Mesoporous silicas as versatile supports to tune the palladium-catalyzed selective aerobic oxidation of allylic alcohols

Surfactant templating offers a simple route to synthesize high-surface area silicas with ordered, tunable mesopore architectures. The use of these materials as versatile catalyst supports for palladium nanoparticles has been explored in the aerobic selective oxidation (selox) of allylic alcohols under mild conditions. Families of Pd/mesoporous silicas, synthesized through incipient wetness impregnation of SBA-15, SBA-16, and KIT-6, have been characterized by using nitrogen porosimetry, CO chemisorption, diffuse reflection infrared Fourier transform spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, and high-resolution TEM and benchmarked in liquid phase allylic alcohol selox against a Pd/amorphous SiO2 standard. The transition from amorphous to two-dimensional parallel and three-dimensional interpenetrating porous silica networks conferred significant selox rate enhancements associated with higher surface densities of active palladium oxide sites. Dissolved oxygen was essential for insitu stabilization of palladium oxide, and thus maintenance of high activity on-stream, whereas selectivity to the desired aldehyde selox product over competing hydrogenolysis pathways was directed by using palladium metal. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Improved photovoltaic performance of dye-sensitized solar cells with modified self-assembling highly ordered mesoporous TiO 2 photoanodes

Strategies for improving the photovoltaic performance of dye-sensitized solar cells (DSSCs) are proposed by modifying highly transparent and highly ordered multilayer mesoporous TiO 2 photoanodes through nitrogen-doping and top-coating with a light-scattering layer. The mesoporous TiO 2 photoanodes were fabricated by an evaporation-induced self-assembly method. In regard to the modification methods, the light-scattering layer as a top-coating was proved to be superior to nitrogen-doping in enhancing not only the power conversion efficiency but also the fill factor of DSSCs. The optimized bifunctional photoanode consisted of a 30-layer mesoporous TiO 2 thin film (4.15 μm) and a Degussa P25 light-scattering top-layer (4 μm), which gives rise to a ∼200% higher cell efficiency than for unmodified cells and a fill factor of 0.72. These advantages are attributed to its higher dye adsorption, better light scattering, and faster photon-electron transport. Such a photoanode configuration provides an efficient way to enhance the energy conversion efficiency of DSSCs.

Nano-confined synthesis of highly ordered mesoporous carbon and its performance as electrode material for electrochemical behavior of riboflavin (vitamin B2) and dopamine

Highly ordered mesoporous carbon (MC) has been synthesized from sucrose, a non-toxic and costeffective source of carbon. X-ray diffraction, N2 adsorption–desorption isotherm and transmission electron micrograph (TEM) were used to characterize the MC. The XRD patterns show the formation of highly ordered mesoporous structures of SBA15 and mesoporous carbon. The N2 adsorptiondesorption isotherms suggest that the MC exhibits a narrow pore-size distribution with high surface area of 1559 m2/g. The potential application of MC as a novel electrode material was investigated using cyclic voltammetry for riboflavin (vitamin B2) and dopamine. MC-modified glassy carbon electrode (MC/GC) shows increase in peak current compared to GC electrode in potassium ferricyanide which clearly suggest that MC/GC possesses larger electrode area (1.8 fold) compared with bare GC electrode. The electrocatalytic behavior of MC/GC was investigated towards the oxidation of riboflavin (vitamin B2) and dopamine using cyclic voltammetry which show larger oxidation current compared to unmodified electrode and thus MC/GC may have the potential to be used as a chemically modified electrode.

Mesoporous silica- and silicon-based materials as carriers for poorly water soluble drugs

