| 摘要: | 本計畫旨在研究中孔洞材料具有酸性官能基的合成與鑑定，進一步探索其可能在環境化學、催化及藥物傳送等等領域的應用可能性，這些酸性官能基包括羰基、磺酸基及磷酸基等。我們將使用所謂「直接合成法」，亦即利用含有這些官能基的矽源在適當的酸性條件下與其它一般常見的矽源如TEOS、BTEE 及 BTEB 等當作共同的矽源，首先我們將研究這些酸性官能基在中孔洞材料在有序結構的維持條件下的最大可能的量，並使用一些鑑定方法如X-ray 繞射、氮氣吸脫附、熱重分析、紅外線光譜、掃瞄電子顯微鏡、穿透式電子顯微鏡及固態核磁共振技術等。特別是我們將利用固態核磁共振技術如多核種的量測、1H 之超高魔角旋轉、二維異核關連圖譜及雙量子圖譜及REDOR (如31P-29Si、31P-13C) 深入研究這些酸性關能基與鄰近矽骨架之間的可能作用的情形，進而提供這些官能基在中孔孔洞中的可能分佈狀態，這對於我們對這些材料在環境化學、催化及藥物傳送方面的研究將會很有助益。我們將發展以下的材料及探討相關議題： (1) 合成具高含量的酸性官能基的中孔洞相關材料，這些酸性官能基包括羰基、磺酸基及磷酸基等；中孔洞相關材料包括 SBA-15, MCM-48, SBA-1, PMOs 等。 (2) 探究並開發酸性官能基的中孔洞相關材料在藥物傳送、催化及蛋白質吸附上的潛在應用。 This proposal aims to synthesize and characterize mesoporous silica materials and periodic mesoporous organosilicas (PMOs) functionalized with a variety of acidic functional groups including carboxylic acid groups (-COOH), sulfonic acid groups (-SO3H) and phosphonic acid groups (-PO3H2). These materials will be prepared by so called “direct synthesis route”, in which the organosilanes containing these acidic functional groups will condense with some conventional silica sources such as TEOS, BTEE and BTEB templated by surfactant molecules under suitable acidic conditions. First, we will investigate the influence of the loading of functional groups on the structuring ordering of the resultant materials in a systematic way. A variety of characterization techniques, including Powder X-ray, nitrogen adsorption-desorption, TGA, SEM, TEM, and solid-state NMR techniques, will be employed to characterize the materials thus obtained. In particular, solid-state NMR techniques such as multiple nuclear (1H, 13C, 29Si and 31P) measurements, ultrafast magic angle spinning for 1H (spinning speed up to 60 kHz), 2D heteronuclear correlation spectroscopy (HETCOR), 2D double quantum spectroscopy, and rotational echo double resonance (REDOR, e.g., 31P-29Si and 31P-13C) will be implemented to explore the possible interaction between the acidic functional groups and nearby silicon species in the silica framework. A combination of solid-state NMR experiments and DFT calculations will be employed to probe the local structure and framework distribution of acidic functionalized mesoporous silicas and PMOs. NMR distance measurements involving relatively isolated spin pairs such as 31P-29Si and 31P-13C allowed accurate distance information to be obtained. Further, a better understanding of the distribution of these functional groups may be obtained, which will be very helpful for applications of these materials in various research fields such as environmental remediation, adsorption, catalysis, and drug delivery, etc. We aim to synthesize the following materials and to address the following issues: (1) synthesize mesoporous materials with high loading of acidic functional groups. These functional groups include sulfonic, carboxylic, and phosphonic acid groups and the materials include SBA-15, MCM-48, SBA-1, KIT-6, and PMOs. (2) explore potential applications of these materials in the fields of drug delivery, catalysis, and protein immobilization. 研究期間：10008 ~ 10107 |
