铜（Ⅰ）-2，9-二甲基-4，7-二苯基-1，10-邻菲啰啉体系间接分光光度法测定盐酸羟

基于盐酸羟胺能定量还原铜（Ⅱ）离子为铜（Ⅰ）离子,利用显色剂2,9-二甲基-4,7-二苯基-1,10-邻菲啰啉建立了间接分光光度法测定盐酸羟胺的方法。在pH35的乙酸-乙酸钠缓冲溶液中,铜（Ⅰ）-2,9-二甲基-4,7-二苯基-1,10-邻菲啰啉络合物最大吸波长475nm处,盐酸羟胺含量在0～2．0mg．L-l范围内,络合物吸光度符合比耳定律,ε=2．3×10^4L·cm^-1·mol^-1。这个方法用于盐酸羟胺（工业品）的测定,结果令人满意。     

4，5-二甲基-2-（2-吡啶基）咪唑的合成、晶体结构及表征

2-取代咪唑是-种用途广泛的精细化学品,不仅可以作为医药中间体、杀虫剂及杀菌剂,还可以作为催化剂、环氧树脂固化剂、交联剂等。2-取代咪唑与过度金属离子形成的配合物在光学材料、磁性材料及超导材料等诸多方面有极好的应用前景。为了制备研究2-取代咪唑配合物,设计合成了4,5-二甲基-2-（2-吡啶基）咪唑,用IR、MS、1H—NMR对其结构进行了确证,并对其晶体结构进行了分析。     

2,2′-联咪唑衍生物铜配合物的合成、表征及光谱性质

本文合成了1,1′-二（丙酸甲酯）-2,2′-联咪唑和1,1′-二（丙酸乙酯）-2,2′-联咪唑两个配体,并以无水乙醇为溶剂,在常温条件下合成了配体与铜的配合物。通过IR、UV、EA表征,推测其形成了1：1的配合物。铜配位后使两种配体发生荧光猝灭。     

2-(4'''',5''''-二甲基-2''''-噻唑偶氮)-5-二甲氨基苯胺与钯反应的分光光度法研究

以4,5-二甲基噻唑为母体合成了2-(4′,5′-二甲基-2′-噻唑偶氮)-5-二甲氨基苯胺。研究了试剂与钯反应的适宜条件。在1.2 mol/L 高氯酸溶液中,试剂与钯形成1:1的稳定青蓝色配合物。配合物的最大吸收波长位于648 nm。表观摩尔吸光系数ε_(648)=6.7×10~4。Pd(Ⅱ)的浓度在0～35μg/25 mL范围内符合比尔定律。多种离子不于扰,磷酸可掩蔽 Fe~(3+)的干扰。可用于含钯样品的分析,结果满意。     

不对称大环铜(Ⅱ)配合物的合成及其晶体结构

以5-氯水杨醛、N,N′-二甲基乙二胺和多聚甲醛合成N,N′-二甲基-N,N′-二(3-甲酰基-5-氯水杨醛)乙二胺(1),化合物1与乙二胺、醋酸铜、高氯酸铅通过模板反应缩合制备了不对称大环铜(Ⅱ)配合物(2),用元素分析、红外光谱、电喷雾质谱对其进行结构表征,X射线单晶衍射分析配合物2晶体(CCDC:787806)属于三斜晶系,P-1空间群,铜(Ⅱ)离子与大环中两个亚胺氮原子、两个酚羟基的氧原子形成4配位。     

2-[5-甲基-(1,3,4-噻二唑偶氮)]-2-萘酚的合成及其与铜的显色反应研究

合成了偶氮显色剂2-[5-甲基-(1,3,4-噻二唑偶氮)]-2-萘酚(MTDAN),研究了它与铜的显色反应。实验结果表明,pH7.0~8.0的水溶液中铜与MTDAN形成了一种稳定的紫红色配合物,其最大吸收波长为540nm,表观摩尔吸光系数为4.16×104L.mol-1cm-1,配合物组成nCu2+∶nMTDAN=1∶1。Cu2+浓度在0~1.1mg/L范围内服从比尔定律,可用于测量矿石及土壤样品中的微量铜,准确度较好。     

