大肠杆菌异源表达pmoB及催化甲烷氧化生成甲醇的研究

颗粒甲烷单加氧酶(pMMO)是甲烷氧化菌中催化甲烷氧化生成甲醇的一种酶.Methylococcus capsulatus IMV3021的pMMO活性位点是pmoB亚基,该亚基是一种可溶性蛋白.我们研究将pmoB亚基进行异源表达及生物催化活性的验证.当培养基中烟酰胺腺嘌呤二核苷酸(NADH)浓度为5 mmol/L时,可以观察到异源表达pmoB亚基具有催化甲烷氧化成甲醇活性,生成甲醇浓度为1.04 mmol/L.研究pMMO活性对于开发能直接将甲烷转化成甲醇的新型、环保催化剂有非常重要意义.     

大肠杆菌异源表达pMMO活性中心pmoB及生物催化研究

颗粒甲烷单加氧酶（pMMO）是甲烷氧化菌中催化甲烷氧化生成甲醇的一种酶．Methylococcus capsulatus IMV 3021的pMMO活性位点是pmoB亚基,该亚基是一种可溶性蛋白．我们研究将pmoB亚基进行异源表达及生物催化活性的验证．当培养基中烟酰胺腺嘌呤二核苷酸（NADH）浓度为5 mmol／L时,可以观察到异源表达pmoB亚基具有催化甲烷氧化成甲醇活性,生成甲醇浓度为1．04 mmol／L．研究pMMO活性对于开发能直接将甲烷转化成甲醇的新型、环保催化剂有非常重要意义．     

离子色谱法测定浴盐中的阴、阳离子

用离子色谱法测定浴盐中的Na^ 、K^ 、Mg^2 、Ca^2 、Cl^-、Br^-、SO4^2-时，分离阳离子的色谱柱为ICS-C25阳离子交换柱，淋洗液为2.0mmol/L均苯四甲酸溶液，流速为0.6mL/min；分离阴离子时的色谱柱为shim-pack IC-Al阴离子交换柱，淋洗液为2.5mmol/L邻苯二甲酸溶液－2.4mmol/L三羟基氨基甲烷溶液（体积比为1：1），流速为1.0mL/min。所测离子Na^ 、K^ 、Mg^2 、Ca^2 、Cl^-、Br^-、SO4^2-在较宽浓度范围内有良好的线性关系，回收率为94.7%-102.4%，检出限为0.001-0.02mg/L，相对标准偏差为1.03%-1.63%。     

甲烷生物催化氧化制甲醇——几种化学物质对Methylosinus trichosporium 3011甲醇累积的影响

本文报导了在 Methylosinus trichosporium 3011细胞反应液中加入一些化学物质对甲醇累积的影响。结果表明,Na~+抑制甲烷单加氧酶的活性。当 M.trichosporium 3011细胞反应液中含高浓度磷酸根时,只有很少量甲醇累积下来。EDTA 和 Na_2EDTA 甲醇累积的促进作用小于甲酸钠或甲酸的作用。但由于 EDTA 不仅可以抑制甲醇脱氢酶的活性,而且可以螯合 Na~+,而甲酸则可使 NADH 辅酶再生。因此,反应液中含有2mM EDTA 和20mM 甲酸时甲醇累积量最高。     

甲基弯菌IMV3011细胞生物催化二氧化碳制甲醇

甲基弯菌IMV 3011可以催化二氧化碳生物转化生成甲醇.在细胞悬浮液中充入二氧化碳后,反应一段时间后在反应液中检测到了甲醇产生.但是甲烷氧化细菌细胞合成甲醇的能力受到了细胞内还原当量的限制.研究发现,细胞内贮存的聚-β羟基丁酸(PHB)分解后能够产生还原当量,可以提高甲醇的产生能力.本文通过改变培养基中氮和铜的起始浓度对PHB积累量进行调节来提高甲基弯菌IMV 3011还原二氧化碳生成甲醇的能力.结果表明,随着细胞内PHB含量的增加甲醇的产生能力也会增加.当细胞内PHB的积累量达到38.6%时,将二氧化碳还原成甲醇的能力最强.当PHB的积累量超过38.6%时细胞生成甲醇的能力反而降低.     

甲醇驱动的环氧丙烷连续生物合成

采用甲醇蒸气作为碳源对甲基弯菌IMV 3011进行驯化培养,然后逐渐增加液态甲醇的浓度使其适应,得到了能耐受甲醇(φ(MeOH)=1%)的甲基弯菌IMV 3011.对甲基弯菌IMV 3011进行甲烷-甲醇共培养可得到大量具有甲烷单加氧酶(MMO)活性的细胞.研究了添加甲醇对甲基弯菌IMV 3011生长和MMO活性的影响,发现甲醇能够促进甲基弯菌IMV3011的生长.在批式反应器中,添加甲醇能够提高甲基弯菌IMV 3011的催化环氧化能力,说明甲醇可以作为电子供体通过再生辅酶NADH驱动环氧丙烷合成.考察了在膜反应器中用细胞悬浮液连续合成环氧丙烷的可行性.结果表明,通过192 h连续抽提产物环氧丙烷,避免了其对环氧化反应的抑制,流出液中环氧丙烷的浓度仍保持在1.35 mmol/L左右.     

