含有4-对溴苯基-3，5-二(2-吡啶基)-1，2，4-三氮唑钴配合物的合成，晶体结构和磁性

本文合成了一个二价钴配合物[CoL₂⁵(NCS)₂],(配体L⁵=4-对溴苯基-3,5-二(2-吡啶基)-1,2,4-三氮唑)。其结构由单晶X衍射结构分析,红外和电喷雾离子质谱表征。该配合物晶体属于三斜晶系,空间群为P1,钴原子和2个三芳基三氮唑配体的4个氮原子(平面)和2个硫氰根的氮原子(轴向)配位形成扭曲的八面体构型。磁性测定表明在1.8～300 K的温度范围内该配合物处于高自旋态。     

烃基硅铜酸盐与2-芳基-2-环烯酮1,4-加成反应的立体选择性及2-取代- 3-硅基环烷酮的合成

研究了烷基苯基硅铜酸盐与2-环烯酮的1,4-加成反应的立体选择性, 并合成了一系列新的2-取代-3-硅基环烷酮. 结果表明, 在0 ℃下用饱和NH₄Cl溶液处理, 烷基苯基硅铜酸盐与2-芳基-2-环烯酮的1,4-加成反应的立体选择性不同程度地受芳基和环的大小影响, 得到顺、反两种产物; 并首次发现室温下用甲醇处理反应时, 其立体选择性不受或者很少受环大小、芳基的性质以及与硅原子相连的取代基的影响, 只得到反式产物. 芳基溴甲烷与由烷基苯基硅铜酸盐与2-环烯酮1,4-加成所得的烯醇盐反应时, 只得到反式产物. 合成产物的结构用IR, ¹H NMR, ¹³C NMR, MS和HRMS等进行了表征.     

由1,1-二溴烯烃一锅法合成1,4-二取代-1,2,3-三氮唑

以1,1-二溴乙烯和芳基叠氮化合物为原料,碘化亚铜为催化剂,室温下通过一锅法合成了1,4-二取代-1,2,3-三氮唑衍生物。考察了催化剂用量、反应溶剂、反应温度对产品收率的影响。通过IR,MS,_¹H NMR及_¹³C NMR等对目标产物结构进行确证,并提出了可能的反应机理。该合成方法具有环境友好、条件温和、操作简单、收率高等特点。     

2-(1-苯基-1H-四唑-5-硫基)-N-芳基乙酰胺的合成及其生物活性研究

采用微波法通过2-氯乙酰芳胺与1-苯基-1H-四唑-5-硫醇反应合成了一系列2-(1-苯基-1H-四唑-5-硫基)-N-芳基乙酰胺. 其结构经 IR, ¹H NMR, ¹³C NMR 和元素分析表征. 生物活性实验结果表明, 该类化合物在较低浓度下对油菜籽和小麦的生长表现出良好的促进作用.     

2-取代苯基-5-(3,4,5-三甲氧基苯基)-1,3,4-噁二唑衍生物的合成及生物活性研究

合成了10个2-取代苯基-5-(3,4,5-三甲氧基苯基)-1,3,4-噁二唑衍生物. 并经过元素分析, IR, ¹H NMR, ¹³C NMR对其结构进行了确认. 初步生物活性测试表明, 部分化合物具有一定抗癌活性.     

有机锡9-芴酮-4-甲酸酯的合成、结构及抗癌活性

合成了 3 个有机锡 9-芴酮-4-甲酸酯:三苯基锡 9-芴酮-4-甲酸酯[(C₆H₅)₃Sn(C₁₄H₇O₃)] (1)、三环己基锡 9-芴酮-4-甲酸酯[(C₆H₁₁)₃Sn(C₁₄H₇O₃)] (2)和三(2-甲基-2-苯基丙基)锡 9-芴酮-4-甲酸酯[(C₆H₅C(CH₃)₂CH₂)₃Sn(C₁₄H₇O₃)] (3)。通过元素分析、红外光谱、核磁共振谱(¹H、¹³C和 ¹¹⁹Sn)、热重分析进行了表征;用单晶X射线衍射方法测定了化合物的晶体结构,并对其进行了量子化学计算和体外抗癌活性研究。结果显示:化合物1为一维链状结构,中心锡原子为五配位的畸变三角双锥构型;化合物2和3均为单核分子,锡原子均为四配位的畸变四面体构型。化合物对人宫颈癌细(HeLa)、人肝癌细胞(HUH-7)、人非小细胞肺癌细胞(A549)、人肺腺癌细胞(H1975)和人乳腺癌细胞(MCF-7)都有较好的抑制活性。     

