Department of Applied Chemistry, College of Applied Science and Institute of Natural Sciences , Kyung Hee University , Yongin , Gyeonggi 17104 , Korea.
ACS Appl Mater Interfaces. 2018 Dec 12;10(49):43112-43121. doi: 10.1021/acsami.8b18114. Epub 2018 Nov 27.
Layered rare-earth hydroxides (LRHs) with high anion exchangeability between the hydroxocation layers, where a large variety of organic anions can be sheltered, are employed to construct hybrid systems that slowly release active organic ingredients. More importantly, it is possible to endow LRHs with a photoluminescence capability by doping activator ions such as Ce, Eu, and Tb into matrices. In the present work, we explored Tb-doped layered yttrium hydroxide YTb(OH)Cl· nHO (LYH:Tb) nanosheets as a luminescent carrier for sustained release of salicylic acid (2-hydroxybenzoic acid), an example of nonsteroidal anti-inflammatory drugs and antimicrobial agents. Salicylate (sal) was intercalated into the interlayer gallery of LYH:Tb via a direct ion-exchange reaction. An observed variation in basal spacing suggested that salicylate anions are arranged in an interdigitated bilayer manner in the interlayer space of LYH:Tb. As generally observed in organic/inorganic hybrid systems, the thermal and photostabilities of salicylate were significantly improved after intercalation compared to its free state. The release kinetics of salicylate from sal-LYH:Tb hybrids in a saline solution at pH = 7.4 showed a highly sustained release of salicylate. Among various examined mathematical models, the parabolic diffusion equation best described the cumulative salicylate release. In particular, the salicylate intercalation led to the characteristic D → F ( J = 6, 5, and 4) green emission of Tb by its sensitization followed by the energy transfer to sal-LYH:Tb, whereas typical blue emission of salicylate was recovered after its release from the interlayer gallery of the LYH:Tb carrier. This green/blue luminescence change behavior provides a useful technique for in situ monitoring of the delivery and release of salicylate at target sites. The sal-LYH:Tb hybrid, with antimicrobial properties, was readily dispersed into a biodegradable polymer, polyvinyl alcohol, to prepare a transparent, UV-shielding, and luminescent composite that is applicable as an antimicrobial polymer to retard or prevent microbial growth.
层状稀土氢氧化物 (LRHs) 具有羟基阳离子层之间高阴离子可交换性,可容纳各种有机阴离子,因此被用于构建可缓慢释放活性有机成分的混合体系。更重要的是,可以通过将激活剂离子(如 Ce、Eu 和 Tb)掺杂到基质中,使 LRHs 具有荧光能力。在本工作中,我们探索了 Tb 掺杂的层状氢氧化钇 YTb(OH)Cl·nH 2 O (LYH:Tb) 纳米片作为水杨酸(2-羟基苯甲酸)的发光载体,水杨酸是一种非甾体抗炎药和抗菌剂。水杨酸根离子通过直接离子交换反应插入到 LYH:Tb 的层间腔中。观察到的基面间距变化表明,水杨酸根阴离子在 LYH:Tb 的层间空间中以交错双层的方式排列。与游离状态相比,通常在有机/无机杂化体系中,水杨酸根离子的热稳定性和光稳定性在插层后得到显著提高。在 pH = 7.4 的盐溶液中,水杨酸从 sal-LYH:Tb 杂化物中的释放动力学表现出水杨酸的高度持续释放。在所检查的各种数学模型中,抛物线扩散方程最能描述水杨酸的累积释放。特别是,水杨酸的插层导致了 Tb 的特征 D→F (J = 6、5 和 4)绿色发射,这是通过其敏化作用产生的,随后能量转移到 sal-LYH:Tb,而典型的水杨酸蓝色发射在其从 LYH:Tb 载体的层间腔中释放后恢复。这种绿色/蓝色发光变化行为为原位监测水杨酸在靶部位的输送和释放提供了一种有用的技术。具有抗菌性能的 sal-LYH:Tb 杂化物很容易分散到可生物降解聚合物聚乙烯醇中,以制备透明、防紫外线和发光的复合材料,可作为抗菌聚合物用于延缓或防止微生物生长。