铂类抗肿瘤药物甲啶铂破坏性试验研究

根据药品稳定性试验的要求,采用高效液相色谱分析方法研究甲啶铂在酸、碱、氧化和还原条件下的稳定性,并研究了不同p H值对甲啶铂稳定性的影响,所有溶剂均用0.9%Na Cl溶液配制。研究结果表明,甲啶铂在0.01 mol/L HCl溶液中放置24 h含量降解约7%;在0.01 mol/L Na OH溶液中放置24 h含量降解约78%;在0.3%H2O2溶液中放置24 h含量降解约49%;在0.01%Na HSO3溶液中放置24 h含量降解约9%;p H太高或者太低均不利于甲啶铂的稳定,最稳定的p H在3~5之间。结果说明,甲啶铂在碱性和氧化性环境中极不稳定,在还原性和酸性环境中相对稳定,但还原剂和酸的加入量需严格控制。     

铂(Ⅱ)类抗癌药物的溶液化学反应特性

铂（Ⅱ）类抗癌药物的溶液化学反应特性是此类药物化学基础理论的重要组成部分,本文综述了此类药物的溶液化学反应研究状况,包括顺铂、碳铂、草酸铂等的水合反应以及与Cl∧-、生物分子等的取代反应。     

甲啶铂在玻碳电极上的电化学行为及其与DNA相互作用研究

采用循环伏安法(CV)和差分脉冲伏安法(DPV),研究了甲啶铂在多壁碳纳米管-离子液体修饰玻碳电极(MWNTs-[ODMIM]PF6/GCE)上的电化学行为,建立了甲啶铂的测定方法;以紫外-可见光谱法和电化学方法相结合,研究了甲啶铂与DNA的嵌插结合作用。结果表明:甲啶铂在MWNTs-[ODMIM]PF6/GCE上有一对氧化还原峰,氧化峰电位Epa与还原峰电位Epc分别为-0.07 V、-0.36 V,峰电位之差为ΔE=0.29 V,Ipa/Ipc=1.11。在优化条件下,甲啶铂的氧化峰电流与其浓度在2.66~532μmol/L范围内成良好的线性关系(r=0.9994),检出限为1.33μmol/L。方法操作简便,准确可靠、灵敏度高,可用于甲啶铂含量的直接测定。     

抗肿瘤新药甲啶铂的合成工艺研究

为合成抗肿瘤药物甲啶铂，采用醋酸铵与K2PtCl4反应生成K[Pt(NH3)Cl3]，再先后与碘化钾、2-甲基吡啶、硝酸银、氯化钾反应生成甲啶铂。采用元素分析、质谱、核磁共振氢谱和红外光谱对其结构进行了表征。结果显示合成的化合物与理论一致，产率约为40%，可为甲啶铂的合成提供一条新的工艺路线。     

甲啶铂与牛血清白蛋白相互作用的荧光光谱研究

用稳态荧光光谱及时间分辨荧光技术研究水溶液中甲啶铂与牛血清白蛋白(BSA)的相互作用。加入甲啶铂后,BSA荧光发射峰从335 nm红移到337.5 nm,并伴随着荧光强度的猝灭,表明甲啶铂与BSA发生了相互作用;单指数拟合得到的荧光寿命结果证实,甲啶铂对BSA的猝灭为静态猝灭;荧光寿命的双指数拟合结果表明,BSA的内在荧光主要是由第212位和第134位的色氨酸残基贡献的,BSA中第212位色氨酸残基和苯丙氨酸残基可能是甲啶铂的靶向目标。     

JM216的水合反应及其稳定性影响因素

研究了JM2 1 6的水合反应动力学 ,并考察了光照、稀酸对其稳定性的影响。结果表明 ,JM2 1 6的水合反应为准一级反应 ,反应对JM2 1 6为一级 ,37°C时水合反应表观速率常数为kobs=5 0× 1 0 - 6 min- 1,半衰期t1 2 =96 2 5d。在光照下 ,JM2 1 6溶液稳定。而在稀HCl溶液中 ,随着酸浓度增加 ,JM2 1 6的稳定性降低 ,但在胃液酸度范围、口服用药时间内可保持稳定 ,因此口服用药过程不会影响JM2 1 6的稳定性。     

卡铂在氯化钠或葡萄糖水溶液中的取代动力学研究

用薄层色谱法确定在25℃时卡铂在氯化钠或葡萄糖水溶液中热反应的取代产物。用分光光度法测定在氯化钠水溶液中的热反应速率常数和低pH下的速率常数,探讨其反应和酸催化机理。用电导法测定卡铂在葡萄糖水溶液中的取代速率常数。通过比较,认为卡铂用葡萄糖作溶剂较好。     

