Thermostable invertases from Paecylomyces variotii produced under submerged and solid-state fermentation using agroindustrial residues

The filamentous fungus Paecylomices variotii was able to produce high levels of cell extract and extracellular invertases when grown under submerged fermentation (SbmF) and solid-state fermentation, using agroindustrial products or residues as substrates, mainly soy bran and wheat bran, at 40A degrees C for 72 h and 96 h, respectively. Addition of glucose or fructose (a parts per thousand yen1%; w/v) in SbmF inhibited enzyme production, while the addition of 1% (w/v) peptone as organic nitrogen source enhanced the production by 3.7-fold. However, 1% (w/v) (NH4)(2)HPO4 inhibited enzyme production around 80%. The extracellular form was purified until electrophoretic homogeneity (10.5-fold with 33% recovery) by DEAE-Fractogel and Sephacryl S-200 chromatography. The enzyme is a monomer with molecular mass of 102 kDa estimated by SDS-PAGE with carbohydrate content of 53.6%. Optima of temperature and pH for both, extracellular and cell extract invertases, were 60A degrees C and 4.0-4.5, respectively. Both invertases were stable for 1 h at 60A degrees C with half-lives of 10 min at 70A degrees C. Mg2+, Ba2+ and Mn2+ activated both extracellular and cell extract invertases from P. variotii. The kinetic parameters K-m and V-max for the purified extracellular enzyme corresponded to 2.5 mM and 481 U/mg prot(-1), respectively.

Incorporation of PbF2 into Heavy Metal Oxide Borate Glasses. Structural Studies by Solid State NMR

A series of heavy metal oxide (HMO) glasses with composition 26.66B(2)O(3)-16GeO(2)-4 Bi2O3-(53.33-x)PbO-xPbF2 (0 <= x <= 40) were prepared and characterized with respect to their bulk (glass transition and crystallization temperatures, densities, molar volumes) and spectroscopic properties. Homogeneous glasses are formed up to x = 30, while crystallization of beta-PbF2 takes place at higher contents. Substitution of PbO by PbF2 shifts the optical band gap toward higher energies, thereby extending the UV transmission window significantly toward higher frequencies. Raman and infrared absorption spectra can be interpreted in conjunction with published reference data. Using B-11 and F-19 high-resolution solid state NMR as well as B-11/F-19 double resonance methodologies, we develop a quantitative structural description of this material. The fraction of four-coordinate boron is found to be moderately higher compared to that in glasses with the same PbO/B2O3 ratios, suggesting some participation of PbF2 in the network transformation process. This suggestion is confirmed by the F-19 NMR spectra. While the majority of the fluoride ions is present as ionic fluoride, similar to 20% of the fluorine inventory acts as a network modifier, resulting in the formation of four-coordinate BO3/2F- units. These units can be identified by F-19{B-11} rotational echo double resonance and B-11{F-19} cross-polarization magic angle spinning (CPMAS) data. These results provide the first unambiguous evidence of B-F bonding in a PbF2-modified glass system. The majority of the fluoride ions are found in a lead-dominated environment. F-19-F-19 homonuclear dipolar second moments measured by spin echo decay spectroscopy are quantitatively consistent with a model in which these ions are randomly distributed within the network modifier subdomain consisting of PbO, Bi2O3, and PbF2. This model, which implies both the features of atomic scale mixing with the network former borate species and some degree of fluoride ion clustering is consistent with all of the experimental data obtained on these glasses.

Caffeine Determination at a Carbon Fiber Ultramicroelectrodes by Fast-Scan Cyclic Voltammetry

Caffeine determination using a fast-scan voltammetric procedure at a carbon fiber ultramicroelectrode (CF-UME) is described. The CF-UME was submitted to electrochemical pretreatment. Parameters such as number of acquisition cycles, scan rate, potential window, and the electrochemical surface pretreatment were optimized. Using the optimized conditions, it was possible to achieve a LDR from 10.0 up to 200 mu mol L-1, with a LOD of 3.33 mu mol L-1. The method has been applied in the determination of caffeine in commercial samples, with errors of 1.0-3.5% in relation to the label values and recoveries of 97-114% within the linear range.

