顺式-和反式-二氯二(乙硫醚)合铂(Ⅱ)的合成和结构表征

研究了2种硅氢化反应催化剂顺式-和反式-二氯二(乙硫醚)合铂(Ⅱ)的合成方法,并通过红外光谱、质谱、1H和13C核磁共振对这两种配合物进行了表征,确证了其化学结构。结果表明:适量的乙硫醚得到的是反式-二氯二(乙硫醚)合铂(Ⅱ),而过量的乙硫醚得到的是顺式-二氯二(乙硫醚)合铂(Ⅱ)。     

甲基丙二酸-(反式-1,2-二甲胺基环丁烷)合铂(II)的合成、结构及抗肿瘤活性

通过水解法合成了甲基丙二酸-(反式-1,2-二甲胺基环丁烷)合铂(Ⅱ)。采用元素分析、质谱(ESI-MS)、红外光谱(IR)和核磁共振氢谱(¹H NMR)确证了该配合物的组成和化学结构。采用MTS法评价其抗肿瘤活性,发现该配合物对常见5种癌细胞的生长有明显的抑制活性。     

顺式-水杨酸-(反式-(-)-1,2-环己二胺)合铂(II)的合成、表征及抗肿瘤活性

用顺式-二碘-(反式-(-)-1,2-环己二胺)合铂(Ⅱ)先后与硝酸银和水杨酸反应,制备得到新的铂配合物顺式-水杨酸-(反式-(-)-1,2-环己二胺)合铂(Ⅱ)。采用元素分析、质谱、核磁共振氢谱和红外光谱等方法分析了其组成和结构,采用SRB比色法对配合物进行了初步体外活性评价。结果显示合成的化合物结构与理论一致,化合物对肺癌细胞株(A549)和口腔表皮样癌细胞株(KB)的IC50值分别为2.3和3.1μg/mL。     

双(2,2,6,6-四甲基-3,5-庚二酮酸)钯(Ⅱ)的合成及其晶体结构

以二氯化钯和2,2,6,6-四甲基-3,5-庚二酮为原料,在甲醇中合成了一种新的β二酮前驱体—双(2,2,6,6-四甲基-3,5-庚二酮酸)钯(Ⅱ)。通过元素分析、红外光谱、核磁共振氢谱和单晶X射线衍射技术对其进行了表征,确定了配合物的结构组成。用热重法分析了配合物在氮气气氛中的热分解行为,当温度升到295℃,前驱体基本挥发完全,表明双(2,2,6,6-四甲基-3,5-庚二酮酸)钯(Ⅱ)是一种理想的MOCVD前驱体。     

双(2,2,6,6-四甲基-3,5-庚二酮酸)钯(Ⅱ)的制备及成膜性能

以二氯化钯和2,2,6,6-四甲基-3,5-庚二酮为原料,在甲醇中合成了一种新的β二酮前驱体-双(2,2,6,6-四甲基-3,5-庚二酮酸)钯(Ⅱ)。通过元素分析、红外光谱、核磁共振氢谱及单晶X射线衍射等技术对合成的前驱体进行了结构表征。热重-差热分析表明,在N2气氛中,当温度升到291℃时,前驱体基本挥发完全。采用合成的前驱体通过金属有机化学气相沉积(MOCVD)技术在石英上沉积制备钯薄膜,利用XRD和AFM分析手段对薄膜的结构和表面形貌进行了表征。结果表明,所得到的薄膜纯净,无其他杂质存在,薄膜表面连续、致密。     

铑(Ⅲ)氯水配合物在水溶液中的热力学和动力学平衡行为研究

作者详细研究了各铑(Ⅲ)氯水配合物在水溶液中随时间、温度变化而变化的规律,获得的结果表明,CT浓度是影响铑(Ⅲ)在各种态中分布的主要因数,但是,对于阴离子种态,其放置的时间和温度也是不可忽略的。对于下面这个短的平衡反应链：fac-[RhCl3(H2O)3]→←K34^c cis-[RhCl4(H2O)2]^-→←K45^c [RhCl5(H2O)]^2-→←K56^c [RhCl6]^3-作者系统的研究了在不同温度下其各种态的分布,结果发现,fac-[RhCl3(H2O)3]的含量随温度的升高而增加,而cis-[RhCl4(H2O)2]^-、RhCl5(H2O)]^2-和[RhCl6]^3-却随温度的升高而降低。氯代和水合作为铑(Ⅲ)氯水配合物在溶液中的竞争反应,在放置开始,氯代占优势,但随时间的延长,水合逐渐趋于优势。     

