以乙酸为模型反应物的Ti-Ce复合氧化物湿式氧化催化剂的研制

催化湿式氧化(catalytic wet air oxidation, CWAO)为高浓度难降解有机废水提供了一种有效可行的处理技术[1～8],它可使难降解有机物分子在相对较低的反应温与压力下降解矿化或生成易生物处理的小分子有机物.     

一维配位聚合物[Cu(2-pac)2·2H2O]n的合成与结构

近年来,配位聚合物由于在光学、电学、磁学、催化、分离及吸附等方面具有潜在的功能性,处于化学、材料、生物、物理等许多学科的交叉点,成为当前最活跃的前沿研究领域之一[1～8],因此进一步合成具有特定结构和功能的配位聚合物具有非常重要的意义和价值[9～12].     

椰壳炭磺酸催化剂制备及其对杯[4]芳烃合成反应的催化应用

以废弃椰壳为原料,经炭化和磺化制得新型固体磺酸催化剂,用于催化各种芳醛与间苯二酚的缩合反应,以较高收率(49%～95%)制得一系列杯[4]芳烃化合物,产物结构经IR、1H NMR和MS测试技术表征得以确证。     

配合[Cu(o-ABA)2(2,2''-bipy)]·(H2O)的水热合成、晶体结构及电化学性质

铜是生物体内重要的微量元素,广泛地存在于动物、植物和微生物体内,并且通常与生物配体形成稳定的混配配合物,在生命过程中(酶的催化、物质的储存和运送以及铜离子的转运等)起着极其重要的作用,因此研究铜生物配体配合物对探索铜在生物体内的作用机制有重要意义[1～3].     

不同催化剂条件下高温煤气中焦油组分的催化裂解

高温煤气净化技术是正在开发的煤气化联合循环发电(ＩＧＣＣ)和煤气化燃料电池(ＭＣＦＣ)的关键技术之一。高温煤气中焦油蒸汽通过催化裂解方法去除,不但可以排除焦油堵塞管道,腐蚀设备,而且可以提高发电效率。Ｂａｋｅｒ等[1]对模拟煤气中焦油催化裂解研究得出:在450～690℃和1010～1818ｋＰａ的条件下,ＹＺ-Ｙ82催化剂最好,焦油转化率达74%,同时催化剂积炭最高达055ｇｇ焦油。Ａｚｎａｒ等[2]研究了Ｎｉ基催化剂对生物质气化气体中焦油的催化裂解得出:在780～830℃的温度下,所有催化剂对焦油的脱除都显示出很高的活性,反应时间48ｈ内催化…     

膦催化水杨醛亚胺与马来酰亚胺的[4+1]环化反应及螺[苯并呋喃-2,3'-吡咯烷]衍生物的合成（英文）

报道了一个膦催化水杨醛亚胺与马来酰亚胺的[4+1]环化反应,以44%～99%收率生成螺[苯并呋喃-2,3'-吡咯烷]衍生物.产物包含一对可经硅胶柱层析分离的syn和anti异构体(dr 1.6∶1～5∶1),由此提供了合成螺[苯并呋喃-2,3'-吡咯烷]简单有效的方法.该反应起始于PPh_3与马来酰亚胺原位形成非烯丙基磷叶立德活性中间体,经亲核加成/分子内取代的串联过程完成,代表了新的一例经此类磷叶立德完成的膦催化[4+1]环化反应.     

钌卟啉[Ru(bpy)2(MPyTPP)Cl]+与DNA作用的研究

钌卟啉(ruthenated porphyrin)是通过卟啉环上的配位基团与多吡啶钌配位而得到的一类具有丰富的光谱和化学活性的大分子配合物[1～5]. 目前, 对钌卟啉的研究大都集中在其氧化还原、电化学以及催化氧化反应活性和超分子自组装等方面, 而对钌卟啉生物功能方面的研究则鲜为报道[6].     

华根霉全细胞脂肪酶催化合成生物柴油

比较了5种不同商品化脂肪酶和自制的华根霉CCTCCM201021全细胞脂肪酶(RCL)催化油脂合成生物柴油的转化效果,结果表明,RCL能有效应用于无溶剂体系催化合成生物柴油.在无溶剂体系中对该酶催化生物柴油的转酯化反应工艺进行优化,考察了甲醇用量、体系含水量、酶的添加量和反应温度对生物柴油收率的影响,使生物柴油最终收率大于86.0%.在有机溶剂体系中选择不同有机溶剂作为助溶剂进行转酯化反应,发现logP值在4.0～4.5的有机溶剂具有较好的转化效果.其中以正庚烷为助溶剂的转酯化反应具有最高的生物柴油收率86.7%.在无溶剂体系中RCL催化转化油酸和模拟高酸价油脂合成脂肪酸甲酯的研究表明,该酶具有很好的催化合成生物柴油的潜力.     

