载有量子点的介孔二氧化硅微球的制备与性能研究

采用自组装方法制备了一种磁核/介孔二氧化硅壳的微球, 调节体系中C₁₈TMS的加入量可控制介孔硅球的比表面积; 并通过化学修饰的方法对介孔微球表面进行巯基功能化修饰. 利用巯基与量子点之间的相互作用可将一定尺寸的量子点吸附于介孔二氧化硅球的孔中, 令介孔微球具有荧光效应; 同时可以利用吸附不同粒径的量子点的荧光光谱对介孔二氧化硅微球孔径的大小进行近似考察.     

pH荧光纳米传感器的研制及表征

利用溶胶-凝胶技术制得了单分散性很好的二氧化硅纳米微球,通过共价偶联方式引入对pH变化敏感的荧光素异硫氰酸酯（FITC）,这种FITC功能化二氧化硅纳米微球（FITC功能化硅微球）可作为pH荧光纳米传感器。当pH值从4.0变至7.5时,荧光强度增大约30倍。该传感器灵敏度高,响应速度快,容易制备,光稳定性好,可望用于单细胞的pH分析。     

中空SiO_2纳米微球的制备与表征

在乙醇/氨水介质中,将SiO2包覆在聚乙烯吡咯烷酮(PVP)功能化的聚苯乙烯(PS)微粒表面,利用一步法得到了中空纳米二氧化硅微球;研究了影响中空纳米二氧化硅微球形成的主要因素,并探讨了中空纳米SiO2微球的可能形成机理.结果表明,在一定的反应时间下,当氨水用量为0.6 mL、温度为70℃时,可以获得空心结构的SiO2纳米微球;通过控制四乙基原硅酸盐(TEOS)的量可以调节微球的包覆层厚度.     

磁性核壳介孔氧化硅微球的制备与应用

磁性核壳介孔氧化硅微球作为一种新型功能复合材料,已成为众多研究领域的一个研究热点。本文综述了近年来利用模板法合成磁性核壳介孔氧化硅微球的研究进展,重点阐述了溶胶-凝胶法和微乳液法在实心微球和中空微球制备中的应用。介绍了磁性介孔二氧化硅微球在蛋白质、DNA分离,靶向药物传输等生物医学上的应用以及磁性酸催化、加氢催化、纳米贵金属催化、光催化等催化领域的应用,并对其未来的发展趋势做了展望。     

智能纳米容器对缓蚀剂酸/碱双刺激的响应释放性能

以聚苯乙烯(PS)微球为硬模板,制备中空介孔二氧化硅纳米微球(HMSs),通过在其表面安装双稳态准轮烷分子作为超分子纳米阀门,实现对缓蚀剂分子苯骈三氮唑(BTA)的酸/碱双刺激的响应释放功效.采用透射电子显微镜(TEM)、X射线衍射(XRD)和比表面积分析等手段表征了HMSs的形貌和结构,使用傅里叶红外光谱(FTIR)和热重分析(TGA)验证了HMSs表面功能化过程,利用紫外-可见分光光度计(UV-Vis)实时监测缓蚀剂分子在不同pH值下的释放过程.实验结果表明,合成的HMSs呈单分散,比表面积为1141.16 m2/g.利用超分子自组装技术制得的智能纳米容器实现了在中性条件下"零释放",而在酸性或碱性条件下大量释放的效果.     

草莓型PMMA/SiO_2有机-无机复合微球的合成与表征

在纳米二氧化硅水分散介质中,借助于正离子单体甲基丙烯酰氧乙基三甲基氯化铵(MTC)与未改性纳米二氧化硅颗粒之间的电荷作用,通过MTC与甲基丙烯酸甲酯(MMA)的自由基共聚合,制备了草莓型的PMMA/SiO2复合微球.整个制备反应过程中,纳米二氧化硅无需表面处理,体系中无需另外加入乳化剂或助乳化剂,微球表面吸附的纳米二氧化硅对颗粒起稳定作用.详细讨论了纳米二氧化硅初始添加量、MTC浓度对复合微球的平均粒径、复合微球中二氧化硅含量及微球形态的影响.动态光散射粒度分布仪(DLS)测得复合微球粒径在180~300 nm之间,热重分析(TGA)表明复合微球中二氧化硅含量介于16.4%~40.8%之间.透射电镜(TEM)显示所得复合微球具有草莓型结构,二氧化硅于表面富集.     