酸度在抗癌新药卡铂光反应中之应用

用高效液相色谱研究卡铂的酸性溶液在３１３ｎｍ紫外光作用下的光化学反应，测定反应产物和量子产率。结果表明酸度在卡铂的光反应中起重要作用。还讨论酸度的作用机制。     

硫酸加压溶解法从氧化铝基废催化剂中回收铂

研究了硫酸加压溶解法从氧化铝基含铂废催化剂中回收铂。在高压釜中,反应温度130℃,压力4.5 kg/cm2,时间4 h,氧化铝载体的溶解效率较好;添加Ti Cl3溶液可将分散到溶液中的铂浓度降低至0.0005 g/L以下;富集物经溶解-精炼得到纯度大于99.98%的海绵铂,铂直收率为98.71%。     

制备条件对卡斯特铂催化剂稳定性影响的研究

研究了四甲基二乙烯基二硅氧烷(MviMvi)用量、反应温度、反应时间、其他因素对制备卡斯特铂[Karstedt铂]催化剂的影响,对其结构进行了探析。结果表明,n(MviMvi)/n(氯铂酸)比值为14:1,70 ℃下回流反应1.5 h为适宜反应条件,制备出的卡斯特铂催化剂的室温稳定性达6个月。制备过程的优化,优势结构的获得以及低挥发物质的及时去除都有利于卡斯特铂的稳定性。     

Effect of calcium ions on pitting corrosion and inhibition performance in CO2 corrosion of N80 steel

The electrochemical impedance spectroscopy (EIS) and polarization resistance technique were used to investigate the susceptibility of N80 steel to pitting corrosion under stagnant condition and the corrosion behavior under flowing condition with/without precorrosion in 3% NaCl solution, in 3% NaCl + 1.5% CaCl₂ solution and in 4.6% NaCl solution (equivalent Cl⁻ concentration to 3% NaCl + 1.5% CaCl₂ solution) saturated by CO₂ at 57 °C. The results showed that under stagnant condition the initiation period of pitting corrosion decreased with increasing Cl⁻ concentration, but at the same Cl⁻ concentration, Ca²⁺ could prolong the initiation period. Under flowing condition the corrosion rate without stagnant precorrosion was bigger than that with precorrosion, and the corrosion rate with precorrosion in 3% NaCl solution was bigger than that in 3% NaCl + 1.5% CaCl₂ solution. Inhibition of quaternary alkynoxymethyl amine (IMC-80-Q) under stagnant condition showed that the optimum inhibitor concentration significantly increased with the increase of Cl⁻ concentration from 3% NaCl solution to 4.6% NaCl solution, and for the solutions with the same Cl⁻ concentration, adding Ca²⁺ did not change the optimum inhibitor concentration.     

Corrosion behavior of as-cast and hot rolled pure magnesium in simulated physiological media

Magnesium is a biodegradable metal that has significant potential advantages as an implant material. However, the fast degradation rate in the biological environment has limits the application. In this article, corrosion behaviors of as-cast and hot rolled pure magnesium in 0.9% NaCl, Ringer’s, and Tas-SBF solutions were studied. Potentiodynamic polarization and hydrogen evolution test were employed to assess the corrosion behaviors. The magnesium specimens were characterized using field emission scanning electron microscopy equipped with energy-dispersive X-ray analysis and X-ray diffraction. The as-cast specimens in 0.9% NaCl and Ringer’s solutions had lower corrosion potentials and corrosion rates than the hot rolled specimens. However, the as-cast specimen in the Tas-SBF solution had a higher corrosion potential and a lower corrosion rate than the hot rolled specimen. Only the specimens in the Tas-SBF solution showed passivation behavior due to the presence of HCO₃ ^? ions. The hot rolled specimen could form apatite more easily on its surface than the as-cast specimen in Tas-SBF.

