Functionalized bimodal mesoporous silicas as carriers for controlled aspirin delivery

The bimodal mesoporous silica modified with 3-aminopropyltriethoxysilane was performed as the aspirin carrier. The samples’ structure, drug loading and release profiles were characterized with X-ray diffraction, scanning electron microscopy, N₂ adsorption and desorption, Fourier transform infrared spectroscopy, TG analysis, elemental analysis and UV-spectrophotometer. For further exploring the effects of the bimodal mesopores on the drug delivery behavior, the unimodal mesoporous material MCM-41 was also modified as the aspirin carrier. Meantime, Korsmeyer-Peppas equation f_t=ktⁿ was employed to analyze the dissolution data in details. It is indicated that the bimodal mesopores are beneficial for unrestricted drug molecules diffusing and therefore lead to a higher loading and faster releasing than that of MCM-41. The results show that the aspirin delivery properties are influenced considerably by the mesoporous matrix, whereas the large pore of bimodal mesoporous silica is the key point for the improved controlled-release properties.     

(MCM-41)-La_2O_3纳米复合材料的制备、表征及光学性质

借助水热法,以正硅酸乙酯为硅源,十六烷基三甲基溴化铵为模板剂,在碱性条件下制备了纳米MCM-41分子筛。通过固相热扩散法将La2O3组装到MCM-41介孔孔道中,制备出含La2O3不同浓度的(MCM-41)-La2O3主-客体纳米复合材料。采用化学分析、粉末XRD、FTIR、77K低温N2吸附-解吸附、固体扩散漫反射吸收光谱、拉曼光谱、扫描电镜和发光光谱对主-客体复合材料进行表征。粉末XRD结果表明,La2O3组装到MCM-41分子筛的孔道后并未破坏分子筛骨架,在所制备的(MCM-41)-La2O3主-客体纳米复合材料中MCM-41骨架结构仍然具有较高的有序性,并且,随着植入客体材料浓度的增加复合材料的有序度有所降低。红外光谱表明所制备的纳米复合材料主体分子筛骨架完好;低温氮气吸附-解吸附技术表明La2O3已经部分地占据了MCM-41分子筛孔道,导致分子筛的比表面积和孔体积都有所降低;固体扩散漫反射吸收光谱表明吸收光谱的吸收峰发生了蓝移现象,并表现出量子限域效应,说明La2O3已经组装到了MCM-41分子筛的孔道中;拉曼光谱表明所制备的复合材料没有出现新的特征峰,表明La2O3已经组装到了MCM-41分子筛的孔道中;扫描电镜表明(MCM-41)-La2O3样品的外观非常规整,主要呈现的是球状结构,La2O3含量为10%时,(MCM-41)-La2O3的平均粒径为(114±10)nm。发光光谱研究结果表明,所制备的复合材料(MCM-41)-La2O3样品在396nm处具有较好的发光性质,因而具有作为发光材料潜在应用前景。     

Mesostructured silica matrix for irinotecan delivery systems

Three mesostructured silica-type carriers, MCM-41 and MCM-41 functionalized by a postsynthesis grafting procedure with hydrophilic aminopropyl groups (MCM-APTES) and hydrophobic vinyl moieties (MCM-VTES), respectively, were investigated in order to elaborate drug delivery systems (DDS) for irinotecan molecules. All studied drug delivery systems exhibited higher cytotoxicity on murine embrionary fibroblastic (MEF) cells than free irinotecan at the same content of the cytostatic agent, whereas no toxicity was observed for the three unloaded carriers. The cytotoxic effect of irinotecan loaded on MCM-41-type carriers continued to increase even 24 h after ceasing the cell exposure to the drug and remained significantly higher than that of free irinotecan. The cellular uptake of silica-type hybrids was investigated by labelling MCM-APTES with Rhodamine B. In the case of the studied DDS, an endocytotic mechanism was found to be involved in the cell uptake process, and it was used to explain the cytotoxicity differences between free irinotecan and drug loaded on MCM-41-type supports.

