水溶性聚合物和两亲聚合物：23.两亲聚合物PAMC16S对螺恶嗪？…

研究了两亲聚合物聚（２－丙烯酰胺基十六烷磺酸）（ＰＡＭＣ１６Ｓ）存在下１－乙基－２,３－二甲基螺［吲哚啉－萘并恶嗪］（ＳＯ－Ｅ）在水溶液中的增溶作用及ＰＡＭＣ１６Ｓ对ＳＯ－Ｅ化学和光化学性质的影响。ＰＡＭＣ１６Ｓ明显增加了ＳＯ－Ｅ在水相的溶解性,ＳＯ－Ｅ的最大增溶浓度随ＰＡＭＣ１６Ｓ浓度增加呈线性增加规律。在ＰＡＭＣ１６Ｓ存在下,新配制的ＳＯ－Ｅ溶液显示可逆的光致变色性,显色体呈红色,最大吸收峰位     

FACTORS AFFECTING THE CATALYTIC ACTIVTTIES OF THE Cp2TiCl_2／n－BuLi SYSTEM FOR THE OLEFIN HYDROGENATION

ＦＡＣＴＯＲＳＡＦＦＥＣＴＩＮＧＴＨＥＣＡＴＡＬＹＴＩＣＡＣＴＩＶＴＴＩＥＳＯＦＴＨＥＣｐ２ＴｉＣｌ_２／ｎ－ＢｕＬｉＳＹＳＴＥＭＦＯＲＴＨＥＯＬＥＦＩＮＨＹＤＲＯＧＥＮＡＴＩＯＮ￥ＳｈｉＪｉａｎＬＩＡＯ；ＹｕｎＸＵ；ＹｉＰｉｎｇＺＨＡＮＧ（Ｄａｌｉ?..     

导电高聚物聚2，5－二甲基苯胺的化学合成与特性

报道了聚２，５－二甲基苯胺（ＰＤＭｅＡｎ）的化学合成，并用标准四探针方法测定其电导率，以ＦＴＩＲ、ＵＶ－Ｖｉｓ吸收光谱、元素分析和ＣＶ法对其性质进行了研究，ＰＤＭｅＡｎ的结构与聚苯胺和聚２，５－二甲氧基苯胺的结构类似，是由其单元通过氮原子（Ｎ）在对位上键合而成，本征态的ＰＤＭｅＡｎ能溶于多种有机溶剂，如ＣＨ２Ｃｌ２、ＣＨＣｌ３、ＤＭＳＯ、ＤＭＦ等。     

THE CONVERSION OF SYNGAS ON Fe／MnOⅡ．The Role of K in Modified Fe／MnO Catalysts

ＴＨＥＣＯＮＶＥＲＳＩＯＮＯＦＳＹＮＧＡＳＯＮＦｅ／ＭｎＯⅡ．ＴｈｅＲｏｌｅｏｆＫｉｎＭｏｄｉｆｉｅｄＦｅ／ＭｎＯＣａｔａｌｙｓｔｓＧｕａｎＮａｉｊｉａ（ＤｅｐａｒｔｍｅｎｔｏｆＣｈｅｍｉｓｔｒｙ，ＮａｎｋａｉＵｎｉｖｅｒｓｉｔｙ，Ｔｉａｎｊｉｎ３０...     

VAPOR PHASE CARBONYLATION OF ETHANOL OVER Ni－Pb／C CATALYST AT ATMOSPHERIC PRESSURE

ＶＡＰＯＲＰＨＡＳＥＣＡＲＢＯＮＹＬＡＴＩＯＮＯＦＥＴＨＡＮＯＬＯＶＥＲＮｉ－Ｐｂ／ＣＣＡＴＡＬＹＳＴＡＴＡＴＭＯＳＰＨＥＲＩＣＰＲＥＳＳＵＲＥ￥Ｗａｎｇ，Ｄａ－ｗｅｉ；Ｆｅｎｇ，Ｊｉｎｇ－ｘｉａｎａｎｄＨｕａｎｇ，Ｚｈｏｎｇ－ｔａｏ（Ｄｅｐａｒｔｍ...     

