水飞蓟宾与水杨酸、丁香酸、水杨酰胺的共晶

水飞蓟宾在水和脂质介质中溶解性较差，生物利用度低，而药物共晶给药技术可在不改变药物药效的前提下提高药物溶解度、溶出速率、生物利用度和稳定性等理化性质。采用溶剂蒸发法在不同溶剂中成功制备出水飞蓟宾-水杨酸、水飞蓟宾-丁香酸、水飞蓟宾-水杨酰胺3种共晶。通过X-射线衍射、傅里叶变换红外光耦等表征手段确定了共晶的形成，且对3种共晶进行溶解度测定，结果表明3种共晶增加了水飞蓟宾在水中的溶解度。     

布洛芬-烟酰胺共晶制备及其溶解度测定

采用乙醇-水混合溶剂,对布洛芬-烟酰胺共晶的溶液结晶法制备过程进行了研究,制备样品的PXRD和DSC表征结果证明了通过溶液结晶法大规模制备布洛芬 烟酰胺共晶的可行性。制备过程研究结果表明,当混合溶剂中乙醇与水的体积配比为1.82～7.11时,可以制备出布洛芬-烟酰胺共晶;而且随着乙醇与水体积配比的增大,共晶收率呈现先增大再减小的趋势,当体积配比为2.76时,共晶收率达到最大值(76.31%)。还在不同温度下测定了布洛芬-烟酰胺共晶在不同体积配比乙醇-水混合溶剂中的溶解度,结果表明随着温度和乙醇体积比例的升高,布洛芬-烟酰胺共晶的溶解度增大,最后用 Apelblat方程对溶解度数据进行拟合。     

茶碱、烟酰胺与异丙醇三元系统在298.15和308.15 K的相图研究

以茶碱、烟酰胺通过分子间氢键形成的共晶为例研究了共晶的热力学性质,测量了以异丙醇为溶剂茶碱 烟酰胺共晶在298.15和308.15 K 下的溶解度,同时测定了茶碱 烟酰胺共晶的溶度积（KSP）。通过对溶解度数据的分析表明茶碱 烟酰胺共晶在溶液中会形成1∶1的溶液络合,测定了溶液中共晶的溶度积及络合常数以及共晶组元对共晶溶解度的影响,同时考察了温度对溶度积和络合常数的影响。为了深入了解共晶在不同温度下的形成规律,绘制了在298.15和308.15 K茶碱 烟酰胺在异丙醇中的三元相图,分析了共晶的三元相图随温度的变化趋势,为药物共晶生产中目标产物的控制提供理论支持。     

水飞蓟素固体分散体的制备及溶解性能研究

筛选出高分子材料制备水飞蓟素固体分散体,提高水飞蓟素的溶解度和溶出速率。分别采用聚乙二醇6000（PEG6000）、聚维酮K30（PVPK30）为载体,制备水飞蓟素固体分散体。采用高效液相法进行含量测定,差示热分析法鉴别药物在载体中的存在状态,并进行溶解度、体外溶出速率实验。结果表明,两种载体的固体分散体均能增加水飞蓟素的溶解度和溶出速率,水飞蓟素在载体中以高度分散状态存在,而非晶型形态存在。以PVPK30为载体明显优于以PEG6000为载体的水飞蓟素固体分散体体外溶解度和溶出速率。     

药物共晶制备方法研究进展

药物共晶是药物活性成分和共晶形成物按照一定的比例通过氢键等分子间作用力形成的一种新晶型,它能够有效提高药物的溶解度、溶出速度、生物利用度等,受到了药学研究者们越来越广泛的关注。对药物共晶的制备方法做了一个简短的综述,希望能够为药物共晶在药学领域的应用提供参考和借鉴。     