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Characterization and optimization of mesoporous magnetic nanoparticles for immobilization and enhanced performance of porcine pancreatic lipase

In this paper, Fe₃O₄ nanoparticles coated with mesoporous silica were prepared successfully, noted as Fe₃O₄ at the mobile composition of matter No. 41 (MCM-41). Also, Fe₃O₄ at MCM-41 was grafted by both 3-aminopropyltriethoxysilane (APTS) and 3-chloropropyltriethoxysilane (CPS), noted as Fe₃O₄ at MCM-41/APTS and Fe₃O₄ at MCM-41/CPS. The compounds were characterized by X-ray powder diffraction, scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, vibrating sample magnetometry, thermogravimetry and N₂ adsorption/desorption. Then, the enzyme, porcine pancreas lipase (PPL), was immobilized onto these modified nanoparticles by covalent attachment, physical adsorption and cross-linking, noted as Fe₃O₄ at MCM-41/CPS-PPL, Fe₃O₄ at MCM-41-PPL and Fe₃O₄ at MCM-41/APTS-PPL, respectively. The results showed that Fe₃O₄ at MCM-41/CPS was the best nanomaterial for PPL immobilization, exhibiting enhanced immobilization efficiency (maximum 96%), maximum relative activity (up to 96%), high stability and reusability (83% 56 days and 86.7% ten cycles). Additionally, it offered some other advantages, such as easy recycling and reuse, complying with the trend of green chemistry. Therefore, Fe₃O₄ at MCM-41/CPS in combination with a relevant method can be proposed for commercial applications.     

Matrices based on meso antibacterial framework

In this paper, the synthesis of three types of porous materials (PMs) (porous Fe₃O₄, MIL-101 metal-organic framework (MOF), and MCM-41 mesoporous silica) by hydrothermal method was performed. The incorporation of Ag nanoparticles (Ag NPs) was carried out after the synthesis reaction of supports in MCM-41 and MIL-101 MOF. Ag core@ porous Fe₃O₄ core–shell system was prepared via a one-pot hydrothermal method. Ag-MIL-101 was obtained using Urtica dioica leaf extract as the green solvent and reducing agent. The antibacterial activity of Ag-PM nanocomposites (NCs) was investigated on both Gram-negative and Gram-positive bacteria. The size of the silver NPs was determined to be 12 and 30 nm in MCM-41 and MIL-101 MOF, respectively. The diameter of Ag core in Ag@Fe₃O₄ shell was ~135 nm. The antibacterial activity of Ag-PMs was in the order Ag-MCM-41 > Ag-MIL-101 > Ag core@Fe₃O₄ shell. The loading percent of Ag NPs in MCM-41 (84%) was more than that in MIL-101 (53%) and Fe₃O₄ (31%). The release of Ag⁺ ions from Ag-MCM-41, Ag-MIL-101, and Ag@Fe₃O₄ NCs was 46, 2, and 1 ppm, respectively. The release of the Ag⁺ ions and, consequently, the antibacterial activity of NCs depend on the uniform distribution, particles size, and the absence of aggregation of Ag NPs in PMs.     

Modified nanoporous silicas for oral delivery of the water insoluble organotin compound: loading and release of methylphenyltin dichloride as an anti-tumor drug model

Different nanoporous silica materials, MCM-41, MCM-48 and SBA-15, were modified by pyridine and their applications for oral drug delivery system were evaluated. These pyridine functionalized nanoporous silicas were loaded with a water insoluble diorganotin(IV) dichloride complex as an antitumor drug model and its release from them were investigated by changing pH. An efficient pH-responsive carrier system was constructed by coordination of the pyridine group in modified nonoporous materials to tin complex. In vitro, releasing of loaded tin complex was studied in three different kinds of fluids, including a simulated gastric medium and a simulated body fluid. The loading and releasing of the diorganotin(IV) dichloride from various modified nanoporous silicas and also a non-porous silica (SiO₂) were investigated, and the results were compared. In addition, the effect of some factors such as pH, time of loading and releasing were investigated through this study.     