STUDIES ON THE NON－ISOTHERMAL KINETICS OF THERMAL DECOMPOSITIONS OF THE COMPLEXES OF Cd（II）WITH O－VANILLIN THIOSEMICARBAZONE AND IRON（III）WITH 2－［（O－HYDROXYBENZYLIDENE）AMINO］PHENOL AND PYRIDINE

ＳＴＵＤＩＥＳＯＮＴＨＥＮＯＮ－ＩＳＯＴＨＥＲＭＡＬＫＩＮＥＴＩＣＳＯＦＴＨＥＲＭＡＬＤＥＣＯＭＰＯＳＩＴＩＯＮＳＯＦＴＨＥＣＯＭＰＬＥＸＥＳＯＦＣｄ（ＩＩ）ＷＩＴＨＯ－ＶＡＮＩＬＬＩＮＴＨＩＯＳＥＭＩＣＡＲＢＡＺＯＮＥＡＮＤＩＲＯＮ（ＩＩＩ）ＷＩＴ...     

BEHAVIOUR OF THE ELECTROSYNTHESIS OF 1,5-DIAMINO-4,8-DIHYDROXYANTHRAQUINONE

ＢＥＨＡＶＩＯＵＲＯＦＴＨＥＥＬＥＣＴＲＯＳＹＮＴＨＥＳＩＳＯＦ１，５－ＤＩＡＭＩＮＯ－４，８－ＤＩＨＹＤＲＯＸＹＡＮＴＨＲＡＱＵＩＮＯＮＥ￥ＣｈｕｎＡｎＭＡ；（ＣｈｅｍｉｃａｌＥｎｇｉｎｅｅｒｉｎｇＤｅｐａｒｔｍｅｎｔ，ＺｈｅｊｉａｎｇＵｎｉｖｅｒ...     

THE CONVERSION OF SYNGAS ON Fe／MnOⅠ．Efects of Metal Modification on Product Distribution

ＴＨＥＣＯＮＶＥＲＳＩＯＮＯＦＳＹＮＧＡＳＯＮＦｅ／ＭｎＯⅠ．ＥｆｅｃｔｓｏｆＭｅｔａｌＭｏｄｉｆｉｃａｔｉｏｎｏｎＰｒｏｄｕｃｔＤｉｓｔｒｉｂｕｔｉｏｎＧｕａｎＮａｉｊｉａ（ＤｅｐａｒｔｍｅｎｔｏｆＣｈｅｍｉｓｔｒｙ，ＮａｎｋａｉＵｎｉｖｅｒｓｉｔ...     

SELF SUSTAINED SURFACE CHEMICAL OSCHLATION AND IT＇S MATHEMATICAL SIMULATION OF THE COMPLETE OXIDATION OF MATHANOL OVER Pt／Al_2o_3 CATALYST

ＳＥＬＦＳＵＳＴＡＩＮＥＤＳＵＲＦＡＣＥＣＨＥＭＩＣＡＬＯＳＣＨＬＡＴＩＯＮＡＮＤＩＴ’ＳＭＡＴＨＥＭＡＴＩＣＡＬＳＩＭＵＬＡＴＩＯＮＯＦＴＨＥＣＯＭＰＬＥＴＥＯＸＩＤＡＴＩＯＮＯＦＭＡＴＨＡＮＯＬＯＶＥＲＰｔ／Ａｌ_２ｏ_３ＣＡＴＡＬＹＳＴＣｏｎｇＱ...     

STUDIES ON CHIRAL THIOPHOSPHORIC ACIDS AND THEIR DERIVATIVES 13．THE ASYMMETRIC CYCLIZATION OF （＋）－SUBSTITUTED CYCLOPENTANODIAMINE WITH O－ARYL THIOPHOSPHOROCHLORIDATES

ＳＴＵＤＩＥＳＯＮＣＨＩＲＡＬＴＨＩＯＰＨＯＳＰＨＯＲＩＣＡＣＩＤＳＡＮＤＴＨＥＩＲＤＥＲＩＶＡＴＩＶＥＳ１３．ＴＨＥＡＳＹＭＭＥＴＲＩＣＣＹＣＬＩＺＡＴＩＯＮＯＦ（＋）－ＳＵＢＳＴＩＴＵＴＥＤＣＹＣＬＯＰＥＮＴＡＮＯＤＩＡＭＩＮＥＷＩＴＨＯ－ＡＲＹ...     

