Faroongsarng Damrongsak, Sukonrat Patchara
Drug Delivery Systems Research Center, Department of Pharmaceutical Technology, Faculty of Pharmaceutical Sciences, Prince of Songkla University, Hat Yai 90112, Thailand.
Int J Pharm. 2008 Mar 20;352(1-2):152-8. doi: 10.1016/j.ijpharm.2007.10.022. Epub 2007 Oct 26.
In a polymer-water matrix, freezable water is depressed due to either porosity confinement or interaction. The aim of the study was to examine water crystallization/melting depression by sub-ambient differential scanning calorimetry. The selected starch- and cellulose-based polymers including pre-gelatinized starch (PS), sodium alginate, sodium starch glycolate, hydroxypropylmethyl cellulose (HPMC), sodium carboxymethyl cellulose, and croscarmellose sodium were employed. The pre-treated with ambient humidity (85-100% relative humidity, at 30.0+/-0.2 degrees C for 10 days) and with excess water (hydrogels) samples were subjected to between 25 and -150 degrees C cooling-heating cycle at 5.00 degrees C/min rate. The volume fractions of hydrogels were measured by light scattering technique. It was observed that all polymers but PS and HPMC with ambient humidity presented freezable water in two distinct fractions namely bound water where crystallizing/melting temperature was depressed and bulk water. The water transition in samples with various contents exhibited the pattern as a polymer solution, thus rather than confinement, the depression was due to interaction. The volume fraction-melting temperature data derived from endotherms of hydrogels were successfully fitted to Flory's model (r(2): 0.934-0.999). The Flory's interaction parameters (chi(1)) were found to vary between 0.520 and 0.847. In addition, the smaller the value of chi(1), the larger melting was depressed, i.e., stronger affinity for water.
在聚合物-水基质中,由于孔隙限制或相互作用,可冻结水会减少。本研究的目的是通过亚环境差示扫描量热法研究水的结晶/熔化减少情况。选用了基于淀粉和纤维素的聚合物,包括预糊化淀粉(PS)、海藻酸钠、淀粉乙醇酸钠、羟丙基甲基纤维素(HPMC)、羧甲基纤维素钠和交联羧甲基纤维素钠。将经过环境湿度预处理(相对湿度85-100%,在30.0±0.2℃下处理10天)和过量水(水凝胶)处理的样品,以5.00℃/分钟的速率在25至-150℃之间进行冷却-加热循环。通过光散射技术测量水凝胶的体积分数。观察到,除了处于环境湿度下的PS和HPMC外,所有聚合物都呈现出两个不同部分的可冻结水,即结晶/熔化温度降低的结合水和大量水。不同含量样品中的水转变呈现出聚合物溶液的模式,因此,这种降低不是由于限制,而是由于相互作用。从水凝胶的吸热曲线得出的体积分数-熔化温度数据成功拟合了弗洛里模型(r²:0.934-0.999)。发现弗洛里相互作用参数(χ₁)在0.520至0.847之间变化。此外,χ₁的值越小,熔化降低得越大,即对水的亲和力越强。