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。     

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.     

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     

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.     

乙醇增敏光泽精－H_2O_2－Pb（Ⅱ）化学发光体系的研究及应用

本文研究了Ｈ＿２Ｏ＿２氧化光泽精发光反应及乙醇的敏化作用，发现加入乙醇可使铅催化Ｈ＿２Ｏ＿２，氧化光泽精的发光强度有较大幅度的增强；铅量在３×１０￣（－７）～８×１０￣（－５）ｇ／ｍＬ。范围内与发光强度成正比．方法检出限为０．１０μｇ／ｍＬ；对含４μｇ／ｍＬＰｂ（Ⅱ）１１次重复测定，其ＲＳＤ为２．３％．对３２种常见的阴阳离子进行了干扰实验，表明方法具有较好的选择性。本法应用于水样及沉积物标样中痕量铅的测定，结果良好。     

Absorption spectra and the nature of complexes in the polyvinyl Alcohol-Nickel (II) chloride system

We have used electronic spectroscopy in the 160–1100 nm range to study the polyvinyl alcohol-nickel(II) chloride system. Based on the results obtained, we hypothesize formation of mixed-ligand complexes of the type [Ni(H₂O)_6-nCl_n]^2-n (n = 0, 1,..., 5) in the polyvinyl alcohol matrix. Transformation of the coordination sphere as the NiCl₂ concentration changes is apparent both in the region of the d-d transition bands (350–1100 nm) and in the region of the charge transfer bands (160–250 nm). We propose assigning the absorption bands separated by mathematical treatment to complexes of specific compositions. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 1, pp. 136–138, January–February, 2006.     

慢速饮酒血液中酒精含量的数学模型

描述的是在一定时间内慢慢地匀速喝完一定数量酒的问题,并建立了相应的数学模型.同时也建立了快速饮酒的数学模型,以及证明了在各次饮酒后的某时刻酒精含量的可叠加性.     

La对选择性加氢催化剂Co/γ-Al2O3的改性研究

应用XPS、DTG、DTA和XRD技术，分析了La提高催化剂Co-La／γ-Al2O3活性的原因．加入La后，XPS分析得出，Co2p在催化剂表层含量是未加前的1．65倍；DTG和DTA表征显示，La对催化剂的热效应影响很小；XRD分析表明，La的加入提高了Co3O4的分散度．     

低碳醇合成Raney Cu－Co催化剂的表征

本文采用ＸＲＤ、ＸＰＳ、及Ｈ_２—ＴＰＤ技术对不同Ｃｕ／Ｃｏ比的几个ＲａｎｅｙＣｕ－Ｃｏ催化剂进行了表征．并与反应醇选择性进行了关联．结果表明：ＲａｎｅｙＣｕ－Ｃｏ催化剂均由不同Ｃｕ／Ｃｏ比的两个Ｃｕ－Ｃｏ固溶体相组成，还原（Ｈ_２，５６３Ｋ，２ｈ）前，表面除有Ｃｕ￣０和Ｃｏ￣０外，尚有少量Ｃｕ￣（＋１）和显著量的Ｃｏ￣（＋２）存在，还原后，Ｃｕ￣（＋１）几乎消失，Ｃｏ￣（＋２）仍有一定量存在，在反应温度下（５６３Ｋ），ＣＯ和ＣＯ_２均能使表面Ｃｏ￣０部分氧化，且ＣＯ_２氧化能力大于ＣＯ，而合成气（Ｈ_２／ＣＯ＝２）表现为还原的性质。三种气氛对Ｃｕ￣０无明显影响。催化剂表面Ｃｕ／Ｃｏ比高于体相Ｃｕ／Ｃｏ比，表面Ｃｕ富集显著．ＲａｎｅｙＣｕ－Ｃｏ催化剂表面有四种吸氢中心：Ｃｕ（弱吸氢中心），高配位Ｃｏ（弱吸氢中心），低配位Ｃｏ（活化吸氢中心），及强吸氢中心；对不同催化剂，表面低配位Ｃｏ中心的比例与醇选择性有一致的变化规律。基于上述结果，就ＣＯ播入中心进行了讨论。