脂质体中不同种类羧酸钾对草酸钙晶体生长的调控作用

首次研究了狼磷脂-水脂质体中不同种类羧酯钾对草酸钙晶体生长的调控作用 。加入一元DAc只诱导一水草酸钙（COM）生成。二元K_2tart在其浓度大于1. 0mmol/L时可以诱导三水草酸钙（COT）生成。而加入三元的K_3cit和四元的 K_2edta后， 在不同的浓度下，可以分别诱导COM，二水草酸钙（COD）和COT的生 成。在低浓度（—3.3-17mmol/L）范围，， COD含量达到100%；而在较高浓度(＞ 17mmol/L)时，COD减少，COT含量增加。在不同的浓度区间，无论是COM含量减少， 还是COT含量增加，或者是COD含量的先增加后减少，均与该羧酸钾浓度的对数呈线 性关系。不同羧酯钾抑制COM生长并诱导COD形成的能力顺序为：K_3cit＞K_2edta ＞＞K_2tart-KAC,诱导COT生长的能力顺序为：K_2tart＞＞K_3cit＞K_2edta＞＞ KAc.由此推测抑制草酸钙结石形成的潜在效率依次为：K_3cit＞K_2edta＞＞ K_2tart＞＞KAc.     

凝胶体系中不同结构羧酸盐对草酸钙生物矿化的影响

采用双扩散法研究了凝胶体系中四元羧酸盐(Na2EDTA)、三元羧酸盐柠檬酸钠（Na3cit）、二元羧酸盐酒石酸钠（Na2tart）和一元羧酸盐醋酸钠（NaAc）对草酸钙（CaOx）结晶的影响.抑制一水草酸钙（COM）聚集的能力为:Na2EDTA >Na3cit >Na2tart >NaAc；诱导二水草酸钙（COD）的能力为：Na3cit >Na2tart >Na2EDTA >NaAc.羧酸的抗衡阳离子影响CaOx的结晶. H3cit、Na3cit和K3cit抑制COM聚集和诱导COD形成的能力均为:K3cit-Na3cit >H3cit.无论是诱导COD生成，还是抑制COM聚集，均可以减小结石形成的几率，对临床上防治结石具有积极的意义.     

草酸钾诱导的LB膜缺陷及对草酸钙堆积图形的影响

采用扫描电子显微镜(SEM)和原子力显微镜(AFM)研究了经不同浓度草酸钾(K2C2O4)处理后二棕榈酰磷酯酰胆碱(DPPC)的缺陷LB膜及其对一水草酸钙(COM)成核和生长的影响. K2C2O4的处理可进一步破坏LB膜中圆形畴区内的分子列阵, 尤其是使处在液态扩张相(LE)/液态凝集相(LC)边界的分子列阵无序程度增加, 从而促进了COM晶体在此处的成核和生长, 最终诱导圆形堆积的COM晶体图形出现. 随着损伤LB膜的K2C2O4浓度c(K2C2O4)从0.3 mmol/L增加到5.0 mmol/L, 其对LB膜畴区有序结构的破坏作用逐渐增强, 圈状堆积的晶体图形数量增多. 当c(K2C2O4)为0.3 mmol/L时, 主要诱导实心的圆形堆积的COM晶体图形, 而当c(K2C2O4)增加至5.0 mmol/L时, 生成圈状COM晶体图形, 且图形的半径减小. 这一研究结果将有助于从分子和超分子水平上了解肾小管上皮细胞膜损伤后的微结构变化及其与肾结石形成的关系.     

不同介质凝胶体系中草酸钙结晶的研究

研究了五种不同介质（水、氯化钠、合成尿、正常人尿液和尿石患者尿液）的凝胶体系中草酸钙（CaC2O4）晶体的生长,及各种体系中防石药物柠檬酸钾（K3cit）对CaC2O4生长的影响.没有加K3cit时,CaC2O4晶体以一水草酸钙（calcium oxalate monohydrate, COM）为主要物相,但在氯化钠和合成尿的凝胶体系中同时出现了二水草酸钙（calcium oxalate dihydrate, COD）和三水草酸钙（calcium oxalate trihydrate, COT）,肾结石患者尿液中出现COD,而正常人尿液中没有COD和COT生成.加入K3cit后,水、氯化钠和合成尿介质的凝胶体系中,COT的含量显著增加,患者尿液中产生大量COD,而正常人尿液中出现了少量的COD和极个别的COT.COT的增加与低温、体系中高的离子强度及金属离子等因素有关.K3cit具有诱导COD和COT的生成、减小COM晶体比表面积的作用,从而有利于防治草酸钙结石的形成.     

