Ethanol/water pulps from sugar cane straw and their biobleaching with xylanase from Bacillus pumilus

The influence of independent variables (temperature and time) on the cooking of sugar cane straw with ethanol/water mixtures was studied to determine operating conditions that obtain pulp with high cellulose contents and a low lignin content. An experimental 2(2) design was applied for temperatures of 185 and 215 degrees C, and time of 1 and 2.5 h with the ethanol/water mixture concentration and constant straw-to-solvent ratio. The system was scaled-up at 200 degrees C cooking temperature for 2 h with 50% ethanol-water concentration, and 1:10 (w/v) straw-to-solvent ratio to obtain a pulp with 3.14 cP viscosity, 58.09 kappa-number, and the chemical composition of the pulps were 3.2% pentosan and 31.5% lignin. Xylanase from Bacillus pumilus was then applied at a loading of 5-150 IU/g dry pulp in the sugar cane straw ethanol/water pulp at 50 degrees C for 2 and 20 h. To ethanol/water pulps, the best enzyme dosage was found to be 20 IU/g dry pulp at 20 h, and a high enzyme dosage of 150 IU/g dry pulp did not decrease the kappa-number of the pulp.     

Optically active vibrational modes in the photoluminescence line shape of BDMO-PPV films

In this work we simulate the photoluminescence (PL) spectra of BDMO-PPV thin films prepared by spin-coating technique on glass and on copper, as a function of temperature (12-300 K). Simulations were done using two theoretical models based on (i) the SSH theory where the line shape of the purely electronic transition is partly generated by localized states and partly by delocalized states and (ii) the semi-empirical model containing the coupling between localized molecular excitons and vibrational modes in Franck-Condon approach. Four active vibrational modes have been considered: C-C stretching coupled to a C-H bending of the phenyl ring at 1111.5 cm⁻¹, inter-rings C-C stretching at 1282.2 cm⁻¹, CC stretching coupled to a C-H bending of the vinyl group at 1309.3 cm⁻¹, C-C stretching of the phenyl ring at 1580.2 cm⁻¹. Additional vibrational mode of 403 cm⁻¹ associated with C-C-C out-of-plane bending allowed leastwise for this material to adjust well with the characteristic asymmetry of the purely electronic transition. Finally, application of theoretical models are strongly dependent on the well-resolved PL spectra, i.e., electronic transition peak presented a relatively thinner HWHM and an asymmetric line shape.     

Influence of viral infection on essential oil composition of Ocimum basilicum (Lamiaceae)

Ocimum basilicum L., popularly known as sweet basil, is a Lamiaceae species whose essential oil is mainly composed of monoterpenes, sesquiterpenes and phenylpropanoids. The contents of these compounds can be affected by abiotic and biotic factors such as infections caused by viruses. The main goal of this research was an investigation of the effects of viral infection on the essential oil profile of common basil. Seeds of O. basilicum L. cv. Genovese were sowed and kept in a greenhouse. Plants presenting two pairs of leaves above the cotyledons were inoculated with an unidentified virus isolated from a field plant showing chlorotic yellow spots and foliar deformation. Essential oils of healthy and infected plants were extracted by hydrodistillation and analyzed by GCMS. Changes in essential oil composition due to viral infection were observed. Methyleugenol and p-cresol,2,6-di-tert-butyl were the main constituents. However, methyleugenol contents were significantly decreased in infected plants.     

NMR, DFT and luminescence studies of the complexation of Zn(II) with 8-hydroxyquinoline-5-sulfonate

Multinuclear ((1)H, (13)C) magnetic resonance spectroscopy, DFT calculations and luminescence techniques have been used to study 8-hydroxyquinoline-5-sulfonate (8-HQS) and its complexes with Zn(ii), in aqueous solution. The study combines the high sensitivity of luminescence techniques, the selectivity of multinuclear NMR spectroscopy with the structural details accessible through DFT calculations, and aims to obtain a detailed understanding of the complexation between the Zn(2+) ion and 8-HQS. In addition to a complete assignment of the (1)H and (13)C NMR signals of 8-HQS, a full speciation study has been performed. Over the concentration region studied, Zn(2+) metal ion forms only one significant complex species with 8-HQS in aqueous solution in the pH range 6-8. Job's method shows that this species has a 1:2 (metal:ligand) stoichiometry. The geometry around the metal centre, according to structural optimization using DFT calculations, is suggested to be square bipyramidal, with two coordinated water molecules mutually trans, and the remaining positions occupied by the donor groups of the two coordinated 8-HQS ligands. On binding to Zn(ii), 8-HQS shows a marked fluorescence compared with the weakly-luminescent free ligand. In addition, as previously noted, there are marked changes in the absorption spectra, which support the use of 8-HQS as a sensitive fluorescent sensor to detect Zn(2+) metal ion in surface waters, biological fluids, etc. Based on results of the structural studies, suggestions are made of ways for enhancing fluorescence sensitivity.     

