以手性两亲小分子为模板剂制备介孔二氧化硅纳米空心球

以L-亮氨酸为手性源合成了手性阳离子两亲性小分子化合物L-18Leu6NEtBr,用其自组装体作为模板,氢氧化钠为催化剂,经溶胶-凝胶过程制备出介孔二氧化硅纳米空心球;分析了介孔二氧化硅纳米空心球的尺寸和孔径.结果表明,所制备的二氧化硅空心球直径约100nm;其介孔孔道平行于壳表面,孔径为3.1nm.     

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.     

Characterization of gold nanoparticles electrochemically deposited on amine-functioned mesoporous silica films and electrocatalytic oxidation of glucose

This study reports the preparation and characterization of gold nanoparticles deposited on amine-functioned hexagonal mesoporous silica (NH₂–HSM) films and the electrocatalytic oxidation of glucose. Gold nanoparticles are fabricated by electrochemically reducing chloroauric acid on the surface of NH₂–HSM film, using potential step technology. The gold nanoparticles deposited have an average diameter of 80 nm and show high electroactivity. Prussian blue film can form easily on them while cycling the potential between −0.2 and 0.6 V (vs saturated calomel electrode) in single ferricyanide solution. The gold nanoparticles loading NH₂–HSM-film-coated glassy carbon electrode (Au–NH₂–HSM/GCE) shows strong catalysis to the oxidation of glucose, and according to the cathodic oxidation peak at about 0.16 V, the catalytic current is about 2.5 μA mM⁻¹. Under optimized conditions, the peak current of the cathodic oxidation peak is linear to the concentration of glucose in the range of 0.2 to 70 mM. The detection limit is estimated to be 0.1 mM. In addition, some electrochemical parameters about glucose oxidation are estimated.     

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.     

Emulsion polymerization of ethylene from mesoporous silica nanoparticles with vinyl functionalized monolayers

Emulsion polymerization of ethylene from vinyl functionalized mesoporous silica nanoparticles (V‐MSNs) was reported. V‐MSNs were synthesized via deposition of vinyl monolayers on the pore walls, and the relative surface coverage of the vinyl monolayers was 74%. A fluorinated P‐O‐chelated nickel catalyst coordinated to the vinyl groups. These V‐MSNs hosting catalysts were full dispersed in water assisted by ultrasonic processor in the presence of surfactants. After addition of ethylene, polyethylene (PE) chains grew from the pores of V‐MSNs, formation of stable nanocomposite latices with solid content up to 17.3%. Our method made V‐MSNs well‐dispersed in the PE matrix. Especially, because of a strong interaction between PE and nanoparticles, a stable V‐MSNs core/PE shell structure was formed upon thermal treatment above melting temperature of the PE. Samples were analyzed by a number of techniques including TEM, N₂ adsorption‐desorption, FTIR, and solid state ²⁹Si NMR, DLS, ¹H NMR, GPC, and DSC. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1393–1402, 2009     

Hollow mesoporous silica nanoparticles modified with coumarin‐containing copolymer for photo‐modulated loading and releasing guest molecule

Hollow mesoporous silica nanoparticles (HMSNs) grafted with a photo‐responsive copolymer containing coumarin groups were successfully prepared. With uniform polystyrene nanoparticles and cetyltrimethylammonium bromide correspondingly as the template of core and channel, HMSNs were made from tetraethyloxysilane in alkalic condition. Epoxy groups were introduced onto the outer surface of HMSNs with γ‐(2,3‐epoxypropoxy)propyltrimethoxysilane and converted into azido groups with sodium azide, resulting in azido‐functionalized HMSNs (azido‐HMSNs). Meanwhile, single‐electron transfer‐living radical copolymerization of methyl methacrylate (MMA) and 7‐(2‐methacryloyloxy)‐4‐methylcoumarin (CMA) with propargyl 2‐bromoisobutyrate as the initiator produced alkynyl‐capped P(MMA‐co‐CMA) [alkynyl‐P(MMA‐co‐CMA)]. Finally, photo‐responsive HMSNs grafted with P(MMA‐co‐CMA) [HMSN‐g‐P(MMA‐co‐CMA)] was achieved through the click reaction between azido‐HMSNs and alkynyl‐P(MMA‐co‐CMA). Different techniques such as transmission electron microscopy, Fourier transform infrared spectroscopy, and thermal gravimetric analysis confirmed the successful preparation of the resultant hybrid nanoparticles and their intermediates. Because of its hollow core, mesoporous shell channels and light responsiveness, the coumarin‐modified HMSNs would be an interesting nano‐vehicle for guest molecules. Thus, the loading and release of pyrene with HMSN‐g‐P(MMA‐co‐CMA) was studied. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 3791–3799     