Preliminary Characterization of Novel Extra-cellular Lipase from Penicillium crustosum Under Solid-State Fermentation and its Potential Application for Triglycerides Hydrolysis

Current studies about lipase production involve the use of agro-industrial residues and newly isolated microorganisms aimed at increasing economic attractiveness of the process. Based on these aspects, the main objective of this work is to perform the partial characterization of enzymatic extracts produced by a newly isolated Penicillium crustosum in solid-state fermentation. Lipase extract presented optimal temperature and pH of 37 A degrees C and 9-10, respectively. The concentrated enzymatic extract showed more stability at 25 A degrees C and pH 7. The enzymes kept 100% of their enzymatic activity until 60 days of storage at 4 and -10 A degrees C. The stability under calcium salts indicated that the hydrolytic activity presented decay with the increase of calcium concentration. The specificity under several substrates indicated good enzyme activities in triglycerides from C4 to C18.

Production of a xylose-stimulated beta-glucosidase and a cellulase-free thermostable xylanase by the thermophilic fungus Humicola brevis var. thermoidea under solid state fermentation

Humicola brevis var. thermoidea cultivated under solid state fermentation in wheat bran and water (1:2 w/v) was a good producer of beta-glucosidase and xylanase. After optimization using response surface methodology the level of xylanase reached 5,791.2 +/- A 411.2 U g(-1), while beta-glucosidase production was increased about 2.6-fold, reaching 20.7 +/- A 1.5 U g(-1). Cellulase levels were negligible. Biochemical characterization of H. brevis beta-glucosidase and xylanase activities showed that they were stable in a wide pH range. Optimum pH for beta-glucosidase and xylanase activities were 5.0 and 5.5, respectively, but the xylanase showed 80 % of maximal activity when assayed at pH 8.0. Both enzymes presented high thermal stability. The beta-glucosidase maintained about 95 % of its activity after 26 h in water at 55 A degrees C, with half-lives of 15.7 h at 60 A degrees C and 5.1 h at 65 A degrees C. The presence of xylose during heat treatment at 65 A degrees C protected beta-glucosidase against thermal inactivation. Xylanase maintained about 80 % of its activity after 200 h in water at 60 A degrees C. Xylose stimulated beta-glucosidase activity up to 1.7-fold, at 200 mmol L-1. The notable features of both xylanase and beta-glucosidase suggest that H. brevis crude culture extract may be useful to compose efficient enzymatic cocktails for lignocellulosic materials treatment or paper pulp biobleaching.

Transverse pseudo-nonlinear effects measured in solid-state laser materials using a sensitive time-resolved technique

We present a detailed study of the Baryscan technique, a new efficient alternative to the widespread Z-scan technique which has been demonstrated [Opt. Lett. 36:8, 2011] to reach among the highest sensitivity levels. This method is based upon the measurement of optical nonlinearities by means of beam centroid displacements with a position sensitive detector and is able to deal with any kind of lensing effect. This technique is applied here to measure pump-induced electronic refractive index changes (population lens), which can be discriminated from parasitic thermal effects by using a time-resolved Baryscan experiment. This method is validated by evaluating the polarizability variation at the origin of the population lens observed in the reference Cr3+:GSGG laser material.

Cyclic Voltammetry and Computational Chemistry Studies on the Evaluation of the Redox Behavior of Parabens and other Analogues

Parabens are antimicrobial preservatives widely used in pharmaceutical, cosmetic and food industries. The alkyl chain connected to the ester group defines some important physicochemical characteristics of these compounds, including the partition coefficient and redox properties. The voltammetric and computational analyses were carried out in order to evaluate the redox behavior of these compounds and other phenolic analogues. A strong correlation between chemical substituents inductive effects of parabens with redox potentials was observed. Using cyclic voltammetry and glassy carbon working electrode, only one irreversible anodic peak was observed around 0.8 V for methylparaben (MP), ethylparaben (EP), propylparaben (PP), butylparaben (BP), benzylparaben (BzP) and p-substituted phenolic analogues. The electrodonating inductive effect of alkyl groups was demonstrated by the anodic oxidation potential shift to lower values as the carbon number increases and, therefore the parabens (and other phenolic analogues) oxidation processes to the quinonoidic forms showed great dependence on the substituent pattern.

