will depend on sound scientific argument built upon the totality of the existing scientific data as there are strong arguments supporting the registration of this compound.

  3. 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.

  4. Microwave absorbing property of a hybrid absorbent with carbonyl irons coating on the graphite

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Yonggang, E-mail: xuyonggang221@163.com [Science and Technology on Electromagnetic Scattering Laboratory, Shanghai, 200438 (China); Yan, Zhenqiang; Zhang, Deyuan [Bionic and Micro/Nano/Bio Manufacturing Technology Research Center, School of Mechanical Engineering and Automation, Beihang University, Beijing 100191 (China)

    2015-11-30

    Graphical abstract: The absorbing property could be enhanced as the CIPs coated on the graphite. - Highlights: • Absorbers filled with CIPs coating on the graphite was fabricated. • The permittivity and permeability increased as CIPs coated. • The CIP materials enhanced the electromagnetic property. • The graphite coated CIPs were effective in 2–18 GHz. - Abstract: The hybrid absorbent filled with carbonyl iron particles (CIPs) coating on the graphite was prepared using a chemical vapor decomposition (CVD) process. 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. The results showed that α-Fe appeared in the super-lattice diffraction peaks in XRD graph. The composites added CIPs coating on the graphite had a higher permittivity and imaginary permeability due to the superior microwave dielectric loss and magnetic loss of the CIPs. The reflection loss (RL) result showed that composites filled with 5 vol% Fe-graphite had an excellent absorbing property in the 2–18 GHz, the minimum RL was −25.14 dB at 6 mm and −26.52 dB at 8 mm, respectively.

  5. From small molecules to polymeric catalysts in the oscillatory carbonylation reaction: multiple effects of adding HI.

    Science.gov (United States)

    Isakova, Anna; Murdoch, Billy J; Novakovic, Katarina

    2018-04-04

    The oscillatory palladium-catalysed carbonylation reaction opens new horizons for applications in smart materials due to the versatility of its conditions and substrates, as well as the adjustability of amplitude and period of pH oscillations. A variety of viable substrates have been demonstrated, including polymeric alkyne-terminated substrates. However, so far, there have not been any reports of polymer-based palladium catalysts in oscillatory mode. In this paper, we demonstrate pH oscillations in various systems, using commercially available palladium acetate, a triphenylphosphine palladium acetate complex and a polymer-bound palladium catalyst. While palladium acetate was able to generate oscillations under the conditions already established in our previous research on PdI2-catalysed oscillators, the other two catalysts needed the addition of HI to induce oscillations. HI forced an initial pH drop, bringing pH into the range where oscillations generally occur. Addition of HI had a significant effect on all catalysts, modifying the amplitude and period of oscillations, oscillation mode, as well as starting material conversion and product distribution.

  6. 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%.

  7. Enhanced Microwave Absorption Properties of Oriented Carbonyl Iron/Carbon Black Composite Induced by Shear Force

    Science.gov (United States)

    Min, Dandan; Zhou, Wancheng; Qing, Yuchang; Luo, Fa; Zhu, Dongmei

    2017-08-01

    Oriented carbonyl iron/carbon black (CI/CB) composite with enhanced microwave absorption properties was prepared by shear force which was applied to make the planes of CI parallel to each other. The effects of orientation, CB content and thickness on the microwave absorption properties were investigated. The measurement results showed that higher permeability and modest permittivity of the composite were obtained after CI orientation in a 2-18-GHz frequency range. The complex permittivity of the CI/CB composite increased with increasing CB content, which was mainly attributed to the interfacial polarization at the CI/resin/CB particle interfaces. The calculated microwave absorption properties indicated that the orientation plays an important role in decreasing the absorber thickness and broadening the absorption bandwidth. The oriented CI/CB composite containing 65 wt.% CI and 3.0 wt.% CB showed a wider absorption frequency range of 12.5 GHz from 5.5 GHz to 18 GHz with reflection loss (RL) below -5 dB at a thickness of 0.9 mm. This work offers a promising approach for the fabrication of microwave absorbing materials with thin thickness and an adjustable wider working frequency range.

  8. Relationships between carbonyl sulfide (COS) and CO2 during leaf gas exchange.

    Science.gov (United States)

    Stimler, Keren; Montzka, Stephen A; Berry, Joseph A; Rudich, Yinon; Yakir, Dan

    2010-06-01

    *Carbonyl sulfide (COS) exchange in C(3) leaves is linked to that of CO(2), providing a basis for the use of COS as a powerful tracer of gross CO(2) fluxes between plants and the atmosphere, a critical element in understanding the response of the land biosphere to global change. *Here, we carried out controlled leaf-scale gas-exchange measurements of COS and CO(2) in representative C(3) plants under a range of light intensities, relative humidities and temperatures, CO(2) and COS concentrations, and following abscisic acid treatments. *No 'respiration-like' emission of COS or detectable compensation point, and no cross-inhibition effects between COS and CO(2) were observed. The mean ratio of COS to CO(2) assimilation flux rates, A(s)/A(c), was c. 1.4 pmol micromol(-1) and the leaf relative uptake (assimilation normalized to ambient concentrations, (A(s)/A(c))(C(a)(c)/C(a)(s))) was 1.6-1.7 across species and conditions, with significant deviations under certain conditions. Stomatal conductance was enhanced by increasing COS, which was possibly mediated by hydrogen sulfide (H(2)S) produced from COS hydrolysis, and a correlation was observed between A(s) and leaf discrimination against C(18)OO. *The results provide systematic and quantitative information necessary for the use of COS in photosynthesis and carbon-cycle research on the physiological to global scales.

  9. The flux of carbonyl sulfide and carbon disulfide between the atmosphere and a spruce forest

    Directory of Open Access Journals (Sweden)

    X. Xu

    2002-01-01

    Full Text Available Turbulent fluxes of carbonyl sulfide (COS and carbon disulfide (CS2 were measured over a spruce forest in Central Germany using the relaxed eddy accumulation (REA technique. A REA sampler was developed and validated using simultaneous measurements of CO2 fluxes by REA and by eddy correlation. REA measurements were conducted during six campaigns covering spring, summer, and fall between 1997 and 1999. Both uptake and emission of COS and CS2 by the forest were observed, with deposition occurring mainly during the sunlit period and emission mainly during the dark period. On the average, however, the forest acts as a sink for both gases. The average fluxes for COS and CS2 are  -93 ± 11.7 pmol m-2 s-1 and  -18 ± 7.6 pmol m-2 s-1, respectively. The fluxes of both gases appear to be correlated to photosynthetically active radiation and to the CO2 and chem{H_2O} fluxes, supporting the idea that the air-vegetation exchange of both gases is controlled by stomata. An uptake ratio COS/CO2 of 10 ± 1.7 pmol m mol-1 has been derived from the regression line for the correlation between the COS and CO2 fluxes. This uptake ratio, if representative for the global terrestrial net primary production, would correspond to a sink of 2.3 ± 0.5 Tg COS yr-1.

  10. Enhanced microwave absorbing properties of carbonyl iron-doped Ag/ordered mesoporous carbon nanocomposites

    International Nuclear Information System (INIS)

    Wu Hongjing; Wang Liuding; Wang Yiming; Guo Shaoli; Shen Zhongyuan

    2012-01-01

    Highlights: ► Ag/OMC-CI paraffin wax composites were successfully prepared. ► Reflection loss value below −10 dB at 12 GHz was obtained. ► Ag/OMC-CI showed excellent microwave absorption with respect to OMC-CI and Ag/OMC. ► This could be attributed to the enhancement of interfacial polarization. - Abstract: Microwave absorbing materials carbonyl iron (CI)-doped Ag/ordered mesoporous carbon (OMC) paraffin wax composites were prepared by colloidal deposition and impregnation methods, and their electromagnetic and microwave absorbing properties were investigated in the frequency ranging from 2 to 18 GHz. The microstructures and chemical compositions of the Ag/OMC and Ag/OMC-CI paraffin wax composites were characterized by TEM, XRD, XPS, SEM and EDS, respectively. The complex permittivity of the paraffin wax composites show dual resonance behavior, resulting from the multi-interfaces among Ag nanoparticles, OMC nanorods, CI and paraffin wax. The magnetic loss was mainly caused by natural resonance and eddy current loss, respectively. The minimum reflection loss (RL) value of Ag/OMC-CI was below −10 dB at 12 GHz, which were superior to those of OMC-CI and Ag/OMC. This phenomenon is attributed to the enhancement of dielectric polarization and magnetic loss.

  11. Synthesis, characterization and magnetorheological properties of carbonyl iron suspension with superparamagnetic nanoparticles as an additive

    International Nuclear Information System (INIS)

    Leong, Siti Asma’ Nikmat; Mohd Samin, Pakharuddin; Idris, Ani; Rahman, Azura Hanis A; Mazlan, Saiful Amri

    2016-01-01

    Magnetorheological (MR) fluids are suspensions of micron-sized particles dispersed in carrier fluid. Due to high density magnetic particles, MR fluids are facing the problem with the instability of the suspension caused by high settling rate. Recently, researches have been conducted on the advantages of using the mixture of magnetic nanoparticles and microparticles, called bidisperse MR fluids. However, even though the sedimentation stability is improved, there is a reduction in dynamic yield stress when the nanoparticle is introduced. In this work, the investigation of magnetic iron nanoparticles (γ-Fe 2 O 3 ) as an additive to magnetic carbonyl iron (CI) suspension has been proposed so as to improve the sedimentation stability and redispersibility, but at the same time enhance the MR performance. The results indicated that the addition of nanoparticles reduced the sedimentation rate, improved redispersibility and enhanced the rheological performance of MR fluids as the particle fill the voids between the microparticles and strengthened the interparticle chains contributing to well-arranged particle structures. (paper)

  12. 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.

  13. Comparison of extraction techniques and mass spectrometric ionization modes in the analysis of wine volatile carbonyls

    International Nuclear Information System (INIS)

    Zapata, Julian; Mateo-Vivaracho, Laura; Cacho, Juan; Ferreira, Vicente

    2010-01-01

    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 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%.

  14. Ester Carbonyl Vibration as a Sensitive Probe of Protein Local Electric Field

    Science.gov (United States)

    Pazos, Ileana M.; Ghosh, Ayanjeet; Tucker, Matthew J.; Gai, Feng

    2014-01-01

    The ability to quantify the local electrostatic environment of proteins and protein/peptide assemblies is key to yielding a microscopic understanding of many biological interactions and processes. Herein, we show that the ester carbonyl stretching vibration of two non-natural amino acids, L-aspartic acid 4-methyl ester and L-glutamic acid 5-methyl ester, is a convenient and sensitive probe in this regard since its frequency correlates linearly with the local electrostatic field for both hydrogen-bonding and non-hydrogen-bonding environments. We expect that the resultant frequency-electric field map will find use in various applications. In addition, we show that, when situated in a non-hydrogen bonding environment, this probe can also be used to measure the local dielectric constant (ε). For example, applying it to amyloid fibrils formed by Aβ16-22 reveals that the interior of such β-sheet assemblies has a ε of ~5.6. PMID:24788907

  15. Ester carbonyl vibration as a sensitive probe of protein local electric field.

    Science.gov (United States)

    Pazos, Ileana M; Ghosh, Ayanjeet; Tucker, Matthew J; Gai, Feng

    2014-06-10

    The ability to quantify the local electrostatic environment of proteins and protein/peptide assemblies is key to gaining a microscopic understanding of many biological interactions and processes. Herein, we show that the ester carbonyl stretching vibration of two non-natural amino acids, L-aspartic acid 4-methyl ester and L-glutamic acid 5-methyl ester, is a convenient and sensitive probe in this regard, since its frequency correlates linearly with the local electrostatic field for both hydrogen-bonding and non-hydrogen-bonding environments. We expect that the resultant frequency-electric-field map will find use in various applications. Furthermore, we show that, when situated in a non-hydrogen-bonding environment, this probe can also be used to measure the local dielectric constant (ε). For example, its application to amyloid fibrils formed by Aβ(16-22) revealed that the interior of such β-sheet assemblies has an ε value of approximately 5.6. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Emissions of polyciclic aromatic hydrocarbons and polyciclic carbonyl biphenils from electric arc furnaces

    Directory of Open Access Journals (Sweden)

    P. Gomes, J. F.

    2008-06-01

    Full Text Available This paper describes work done in order to determine the emissions of highly toxic organic micropollutants from electric arc furnaces used in the production of carbon steel from scrap. The study will be allowing to derive relationships between the levels of airborne micropollutants and the operational parameters of the production process so that an abatement of pollution could be achieved. By using the European standard method CEN 1948 for dioxin like compounds sampling and measurement, it was possible to determine the characteristic fingerprint of micropollutants such as polyciclic aromatic hydrocarbons (PAHs and polycyclic carbonyl biphenils (PCBs emitted by this particular stationary source.

    Este artículo contiene resultados del trabajo ejecutado para estudiar la determinación de las emisiones de los micropolutantes orgánicos muy tóxicos que se emiten por los hornos eléctricos de arco utilizados en la producción de acero. Este estudio inicial va a permitir relacionar las concentraciones de polutantes emitidos a la atmósfera con las condiciones de operación del horno eléctrico de arco. Utilizando el método normalizado CEN 1948 para captación y análisis de muestras de compuestos análogos a las dioxinas ha sido posible determinar el perfil característico de los micropolutantes tales como PAHs y PCBs emitidos por esta fuente.

  17. 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.

  18. Seasonal carbon fluxes for an old-growth temperate forest inferred from carbonyl sulphide

    Science.gov (United States)

    Rastogi, Bharat; Jiang, Yueyang; Berkelhammer, Maxwell; Wharton, Sonia; Noone, David; Still, Christopher

    2017-04-01

    Characterizing and quantifying the processes that control terrestrial ecosystem exchanges of carbon and water are critical for understanding how forested ecosystems respond to a changing climate. A small but increasing number of studies has identified carbonyl sulfide (OCS) as a potential tracer of canopy photosynthesis and stomatal function. Here we present seasonal fluxes of OCS from a 60m tall old-growth temperate forest. An off-axis integrated cavity output spectroscopy analyzer (Los Gatos Research Inc.) was deployed at the Wind River Experimental Forest in Washington (45.8205°N, 121.9519°W) in 2014 and 2015. GPP (Gross Primary Production) is inferred from OCS fluxes and compared with estimates derived from measurements of NEE (Net Ecosystem Exchange) from eddy flux data as well as GPP predictions using a process based model. Our findings seek to resolve scientific questions regarding ecosystem carbon exchange from tall old growth forests, which have a complicated vertical leaf area structure, high above ground biomass and amount and aerial cover of epiphytic vegetation. Estimates of canopy conductance calculated using tower flux data are also combined with measurements of stable isotopologues of CO2 to infer emergent ecosystem properties such as canopy ci/ca and water use efficiency.

  19. Explicit solvation effects on the conventional resonance model for protonated imine, carbonyl, and thiocarbonyl compounds

    Science.gov (United States)

    Braïda, Benoît; Hiberty, Philippe C.

    The conventional resonance model describes carbonyls, imines, and thiocarbonyls, as well as their protonated analogues, by a superposition of two valence bond structures. Ab initio Breathing-Orbital Valence Bond computations on formaldehyde, formimine, and thioformaldehyde as well as their protonated forms are performed to directly quantify the weights of their valence bond structures. Following a gas phase study that showed that protonation significantly increases the weight of the carbenic form relative to the π polar-covalent bonded form (Braida, et al., Org Lett, 2008, 10, 1951), the present work estimates the influence of a polar protic solvent, modelized by water. Solvation effects are modeled explicitly by performing VB calculations on supersystems made of the organic substrate surrounded by four water molecules. It is shown that protonation significantly increases the polarity of the C=X π bond in all three cases (X = O, NH, S) in solvated phase, in line with the known acceleration of nucleophilic additions on these compounds by acidic catalysis. Moreover, solvation significantly enhances the polarity of the C=X π bond in the protonated forms of formaldehyde and thioformaldehyde, but has practically no effect on the C=X π bond of protonated formimine.

  20. An oxidoreductase from 'Alphonso' mango catalyzing biosynthesis of furaneol and reduction of reactive carbonyls.

    Science.gov (United States)

    Kulkarni, Ram; Chidley, Hemangi; Deshpande, Ashish; Schmidt, Axel; Pujari, Keshav; Giri, Ashok; Gershenzon, Jonathan; Gupta, Vidya

    2013-01-01

    Two furanones, furaneol (4-hydroxy-2,5-dimethyl-3(2H)-furanone) and mesifuran (2,5-dimethyl-4-methoxy-3(2H)-furanone), are important constituents of flavor of the Alphonso cultivar of mango (Mangifera indica). To get insights into the biosynthesis of these furanones, we isolated an enone oxidoreductase gene from the Alphonso mango. It has high sequence similarity to an alkenal/one oxidoreductase from cucumber (79% identity) and enone oxidoreductases from tomato (73% identity) and strawberry (72% identity). The complete open reading frame was expressed in E. coli and the (his)6-tagged recombinant protein was purified by affinity chromatography. The purified protein assayed with NADH as a reducing agent converted D-fructose-1,6-diphosphate into furaneol, the immediate precursor of mesifuran. The enzyme was also able to convert two highly reactive carbonyls, 3-buten-2-one and 1-penten-3-one, produced by lipid peroxidation in plants, into their saturated derivatives. Expression profiling in various ripening stages of Alphonso fruits depicted an expression maxima at 10 days after harvest stage, shortly before the appearance of the maximum amount of furanones (completely ripe stage, 15 days after harvest). Although no furanones were detected at the 0 day after harvest stage, significant expression of this gene was detected in the fruits at this stage. Overall, the results suggest that this oxidoreductase plays important roles in Alphonso mango fruits.

  1. The Field-Dependent Rheological Properties of Magnetorheological Grease Based on Carbonyl-Iron-Particles

    Science.gov (United States)

    Mohamad, N.; Mazlan, S. A.; Ubaidillah; Choi, Seung-Bok; Nordin, M. F. M.