山豆根中苦参碱和氧化苦参碱的胶束毛细管电泳法测定

用胶束毛细管电泳法（MECC）测定山豆根中的苦参碱及氧化苦参碱的含量，以盐酸麻黄碱作内标物，20mmol/L硼砂缓冲溶液（含30mmol/L十二烷基硫酸纳，体积分数40％甲醇）作电解质（pH=9.35），于208nm紫外检测，山豆根提取液中有效成分都获得基线分离；定量分析表明，苦参碱的质量浓度在0．08－0．52g/L、氧化苦参碱质量浓度在0．03－0．44g/L其峰面积与质量浓度呈线性关系（r分别为0．9987和0．9976）；此外，还讨论了不同缓冲液浓度、十二烷基硫酸钠（SDS）浓度及甲醇含量对2种有效成分迁移行为的影响。     

预富集电感耦合等离子体质谱法测定地下水中超痕量稀土元素及钪、钇

以P507萃淋树脂为固定相，HCl/EDTA为流动相，建立了地下水中超痕量稀土元素及钪、钇的ICP－MS测定的新方法。详细探讨了稀土元素（REEs）、Sc、Y与基体元素的分离、EDTA小体积洗脱的实验条件及ICP－MS工作参数。在pH2.6时上柱，大部分Ca、Mg，其体可不经淋洗而直接与REEs分离；以100mmol的EDTA洗脱，5mL淋洗体积REEs、Y、Sc回收率为96％－98.5%。详细考察了La、Ce、Pr的氧化物离子及氢氧化物离子的干扰及校正方法。分析方法的检测限为0.7-10.1ng/L，加标回收率为95％－99％。用于实际地下水及人工模拟水样的分析，结果令人满意。     

微生物燃料电池逆转化CO_2合成甲醇研究

微生物燃料电池(MFC)反应器是利用附着在阳极上的产氢微生物,在吸收烟气CO2的同时将其逆转化合成高附加值的生物合成燃料的装置。实验选用从牛粪中分离筛选出的梭状芽孢菌(Clostridium sp.)作为合成生物燃料的合成菌。将MFC反应装置接入电化学工作站进行循环伏安测试,当发生还原反应时,在-0.5V时出现还原峰。利用直流稳压电源恒电压电解,检测到合成的生物燃料为甲醇,在24h时甲醇的积累量达到最大3.13mmol/L;当CO2气体比例为15%时甲醇积累量最大,为2.98mmol/L。在细菌接种量为1m L时,甲醇积累量达到最大,为2.76mmol/L,最适条件下的CO2转化率为7.5%。     

MFC逆转化CO2合成甲醇研究

微生物燃料电池(MFC)反应器是利用附着在阳极上的产氢微生物,在吸收烟气CO2的同时将CO2逆转化合成高附加值的生物合成燃料的装置。试验选用从牛粪中分离筛选出的梭状芽孢菌(Clostridium.sp)作为合成生物燃料的合成菌,将MFC反应装置接入电化学工作站进行CV测试,当发生还原反应时,在-0.5 V时出现还原峰,利用直流稳压电源恒电压电解,检测到合成的生物燃料为甲醇。在24 h时甲醇的积累量达到最大3.13 mmol/L;当CO2气体比例为15%时甲醇积累量最大,为2.98 mmol/L。在细菌接种量为1 mL时,甲醇积累量达到最大,为2.76 mmol/L。,最适条件下的CO2转化率为7.5%。     

Dichroism of absorption and polarization of phosphorescence of molecules of the closed form of nitrobenzospirothiopyran

The spectral-polarization characteristics of absorption and phosphorescence of molecules of the initial form of nitro-substituted indolinospirobenzothiopyran were studied in oriented polyethylene films and in solutions with different polarity. An oscillator model of the electron transitions responsible for the formation of absorption and luminescence spectra was suggested. It was established that the principal differences in the spectral and photophysical properties of the compound studied and its oxygen-containing analog are associated with the fact that the electronegativity of the S atom is lower than that of the O atom. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1143–1146, June, 1997.     

非那雄胺合成工艺改进

非那雄胺能抑制5α-还原酶的活性,明显降低二氢睾酮水平,是一种治疗良性前列腺增生的有效药品。该合成工艺以甾烯酮酸为原料,将其与氯化亚砜反应,无须分离即与叔丁胺反应得17β-酰胺化合物,再氧化开环,环合,氢化,脱氢合成了非那雄胺。经元素分析、IR、1HNMR、13CNMR、MS分析表征了其结构。该法无须使用昂贵的2,2-二吡啶二硫化物和剧毒药品苯亚硒酸酐,且以乙酸铵代替氨气,降低了对设备的要求和腐蚀,更适用于工业生产。     

Synthesis of phenolic components of Grains of Paradise

Two vanilloids, (5E)-8-(4-hydroxy-3-methoxyphenyl)oct-5-en-4-one (1) and 4-[3-hydroxydecyl]-2-methoxyphenol (2), isolated from the dried seeds of Grains of Paradise (Aframomum melegueta), were synthesized; the latter compound was made as the S-enantiomer and the material derived from the seeds was found to be a 1:1.7 mixture of the R and S isomers. The synthetic route used should allow the preparation of analogs having extended alkyl chains and consequently different lipophilicity, and 3, a homolog of 2, was also prepared.     