Luminescent core–shell Ca2MoO5:Eu3+-MCM-41 structure for sustained drug release

The spherical mesoporous MCM-41 coated with a novel Ca₂MoO₅:Eu³⁺ phosphor layer was prepared for the first time. The obtained Ca₂MoO₅:Eu³⁺-MCM-41 was characterized via XRD and FT-IR. The crystal system of the Ca₂MoO₅ phase was determined to be orthorhombic, and its space group was found to be Ima2 (46), and its cell parameters were a = 16.175, b = 5.1514, c = 5.6977 A°; α = β = γ = 90°. The particle dimensions of MCM-41 and Ca₂MoO₅:Eu³⁺-MCM-41 nanoparticles were determined to be 260 nm and 229 nm via scanning electron microscopy analysis. Bortezomib was loaded into the Ca₂MoO₅:Eu³⁺-MCM-41 nanoparticles under scCO₂ at 200 bars and 40 °C. The results of the TG analysis showed that the amount of drug-loaded to MCM-41 and Ca₂MoO₅:Eu³⁺-MCM-41 nanoparticles were determined to be 14.02% and 3.02%, respectively. The BET analysis showed that while the specific surface area and pore volume of MCM-41 and Ca₂MoO₅:Eu³⁺ before Bortezomib (BTZ) loading were 1,506 m²/g and 267 m²/g, respectively, after drug loading these values were found to decrease to 488 m²/g and 7.883 m²/g. It was determined that BTZ was released from the nanoparticles in a sustained manner over 66 h. The R² value, which was calculated to be 0.9739, indicated that the release kinetic of BTZ followed the Korsmeyer–Peppas model.     

Application of RuO<Subscript>2</Subscript> Nanoparticles as Catalyst in Preparation of Indolo[3,2-a]Carbazoles

RuO₂ nanoparticles were readily prepared from RuCl₃·3H₂O via the formation of Ru-hydroxide precursor, followed by calcination at 550 °C. Under similar conditions, uniform dispersion of spherical RuO₂ nanoparticles over the surface of MCM-41 was also obtained. The synthesized materials were characterized by transmission electron microscopy (TEM), infrared spectroscopy (FT-IR), X-ray diffraction (XRD), BET surface area measurements, and magnetic measurements (VSM). The obtained RuO₂ nanoparticles found application as catalyst in preparation of indolo[3,2-a]carbazoles from the reaction of indoles and benzils. Under mild reaction conditions, satisfactory yields of the desired products were obtained. Stabilization of RuO₂ nanoparticles over the surface of MCM-41 (RuO₂–MCM41), however, had the advantage of easy recycling, although a slight decrease in efficiency after five successive runs was observed.     

Iron oxide/MCM-41 mesoporous nanocomposites and their magnetorheology

Mesoporous nanocomposite materials of magnetic iron oxide-containing MCM-41 (IO/MCM-41) were prepared by simple thermal oxidation of Fe-containing MCM-41 initially prepared by a direct synthesis route using Fe³⁺ salt. The magnetic saturation of the fabricated nanocomposite materials was measured using a vibrating sample magnetometer, while surface morphology and inner framework of the composite materials were studied using a field emission scanning electron microscope and a transmission electron microscope to confirm their mesoporous nanocomposite formation. The fabricated magnetic materials were then adopted as a magnetorheological (MR) fluid, where the IO/MCM-41 magnetic nanocomposites were dispersed in a nonmagnetic medium oil in addition to as an additive for carbonyl iron-based MR fluid. Their MR properties of flow curve along with yield stress and viscoelastic properties under applied magnetic fields were investigated using a rotational rheometer.     