New chemical entities with unfavorable water solubility properties are continuously emerging in drug discovery. Without pharmaceutical manipulations inefficient concentrations of these drugs in the systemic circulation are probable. Typically, in order to be absorbed from the gastrointestinal tract, the drug has to be dissolved. Several methods have been developed to improve the dissolution of poorly soluble drugs. In this study, the applicability of different types of mesoporous (pore diameters between 2 and 50 nm) silicon- and silica-based materials as pharmaceutical carriers for poorly water soluble drugs was evaluated. Thermally oxidized and carbonized mesoporous silicon materials, ordered mesoporous silicas MCM-41 and SBA-15, and non-treated mesoporous silicon and silica gel were assessed in the experiments. The characteristic properties of these materials are the narrow pore diameters and the large surface areas up to over 900 m²/g. Loading of poorly water soluble drugs into these pores restricts their crystallization, and thus, improves drug dissolution from the materials as compared to the bulk drug molecules. In addition, the wide surface area provides possibilities for interactions between the loaded substance and the carrier particle, allowing the stabilization of the system. Ibuprofen, indomethacin and furosemide were selected as poorly soluble model drugs in this study. Their solubilities are strongly pH-dependent and the poorest (< 100 µg/ml) at low pH values. The pharmaceutical performance of the studied materials was evaluated by several methods. In this work, drug loading was performed successfully using rotavapor and fluid bed equipment in a larger scale and in a more efficient manner than with the commonly used immersion methods. It was shown that several carrier particle properties, in particular the pore diameter, affect the loading efficiency (typically ~25-40 w-%) and the release rate of the drug from the mesoporous carriers. A wide pore diameter provided easier loading and faster release of the drug. The ordering and length of the pores also affected the efficiency of the drug diffusion. However, these properties can also compensate the effects of each other. The surface treatment of porous silicon was important in stabilizing the system, as the non-treated mesoporous silicon was easily oxidized at room temperature. Different surface chemical treatments changed the hydrophilicity of the porous silicon materials and also the potential interactions between the loaded drug and the particle, which further affected the drug release properties. In all of the studies, it was demonstrated that loading into mesoporous silicon and silica materials improved the dissolution of the poorly soluble drugs as compared to the corresponding bulk compounds (e.g. after 30 min ~2-7 times more drug was dissolved depending on the materials). The release profile of the loaded substances remained similar also after 3 months of storage at 30°C/56% RH. The thermally carbonized mesoporous silicon did not compromise the Caco-2 monolayer integrity in the permeation studies and improved drug permeability was observed. The loaded mesoporous silica materials were also successfully compressed into tablets without compromising their characteristic structural and drug releasing properties. The results of this research indicated that mesoporous silicon/silica-based materials are promising materials to improve the dissolution of poorly water soluble drugs. Their feasibility in pharmaceutical laboratory scale processes was also confirmed in this thesis.

Highly ordered mesoporous carbons as electrode material for the construction of electrochemical dehydrogenase- and oxidase-based biosensors

In this work, the excel lent catalytic activity of highly ordered mesoporous carbons (OMCs) to the electrooxidation of nicotinamide adenine dinucleotide (NADH) and hydrogen peroxide (H2O2) was described for the construction of electrochemical alcohol dehydrogenase (ADH) and glucose oxidase (GOD)-based biosensors.

The characteristics of highly ordered mesoporous carbons as electrode material for electrochemical sensing as compared with carbon nanotubes

In this paper, the unique properties of highly ordered mesoporous carbons modified glassy carbon electrode (OMCs/GE) are illustrated from comparison with carbon nanotubes modified glassy carbon electrode (CNTs/GE) for the electrochemical sensing applications.

Synthesis, characterization and catalytic properties of chiral BINOL functionalized mesoporous silicas for enantioselective Morita-Baylis-Hillman reaction

Several Chiral BINOL functionalized mesoporous silicas were prepared by post grafting of organosilane derivatives of (S)-BINOL (1,1'-bi-2-naphthol) on SBA-15 and characterized by C-13 CP/MAS NMR, FT-IR, UV-visible absorption spectra, elemental analysis, powder XRD, nitrogen adsorption-desorption isotherms and TEM techniques. Their catalytic properties were demonstrated in enantioselective Morita-Baylis-Hillman reaction of 3-phenylpropanal and cyclohexenone.

Direct electrochemistry and electrocatalysis of glucose oxidase immobilized on glassy carbon electrode modified by Nafion and ordered mesoporous silica-SBA-15

In this paper, it was found that glucose oxidase (GOD) has been stably immobilized on glassy carbon electrode modified by ordered mesoporous silica-SBA-15 and Nafion. The sorption behavior of GOD immobilized on SBA-15 matrix was characterized by transmission electron microscopy (TEM), ultraviolet-visible (UV-vis), FTIR, respectively, which demonstrated that SBA-15 can facilitate the electron exchange between the electroactive center of GOD and electrode. The direct electrochemistry and electrocatalysis behavior of GOD on modified electrode were characterized by cyclic voltammogram (CV) which indicated that GOD immobilized on Nafion and SBA-15 matrices displays direct, nearly reversible and surface-controlled redox reaction with an enhanced electron transfer rate constant of 3.89 s(-1) in 0.1 M phosphate buffer solution (PBS) (pH 7.12).

