两种新型水溶性庚铂衍生物的合成和抗癌活性研究

设计、合成出两种新型的水溶性庚铂衍生物cis-(4R,5R)-4,5-双(氨甲基)-2-乙基-1,3-二氧环戊烷·3-羟基-1,1-环丁烷二羧酸根合铂(Ⅱ)和cis-(4R,5R)-4,5-双(氨甲基)-2-甲基-1,3-二氧环戊烷·3-羟基-1,1-环丁烷二羧酸根合铂(Ⅱ),并采用元素分析、质谱、红外光谱和核磁共振谱表征了它们的化学结构。体内外抗癌试验表明,虽然它们的细胞毒性不如庚铂,但体内抗癌作用优于庚铂,且水溶性明显高于庚铂,值得进一步研究。     

cis-[(trans-1,2-双(氨甲基)环丁烷)(3-羟基-1,1-环丁烷二羧酸根)合铂(Ⅱ)]的合成和抗癌活性

通过对洛铂和卡铂的结构进行重组和优化,合成了一种新型洛铂衍生物cis-[(trans-1,2-双(氨甲基)环丁烷)(3-羟基-1,1-环丁烷二羧酸根)合铂(Ⅱ)],采用元素分析、红外光谱、质谱和核磁共振表征了其化学结构,并考察了此化合物的水溶性和稳定性。应用标准SRB法测试了目标化合物对人肺癌细胞株(NCI-H460、A549)、人乳腺癌细胞株(DU4475)、人白血病细胞株(Sup-B15)生长的抑制活性,评价了它对人肺癌细胞NCI-H460裸鼠移植瘤的治疗作用。结果表明:目标化合物水溶性好、稳定,对多种癌细胞的生长有明显的抑制活性,IC_(50)均小于10μmol·L~(-1)。更重要的是,其体内对人肺癌细胞NCI-H460裸鼠移植瘤的治疗效果明显,与洛铂相当。     

碳铂类似物的合成,表征及对大鼠W—256肉瘤的抑制作用

合成了十八种〔PtA_2X〕·yH_2O,其中A分别为NH_3、CH_3NH_2、1/2乙二胺和1/2(2,3-二甲基-2,3-丁二胺),X分别为1,1-环丙烷二羧酸根(CPrDCA)、2-甲-1,1-环丙烷二羧酸根(2-M-CPrDCA)、2-甲-1,1-环丁烷二羧酸根(2-M-CBDCA)、1,2-环戊烷二羧酸根(CPDCA)和1,1-环已烷二羧酸根(CHDCA),并进行了表征。测定了配合物抑制大鼠W-256肉瘤的活性,发现配合物〔Pt(NH_3)_2X〕系列按X不同有以下的活性次序:CPrDCA>2-M-CPrDCA>CPDCA>CBDCA(碳铂)≥2-M-CBDCA。     

新型庚铂衍生物的合成

以D-酒石酸与芳香醛为起始原料,经缩合、氨解和还原反应制得中间体(4R,5R)-4,5-双(氨甲基)-1,3-二氧戊环类化合物(5a~5n);5a~5n分别与氯亚铂酸钾经配位反应合成了14个新型庚铂衍生物(6a~6n);6a~6j依次与硝酸银和丙二酸钠反应合成了10个新型庚铂衍生物,收率18.29%~50.91%,其结构经1H NMR,ESI-MS和元素分析表征。     

某些环丙烷二羧酸根合铂的结构研究

本文测定了1,1-环丙烷二羧酸根二氨合鉑(Ⅰ)、1,1-环丙烷二羧酸根二甲胺合铂(Ⅱ)以及1,1-环丙烷二羧酸根2,3-二甲基-2,3-丁二胺合鉑(Ⅲ)的晶体结构。晶体Ⅰ属正交晶系,空间群Pnma,a=6.571(2),b=9.709(3),c=14.205(5),Z=4,R=0.058;晶体Ⅱ属单斜晶系,空间群P2_1/n,a=9.648(3),b=8.720(2),c=12.770(4),β=107.12(2)°,Z=4,R=0.059;晶体Ⅲ属单斜晶系,空间群P2_1/m,a=6.494(1),b=19.638(3),c=6.606(1),β=94.44(1)°,Z=2,R=0.038。研究了三种晶体的电子结构,探讨了配位胺基对其生物活性的影响。     

