α—羰基烯酮环二硫代缩醛化学：XXI：β,β—1,3—亚丙二硫基—α,β—不饱和酮？

在乙醇为溶剂，乙醇钠为碱的条件下，标题类化合物１ａ～ｃ，３ａ，４ａ与胍缩合反应生成相应的嘧啶类化合物２ａ～ｃ，３ｂ，３ｃ，４ｂ。在以ＤＭＦ为溶剂，乙醇钠为碱的条件下，化合物１ａ与胍反应可生成２－氨基－４－二甲氨基－６－苯基嘧啶２ａ，该缩反应的特点为标题类化合物与胍缩合生成嘧啶类化合物的同时，将乙氧基或二甲氨基引入嘧啶环的确定位置，２ａ，２ａ，３ｂ，３ｃ，４ｂ为新的嘧啶在化合物。     

噻吩及衍生物的微波反应机理研究

应用量子化学理论，初步探讨了苯－噻吩协同分离的可能性，利用微波诱导反应提高了选择性，介绍了在复合催化作用下，对Ｄｉｅｌｓ－Ａｌｄｅｒ，ａｃｙｌａｃｙｌａｔｉｏｎ，ＨｙｄｒｏｇｅｎＥｘｃｈａｎｇｅ几个基元反应的机理。     

双膦配体DPPB的铑配合物催化烯烃氢甲酰化反应研究

研究了由Ｒｈ（ａｃａｃ）（ＣＯ２）和１,４－双（二苯膦基）苯（简称ＤＰＰＢ）组成的体系对烯烃氢甲酰化反应的催化作用。考察了反应温度、压力、Ｐ／Ｒｈ比、催化剂浓度等对１－己烯氢甲酰化反应的影响,得到了较适宜的反应条件。在相同条件下比较了该体系催化１－己烯、１－辛烯、１－十二烯的氢甲酰化反应的性能。结果表明,随着底物碳链的增长,反应活性呈提高优势。实验证明,ＤＰＰＢ－铑配合物对苯乙烯的氢甲酰化反应有较     

聚丙烯酸类pH敏感水凝胶

通过共聚制得聚丙烯酸 ｃｏ 丙烯腈水凝胶和聚丙烯酸 ｃｏ 甲基丙烯酸水凝胶 ,研究了它们在恒温下不同ｐＨ时的溶胀率 ,以及在恒定ｐＨ时 ,交联剂、单体浓度对它们溶胀率的影响。Ｐｏｌｙ(ａｃｒｙｌｉｃａｃｉｄ) ｃｏ (ａｃｒｙｌｏｎｉｔｒｉｌｅ)ｈｙｄｒｏｇｅｌｓａｎｄｐｏｌｙ(ａｃｒｙｌｉｃａｃｉｄ) ｃｏ (ｍｅｔｈｙｌｍｅｔｈａｃｒｙｌｉｃａｃｉｄ)ｈｙｄｒｏｇｅｌｓｗｅｒｅｐｒｅｐａｒｅｄｔｈｒｏｕｇｈｔｈｅｃｏ ｐｏｌｙｍｅｒｉｚａｔｉｏｎ .Ａｎｄｓｗｅｌｌｉｎｇｒａｔｉｏｏｆｔｈｅｍｗｅｒｅｓｔｕｄｉ…     

偶联剂汞代异烟酸-N-丁二酰亚胺酯的合成研究

用亲电取代法通过异烟酸与氧化汞直接反应 ,合成汞代吡啶羧酸再进行酯化 ,制得一种适合于各种蛋白质碘标记的偶联剂 :氯化汞代异烟酸 Ｎ 丁二酰亚胺酯。用该试剂结合固相分离技术来建立一简便的标记抗体途径。其蛋白质标记率可达 4 0 %～ 60 %。Ｂｙｖｉｒｔｕｅｏｆｉｓｏｎｉｃｏｔｉｎｉｃａｃｉｄａｓｐｒｅｃｕｒｓｏｒｃｏｍｐｏｕｎｄ ,Ｎ ｓａｃｃｉｎｉｍｉｄｙｌｉｓｏｎｉｃｏｔｉｎｉｚｕｔｅｈａｓｂｅｅｎｓｙｎｔｈｅｓｉｚｅｄｔｈｒｏｕｇｈｅｌｅｔｒｏｐｈｉｌｉｃｒｅａｃｔｉｏｎａｎｄｔｈｅｎｂｅｉｎｇｅｓｔｅｒ…     