新的二[4-对甲基苯基-3，5-二(2-吡啶基)-1，2，4-三氮唑]双硫氰根合锰配合物的合成，晶体结构和磁性(英)

本文合成了一个新的含有4-对甲基苯基-3，5-二(2-吡啶基)-1，2，4-三氮唑配体(L)的锰(Ⅱ)配合物，[MnL₂(NCS)₂]。其结构由X射线晶体学，红外和电喷雾离子质谱表征。在晶体结构中, 锰原子有一反演中心并由2个三芳基三氮唑配体的4个氮原子和2个反式硫氰根的2个氮原子八面体配位。磁性测定表明在75～300 K的温度范围内该配合物是顺磁性的。     

3-芳基-6-甲基-1,6-二氢-1,2,4,5-四嗪及其衍生物的合成和晶体结构

以乙腈和芳基腈为原料, 经过醚化、环化和还原三步方便且有效地合成了3-芳基-6-甲基-1,6-二氢-1,2,4,5-四嗪, 并在此基础上合成了一系列新的3-芳基-6-甲基-1,6-二氢-1,2,4,5-四嗪衍生物, 通过元素分析, ¹H NMR, IR和HRMS对这些化合物进行了表征. 对化合物N-邻甲基苯-3-苯基-6-甲基-1,6-二氢-1,2,4,5-四嗪-1-甲酰胺(5a)的X射线晶体衍射研究表明: 其属于单斜晶系, P2_{1 /c空间群, 晶胞参数a＝1.3941(6) nm, b＝0.5675(2) nm, c＝2.0614(8) nm; α＝γ＝90°, β＝102.055(6)°; V＝1.5949(11) nm³, 此类化合物的四嗪环采用不对称船式结构, 且具有同芳香性.}     

2-{5-[(1H-1,2,4-三唑-1-基)甲基]-4-苯基-4H-1,2,4-三唑-3-硫基}-1-芳基乙酮类化合物的合成、表征及生物活性测试

通过α-卤代芳基乙酮和5-[(1H-1,2,4-三唑-1-基)甲基]-4-苯基-2H-1,2,4-三唑-3(4H)-硫酮反应, 合成了11个新的2-{5-[(1H-1,2,4-三唑-1-基)甲基]-4-苯基-4H-1,2,4-三唑-3-硫基}-1-芳基乙酮类化合物. 其结构经元素分析, IR, ¹H NMR等确证, 并用X射线单晶衍射测定了化合物6f的晶体结构. 生物活性测试结果表明, 部分化合物具有一定的杀菌活性.     

二[三(2-甲基-2-苯基)丙基锡]二元酸酯(CH2)n[CO2Sn(CH2CMe2Ph)3]2(n=2, 3, 4)的合成、结构及体外抗癌活性

丁二酸、戊二酸和己二酸分别与μ-氧-双[三(2-甲基-2-苯基)丙基]锡反应, 合成了3个二[三(2-甲基-2-苯基)丙基锡]二元酸酯(CH₂)_n[CO₂Sn(CH₂CMe₂Ph)₃]₂(n=2 (1), 3 (2), 4 (3))。对化合物1~3进行了元素分析、红外光谱及核磁共振(¹H, ¹³C)表征, 并通过X-射线晶体衍射分析测定晶体结构。化合物中锡与配基原子构成畸型四面体构型。试验表明, 化合物2和3均对人癌细胞Colo205、HepG2、MCF-7、Hela、NCI-H460的增殖具有较强的抑制作用。     

