药用载体星状聚乳酸-羟基乙酸共聚物的合成与表征

目的降低水溶性药物微球制剂突释现象。方法以辛酸亚锡为催化剂,采用熔融缩聚法合成星状聚乳酸-羟基乙酸共聚物(star-poly(lactic acid-glycollic acid)copolymer,star-PLGA);采用IR、1H-NMR、GPC、DSC及葡萄糖鉴别反应确证共聚物结构,考察理化性质;以天麻素为模型药物,考察star-PLGA微球和聚乳酸-羟基乙酸共聚物(poly(lactic acid-glycollic acid)copolymer,PLGA)微球的释放行为。结果红外光谱和核磁共振分析结果与文献报道一致;凝胶渗透色谱测定重均相对分子质量为15 178;差示扫描量热分析结果表明star-PLGA为非结晶态;葡萄糖鉴别反应表明star-PLGA中有共价键结合的葡萄糖。Star-PLGA微球能很好地控制突释现象,释放行为平稳,其释放曲线符合Higuchi方程。结论成功合成了star-PLGA(物质的量比50∶50),作为微球制剂的载体star-PLGA能降低水溶性药物的突释现象。

Apparent activation energy for spontaneous combustion of sulfide concentrates in storage yard

In order to evaluate the spontaneous combustion hazard of sulfide concentrates in storage, three different kinds of sulfide concentrates （sulfur-rich sulfide concentrate, iron sulfide concentrate and copper sulfide concentrate） were obtained from a storage yard in Dongguashan Copper Mine, China. The reaction processes at different heating rates of 5, 10, 15, 20, and 25 ℃/min in air flow from ambient temperature to 1 000 ℃ were studied by TG-DTG-DSC analysis. By the peak temperatures of DTG curves, the whole reaction process for each sample was divided into different stages, and the corresponding apparent activation energies were calculated by the Ozawa-Flynn-Wall method. It is found that the reaction process of each sample is considerably complex; the apparent activation energy values change from 36 to 160 kJ/mol in different temperature ranges; sulfur-rich sulfide and iron sulfide concentrates have lower apparent activation energy than copper sulfide concentrate below 150 ℃; so they are more inclined to cause spontaneous combustion at ambient temperature.

Continuous cooling precipitation diagram of high alloyed Al-Zn-Mg-Cu 7049A alloy

The precipitation behaviour during cooling from solution annealing of high alloyed 7049A aluminium alloy was investigated, covering the complete cooling-rate-range of technical interest. This ranges from slow cooling rates close to equilibrium up to rates above complete supersaturation and is covering seven orders of magnitude in cooling rate （0.0005 to 5000 K/s）. The continuous cooling precipitation behaviour of 7049A alloy was recorded by combining different differential scanning calorimetry （DSC） techniques and microstructure analysis by SEM and Vickers hardness testing. The high alloyed, high strength and quench sensitive wrought aluminium alloy 7049A was investigated during quenching from solution annealing by conventional DSC in the cooling rate range of 0.0005 to 4 K/s. In this range at least two exothermal precipitation reactions were observed： a high temperature reaction in a narrow temperature interval of 450-430℃, and a low temperature reaction in a broad temperature interval down to about 200 ℃. Intensities of both reactions decreased with increasing cooling rate. Quenching from solution annealing with rates up to 1000 K/s was investigated by differential fast scanning calorimetry （DFSC） and the differential reheating method （DRM）. A critical quenching rate to suppress all precipitation reactions of 100-300 K/s was been determined.

Effect of a Novel Nucleating Agent on Isothermal Crystallization of Poly（L-lactic acid）

The effect of a novel active nucleating agent(TBC8-eb) on the isothermal crystallization of poly(L-lactic acid) (PLLA) was studied by differential scanning calorimetry(DSC) and Fourier transform infrared spectroscopy(FTIR) . The analysis on kinetics demonstrates that TBC8-eb can not only accelerate the crystallization rate but also transform most of the original spherulite crystals of PLLA into sheaf-like crystals. Furthermore,the free energy of folding(σe) of PLLA and PLLA with TBC8-eb is 0.15 and 0.06 J·m-2,respectively,which suggests that the addition of TBC8-eb favors the regular folding of molecule chains in the crystallization of PLLA,improv-ing its crystallization rate. The FTIR results show that TBC8-eb can accelerate the conformational ordering of PLLA in the isothermal crystallization. The conformational ordering of PLLA nucleated with TBC8-eb begins with the interchain interaction of CH3,and then a short helix emerges where a couple of CH3 groups interact.

Enthalpy of phase transition of isonicotinic acid

In this work, the group contribution method of Chickos et al. was applied to estimate the fusion enthalpy of isonicotinic acid, and the obtained result(29.2 k J·mol^(-1)) showed a large difference with the value(135 k J·mol^(-1)) as reported from literatures and as determined by differential scanning calorimetry(DSC). The results of DSC/TG measurement showed that the phase transition of isonicotinic acid from 187.27 °C to277.47 °C underwent a sublimation process, with a sublimation enthalpy of 128.03 k J·mol^(-1). An efficient analytical technique combining pyrolysis and gas chromatography/mass spectrometry(Py-GC/MS) was used to prove this conclusion.

Investigation of the Drug Stability at the Amorphous State Using Thermal Analysis

Formulation of poorly water-soluble crystalline drugs in their amorphous counterpart is a common approach to enhance their biodisponibility. In this study, the amorphous forms of ketoprofen and flurbiprofen were obtained by supercooling of the melt in a DSC （differential scanning calorimetry） apparatus and then investigated, especially under the stability point of view. The average rate of molecular motions at any given temperature is probably the most important parameter to know for amorphous pharmaceutical materials, and it was used to explain and predict the stability of ketoprofen and flurbiprofen. A quantitative estimate of the product＇s behaviour upon storage is obtained with additional data, such as the heat capacity of crystalline and amorphous samples and the distribution of molecular relaxation times. Amorphous flurbiprofen demonstrated greater physical stability at any aging temperature tested, when compared to ketoprofen and a different dependence from aging temperature. Both amorphous drugs could he classified as ＂fragile＂ ones.

New method for analyzing recrystallization kinetics of deformed metal by differential scanning calorimeter

The drawn copper wires have been analyzed by differential scanning calorimeter(DSC) and a new method, which uses DSC measurements to determine the Johnson-Mehl-Avrami-Kolmogorov(JMAK) exponent via introducing Arrhenius behavior and modifying the baseline of DSC curves, has been proposed. The results show that JMAK exponent and recrystallization activation energy of the drawn copper wires with a strain of 2.77 are about 2.39 and 125 k J/mol, respectively. The line linking the tangency points of DSC curve hypotenuse can be used as the baseline when calculating recrystallization fraction. The JMAK exponent obtained by the DSC method is in a good agreement with that obtained by microhardness measurements. Compared to traditional methods to measure the exponent, the proposed method is faster and less labor intensive.

Phase transitions in two organic salts based on 1,5-naphthalenedisulfonate

Two phase transition compounds,diethylammonium 1,5-naphthalenedisulfonate(1)and cyclohexylammonium 1,5-naphthalenedisulfonate(2),were screened from a series of organic salts based on 1,5-naphthalenedisulfonate.The phase transition behaviors were studied by differential scanning calorimetry,single-crystal X-ray analysis and dielectric measurements.Compounds 1 and 2 undergo phase transitions at about 202 and 148 K,respectively,accompanied by distinct dielectric changes.The origin of the phase transitions was ascribed to motional changes of the cations in the crystal lattices.