苯甲酸系列邻菲啰啉硝酸根稀土四元混配配合物的合成、表征和抗菌活性研究

在酸性介质 ,乙醇 /水混合溶剂中合成得到了四元混配配合物 [Ln(C6 H5COO) 2 (NO3)(phen) ]2 (Ln =La ,Ce ,Pr ,Nd ,Sm ,Eu ,Gd ,Er ,Tm)和 [Nd(x MBA) 2 (NO3) (phen) ]2 (x =o、p、m) (MBA =甲基苯甲酸 )。用元素分析、IR和UV方法对配合物进行了表征 ,并对配合物的抗枯草杆菌、大肠杆菌、金黄色葡萄球菌、酵母菌、白念珠菌、和霉菌的性能进行了研究。     

新型水杨醛亚胺钛配合物的合成及催化乙烯聚合

以价廉的水杨醛和Ti Cl4为主要原料,合成了四种水杨醛亚胺配体(5-8)及含(双苯氧基亚胺)配体的钛配合物[O-C6H4-ortho-CH=N-2,6-(i-Pr)2-C6H3]2Ti Cl2(13),[O-(5-NO2)-C6H3-ortho-CH=N-2,6-(i-Pr)2-C6H3]2Ti Cl2(14),[O-(3,5-di-Br)-C6H2-orthoCH=N-2,6-(i-Pr)2-C6H3]2Ti Cl2(15)和[O-(3,5-di-C(CH3)3)-C6H2-ortho-CH=N-2,6-(i-Pr)2-C6H3]2Ti Cl2(16)。用MS、1H-NMR和元素分析等手段表征了配体5-8分子结构,用1H-NMR和元素分析表征了配合物13-16的分子结构。经MAO(甲基铝氧烷)活化后,钛配合物(13-16)在甲苯溶剂中能有效催化乙烯聚合。在60℃,2.0 MPa及助催化剂与主催化剂摩尔比n(MAO)/n(cat)=1500∶1条件下钛配合物(14-16)催化乙烯聚合活性为1022.73-1302.27 g·PE/(mmol·Ti·h·MPa)),远高于无取代水杨醛亚胺钛配合物(13)。所得聚乙烯粘均分子量(粘度法)为19266-44754,GPC测定分子量分布Mw/Mn为1.88-2.12。具有最高活性的催化剂15催化乙烯聚合得到的聚合物样品,经13C-NMR和DSC的表征,结果表明为线型结晶聚乙烯。     

亚胺基吡啶铁配合物/茂金属催化乙烯原位共聚中的共单体效应

研究了亚胺基吡啶铁配合物{[(2-Me-4-R-C6H4N=C(Me))2C5H3N]FeCl2}(1R=Br,2R=OMe)分别与茂金属Et[Ind]2ZrCl2复配催化乙烯原位共聚中的共单体效应．探讨了齐聚催化剂的活性和聚合反应温度对共单体效应的影响,以及共单体效应对所得产物物理性能的影响．结果表明,随着齐聚催化剂活性的降低,出现共单体效应时两种主催化剂的最佳配比值增加;聚合温度的升高使最高活性值下降．共单体效应对所得共聚物的物理性能影响不明显．     

2,2-联吡啶-6,6-二羧酸与稀土配合物的合成及性能

利用2,2-联吡啶-6,6-二羧酸作为配体,合成了稀土配合物[Ln2(bpydc)3·3H2O]·H2O·3CH3OH(1,Ln=Eu,Tb,Yb,Gd;Hbpydc=2,2-联吡啶-6,6-二羧酸)。使用单晶X射线衍射仪、傅里叶红外光谱、紫外吸收光谱、荧光光谱以及磷光光谱等对其进行了表征和配体与发光中心的能级匹配程度的测定,探讨了配合物的荧光性能与能量传递效率。结果表明:配合物具有两种不同环境的配位中心,促使配合物在空间上具有层状堆积结构;Eu(Ⅲ)与Tb(Ⅲ)配合物分别在612与548nm处有强烈的红色与绿色荧光发射,特征荧光敏化效果明显;配体三重态能级26666cm-1与稀土离子Eu3+(5D0,17300cm-1)、Tb3+(5D4,20500cm-1)最低激发态能级匹配,存在明显天线效应,具有优良的能量传递效率。     

α-二亚胺合镍氯化物/MgCl2(THF)2负载催化剂合成支化聚乙烯

以MgCl2(THF)2负载 [C6H5-N=C (CH3)C(CH3)=N-C6H5]NiCl2和AlEt2Cl组成的催化体系进行乙烯聚合,庚烷为溶剂制备支化聚乙烯(w=24000～34000).聚合条件如助催化剂、铝镍摩尔比、聚合温度和金属镍浓度对催化活性有很大的影响.负载催化剂在AlEt2Cl为助催化剂、聚合温度14 ℃、铝镍摩尔比80、金属镍浓度0.18 mmol/L的条件下催化活性达到51 kg PE/mol Ni·h.聚乙烯的支化度随着聚合温度的升高而迅速增加,受铝镍摩尔比的影响不大.     

