以吡啶为配体的双金属Co(Ⅱ)和Ni(Ⅱ)单核配合物的合成、晶体结构及表征

采用缓慢蒸发溶剂的方法,在去离子水溶剂中合成了双金属Co(Ⅱ)和Ni(Ⅱ)单核配合物[Co0.78Ni0.22(py)3(H2O)3](1,5-nds)(1,5-nds=1,5-萘二磺酸根离子,py=吡啶)。利用X射线单晶衍射以及红外光谱等表征手段确定了其结构和组成。该配合物属于单斜晶系,空间群为C2/c。该配合物为单核配合物,中心离子为双金属Co(Ⅱ)和Ni(Ⅱ)。中心离子与三个吡啶和三个水分子配位。1,5-萘二磺酸根离子没有与中心离子配位,只起到平衡电荷的作用。     

钴(Ⅱ)配合物[Co(2,2′-bipy)2(NO3)]2SO4·(H2O)5的水热合成和晶体结构

以2,2′-联吡啶和硝酸根为混合配体,通过水热反应合成了一个新的钴(Ⅱ)配合物[Co(2,2′-bipy)2(NO3)]2SO4·(H2O)5,用元素分析、红外光谱、X-射线单晶衍射表征了配合物的结构.标题配合物晶体属单斜晶系,P2(1)/n空间群,晶体学参数:a=0.709 32(9) nm,b=1.952 8(2) nm,c=1.684 1(2) nm,β=96.835(2)°,V=2.316 1(5) nm3,Z=2,D=1.495 g/cm3.配合物中每个钴(Ⅱ)离子与两个2,2′-联吡啶分子中的4个N原子、1个硝酸根的两个O原子形成六配位的变形八面体结构.     

新显色剂2-(四氮唑偶氮)-5-二乙氨基苯甲酸光度法测定钴的研究

研究了新显色剂 2 - (四氮唑偶氮 ) - 5 -二乙氨基苯甲酸 (简称 TTZDBA)与钴的显色反应 ,试剂与钴在 p H3 .5的 HAc- Na Ac缓冲溶液中形成稳定的紫红色配合物 ,其组成比为 Co2 + :TZDBA=1∶ 2 ,λmax=6 2 0 nm;试剂的 λmax为 5 0 0 nm,对比度 Δλ为 1 2 0 nm,配合物表观摩尔吸光系数为 ε=9.1 1× 1 0 4。Co2 +浓度在 0～ 0 .5 mg/L范围内符合比尔定律。配合物形成后在强酸溶液中能稳定存在 ,可消除大量金属离子的干扰 ,有良好的选择性。方法可以不经分离直接测定维生素 B12 和工业废水中的微量钴 ,结果令人满意     

超分子化合物[(C6H6N2O)2Co·2H2O]·2NO3的合成和晶体结构

合成了一个钴配合物[(C6H6N2O)2Co.2H2O].2NO3。该化合物属单斜晶系,P2(1)/n空间群,其化学式为:C12H16CoN6O10,Mr=463.24;晶胞参数:a=0.69527(10)nm,b=1.12250(15)nm,c=1.20352(17)nm,β=97.740(2)°,V=0.9307(2)(nm)3,Z=2,Dc=1.653 mg/m3,F(000)=474,μ=0.989 mm-1,最终偏离因子R1=0.0301,wR2=0.0791。配合物基本单元中含有一个Co(Ⅱ)离子、两分子吡啶酰胺、两分子配位水和两分子硝酸根离子。Co2 离子为六配位的畸变的八面体构型。另外,配合物中存在着丰富的氢键,这些分子间氢键相互加强了相邻单元间的结合,使晶体呈现三维网络超分子结构。     

[Ni(phen)_2·Co(phen)_2·2Co(DPC)_2·4H_2O]·13H_2O双金属配合物的合成及其晶体结构

采用水热法成功合成了一种结构新颖的二维层状钴镍双金属配合物[Ni(phen)2·Co(phen)2·2Co(DPC)2·4H2O]·13H2O(phen=1,10-菲啰啉,DPC=2,6-吡啶二羧酸),采用单晶X射线衍射对其结构进行了表征。结果表明该配合物属于三斜晶系、P1空间群,其晶胞参数为:Mr=1922.98,a=10.0585(18)nm,b=14.684(3)nm,c=14.931(3)nm,α=74.078(6)°,β=78.399(6)°,γ=75.279(6)°,V=2030.5(7)nm3,Z=1。     

