纳米Au团簇在氧化钛修饰的介孔分子筛MCM-41中的组装

以钛酸丁酯为ＴｉＯ_２前驱体,使ＴｉＯ_２均匀分散于纯硅介孔分子筛ＭＣＭ－４１的介孔孔道内表面,利用ＴｉＯ_２光学性质将ＡｕＣｌ－４还原为Ａｕ（０）并组装于氧化钛修饰的ＭＣＭ－４１孔道中．对所合成的Ａｕ负载的氧化钛修饰的ＭＣＭ－４１进行了ＸＲＤ,ＸＰＳ,Ｎ_２吸附－脱附曲线,及固体ＵＶ－Ｖｉｓ漫反射等多种结构表征．由ＸＰＳ谱和固体ＵＶ－Ｖｉｓ漫反射吸收光谱的ｐｌａｓｍｏｎ吸收峰证明Ａｕ团簇呈现０价的金属状态．     

温和条件下介孔分子筛MCM-41的修饰与表征

在温和条件下,以３－氨丙基三乙氧基硅烷为偶联剂,修饰介孔分子筛 ＭＣＭ－４１（Ｓｉ／Ａｌ＝３５）,成功地将有机官能团引入到介孔分子筛孔道中,制备了一种无机一有机复合材料ＭＣＭ－（ＣＨ_２）_３ＮＨ_２,以 ＸＲＤ、ＦＴＩＲ、ＤＴＡ－ＴＧＡ、 Ｎ_２吸附－脱附和 ＨＲＥＭ表征了复合材料;结果表明：有机基团－（ＣＨ_２）_３ＮＨ_２不仅进人孔道、修饰了ＭＣＭ－４１的孔壁,而且使介孔分子筛ＭＣＭ－４１保持了有序的孔道结构．     

配合物[Fe(bipy)2]3+修饰的MCM-41的合成与表征

以γ－氨丙基修饰介孔分子筛ＭＣＭ－４１内孔壁,将引入的γ－氨丙基与金属配位离子［Ｆｅ（ｂｉｐｙ）_２］^３＋通过配位键首次合成了金属配位化合物修饰的ＭＣＭ－４１（ＭＣＭ－ａｐ－Ｆｅ（ｂｉｐｙ）_２）．通过ＸＲＤ,７７Ｋ氮气吸附－脱附曲线,固体ＵＶ－ｖｉｓ漫反射光谱和循环伏安曲线表征了复合物ＭＣＭ－ａｐ－Ｆｅ（ｂｉｐｙ）_２。由于［Ｆｅ（ｂｉｐｙ）_２］^３＋的引入,使 ＭＣＭ－ａｐ－Ｆｅ（ｂｉｐｙ）_２的结晶度降低, ＢＥＴ比表面积、孔容和最可几孔径急剧下降．γ－氨丙基与Ｆｅ^３＋的配位而使其ＵＶ－ｖｉｓ漫反射吸收光谱与ＭＣＭ－Ｆｅ（ｂｉｐｙ）_２不同;循环伏安特性曲线表明ＭＣＭ－ａｐ－Ｆｅ（ｂｉｐｙ）_２在电化学上比浸渍法制备的ＭＣＭ－Ｆｅ（ｂｉｐｙ）_２稳定．     

Ti(IV)在介孔氧化硅MCM-41中的液相移植

以钛酸丁酯为原料,通过液相移植反应,在介孔氧化硅ＭＣＭ－４１中成功地组装了Ｔｉ（ＩＶ）,利用ＸＲＤ、ＴＥＭ、ＥＤＳ、ＦＴ－ＩＲ、Ｎ_２吸附－脱附、^２９Ｓｉ ＭＡＳ ＮＭＲ等多种实验方法对材料进行了表征,并讨论了液相移植反应的机理．实验表明,通过与介孔材料骨架表面Ｑ^３硅原子中的硅醇键（Ｓｉ－ＯＨ）的反应而形成钛－氧－硅（Ｔｉ－Ｏ－Ｓｉ）键,Ｔｉ（ＩＶ）被成功地固定到介孔材料的骨架上面; ９５０～９６０ｃｍ^－１红外共振吸收的加强是Ｓｉ－Ｏ－Ｔｉ键形成的标志．     