New tetradentate N,N,N,N-chelating α-diimine ligands and their corresponding zinc and nickel complexes: synthesis, characterisation and testing as olefin polymerisation catalysts

A series of zinc complexes of the general formula {[ZnCl(ArN=C(An)-C(An)=NAr)](+)}(2)[Zn(2)Cl(6)](2-) (where Ar = 2-(1-benzyl-1H-1,2,3-triazol-4-yl)phenyl 2a, 2-(1-(1-phenylethyl)-1H-1,2,3-triazol-4-yl)phenyl 2b, 2-(1-phenyl-1H-1,2,3-triazol-4-yl)phenyl 2c; An = acenaphthene backbone) were prepared by the condensation of acenaphthenequinone with the corresponding o-triazolyl-substituted anilines (2-(1-benzyl-1H-1,2,3-triazol-4-yl)aniline 1a, 2-(1-(1-phenylethyl)-1H-1,2,3-triazol-4-yl)aniline 1b, 2-(1-phenyl-1H-1,2,3-triazol-4-yl)aniline 1c) which were formed by the copper(I)-catalyzed Huisgen[3+2] dipolar cycloaddition between 2-ethynylaniline and the corresponding azides in high yields, using anhydrous ZnCl(2) as the metal template, in boiling glacial acetic acid. Zinc complexes of the type [ZnCl(ArN=C(An)-C(An)=NAr)](+)[ZnCl(3)(NCCH(3))](-) (4a-c) were synthesized by crystallisation of the corresponding complexes 2a-c in acetonitrile, at -20 °C. After removal of zinc dichloride from complexes 2a-c by the addition of potassium oxalate, in dichloromethane, the tetradentate N,N,N,N-chelating α-diimine ligands of the type ArN=C(An)-C(An)=NAr (5a-c) were obtained. The new ligand precursors and zinc complexes were characterised by elemental analysis, (1)H and (13)C{(1)H} NMR spectroscopy, two-dimensional NMR spectroscopy, and X-ray diffraction. Reaction of the ligand precursors 5a-c with [NiBr(2)(DME)], in dichloromethane, gave nickel complexes of the type [NiBr(2)(ArN=C(An)-C(An)=NAr)] (6a-c). The results of single crystal X-ray diffraction characterisation and magnetic susceptibility measurements demonstrated that nickel complexes 6a-c possess octahedral geometries around the nickel atoms with variable configurations, the Br atoms of which can be ionized when dissolved in methanol. In preliminary catalytic tests, complexes 6a-c revealed to be active as catalysts for the polymerisation of norbornene and styrene, when activated by cocatalyst MAO. The characterisation of the polymers by (1)H and (13)C{(1)H} NMR spectroscopy, gel permeation chromatography/size-exclusion chromatography (GPC/SEC) revealed that these polymers were formed by a coordination addition mechanism.     

Comparative study of oxidative stability of sunflower and cotton biodiesel through P-DSC

Biodiesel can contain unsaturated fatty acids, which are susceptible to oxidation, being able to change into polymerized compounds. Oxidative stability is very important in the quality control of oils and biodiesel. In this study, biodiesel samples were produced through the methyl route, using a homogeneous catalyst. The determination of methyl esters was performed by gas chromatography in order to confirm the conversion of the carboxylic acids present in the raw material for the methyl esters. Also proved the presence of methyl linoleate and methyl oleate to the major constituent of biodiesel. The thermal and oxidative stability of sunflower and cotton oils and their biodiesel, using TG and P-DSC techniques were investigated. The use of P-DSC to measure the oxidative induction time was very important. These measurements were used to evaluate the cotton and sunflower oils, and their respective biodiesel. It was found that the thermal-oxidative stability of vegetable oils and their biodiesel were similar, due to the fact that both presented chemical composition and percentages of fatty acids similar.     