    2016-09-01

    This paper presents dynamic viscoelastic properties of magnetorheological (MR) grease under variation of magnetic fields and magnetic particle fractions. The tests to discern the field-dependent properties are undertaken using both rotational and oscillatory shear rheometers. As a first step, the MR grease is developed by dispersing the carbonyl iron (CI) particles into grease medium with a mechanical stirrer. Experimental data are obtained by changing the magnetic field from 0 to 0.7 T at room temperature of 25 °C. It is found that a strong Payne effect limits the linear viscoelastic region of MR grease at strains above 0.1%. The results exhibit a high dynamic yield stress which is equivalent to Bingham plastic rheological model, and show relatively good MR effect at high shear rate of 2000 s-1. In addition, high dispersion of the magnetic particles and good thermal properties are proven. The results presented in this work directly indicate that MR grease is a smart material candidate that could be widely applicable to various fields including vibration control.

  2. The Behaviour of Protein Carbonyls in Newborns with Birth Respiratory Distress and Asphyxia

    Directory of Open Access Journals (Sweden)

    Gabriela ZAHARIE

    2009-12-01

    Full Text Available Objective: A prospective study was carried out in premature newborns with respiratory distress syndrome (RDS and asphyxia at birth in order to identify and analyze the effects of RDS on proteins. Material and Methods: Protein peroxidation was studied using the Reznick spectrophotometric method. The study group included 14 premature newborns with respiratory distress and asphyxia at birth. The control group included 13 newborns that were born on term, eutrophic and healthy. The determinations were carried out using venous blood. Statistical data analyses were performed using Statistica software. The comparisons between groups (study and controls were performed by applying parametric and non-parametric tests according with the type of distribution. Results: Statistically significant correlations were found between the value of protein carbonyls (PC and the weight of premature newborns in the case group (p < 0.05, as well as between the PC value and the presence of respiratory distress due to surfactant deficiency in the study group. The average PC value in the study group was higher in the third day as compared with the first day. The PC value was significantly higher in the control group as compared with study group. Conclusion: The results of our study revealed that the respiratory distress in the premature newborn and oxygen therapy stimulate the peroxidation of proteins.

  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. Hafnium trifluoromethanesulfonate (hafnium triflate) as a highly efficient catalyst for chemoselective thioacetalization and transthioacetalization of carbonyl compounds.

    Science.gov (United States)

    Wu, Yan-Chao; Zhu, Jieping

    2008-12-05

    A range of carbonyl compounds including aliphatic and aromatic aldehydes and ketones were converted to the corresponding thioacetals in high yields in the presence of a catalytic amount of hafnium trifluoromethanesulfonate (0.1 mol %, room temperature). The mild conditions tolerated various sensitive functional and protecting groups and were racemization-free when applied to alpha-aminoaldehydes. Transacetalization and chemoselective thioacetalization of aromatic aldehydes in the presence of aliphatic aldehydes and ketones were also documented.

  5. Amberlyst-15: An Efficient and reusable heterogeneous catalyst for the synthesis of β-amino carbonyl compounds

    Directory of Open Access Journals (Sweden)

    Pathakota Venkata Ramana

    2015-12-01

    Full Text Available A simple and efficient method has been developed for the synthesis of β-amino carbonyl compounds from aromatic ketones, aldehydes and amines by Mannich reaction in the presence of amberlyst-15 as a reusable heterogeneous catalyst at room temperature under solvent-free conditions. The noteworthy advantages of the present method are short reaction times, good product yields, simple procedures and use of non-toxic catalyst.

  6. Bio-orthogonal "click-and-release" donation of caged carbonyl sulfide (COS) and hydrogen sulfide (H2S).

    Science.gov (United States)

    Steiger, Andrea K; Yang, Yang; Royzen, Maksim; Pluth, Michael D

    2017-01-24

    Hydrogen sulfide (H 2 S) is an important biomolecule with high therapeutic potential. Here we leverage the inverse-electron demand Diels-Alder (IEDDA) click reaction between a thiocarbamate-functionalized trans-cyclooctene and a tetrazine to deliver carbonyl sulfide (COS), which is quickly converted to H 2 S by the uniquitous enzyme carbonic anhydrase (CA), thus providing a new strategy for bio-orthogonal COS/H 2 S donation.

  7. Increased nitration and carbonylation of proteins in MRL +/+ mice exposed to trichloroethene: Potential role of protein oxidation in autoimmunity

    International Nuclear Information System (INIS)

    Wang Gangduo; Wang Jianling; Ma Huaxian; Khan, M. Firoze

    2009-01-01

    Even though reactive oxygen and nitrogen species (RONS) are implicated as mediators of autoimmune diseases (ADs), little is known about contribution of protein oxidation (carbonylation and nitration) in the pathogenesis of such diseases. The focus of this study was, therefore, to establish a link between protein oxidation and induction and/or exacerbation of autoimmunity. To achieve this, female MRL +/+ mice were treated with trichloroethene (TCE), an environmental contaminant known to induce autoimmune response, for 6 or 12 weeks (10 mmol/kg, i.p., every 4 th day). TCE treatment resulted in significantly increased formation of nitrotyrosine (NT) and induction of iNOS in the serum at both 6 and 12 weeks of treatment, but the response was greater at 12 weeks. Likewise, TCE treatment led to greater NT formation, and iNOS protein and mRNA expression in the livers and kidneys. Moreover, TCE treatment also caused significant increases (∼3 fold) in serum protein carbonyls (a marker of protein oxidation) at both 6 and 12 weeks. Significantly increased protein carbonyls were also observed in the livers and kidneys (2.1 and 1.3 fold, respectively) at 6 weeks, and to a greater extent at 12 weeks (3.5 and 2.1 fold, respectively) following TCE treatment. The increases in TCE-induced protein oxidation (carbonylation and nitration) were associated with significant increases in Th1 specific cytokine (IL-2, IFN-γ) release into splenocyte cultures. These results suggest an association between protein oxidation and induction/exacerbation of autoimmune response. The results present a potential mechanism by which oxidatively modified proteins could contribute to TCE-induced autoimmune response and necessitates further investigations for clearly establishing the role of protein oxidation in the pathogenesis of ADs.

  8. Synthesis and magnetorheological characteristics of ribbon-like, polypyrrole-coated carbonyl iron suspensions under oscillatory shear

    Czech Academy of Sciences Publication Activity Database

    Mrlik, M.; Sedlačík, M.; Pavlinek, V.; Bažant, P.; Sáha, P.; Peer, Petra; Filip, Petr

    2013-01-01

    Roč. 128, č. 5 (2013), s. 2977-2982 ISSN 0021-8995 Grant - others:GA MŠk(CZ) ED2.1.00/03.0111; UTB Zlín(CZ) IGA/1/FT/11/D Institutional support: RVO:67985874 Keywords : carbonyl iron * core - shell * magnetorheological fluid * polypyrrole * viscoelasticity * ribbon-like particles Subject RIV: BK - Fluid Dynamics Impact factor: 1.640, year: 2013

  9. Synthesis and characterization of an iron complex bearing a hemilabile NNN-pincer for catalytic hydrosilylation of organic carbonyl compounds.

    Science.gov (United States)

    Lin, Hsiu-Jung; Lutz, Sean; O'Kane, Catherine; Zeller, Matthias; Chen, Chun-Hsing; Al Assil, Talal; Lee, Wei-Tsung

    2018-03-06

    A low-coordinate iron(ii) complex (Cz tBu (Pz tBu ) 2 )Fe[N(SiMe 3 ) 2 ], 1 bearing an NNN-pincer ligand was prepared and fully characterized. Intramolecular C-H activation on the 5-position of a pyrazole at elevated temperatures was observed. Complex 1 was found to be an efficient and chemoselective pre-catalyst for the hydrosilylation of organo carbonyl substrates.

  10. Cholesteryl-coated carbonyl iron particles with improved anti-corrosion stability and their viscoelastic behaviour under magnetic field

    Czech Academy of Sciences Publication Activity Database

    Mrlik, M.; Ilčíková, M.; Sedlačík, M.; Mosnáček, J.; Peer, Petra; Filip, Petr

    2014-01-01

    Roč. 292, č. 9 (2014), s. 2137-2143 ISSN 0303-402X R&D Projects: GA ČR(CZ) GP14-32114P Grant - others:GA MŠk(CZ) ED2.1.00/03.0111 Institutional support: RVO:67985874 Keywords : carbonyl iron * cholesteryl chloroformate * silicone oil suspensions * viscoelasticity * magnetorheology Subject RIV: BK - Fluid Dynamics Impact factor: 1.865, year: 2014

  11. Synthesis and magnetorheological characteristics of ribbon-like, polypyrrole-coated carbonyl iron suspensions under oscillatory shear

    Czech Academy of Sciences Publication Activity Database

    Mrlik, M.; Sedlačík, M.; Pavlinek, V.; Bažant, P.; Sáha, P.; Peer, Petra; Filip, Petr

    2013-01-01

    Roč. 128, č. 5 (2013), s. 2977-2982 ISSN 0021-8995 Grant - others:GA MŠk(CZ) ED2.1.00/03.0111; UTB Zlín(CZ) IGA/1/FT/11/D Institutional support: RVO:67985874 Keywords : carbonyl iron * core-shell * magnetorheological fluid * polypyrrole * viscoelasticity * ribbon-like particles Subject RIV: BK - Fluid Dynamics Impact factor: 1.640, year: 2013

  12. Correlation of Plasma Protein Carbonyls and C-Reactive Protein with GOLD Stage Progression in COPD Patients

    OpenAIRE

    Torres-Ramos, Yessica D; Garc?a-Guillen, Mar?a L; Olivares-Corichi, Ivonne M; Hicks, J. J

    2009-01-01

    Oxidative stress plays an important role in the pathogenesis of chronic obstructive pulmonary disease (COPD). To investigate the correlation between the progression of COPD and plasma biomarkers of chronic inflammation and oxidative injury, blood samples were obtained from healthy volunteers (HV, n = 14) and stabilized COPD patients. The patients were divided into three groups according to their GOLD stage (II, n = 34; III, n = 18; IV, n = 20). C-reactive protein (CRP), protein carbonyls (PC)...

  13. Binding of the 9-O-N-aryl/arylalkyl amino carbonyl methyl substituted berberine analogs to tRNA(phe..

    Directory of Open Access Journals (Sweden)

    Anirban Basu

    Full Text Available BACKGROUND: Three new analogs of berberine with aryl/ arylalkyl amino carbonyl methyl substituent at the 9-position of the isoquinoline chromophore along with berberrubine were studied for their binding to tRNA(phe by wide variety of biophysical techniques like spectrophotometry, spectrofluorimetry, circular dichroism, thermal melting, viscosity and isothermal titration calorimetry. METHODOLOGY/ PRINCIPAL FINDINGS: Scatchard binding isotherms revealed that the cooperative binding mode of berberine was propagated in the analogs also. Thermal melting studies showed that all the 9-O-N-aryl/arylalkyl amino carbonyl methyl substituted berberine analogs stabilized the tRNA(phe more in comparison to berberine. Circular dichroism studies showed that these analogs perturbed the structure of tRNA(phe more in comparison to berberine. Ferrocyanide quenching studies and viscosity results proved the intercalative binding mode of these analogs into the helical organization of tRNA(phe. The binding was entropy driven for the analogs in sharp contrast to the enthalpy driven binding of berberine. The introduction of the aryl/arylalkyl amino carbonyl methyl substituent at the 9-position thus switched the enthalpy driven binding of berberine to entropy dominated binding. Salt and temperature dependent calorimetric studies established the involvement of multiple weak noncovalent interactions in the binding process. CONCLUSIONS/ SIGNIFICANCE: The results showed that 9-O-N-aryl/arylalkyl amino carbonyl methyl substituted berberine analogs exhibited almost ten folds higher binding affinity to tRNA(phe compared to berberine whereas the binding of berberrubine was dramatically reduced by about twenty fold in comparison to berberine. The spacer length of the substitution at the 9-position of the isoquinoline chromophore appears to be critical in modulating the binding affinities towards tRNA(phe.

  14. Carbon-based Solid Acid Catalyzed One-pot Mannich Reaction: A Facile Synthesis of β-Amino Carbonyl Compounds

    Energy Technology Data Exchange (ETDEWEB)

    Davoodnia, Abolghasem; Tavakoli-Nishaburi, Afsaneh; Tavakoli-Hoseini, Niloofar [Islamic Azad University, Mashhad (Iran, Islamic Republic of)

    2011-02-15

    A simple and efficient method for the synthesis of β-amino carbonyl compounds by one-pot three-component Mannich reaction of acetophenone, aromatic aldehydes and aromatic amines using a carbon-based solid acid (CBSA), as an effective and reusable catalyst, is described. The present methodology offers several advantages such as simple procedure with an easy work-up, shorter reaction times, and high yields.

  15. Silicone metalization

    Energy Technology Data Exchange (ETDEWEB)

    Maghribi, Mariam N. (Livermore, CA); Krulevitch, Peter (Pleasanton, CA); Hamilton, Julie (Tracy, CA)

    2008-12-09

    A system for providing metal features on silicone comprising providing a silicone layer on a matrix and providing a metal layer on the silicone layer. An electronic apparatus can be produced by the system. The electronic apparatus comprises a silicone body and metal features on the silicone body that provide an electronic device.

  16. General and Efficient a-Oxygenation of Carbonyl Compounds by TEMPO Induced by Single-Electron-Transfer Oxidation of Their Enolates

    Czech Academy of Sciences Publication Activity Database

    Dinca, E.; Hartmann, P.; Smrček, Jakub; Dix, I.; Jones, P. G.; Jahn, Ullrich

    -, č. 24 (2012), s. 4461-4482 ISSN 1434-193X Institutional support: RVO:61388963 Keywords : carbonyl compounds * oxidation * radicals * electron transfer * enolates Subject RIV: CC - Organic Chemistry Impact factor: 3.344, year: 2012

  17. Platinum catalysed 3,4- and 1,4-diboration of alpha,beta-unsaturated carbonyl compounds using bis-pinacolatodiboron.

    Science.gov (United States)

    Bell, Nathan J; Cox, Andrew J; Cameron, Neil R; Evans, John S O; Marder, Todd B; Duin, Marcel A; Elsevier, Cornelis J; Baucherel, Xavier; Tulloch, Arran A D; Tooze, Robert P

    2004-08-21

    Bis-pinacolatodiboron reacts with [small alpha],[small beta]-unsaturated carbonyl compounds to give 1,4- and unprecedented 3,4-additions in the presence of a second generation Pt(0) catalyst at ambient temperature.

  18. Determination of protein carbonyls in plasma, cell extracts, tissue homogenates, isolated proteins: Focus on sample preparation and derivatization conditions.

    Science.gov (United States)

    Weber, Daniela; Davies, Michael J; Grune, Tilman

    2015-08-01

    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 different reactive oxygen species in blood, tissues and cells. Sample preparation and stabilization are key steps in the accurate quantification of oxidation-related products and examination of physiological/pathological processes. This review therefore focuses on the sample preparation processes used in the most relevant methods to detect protein carbonyls after derivatization with 2,4-dinitrophenylhydrazine with an emphasis on measurement in plasma, cells, organ homogenates, isolated proteins and organelles. Sample preparation, derivatization conditions and protein handling are presented for the spectrophotometric and HPLC method as well as for immunoblotting and ELISA. An extensive overview covering these methods in previously published articles is given for researchers who plan to measure protein carbonyls in different samples. © 2015 Published by Elsevier Ltd.

  19. Effects of low concentration biodiesel blends application on modern passenger cars. Part 2: Impact on carbonyl compound emissions

    International Nuclear Information System (INIS)

    Fontaras, Georgios; Karavalakis, Georgios; Kousoulidou, Marina; Ntziachristos, Leonidas; Bakeas, Evangelos; Stournas, Stamoulis; Samaras, Zissis

    2010-01-01

    Today in most European member states diesel contains up to 5% vol biodiesel. Since blending is expected to increase to 10% vol, the question arises, how this higher mixing ratio will affect tailpipe emissions particularly those linked to adverse health effects. This paper focuses on the impact of biodiesel on carbonyl compound emissions, attempting also to identify possible relationship between biodiesel feedstock and emissions. The blends were produced from five different feedstocks, commonly used in Europe. Measurements were conducted on a Euro 3 common-rail passenger car over various driving cycles. Results indicate that generally the use of biodiesel at low concentrations has a minor effect on carbonyl compound emissions. However, certain biodiesels resulted in significant increases while others led to decreases. Biodiesels associated with increases were those derived from rapeseed oil (approx. 200%) and palm oil (approx. 180%), with the highest average increases observed at formaldehyde and acroleine/acetone. - Biodiesel application, may increase the levels of certain pollutants such as carbonyl compounds which are associated with both environmental and health risks.

  20. Quantifying millisecond time-scale exchange in proteins by CPMG relaxation dispersion NMR spectroscopy of side-chain carbonyl groups

    Energy Technology Data Exchange (ETDEWEB)

    Hansen, Alexandar L.; Kay, Lewis E., E-mail: kay@pound.med.utoronto.ca [University of Toronto, Departments of Molecular Genetics, Biochemistry and Chemistry (Canada)

    2011-08-15

    A new pulse sequence is presented for the measurement of relaxation dispersion profiles quantifying millisecond time-scale exchange dynamics of side-chain carbonyl groups in uniformly {sup 13}C labeled proteins. The methodology has been tested using the 87-residue colicin E7 immunity protein, Im7, which is known to fold via a partially structured low populated intermediate that interconverts with the folded, ground state on the millisecond time-scale. Comparison of exchange parameters extracted for this folding 'reaction' using the present methodology with those obtained from more 'traditional' {sup 15}N and backbone carbonyl probes establishes the utility of the approach. The extracted excited state side-chain carbonyl chemical shifts indicate that the Asx/Glx side-chains are predominantly unstructured in the Im7 folding intermediate. However, several crucial salt-bridges that exist in the native structure appear to be already formed in the excited state, either in part or in full. This information, in concert with that obtained from existing backbone and side-chain methyl relaxation dispersion experiments, will ultimately facilitate a detailed description of the structure of the Im7 folding intermediate.

  1. Carbonyl Activation by Borane Lewis Acid Complexation: Transition States of H2 Splitting at the Activated Carbonyl Carbon Atom in a Lewis Basic Solvent and the Proton-Transfer Dynamics of the Boroalkoxide Intermediate.

