Hussein Mohd Zobir, Nasir Norashikin Mat, Yahaya Asmah Hj
Advanced Materials and Nanotechnology Laboratory, Institute of Advanced Technology (ITMA), University Putra Malaysia, 43400 Serdang, Selangor, Malaysia.
J Nanosci Nanotechnol. 2008 Nov;8(11):5921-8. doi: 10.1166/jnn.2008.252.
Metanilate-layered double hydroxide nanohybrid compound was synthesized for controlled release purposes through co-precipitation method of the metal cations and organic anion. The effect of various divalent metal cations (M2+), namely Zn2+, Mg2+ and Ca2+ on the formation of metanilate-LDH nanohybrids, in which metanilate anion was intercalated into three different layered double hydroxide (LDH) systems; Zn-Al, Mg-Al and Ca-Al were investigated. The syntheses were carried out with M2+ to Al3+ initial molar ratio, R of 4. The pH of the mother liquor was maintained at pH 7.5 and 10 during the synthesis, and the resulting mixture was aged at around 70 degrees C for about 18 h. The intercalation of metanilate anion into the host was found to be strongly influenced by the M2+ that formed the inorganic metal hydroxide layers. Under our experimental condition, the formation of the nanohybrid materials was found to be more feasible for the Zn-Al than for the other two systems, in which the former showed well-ordered layered organic-inorganic nanohybrid structure with good crystallinity. Intercalation is confirmed by the expansion of the interlayer spacing to about 15-17 A when metanilate was introduced into the interlamellae of Zn-Al LDHs. In addition, CHNS and FTIR analyses also support that metanilate anion has been successfully intercalated into the interlamellae of the inorganic LDH. Apart from M2+, this study also shows that the initial pH of the mother liquor plays an important role in determining the physicochemical properties of the resulting nanohybrids, especially the mole fraction of the Zn2+ substituted by the Al3+ ion in the LDH inorganic sheets which in turn controlled the loading percentage of the organic anion, surface properties and the true density. Preliminary study shows that LDH can be used to host beneficial guests, active agent with controlled release capability of the guests. Generally the overall process is governed by pseudo second order kinetic but for the first 180 min, the release process can be slightly better described by parabolic diffusion than the other models.
通过金属阳离子和有机阴离子的共沉淀法合成了间苯二甲酸层状双氢氧化物纳米杂化化合物用于控释目的。研究了各种二价金属阳离子(M2+),即Zn2+、Mg2+和Ca2+对间苯二甲酸-LDH纳米杂化物形成的影响,其中间苯二甲酸根阴离子插入到三种不同的层状双氢氧化物(LDH)体系中;Zn-Al、Mg-Al和Ca-Al。合成时M2+与Al3+的初始摩尔比R为4。在合成过程中,母液的pH值保持在7.5和10,所得混合物在约70℃下老化约18小时。发现间苯二甲酸根阴离子插入主体受到形成无机金属氢氧化物层的M2+的强烈影响。在我们的实验条件下,发现纳米杂化材料的形成对于Zn-Al比其他两个体系更可行,其中前者显示出具有良好结晶度的有序层状有机-无机纳米杂化结构。当间苯二甲酸引入到Zn-Al LDHs的层间时,层间距扩大到约15-17 Å,证实了插入。此外,CHNS和FTIR分析也支持间苯二甲酸根阴离子已成功插入无机LDH的层间。除了M2+,本研究还表明母液的初始pH值在决定所得纳米杂化物的物理化学性质方面起着重要作用,特别是在LDH无机片中被Al3+离子取代的Zn2+的摩尔分数,这反过来又控制了有机阴离子的负载百分比、表面性质和真密度。初步研究表明,LDH可用于容纳有益客体,即具有客体控释能力的活性剂。一般来说,整个过程受伪二级动力学控制,但在前180分钟内,释放过程用抛物线扩散比其他模型能更好地描述。