Aqueous heavy metals removal by adsorption on amine-functionalized mesoporous silica

Amino functional mesoporous silica SBA-15 materials have been prepared to develop efficient adsorbents of heavy metals in wastewater. Functionalization with amino groups has been carried out by using two independent methods, grafting and co-condensation. Three organic moieties have been selected to incorporate the active amino sites: aminopropyl (H(2)N-(CH(2))(3)-), [2-aminoethylamino]-propyl (H(2)N-(CH(2))(2)-NH-(CH(2))(3)-) and [(2-aminoethylamino)-ethylamino]-propyl (H(2)N-(CH(2))(2)-NH-(CH(2))(2)-NH-(CH(2))(3)-). Materials have been characterized by XRD, nitrogen sorption measurements and chemical analysis. We have found that all materials preserve the mesoscopic order and exhibit suitable textural properties and nitrogen contents to act as potential adsorbents. Metal removal from aqueous solution has been examined for Cu(II), Ni(II), Pb(II), Cd(II), and Zn(II); adsorption performances of materials prepared by the two functionalization methods have been compared. In addition, copper adsorption process has been thoroughly studied from both kinetic and equilibrium points of view for some selected materials. Aqueous Cu(II) adsorption rates show that the overall process is fast and the time evolution can be successfully reproduced with a pseudo-second-order kinetic model. Whole copper adsorption isotherms have been obtained at 25 degrees C. Significant maximum adsorption capacities have been found with excellent behavior at low concentration.     

ZnO clusters in situ generated inside mesoporous silica

A new aqueous chemical growth method for in situ generation of ZnO clusters inside MCM-41 without modification scheme has been developed. Different from classical methods, the host MCM-41 does not need to be surface modified. Furthermore, ZnO clusters were prepared without calcinations, which could pack in the channels of mesoporous materials to produce quantum size effects. The PL emission peak was blue shifted to 420 nm.     

Preparation,characterization and photocatalytic applications of amine-functionalized mesoporous silica impregnated with transition-metal-monosubstituted polyoxometalates

Amine-functionalized mesoporous silica materials impregnated with transition-metal-monosubstituted polyoxometalates, K₅[M(H₂O)PW₁₁O₃₉]–(EtO)₃SiCH₂CH₂CH₂NH₂–MCM-48 (M = Co/Ni), were prepared by coordination of nickel/cobalt centers in the clusters with the amine surface groups in amine-functionalized mesoporous silica supports. The materials obtained were characterized by powder X-ray diffraction (XRD), UV–vis diffuse reflectance spectra (UV–vis-DR), infrared (IR) spectra, magic-angle spinning ³¹P MAS NMR, transmission electron microscopy (TEM) and nitrogen adsorption measurements, indicating that the primary Keggin structures remained intact in as-prepared composites, and the composites possessed mesoporous structures. The composites exhibited UV-photocatalytic activity to degrade dye rhodamine B (RB), and the pesticides including hexachlorobenzene (HCB) and methylparathion (MPT). Leakage of K₅[M(H₂O)PW₁₁O₃₉] from the support was hardly observed during the photocatalytic tests, attributed to strong coordination interactions between the Keggin units and the amine-functionalized silica surface.     

Stimulus-responsive mesoporous silica particles

The field of stimulus-responsive mesoporous silica nanoparticles has expanded greatly over the last decade. Novel advanced drug delivery systems (DDSs) that are using interesting techniques to achieve stimulus responsiveness were developed, advancing the knowledge in both the pharmaceutical and material science fields. In this review, we focus on the stimulus-responsive mesoporous silica systems with gate-like assemblies on pore openings. These assemblies are sensitive to a particular stimulus and allow precise control over the release of cargo. An overview of a variety of gating assemblies in connection with respective stimuli will provide the reader with an insight in the field with the emphasis on the construction of complete drug carrier systems. Systems are presented based on the structure of the nano-gates on pore openings in combination with the release stimuli. New achievements such as co-delivery of drugs, combining multiple stimuli with AND logic and coupling DDSs with targeting moieties and reporting systems are also highlighted.     

