Cu^@＋,吡啶,环烷酸三元配合物的组成研究

通过摩尔比法（饱和法）对Ｃｕ＾２＋、吡啶（Ｐｙ）、环烷酸（Ｒ）三元配合物的组成进行了研究，并通过环烷酸铜、Ｃｕ＾２＋、Ｐｙ、Ｒ三元配合物和吡啶红外光谱对Ｃｕ＾２＋、Ｐｙ、Ｒ三元配合物的结构进行了分析，认为此三元配合的组成为Ｃｕ＾２＋：吡啶：环烷酸＝１：４：２，且为缔合型三元配合物，其结构简式为「Ｃｕ（Ｐｙ）４」Ｒ２。     

稀土钐二元、三元配合物的合成、表征及其生物活性研究

以氯化钐、2-氨基嘧啶和钼酸钠为原料,制备了两种新型稀土钐二元、三元配合物,通过元素分析、紫外光谱、红外光谱等手段对其进行了表征,确定了二元配合物的化学组成为Sm2(AP)(H2O)2Cl3(AP=2-氨基嘧啶),三元配合物的化学组成为:Sm3(AP)(MoO4)2(CH3OH)4Cl5。抗菌结果表明,二元配合物对大肠杆菌和金黄色葡萄球菌的抑菌圈直径分别为13 mm和15 mm,三元配合物分别为13 mm和13 mm,两种配合物对大肠杆菌、金黄色葡萄球菌都有一定的抑制作用。采用MTT法对两种配合物诱导癌细胞凋亡能力做了初步研究,两种配合物的半数抑制浓度IC50在0.001~0.01 mg/mL之间,证明其具有诱导癌细胞凋亡的作用。     

稀土-蛋氨酸-邻菲咯啉配合物的合成、表征及抗菌活性研究

采用冷凝回流法合成了4种新型稀土(镧、铕、钐和钕)-蛋氨酸-邻菲咯啉三元配合物,通过元素分析、EDTA-滴定、摩尔电导、红外光谱,确定了配合物的组成为RE(Met)_3phenCl_3·3H_2O(RE:La~(3+)、Eu~(3+)、Sm~(3+)、Nd~(3+);Met=L-蛋氨酸;phen=邻菲咯啉).抗菌活性的研究表明,与配体相比,稀土三元配合物对大肠杆菌(Escherichia coli)和金黄色葡萄球菌(Staphylococcus aureus)均具有更强的抑菌能力.     

尾式亮氨酸卟啉锌配合物的合成和光谱性质研究

合成了尾式亮氨酸卟啉—— [5- (对亮氨酸丁氧苯基 ) - 1 0 ,1 5,2 0 -三苯基卟啉及其锌 ( )的配合物 ( Zn[Leu- TPP]) ,用元素分析、红外光谱、电子吸收光谱和激光拉曼光谱等手段对其结构进行了表征。研究了吡啶 ( Py)、4-甲基吡啶 ( 4 - Me Py)、4-醛基吡啶 ( 4 - CHOPy)、4-氨基吡啶 ( 4 - Am Py)等化合物对 Zn[Leu- TPP]电子光谱的影响     

配合物Ni（bacbh）2（Py）2的合成、晶体结构及热稳定性

以苯亚甲基苯乙酮-4-氯苯甲酰腙为配体,水热合成了一个镍的单核配合物Ni(bacbh)2(Py)2(bacbh:苯亚甲基苯乙酮-4-氯苯甲酰腙;Py:吡啶),并利用元素分析、红外光谱、X射线单晶衍射及热失重分析对配合物进行了表征。该配合物为单斜晶系,空间群为P2(1)/n,晶胞学数据:a=1.344 3(6)nm,b=2.471 7(12)nm,c=1.465 1(7)nm,β=98.47°,V=4.815(4)nm3,Z=4,μ=0.561 mm-1,Dc=1.292 mg/m3,F(000)=1 944,最终偏离因子[I>2sigma(I)]R1=0.038 6,wR2=0.096 1(all data),GOF=1.007(CCDC:840865)。     

用环烷酸萃取Cu~(2+)、Fe~(3+)净化硫酸镍

本文介绍了在硫酸体系中用环烷酸镍皂萃取 Cu~(2+)、Fe~(3+)萃取和反萃取的最佳条件;用30％环烷酸镍皂从实际生产料液中多级对流萃取 Cu~(2+)、Fe~(3+)净化硫酸镍的工艺是可行的,产品质量符合要求。     

