Investigation on the mechanism of crystallization and aggregation of small molecules in the polymer matrices

以下内容已被披露。1)小分子的聚集和凝胶链的凝结是高度耦合的，前者和后者相互作用强烈。2)凝胶在聚集过程中形成聚集模式。n -异丙基丙烯酰胺（NIPA）的体积变化行为和体积相变可以用温度、盐浓度和糖浓度的函数——化学势与热能之比来描述。由此，提出了一种新的凝胶体积相变力学-化学耦合理论。3)再次证实了KNO_3结晶在丙烯酰胺凝胶中的奥斯特瓦尔德成熟。人们发现，在一边成熟而在另一边融化的晶体在凝胶中会移动。4) CaCO_3晶体在两层纤维素膜与Na_2CO_3和CaCl_2凝胶接触时生成。随着Na_2CO_3和CaCl_2.5浓度的增加，晶体尺寸增大。疏水反离子（十二烷基吡啶离子）与离子凝胶（丙烯酸酯与丙烯酸甲酯、丙烯酸乙酯、正丙酯或正丁酯共聚物的凝胶）结合的协同性降低，凝胶链的疏水性增强。结合的反离子之间的疏水相互作用使结合协同，被结合的反离子与链之间的疏水相互作用所屏蔽。还发现链的疏水性促进了Ca^<2+>与链上离子基团的结合。6)在凝胶链中引入电荷后，NIPA凝胶的体积相变消失。这一发现与电荷是体积相变所必需的理论不一致。

The followings have been revealed. 1) The aggregation of small molecules and the condensation of gel chains are highly coupled in the case that the former and the latter are strongly interacting with each other. 2) The aggregation patterns form in the gel in the aggregation processes. The volume change behvior and the volume phase transition of N-isopropylacrylamide (NIPA) are found to be well described by the ratio of the chemical potential to the thermal energy, which are functions of the temperature, the salt concentration, and the sugar concentration. From this fact, a new theory of mechano-chemical coupling for the volume phase transition of gel has been developed. 3) The Ostwald ripening of KNO_3 crystanllization in the acrylamide gel has been reconfirmed. It has been found that the crystals which ripen at one side and melt at the other side looK to move in the gel. 4) The CaCO_3 crystals are produced between two cellulose membranes that contact with the gels containing Na_2CO_3 and CaCl_2. The size of crystals increases with increase in the concentration of Na_2CO_3 and CaCl_2.5) The cooperativity of the hydrcphobic counterion (dodecylpyridinium ion) binding to ionic gels (gels of acrylate copolymer with methylacrylate, ethylacrylate, n-propylacrylate, or n-butylacrylate) reduces in strengthening the hydrophobicity of gel chains. The hydrophobic interaction between the bound counterions, which makes the binding cooperative, is shielded with the hydrophobic inteaction between the bound counterion and the chain.It has been also found that the hydrohobicity of chains promotes the Ca^<2+> binding to ionic groups of the chains. 6) The volume phase transition of the NIPA gel disappears in introducing the electric charges into the gel chain. This finding is inconsistent with the theory that the charge is necessary for the volume phase transition.