植物组织基膜生物传感器的研制

应用微生物及动、植物组织的生物催化材料作传感器已越益引起人们的注意,已有用植物的叶、果、花等研制植物组织电极的报道。 香蕉皮中含有草酸盐氧化酶,苹果中含有L-天冬酸脱羧酶。我们选择了香蕉皮和苹果作为生物催化材料,以二氧化碳气敏电极为基础电极,研制了两种植物组织电极。     

乙炔电催化氧化制备草酸的机理研究

选择铂为电极电催化乙炔合成草酸,通过紫外-可见分光光度法和红外光谱法对产品进行表征,利用第一性原理计算方法探讨乙炔在催化剂Pt(111)表面的吸附情况,采用循环伏安法（CV）研究铂电极在硫酸钠溶液中氧化乙炔的电极过程,重点测定电极的稳态极化曲线并根据极化曲线推算塔菲尔斜率,结合表观传递系数及反应级数对拟定的乙炔电催化氧化制备草酸的反应机理进行验证. 实验结果表明,乙炔分子在Pt(111)面上呈平行桥键构型时吸附最稳定;铂电极在含体积分数为2%丙酮的0.4 mol·L^-1硫酸钠溶液中可将乙炔电催化氧化为草酸;反应的速率控制步骤为.     

香蕉组织膜草酸电极的研究

将香焦组织与氧电极偶合,制成了草酸生物组织电极。在静态和流动条件下,测得电极的线性响应范围分别为8.8×10~(-5)～6.3×10~(-4)mol/L和5.0×10~(-5)～1.8×10~(-3)mol/L,二者的相关系数均为0.9998。研究了介质条件、pH、温度、流速、取样量和固定化等条件的影响。测定了电极的选择性和使用寿命等性能。计算了该实验条件下酶反应的米氏常数。采用静态法和流动注射法测得7份草酸标液的平均回收率分别为98.4％和98.9％。电极已用于一些食品中草酸的测定,所得结果与文献报道基本一致。     

多酚氧化酶催化反应的抑制动力学及机理

用丙酮自香蕉皮中提取多酚氧化酶，用氧电极法测得酶促儿茶酚氧化反应的表现活化能为２３．６ｋＪ·ｍｏｌ－１，米氏常数为１．５８×１０－２ｍｏｌ／Ｌ，测试了９种化合物对酶活性的抑制效果。以苯甲酸为抑制剂研究了抑制动力学及机理，测出蕉皮酚酶中含有铜离子，它起着活化反应物的作用，抑制剂与铜离子的结合抑制了酶的催化活性。     

基于三辛胺缔合作用的草酸及柠檬酸电极的制备

草酸、柠檬酸可分别与三辛胺(TOA)生成稳定的缔合物,化学分析和红外光谱表明缔合比为1∶1。以此缔合物为活性物质制作的PVC膜电极,测定溶液中的草酸盐、柠檬酸盐的线性范围分别为1.0×10-4~1.0×10-1mol.L-1和1.0×10-5~1.0×10-2mol.L-1。该电极用于简单模拟体系中草酸和柠檬酸浓度的测定,效果良好。     

炭基氧电极开路电位的研究

本文研究了以不同炭材料为载体的氧电极开路电位。用旋转电极测得氧还原表观交换电流;量气法测得金属氧化物催化剂分解H_2O_2速度常数,流动气相色谱法测得炭载体的BET表面积。实验结果表明,一定的炭载体比表面,团粒结构小的催化剂分解H_2O_2速度常数大,催化剂与载体混合均匀,所得氧电极的开路电位越正。     

恩诺沙星-H2O2吸附催化波的研究

恩诺沙星 (Ｅｎｏｘａｃｉｎ ,ＥＮＯＸ)是第三代氟诺酮类抗生素 ,其分析方法主要有色谱法[1,2 ] ,吸光光度法[3 ] ,高效毛细管电泳法[4 ,5] 。本文研究了恩诺沙星在磷酸盐底液中 ,Ｈ2 Ｏ2 存在下的催化吸附特性 ,试验了各测试条件对溶出峰电流的影响。用本法可测定样品中痕量恩诺沙星。检出限为 5 .0× 10 - 9ｍｏｌ·Ｌ- 1。1　试验部分1.1　仪器与试剂ＪＰ3 1型示波极谱仪 (山东电讯七厂 )ＭＦ 1型多功能伏安分析仪 (上海工业大学江苏电分析仪器厂 )三电极体系 (悬汞电极 ,Ｐｔ电极 ,饱和甘汞电极(ＳＣＥ) )5 0 1超级恒温槽 ,夹层恒温电…     