4-(6′甲基苯并噻唑-2′-偶氮)-3,5-二氨基吡唑与钯显色反应的研究和应用

对6种苯并噻唑偶氮吡唑化合物的分析特性进行了探讨,着重研究了4—(6′—甲基苯并噻唑-2′-偶氮)-3,5-二氨基吡唑(MBTAP)与钯离子显色反应的光度性质。在非离子表面活性剂 Brij35存在下与钯离子形成橙红色的配合物。适宜的 pH 值范围为9.0～10.5.配合物的最大吸收波长为510nm,表观摩尔吸光系数为3.01×10~4L·mol~(-1)·cm~(-1)。钯在0～14μg/25mL,范围内服从比尔定律.显色体系可稳定11h。在柠檬酸存在下可消除 Fe~(3+)、Co~(2+)、Cu~(2+)、Ni~(2+)等离子的干扰。     

含有蒽酰亚胺的铜（Ⅰ）配合物的合成、结构及光谱研究

合成了两个含蒽酰亚胺基团的新配体N-（2-（6-氨基吡啶））-9-蒽酰亚胺（L^1）和N,N’-（2,6-吡啶基）-二（9-蒽酰亚胺）（L^2）,以及L^1的铜（Ⅰ）配合物[CuL^1（PPh3）2]（BF4）（1）,并研究了它们的结构和光谱性质．理论计算表明配体L^1配位前为反式构象,配合物1的晶体结构显示L^1配位后发生结构扭曲呈顺式构象,羰基氧原子与铜（Ⅰ）离子配位、光谱研究表明配体L^1和配合物1都表现出蒽的特征吸收和发射峰．     

2-(5-溴-2-吡啶偶氮)-5-二甲氨基苯胺分光光度法测定铜的研究

以2-(5-溴-2-吡啶偶氮)-5-二甲氨基苯胺(5-Br-PADMA)为显色剂,建立了分光光度法测定铜的新体系。实验结果表明,在p H=3.75~5.75的HAc-Na Ac缓冲溶液中,室温下铜与试剂形成配位比为1∶2的紫红色配合物,配合物最大吸收波长位于573 nm,表观摩尔吸光系数为5.89×104L·mol-1·cm-1。铜浓度在0~18μg/10 m L范围内符合比耳定律。所拟方法用于矿样中铜的测定,结果满意。     

3-甲基-4-对甲苯基-5-（2-吡啶基）-1，2，4-三唑的合成和表征

1,2,4-三唑类化合物在农药、医药及化工领域有着广泛的应用,其与-些金属离子形成的配合物具有自旋转换功能。为了制备研究新的具有自旋转换功能的1,2,4-三唑配合物,以a-吡啶甲酸为原料,经多步反应合成3-甲基-4-对甲苯基-5-（2-吡啶基）-1,2,4-三唑,并用IR、MS、^1H—NMR对其结构进行了确证。     

新试剂3,3'-二甲基-4,4'-二(2-重氮氨基噻唑)联苯与铜的显色反应及其应用

研究了一个新试剂3,3' 二甲基 4,4' 二(2 重氮氨基噻唑)联苯(DDATBP)与Cu(Ⅱ)的显色反应,并建立了一个测定铜的光度分析新方法。在pH10.5的缓冲介质和Tween 80存在下,沸水浴中加热10min后,铜与DDATBP发生显色反应并形成褐色络合物,其最大吸收波长位于500nm,表观摩尔系数ε为1.60×104L·mol-1·cm-1,且铜的质量浓度在0.10～3.6μg/mL范围内符合比尔定律。用该方法测定了食品中的微量铜,结果满意。     

