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1.
A nitroalkane-oxidizing enzyme was purified to homogeneity from Neurospora crassa. The enzyme is composed of two subunits; the molecular weight of each subunit is approximately 40,000. The enzyme catalyzes the oxidation of nitroalkanes to produce the corresponding carbonyl compounds. It acts on 2-nitropropane better than on nitroethane and 1-nitropropane, and anionic forms of nitroalkanes are much better substrates than are neutral forms. The enzyme does not act on aromatic compounds. When the enzyme reaction was conducted in an 18O2 atmosphere with the anionic form of 2-nitropropane as the substrate, acetone (with a molecular mass of 60 Da) was produced. This indicates that the oxygen atom of acetone was derived from molecular oxygen, not from water; hence, the enzyme is an oxygenase. The reaction stoichiometry was 2CH3CH(NO2)CH3 + O2-->2CH3COCH3 + 2HNO2, which is identical to that of the reaction of 2-nitropropane dioxygenase from Hansenula mrakii. The reaction of the Neurospora enzyme was inhibited by superoxide anion scavengers in the same manner as that of the Hansenula enzyme. Both of these enzymes are flavoenzymes; however, the Neurospora enzyme contains flavin mononucleotide as a prosthetic group, whereas the Hansenula enzyme contains flavin adenine dinucleotide.  相似文献   

2.
对钙钛矿(CaTiO_3)硫酸化分解,使钛组分转化为假板钛矿(Fe_2TiO_5)的反应体系进行分析,结果表明,采用在CaTiO_3/Fe SO4体系中通入SO_2+O_2混合气体的方法可以将钛组分一步转化为假板钛矿。基于此,考察了反应温度、配料比、气相中SO_2浓度以及反应时间等因素对硫酸化转化的影响。研究表明,在反应温度1 473 K、SO_2浓度为25%(体积分数)、反应时间120 min、CaTiO_3/Fe SO_4摩尔比1∶2.1条件下,钙钛矿中92%的钛组分可以转化成为假板钛矿;钙钛矿硫酸化分解机理随温度而变化,在温度为973~1 373 K时,钙钛矿是按照CaTiO_3+SO_2+1/2O_2=Ca SO4+TiO_2进行分解,而在1 473 K时,钙钛矿是按照CaTiO_3+SO_2+1/2O_2+Fe_2O_3=Ca SO4+Fe_2TiO_5进行分解。  相似文献   

3.
The SN2 displacements of chloride ion from CH3Cl, C2H5Cl, and C2H4Cl2 by acetate and hydroxide ions have been investigated, using ab initio molecular orbital theory at the HF/6-31+G(d), MP2/6-31+G(d), and MP4/6-31+G(d) levels of theory. The central barriers (calculated from the initial ion-molecule complex) of the reactions, the differences of the overall reaction energies, and the geometries of the transition states are compared. Essential stereochemical changes before and after the displacement reactions are described for selected cases. The gas phase reactions of hydroxide with CH3Cl, C2H5Cl, and C2H4Cl2 have no overall barrier, but there is a small overall barrier for the reactions of acetate with CH3Cl, C2H5Cl, and C2H4Cl2. A self-consistent reaction field solvation model was used to examine the SN2 reactions between methyl chloride and hydroxide ion and between 1,2-dichloroethane and acetate in solution. As expected, the reactions in polar solvent have a large barrier. However, the transition state structures determined by ab initio calculations change only slightly in the presence of a highly polar solvent as compared with the gas phase. We also calibrated the PM3 method for future study of an enzymatic SN2 displacement of halogen.  相似文献   

4.
Bothrareearthions[1 ] and 8 hydrox yquinolinepossessantibacterialfunction[2 ] ,andtheircomplexeshavemorepowerfuldisin fection .Thebinarycomplexesofthemwerere portedasearlyas 1 96 3.Meanwhile ,there searchontheternarycomplexesofthemhasbecomeveryactiveinrecentyearsan…  相似文献   

