Optimization of acid hydrolysis of sugarcane bagasse and investigations on its fermentability for the production of xylitol by Candida guilliermondii

The dilute-acid hydrolysis of sugarcane bagasse was optimized using a statistical experimental design resulting in hydrolysates containing 57.25 g/L of xylose, which were fermented with a high inoculum concentration (10 g/L of the yeast Candida guilliermondii IM/UFRJ 50088). The addition of urea reduced the time of conversion (t _C) to 75 h (without nitrogen source addition t _C>127 h), and, consequently, improving the rates of xylitol bioproduction. Fermentator experiments, using the optimized conditions, resulted in enhanced conversion rates, reducing t _C to 30 h. The stability of the yeast in the hydrolysate was also verified in a 480-h cultivation.     

Extraction of Pb(II), Cd(II), and Hg(II) from aqueous solution by nitrogen and thiol functionality grafted to silica gel measured by calorimetry

The reaction of ethylene sulfide with 3-aminopropyltrimethoxysilane gave a new silylating agent, which was anchored onto a silica surface via the sol–gel procedure. This surface displayed a chelating moiety containing nitrogen and two sulfur basic centers potentially capable of extracting cations from aqueous solutions. The process of metal extraction was followed by a batch method, and fitted to a modified Langmuir equation. The maximum adsorption capacities found were: 2.06 ± 0.01, 3.72 ± 0.02, and 5.14 ± 0.02 mmol g⁻¹ for Pb(II), Cd(II), and Hg(II), respectively. The enthalpies of bending are: −1.16 ± 0.04, −3.60 ± 0.10, and −8.94 ± 0.03 kJ mol⁻¹ for Cd(II), Pb(II), and Hg(II), respectively. The Gibbs free energies of binding agree with the spontaneity of the proposed reactions between cations and basic centers.     

Thermolysis and Chemiluminescence of Monocyclic 1,2,4-Trioxan-5-ones

The 3,6-substituted 1,2,4-trioxan-5-ones 11 – 14 , on heating to 170–200°, underwent unimolecular thermolysis to generate electronically excited singlet ketones with an efficiency of ca. 0.2%. The chemiluminescence quantum yields (?oS_CL) depended on the nature of the 6-substitutents and increased linearly with temperature. The Arrhenius activation energies were obtained by measuring the rate of decay of luminescence and determined as 22.9, 30.4, 35.6, and 34.2 kcal/mol for 11 – 14 , respectively. Step analysis of the chemiluminescence of 14 afforded an average activation energy of 44.3 kcal/mol. This latter result is explicable in terms of two decomposition paths, higher and lower in energy, leading to excited and ‘dark’ products, respectively. The thermolysis of trioxanones 12 – 14 lacking a H-atom at the 6-position is interpreted as involving successive rupture of the peroxide bond, excision of ketone at the 3-substituted end, and loss of CO₂, to finally produce ketone originating from the 6-position (see Scheme 4).     

Neutron powder diffraction study of A2BeF4 (A=K, Rb, Cs): Structure refinement and analysis of background

The crystal structure of potassium, rubidium and caesium fluoroberyllates have been re-examined by neutron powder diffraction at room temperature and at 1.5 K. Previously, their structures, obtained from X-ray data, were described in the Pn2₁a space group. However, the results obtained from Rietveld refinements, using powder neutron diffraction, at both temperatures, indicated that all structures are orthorhombic with space group Pnma. The known phase transition at high temperature is probably related to the appearance of a hexagonal pseudo-symmetry instead of the elimination of the mirror plane between the above mentioned orthorhombic space groups. A possible phase transition, at very low temperature, was discarded considering the stereochemical criteria concerning the structural stability of A₂BX₄ compounds. This was confirmed by thermal analysis. On the other hand, a modulated background has been detected in all samples during the refinements. This is compatible with the presence of an amorphous phase, coexisting with the crystalline phase, or with a disordered component within the main crystalline phase. Instead of using a polynomial function, the background was modelled by Fourier filtering improving the fit for all patterns. The radial distribution function (RDF) was obtained from the analysis of the calculated background and compared with the RDF from the average crystal structure. The advantages of neutron with respect to X-ray diffraction were evidenced for this type of compound with β-K₂SO₄-type structure.     

Adsorption of crude oil on anhydrous and hydrophobized vermiculite

This publication reports the adsorption of crude oil on vermiculite samples, expanded and hydrophobized with carnauba (Copernícia Cerífera) wax. The adsorption studies were performed by using columns filled with the vermiculite matrices and by dispersion of the vermiculite samples in an oil-water (50 ppm of oil) emulsion. The hydrate vermiculite exhibits a very low adsorption capacity against crude oil. On the other hand, anhydrous (expanded) and hydrophobized matrices show a high adsorption capacity. The 10% hydrophobized matrix show a 50% increased adsorption capacity, in comparison with the expanded one. For adsorption performed in the water-oil emulsion, saturation of the solid hydrophobized matrix is achieved after 60 min. The hydrophobized samples exhibit adsorption factors in the 0.7-1.0 range.     

