Treatment and characterization of biomass of soybean and rice hulls using ionic liquids for the liberation of fermentable sugars.

We investigated the changes in the physical structure of cellulose recovered from soybean and rice hulls treated with the ionic liquids 1-butyl-3-methylimidazolium chloride ([bmim][Cl]) and 1-butyl-3-methylimidazolium acetate ([bmim][Ac]). The characterization was carried out by a combination of thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), and scanning electron microscopy (SEM). Regenerated cellulose from soybean hull showed loss of crystallinity and high structural disruption caused by both ionic liquid treatments as compared to the untreated material. In contrast, rice hull presented only a small structural disruption when treated with [bmim][Ac] and was practically unaffected by [bmim][Cl], showing that this biomass residue is recalcitrance towards physico-chemical treatments, possibly as a consequence of its high composition content in silica. These results suggest the use of soybean hull as a substrate to be treated with ionic liquids in the preparation of lignocellulosic hydrolysates to be used in second-generation ethanol production, whereas other methods should be considered to treat rice hull biomass.

New strategy to obtain high surface area anatase nanotube/AuNP photocatalyst.

Anatase nanotubes with high surface area (ca. 350 m2 g-1), containing gold nanoparticles, were successfully obtained from trititanate nanotubes, prepared by a template-free hydrothermal method, and calcined at 450 °C. The high surface area and tubular morphology were attained due to the presence of ionic silsesquioxane, which acts as anti-sintering agent for titania during calcination process, by forming a thin silica coating between anatase nanotubes. Additionally, the ionic silsesquioxane also acts as stabilizing and adhesion agent for gold nanoparticles on the surface of anatase nanotubes. The influence of the ionic silsesquioxane on the morphological and textural properties of anatase nanotubes was studied in three different moments during the synthesis: before, after and before/after nanotubes were rolled up. The photocatalytic activity of the nanotube samples was evaluated by hydrogen generation showing remarkable enhancement in hydrogen production and stability of catalyst when compare with the bare anatase sample and commercial P-25.

Surfactant-based dispersant for multiwall carbon nanotubes to prepare ceramic composites by a sol-gel method.

A dispersant for multiwall carbon nanotubes (MWCNTs) is proposed that fulfils the requirements of creating a uniform dispersion in the matrix and obtaining a good interface between CNTs and the matrix, and is soluble in generic nonpolar solvents. This dispersant is based on a long chain surfactant, called in this work dabcosil stearate, containing a stearate-based 18-carbon alkyl chain as an anion, and a silsesquioxane containing a bridged, positively charged 1,4-diazoniabicyclo[2.2.2]octane group. It provides not only a very good dispersion medium for the MWCNTs, but also a very good interface between MWCNTs and ceramic matrices, such as alumina and zirconia, prepared by the sol-gel method.

Effect of the support size on the properties of ß-galactosidase immobilized on chitosan: advantages and disadvantages of macro and nanoparticles.

The effect of the support size on the properties of enzyme immobilization was investigated by using chitosan macroparticles and nanoparticles. They were prepared by precipitation and ionotropic gelation, respectively, and were characterized by Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry (DSC), transmission electron microscopy (TEM), light scattering analysis (LSA), and N(2) adsorption-desorption isotherms. ß-Galactosidase was used as a model enzyme. It was found that the different sizes and porosities of the particles modify the enzymatic load, activity, and thermal stability of the immobilized biocatalysts. The highest activity was shown by the enzyme immobilized on nanoparticles when 204.2 mg protein·(g dry support)(-1) were attached. On the other hand, the same biocatalysts presented lower thermal stability than macroparticles. ß-Galactosidase immobilized on chitosan macro and nanoparticles exhibited excellent operational stability at 37 °C, because it was still able to hydrolyze 83.2 and 75.93% of lactose, respectively, after 50 cycles of reuse.

Synthesis, characterization, and spectroscopic investigation of benzoxazole conjugated Schiff bases.

Two Schiff bases were synthesized by reaction of 2-(4'-aminophenyl)benzoxazole derivatives with 4-N,N-diethylaminobenzaldehyde. UV-visible (UV-vis) and steady-state fluorescence in solution were applied in order to characterize its photophysical behavior. The Schiff bases present absorption in the UV region with fluorescence emission in the blue-green region, with a large Stokes' shift. The UV-vis data indicates that each dye behaves as two different chromophores in solution in the ground state. The fluorescence emission spectra of the dye 5a show that an intramolecular proton transfer (ESIPT) mechanism takes place in the excited state, whereas a twisted internal charge transfer (TICT) state is observed for the dye 5b. Theoretical calculations were performed in order to study the conformation and polarity of the molecules at their ground and excited electronic states. Using density functional theory (DFT) methods at theoretical levels BLYP/Aug-SV(P) for geometry optimizations and B3LYP/6-311++G(2d,p) for single-point energy evaluations, the calculations indicate that the lowest energy conformations are in all cases nonplanar and that the dipole moments of the excited state relaxed structures are much larger than those of the ground state structures, which corroborates the experimental UV-vis absorption results.

