Preparation, Characterization, and In Vitro Sustained Release Profile of Resveratrol-Loaded Silica Aerogel.

Silica aerogel, a kind of nanoporous material, is regarded as a desired drug carrier for its low toxicity, high specific surface area, and excellent biocompatibility. Using silica aerogel in a drug carrier may be an appropriate method to improve the performance of pure resveratrol. In this study, resveratrol-loaded silica aerogel (RSA) as a drug delivery system was prepared by the sol-gel method. Before gelling, resveratrol was added into the hydrolyzed tetraethyl orthosilicate (TEOS) ethanol solution then dispersed by stir and ultrasound. The results showed that RSA has a high loading rate of 19% with low cost and excellent biocompatibility. The SEM images showed that silica aerogel wraps up outside the resveratrol. Sustained releasing effect could be observed in RSA after 1 h, while pure resveratrol did not display this. The release of RSA lasted for over 6 h, and the release amount reached over 90% and 80% in either simulated gastric fluid (pH = 2.0) or phosphate-buffered saline (pH = 7.4) at 37 °C. Preliminary in vitro toxicity test revealed RSA to be biocompatible and stable; and when coupled with the anti-inflammatory effects of resveratrol, showed good potential for osteoarthritis treatment.

Efficacy of removal of a popular NSAID from aqueous solutions with metalloligs.

Acetaminophen, a popular NSAID (Non-steroidal anti-inflammatory drug), was studied for efficacy of removal from aqueous solutions. While Octolig® (a polyethylenediimine covalently attached to silica gel) is able to remove many simple anions and some acidic pharmaceuticals having a pKa value less than 4.5, it lacked efficacy with acetaminophen. Accordingly different transition- metal derivatives of Octolig® were tested by column chromatography using as substrates Octolig® derivatives of copper(II), cobalt(II), iron(III), manganese(II), nickel(II), and zinc(II).

ß-sheet to α-helix conversion and thermal stability of ß-Galactosidase encapsulated in a nanoporous silica gel.

The effect on protein conformation and thermal stability was studied for ß-Galactosidase (ß-Gal) encapsulated in the nanopores of a silicate matrix (Eß-Gal). Circular dichroism spectra showed that, compared with the enzyme in buffer (Sß-Gal), Eß-Gal exhibited a higher content of α-helix structure. Heating Eß-Gal up to 75 °C caused a decrease in the content of ß-sheet structure and additional augments on Eß-Gal components attributed to helical content, instead of the generalized loss of the ellipticity signal observed with Sß-Gal. Steady state fluorescence spectroscopy analysis evidenced an Eß-Gal structure less compact and more accessible to solvent and also less stable against temperature increase. While for Sß-Gal the denaturation midpoint (Tm) was 59 °C, for Eß-Galit was 48 °C. The enzymatic activity assays at increasing temperatures showed that in both conditions, the enzyme lost most of its hydrolytic activity against ONPG at temperatures above 65 °C and Eß-Gal did it even at lower T values. Concluding, confinement in silica nanopores induced conformational changes on the tertiary/cuaternary structure of Eß-Gal leading to the loss of thermal stability and enzymatic activity.

Mutual interaction between guest drug molecules and host nanoporous silica xerogel studied using central composite design.

In the present study, three water-soluble drugs (propranolol hydrochloride, PNH; diltiazem hydrochloride, DZH; levofloxacin hydrochloride, LFH) with different number of hydrogen bonding acceptors were used as guest drug molecules, and three kinds of biomimetic synthesized nanoporous silica@poly(ethyleneimine)s xerogel (NS@P xerogel, 25%NS@P xerogel and 75%NS@P xerogel) were taken as host drug carriers. Mutural interaction formed between guest drug molecules and host drug carriers were investigated using a two-level three-factorial central composite design. The results confirmed that water-soluble drug loaded three nanoporous silica carriers presented the same regular controlled release effect, which was 75%NS@P xerogel>25%NS@P xerogel>NS@P xerogel. The main contribution to burst release was the pore diameter of host carrier. Accomplishment of cumulative release in 24h can be obtained when loading guest drug molecules with small number of hydrogen bonding acceptors to host carriers with either quite small or large pore diameter. The present work can favor to explore the mutural interaction between host carrier and guest drug molecules and thus promoted the development of nanoporous silica in pharmaceutical application.