5.
The kinetics of the reaction between the octanucleotide d(TTGGCCAA) in the single-stranded form in pure water and the platinum complex [Pt(NH3)3(H2O)]2+ was investigated by electrospray ionization and matrix-assisted laser desorption/ionization (MALDI) mass spectrometries coupled with enzymatic degradation of the adducts. These methods led to the determination of specific rate constants of platination. The global rate constant characteristic of the formation of adducts on each 5'- or 3'-guanine were measured by electrospray ionization analysis. The ratios between the 5'- and 3'-adducts were determined from enzymatic degradation of the final reaction mixture and MALDI analysis. The platination in water is approximately eight times faster than in 0.1 M NaClO4. The selectivity of platination is a factor of 2 in favor of the 5'-guanine, and similar to that observed for the reaction between d(CTGGCTCA) and [Pt(NH3)3(H2O)]2+ in 0.1 M NaClO4.  相似文献   

6.
The characteristics of the mass spectra of sixty steroids were investigated using atmospheric pressure chemical ionization-mass spectrometry (APCI-MS). In APCI-MS, the drift voltage and nebulizer temperature affected the appearance of molecular ions. Solvent adducted ions [M+H+CH3CN]+ and [M+H+H2O]+ were decreased with an increase in drift voltage. The optimum drift voltage differed slightly for each steroid. These sixty steroids were divided into two groups according to their mass spectra profiles: one having a carbonyl group at position 3 together with a double bond at position 4 (group A) and the other bearing a hydroxyl group at the 3 position (group B). In group A, the predominant peak observed corresponded to the protonated molecular ion [M+H]+. The fragment ion corresponding to the elimination of CH2OH, COCH3 and/or COCH2OH from the steroid skeleton appeared as a base peak in some steroids of group A. In group B, predominantly [M+H-H2O]+ and/or [M+H-2H2O]+ ion(s), originating from the loss of water molecules, were observed. Other major ions in this group were the protonated molecular ions. Like other chemical ionization mass spectrometry, the mass spectrum of each steroid was very simple. These results suggest that APCI-MS is a suitable tool for the determination of the mass number of polar, nonvolatile and thermolabile steroids without derivatization.  相似文献   

7.
Two series of modified oligonucleotides based on the self-complementary dodecamer d(CGCTAATTAGCG) were synthesized. The first contained the -C identical withCCH2R linker at C5 of deoxyuridine at position 4 (T*) of d(CGCT*AATTAGCG) and the second contained the -SR linker. The goal of the study was to evaluate and compare these two types of side chains for suitability as tethers for linking reporter groups to oligonucleotides. Our primary concern was how these tethers would effect duplex stability. The modified nucleosides were synthesized by palladium-mediated coupling reactions between the substituted alkyne and 5'-(4, 4'-dimethoxytrityl)-5-iodo-2'-deoxyuridine and between a disulfide and 5-chloromercurio-2'-deoxyuridine. The C5 deoxyuridine side chains evaluated included C identical with CCH3, C identical with CCH2NHC(O)CH3, C identical with CCH2N(CH3)2, C identical with CCH2N-HC(O)C5H4N, C identical with CCH2NHC(O)C10H15, SCH3, SC6H5 and SCH2CH2NHC(O)CH3. The nucleosides containing these substituents were incorporated into oligo-deoxyribonucleotides by standard phosphoramidite methodology. Melting studies demonstrated that the sequence containing the C identical with CCH3side chain had the highest T m value (59.1 degrees C) in comparison with the control sequence (T m = 55.2 degrees C) and that any additional substituent on C3 of the propynyl group lowered the T m value relative to propynyl. Nevertheless, even the most destabilizing substituent, adamantylcarbamoyl, yielded an oligodeoxyribonucleotide that dissociated with a T m of 54 degrees C, which is only 1.2 degrees C less than the control sequence. In contrast, the thioether substituents led to lower T m values, ranging from as low as 45.1 degrees C for SPh up to 52.2 degrees C for SMe. Replacing the methyl of the SMe substituent with a CH2CH2NHC(O)CH3 tether led to no further reduction in melting temperature. The T m value of the CH2CH2NHC(O)CH3-containing oligonucleotide was less than the natural sequence by 1.6 degrees C/substituent. This is sufficiently small that it is anticipated that the C5 thioether linkage may be as useful as the acetylenic linkage for tethering reporter groups to oligonucleotides. More importantly, the thioether linkage provides a means to position functional groups to interact specifically with opposing complementary (target) sequences.  相似文献   

