Two nickel coordination polymers with flexible ligand 1,3,5-tri(1,2,4-triazol-1-ylmethyl)-2,4,6-trimethylbenzene

The reaction of 1,3,5-tri(1,2,4-triazol-1-ylmethyl)-2,4,6-trimethylbenzene (ttmb) with Ni(II) salts yields two coordination polymers [Ni₃(ttmb)₂(H₂O)₆Cl₆](H₂O)₃ (1) and [Ni(ttmb)₂(H₂O)₂](NO₃)₂(H₂O)₄ (2). The flexible ligand ttmb shows the cis,cis,cis-conformation and a tri-monodentate coordination mode in 1. Each ttmb links three Ni(II) atoms to form an undulated (3, 4)-connected two-dimensional network. Each undulated two-dimensional network polycatenates other two identical networks, thus giving a rare (2D → 3D) parallel polycatenation network in 1. The ttmb ligand exhibits the cis,trans,trans-conformation and a two-monodentate coordination mode in 2. Each ttmb connects two Ni(II) atoms to construct a two-dimensional (4, 4) network in 2. The thermal stability of compounds 1 and 2 was studied.     

A new 2D 5-connected coordination polymer based on 3,4-bis(pyridin-4-ylmethoxy)benzoic acid ligand

A new 2D 5-connected coordination polymer [Zn₃(HL²)(1,4-bdc)₃] (1) (HL² = 3,4-bis(pyridin-4-ylmethoxy)benzoic acid, 1,4-H₂bdc = 1,4-benzenedicarboxylate) has been hydrothermally constructed using HL², 1,4-bdc ligands as linear linkers and Zn₃-clusters as 5-connected nodes. In addition, powder X-ray diffraction, photoluminescent property and thermogravimetric analysis for 1 are investigated in detail.     

DNA与（S）-2-（5-氟尿嘧啶-1-基-乙酰基）氨基-1，4-丁二酸相互作用的电化学和光谱学研究

以自组装制得的DNA修饰电极为工作电极,采用循环伏安研究了抗癌药物（S）-2-（5-氟尿嘧啶-1-基-乙酰基）氨基-1,4-丁二酸（5FUASP）与DNA的相互作用,还结合紫外-可见光谱进一步研究了这种相互作用。循环伏安测试结果表明：5FUASP与DNA在pH=6．86的缓冲溶液中有强烈的相互作用,在电极表面反应的过程为准可逆电化学反应一化学反应偶合（Ec）过程。当扫描速度较低时,EC反应是扩散控制过程;紫外吸收光谱表明抗癌药物5FUASP与DNA通过插入作用相互结合。     

Assembly of one 2D layer and two 3D pillared-layer structures derived from metal ions and 5-(pyridin-4-yl)isophthalic acid with or without pillars

Three new coordination polymers, [Mn(L)(H₂O)₂]₂·5H₂O (1), [Cu(L)(4,4′-bipy)]₂·H₂O (2) and [Pb(L)(4,4′-bipy)_0.5] (3) (H₂L = 5-(pyridin-4-yl)isophthalic acid; 4,4′-bipy = 4,4′-bipyridine) have been synthesized and characterized by IR, thermogravimetric analysis, X-ray powder diffraction and X-ray single crystal diffraction. Complex 1 shows a 2D layer structure which stacks with the other ones to form 1D channels to hold 1D water chains. Complex 2 displays a 3D + 3D → 3D polycatenation network. 3 shows a unique 2D + 2D → 3D polycatenation net in which each Pb center has a hemidirected coordination geometry due to the existence of “inert pair effect”. The thermal and luminescent properties of 1–3 were also examined.     