铕掺杂聚甲基丙烯酸甲酯的光致发光性能

利用不饱和二元羧酸3-己烯二酸(H2L)、1,10-邻菲咯啉(Phen)与稀土铕的氯化物EuCl3反应,合成了具有发光性能的稀土铕三元配合物Eu2L3Phen.4H2O。将铕配合物与聚甲基丙烯酸甲酯(PMMA)掺杂后,研究了掺杂型高分子材料的光致发光性能。研究结果表明,Eu配合物能发出很强的铕离子特征荧光,当配合物Eu2L3Phen.4H2O与聚甲基丙烯酸甲酯掺杂后,高分子材料仍能发出配合物Eu2L3Phen.4H2O的特征荧光,高分子材料的发光强度随着配合物在聚甲基丙烯酸甲酯中掺杂量的增加而增加。     

含半不稳定边臂配体的钛配合物催化丙交酯聚合

聚乳酸类材料作为可生物降解性材料具有广阔的应用前景。设计、合成了6种含半不稳定边臂的希夫碱配体L1—L6,并与钛酸四异丙酯络合合成相应的6种配合物C1—C6,配合物的结构和化学组成经元素分析、红外测试确定。将其作为催化剂催化丙交酯开环聚合,以催化剂C1为考察对象,系统研究了催化剂用量、温度、时间对聚合反应的影响,发现当单体与催化剂配比为2 000,温度为160℃,反应24h时,聚合产率最高,达90.35%,聚合物分子量达8.41×104。在上述优化条件下,比较了催化剂C1—C6的活性,结果表明催化剂活性按以下顺序递减:C6C4C3C1C2C5,同时,催化剂中心金属钛原子周围位阻相对稍小,配体中含配位能力较弱的半不稳定O边臂均有利于提高催化剂的活性。     

新型多核苊二亚胺镍配合物复合负载催化剂催化乙烯聚合

制备了两种多核苊二亚胺镍配合物N imL1C l2m和N imL2C l2m,并将其负载于M gC l2和S iO2上制备复合载体催化剂,与通用烷基铝组成新的催化体系催化乙烯聚合。研究结果表明,在A lE t2C l为助催化剂的条件下,两种多核苊二亚胺镍配合物能高效催化乙烯进行聚合,制得不同支链的各种支化聚乙烯;聚合条件对乙烯聚合活性和产物性能有较大的影响。制得产物的支链使聚乙烯的熔融峰变宽,并且支化度越高,熔融峰越宽。     

(N^O^S)三齿配体的钴配合物催化异戊二烯聚合的研究

采用含氮氧硫三齿配体与无水氯化钴反应制得一系列相应的(N^O^S)钴配合物,研究了该系列钴配合物对异戊二烯聚合的催化性能。在助催化剂AlEt2Cl的活化下,该系列钴配合物对异戊二烯聚合表现出高的催化活性。考察了不同单体浓度、助催化剂用量(Al/Co物质的量比)、聚合温度以及催化剂的配体环境等因素对聚合反应和聚合产物性能的影响。通过凝胶渗透色谱法(GPC)和核磁共振氢谱(1 H-NMR)对聚合产物进行表征。结果显示,所得异戊二烯分子量(Mn)在30000~242000,分子量分布在1.14~2.38之间。     

银的电沉积过程与5,5-二甲基乙内酰脲配位剂浓度及pH值的关系

目前,对无氰镀银的电沉积机理及从分子配位机理角度的研究报道较少。采用循环伏安法(CV)测试,结合量子化学计算和镀银层表面形貌的SEM分析,研究了配位剂5,5-二甲基乙内酰脲(DMH)对银电沉积过程的影响。结果表明,Ag+与DMH配位后,还原电位负移;不同DMH浓度和p H值条件下,DMH与Ag+形成的配合物形式以及配合物稳定性均不同,随着DMH浓度增大及p H值升高,形成的配合物也更稳定;当p H值为10时,DMH与Ag+能够形成稳定的配合物[Ag(C5H7N2O2)]和[Ag(C5H7N2O2)2]-,在适宜的电位范围内能够制备出结构致密、表面平整、光亮的银镀层。     

Dinickel Bisphenoxyiminato Complexes for the Polymerization of Ethylene and α-Olefins