Au@SiO_2中空微球的制备及催化性能

以天然高分子阿拉伯树胶(AG)为还原剂和稳定剂制备了金纳米粒子;将含有金纳米粒子(Au NPs)、阿拉伯树胶和氨水的溶液滴加到乙醇中形成AG-Au NPs复合胶团;利用正硅酸乙酯水解,在AG-Au NPs表面包覆二氧化硅壳层;通过简单水洗的方法得到了金纳米粒子@二氧化硅(Au@SiO_2)中空微球.采用透射电子显微镜(TEM)、X射线衍射仪(XRD)和氮气吸附实验等对Au@SiO_2中空微球进行表征.通过设计对比实验,证实阿拉伯树胶在中空结构形成过程中起到模板剂的作用.催化性能测试结果表明,所制备的Au@SiO_2中空微球在硼氢化钠还原亚甲基蓝的反应中表现出良好的催化活性和重复使用性.     

聚合物模板微球表面电性对中空二氧化硅微球形貌的影响

分别以过硫酸钾和偶氮二异丁基脒盐酸盐为引发剂,以聚乙烯吡咯烷酮(PVP)为分散剂,在水中引发苯乙烯聚合制备了2种表面分别带负电性和正电性基团的聚苯乙烯(PS)模板微球.在氨水催化下,利用正硅酸乙酯的水解缩合,形成PS/SiO_2复合微球,去除模板后得到中空SiO_2微球,并对其进行FTIR、电子显微镜、TGA以及氮气吸附等分析表征.结果表明,PS模板微球表面的电性决定了OH-的分布,从而导致PS模板微球表面SiO_2壳层不同的形成机制.当以表面带负电的PS微球为模板时,可得到树莓状的中空SiO_2微球;而以表面带正电的PS微球为模板时,得到是表面光滑的,具有介孔结构的中空SiO_2微球.     

巯丙基功能化介孔纳米二氧化硅的合成

用三种不同的方法将巯基丙基三甲氧基硅烷(MPTMS)引入二氧化硅网络中, 合成了粒径为50-200 nm的巯丙基功能化的介孔纳米二氧化硅, 并利用透射电子显微镜, 热重分析等手段对其形貌与性能进行了表征. 在巯丙基官能团的作用下介孔纳米二氧化硅的形貌发生了重大改变, 由非常规则的六角形变为纳米棒. 控制反应时间可以调节介孔纳米二氧化硅的粒径大小, 用三乙醇胺代替氢氧化钠可以合成直径在100 nm以下的功能化介孔二氧化硅粒子. 为了保护巯基官能团, 选用了酸醇提取法去除模板. 另外, 对介孔二氧化硅粒子的形成机制也进行了探讨.     

草莓型SiO2/PMMA纳米复合微球的制备

在纳米二氧化硅水分散体系中,借助于碱性辅助单体1-乙烯基咪唑(1-VID)与未改性纳米二氧化硅表面羟基之间的酸-碱作用,通过1-VID与甲基丙烯酸甲酯(MMA)的自由基共聚合,制备了草莓型的SiO2/PMMA复合微球.整个反应过程中,纳米二氧化硅无需表面处理,体系中无需另外加入乳化剂或助乳化剂,微球表面吸附的纳米二氧化硅对颗粒起稳定作用.用动态光散射粒度分布仪测得复合微球粒径在120-330nm之间,热重分析结果表明,复合微球中二氧化硅含量介于15%-20%之间.透射电镜和扫描电镜显示所得复合微球具有草莓型结构,二氧化硅富集在表面.     

不同酸对介孔二氧化硅球表面形貌和介相结构的影响

在室温、不同酸性条件下合成出微米级球形介孔二氧化硅材料，通过XRD、SEM以及氮气吸附等手段对介孔二氧化硅材料进行了表征。用TEM跟踪不同反应时间介孔二氧化硅球的形成，对这些球颗粒的合成机理进行了讨论，同时探讨了不同酸性条件下介孔二氧化硅表面形貌和介相结构的变化。     

以手性两亲小分子自组装体为模板制备介孔二氧化硅空心球

合成了手性阳离子型两亲性小分子化合物,利用圆二色谱分析了其在水中形成的自组装体的结构;以该化合物的自组装体为模板,在正丙醇和氨水的混合溶剂中制备得到了介孔二氧化硅空心球;利用扫描电镜、透射电镜、X射线衍射仪以及氮气吸附-脱附试验装置分析了二氧化硅空心球的形貌及孔结构.结果表明,两亲性小分子在水中形成的自组装体呈现手性堆积;合成的介孔二氧化硅空心球的直径约为600~800nm,壁厚约为100~150nm,其孔道垂直于球的表面,孔径约为3.0nm,比表面积约为306m2·g-1.正丙醇作为模板控制二氧化硅空心球的空腔尺寸和形貌,而两亲性小分子的自组装体作为模板控制放射状孔道的形貌和尺寸.     