1,4-双(1′,3′-二苯基-5′-吡唑酮-4′)-1,4-丁二酮的合成及其稀土配合物的荧光性质

以1，3－二苯基－5－吡唑酮与丁二酰氯作用，合成了一种新的β-二酮螯合剂－1，4－双（1′，3′－二苯基－5′－吡唑酮－4′）－1，4－丁二酮（BDPPBD），收率64．5％。通过元素分析，红外光谱和核磁共振氢谱证实了产物的结构。以BDPPBD为配体制备了其Tb(Ⅲ）、Eu(Ⅲ）配合物，测定了配合物的荧光光谱，结果表明BDPPBD是Ｔb(Ⅲ）发光配合物的优良配体。     

Synthesis and degradation study of novel polyamides derived from a biologically active aromatic diacid monomer 5-(2-phthalimidoethanesulfonamido) isophthalic acid

In this study, 5-(2-phthalimidoethanesulfonamido) isophthalic acid (6) as a bioactive diacid monomer derived from taurine was successfully synthesized in three steps. The direct polycondensation reactions of this diacid monomer with several aromatic and aliphatic diisocyanates were carried out under conventional heating. All of the polyamides (PAs) were characterized by Fourier transform infrared (FT-IR), proton nuclear magnetic resonance (¹ H NMR) and elemental analyses methods. The thermal stability of the resulting PAs was evaluated with thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) techniques under a nitrogen atmosphere. The dehydrogenase activities of treated soils with obtained compounds were also studied. The results showed that the dehydrogenase activity of treated soils with obtained compounds was 2–3 times higher than control soil, indicating that the abundance and activity of the microbial communities in the treated soils were enhanced by the presence of monomers and obtained polymers. This may show biodegradability of polymers under soil burial in natural environments and non-toxic behavior of compounds for soil microorganisms.     

2-甲基-1-(4-氯苯甲酰基)-5-苄氧基-1H-吲哚-3-乙酸的合成

GY3是1个具有胰岛素增敏活性的化合物.以对硝基苯酚为原料,经7步反应,建立了1条GY3的合成工艺路线,为大量制备GY3及其他吲哚类胰岛素增敏剂的合成提供了较好的方法.     

Safe and fast polyamidation of 5-[4-(2-phthalimidiylpropanoylamino)benzoylamino]isophthalic acid with aromatic diamines in ionic liquid under microwave irradiation

Ionic liquids are outstanding microwave-absorbing agents owing to their high ionic conductivity and polarizability, thus leading to a high heating rate and a considerably shortened reaction time. In this study, a series of novel optically active polyamides (PA)s with pendent 4-(2-phthalimidiyl-propanoylamino)benzamide units were prepared with excellent yields via a simple microwave heating method using 1,3-dipropylimidazolium bromide and triphenyl phosphite. In comparison with classical heating, microwave irradiation was demonstrated to be a more effective energy source. The resulting PAs have inherent viscosity in the range of 0.52–0.71 dL/g. All of the polymers were readily soluble in many organic solvents and showed good thermal stability associated with high glass-transition temperatures above 200 °C as measured by differential scanning calorimetry. Thermogravimetric analysis showed that the 10% weight-loss temperatures in nitrogen were 455 and 410 °C, a significant improvement in thermal stability having been observed with the increase in the side-chain length.     

High-quality freestanding flexible poly(5-(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)-1H-indole) film: Electrosyntheses,characterization, and optical properties

The electron-donating substituted indole is generally difficult to be polymerized into high-quality film. The electrochemical polymerization of the electron-donating 3,4-ethylenedioxythiophene (EDOT)-monosubstituted indole may be a challenge. Herein, we designed and synthesized a novel fluorescent comonomer based on the combination of indole and EDOT groups, namely, 5-(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)-1H-indole (EDTI), and subsequently electrodeposited into flawless freestanding flexible poly(5-(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)-1H-indole) (PEDTI) film with a resistance of 60 MΩ/cm in CH₂Cl₂ containing 0.1 M Bu₄NBF₄. Electrochemical results showed that the oxidation onset potential of EDTI was at 0.8 V vs Ag/AgCl, which was lower than those of indole (0.96 V vs Ag/AgCl) and EDOT (1.35 V vs Ag/AgCl). FTIR spectra indicated that the polymerization of EDTI occurred at the 5-position on thiophene ring and 2,3-positions on indole ring, forming the crosslinking polymer film. The colors of as-prepared PEDTI could switch reversibly from purple to brown under applied potentials of 1.3 and −1.3 V, which were distinctly different from those of polyindole, poly(3,4-ethylenedioxythiophene) (PEDOT), and poly(EDOT-bis-substituted indole) (PETI). Fluorescence spectral studies revealed that the comonomer and corresponding polymer were good blue-green light emitters. These results implied that PEDTI had potential applications for photoelectric devices such as electrochromic devices, light-emitting diodes, and fluorescence sensors. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47016.     