冷冻共晶法结晶谷氨酸钠介稳区测定

冷冻共晶技术的最大特点是冰晶和固体盐同时结晶析出,介稳区的测定是冷冻共晶操作的关键研究之一。文中采用静态法测定了谷氨酸钠在0℃以下的溶解度。实验结果表明:随着温度的降低,谷氨酸钠的溶解度降低。利用FBRM,PVM在线监测系统测定了谷氨酸钠在不同的搅拌速率、降温速率、晶种加入量条件下的超溶解度。根据溶解度和超溶解度曲线,确定了谷氨酸钠的介稳区宽度。研究表明:在一定条件下,搅拌速率越小、降温速率越快、加入晶种量越多,谷氨酸钠介稳区越宽。测定的介稳区数据为后续谷氨酸钠冷冻共结晶实验打下基础。     

三种亲水性聚合物对多西他赛/磺丁基醚-β-环糊精二元体系的影响

目的：研究添加了亲水性聚合物后对多西他赛/磺丁基醚-β-环糊精二元体系的影响。方法：在多西他赛/磺丁基醚-β-环糊精中不加或分别添加1%的3种亲水聚合物,聚乙烯吡咯烷酮(PVP)、聚乙二醇(PEG)和泊洛沙姆(P188)。采用相溶解度法,于25℃、37℃和45℃下,绘制相溶解曲线,考察药物溶解度、稳定性常数(K)、络合效率及相关热力学参数。结果：PVP的加入,最有利于增强多西他赛/磺丁基醚-β-环糊精二元体系的稳定性及药物的溶解度。与固有溶解度相比,多西他赛的溶解度提高了75倍,稳定性常数从1922.84 L/mol提高到2449.44 L/mol。结论：在多西他赛/磺丁基醚-β-环糊精中加入适量亲水聚合物后可形成三元体系,提高络合效率,增加多西他赛的溶解度。     

溶解度与多晶型浅谈

许多热力学和动力学因素都对晶体的晶型控制有影响,文章中主要介绍溶解度与晶体多晶型之间的内在联系.首先,介绍了晶体学的一些基本理论,其次,介绍溶解度曲线在判定多晶型稳定性中的应用；溶解度曲线对多晶型成核速率的影响,最后,介绍溶解度曲线在溶剂介导晶型转化机制中的贡献.     

来那度胺-烟酰胺共晶的制备与表征

采用溶剂研磨法制备了难溶性药物来那度胺与烟酰胺的共晶,并使用差示扫描量热分析(DSC)、热重分析(TGA)、X射线粉末衍射(PXRD)和红外光谱(IR)对其进行了表征。此外,采用密度泛函理论(DFT)和B3LYP/6-31G(d)基组,通过高斯计算对来那度胺和烟酰胺之间的作用力进行了理论分析。计算和实验结果均表明了来那度胺与烟酰胺之间可形成共晶(1∶1)。     

盐酸倍他司汀片溶出度测定方法的研究

建立了测定盐酸倍他司汀片溶出度的方法。采用柱,以0.01 mol/L醋酸钠缓冲液-甲醇(体积比为70∶30)为流动相,在检测波长为261 nm的条件下进行高效液相色谱(HPLC)测定。在该色谱条件表明建立的溶出度测定方法简便、精密度高,可用于盐酸倍他司汀片溶出度的质量控制。     

Development of structural characterization and physicochemical behaviour of triphenylamine blocks

A novel multitriphenylamine substituted derivatives, possessing the respective photochromic groups were synthesized by Stille cross-coupling methodology. The hyperbranched structures have been characterized by ¹H NMR, ¹³C NMR. Obtained structures show good stability in common organic solvents such as CHCl₃, toluene and CH₂Cl₂ and exhibit excellent thermal stability. Electrochemical results and theoretical calculation suggest that oxidation and reduction start from the side of amine and branching five member heterocycle ring moieties, respectively.     

Factors governing the solubility of mesophase into pitch distillate

To explain the dissolution phenomena of mesophase into pitch distillate, the hydrogen donor ability of the distillate and the acceptor ability of the mesophase were examined using ¹H n.m.r. The mixtures which consisted of 9,10-dihydroanthracene(9,10-DHA) and mesophase samples or organic compounds(9,10-DHA/mesophase or organic COMPOUND = 1/5wt/wt) were heated at 618K for 1 h in sealed glass tubing, and then measured by ¹H n.m.r. The acceptor ability (Aa) of the mesophase was evaluated from the integrated intensity ratio between two peaks at 8.4 and 3.9 ppm, attributable to the resulting anthracene and the remaining 9,10-DHA, respectively. The solubility of a combination of mesophase and a distillate decreased with decreasing (Da + Aa) value, in which Da is the hydrogen donor ability of the distillate.     

