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1.
Porcine pancreatic lipase can catalyze transesterification reac tions in organic solvents in a highly regioselective manner. Lipase powder was suspended in solutions of various diols in ethyl carboxylates, and the mixtures were shaken at 30°C; as a result, pri mary monoesters of glycols were produced on a preparative scale.  相似文献   

2.
Evolved gas analysis‐mass spectrometry (EGA‐MS) was used for the first time to study archaeological wood, in order to investigate its chemical degradation. The archaeological wood was from an oak pile from a stilt house found in the Neolithic ‘La Marmotta’ village (Lake Bracciano, Rome, Italy). The sampling was performed from the external to the internal part of the pile, following the annual growth rings in groups of five. In addition, sound oak wood and isolated wood components (holocellulose and cellulose) were also analyzed, and the results were used to highlight differences because of degradation. Our study demonstrated that EGA‐MS provides information on the thermo‐chemistry of archaeological wood along with in‐depth compositional data thanks to the use of MS. Our investigations not only highlighted wood degradation in terms of differences between carbohydrates and lignin content, but also showed that lignin oxidation and depolymerization took place in the archaeological wood. Mass spectral data revealed differences among the archaeological samples from the internal to the external part of the pile. An increase in the formation of wood pyrolysis products bearing a carbonyl group at the benzylic position and a decrease in the amount of lignin dimers were observed. These were related to oxidation and depolymerization reactions, respectively. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   

3.
The lignin peroxidase (LiP) catalyzed oxidation of pyrogallol red (PR) in the absence and presence of veratryl alcohol (3,4-dimethoxybenzyl alcohol, VA) was carried out in bis (2-ethylhexyl) sulfosuccinate sodium (AOT)/ polyoxyethylene lauryl ether (Brij30) reversed micelles to elucidate the role of VA. Results indicated that VA could accelerate the LiP catalyzed oxidation of PR, especially at low H2O2 concentrations. Unlike in bulk aqueous medium, the protection of LiP by VA in the present medium was relatively unsubstantial, even at high H2O2 concentrations. Analysis of data from a series of experiments showed that the enhancement of the PR oxidation caused by VA was mainly due to the indirect oxidation of PR by VA+∙ from the LiP catalyzed oxidation of VA. It was also found that at the same protector concentration (40 μM), VA (the physiological substrate of LiP) was less effective than PR (a phenolic compound) in protecting LiP from the H2O2 derived inactivation. This novel phenomenon deserves further study.   相似文献   

4.
水溶性电泳漆溶剂中有机成分的气相色谱分析   总被引:2,自引:0,他引:2  
异丙醇,正丁醇,乙二醇单丁醚均为水溶性电泳漆溶剂中添加的有效成分,其含量的大小影响金属件着漆效果及经济成本,其中乙二醇单丁醚是电泳漆中高沸点溶剂,用作分散剂、湿润剂[1,2]。本文在文献[3,4]的基础上,考察了三种成分的气相色谱分离,确定了测定条件。1 实验部分1 1 仪器与测试条件日本产岛津GC-9A型气相色谱仪带C-R3A型色谱数据处理机。FID为检测器,1 6m×3 2mm玻璃柱,固定相GDX-103(60 80目),气化温度200℃,检测温度250℃,柱温144℃。载气:氮气50ml/min,氢气40ml/min,空气450ml/min。以保留时间定性,采用内标乙二醇单乙醚…  相似文献   

5.
The solubility of daidzin in different organic solvents and (ethyl alcohol + water) mixed solvents was measured by high performance liquid chromatography (HPLC) analysis method from T = (283.2 to 323.2) K at atmosphere pressure. The results show that at higher temperature more daidzin dissolves, and moreover, the solubility increases with the ethyl alcohol mole fraction increase in the (ethyl alcohol + water) mixed solvents. The experimental solubility values were correlated by a simplified thermodynamic equation, λh equation and modified Apelblat equation. Based on the solubility of daidzin, the enthalpy and entropy of solution were also evaluated by van’t Hoff equation. The results illustrated that the dissolution process of daidzin is endothermic and entropy driven.  相似文献   