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.     

Microwave-induced synthesis of highly dispersed gold nanoparticles within the pore channels of mesoporous silica

Highly dispersed gold nanoparticles have been incorporated into the pore channels of SBA-15 mesoporous silica through a newly developed strategy assisted by microwave radiation (MR). The sizes of gold are effectively controlled attributed to the rapid and homogeneous nucleation, simultaneous propagation and termination of gold precursor by MR. Diol moieties with high dielectric and dielectric loss constants, and hence a high microwave activation, were firstly introduced to the pore channels of SBA-15 by a simple addition reaction between amino group and glycidiol and subsequently served as the reduction centers for gold nanoparticles. Extraction of the entrapped gold from the nanocomposite resulted in milligram quantities of gold nanoparticles with low dispersity. The successful assembly process of diol groups and formation of gold nanoparticles were monitored and tracked by solid-state NMR and UV-vis measurements. Characterization by small angle X-ray diffraction (XRD) and transmission electron microscopy (TEM) indicated that the incorporation of gold nanoparticles would not breakup the structural integrity and long-range periodicity of SBA-15. The gold nanoparticles had a narrow size distribution with diameters in the size range of 5-10 nm through TEM observation. The average particles size is 7.9 nm via calculation by the Scherrer formula and TEM measurements. Nitrogen adsorption and desorption isotherms gave further evidence that the employed method was efficient and gold nanoparticles were successfully incorporated into the pore channels of SBA-15.     

Thioether moiety functionalization of mesoporous silica films for the encapsulation of highly dispersed gold nanoparticles

Highly dispersed gold nanoparticles within mesoporous thin films (MTFs) have been synthesized through a newly developed controllable strategy, in which (1,4)-bis(triethoxysilyl)propane tetrasufide (BPTS) organosiloxane coupling agent was co-assembled with tetraethyl orthosilicate (TEOS) to form organic groups functionalized mesoporous composite films followed with oxidization, ion-exchange with Au(en)₂Cl₃ (en: 1,2-ethanediamine) compound and calcination under hydrogen/nitrogen mixing atmosphere. Small-angle X-ray diffraction (XRD) characterization indicated that up to 10 mol% of BPTS could be incorporated into mesoporous hybrid films, and that would not breakup the structural integrity and long-range periodicity. The loaded gold nanoparticles were uniformly distributed due to the molecular level homogenous mixing of the BPTS precursor with TEOS, and its concentration could be controlled via the original ratio of BPTS to TEOS. The nanoparticles had a narrow size distribution with diameters in the size range of 3-7 nm through transmission electron microscopy (TEM) observation and underwent a slight size increase with the higher gold load level. An overall increase in the absorption intensity, a red shift of absorption peak, together with a comparatively narrower bandwidth could be observed at higher gold concentration within composite films from UV-vis spectra. Wide-angle XRD, TEM, X-ray photoelectron spectroscopy (XPS) and UV-vis spectra characterizations all agreed on the fact that the gold loading level could be controlled by the amount of BPTS in the starting sol for preparing MTFs.     