Experimental basis for a new allosteric model for multisubunit proteins.

Monod, Wyman, and Changeux (MWC) explained allostery in multisubunit proteins with a widely applied theoretical model in which binding of small molecules, so-called allosteric effectors, affects reactivity by altering the equilibrium between more reactive (R) and less reactive (T) quaternary structures. In their model, each quaternary structure has a single reactivity. Here, we use silica gels to trap protein conformations and a new kind of laser photolysis experiment to show that hemoglobin, the paradigm of allostery, exhibits two ligand binding phases with the same fast and slow rates in both R and T quaternary structures. Allosteric effectors change the fraction of each phase but not the rates. These surprising results are readily explained by the simplest possible extension of the MWC model to include a preequilibrium between two tertiary conformations that have the same functional properties within each quaternary structure. They also have important implications for the long-standing question of a structural explanation for the difference in hemoglobin oxygen affinity of the two quaternary structures.

Interactions of three soil bacteria species with phyllosilicate surfaces in hybrid silica gels.

To simulate iron consumption in soils, iron leaching from silicate minerals due to three heterotrophic bacterial strains and a chemical treatment was studied using hybrid silica gel (HSG) doped with two phyllosilicates, nontronite (NAu-2) or low-iron-content montmorillonite (SWy-2). HSG methodology, a novel way of separating bacteria cells from a colloidal mineral source, consisted in embedding colloidal mineral particles into an amorphous porous silica matrix using a classical sol-gel procedure. Pantoae agglomerans PA1 and Rahnella aquatilis RA1 were isolated from silicate-rich soils, that is, beech and wheat rhizospheres (Vosges, France); Burkholderia sp. G5 was selected from acidic and nutrient-poor podzol soils (Vosges, France). Fe release from clay minerals and production of bacterial metabolites, that is, low molecular weight organic acids (LMWOA) and siderophores, were monitored. Two LMWOA profiles were observed with major gluconate production (> 9000 µM) for Burkholderia sp. G5 and moderate production of lactate, acetate, propionate, formate, oxalate, citrate, and succinate (< 300 µM) for R. aquatilis RA1 and P. agglomerans PA1. HSG demonstrated its usefulness in revealing clay mineral-microorganisms interactions. The effect of bacterial exsudates was clearly separated from physical contact effect.

Bioweathering of nontronite colloids in hybrid silica gel: implications for iron mobilization.

AIMS: This study aimed to study biotic iron dissolution using a new hybrid material constituted of well-dispersed mineral colloids in a silica gel matrix. This permitted to prevent adsorption of colloidal mineral particles on bacteria. Hybrid silica gel (HSG) permitted to study bioweathering mechanisms by diffusing molecules. METHODS AND RESULTS: Hybrid silica gel was synthesized through a classical sol-gel procedure in which mineral colloidal particles (NAu-2) were embedded in a porous silica matrix. Rahnella aquatilis RA1, isolated from a wheat rhizosphere was chosen for its ability to dissolve minerals by producing various organic acids and siderophores. Pyruvic, acetic and lactic acids were the major organic acids produced by R. aquatilis RA1 followed by oxalic and citric acids at the end of incubation. Comparison of abiotic and biotic experiments revealed a high efficiency of R. aquatilis RA1 for iron dissolution suggesting an optimized action of different ligands that solubilized or mobilized iron. CONCLUSIONS: Hybrid silica gel allowed focusing on the colloidal mineral weathering by metabolites diffusion without mineral adsorption on bacteria. SIGNIFICANCE AND IMPACT OF THE STUDY: Hybrid silica gels are new and efficient tools to study colloidal mineral bioweathering. Adjusting HSG porosity and hydrophobicity should permit to precise the influence of limiting diffusion of siderophores or aliphatic organic acids on mineral weathering.