阳极溶出法测定精铝中微量铁

阳极溶出法测定铁国外已有报导。等和等用石墨电极在1M氢氧化钾+2％酒石酸中测定了纯铝中的铁,定量下限达10~(-7)克/毫升。等用石墨汞膜电极在2％氢氧化钾+2％柠檬酸中测定了二氧化硅和氮化硅薄膜中的铁,定量下限达10~(-9)克/毫升。等用石墨汞膜电极在1M氢氧化钠+0.02M草酸(1:1)中测定了纯汞中的铁,定量下限达10~(-9)克/毫升。     

P507萃取纯化V(Ⅳ)制备草酸氧钒及其物化性能

从钒渣钠化焙烧后的含钒浸液中, 采用2-乙基己基磷酸单-2-乙基己酯(P507)萃取-草酸反萃取-蒸发结晶新工艺制备了草酸氧钒, 优化了草酸反萃取工艺的条件. 研究结果表明, 采用2.0 mol/L草酸溶液, 在水相与有机相体积比V(A):V(O)为1:5时, 于50 ℃下经过三级(理论)反萃取, 钒的反萃取率可达到99.98%, 反萃取液中VOC₂O₄浓度可达290.0 g/L以上. 负载的反萃取液经膜过滤除去残留有机物后, 再经蒸发结晶得到草酸氧钒. 采用X射线衍射、 X射线能谱、 热场发射扫描电子显微镜及同步热分析等手段表征了草酸氧钒的物化性能, 结果表明, 草酸氧钒的结构为VOC₂O₄·2H₂O, 粒度分布均匀, 结晶度高.     

衍生气相色谱法分析蔬菜中的草酸

某些蔬菜中所含的草酸能和人体血液中的钙离子生成草酸钙沉淀,这种沉淀物既是引起尿结石病的主要原因,又会引起人体缺钙。但医学上认为,适量的草酸对人体来说是必要的。蔬菜中草酸的测定已有多种方法,但这些方法均存在不同的缺点。本文采用衍生气相色谱法将蔬菜用乙醇盐酸溶液浸泡,浸出的草酸衍生成草酸二乙酯,经氯仿萃取后用气相色谱法测定,获得了满意的结果。     

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.     

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.

     

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.     

恶臭嗅辨实验室建设探讨

针对恶臭测试的环境影响问题,提出了解决的实例方案,并对方案的要点及优缺点进行讨论,此方案在实际操作中具有较好的效果。     

Summary of development of the theory of stability of colloids and thin films

In this review, the research of the author in the field of colloidal systems is summarized. The factors influencing colloidal stability are systematized and analyzed. Examples are presented to illustrate the practical utilization of the theory of stability of colloids and thin films.This review was prepared on the basis of the works of the author, which were awarded the State Premium for 1991 in the field of science and technology, chemistry section.Institute of Physical Chemistry, Russian Academy of Sciences, 117915 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1708–1717, August, 1992.     

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.     

解决能源问题的新途径——光解水制氢的研究

面对日益枯竭的能源危机,氢能是一种洁净、最有前景的替代能源。目前在各种制氢的方法中光催化分解水制氢的研究最多,光解水过程中催化剂最关键,本文对利用太阳能光解水的途径、提高光催化反应效率以及光催化剂的开发研究进行了综述。     

黄酮化合物的合成研究进展

黄酮化合物是一类具有多种生物活性的天然产物,其经典的合成方法主要为查耳酮路线和β-丙二酮路线.近年来出现了许多新技术、新方法.本文介绍了2'-羟基查尔酮的氧化关环法、黄烷酮氧化法、改进的Baker-Venkataraman法及其他合成黄酮化合物的方法.