三(2,2,6,6-四甲基-3,5-庚二酮)酸钌(Ⅲ)的合成及性质

以三氯化钌和2,2,6,6-四甲基-3,5-庚二酮为原料,在甲醇中合成了β-二酮前驱体—三(2,2,6,6-四甲基-3,5-庚二酮)酸钌(Ⅲ)。通过元素分析、红外光谱、核磁共振谱、紫外-可见光谱等对其进行了表征,确定了配合物的结构组成。采用TG-DTA分析了配合物在空气和氮气中的热分解行为,为MOCVD镀钌和钌的氧化物薄膜工艺提供热力学数据与参考。     

铅离子-苯甲羟肟酸配合物捕收剂(Pb-BHA)的单晶结构分析

铅离子-苯甲羟肟酸配合物捕收剂(Pb-BHA)在钨矿、锡石和钛铁矿等氧化矿浮选中展现出良好的浮选性能和应用前景,但其精确分子结构尚不清楚,阻碍了配合物浮选作用机理的深入认识和金属基捕收剂分子设计的开展。本文培养了铅离子与BHA摩尔比分别为1∶1和2∶1的两种Pb-BHA配合物单晶(配合物1和配合物2),并采用X射线结构分析方法对其结构进行解析,包括配合物晶体结构、分子结构、空间堆积结构、分子间相互作用等。结果表明：配合物1的分子式为Pb₆L₈(NO₃)₄ (HL=BHA),配合物2的分子式为[Pb₆L₈(NO₃)₃]NO₃,铅离子与配体氧原子配位形成非平面“O,O”五元环螯合物构型,铅离子配位数为五配位、六配位和七配位。配合物分子通过Pb—O键与临近配合物相键接形成具有单体重复结构的三维扩展堆积聚合物。配合物中弱相互作用以O···H、H···H、Pb···O为主,π-π相互作用在分子间相互作...     

Pr_(0.7)Zr_(0.3)O_(2-δ)选择性氧化甲烷制取合成气:氧载体稳定性（英文）

以共沉淀法制备的Pr0.7Zr0.3O2-δ固溶体作为氧载体,研究其在选择性氧化甲烷制取合成气工艺(CH4/空气氧化还原循环)中的服役性能。结合X射线衍射(XRD)、H2-程序升温还原(H2-TPR)、O2-程序升温脱附(O2-TPD)、比表面测试(BET)、X射线光电子能谱(XPS)表征手段描述氧载体在氧化还原循环反应过程中物化特性演变。结果表明,Pr0.7Zr0.3O2-δ固溶体在氧化还原反应中保持较高的甲烷反应活性与CO选择性,且能够保持反应性能稳定(CO选择性为83.5%~83.1%)。随着循环反应的进行,Pr-Zr固溶体保持了较高的热稳定性,但是表面氧的消失导致其还原性能下降。然而,表面氧的消失促进了氧空位的增加从而在一定程度上增强了氧移动能力,使足够的晶格氧参与到甲烷选择性氧化反应中,保证了较高的反应活性。通过比较新鲜、循环与老化后材料结构与还原性能,认为甲烷选择性氧化制取合成气工艺中的热点问题可以避免。     

((R)-(-)-1,2-丙二胺)(1,3-丙二酸)合铂(II)的合成、表征及抗肿瘤活性研究

以1,2-丙二胺为起始原料,经手性拆分得到R-(-)-1,2-丙二胺,再同氯亚铂酸钾、碘化钾、硝酸银、1,3-丙二酸钠等物质反应,制成((R)-(-)-1,2-丙二胺)(1,3-丙二酸)合铂(II),通过元素分析、红外光谱、核磁共振等对其进行化恘结构确证,结果表明所合成产品同理论一致,并进行初步体外活性评价,表明该化合物对于肺癌A-549及白血病HL-60肿瘤细胞有一定活性。     

Catalytic-kinetic spectrophotometric determination of vanadium （V） based on the Celestine blue-bromate-vanadium （V）-citric acid reaction

A novel sensitive and relatively selective kinetic method is presented for the determination of V(V) based on its catalytic effect on the oxidation reaction of Celestine blue by potassium bromate in the presence of citric acid as an activator.The reaction was monitored spectrophotometrically by measuring the decrease in absorbance of Celestine blue at a maximum absorption wavelength of 540 nm between 0.5 and 9 min(the fixed-time method) in an H3PO4 medium at 45°C.The effect of various parameters such as con...     