6.
Acetic acid exists as dimers in organic solvents like benzene, toluene and xylene. Adsorption of dimeric acetic acid on activated charcoal (AC) at various temperatures from benzene, toluene and xylene solutions have been studied. The system obeys Langmuir isotherm, thus signifying a monolayer adsorption of dimers. Corrections on AC-solvent pore volume fillings, molecular cross sectional surface area of acetic acid dimers, the adsorption equilibrium constants, the free energy change and the enthalpy change values are computed at different temperatures for the three solvents. The adsorption process has been found to be physisorption type. The FTIR measurements show that the adsorbed acetic acid dimer seems to retain the cyclic structure against the open chain non-cyclic structure.  相似文献   

7.
Condensed tannins take an important part in the sensory quality of food and beverage. Sensory analyses are usually carried out with various tannin fractions isolated from food or beverage, and their interpretation are limited by the lack of knowledge in the fine and accurate molecular composition of the tannin fractions. Besides, the studies of the chemical reactivity conducted in model solutions with ‘simple’ flavanols allow a better understanding of their evolution pathways, but they cannot take into account their reactivity as polymers, specifically regarding oxidation. In particular, competition between intramolecular and intermolecular reactions may strongly impact on the tannin structures (size, branching and conformation) and consequently on their properties. An ultra‐performance liquid chromatography‐mass spectrometry electrospray ionization mass spectrometer analytical method was thus developed in order to identify oxidized tannins generated by autoxidation. Given the difficulties to separate and detect tannins with high DP, samples were depolymerized by chemical depolymerization prior to analysis. Since the linkages created by oxidation are not cleavable in the usual depolymerization conditions (contrarily to the original interflavanic linkages), specific oxidation residues are released from tannins structures after their autoxidation. Oxidation markers of both intermolecular and intramolecular mechanisms have been identified; these are mainly dimers and trimers, more or less oxidized, and some contain additional hydroxyl groups. Furthermore, the nature of the subunits (extension vs terminal) making up these dimers and trimers was clearly established. Copyright © 2012 John Wiley & Sons, Ltd.  相似文献   

8.
Kinetic studies on the oxidation of 1-phenyl ethanol and its para-methyl, para-methoxy and para chloro derivatives have been carried out using phase transferred chromate as oxidant in pure organic solvents. The inorganic oxidant was transferred to the non polar media using the phase transfer catalyst, tetrabutyl phosphonium bromide (TB PB). The electronic effects of the substituents, effect of varying the temperature on the rate, as well as the effect of varying the dielectric constant of the medium on the rate have been investigated. The rate data fitted well with the Hammett equation.  相似文献   

9.
Isothermal depolymerization of the two polymers of C60, i.e. of 1D orthorhombic phase (O) and of “dimer state” (DS) have been studied by means of Infra-red spectroscopy in the temperature ranges 383-423 and 453-503 K, respectively. Differential Scanning Calorimetry (DSC) has been used to obtained depolymerization polytherms for O-phase and DS. Standard set of reaction models have been applied to describe depolymerization behavior of O-phase and DS. The choice of the reaction models was based primarily on the isotherms. Several models however demonstrated almost equal goodness of fit and were statistically indistinguishable. In this case we looked for simpler/more realistic mechanistic model of the reaction. For DS the first-order expression (Mampel equation) with the activation energy Ea = 134 ± 7 kJ mol−1 and preexponential factor ln(A/s−1) = 30.6 ± 2.1, fitted the isothermal data. This activation energy was nearly the same as the activation energy of the solid-state reaction of dimerization of C60 reported in the literature. This made the enthalpy of depolymerization close to zero in accord with the DSC data on depolymerization of DS. Mampel equation gave the best fit to the polythermal data with Ea = 153 kJ mol−1 and preexponential factor ln(A/s−1) = 35.8. For O-phase two reasonable reaction models, i.e. Mampel equation and “contracting spheres” model equally fitted to the isothermal data with Ea = 196 ± 2 and 194 ± 8 kJ mol−1, respectively and ln(A/s−1) = 39.1 ± 0.5 and 37.4 ± 0.2, respectively and to polythermal data with Ea = 163 and 170 kJ mol−1, respectively and ln(A/s−1) = 32.5 and 29.5, respectively.  相似文献   