    Science.gov (United States)

    Heshmat, Mojgan; Privalov, Timofei

    2017-07-06

    By using transition-state (TS) calculations, we examined how Lewis acid (LA) complexation activates carbonyl compounds in the context of hydrogenation of carbonyl compounds by H 2 in Lewis basic (ethereal) solvents containing borane LAs of the type (C 6 F 5 ) 3 B. According to our calculations, LA complexation does not activate a ketone sufficiently enough for the direct addition of H 2 to the O=C unsaturated bond; but, calculations indicate a possibly facile heterolytic cleavage of H 2 at the activated and thus sufficiently Lewis acidic carbonyl carbon atom with the assistance of the Lewis basic solvent (i.e., 1,4-dioxane or THF). For the solvent-assisted H 2 splitting at the carbonyl carbon atom of (C 6 F 5 ) 3 B adducts with different ketones, a number of TSs are computed and the obtained results are related to insights from experiment. By using the Born-Oppenheimer molecular dynamics with the DFT for electronic structure calculations, the evolution of the (C 6 F 5 ) 3 B-alkoxide ionic intermediate and the proton transfer to the alkoxide oxygen atom were investigated. The results indicate a plausible hydrogenation mechanism with a LA, that is, (C 6 F 5 ) 3 B, as a catalyst, namely, 1) the step of H 2 cleavage that involves a Lewis basic solvent molecule plus the carbonyl carbon atom of thermodynamically stable and experimentally identifiable (C 6 F 5 ) 3 B-ketone adducts in which (C 6 F 5 ) 3 B is the "Lewis acid promoter", 2) the transfer of the solvent-bound proton to the oxygen atom of the (C 6 F 5 ) 3 B-alkoxide intermediate giving the (C 6 F 5 ) 3 B-alcohol adduct, and 3) the S N 2-style displacement of the alcohol by a ketone or a Lewis basic solvent molecule. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. 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.

  3. Metabolic mechanisms of methanol/formaldehyde in isolated rat hepatocytes: carbonyl-metabolizing enzymes versus oxidative stress.

    Science.gov (United States)

    MacAllister, Stephanie L; Choi, Joanna; Dedina, Liana; O'Brien, Peter J

    2011-05-30

    Methanol (CH(3)OH), a common industrial solvent, is metabolized to toxic compounds by several enzymatic as well as free radical pathways. Identifying which process best enhances or prevents CH(3)OH-induced cytotoxicity could provide insight into the molecular basis for acute CH(3)OH-induced hepatoxicity. Metabolic pathways studied include those found in 1) an isolated hepatocyte system and 2) cell-free systems. Accelerated Cytotoxicity Mechanism Screening (ACMS) techniques demonstrated that CH(3)OH had little toxicity towards rat hepatocytes in 95% O(2), even at 2M concentration, whereas 50 mM was the estimated LC(50) (2h) in 1% O(2), estimated to be the physiological concentration in the centrilobular region of the liver and also the target region for ethanol toxicity. Cytotoxicity was attributed to increased NADH levels caused by CH(3)OH metabolism, catalyzed by ADH1, resulting in reductive stress, which reduced and released ferrous iron from Ferritin causing oxygen activation. A similar cytotoxic mechanism at 1% O(2) was previous found for ethanol. With 95% O(2), the addition of Fe(II)/H(2)O(2), at non-toxic concentrations were the most effective agents for increasing hepatocyte toxicity induced by 1M CH(3)OH, with a 3-fold increase in cytotoxicity and ROS formation. Iron chelators, desferoxamine, and NADH oxidizers and ATP generators, e.g. fructose, also protected hepatocytes and decreased ROS formation and cytotoxicity. Hepatocyte protein carbonylation induced by formaldehyde (HCHO) formation was also increased about 4-fold, when CH(3)OH was oxidized by the Fenton-like system, Fe(II)/H(2)O(2), and correlated with increased cytotoxicity. In a cell-free bovine serum albumin system, Fe(II)/H(2)O(2) also increased CH(3)OH oxidation as well as HCHO protein carbonylation. Nontoxic ferrous iron and a H(2)O(2) generating system increased HCHO-induced cytotoxicity and hepatocyte protein carbonylation. In addition, HCHO cytotoxicity was markedly increased by ADH1 and

  4. Metal Ion Selectivity of Kojate Complexes: A Theoretical Study

    Directory of Open Access Journals (Sweden)

    Sarita Singh

    2013-01-01

    Full Text Available Density functional calculations have been performed on four-coordinate kojate complexes of selected divalent metal ions in order to determine the affinity of the metal ions for the kojate ion. The complexation reactions are characterized by high energies, showing that they are highly exothermic. It is found that Ni(II exhibits the highest affinity for the kojate ion, and this is attributed to the largest amount of charge transfer from the ligand to the metal ion. The Ni(II complex has distorted square planar structure. The HOMOs and LUMOs of the complexes are also discussed. All complexes display a strong band at ~1500 cm−1 corresponding to the stretching frequency of the weakened carbonyl bond. Comparison of the complexation energies for the two steps shows that most of the complexation energy is realized in the first step. The energy released in the second step is about one-third that of the first step.

  5. High winter ozone pollution from carbonyl photolysis in an oil and gas basin

    Science.gov (United States)

    Edwards, Peter M.; Brown, Steven S.; Roberts, James M.; Ahmadov, Ravan; Banta, Robert M.; Degouw, Joost A.; Dubé, William P.; Field, Robert A.; Flynn, James H.; Gilman, Jessica B.; Graus, Martin; Helmig, Detlev; Koss, Abigail; Langford, Andrew O.; Lefer, Barry L.; Lerner, Brian M.; Li, Rui; Li, Shao-Meng; McKeen, Stuart A.; Murphy, Shane M.; Parrish, David D.; Senff, Christoph J.; Soltis, Jeffrey; Stutz, Jochen; Sweeney, Colm; Thompson, Chelsea R.; Trainer, Michael K.; Tsai, Catalina; Veres, Patrick R.; Washenfelder, Rebecca A.; Warneke, Carsten; Wild, Robert J.; Young, Cora J.; Yuan, Bin; Zamora, Robert

    2014-10-01

    The United States is now experiencing the most rapid expansion in oil and gas production in four decades, owing in large part to implementation of new extraction technologies such as horizontal drilling combined with hydraulic fracturing. The environmental impacts of this development, from its effect on water quality to the influence of increased methane leakage on climate, have been a matter of intense debate. Air quality impacts are associated with emissions of nitrogen oxides (NOx = NO + NO2) and volatile organic compounds (VOCs), whose photochemistry leads to production of ozone, a secondary pollutant with negative health effects. Recent observations in oil- and gas-producing basins in the western United States have identified ozone mixing ratios well in excess of present air quality standards, but only during winter. Understanding winter ozone production in these regions is scientifically challenging. It occurs during cold periods of snow cover when meteorological inversions concentrate air pollutants from oil and gas activities, but when solar irradiance and absolute humidity, which are both required to initiate conventional photochemistry essential for ozone production, are at a minimum. Here, using data from a remote location in the oil and gas basin of northeastern Utah and a box model, we provide a quantitative assessment of the photochemistry that leads to these extreme winter ozone pollution events, and identify key factors that control ozone production in this unique environment. We find that ozone production occurs at lower NOx and much larger VOC concentrations than does its summertime urban counterpart, leading to carbonyl (oxygenated VOCs with a C = O moiety) photolysis as a dominant oxidant source. Extreme VOC concentrations optimize the ozone production efficiency of NOx. There is considerable potential for global growth in oil and gas extraction from shale. This analysis could help inform strategies to monitor and mitigate air quality impacts

  6. Towards the understanding of biogeochemical processes involved in the release of carbonyl sulfide (COS) from soil

    Science.gov (United States)

    Behrendt, Thomas; Catao, Elisa; Bunk, Rüdiger; Yi, Zhigang; Greule, Markus; Keppler, Frank; Kesselmeier, Jürgen; Trumbore, Susan

    2017-04-01

    Carbonyl sulfide (COS) is present in the atmosphere in low mixing ratio ( 500ppt). It is relevant in climate change through the effect in aerosol formation. Soils can act as source of COS, e.g. by microbial degradation of thiocyanate from plant material. On the other side it is known that COS can be consumed via various enzymatic pathways. Assuming that biogenic processes dominate over chemical reactions we extracted nucleic acids and performed amplicon sequencing for bacteria (16S rRNA) and fungi (ITS region) from a mid-latitude agricultural maize soil which was previously incubated under ambient COS and COS fumigation ( 1000ppt). The mixing ratios of COS have been measured online from soil samples in a dynamic chamber system under laboratory conditions by an integrated cavity output spectroscopy (IOCS) analyzer (Los Gatos Research Inc., USA). Additionally stable carbon isotope values (δ13C values) of COS were measured using a pre-concentration method and stable isotope ratio mass spectrometry (IRMS). Under low COS mixing ratio ( 50ppt) δ13C +4.7 ‰ for spruce forest ( 23°C), and -24.4‰ for mid-latitude cornfield ( 22°C), respectively. Linking gas release rates of (COS, CO2, CO, NO) to isotopic signatures of COS and molecular results might allow us to indicate bacterial s-compound degradation related to the higher activity of β-Proteobacteria and of the family Acetobacteraceae from the α-Proteobacteria phylum, potentially involved with the hydrolysis of thiocyanate in the soil releasing COS. Furthermore, our study reports the first COS data for rainforest and desert soils which are in the order of 0.5 pmol gdw-1 h-1 and 2 pmol gdw-1 h-1, respectively.

  7. CARIBIC observations of short-lived halocarbons and carbonyl sulphide over Asia

    Science.gov (United States)

    Leedham, E.; Wisher, A.; Oram, D.; Baker, A. K.; Brenninkmeijer, C. A.

    2013-12-01

    The CARIBIC project (Civil Aircraft for the Regular Investigation of the atmosphere Based on an Instrument Container, www.caribic-atmospheric.com) aims to investigate the spatial and temporal distribution of a wide-range of compounds, including those of marine origin/influence, via ~monthly flights to collect in situ data and whole air samples aboard a commercial Lufthansa aircraft. CARIBIC measures up to an altitude of 12 km, allowing the influence of marine compounds on the upper troposphere/lower stratosphere (UTLS) to be explored. In particular, CARIBIC is a useful tool for exploring the impact of very short lived halocarbons (e.g. CH2Br2, CHBr3), whose impact on stratospheric ozone is dependent on convective uplift to the UTLS, a process which is not yet fully quantified. As part of the suite of CARIBIC measurements, whole air samples are analysed at the University of East Anglia (UEA) via gas chromatography mass spectrometry for carbonyl sulphide (OCS) and up to 40 halocarbons (accounting for virtually 100% of organic chlorine, bromine and iodine in the UTLS). Here we present an overview of short-lived halocarbons and OCS measured by CARIBIC. We focus on two regions of particular interest. (1) measurements made in 2012 over the tropical west Pacific to link with UEA measurements made during the SHIVA campaign. (2) measurements made during a collection of flights over India in 2008. Flights over India investigated the impact of monsoon circulation on the distribution of these compounds; for example, elevated concentrations of OCS were seen in CARIBIC samples taken over India during the summer monsoon (July - September). These flights, along with a wider range of flights over Asia (from Frankfurt to Guangzhou, Manila, Bangkok and Kuala Lumpur) can provide unique information on the influence of tropical convection and monsoon circulation on halocarbon and OCS transport within this region.

  8. 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.

  9. Soil-atmosphere carbonyl sulfide (COS) exchange in a tropical rainforest at La Selva, Costa Rica

    Science.gov (United States)

    Sun, W.; Maseyk, K. S.; Juarez, S.; Lett, C.; Seibt, U. H.

    2014-12-01

    Carbonyl sulfide (COS) has recently been proposed as a promising tracer for partitioning ecosystem carbon assimilation due to the close analogy between leaf uptake processes of COS and CO2. This emerging framework requires accurate characterization of the source and sink components of COS, including soil fluxes. Here we present the first direct, continuous observations of soil COS fluxes for 4 months at a tropical rainforest, La Selva Biological Station, Costa Rica. Three soil plots with contrasting water content were selected for chamber measurements. Our observations confirmed that soils are principally COS sinks, with daily mean COS fluxes averaged across all chambers ranging from -3 to 0 pmol m-2 s-1. When compared with net ecosystem COS uptake which peaks around -30 pmol m-2 s-1, their contributions should be considered in ecosystem COS balance. We did not find a temperature optimum, but soil COS uptake slightly increased with soil temperature, indicating biotic control on soil COS fluxes. Diurnal cycles of COS fluxes were observed during drying out periods after rain. The diel periodicity of COS fluxes was probably obscured by frequent raining at the site. Diffusional control of soil COS fluxes is shown from increasing soil COS uptake at lower soil water-filled pore space. These confirm that soil COS fluxes are mediated both by soil physical and biological factors. Using a depth-resolved diffusion-reaction model with data-driven enzyme activity parameterization, we simulated the COS fluxes from measured soil environmental variables, consistent with observations. This modeling scheme is useful for separating soil COS fluxes from net ecosystem COS fluxes, which lends support to the emergent COS-based approach of carbon flux partitioning.

  10. Sources and sinks of carbonyl sulfide in an agricultural field in the Southern Great Plains

    Science.gov (United States)

    Maseyk, Kadmiel; Berry, Joseph A.; Billesbach, Dave; Campbell, John Elliott; Torn, Margaret S.; Zahniser, Mark; Seibt, Ulli

    2014-01-01

    Net photosynthesis is the largest single flux in the global carbon cycle, but controls over its variability are poorly understood because there is no direct way of measuring it at the ecosystem scale. We report observations of ecosystem carbonyl sulfide (COS) and CO2 fluxes that resolve key gaps in an emerging framework for using concurrent COS and CO2 measurements to quantify terrestrial gross primary productivity. At a wheat field in Oklahoma we found that in the peak growing season the flux-weighted leaf relative uptake of COS and CO2 during photosynthesis was 1.3, at the lower end of values from laboratory studies, and varied systematically with light. Due to nocturnal stomatal conductance, COS uptake by vegetation continued at night, contributing a large fraction (29%) of daily net ecosystem COS fluxes. In comparison, the contribution of soil fluxes was small (1–6%) during the peak growing season. Upland soils are usually considered sinks of COS. In contrast, the well-aerated soil at the site switched from COS uptake to emissions at a soil temperature of around 15 °C. We observed COS production from the roots of wheat and other species and COS uptake by root-free soil up to a soil temperature of around 25 °C. Our dataset demonstrates that vegetation uptake is the dominant ecosystem COS flux in the peak growing season, providing support of COS as an independent tracer of terrestrial photosynthesis. However, the observation that ecosystems may become a COS source at high temperature needs to be considered in global modeling studies. PMID:24927594

  11. Carbonyl sulfide (COS) as a tracer for canopy photosynthesis, transpiration and stomatal conductance: potential and limitations.

    Science.gov (United States)

    Wohlfahrt, Georg; Brilli, Federico; Hörtnagl, Lukas; Xu, Xiaobin; Bingemer, Heinz; Hansel, Armin; Loreto, Francesco

    2012-04-01

    The theoretical basis for the link between the leaf exchange of carbonyl sulfide (COS), carbon dioxide (CO(2)) and water vapour (H(2)O) and the assumptions that need to be made in order to use COS as a tracer for canopy net photosynthesis, transpiration and stomatal conductance, are reviewed. The ratios of COS to CO(2) and H(2)O deposition velocities used to this end are shown to vary with the ratio of the internal to ambient CO(2) and H(2)O mole fractions and the relative limitations by boundary layer, stomatal and internal conductance for COS. It is suggested that these deposition velocity ratios exhibit considerable variability, a finding that challenges current parameterizations, which treat these as vegetation-specific constants. COS is shown to represent a better tracer for CO(2) than H(2)O. Using COS as a tracer for stomatal conductance is hampered by our present poor understanding of the leaf internal conductance to COS. Estimating canopy level CO(2) and H(2)O fluxes requires disentangling leaf COS exchange from other ecosystem sources/sinks of COS. We conclude that future priorities for COS research should be to improve the quantitative understanding of the variability in the ratios of COS to CO(2) and H(2)O deposition velocities and the controlling factors, and to develop operational methods for disentangling ecosystem COS exchange into contributions by leaves and other sources/sinks. To this end, integrated studies, which concurrently quantify the ecosystem-scale CO(2), H(2)O and COS exchange and the corresponding component fluxes, are urgently needed. © 2011 Blackwell Publishing Ltd.

  12. Indoor Air Quality Investigations on Particulate Matter, Carbonyls, and Tobacco Specific Nitrosamines

    Science.gov (United States)

    Frey, Sarah E.

    Americans spend upwards of 90% of their time indoors, hence indoor air quality (IAQ) and the impact of IAQ on human health is a major public health concern. IAQ can be negatively impacted by outdoor pollution infiltrating indoors, the emission of indoor pollutants, indoor atmospheric chemistry and poor ventilation. Energy saving measures like retrofits to seal the building envelope to prevent the leakage of heated or cooled air will impact IAQ. However, existing studies have been inconclusive as to whether increased energy efficiency is leading to detrimental IAQ. In this work, field campaigns were conducted in apartment homes in Phoenix, Arizona to evaluate IAQ as it relates to particulate matter (PM), carbonyls, and tobacco specific nitrosamines (TSNA). To investigate the impacts of an energy efficiency retrofit on IAQ, indoor and outdoor air quality sampling was carried out at Sunnyslope Manor, a city-subsidized senior living apartment complex. Measured indoor formaldehyde levels before the building retrofit exceeded reference exposure limits, but in the long term follow-up sampling, indoor formaldehyde decreased for the entire study population by a statistically significant margin. Indoor PM levels were dominated by fine particles and showed a statistically significant decrease in the long term follow-up sampling within certain resident subpopulations (i.e. residents who reported smoking and residents who had lived longer at the apartment complex). Additionally, indoor glyoxal and methylglyoxal exceeded outdoor concentrations, with methylglyoxal being more prevalent pre-retrofit than glyoxal, suggesting different chemical pathways are involved. Indoor concentrations reported are larger than previous studies. TSNAs, specifically N'-nitrosonornicotine (NNN), 4-(methyl-nitrosamino)-4-(3-pyridyl)-butanal (NNA) and 4-(methylnitrosoamino)-1-(3-pyridyl)-1-butanone (NNK) were evaluated post-retrofit at Sunnyslope Manor. Of the units tested, 86% of the smoking units and

  13. Exchange of carbonyl sulfide (OCS) between soils and atmosphere under various CO2 concentrations

    Science.gov (United States)

    Bunk, Rüdiger; Behrendt, Thomas; Yi, Zhigang; Andreae, Meinrat O.; Kesselmeier, Jürgen

    2017-06-01

    A new continuous integrated cavity output spectroscopy analyzer and an automated soil chamber system were used to investigate the exchange processes of carbonyl sulfide (OCS) between soils and the atmosphere under laboratory conditions. The exchange patterns of OCS between soils and the atmosphere were found to be highly dependent on soil moisture and ambient CO2 concentration. With increasing soil moisture, OCS exchange ranged from emission under dry conditions to an uptake within an optimum moisture range, followed again by emission at high soil moisture. Elevated CO2 was found to have a significant impact on the exchange rate and direction as tested with several soils. There is a clear tendency toward a release of OCS at higher CO2 levels (up to 7600 ppm), which are typical for the upper few centimeters within soils. At high soil moisture, the release of OCS increased sharply. Measurements after chloroform vapor application show that there is a biotic component to the observed OCS exchange. Furthermore, soil treatment with the fungi inhibitor nystatin showed that fungi might be the dominant OCS consumers in the soils we examined. We discuss the influence of soil moisture and elevated CO2 on the OCS exchange as a change in the activity of microbial communities. Physical factors such as diffusivity that are governed by soil moisture also play a role. Comparing KM values of the enzymes to projected soil water CO2 concentrations showed that competitive inhibition is unlikely for carbonic anhydrase and PEPCO but might occur for RubisCO at higher CO2 concentrations.