Silica gel-encapsulated AtzA biocatalyst for atrazine biodegradation.

Encapsulation of recombinant Escherichia coli cells expressing a biocatalyst has the potential to produce stable, long-lasting enzyme activity that can be used for numerous applications. The current study describes the use of this technology with recombinant E. coli cells expressing the atrazine-dechlorinating enzyme AtzA in a silica/polymer porous gel. This novel recombinant enzyme-based method utilizes both adsorption and degradation to remove atrazine from water. A combination of silica nanoparticles (Ludox TM40), alkoxides, and an organic polymer was used to synthesize a porous gel. Gel curing temperatures of 23 or 45 °C were used either to maintain cell viability or to render the cells non-viable, respectively. The enzymatic activity of the encapsulated viable and non-viable cells was high and extremely stable over the time period analyzed. At room temperature, the encapsulated non-viable cells maintained a specific activity between (0.44 ± 0.06) µmol/g/min and (0.66 ± 0.12) µmol/g/min for up to 4 months, comparing well with free, viable cell-specific activities (0.61 ± 0.04 µmol/g/min). Gels cured at 45 °C had excellent structural rigidity and contained few viable cells, making these gels potentially compatible with water treatment facility applications. When encapsulated, non-viable cells were assayed at 4 °C, the activity increased threefold over free cells, potentially due to differences in lipid membranes as shown by FTIR spectroscopy and electron microscopy.

Two-dimensional pH mapping of release kinetics of silica-encapsulated drugs.

The encapsulation of pharmaceutical drug molecules in silica gels during the sol-gel synthesis and their kinetic release profile in aqueous solutions were systematically investigated in dependence of synthesis pH(S) and extraction pH(E) values. Six pH values in the range from 1 to 6 were chosen in a 6 × 6 two-dimensional matrix to screen the first-order initial dissolution rate constant and the total amount of released drug. Characteristic differences are discovered in such two-dimensional pH mapping profiles for the molecules with different ionization behavior and they are explained by surface imprinting and encapsulation processes. Remarkably, these encapsulations must occur either in the particles of the sol solutions or during the rapid liquid-solid transition of the spray-drying process employed in this study. This pH mapping method is suggested as a novel tool to probe noncovalent imprinting and encapsulation processes in sol-gel-derived materials with embedded guest molecules.

Entrapment of enzymes in nanoporous sol-gels.

The prerequisite for many successful enzyme-based biotechnologies is the preparation of highly stable and active biocatalysts, which can be achieved effectively by immobilization. This chapter introduces the immobilization of enzymes by entrapment in nanoporous silica particles made in a sol-gel process. These easily tailorable materials have been proven very beneficial for a broad variety of applications of biocatalysts. Besides the spatial confinement in silica sol-gels, another advantage is given by the easy possibility of fine-tuning the physicochemical properties of the matrix itself to provide the ideal environment for the reaction and the biocatalyst. Preparation details are demonstrated using the process of immobilizing a lipase in a sol-gel matrix, which is chemically modified by using methyl-, ethyl-, propyl-, and i-butyltrimethoxysilane. The transesterification of canola oil with methanol is used as a model reaction.

Adsorption of atrazine from aqueous electrolyte solutions on humic acid and silica.