Modulation of the ESIPT emission of benzothiazole type dye incorporated in silica-based hybrid materials.

A set of silica-based hybrid material samples was obtained, with different molar fractions of tetraethylorthosilicate and dimethyldimethoxysilane, as inorganic and organic sol-gel precursors, respectively. The hybrid material was used as a matrix to disperse the 2-(4'-amino-2'-hydroxyphenyl)benzothiazole, a fluorophore with large Stokes shift caused by an excited state intramolecular proton transfer phenomena (ESIPT). UV-vis and steady-state fluorescence in the solid state were applied in order to characterize the photophysical behavior of the dye. The set of samples was characterized by infrared spectroscopy, elemental analysis, and N(2) isotherms. The fluorescent pyrene dye was used as a probe for local polarity environment. For the first time, a modulation in the ESIPT fluorescence emission was achieved, being correlated to the methyl organic content of the hybrid matrix. The equilibrium between the conformers in the ground state is affected by changes in the matrix hydrophobicity. The replacement of silanol groups by methyl groups on matrix surface decreases the hydrogen bond capacity with the dye stabilizing the ESIPT conformer, in spite of the normal conformers, which will present a short wavelength emission band.

Nanocapsule@xerogel microparticles containing sodium diclofenac: a new strategy to control the release of drugs.

The aim of this work was to evaluate the potentiality to control the drug release of a new architecture of microparticles organized at the nanoscopic scale by assembling polymeric nanocapsules at the surface of drug-loaded xerogels. Xerogel was prepared by sol-gel method using sodium diclofenac, as hydrophilic drug model, and coated by spray-drying. After coating, the surface areas decreased from 82 to 28 m(2)/g, the encapsulation efficiency was 71% and SEM analysis showed irregular microparticles coated by the nanocapsules. Formulation showed satisfactory gastro-resistance presenting drug release lower than 3% (60 min) in acid medium. In water, the pure drug dissolved 92% after 5 min, uncoated drug-loaded xerogel released 60% and nanocapsule coated drug-loaded xerogel 36%. After 60 min, uncoated drug-loaded xerogel released 82% and nanocapsule coated drug-loaded xerogel 62%. In conclusion, the new system was able to control the release of the hydrophilic drug model.

Anisotropic self-organization of hybrid silica based xerogels containing bridged positively charged 1,4-diazoniabicycle[2.2.2]octane chloride group.

Anisotropic self-organized hybrid silica based xerogels were obtained. The ordered structure was imposed by the double charged 1,4-diazoniabicycle[2.2.2]octane chloride group bonded in a bridged way. This was confirmed by the presence of well defined X-ray diffraction peaks corresponding to an interplanar distance with the same length estimated for the organic bridged groups. The material was characterized by elemental analysis using CHN technique and the chloride ion was analyzed by a potentiometric titration. (13)C and (29)Si CP MAS solid state NMR spectroscopy and thermogravimetric analysis were also performed. The material that can be obtained in the form of powders and transparent monoliths or films, is thermally stable up to 260 degrees C and the samples with high organic content presented birefringence properties.

Structure and property studies of hybrid xerogels containing bridged positively charged 1,4-diazoniabicycle[2.2.2]octane dichloride.

The compound di-3-n-propyltrimethoxysilane (1,4-diazoniabicycle[2.2.2]octane) dichloride, [(MeO)3Si(CH2)3N+ (CH2CH2)3N+ (CH2)3Si(OME)3]Cl2 was obtained and was used as a precursor reagent to obtain hybrid xerogels where the organic molecule was bonded to a silica framework by reacting the ends of both sides of the precursor reagent. That is, both -Si(OME)3 groups react with tetraethylorthosilicate (TEOS) by hydrolysis-condensation reactions. The resulting hybrid xerogels with variable C/Si mole ratios were prepared and analyzed and their textural characteristics determined. The samples prepared presented micropores with diameter 1.5 nm, the chain length of which matched with the estimated length of the organic bridging group. The charged organic bridging groups allow the immobilization of hexacyanoferrate ions by an ion exchange process. The electron transfer process of the hexacyanoferrate anionic complex confined in the pores of the matrices was studied by cyclovoltammetry.