Cyclic voltammetry and computational chemistry studies on the evaluation of the redox behavior of parabens and other analogues

Parabens are antimicrobial preservatives widely used in pharmaceutical, cosmetic and food industries. The alkyl chain connected to the ester group defines some important physicochemical characteristics of these compounds, including the partition coefficient and redox properties. The voltammetric and computational analyses were carried out in order to evaluate the redox behavior of these compounds and other phenolic analogues. A strong correlation between chemical substituents inductive effects of parabens with redox potentials was observed. Using cyclic voltammetry and glassy carbon working electrode, only one irreversible anodic peak was observed around 0.8 V for methylparaben (MP), ethylparaben (EP), propylparaben (PP), butylparaben (BP), benzylparaben (BzP) and p-substituted phenolic analogues. The electrodonating inductive effect of alkyl groups was demonstrated by the anodic oxidation potential shift to lower values as the carbon number increases and, therefore the parabens (and other phenolic analogues) oxidation processes to the quinonoidic forms showed great dependence on the substituent pattern.

Caffeine determination at a carbon fiber ultramicroelectrodes by fast-scan cyclic voltammetry

Caffeine determination using a fast-scan voltammetric procedure at a carbon fiber ultramicroelectrode (CF-UME) is described. The CF-UME was submitted to electrochemical pretreatment. Parameters such as number of acquisition cycles, scan rate, potential window, and the electrochemical surface pretreatment were optimized. Using the optimized conditions, it was possible to achieve a LDR from 10.0 up to 200 μmol L-1, with a LOD of 3.33 μmol L-1. The method has been applied in the determination of caffeine in commercial samples, with errors of 1.0-3.5% in relation to the label values and recoveries of 97-114% within the linear range.

Molecular dynamics of poly(Ethylene Glycol) intercalated in clay, studied using 13C solid-state NMR

In this study, Cross-Polarization Magic-angle Spinning CP/MAS, 2D Exchange, Centerband-Only Detection of Exchange (CODEX), and Separated-Local-Field (SLF) NMR experiments were used to study the molecular dynamics of poly(ethylene glycol) (PEG) inside Hectorite/PEG intercalation compounds in both single- and double-layer configurations. The results revealed that the overall amplitude of the motions of the PEG chain in the single-layer configuration is considerably smaller than that observed for the double-layer intercalation compound. This result indicates that the effect of having the polymer chain interacting with both clay platelets is to produce a substantial decrease in the motional amplitudes of those chains. The presence of these dynamically restricted segments might be explained by the presence of anchoring points between the clay platelets and the PEG oxygen atoms, which was induced by the Na+ cations. By comparing the PEG motional amplitudes of the double-layered nanocomposites composed of polymers with different molecular weights, a decrease in the motional amplitude for the smaller PEG chain was observed, which might also be understood using the presence of anchoring points.

ScPdZn and ScPtZn with YAlGe type structure: group-subgroup relation and 45Sc solid state NMR spectroscopy

The intermetallic compounds ScPdZn and ScPtZn were prepared from the elements by high-frequency melting in sealed tantalum ampoules. Both structures were refined from single crystal X-ray diffractometer data: YAlGe type, Cmcm, a = 429.53(8), b = 907.7(1), c = 527.86(1) pm, wR2 = 0.0375, 231 F2 values, for ScPdZn and a = 425.3(1), b = 918.4(2), c = 523.3(1) pm, wR2 = 0.0399, 213 F2 values for ScPtZn with 14 variables per refinement. The structures are orthorhombically distorted variants of the AlB2 type. The scandium and palladium (platinum atoms) build up ordered networks Sc3Pd3 and Sc3Pt3 (boron networks) which are slightly shifted with respect to each other. These networks are penetrated by chains of zinc atoms (262 pm in ScPtZn) which correspond to the aluminum positions, i.e. Zn(ScPd) and Zn(ScPt). The corresponding group-subgroup scheme and the differences in chemical bonding with respect to other AlB2-derived REPdZn and REPtZn compounds are discussed. 45Sc solid state NMR spectra confirm the single crystallographic scandium sites. From electronic band structure calculations the two compounds are found metallic with free electron like behavior at the Fermi level. A larger cohesive energy for ScPtZn suggests a more strongly bonded intermetallic than ScPdZn. Electron localization and overlap population analyses identify the largest bonding for scandium with the transition metal (Pd, Pt).

