cis-Diaminedichloroplatinum(II) Complexes Reversibly Linked into the Main Chain of Water-Soluble Polyamides

As a follow-up study to previous work involving the platination of polyamide carriers through metal chelation by side group-incorporated ethylenediamine ligands, the present investigation is concerned with the synthesis of platinum-containing polymers in which the metal-coordinating ethylenediamine segments are components of the main chain. Two chloro groups in cis geometry are attached to each Pt atom as additional ligands, complementing a square-planar cis-diaminedichloroplatinum(II) complex system. The water-soluble polymeric carriers are synthesized by Michael-type addition polymerization, interfacial polymerization, and high-temperature solution polycondensation techniques and are crudely fractionated by stepwise aqueous dialysis, ultimately in tubing with a molecular mass cutoff of 25,000. Carrier platination is brought about by treatment with tetrachloroplatinate(II) anion in aqueous solution, care being taken to exercise strict control of reaction variables and workup conditions in an effort to restrict platination to the given ligands and avoid metal aquation or hydroxylation. The platinum conjugates, with Pt contents ranging from about 11 to 23% by mass, are completely soluble in aqueous media when freshly prepared, although long-term storage at room temperature in the solid state is conducive to gradual loss of solubility. The conjugates are of interest as carcinostatic agents.     

cis-Diaminedichloroplatinum(II) Complexes Reversibly Linked into the Main Chain of Water-Soluble Polyamides

As a follow-up study to previous work involving the platination of polyamide carriers through metal chelation by side group-incorporated ethylenediamine ligands, the present investigation is concerned with the synthesis of platinum-containing polymers in which the metal-coordinating ethylenediamine segments are components of the main chain. Two chloro groups in cis geometry are attached to each Pt atom as additional ligands, complementing a square-planar cis-diaminedichloroplatinum(II) complex system. The water-soluble polymeric carriers are synthesized by Michael-type addition polymerization, interfacial polymerization, and high-temperature solution polycondensation techniques and are crudely fractionated by stepwise aqueous dialysis, ultimately in tubing with a molecular mass cutoff of 25,000. Carrier platination is brought about by treatment with tetrachloroplatinate(II) anion in aqueous solution, care being taken to exercise strict control of reaction variables and workup conditions in an effort to restrict platination to the given ligands and avoid metal aquation or hydroxylation. The platinum conjugates, with Pt contents ranging from about 11 to 23% by mass, are completely soluble in aqueous media when freshly prepared, although long-term storage at room temperature in the solid state is conducive to gradual loss of solubility. The conjugates are of interest as carcinostatic agents.     

Aromatic Rigid Poly(urethanes) Containing Silicon and/or Germanium in the Main Chain

Summary The synthesis and characterization of aromatic rigid poly(urethanes) containing silicon and/or germanium in the main chain is described. These polymers were synthesized by condensation of aromatic diamines and the bis(chloroformates) of diphenols containing silicon or germanium as central atom and bonded to alkyl and aryl groups. The poly(urethanes) were characterized by FT-IR, ¹H, ¹³C and ²⁹Si NMR spectroscopy and the results were in according with the proposed structures. In addition, thermal characterizations were developed using DSC and TG techniques and the intrinsic viscosity were determined as evaluation of the molecular size. In all cases, the thermal properties were depending of the nature of the heteroatoms present in the repetitive unit.     

Synthesis and Reactions of Organometallic Polymers Containing Titanacyclobutene Units in the Main Chain

A new class of polymers containing titanacyclobutene units in the main chain were prepared by the reaction of organic dihalides (2) with a binuclear titanium propargyl complex (3) generated in situ from bis(pentamethylcyclopentadienyl)titanium chloride (Cp*₂TiCl, 1), SmI₂, and 1,4-bis(3-bromopropynyl)benzene (2a). The dark red colored polymers (4) thus obtained are soluble in organic solvents such as tetrahydrofuran and chloroform, and they are stable at ambient temperature under argon atmosphere. The reaction of the titanium-containing polymers (4) with hydrogen chloride was found to give organic polymers (7) containing unsaturated main chain.     

含吡咯亚胺铜配合物的合成、表征及晶体结构

合成了一种新型含吡咯亚胺铜配合物,用元素分析、红外光谱及X射线单晶衍射对其进行了表征。结构解析表明,每个铜配合物分子含有两个吡咯亚胺配体,每个配体用两个氮原子与中心金属铜离子螯合,每个铜离子均采取平面四边形构型与配体中的四个氮原子配位。     

Novel Assemblies of Sn(II) Coordinated Polyimide Supported by a Ligand Containing N-Heterocyclic Phenantroline Unit

The purpose of this work is to investigate the possibility of the production of novel metal coordinated polyimides. This research primarily focuses on novel metal complex assemblies of Sn(II) linked to the polymer molecule by a ligand containing an N-heterocyclic phenantroline unit in the main chain. Polyimide with phenantroline units in the main chain was synthesized utilizing condensation polymerization of aromatic dianhyrides and the bis(5-aminophenantroline)dichlorotin(II) to yield metal coordinated polyimides. Characterization by thermal analysis, refractive index, and dielectric analysis revealed distinct differences between these new materials and the classical polyimides.     