Label-free detection of adenosine based on fluorescence resonance energy transfer between fluorescent silica nanoparticles and unmodified gold nanoparticles

A sensitive and convenient strategy was developed for label-free assay of adenosine. The strategy adapted the fluorescence resonance energy transfer property between Rhodamine B doped fluorescent silica nanoparticles (SiNPs) and gold nanoparticles (AuNPs) to generate signal. The different affinities of AuNPs toward the unfolded and folded aptamers were employed for the signal transfer in the system. In the presence of adenosine, the split aptamer fragments react with adenosine to form a structured complex. The folded aptamer cannot be adsorbed on the surface of AuNPs, which induces the aggregation of AuNPs under high ionic concentration conditions, and the aggregation of AuNPs leads to the decrease of the quenching ability. Therefore, the fluorescence intensity of Rhodamine B doped fluorescent SiNPs increased along with the concentration of adenosine. Because of the highly specific recognition ability of the aptamer toward adenosine and the strong quenching ability of AuNPs, the proposed strategy demonstrated good selectivity and high sensitivity for the detection of adenosine. Under the optimum conditions in the experiments, a linear range from 98 nM to 100 μM was obtained with a detection limit of 45 nM. As this strategy is convenient, practical and sensitive, it will provide a promising potential for label-free aptamer-based protein detection.     

Preparation and characterization of gold nanoparticles and nanowires loaded into rod-shaped silica by a one-step procedure

Rod-shaped mesoporous silica nanoparticles (RMSN) with built-in gold nanoparticles or thin gold nanowires in the pore channels were in situ synthesized via a one-step procedure. The insertion of a hydrophobic gold precursor into the mesopores of RMSN was reached through a micellar solubilization mechanism and gold nanoparticles were achieved through a thermal reduction. The resulting RMSN and Au-RMSN samples were characterized by using X-ray diffraction, transmission and scanning microscopies (TEM and SEM), X-ray photoelectron spectroscopy (XPS), nitrogen physisorption and solid-state Nuclear Magnetic Resonance (NMR). The interaction of Au precursor (a carbene complex) with the thiol group at the silica surface was identified and found to play a crucial role in the dispersion of the uniform metal nanoparticles at the internal surface of RMSN. Moreover, TEM micrographs revealed the absence of large gold particles outside the mesopore network. The shape of Au nanoparticles and their loading amount in the mesoporous silica could be easily tuned by altering the concentration of gold precursor.     

Photogeneration of nanosized gold on the surface of mesoporous silica modified by benzophenone

We have studied the photocatalytic activity of porous silicas (silica gel, mesoporous sol-gel films) modified by benzophenone molecules, in the reaction of reduction of gold from tetrachloroaurate ions. Stable colloids of nanosized gold were obtained as a result of irradiating aqueous alcoholic solutions of HAuCl₄·3H₂O in the presence of the photocatalyst SiO₂-BP using as the stabilizers: a colloidal solution of silica (Ludox) or the surfactant sodium dodecyl sulfate (SDS). We have studied the effect of the stabilizer on the kinetics of the photoreduction reaction, and also on the shape and size of the nanoparticles formed. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 41, No. 6, pp. 348–353, November–December, 2005.     

Grafting of vanadyl acetylacetonate onto organo-hexagonal mesoporous silica and catalytic activity in the allylic epoxidation of geraniol

Vanadyl(IV) acetylacetonate ([VO(acac)₂]) was grafted onto a hexagonal mesoporous silica (HMS) using three different methodologies: method A – direct complex immobilisation; method B – functionalisation of the HMS with 3-aminopropyltriethoxysilane (APTES) followed by the complex immobilisation; and method C – treatment of the APTES functionalised support prepared by method B with trimethylethoxysilane (TMS) to deactivate eventually unreacted surface silanol groups, followed by complex grafting.     