  14. Continuous In-situ Measurements of Carbonyl Sulfide to Constrain Ecosystem Carbon and Water Exchange

    Science.gov (United States)

    Rastogi, B.; Kim, Y.; Berkelhammer, M. B.; Noone, D. C.; Lai, C. T.; Hollinger, D. Y.; Bible, K.; Leen, J. B.; Gupta, M.; Still, C. J.

    2014-12-01

    Understanding the processes that control the terrestrial exchange of carbon and water are critical for examining the role of forested ecosystems in changing climates. A small but increasing number of studies have identified Carbonyl Sulfide (OCS) as a potential tracer for photosynthesis. OCS is hydrolyzed by an irreversible reaction in leaf mesophyll cells that is catalyzed by the enzyme, carbonic anhydrase. Leaf-level field and greenhouse studies indicate that OCS uptake is controlled by stomatal activity and that the ratio of OCS and CO2 uptake is reasonably constant. Existing studies on ecosystem OCS exchange have been based on laboratory measurements or short field campaigns and therefore little information on OCS exchange in a natural ecosystem over longer timescales is available. The objective of this study is to further assess the stability of OCS as a tracer for canopy photosynthesis in an active forested ecosystem and also to assess its utility for constraining transpiration, since both fluxes are mediated by canopy stomatal conductance. An off-axis integrated cavity output spectroscopy analyzer (Los Gatos Research Inc.) was deployed at the Wind River Experimental Forest in Washington (45.8205°N, 121.9519°W). Canopy air was sampled from three heights to measure vertical gradients of OCS within the canopy, and OCS exchange between the forest and the atmosphere. Here we take advantage of simultaneous measurements of the stable isotopologues of H2O and CO2 at corresponding heights as well as NEE (Net Ecosystem Exchange) from eddy covariance measurements to compare GPP (Gross Primary Production) and transpiration estimates from a variety of independent techniques. Our findings seek to allow assessment of the environmental and ecophysicological controls on evapotranspiration rates, which are projected to change in coming decades, and are otherwise poorly constrained.

  15. Molecular Nickel Phosphide Carbonyl Nanoclusters: Synthesis, Structure, and Electrochemistry of [Ni11P(CO)18]3- and [H6-nNi31P4(CO)39]n- (n = 4 and 5).

    Science.gov (United States)

    Capacci, Chiara; Ciabatti, Iacopo; Femoni, Cristina; Iapalucci, Maria Carmela; Funaioli, Tiziana; Zacchini, Stefano; Zanotti, Valerio

    2018-02-05

    The reaction of [NEt 4 ] 2 [Ni 6 (CO) 12 ] in thf with 0.5 equiv of PCl 3 affords the monophosphide [Ni 11 P(CO) 18 ] 3- that in turn further reacts with PCl 3 resulting in the tetra-phosphide carbonyl cluster [HNi 31 P 4 (CO) 39 ] 5- . Alternatively, the latter can be obtained from the reaction of [NEt 4 ] 2 [Ni 6 (CO) 12 ] in thf with 0.8-0.9 equiv of PCl 3 . The [HNi 31 P 4 (CO) 39 ] 5- penta-anion is reversibly protonated by strong acids leading to the [H 2 Ni 31 P 4 (CO) 39 ] 4- tetra-anion, whereas deprotonation affords the [Ni 31 P 4 (CO) 39 ] 6- hexa-anion. The latter is reduced with Na/naphthalene yielding the [Ni 31 P 4 (CO) 39 ] 7- hepta-anion. In order to shed light on the polyhydride nature and redox behavior of these clusters, electrochemical and spectroelectrochemical studies were carried out on [Ni 11 P(CO) 18 ] 3- , [HNi 31 P 4 (CO) 39 ] 5- , and [H 2 Ni 31 P 4 (CO) 39 ] 4- . The reversible formation of the stable [Ni 11 P(CO) 18 ] 4- tetra-anion is demonstrated through the spectroelectrochemical investigation of [Ni 11 P(CO) 18 ] 3- . The redox changes of [HNi 31 P 4 (CO) 39 ] 5- show features of chemical reversibility and the vibrational spectra in the ν CO region of the nine redox states of the cluster [HNi 31 P 4 (CO) 39 ] n- (n = 3-11) are reported. The spectroelectrochemical investigation of [H 2 Ni 31 P 4 (CO) 39 ] 4- revealed the presence of three chemically reversible reduction processes, and the IR spectra of [H 2 Ni 31 P 4 (CO) 39 ] n- (n = 4-7) have been recorded. The different spectroelectrochemical behavior of [HNi 31 P 4 (CO) 39 ] 5- and [H 2 Ni 31 P 4 (CO) 39 ] 4- support their formulations as polyhydrides. Unfortunately, all the attempts to directly confirm their poly hydrido nature by 1 H NMR spectroscopy failed, as previously found for related large metal carbonyl clusters. Thus, the presence and number of hydride ligands have been based on the observed protonation/deprotonation reactions and the spectroelectrochemical

  16. Measurements of C{sub 1}-C{sub 4} carbonyls at forested regions in Mexico

    Energy Technology Data Exchange (ETDEWEB)

    Ceron Breton, J.B.; Padilla, H.; Belmont, R.; Torres, M.C.; Moya, M.; Baez, A.P. [Centro de Ciencias de la Atmosfera, Universidad Nacional Autonoma de Mexico, UNAM, Mexico, D.F. (Mexico)

    2005-04-01

    Measurements of formaldehyde, acetaldehyde, acetone, propionaldehyde and butyraldehyde concentrations were made at five different forested regions in Mexico. One set of two simultaneous samplings was performed at two sites located in the Mexico State, one semi rural area (Temascaltepec), and the other, a forested area (Rancho Viejo). A second set of two simultaneous samplings were made in southern Veracruz State, in one rural area (Monte Pio) and inside a tropical rainforest (at the Biology Station of the University of Mexico). Finally, one sampling was performed in the Sierra of Puebla State (Cuetzalan). Propionaldehyde and butyraldehyde were nor reported because their concentrations were always below or near the detection limit of the technique. The highest concentrations were found from 7:00 to 11:00 and from 11:00 to 19:00 h in all the sampling sites. Arithmetic mean concentrations of acetone were the highest observed among the detected carbonyl compounds in almost all sites, ranging from 0.5 to 8.4 {mu}g m{sup -}3. Arithmetic mean concentrations of formaldehyde and acetaldehyde ranged from 0.83 to 6 {mu}g m{sup -}3 and 0.53 to 4.7 {mu}g m{sup -}3, respectively. The Spearman's correlations between formaldehyde and acetone, and between acetaldehyde and acetone were statistically significant at p<0.05 in almost all sites. A significant correlation (p<0.05) between formaldehyde and acetaldehyde was observed in Mexico State at Rancho Viejo and Temascaltepec. The mean ratio HCHO/CH{sub 3}CHO of concentrations was 1.83 and 1.31 in the forested area of Rancho Viejo, first and second sampling periods, respectively; 1.71 and 1.62 in the semi rural area of Temascaltepec, first and second sampling periods respectively; 1.70 in Cuetzalan; 2.90 in the rural area of Monte Pio; and 1.61 in the Biology Station tropical rainforest. These values show a greater influence of atmospheric pollutants transported from sites with anthropogenic activities, because HCHO/CH{sub 3}CHO

  17. Recyclable Earth-Abundant Metal Nanoparticle Catalysts for Selective Transfer Hydrogenation of Levulinic Acid to Produce γ-Valerolactone.

    Science.gov (United States)

    Gowda, Ravikumar R; Chen, Eugene Y-X

    2016-01-01

    Nanoparticles (NPs) derived from earth-abundant metal(0) carbonyls catalyze conversion of bio-derived levulinic acid into γ-valerolactone in up to 93% isolated yield. This sustainable and green route uses non-precious metal catalysts and can be performed in aqueous or ethanol solution without using hydrogen gas as the hydrogen source. Generation of metal NPs using microwave irradiation greatly enhances the rate of the conversion, enables the use of ethanol as both solvent and hydrogen source without forming the undesired ethyl levulinate, and affords recyclable polymer-stabilized NPs. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Metallic nanomesh

    Energy Technology Data Exchange (ETDEWEB)

    Ren, Zhifeng; Sun, Tianyi; Guo, Chuanfei

    2018-02-20

    A transparent flexible nanomesh having at least one conductive element and sheet resistance less than 300.OMEGA./.quadrature. when stretched to a strain of 200% in at least one direction. The nanomesh is formed by depositing a sacrificial film, depositing, etching, and oxidizing a first metal layer on the film, etching the sacrificial film, depositing a second metal layer, and removing the first metal layer to form a nanomesh on the substrate.

  19. VLSI metallization

    CERN Document Server

    Einspruch, Norman G; Gildenblat, Gennady Sh

    1987-01-01

    VLSI Electronics Microstructure Science, Volume 15: VLSI Metallization discusses the various issues and problems related to VLSI metallization. It details the available solutions and presents emerging trends.This volume is comprised of 10 chapters. The two introductory chapters, Chapter 1 and 2 serve as general references for the electrical and metallurgical properties of thin conducting films. Subsequent chapters review the various aspects of VLSI metallization. The order of presentation has been chosen to follow the common processing sequence. In Chapter 3, some relevant metal deposition tec

  20. A novel NAD(P)H-dependent carbonyl reductase specifically expressed in the thyroidectomized chicken fatty liver: catalytic properties and crystal structure.

    Science.gov (United States)

    Fukuda, Yudai; Sone, Takeki; Sakuraba, Haruhiko; Araki, Tomohiro; Ohshima, Toshihisa; Shibata, Takeshi; Yoneda, Kazunari

    2015-10-01

    A gene encoding a functionally unknown protein that is specifically expressed in the thyroidectomized chicken fatty liver and has a predicted amino acid sequence similar to that of NAD(P)H-dependent carbonyl reductase was overexpressed in Escherichia coli; its product was purified and characterized. The expressed enzyme was an NAD(P)H-dependent broad substrate specificity carbonyl reductase and was inhibited by arachidonic acid at 1.5 μm. Enzymological characterization indicated that the enzyme could be classified as a cytosolic-type carbonyl reductase. The enzyme's 3D structure was determined using the molecular replacement method at 1.98 Å resolution in the presence of NADPH and ethylene glycol. The asymmetric unit consisted of two subunits, and a noncrystallographic twofold axis generated the functional dimer. The structures of the subunits, A and B, differed from each other. In subunit A, the active site contained an ethylene glycol molecule absent in subunit B. Consequently, Tyr172 in subunit A rotated by 103.7° in comparison with subunit B, which leads to active site closure in subunit A. In Y172A mutant, the Km value for 9,10-phenanthrenequinone (model substrate) was 12.5 times higher than that for the wild-type enzyme, indicating that Tyr172 plays a key role in substrate binding in this carbonyl reductase. Because the Tyr172-containing active site lid structure (Ile164-Gln174) is not conserved in all known carbonyl reductases, our results provide new insights into substrate binding of carbonyl reductase. The catalytic properties and crystal structure revealed that thyroidectomized chicken fatty liver carbonyl reductase is a novel enzyme. © 2015 FEBS.

  1. Development and application of a sensitive method to determine concentrations of acrolein and other carbonyls in ambient air.

    Science.gov (United States)

    Cahill, Thomas M; Charles, M Judith; Seaman, Vincent Y

    2010-05-01

    Acrolein, an unsaturated aldehyde, has been identified as one of the most important toxic air pollutants in recent assessments of ambient air quality. Current methods for determining acrolein concentrations, however, suffer from poor sensitivity, selectivity, and reproducibility. The collection and analysis of unsaturated carbonyls, and acrolein in particular, is complicated by unstable derivatives, coelution of similar compounds, and ozone interference. The primary objective of this research was to develop an analytical method to measure acrolein and other volatile carbonyls present in low part-per-trillion concentrations in ambient air samples obtained over short sampling periods. The method we devised uses a mist chamber in which carbonyls from air samples form water-soluble adducts with bisulfite in the chamber solution, effectively trapping the carbonyls in the solution. The mist chamber methodology proved effective, with collection efficiency for acrolein of at least 70% for each mist chamber at a flow rate of approximately 17 L/min. After the sample collection, the carbonyls are liberated from the bisulfite adducts through the addition of hydrogen peroxide, which converts the bisulfite to sulfate, reversing the bisulfite addition reaction. The free carbonyls are then derivatized by o-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine (PFBHA*), which stabilizes the analytes and makes them easier to detect by electron-capture negative ionization mass spectrometry (ECNI-MS). The derivatives are then extracted and analyzed by gas chromatography-mass spectrometry (GC-MS). The mist chamber method was applied in a field test to determine the extent of acrolein in ambient air near the Peace Bridge plaza in Buffalo, New York, an area of heavy traffic near a major border crossing between the United States and Canada. In addition, XAD-2 adsorbent cartridges coated with 2-(hydroxymethyl)piperidine (2-HMP) according to Occupational Safety and Health Administration (OSHA) Method

  2. Heavy metal

    African Journals Online (AJOL)

    of spawning, resistance to diseases and social acceptability (Pillay, 1993). This study aimed at determining the carbohydrate reserves and heavy metal accumulation of the Nile tilapia, Oreochromis miloticus after treatment with heavy metals such as lead, copper and zinc. 2. Materials and Methods. Test organism: Nile tilapia ...

  3. 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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Bonnet, J.; Bounor-Legare, V.; Alcouffe, P. [Universite de Lyon, 69003 Lyon (France); Universite de Lyon 1, CNRS UMR5223, Ingenierie des Materiaux Polymeres, 15 Boulevard Latarjet, F-69622 Villeurbanne (France); Cassagnau, P., E-mail: philippe.cassagnau@univ-lyon1.fr [Universite de Lyon, 69003 Lyon (France); Universite de Lyon 1, CNRS UMR5223, Ingenierie des Materiaux Polymeres, 15 Boulevard Latarjet, F-69622 Villeurbanne (France)

    2012-10-15

    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 ({lambda}{sub polysiloxane/EVA} = 4.0 Multiplication-Sign 10{sup -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{sup -1}) with a low concentration of SiH ([SiH]/[VA] < 4.0 Multiplication-Sign 10{sup -3}). -- Highlights: Black-Right-Pointing-Pointer Carbonyl hydrosilylation reaction was found to enhance EVA/polysiloxane immiscible blends. Black-Right-Pointing-Pointer EVA crosslinking was obtained with a low molar mass polysiloxane. Black-Right-Pointing-Pointer EVA compatibilisation was obtained with a high molar mass polysiloxane. Black-Right-Pointing-Pointer Shear rate was found to improve the hydrosilylation reaction at the interface. Black-Right-Pointing-Pointer A two-phase morphology of the blends was observed after reaction with fine polysiloxane nodules.

  5. Compostos carbonílicos atmosféricos: fontes, reatividade, níveis de concentração e efeitos toxicológicos Atmospheric carbonyl compounds: sources, reactivity, concentration levels and toxicologic effects

    Directory of Open Access Journals (Sweden)

    Marta Valéria Almeida Santana de Andrade

    2002-12-01

    Full Text Available In the last three decades carbonyl compounds, aldehydes and ketones, have received a great deal of attention due to their strong influence on photochemical smog formation and their recognized adverse human health effects. Carbonyl compounds are directly emitted into the atmosphere by combustion sources and also produced from photochemical oxidation of hydrocarbons and other organic compounds. In this paper it is presented a general overview about the carbonyl compounds sources, reactivity, concentration levels and toxicological effects.

