那格列奈的多晶型与溶解度

分别对那格列奈B, H和S三种晶型的溶解度、溶解热进行了测定和计算. 结果表明: 那格列奈的S晶型与临床使用的H晶型溶解度均明显大于B晶型. B, H和S三种晶型的溶解热分别为42.84, 28.44 和29.14 kJ•mol^－1. 此外, 我们还新发现了不同于B, H, S晶型的X2晶型, 并且制备出了无定型的那格列奈.     

有关那格列奈晶型的研究

Ｎ (反式 4 异丙基环己基 1 甲酰基 ) Ｄ 苯丙氨酸 ,药品名那格列奈 ,作为治疗二型糖尿病的药物1 999年在日本上市 ,药效与其晶体存在的型态密切相关。Ｂ型晶不稳定 ,Ｈ型晶对研磨的稳定性较高 ,比Ｂ型晶更适合于制药[1 ] 。此外 ,我们发现Ｂ型或Ｈ型晶在一定条件下可转化为熔点较高的第三种样品———ＶＨ型晶。测定了三种那格列奈样品的熔点 ,用示差扫描量热 (ＤＳＣ)、热重差热 (ＴＧＡ ＤＴＡ )、红外 (ＩＲ)及Ｘ 射线粉末衍射 (ＸＲＤ)等对它们进行了表征。那格列奈的分子结构如下图所示 :1　实验部分1 1　制备Ｂ晶熔点 1 2 8～ 1 3…     

那格列奈的合成研究

报道了抗糖尿病新药那格列标的全合成及工艺改进。     

共沉淀法合成复合碳酸钙及其形貌和晶型的研究

以硬脂酸钠盐皂化液为介质，共沉淀法合成碳酸钙/硬脂酸钙复合物。SEM， XRD等测试手段表明：不同反应温度及有机物尝试条件下得到的复合物具有多变的 外观外形貌；其中碳酸钙以方妥石和球霰石的混晶形式存在，两者经例呈一定变化 规律，并对其进行了合理的解释，认为有机物的浓度和温度不同，使其在溶液中形 成的胶束结构及其亲水基团有不同排列，并以不同匹配方式影响碳酸钙结晶行为， 从而影响复合碳酸钙的形貌和晶型。     

热处理对聚醚醚酮晶体结构参数及结晶度的影响

采用广角Ｘ射线衍射（ＷＡＸＤ）方法研究了不同热处理温度下聚醚醚酮（ＰＥＥＫ）的晶胞参数、微晶尺寸及结晶度的变化。根据Ｘ射线散射强度理论，运用图解多重峰方法导出了以ＷＡＸＤ方法计算ＰＥＥＫ结晶度的公式；用此公式对经不同热处理的ＰＥＥＫ样品进行计算，结果与由密度法及量热法测定的结果具有较好的可比性。     

X-射线粉晶衍射谱图的计算机模拟

编写了一个FORTRAN程序,用于从单晶结构计算粉晶X射线衍射数据,并进一步用ORIGIN软件绘制出粉晶衍射图谱,选择了13个代表性经典化合物进行计算,结果与粉晶卡片上的实验数据相当一致,本文模拟方法,即可弥补粉晶图谱缺乏的不足,也可用于]校验粉晶衍射实验结果的可靠性。     

硫化银纳米晶的γ辐射制备

γ射线辐射法是一种在常温常压下制备纳米材料的方法 ,它是利用水在γ射线的作用下产生的大量还原性粒子 (如水合电子等 )把许多金属离子还原 ,或者把一些较高价态的非金属元素 (如硫 )还原成最低价态 ,以制备纳米金属粒子 [1～ 3]、纳米合金粉末 [1～ 4 ]、纳米金属氧化物粉末 [5]、纳米复合材料 [6]和半导体硫化物纳米材料 [7]等 .但对硫化物的研究仅局限于 B- A族化合物 .现在 ,各种 B- A族化合物纳米材料的制备研究也逐渐受到人们的关注 ,因为这些化合物同时具有部分电子导电性能和部分离子导电性能 ,可用作超离子导体和半导体 [8…     

尼群地平晶型转变条件及其影响因素的确定

根据熔化数据推算相变稳定性理论计算了尼群地平不同晶型之间的相变温度, 并分别考察了高温、高温和高湿及高压条件下的晶型转变. 理论推导尼群地平I与II, 尼群地平I与III, 尼群地平II与III的转化温度分别为158.88, 160.50和158.65 ℃, 三者均为单变关系, 且在高温条件下尼群地平II, III都转变为尼群地平I, 在高压条件下, II易转变为I. 试验结果表明室温下尼群地平I为稳定型, II和III为亚稳定型, 3种晶型稳定性顺序为尼群地平I＞II＞III.     