单分散纳米介孔二氧化硅的制备

在温和碱性条件下,以十六烷基三甲基溴化铵为模板剂,正硅酸乙酯为硅源,三嵌段共聚物F127为助剂,制备出粒径为60～80 nm的单分散纳米介孔二氧化硅MCM-41.研究了F127的用量对介孔结构和纳米粒子分散性的影响.结果表明,适量的非离子表面活性剂F127具有助模板剂的作用,可以有效地提高纳米介孔粉体的有序性;过量的F127阻碍六方介孔相的形成,降低样品的有序性.F127与十六烷基三甲基溴化铵的摩尔比在0.04～0.08范围内,可以得到有序性好、孔径均一和孔隙率大的单分散纳米介孔二氧化硅MCM-41.     

Self-assembly of nanohydroxyapatite in mesoporous silica

A novel material hexagonal mesoporous silica-hydroxyapatite (HMS-HA) has been developed based on self-assembly of nanohydroxyapatite in mesoporous silica in situ. The structural and textural properties of the materials are, respectively, characterized via X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), N(2) adsorption, thermogravimetic analysis, and high-resolution transmission electron spectroscopy (HRTEM). Variable crystallinity of HA involved in the mesopores yields from different sintering temperature, and correspondingly determines different degradation manners. This biocompatible new material hybridized nanoporosity to well acknowledge biofunctional scaffold (HA). It promises a high potential for application in drug and gene delivery.     

Gelatin-assisted porous expansion of mesoporous silica

In this study, we report the pore expansion effect of gelatin, a common amphoteric biological protein, on the hexagonal mesoporous silica materials. Tetraethyl orthosilicate (TEOS) was used as silica source and the nonionic surfactant P123 (EO₂₀PO₇₀EO₂₀) as template. The microstructure characters of products were investigated by low-angle X-ray diffraction (LAXRD), transmission electron microscope (TEM), and N₂ adsorption–desorption measurements. The results show that the products prepared with gelatin have the mild expansion ratios of 29–39% and 5–22% in pore diameter and pore volume, respectively. The specific surface area of products ranges from 445 to 590 m² g⁻¹. Moreover, it is revealed that the presence of gelatin did not change the intact 2D-hexagonal mesoporous structure of materials. The ultraviolet–visible absorption spectroscopy (UV–Vis) analysis indicates that there is an interaction between the oxygen atoms of P123 and gelatin molecules. The pore expansion may be because the gelatin can interact with the hydrophilic sides of P123 micelles via hydrogen bonds interaction, which is different from the reported pore expansion mechanisms for other systems.     

Mixed micelle-template route to mesoporous silica

Mesoporous silica materials were prepared through a novel mixed micelle-template method which was employed by alkyl polyethylene oxide (C16,E20) and C2-ceramide. X-ray diffraction patterns clearly showed the formation of mesoporous silica by contribution of mixed micelle-template up to 3/1 weight ratio (C16E20/C2-ceramide). TEM and N2 adsorption isotherms analyses indicated that the mesoporous structure was maintained even after encased C2-ceramides. However, when the weight ratio of C16E20/C2-ceramide exceeds 2/2, less ordered and irregular pore structure was observed. According to the in-vitro experiment on cancer cells such as MCF-7, HOS, and HepG2, the simultaneously encapsulated C2-ceramide shows apoptosis. Therefore, the present results could provide a new method for mesoporous material as drug delivery system.     

