Die stufenweise Syntheseo,o′-methylenverbrückter Cyclohexamerer mitp-Kresol- oderP-Kresol- und 4-tert-Butylphenol-Bausteinen Vergleich mit ähnlich strukturierten Kettenoligomeren

Two phenolic alcohols with six phenolic units in their molecules have been obtained by stepwise syntheses starting from simple phenolic derivatives. The phenolic alcohols were cyclized in a one step cyclization by boiling in a very diluted acetic acid solution. A two step cyclization of a phenolic alcohol with three phenolic units to a cyclohexamer proceeds only with poor yields. The cyclic compounds were compared with chainlike oligomers containing six phenolic units in their molecules.

Herrn Prof. Dr.H. F. Mark mit allen guten Wünschen zum 85. Geburtstag gewidmet.     

Charge control in the formation of complexes of phenol with ethylene derivatives containing organoelemental group IVB substituants

The v(OH) frequency shifts of phenol and the v_R resonance components of these shifts in the IR spectra of phenol H-complexes with ethylene derivatives containing various substituents including organosilicon, organogermanium, and organotin groups have been studied. The relationship between v and v_R and the values that characterize the influence of substituents on the effective charges of the double bonded carbon atoms was established; the latter values have been calculated previously usingab initio quantum chemical methods. The effective charges for the compounds with organoelemental substituents have been calculated. It has been elucidated that of the two types of possible interactions, charge controlled and orbital controlled, occurring in the formation of a complex of a hard acid, phenol, with the studied ethylene derivatives, the former is predominant.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1383–1387, August, 1993.     

Total synthesis of apigenin 7,4′-di-O-β-glucopyranoside, a component of blue flower pigment of Salvia patens, and seven chiral analogues

We have succeeded in the first total synthesis of apigenin 7,4′-di-O-β-d-glucopyranoside (1a), a component of blue pigment, protodelphin, from naringenin (2). Glycosylation of 2 according to Koenigs-Knorr reaction provided a monoglucoside 4a in 80% yield, and this was followed by DDQ oxidation to give apigenin 7-O-glucoside (12a). Further glycosylation of 4′-OH of 12a with 2,3,4,6-tetra-O-acetyl-α-d-glucopyranosyl fluoride (5a) was achieved using a Lewis acid-and-base promotion system (BF₃·Et₂O, 2,6-di-tert-butyl-4-methylpyridine, and 1,1,3,3-tetramethylguanidine) in 70% yield, and subsequent deprotection produced 1a. Synthesis of three other chiral isomers of 1a, with replacement of d-glucose at 7 and/or 4′-OH by l-glucose (1b-d), and four chiral isomers of apigenin 7-O-β-glucosides (6a,b) and 4′-O-β-glucosides (7a,b) also proved possible.     

催化膜和催化膜反应器:整合的高效和环保催化过程

 The design of new heterogeneous photooxygenation systems able to employ visible light, oxygen, mild temperatures, and solvent with a low environmental impact has been investigated. In particular, the heterogenization of decatungstate (W10O4-32), a polyoxometalate with photocatalytic activity in oxidation reactions, has been carried out in polymeric membranes of polyvinylidenefluoride. The polymeric catalytic membranes prepared by phase inversion technique have been successfully applied in the aerobic mineralization of phenol in water, which was used as an example of organic pollutant. In order to evaluate the effect of the polymeric environment on the overall catalyst behavior, we have also heterogenized the decatungstate (opportunely functionalized) in perfluorinated membrane made of Hyflon. The photocatalytic composite membranes are characterized by different and tuneable properties depending on the nature of the polymeric micro-environment, in which the catalyst is confined. Moreover, the selective separation function of the membrane results in enhanced performance in comparison with homogeneous reactions.     