Novel Anti-Neuroinflammatory Properties of a Thiosemicarbazone–Pyridylhydrazone Copper(II) Complex

Neuroinflammation has a major role in several brain disorders including Alzheimer’s disease (AD), yet at present there are no effective anti-neuroinflammatory therapeutics available. Copper(II) complexes of bis(thiosemicarbazones) (Cu^II(gtsm) and Cu^II(atsm)) have broad therapeutic actions in preclinical models of neurodegeneration, with Cu^II(atsm) demonstrating beneficial outcomes on neuroinflammatory markers in vitro and in vivo. These findings suggest that copper(II) complexes could be harnessed as a new approach to modulate immune function in neurodegenerative diseases. In this study, we examined the anti-neuroinflammatory action of several low-molecular-weight, charge-neutral and lipophilic copper(II) complexes. Our analysis revealed that one compound, a thiosemicarbazone–pyridylhydrazone copper(II) complex (CuL⁵), delivered copper into cells in vitro and increased the concentration of copper in the brain in vivo. In a primary murine microglia culture, CuL⁵ was shown to decrease secretion of pro-inflammatory cytokine macrophage chemoattractant protein 1 (MCP-1) and expression of tumor necrosis factor alpha (Tnf), increase expression of metallothionein (Mt1), and modulate expression of Alzheimer’s disease-associated risk genes, Trem2 and Cd33. CuL⁵ also improved the phagocytic function of microglia in vitro. In 5xFAD model AD mice, treatment with CuL⁵ led to an improved performance in a spatial working memory test, while, interestingly, increased accumulation of amyloid plaques in treated mice. These findings demonstrate that CuL⁵ can induce anti-neuroinflammatory effects in vitro and provide selective benefit in vivo. The outcomes provide further support for the development of copper-based compounds to modulate neuroinflammation in brain diseases.     

Synthesis and Properties of Novel Poly(p-phenylenevinylene)s Containing a Tricarbonyl(arene)chromium Unit in the Main Chain

Summary Novel π-conjugated polymers based on poly(p-phenylenevinylene)s (PPVs) containing a tricarbonyl(arene)chromium unit in the main chain were synthesized by Horner-Wadsworth-Emmons olefination. The structures of the polymers were supported by ^lH NMR and IR spectra. The polymers obtained were soluble in common solvents such as THF, CH₂Cl₂, CHCl₃ and toluene. The molecular weights of the polymers were determined by GPC. Their thermal, optical, and electrochemical properties were investigated in detail. Received: 18 November 2002/Revised version: 10 February 2003/ Accepted: 11 February 2003 Correspondence to Yoshiki Chujo     

Synthesis and Light‐Emitting Properties of New Polyimides Containing Ethynylene Units in the Main Chain

Two new polyimides (ODA‐PI and HDA‐PI) having 1,4‐phenylenediethynylene unit and octyloxy groups were synthesized. Judging from inherent viscosities of their precursor PAAs (1.42 and 1.62 dL · g^?1), the two PIs were very high in molecular weight. Casting and thermal imidization of PAAs results polyimides with good‐quality films. They were stable up to 364 °C and showed no crystallites. UV‐vis and PL spectra in NMP solutions of both PIs showed maxima at 442 and 501 nm, respectively, while PL spectra in ≈10 µm thick films exhibited a maximum at 540 nm. CV indicates that two PIs were electrochemically active in redox region. The devices with construction of ITO/PEDOT/PIs/BAlq₃/LiF/Al exhibited turn‐on voltages of 6.5 V in ODA‐PI and 7.5 V in HDA‐PI and emitted a bright bluish‐green light. ODA‐PI and HDA‐PI showed maximum luminescence of 256 and 316 cd · cm^?2, respectively, at the same voltage of 12 V.

     

Interesting Copper(I) Coordination Polymers of Heterocyclic Monothioether Ligand Containing Long S-Hexadecyl Chain: Syntheses,Structures and Properties

Two structurally related heterocyclic monothioether ligands containing long S-alkyl(hexadecyl) chain, 2-methyl-5-(1-n-hexadecylsulfanyl)-1,3,4-thiadiazole (L ¹ ) and 2-(1-n-hexadecylsulfanyl) pyridine (L ² ), have been designed, and two CuI complexes with these ligands, [Cu₄I₄(L¹)₂] _n (1) and [Cu₄I₄(L²)₂] _n (2), have been synthesized and characterized by IR, elemental analysis, UV–vis spectra, thermal analysis and X-ray diffraction analysis. Single-crystal X-ray analyses show that two complexes are all 1-D coordination polymer with a double-stranded stair CuI-chain. Optical diffuse-reflection spectra results complex 1 and 2 have the properties of the semiconductor.     