单分散短棒状介孔二氧化硅的制备

在温和碱性条件下,以十六烷基三甲基溴化铵为模板剂,正硅酸乙酯为硅源,平平加Os-25为助剂,制备出轴向尺寸为200nm左右,径向尺寸在60-80nm范围内的单分散短棒状纳米介孔二氧化硅MCM-41．研究了CTAB用量、平平加Os-25的用量、反应时间等因素对介孔形貌和纳米粒子分散性的影响．结果表明,适量的非离子表面活性剂平平加Os-25具有助模板剂的作用,可以有效地提高纳米介孔粉体的有序性．平平加Os-25与十六烷基三甲基溴化铵的摩尔比在0．02-0．06范围内,可以得到有序性好、分散性好的短棒状介孔二氧化硅MCM-41．     

Recent advances in functionalization of mesoporous silica

Mesoporous silica with regular geometries have been recently paid much attention owing to their scientific importance and great potentials in practical applications such as catalysis, adsorption, separation, sensing, medical usage, ecology, and nanotechnology. Especially, applications often require immobilization of the related functional groups in the mesopores. In order to achieve desire applications, modification of these mesoporous silica are indispensable. In this review, recent progresses of functionalization of mesoporous silica are comprehensively summarized. In the first parts, advances in three major methods, grafting (post-synthetic modification), co-condensation (direct synthesis), and techniques related with periodic mesoporous organosilicates, are explained. In the latter parts, new concepts for functionalization of mesoporous silica including functional template method and lizard template method are introduced. Most of the examples described here have been published in a new millennium.     

Chemiluminescence immunoassay based on dual signal amplification strategy of Au/mesoporous silica and multienzyme functionalized mesoporous silica

A chemiluminescent dual signal amplification strategy for the determination of α-fetoprotein (AFP) was proposed based on a sandwich immunoassay format. Monoclonal antibody of AFP immobilized on the gold nanoparticles doped mesoporous SiO₂ (Au/SiO₂) were prepared and used as a primary antibody. Horseradish peroxidase (HRP) and HRP-labeled secondary antibody (Ab₂) co-immobilized into the mesoporous SiO₂ nanoparticles (HRP-Ab₂/SiO₂) were used as the labeled immunological probe. Due to the high ratio surface areas and pore volumes of the mesoporous SiO₂, not only the amount of AFP monoclonal antibody but also the amount of the modified HRP and Ab₂ in HRP-Ab₂/SiO₂ were largely increased. Thus the chemiluminescent signal was amplified by using the system of luminol and H₂O₂ under the catalysis of HRP. Under the optimal conditions, two linear ranges for AFP were obtained from 0.01 to 0.5 ng mL⁻¹ and 0.5 to 100 ng mL⁻¹ with a detection limit of 0.005 ng mL⁻¹ (3σ). The fabricated signal amplification strategy showed an excellent promise for sensitive detection of AFP and other tumor markers.     

介孔SiO_2纳米微球的生物相容性研究进展

介孔SiO2纳米微球(MSNs)具有良好的理化性能,在疾病诊治方面具有广阔的应用前景,但若要成功应用于人体,需要完善其生物相容性研究。MSNs对于细胞的毒性与MSNs能否被摄取进入细胞,以及进入细胞的量有关,并取决于细胞的类型和MSNs本身的性状。通过一系列物理和化学方法的改进,可以明显改善MSNs的血液相容性,降低溶血作用。介孔SiO2纳米微球经静脉注射后分布于动物的肝脏、脾脏、肾脏、心脏、肠胃、肌肉和肺脏,其毒性作用与浓度有关;MSNs作为一种异物进入体内后可能会诱发机体产生一定程度的超敏反应。介孔SiO2纳米微球具有较好的生物相容性,但其采用何种方式应用仍需进一步研究。     

Aligned bioactive mesoporous silica coatings for implants

Ongoing research is reported aimed at preparing mesoporous silica coatings on various substrates for medical applications by a biomimetic approach (self-assembling of organic/inorganic sol-gel systems into ordered structures). Tetraethylorthosilicate (TEOS) was selected as the silica precursor, and amphiphilic triblock copolymers poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide), and the cationic surfactant cetyltrimethyl ammonium chloride (CTAC), as structure-directing agents. The mesochannels diameter could be adjusted by changing the directing agent, and a preferred alignment of the mesostructure was observed independently of the used substrate (glass, silicon, Ti or Ti6Al4V). Three different treatments (thermocalcination, photocalcination, and solvent extraction) have been also studied to remove the organic templates, of which photocalcination showed to be the most versatile. When soaked in a simulated body fluid, mesoporous silica coatings induced apatite formation after seven days.     