1-溴-2-对硝基苯氧基乙烷与1,2-二对硝基苯氧基乙烷的分离

以对硝基苯酚与1，2-二溴乙烷反应，合成了有机中间体1-溴-2-对硝基苯氧基乙烷，同时得到另一副产物1，2-二对硝基苯氧基乙烷。对两者的溶解性能进行了简单的探索，并选用石油醚作溶剂，较好地分离并提纯了目标化合物。     

Itaconic acid grafting on LDPE blended in molten state

Grafting of itaconic acid on low density polyethylene in the molten state has been investigated. Static and dynamic mixers assembled on the Brabender plastograph have been used as a blender of reagents and as a chemical reactor. Shear rates were 50 and 100 s⁻¹. Dicumyl peroxide; 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane; 2,2-di-(tert-butyl-peroxy)-5,5,6-trimethylbicyclo-[2,2,1]-heptane; 2,2-di(3-methyl-1-butyne-3-peroxy)-5,5,6-trimethylbicyclo[2,2,1]heptane; 2,5-dimethyl-2-hydroxy-5-tert-butylperoxy-3-hexyne were used as peroxide initiators of grafting. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:1493–1502, 1997     

Metal-Organic Sheets for Efficient Drug Delivery and Bioimaging

Metal-organic frameworks (MOFs) formed by coordination between metal ions or clusters and organic bridging ligands possess great potential for biomedicine applications, given their high biocompatibility and biodegradability. Compared with the traditional three-dimensional (3D) MOFs, two-dimensional (2D) MOFs with sheet-like morphologies exhibit unique properties. In this study, a nanoscale 2D leaf-shaped MOF (NZIF−L) was synthesized via coordination self-assembly between 2-methylimidazole (Hmim) and Zn²⁺ with subsequent morphology and size control. The fabricated NZIF−L is cytocompatible and can be quickly endocytosed, which makes it an excellent cargo carrier. Subsequent to loading with either doxorubicin (DOX) or 4,4′-(1,2-diphenylvinyl)-1,2-di-(phenylcarboxylic acid) (TCPE), the respectively obtained DOX@NZIF−L and TCPE@NZIF−L showed promise for killing and imaging cancer cells.     

Epoxidation of ethylenic linkages by chromic acid IV. Oxidation of triaryl olefins by chromium trioxide

The oxidation of 1,1,2-triphenylbut-1-ene by chromium trioxide in acetic anhydride gives 1,2-epoxy-1,1,2-triphenylbutane with fission products and 1,1,2-triphenylacetylethylene. Cis- and trans-1-p-chlorophenyl-1,2-diphenylprop-1-ene yield crystalline epoxides in satisfactory yields under similar conditions. The epoxides are stable towards aqueous sulphuric acid. 1,1,2-Triphenylethylene, 1,1-di-(p-chlorophenyl)-2-phenylethylene and 1,1-di-(p-bromophenyl)-2-phenylethylene are similarly oxidised but the epoxides are hydrated to the glycols by the action of aqueous sulphuric acid. Chromic acid in aqueous sulphuric acid brings about oxidative fission of the double bond without any rearrangement.     

Ring transformation and cyclization reactions of 1,1-dioxo-1,2-thiazines – syntheses of pyridines and benzo[c]thiazines with new substitution pattern

In presence of ammonia/ammonium acetate the 3,5-dimethyl-2-phenyl-1,1-dioxo-1,2-thiazine-4-carbaldehyde ( 1 ) reacts with ethyl cyanoacetate to the ethyl 2-cyano-4-[1-methyl-2-methylthio-2-(N-phenylsulfamoyl)vinyl)-hexa-2,4-dienoate] ( 3 ) and the Knoevenagel condensation product 4-(2-ethoxycarbonyl-2-cyanovinyl)-3,5-dimethyl-6-methylthio-1,1-dioxo-2-phenyl-2H-1,2-thiazine ( 2 a). The 4-(2,2-dicyanovinyl)-3,5-dimethyl-6-methylthio-1,1-dioxo-2-phenyl-2H-1,2-thiazine ( 2b ) is obtained from 1 and malononitril. The masked 1,5-dicarbonyl compound 2a undergoes ring transformation to the 3-cyano-1,6-dimethyl-5-[1-methylthio-2-(N-phenylsulfamoyl)vinyl]pyridin-2-one ( 5 ) with methylamine. With ethanolic ethoxide the condensation products 2a,b afford the 7-amino-6-ethoxycarbonyl-4-methylthio-2,2-dioxo-1-phenyl-benzo[c]1,2-thiazine ( 6a ), respectively the corresponding 6-cyano derivative 6b , while 3 cyclizises to furnish ethyl 2-amino-6-methyl-5-[1-methyl-2-methylthio-2-(N-phenyl-sulfamoyl)vinyl]nicotinate ( 4 ).     