  6. S-nitrosoglutathione covalently modifies cysteine residues of human carbonyl reductase 1 and affects its activity.

    Science.gov (United States)

    Hartmanová, Tereza; Tambor, Vojtěch; Lenčo, Juraj; Staab-Weijnitz, Claudia A; Maser, Edmund; Wsól, Vladimír

    2013-02-25

    Carbonyl reductase 1 (CBR1 or SDR21C1) is a ubiquitously-expressed, cytosolic, monomeric, and NADPH-dependent enzyme. CBR1 participates in apoptosis, carcinogenesis and drug resistance, and has a protective role in oxidative stress, cancer and neurodegeneration. S-Nitrosoglutathione (GSNO) represents the newest addition to its diverse substrate spectrum, which includes a wide range of xenobiotics and endogenous substances. GSNO has also been shown to covalently modify and inhibit CBR1. The aim of the present study was to quantify and characterize the resulting modifications. Of five candidate cysteines for modification by 2 mM GSNO (positions 26, 122, 150, 226, 227), the last four were analyzed using MALDI-TOF/TOF mass spectrometry and then quantified using the Selected Reaction Monitoring Approach on hyphenated HPLC with a triple quadrupole mass spectrometer. The analysis confirmed GSNO concentration-dependent S-glutathionylation of cysteines at positions 122, 150, 226, 227 which was 2-700 times higher compared to wild-type CBR1 (WT-CBR1). Moreover, a disulfide bond between neighboring Cys-226 and Cys-227 was detected. We suggest a role of these two cysteines as a redox-sensitive cysteine pair. The catalytic properties of wild-type and enzyme modified with 2 mM GSNO were also investigated by steady state kinetic experiments with various substrates. GSNO treatment of CBR1 resulted in a 2-5-fold decrease in kcat with menadione, 4-benzoylpyridine, 2,3-hexanedione, daunorubicin and 1,4-naphthoquinone. In contrast, the same treatment increased kcat for substrates containing a 1,2-diketo group in a ring structure (1,2-naphthoquinone, 9,10-phenanthrenequinone, isatin). Except for 9,10-phenanthrenequinone, all changes in kcat were at least in part compensated for by a similar change in Km, overall yielding no drastic changes in catalytic efficiency. The findings indicate that GSNO-induced covalent modification of cysteine residues affects the kinetic mechanism of CBR1

  7. Proteome Expression and Carbonylation Changes During Trypanosoma cruzi Infection and Chagas Disease in Rats*

    Science.gov (United States)

    Wen, Jian-Jun; Garg, Nisha Jain

    2012-01-01

    Inflammation and oxidative stress, elicited by Trypanosoma cruzi infection, are important pathologic events during progressive Chagasic cardiomyopathy. In this study, we infected Sprague-Dawley rats with T. cruzi, and treated with phenyl-α-tert-butylnitrone (PBN-antioxidant) and/or benznidazole (BZ-anti-parasite). We employed two-dimensional gel electrophoresis/mass spectrometry to investigate (a) the plasma proteomic changes associated with infection and disease development, and (b) the beneficial effects of PBN and BZ in controlling the disease-associated plasma profile. Matrix-assisted laser desorption ionization/time of flight (MALDI-TOF) tandem MS (MS/MS) analysis of differentially expressed (total 146) and oxidized (total 48) protein spots yielded 92 unique proteins. Our data showed that treatment with PBN and BZ restored the differential expression of 65% and 30% of the disease-associated proteins to normal level, respectively, and PBN prevented development of oxidative adducts on plasma proteins. Western blotting to detect dinitrophenyl-derivatized carbonyl-proteins revealed plasma proteins were maximally oxidized during acute infection. Functional and disease/disorder analyses allocated a majority of the differentially expressed and oxidized proteins into inflammation/immunity and lipid metabolism categories and to molecular pathways associated with heart disease (e.g. cardiac infarction, contractile dysfunction, hypertrophy, and hypertension) in chagasic rats, and to curative pathways (e.g. ROS scavenging capacity, immune regulation) in infected rats treated with PBN and/or BZ. We validated the two-dimensional gel electrophoresis results by Western blotting, and demonstrated that the disease-associated increased expression of gelsolin and vimentin and release of cardiac MYL2 in the plasma of chagasic rats was returned to control level by PBN/BZ treatment. Increased plasma levels of gelsolin, MYL2 and vimentin were directly correlated with the severity of

  8. Proteome expression and carbonylation changes during Trypanosoma cruzi infection and Chagas disease in rats.

    Science.gov (United States)

    Wen, Jian-Jun; Garg, Nisha Jain

    2012-04-01

    Inflammation and oxidative stress, elicited by Trypanosoma cruzi infection, are important pathologic events during progressive Chagasic cardiomyopathy. In this study, we infected Sprague-Dawley rats with T. cruzi, and treated with phenyl-α-tert-butylnitrone (PBN-antioxidant) and/or benznidazole (BZ-anti-parasite). We employed two-dimensional gel electrophoresis/mass spectrometry to investigate (a) the plasma proteomic changes associated with infection and disease development, and (b) the beneficial effects of PBN and BZ in controlling the disease-associated plasma profile. Matrix-assisted laser desorption ionization/time of flight (MALDI-TOF) tandem MS (MS/MS) analysis of differentially expressed (total 146) and oxidized (total 48) protein spots yielded 92 unique proteins. Our data showed that treatment with PBN and BZ restored the differential expression of 65% and 30% of the disease-associated proteins to normal level, respectively, and PBN prevented development of oxidative adducts on plasma proteins. Western blotting to detect dinitrophenyl-derivatized carbonyl-proteins revealed plasma proteins were maximally oxidized during acute infection. Functional and disease/disorder analyses allocated a majority of the differentially expressed and oxidized proteins into inflammation/immunity and lipid metabolism categories and to molecular pathways associated with heart disease (e.g. cardiac infarction, contractile dysfunction, hypertrophy, and hypertension) in chagasic rats, and to curative pathways (e.g. ROS scavenging capacity, immune regulation) in infected rats treated with PBN and/or BZ. We validated the two-dimensional gel electrophoresis results by Western blotting, and demonstrated that the disease-associated increased expression of gelsolin and vimentin and release of cardiac MYL2 in the plasma of chagasic rats was returned to control level by PBN/BZ treatment. Increased plasma levels of gelsolin, MYL2 and vimentin were directly correlated with the severity of

  9. Kinetics of reversible reductive carbonylation of heme in human cystathionine β-synthase.

    Science.gov (United States)

    Carballal, Sebastián; Cuevasanta, Ernesto; Marmisolle, Inés; Kabil, Omer; Gherasim, Carmen; Ballou, David P; Banerjee, Ruma; Alvarez, Beatriz

    2013-07-02

    Cystathionine β-synthase (CBS) catalyzes the condensation of homocysteine with serine or cysteine to form cystathionine and water or hydrogen sulfide (H2S), respectively. In addition to pyridoxal phosphate, human CBS has a heme cofactor with cysteine and histidine as ligands. While Fe(III)-CBS is inert to exogenous ligands, Fe(II)-CBS can be reversibly inhibited by carbon monoxide (CO) and reoxidized by O2 to yield superoxide radical. In this study, we have examined the kinetics of Fe(II)CO-CBS formation and reoxidation. Reduction of Fe(III)-CBS by dithionite showed a square root dependence on concentration, indicating that the reductant species was the sulfur dioxide radical anion (SO2(•-)) that exists in rapid equilibrium with S2O4(2-). Formation of Fe(II)CO-CBS from Fe(II)-CBS and 1 mM CO occurred with a rate constant of (3.1 ± 0.4) × 10(-3) s(-1) (pH 7.4, 25 °C). The reaction of Fe(III)-CBS with the reduced form of the flavoprotein methionine synthase reductase in the presence of CO and NADPH resulted in its reduction and carbonylation to form Fe(II)CO-CBS. Fe(II)-CBS was formed as an intermediate with a rate constant of (9.3 ± 2.5) × 10(2) M(-1) s(-1). Reoxidation of Fe(II)CO-CBS by O2 was multiphasic. The major phase showed a hyperbolic dependence on O2 concentration. Although H2S is a product of the CBS reaction and a potential heme ligand, we did not find evidence of an effect of exogenous H2S on activity or heme binding. Reversible reduction of CBS by a physiologically relevant oxidoreductase is consistent with a regulatory role for the heme and could constitute a mechanism for cross talk among the CO, H2S, and superoxide signaling pathways.

  10. Reactive Carbonyl Species Activate Caspase-3-Like Protease to Initiate Programmed Cell Death in Plants.

    Science.gov (United States)

    Biswas, Md Sanaullah; Mano, Jun'ichi

    2016-07-01

    Reactive oxygen species (ROS)-triggered programmed cell death (PCD) is a typical plant response to biotic and abiotic stressors. We have recently shown that lipid peroxide-derived reactive carbonyl species (RCS), downstream products of ROS, mediate oxidative signal to initiate PCD. Here we investigated the mechanism by which RCS initiate PCD. Tobacco Bright Yellow-2 cultured cells were treated with acrolein, one of the most potent RCS. Acrolein at 0.2 mM caused PCD in 5 h (i.e. lethal), but at 0.1 mM it did not (sublethal). Specifically, these two doses caused critically different effects on the cells. Both lethal and sublethal doses of acrolein exhausted the cellular glutathione pool in 30 min, while the lethal dose only caused a significant ascorbate decrease and ROS increase in 1-2 h. Prior to such redox changes, we found that acrolein caused significant increases in the activities of caspase-1-like protease (C1LP) and caspase-3-like protease (C3LP), the proteases which trigger PCD. The lethal dose of acrolein increased the C3LP activity 2-fold more than did the sublethal dose. In contrast, C1LP activity increments caused by the two doses were not different. Acrolein and 4-hydroxy-(E)-2-nonenal, another RCS, activated both proteases in a cell-free extract from untreated cells. H 2 O 2 at 1 mM added to the cells increased C1LP and C3LP activities and caused PCD, and the RCS scavenger carnosine suppressed their activation and PCD. However, H 2 O 2 did not activate the proteases in a cell-free extract. Thus the activation of caspase-like proteases, particularly C3LP, by RCS is an initial biochemical event in oxidative signal-stimulated PCD in plants. © The Author 2016. Published by Oxford University Press on behalf of Japanese Society of Plant Physiologists. All rights reserved. For permissions, please email: journals.permissions@oup.com.

  11. 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.

  12. Moessbauer and EXAFS studies of amorphous iron produced by thermal decomposition of carbonyl iron in liquid phase

    International Nuclear Information System (INIS)

    Nomura, Kiyoshi; Tanaka, Junichi; Ujihira, Yusuke; Takahashi, Tamotu; Uchida, Yasuzo

    1990-01-01

    Decomposition of iron carbonyl Fe(CO) 5 and Fe 2 (CO) 9 in liquid phase gave amorphous and crystalline iron powders in the absence and presence of catalyst, respectively. The hyperfine fields were large in amorphous phases prepared from Fe(CO) 5 than from Fe 2 (CO) 9 . Crystalline iron, iron carbide and a trace amount of Fe 3 O 4 were detected in the decomposition products of the amorphous phase prepared from Fe(CO) 5 , and iron carbide was mainly included in the decomposition products of the amorphous phase prepared from Fe 2 (CO) 9 . (orig.)

  13. Radiosynthesis and Evaluation of [11C-Carbonyl]-Labeled Carbamates as Fatty Acid Amide Hydrolase Radiotracers for Positron Emission Tomography

    OpenAIRE

    Wilson, Alan A.; Hicks, Justin W.; Sadovski, Oleg; Parkes, Jun; Tong, Junchao; Houle, Sylvain; Fowler, Christopher J.; Vasdev, Neil

    2012-01-01

    Fatty acid amide hydrolase (FAAH) plays a key role in regulating the tone of the endocannabinoid system. Radiotracers are required to image and quantify FAAH activity in vivo. We have synthesized a series of potent FAAH inhibitors encompassing two classes of N-alkyl-O-arylcarbamates and radiolabeled eight of them with carbon-11. The [11C-carbonyl]-radiotracers were evaluated in vitro and ex vivo in rats as potential FAAH imaging agents for positron emission tomography (PET). Both sets of [11C...

  14. Synthesis of acyl carbamates via four component Pd-catalyzed carbonylative coupling of aryl halides, potassium cyanate, and alcohols.

    Science.gov (United States)

    Yin, Hongfei; de Almeida, Angelina M; de Almeida, Mauro V; Lindhardt, Anders T; Skrydstrup, Troels

    2015-03-06

    A simple and mild method is demonstrated for assembling acyl carbamates through a base-free four-component Pd-catalyzed carbonylation of aryl halides in the presence of potassium cyanate and alcohols in a two-chamber system. This approach produces a wide range of aryl acyl carbamates in good to excellent yields from the corresponding aryl bromides or iodides with near-stoichiometric carbon monoxide. In addition, the method can be extended to the synthesis of primary amides thereby expanding the usefulness of cyanate as an ammonia equivalent.

  15. Lewis base catalyzed 1,3-dithiane addition to carbonyl and imino compounds using 2-trimethylsilyl-1,3-dithiane.

    Science.gov (United States)

    Michida, Makoto; Mukaiyama, Teruaki

    2008-09-01

    Lewis base-catalyzed 1,3-dithiane addition to electrophiles such as carbonyl compounds and N-substituted aldimines with 2-trimethylsilyl-1,3-dithiane (TMS-dithiane) is described. By the activation of the carbon-silicon bond in the presence of a Lewis base catalyst such as tetrabutylammonium phenoxide (PhONnBu(4)), a 1,3-dithiane addition reaction proceeded smoothly to afford the corresponding adducts in good to high yields under mild conditions. This synthesis is also applied to the reactions of ketones having alpha-protons, and of N-substituted aldimines.

  16. Plasma metallization

    International Nuclear Information System (INIS)

    Crowther, J.M.

    1997-09-01

    Many methods are currently used for the production of thin metal films. However, all of these have drawbacks associated with them, for example the need for UHV conditions, high temperatures, exotic metal precursors, or the inability to coat complex shaped objects. Reduction of supported metal salts by non-isothermal plasma treatment does not suffer from these drawbacks. In order to produce and analyse metal films before they become contaminated, a plasma chamber which could be attached directly to a UHV chamber with XPS capability was designed and built. This allowed plasma treatment of supported metal salts and surface analysis by XPS to be performed without exposure of the metal film to the atmosphere. Non-equilibrium plasma treatment of Nylon 66 supported gold(lll) chloride using hydrogen as the feed gas resulted in a 95% pure gold film, the remaining 5% of the film being carbon. If argon or helium were used as the feed gases during plasma treatment the resultant gold films were 100% pure. Some degree of surface contamination of the films due to plasma treatment was observed but was easily removed by argon ion cleaning. Hydrogen plasma reduction of glass supported silver(l) nitrate and palladium(ll) acetate films reveals that this metallization technique is applicable to a wide variety of metal salts and supports, and has also shown the ability of plasma reduction to retain the complex 'fern-like' structures seen for spin coated silver(l) nitrate layers. Some metal salts are susceptible to decomposition by X-rays. The reduction of Nylon 66 supported gold(lll) chloride films by soft X-rays to produce nanoscopic gold particles has been studied. The spontaneous reduction of these X-ray irradiated support gold(lll) chloride films on exposure to the atmosphere to produce gold rich metallic films has also been reported. (author)

  17. 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

  18. Cobalt Carbonyl Hydrides with 1,1´-Diphosphinylferrocene Ligands - Structural and Electrochemical Diversity

    Czech Academy of Sciences Publication Activity Database

    Krafft, M. J.; Lissner, F.; Fiedler, Jan; Kaim, W.

    2017-01-01

    Roč. 643, č. 23 (2017), s. 1971-1977 ISSN 0044-2313 Institutional support: RVO:61388955 Keywords : 1,1´-bis(diorganophosphanyl)ferrocenes * cobalt * electrochemistry Subject RIV: CG - Electrochemistry OBOR OECD: Electrochemistry (dry cells, batteries, fuel cells, corrosion metals, electrolysis) Impact factor: 1.144, year: 2016

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

    Science.gov (United States)

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

    2013-07-01

    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. Copyright © 2013 Elsevier Ltd. All rights reserved.

  20. 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.

  1. Isolation and characterization of a novel Rhodococcus strain with switchable carbonyl reductase and para-acetylphenol hydroxylase activities.

    Science.gov (United States)

    Zhang, Rui; Ren, Jie; Wang, Yu; Wu, Qiaqing; Wang, Min; Zhu, Dunming

    2013-01-01

    In the search for an effective biocatalyst for the reduction of acetophenones with unprotected hydroxy group on the benzene ring, a microorganism, which reduced para-acetylphenol to S-(-)-1-(para-hydroxyphenyl)ethanol under anaerobic conditions, was isolated from soil samples and the 16S rDNA study showed that it was phylogenetically affiliated with species of the genus Rhodococcus and was most similar to Rhodococcus pyridinivorans. Unexpectedly, this strain also hydroxylated para-acetylphenol to give 4-acetylcatechol in presence of oxygen, possessing para-acetylphenol hydroxylase activity. While the reduction of para-acetylphenol had an optimal reaction pH at 7 and a broad optimal temperature range (35-45 °C), the hydroxylation reached the maximum conversion at the pH range of 7-8 and 35 °C. This study identified for the first time a Rhodococcus strain with para-acetylphenol hydroxylase activity, which also contains highly enantioselective carbonyl reductase activity with potential applications for the asymmetric reduction of these less-explored but important ketones such as α-aminoacetophenone, 3'-hydroxyacetophenone and 4'-hydroxyacetophenone. The para-acetylphenol hydroxylase and carbonyl reductase activity are switchable by the reaction conditions.

  2. [1,1′-Bis(diphenylphosphinoferrocene]carbonyl[dihydrobis(pyrazol-1-ylborato]hydridoruthenium(II acetone solvate

    Directory of Open Access Journals (Sweden)

    Alan J. Lough

    2008-12-01

    Full Text Available In the title compound, [FeRu(C17H14P2(C6H8BN4H(CO]·C3H6O, the RuII ion is coordinated in a distorted octahedral environment involving a hydride ligand, a carbonyl ligand and two bidentate ligands. Of the two bidentate ligands, the bulky 1,1′-bis(diphenylphosphinoferrocene (dppf ligand chelates with a larger bite angle of 101.90 (2°, whereas the bite angle of the [H2Bpz2]− ligand (pz = pyrazolyl is 85.67 (7°. The latter ligand creates an RuN4B six-membered ring with a boat conformation, which puckers towards the site of the small hydride ligand. The hydride ligand is cis with respect to the carbonyl ligand and trans to one of the P atoms of the dppf ligand. In the crystal structure, there are weak intermolecular C—H...O hydrogen bonds between complex molecules and acetone solvent molecules.

  3. 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.

  4. Carbonyl reduction in the biosynthesis of a male sex pheromone secreted by the grape borer Xylotrechus pyrrhoderus.

    Science.gov (United States)

    Iwabuchi, Kikuo; Arakawa, Maki; Kiyota, Ryutaro; Hoshino, Keita; Ando, Tetsu

    2014-10-01

    Males of the cerambycid beetle Xylotrechus pyrrhoderus release a mixture of (S)-2-hydroxy-3-octanone [(S)-1] and (2S,3S)-2,3-octanediol [(2S,3S)-2] as a sex pheromone that attracts conspecific females. The chemical structures of these pheromone components include a common motif and are assumed to be biosynthetically related. Here, we show that deuterated (S)-1, applied on the cuticle of a pronotal pheromone gland, was converted into (2S,3S)-2, that included deuterium atoms, but a reverse conversion did not take place. These results reveal a carbonyl reductase to be active in the pheromone gland, and that the ketol is a biosynthetic precursor of the diol. Males did not produce (R)-1; however, deuterated (R)-1 was converted into (2R,3R)-2, indicating an attack of the enzyme from the opposite side of the hydroxyl group at the 2-position. Furthermore, to understand the substrate specificity of the enzyme, racemates of 2-hydroxy-3-hexanone and 2-hydroxy-3-decanone were synthesized and applied to the gland. Their conversion into the corresponding diols suggests that the enzyme reduces the carbonyl group at the 3-position, regardless of the chain length.