Supramolecular Arrays of Cationic Complexes Containing Pyrazole Ligands and Tetrafluoroborate,Trifluoromethanesulfonate, or Nitrate as Counterions. Crystal Structure of Bis(3,5‐dimethyl‐4‐nitro‐1H‐pyrazole‐κN2)silver(1+) Nitrate ([Ag(HpzNO2)2](NO3))

The structures of [Pd(η³‐C₃H₅)(Hpz^R2)₂](BF₄) (Hpz^R2=Hpz^bp2=3,5‐bis(4‐butoxyphenyl)‐1H‐pyrazole, 1 ; Hpz^R2=Hpz^NO2=3,5‐dimethyl‐4‐nitro‐1H‐pyrazole=Hdmnpz, 2 ) and [Ag(Hpz^R2)₂](A) (Hpz^R2=Hpz^bp2, A= , 3 ; Hpz^R2=Hpz^NO2, A= , 4 ) were comparatively analyzed to determine the factors responsible for polymeric assemblies. In all cases, the H‐bonding interactions between the pyrazole moieties and the appropriate counterion and, in particular, the orientation of the NH groups of the pyrazole ligands are determinant of one‐dimensional polymeric arrays. In this context, the new compound [Ag(Hpz^NO2)₂](NO₃) ( 5 ) was synthesized and its structure analyzed by X‐ray diffraction (Fig. 4). The Hpz^NO2 serves as N‐monodentate ligand, which coordinates to the Ag^I center through its pyrazole N‐atom giving rise to an almost linear N Ag N geometry. The planar NO counterion bridges two adjacent Ag^I centers to form a one‐dimensional zigzag‐shaped chain which is also supported by the presence of N H⋅⋅⋅O bonds between the pyrazole NH group of adjacent cationic entities and the remaining O‐atom of the bridging NO (Fig. 5). The chains are further extended to a two‐dimensional layer‐like structure through additional Ag⋅⋅⋅O interactions involving the NO₂ substituents at the pyrazole ligands (Fig. 6).     

Lamellar Copper(I) Thiocyanate‐Based Coordination Polymers containing the Alkali Cation ligating Thiacrown Ether 1,10‐Dithia‐18‐crown‐6

The lamellar coordination polymer [(CuSCN)₂(μ‐1,10DT18C6)] (1,10DT18C6 = 1,10‐dithia‐18‐crown‐6), in which staircase‐like CuSCN double chains are bridged by thiacrown ether ligands, may be prepared in two triclinic modifications 1 a and 1 b by reaction of CuSCN with 1,10DT18C6 in respectively benzonitrile or water. Performing the reaction in acetonitrile in the presence of an equimolar quantity of KSCN leads, in contrast, to formation of the K⁺ ligating 2‐dimensional thiocyanatocuprate(I) net [{Cu₂(SCN)₃}^–] of 2 , half of whose Cu(I) atoms are connected by 1,10DT18C6 macrocycles. The potassium cations in [{K(CH₃CN)}{Cu₂(SCN)₃(μ‐1,10DT18C6)}] ( 2 ) are coordinated by all six potential donor atoms of a single thiacrown ether in addition to a thiocyanate S and an acetonitrile N atom. Under similar conditions, reaction of CuI, NaSCN and 1,10DT18C6 affords [{Na(CH₃CN)₂}{Cu₄I₄(SCN)(μ‐1,10DT18C6)}] ( 3 ), which contains distorted Cu₄I₄ cubes as characteristic molecular building units. These are bridged by thiocyanate and thiacrown ether ligands into corrugated Na⁺ ligating sheets. In the presence of divalent Ba²⁺ cations, charge compensation requirements lead to formation of discrete [Cu(SCN)₃(1,10DT18C6‐κS)]^2– anions in [Ba{Cu(SCN)₃(1,10DT18C6‐κS)}] ( 4 ).     

