Ph(SiMe_2)_nPh体系π→π~*UV谱的研究

本文依据Spin-Free理论,使用Gelfand基构造多电子波函数,采用四轨道模型,对Ph(SiMe_2)_nPh体系(n=1～6)的π→π*跃迁进行了EHMO-CI计算,所得第一及第二跃迁能与UV谱的实验结果基本一致。当体系硅链原子数增加时,第一吸收带红移的现象起因于LUMO中d轨道成份增加,导致电子排斥作用变化。在LUMO中,硅链上的d轨道以πd的形式与苯环π~*轨道进行πd—π~*共轭互相作用,这种作用很可能与第一吸收带的强度有内在的联系。     

Kinetics of uranium(VI) extraction by bis(octylsulfinyl)methane

The kinetics and mechanism of uranium(VI) extraction from nitric acid solution by bis(octylsulfinyl)methane (BOSM) are studied with the method of stationary interface cell. The effects of temperature, extractant and nitric acid concentrations are discussed. The results showed that the extraction process is controlled by the following reaction: UO₂(NO₃)₂ + BOSM_(i)⇄_k1 ^k-1UO₂(NO₃)₂BOSM_(i). The variation of enthalpy associated with the extraction is -22.1±2.1 kJ/mol. This revised version was published online in July 2006 with corrections to the Cover Date.     

Elimination of matrix effects for headspace solid-phase microextraction of important volatile compounds in red wine using a novel coating

In this paper, hydroxy-terminated silicone oil-butyl methacrylate-divinylbenzene (OH-TSO-BMA-DVB) copolymer was first synthesized and used as stationary phase with the aid of γ-methacryloxypropyltrimethoxylsilane (KH-570) as bridge in solid-phase microextraction (SPME) using sol–gel method and cross-linking technique. It has high extraction efficiency for both polar alcohols and fatty acids and nonpolar esters in comparison with commercial PDMS, PDMS-DVB and PA fibers. A simple and sensitive headspace SPME-gas chromatography (HS-SPME-GC) method using the novel fiber was presented for the simultaneous analysis of both polar alcohols and fatty acids and nonpolar esters in wine. To check the matrix effects, various model wine matrices, including distilled water; 11.5% ethanol/water (v/v) solution; a concentrated synthetic wine; a ‘volatile-free’ wine and a real wine were investigated in detail. Matrix effects were compensated for by using internal standard method and selecting the ‘volatile-free’ wine as working standard. The method presented in this study showed satisfactory linearity, precision, detection limits and accuracy. The recoveries obtained ranged from 85.87 to 104.2%, and the relative standard deviation values were below 9%. The results obtained indicated that the present method is a validated and accurate procedure for the simultaneous determination of both polar and nonpolar aroma compounds in wine.     

白酒中C_9－C_（18）脂肪酸的气相色谱分析

白酒中Ｃ＿９－Ｃ＿（１８）脂肪酸的气相色谱分析周在德，曾永昌（四川大学化学系成都６１００６４）关键词气相色谱法，白酒，Ｃ＿９－Ｃ＿（１８）脂肪酸。白酒中脂肪酸的含量及相互比例关系，极大地影响着白酒的色，香，味，风格￣（［１］［２］）。一般采用的化学分...     

La2O3对氧化铝透明陶瓷显微结构和透光性能的影响

采用传统无压烧结工艺在氢气氛下制备Al2O3透明陶瓷。实验结果表明：MgO和La2O3复合添加时，随着La2O3掺杂量的增加体积密度总体上保持上升的趋势。随着保温时间的延长，陶瓷的致密化程度增大，残余气孔逐步排出，晶粒进一步长大。采用La2O3和MgO复合添加比单独掺入MgO陶瓷样品透过率更高，掺杂效果更好。在烧结温度为1750℃，保温时问为1h条件下，在波艮为300～800nm测试范围内，陶瓷样品的全透过率大于82％，最大值为86％。     

Development of an alcohol optode membrane based on fluorescence enhancement of fluorescein derivatives

A new type of optode membrane for the determination of alcohols, such as methanol, ethanol, propan-1-ol and propan-2-ol etc, is presented that can be exploited in optical and fibre-optic sensors. It is based on the use of a new lipophilic fluorescent reagent, namely fluorescein octadecyl ester (FODE), which is immobilized in a plasticized PVC membrane. The response mechanism relies on the fact that FODE can reversibly recognize alcohol molecules due to the hydrogen bonding formation between FODE and alcohol molecules. The analytical information in this membrane is the enhancement of the relative fluorescence intensity measured at 527 nm (463 nm, excitation). Under the optimum condition, the membrane has a wide measuring range for alcohol samples. The membrane has been applied to determine the concentration of ethanol in alcoholic drinks with satisfactory results.     

新型含金属元素二胺的合成与表征

本文分别用液相法和固相法合成了一系列含不同金属元素的二胺,并通过红外光谱,~1HNMR、~(13)CNMR,紫外光谱,电化学分析及元素分析对其进行表征,还通过DSC和TG对其热性能进行了研究,结果发现这些二胺具有良好的耐热性,是合成一些耐热高聚物的优良原料.     

自动化流动注射停流动力学分析仪的研制及其性能测试

本文研制了一套自动化流动注射停流动力学分析仪，该仪器由苹果Ⅱ型微机通过１２位ＡＤ／ＤＡ卡，流动注射停流控制仪及用ＢＡＳＩＣ语言编制的软件控制泵的起动和停止，试样的输送和混合，数据采集和处理，结果显示和打印，通过以铁（Ⅲ）与硫氰酸盐的反应体系采用固定时间法和以钒（Ｖ）的胶束催化反庆体系采用安始速法的现场测试证明，该仪器具有结构简单，操作方便，恒温性能好，通用性强等特点。