  5. Derivatization Technique To Identify Specifically Carbonyl Groups by Infrared Spectroscopy: Characterization of Photooxidative Aging Products in Terpenes and Terpeneous Resins.

    Science.gov (United States)

    Zumbühl, Stefan; Brändle, Andreas; Hochuli, Andreas; Scherrer, Nadim C; Caseri, Walter

    2017-02-07

    Analysis of bioorganic materials by infrared spectroscopy (FT-IR) is frequently limited due to overlapping of diagnostic bands from the various components, which poses a fundamental problem to this analytical technique. The distinction of oxidized di- and triterpenes, for example, is hindered by the superposition of similar absorption bands of carbonyl functional groups summing up to a broad, nondistinctive signal. This study presents a technique for selective fluorination of various carboxylic acids by exposure to gaseous sulfur tetrafluoride. The derivatization treatment leads to characteristic band shifts, allowing the separation of otherwise overlapping bands. Accordingly, the IR bands of primary acids, α,β-unsaturated acids, tertiary acids, peroxy acids, esters, ketones, and α,β-unsaturated ketones are split into distinct absorption bands. The capability of this method is demonstrated on the example of natural resins and their ingredients, which are commonly known to be susceptible to oxidation at ambient conditions. The derivatization method enables one to identify various carbonyl containing functional groups by infrared spectroscopy, even in complex mixtures of terpenes. It unveils previously hidden degradation reactions running in terpenes and natural resins exposed to artificial aging by irradiation with light. New insight is presented on the individual reaction pathways of the terpenes hydroxydammarenone and abietic acid as well as of natural resin varnishes made from dammar and colophony.

  6. 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.

  7. 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.

  8. Corrosion and magnetic properties of encapsulated carbonyl iron particles in aqueous suspension by inorganic thin films for magnetorheological finishing application

    Science.gov (United States)

    Esmaeilzare, Amir; Rezaei, Seyed Mehdi; Ramezanzadeh, Bahram

    2018-04-01

    Magnetorheological fluid is composed of micro-size carbonyl iron (CI) particles for polishing of optical substrates. In this paper, the corrosion resistance of carbonyl iron (CI) particles modified with three inorganic thin films based on rare earth elements, including cerium oxide (CeO2), lanthanum oxide (La2O3) and praseodymium oxide (Pr2O3), was investigated. The morphology and chemistry of the CI-Ce, CI-Pr and CI-La particles were examined by high resolution Field Emission-Scanning Electron Microscopy (FE-SEM), X-ray energy dispersive spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS). The electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization tests were carried out to investigate the corrosion behavior of CI particles in aquatic environment. In addition, the Vibrating Sample Magnetometer (VSM) technique was utilized for determination of magnetic saturation properties of the coated particles. Afterwards, gas pycnometry and contact angle measurement methods were implemented to evaluate the density and hydrophilic properties of these particles. The results showed that deposition of all thin films increased the hydrophilic nature of these particles. In addition, it was observed that the amount of magnetic saturation properties attenuation for Pr2O3 and La2O3 films is greater than the CeO2 film. The EIS and polarization tests results confirmed that the CI-Ce had the maximum corrosion resistant among other samples. In addition, the thermogravimetric analysis (TGA) showed that the ceria coating provided particles with enhanced surface oxidation resistance.

  9. Metals 2000

    Energy Technology Data Exchange (ETDEWEB)

    Allison, S.W.; Rogers, L.C.; Slaughter, G. [Oak Ridge National Lab., TN (United States); Boensch, F.D. [6025 Oak Hill Lane, Centerville, OH (United States); Claus, R.O.; de Vries, M. [Virginia Polytechnic Inst. and State Univ., Blacksburg, VA (United States)

    1993-05-01

    This strategic planning exercise identified and characterized new and emerging advanced metallic technologies in the context of the drastic changes in global politics and decreasing fiscal resources. In consideration of a hierarchy of technology thrusts stated by various Department of Defense (DOD) spokesmen, and the need to find new and creative ways to acquire and organize programs within an evolving Wright Laboratory, five major candidate programs identified are: C-17 Flap, Transport Fuselage, Mach 5 Aircraft, 4.Fighter Structures, and 5. Missile Structures. These results were formed by extensive discussion with selected major contractors and other experts, and a survey of advanced metallic structure materials. Candidate structural applications with detailed metal structure descriptions bracket a wide variety of uses which warrant consideration for the suggested programs. An analysis on implementing smart skins and structures concepts is given from a metal structures perspective.

  10. Metal carbides

    International Nuclear Information System (INIS)

    Wells, A.F.

    1988-01-01

    From the viewpoint of general crystal chemistry principles and on the base of modern data the structural chemistry of metal carbides is presented. The classification deviding metal carbides into 4 groups depending on chemical and physical properties is presented. The features of the crystal structure of carbides of alkali alkaline earth, transition, 4 f- and 5f-elements and their effect on physical and chemical properties are considered

  11. Characterisation and optimisation of a sample preparation 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.

    2015-06-01

    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. 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. 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). With the present method quantification can be carried out for each carbonyl compound originating from fog, cloud and rain or sampled from the gas- and particle phase in water. Detection limits between 0.01 and 0.17 μmol L-1 were found, depending on carbonyl compounds. Furthermore, best results were found for the derivatisation with a PFBHA concentration of 0.43 mg mL-1 for 24 h followed by a subsequent extraction with dichloromethane for 30 min at pH = 1. 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 after a reaction time of 5 h.

  12. Levels of Crotonaldehyde and 4-hydroxy-(E-2-nonenal and Expression of Genes Encoding Carbonyl-Scavenging Enzyme at Critical Node During Rice Seed Aging

    Directory of Open Access Journals (Sweden)

    Fu Shenzao

    2018-05-01

    Full Text Available Abstract:: The critical node (CN is an important stage during seed aging, which is related to effective genebank conservation. Previous studies have demonstrated that proteins undergo carbonylated modification at the CN in rice, indicating oxidative damage. However, the levels of reactive carbonyl species (RCS and the associated scavenging system at the CN are largely unknown. In this study, we optimized methods for the extraction and analysis of RCS from dry rice embryos. In order to acquire seeds at the CN, rice seeds were subjected to natural conditions for 7, 9, 11 and 13 months, and the seed germination rates were reduced to 90%, 82%, 71% and 57%, respectively. We chose the stage with seed germination rate of 82% as the CN according to the rice seed vigor loss curve. The levels of crotonaldehyde and 4-hydroxy-(E-2-nonenal (HNE were significantly increased at the CN. In addition, genes encoding carbonyl-scavenging enzyme, including OsALDHs and OsAKRs, were significantly down-regulated at the CN, and reductions in the expression of OsALDH2-2, OsALDH2-5, OsALDH3-4, OsALDH7, OsAKR1 and OsAKR2 in particular could be responsible for RCS accumulation. Thus, the accumulations of crotonaldehyde and HNE and down-regulation of genes encoding carbonyl-scavenging enzyme might be related to an accelerating loss of seed viability at the CN. Key words: carbonyl-scavenging system, reactive carbonyl species, seed aging, crotonaldehyde, critical node, rice storage

  13. A High Resolution/Accurate Mass (HRAM) Data-Dependent MS3 Neutral Loss Screening, Classification, and Relative Quantitation Methodology for Carbonyl Compounds in Saliva

    Science.gov (United States)

    Dator, Romel; Carrà, Andrea; Maertens, Laura; Guidolin, Valeria; Villalta, Peter W.; Balbo, Silvia

    2017-04-01

    Reactive carbonyl compounds (RCCs) are ubiquitous in the environment and are generated endogenously as a result of various physiological and pathological processes. These compounds can react with biological molecules inducing deleterious processes believed to be at the basis of their toxic effects. Several of these compounds are implicated in neurotoxic processes, aging disorders, and cancer. Therefore, a method characterizing exposures to these chemicals will provide insights into how they may influence overall health and contribute to disease pathogenesis. Here, we have developed a high resolution accurate mass (HRAM) screening strategy allowing simultaneous identification and relative quantitation of DNPH-derivatized carbonyls in human biological fluids. The screening strategy involves the diagnostic neutral loss of hydroxyl radical triggering MS3 fragmentation, which is only observed in positive ionization mode of DNPH-derivatized carbonyls. Unique fragmentation pathways were used to develop a classification scheme for characterizing known and unanticipated/unknown carbonyl compounds present in saliva. Furthermore, a relative quantitation strategy was implemented to assess variations in the levels of carbonyl compounds before and after exposure using deuterated d 3 -DNPH. This relative quantitation method was tested on human samples before and after exposure to specific amounts of alcohol. The nano-electrospray ionization (nano-ESI) in positive mode afforded excellent sensitivity with detection limits on-column in the high-attomole levels. To the best of our knowledge, this is the first report of a method using HRAM neutral loss screening of carbonyl compounds. In addition, the method allows simultaneous characterization and relative quantitation of DNPH-derivatized compounds using nano-ESI in positive mode.

  14. 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

  15. Unusual structures and reactivity of mixed metal cluster complexes containing the palladium/platinum tri-t-butylphosphine grouping.

    Science.gov (United States)

    Adams, Richard D; Captain, Burjor

    2009-03-17

    Polynuclear metal carbonyl complexes have a range of applications in chemical research: for example, they can serve as surface models to probe features of heterogeneous catalysis and can perform novel transformations of organic molecules in solutions. Mixed metal complexes can demonstrate bimetallic cooperativity and synergism and can also serve as precursors to multimetallic heterogeneous catalysts that have superior activities and selectivities. This Account describes the results of our recent comprehensive study of the chemistry of mixed metal cluster complexes containing the sterically encumbered M(PBu(t)(3)), M = Pd or Pt, group. This grouping readily adds to the metal-metal bonds of metal carbonyl cluster complexes and modifies their reactivity. We have prepared new, highly electronically unsaturated mixed metal complexes that exhibit unusually high reactivity toward hydrogen. The platinum atom of the Pt(PBu(t)(3)) grouping can bond to as many as five metal atoms, and it can interconvert, sometimes rapidly, between the different bonding modes. The large steric effects of the PBu(t)(3) ligand allowed us to prepare highly unsaturated, stable, mixed-metal complexes, and these complexes react with hydrogen, sometimes reversibly, under very mild conditions to yield polyhydride complexes. Strong evidence suggests that the Pt(PBu(t)(3)) group can also activate metal-hydrogen bonds in other complexes. In the future, we expect that researchers will prepare a greater variety of mixed metal complexes containing the Pd/Pt(PBu(t)(3)) group or other similar bulky groups, and that some of these complexes will exhibit even more unusual chemistry than what we have observed so far.

  16. Synthesis, characterization, biological evaluation and docking studies of 2‧-[(2″,4″-difluorobiphenyl-4-yl)carbonyl]-1‧-aryl-1‧,2‧,5‧,6‧,7‧,7a‧-hexahydrospiro[indole-3,3‧-pyrrolizin]-2(1H)-ones

    Science.gov (United States)

    Fathimunnisa, M.; Manikandan, H.; Neelakandan, K.; Rajendra Prasad, N.; Selvanayagam, S.; Sridhar, B.

    2016-10-01

    A series of novel 2‧-[(2″,4″-difluorobiphenyl-4-yl)carbonyl]-1‧-aryl-1‧,2‧,5‧,6‧,7‧,7a‧-hexahydrospiro[indole-3,3‧-pyrrolizin]-2(1H)-ones were regioselectively synthesized by multicomponent reaction with excellent yield. They were characterized by elemental analysis and various spectral techniques. Sensing ability of the compound to different metal ions was investigated. To ascertain the inhibitory activity of the compounds they were subjected to in vitro antimicrobial studies against various microbes and cytotoxic studies against Hep-2 cell line. The ligand-receptor interaction of the compounds was explored by molecular docking and the human folate receptor (4LRH) was identified as the potential target protein. DFT calculations were incorporated in the study to compare the molecular structure and geometrical parameters of 2‧-[(2″,4″-difluorobiphenyl-4-yl)carbonyl]-1‧-phenyl-1‧,2‧,5‧,6‧,7‧,7a‧-hexahydrospiro[indole-3,3‧-pyrrolizin]-2(1H)-one with experimental data.

  17. Effect of pretreatment temperature on catalytic performance of the catalysts derived from cobalt carbonyl cluster in Fischer-Tropsch Synthesis

    Directory of Open Access Journals (Sweden)

    Byambasuren O

    2017-02-01

    Full Text Available The monometallic cobalt-based catalysts were prepared by pretreating the catalysts derived from carbonyl cluster precursor (CO6Co2CC(COOH2 supported on γ-Al2O3 with hydrogen at 180, 220, and 260°C respectively. The temperature effect of the pretreatments on the structure evolution of cluster precursors and the catalytic performance of the Fischer-Tropsch (F-T synthesis was investigated. The pretreated catalyst at 220°C with unique phase structure exhibited best catalytic activity and selectivity among three pretreated catalysts. Moreover, the catalysts exhibited high dispersion due to the formation of hydrogen bonds between the cluster precursor and γ-Al2O3 support.

  18. Increase of gluthatione S-transferase, carboxyl esterase and carbonyl reductase in Fasciola hepatica recovered from triclabendazole treated sheep.

    Science.gov (United States)

    Scarcella, S; Solana, M V; Fernandez, V; Lamenza, P; Ceballos, L; Solana, H

    2013-10-01

    Fasciolasis is a zoonotic parasitic disease caused by Fasciola hepatica and its control is mainly based on the use of triclabendazole (TCBZ). Parasite resistance to different anthelmintics is growing worldwide, including the resistance of F. hepatica to TCBZ. In the present work we evaluate "in vivo" the activity of xenobiotic metabolizing enzymes of phase I (carboxyl esterases) and phase II (glutathione S-transferases and carbonyl reductases) recovered of flukes from sheep treated with TCBZ. All three enzymes showed increased activity in TCBZ flukes returning 60h post-treatment at similar to baseline unexposed flukes. TCBZ action may induce secondary oxidative stress, which may explain the observed increment in activities of the analyzed enzymes as a defensive mechanism. The enzymes analyzed are candidates to participate actively in the development of resistance at TCBZ in F. hepatica. Copyright © 2013 Elsevier B.V. All rights reserved.

  19. Aldo-keto reductase family 1 B10 protein detoxifies dietary and lipid-derived alpha, beta-unsaturated carbonyls at physiological levels

    Energy Technology Data Exchange (ETDEWEB)

    Zhong, Linlin [Department of Medical Microbiology, Immunology, and Cell Biology, SimmonsCooper Cancer Institute, Southern Illinois University School of Medicine, 913 N. Rutledge Street, Springfield, IL 62794-9626 (United States); Department of Neurobiology and Anatomy, China Medical University, Shenyang 110001 (China); Liu, Ziwen [Department of Medical Microbiology, Immunology, and Cell Biology, SimmonsCooper Cancer Institute, Southern Illinois University School of Medicine, 913 N. Rutledge Street, Springfield, IL 62794-9626 (United States); Department of Surgery, Peking Union Medical College Hospital, Beijing 100730 (China); Yan, Ruilan [Department of Medical Microbiology, Immunology, and Cell Biology, SimmonsCooper Cancer Institute, Southern Illinois University School of Medicine, 913 N. Rutledge Street, Springfield, IL 62794-9626 (United States); Johnson, Stephen [Carbon Dynamics Institute, LLC, 2835 via Verde Drive, Springfield, IL 62703-4325 (United States); Zhao, Yupei [Department of Surgery, Peking Union Medical College Hospital, Beijing 100730 (China); Fang, Xiubin [Department of Neurobiology and Anatomy, China Medical University, Shenyang 110001 (China); Cao, Deliang, E-mail: dcao@siumed.edu [Department of Medical Microbiology, Immunology, and Cell Biology, SimmonsCooper Cancer Institute, Southern Illinois University School of Medicine, 913 N. Rutledge Street, Springfield, IL 62794-9626 (United States)

    2009-09-18

    Alpha, beta-unsaturated carbonyls are highly reactive mutagens and carcinogens to which humans are exposed on a daily basis. This study demonstrates that aldo-keto reductase family 1 member B10 (AKR1B10) is a critical protein in detoxifying dietary and lipid-derived unsaturated carbonyls. Purified AKR1B10 recombinant protein efficiently catalyzed the reduction to less toxic alcohol forms of crotonaldehyde at 0.90 {mu}M, 4-hydroxynonenal (HNE) at 0.10 {mu}M, trans-2-hexanal at 0.10 {mu}M, and trans-2,4-hexadienal at 0.05 {mu}M, the concentrations at or lower than physiological exposures. Ectopically expressed AKR1B10 in 293T cells eliminated immediately HNE at 1 (subtoxic) or 5 {mu}M (toxic) by converting to 1,4-dihydroxynonene, protecting the cells from HNE toxicity. AKR1B10 protein also showed strong enzymatic activity toward glutathione-conjugated carbonyls. Taken together, our study results suggest that AKR1B10 specifically expressed in the intestine is physiologically important in protecting the host cell against dietary and lipid-derived cytotoxic carbonyls.

  20. 2,2'-Fluorine mono-carbonyl curcumin induce reactive oxygen species-Mediated apoptosis in Human lung cancer NCI-H460 cells.

    Science.gov (United States)

    Liu, Guo-Yun; Zhai, Qiang; Chen, Jia-Zhuang; Zhang, Zhuo-Qing; Yang, Jie

    2016-09-05

    In this paper, we synthesized three fluorine-substituted mono-carbonyl curcumin analogs and evaluated their cytotoxicity against several cancer cells by the MTT assay. The results exhibited that all the three compounds were more active than the leading curcumin. Especially, 2,2'-F mono-carbonyl curcumin, 1a, surfaced as an important lead compound displaying almost 4-fold cytotoxicity relative to curcumin. More importantly, 1a was more stable in (RPMI)-1640 medium and more massive uptake than curcumin, which may be relationship to their cytotoxicity, apoptotic acitivity and reactive oxygen species generation. And then, the generation of reactive oxygen species can disrupt the intracellular redox balance, induce lipid peroxidation, cause the collapse of the mitochondrial membrane potential and ultimately lead to apoptosis. The results not only suggest that 2,2'-F mono-carbonyl curcumin (1a) may cause cancer cells apoptosis through reactive oxygen species-Mediated pathway, but also gives us an important information for design of mono-carbonyl curcumin analog. Copyright © 2016 Elsevier B.V. All rights reserved.