Fabrication linalool-functionalized hollow mesoporous silica spheres nanoparticles for efficiently enhance bactericidal activity

To develop a novel food preservation technology for efficiently enhance bactericidal activity in a long term, hollow mesoporous silica spheres (HMSS) with regular nanostructures were applied to encapsulate natural organic antimicrobial agents. The chemical structures, morphologies and thermal stabilities of linalool, HMSS and linalool-functionalized hollow mesoporous silica spheres (L-HMSS) nanoparticles were evaluated by polarimeter, field emission scanning electron microscope (FE-SEM), transmission electron microscope (TEM), fourier transform infrared (FT-IR), thermal gravimetric analyzer (TGA), nitrogen adsorption-desorption, zeta potential and small angle X-ray diffraction (SXRD). The results show that the linalool was successfully introduced into the cavities of HMSS, and the inorganic host exhibited a high loading capacity of about 1500 mg/g. In addition, after 48 h of incubation, the minimum bactericidal concentrations (MBC) of L-HMSS against Escherichia coli (E. coli), Salmonella enterica (S. enterica) and Staphylococcus aureus (S. aureus), Listeria monocytogenes (L. monocytogenes) were decreased to be 4 (< 5) mg/mL and 8 (< 10) mg/mL, respectively. These results revealed linalool-functionalized hollow mesoporous spheres could efficiently improve the bactericidal activities of the organic component. Furthermore, SEM images clearly showed that L-HMSS indeed had an extremely inhibitory effect against gram-negative (E. coli) and gram-positive (S. aureus) by breaking the structure of the cell membrane. This research is of great significance in the application of linalool in nano-delivery system as well as food industry.     

Titanium-containing magnetic mesoporous silica spheres: effective enrichment of peptides and simultaneous separation of nonphosphopeptides and phosphopeptides

Protein phosphorylation is a common posttranslational modification, and involved in many cellular processes. Like endogenous peptides, endogenous phosphopeptides contain many biomarkers of preclinical screening and disease diagnosis. In this work, titanium-containing magnetic mesoporous silica spheres were synthesized and applied for effective enrichment of peptides from both tryptic digests of standard proteins and human serum. Besides, the enriched peptides can be further separated into nonphosphopeptides and phosphopeptides by a simple elution. First, titanium-containing magnetic mesoporous silica spheres were synthesized by a sol-gel method and found to have high surface area, narrow pore size distribution, and useful magnetic responsivity. Then, as the prepared material was used for selective capturing of phosphopeptides, it demonstrated to have higher selectivity than commercial titanium dioxide. Moreover, via combination of size-exclusion mechanism, hydrophobic interaction, and affinity chromatography, titanium-containing magnetic mesoporous silica spheres were successfully applied to simultaneously extract and separate nonphosphopeptides and phosphopeptides from standard protein digestion and human serum.     

Electrochemical Characteristics of Discrete,Uniform, and Monodispersed Hollow Mesoporous Carbon Spheres in Double‐Layered Supercapacitors

Core–shell‐structured mesoporous silica spheres were prepared by using n‐octadecyltrimethoxysilane (C18TMS) as the surfactant. Hollow mesoporous carbon spheres with controllable diameters were fabricated from core–shell‐structured mesoporous silica sphere templates by chemical vapor deposition (CVD). By controlling the thickness of the silica shell, hollow carbon spheres (HCSs) with different diameters can be obtained. The use of ethylene as the carbon precursor in the CVD process produces the materials in a single step without the need to remove the surfactant. The mechanism of formation and the role played by the surfactant, C18TMS, are investigated. The materials have large potential in double‐layer supercapacitors, and their electrochemical properties were determined. HCSs with thicker mesoporous shells possess a larger surface area, which in turn increases their electrochemical capacitance. The samples prepared at a lower temperature also exhibit increased capacitance as a result of the Brunauer–Emmett–Teller (BET) area and larger pore size.     