cis-[（trans-1，2-双（氨甲基）环丁烷）（3-羟基-1，1-环丁烷二羧酸根）合铂（Ⅱ）]的合成和抗癌活性

通过对洛铂和卡铂的结构进行重组和优化,合成了一种新型洛铂衍生物cis-[（trans-1,2-双（氨甲基）环丁烷）（3-羟基-1,1-环丁烷二羧酸根）合铂（Ⅱ）],采用元素分析、红外光谱、质谱和核磁共振表征了其化学结构,并考察了此化合物的水溶性和稳定性。应用标准SRB法测试了目标化合物对人肺癌细胞株（NCI-H460、A549）、人乳腺癌细胞株（DU4475）、人白血病细胞株（Sup-B15）生长的抑制活性,评价了它对人肺癌细胞NCI-H460裸鼠移植瘤的治疗作用。结果表明：目标化合物水溶性好、稳定,对多种癌细胞的生长有明显的抑制活性,IC₅₀均小于10 μmol·L^-1。更重要的是,其体内对人肺癌细胞NCI-H460裸鼠移植瘤的治疗效果明显,与洛铂相当。     

替格瑞洛中间体的合成

以(3a S,4R,6S,6aR)-6-羟基-2,2-二甲基-四氢-3a H-环戊烷并[d][1,3]-二氧环戊烯-4-氨基甲酸苄酯为原料,经烯丙基取代、双键双羟基化、Smith降解、脱保护基和成盐反应,合成了替格瑞洛中间体(3a S,4R,6S,6aR)-6-(2-羟基乙氧基)-2,2-二甲基-四氢-3a H-环戊烷并[d][1,3]-二氧环戊烯-4-氨基草酸盐,总收率56.0%,其结构经1H NMR,13C NMR和ESI-MS确证。     

1R,35-1,2,2-三甲基-1,3-环戊二胺为配体的铂(Ⅱ)配合物的合成、表征和抗肿瘤活性

本文合成了9种含有由天然D(+)-樟脑衍生的1R,3S-1,2,2-三甲基-1,3-环戊二胺(A)为配体的铂(Ⅱ)配合物[Pt(Ⅱ)AX]{其中,X=(CH2)3C(COO-)2(1,1-环丁烷二羧酸根),2CH3OCH2COO-,2CH3CH2OCH2COO-,2CH3(CH2)3OCH2COO-,[OCH(CH3)COO]2-(乳酸根),(OCH2COO)2-(乙醇酸根),2CH3OCH2CH2OCH2OO-,2CH3CH2OCH2CH2OCH2COO-和2CH3(CH2)3OCH2CH2OCH2COO-).通过元素分析、热重分析、红外光谱、1H核磁共振谱和电喷雾质谱等对配合物进行了表征.体外生物活性测试表明,部分配合物对A549人肺癌细胞和HCT-116人结肠癌细胞具有较强的抗肿瘤活性.     

磷钨酸铜绿色催化合成缩醛(酮)及其催化活性测定

合成了绿色杂多酸盐催化剂磷钨酸铜;将环己酮、苯甲醛同乙二醇、1,2-丙二醇的缩合反应作为探针反应,测定了催化剂的催化活性,比较系统地考察了催化剂用量、物料配比、反应时间、带水剂用量等因素对反应产率的影响.结果表明:在底物醛(酮)用量0.2 mol、醛(酮)/乙二醇(1,2-丙二醇)摩尔比1.0/1.5、催化剂用量0.5 g、带水剂环己烷用量18 mL、一定温度下回流反应2.0 h,1,4-二氧螺[4,5]癸烷产率为83.3%,3-甲基-1,4-二氧螺[4,5]癸烷产率为89.7%,2-苯基-1,3-二氧环戊烷产率为66.7%,4-甲基-2-苯基-1,3-二氧环戊烷产率为78.5%.     