溶胶-凝胶法制备用于CO2气氛下乙苯胶氢反应的高活性Cr2O3-SiO2催化剂

苯乙烯是石化工业中十分重要的化学品,全世界每年生产大约 1300 万吨苯乙烯,其中有90%的苯乙烯是在大量过热水蒸气存在下,于550～650 ℃由乙苯在铁-钾基催化剂上脱氢制得的. 该工艺受热力学平衡限制,并且由于采用大量过热的水蒸气和较高的反应温度而能耗很高,因此人们一直试图寻找新的替代工艺. 最近,利用CO2作为温和氧化剂进行乙苯脱氢制苯乙烯引起人们浓厚的兴趣[1～3]. 利用CO2进行乙苯脱氢能够大幅度降低能耗,并且提高苯乙烯的平衡收率[4]. 但是,现行乙苯脱氢传统工艺中使用的铁-钾基催化剂在CO2气氛下不能有效地催化乙苯脱氢,因此有必要寻找适合这一新工艺的高性能催化剂. 人们已经研究了CO2气氛下各种氧化物催化剂上的乙苯脱氢反应,在这些催化剂中,氧化铬和氧化钒表现出较好的催化性能.     

Fe2+/UV催化臭氧-曝气生物滤池降解腈纶废水研究

腈纶废水是一种难降解的有毒有机废水。本文采用Fe2+/UV催化臭氧-曝气生物滤池降解腈纶废水,探讨了臭氧浓度和紫外光辐射强度等影响因素对腈纶废水的COD去除效果的影响,并考察了紫外催化臭氧氧化单元和曝气生物滤池单元对COD去除的协同作用。结果表明,臭氧浓度对COD的去除率影响较大,臭氧浓度下降25%时,臭氧催化氧化和曝气生物滤池单元处理的COD去除率分别下降了12.53%和15.98%。紫外光强度对臭氧催化氧化单元的COD去除率影响较小,但对曝气生物滤池单元影响较大。臭氧催化氧化单元和曝气生物滤池单元COD去除率之比为1∶2,其协同作用使总出水COD值稳定在较低水平。     

利用手持技术改进测定乙醇分子结构实验

利用压强传感器代替排水集气法,改进测定乙醇分子结构实验的仪器装置,并探索最佳反应条件。另外,设计两个空白实验,结合压强变化曲线对实验误差进行相关讨论。     

光谱仪测试范围的扩展

由于石化行业的生产需要，其材质的使用具有多样性和广泛性，经常会出现顾客委托的测试样品的一个或几个元素跨越光谱仪现有测试程序测量范围的情况。本法通过对光谱仪测试原理的认识，根据光谱仪的测试能力及标样的采集，实现了一个或几个元素测量范围的扩展，并对其测量的影响因素进行了研究。     

Influence of viscosity of medium on processes of oxygen quenching of excited states of mesoporphyrin

The oxygen quenching rate constants for singlet and triplet excited states of the dimethyl ester of mesoporphyrin IX increase with decreasing viscosity of the medium and reach a maximum at a viscosity of approximately 0.4 mPa·sec, after which the rate constants begin to decrease. The drop in rate constant with increasing fluidity of the medium may be related to a nonequilibrium character of the elementary act in the interaction of the reactants in the solvent cage. In viscous media such as isopropyl alcohol, isobutyl alcohol, and isoamyl alcohol, the reaction radius is greater than the sum of the radii of the reacting particles. The long-range character of these processes is due to the relatively weak dependence of the quenching probability on distance.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 25, No. 2, pp. 161–167, March–April, 1989.     

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.

     

物质分配系数的测定实验改进

实验教学目的是从解决实际问题出发,以实验技术训练和实验设计思想培养为目标。介绍了将单一的物质分配系数测定实验改进为综合实验,提高了实验效果及实验资源利用率。     

Neutral diterpenoids of oleoresins of five species of conifers of Transcarpathia

The compositions of the neutral diterpenoids of the oleoresins of five species of conifers growing in the Transcarpathia have been studied. It has been found that the oleoresins ofAbies alba M.,Larix decidua M., andPicea excelsa L. contain more than 50% of neutral diterpenoids. The group and qualitative compositions of the oxygen-containing diterpenoids have been determined. In the oleoresins ofAbies alba,Picea excelsa, andPicea abies tertiary alcohols — cis-abienol and isocembrol — predominate, while inLarix decidua the main component is the hydroxy ester larixyl acetate. Primary alcohols related to the resin acids have been found in all the oleoresins investigated. Features of the distribution of diterpenoids according to the species of conifers have been revealed. The results obtained are necessary for the chemotaxonomy of conifers of the family Pinceae.Novosibirsk Institute of Organic Chemistry, Siberian Branch, Academy of Sciences of the USSR. Translated from Khimiya Prirodynkh Soedinenii, No. 6, pp. 812–816, November–December, 1988.     

Calculation of enthalpies of hydrogenation of hydrocarbons

Sets of hydrogen molecule equivalents have been developed which permit the calculation of hydrogenation of different types of carbon-carbon bonds from ab initio total energies (3-21G and 6-31G* basis sets, and, to a more limited extent, for MP2/6-31G* data) of reactants and products. The calculated enthalpies of hydrogenation are in good agreement with experiment for unstrained molecules, with average errors on the order of 2 kcal/mol. The 6-31G* equivalents allow the enthalpies for strained molecules to be calculated accurately, but the 3-21G equivalents do not. The equivalents for both basis sets have been tested by calculating the enthalpies of hydrogenation of carbon-carbon bonds in nitrogen- and oxygen-containing organic molecules, free radicals, and classical carbocations. The results are in good agreement with experiment in most cases.     

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。