Nd_(60)Fe_(30)Al_(10)大块非晶的制备及其热稳定性

采用熔渣包覆水淬法获得了直径为 ６ ｍｍ,长度为 ５０ ｍｍ的非晶 Ｎｄ６０Ｆｅ３０Ａｌ１０合金,并对其非晶形成能力进行了研究．在三元系非晶合金中,除 Ｐｄ基合金外,这是目前所报道的采用水淬法所能获得的最大尺寸的非晶合金 对 Ｎｄ７０Ｆｅ２０Ａｌ１０,在同样的条件下可获得直径为 ３ ｍｍ,长度为 ５０ ｍｍ的部分非晶组织 与普通铜模铸造方法所获得的临界直径相比,前者提高了 ２ ｍｍ,而后者降低了 ４ ｍｍ．利用 ＤＴＡ 和 ＤＳＣ 对 Ｎｄ６０Ｆｅ３０Ａｌ１０合金的熔点和形成能力进行了分析,所计算的临界冷却速率为０．５５Ｋ／ｓ,表明该合金具有较大的非晶形成能力．表观晶化能计算结果和 ＤＳＣ曲线分析表明,Ｎｄ６０Ｆｅ３０Ａｌ１０非晶的热稳定性较低     

Surface modifications of polycarbonate (PC) and acrylonitrile butadiene styrene (ABS) copolymer by treatment with atmospheric plasma

Two engineering thermoplastic polymers (polycarbonate, PC, and acrylonitrile butadiene styrene copolymer, ABS) were treated with atmospheric plasma torch using different treatment rates (1, 5 and 10 m/min). The modifications produced by the treatment were analysed by contact angle measurements, XPS, SEM and ATR-IR spectroscopy. Particular emphasis was placed on the ageing (up to 30 days) after atmospheric plasma treatment on both polymers.The slower the atmospheric plasma treatment, the greater the wettability of the treated polymers. The decrease in water contact angle was mainly ascribed to a significant increase in oxygen content due to the formation of carboxylic and hydroxyl groups and a decrease in the carbon content on the polymer surfaces. After natural ageing, there was an increase in the water contact angle, although the values of the untreated polymer surface were never reached.     

快速压铸法制备(Zr_(0.55)Al_(0.10)Ni_(0.05)Cu_(0.30))_98Er_2多孔非晶合金

采用快速压铸法制备了多孔非晶合金。利用NaCl颗粒作为预制型,将熔融的合金倒入卧式压铸机的容杯中进行快速压铸,然后去除盐型,得到直径达40mm、长度大于10mm、孔隙率大于50%、孔隙直径可控制在0.3～3mm之间的(Zr0.55Al0.10Ni0.05Cu0.30)98Er2多孔非晶合金。XRD分析表明所制备的多孔试样组织为非晶结构。采用SEM观察到孔隙之间具有良好的连通性,孔壁厚度小于1mm。热分析结果表明该泡沫的玻璃转变温度、晶化温度和晶化放热量分别为388℃、476℃和-37J/g,与实体非晶合金一致。     

热处理对Co_(38)Ni_(34)Al_(28-x)Cu_x合金组织和显微硬度的影响

在Co-Ni-Al系合金的基础上用Cu部分代替Al,制备4种不同成分的合金,研究热处理对Co38Ni34Al28-xCux显微组织和显微硬度的影响。结果表明,Co38Ni34Al27.5Cu0.5合金经1350℃×2 h加热、冰水冷却至室温处理后,β基体内出现马氏体,而Co38Ni34Al27Cu1则在1350℃×2 h和1300℃×4 h处理时都出现马氏体。随铜含量的增加和铝含量的减少,合金β相晶粒变小,γ相晶粒和含量变大。Co38Ni34Al27.5Cu0.5的显微硬度随温度升高而升高,在β相晶粒内出现马氏体时,Co38Ni34Al27Cu1合金的显微硬度骤降。     

Surface spectroscopy and temperature-programmed desorption studies of the interaction of water vapor with Ni3(Al, Ti) (100) and (111) surfaces as a function of temperature

The interaction of water vapor with single crystal Ni₃(Al, Ti) has been studied with Auger electron spectroscopy, photoemission spectroscopy and thermal desorption. Water adsorbs molecularly onto the (111) and (100) surfaces at 140 K. When warmed up to room temperature, water remains as an intact molecule on (111), but dissociates to surface hydroxyl and atomic oxygen on (100). The latter process is accompanied by the evolution of hydrogen and oxidation of Al. It appears that the dissociation of water is structure-sensitive and that Al is the active species in controlling the dissociation of water on Ni₃Al surfaces.     