固体超强酸催化剂SO_4~(2-)/TiO_2-WO_3的制备及其催化性能研究

制备了固体超强酸催化剂SO2 -4/TiO2 WO3 ,并以丁酸丁酯的合成作为探针反应 ,系统考察了WO3 的含量、硫酸浸渍浓度、焙烧温度等制备条件对SO2 -4/TiO2 WO3 催化活性的影响 .实验表明 :制备催化剂的适宜条件为m(H2 WO4) =12 5 % ,硫酸浸渍浓度为 1 0mol·L-1,焙烧温度为 5 80℃ ,活化时间 3h .利用优化条件下制备的催化剂SO2 -4/TiO2 WO3 催化合成缩醛 (酮 ) ,在醛 /酮与二元醇 (乙二醇 ,1,2 丙二醇 )的投料摩尔比为 1∶1 5 ,催化剂的用量占反应物总投料质量的 0 5 % ,反应时间为 1h条件下 ,2 甲基 2 乙氧羰甲基 1,3 二氧环戊烷的收率为 78 7% ,2 ,4 二甲基 2 乙氧羰甲基 1,3 二氧环戊烷的收率为 83 0 % ,环己酮 -乙二醇缩酮的收率为 85 9% ,环己酮 1,2 丙二醇缩酮的收率为 84 6% ,丁酮 -乙二醇缩酮的收率为70 7% ,丁酮 1,2 丙二醇缩酮的收率为 88 3 % ,2 丙基 1,3 二氧环戊烷的收率为 80 6% ,4 甲基 2 丙基 1,3 二氧环戊烷的收率为 79 6% ,2 异丙基 1,3 二氧环戊烷的收率为 64 2 % ,4 甲基 2 异丙基 1,3 二氧环戊烷的收率为 83 3 % ,2 苯基 1,3 二氧环戊烷的收率为 75 3 % ,4 甲基 2 苯基 1,3 二氧环戊烷的收率为 95 1% .     

非那雄胺合成工艺改进

非那雄胺能抑制5α-还原酶的活性,明显降低二氢睾酮水平,是一种治疗良性前列腺增生的有效药品。该合成工艺以甾烯酮酸为原料,将其与氯化亚砜反应,无须分离即与叔丁胺反应得17β-酰胺化合物,再氧化开环,环合,氢化,脱氢合成了非那雄胺。经元素分析、IR、1HNMR、13CNMR、MS分析表征了其结构。该法无须使用昂贵的2,2-二吡啶二硫化物和剧毒药品苯亚硒酸酐,且以乙酸铵代替氨气,降低了对设备的要求和腐蚀,更适用于工业生产。     

Dichroism of absorption and polarization of phosphorescence of molecules of the closed form of nitrobenzospirothiopyran

The spectral-polarization characteristics of absorption and phosphorescence of molecules of the initial form of nitro-substituted indolinospirobenzothiopyran were studied in oriented polyethylene films and in solutions with different polarity. An oscillator model of the electron transitions responsible for the formation of absorption and luminescence spectra was suggested. It was established that the principal differences in the spectral and photophysical properties of the compound studied and its oxygen-containing analog are associated with the fact that the electronegativity of the S atom is lower than that of the O atom. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1143–1146, June, 1997.     

Acid hydrolysis of carboxymethylcellulose of low degree of substitution

Cotton cellulose was swollen in a sodium hydroxide solution and carboxymethylated by a two-bath method for different periods of time for each process. The kinetics of acid hydrolysis and the crystallinity of the swollen and carboxymethylated samples were measured. The proportion of broken bonds, rate constants for hydrolysis, and permeability of cellulose to hydrolyzing agents were calculated. The susceptibility of glycosidic linkages to acid hydrolysis was improved by carboxymethylation more than by swelling in alkali. The increased accessibility of carboxymethylcellulose to acid was regarded as a consequence of increased intra-and intercrystalline swelling and of the glycosidic bonds' weakness caused by the electron-attracting carboxymethyl group on the C-6 position.     