Solid electrolytes for electrochromic devices based on reversible metal electrodeposition

Air conditioning and lighting costs can be reduced substantially by changing the optical properties of "intelligent windows." The electrochromic devices studied to date have used copper as an additive. Copper, used here as an electrochromic material, was dissolved in an aqueous animal protein-derived gel electrolyte. This combination constitutes the electrochromic system for reversible electrodeposition. Cyclic voltammetry, chronoamperometric and chromogenic analyses indicated that were obtained good conditions of transparency (initial transmittance of 70%), optical reversibility, small potential window (2.1 V), variation of transmittance in visible light (63.6%) and near infrared (20%) spectral regions. Permanence in the darkened state was achieved by maintaining a lower pulse potential (-0.16 V) than the deposition potential (-1.0 V). Increasing the number of deposition and dissolution cycles favored the transmittance and photoelectrochemical reversibility of the device. The conductivity of the electrolyte (10(-3) S/cm) at several concentrations of CuCl2 was determined by electrochemical impedance spectroscopy. A thermogravimetric analysis confirmed the good thermal stability of the electrolyte, since the mass loss detected up to 100 degrees C corresponded to water evaporation and decomposition of the gel started only at 200 degrees C. Micrographic and small angle X-ray scattering analyses indicated the formation of a persistent deposit of copper particles on the ITO. (C) 2012 Elsevier B.V. All rights reserved.

Determination of Tetradifon in Brazilian Green Bell Pepper by Differential Pulse Voltammetry

Tetradifon, a potentially carcinogenic and mutagenic pesticide, can contribute to environmental and human contamination when applied to green bell pepper crops. In this context, in this work, a reliable and sensitive method for determination of tetradifon in Brazilian green bell pepper samples involving a differential pulse voltammetry (DPV) technique on a glassy carbon electrode is proposed. The electrochemical behavior of tetradifon as followed by cyclic voltammetry (CV) suggests that its reduction occurs via an irreversible five-electron transfer vs. Ag vertical bar AgCl, KCl 3 M reference electrode. Very well-resolved diffusion controlled voltammetric peaks have been obtained in a supporting electrolyte solution composed of a mixture of 40% dimethylformamide (DMF), 30% methanol, and 30% NaOH 0.3 mol L-1 at -1.43, -1.57, -1.73, -1.88, and -2.05 V. The proposed DPV method has a good linear response in the 3.00 - 10.0 mu mol L-1 range, with a limit of detection (L.O.D) of 0.756 mu mol L-1 and 0.831 mu mol L-1 in the absence and in the presence of the matrix, respectively. Moreover, improved L.O.D results (0.607 mu mol L-1) have been achieved in the absence of DMF from the supporting electrolyte solution. Recovery has been evaluated in five commercial green bell pepper samples, and recovery percentages ranging from 91.0 to 109 have been obtained for tetradifon determinations. The proposed voltammetric method has also been tested for reproducibility, repeatability, and potential interferents, and the results obtained for these three analytical parameters are satisfactory for electroanalytical purposes. (C) 2012 The Electrochemical Society. [DOI: 10.1149/2.024207jes] All rights reserved.

Local electrochemical investigation of copper patina

The patination of copper is known for its complexity and heterogeneous formation. For a deeper investigation, a locally resolved surface analysis was considered. An exact determination of the accessed area and a potentiostatic control in a three-electrode configuration was reached with the use of the electrochemical microcell technique, which enables local electrochemical measurement such as local electrochemical impedance spectroscopy and cyclic voltammetry. Such a technique provides a unique way for performing the investigation of heterogeneities on electrode surfaces. The local electrochemical measurements on the artificially patinated surface have allowed distinguishing areas of different reactivity even when the analysis of the surface revealed a homogenous chemical composition of patina. Local measurements with the electrochemical microcell showed the presence of small defects on the patina layer that can be modelled by considering a hemispherical diffusion process at small active areas surrounded by larger less reactive domains.