Study on the properties of the photoluminescence material Tb(aspirin)3phen-MCM-41

Assembly system with MCM-41 as a host and TAP (Tb(aspirin)₃phen) as an active optical guest was synthesized at room temperature, and the interrelated products of MCM-41 and TAP systems were examined for comparison. The structures and the physical properties of the samples were characterized by a combination of techniques, such as XRD and N₂ adsorption–desorption. Excitation and emission spectra were carried out to explore the photoluminescence (PL) properties of the samples and the relationships between the optical guest and the inorganic host. The results from these characterizations showed that the TAP is incorporated into the channels of MCM-41 and can increase the framework order of MCM-41. The reduction in the specific surface area of TAPMA (Tb(aspirin)₃phen-MCM-41A) compared with that of MA (MCM-41A) imply that the TAP is confined inside the channels of MA. Based on the analyses of the excitation spectra, we suggested that the surface environment of MCM-41 affects the energy absorption of the organic ligands. PL of TAPMA and TAPMB show TAP in the different chemical environments, and a strong green PL had been observed in the TAPMA system while a much weaker light in the TAPMB system.     

Steam reforming of glycerol over Pt-MCM-41 synthesized in a one-step process

Pt-MCM-41 materials were synthesized by a simple method via simultaneous self-assembling and Pt incorporation using cetyltrimethylammonium chloride (CTAC) as a structure directing agent. Structural characterization of the sample was carried out by N₂ sorption, XRD and TEM measurements. The highly ordered structure of MCM-41 was not appreciably affected by the formation of the Pt particles. Unlike related results, the Pt nanoparticles were incorporated into the mesopores and embedded into the pore walls as framework. The Pt-MCM-41 sample was tested as a catalyst in the steam reforming of glycerol in which it exhibited moderate activity, high selectivity to hydrogen, and very low selectivity to light alkanes.     

Light‐sensitive Intelligent Drug Delivery Systems†

Drug delivery systems (DDS) capable of releasing an active molecule at the appropriate site and at a rate that adjusts in response to the progression of the disease or to certain functions/biorhythms of the organism are particularly appealing. Biocompatible materials sensitive to certain physiological variables or external physicochemical stimuli (intelligent materials) can be used for achieving this aim. Light‐responsiveness is receiving increasing attention owing to the possibility of developing materials sensitive to innocuous electromagnetic radiation (mainly in the UV, visible and near‐infrared range), which can be applied on demand at well delimited sites of the body. Some light‐responsive DDS are of a single use (i.e. the light triggers an irreversible structural change that provokes the delivery of the entire dose) while others able to undergo reversible structural changes when cycles of light/dark are applied, behave as multi‐switchable carriers (releasing the drug in a pulsatile manner). In this review, the mechanisms used to develop polymeric micelles, gels, liposomes and nanocomposites with light‐sensitiveness are analyzed. Examples of the capability of some polymeric, lipidic and inorganic structures to regulate the release of small solutes and biomacromolecules are presented and the potential of light‐sensitive carriers as functional components of intelligent DDS is discussed.     

Thiol modified chitosan-silica nanohybrid for antibacterial,antioxidant and drug delivery application

Chitosan exhibits great versatility in various biomedical fields and mesoporous silica nanoparticles have emerged as an interesting material in biomedical areas owing to their outstanding physio-chemical properties. The combination of inorganic silica and organic polymer such as chitosan, make them suitable for a wide range of biomedical applications. Here, we have explored the benefits of chitosan and silica by synthesizing chitosan-silica nanohybrid. In the synthesis of chitosan-silica (CS–Si) nanohybrid, chitosan is modified by thioglycolic acid and mesoporous silica MCM-41(Mobil Composition of Matter number 41) is functionalized by 3-(trimethoxysilyl)-1-propane thiol (TMSP). The modified chitosan and thiol functionalized MCM-41(inorganic network) is then linked through disulfide bond by oxidation process or oxidative coupling, resulting in the formation of inorganic-organic hybrid material. The hybrid material was characterized by FTIR, Raman, XRD, TGA, Zeta potential, EDX, Proton NMR and SEM techniques. The antibacterial results indicated that gram-negative (E. coli) bacteria exhibit better inhibition zone than gram-positive (B. subtilis) bacteria. The DPPH scavenging capability of synthesized hybrid was found to be 68%. The drug (quercetin) encapsulation efficiency of hybrid material was calculated to be 92.38% and more drug releases in acidic medium (pH 5.0) than at pH 7.4, so we can conclude that hybrid material shows pH-dependent drug releasing behavior. The results show that synthesized nano-hybrid material possess good antibacterial and antioxidant activities and is also a good nanocarrier for drug delivery application.     