氯氧化镁生成热的研究

用氧化镁氯化镁水溶液制备了8水合氯氧化镁[nMg(OH)2·MgCl2·8H2O], 并测定了其在盐酸中的溶解热, 实验结果表明, 氯氧化镁溶解热与n值呈线性关系, 根据溶解热求出5Mg(OH)2·MgCl2·8H2O和3Mg(OH)2·MgCl2·8H2O的生成热分别为-7727.1和5888.1kJ·mol^1^-。     

Mechanism of action of base-catalyzed oxygenation of phenol derivatives

Cyclopropyl derivative of 2,6-di-tert-butylphenol is synthesized as a probe to investigate the mechanism of base-catalyzed autooxidation of phenol derivatives. Our study indicates that one electron reduction of molecular oxygen from phenolate gives phenoxyl radical 3, a key intermediate of autooxidation. The coupling of phenoxyl radical and superoxide radical gives peroxylate anion 4 and produces the final epoxy alcohol adduct 6.     

Estimation of Kinetic Parameters of Thermal Oxidation of Ilmenite

The aim of the presented work was the investigation of thermal oxidation of ilmenite in static air atmosphere. The investigations were carried out by use of a derivatograph (MOM, Hungary). The changes of crystallographic structure of investigated samples were identified by X-ray diffractometry on Philips PW-1710 diffractometer. In temperature above 500°C appears structure of hematite Fe₂O₃. On the basis of the thermogravimetric measurements, the contracting area and contracting volume models were found as the best fitting experimental data. This revised version was published online in August 2006 with corrections to the Cover Date.     

化学计量中不确定度评定研究进展

测量不确定度是表征合理地赋予被测量之值的分散性的参数。本文针对化学计量不确定度评定基础模型仅适用于线性模型、概率分布为正态分布或缩放位移t分布等局限,介绍了近年来不确定度评定的研究热点:蒙特卡罗方法(Monte Carlo Method,MCM),不确定度评定的来源、评定概念、评估方法及其发展过程,扩大了测量不确定度评定与表示的适用范围。     

微量钙的测定方法研究进展

介绍了1995-2006年期间测定微量和痕量钙的方法,如电感耦合等离子体-原子发射光谱法、原子吸收光谱法以及离子色谱法等的工作原理和特点,并说明了其测定微量钙的应用领域。并对微量钙的测定技术进行了展望(引用文献55篇)。     

Stages of thermal decomposition of sodium oxo-salts of sulphur

Thermal behaviour of sodium oxo-salts of sulphur: Na₂SO₄, Na₂S₂O₇, Na₂S₂O₆, Na₂SO₃, Na₂S₂O₅, Na₂S₂O₄, Na₂S₂O₃, Na₂S₃O₆ and of sulphides Na₂S and Na₂S₂ was studied on heating up to 1000°C. The experiments were performed with anhydrous compounds obtained from commercial products by recrystallisation and dehydration. The stage mechanisms of decomposition of anionic sub-lattices of the salts have been proposed basing on the Górski’s morphological classification of simple species. The thermal stability and the stage decomposition mechanisms were correlated with the structure and the potential chemical properties of the salt anions. The thermal decomposition processes were studied by means of thermal analysis, and the decomposition products were identified by means of X-ray phase analysis.     

Determination of heats of detonation and influence of components of composite explosives on heats of detonation of high explosives

The heats of detonation of 20 simple high explosives and explosive mixtures were determined by means of an adiabatic detonation calorimeter designed by the authors. The results indicated that the performance of the instrument was reliable and the experimental data were very accurate. For explosive mixtures, there was a linear accumulative relationship between the heats of detonation of the explosive mixture and its components. Accordingly, the heats of detonation of explosive mixtures could be calculated directly from the heats of detonation of simple explosives and the characteristic heats of other components. The experiments showed that the gold or brass shell of the cylindrical charge could be substituted by a thick-walled porcelain shell, which had the advantage of cheapness.