盐酸林可霉素晶型研究

药物的多晶型对药品质量和临床药效有较大的影响,药物多晶型的研究方法有x—射线单晶结构分析,x—射线粉末法,差热分析,红外光谱分析等。影响晶型转变的因素很多,如研磨,结晶溶剂不同或改变结晶条件,所得产品晶型即有变化。本实验通过盐酸林可霉素针、片剂红外光谱测定,x—射线衍射分析,差示扫描量热法,晶型转化实验等手段,证明盐酸林可霉素为一多晶型药物,晶型之间存在互变,晶型的不同是由于精制浓度及速度不同所致,其中晶B、晶C为稳定型晶态,晶A为亚稳态晶型。     

Study on Stability of Nateglinide Polymorphism

The stability of three forms of nateglinide, especially S-form and H-form, was determined. S-form was a new crystal structure of nateglinide. Three forms of nateglinide were treated in different conditions, such as in various temperatures, humidity, light and so on.Analysis of their crystal structures was performed by X-ray powder diffraction ( XRD ) and their particle shapes were observed with scanning electron microscope ( SEM ). The results indicated that the stability of S-form of nateglinide is the best among the three forms and their particle shapes are quite difference. S-form is the sheet structure of layer upon layer, H-form looks like a hank of silk lines and B-form is the clubbed shape.     

离子液体中Pb^2+／Pb^4+溶质局域结构的EXAFS研究

在超稀浓度条件下ω[Pb(OAc)2]或ω[Pb(OAc)4]<0.2,我们使用EXAFS方法对 溶解在离子液体中的铅化合物的局域结构进行了研究。从结果中可以看出,Pb (OAc)4的铅中心在（0.200±0.003）nm处有8个氧近邻,而Pb(OAc）2的铅中心在（ 0.225±0.003)nm处有6个氧近邻。但是溶解在离子液体中的铅化合物均具有较低的 配位数（一般小于4）,这显示出离子液体具有较低的配位性能。另一方面,铅中 心与最近邻氧的原子间距有较大的变化。例如：溶解于[bmim]PF6的Pb^4+的Pb-O间 距为（0.186±0.005)nm,配位数仅为2.4,从Fourier变换谱上可清楚地看出有第 二配位壳层的贡献;溶解于[bmim]PF6的Pb^2+的Pb-O间距也明显地小于纯样品中 Pb-O的间距。相比之下,溶解于[ bmim]BF4的铅离子显示出的Pb-O间距与纯样品几 乎没有差别,对于Pb^2+为0.223nm,而对于Pb^4+为0.210nm。     

Development of a New Analytical Method for Determination of Related Components in Nateglinide

An isocratic reverse phase liquid chromatographic (RP-LC) assay method has been developed for the quantitative determination of nateglinide and its related components namely imp-1 and imp-2 in bulk drug and in pharmaceutical dosage form, used for the treatment of type II diabetes mellitus. The developed method is stability indicating and also can be used for stability testing. The chromatographic separation was achieved on C-8, 150 × 4.6 mm, 3.5 μm stationary phase. The LC method employs solution A as mobile phase. Solution A contains a mixture of phosphate buffer pH 3.0: acetonitrile (50:50 v/v). The flow rate was 1.0 mL min⁻¹ and the detection wavelength was 210 nm. In the developed LC method the resolution between nateglinide and its potential impurities namely imp-1 and imp-2 was found to be greater than 5.0. The drug was subjected to stress conditions of hydrolysis, oxidation, photolysis and thermal degradation. Considerable degradation was found to occur in acid medium, alkaline medium and oxidative stress conditions. The stress samples were assayed against a qualified reference standard and the mass balance was found close to 99.2%. The developed RP-LC method was validated with respect to linearity, accuracy, precision and robustness.     