8.
The acidic reduction of Hg using a continuous-flow analytical system was evaluated. With 25% SnCl2 as the reductant, characteristic concentrations (sensitivities) of 0.44 microgram/L (open cell) and 0.29 microgram/L (flow-through cell) were obtained using inorganic Hg2+ standards in 1.5% HCl. When CH3Hg+ standards were used, absorption signals were an order of magnitude lower, indicating that Sn(II) is incapable of producing Hg degree from organic Hg in this acidic reduction system. Addition of CdCl2 to the SnCl2 reductant, as suggested by Magos (1) for the reduction of organomercurials under alkaline conditions, was without beneficial effect. Similarly, combining Sn with another reducing agent (hydroxylamine hydrochloride), or a strong alkaline solution (40% NaOH), in the reaction coil of the flow-through system did not significantly enhance the Hg absorption signal for either inorganic or organic Hg. Recovery of Hg from spiked liver homogenates digested at 70-80 degrees C using a HNO3/H2SO4/HCl procedure and stabilized with 0.5 mM K2Cr2O7 was > 85% using either inorganic Hg2+ or CH3Hg+, indicating that this digestion procedure successfully breaks the C-Hg bond to form readily reducible Hg species. Using L-cysteine to stabilize standards of inorganic Hg2+ in HCl caused significant depressions of the Hg absorption signal at L-cysteine concentrations > 0.001% (approximately 0.5 mM); 0.1% L-cysteine caused total suppression of the Hg signal. These results indicate that: (1) acidic reduction of Hg by Sn in this continuous-flow system requires breakdown of organomercurials prior to analysis; (2) tissue digestion using HNO3/H2SO4/HCl followed by the addition of K2Cr2O7 to stabilize Hg2+ achieves this breakdown and allows good recovery of total Hg; and (3) use of L-cysteine to complex and prevent losses of Hg should be avoided in systems using acidic reduction of Hg. Concentrations of endogenous tissue sulfhydryls are generally lower than those associated with depressed absorbance signals during the acidic reduction of Hg.  相似文献   

9.
IRL 3630 (3), a single enantiomer of IRL 3461 with more potency was identified. Coupling reaction of the racemic fragment (1) with the chiral (L)-valinesulfonamide (2) under a biphasic solvent system (CH2Cl2-H2O) successfully led to the predominant formation of the desired isomer (3) with concomitant isomerization of 1. IRL 3630, N-butanesulfonyl-[N-(3,5-dimethylbenzoyl)-N-methyl-3-[4-(5-+ ++isoxazolyl) -phenyl]-(D)-alanyl]-(L)-valineamide, is a highly potent and bifunctional (ETA + ETB) antagonist [Ki(ETA) = 1.5 nM, Ki(ETB) = 1.2 nM].  相似文献   

10.
In laboratory-scale experiments with growing cells of the obligate methane-oxidizing strain M 102, an overall molar gas turnover ratio of the order given below could be postulated: 1 CH4+1--1.2 O2=0.3 CO2+water. Expectations that the optimal gas mixture of methane and oxygen should lie within the range of this stoichiometric consumption ratio have been verified in fermenter 5 1 batch culture experiments. The optimal range of methane-oxygen mixture, found under the experimental conditions described, is based on the estimated growth parameters as generation and doubling times, yield coefficients related to methane and oxygen, and the efficiency of methane metabolism as indicated in the absolute amounts of CH4, O2, and CO2 turned over. The mentioned stoichiometric relation of 1 CH4:1--1.202 did not change with varying the composition, i.e. the partial pressures of CH4 and O2 introduced as a mixture to the cells. The efficiency of methane oxidation was obviously influenced and decreased markedly when deviating from the broad optimal range of CH4/O2 mixtures. With non-growing cells, on the other hand, the stoichiometric relation showed a considerable shift (1:1.4--1.8 CH4:O2) with a clear tendency towards more O2 consumption. The oxidation potential of growing cells, seems then to have a linear interdependence to the substrate concentrations, i.e. partial pressures.  相似文献   