Studies on diastereoselective reduction of cyclic β-ketoesters with boron hydrides. Part 4: The reductive profile of functionalized cyclohexanone derivatives

Reduction of 2-allyl-2-carboalkoxycyclohexanones (3d-f), 2-propyl-2-carboethoxycyclohexanone (3g) and 2-benzyl-2-carboethoxycyclohexanone (3h) with boron hydrides in the presence and absence of several chelating agents were studied. Molecular modeling studies using semiempirical PM3 method were performed in order to find a suitable explanation of the diastereoselection of ketone carbonyl faces during the reductive process, which yielded trans-2-allyl-2-carboethoxycyclohexanol (6e) and cis-2-allyl-2-carboethoxycyclohexanol (7e) in good diastereomeric excess by using inexpensive sodium and tetrabutylammonium borohydrides.     

Determination of lithium in pharmaceutical formulations used in the treatment of bipolar disorder by flow injection analysis with spectrophotometric detection

In this work, a flow injection system with spectrophotometric detection was developed for the determination of lithium in pharmaceutical formulations used in the treatment of bipolar disorder. Reaction between Quinizarine (1,4-dihydroxyanthraquinone) and Li(I) ion in alkaline medium containing dimethylsulfoxide (DMSO) was explored for this purpose. The flow system was optimized regarding to its chemical (DMSO, Quinizarine and NaOH concentrations and sample pH) and physical parameters (sample loop volume, carrier flow rate and reactor length) in order to establish better conditions in terms of sensitivity and sampling frequency. The results obtained showed that the concentration of DMSO in the reagent solution presents remarkable influence on the magnitude of analytical signal. Chemical species that could be found in the formulations such as Na(I), K(I), Mg(II), Ca(II), Ti(IV), Cl⁻, CO₃²⁻ e sodium dodecylsulfate were tested as possible interfering ions. Among them, only non-monovalent cations presented noticeable interference on lithium signal. However, they were not found in concentrations high enough to cause interference in the determination of lithium in the samples. Sample preparation was performed by sonicating a slurry prepared by dispersing 100 mg of powdered sample in 15 mL of 0.10 mol L⁻¹ HCl solution. Results obtained by developed methodology were not statistically different from those obtained by flame emission spectrometry. In the optimized conditions the method presented a linear range of 5-40 mg L⁻¹ and a relative standard deviation of 3.6% at 5 mg L⁻¹ Li concentration. Detection and quantification limits were 0.54 and 1.8 mg L⁻¹, respectively. Sampling frequency, calculated as the time interval passed between two consecutive injections, was 60 samples per hour. The methodology was successfully applied in the determination of lithium in three commercial samples.     

Latex Fractionation by Sedimentation and Colloidal Crystallization: The Case of Poly(styrene-co-acrylamide)

Poly(styrene-co-acrylamide) (PS-AAM) latex was prepared, fractionated by sedimentation under gravity, and characterized by PCS, infrared spectra, secondary and backscattered electron imaging in the scanning electron microscope, and electron spectroscopy imaging in an analytical transmission electron microscope. Three latex fractions were obtained. The lower fraction was opalescent and its particles were the more uniform, concerning size, chemical composition, and topochemical features. This lower fraction was still further fractionated by zonal centrifugation in a density gradient, yielding two fractions with similar macrocrystal-forming abilities but different sizes and chemical compositions. These results confirm those previously obtained for the PS-HEMA latex. Copyright 2000 Academic Press.     

A synthetic approach to bicyclo[6.2.1]undecane ring systems

A synthesis of a functionalized bicyclo[6.2.1]undecane, N-(7-hydroxymethyl-bicyclo[6.2.1]undeca-3,5,9-trien-2-yl)-4-methyl-benzenesulfonamide, is described. Starting with a [6+4] cycloaddition between cyclopentadiene and cycloheptatrienone, the final product was prepared in five steps with an overall 37% yield. The remarkable resistance to hydrolysis of an intermediate lactam was overcome by tosylating the amide and reducing with LiAlH₄.     

Ligand adsorption on an activated carbon for the removal of chromate ions from aqueous solutions

The results presented in this work are related to the design of a guideline to develop specific properties at the surface of an activated carbon (AC). For this, two model aromatic compounds have been synthesized and their electrolytic behavior in aqueous solutions was studied by a potentiometric method. The textural characteristics of the activated carbon were determined by porosimetry methods. The nature of oxygen-carrying functions and the acid-base behavior of the AC surface were characterized by TPD and potentiometric titration methods, respectively. The adsorption and desorption equilibria of the aromatic compounds on activated carbon were measured in aqueous solutions, and the hysteresis between adsorption and desorption, which reveals irreversible adsorption, was discussed on the basis of the frontier orbital theory. HOMO and LUMO orbitals of the adsorbent and adsorbates were calculated, and irreversible adsorption was attributed to the small energy difference between HOMO and LUMO of the aromatic adsorbates and the adsorbent. Adsorption equilibria of K2CrO4 in aqueous solution on the AC alone and on the AC-aromatic ligand adsorbents, respectively, prove the efficient development of specific chemical functions at the carbon surface provided by the adsorbed aromatic compounds.