  1. 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.

  2. INHALATIONAL EXPOSURE TO CARBONYL SULFIDE (COS) PRODUCES BRAIN LESIONS AND ALTERED BRAINSTEM AUDITORY (BAER) AND SOMATOSENSORY (SEP) EVOKED POTENTIALS IN FISHCER 344N RATS.

    Science.gov (United States)

    Because of the amount of carbonyl sulfide (COS) emissions and the lack of toxicological data, COS was listed in the Clean Air Act of 1990 as a Hazardous Air Pollutant. In 1999 COS was nominated by the US EPA to the National Toxicology Program for additional toxicological investig...

  3. Probing the Reactivity of Dimethylsulfoxonium Methylide with Conjugated and Nonconjugated Carbonyl Compounds: An Undergraduate Experiment Combining Synthesis, Spectral Analysis, and Mechanistic Discovery

    Science.gov (United States)

    Ciaccio, James A.; Guevara, Elena L.; Alam, Rabeka; D'agrosa, Christina D.

    2010-01-01

    We introduce students to dimethylsulfoxonium methylide (DMSY) epoxidation of aryl and nonconjugated aliphatic aldehydes and ketones without revealing that DMSY cyclopropanates enones by Michael-initiated ring closure (MIRC). Each student performs the reaction of DMSY with one of nine carbonyl compounds, including four enones, and then analyzes the…

  4. 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.

  5. Hydroformylation of olefins and reductive carbonylation of aryl halides with syngas formed ex situ from dehydrogenative decarbonylation of hexane-1,6-diol

    DEFF Research Database (Denmark)

    Christensen, Stig Holden; Olsen, Esben Paul Krogh; Rosenbaum, Jascha

    2014-01-01

    and then consumed in the other chamber in either a rhodium-catalysed hydroformylation of olefins or a palladium-catalysed reductive carbonylation of aryl halides. Hexane-1,6-diol was found to be the optimum alcohol for both reactions where moderate to excellent yields were obtained of the product aldehydes...

  6. 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.

  7. 1,n-glycols as dialdehyde equivalents in iridium-catalyzed enantioselective carbonyl allylation and iterative two-directional assembly of 1,3-polyols.

    Science.gov (United States)

    Lu, Yu; Kim, In Su; Hassan, Abbas; Del Valle, David J; Krische, Michael J

    2009-01-01

    Unstable? We're able! 1,n-Glycols serve as synthetic equivalents to unstable dialdehydes in two-directional carbonyl allylation from the alcohol oxidation level under iridium-catalyzed transfer hydrogenation conditions. Iterative asymmetric allylation employing 1,3-propanediol enables the rapid assembly of protected 1,3-polyol substructures with exceptional levels of stereocontrol.

  8. Highly efficient energy transfer from a carbonyl carotenoid to chlorophyll a in the main light harvesting complex of Chromera velia.

    Science.gov (United States)

    Durchan, Milan; Keşan, Gürkan; Slouf, Václav; Fuciman, Marcel; Staleva, Hristina; Tichý, Josef; Litvín, Radek; Bína, David; Vácha, František; Polívka, Tomáš

    2014-10-01

    We report on energy transfer pathways in the main light-harvesting complex of photosynthetic relative of apicomplexan parasites, Chromera velia. This complex, denoted CLH, belongs to the family of FCP proteins and contains chlorophyll (Chl) a, violaxanthin, and the so far unidentified carbonyl carotenoid related to isofucoxanthin. The overall carotenoid-to-Chl-a energy transfer exhibits efficiency over 90% which is the largest among the FCP-like proteins studied so far. Three spectroscopically different isofucoxanthin-like molecules were identified in CLH, each having slightly different energy transfer efficiency that increases from isofucoxanthin-like molecules absorbing in the blue part of the spectrum to those absorbing in the reddest part of spectrum. Part of the energy transfer from carotenoids proceeds via the ultrafast S2 channel of both the violaxanthin and isofucoxanthin-like carotenoid, but major energy transfer pathway proceeds via the S1/ICT state of the isofucoxanthin-like carotenoid. Two S1/ICT-mediated channels characterized by time constants of ~0.5 and ~4ps were found. For the isofucoxanthin-like carotenoid excited at 480nm the slower channel dominates, while those excited at 540nm employs predominantly the fast 0.5ps channel. Comparing these data with the excited-state properties of the isofucoxanthin-like carotenoid in solution we conclude that, contrary to other members of the FCP family employing carbonyl carotenoids, CLH complex suppresses the charge transfer character of the S1/ICT state of the isofucoxanthin-like carotenoid to achieve the high carotenoid-to-Chl-a energy transfer efficiency. Copyright © 2014 Elsevier B.V. All rights reserved.

  9. 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)

  10. Facile preparation and enhanced microwave absorption properties of flake carbonyl iron/Fe{sub 3}O{sub 4} composite

    Energy Technology Data Exchange (ETDEWEB)

    Min, Dandan, E-mail: mdd4776@126.com; Zhou, Wancheng; Luo, Fa; Zhu, Dongmei

    2017-08-01

    Highlights: • Flake carbonyl iron/Fe{sub 3}O{sub 4} composites were prepared by surface oxidation technique. • Lower permittivity and modest permeability was obtained by the FCI/Fe{sub 3}O{sub 4} composites. • Enhanced absorption efficiency and broader absorption band were obtained. - Abstract: Flake carbonyl iron/Fe{sub 3}O{sub 4} (FCI/Fe{sub 3}O{sub 4}) composites with enhanced microwave absorption properties were prepared by a direct and flexible surface oxidation technique. The phase structures, morphology, magnetic properties, frequency-dependent electromagnetic and microwave absorption properties of the composites were investigated. The measurement results showed that lower permittivity as well as modest permeability was obtained by the FCI/Fe{sub 3}O{sub 4} composites. The calculated microwave absorption properties indicated that enhanced absorption efficiency and broader absorption band were obtained by the FCI/Fe{sub 3}O{sub 4} composite comparing with the FCI composite. The absorption frequency range with reflection loss (RL) below −5 dB of FCI/Fe{sub 3}O{sub 4} composites at reaction time of 90 min at thickness of 1.5 mm is 13.3 GHz from 4.7 to 18 GHz, while the bandwidth of the FCI composite is only 5.9 GHz from 2.6 to 8.5 GHz at the same thickness. Thus, such absorbers could act as effective and wide broadband microwave absorbers in the GHz range.

  11. metal alkoxides

    Indian Academy of Sciences (India)

    substituent effects in the head-to-tail double insertion reactions observed ... an internal standard. The yield of diphenyl carbodii- mide was further verified by isolating it as diphenyl urea after hydrolysis. The organic fraction obtained in the catalytic metathesis .... insertion of PhNCO into metal alkoxide 1a to generate. Table 1.

  12. Metallic glasses

    NARCIS (Netherlands)

    Schaafsma, Arjen Sybren

    1981-01-01

    It is shown in section 7.1. that the influence of topological disorder on the range of magnetic interactions in ferromagnetic transition metal-metalloid (TM-M) glasses, is much less than often assumed. This is demonstrated via a study of the temperature dependence of the average iron hyperfine field

  13. Highly-phosphorescent tungsten(0) carbonyl pyridyl-imidazole complexes as photosensitisers.

    Science.gov (United States)

    Lee, Jia Jin; Yap, Chew Pheng; Chwee, Tsz Sian; Fan, Wai Yip

    2017-08-22

    Photoluminescence data are reported for two W(CO) 4 L complexes (L = 2-(1H-imidazol-2-yl)pyridine and 2-(2'-pyridyl)benzimidazole) in room-temperature solutions. The bidentate ligands consist of a pyridine and an imidazole moiety connected by a C-C bond. The complexes have been found to exhibit enhanced phosphorescence from the metal-to-ligand charge transfer (MLCT) excited state with quantum yields in the order of 10 -3 , almost two orders of magnitude higher than those reported for W(CO) 4 (diimine) complexes. One of the complexes W(CO) 4 (2-(2'-pyridyl)benzimidazole) can serve as an efficient visible-light photosensitiser for the isomerisation of aromatic alkenes with efficiency comparable to and even exceeding that of the well-studied ruthenium tris-bipyridine complex, Ru(bpy)Cl 2 .

  14. A simple and highly selective ‘turn-on’ type fluorescence chemodosimeter for Hg2+ based on 1-(2-phenyl-2H-[1,2,3]triazole-4-carbonyl)thiosemicarbazide

    International Nuclear Information System (INIS)

    Lin, Hui; Shi, Wei; Tian, Yong; Ma, Fudong; Xu, Linxian; Ma, Junchi; Hui, Yonghai; Xie, Zhengfeng

    2015-01-01

    1-(2-phenyl-2H-[1,2,3]triazole-4-carbonyl)-4- (4-methylphenyl)thiosemicarbazide (M1) has been synthesized and investigated as a fluorescence chemodosimeter for Hg 2+ in dimethylsulfoxide. Highly selective ‘turn-on’ fluorescence alterations of M1 were observed upon the addition of Hg 2+ . Detection limit of Hg 2+ by M1 reaches ~3.7×10 −8 mol/L (evaluated by 3σ criteria).The coexistent metal ions rendered no obvious interference toward the optical response of M1 for Hg 2+ .The mechanism of M1 for the recognition of Hg 2+ has been investigated by FT-IR, 1 H NMR and MS analyses. - Highlights: • A type of thiosemicarbazide-derivatived compound (M1) was synthesized. • The fluorescence of M1 displayed highly selective ‘turn-on’ type fluorescence alteration with the presence of Hg 2+ . • Detection limit of ~3.7×10 −8 M for Hg 2+ can be obtained by this probing system. • Hg 2+ -induced intramolecular desulfurization and cyclization process of thiosemicarbazide moieties is the plausible probing mechanism

  15. Multivariate analysis of potential biomarkers of oxidative stress in Notopterus notopterus tissues from Mahanadi River as a function of concentration of heavy metals.

    Science.gov (United States)

    Mohanty, Deepali; Samanta, Luna

    2016-07-01

    In this study, investigation were done on the Mahanadi River water and health of dwelling Indian Knife fish Notopterus notopterus from three sites along the course of the river in an around Cuttack city (Odisha). Oxidative stress biomarker assays such as thiobarbituric acid reactive substances, protein carbonyls, protein and non-protein thionyls, reduced glutathione, metallothionein, superoxide dismutase, catalase, glutathione peroxidase/reductase couple, glutathione-S-transferase, and tissue metal (Fe, Cu, Ni, Cd, Pb and Zn) levels along with water quality assessments were assayed to measure the impacts on fish health. Results indicate that except Fe all other metals studied were within approved limits for fish liver and gill as approved by FAO/WHO. However, the muscle tissue do not have any metal beyond the permissible limit. A site and tissue specific response of the above mentioned oxidative biomarkers as well as metal accumulation in the fish tissues were noticed. Lipid peroxidation and protein carbonylation were increased gradually in the fish tissues collected from experimental sites along the course of the River in comparison to upstream reference site. Glutathione-S-transferase, glutathione peroxidase/reductase couple, reduced glutathione and non-protein thiol content were significantly decreased in fish tissues from experimental sites. An increase in metallothionein content was observed while superoxide dismutase and catalase showed tissue specific responses. Multivariate (Discriminant Function) analysis revealed that lipid peroxidation, protein carbonylation and superoxide dismutase have highest association as predictors of impact in the muscle and liver while that for gill is protein carbonylation, superoxide dismutase and glutathione reductase. Copyright © 2016 Elsevier Ltd. All rights reserved.

  16. 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.

  17. Chemical activation of molecules by metals: Experimental studies of electron distributions and bonding

    International Nuclear Information System (INIS)

    Lichtenberger, D.L.

    1991-10-01

    The formal relationship between measured molecular ionization energies and thermodynamic bond dissociation energies has been developed into a single equation which unifies the treatment of covalent bonds, ionic bonds, and partially ionic bonds. This relationship has been used to clarify the fundamental thermodynamic information relating to metal-hydrogen, metal-alkyl, and metal-metal bond energies. We have been able to obtain a direct observation and measurement of the stabilization energy provided by the agostic interaction of the C-H bond with the metal. The ionization energies have also been used to correlate the rates of carbonyl substitution reactions of (η 5 -C 5 H 4 X)Rh(CO) 2 complexes, and to reveal the electronic factors that control the stability of the transition state. The extent that the electronic features of these bonding interactions transfer to other chemical systems is being investigated in terms of the principle of additivity of ligand electronic effects. Specific examples under study include metal- phosphines, metal-halides, and metallocenes. Especially interesting has been the recent application of these techniques to the characterization of the soccer-ball shaped C 60 molecule, buckminsterfullerene, and its interaction with a metal surface. The high-resolution valence ionizations in the gas phase reveal the high symmetry of the molecule, and studies of thin films of C 60 reveal weak intermolecular interactions. Scanning tunneling and atomic force microscopy reveal the arrangement of spherical molecules on gold substrates, with significant delocalization of charge from the metal surface. 21 refs

  18. Corrosion of valve metals

    International Nuclear Information System (INIS)

    Draley, J.E.

    1976-01-01

    A general survey related to the corrosion of valve metals or film-forming metals. The way these metals corrode with some general examples is described. Valve metals form relatively perfect oxide films with little breakdown or leakage when anodized

  19. Metal phosphides

    International Nuclear Information System (INIS)

    Uehlls, A.

    1987-01-01

    The structure of phosphides of the most of elements: alkali, alkaline earth, rare earth, transition metals, actinides, indium, beryllium, cadmium forming the variety of formulae and types of structures, is considered. The ways of P atom combination in phosphides vary from single atoms (ions P 3- in compounds of electropositive elements) through one-, two-dimensional complexes P n up to three-dimensional (charged) grids. In all phosphides, containing the systems of bound atoms of phosphorus, certain or all from these atoms form less than three bonds P-P. The formation of one bond P-P by every atom leads to group P 2 found as P 2 4- ion in diphosphides of transition metals with the structure of the pyrite or marcasite type (RuP 2 ). LaP, SmP, ThP, UP, ZrP form structural type NaCl

  20. Crystal structure of the cis and trans polymorphs of bis-[μ-2-(1,3-benzo-thia-zol-2-yl)phenolato]-κ3N,O:O;κ3O:N,O-bis-[fac-tri-carbonyl-rhenium(I)].

    Science.gov (United States)

    Priyatharsini, Maruthupandiyan; Shankar, Bhaskaran; Sathiyendiran, Malaichamy; Srinivasan, Navaneethakrishnan; Krishnakumar, Rajaputi Venkatraman

    2017-02-01

    The title dinuclear complex, [Re 2 (C 13 H 8 NOS) 2 (CO) 6 ], crystallizes in two polymorphs where the 2-(1,3-benzo-thia-zol-2-yl)phenolate ligands and two carbonyl groups are trans - ( I ) or cis -arranged ( II ) with respect to the [Re 2 O 2 (CO) 4 ] core. Polymorphs I and II exhibit a crystallographically imposed centre of symmetry and a twofold rotation axis, respectively. The structures may be described as being formed by two octa-hedrally distorted metal-coordinating units fused through μ-oxido bridges, leading to edge-sharing dimers. The crystal packing is governed by C-H⋯O hydrogen-bonding inter-actions, forming chains parallel to the c axis in I and a three-dimensional network in II .

  1. Analysis of Selected Carbonyl Compounds in Tobacco Samples by Using Pentafluorobenzylhydroxylamine Derivatization and Gas Chromatography-Mass Spectrometry

    Directory of Open Access Journals (Sweden)

    Bao Mingliang

    2014-09-01

    Full Text Available Nous avons mis au point une méthode, à la fois fiable, précise et simple, d’analyse courante des composés carbonylés, en ce compris le formaldéhyde, l’acétaldéhyde, l’acétone, le propionaldéhyde, la méthyléthylcétone (MEC, le butyraldéhyde et le crotonaldéhyde, présents à l’état de traces dans les produits de tabac ouvré. Un échantillon d’un gramme de tabac, additionné d’un mélange de carbonyles marqués d’un isotope en guise de normes internes, a été extrait par l’eau. Une part de l’extrait aqueux a subi un processus de dérivatisation à l’aide de chlorhydrate d’o-(2,3,4,5,6-pentafluorobenzyle-hydroxylamine (PFBHA. Les dérivés carbonylés obtenus à l’aide du PFBHA ont ensuite été extraits par l’hexane et analysés par chromatographie en phase gazeuse couplée à la spectrométrie de masse (GC-MS. La précision et l’exactitude de la méthode ont été évaluées au regard d’une cigarette de référence Kentucky « additionnée » 3R4F et de produits de référence sans fumée CORESTA CRP1, CRP2, CRP3 et CRP4. Eu égard aux composés carbonylés analysés, d’excellents taux de précision (5-10% et de récupération (95-107% ont été observés avec divers produits du tabac « additionnés », à l’exception de l’acroléine, qui s’est avérée instable dans tous les produits du tabac testés. L’intervalle linéaire de la méthode mise au point s’est étendu de 0,07 à 36 μg/g avec des limites de quantification variant de 0,10 à 0,15 μg/g. Grâce à la présente méthode, le formaldéhyde (0,31-6,24 μg/g et l’acétaldéhyde (0,84- 17,7 μg/g ont été décelés dans tous les produits de référence testés. L’acétone (0,55-2,12 μg/g a été trouvée dans les produits 3R4F, CRP1, CRP2 et CRP3. Des niveaux décelables de propionaldéhyde n’ont été observés que dans les produits CRP1 et CRP3. Les niveaux de MEC, butyraldéhyde et crotonaldéhyde décelés dans tous

  2. Effect of pyridine and vanadium-, iron- and molybdenum compounds on carbonylation of azo- and nitro compounds in the presence of RhCl3x4H2O

    International Nuclear Information System (INIS)

    Manov-Yuvenskij, V.I.; Petrovskij, K.B.; Lapidus, A.L.