固相配位化学反应研究 LXXⅣ.固相化学反应中的晶态┐非晶态┐晶态的变化

本文用近室温固相化学反应方法合成了一个新化合物Ｃｏ（ａｃａｃ）Ｑ（ｂｉｐｙ）（Ｈａｃａｃ＝乙酰丙酮，ｂｉｐｙ＝２，２′－联吡啶，８－ＨＱ＝８－羟基喹啉）。发现了化学反应中晶态－非晶态－晶态的变化过程，用扩散－反应－成核及成长机理的三步过程阐明了固相化学反应机理。     

单磺化酞菁镓在水、微乳液中的解聚反应动力学研究

本文研究了单磺化酞菁镓（ＳＰｃＧａ）在水、微乳液（ＴｒｉｔｏｎＸ－１００－壬烷－正戊醇－水）中的二聚现象和解聚反应动力学，测定了二聚平衡常数ＫＤ和解聚速率常数ｋ。结果表明：ＳＰｃＧａ的解聚反应速率与ＳＰｃＧａ的单体浓度ＣＭ和双体浓度ＣＤ的关系为：Ｖ＝ｋ１ＣＤ－ｋ２ＣＭ２     

α－羰基烯酮环二硫代缩醛化学XXI：β，β－1，3－亚丙二硫基－α，β－不饱和酮与胍的缩合反应

在乙醇为溶剂，乙醇钠为碱的条件下，标题类化合物归１ａ～ｃ，３ａ，４ａ与胍缩合反应生成相应的嘧啶类化合物２ａ～ｃ，３ｂ，３ｃ，４ｂ。在以ＤＭＦ为溶剂，乙醇钠为碱的条件下，化合物与胍反应可生成２－氨基－４－二甲氨基－６－苯基嘧啶２ａ’。该缩合反应的特点为标题类化合物与肌缩合生成嘧啶类化合物的同时，将乙氧基或二甲氨基引入嘧啶环的确定位置。为新的嘧啶类化合物。     

钙—亚硫酰氯电池的研究

应用交流阻抗，恒电流，ＳＥＭ等方法，研究了Ｃａ－ＳＯＣｌ２电池中ＣａＣｌ２（ＳＥＩ）膜的性质，不同电解质和添加剂对电极性的影响，结果表明，ＣａＣｌ２ＳＥＩ膜在阳极反应电阻下降，ＣｕＣｌ２，ＣｕＢｒ２可改变ＣａＣｌ２沉积形态，提高阴极性能，组装的Ｃａ－ＳＯＣｌ２电池可高速率放电，在５０ｍＡ．ｃｍ＾－２的条件下，达到了１７．５ｍＡｈ．ｃｍ＾－２。     

钙－亚硫酰氯电池的研究

应用交流阻抗、恒电流、ＳＥＭ等方法,研究了Ｃａ－ＳＯＣｌ２电池中ＣａＣｌ２（ＳＥＩ）膜的性质;不同电解质和添加剂对电极性能的影响．结果表明,ＣａＣｌ２ＳＥＩ膜在阳极反应时电阻下降。ＣｕＣｌ２、ＣｕＢｒ２可改变ＣａＣｌ２沉积形态,提高阴极性能．组装的Ｃａ－ＳＯＣｌ２电池可高速率放电,在５０ｍＡ·ｃｍ－２的条件下,达到１７．５ｍＡｈ·ｃｍ－２。     

Chiral separation of amino acids by capillary electrophoresis with 3-[(3-cholamidopropyl)-dimethylammonio]-1-propane sulfonate as chiral selector

Summary 3-[(3-cholamidopropyl)-dimethylammoniol-1-propane sulfonate (CHAPS) can be used as an effective chiral selector for the separation of dansyl-amino acids by capillary electrophoresis (CE). While CHAPS can serve as an chiral selector, better enantiomeric separation can be performed by using CHAPS not as the sole chiral selector but as one of a [CHAPS-SDS-cyclodextrin] three-component system. In this CHAPS-SDS-CD system, enantiomeric separations of the amino acids can be readily accomplished by judiciously adjusting the pH of the solution, concentrations of CHAPS and SDS, and the concentration and type of CD. All amino acids can be baseline resolved in less than 15 minutes with resolution as high as 2.01 at pH 6.5 with 50 mM of CHAPS and 75 mM of SDS. The resolution is also dependent on the size of the CD. Substantial increase in the resolution can be readily achieved by replacing β-CD with γ-CD. For example, theR _s for Leu was increased by four-folds (from 1.65 to 6.29) while the elution time still remains as short as 20 min when β-CD was replaced by γ-CD.     