10.
The catecholamine oxidation process induces cardiotoxicity and neurotoxicity. Catecholamines can oxidize to aminochromes through autoxidation or by enzymatic or non-enzymatic catalysis. Although some toxic effects seem to be related to the formation of aminochromes there is still scarce information concerning the identification and evaluation of these compounds in in vivo models. In this study five catecholamines were oxidized to their respective aminochromes: adrenaline/adrenochrome; noradrenaline/noradrenochrome; dopa/dopachrome; dopamine/dopaminochrome; and isoproterenol/isoprenochrome. The evaluation of the catecholamines oxidation profile was performed by HPLC with photodiode array detection and using either enzymatic (tyrosinase) or non-enzymatic [Ag(2)O, CuSO(4), NaIO(4) and K(3)Fe(CN)(6)] catalytic systems. The NaIO(4) was found to be the most efficient oxidant of catecholamines. An isocratic reverse-phase HPLC method was developed to analyse each pair of catecholamine-aminochrome. The analytical system was then applied to the detection of adrenochrome in rat blood at 490 nm. Thus, adrenochrome was administered i.p. to rats and its concentration in whole blood was monitored after 5, 15 and 25 min. Blood treatment for adrenochrome evaluation consists of an acidification for protein precipitation followed by a rapid neutralization. The results showed a rapid decrease of adrenochrome concentration in blood after its administration. The adrenochrome present in blood was characterized by UV and tandem mass spectrometry.  相似文献   

11.
煤中可溶有机质对煤的孔隙结构及甲烷吸附特性影响   总被引:1,自引:0,他引:1  
采用四氢呋喃对临涣7煤和祁南3煤进行微波辅助抽提,进行了原煤和残煤等温吸附实验和低温氮气吸附测试,对比分析了抽提前后原煤和残煤的甲烷吸附量和比表面积、孔分布情况,并理论测算煤中可溶有机质吸附溶解甲烷量.结果表明,残煤的甲烷吸附能力低于原煤;抽提后,煤的比表面积和总孔体积增大,平均孔径减少,影响煤吸附气体能力的主要孔径为1.7~5.0 nm,且该范围内的孔数有不同程度的增加;压力为0.1~5.0 MPa时,两煤样中可溶有机质吸附溶解的甲烷量分别为0.45~4.22 mL/g、0.69~4.99 mL/g,最大吸附量分别占到原煤最大吸附量的30%和38%.分析认为,煤中可溶有机质占据部分煤中孔隙,影响煤孔隙结构,同时,在压力的作用下,甲烷可以溶解和吸附煤中可溶有机质.  相似文献   

12.
The efficiency of the bromide mediated benzoylperoxide oxidation of 2° alcohols to ketones was greatly improved by the addition of water. The aqueous oxidation protocol allows also the direct use of off-the-shelf benzoylperoxide reagent without an otherwise necessary and potentially dangerous drying procedure. The oxidation of cyclopentanol, cyclohexanol, 1-phenyl-ethanol and three menthol isomers occurred in good to excellent yields. The oxidation reaction tolerated N,N-dimethylacetamide (DMA) as the solvent, which resulted in a slightly lower oxidation rate than acetonitrile. Chemoselective oxidation of vicinal diols to α-hydroxy ketones did not succeed under the aqueous organic conditions employed as over-oxidation and bromination side-reactions were observed. The impact of water content, solvent, oxidant source and type of alcohol substrates employed was investigated.  相似文献   