两亲无规聚合物的聚集行为及其与非离子表面活性剂的相互作用

以2-丙烯酰胺基-十二烷基磺酸(AMC12S)与2-丙烯酰胺基-2-甲基丙磺酸(AMPS)进行无规共聚,合成了含AMC12S摩尔分数(X)较高(X=0.1,0.3,0.5)的一系列两亲聚合物.采用稳态荧光及动态光散射技术对聚合物在水溶液中的聚集行为及其与三种非离子表面活性剂(HO(CH2CH2O)10C12H25(C12E10)、HO(CH2CH2O)20C12H25(C12E20)和HO(CH2CH2O)40C12H25(C12E40))的相互作用进行了研究,并考察了X对聚集行为的影响以及表面活性剂亲水基团长度对相互作用的影响.随着X的增大,聚合物的临界聚集浓度(CAC)明显减小,X=0.5时聚合物的CAC低达0.0039g·L-1.聚集体的流体力学半径(Rh)都大于26nm,并随着聚合物浓度的升高而增大,说明聚合物分子主要以分子间的聚集方式聚集,形成多分子聚集体.随X的增大,聚集体Rh减小,同时Rh随聚合物浓度升高而增大的幅度减小,说明聚集体结构变得更加紧实.表面活性剂与聚合物之间存在很强的相互作用,在混合溶液中表面活性剂浓度达到临界胶束浓度(CMC)左右时聚合物聚集体开始解离,形成混合聚集体.亲水基团长度增长,表面活性剂对聚合物聚集体的解离能力随之增强.C12E40与X=0.5的聚合物形成的混合聚集体Rh为6.8nm,与C12E40自身形成的聚集体尺寸相当.     

Self-assembly of brush-like amphiphilic statistical polymers: the effect of salt stimulus on the molecular associative mode

The solution properties of amphiphilic statistical polymers, originating from the nanostructures of macromolecular assemblies, strongly depend on the associative behaviours of the polymers. In this paper, we report the effect of salt stimulus on the associative mode of the 2-(acrylamido)-2-methylpropanesulphonic acid–2-(acrylamido)-dodecane sulphonic acid brush-like amphiphilic statistical polymers, employing steady-state fluorescence, dynamic light scattering and transmission electron micrograph methods. It was found that the stimulus effects work more intensely for the polymers with less hydrophobic side chains. As the salt concentration increases, the salt valence state increases or the salt structure adds an organic group, the polymer molecules associate at a lower critical concentration. Meanwhile the molecules undergo an intramolecular associative mode in preference to an intermolecular associative mode, forming hundreds of times smaller unimers rather than giant multipolymer aggregates.     

水溶性聚合物和两亲聚合物:9.新型丙烯酰胺基两亲单体及其两亲聚合物的单层膜研究

本文对新型两亲单体,2-丙烯酰胺基十六烷磺酸(AMC_(16)S),及其两亲聚合物PAMC_(16)S在空气-水界面上形成单层膜的特点进行了研究。AMC_(16)S可通过在亚相中添加Ca~(2+)或Cd~(2+)等多价阳离子在界面上原位生成不溶性磺酸盐的方法获得满意的成膜行为。PAMC_(16)S不溶于水,可直接成膜。发现,PAMC_(16)S的成膜行为与亚相的性质明显相关。纯水亚相下PAMC_(16)S的极限单体链节面积较大,如亚相含有Ca~(2+)或Cd~(2+),极限面积明显缩小,说明烷基碳氢链的排列趋向紧密。     