Dinuclear nickelphenoxyiminato olefin polymerization catalysts based on rigid p-terphenyl frameworks are reported. Permethylation of the central arene of the terphenyl unit and oxygen substitution of the peripheral rings ortho to the aryl-aryl linkages blocks rotation around these linkages allowing atropisomers of the ligand to be isolated. The corresponding syn and anti dinickel complexes (25-s and 25-a) were synthesized and characterized by single crystal X-ray diffraction. These frameworks limit the relative movement of the metal centers restricting the metal-metal distance. Kinetics studies of isomerization of a ligand precursor (7-a) allowed the calculation of the activation parameters for the isomerization process (ΔH(?) = 28.0 ± 0.4 kcal×mol(-1) and ΔS(?) = -12.3 ± 0.4 cal×mol(-1)×K(-1)). The reported nickel complexes are active for ethylene polymerization [TOF up to 3700 (mol C(2)H(4))×(mol Ni)(-1)×h(-1)] and ethylene/α-olefin copolymerization. Only methyl branches are observed in the polymerization of ethylene, while α-olefins are incorporated without apparent chain walking. These catalysts are active in the presence of polar additives and in neat tetrahydrofuran. The syn and anti isomers differ in polymerization activity and polymer degree of branching and molecular weight. For comparison, a series of mononuclear nickel complexes (26, 27-s, 27-a, 28, 30) was prepared and studied. The effects of structure and catalyst nuclearity on reactivity are discussed.     

A CHEMICAL ROUTE FOR THE PREPARATION OF NANOSIZED RARE EARTH PEROVSKITE-TYPE OXIDES FOR ELECTROCERAMIC APPLICATIONS

This paper reviews the work performed by the authors on the preparation of LnTO₃ (Ln = rare earth elements, and T = transition metals) perovskite-type oxides by the thermal decomposition at low temperatures of the corresponding heteronuclear complexes. Bimetallic complexes in the series Ln[Fe(CN₆)]·nH₂O and Ln[Co(CN₆)] nH₂O, with Ln = from La through Yb, and trimetallic complexes in the series Ln¹_xLnnl-x[Co(CN₆)] nH₂O and Ln[FeyCo1-_y(CN₆)] nH₂O were prepared. The formation of the perovskite-type oxides by the thermal decomposition of the complexes has been studied by simultaneous thermogravimetric and differential thermal analysis (TG/DTA), x-ray fluorescence (XRF), Fourier transform infrared (FTTR) spectroscopy, x-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The composition and temperature limits of stability for the dimetallic and trimetallic perovskite-type oxides have been clarified. The major role played by the ionic radii of the Ln3⁺ and T3⁺ ions on the formation of the perovskite-type oxides has been identified. Homogeneous perovskite-type oxide powders with nanosized particles, which possess promising characteristics for their applications as functional ceramics, are easily synthesized with this method.     

Anticancer Activity of Self-Assembled Molecular Rectangles via Arene-Ruthenium Acceptors and a New Unsymmetrical Amide Ligand

Two new and large molecular rectangles 4 and 5 were synthesized from two different arene-ruthenium [Ru(2)(μ-η(4)-C(2)O(4))(MeOH)(2)(η(6)-p-Pr(i)C(6)H(4)Me)(2)][O(3)SCF(3)](2) (2), and [Ru(2) (p-cymene)(2) (donq) (OH(2))(2)] [O(3)SCF(3)](2) (donq = 5,8-dioxydo-1,4-naphthaquinonato) (3) acceptors and a new unsymmetrical N-(4-(pyridin-4-ylethynyl)phenyl) isonicotinamide (1) donor ligand. X-ray crystallography of 4 confirmed a molecular rectangle. The (1)H NMR spectra of both rectangles 4 and 5 showed a mixture of two structural, head-to-tail (HTL) and head-to-head (HTH) type, isomers in a 1:1 ratio. The cytotoxicities of both rectangles have been established against Colo320 (colorectal cancer), A549 (lung cancer), MCF-7(breast cancer) and H1299 (lung cancer) human cancer cell lines. The cytotoxicity of rectangle 5 was found to be considerably stronger against all cancer cell lines than that of the reference drug cisplatin.     

链转移剂对高团含量共聚物乳液的影响

分别合成了固含量７０％、６７％左右的ＢＡ／ＭＭＡ／ＨＡＭ、ＢＡ／ＭＭＡ／ＭＡＡ共聚物乳液。发现：链转移剂Ｃ１２Ｈ２３ＳＨ的使用,使乳胶粒粒径变大,乳液粘度变小,聚合物应力松驰时间缩短,未使用链转移剂的胶膜其拉伸为脆性断裂,使用的为韧性断裂。     

Mutual Influence of Lanthanides(III) in Their Joint Extraction from Aqueous Multicomponent Solutions with a Toluene Solution of Trialkylbenzylammonium Naphthenate

Extraction of lanthanides(III) [Sm(III)-Lu(III), including also yttrium(III)] from their aqueous multicomponent solutions with a toluene solution of trialkylbenzylammonium naphthenate was studied at 298 K and pH 3. Physicochemical and mathematical models describing distribution and mutual influence of lanthanides(III) [Ln(III)] in their joint extraction from multicomponent aqueous solutions were developed. Distribution of Ln(III) was studied as a function of the total concentration and composition of Ln(III) mixture in the aqueous phase taking into account that the Ln(III) extractable complexes (R₄N)₂[Ln(NO₃)₃A₂] (A is naphthenate anion) are formed in the organic phase.     