尾式亮氨酸卟啉锌与吡啶类化合物轴配反应热力学性质研究

研究了尾式亮氨酸卟啉—— 5 -(对亮氨酸丁氧苯基 ) -1 0 ,1 5 ,2 0 -三苯基卟啉锌 ( )配合物 ( Zn[Leu-TPP]与吡啶( Py)、4 -甲基吡啶 ( 4-Me Py)、4 -醛基吡啶 ( 4-CHOPy)、4 -氨基吡啶 ( 4-Am Py)等化合物轴配反应的电子光谱 ,用紫外可见光谱法测定了轴配反应的配位数和平衡常数 ,利用温度系数法测定了体系的标准摩尔焓变△ r H0 m 和标准摩尔熵变△r S0 m。结果表明 ,Zn[Leu-TPP]与吡啶类化合物轴配反应是放热和熵降低的过程。Zn[Leu-TPP]可通过配位键和氢键与 4 -Am Py结合 ,轴配物 Zn[Leu-TPP]· ( 4-Am Py)稳定性最强     

新型稀土Eu3+四元配合物的制备及荧光性能研究

以稀土Eu~(3+)为中心离子,2,6-二(4-乙氧基苯甲酰基)吡啶(L)、1,10-邻菲罗啉(Phen)、丙烯腈(AN)和三苯基氧膦(TPPO)为配体,制备了EuL(Phen)_2、EuL(Phen)_2TPPO和EuL(Phen)_2AN三种配合物,其中EuL(Phen)_2AN为新型四元配合物。结构通过红外光谱进行表征。通过荧光光谱仪分析三种配合物的荧光性能,结果表明,新型四元配合物EuL(Phen)_2AN在594,617 nm处出现Eu~(3+)特征发射峰,617 nm处峰值最大,两处峰值的比值为2.18,说明配合物单色性好,是一种合适的红光材料;荧光强度大小顺序为EuL(Phen)_2EuL(Phen)_2ANEuL(Phen)_2TPPO;EuL(Phen)_2AN在不同溶剂中的荧光强度呈现一定规律性,即溶剂的偶极矩极性与体系的荧光强度值成反比。     

N-(2-羟苄基)-DL-丙氨酸铕(Ⅲ)配合物的合成及荧光性质

以发光的三价铕离子为中心体,N-(2-羟苄基)-DL-丙氨酸(H2sala)和1,10-邻菲咯啉(phen)为配体,在混合溶剂中合成了二元铕配合物[Eu(sala)(H2O)4].Cl和三元铕配合物[Eu(sala)(phen)2].Cl。通过元素分析、摩尔电导、红外光谱和热重分析等手段确定了配合物的组成及结构。荧光光谱数据表明,三元配合物的荧光强度高于二元配合物。     

镍与铬天青S、芳环氮碱、阳离子表面活性剂的四元络合显色反应

四条好雄等提出,在吡啶存在的水溶液中,Ni~(2+)与铬天青S(CAS)、溴化羟十二烷基三甲铵可形成高灵敏的三元有色络合物。但未确定络合物的组成,也来说明吡啶的作用。我们的实验表明,无吡啶类化合物存在,Ni~(2+)与CAS、阳离子表面活性剂形成灵敏度低的络合物,且不稳定,不能用于测定。为了弄清吡啶在络合物形成中的作用及寻找吡啶的代用品,以便拟定具有实用价值的镍的分光光度法,系统地研究了Ni~(2+)CAS-芳环氮碱-阳离子表面活性剂四元体系的显色反应。     

Polycondensation of structurally divergent tetraamine monomers with dicarboxylic acids to synthesize polybenzimidazole copolymers for polymer electrolyte membranes