盐对刷型两亲聚合物聚集行为的调控作用

两亲聚合物奇异的功能特性源于分子独特的骨架结构和在溶液中的自组装聚集行为. 本文向以2-丙烯酰胺基-十二烷基磺酸(AMC₁₂S)与2-丙烯酰胺基-2-甲基丙磺酸(AMPS)进行无规共聚所制备的AMPS-AMC₁₂S刷型两亲聚合物溶液体系中引入不同用量的NaCl, 采用稳态荧光、动态光散射(DLS)和透射电子显微镜(TEM)系统考察NaCl 对聚合物聚集行为的调控作用. 研究发现, 聚合物结构中疏水侧链含量越低, NaCl 对聚集行为的调控作用越强; NaCl浓度增加会明显降低聚合物的临界聚集浓度; 与此同时, 聚合物分子链自组装由分子间的聚集方式向分子内的聚集方式转变, 形成的聚集形态由大型多分子聚集体变化为尺寸数百分之一的单聚体.     

Application of umbelliferone molecularly imprinted polymer in analysis of plant samples

The molecularly imprinted polymers (MIPs) were synthesised and the influence of the type of porogen, the nature of sample solvent, and the binding capacity of material were tested by high-performance liquid chromatography (HPLC). Umbelliferone was used as the template for imprint formation. Methacrylic acid was used as the monomer and acetonitrile, ethanol, and chloroform as porogen. Non-imprinted polymers (NIPs) were prepared by the same procedure. The highest value of the specific binding capacity (269 μg of umbelliferone per 100 mg of polymer) was obtained for polymers prepared in chloroform as porogen and methanol/water (φ _r = 1: 1) as the sample solvent. The group-selective MIP was used as sorbent for the SPE pre-treatment of umbelliferone from plant extracts prior to HPLC analysis. Analysis of the spiked samples showed good recoveries (> 77 %). The limit of detection, limit of determination, and repeatability of the method were also calculated.     

Highly stereoselective, uniformly sized molecularly imprinted polymers for cinchona alkaloids in hydro-organic mobile phases.

Highly stereoselective, uniformly sized molecularly imprinted polymers (MIPs) for cinchona alkaloids, cinchonine (CN) and cinchonidine (CD), were prepared using methacrylic acid (MAA) as a functional monomer and ethylene glycol dimethacrylate (EDMA) as a cross-linker. The MIPs were evaluated using a mixture of phosphate buffer and acetonitrile as the mobile phase. The CN- and CD-imprinted MAA-co-EDMA polymers can recognize the respective template molecule more than the other diastereomer, and afford an excellent diastereomer separation of CN and CD. In addition, the MIPs gave diastereomer separations of structurally related compounds, quinidine and quinine. The retentive and stereoselective properties of those compounds on the MIPs suggest that electrostatic and hydrophobic interactions can work to recognize these compounds. Furthermore, thermodynamic studies reveal that the entropy-driven effect is significant at mobile-phase pH 5.4, while the enthalpy-driven interactions seem to be dominant at mobile-phase pH 9.6.     

采用阴离子、基团转移及自由基聚合方法合成旋光性聚甲基丙烯酸薄荷酯

近年来, 旋光性高分子的广泛应用及其特有的功能已引起了广泛关注, 尤其在手性记忆功能材料[1～3]、液晶及手性催化等方面[4～6]皆表现出良好的应用前景. 用旋光性单体合成旋光性聚合物是最常用的方法之一. 早在20世纪70年代, 就有关于聚甲基丙烯酸薄荷酯(PMnMA)的研究[7], 但有关配体参与的阴离子聚合, 基团转移聚合(GTP)及其立构规整性的研究还未见报道.     