Highly ordered mesoporous carbons-based glucose/O-2 biofuel cell

This study demonstrates a novel compartment-less glucose/O-2 biofuel cell (BFC) based on highly ordered mesoporous carbons (OMCs) with three-dimensionally (3D) interconnected and ordered pore structures. OMCs are used as supports for both stably confining the electrocatalyst (i.e., meldola's blue, MDB) for NADH oxidation and the anodic biocatalyst (i.e., NAD(+)-dependent glucose dehydrogenase, GDH) for glucose oxidation, and for facilitating direct electrochemistry of the cathodic biocatalyst (i.e., laccase, LAC) for O-2 electroreduction. In 0.10 M pH 6.0 PBS containing 20 mM NAD(+) and 60 mM glucose under the air-saturated atmosphere, the open circuit voltage (0.82 V) and the maximum power output (38.7 mu W cm(-2) (at 0.54V)) of the assembled compartment-less OMCs-based BFC are both higher than those of carbon nanotubes (CNTs)-based BFC (0.75 V and 2.1 mu W cm(-2) (at 0.46 V)).

Stable ordered mesoporous silica materials templated by high-temperature stable surfactant micelle in alkaline media

Ordered hexagonal mesoporous silica material (JLU-30) has been successfully synthesized in alkaline media at high temperature (> 160 degreesC, using cationic (1,3-dimethyl-2-imidazolidin-2-ylidene)hexadecylmethyl-ammonium bromide (DIHAB) as a template, and characterized with X-ray diffraction (XRD), transmission electron microscopy (TEM), nitrogen adsorption-desorption isotherms, differential thermal analysis (DTA), and thermogravimetric analysis (TG), as well as Al-27 and Si-29 nuclear magnetic resonance (NMR) spectroscopy. Mesoporous JLU-30 shows much higher hydrothermal stability than MCM-41. Si-29 NMR spectra indicate that the pore walls of JLU-30 samples synthesized at high temperature (160 degreesC) are fully condensed, giving a Q(4)/Q(3) ratio as high as 6.2. In contrast, MCM-41 synthesized at relatively low temperature (100 degreesC) shows the Q(4)/Q(3) + Q(2) ratio at 1.1. Such unique structural feature might be responsible for the observed highly hydrothermal stability of the mesoporous silica materials (JLU-30).

A novel way to synthesize high regular and periodic organic mesoporous silicas

Organic mesoporous silicas (OMSs) were synthesized in the presence of urea via one-pot synthesis method, in which tetraethyl orthosilicate (TEOS) and 3-aminopropyltriethoxysilica (APTES) were used as the silica resources, non-ionic surfactant was used as the template. XRD results showed that the average periodic mesopore sizes of OMSs in the presence of urea were larger than those in the absence of urea. It was also found that the pore sizes of the products in the presence of urea distributed more narrowly than those in the absence of urea, and the contents of organosiloxane incorporated into OMSs, the pore wall thicknesses, the pore volumes and the surface areas of the products all increased with the use of urea. This shows a novel way to synthesize high regular and periodic organic mesoporous silicas.

Synthesis of ordered mesoporous carbons composed of nanotubes via catalytic chemical vapor deposition

Ordered mesoporous carbons composed of arrays of nanotubes have been synthesized using ordered mesoporous silica templates via catalytic chemical vapor deposition. The ordered carbons possess bimodal pores, namely, the pores arise from the "replica" of frameworks of the template and the pores correspond to carbon nanotubes formed in the channels of the template (see Figure).

Inclusion of poorly soluble drugs in highly ordered mesoporous silica nanoparticles

Silica nanoparticles (MSNs) with a highly ordered mesoporous structures (103A) with cubic Im3 m have been synthesized using triblock copolymers with high poly(alkylene oxide) (EO) segments in acid media. The produced nanoparticles displayed large specific surface area (approximately 765 cm(2)/g) with an average particles size of 120 nm. The loading efficiency was assessed by incorporating three major antiepileptic active substances via passive loading and it was found to varying from 17 to 25%. The state of the adsorbed active agents was further analyzed using differential scanning calorimetry (DSC) and X-ray powder diffraction (XRPD). Dissolution studies revealed rapid release profiles within the first 3 h. The viability of 3T3 endothelial cells was not affected in the presence of MSNs indicating negligible cytotoxicity. 2009 Elsevier B.V. All rights reserved.