Direct Cyclodextrin‐Mediated Ring Opening Polymerization of ϵ‐Caprolactone in the Presence of Yttrium Trisphenolate Catalyst

Unmodified β‐cyclodextrin has been directly used to initiate ring‐opening polymerization of ϵ‐caprolactone in the presence of yttrium trisphenolate. Well‐defined cyclodextrin (CD)‐centered star‐shaped poly(ϵ‐caprolactone)s have been successfully synthesized containing definite average numbers of arms (N_arm = 4–6) and narrow polydispersity indexes (below 1.10). The number‐average molecular weight ( ) and average molecular weight per arm ( ) are controlled by the feeding molar ratio of monomer to initiator. The prepared star‐PCL with of 2.7 × 10³ is in fully amorphous and that with of 13.3 × 10³ is crystallized. In addition, the obtained poly(e‐caprolactone) (PCL) stars with various molecular weights have different solubilities in methanol and tetrahydrofuran, which can be applied for further modifications.     

Iodostannate(II) mit kettenförmigen [SnI3]–‐Anionen – der Übergang von fünffach zu sechsfach koordinierten SnII‐Zentralatomen

Iodostannates(II) with Anionic [SnI₃]^– Chains – the Transition from Five to Six‐coordinated Sn^II The iodostannates (Me₄N) [SnI₃] ( 1 ), [Et₃N–(CH₂)₄–NEt₃] [SnI₃]₂ ( 2 ), [EtMe₂N–(CH₂)₂–NEtMe₂] [SnI₃]₂ ( 3 ), [Me₂HN–(CH₂)₂–NH–(CH₂)₂–NMe₂H] [SnI₃]₂ ( 4 ), [Et₃N–(CH₂)₆–NEt₃] [SnI₃]₂ ( 5 ) and [Pr₃N–(CH₂)₄–NPr₃]‐ [SnI₃]₂ · 2 DMF ( 6 ) with the same composition of the anionic [SnI₃]^– chains show differences in the coordination of the Sn^II central atoms. Whereas the Sn atoms in 1 and 2 are coordinated in an approximately regular octahedral fashion, in compounds 3 – 6 the continuous transition to coordination number five in (Pr₄N) [SnI₃] ( 7 ) or [Fe(dmf)₆] [SnI₃]₂ ( 8 ) can be observed. Together with the shortening of two or three Sn–I bonds, the bonds in trans position are elongated. Thus weak, long‐range Sn…I interactions complete the distorted octahedral environment of SnI₄ groups in 3 and 4 and SnI₃ groups in 5 and 6 . Obviously the shape, size and charge of the counterions and the related cation‐anion interactions are responsible for the variants in structure and distortion.     

Incorporating glycidyl methacrylate into block copolymers using poly(methacrylate‐ran‐styrene) macroinitiators synthesized by nitroxide‐mediated polymerization

Methyl methacrylate/styrene (MMA/S), ethyl methacrylate/styrene (EMA/S) and butyl methacrylate/styrene (BMA/S) feeds (>90 mol % methacrylate) were copolymerized in 50 wt % p‐xylene at 90 °C with 10 mol % of additional SG1‐free nitroxide mediator relative to unimolecular initiator (BlocBuilder^®) to yield methacrylate rich copolymers with polydispersities _w/ _n = 1.23–1.46. k_pK values (k_p = propagation rate constant, K = equilibrium constant) for MMA/S copolymerizations were comparable with previous literature, whereas EMA/S and BMA/S copolymerizations were characterized by slightly higher k_pK's. Chain extensions with styrene at 110 °C initiated by the methacrylate‐rich macroinitiators (number average molecular weight _n = 12.9–33.5 kg mol^?1) resulted in slightly broader molecular weight distributions with _w/ _n = 1.24–1.86 and were often bimodal. Chain extensions with glycidyl methacrylate/styrene/methacrylate (GMA/S/XMA where XMA = MMA, EMA or BMA) mixtures at 90 °C using the same macroinitiators resulted frequently in bimodal molecular weight distributions with many inactive macroinitiators and higher _w/ _n = 2.01–2.48. P(XMA/S) macroinitiators ( _n = 4.9–8.9 kg mol^?1), polymerized to low conversion and purified to remove “dead” chains, initiated chain extensions with GMA/MMA/S and GMA/EMA/S giving products with _w/ _n ～ 1.5 and much fewer unreacted macroinitiators (<5%), whereas the GMA/BMA/S chain extension was characterized by slightly more unreacted macroinitiators (～20%). © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2574–2588, 2009     