TiO_2在MCM-41内表面单层及双层分散的结构表征

首次以有机物钛酸丁酯为前驱体,合成了ＴｉＯ２呈单层分散状态（Ｔｉ／Ｓｉ＝０.２０）或双层分散状态（Ｔｉ／Ｓｉ＝０．３９）的介孔分子筛ＭＣＭ－４１（Ｓｉ／Ａｌ＝３５）,并以 ＸＲＤ,ＦＴＩＲ,Ｎ２吸附－脱附,固体ＵＶ－ｖｉｓ 漫反射等表征手段对其结构特征和氧化钛分散状态进行了研究．结果表明： ＴｉＯ２在介孔分子筛ＭＣＭ－４１孔道中分散, ＭＣＭ－４１骨架结构结晶度降低,但是附着二层ＴｉＯ２后,仍能保持长程有序结构; ＴｉＯ２与ＭＣＭ－４１孔道表面的ＳｉＯ２以化学键连接,生成Ｓｉ－Ｏ—Ｔｉ键;无论是单层还是双层分散的 ＴｉＯ２在 ＭＣＭ－４１内孔壁均匀分散;且由于ＴｉＯ２粒子的减小使其对紫外光的吸收发生明显的蓝移现象．     

Li2MnO3的柠檬酸盐溶胶-凝胶法合成及离子导电性

以Ｌｉ_２ＣＯ_３、ＭｎＣＯ_３为原料,用柠檬酸盐溶胶凝胶法合成了Ｌｉ_２ＭｎＯ_３超微粉．对合成的材料进行了ＤＴＡ、ＴＧ、ＸＲＤ和ＴＥＭ等表征,并应用交流阻抗谱技术测定了样品的电导率．结果表明,６５０。Ｃ以上生成Ｌｉ_２ＭｎＯ_３纯相超微粉,粒径在５０nｍ以下．在１８～４００℃温度范围内,产物烧结体的离子导电率为１０^－６～１０^－３Ｓ·ｃｍ^－１,其电导活化能为４４．８７ｋＪ·ｍｏｌ^－１．     

TiO2在MCM-41内表面单层及双层分散的结构表征

首次以有机物钛酸丁酯为前驱体,合成了ＴiO2呈单层分散状态（Ｔi/Si=0．２０）或双层分散状态（Ｔi/Si=0．39)的介孔分子筛ＭＣＭ－４１（Si/Al=35）,并以ＸＲＤ,ＦＴＩＲ,Ｎ２吸附－脱附,固体ＵＶ－vis漫反等表征手段对其结构特征的氧化钛分散状态进行了研究,结果表明：ＴiO2在介孔分子筛ＭＣＭ－４１孔道中分散,ＭＣＭ－４１骨架结构结晶度降低,但是附着二层ＴiO2后,仍能保持长程有序结构;ＴiO2与ＭＣＭ－４１骨架结构结果度降低低,但是附着二层ＴiO2后,仍能保持长程有序结构,ＴiO2与ＭＣＭ－４１孔道表面的ＳiO2比化学键连接,生成Ｓi-O-Ti键;无论是单层还是双层分散的ＴiO2在ＭＣＭ－４１内孔壁均匀分散,且由于ＴiO2粒子的减小使其对紫外光的吸收发生明显的蓝移现象。.     

纳米级LiMn2O4尖晶石合成及电化学性能研究

以Ｌｉ_２ＣＯ_３和Ｍｎ（ＮＯ_３）_２为原料,以聚丙烯酰胺为高分子网络剂制得前驱体后,用微波加热技术合成了纳米晶尖晶石ＬｉＭｎ_２Ｏ_４粉体,通过循环伏安及充放电技术对其进行电化学性能测试表明,该材料的电化学比容量为 １２０ｍＡｈ／ｇ;循环 ５０次后衰减率为 ４．７％;通过 ＳＥＭ及ＸＲＤ分析其微观形貌表明,该材料不仅相纯度高,而且颗粒粒度近于纳米级,有利于Ｌｉ^＋的嵌入／脱嵌．本文所提供的微波一高分子网络技术不仅为合成具有优良性能的锂锰尖晶石氧化物材料提供了一个新方法,而且为合成其他类型高性能氧化物陶瓷材料提供了一条新思路．     