Experimental study on the rheological behavior of nanolubricant-containing MCM-41 nanoparticles with viscosity measurement

In this study, the rheological behavior and viscosity of a stable nanofluid, which is prepared with the suspension of MCM-41 nanoparticles in SAE40 engine oil as base fluid, would be presented. Two-step method has been used to stabilize the nanoparticles in engine oil. To obtain structural and morphological properties of the synthesized nanoparticles, small-angle X-ray scattering, N₂ adsorption/desorption analysis and scanning electron microscopy have been done. Then, viscosity of nanofluids has been measured in temperature range of 25–55 °C, shear rates up to 13,000 s^?1 and different concentrations (0 mass%, 0.5 mass%, 1 mass%, 3 mass% and 5 mass% of MCM-41 nanoparticles). For all the samples, the shear stress versus shear rate diagrams showed that SAE40 oil has Newtonian behavior, in which adding mesoporous silica nanoparticles causes non-Newtonian or pseudoplastic behavior. The results declared that viscosity decreases with increasing temperature and increases with an enhancement in concentration. Furthermore, based on experimental results, an accurate correlation has been proposed to predict the viscosity of SAE40/MCM-41 nanolubricants.

     

Bright photoluminescent hybrid mesostructured silica nanoparticles

Bright photoluminescent mesostructured silica nanoparticles were synthesized by the incorporation of fluorescent cyanine dyes into the channels of MCM-41 mesoporous silica. Cyanine molecules were introduced into MCM-41 nanoparticles by physical adsorption and covalent grafting. Several photoluminescent nanoparticles with different organic loadings have been synthesized and characterized by X-ray powder diffraction, high resolution transmission electron microscopy and nitrogen physisorption porosimetry. A detailed photoluminescence study with the analysis of fluorescence lifetimes was carried out to elucidate the cyanine molecules distribution within the pores of MCM-41 nanoparticles and the influence of the encapsulation on the photoemission properties of the guests. The results show that highly stable photoluminescent hybrid materials with interesting potential applications as photoluminescent probes for diagnostics and imaging can be prepared by both methods.     

Effect of polyether diamine on gas permeation properties of organic-inorganic hybrid membranes

The quantitative incorporation and high dispersion of platinum nanoparticles into MCM-41 has been carried out by the coordination between Pt(IV) ion and APTMS-anchored MCM-41. Before and after calcination of Pt/APTMS/MCM41 samples, the Pt content in samples was evaluated from home-made photoacoustic spectrometer (PAS). The PAS bands at 350 nm and 450 nm can be assigned to d–d transition bands of Pt complexes. By increasing the concentration of Pt solution, the PAS intensity of Pt/APTMS/MCM41 was increased proportionally up to 1.0×10⁻² M, and remained constant above 1.0×10⁻² M. It can be attributed to the saturation of Pt content within Pt/APTMS/MCM41. The Pt content in the saturated Pt/APTMS/MCM41 was 8.5 wt% (the theoretical value), 9.7 wt% (measured by EDX) and 9.2 wt% (measured by ESCA), respectively. This indicates that the content of Pt precursor within MCM-41 could be controlled by the concentration of Pt precursor solution. The PAS intensity of calcined Pt/APTMS/MCM41's in H₂ flow was increased up to 1.0×10⁻² M and remained nearly constant above 1.0×10⁻² M. Therefore, we suggest that the formation of Pt complexes with APTMS-anchored MCM-41 made it possible to incorporate quantitatively Pt nanoparticles in the range of 0.5–9.2 wt% within MCM-41 channels.     