Cross-linked polymers based on 2,3,5,6-tetra-substituted pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione (DPP): Synthesis, optical and electronic properties

A series of 2,3,5,6-tetra-substituted pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione (DPP) derivatives carrying thienyl-, 3,4-ethylenedioxy-thienyl- (EDOT-) and 3,4-ethylenedithiathienyl- (EDTT-) substituent groups have been synthesized and electrochemically polymerized. The polymers were investigated using UV/vis absorption spectroscopy and cyclic voltammetry. It was found that the growth of the polymers proceeded as random coupling of the thiophene groups in the 2-,3-,5-, and 6-positions of the DPP chromophore. In the cross-linked polymers, conjugated sequences were only built through coupling of thiophene groups in 3,6-positions, and separated by non-conjugated sequences through coupling with thiophene units in other positions of the DPP core.     

High-refractive index polythiourethane resin based on 2,3-bis((2-mercaptoethyl) thio)-1-propanethiol and 1,3-bis(isocyanantomethyl) cyclohexane using tertiary amine catalyst

High-refractive index (RI) polythiourethane (PTU) resin with good thermal, optical, and mechanical properties was synthesized via thiol-isocynanate click reaction of 2,3-bis((2-mercaptoethyl)thio)-1-propanethiol and 1,3-bis(isocyanantomethyl) cyclohexane using a new tertiary amine catalyst N,N,N′,N′-tetramethyl-1,4-diaminobutane (TMDB). Curing behavior of PTU resin was studied by dynamic differential scanning calorimetry (DSC) technique. Curing technology parameters were optimized by combined use of DSC and fourier transform infrared spectrometry (FTIR). The results indicate that TMDB exhibits higher catalytic activity than commonly used dibutyltin dichloride (DBTC). The Kissinger apparent activation energies at a dosage of 150 ppm TMDB and 150 ppm DBTC are 31.7 and 43.2 kJ mol⁻¹, respectively. PTU resin with a full conversion of thiol and isocynanate was prepared, which exhibited better thermal, optical, and mechanical properties than that reported previously. The resin displays a glass transition temperature of 102 and 129°C determined by DSC and dynamic thermomechanical analysis (DMA), respectively, a 5% weight loss temperature of 279°C in nitrogen, a light transmittance of 87% in the wavelength range of 410–900 nm, a water contact angle of 100°, a high-RI of 1.617, and an Abbe number of 38. The resin was successfully applied in ophthalmic lenses.     

5-硝基苯并三唑-1-乙酸镝与1,10-邻菲啰啉配合物的合成和性质研究

采用溶液合成法,合成了标题化合物,通过元素分析、摩尔电导率、紫外光谱、红外光谱和热分析法确定配合物的组成为Dy(L)3phen.1.5H2O(HL=5-硝基苯并三唑-1-乙酸;phen=1,10-邻菲啰啉)。荧光光谱表明:镝配合物的荧光强度较强,说明配体5-硝基苯并三唑-1-乙酸和1,10-邻菲啰啉是很好的敏化剂。     

（E）-2-（2-（（3-（2，4-二甲基苯基）-1，4-二甲基-1H-吡唑-5-基氧基）甲基）苯基）-3-甲氧基丙烯酸甲酯（SYP-4903）的合成及杀虫杀螨活性

以间二甲苯为原料,经酰化、酯化、环化和缩合4步制得化合物(E)-2-(2-((3-(2-4-二甲基苯基)-1,4-二甲基-1H-吡唑-5-基氧基)甲基)苯基)-3-甲氧基丙烯酸甲酯(SYP-4903),其结构经红外、核磁及元素分析确认.生物活性测定结果表明:该化合物在600 mg/L下对黏虫、小菜蛾、朱砂叶螨、淡色库蚊具有很好的杀虫杀螨活性,在20 mg/L时,对朱砂叶螨的死亡率达到了100%;防治柑橘红蜘蛛田间药效试验,结果表明其活性与对照药剂哒螨酮基本一致.     