In our effort to promote 2,6‐bis(3,4‐diaminophenyl)‐4‐phenylpyridine (Py‐TAB) as an alternative tetraamine monomer to conventionally used 3,3′,4,4′‐tetraaminobiphenyl (TAB) for synthesizing readily processable pyridine bridged polybenzimidazoles (Py‐PBIs), two series of random copolymers (PBI‐co‐Py‐PBI) were synthesized by polymerizing Py‐TAB and TAB with isophthalic acid or terephthalic acid to produce meta (mPBI‐co‐mPy‐PBI) and para (pPBI‐co‐pPy‐PBI) connected copolymers, respectively. For the first time in the PBI literature, copolymers were synthesized by varying the relative compositions of tetraamines (TAB and Py‐TAB) in the polymerization feed with a single dicarboxylic acid (DCA) instead of the traditionally used method where two DCAs with variable compositions were polymerized with a single tetraamine. The solubility and hence the processability of the copolymers were improved significantly upon introduction of Py‐PBI in the copolymer. The detailed characterizations of both meta and para series copolymers compellingly established that thermal, chemical and mechanical stabilities can be easily modulated according to need by altering the relative compositions of PBI and Py‐PBI. The phosphoric acid (PA) loading of the copolymers increased gradually with increasing Py‐PBI content since the bulky pyridine moiety facilitated the absorption of PA. The presence of pyridine functionality and a larger PA loading caused a higher proton conductivity of PA doped copolymer membranes. © 2014 Society of Chemical Industry     

Cu(Ⅱ)-phen超分子配合物的合成及结构表征

以Cu(phen)2Cl2为前体,采用水热合成方法,辅以均苯四甲酸酐合成了2个超分子配合物[Cu(phen)2Cl]+.[C10H5O8]-和[Cu(phen)2Cl]+.0.5[C10H4O8]2-。采用单晶X-射线衍射、X-粉末衍射、FT-IR对这2个配合物的晶体结构和组成进行了表征。单晶衍射结果表明,2个配合物均为三斜晶系,P-1空间群。在2个配合物中,金属Cu的配位数都由前体中的6转变为5,由原来前体中的畸变的八面体结构转变成畸变的三角双锥结构。配合物(2)通过游离的均苯四甲酸配体之间的氢键作用和phen配体之间的π-π堆积作用形成了3D超分子结构,而配合物(3)则只是通过phen配体之间的π-π堆积作用形成3D超分子结构。     

配合物Ni（bacbh）_2（Py）_2的合成、晶体结构及热稳定性

以苯亚甲基苯乙酮-4-氯苯甲酰腙为配体,水热合成了一个镍的单核配合物Ni（bacbh）2（Py）2（bacbh：苯亚甲基苯乙酮-4-氯苯甲酰腙;Py：吡啶）,并利用元素分析、红外光谱、X射线单晶衍射及热失重分析对配合物进行了表征。该配合物为单斜晶系,空间群为P2（1）/n,晶胞学数据：a=1.344 3（6）nm,b=2.471 7（12）nm,c=1.465 1（7）nm,β=98.47°,V=4.815（4）nm3,Z=4,μ=0.561 mm-1,Dc=1.292 mg/m3,F（000）=1 944,最终偏离因子[I〉2sigma（I）]R1=0.038 6,wR2=0.096 1（all data）,GOF=1.007（CCDC：840865）。     

Synthesis and characterization of novel heat resistance poly(amide‐imide)s from N,N′‐[2,5‐bis(4‐aminobenzylidene) cyclopentanone] bistrimellitimide acid and various aromatic diamines

A new‐type of dicarboxylic acid was synthesized from the reaction of 2,5‐bis(4‐aminobenzylidene)cyclopentanone with trimellitic anhydride in a solution of glacial acetic acid/pyridine (Py) at refluxing temperature. Six novel heat resistance poly(amide‐imide)s (PAIs) with good inherent viscosities were synthesized, from the direct polycondensation reaction of N,N′‐[2,5‐bis(4‐aminobenzylidene)cyclopentanone]bistrimellitimide acid with several aromatic diamines, by two different methods such as direct polycondensation in a medium consisting of N‐methyl‐2‐pyrrolidone (NMP)/triphenyl phosphite (TPP)/calcium chloride (CaCl₂)/pyridine (Py) and direct polycondensation in a p‐toluene sulfonyl chloride (tosyl chloride, TsCl)/pyridine (Py)/N,N‐dimethylformamide (DMF) system. All of the above polymers were fully characterized by ¹H NMR, FTIR, elemental analysis, inherent viscosity, solubility tests, UV‐vis spectroscopy, differential scanning calorimeter (DSC), thermogravimetric analysis (TGA), and derivative of thermaogravimetric (DTG). The resulted poly(amide‐imide)s (PAIs) have showed admirable good inherent viscosities, thermal stability, and solubility. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Bromination of p-Bromophenol in the Presence of Pyridine

The role of pyridine (Py) in the bromination of p-bromophenol (ArH) in CCl₄ has been investigated. At constant concentrations of ArH and Br₂, the rate of disappearance of Br₂ increases to reach a limiting value as the concentration of Py is increased. The mechanism suggested to account for the rate expression, Rate = constant [ArH] [Br₂]_T[Py]_T, obtained from the initial rate studies, involves the interaction between ArH and the brominating species Py. Br₂, in the rate determining step. Py acts as a catalyst probably by virtue of its ability to polarise the Br-Br bond.     