Langmuir monolayers as models to study processes at membrane surfaces

The use of new sophisticated and highly surface sensitive techniques as synchrotron based X-ray scattering techniques and in-house infrared reflection absorption spectroscopy (IRRAS) has revolutionized the monolayer research. Not only the determination of monolayer structures but also interactions between amphiphilic monolayers at the soft air/liquid interface and molecules dissolved in the subphase are important for many areas in material and life sciences. Monolayers are convenient quasi-two-dimensional model systems. This review focuses on interactions between amphiphilic molecules in binary and ternary mixtures as well as on interfacial interactions with interesting biomolecules dissolved in the subphase. The phase state of monolayers can be easily triggered at constant temperature by increasing the packing density of the lipids by compression. Simultaneously the monolayer structure changes are followed in situ by grazing incidence X-ray diffraction or IRRAS. The interactions can be indirectly determined by the observed structure changes. Additionally, the yield of enzymatic reaction can be quantitatively determined, secondary structures of peptides and proteins can be measured and compared with those observed in bulk. In this way, the influence of a confinement on the structural properties of biomolecules can be determined. The adsorption of DNA can be quantified as well as the competing adsorption of ions at charged interfaces. The influence of modified nanoparticles on model membranes can be clearly determined. In this review, the relevance and utility of Langmuir monolayers as suitable models to study physical and chemical interactions at membrane surfaces are clearly demonstrated.     

Improving chemical recycling rate by reclaiming polyurethane elastomer from polyurethane foam

Flexible polyurethane foam was decomposed into a polyol mixture by an extruder with diethanolamine (DEA) as a decomposing agent. The resulting decomposed product could be used as an alternative virgin polyol in reclaiming polyurethane. In the case of reclaiming elastomer by using the decomposed product without any purification, virgin polyol could be alternated by the decomposed product up to 80%. It is a great improvement compared with the reclamation to foam, whose percentage was maximum 5%. Furthermore, the percentage could be improved up to 100% by purifying the decomposed product. We have found that physical properties of reclaimed polyurethane elastomer, such as tensile strength, hardness, and elongation, can be regulated by the ratio of unrefined/refined polyol. Whereas the tensile strength and the hardness increased as the content increased, the elongation decreased.     

On the use of alumina in HPLC with aqueous mobile phases at extreme pH

Summary The applicability of alumina as a stationary phase in liquid chromatography is considered. Despite the presence of hydroxyl groups on wetted alumina, chemical modification with silanes by analogy to silica is not successful. Although depolarisation can be achieved with hexamethyldisilazane, the product is not stable to hydrolysis in aqueous media. The use of alumina as an ion-exchanger is more promising, especially because alumina appears to be stable over a very broad pH range. As a result of its amphoteric character alumina can be used either as an anion-exchanger or as a cation-exchanger. The latter possibility is more profitable in alkaline solvents and allows the separation of strongly basic compounds at pH values as high as 12. Retention can be controlled by judicious choice of ionic strength, counter ion and pH.     

Electrical conductivity of partly oxidized aromatic and heteroaromatic polymers

The electrical conductivity of aromatic and heteroaromatic polymers as well as polymers with aromatic, heteroaromatic and vinylene units in the main chain, can be enhanced by oxidation. In a single electron transfer reaction, a polymer with a salt structure (“doped polymer”) can be formed. Such polymers can also be prepared in a one-step reaction from low-molecular weight compounds by oxidants, as well as by electrochemical reaction. Electrochemically produced samples have higher electrical conductivities (as high as 6298K = 0,5 Ω⁻¹ · cm⁻¹) than samples made by chemical oxidation from the same starting material.     