热分解二聚体锰配合物制备氧化锰纳米材料

采用MnCl2,1,10-邻菲罗啉与1,6-萘二磺酸钠水热合成得到了具有二聚体结构的锰配合物[Mn(1,6-nds)(phen)2(H2O)]2·(CH3OH)3·(H2O)2(1,6-nds=1,6-萘二磺酸根离子,phen=1,10-邻菲罗啉)。在850℃下焙烧处理该配合物。采用X-射线衍射、热重分析和透射电子显微镜等手段表征了高温处理得到的产物。热重分析结果表明:该配合物的起始分解温度为185℃;X-射线衍射的结果说明焙烧后的产物是氧化锰;TEM表征结果表明:氧化锰纳米颗粒的直径在40~230nm之间。采用热分解二聚体锰配合物制备纳米氧化锰的方法具有效率高,简单和无污染等特点。     

双水杨醛合铜(Ⅱ)配合物的合成及抗肿瘤活性

通过铜(Ⅱ)离子诱导N-亚水杨基-4-氨基-3,5-二溴苯磺酰胺Schiff碱水解合成了双水杨醛合铜(Ⅱ)配合物。结构测试表明,双水杨醛合铜(Ⅱ)配合物是一个以Cu(Ⅱ)离子为对称中心的四配位平面四边形,晶体属于单斜晶系,空间群为P2(1)/n,a=0.8646(3)nm,b=1.1231(2)nm,c=1.1146(4)nm;α=74.294(8)°,β=88.6715(6)°,γ=86.9573(7)°,Z=2,最终偏差因子R_1=0.0592,ωR_2=0.1770,并通过分子间的作用力形成三维网状空间结构;抗肿瘤活性检测表明,双水杨醛合铜配合物对MCF-7、HepG2、Hela、PC-3和KB肿瘤细胞均有的抑制活性,并强于配体水杨醛。     

〔Co(CHZ)_3〕(ClO_4)_2的制备、分子结构及爆炸性能研究

报道了高氯酸三碳酰肼合钴()的制备、分子结构及其爆炸性能。该配合物的分子式为:〔Co(CHZ)3〕(ClO4)2。其晶体属于单斜晶系,空间群为P21/n,晶胞参数为:a=10.0490(10)×10-10m,b=8.5350(1)×10-10m,c=21.430(4)×10-10m,β=101.170(1)°。最终偏离因子R1=0.0657,wR2=0.1380。在该配合物中,钴离子的配位数为6,与之配合的碳酰肼分子为三个,每个碳酰肼分子都作为二齿配体,中心原子与它的六个配位原子形成畸变八面体结构。该配合物具有良好起爆能力,可作为起爆药用于雷管中。     

配合物[Co(C9H6NO)3]·C2H5OH的醇热合成与表征

采用醇热合成法合成了标题化合物[Co(C9H6NO)3]·C2H5OH,测定了其晶体结构,晶体属于单斜晶系,P21/n空间群,晶体学参数为:a=1.1268(2)nm,b=1.3034(2)nm,c=1.6606nm(3),β=94.15(1)°,ν=2.4325(8)nm3,Ζ=4,Dc=1.468Mg/m3,F(000)=1112.配合物中有三个N原子和三个O原子与中心离子Co(Ⅲ)配位,形成畸变的八面体配位环境.配合物通过分子间氢键作用与溶剂乙醇分子形成二维超分子的晶体结构.     

超分子化合物[Co(HL)(2,2'-bipy)2]·9.5H2O的合成、晶体结构和热性质

合成了超分子化合物[Co(HL)(2,2'-bipy)2]·9.5H2O(H3L=对羧基苯磺酰甘氨酸,2,2'-bipy=2,2'-联吡啶),并通过单晶X射线衍射确定了晶体结构,晶体结构分析表明化合物C29H42CoN5O15.5S属单斜品系,C2/c空间群.Co(Ⅱ)离子为6配位的八面体结构,对羧基苯磺酰甘氨酸作为双齿配体与Co(Ⅱ)离子配位,2,2'-联吡啶和co(Ⅱ)离子双齿螯合配位.配合物通过氧键和π-π堆积作用形成三维结构,配合物中含有一个由18个水分子组成的独立水簇.在氮气气氛中对该化合物进行了热重分析,结果表明:该化合物在30.1℃时开始失重,440℃时分解完全.     

以( )-脱氢枞胺为原料合成( )-弥罗松酚

报道了以(+)-脱氢枞胺为起始原料,通过两条路线合成生物活性的二萜化合物(+)-弥罗松酚。路线(1):(+)-脱氢枞胺在羟氨-O-磺酸和氢氧化钠作用下还原脱氨生成脱氢松香烷,再经Friedele-Crafts乙酰化、BaeyerVilliger氧化、水解生成(+)-弥罗松酚,总产率29.5%。路线(2):(+)-脱氢枞胺还原脱氨,然后与过氧化邻苯二甲酰反应得到(+)-弥罗松酚,总产率31.9%。     

Photopyroelectric Spectroscopic Studies of ZnO-MnO(2)-Co(3)O(4)-V(2)O(5) Ceramics

