新型5-取代吲哚-3-甲酰胺化合物的合成

以5-取代吲哚为原料,经维尔斯迈尔-哈克反应制得5-取代吲哚-3-甲醛(2a~2e); 2a~2e在DMF催化下,与盐酸羟胺反应制得5-取代吲哚-3-甲腈（3a~3e）; 3a~3e在H₂O₂和NaOH溶液中水解合成了5-取代吲哚-3-甲酰胺（4a~4e, 4b~4e为新化合物）,产率62.0%~75.0%,其结构经¹H NMR, ¹³C NMR和ESI-MS表征。     

高浓度体系制备ZSM-5分子筛及碱处理后甲醇制丙烯性能

在高浓度体系下,以粗孔硅胶和偏铝酸钠为原料,TPABr为模板剂,水热晶化法制备了ZSM-5分子筛,单釜产率23％.用不同浓度的氢氧化钠溶液对ZSM-5分子筛进行改性,采用XRD、FT-IR、SEM、NH3-TPD、XRF、N2物理吸附等方法对改性前后的样品进行了表征,并考察了改性后ZSM-5分子筛甲醇催化转化制丙烯(MTP)反应性能.结果表明,氢氧化钠改性未破坏分子筛的骨架结构,改性后样品的酸量、介孔孔容和BET比表面积均有增加,从而改善了催化剂的抗积碳性能和反应性能.在MTP反应中,增产丙烯的效果不明显,但表现出了更好的催化稳定性(催化剂使用寿命从85 h提升至110 h),并且有利于提高副产物汽油组分(∑C5+)的产量.     

环糊精基的金属有机骨架的合成及负载5-氟尿嘧啶的研究

用溶剂热法合成了基于环糊精的金属有机骨架化合物(Na-CD-MOF),采用X-射线单晶衍射、红外光谱和元素分析进行了结构表征.以5-氟尿嘧啶(5-FU)为模型药物,研究了Na-CD-MOF的细胞毒性和载药及体外释药的能力.研究结果表明,新合成的Na-CD-MOF对5-FU的负载量最大为1.18g/g,且具有明显的缓释作用.体外细胞毒性实验表明,Na-CD-MOF具有良好的生物相容性,有望成为一种绿色的药物载体.     

导电玻璃负载CuO/V_2O_5复合纳米纤维光电极的制备及光电催化性能

以聚乙烯吡咯烷酮(PVP)为高分子模板剂,乙酰丙酮钒(C_(15)H_(21)O_6V)和三水合硝酸铜[Cu(NO_3)_2·3H_2O]为原料,导电玻璃(FTO)为载体,结合溶胶-凝胶法和静电纺丝技术制备了前驱体纤维,经高温焙烧后得到分布均匀、具有纤维结构的导电玻璃负载的CuO/V_2O_5复合光电极(CuO/V_2O_5/FTO).采用热重-差热分析仪(TG-DTA)、X射线衍射仪(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)和X射线光电子能谱仪(XPS)等对材料的结构进行表征,以亚甲基蓝(MB)为目标降解物,探讨了合成产物的光电催化性能.结果表明,CuO与V_2O_5能有效形成异质结构,其光电催化活性均比纯V_2O_5有明显提高,并且改变CuO与V_2O_5的比例对光电催化性能有较大影响,其中n(Cu)∶n(V)=1∶1时降解效率最高,达到96%.     

Supramolecular polymer networks based on calix[5]arene chained poly(p-phenyleneethynylene) and C60 fulleropyrrolidine

Abstract

A poly(p-phenyleneethynylene) polymer (PCF[5]), bearing two π-rich cone-like calix[5]arene cavities (assembling cores) attached to a rigid p-phenyleneethynylene spacer, was synthesised by a Pd-catalysed cross-coupling reaction. UV–vis absorption and fluorescence spectroscopies combined with dynamic light scattering measurements provide evidence for the self-assembly of PCF[5] (homopolytopic host molecule) with a complementary C₆₀ fulleropyrrolidine (C₆₀-Pyr) guest in solution, in the construction of a supramolecular polymer network. Atomic force microscopy analysis of PCF[5]/C₆₀-Pyr highlights the formation of a bicontinuous network consisting of a uniform distribution of prominent structures, within a polymeric background forming a biphasic structure.     

Synthesis and insecticidal evaluation of tetrahydroimidazo[1,2-a]pyridin-5(1H)-one derivatives

A series of novel tetrahydroimidazo[1,2-a]pyridine-5(1H)-one derivatives containing a electronegative pharmacophore(=CNO₂) were synthesized via practical aza-ene reaction and characterized by ¹H NMR, ¹³C NMR, ¹⁹F NMR and HRMS. Preliminary bioassays showed that some of the target compounds exhibited good insecticidal activity against brown planthopper(Nilaparvata lugens) and cowpea aphids(Aphis craccivora) at 500 mg L^-1. Among them, compound 11h was active against brown planthopper at 100 mg L^-1. The insecticidal activities varied significantly depending on the types and patterns of the substituents, which provided guidance for further investigation on structure modifications.     

Efficient synthetic route toward biologically active γ-carboline derivatives

An efficient and short route was established for the synthesis of anti-bovine viral diarrhea virus agents, namely 4-methyl-γ-carboline (SK4M) 1, 3-methyl-γ-carboline (SK3M) 2, 5-methyl-γ-carboline (SK5M) 3, and a new γ-carboline derivative 4, using thermal electrocyclization reaction as a key step. The evaluation of cytotoxicity of compound 4 against human cervical cancer cell line HeLa and leukemic cell line HL-60 furnished CC₅₀ value of 19.5 and 18.8 µM respectively.     