流动注射-化学发光法定量测定同一水域中的腐殖酸

采用流动注射-化学发光(FI-CL)这一灵敏的检测方法,通过条件实验与参数优化,优选了测定环境中痕量多羟基酚类化合物的发光体系,通过考察天然水体中的腐殖酸对化学发光-多羟基酚测定体系的影响,为来自于水及土壤中的实际样品中腐殖酸的检测提供了参考,建立了同一区域水体中腐殖酸的化学发光定量测定方法。 所得线性回归方程y=70.36x+540.1,相关系数r=0.995 4,线性范围为3～15 mg·L-1,检测限为0.749 mg·L-1,HA浓度为6 mg·L-1时的相对标准偏差(RSD)为1.08%。     

离散小波变换-支持向量回归方法同时测定苯酚、苯胺和苯甲酸

在波长范围200～400nm测定苯酚、苯胺和苯甲酸混合液的吸收光谱,用离散小波变换（DWT）对光谱数据进行处理,再用支持向量回归SVR方法进行建模,建立了离散小波变换一支持向量回归方法（DWT—SVR）。方法用于模拟样品和污染水样中苯酚、苯胺和苯甲酸的同时测定,结果满意。     

长光程比色池-流动注射测定水中微量挥发酚

利用长光程比色池 流动注射系统快速测定水样中的微量挥发酚.该方法的检出限为0.232 μg·L^-1,相对标准偏差小于0.553%,相对误差小于0.185%,样品加标回收率在91.0%~99.8%,且标准曲线具有良好线性（r =0.999 9）.与传统国标方法（《水质挥发酚的测定4-氨基安替比林分光光度法》,HJ503-2009）相比,样品浓度测定偏差为2.59%~8.25%,在分析速率上,传统的国标方法约为5个·h^-1,而该方法分析速率达24个·h^-1,能满足大批量样品连续准确测定的要求,特别适合事故性的应急监测.     

颗粒堆的体积分数与制备流量关系的实验研究

通过实验研究发现,颗粒堆的体积分数随制备颗粒堆的颗粒流流量指数衰减,减小或增加流量到一定程度时,体积分数都达到饱和;出料口直径与颗粒粒径的比值小到一临界值时,随着流量的减小体积分数增加急剧变缓;颗粒粒径小到一临界值时,随着流量的增加,体积分数的减小急剧变缓.结合颗粒物质的强耗散性、空气作用、瓶颈效应和碰撞理论解释了实验现象,从连续性原理出发推出的颗粒堆体积分数随制备流量变化的函数与实验数据的拟合公式相同.     

液态金属熔池中气泡-液体两相湍流的数值模拟研究

应用欧拉-欧拉双流体模型,以及分别描述气泡和液体湍流的两相湍流模型,描述液态金属中气体射流发泡过程的两相流动及气泡分布。与实验结果的对比表明,本模型的预测能力优于前人未考虑气相湍流的模型。考查了液体物性和气泡尺寸对流场特性的影响,结果发现,液体密度越低,气泡尺寸越小,气泡分布就越均匀。     

Preparation and characterization of vanadium(IV) oxide supported on SBA-15 and its catalytic performance in benzene hydroxylation to phenol using molecular oxygen

Preparation of dispersed transition metal oxides catalyst with low oxidation state still remains a challenging task in heterogeneous catalysis.In this study,vanadium oxides supported on zeolite SBA-15 have been prepared under hydrothermal condition using V 2 O 5 and oxalic acid as sources of vanadium and reductant,respectively.The structures of samples,especially the oxidation state of vanadium,and the surface distribution of vanadium oxide species,have been thoroughly characterized using various techniques,including N 2-physisorption,X-ray diffraction(XRD),transmission electron microscopy(TEM),X-ray photoelectron spectroscopy(XPS),UV-visible spectra(UV-Vis) and UV-visible-near infrared spectra(UV-Vis-NIR).It is found that the majority of supported vanadium was in the form of vanadium(IV) oxide species with the low valence of vanadium.By adjusting hydrothermal treatment time,the surface distribution of vanadium(IV) oxide species can be tuned from vanadium(IV) oxide cluster to crystallites.These materials have been tested in the hydroxylation of benzene to phenol in liquid-phase with molecular oxygen in the absence of reductant.The catalyst exhibits high selectivity for phenol(61%) at benzene conversion of 4.6%,which is a relatively good result in comparison with other studies employing molecular oxygen as the oxidant.