Organosulfonic acid-functionalized mesoporous composites based on natural rubber and hexagonal mesoporous silica

This study is the first report on synthesis, characterization and catalytic application of propylsulfonic acid-functionalized mesoporous composites based on natural rubber (NR) and hexagonal mesoporous silica (HMS). In comparison with propylsulfonic acid-functionalized HMS (HMS-SO₃H), a series of NR/HMS-SO₃H composites were prepared via an in situ sol–gel process using tetrahydrofuran as the synthesis media. Tetraethylorthosilicate as the silica source, was simultaneously condensed with 3-mercaptopropyltrimethoxysilane in a solution of NR followed by oxidation with hydrogen peroxide to achieve the mesoporous composites containing propylsulfonic acid groups. Fourier-transform infrared spectroscopy and ²⁹Si MAS nuclear magnetic resonance spectroscopy results verified that the silica surfaces of the NR/HMS-SO₃H composites were functionalized with propylsulfonic acid groups and covered with NR molecules. After the incorporation of NR and organo-functional group into HMS, the hexagonal mesostructure remained intact concomitantly with an increased framework wall thickness and unit cell size, as evidenced by the X-ray powder diffraction analysis. Scanning electron microscopy analysis indicated a high interparticle porosity of NR/HMS-SO₃H composites. The textural properties of NR/HMS-SO₃H were affected by the amount of MPTMS loading to a smaller extent than that of HMS-SO₃H. NR/HMS-SO₃H exhibited higher hydrophobicity than HMS-SO₃H, as revealed by H₂O adsorption–desorption measurements. Moreover, the NR/HMS-SO₃H catalysts possessed a superior specific activity to HMS-SO₃H in the esterification of lauric acid with ethanol, resulting in a higher conversion level.     

Electrochemically assisted self-assembly of mesoporous silica thin films

Supported mesostructured thin films are of major importance for applications in optical, electrochemical and sensing devices. However, good performance is restricted to mesostructured phases ensuring good accessibility from the film surface, which would be straightforward with cylindrical pores oriented normal to the underlying support, but this remains challenging. Here, we demonstrate that electrochemistry is likely to induce self-assembly of surfactant-templated (organo)silica thin films on various conducting supports, homogeneously over wide areas. The method involves the application of a suitable cathodic potential to an electrode immersed in a surfactant-containing hydrolysed sol solution to generate the hydroxyl ions that are necessary to catalyse polycondensation of the precursors and self-assembly of hexagonally packed one-dimensional channels that grow perpendicularly to the electrode surface. The method is compatible with controlled and localized deposition on heterogeneous supports, opening the way to electrochemically driven nanolithography for designing complex patterns of widely accessible mesostructured materials.     

Synthesis of mesoporous silica grafted with 3-glycidoxypropyltrimethoxy-silane

Hexagonal mesoporous silicas chemically modified with 3-glycidoxypropyltrimethoxy-silane functional groups were synthesized through the post-synthesis of surfactant free mesoporous silica (OSU-6-W). The solid state ²⁹Si NMR, titration method and elemental analysis of the modified samples showed that the average number of pendant groups in these hybrids were around 2.17 and 3.49 group/nm², respectively. The surface area analysis showed that these materials have pore diameters of 40.7 and 33.2 Å and surface areas of 966 and 720 m²/g, respectively. Infrared spectroscopy, solid state NMR for ¹³C and ²⁹Si nuclei and X-ray diffraction patterns are in agreement with the success of the proposed synthetic procedures, as confirmed for the formation of the mesoporous hybrids. They have shown good performance towards metal-ion adsorption.