单分子膜诱导下尿大分子对草酸钙晶体物相和晶面的调控作用

采用SEM,XRD和FTIR手段比较研究了DPPC单分子膜诱导下尿大分子硫酸软骨素A(C₄S)、硫酸软骨素C(C₆S)和血清蛋白(SA)对尿石盐草酸钙晶体生长的影响.DPPC单分子膜不但优先选择一水草酸钙(COM)物相成核生长,而且优先选择COM的(101)晶面.没有添加剂时,得到的COM为三维的六棱柱和三维的菱形晶体;加入尿大分子抑制剂后,COM的(101)晶面进一步加强,其它晶面减弱,导致二维晶体的形成.COM的(101)晶面为富钙离子晶面,带有过剩的正电荷,而DPPC单分子膜头基带有负电荷,几种尿大分子在实验条件下亦带有负电荷,带负电荷的单分子膜及带负电荷的大分子共同作用于富钙离子的(101)晶面,使得COM的(101)晶面择优生长.C₄S,C₆S和SA的存在均能有效地抑制COM生长.     

服用柠檬酸钾前后草酸钙结石患者的尿微晶和尿液性质变化

采用透射电子显微镜(TEM)、扫描电子显微镜(SEM)、X射线衍射(XRD)、傅立叶变换红外光谱(FTIR)和ζ电位分析仪研究了草酸钙(CaOxa)结石患者在服用柠檬酸钾(K3cit)前后尿液中微晶的性质变化,这些性质包括:尿微晶的形貌、尺寸、聚集状态、质量、种类和ζ电位,并研究了服药前后尿液的稳定性差异和pH值变化。服用K3cit前,结石患者的尿微晶棱角尖锐,聚集明显,尺寸从几十纳米到几百微米不等,主要为一水草酸钙(COM)、尿酸等;而服用K3cit一周后,部分尿微晶的形状变得圆钝,聚集现象明显减少,平均粒径减小,部分尿微晶的表面出现凹陷,二水草酸钙(COD)和尿酸盐的百分含量增加,尿微晶的数量和种类减少,尿液pH值上升,ζ电位绝对值增加,自相关时间增加。从患者服用K3cit后引起尿pH值增加、尿液中排泄的柠檬酸和Tamm-Horsfall蛋白浓度增加、柠檬酸与Ca2+离子配位等角度,讨论了K3cit抑制CaOxa结石形成的机制。     

L-半胱氨酸自组装膜诱导草酸钙结晶研究

在CaCl2.H2O和Na2C2O4配制的过饱和溶液中,利用L-半胱氨酸(L-Cys)在金片上形成的自组装膜为模板,研究了草酸钙(CaOxa)在自组装膜上的结晶行为,并探讨了溶液pH对CaOxa晶体组成、晶型及其形貌的影响。采用X射线衍射(XRD)和扫描电子显微镜(SEM)等技术对CaOxa晶体的结构和形貌进行了表征。实验结果表明:当溶液pH=3.0时,溶液中可以形成一水草酸钙(CaC2O4.H2O,COM)和二水草酸钙(CaC2O4.2H2O,COD)晶体,而在同样pH条件下,在L-Cys自组装膜上只形成COD晶体,表明自组装单层对CaOxa晶体的成核和生长有重要影响。通过改变溶液的pH,在自组装单层上可以得到不同晶型和不同形状的CaOxa晶体。当pH=3.0时得到四方块状的COD晶体,而pH=5.0和pH=7.0时分别得到六边形和拉长六边形的COM晶体。     

酒石酸与La~(3+)对草酸钙结晶的影响

采用X射线衍射(XRD)、傅立叶红外光谱(FTIR)和扫描电镜(SEM)分析了凝胶体系中混合添加剂酒石酸和La~(3+)对草酸钙(Ca Oxa)晶体生长的影响。研究结果显示,酒石酸可以抑制Ca Oxa晶体的生长、聚集,并诱导二水草酸钙(COD)生成;La~(3+)不仅可诱导COD生成,而且可使一水草酸钙(COM)的形貌发生变化;而酒石酸和La~(3+)的联合作用则不仅增强了对COD的诱导能力,并使COM的聚集程度降低、比表面积减小。酒石酸和La~(3+)的联合疗法对尿石病的预防和治疗有较大的参考价值。     