Polymorphism of (+)N-tosyl-L-glutamic acid

It has been shown that polymorphism is the reason for the occurrence of (+)N-tosyl-L-glutamic acid 1 with various melting points. 1 occurs in two crystalline forms: and . Form -1 (prisms) having a melting point of 145–147°C is chemically pure and stable. Form -1, however, is unstable and is formed as a result of the stabilizing effect of an organic solvent not introduced into the structure of the crystal. At about 125°C the forms is transformed to the form. The melting point of the form depends on the amount and type of solvent contained in the crystal, which, during measurement cannot leave the system.     

DSC and X-ray Diffraction Study of Polymorphism in n-Alkylammonium Chlorides

The influence of the hydrocarbon chain length in the formation of interdigitated and non-interdigitated bilayers in n -alkylammonium chlorides has been investigated for chain lengths varying between 8 and 14 carbon atoms. The formation of non-interdigitated bilayers during crystallization from solution is favoured for shorter chains whilst the interdigitated structure is predominant for larger chains. The thermodynamic parameters of the solid to solid phase transitions in the non-interdigitated samples depend on chain length showing the odd-even alternation that characterized homologous series in n -paraffins. The solid to liquid crystal phase transition temperatures and enthalpies show a linear dependence with the chain length. This revised version was published online in July 2006 with corrections to the Cover Date.     

Stability of Rare-Earth Oxychloride Phases: Bond Valence Study

The crystal structures of the tetragonal rare earth (RE) oxychlorides, REOCl (RE=La-Nd, Sm-Ho, and Y) were studied by X-ray powder diffraction measurements, Rietveld analyses, and bond valence calculations. The tetragonal structure (space group P4/nmm, No. 129, Z=2) is stable for all but Er-Lu oxychlorides, which possess a hexagonal structure. The tetragonal structure consists of alternating layers of (REO)_nⁿ⁺ complex cations and Xⁿ⁻ anions, where the rare earth is coordinated to four oxygens and four plus one chlorines in a monocapped tetragonal antiprism arrangement. The Rietveld analyses yielded a coherent series of structural parameters. Preferred orientation and microabsorption effects were found significant. The evolution of interatomic distances and bond angles indicated that the reason for the preferred structure changing from tetragonal to hexagonal is the strain in the chlorine layer. The bond valence parameter B for the RE-O bonds had to be recalculated due to the covalent nature of the (REO)_nⁿ⁺ unit. The results obtained with the new parameter confirmed the strains in the chlorine layer to be the cause for the phase transition.     

钛粉质量鉴定新方法试验研究

钛粉质量鉴定一直是用化学分析测定全钛含量，而不能确定单质态的钛含量，实验表明用Ｘ射线衍射分析鉴定钛粉质量效果较好，避名了化学分析的缺点，是一种值得推广的鉴定方法。     

Phase Behavior and Polymorphism of Saturated and Unsaturated Phytosterol Esters

This study investigated how the physicochemical characteristics of phytosterol esters are influenced by the chain length and degree of unsaturation of the fatty acid ester moiety. Saturated and unsaturated phytosterol esters (PEs) were synthesized by the esterification of different types of fatty acids (stearic, palmitic, lauric, oleic, and linoleic acid) to β-sitosterol. The non-isothermal crystallization and melting behavior of the pure PEs were analyzed. It was proven by X-ray diffraction that saturated β-sitosteryl esters and β-sitosteryl oleate formed a bilayer crystal structure. The lamellar spacings of the bilayer structure decreased with decreasing fatty acid chain length and with an increasing degree in unsaturation. The degree of unsaturation of the fatty acid chain of the β-sitosteryl esters also influenced the type of subcell packing of the fatty acid moieties in the bilayer structure, whether or not a metastable or stable liquid crystalline phase was formed during cooling. Furthermore, it was found that the melting temperature and enthalpy of the β-sitosteryl esters increased with an increasing fatty acid chain length while they decreased with an increasing degree of unsaturation. The microscopic analyses demonstrated that β-sitosteryl oleate formed much smaller spherulites than their saturated β-sitosteryl analogues.