Radiolysis of astrophysical ice analogs by energetic ions: the effect of projectile mass and ice temperature

An experimental study of the interaction of highly charged, energetic ions (52 MeV (58)Ni(13+) and 15.7 MeV (16)O(5+)) with mixed H(2)O : C(18)O(2) astrophysical ice analogs at two different temperatures is presented. This analysis aims to simulate the chemical and the physicochemical interactions induced by cosmic rays inside dense, cold astrophysical environments, such as molecular clouds or protostellar clouds as well at the surface of outer solar system bodies. The measurements were performed at the heavy ion accelerator GANIL (Grand Accelerateur National d'Ions Lourds) in Caen, France. The gas samples were deposited onto a CsI substrate at 13 K and 80 K. In situ analysis was performed by a Fourier transform infrared (FTIR) spectrometer at different fluences. Radiolysis yields of the produced species were quantified. The dissociation cross section at 13 K of both H(2)O and CO(2) is about 3-4 times smaller when O ions are employed. The ice temperature seems to affect differently each species when the same projectile was employed. The formation cross section at 13 K of molecules such as C(18)O, CO (with oxygen from water), and H(2)O(2) increases when Ni ions are employed. The formation of organic compounds seems to be enhanced by the oxygen projectiles and at lower temperatures. In addition, because the organic production at 13 K is at least 4 times higher than the value at 80 K, we also expect that interstellar ices are more organic-rich than the surfaces of outer solar system bodies.     

Determination of triamcinolone in human plasma by a sensitive HPLC-ESI-MS/MS method: application for a pharmacokinetic study using nasal spray formulation

A liquid chromatography-electrospray ionization tandem mass spectrometry (HPLC-ESI-MS/MS) method for the quantitation of triamcinolone in human plasma after nasal spray application was developed and validated. Betamethasone was used as internal standard (IS). The analytes were extracted by a liquid-liquid procedure and separated on a Zorbax Eclipse XDB C(18) column with a mobile phase composed of 2 mM aqueous ammonium acetate pH 3.2 and acetonitrile (55:45). Selected reaction monitoring was performed using the transitions m/z 435 → 415 and m/z 393 → 373 to quantify triamcinolone acetonide and betamethasone, respectively. Calibration curve was constructed over the range of 20-2000 pg/ml for triamcinolone acetonide. The lower limit of quantitation was 20 pg/ml. The mean RSD values were 4.6% and 5.7% for the intra-run and inter-run precision, respectively. The mean accuracy value was 98.5% and a recovery rate corresponding to 97.5% was achieved. No matrix effect was detected in the samples. The validated method was successfully applied to determine the plasma concentrations of triamcinolone acetonide in healthy volunteers, in a pharmacokinetic study with nasal spray formulation.     

Development and validation of a high-performance liquid chromatography-electrospray ionization-MS/MS method for the simultaneous quantitation of levodopa and carbidopa in human plasma

A sensitive and fast high‐performance liquid chromatography–electrospray ionization–MS/MS method for the simultaneous quantitation of levodopa and carbidopa in human plasma was developed and validated. A simple protein precipitation step with perchloric acid was used for the cleanup of plasma, and methyldopa was added as an internal standard. The analyses were carried out using an ACE C₁₈ column (50 × 4.6 mm i.d.; 5 µm particle size) and a mobile phase consisting of 0.2% formic acid and acetonitrile (90:10). The triple‐quadrupole mass spectrometer equipped with an electrospray source in positive mode was set up in the selective reaction monitoring mode to detect the ion transitions m/z 198.1 → m/z 107.0, m/z 227.2 → m/z 181.0, and m/z 212.1 → m/z 139.2 for levodopa, carbidopa, and methyldopa, respectively. The method was validated and proved to be linear, accurate, and precise over the range 50–5000 ng/mL for levodopa and 3–600 ng/mL for carbidopa. The proposed method was successfully applied in a pharmacokinetic study with a levodopa/carbidopa tablet formulation in healthy volunteers. Copyright © 2011 John Wiley & Sons, Ltd.     

Multiobjective GRASP with Path Relinking

In this paper we review and propose different adaptations of the GRASP metaheuristic to solve multiobjective combinatorial optimization problems. In particular, we describe several alternatives to specialize the construction and improvement components of GRASP when two or more objectives are considered. GRASP has been successfully coupled with Path Relinking for single-objective optimization. Moreover, we propose different hybridizations of GRASP and Path Relinking for multiobjective optimization. We apply the proposed GRASP with Path Relinking variants to two combinatorial optimization problems, the biobjective orienteering problem and the biobjective path dissimilarity problem. We report on empirical tests with 70 instances and 30 algorithms, that show that the proposed heuristics are competitive with the state-of-the-art methods for these problems.