Spectroelectrochemical studies of poly(3,4-ethylenedioxythiophene) in aqueous medium

The in situ electrochemical doping process of the poly(3,4-ethylenedioxythiophene) (PEDT) has been studied in an aqueous micellar medium by means of optical spectroscopies. The cyclic voltammetry (CV) and optical absorption results were compared with previous ones obtained either in acetonitrile or in water without surfactant. No significant effect of the medium, water or acetonitrile, was found, but the presence or absence of surfactant in water give rise to different doping CVs, especially in the reductive part. Resonant Raman scattering experiments show a behavior of PEDT different from the one in acetonitrile. The doping mechanism we deduced from these results should imply a variation between an “intermediate” electronic conformation of the polymer in the reduced state to a predominant benzenic one during doping. The comparison with our previous results obtained in acetonitrile leads us to think that the reduced PEDT is in fact slightly oxidized by the aqueous medium.     

Polypyrrole/thermally sensitive polyelectrolyte composite (I)

Polypyrrole (PPy) was prepared by electrochemical polymerization with the polyelectrolyte (PE) as a dopant. The PEs were copolymers of the water soluble polymers and 2-acrylamido-2-methyl-1-propane sulfonic acid (AMPS). The water soluble polymers were thermally sensitive poly(N-isopropyl acrylamide), P(NiPAAm) and thermally insensitive poly(acrylamide), P(AAm). The surface of PPy/PE film observed by SEM was smoother than that of PPy film doped with a monoelectrolyte. PPy/PE composites were fairly conductive, whose electrical conductivities measured by the four-probe method were in the range of 10⁻¹ to 10⁻² S/cm. The characteristics of cation and anion exchange during redox processes were investigated by applying potential from −0.8 to 0.5 V vs. an Ag/AgCl reference electrode to the PPy. The effect of temperature on the doping–dedoping behavior and mass change of PPy composites was investigated by potentiodynamic voltammetry and electrochemical quartz crystal microbalance (EQCM). The electrochemical activity of the PPy/PE gradually decreased with increasing temperature. PPy/P(NiPAAm/AMPS) showed much greater mass change with increasing temperature than PPy/P(AAm/AMPS), mainly because of a decrease in the degree of swelling of thermally sensitive moiety. This confirms that PPy/P(NiPAAm/AMPS) possesses temperature-dependent electrochemical activity, which indicates that it can be utilized for many attractive applications. The thermal volume transition temperature of PPy/P(NiPAAm/AMPS) was estimated from the slope change of mass decrease. The transition temperature of the oxidized state of PPy/P(NiPAAm/AMPS) was higher than that of the reduced state.     

Non-woven fabric of poly(N-isopropylacrylamide) nanofibers fabricated by electrospinning

We have succeeded in fabricating non-woven fabric of a typical thermo-responsive polymer, poly(N-isopropylacrylamide) (PNIPAM) with a low critical solution temperature (LCST) in water at 32 °C, by the electrospinning, a simple and facile method which enables to form a mat of nanofibers directly deposited on the grounded target. The PNIPAM nanofibers electrospun at concentration and applied voltage of 15 wt% and 20 kV, respectively, had an average diameter of 165 nm. The moisture sorption isotherms of the PNIPAM nanofibers belonged to the type II of IUPAC classification, in which the interaction between polymer and water molecule was stronger than that between water molecules.     

Comparing thermal and mechanochemical decomposition of ammonium paratungstate (APT)

In this research, the possibility of mechanochemical decomposition of ammonium paratungstate (APT) has been studied, and compared with thermal decomposition method. For this purpose, APT powders were milled using a planetary ball mill up to 36 h and under air atmosphere. For thermal decomposition, APT powders were heated for 30 minutes at 300 and 450 °C in air atmosphere. X-ray diffraction (XRD), differential scanning calorimeter (DSC), and thermo gravimetric analyzer (TGA) were used to study the decomposition progress, and products. The XRD results showed that APT completely decomposed to WO₃ by thermal decomposition, while the final product of mechanochemical decomposition was WO₃ (H₂O)_0.5. According to DSC and TGA results, during thermal decomposition, ammonia and water released in four steps, and leaved WO₃. By mechanochemical decomposition crystal water and ammonia liberated from APT structure, but structural water of APT remained. In both methods, an X-ray amorphous phase was the intermediate product of APT decomposition.