Ordered porous films based on fluorinated polyimide derived from 2,2′-bis(3,4-dicarboxyphenyl) hexafluoropropane dianhydride and 3,3′-dimethyl-4,4′-diaminodiphenylmethane

One of fluorinated polyimides was synthesized from 2,2′-bis(3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA) and 3,3′-dimethyl-4,4′-diaminodiphenylmethane (DMMDA) by two-steps method, which had good solubility and hydrophilicity. 6FDA-DMMDA polyimide was dissolved in chloroform (CHCl₃) and cast on a glass substrate in a humid atmosphere. It was found that 6FDA-DMMDA/CHCl₃ solution was easy to form ordered porous structure at high concentration, and the reason was discussed in detail. In addition, the influences of solution concentration, the atmosphere humidity, were also tested.     

PVA固定化脲酶电极的制作及电极特性的研究

利用PVA低温下的物理交联固定酶,制成酶电极并在不同尿素浓度、pH值、温度等条件下进一步研究这种酶电极的响应特性.     

光学分析方法在DNA检测中的应用

介绍了用于DNA检测的各种光学分析方法及其原理,主要包括荧光法、化学发光法、光纤传感法、比色法、表面等离子共振法以及其他光学衍生方法。     

Remote substituent effect favoring the formation of syn-adducts in the chelation controlled radical reactions of γ-benzyloxy-α-methylenecarboxylic acid esters

The chelation controlled radical reactions of ethyl γ-benzyloxy-α-methylenecarboxylates bearing a bulky γ-substituent, such as CHMe₂, CHPh₂, c-C₆H₁₁ and CH(Ph)OTBDMS, with alkyl iodides gave the syn-adducts with high diastereoselectivities. However, the diastereoselectivity for the substrates bearing a γ-substituent CH(i-Pr)OTBDMS depended critically on the configuration of the substituent; the substrate bearing the OTBDMS group anti to the γ-benzyloxy group showed poor diastereoselectivity, but its diastereomer gave syn-adduct exclusively. The high syn-selectivitiy is referred to the H-atom transfer to the outside face of radical center in the sharply folded seven-membered chelate intermediate bearing the ethoxy group with Z-geometry. The corner flapping of the radical center atom of the global minimum energy conformer generates a local minimum conformer and the H-atom transfer to the outside face of the radical center of the newly formed structure gives the anti-adduct. The poor diastereoselectivity is due to the very small energy difference between the two conformers and consequently both the syn- and anti-adducts are yielded in nearly equal amounts.     

基于芘的荧光熄灭的单质碘荧光敏感膜的研究

单质碘熄灭固定于增塑的ＰＶＣ膜中的芘的荧光，且这种熄灭作用可逆。本据此研制了用于测定单质碘浓度的荧光敏感膜，最佳膜组成为２～４ｍｇ芘、５０ｍｇＰＶＣ粉、１００ｍｇ邻苯二甲酸二异辛酯，测定碘的浓度范围为２．２６×１０＾－５～１．０４×１０＾－３ｍｏｌ／Ｌ。此膜测定单质碘的重现性好，响应时间小于４０ｓ。除Ｆｅ＾３＋、Ｂｉ＾３＋外，其它常见离子均无干扰。将此膜用于食盐中碘的测定，结果令人满意。     

Effect of solvent on the cation-sensitive fluorescence of polyanions bearing 4′-acryloylbenzo-18-crown-6 Units

Changes in the fluorescence intensity of polyanions bearing 4-acryloylbenzo-18-crown-6 units on the addition of cations were studied in a mixed solvent of methanol and water at 30°C. The sensitivity of the change in fluorescence intensities of the polymers toward cations was strongly enhanced compared to that of the corresponding model compound. When alkali metal cations were added, the fluorescence intensity of the polymers decreased in the orders Li⁺>Na⁺>Cs⁺>Rb⁺>K⁺ in a methanol-water (19) mixture and Li⁺>Na⁺>Rb⁺>K⁺Cs⁺ in a methanol-water (91) mixture. Alkaline earth metal cations and alkylamine hydrochlorides decreased the fluorescence intensity of the polymers in a methanol-water (19) mixture. The cation-dependent decrease in the fluorescence intensity of the polymers was affected by the water fraction in a mixed solvent of methanol and water.     