Construction of four d10 coordination polymers containing binuclear rings as building blocks from 4′-(2H-tetrazol-5-yl)biphenyl-4-carboxylic acid

Four coordination polymers based on 4′-(2H-tetrazol-5-yl)biphenyl-4-carboxylic acid (H₂TBPC), [Zn(μ₃-TBPC)(H₂O)]_n (1), [Zn(μ₃-TBPC)(Me₂NH)]_n (2), [Cd(μ₃-TBPC)(bpy)]_n (bpy = 4,4′-bipyridine, 3), and [Cd(μ₄-TBPC)(H₂O)]_n (4), were constructed under hydrothermal conditions. The compounds are composed of M₂(TBPC)₂ binuclear ring as a building block. In 1–3, the binuclear rings are interconnected to three different 2-D networks with the same (4·8²) topology. In 4, the binuclear rings are arranged into a 3-D framework with PtS-type topology. The results revealed that the structural diversity is mainly attributed to the coordination geometries of metal ion, the coordination modes of TBPC^2?, and the auxiliary ligand. The thermal stabilities and luminescent properties of 1–4 have also been studied.     

π–π stacking motifs in dialkylbis{5‐[(E)‐2‐aryldiazen‐1‐yl]‐2‐hydroxybenzoato}tin(IV) complexes

The diorganotin(IV) complexes of 5‐[(E)‐2‐aryldiazen‐1‐yl]‐2‐hydroxybenzoic acid are of interest because of their structural diversity in the crystalline state and their interesting biological activity. The structures of dimethylbis{2‐hydroxy‐5‐[(E)‐2‐(4‐methylphenyl)diazen‐1‐yl]benzoato}tin(IV), [Sn(CH₃)₂(C₁₄H₁₁N₂O₃)₂], and di‐n‐butylbis{2‐hydroxy‐5‐[(E)‐2‐(4‐methylphenyl)diazen‐1‐yl]benzoato}tin(IV) benzene hemisolvate, [Sn(C₄H₉)₂(C₁₄H₁₁N₂O₃)₂]·0.5C₆H₆, exhibit the usual skew‐trapezoidal bipyramidal coordination geometry observed for related complexes of this class. Each structure has two independent molecules of the Sn^IV complex in the asymmetric unit. In the dimethyltin structure, intermolecular O—H…O hydrogen bonds and a very weak Sn…O interaction link the independent molecules into dimers. The planar carboxylate ligands lend themselves to π–π stacking interactions and the diversity of supramolecular structural motifs formed by these interactions has been examined in detail for these two structures and four closely related analogues. While there are some recurring basic motifs amongst the observed stacking arrangements, such as dimers and step‐like chains, variations through longitudinal slipping and inversion of the direction of the overlay add complexity. The π–π stacking motifs in the two title complexes are combinations of some of those observed in the other structures and are the most complex of the structures examined.     

A three‐dimensional mixed‐valence CuII/CuI coordination polymer constructed from biphenyl‐3,4′,5‐tricarboxylate and 1,4‐bis(1H‐imidazol‐1‐yl)benzene ligands

Coordination polymers (CPs) built by coordination bonds between metal ions/clusters and multidentate organic ligands exhibit fascinating structural topologies and potential applications as functional solid materials. The title coordination polymer, poly[diaquabis(μ₄‐biphenyl‐3,4′,5‐tricarboxylato‐κ⁴O³:O^3′:O^4′:O⁵)tris[μ₂‐1,4‐bis(1H‐imidazol‐1‐yl)benzene‐κ²N³:N^3′]dicopper(II)dicopper(I)], [Cu^II₂Cu^I₂(C₁₅H₇O₆)₂(C₁₂H₁₀N₄)₃(H₂O)₂]_n, was crystallized from a mixture of biphenyl‐3,4′,5‐tricarboxylic acid (H₃bpt), 1,4‐bis(1H‐imidazol‐1‐yl)benzene (1,4‐bib) and copper(II) chloride in a water–CH₃CN mixture under solvothermal reaction conditions. The asymmetric unit consists of two crystallographically independent Cu atoms, one of which is Cu^II, while the other has been reduced to the Cu^I ion. The Cu^II centre is pentacoordinated by three O atoms from three bpt³⁻ ligands, one N atom from a 1,4‐bib ligand and one O atom from a coordinated water molecule, and the coordination geometry can be described as distorted trigonal bipyramidal. The Cu^I atom exhibits a T‐shaped geometry (CuN₂O) coordinated by one O atom from a bpt³⁻ ligand and two N atoms from two 1,4‐bib ligands. The Cu^II atoms are extended by bpt³⁻ and 1,4‐bib linkers to generate a two‐dimensional network, while the Cu^I atoms are linked by 1,4‐bib ligands, forming one‐dimensional chains along the [20] direction. In addition, the completely deprotonated μ₄‐η¹:η¹:η¹:η¹ bpt³⁻ ligands bridge one Cu^I and three Cu^II cations along the a (or [100]) direction to form a three‐dimensional framework with a (10³)₂(10)₂(4².6.10².12)₂(4².6.8².10)₂(8) topology via a 2,2,3,4,4‐connected net. An investigation of the magnetic properties indicated a very weak ferromagnetic behaviour.