二元中性体系对金(Ⅲ)的协同萃取研究 Ⅱ. TBP+DPSO的苯溶液协萃金(Ⅲ)及其机理

本文研究磷酸三丁酯(TBP)与二苯基亚砜(DPSO)组成的二元中性体系(B-B体系)在HCl介质中对金(Ⅲ)的萃取行为,发现该体系有明显的协同萃取效应。用斜率法和紫外光谱法确定了协萃配合物的组成为H_3O~+·2TBP·DPSO·yH_2O……AuCl_4~-·HCl。协萃反应的平衡常数log K_(1,2)~′=3.33。对协萃反应的机理和可能的结构也进行了讨论。     

酞菁分子XPS的CNDO研究

基于在生理、催化等方面研究中的重要作用,H_2Pc分子的电子结构一直受到广泛的注意和研究。但是,理论上算出的电荷分布与实验上测出的NIS XPS信息,目前还不相符。为此,本文用CNDO/2计算方法,对应H_2Pc的文献几何构型,进一步考察了H_2Pc与H_2Pc＇的电子结构。计算方法和结果H_2Pc和H_2Pc＇的骨架构型见图1。对于固态与气态的H_2Pc,目前多数人认为其具有D_(2h)点群对称性(尽管作为D_(4h)点群对称性的根据也是存在的)。为考察分子构型改变(特别是切割)对分子的电子结构、特别是电荷分布的影响,我们     

用双表面活性剂为共模板合成中孔分子筛MCM-48

利用水热法以非离子表面活性剂聚乙二醇辛基苯基醚和阳离子表面活性剂十六烷基三甲基溴化铵为共模板合成了中孔分子筛MCM-48.实验中发现利用较强的范德华力和氢键,聚乙二醇辛基苯基醚可在很大程度上降低合成MCM-48所需阳离子表面活性剂的用量,且利于制备有序性好、骨架聚合度高、稳定性好的MCM-48.通过调节聚乙二醇辛基苯基醚与十六烷基三甲基溴化铵的比例,可得到不同物相结构的分子筛.     

还原席夫碱型三角架式金属配合物的合成和性质研究

由2，2，′，2＂-三氨基三乙胺(tren)与N-氧化吡啶醛经席夫碱型缩合，然后还原C=N双键形成的产物为配体(L¹)，合成了一系列新三角架式过渡金属配合物：［ML¹］²⁺［M=Mn(Ⅱ)、Ni(Ⅱ)和Zn(Ⅱ)］。利用元素分析、红外光谱、电子光谱和室温磁化率对配合物的结构和性质进行了研究。     

Effects of pressure pulsation on oxygen transfer rate measured by sulfite method

Pressure pulsation (PP) was investigated for its effects on oxygen transfer rate (OTR) measured by sulfite oxidation. By manipulating airflow rate, 0.41–1.2 vvm, and a control valve in a 4-L bioreactor, the frequency of PP was varied at different gas pressures3–15 psig. A mathematical model of OTR was built and compared to experimental data. OTR was also examined at constant gas pressure, 4.5–15.0 psig. The results indicate a good agreement between measurement and model prediction. OTR above 9 psig during PP showed significant enhancement at 25°C. This proves that PP not only affects the elevation of DO level, but also increases the interfacial area and mass transfer coefficient.     

Production of 2,3- butanediol from pretreated corn cob byKlebsiella oxytoca in the presence of fungal cellulase

A simple and effective method of treatment of lignocellulosic material was used for the preparation of corn cob for the production of 2,3-butanediol byKlebsiella oxytoca ATCC 8724 in a simultaneous saccharification and fermentation process. During the treatment, lignin, and alkaline extractives were solubilized and separated from cellulose and hemicellulose fractions by dilute ammonia (10%) steeping. Hemicellulose was then hydrolyzed by dilute hydrochloric acid (1%, wJv) hydrolysis at 100°C at atmospheric pressure and separated from cellulose fraction. The remaining solid, with 90% of cellulose, was then used as the substrate. A butanediol concentration of 25 g/L and an ethanol concentration of 7 g/L were produced byK. oxytoca from 80 g/L of corn cob cellulose with a cellulase dosage of 8.5 IFPU/g corn cob cellulose after 72 h of SSF. With only dilute acid hydrolysis, a butanediol production rate of 0.21 g/L/h was obtained that is much lower than the case in which corn cob was treated with ammonia steeping prior to acid hydrolysis. The butanediol production rate for the latter was 0.36 g/L/h.     