    1983-01-01

    The reaction of azo- and nitro compounds carbonylation in the presence of RhCl 3 x4H 2 0 and the effect of pyridine and vanadium-, iron-, molybdenum compounds, on the reaction are studied. Rhodium trichloride tetrahydrate without promotors catalyses the synthesis of isocyanates by carbonylation of azobenzenes. Pyridine, vanadium-, molybdenum compounds iron acetyl-acetonate inhibit this reaction. Molybdic acid, its salts, molybdenum trioxide, vanadium pentoxide, vanadium (4) oxichloride complex with dioxane, organometallic vanadium compounds, iron acetylacetonates and vanadium monoxide promote rhodiUm trichloride in carbonylation of nitrocompounds with carbon oxide

  3. Effect of pyridine and vanadium-, iron- and molybdenum compounds on carbonylation of azo- and nitro compounds in the presence of RhCl/sub 3/x4H/sub 2/O

    Energy Technology Data Exchange (ETDEWEB)

    Manov-Yuvenskij, V.I.; Petrovskij, K.B.; Lapidus, A.L. (AN SSSR, Moscow. Inst. Organicheskoj Khimii)

    1983-03-01

    The reaction of azo- and nitro compounds carbonylation in the presence of RhCl/sub 3/x4H/sub 2/0 and the effect of pyridine and vanadium-, iron-, molybdenum compounds, on the reaction are studied. Rhodium trichloride tetrahydrate without promotors catalyses the synthesis of isocyanates by carbonylation of azobenzenes. Pyridine, vanadium-, molybdenum compounds iron acetyl-acetonate inhibit this reaction. Molybdic acid, its salts, molybdenum trioxide, vanadium pentoxide, vanadium (4) oxichloride complex with dioxane, organometallic vanadium compounds, iron acetylacetonates and vanadium monoxide promote rhodium trichloride in carbonylation of nitrocompounds with carbon oxide.

  4. Prebiotic coordination chemistry: The potential role of transition-metal complexes in the chemical evolution

    Science.gov (United States)

    Beck, M.

    1979-01-01

    In approaching the extremely involved and complex problem of the origin of life, consideration of the coordination chemistry appeared not only as a possibility but as a necessity. The first model experiments appear to be promising because of prebiotic-type synthesis by means of transition-metal complexes. It is especially significant that in some instances various types of vitally important substances (nucleic bases, amino acids) are formed simultaneously. There is ground to hope that systematic studies in this field will clarify the role of transition-metal complexes in the organizatorial phase of chemical evolution. It is obvious that researchers working in the fields of the chemistry of cyano and carbonyl complexes, and of the catalytic effect of transition-metal complexes are best suited to study these aspects of the attractive and interesting problem of the origin of life.

  5. The use of biosorbents for heavy metals removal from aqueous media

    International Nuclear Information System (INIS)

    Al-Masri, M. S.; Amin, Y.

    2010-04-01

    Biomaterials, which could be adsorbed heavy metals, such bacteria, algae, yeasts, fungi and agricultural waste, is called Biomass. Recently, they are widely used for heavy metal removal from aqueous media, due to their large available quantities, low cost and good performance. The biosorbent, unlike mono functional ion exchange resins, contains variety of functional sites including carboxyl, imidazole, sulphydryl, amino, phosphate, sulfate, thioether, phenol, carbonyl, amide and hydroxyl moieties. In this paper, the biosorbents word widely and nationally used for heavy metal removal were reviewed. Their biosorption performance, their pretreatment and modification, aiming to improve their sorption capacity, and regeneration/reuse was introduced and evaluated. The potential application of biosorption and biosorbents was discussed. (author)

  6. UV laser deposition of metal films by photogenerated free radicals

    Science.gov (United States)

    Montgomery, R. K.; Mantei, T. D.

    1986-01-01

    A novel photochemical method for liquid-phase deposition of metal films is described. In the liquid phase deposition scheme, a metal containing compound and a metal-metal bonded carbonyl complex are dissolved together in a polar solvent and the mixture is irradiated using a UV laser. The optical arrangement consists of a HeCd laser which provides 7 mW of power at a wavelength of 325 nm in the TEM(OO) mode. The beam is attenuated and may be expanded to a diameter of 5-20 mm. Experiments with photochemical deposition of silver films onto glass and quartz substrates are described in detail. Mass spectrometric analysis of deposited silver films indicated a deposition rate of about 1 A/s at incident power levels of 0.01 W/sq cm. UV laser-induced copper and palladium films have also been obtained. A black and white photograph showing the silver Van Der Pauw pattern of a solution-deposited film is provided.

  7. Metal-Support Cooperative Catalysts for Environmentally Benign Molecular Transformations.

    Science.gov (United States)

    Kaneda, Kiyotomi; Mitsudome, Takato

    2017-01-01

    Metal-support cooperative catalysts have been developed for sustainable and environmentally benign molecular transformations. The active metal centers and supports in these catalysts could cooperatively activate substrates, resulting in high catalytic performance for liquid-phase reactions under mild conditions. These catalysts involved hydrotalcite-supported gold and silver nanoparticles with high catalytic activity for organic reactions such as aerobic oxidation, oxidative carbonylation, and chemoselective reduction of epoxides to alkenes and nitrostyrenes to aminostyrenes using alcohols and CO/H 2 O as reducing reagents. This high catalytic performance was due to cooperative catalysis between the metal nanoparticles and basic sites of the hydrotalcite support. To increase the metal-support cooperative effect, core-shell nanostructured catalysts consisting of gold or silver nanoparticles in the core and ceria supports in the shell were designed. These core-shell nanocomposite catalysts were effective for the chemoselective hydrogenation of nitrostyrenes to aminostyrenes, unsaturated aldehydes to allyl alcohols, and alkynes to alkenes using H 2 as a clean reductant. In addition, these solid catalysts could be recovered easily from the reaction mixture by simple filtration, and were reusable with high catalytic activity. © 2017 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Glassy metals

    CERN Document Server

    Russew, Krassimir

    2016-01-01

    The topics discussed in this book focus on fundamental problems concerning the structural relaxation of amorphous metallic alloys, above all the possibility of studying it on the basis of viscous flow behavior and its relation to rheological anomalies, such as bend stress relaxation, thermal expansion, specific heat, density changes, and crystallization. Most relaxation studies deal with the relaxation changes of a single definite material property, and not with a wider spectrum of physical properties integrated into a common framework. This book shows that it is possible to describe these property changes on the basis of a more comprehensive theoretical understanding of their mechanism.

  9. Mechanochemical processing for metals and metal alloys

    Science.gov (United States)

    Froes, Francis H.; Eranezhuth, Baburaj G.; Prisbrey, Keith

    2001-01-01

    A set of processes for preparing metal powders, including metal alloy powders, by ambient temperature reduction of a reducible metal compound by a reactive metal or metal hydride through mechanochemical processing. The reduction process includes milling reactants to induce and complete the reduction reaction. The preferred reducing agents include magnesium and calcium hydride powders. A process of pre-milling magnesium as a reducing agent to increase the activity of the magnesium has been established as one part of the invention.

  10. Visible-light-induced, Ir-catalyzed reactions of N-methyl-N-((trimethylsilylmethylaniline with cyclic α,β-unsaturated carbonyl compounds

    Directory of Open Access Journals (Sweden)

    Dominik Lenhart

    2014-04-01

    Full Text Available N-Methyl-N-((trimethylsilylmethylaniline was employed as reagent in visible-light-induced, iridium-catalyzed addition reactions to cyclic α,β-unsaturated carbonyl compounds. Typical reaction conditions included the use of one equivalent of the reaction substrate, 1.5 equivalents of the aniline and 2.5 mol % (in MeOH or 1.0 mol % (in CH2Cl2 [Ir(ppy2(dtbbpy]BF4 as the catalyst. Two major reaction products were obtained in combined yields of 30–67%. One product resulted from aminomethyl radical addition, the other product was a tricyclic compound, which is likely formed by attack of the intermediately formed α-carbonyl radical at the phenyl ring. For five-membered α,β-unsaturated lactone and lactam substrates, the latter products were the only products isolated. For the six-membered lactones and lactams and for cyclopentenone the simple addition products prevailed.

  11. Tracking reactive intermediates by FTIR monitoring of reactions in low-temperature sublimed solids: nitric oxide disproportionation mediated by ruthenium(II) carbonyl porphyrin Ru(TPP)(CO).

    Science.gov (United States)

    Azizyan, Arsen S; Kurtikyan, Tigran S; Martirosyan, Garik G; Ford, Peter C

    2013-05-06

    Interaction of NO ((15)NO) with amorphous layers of Ru(II) carbonyl porphyrin (Ru(TPP)(CO), TPP(2-) = meso-tetraphenylporphyrinato dianion) was monitored by FTIR spectroscopy from 80 K to room temperature. An intermediate spectrally characterized at very low temperatures (110 K) with ν(CO) at 2001 cm(-1) and ν(NO) at 1810 cm(-1) (1777 cm(-1) for (15)NO isotopomer) was readily assigned to the mixed carbonyl-nitrosyl complex Ru(TPP)(CO)(NO), which is the logical precursor to CO labilization. Remarkably, Ru(TPP)-mediated disproportionation of NO is seen even at 110 K, an indication of how facile this reaction is. By varying the quantity of supplied NO, it was also demonstrated that the key intermediate responsible for NO disproportionation is the dinitrosyl complex Ru(TPP)(NO)2, supporting the conclusion previously made from solution experiments.

  12. Reductive Umpolung of Carbonyl Derivatives with Visible-Light Photoredox Catalysis: Direct Access to Vicinal Diamines and Amino Alcohols via α-Amino Radicals and Ketyl Radicals

    KAUST Repository

    Fava, Eleonora

    2016-05-02

    Visible-light-mediated photoredox-catalyzed aldimine-aniline and aldehyde-aniline couplings have been realized. The reductive single electron transfer (SET) umpolung of various carbonyl derivatives enabled the generation of intermediary ketyl and α-amino radical anions, which were utilized for the synthesis of unsymmetrically substituted 1,2-diamines and amino alcohols. Anilines can be coupled with aldimines or aldehydes in a visible-light-mediated photoredox-catalyzed process. Reductive single electron transfer (SET) umpolung of the carbonyl derivatives leads to the generation of intermediary ketyl and α-amino radical anions, which were used for the synthesis of unsymmetrically substituted 1,2-diamines and amino alcohols.

  13. Principais carbonilas no ar de locais públicos no Rio de Janeiro Main carbonyls at indor public places of Rio de Janeiro

    Directory of Open Access Journals (Sweden)

    Eduardo Delfino Sodré

    2008-01-01

    Full Text Available An air quality evaluation of indoor environments with focus on lower carbonyls was carried out in 50 public places using TO-11A methodology. Formaldehyde levels (ranging from 12.5 to 1034 mg m-3 were above the threshold limit in 49 of 50 analyzed samples while acetaldehyde (ranging from 5.2 to 840 mg m-3 and acetone (ranging from 5.5 to 4839 mg m-3 were respectively bellow the limits of OSHA and NIOSH in all samples. However all samples were bellow the threshold limits suggested by the Brazilian legislation - NR-15. A correlation study between the carbonyls and temperature and humidity was also done.

  14. Metal filled porous carbon

    Science.gov (United States)

    Gross, Adam F [Los Angeles, CA; Vajo, John J [West Hills, CA; Cumberland, Robert W [Malibu, CA; Liu, Ping [Irvine, CA; Salguero, Tina T [Encino, CA

    2011-03-22

    A porous carbon scaffold with a surface and pores, the porous carbon scaffold containing a primary metal and a secondary metal, where the primary metal is a metal that does not wet the surface of the pores of the carbon scaffold but wets the surface of the secondary metal, and the secondary metal is interspersed between the surface of the pores of the carbon scaffold and the primary metal.

  15. Involvement of carbonyl reductase in superoxide formation through redox cycling of adrenochrome and 9,10-phenanthrenequinone in pig heart.

    Science.gov (United States)

    Oginuma, Michiko; Shimada, Hideaki; Imamura, Yorishige

    2005-08-15

    The effects of adrenochrome, a metabolite of epinephrine (adrenaline), and 9,10-phenanthrenequinone (PQ), a component of diesel exhaust particles, on the stereoselective reduction of 4-benzoylpyridine (4-BP) were examined in pig heart cytosol. PQ was a potent inhibitor for the 4-BP reduction, while adrenochrome was a poor inhibitor. A similar result was observed in the effects of adrenochrome and PQ on the reduction of all-trans retinal. Furthermore, although PQ mediated efficiently the formation of superoxide anion radical through its redox cycling in pig heart cytosol, adrenochrome had no ability to mediate the superoxide formation. These may be because the reactivity for adrenochrome, catalyzed by pig heart carbonyl reductase (PHCR), is much lower than that for PQ. The optimal pH for the reduction of PQ in pig heart cytosol was around 5.5. Dicumarol, a potent inhibitor of DT-diaphorase, had little effect on the time course of NADPH oxidation during the reduction of PQ. Therefore, it is concluded that PHCR plays a critical role in superoxide formation through redox cycling of PQ.

  16. 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.

  17. A combined experimental and theoretical study of the thermal [3+2] cycloaddition of carbonyl ylides with activated alkenes

    Science.gov (United States)

    Hamza-Reguig, Samira; Bentabed-Ababsa, Ghenia; Domingo, Luis R.; Ríos-Gutiérrez, Mar; Philippot, Stéphanie; Fontanay, Stéphane; Duval, Raphaël E.; Ruchaud, Sandrine; Bach, Stéphane; Roisnel, Thierry; Mongin, Florence

    2018-04-01

    4-Benzoyl-3,5-diaryltetrahydrofuran-2,2-dicarbonitriles were first synthesized from 2,2-dicyano-3-aryloxiranes and chalcones at toluene reflux; the 4,5-cis products proved to be predominantly formed and were isolated. Whereas shortened reaction times were observed by using microwave irradiation or catalytic cuprous chloride, no significant stereoselectivity change was in general noticed. Reacting 2,2-dicyano-3-aryloxiranes with 2-cyclopentenone next afforded 3-aryl-4-oxohexahydro-1H-cyclopenta[c]furan-1,1-dicarbonitriles, and the endo stereoisomers were isolated. That no stereoselectivity change was noticed in the presence of cuprous chloride rather suggests an impact of the salt on the epoxide ring opening. Finally, treatment of 2,2-dicyano-3-aryloxiranes by 2-morpholinoacrylonitrile yielded 3-cyano-3-morpholino-5-phenyltetrahydrofuran-2,2-dicarbonitriles from which the preponderant trans isomers were isolated. Importantly, the molecular mechanism of the domino reaction between 2,2-dicyano-3-phenyloxirane and 2-cyclopentenone was studied. The rate-determining thermal ring opening of the oxirane is followed by a non-concerted pseudoradical-type reaction of the carbonyl ylide with 2-cyclopentenone. Using the bond evolution theory also allowed the regioselectivity of this non-polar reaction to be explained.

  18. Radiosynthesis and Evaluation of [11C-Carbonyl]-Labeled Carbamates as Fatty Acid Amide Hydrolase Radiotracers for Positron Emission Tomography

    Science.gov (United States)

    2012-01-01

    Fatty acid amide hydrolase (FAAH) plays a key role in regulating the tone of the endocannabinoid system. Radiotracers are required to image and quantify FAAH activity in vivo. We have synthesized a series of potent FAAH inhibitors encompassing two classes of N-alkyl-O-arylcarbamates and radiolabeled eight of them with carbon-11. The [11C-carbonyl]-radiotracers were evaluated in vitro and ex vivo in rats as potential FAAH imaging agents for positron emission tomography (PET). Both sets of [11C]O-arylcarbamates showed good to excellent brain penetration and an appropriate regional distribution. Pretreatments with a FAAH inhibitor demonstrated that 80–95% of brain uptake of radioactivity constituted binding of the radiotracers to FAAH. Brain extraction measurements showed that binding to FAAH was irreversible and kinetically different for the two classes of carbamates. These promising results are discussed in terms of the requirements of a suitable radiotracer for the in vivo imaging of FAAH using PET. PMID:23214511

  19. Antibacterial and DNA cleavage activity of carbonyl functionalized N-heterocyclic carbene-silver(I) and selenium compounds

    Science.gov (United States)

    Haque, Rosenani A.; Iqbal, Muhammad Adnan; Mohamad, Faisal; Razali, Mohd R.

    2018-03-01

    The article describes syntheses and characterizations of carbonyl functionalized benzimidazolium salts, I-IV. While salts I-III are unstable at room temperature, salt IV remained stable and was further utilised to form N-heterocyclic carbene (NHC) compounds of silver(I), V and VI, and selenium compound, VII respectively. Compounds IV-VII were tested for their antibacterial potential against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus). Salt IV shows a very low inhibition potential (minimum inhibitory concentration, MIC 500 μg/mL) compared to the respective silver(I)-NHC, V and VI (MIC 31.25 μg/mL against both, E. coli and S. aureus) and selenium compound, VII (MIC 125 μg/mL against E. coli and 62.50 μg/mL against S. aureus). In DNA cleavage abilities, all the test compounds cleave DNA in which the VII cleaves the DNA at the faster rate. Meanwhile, the silver(I)-NHC complexes V and VI act at the same mode and pattern of DNA cleavage while VII is similar to IV.

  20. Multiple magnetic resonance and microwave absorption of metamaterial absorbers composed of double split ring resonators on grounded carbonyl iron composites

    Science.gov (United States)

    Lim, Jun-Hee; Kim, Sung-Soo

    2017-12-01

    This study investigates the triple-band absorption properties of metamaterial absorbers composed of a double split ring resonator (DSRR) on a grounded magnetic substrate of carbonyl iron powders. Computational tools are used to model the interaction between electromagnetic waves and the metamaterial structure. For perpendicular polarization with the electric field perpendicular to the SRR gap, triple-band absorption peaks are predicted in the simulation result of reflection loss. Magnetic resonance resulting from antiparallel currents between the upper DSRR and the lower ground plane is identified at the frequencies of the absorption peaks. The orientation of the two resonators influences the absorption characteristics, especially in the second and third peaks where the coupling between the inner SRR and outer SRR is strong. The current density distribution indicates that the two resonators oriented in the same direction achieve reduced coupling between them, which results in two absorption frequencies close to each other. For parallel polarization with the electric field parallel to the SRR gap, this study predicts dual-band absorption peaks corresponding to the magnetic resonance at the SRR wire.