Ab initio modelling of crosslinking in polymers. A case of chains with furan rings

A quantum chemical model (Abinitio HF-MO and DFT-B3LYP) of polyfurfuryl alcohol crosslinking is shown. Two pathways were considered: (a) a Diels–Alder (D–A) reaction between a dihydrofuran moiety and a furan ring; (b) the addition reaction of electrophilic specimens on conjugated double bonds. The ability for the formation of D–A adducts (dienes and dienophiles) was investigated by the frontier molecular orbital (FMO) theory. Energy gaps between the FMO's of diene and dienophile structures suggest that the occurrence of the D–A reaction is possible. The results suggest that the carbons of the exo double bonds attached to dihydrofuran rings are the sites most likely to be attacked by electrophilic species, while the C₃ and C₄ atoms display the opposite tendency due to their low HOMO electron densities. Results of a thermochemical approach to these reactions at the MP2 level was in agreement with reactivity modelled by MO predictions.     

甜菜糖蜜酒精废液生产菌体蛋白饲料初探

甜菜糖蜜酒精废液含有大量的有机物，pH值低，BOD、CDO值高，直接排和会造成环境的严重污染，又损失了一些有机物，在此废液中可直接接入酵母菌，使其大量繁殖，生产出的菌体粗蛋白含量达41．7％，CDO值降低了20％以上，减轻了环境污染。     

Synthesis of vinyl-substituted oxiranes and their transformation to dihydrofurans

The reaction of dimethylsulfonium methylide with the carbonyl function of 2-arylidene-cyclohexanones obtained from 2-methylcyclohexanone affords the corresponding spirooxiranes. The application of this reaction to 2,2-dimethyl-6-(5-methylfurfurylidene)cyclohexanone and 2,2-dimethyl-6-(5-chlorofurfurylidene)cyclohexanone leads to substituted 4,4-dimethyl-1-furyl-1,-3,4,5,6,7-hexahydroisobenzofurans.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1439–1443, August, 1994.     

甲基红染料掺杂的聚乙烯醇薄膜光存储特性的实验研究

用2倍频小型YAG激光(532nm)作为写入光和擦除光,用He-Ne激光器623.8nm线作为读出光,用CCD作为探测器,研究了不同写入光功率下,甲基红/聚乙烯醇(MR/PVA)薄膜光栅生长的动力学过程和不同擦除光功率下,光栅擦除的动力学过程.结合光栅生长曲线的波动现象,对光存储机制进行了新的探讨.实验发现,两写入光和读出光的功率配比为1:1:1时,可获得最大衍射效率,提出读出光对写入过程具有双重作用的物理模型,对此实验结果给出了合理的解释.     

Nitrated polynuclear aromatic hydrocarbons in ambient air in Italy. A brief overview

When nitrated polynuclear aromatic hydrocarbons (NPAH) were recognised as long‐term toxic compounds and were also identified in several anthropogenic emissions and among the by‐products of photochemical smog they became objects of investigation in ambient air in both polluted and clean environments. In Italy the first investigations focussing on atmospheric NPAH were performed in the early eighties and encompassed both the canyon streets and dwelling areas of Rome. Because NPAH were indicated as markers of vehicle emission, new investigations were performed in other cities and also in rural and (nominally) unpolluted locations. In general, the first measurements of NPAH were episodic and could not be assumed to be strictly representative of the sites investigated. In contrast, nowadays consistent data bases on NPAH have been built up and are discussed in the technical literature, so that both neat concentrations and the yearly timed variation of the most important NPAH congeners have been measured in Italian air. Although concentrations of NPAH in air are usually much lower than those of PAH, owing to their very high potency in inducing mutations and tumours NPAH are regarded as having an important health impact on populations living in Italian urban areas. In this regard the genotoxicity of atmospheric aerosols is partly associated with nitrofluoranthenes and nitropyrenes whereas nitronaphthalenes and methylnitronaphthalenes seem to contribute to that of the gaseous organic fraction. Several civic and regional administrations are introducing control of atmospheric NPAH among ways of improving air quality in cities.     

Synthesis and characterization of poly(vinyl alcohol)‐graft‐[poly(D,L‐lactide)/poly(D,L‐lactide‐co‐glycolide)] hydrogels

Poly(D ,L ‐lactide) and poly(D ,L ‐lactide‐co‐glycolide) with various composition and with one methacrylate and one carboxylate end group were synthesized and grafted onto poly(vinyl alcohol) (PVA) via the carboxylate group. The graft copolymers were crosslinked via the methacrylate groups using a free radical initiator. The polymer networks were characterized by means of NMR and studied qualitatively by means of IR spectroscopy. The influence of the glycolide content in the polyester grafts and of the number of ester units in the grafts on thermal properties and swellability were studied as well. The high swellability in water is characteristic of all hydrogels. Differential scanning calorimetry (DSC) showed a single glass transition temperature that occurs in the range between 51 and 69 °C. Thermogravimetric analysis (TGA) of the networks showed the main loss in weight in the temperature range between 290 and 370 °C. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4536–4544, 2007     

芳环羟基化HPLC分离荧光法检测Cu(Ⅱ)-H2O2体系中产生的·OH

采用L-苯丙氨酸为探针,使用液相色谱分离荧光检测(FLD)和荧光分光光度分析(FS)两种方法平行检测Cu(Ⅱ)-H2O2 体系中产生的·OH.试验采用的激发波长277 nm,发射波长306 nm.体系在反应前后的荧光变化,可反映·OH产生量.对FLD与FS所得数据进行了比较分析,结果显示两种方法具有较高一致性.FS使用混合体系检测,易对荧光的产生造成干扰,而FLD法没有干扰.     

Preparation of a new hydrophilic copolymer from a polylactone and the structure analyses

A new hydrophilic copolymer having three kinds of hydroxyl groups, i.e. primary OH on -hydroxy allyl alcohol component, secondary OH on cyclic hemiacetal component and tertiary OH on -hydroxy acrylate component, was prepared by reducing a ‘polylactone’, poly(1-oxa-2-oxobutane-1,4:3,3-tetrayl), with NaBH₄ in mixed solvents containing an alcohol. The structural analyses were performed by the solution ¹H NMR and the solid state ¹³C NMR spectroscopies of the reduced samples. The composition of the three components turned out to be variable to the alcohol species used for the mixed solvent.