Synthesis and aqueous solution characterization of novel diblock polyampholytes containing imidazole

A series of diblock copolymers of 2-(1-imidazolyl)ethyl methacrylate and tetrahydropyranyl methacrylate (THPMA) were synthesized by group transfer polymerization using propylene carbonate rather than tetrahydrofuran as the solvent to ensure homogeneous polymerizations. The resulting copolymers were characterized by gel permeation chromatography and proton nuclear magnetic resonance spectroscopy (¹H NMR) to determine their molecular weights and compositions, respectively. The THPMA units of the copolymers were subsequently converted to methacrylic acid units by acid hydrolysis. The resulting polyampholytes were characterized in terms of their composition and solubility characteristics using ¹H NMR and hydrogen ion titration. Moreover, dynamic light scattering in alkaline water (pH 9.3) indicated the presence of large non-micellar aggregates of the block polyampholytes.     

水溶性氮杂环修饰小檗碱衍生物的合成

为了提高小檗碱的水溶性，增加其在体内的吸收和转运效率，以小檗碱为初始原料，经高温脱去C(9)位甲基，然后与二溴烷烃进行单边溴烷基化反应，再与苯并咪唑、1,2,4-三氮唑和吡唑经亲核取代反应制得了一系列氮杂环修饰的小檗碱衍生物（4～6）。除了化合物6a，所得衍生物均为新化合物，其结构经核磁氢谱/碳谱（¹H NMR/¹³C NMR）、电喷雾质谱[MS（ESI）]多重表征确认。随后，利用紫外分光光度法测定了部分衍生物在水中的溶解度，结果显示奇数链长烷基取代1,2,4-三氮唑的引入使小檗碱在水中的溶解度大幅度提升。其中，1,3-亚丙基桥连的1,2,4-三氮唑小檗碱衍生物的水溶性高达13.87mg/mL，是小檗碱的12倍，因此它是潜在的具有更高生物利用度的小檗碱药物前体。     

Conversion of propylene into cyclohexane on PtGaZr/SiO2 catalyst

The light olefins present in Delay Coker and fluid catalytic cracker dry gas can be valorized into naphthenes using a new PtGaZr/SiO₂ catalyst. This catalyst was compared to a GaZrSiO₂ catalyst prepared with the same methodology. Both were characterized by XRD, and FTIR, XPS, ⁷¹Ga, ²⁹Si and ¹H NMR spectroscopies. Propylene is treated in the presence of CS₂, hydrogen, and benzene in a semi-batch type reactor and the product composition is analyzed by GC and MS techniques. The different operating variables were explored to study the effect of Pt on activity, selectivity and catalyst stability. The spent catalysts after 10 cycles in operation were analyzed using ¹³C NMR, ¹H NMR, IR, and XPS spectroscopies. The paper discusses the catalytic surface composition, the effect of temperature, contact time, hydrogen partial pressure and benzene in the feed. The study demonstrated that the effect of Pt, hydrogen and benzene is crucial to orient the reaction toward naphthenes production.     

Thermal and UV-curing behavior of phosphate diacrylate used for flame retardant coatings

A novel phosphorus-on-skeleton compound has been synthesized by allowing phosphorus oxychloride to react with 1-oxo-4-hydroxymethyl-2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane (PEPA) and 2-hydroxyethyl acrylate (HEA). Its structure was characterized by Fourier transformed infrared spectroscopy (FTIR) and ¹H nuclear magnetic resonance spectroscopy (¹H NMR). The UV-curing behavior was investigated using FTIR. Results show that the conversion of the unsaturated bond of the monomer exposed to UV light for 100 s is approximately 84%. Flame-retardant effectiveness was estimated from the limiting oxygen index (LOI) and thermal stability was characterized by thermogravimetric analysis (TGA). The LOI value was 39 and the char yield was 53% at 600 °C. TG data indicate that the material undergoes degradation in three characteristic temperature stages, which may be attributed to the decomposition of the phosphate, thermal pyrolysis of aliphatic chains, and degradation of an unstable structure in char, respectively. These were further characterized by real time Fourier-transform infrared measurement. It is proposed that the flame retardant action results from decomposition of phosphate to form poly(phosphoric acid), which catalyses the breakage of bonds adjacent to carbonyl groups to form an intumescent char, preventing the sample from burning further.     