Photopyroelectric (PPE) spectroscopy is a nondestructive tool that is used to study the optical properties of the ceramics (ZnO + 0.4MnO(2) + 0.4Co(3)O(4) + xV(2)O(5)), x = 0-1 mol%. Wavelength of incident light, modulated at 10 Hz, was in the range of 300-800 nm. PPE spectrum with reference to the doping level and sintering temperature is discussed. Optical energy band-gap (E(g)) was 2.11 eV for 0.3 mol% V(2)O(5) at a sintering temperature of 1025 °C as determined from the plot (ρhυ)(2)versushυ. With a further increase in V(2)O(5), the value of E(g) was found to be 2.59 eV. Steepness factor 'σ(A)' and 'σ(B)', which characterize the slope of exponential optical absorption, is discussed with reference to the variation of E(g). XRD, SEM and EDAX are also used for characterization of the ceramic. For this ceramic, the maximum relative density and grain size was observed to be 91.8% and 9.5 μm, respectively.     

Biological Properties of IRIM, the Iridium(III) Analogue of (Imidazolium (Bisimidazole) Tetrachlororuthenate) (ICR)

Some biological aspects of the new complex imidazolium bisimidazole tetrachloro iridate(III)-IRIM- the iridium(III) analogue of ICR, were considered. More in detail the conformational effects produced by IRIM on DNA and the cytotoxic properties of IRIM on some selected human cell lines were measured. Dialysis experiments and DNA thermal denaturation studies are suggestive of poor binding of IRIM to DNA; formation of interstrand crosslinks is not observed. In any case CD measurements suggest that addition of increasing amounts of IRIM to calf thymus DNA results into significant spectral changes, that are diagnostic of a direct interaction with DNA. A number of experiments carried out on the A2780 human ovarian carcinoma, B16 murine melanoma, MCF7 and TS mammary adenocarcinoma tumor cell lines strongly point out that IRIM does not exhibit significant growth inhibition effects within the concentration range 10(-4)-10(-6) M. It is suggested that the lower biological effects of IRIM compared to ICR are a consequence of the larger kinetic inertness of the iridium(III) center with respect to ruthenium(III).     

镀银镍粉/硅橡胶高导电复合材料的制备及性能研究

研究镀银镍粉体积分数对镀银镍粉/硅橡胶高导电复合材料性能的影响。结果表明:随着镀银镍粉体积分数增大,复合材料的邵尔A型硬度增大,拉断伸长率快速减小,体积电阻率减小并出现明显逾渗现象;当镀银镍粉体积分数为0.44时,复合材料具有良好的导电稳定性和优异的电磁屏蔽效能,但耐电化学腐蚀性能较差。     

Rheological behavior of blends of poly(methyl methacrylate) (PMMA) and poly(acrylonitrile-stat-styrene)-graft-polybutadiene (ABS)

The rheological behavior of blends of poly(methyl methacrylate) (PMMA) and poly(acrylonitrile-stat-styrene)-graft-polybutadiene (ABS) was investigated using a cone-and-plate rheometer. The rheological properties measured were shear stress (σ₁₂), viscosity (η), and first normal stress difference (N₁) as functions of shear rate (\documentclass{article}\pagestyle{empty}\begin{document}$ \dot \gamma$ \end{document}) in steady shearing flow, and storage modulus (G′) and loss modulus (G″) as functions of frequency (ω) in oscillatory shearing flow. It has been found that the rheological behavior of blends of ABS and PMMA was very similar to that of blends of poly(styrene-stat-acrylonitrile) (SAN) and PMMA, in that N₁ in logarithmic plots of N₁ versus σ₁₂, and G′ in logarithmic plots of G′ versus G″, vary regularly with blend composition. This has led us to conclude that the rubber particles that are grafted on an SAN resinous matrix in ABS resin plays only a minor role in influencing the compatibility of ABS/PMMA blends, and that the SAN chains attached to the surface of rubber particles, and the SAN matrix phase, play a major role in compatibilizing ABS resin with PMMA.     

Thermal studies of blends of poly(phenylene sulfide) (PPS) with poly(phenylene sulfide sulfone) (PPSS) and with poly(phenylene sulfide ether) (PPSE)

The miscibilities of poly(phenylene) sulfide/poly(phenylene sulfide sulfone) (PPS/PPSS) and poly(phenylene) sulfide/poly(phenylene sulfide ether) (PPS/PPSE) blends were invesigated in terms of shifts of glass transition temperatures T_g of pure PPS, PPSS, a dn PPSE. The crystallization kinetics of PPS/PPSS blends was also studied as a function of molar composition. The PPS/PPSS and PPS/PPSE blends are respectively partially and fully miscible. PPSE shows a plasticizing effect on PPS as does PPS on PPSS, which necessarily improves te processibility in the respective systems. We can control T_g and melting temperature T_m of PPS by varying amounts of PPSE in blends. The melt crystallization temperature T_mc of PPS/PPSE blends was higher than that of the PPSE homopolymer. Therefore, these blends require shorter cycle times in processing than pure PPSE. The overall rate of crystallization for PPS/PPSS blends follows the Avrami equation with an exponent ?2. The maximal rate of crystallization for PPS/PPSS blends occurs at a temperatre higher by 10°C than that for PPS, while the crystallization half time t_1/2 is 4 times shorter. In the cold crystallization range, crystal growth rates increase and Avrami exponents decrease significantly as the temperature increases.     