介孔氧化硅球负载钴基催化剂在费托合成中的应用

以介孔氧化硅空心球(HMSS)为载体, 采用双溶剂法浸渍硝酸钴溶液制备了高分散度的钴催化剂, 并表征了催化剂中Co3O4颗粒的负载情况和费托(F-T)反应性能. 结果表明: Co3O4颗粒在介孔硅球孔道内形成100～200 nm左右分散良好的簇团, 将催化剂压碎和刻蚀后的透射电子显微镜(TEM)证实, 这些簇团是由尺寸约为10～15 nm大小均匀的Co3O4单分散颗粒组成, 这些单分散颗粒锚定在介孔硅球孔道内, 彼此之间被相邻孔壁隔开; 催化剂中钴-硅作用很弱, 在600 K下即可被还原; F-T反应评价表明, 所得产物保持了良好的烃分布, 主要集中于C5～C18烃, 选择性在60%左右, C5＋选择性达到80%以上.     

Green preparation of hollow mesoporous silica nanosphere inside-loaded gold nanoparticles and the catalytic activity

In this work, an active nano-catalyst with gold nanoparticles loaded in hollow mesoporous silica nanospheres (HMSNs/Au) was prepared by a one-pot sol-gel method, in which gold ions were loaded in hollow mesoporous silica spheres followed by sodium alginate reduction. The characterization of the HMSNs/Au were determined by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), N₂ adsorption–desorption isotherms (BET). The high catalytic activity of HMSNs/Au, denoted as apparent turn-over frequency (TOF), was detected by UV-Vis spectrophotometer for the catalytic reduction of 4-nitrophenol (74.5 h^?1) and 2-nitrophenol (108.7 h^?1) in the presence of sodium borohydride solution due to the small gold nanoparticles size and overall exposure of active sites. It is expected that this ecofriendly approach to prepare inorganic composited nanoparticles as high active catalysts based on hollow mesoporous materials was a promising platform for loading noble metal nanoparticles.     

一种新型的空心镍纳米球的合成

通过以二氧化硅粒子作为模板和金纳米粒子为表面晶种的方法制备了壳厚度可控的镍空心球。采用TEM﹑XRD对二氧化硅/镍复合球和镍空心球进行了表征和研究。结果表明镍纳米壳是由似针状的面心立方的镍纳米粒子构成的，碱溶液处理过程不影响镍纳米壳的形貌。高温处理显示镍空心球具有良好的热稳定性。     

A General Route to Hollow Mesoporous Rare‐Earth Silicate Nanospheres as a Catalyst Support

Hollow mesoporous structures have recently aroused intense research interest owing to their unique structural features. Herein, an effective and precisely controlled synthesis of hollow rare‐earth silicate spheres with mesoporous shells is reported for the first time, produced by a simple hydrothermal method, using silica spheres as the silica precursors. The as‐prepared hollow rare‐earth silicate spheres have large specific surface area, high pore volume, and controllable structure parameters. The results demonstrate that the selection of the chelating reagent plays critical roles in forming the hollow mesoporous structures. In addition, a simple and low‐energy‐consuming approach to synthesize highly stable and dispersive gold nanoparticle–yttrium silicate (AuNPs/YSiO) hollow nanocomposites has also been developed. The reduction of 4‐nitrophenol with AuNPs/YSiO hollow nanocomposites as the catalyst has clearly demonstrated that the hollow rare‐earth silicate spheres are good carriers for Au nanoparticles. This strategy can be extended as a general approach to prepare multifunctional yolk–shell structures with diverse compositions and morphologies simply by replacing silica spheres with silica‐coated nanocomposites.     

Step-by-step synthesis of copper(I) complex supported on platinum nanoparticle-decorated mesoporous silica hollow spheres and its remarkable catalytic performance in Sonogashira coupling reaction

In this study, a step-by-step method for the synthesis of platinum nanoparticles and copper(I) complex supported on mesoporous silica hollow spheres (Pt-MSHSs-Cu) is introduced. Scanning electron microscopy, transmission electron microscopy, powder X-ray diffraction, Fourier transform infrared spectroscopy, nitrogen adsorption–desorption, energy-dispersive X-ray spectrometry, X-ray photoelectron spectroscopy, and elemental and thermogravimetric analyses were applied for characterization of the surface, structure, size, phase composition, and morphology of the synthesized materials. The characterized material, Pt-MSHSs-Cu, was used as an efficient and heterogeneous catalyst in the Sonogashira coupling reaction under different reaction conditions. In comparison with MSHSs, Cu(I)-functionalized MSHSs (MSHSs-Cu), and Pt-MSHSs samples, the Pt-MSHSs-Cu catalyst exhibited significantly increased catalytic performance with 91.50% yield. Therefore, the results obtained suggested a synergistic effect derived from platinum nanoparticles, MSHSs substrate, and copper(I) complex, which enhanced the rate of the Sonogashira coupling reaction.