Synthesis and Crystal Structure of 4-(N,N-Diphenylamino)styrene- 4′-N-methylpyridinium Iodine

The title compound 4-(N,N-diphenylamino)styrene-4′-N-methylpyridinium iodine (abbreviated to PASMPI) was synthesized by a facile condensation reaction with a high yield. The red crystal including a molecule of CHCl3 was obtained by recrystallization in chloroform/ethanol. Its crystal structure was determined by a four-circle diffractometer. The crystal data: C26H23N2ICHCl3, Mr = 609.73, orthorhombic, space group Pbca, a = 15.422(5), b = 14.042(5), c = 24.693(5) , V = 5347(3) 3, Z = 8, Dc = 1.515 g/cm3, F(000) = 2432, μ(MoKa) = 0.057 mm-1, the final R = 0.0439 and wR = 0.0772. The results reveal that the molecule is a completely reverse system. The molecular rotation from non-coplanar to coplanar may play an important role in increasing the fluorescence intensity under the condition of staining DNA.     

New Insights into Cinchonine–Aluminium Complexes and Their Application as Chiral Building Blocks: Unprecedented Ligand‐Exchange Processes in the Presence of ZnR2 Compounds

Previous studies have demonstrated that [(CN)₂AlCl] and [R₂Al(μ‐CN)]₂ (CN=deprotonated cinchonine) complexes can effectively act as chiral, semirigid, N,N‐ditopic metalloligands for Zn‐containing nodes, and provide viable means for constructing new, homochiral, heterometallic, coordination polymers of zigzag and helical topologies. These findings have prompted further investigations on the organometallic analogues of the formula [(CN)₂AlR], anticipating their utility as N,N‐metalloligands for ZnR₂ units. Surprisingly, reactions of [(CN)₂AlMe]‐type metalloligands with ZnR₂ compounds (R=Me or Et) revealed unprecedented ligand‐exchange processes, including zinc‐to‐aluminium and aluminium‐to‐zinc transmetalations of alkyl groups. The molecular and crystal structure of the resulting compounds was determined by X‐ray diffraction analysis. From the reaction of [(CN)₂AlMe] with ZnMe₂ a new pseudopolymorphic form of a noncovalent porous material based on [Me₂Al(μ‐CN)]₂ molecules was isolated. Strikingly, the analogous reaction involving ZnEt₂ led to the generation of a new chiral 4N‐tetratopic heterometalloligand [(CN)EtAl(μ‐CN)₂ZnEt]. The latter unit was successfully connected by alkyl‐exchanged ZnMe₂ nodes to give an original homochiral heterometallic {[(CN)EtAl(μ‐CN)₂ZnEt]ZnMe₂}_n coordination polymer adopting a snake 1D motif. The outcome of the revealed reactions indicates the complicated multistep reaction route that involves redistribution of cinchonine and alkyl ligands among the Al and Zn centers, and a general reaction scheme is proposed. The results are in strong contrast with the previously studied inorganic–organic [(CN)₂AlCl/ZnCl₂] system, which exclusively affords a helical coordination polymer based on ZnCl₂ nodes and (CN)₂AlCl metalloligands and lacks the exchange of CN ligands.     

Modification of porous poly(vinylidene fluoride) membrane using amphiphilic polymers with different structures in phase inversion process

Three kinds of amphiphilic polymers, including the tri-block copolymer of (polyethylene oxide)–(polypropylene oxide)–(polyethylene oxide) (I, EPTBP), the comb-like copolymer of polysiloxane with polyethylene oxide and polypropylene oxide side chains (II, ACPS) and the hyperbranched star copolymer of polyester-g-methoxyl polyethylene glycol (III, HPE-g-MPEG), were blended with PVDF to fabricate porous membranes via a phase inversion process, respectively, and the effects of the different structures of the amphiphilic polymers on the properties of the blend membranes were compared. The membranes were characterized by scanning electron microscopy (SEM), elemental analysis, X-ray photoelectron spectroscopy (XPS) analysis, mercury porosimetry, water contact angle measurements, etc. The anti-fouling properties of the prepared membranes were evaluated by static and dynamic bovine serum albumin (BSA) adsorptions. Specially, the stabilities of these amphiphilic polymers in the final membranes were estimated by continuous leaching tests. At the same time, the properties of the membranes using the amphiphilic polymers as modifiers were compared with those of the membrane using poly(ethylene glycol) (PEG) as modifier.