含氮杂环的酯或酰胺类衍生物的制备及其摩擦学性能

设计合成了4种含氮杂环的酯或酰胺类衍生物润滑油添加剂（Ⅰ~Ⅳ）。采用核磁共振氢谱（¹H NMR）和飞行时间质谱（MALDI-TOF-MS）对所得产物的结构进行了表征;研究了4种添加剂的油溶性、热稳定性和抗腐蚀性;在四球摩擦磨损试验机上系统考察了添加剂在液体石蜡中的摩擦学性能;利用扫描电子显微镜（SEM）和能谱分析仪（EDS）观察和分析了钢球磨斑的表面形貌和元素组成。结果表明,4种添加剂均具有良好的油溶性、热稳定性和抗腐蚀性,当添加剂Ⅰ的质量分数达到1.0%时,钢球的磨斑直径（WSD）和摩擦系数分别比在液体石蜡中降低了33%和26%。SEM结果显示4种添加剂的加入能明显减小WSD,减少表面磨损,EDS结果表明添加剂在摩擦过程中形成了复杂的反应膜。     

以低分子量聚乙烯基苯磺酸钠为模板的聚3,4-二氧乙烯噻吩水分散体的制备及性能

通过RAFT聚合,制备了低分子量的聚乙烯基苯磺酸钠（PSS）;其次以低分子量的聚乙烯基苯磺酸钠为模板制备了聚3,4-二氧乙烯噻吩（PEDOT）：聚乙烯基苯磺酸钠（PSS）水分散体,研究了作为模板的聚乙烯基苯磺酸钠的不同分子量对PEDOT：PSS水分散体结构和性能的影响。结果显示：通过核磁氢谱（¹H NMR）表征,证明成功制备了分子量为3900,4900,9600和18300的聚乙烯基苯磺酸钠。用荧光探针法发现低分子量PSS在水中能形成胶束,临界胶束浓度在10^-6g·ml^-1左右。用四探针表面电阻测试发现,低分子量PSS为模板可明显提高PEDOT薄膜的导电性,最大提高了近3倍。用紫外可见分光光度计（UV）研究发现,以低分子量PSS为模板使PEDOT的透明性有一定的下降,这主要是由于RAFT试剂部分和PEDOT：PSS的相分离造成的。热稳定性的测试表明,低分子量PSS为模板对PEDOT的热稳定性没有明显的影响。     

新型卟啉及其金属配合物的合成与性能

通过琥珀酰基、马来酰基和邻苯二甲酰基对四-(4-氨基苯基)卟啉进行修饰改性,合成不同结构的新型卟啉及其铜配合物。对合成的新型结构卟啉配体进行核磁共振、质谱和红外表征,对其铜配合物进行质谱表征,结果表明,所合成的化合物是目标产物。通过紫外-可见、荧光发射、热重、循环伏安法进行性质测试,计算出HOMO和LUMO能级。结果表明,新型化合物具有良好的可见光区吸收和纯红光发射光谱,热稳定性高,可以作为红光材料的备选材料。     

Polymeric ionic liquid—assisted polymerization for soluble polyaniline nanofibers

To enhance the solubility of polyanilines(PANI),polymeric ionic liquid(PIL)was introduced into the polymerization synthesis of PANI with various proportions.The structure and properties of the modified PANIs were characterized by 1H NMR,Fourier transform infrared spectroscopy,thermogravimetric analysis,ultraviolet-visible spectrum,etc.It was found that the obtained PANIs doped with PILs were soluble in various organic solvents such as N,N-dimethyl formamide and acetonitrile.Compared with the pure PANI,the PANIs doped by PILs showed remarkable solubility and their chemical structure and conductivity kept integrated.