14N遥测核四极共振中的偏离共振效应

本文对遥测NQR谱中的偏离共振效应作了较详细地研究,发现¹⁴N谱线的强度随偏离共振效应而变化。当偏离共振强度与射频场强度接近时,测得的谱线强度最大。该效应可用来增强¹⁴N遥测NQR谱仪的灵敏度。上述实验现象在理论上采用脉冲的激发带宽方法作了解释和讨论。     

The effect of humidity on thermal process of zinc acetate

The thermal decomposition of zinc acetate dihydrate Zn(CH₃CO₂)₂·2H₂O in some humidity-controlled atmospheres has been successfully investigated by novel thermal analyses, which are sample-controlled thermogravimetry (SCTG), thermogravimety combined with evolved gas analysis using mass spectrometry (TG–MS) and simultaneous measurement of differential scanning calorimetry and X-ray diffractometry (XRD–DSC). The thermal processes of anhydrous zinc acetate in dry gas atmosphere by conventional linear heating experiment initiated with the sublimation around 180 °C, followed by the fusion and the decomposition over 250 °C. SCTG was useful to interpret clearly the successive reaction because the high-temperature parallel decompositions were effectively inhibited. The thermal behavior changed dramatically by introducing water vapor in the atmosphere and the thermal process was quite different from that in dry gas atmosphere. Zinc oxide (ZnO) was formed only in a humidity-controlled atmosphere, and could be easily synthesized at temperatures below 300 °C. XRD–DSC equipped with a humidity generator revealed directly the crystalline change from Zn(CH₃CO₂)₂ to ZnO. A detailed thermal process of Zn(CH₃CO₂)₂·2H₂O and the effect of water vapor are discussed.     

SYNTHESIS AND THERMAL PROPERTIES OF POLYBENZOXAZOLE FROM SOLUBLE PRECURSOR WITH HYDROXY-SUBSTITUTED POLYENAMINONITRILE

Aromatic polybenzoxazole (PBO) precursor, hydroxy-substituted polyenaminonitrile, was prepared by direct polycondensation of 1,4-bis(l-chloro-2,2-dicyanovinyl)benzene (CCB) and 4,6-diaminoresorcinol dihydrochloride (DAR) using pyridine and N,N-dimethylacetamide as condensing agent and solvent. The precursor has good solubility in polar aprotic solvent which is due to the strong dipolar nature of the main chain. The soluble precursor was subjected to thermal cyclization in an inert atmosphere to convert it into the corresponding PBO, which has its 5% weight loss temperature at 540℃ The fully cyclized PBO were characterized by FT-IR and TGA. The introduction of 10% mol 1,3,5-benzenetricarboxylic chloride (BTC) into the main chain not only has little effect on the solubility of PBO precursor but also raises its 5% weight loss temperature to 552℃ and char yield at 700℃ for the cyclized PBO with BTC.     

Quantitative Comparison Between Vacuum-Ultraviolet Irradiation and Remote Hydrogen Plasma Treatment of Hydrocarbon Polymers

The photon flux of vacuum ultraviolet (VUV) and ultraviolet (UV) radiation of a hydrogen plasma with and without a MgF₂window was recorded by fluorescence measurements of sodium salicylate layers. After the compensation of the MgF₂absorption by increasing the input power into the plasma source, a comparison between afterglow hydrogen plasma and VUV treatments was made. Polyethylene (PE), polypropylene (PP), and polystyrene (PS) were treated either with VUV radiation or with remote hydrogen plasma and mass loss and CH absorption loss were measured by a quartz crystal microbalance and by infrared reflection absorption spectroscopy, respectively. In the case of PE the effects of both treatments were found to be very similar white for PP slight differences were observed. For the actual set of experimental conditions, the radiation component is largely responsible for the efficiency of the plasma treatment. VUV and remote hydrogen plasma treatments of PS showed only a negligible loss of mass and CH absorption.