11.
A series of monolithic Ni/γ-Al2O3 catalysts with and without basic promoters (Na, Sr, La, Ce) were prepared. Partial oxidation of methane (POM) to syngas was carried out in a continuous-flow, fixed-bed reactor. The influences of reaction conditions, including temperature, CH4/O2 ratio and space velocity, on the performance of the catalyst were investigated. The results show that at a high space velocity of 1×105 h-1, optimal CH4 conversion can be obtained. Effects of promoters such as Na, Sr, Ce, La were also investigated, and the catalyst samples were characterized by means of temperature-programmed reduction and XRD techniques. XRD suggests that the addition of promoters has no influence on the crystal structure of Ni/γ-Al2O3 catalyst. The results show that the addition of a small amount of promoters improves the reducibility and activity of the catalyst. The side reaction CH4 2 O2→CO2 H2O, is fully restrained and 100% H2 selectivity is achieved when Ce and La are used as promoters, respectively.  相似文献   

12.
Seven analogues of the trisaccharide beta-D-Galp-(1-->4)-beta-D-GlcpNAc-(1-->2)-alpha-D-Manp-(1-->O)(CH 2)7CH3 have been synthesized as potential substrates for glycosyltransferases involved in the chain-termination of N-acetyllactosamine-type N-glycans. These compounds include: 3-O-methyl-beta-D-Galp-(1-->4)-beta-D-GlcpNAc-(1-->2)-alpha-D-Manp -(1-->O) (CH2)7CH3, 3-deoxy-beta-D-Galp-(1-->4)-beta-D-GlcpNAc-(1-->2)-alpha-D-Manp-(1 -->O) (CH2)7CH3, 3-deoxy-3-fluoro-beta-D-Galp-(1-->4)-beta-D-GlcpNAc-(1-->2)-alpha-D-M anp- (1-->O)(CH2)7Ch3, 3-amino-3-deoxy-beta-D-Galp-(1-->4)-beta-D-GlcpNAc-(1-->2)-alpha-D-Ma np- (1-->O)(CH2)7CH3, beta-D-Gulp-(1-->4)-beta-D-GlcpNAc-(1-->2)-alpha-D-Manp-(1-- >O)(CH2)7CH3, beta-L-Galp-(1-->4)-beta-D-GlcpNAc-(1-->2)-alpha-D-Manp-(1-->O)(CH 2)7CH3, and alpha-L-Altp-(1-->4)-beta-D-GlcpNAc-(1-->2)-alpha-D-Manp-(1- ->O) (CH2)7CH3. All trisaccharides were obtained by condensation of suitably modified glycosyl donors based on imidates or thioglycosides with the same disaccharide acceptor, octyl 3,4,6-tri-O-benzyl-2-O-(3,6-di-O-benzyl-2-deoxy-2-phthalimido-beta-D- glucopyranosyl)-alpha-D-mannopyranoside, followed by deprotection.  相似文献   