13.
A spiro orthoester having an ester moiety, 2-acetoxymethyl-1,4,6-trioxaspiro[4.6]undecane (4) was synthesized, and its cationic polymerization and depolymerization of the obtained polymer (5) were carried out. The monomer 4 underwent cationic polymerization with a cationic catalyst to afford the corresponding poly(cyclic orthoester) 5. The obtained polymer 5 could be depolymerized with a cationic catalyst to regenerate the monomer 4 in an excellent yield. Further, bifunctional spiro orthoesters (6, 8, 9) having diester moieties were synthesized from terephthalic acid, succinic acid, and 1,4-cyclohexanedicarboxylic acid, and their acid-catalyzed reversible crosslinking–decrosslinking was examined. The bifunctional monomer 6 derived from terephthalic acid underwent cationic crosslinking to afford the corresponding network polymer (7), which could be also depolymerized to regenerate the original bifunctional monomer 6. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2551–2558, 1999  相似文献   

14.
顾方伟  刘海超 《催化学报》2020,(7):1073-1080
纤维素是葡萄糖通过β-1,4-糖苷键链接而成的高聚物,在木质纤维素中含量最高,结构稳定,较难水解.糖苷键的解聚主要有三种方式:酶水解、酸水解以及碱降解.酶解的优点是反应条件温和、副产物少,但存在成本高、活性低等缺点,限制了其大规模的工业化生产.碱水解纤维素的同时伴随着葡萄糖的peeling-off反应得到异变糖酸,需要消耗大量的碱,并且强碱也存在腐蚀性强和回收难等问题.酸水解是目前工业上常用的纤维素水解方法,在保持较高葡萄糖选择性的同时,通过对反应条件的控制(提高反应温度和酸浓度)来提高纤维素的水解效率,但是硫酸对设备的腐蚀性强,也难以回收,不符合绿色化学的发展要求.固体酸是近年来研究较多的纤维素水解催化剂.固体酸虽然腐蚀性弱、易回收,但是其活性低,水热稳定性较差,目前还不具备大规模生产的条件.本文发展了一种羟基自由基活化断裂糖苷键的方法,利用羟基自由基的高活性在低温下实现糖苷键的选择性断裂,同时羟基自由基与糖苷键作用后转化为无毒无害的水和氧气,将不会对环境造成污染.我们首先以纤维二糖作为纤维素的模型分子,通过羟基自由基能够优先与糖苷键反应得到葡萄糖和葡萄糖酸的实验证实所提出的方法的可行性.实验表明,来自H2O2的·OH自由基能够在铜基催化剂作用下选择性氧化断裂其糖苷键,生成葡萄糖和葡萄糖酸.比如:采用均相CuSO4体系,纤维二糖转化率约为20%时,葡萄糖和葡萄糖酸的选择性分别为28.5%和32.3%.采用多相CuO/SiO2(4 wt%CuO)体系,纤维二糖转化率约为20%时,葡萄糖和葡萄糖酸的选择性约分别为23.3%和25.7%,并且该催化剂具有良好的循环使用性能.与·OH类似,CuSO4催化过硫酸钾生成的·SO4-自由基也能够有效转化纤维二糖,在纤维二糖转化率为20%时,葡萄糖和葡萄糖酸的选择性分别为36.6%和39.9%.利用这种·OH和·SO4-自由基氧化的方法,也能够在较低温度下(333 K)解聚纤维素中的糖苷键.我们发展了H2O2浸渍预处理纤维浸渍预处理纤维素的方法,通过部分破坏纤维素糖苷键,提高了纤维素的水解活性.比如:处理后的纤维素在413 K条件下反应12 h,纤维素转化率和葡萄糖选择性分别达到约36.1%和42.5%.XRD结果表明,处理后的纤维素的晶体结构未发生明显的变化.FT-IR表征结果显示处理后的纤维素表面生成了大量的羧酸基团.  相似文献   