Chitosan crosslinked with genipin as support matrix for application in food process: Support characterization and ß-D-galactosidase immobilization.

In order to develop safer processes for the food industry, we prepared a chitosan support with the naturally occurring crosslinking reagent, genipin, for enzyme. As application model, it was tested for the immobilization of ß-D-galactosidase from Aspergillus oryzae. Chitosan particles were obtained by precipitation followed by adsorption of the enzyme and crosslinking with genipin. The particles were characterized by Fourier transform infrared (FTIR) spectroscopy and thermogravimetric analysis (TGA). The immobilization of the enzyme by crosslinking with genipin provided biocatalysts with satisfactory activity retention and thermal stability, comparable with the ones obtained with the traditional methodology of immobilization using glutaraldehyde. ß-D-Galactosidase-chitosan-genipin particles were applied to galactooligosaccharides synthesis, evaluating the initial lactose concentration, pH and temperature, and yields of 30% were achieved. Moreover, excellent operational stability was obtained, since the immobilized enzyme maintained 100% of its initial activity after 25 batches of lactose hydrolysis. Thus, the food grade chitosan-genipin particles seem to be a good alternative for application in food process.

A mathematical simulation of H+ ion chemisorption by anilinepropylsilica xerogels.

A study of the basic characteristics of the hybrid anilinesilica xerogel, which shows promising metal sorption properties, was carried out. A simplified approach to describe the protonization affinity of the immobilized aniline was developed, and it was compared with the known values for free aniline. The proton chemisorption process may be described properly by a model based on the Langmuir equation, and the immobilized groups have less affinity to the H(+) than to the free aniline.

7-amino-4-azaheptyl grafted onto a silica gel as a sorbent for the on-line preconcentration and determination of iron(III) in water samples.

A new sorbent was synthesized by anchoring 7-amino-4-azaheptyltrimetoxisilane, freshly prepared, to silica gel, producing 7-amino-4-azaheptyl anchored silica gel (AAHSG). This material was characterized by infrared spectroscopy (IR), elemental analysis (CHN), and nitrogen adsorption-desorption isotherms. Isotherms of the adsorption of Fe3+, Fe2+ and Cu2+ on AAHSG were recorded, which indicated that Fe3+ presents a higher affinity by the sorbent. Therefore, AAHSG was successfully employed as a sorbent in a simple flow system for the preconcentration of Fe3+ in natural water samples, such as, river water, lagoonwater, springwater, stream water, well water and two water reference materials (NIST-SRM 1640, NIST-SRM 1643d). The obtained preconcentration factor was 82.2, and the detection limit achieved was 5.9 ng ml(-1). The recovery of spiked water samples ranged from 95.0 - 103.1%.

Development of active biofilms of quinoa (Chenopodium quinoa W.) starch containing gold nanoparticles and evaluation of antimicrobial activity.

Active biofilms of quinoa (Chenopodium quinoa, W.) starch were prepared by incorporating gold nanoparticles stabilised by an ionic silsesquioxane that contains the 1,4-diazoniabicyclo[2.2.2]octane chloride group. The biofilms were characterised and their antimicrobial activity was evaluated against Escherichiacoli and Staphylococcusaureus. The presence of gold nanoparticles produces an improvement in the mechanical, optical and morphological properties, maintaining the thermal and barrier properties unchanged when compared to the standard biofilm. The active biofilms exhibited strong antibacterial activity against food-borne pathogens with inhibition percentages of 99% against E. coli and 98% against S. aureus. These quinoa starch biofilms containing gold nanoparticles are very promising to be used as active food packaging for the maintenance of food safety and extension of the shelf life of packaged foods.

Anilinepropylsilica xerogel used as a selective Cu (II) adsorbent in aqueous solution.

The metal ion adsorption properties of the microporous hybrid anilinepropylsilica xerogel were studied using divalent copper, zinc, and cadmium ions in aqueous solutions in concentrations ranging from 10(-4) up to 5x10(-3) moll(-1). At low concentrations the surface of the solid phase presents selectivity for Cu (II), even in competitive conditions. This preferential sorption ability for copper in relation to zinc and cadmium ions was interpreted by considering the xerogel morphology.

Silver nanoparticle-ionic silsesquioxane: a new system proposed as an antibacterial agent.