Tautomerism,crystal structure,and copper(II) complexation of isomeric pyridonylazo dyes derived from 2‐ and 4‐aminobenzoic acids

A pair of isomeric aromatic heterocyclic dyes, bearing the same N‐methyl pyridine‐2,6‐dione coupling component but a different 2‐ or 4‐aminobenzoic acid diazo component, were characterised structurally and spectroscopically. X‐ray single‐crystal diffraction analyses revealed that they both adopt the same hydrazone‐tautomeric form and planar molecular conformation between the pyridine and phenyl rings. Furthermore, azo–hydrazone transformation was achieved for the 2‐aminobenzoic‐acid‐based dye after Cu(II) ion complexation, as verified by the formation of a neutral Cu(II) dye–metal complex. The coordination geometry of the central Cu(II) ion exhibits a slightly distorted pyramid with a value of 0.028, where the ligand loses a proton during complexation and serves as the tridentate coordination mode. In addition, thermogravimetric analysis and corresponding differential thermal analysis for the isomeric pair showed that they both have excellent thermal stability, and 4‐aminobenzoic‐acid‐based dye has a higher decomposition temperature (319 °C) than the 2‐aminobenzoic‐acid‐based dye (312 °C). To the best of our knowledge, this is the first structural study on aromatic heterocyclic dyes having aminobenzoic acid and pyridine‐2,6‐dione components at the same time.     

Miscibility of poly(4-vinyl pyridine) with polysulfone and carboxylated polysulfone

Summary The miscibility of poly(4-vinyl pyridine) (P4Py) with polysulfone (PSf) and four carboxylated polysulfone samples (CPSf) was studied by differential scanning calorimetry. P4Py is immiscible with PSf but is miscible with CPSf having degrees of carboxylation of 0.43, 0.93, 1.38 and 1.93. In some cases, P4Py and CPSf form complexes with varying stoichiometries. A high degree of carboxylation of CPSf and a high CPSf content in the feed favor complexation.     

环烷酸的分析与腐蚀预测方法

以选择高效缓蚀剂,从而最终有效解决原油加工设备的一系列腐蚀问题为目的。介绍了环烷酸的结构及性质,综述原油中环烷酸的分析方法与腐蚀预测方法。通过对有关环烷酸腐蚀预测方法和环烷酸的分析方法的有关报道进行分析得出:以环烷酸腐蚀介质中的高压釜失重实验为基础的金属挂片法是目前较好的预测方法,可提供与环烷酸腐蚀最为直接的参考数据。同时认为应用多种分析手段(如质谱结合色谱、紫外、红外、核磁共振等一些分析手段)来研究环烷酸的组成是较为理想的方法。     

Catalytic Activity of Cu/SBA‐15 for Peroxidation of Pyridine Bearing Wastewater at Atmospheric Condition

In this study, Cu‐loaded Santa Barbara amorphous (SBA)‐15 catalysts were synthesized by impregnation method and further used for catalytic wet peroxidation (CWPO) of pyridine from aqueous solution using hydrogen peroxide as oxidant. The synthesized catalysts have been characterized by Brunauer–Emmett–Teller surface area: temperature‐programmed reduction, H₂‐chemisorption, Fourier transform infrared spectroscopy, and field emission scanning electron microscopy. Characterization results indicate good dispersion of Cu species inside the porous structure of SBA‐15. The effect of various parameters such as Cu loading on SBA‐15, pH, catalyst dose, H₂O₂ concentration, and temperature have been studied for their effect on CWPO of pyridine. More than 97% pyridine removal and 92% total organic carbon removal was achieved at optimum condition. Cu/SBA‐15 showed stable performance during reuse for six cycles with negligible copper leaching. © 2013 American Institute of Chemical Engineers AIChE J, 59: 2577–2586, 2013