15.
湖南辰溪特高有机硫煤的稀土元素特征及其成因   总被引:1,自引:0,他引:1  
采用高分辨率电感耦合等离子质谱(HR-ICP-MS)技术测定辰溪晚二叠世高有机硫(7.75%)煤中的稀土元素(REEs)。辰溪煤中∑REE变化较大,从38.84 μg/g至305.85 μg/g,加权平均值为104.57 μg/g,高于世界煤均值,与中国煤相近。辰溪煤中有明显的Ce负异常(δCe=0.74~0.84)和Eu的负异常(δEu=0.55~0.69)。煤层剖面上稀土元素含量和分布模式的变化反映了成煤环境的波动,从底板到顶板陆源物质的影响减弱,而海水的影响增强。沉积环境的阶段性变化是导致剖面上下有机硫与黄铁矿硫比值相差悬殊的原因。辰溪煤中稀土元素与铁呈现了显著的正相关性(n=11,r=0.95),说明其物质来源和富集条件有一定相似性,即陆源物质和海水共同影响的结果。稀土元素的分布模式以及∑REE与灰分、Si、Al的相关性说明了其主要来源于陆源物质;辰溪煤中δCe与δEu在剖面上变化很小,说明海水对煤中的稀土元素存在重新改造的作用。  相似文献   

16.
To deeply understand the mechanism of inert gases in inhibiting coal spontaneous combustion, the effects of dry air, CO2, and N2 on coal spontaneous combustion were analyzed experimentally. To this end, bituminous coal prepared from Dongrong No. 2 Coal Mine was considered the research object. Based on the adsorption configuration of the oxygen-containing coal, the displacement behavior of O2 by CO2 /N2 was studied using the grand canonical Monte-Carlo (GCMC) and molecular dynamics (MD) methods. The obtained results show that the injection of CO2 and N2 reduces the ability of spontaneous combustion of coal. It is found that among the studied gases, CO2 has a stronger inhibition effect on coal spontaneous combustion, which increases the temperature of CO occurrence by 5℃, decreases the concentration of CO by 29.91%, and inhibits low-temperature oxidation of coal. From the microscopic point of view, CO2 /N2 gases can effectively displace O2 by diffusion and occupying adsorption sites. It is found that after the injection of CO2, the concentration of O2 molecules increases significantly in the vacuum layer. Compared with N2, injection of CO2 increases the diffusion activation of O2 by 5.89%. This indicates that the injection of an inert gas significantly reduces the oxygen absorption capacity of coal, thereby decreasing the coal-oxygen combination reaction and preventing the spontaneous combustion of coal. The performed analyses demonstrate that CO2 outperforms N2 in restraining the spontaneous combustion of coal.  相似文献   

17.
With the object to synthesize polyesters by enzymatic catalysis in organic media, two directions have been investigated: (1) the condensation polymerization of linear ω-hydroxyesters and (2) the ring-opening polymerization of lactones. The commercially-available crude porcine pancreatic lipase (PPL), suspended in organic solvents, was the preferred enzyme for the reactions. In order to determine the optimal conditions for the condensation polymerization, the bifunctional methyl 6-hydroxyhexanoate was used as a model compound to study the influence of the following parameters: type of the enzymecatalyst, kind of solvent, concentration, temperature, duration, size of the reaction mixture, and stirring. Film-forming polyesters with a degree of polymerization (DP) up to about 100 were obtained from linear aliphatic hydroxyesters in n-hexane at reflux temperature (69°C). Yet concurrently with the intermolecular condensation polymerization, macrolactones were also formed by intramolecular reaction. Two aromatic hydroxyesters did not react under these conditions. For the ring-opening polymerization of lactones the reaction of ?-caprolactone with methanol as the preferred nucleophile, was studied. Polyesters with a DP of up to 35 were obtained in n-hexane at temperatures between 25 and 40°C. The degrees of polymerization of the polyesters were determined by comparative analyses of the end groups in the 1H-NMR spectra and by determination of molecular weights either by vapor phase osmometry, gel permeation chromatography, or intrinsic viscosity. © 1993 John Wiley & Sons, Inc.  相似文献   