Solvent-induced 1- and 2-D Cd(II) coordination polymers based on a bent polypyridyl ligand

Two Cd(II)-tppda (tppda = N,N,N′,N′-tetrakis(2-pyridyl)-2,6-pyridinediamine) coordination polymers have been prepared via variations of the templating solvent. The solvated complex [Cd₂(tppda)(DMF)₂(μ-SCN)₂(SCN)₂]_n (1) exhibits a 1-D pseudo-helical structure, whereas the unsolvated complex [Cd₂(tppda)(μ-SCN)₄]_n (2) features a 2-D metal-organic framework (MOF). Both are luminescent in the solid state, with emission maxima 444 and 435 nm for 1 and 2, respectively.     

Synthesis,crystal structure and properties of Zn(II) and Cd(II) complexes with 2-(4-isopropyl-4-methyl-5-oxo-4,5-dihydro-1H-imidazol-2-yl)nicotinic acid ligand

Two novel complexes, namely [Cd(L)₂] (1) and [Zn(L)₂(H₂O)₂] (2) have been synthesized (HL = 2-(4-isopropyl-4-methyl-5-oxo-4,5-dihydro-1H-imidazol-2-yl)nicotinic acid), which are characterized by elemental analysis, infrared spectrum and X-ray crystal diffraction. While strong hydrogen bonds play central roles in the formation of the 3D structure, the combined influence of the weak interactions such as C–H?O bonds, carbonyl?π and C–H?π interactions are also evident in the structures. The preliminary investigation on the thermal and fluorescence property of the complexes are presented.     

Expeditious synthesis of novel aromatic polyamides from 5-[3-phenyl-2-(9,10-dihydro-9,10-ethanoanthracene-11,12-dicarboximido)propanoylamino]isophthalic acid and various diamines using microwave-assisted polycondensation

A new diacid monomer, 5-[3-phenyl-2-(9,10-dihydro-9,10-ethanoanthracene-11,12-dicarboximido)propanoylamino]isophthalic acid was successfully synthesized starting from cis-9,10-dihydro-9,10-ethanoanthracene-11,12-dicarboxylic acid anhydride and l-phenylalanine. A highly effective, very fast microwave method is described to synthesize optically active aromatic polyamides (PA)s under microwave heating for only 3 min. Generally, better yields are obtained under faster and cleaner reactions when compared to those from conventional heating. Therefore, this approach could considerably reduce the synthesis time, cost, and energy. The resulting PAs had inherent viscosities in the range of 0.35–0.58 dL/g. All of the these polymers having bulky anthracenic and amino acid functionality in the side chain showed excellent solubility and readily dissolved in various solvents such as N-methyl-2-pyrrolidinone, N,N-dimethylacetamide and N,N-dimethylformamide. PAs were thermally stable, with 10% weight loss recorded at 385 °C and 341 °C in the nitrogen atmosphere, and char yields at 800 °C higher than 50% and glass transition temperature above 180 °C.     

Pseudo-isomeric zinc/copper coordination polymers based on 3-(2-pyridyl)pyrazole-5-carboxylic acid

Reaction of 3-(2-pyridyl)pyrazole-5-carboxylic acid (H₂L) with Zn(II) or Cu(II) perchlorate yielded [ZnL]_n (1) and [CuL]_n (2) with similar composition. The ligand L^2 − adopts the same μ₃κ⁵ coordination mode. The Zn(II) and Cu(II) atom takes square pyramid coordination polyhedron with some discrepancy. Bigger difference in the dimeric secondary building blocks leads to distinct two-dimensional metal–organic frameworks. The Zn(II) complex fluoresces stronger than the free ligand. The Cu(II) polymer displays strong antiferromagnetic intra-dimer exchange and ferromagnetic inter-dimer exchange.