配合物[Fe(bipy)2]3+修饰的MCM-41的合成与表征

以γ－氨丙基修饰介孔分子筛ＭＣＭ－４１内孔壁,将引入的γ－氨丙基与金属配位离子「Ｆｅ（ｂｉｐｙ）２」＾３＋通过配位键首次合成了金属配位化合物修饰的ＭＣＭ－４１（ＭＣＭ－ａｐ－Ｆｅ（ｂｉｐｙ）２）。通过ＸＲＤ,７７Ｋ氮气吸附－脱附曲线,固体ＵＶ－ｖｉｓ漫反射光谱和循环伏安曲线表征了复合物ＭＣＭ－ａｐ－Ｆｅ（ｂｉｐｙ）２。由于「Ｆｅ（ｂｉｐｙ）２」＾３＋的引入,使ＭＣＭ－ａｐ－Ｆｅ（ｂｉｐｙ）２的结晶     

C60-PMMA复合膜的纳米结构研究

采用化学有机沉积法,在Ｓｉ（１００）、ＫＢｒ压片及微栅衬底上分别制备了 Ｃ_６０／ＰＭＭＡ重量比不同的Ｃ_６０－ＰＭＭＡ复合膜．红外光谱分析表明,Ｃ_６０分子已均匀地分布在Ｃ_６０－ＰＭＭＡ复合膜中．利用Ｘ射线衍射（ＸＲＤ）谱和透射电子显微镜（ＴＥＭ）研究了该复合膜的结构,结果显示原来均匀分布在ＰＭＭＡ中的Ｃ_６０分子经过扩散趋向于形成非晶或晶化的Ｃ_６０颗粒．经过退火,以面心立方结构单晶形式存在的Ｃ_６０颗粒的尺寸为３０～１００ｎｍ,且以规则的几何形体分散在ＰＭＭＡ连续相中．玻耳兹曼能量分布规律能够较好地解释,提高Ｃ_６０含量或退火温度,晶化Ｃ_６０颗粒尺寸增大的现象．     

Pt nanoparticles inside the mesopores of TiO<Subscript>2</Subscript>–MCM-48: synthesis,characterization and catalytic activity for CO oxidation

TiO₂ and Pt nanoparticles were deposited in the channels of siliceous MCM-48 via a sequential incipient wetness-impregnation method employing (NH₄)₂PtCl₄ as platinum source. The resulting composite Pt/TiO₂–MCM-48 (1 wt% Pt, ca. 3 wt% Ti) was characterized using XRD, TEM, nitrogen physisorption, hydrogen chemisorption, UV–vis spectroscopy, and XPS; its catalytic activity for CO oxidation was also explored. These data were compared with those of Pt/MCM-48 prepared via an analogous route. The results reveal that the platinum was deposited inside the intact pore system in both cases. It remains inside upon mild reduction but tends to segregate out of the pore system at higher reduction temperatures or during CO oxidation. Both composites were found to be highly active in CO oxidation, with 50% conversion at 460–475 K after activation of the unreduced catalysts in the (net oxidizing) feed. Striking differences in this activation process between Pt/MCM-48 and Pt/TiO₂–MCM-48 suggest that the precursor reduction is influenced by an interaction with the TiO₂ component in the latter.     

含稳定骨架铁的Fe-MCM-41介孔分子筛的合成与表征

以离子液体1-十六烷基-3-甲基溴代咪唑([C₁₆mim]⁺Br^-)为模板剂合成了含铁介孔分子筛Fe-MCM-41,并对其结构和形态进行了表征. 研究结果表明, 用该方法合成的Fe-MCM-41不仅具有比较大的比表面积, 规则的介孔孔道结构等特征, 而且形成了双孔道结构. UV-Vis和EPR 顺磁共振的表征结果表明, 采用离子液体[C₁₆mim]⁺Br^-为模板剂所合成的Fe-MCM-41介孔分子筛, 铁物种能稳定地存在于介孔分子筛骨架中.     

Investigation of in vitro permeability and in vivo pharmacokinetic behavior of bare and functionalized MCM-41 and MCM-48 mesoporous silica nanoparticles: a burst and controlled drug release system for raloxifene

In the present work, MCM-41 and MCM-48 type of nanoparticles were successfully engineered. Effect of nanosize and amine functionalization on drug release, in vitro intestinal absorption and in vivo pharmacokinetic behavior was investigated in a comprehensive manner. The tailor-made bare and surface decorated MCM-41 and MCM-48 were synthesized and evaluated for their mesoporous skeleton, pore size, particle size, surface area, zeta potential, etc. by nitrogen sorption, DLS, TEM, etc. Incorporation of raloxifene (RLF) was affirmed using optimized immersion-solvent evaporation technique and its success confirmed by DSC, IR, and XRD analysis. TGA analysis revealed higher %grafting of amine groups on the exterior and larger RLF encapsulation into mesoporous derivate. The detailed in vitro release study revealed SGF to be the most compatible media for RLF showing an initial burst release from pristine nanoparticles and a delayed release from surface coated nanoparticles. Furthermore, release kinetics model data demonstrated Weibull and Higuchi as the best fit models for bare and amine-functionalized nanoparticles respectively. Moreover, an in vitro permeability study on Caco-2 cell line revealed higher absorption by engineered nanoparticle as compared to pure RLF and its marketed formulation. The supremacy in the in vivo pharmacokinetic parameters of RLF-41 and RLF-48 was demonstrated with 3.33 and 3.50 times enhancement in the bioavailability of RLF with respect to RLF suspension. To sum up, the results obtained were superior and promising for synthesized nanoparticles and more precisely for MCM-48 amongst them.     