Fabrication and sustained release properties of porous hollow silica nanoparticles

MCM-41-type mesoporous silica nanospheres(MSN) have been prepared using n-cetyltrimethylammonium bromide(CTAB) as a soft template.The pseudo-moire' rotational pattern inside the MSN results in many interior defects.Hollow mesoporous silica(HMS) spheres were synthesized by solvent extraction of the template from MSN.The morphology and structure of MSN and HMS were studied by TEM,XRD and nitrogen sorption techniques.A model drug,bromocresol green dye,was packed inside different regions of HMS through impregna...     

Preparation of hollow mesoporous silica nanorods for encapsulating and slowly releasing eugenol

Fragrances are widely used in many aspects of our lives.They cannot only make people happy,but also treat many diseases.However,excessively fast evaporation rate is one of the main obstacles to the use of spices.In this study,mesoporous silica nanorods(MSNRs) and hollow mesoporous silica nanorods(HMSNRs) were prepared to encapsulate eugenol.These two nano-fragrances were named eugenol@MSNRs and eugenol@HMSNRs,respectively.The morphologies,size,interior structures and pore performances of MSNRs a...     

一种新型介孔空腔二氧化硅纳米微球的制备与缓释行为

本文用十六烷基三甲基溴化铵(CTAB)作为试剂,通过软模板法合成介孔二氧化硅,利用在合成过程中,由伪莫尔转动所引起的微粒内部的大量缺陷,通过溶剂抽提,形成了具有空腔结构的介孔二氧化硅纳米微球.采用透射电子显微镜(TEM)、X射线粉末衍射仪(XRD)、N2吸附-脱附等手段对产物的形貌和结构进行了详细的表征.并以溴甲酚绿作为目标物,通过改变压强和温度,调节溴甲酚绿进入空心SiO2微球中的不同部位,对所制备的空腔介孔二氧化硅微球进行染料的装载和释放试验.结果显示该微球腔壁具有可渗透性和缓释性,而且在负压蒸发溶剂的情况下可以得到较高的药物负载量和极大地提高缓释性能.     

Spherical hollow mesoporous silica supported phosphotungstic acid as a promising catalyst for α-arylstyrenes synthesis via Friedel-Crafts alkenylation

This work presents a scalable approach for preparing spherical hollow mesoporous silica with high surface area/pore volume, serving as outstanding support for supported phosphotungstic acid catalyst with much superior catalytic performance to the one on previously reported spherical mesoporous silica toward diverse transformations, ascribed to the strengthened mass transfer and the enlarged exposure degree of acidic sites to reactants those resulting from unique hollow and mesoporous morphology.     

A facile and controllable one-pot synthesis approach to amino-functionalized hollow silica nanoparticles with accessible ordered mesoporous shells

The development of a practical synthetic method to functionalize hollow mesoporous silica with organic groups is of current intere st for selective adsorption and ene rgy storage applications.Herein,a facile and controllable one-pot approach for the synthesis of monodisperse amino-functionalized hollow mesoporous silica nanoparticles is presented.A novel solid-to-hollow structural transformation procedure of the silica nanoparticles is presented.The structural transformation is easily designed,as obse rved through transmission electro n microscopy,by tailo ring the HCl and N-lauroylsarcosine sodium molar ratio and the water content in the sol-gel.Ordered and radially oriented in situ aminofunctionalized mesochannels were successfully introduced into the shells of the hollow silica nanoparticles.A formation mechanism for the hollow mesoporous silica materials is discussed.     