18.
Living cationic polymerization of fluorine‐containing vinyl ethers [CH2?CH? O? C2H4? O? C3H6? CnF2n+1: 5FVE (n = 2), 13FVE (n = 6)] was investigated in various solvents with a CH3CH(OiBu)OCOCH3/Et1.5AlCl1.5 initiating system in the presence of an added base. 5FVE was polymerized quantitatively in toluene at 0 °C, and the obtained polymers had predetermined molecular weights with narrow molecular weight distributions (Mw/Mn < 1.1). On the other hand, for the polymerization of 13FVE, the product polymers precipitated due to their extremely poor solubility in nonfluorinated organic solvents. Therefore, fluorinated solvents such as hydrochlorofluorocarbons, hydrofluorocarbons, hydrofluoroethers, or α,α,α‐trifluorotoluene, as‐yet uninvestigated for cationic polymerization, were employed. In these solvents, living polymerization was achieved even with 13FVE, yielding well‐defined polymers (Mw/Mn < 1.1, by size exclusion chromatography using a fluorinated solvent as an eluent). The solvents were also shown to be good for living polymerization of isobutyl vinyl ether. The obtained fluorine‐containing polymers underwent temperature‐responsive solubility transitions in organic solvents. Poly(5FVE) showed sensitive upper critical solution temperature (UCST)‐type phase separation behavior in toluene. Copolymers of 13FVE and isobutyl vinyl ether showed UCST‐type phase separation in common organic solvents with different polarities depending on their composition, while a homopolymer of 13FVE was insoluble in all nonfluorinated organic solvents. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011  相似文献   

19.
Partially fluorinated poly(vinyl ether)s with C4F9 and C6F12H groups in the side chain were synthesized via living cationic polymerization in the presence of an added base in a fluorine‐containing solvent, dichloropentafluoropropanes. For comparison, the polymerization of vinyl ether monomers with C2F5 and C6F13 groups and nonfluorinated monomers were also carried out. The characterization of the product polymers using size exclusion chromatography with a fluorinated solvent as an eluent indicated that all polymers had narrow molecular weight distributions (Mw/Mn ~ 1.1). Interestingly, the moderately fluorinated polymers with C4F9 exhibited upper critical solution temperature‐type phase separation in various organic solvents with wide‐ranging polarities, whereas highly fluorinated polymers with C6F13 are insoluble in nonfluorinated solvents. Polymers with C4F9 groups exhibited temperature dependent solubility transitions not only in common organic solvents (e.g., toluene, chloroform, tetrahydrofuran, and acetone) but also in perfluoro solvents [e.g., perfluoro(methylcyclohexane) and perfluorodecalin]. On the other hand, the solubility of polymers with C6F12H showed completely different from that of polymers with C6F13, despite their similar fluorine content. In addition, various types of fluorinated block copolymers were prepared in a living manner. The block copolymers with a thermosensitive fluorinated segment underwent temperature‐induced micellization and sol–gel transition in various organic solvents. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011  相似文献   

20.
内蒙古准格尔黑岱沟6号煤层中微量元素的相分异作用   总被引:2,自引:0,他引:2  
数理统计的方法,研究了准格尔6号煤中微量元素和泥炭沼泽沉积环境的关系。研究表明,煤中微量元素在泥炭沼泽沉积中,有着较为明显的“相分异”规律。多数处在元素周期表中第I、II主族,第四周期副族位置的元素,即相对较“轻”的元素,对镜惰比(V/I)及凝胶化指数(GI)反映比较灵敏或有一定关联性。因而反映潮湿还原的沼泽沉积环境比较有效,其典型代表就是Rb和Cs;而相对较“重”的元素,即第五周期以后的副族元素、第III主族以后的主族元素,则多对氧化指数(OI)和破碎指数(BI)响应比较灵敏或有某种间接的关联性,因而反映干燥氧化的沼泽沉积环境比较有效,其典型代表就是Hg和W。与植物组织保存指数(TPI)、植被指数(VI)和地下水流动指数(GWI)、搬运指数(TI)关联的元素则可看作介于两者之间。总之,微量元素从“轻”元素到“重”元素,从低阶周期到高阶周期,从低次主族到高次主族,有对V/I和GI反映灵敏转为对OI和BI更为灵敏的趋势。从而为微量元素(包括部分常量元素)对泥炭沼泽沉积亚微环境的识别和划分,提供了强有力的依据。  相似文献   

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