A Fully Substituted 3‐Silolene Functions as Promising Building Block for Hyperbranched Poly(Silylenevinylene)

A 3‐silolene derivative, 2,2,5,5‐tetrakis(dimethylsilyl)‐1,1‐dimethyl‐3,4‐diphenyl‐3‐silolene (TDMSHS), is first synthesized and characterized by X‐ray diffraction crystallography and spectroscopic methods. Hydrosilylation polymerization of TDMSHS with 1,1‐dimethyl‐2,5‐bis(4‐ethynylphenyl)‐3,4‐diphenylsilole in the presence of Karstedt's catalyst generates a stereoregular silole‐containing hyperbranched poly(silylenevinylene) (hb‐SPSV) with a high molecular weight ( = 146 000, / = 1.5) in high yield (≈95%). hb‐SPSV exhibits excellent thermal stability and strong fluorescence, and the emission of its aggregates in aqueous mixture can be quenched efficiently by picric acid with large quenching constants K_SV up to 414400 M ⁻¹.     

Selective Detection of Ascorbic Acid Using Octacyanomolybdate‐Doped‐Glutaraldehyde‐Cross‐Linked Poly‐L‐Lysine Film Modified Glassy Carbon Electrode

The present work describes oxidation of ascorbic acid (AA) at octacyanomolybdate‐doped‐glutaraldehyde‐cross‐linked poly‐L ‐lysine (PLL‐GA‐Mo(CN) film modified glassy carbon electrode in 0.1 M H₂SO₄. The modified electrode has been successfully prepared by means of electrostatically trapping Mo(CN) mediator in the cationic film of glutaraldehyde‐cross‐linked poly‐L ‐lysine. The dependence of peak current of modified electrode in pure supporting indicates that the charge transfer in the film was a mixed process at low scan rates (5 to 200 mV s^?1), and kinetically restrained at higher scan rates (200 to 1000 mV s^?1). Cyclic voltammetry and rotating disk electrode (RDE) techniques are used to investigate the electrocatalytic oxidation of ascorbic acid and compared with its oxidation at bare and undoped PLL‐GA film coated electrodes. The rate constant of catalytic reaction k obtained from RDE analysis was found to be 9.5×10⁵ cm³ mol^?1 s^?1. The analytical determination of ascorbic acid has been carried out using RDE technique over the physiological interest of ascorbic acid concentrations with a sensitivity of 75 μA mM^?1. Amperometric estimation of AA in stirred solution shows a sensitivity of 15 μA mM^?1 over the linear concentration range between 50 and 1200 μM. Interestingly, PLL‐GA‐Mo(CN) modified electrode facilitated the oxidation of ascorbic acid but not responded to other electroactive biomolecules such as dopamine, uric acid, NADH, glucose. This unique feature of PLL‐GA‐Mo(CN) modified electrode allowed for the development of a highly selective method for the determination of ascorbic acid in the presence of interferents.     

Fe(CN)$\rm{ {_{6}^{4-}}}$‐Doped‐Glutaraldehyde‐Cross‐Linked Poly‐L‐Lysine Film Electrode. Part 1: Electrochemical Characterization and Its Electrocatalytic Activity Towards Oxidation of Ascorbic Acid

The present work describes preparation, characterization, and electrocatalytic behavior of a hexacyanoferrate‐doped‐glutaraldehyde‐cross‐linked poly‐L ‐lysine (PLL‐GA‐Fe(CN) film modified glassy carbon electrode. The modified electrode has been successfully prepared by electrostatically binding negatively charged Fe(CN) mediator into cross‐linked poly‐L ‐lysine cationic film. The dependence of the peak current of the modified electrode in pure supporting electrolyte (pH 6.8 phosphate buffer solution; PBS) shows that the charge transport in the film is fast and relatively unimpeded at lower scan rates. Cyclic voltammetry and rotating disk electrode (RDE) techniques are used to investigate the electrocatalytic activity of modified electrode towards oxidation of ascorbic acid. The rate constant (k), of catalytic reaction between electrogenerated Fe(CN) ions and ascorbic acid, obtained from RDE analysis was found to be 5.53×10⁵ cm³ mol^?1 s^?1. Finally, the PLL‐GA‐Fe(CN) film electrodes are successfully used for the individual estimation of ascorbic acid in the concentration range of physiological interest.     