A dinuclear copper(II) complex and a zigzag chain iron(II) polymer based on the 4-antipyrine derived Schiff base ligands: The hydroxylation and redox occurred under the solvothermal conditions

A new dinuclear copper(II) compound, [Cu₂(L1-O)₂] (1) (L1 = (4E)-4-(2-hydroxybenzylideneamino)-1,2-dihydro-2,3-dimethyl-1-phenylpyrazol-5-one), and zigzag chain polymer, {[FeCl₂(L2)]}_n (2) (L2 = 1,5-dimethyl-2-phenyl-4-{[(1E)-pyridine-4-ylmethylene]amino}-1,2-dihydro-3H-pyrazol-3-one), were synthesized by solvothermal reactions and structurally characterized. The methyl group hydroxylation and the redox have been observed in the preparation of 1 and 2, respectively.     

Synthesis and Structure of 1,5-Di-(Ethylphenyl)-1,5-Dimethyl-3,3,7,7-Tetraphenylcycloterasiloxane: a Novel Cyclotetramer

Herein we report the first synthesis of 1,5- di-(ethylphenyl)-1,5-dimethyl-3,3,7,7-tetraphenylcyclotetrasiloxane using a new ‘One Pot’ procedure as recently reported for the preparation of strictly alternating 1,1,5,5-tetramethyl-3,3,7,7-tetraphenylcyclotetrasiloxane by the heterofunctional condensation of diphenylsilanediol with (phenylethyl)methyldichlorosilane in the presence of the ter tiary amine, triethylamine (Nguyen et al. Silicon 6:21–26 2014). The prepared 1,5-di-(ethylphenyl)-1,5-dimethyl-3,3,7,7-tetraphenylcyclotetrasi loxane was fully characterized by single-crystal X-ray diffraction, ¹H, ¹³C and ²⁹Si nuclear magnetic resonance spectroscopy, elemental analysis, mass spectroscopy, thermogravimetric analysis and differential scanning calori metric studies.     

Anal gland secretion of the ferret (Mustela putorius formaFuro)

2,2-Dimethylthietane(1),trans-2,3-dimethylthietane(2),cis-2,3-dimethylthietane(3), 2-propylthietane(4), 3,3-dimethyl-1,2-dithiolane(5),trans-3,4-dimethyl-1,2-dithiolane(6),cis-3,4-dimethyl-1,2-dithiolane(7), 2-pentylthietane (8), 3-propyl-1,2-dithiolane(9), quinoline(10), and indole(11) have been identified as components of the anal gland secretion of the ferret,Mustela putorius formafuro. Male and female ferret secretions were indistinguishable except during the breeding season.     

Structural Characterization of a Cu(I) Coordination Polymer Constructed by Weak Intermolecular Cu–Cl⋯Cl–Ar Interaction

The copper(I) complex [Cu(DPPEO)(L₁)Cl] · CH₃CN (1) (DPPEO = 1,2-bis(diphenylphosphino)ethane monoxide; L₁ = 5,7-dimethyl-2-chloronaphthyridine) was prepared by reacting L₁ with CuCl in the presence of DPPE. The compound has been characterized by X-ray diffraction analysis. Compound 1 is a tri-coordinated mononuclear complex, which forms one-dimensional chain through intermolecular halogen-halogen bonds.