Study of hydration of two cements of different strengths

Main hydration products of two cement pastes, i.e. CSH-gel, portlandite (P) (and specific surface S) were studied by static heating, and by SEM, TEM and XRD, as a function of cement strength (C-33 and C-43) hydration time (th) and subsequent hydration in water vapour.Total change in mass on hydration and air drying, M_o, increased with strength of cement paste and with hydration time. Content of water escaping at 110 to 220°C, defined as water bound with low energy, mainly interlayer and hydrate water, was independent on cement strength but its content increased with (th). Content of chemically bound (zeolitic) water in CSH-gel, escaping at 220-400°C, was slightly dependent on strength and increased with (th). It was possibly derived from the dehydroxylation of CSH-gel and AFm phase. Portlandite water, escaping at 400-500°C, was independent on cement strength and was higher on longer hydration. Large P crystals were formed in the weaker cement paste C-33. Smaller crystals were formed in C-43 but they increased with (th). Carbonate formated on contact with air (calcite, vaterite and aragonite), decomposed in cement at 600-700^oC. It was high in pastes C-33(1 month) and C-43(1 month), i.e. 5.7 and 3.3%, respectively; it was less than 1% after 6 hydration months (low sensitivity to carbonation) in agreement with the XRD study showing carbonates in the air dry paste (1month), and its absence on prolonged hydration (6 months) and on acetone treatment. Water vapour treatment of (6 months) pastes or wetting-drying increased this sensitivity.Nanosized P-crystals, detected by TEM, could contribute to the cement strength; carbonate was observed on the rims of gel clusters.This revised version was published online in November 2005 with corrections to the Cover Date.     

Acid hydrolysis of carboxymethylcellulose of low degree of substitution

Cotton cellulose was swollen in a sodium hydroxide solution and carboxymethylated by a two-bath method for different periods of time for each process. The kinetics of acid hydrolysis and the crystallinity of the swollen and carboxymethylated samples were measured. The proportion of broken bonds, rate constants for hydrolysis, and permeability of cellulose to hydrolyzing agents were calculated. The susceptibility of glycosidic linkages to acid hydrolysis was improved by carboxymethylation more than by swelling in alkali. The increased accessibility of carboxymethylcellulose to acid was regarded as a consequence of increased intra-and intercrystalline swelling and of the glycosidic bonds' weakness caused by the electron-attracting carboxymethyl group on the C-6 position.     

氯氧化镁生成热的研究

用氧化镁氯化镁水溶液制备了8水合氯氧化镁[nMg(OH)2·MgCl2·8H2O], 并测定了其在盐酸中的溶解热, 实验结果表明, 氯氧化镁溶解热与n值呈线性关系, 根据溶解热求出5Mg(OH)2·MgCl2·8H2O和3Mg(OH)2·MgCl2·8H2O的生成热分别为-7727.1和5888.1kJ·mol^1^-。     

Determination of heats of detonation and influence of components of composite explosives on heats of detonation of high explosives

The heats of detonation of 20 simple high explosives and explosive mixtures were determined by means of an adiabatic detonation calorimeter designed by the authors. The results indicated that the performance of the instrument was reliable and the experimental data were very accurate. For explosive mixtures, there was a linear accumulative relationship between the heats of detonation of the explosive mixture and its components. Accordingly, the heats of detonation of explosive mixtures could be calculated directly from the heats of detonation of simple explosives and the characteristic heats of other components. The experiments showed that the gold or brass shell of the cylindrical charge could be substituted by a thick-walled porcelain shell, which had the advantage of cheapness.

     

Estimation of Kinetic Parameters of Thermal Oxidation of Ilmenite

The aim of the presented work was the investigation of thermal oxidation of ilmenite in static air atmosphere. The investigations were carried out by use of a derivatograph (MOM, Hungary). The changes of crystallographic structure of investigated samples were identified by X-ray diffractometry on Philips PW-1710 diffractometer. In temperature above 500°C appears structure of hematite Fe₂O₃. On the basis of the thermogravimetric measurements, the contracting area and contracting volume models were found as the best fitting experimental data. This revised version was published online in August 2006 with corrections to the Cover Date.     

Mechanism of action of base-catalyzed oxygenation of phenol derivatives

Cyclopropyl derivative of 2,6-di-tert-butylphenol is synthesized as a probe to investigate the mechanism of base-catalyzed autooxidation of phenol derivatives. Our study indicates that one electron reduction of molecular oxygen from phenolate gives phenoxyl radical 3, a key intermediate of autooxidation. The coupling of phenoxyl radical and superoxide radical gives peroxylate anion 4 and produces the final epoxy alcohol adduct 6.