Mesoporous Silica Supported Multiple Single‐Site Catalysts and Polyethylene Reactor Blends with Tailor‐Made Trimodal and Ultra‐Broad Molecular Weight Distributions

A ternary blend of the bisiminopyridine chromium (III) (Cr‐ 1 ) with the bisiminopyridine iron (II) (Fe‐ 2 ) post‐metallocenes with the quinolylsilylcyclopentadienyl chromium (III) halfsandwich complex (Cr‐ 3 ) was supported on mesoporous silica to produce novel multiple single‐site catalysts and polyethylene reactor blends with tailor‐made molecular weight distributions (MWDs). The preferred cosupporting sequence of this ternary blend on MAO‐treated silica was Fe‐ 2 followed by Cr‐ 1 and Cr‐ 3 . Cosupporting does not impair the single‐site nature of the blend components producing polyethylene fractions with = 10⁴ g · mol⁻¹ on Cr‐ 1 , = 3 × 10⁵ g · mol⁻¹ on Fe‐ 2 , and = 3 × 10⁶ g · mol⁻¹ on Cr‐ 3 . As a function of the Fe‐ 2 /Cr‐ 1 /Cr‐ 2 mixing ratio it is possible to control the weight ratio of these three polyethylenes without affecting the individual average molecular weights and narrow polydispersities of the three polyethylene fractions. Tailor‐made polyethylene reactor blends with ultra‐broad MWD and polydispersities varying between 10 and 420 were obtained. When the molar ratio of Fe‐ 2 /Cr‐ 1 was constant, the ultra‐high molecular polyethylene (UHMWPE, > 10⁶ g · mol⁻¹) content was varied between 8 and 16 wt.‐% as a function of the Cr‐ 3 content without impairing the blend ratio of the other two polyethylene fractions and without sacrificing melt processability. When the molar ratio Fe‐ 2 /Cr‐ 3 was constant, it was possible to selectively increase the content of the low molecular weight fraction by additional cosupporting of Cr‐ 1 . Due to the intimate mixing of low and ultra‐high molecular weight polyethylenes (UHMPEs) produced on cosupported single‐site catalysts a wide range of melt processable polyethylene reactor blends was obtained.

     

Combining Modular Ligation and Supramolecular Self‐Assembly for the Construction of Star‐Shaped Macromolecules

A well‐defined random copolymer of styrene (S) and chloromethylstyrene (CMS) featuring lateral chlorine moieties with an alkyne terminal group is prepared (P(S‐co‐CMS), = 5500 Da, PDI = 1.13). The chloromethyl groups are converted into Hamilton wedge (HW) entities (P(S‐co‐HWS), = 6200 Da, PDI = 1.13). The P(S‐co‐HWS) polymer is subsequently ligated with tetrakis(4‐azidophenyl)methane to give HW‐functional star‐shaped macromolecules (P(S‐co‐HWS))₄, = 25 100 Da, PDI = 1.08). Supramolecular star‐shaped copolymers are then prepared via self‐assembly between the HW‐functionalized four‐arm star‐shaped macromolecules ( P(S‐co‐HW )) ₄ and cyanuric acid (CA) end‐functionalized PS (PS–CA, = 3700 Da, PDI = 1.04), CA end‐functionalized poly(methyl methacrylate) (PMMA–CA, = 8500 Da, PDI = 1.13) and CA end‐functionalized polyethylene glycol (PEG–CA, = 1700 Da, PDI = 1.05). The self‐assembly is monitored by ¹H NMR spectroscopy and light scattering analyses.