Adhesion of UV-Cured Laminates of Poly(ethylene-2,6-naphthalate) (PEN) and Poly(ethylene terephthalate) (PET) films

This paper describes the properties of an ultraviolet (UV) curable laminating adhesive system that can be used with PEN, PET and UV-stabilized PET films. The adhesive system that contains (2,4,6-trimethylbenzoyl) diphenylphosphine oxide (TPO) as photoinitiator was optimally cured with a V-bulb fitted ultraviolet irradiator. The laminated structures built with this adhesive system and PEN, PET and UV-stabilized PET films showed a large manufacturing operating window, both in terms of adhesive layer thickness, initial peel strengths above 1500 N/m, V- and D-bulb UV sources and curing speeds from 5– 10 m/min. The 600-h dry heat aging tests indicated that the UV-stabilized PET films underwent less than approximately 1% decrease in light transmission and less than a 1% gain in color. The UV-stabilized PET film and its laminate showed particularly strong retention of optical properties under damp aging and QUV weathering, compared to PEN and non-UV-stabilized PET films. Finally, the peel strengths of the laminates were retained to greater than 1300 N/m for laminate structures of 50 μm film thickness, whereas structures made from thicker films retained approx. 40–60% (700–1100 N/m) of their initial peel strength.     

Photooxidative stability of substituted poly(phenylene vinylene) (PPV) and poly(phenylene acetylene) (PPA)

The addition of side groups to improve the photooxidative stability of polymers used in polymer-based light-emitting diodes (LEDs) is explored. Infrared spectroscopy and computational chemistry techniques are used to study the effects of chemical substitution of the reactive vinylene moiety in poly(phenylene vinylene) (PPV). The bond order of the vinylene group in small oligomers is calculated using semiempirical techniques to assess the improvement in stability toward oxidants such as singlet oxygen. We find that PPV dimers allow relative comparisons across a range of possible substitutions. Experimental results correlate well with these calculations. The addition of electron-withdrawing substituents, such as nitrile groups, to the vinylene moiety is found to be particularly effective in reducing the reactivity of alkoxy-substituted PPV toward singlet oxygen. The photooxidative stability of a poly(phenylene acetylene) (PPA) derivative is also studied. It appears that this family of polymers is more stable toward photooxidation than are its PPV analogs. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 2451–2458, 1998     

Photo-Initiated Lamination of Polyethylene (PE) and Poly(ethylene terephthalate) (PET)

Besides plasma-based processes, photo-initiated surface modifications have an interesting potential for adhesion promotion. This is of special interest with applications ranging from classical finishing to composites. Photo-chemical processes using continuous UV sources — monochromatic as well as broad band — are based on radical activation and ensuing reaction with the atmosphere. Achievable effects are addition of atoms — e.g., introduction of oxygen (photo-oxidation) resulting in increased surface energy — or grafting of functional groups. Both have certain potentials for adhesion promotion in a physico-chemical way. Based on the fundamental scheme of these processes — i.e., a photon-initiated radical reaction at the substrate-atmosphere interface — a direct 'inter-linking' of coating polymer and substrate is presented in this paper. The principal idea is to apply a thin layer of coating polymer on the substrate and irradiate this composite system at certain UV wavelengths. Given a low absorption of the radiation by the thin coating and — at the same time — a high absorption by the substrate, the radiation will penetrate the coating layer and generate radicals at the interface, which will induce cross-linking between the coating polymer and substrate. It is shown that for the example of laminates of polyethylene (PE) film on fabrics made of poly(ethylene terephthalate) (PET), extremely high adhesion strenghths are achieved without any use of additional adhesion promoters.     

2-(2-(6-氯己氧基)乙氧基)乙氨的合成

2-(2-氨基乙氧基)乙醇溶于乙醇,用叔丁氧羰基酸酐(Boc2O)进行氨基保护得,N-叔丁氧羰基-2-(2-氨基乙氧基)乙醇,与1-氯-6-溴己烷在正已烷及50% NaOH和四丁基溴化铵作用下缩合,得N-叔丁氧羰基-2-(2-(6-氯己氧基)乙氧基)乙氨,最后在二氯甲烷及三氟乙酸混合液中脱保护,得标题化合物,总收率11...