13.
Whether volume expansion influences NaC1 reabsorption by the diluting segment of the nephron remains a matter of controversy. In the present studies this question has been examined in normal unanesthetized dogs, undergoing maximal water diuresis. Free water clearance (CH2O/GFR) has been used as the index of NaC1 reabsorption in the diluting segment. Three expressions have been employed for "distal delivery" of NaC1: a) V/GFR, designated as the "volume term"; b) (CNa/GFR + CH2O/GFR), the "sodium term;" and c) (CC1/GFR + CH2O/GFR), the "chloride term". The validity of these terms is discussed. Three techniques were used to increase distal delivery: 1) the administration of acetazolamide to dogs in which extracellular fluid (ECF) volume was not expanded (grop 1); 2) "moderate" volume expansion (group 2); and 3) "marked" volume expansion (group 3). CH2O/GFR increased progressively with rising values for "distal delivery" regardless of which term was used to calculate the latter. With all three delivery terms, differences in distal NaC1 reabsorption emerged between the two volume-expanded groups, though only with the "chloride" term did substantial differences also emerge between the nonexpanded group 1 dogs and both volume-expanded groups. In group 1, values for CH2O/GFR increased in close to a linear fashion up to distal delivery values equal to 24% of the volume of glomerular filtrate. However, at high rates of distal delivery the rate of rise of CH2O/GFR was less in group 2 than in group 1 and the depression of values was even greater in group 3. Within the limits of the techniques used, the data suggest that volume expansion inhibits fractional NaC1 reabsorption in the diluting segment of the nephron in a dose-related fashion. The "chloride" term was found to be superior to the "volume" and "sodium" terms in revealing these changes.  相似文献   

14.
Ce3+ and Tb3+ co-doped SrSi2N2O2 phosphors were prepared by solid-state reaction. The X-ray diffraction pattern exhibited that the phosphor consisted mainly of oxygen-rich SrSi2N2O2. The optical properties of SrSi2N2O2:Ce3+, SrSi2N2O2:Tb3+ and SrSi2N2O2:Ce3+,Tb3+ were studied, respectively. The emission intensity of Tb3+ at 541 nm was remarkably enhanced by Ce3+ in SrSi2N2O2:Ce3+,Tb3+ phosphor, which was attributed to the energy transfer from Ce3+ to Tb3+. The chromaticity coordinates of phosphors were investigated as a function of Tb3+ concentration. When the Ce3+ and Tb3+ concentrations were 0.02 and 0.18 mol per formula unit, respectively, the chromaticity coordinate was (0.257, 0.337) in the CIE 1931 chromaticity diagram. SrSi2N2O2Ce3+,Tb3+ phosphors could be used for white light emitting diodes.  相似文献   

15.
随着烧结+鼓风炉工艺处理铅锌混合精矿能耗高和环境污染的问题日益凸显,使用熔池熔炼法替代烧结工艺成为铅锌混合精矿较好的火法冶炼工艺选择。采用静态法和XRD技术研究了O2流量、温度、入炉炉料成分对铅锌混合矿脱硫的影响以及脱硫渣物相变化。结果表明:与烧结工艺相比,铅锌混合精矿高温熔融脱硫时间短、脱硫率高。O2流量的增加和温度的提高有利于铅锌混合矿脱硫反应的进行,铅锌混合矿脱硫率随着ω(Fe)/ω(SiO2)和ω(CaO)/ω(SiO2)的增加而降低,但在1 400 ℃时ω(CaO)/>ω(SiO2)的增加有利于脱硫速率的加快和脱硫率的增加。当反应温度为1 250 ℃时,随着熔渣中Fe/SiO2的增加,熔渣中尖晶石相(ZnxFe3-xO4+y)开始形成并增多。   相似文献   

16.
Ce^3+-activated SrGa2O4 phosphor was synthesized by a method of citric gel,wherein citric acid served as a chelate agent,and the as-synthesized powder was calcined in a slightly reduced ambient.The crystallization characteristics of the sample varied with the calcining temperature.Compared with the phosphor prepared by the solid-state reaction,the phosphor synthesized by citric gel was calcined at a relatively lower temperature.Consequently,the volatilization of Ga2O3 during high-temperature calcining process was avoided.The typical double-peak emission of Ce^3+ originated from 2D(5d)→4F5/2(4f),and 2D(5d)→4F7/2(4f)was observed,and the intrinsic emission of SrGa2O4 host was much restricted.The emission intensity varied with the calcining temperature because the different crystallinity and the optimal concentration of Ce-dopant was determined at 3%.  相似文献   