稳定于具有亚5nm窗口的立方介孔氧化硅的金纳米颗粒及其优异的醇氧化活性

金纳米颗粒在烯烃加氢、水气转化、过氧化氢直接合成和醇类选择性氧化等反应中表现出独特的催化性能,引起了人们广泛关注.通常,金纳米颗粒的催化活性受到尺寸、原子堆积形式、暴露晶面及其与载体的相互作用所影响.而金纳米颗粒的烧结往往导致其催化效率迅速下降.为了解决金颗粒烧结问题,提高其使用寿命,必须控制高温处理时颗粒和原子的迁移.尽管已有很多工作见诸报道,然而到目前为止,仍未完全解决金颗粒烧结问题.本文通过调整有机模板剂和反应温度成功地合成了不同窗口尺寸的立方介孔氧化硅材料(FDU-12),并将预先合成的3 nm金颗粒负载于其上,考察了窗口尺寸对金颗粒烧结的影响.首先,采用小角X射线散射、氮气吸附-脱附、透射电镜和扫描电镜等手段证实成功合成了具有亚5 nm窗口的FDU-12材料,同时以3 nm金颗粒为探针,进一步区分了具有<3 nm和3?5 nm窗口的FDU-12样品.在抗烧结实验中发现,具有3?5 nm窗口尺寸的FDU-12能够在一个较宽的金负载量(1.0?8.3 wt%)下稳定金纳米颗粒.在550oC空气中焙烧5 h后,金颗粒的平均尺寸维持在4.5?5.0 nm.更小的窗口尺寸则会导致3 nm金颗粒无法进入FDU-12孔道,从而带来低的负载能力和差的抗烧结性能.另一方面,具有>7 nm窗口尺寸的FDU-12则只在高的金颗粒负载量(>9 wt%)下才表现出较好的抗烧结性能,低负载量时烧结严重(2.1 wt%,14.2?5.5 nm).我们推测,合适的窗口尺寸(3?5 nm)恰好能允许3 nm金颗粒进入FDU-12的孔道,在高温处理过程中,当金颗粒长大到5 nm左右时,窗口极大地限制了金颗粒的移动,导致其不能在孔与孔之间自由迁移.此外,该FDU-12材料的孔径为18 nm,这使得封装在各个孔内部的金颗粒与其他金颗粒距离较远,不利于其通过原子迁移而发生烧结.因此,拥有3?5 nm窗口尺寸的FDU-12在一个宽的金负载量下表现出良好的抗烧结能力.而对于具有>7 nm窗口尺寸的FDU-12,在高的金负载量下,它可通过自聚焦效应抑制原子迁移,从而具有优良的抗烧结性能.但在低负载量时,介孔氧化硅的绝大部分孔内并不包含多个金颗粒,自聚焦效应无法发挥作用,在高温焙烧时金颗粒可以通过大的窗口尺寸相互融合导致烧结.我们将具有不同金尺寸的AuNP/FDU-12催化剂用于环己醇选择性氧化反应中.结果表明,4.5 nm的金催化剂表现出最好的活性(1544 mmol gAu-1 h-1)和大于99%的选择性(230oC),大大超过了先前报道的基于Ag和Mn为活性中心的催化剂.另外,与负载在商用γ-Al2O3上相比,AuNP/FDU-12体系表现出了很好的选择性,直接脱水产物小于1%.同时可以保持100 h内金颗粒不发生烧结,活性不明显下降.     

Preparation of hollow mesoporous silica nanorods for encapsulating and slowly releasing eugenol

Fragrances are widely used in many aspects of our lives. They cannot only make people happy, but also treat many diseases. However, excessively fast evaporation rate is one of the main obstacles to the use of spices. In this study, mesoporous silica nanorods (MSNRs) and hollow mesoporous silica nanorods (HMSNRs) were prepared to encapsulate eugenol. These two nano-fragrances were named eugenol@MSNRs and eugenol@HMSNRs, respectively. The morphologies, size, interior structures and pore performances of MSNRs and HMSNRs. Besides, the performances of encapsulation and fragrance release of eugenol@MSNRs and eugenol@HMSNRs were compared and analyzed. The results showed that eugenol@HMSNRs encapsulated more fragrance and were faster to encapsulate compared with eugenol@MSNRs. Both the release rates of eugenol from eugenol@MSNRs and eugenol@HMSNRs were slow. But the eugenol was released from eugenol@MSNRs more slowly.