Spherical silver nanoparticles with an average size of ca. 5 nm were synthesized in aqueous medium using a charged silsesquioxane containing a quaternary ammonium group, the bridged 1,4-diazoniabicyclo[2.2.2]octane nitrate, as a stabilizer and size controller. For the first time this system was synthesized and applied as an antibacterial agent and its activity was confirmed with excellent results. The new system shows high stability, which can be confirmed by the unchanged UV-Vis band even one year later. The magnitude of the zeta-potential (ζ) (+24.7 mV) indicated electrostatic contribution for the silver nanoparticles stability and the signal showed that the nanoparticles have a positively charged surface. In vitro antibacterial tests were performed against E. coli, P. aeruginosa and S. aureus bacteria, and the minimum concentrations of silver in the nanoparticle form for complete inhibition of bacteria were 0.60, 1.1 and 2.0 µg mL-1, respectively. These values are very low when compared to the previous reports, making this system very promising. The cytotoxicity assay showed that these silver nanoparticles are safe for mammalian cells at the studied concentrations.

Ionic silica based hybrid material containing the pyridinium group used as an adsorbent for textile dye.

The present study reports the development of an ionic silica based hybrid material containing the cationic pyridinium group, which was employed for the removal of the Reactive Red 194 textile dye from aqueous solution. Three hybrid material samples were prepared with planned textural and chemical properties, varying the inorganic precursor molar percentage in the sol-gel synthesis. The obtained samples were defined as Py/Si-90, Py/Si-92 and Py/Si-94, where the number specifies the inorganic molar percentage. The hybrid samples were characterized by elemental, infrared, (13)C and (29)Si NMR, N(2) adsorption-desorption isotherms and thermogravimetric analyses. The dye-removing ability of these adsorbents was determined by the batch contact adsorption procedure. Effects such as pH value and adsorbent dosage on the adsorption capacities were studied. Four kinetic models were applied. The adsorption was best fitted to Avrami fractional-order kinetic model for the three hybrid material samples. The kinetic data were also adjusted to an intra-particle diffusion model resulting three linear regions, indicating that the adsorption kinetics follows multiple sorption rates. The equilibrium data were fitted to Langmuir, Freundlich and Liu isotherm models. The maximum adsorption capacities were 165.4, 190.3 and 195.9 mg g(-1) for Py/Si-90, Py/Si-92 and Py/Si-94, respectively. Simulated dye-house effluents were used to check the applicability of the proposed adsorbents for effluent treatment. Dye loaded adsorbents were regenerated (>98.2%) by using 0.4 mol L(-1) of NaOH solution as an eluent.

Carbon nanotube/silica composites obtained by sol-gel and high-pressure techniques.

The successful incorporation of functionalized single-walled carbon nanotubes (f-SWCNTs) into a silica matrix prepared by the sol-gel method is reported herein. SWCNTs produced through catalytic chemical-vapor deposition (CCVD) have been purified and functionalized with sulfuric, nitric and hydrochloric acids to ensure a good dispersion in an aqueous solution. The nanotube composites are prepared using three concentrations of f-SWCNTs (0.025, 0.050 and 0.075 wt%.) in a silica matrix, resulting in translucent monoliths after gelation. Dense, crack-free and hard compacts are obtained by high-pressure processing at 7.7 GPa and room temperature. Compared to the pure silica compact, compacts containing 0.025 and 0.050 wt% f-SWCNTs show an increased toughness of about 54% and 69%, respectively. The influence of f-SWCNTs on some microstructural aspects of the silica matrix has been studied using nitrogen adsorption/desorption isotherms. Raman spectroscopy has been applied to analyze the effect of the silica matrix and high-pressure compaction on the f-SWCNTs incorporated into the silica matrix. These measurements showed that f-SWCNTs remained in the silica matrix under pressure, suggesting an important interaction with the matrix.

Silica-titania sol-gel hybrid materials: synthesis, characterization and potential application in solid phase extraction.

The biphenilaminepropylsilica and biphenilaminepropylsilicatitania were synthesized by sol-gel method, in two steps: (a) biphenylamine reacts with chloropropyltrimethoxysilane and (b) the product of reaction was polycondensed with tetraethylorthosilicate (TEOS) or TEOS and titanium isopropoxide. The sol-gel materials were characterized using infrared spectroscopy and N(2) adsorption-desorption isotherms and they were employed as sorbents for carcinogenic N-containing compound retention, in aqueous solution, using the SPE technique. The N-containing compounds adsorption was influenced by the titania presence and the sorption process seems to happen in the pores with higher organic density.