17.
Serine and thiol proteases react with peptide substrates to form an acyl-enzyme. We have synthesized inhibitors which are pseudo-substrates and react with the proteases to generate acyl-enzymes which hydrolize slowly. This is achieved by incorporating an electron-donating group near the carbonyl group of inhibitors I [Ac-Phe--C(O)NH--NH--C(O)X] and II [benzyl-O-C(O)-psiAla-Leu-ArgOMe]. The acyl-enzymes derived from the reaction of I with papain and II with chymotrypsin hydrolyze with t1/2 of 12 and 1 h, respectively. The increased electron density on the carbonyl group of the inhibitor also reduces the rate of acyl-enzyme formation. Components were incorporated into the inhibitor which interact with the leaving group binding site (S' subsite) and which accelerate the rate of reaction of inhibitor with enzyme. For inhibitor I, X = NH(CH3), k(on) < 0.13 M(-1) s(-1) for the reaction papain, but if X = psiLeu(CH3)2,k(on) =10(5) M(-1) s(-1). Similar results were obtained with II and chymotrypsin. Concomitant with acyl-enzyme formation, X is released and a slowly hydrolyzing acyl-enzyme remains.  相似文献   

18.
Viscosities were measured for the ternary systems Y(NO3)3+La(NO3)3+H2O, La(NO3)3+Ce(NO3)3+H2O, and La(NO3)3+Nd(NO3)3+ H2O and their binary subsystems Y(NO3)3+H2O, La(NO3)3+H2O, Ce(NO3)3+H2O, and Nd(NO3)3+H2O at 293.15, 298.15 and 308.15 K. The results were used to test the applicability of simple equations for the viscosity of the mixed solutions. The predictions agreed well with measured values, implying that the viscosities of the examined electrolyte solutions could be related to those of their constituent binary solutions using these simple equations.  相似文献   

19.
The chemical synthesis of beta-D-GlcpA-(1-->3)-beta-D-GalpNAc-(1-->O)CH2CH = CH2, beta-D-Galp-NAc-(1-->6)-[beta-D-GlcpA-(1-->3)]-beta-D-GalpNAc-(1-- >O)CH2CH = CH2, and beta-D-GlcpA-(1-->3)-beta-D-GalpNAc-(1-->6)-[beta-D-GlcpA-(1 -->3)] -beta-D-GalpNAc-(1-->O)CH2CH = CH2 is described. These oligosaccharides represent fragments of th circulating anodic antigen, secreted by the parasite Schistosoma mansoni in the circulatory system of the host. The applied synthesis strategy includes the preparation of a non-oxidised backbone oligosaccharide, with a levulinoyl group at O-6 of the beta-D-glucose residue. After the selective removal of the levulinoyl group, the obtained hydroxyl functions were converted into carboxyl groups, using pyridinium dichromate and acetic anhydride in dichloromethane, to afford the desired glucuronic-acid-containing oligosaccharides. Subsequently, the allyl glycosides have been elongated with cysteamine to give the corresponding amine-spacer-containing oligosaccharides.  相似文献   

20.
吴开基  陈凌  张涛  郭敏  鹿存房 《钢铁》2014,49(3):11-16
 利用焦炉煤气+气基竖炉生产优质海绵铁,可延伸焦化行业产业链,同时可促进中国废钢/海绵铁—电炉短流程发展,改变钢铁行业能源、产品结构。针对典型焦炉煤气,通过基础性试验研究了在气基竖炉工况下,温度、H2O和CO2配比,高温海绵铁载体对焦炉煤气中甲烷改质行为的影响。研究结果表明,提高温度有利于焦炉煤气中甲烷的改质反应,1000℃时改质后有效还原气体体积分数最高可达80%;热态海绵铁对焦炉煤气改质有催化促进作用,可提高CO2参与改质反应比例至84.9%、H2O参与反应比例至100%;CO2配入体积分数2%~6%、H2O配入体积分数4%~10%为促进甲烷改质反应的适宜范围。  相似文献   

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