主链含麦芽糖基聚氨酯的合成

以麦芽糖为原料与４，４′－二苯甲烷二异氰酸酯进行直接加聚反应合成主链含麦芽糖基的线性聚氨酯     

主链含三嗪结构的聚对苯撑乙炔的合成及表征

用含1,3,5-三嗪的二元碘代芳烃和1,4-二乙炔苯衍生物,通过Sonogashira钯催化偶联反应,合成了主链含1,3,5-三嗪结构的聚对苯撑乙炔共轭聚合物P1-P3,并用红外光谱、核磁共振氢谱和碳谱对聚合物的结构进行了表征。考察了反应时间、反应温度、单体的摩尔投料比和催化剂用量对聚合物相对分子质量及其分布的影响。紫外及荧光光谱表明,聚合物紫外最大吸收出现在320～380 nm,P2和P3的溶液荧光最大发光波长在442 nm处,且荧光较强,是一类蓝色聚合物发光材料。     

不对称水杨醛亚胺Schiff碱及其铜（Ⅱ）配合物的合成和抑菌活性研究

合成了一种新5-溴水杨醛亚胺席夫碱配体及其与铜(Ⅱ)的配合物，并由元素分析和红外光谱所表征。采用琼脂稀释法测定了配合物的抑菌活性，测得了它们抑制细菌生长的最小浓度。结果表明，Schiff碱对几种受试菌均有较强的抑制作用。配合物比配体有更高的抑菌活性。     

含有萘酰亚胺单元的铕配合物合成及其发光性能研究

通过在邻菲哕啉中性配体上引入萘酰亚胺发色团，合成了新型含有萘酰亚胺单元的铕配合物Eu（DBM）3（PNI—phen）．通过控制激发，可以得到具有萘酰亚胺和Eu^3＋特征友射的荧光光谱．通过荧光光谱和激发光谱研究了铕配合物的能量传递及发光机制．     

One-Dimensional Ni(II) and Cu(II) Coordination Polymers Containing Syn-Syn Thiophene-2,5-dicarboxylate and Propane-1,3-diamine

New thiophene-2,5-dicarboxylate complexes with the formula of [M(μ-tdc)(pen)₂] _n (M = Ni(II) (1) and Cu(II) (2), pen = propane-1,3-diamine, tdc = thiophene-2,5-dicarboxylate) have been synthesized and characterized by using thermal (TG/DTG, DTA and MS) analysis, IR and UV–Vis. spectroscopies, magnetic measurement and single crystal X-Ray diffraction techniques. The Ni(II) and Cu(II) ions are distorted octahedrally coordinated by two oxygen atoms of two bridging thiophene-2,5-dicarboxylate ligands and four nitrogen atoms of the trans-pen ligands. The polymeric chains are connected together by hydrogen bonds interactions, forming three-dimensional network.     

Synthesis and Characterization of New Aromatic Polyamides with N,N′‐Di(4‐n‐alkylphenyl)benzodiimide Unit on the Main Chain

Summary: New aromatic polyamides containing two n‐alkylphenylimide units fused to the main chain were prepared by the activated polyamidation of 3,6‐di(4‐carboxyphenyl)‐N,N′‐di(4‐n‐alkylphenyl)pyromellitimides ( C _m DA , m = 0, 8, 12, 16) with oxy‐4,4′‐dianiline in a mixture of N‐methylpyrrolidone and pyridine (Py) in the presence of triphenyl phosphite and CaCl₂. The imide‐containing dicarboxylic acid monomers were synthesized by the imidization of 3,6‐di(4‐carboxyphenyl)pyromellitic dianhydride with 4‐n‐alkylanilines. The polymers showed both enhanced thermal stability and excellent solubility due to the presence of thermally stable pendent imido groups and internally plasticizing n‐alkyl chains. Their glass transition temperatures were between 225 and 285 °C and decreased with increasing side chain length. Wide‐angle X‐ray diffraction investigations revealed that all the polymers are amorphous and have typical layered structures formed by n‐alkyl side chains.

     

中空纤维支撑液膜技术处理含铜废水

重金属废水的处理在环境保护和重金属资源综合利用方面都受到广泛的关注.采用中空纤维支撑液膜技术,用CuSO4水溶液模拟工业含Cu(Ⅱ)废水,二(2-乙基己基)磷酸(D2EHPA)/煤油为液膜相,盐酸为接受相,研究了液膜相组成、两相流速、流动方式等因素对中空纤维支撑液膜过程传质性能的影响.结果表明,料液相在管程流动时的传质通量大于料液相在壳程流动时的传质通量,传质通量随着管、壳程两相流速的增大及液膜相中载体浓度的增加而增大.模拟实验结果表明,中空纤维支撑液膜技术可同时实现废水中Cu(Ⅱ)的去除与浓缩,处理效果好.废水中Cu(Ⅱ)的去除率达97%以上,富集液中Cu(Ⅱ)浓缩倍数达5倍以上.