The investigation of MCM-48-type and MCM-41-type mesoporous silica as oral solid dispersion carriers for water insoluble cilostazol

Objective: To explore the suitable application of MCM-41 (Mobil Composition of Matter number forty-one)-type and MCM-48-type mesoporous silica in the oral water insoluble drug delivery system.

Methods: Cilostazol (CLT) as a model drug was loaded into synthesized MCM-48 (Mobil Composition of Matter number forty-eight) and commercial MCM-41 by three common methods. The obtained MCM-41, MCM-48 and CLT-loaded samples were characterized by means of nitrogen adsorption, thermogravimetric analysis, ultraviolet-visible spectrophotometry, scanning electron microscopy, transmission electron microscopy, differential scanning calorimetry and powder X-ray diffractometer.

Results: It was found that solvent evaporation method was preferred according to the drug loading efficiency and the maximum percent cumulative drug dissolution. MCM-48 with 3D cubic pore structure and MCM-41 with 2D long tubular structure are nearly spherical particles in 300–500?nm. Nevertheless, the silica carriers with similar large specific surface areas and concentrating pore size distributions (978.66?m²/g, 3.8?nm for MCM-41 and 1108.04?m²/g, 3.6?nm for MCM-48) exhibited different adsorption behaviors for CLT. The maximum percent cumulative drug release of the two CLT/silica solid dispersion (CLT-MCM-48 and CLT-MCM-41) was 63.41% and 85.78% within 60?min, respectively; while in the subsequent 12?h release experiment, almost 100% cumulative drug release were both obtained. In the pharmacokinetics aspect, the maximum plasma concentrations of CLT-MCM-48 reached 3.63?mg/L by 0.92?h. The AUC_0–∞ values of the CLT-MCM-41 and CLT-MCM-48 were 1.14-fold and 1.73-fold, respectively, compared with the commercial preparation.

Conclusion: Our findings suggest that MCM-41-type and MCM-48-type mesoporous silica have great promise as solid dispersion carriers for sustained and immediate release separately.     

金红石TiO2基质中[MoO4]2-基团的上转换发光

在978nm激光二极管的激发下，Mo掺杂的TiO2材料表现出很强的宽带上转换发光，该发光来源于[MoO4]^2-基团的激发态3T1，3T2能级到基态1Al能级的电子跃迁．X射线衍射表明样品为金红石单一相，红外吸收光谱证实了[MoO4]2-的存在．由光电子能谱推测体系中还含有低价态的Mo离子，它们提供了上转换得以进行的中间态．高温下的氧化还原处理会改变低价Mo的数量，从而严重影响样品的发光行为。     

酸催化溶胶-凝胶法Eu2+、Gd3+共掺杂TiO2的制备及光催化活性

采用酸催化溶胶-凝胶法制备了Gd³⁺、Eu²⁺两种稀土金属离子混合掺杂的复合TiO₂光催化剂, 通过TEM、XRD、UV-Vis等分析手段对产物进 行了表征, 结果表明: 样品均呈锐钛矿型结构, 颗粒尺寸的变化只与掺杂离子总量有关, 掺杂量为1.0%时达最小值; 一定比例Eu²⁺、Gd³⁺的混合掺杂, 能增强可见光范围内光响应. 以甲基橙为目标降解物研究了不同比例Eu²⁺、Gd³⁺混合掺杂对纳米二氧化钛光催化活性的影响, Gd³⁺、Eu²⁺适合掺杂量范围分别为0.1%～1.0%和0.5%～1.5%. Eu²⁺、Gd³⁺混和掺入TiO₂光催化剂中产生协同效应, 探讨了Eu²⁺和Gd³⁺与TiO₂之间的相互作用, 讨论了光催化活性与催化剂性质的关系.