Removal of complexed mercury by dithiocarbamate grafted on mesoporous silica

Mesoporous silica (MCM-41) with d ₍₁₀₀₎ interplanar distance of 38 Å was prepared by a room temperature process through low surfactant templation technique. The surface of MCM-41 was functionalized with dithiocarbamate (dtc) ligand, named as MCM-41-dtc and this was characterized by X-ray diffraction, BET surface area, particle size analysis, ²⁹Si MAS NMR spectra and sulphur analysis. The sorption of mercury from 0.1M HCl solution by MCM-41-dtc was studied as a function of pH, [Hg²⁺], time and temperature. The sorption data obtained at various initial concentrations of mercury were fitted into Langmuir adsorption model. Mercury speciation in solution and the sorption capacity measurements indicated possible formation of a 1 : 1 square planar complex in the solid phase. A very rapid sorption of mercury was observed in the initial stages of equilibration, which can be attributed to the large surface area, wide porosity and fine particle size of MCM-41-dtc, facilitating facile accessibility of mercury into the inner pores of the sorbent. The enthalpy change accompanied by the sorption of mercury was found to decrease from 83.7 to 6.2 kJ/mol, when the initial concentration of mercury was increased from 5^.10^-4M to 1.5^.10^-3M.     

Light olefins and light oil production from catalytic pyrolysis of waste tire

This paper investigates the catalytic activity of MCM-41 synthesized via silatrane route and Ru/MCM-41 in waste tire pyrolysis. The experimental results showed that the presence of catalysts strongly influenced the yield and nature of products. Namely, the gas yield increased at the expense of liquid yield. In addition, a considerable high yield of light olefins, 4 times higher than non-catalytic pyrolysis, can be achieved for Ru/MCM-41 catalyst. Furthermore, the uses of catalysts produced much lighter oil and there was a drastic increase in the concentration of single ring aromatics in accordance to a reduction in polycyclic aromatic compounds in the derived oils. Ru/MCM-41 produced the lightest oil and the oil has the highest concentration of mono-aromatics. The high activity of catalysts, particularly Ru/MCM-41 was discussed in relation with the catalyst characterization results obtained from various techniques including TPD-NH₃, H₂-chemisorption, XRD, N₂-adsorption/desorption analysis, and TPO.     

Ultrasonically assisted in situ emulsion polymerization: a facile approach to prepare conducting copolymer/silica nanocomposites

Ultrasonically assisted in situ emulsion polymerization was used to prepare electrically conducting copolymer poly(aniline‐co‐p‐phenylenediamine) [poly(Ani‐co‐pPD)] and silica (SiO₂) nancomposites. This approach can solve problems in the dispersion and stabilization of SiO₂ nanoparticles in the copolymer matrix. It was found that the aggregation of SiO₂ nanoparticles could be reduced under ultrasonic irradiation. Scanning transmission electron microscopy (STEM) confirmed that the resulting poly(Ani‐co‐pPD)/SiO₂ nanocomposite particles were spherical in shape, in which SiO₂ nanoparticles were well dispersed. The comonomer molecules were absorbed on the surface of SiO₂ particles and then polymerized to form core–shell nanocomposite. The incorporation of SiO₂ in the nanocomposite was supported by Fourier transform infrared spectroscopy (FT‐IR). UV‐visible spectra of the diluted colloid dispersion of nanocomposite particles were similar to those of the neat copolymer. Conductivity of nanocomposites was higher than the value obtained for the neat copolymer. Copyright © 2009 John Wiley & Sons, Ltd.     

The composite material of perylene bisimide dye in MCM-41 and its photophysical and photochemical properties

The mesoporous material MCM-41 was synthesized by a hydrothermal method, and perylene bisimide dye was incorporated into its channels by impregnation. The absorption, FTIR, fluorescence emission, and decay spectra of perylene bisimide dye in CHCl₃ and in MCM-41 were studied to investigate the effect of the one-dimensional channel of MCM-41 on the photophysical and photochemical properties of the dye. The results indicated that the nanochannels of MCM-41 shifted the absorption and emission maxima to red and broadened the spectra, with loss of vibrational structure. The fluorescence decay curves fitted a double-exponential function and the lifetime of perylene bisimide dye in MCM-41 was prolonged. The huge surface area of the mesoporous molecular sieve MCM-41 prevented aggregation of dye molecules, which can thus be used at high concentration.