The adsorption of, the still widely used, herbicide atrazine on model soil components, such as humic acid and humic acid-silica gel mixtures, was investigated in a series of batch experiments, under different experimental conditions (ionic strength, temperature, and pH). The investigation aimed at obtaining an estimate of the contribution of each of the soil components on the adsorption of atrazine from aqueous solutions. The kinetics of atrazine adsorption on humic acid showed two steps: a fast step, of a few hours duration, and a second slow step, which continued for weeks. The kinetics of adsorption data gave a satisfactory fit to the Elovich equation. Τhe adsorption of atrazine on the test substrates was found to be reversible in all cases. The atrazine uptake data on the test substrates were fitted best with the Freundlich adsorption isotherm. The ionic strength of the atrazine aqueous solutions did affect the amount of the atrazine adsorbed on the test substrates, suggesting that electrostatic forces between atrazine molecules and soil play a significant role in the adsorption process. An increase of temperature resulted in a decrease of atrazine adsorption on humic acid at low atrazine equilibrium concentrations. However, for higher levels of equilibrium concentrations (≥3 mg/L) the amount of atrazine adsorbed onto the test substrate increased as temperature increased. The calculated isosteric enthalpies of adsorption ranged between slightly exothermic at low atrazine uptake and slightly endothermic at high atrazine uptake, all values being in the range of physisorption.

Prolonging the lifetime and activity of silica immobilised Cyanidium caldarium.

Over the past few years the idea of living photosynthetic materials has advanced from concept to reality. This work outlines the improvements made in the immobilisation of the thermotolerant acidophile Cyanidium caldarium (Tilden) Geitler SAG 16.91 within porous and transparent silica gels with the view to targeting photochemical materials that can be used to mitigate rising CO(2) emissions. Our results suggest that the immobilised cells are autofluorescent for at least 75 days post encapsulation and can maintain a steady oxygen production rate over a similar timeframe corroborating the viability and physiological activity of silica immobilised C. caldarium.

Distribution of mono- through hexa-chlorobenzenes in floodplain soils and sediments of the Tittabawassee and Saginaw Rivers, Michigan.

INTRODUCTION: Chlorobenzenes are used as solvents or as feedstocks in the production of pesticide formulations, dyes, room deodorizers, moth-proofing agents, and de-inking solvents. Chlorobenzenes were produced by the Dow Chemical Company in Midland, Michigan, for several decades. In this study, concentrations of 12 chlorobenzene (CBz) congeners, from mono- to hexachlorobenzenes, were measured in more than 150 floodplain soil (FPS), surface sediment, and sediment core (SC) samples collected during 2002-2004 from the Pine River, Tittabawassee River, Shiawassee River, Saginaw River, and Saginaw Bay, Michigan. METHODS: Five grams of wet sediment were homogenized with anhydrous sodium sulfate and extracted with 20% dichloromethane/hexane. The extracts were purified by silica gel column chromatography and analyzed by a gas chromatograph interfaced with a mass spectrometer (GC/MS). RESULTS: Mean concentrations of ΣCBz in FPS and surface sediment were seven to 30 times higher in the Tittabawassee River (80 and 60 ng/g dry weight (dw), respectively) than in the Saginaw River (2.4 and 8.1 ng/g dw, respectively) and Saginaw Bay (5.5 and 8.0 ng/g dw, respectively). Concentrations of ΣCBz were low in surface sediment and FPS from locations upstream of Midland, Michigan, on the Tittabawassee River. Concentrations of ΣCBz were higher in FPS than in surface sediment of the Tittabawassee River; on the contrary, surface sediment contained higher concentrations of CBz than FPS from the other rivers studied. High concentrations of hexachlorobenzene were found in FPS of the Tittabawassee River. All CBz congeners, except for dichlorobenzenes (DCBz), showed a trend of spatial decrease with downstream of the Dow Chemical Company in Midland. The CBz congener composition of the samples showed multiple patterns that reflected differences in historical emissions and environmental partitioning, arising from variations in physico-chemical properties of CBz. 1,4-Dichlorobenzene (1,4-DCBz) was found in all of the samples and accounted for a high proportion of total CBz. The relationship between concentrations of CBz and previously reported concentrations of PCDD/Fs for the same set of samples (Kannan et al. 2008) was significant, indicating similarities in sources and depositions of these two classes of compounds in the watershed.