Ethanol fermentation in a tower fermenter using self-aggregatingSaccharomyces uvarum

A self-aggregating strain ofSaccharomyces uvarum (U4) was used as a biocatalyst to carry out continuous ethanol fermentation in a tower fermentor equipped with a cell separator. Cell aggregates (2–3 mm) formed a stable packed bed in the fermentor, and the cell separator retained yeast cells effectively. Corn steep liquor was used as a nitrogen source for the fermentation of corn syrup and black strap molasses. An ethanol productivity of 54 g/L/h was reached using corn syrup at a dilution rate of 0.7/h, and sugar concentration in the feed was 15% (w/v). For molasses fermentation, an ethanol productivity of 22 g/L/h was obtained at a dilution rate of 0.7/h, and sugar concentration in the feed was 12.5% (w/v). Ethanol yields obtained from tower fermentation are higher than those obtained from flask fermentation (96% for corn syrup fermentation and 92% for molasses fermentation). No significant loss in fermentation activity was observed after 3 mo of operation.     

Hypervalency avoided: simple substituted BrF3 and BrF5 molecules. Structures, thermochemistry, and electron affinities of the bromine hydrogen fluorides HBrF2 and HBrF4

Five different pure density functional theory (DFT) and hybrid Hartree-Fock/DFT methods have been used to search for the molecular structures, thermochemistry, and electron affinities of the bromine hydrogen fluorides HBrF(n)/HBrF(n)(-) (n = 2, 4). The basis sets used in this work are of double-zeta plus polarization quality in conjunction with s- and p-type diffuse functions, labeled as DZP++. Structures with Br-F and Br-H normal bonds, that is, HBrF(2)/HBrF(2)(-) with C(2v) or C(s) symmetry and HBrF(4)/HBrF(4)(-) with C(4v) or C(s) symmetry, are genuine minima. However, unlike the original BrF(3) and BrF(5) molecules, the global minima for HBrF(n)/HBrF(n)(-) (n = 2, 4) species are predicted to be complexes, some of which contain hydrogen bonds. The demise of the hypervalent structures is due to the availability of favorable dissociation products involving HF, which has a much larger dissociation energy than F(2). Similar reasoning suggests that PF(4)H, SF(3)H, SF(5)H, ClF(2)H, ClF(4)H, AsF(4)H, SeF(3)H, and SeF(5)H will all be hydrogen bond structures incorporating diatomic HF. The most reasonable theoretical values of the adiabatic electron affinities (EA(ad)) are 3.69 (HBrF(2)) and 4.38 eV (HBrF(4)) with the BHLYP method. These electron affinities are comparable to those of the analogous molecules: Br(2)F(n), ClBrF(n), and BrF(n)(+1) systems. The first F-atom dissociation energies for the neutral global minima are 60 (HBrF(2)) and 49 kcal/mol (HBrF(4)) with the B3LYP method. The first H-atom dissociation energies for the same systems are 109 (HBrF(2)) and 116 kcal/mol (HBrF(4)). The large Br-H bond energies are not sufficient to render the hypervalent structures energetically tenable. The dissociation energies for the complexes to their fragments are relatively small.     

Large third-order nonlinear optical properties of C70 fullerene in the infrared regime

The nonlinear third-order optical susceptibility of C₇₀ in a toluene solution is measured for the first time by the method of degenerate four-wave mixing using 10 ns laser pulses at 1.06 m. The third-order susceptibility X _in ⁽³⁾ is 5.6×10^–12 esu for a C₇₀ toluene solution at a concentration of 0.476 g/l. The correspondent magnitude of the hyperpolarizability ₁₁₁₁ of the C₇₀ molecule is 1.2×10^–30 esu which is in a good agreement with the prediction given by the model of a free electron in a spherical box.