     

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。     

MoO42-与 Zn2+对镁合金在 NaCl 溶液中的协同缓蚀作用

采用动电位极化曲线法,结合腐蚀后的表面微观形貌及EDS能谱分析,研究了MoO42-与Zn2+对AZ31镁合金在3.5%NaCl溶液中的协同缓蚀性能。结果表明:0.005 mol/L Zn2+与0.05 mol/L钼酸钠联合作用,可有效抑制镁合金在NaCl溶液中的腐蚀,Zn2+促进MoO42-在合金表面的吸附,缓蚀效果优于单一的钼酸盐缓蚀剂。缓蚀机制是:钼酸盐与Zn2+协同作用,使镁合金表面形成更为致密的钝化膜,从而抑制镁合金的腐蚀。     

Physicochemical study of the nanodiamond surface

Suspensions of five types of ultrafine diamond of a detonation synthesis in distilled water and 0.9 mol/l NaCl solution were found to have pHs in the range of 3–6, which results from the intrinsic acidity of their surfaces. The possibility of quantitatively determining the protogenic groups of a surface is found using the pH-potentiometric method. The data on the kinetics of the varying pH of suspensions in water and 0.9 mol/l NaCl solution and the data on the curves of the alkali titration of the suspensions of nanodiamond in the indicated systems make it possible to infer the presence of one or two types of acid groups on the surface of a diamond. The constants of dissociation (pK ₁) of these groups on the assumption of their single-base nature are estimated. From 1 × 10⁻³−5 × 10⁻² mol/l chloride solutions of H[AuCl₄] and RhCl₃ on the surface of diamond, gold(III) and rhodium(III) are found to be adsorbed; the adsorption of methylene blue from its 2.5 × 10⁻⁴−5 × 10⁻⁴ mol/l solutions reaches more than 90% (upon adsorption from 5 ml of the initial solution by a 0.05-g nanodiamond).     

Inhibition of Tryptophan on AA 2024 in Chloride-Containing Solutions

The inhibitory effects of tryptophan on the corrosion of AA 2024 in 1 M HCl, 20% (wt.%) CaCl₂, and 3.5% (wt.%) NaCl solutions were investigated via polarization techniques, electrochemical impedance spectroscopy, and weight loss methods. The scanning electron microscope technique was employed to observe corrosion morphology. The results suggest that AA 2024 was corroded in these three corrosive media to some extent and that tryptophan can significantly inhibit the corrosion of aluminum alloys. The inhibition efficiency (η) increased with increasing concentrations of tryptophan, and the best inhibition efficiency exhibited was about 87% in 1 M HCl solution with 0.008 M tryptophan. Tryptophan acted as a cathodic corrosion inhibitor and affected the hydrogen evolution reaction, which was the main electrode reaction in the 1 M HCl solution. In solutions with 20% CaCl₂ and 3.5% NaCl, tryptophan was adsorbed onto anodic areas, thus increasing the activation energy of the interface reaction as an anodic corrosion inhibitor. The Dmol³ program of Material Studio 4.0 was used to obtain the optimized geometry of the tryptophan inhibitor and some quantum-chemical parameters. Front orbital distributions and Fukui indices indicate that the molecular active reaction zones were located in the indole ring of tryptophan.     

The influence of alkali-halide additions on the stress corrosion cracking of an austenitic stainless steel in MgCl2 solution

The influence of NaCl, NaBr, NaI additions on the stress corrosion cracking (s.c.c.) of Type 304 stainless steel in 38 wt% aqueous MgCl₂ solution at 135°C has been investigated. Slow strainrate and U-Bend tests, potentiodynamic measurements and fractographic observation were employed. The results indicate clearly that the addition of 1N NaI or NaBr to the boiling MgCl₂ solution prevents stress corrosion cracking of the steel while NaCl additions accelerates cracking. It is suggested that the addition of NaI inhibits mainly the cathodic process. The I^? ion is oxidized by the dissolved oxygen through the following reaction: 41^? + 4H⁺ + O₂ → 2I₂ + 2H₂O.Due to this reaction O₂ and H⁺ are not reacted cathodically with the metal. This process enhanced the cathodic inhibition effect and results in preventing s.c.c. of the AISI 304 stainless steel in 38 wt% MgCl₂ boiling solution.     

Comparison of the in vitro corrosion behavior of biodegradable pure Zn in SBF, 0.9% NaCl,and DMEM

Zn-based alloys are considered to be the new biodegradable implant materials due to their suitable degradation rate and good biocompatibility. The biocorrosion behavior of pure Zn in 0.9% NaCl, simulated body fluid, and Dulbecco's modified Eagle's medium (DMEM) was investigated by electrochemical and immersion tests. These tests revealed that pure Zn has the lowest corrosion rate in DMEM and the highest in 0.9% NaCl. Aggressive Cl⁻ has an important effect on the corrosion process. Buffering agents, amino acids, and glucose have a close connection with corrosion resistance. Among the three solutions, DMEM with a similar ion concentration and necessary nutriments is recommended as the more suitable choice for estimating biodegradable alloys' in vitro degradation.