金属离子与酒石酸对草酸钙结晶的作用

采用双扩散法研究了硅凝胶体系中不同金属离子(K~+、Mg~(2+)、Sr~(2+)、La~(3+))和酒石酸混合溶液对草酸钙(CaOxa)生长的影响。酒石酸能抑制一水草酸钙(COM)的生长、聚集且能诱导二水草酸钙(COD)的生成。添加K~+后,对CaOxa晶体的作用变化不大;添加Mg~(2+)、Sr~(2+)和La~(3+)后,COD的含量明显增多;诱导COD生成的能力依次为:La~(3+)-H_2tartSr~(2+)-H_2tartMg~(2+)-H_2tartK~+-H_2tart。金属离子的加入不仅增强酒石酸对COD的诱导能力,并使COM的形貌产生变化。该结果在预防和治疗泌尿系结石的临床应用上有积极意义。     

缺陷LB膜诱导草酸钙晶体环图形形成

利用存在缺陷的LB膜来模拟受损伤的肾上皮细胞膜, 研究了膜缺陷的微结构及其影响一水草酸钙(COM)晶体成核、生长、沉积图形和黏附的分子机制. 二棕榈酰磷脂酰胆碱(DPPC)LB膜经草酸钾处理后可形成圆形缺陷, 并诱导COM微晶排列成环状图形, 相比之下, 没有经草酸钾处理的LB膜只诱导零散的六边形COM晶体生成. 随着生长时间增加, 环内单个COM晶体的尺寸明显增加, 空心的环状晶体图形倾向于转变为实心的圆形图形, 且小尺寸(5~20 mm)的圆形晶体图案数量增加. 本结果有助于在分子和超分子的水平上进一步了解肾上皮细胞膜损伤后诱导肾结石形成的分子机制.     

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.     

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。     

Synthesis of phenolic components of Grains of Paradise

Two vanilloids, (5E)-8-(4-hydroxy-3-methoxyphenyl)oct-5-en-4-one (1) and 4-[3-hydroxydecyl]-2-methoxyphenol (2), isolated from the dried seeds of Grains of Paradise (Aframomum melegueta), were synthesized; the latter compound was made as the S-enantiomer and the material derived from the seeds was found to be a 1:1.7 mixture of the R and S isomers. The synthetic route used should allow the preparation of analogs having extended alkyl chains and consequently different lipophilicity, and 3, a homolog of 2, was also prepared.     

Study of hydration of two cements of different strengths

Main hydration products of two cement pastes, i.e. CSH-gel, portlandite (P) (and specific surface S) were studied by static heating, and by SEM, TEM and XRD, as a function of cement strength (C-33 and C-43) hydration time (th) and subsequent hydration in water vapour.Total change in mass on hydration and air drying, M_o, increased with strength of cement paste and with hydration time. Content of water escaping at 110 to 220°C, defined as water bound with low energy, mainly interlayer and hydrate water, was independent on cement strength but its content increased with (th). Content of chemically bound (zeolitic) water in CSH-gel, escaping at 220-400°C, was slightly dependent on strength and increased with (th). It was possibly derived from the dehydroxylation of CSH-gel and AFm phase. Portlandite water, escaping at 400-500°C, was independent on cement strength and was higher on longer hydration. Large P crystals were formed in the weaker cement paste C-33. Smaller crystals were formed in C-43 but they increased with (th). Carbonate formated on contact with air (calcite, vaterite and aragonite), decomposed in cement at 600-700^oC. It was high in pastes C-33(1 month) and C-43(1 month), i.e. 5.7 and 3.3%, respectively; it was less than 1% after 6 hydration months (low sensitivity to carbonation) in agreement with the XRD study showing carbonates in the air dry paste (1month), and its absence on prolonged hydration (6 months) and on acetone treatment. Water vapour treatment of (6 months) pastes or wetting-drying increased this sensitivity.Nanosized P-crystals, detected by TEM, could contribute to the cement strength; carbonate was observed on the rims of gel clusters.This revised version was published online in November 2005 with corrections to the Cover Date.     

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^-。     

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.

     

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.     

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.