漂白过程的电化学研究 Ⅲ.利用旋转圆盘电极模拟照相漂白过程

将银旋转圆盘电极在给定时间内浸在漂白液中进行氧化。在氧化过程中,来自漂白液中的卤化物在银电极表面与氧化生成的银离子形成卤化银。氧化反应生成的卤化银量可以用电化学还原方法进行定量测定。利用这种简单的方法可以研究漂白动力学,研究漂白液的组份、浓度和pH对漂白速度的影响。通过记录在银电极上氧化还原对的电流。电位曲线可以定量描述漂白过程。     

可交联聚醚醚酮酮交替共聚物的合成与热交联研究

聚芳醚酮类特种工程塑料以其优异的机械性能、热稳定性、耐溶剂、耐辐照等特性在运输、航空航天、军事、电子、信息、核能等领域得到了广泛应用_{[1].聚醚醚酮的玻璃化转变温度(Tg)和熔点(Tm)分别为416和607 K,其长期使用温度为513 K,而其热分解温度在800 K以上,是热稳定性较好的聚合物之一.为了满足一些特殊需求,人们通过在聚芳醚酮的主链中引入刚性结构链,提高其主链的刚性程度,从而提高其T g和Tm,进而提高其使用温度[2～4].文献[5]报道的新型聚芳醚酮的T g和T m最高可达482和742 K,采用常规方法进行加工难度较大.为了在不提高加工温度的前提下提高聚芳醚酮类材料的使用温度,我们已成功地在聚醚醚酮的主链中引入可交联的硫醚结构,得到使用温度更高的可控交联聚醚醚酮材料,其可利用热塑性材料的加工方法进行加工,加工温度与聚醚醚酮相同,交联后的材料具有热固性材料的使用特性[6,7].为了拓宽可交联聚芳醚酮材料的种类,本文合成了一种类新型的可交联型聚醚醚酮酮材料,并对其热交联性能进行了研究.}     

Theoretical prediction of the cholesteric pitch in thermotropic and lyotropic systems

The expression for the cholesteric pitch given by the theory of Lin-Liu et al. is extended by explicit consideration of the orientational entropy terms. The temperature dependence, as well as the dependence on the mole fraction in non-mesogenic solutions and on the degree of polymerization in polymer cholesterics can be obtained. In some cases helical inversion can be induced by variation of concentration as well as temperature.     

A method for rapid,non-targeted screening for environmental contaminants in household dust

Household dust can be a major source of human exposure to environmental contaminants such as polybrominated diphenyl ethers, pesticides, and other compounds. This work shows a screening technique that may be used to identify components in an environmental sample as xenobiotics based on mass spectral characteristics of classes of compounds that may be expected to be present in the environment. Household dust (SRM-2585) from the National Institute of Standards and Technology (NIST) was extracted with hexane using accelerated solvent extraction. Large molecules, such as triglycerides and fatty acids were removed with gel permeation chromatography. The extract was then concentrated and analyzed by comprehensive two dimensional gas chromatography coupled to a time of flight mass spectrometer. The resulting peak table was automatically filtered to identify compound classes such as phthalates, polycyclic aromatic hydrocarbons and their heterocyclic analogs, chlorinated compounds, brominated compounds, and nitro compounds. While phthalates can be identified by abundances at specific masses, the identification of the remaining classes is based on the identification of the molecular ion and identification of isotope clusters or other spectral characteristics. The technique detected compounds identified and quantified by NIST as well as compounds not identified by NIST in the sample. By comparison with concentrations determined by NIST for the analytes found, the technique is able to identify analytes in these compound classes at concentrations as low as 10–20 ng/g dust.     

Neue verfahren zur jodometrischen mikrobestimmung von jodid- bzw. Bromidion

The methods described above are based on the fact, that iodide can be determined as iodate on iodometric way after oxidation with freshly prepared chlorine water and after removal of excess of free chlorine by means of potassium cyanide. However oxidation may be carried out by adding of hypobromite the excess of which can be removed by adding of phenol water.Bromide can be transformed to BrCl by means of an excess of chlorine water. BrCl reacts with potassium cyanide under formation of cyanogen bromide and chloride. The excess of free chlorine would be removed as cyanogen chlorine and chloride. The cyanogen bromide formed can be measured on the usual iodometric way.