N-(邻硝基苯基)-N′-(甲氧基羰基)硫脲及其过渡金属配合物的NMR研究

本文测定了四个N-(邻硝基苯基)-N＇-(甲氧基羰基)硫脲(H_2omt)(1)及其过渡金属配合物{Cd(Homt)_2 (bpy)(2)、Zn(Homt)_2(phen)(3)、[Cu (H_2om＇t)_2Cl]_2}(4)的~1H、~(13)CNMR谱,归属了它们的所有谱线,对于它们的化学位移与配位行为作了简单讨论。     

Extraction of Lanthanide(III) and Y(III) Nitrates with Trialkylbenzylammonium Nitrate in Toluene

Extraction of lanthanides(III) [La(III)-Lu(III), including also yttrium(III)] from their aqueous solutions with 0.55 M toluene solution of trialkylbenzylammonium nitrate (TABAN) was studied at 298 K. The extraction isotherms were analyzed assuming formation the following extractable complexes: (R₄N)₃·[Ln(NO₃)₆] and (R₄N)[Ln(NO₃N))₇N)] for La(III) and Ce(III), (R₄N)₂[Ln(NO₃)₅] and (R₄N)₃[Ln(NO₃)₆] for Pr(III)-Gd(III), and (R₄N)N)₂N)[Ln(NO₃N))₅N)] for Tb(III)-Lu(III) and Y(III). The extraction constants of Y(III) and Yb(III) are close. The TABAN concentration in the organic phase does not noticeably influence the composition of the extractable complexes and the extraction constants.     

双核水杨醛亚胺镍催化剂的制备及对降冰片烯聚合的催化性能

合成了3种5,5′-亚甲基-双-水杨醛亚胺配体,利用它们和trans-[NiCl(Ph)(PPh3)2]反应得到Cat1、Cat2和Cat3三种双核水杨醛亚胺镍催化剂,并通过红外(FT-IR)和元素分析进行了表征。研究了在甲苯为溶剂,MAO为助催化剂下,催化降冰片烯(NBE)单体聚合的催化性能,考察了聚合条件,如温度、Al/Ni物质的量比对降冰片烯的催化活性、单体转化率、聚合物分子量及分子量分布的影响。当在n(Al)/n(Ni)为1000,聚合温度为80℃的条件下,催化剂的催化活性达到最大值1.16×105g of PNB/(mol of Ni.h)。聚合产物的核磁共振(1H-NMR)和红外光谱分析结果表明,该聚合反应是以单体的乙烯基加成聚合机理进行的。     

Crystal Structure of An(VI) Complexes with Succinate Anions, [PuO2(C4H4O4)(H2O)] and Cs2[(AnO2)2(C4H4O4)3]·H2O (An = U,Np, Pu)

Radiochemistry - Actinide(VI) complexes with succinate anions [PuO2(succ)(H2O)] and Cs2[(AnO2)2(succ)3]·H2O (An = U, Np, Pu), where succ = [C4H4O4]2 ?, were synthesized and studied by...     

钴盐阴离子基团对Co-N-C催化剂电催化活性的影响

采用化学氧化法在苯胺聚合过程中分别加入钴(Co)为Co2+而阴离子基团为(C2H3O2)22-、Cl22-、(NO3)22-、SO42-及C2O42-的乙酸钴、氯化钴、硝酸钴、硫酸钴、草酸钴等钴盐,合成出不同聚苯胺-钴(PANI-Co)配位聚合物。然后将PANI-Co聚合物作为前驱体在N2气氛中900℃热处理,制备出氮掺杂的Co-N-C碳基催化剂。采用SEM、XRD、XPS、Raman等手段分析Co-N-C催化剂的形貌、结构、化学组成及化学价态,并采用电化学方法测试了Co-N-C催化剂的电催化活性。结果表明,Co盐的阴离子基团对Co-N-C催化剂的形貌影响不大,但对Co-N-C催化剂中表面化学组成及含量、碳结构、石墨化程度以及Co的价态影响较大,并且Co盐的阴离子基团会影响Co-N-C催化剂的电催化活性,其氧还原(ORR)活性按照(C2H3O2)22-Cl22-(NO3)22-SO42-C2O42-顺序降低。含(C2H3O2)22-和Cl22-阴离子的钴盐制备的Co-N-C催化剂具有较高的ORR活性,这可能源于其较高含量的石墨氮和吡啶氮。