Exergy efficiency analysis of chemical and biochemical stages involved in liquid biofuels production processes

Liquid biofuels can be produced from a variety of feedstocks and processes. Ethanol and biodiesel production processes based on conventional raw materials are already commercial, but subject to further improvement and optimization. Biofuels production processes using lignocellulosic feedstocks are still in the demonstration phase and require further R&D to increase efficiency. A primary tool to analyze the efficiency of biofuels production processes from an integrated point of view is offered by exergy analysis. To gain further insight into the performance of biofuels production processes, a simulation tool, which allows analyzing the effect of process variables on the exergy efficiency of stages in which chemical or biochemical reactions take place, were implemented. Feedstocks selected for analysis were parts or products of tropical plants such as the fruit and flower stalk of banana tree, palm oil, and glucose syrups. Results of process simulation, taking into account actual process conditions, showed that the exergy efficiencies of the acid hydrolysis of banana fruit and banana pulp were in the same order (between 50% and 60%), lower than the figure for palm oil transesterification (90%), and higher that the exergy efficiency of the enzymatic hydrolysis of flower stalk (20.3%). (C) 2011 Elsevier Ltd. All rights reserved.

QUANTIFICATION OF TRYPTOPHAN IN PLASMA BY HIGH PERFORMANCE LIQUID CHROMATOGRAPHY

A simple, rapid and selective method using high-performance liquid chromatography with ultraviolet detection (267 nm) was applied for the determination of tryptophan in plasma. Separation was carried out on a C18 column (150 x 4.6 mm internal diameter) in 6 min. The mobile phase consisted of 5 mM the sodium acetate and acetonitrile (92:8, v/v). The method was shown to be precise and accurate, and good recovery of analyte was achieved, characterizing the method as efficient and reliable for use in laboratory analysis.

Automated analysis of lidocaine and its metabolite in plasma by in-tube solid-phase microextraction coupled with LC-UV for pharmacokinetic study

A sensitive, selective, and reproducible in-tube solid-phase microextraction and liquid chromatographic (in-tube SPME/LC-UV) method for determination of lidocaine and its metabolite monoethylglycinexylidide (MEGX) in human plasma has been developed, validated, and further applied to pharmacokinetic study in pregnant women with gestational diabetes mellitus (GDM) subjected to epidural anesthesia. Important factors in the optimization of in-tube SPME performance are discussed, including the draw/eject sample volume, draw/eject cycle number, draw/eject flow rate, sample pH, and influence of plasma proteins. The limits of quantification of the in-tube SPME/LC method were 50 ng/mL for both metabolite and lidocaine. The interday and intraday precision had coefficients of variation lower than 8%, and accuracy ranged from 95 to 117%. The response of the in-tube SPME/LC method for analytes was linear over a dynamic range from 50 to 5000 ng/mL, with correlation coefficients higher than 0.9976. The developed in-tube SPME/LC method was successfully used to analyze lidocaine and its metabolite in plasma samples from pregnant women with GDM subjected to epidural anesthesia for pharmacokinetic study.

Enhancement of the Nonlinear Optical Absorption of the E7 Liquid Crystal at the Nematic-Isotropic Transition

We present an experimental study of the nonlinear optical absorption of the eutectic mixture E7 at the nematic-isotropic phase transition by the Z-scan technique, under continuous-wave excitation at 532 nm. In the nematic region, the effective nonlinear optical coefficient beta, which vanishes in the isotropic phase, is negative for the extraordinary beam and positive for an ordinary beam. The parameter , whose definition in terms of the nonlinear absorption coefficient follows the definition of the optical-order parameter in terms of the linear dichroic ratio, behaves like an order parameter with critical exponent 0.22 +/- 0.05, in good agreement with the tricritical hypothesis for the nematic-isotropic transition.

Partitioning and extraction of collagenase from Penicillium aurantiogriseum in poly(ethylene glycol)/phosphate aqueous two-phase system

Purification of collagenase produced by Penicillium aurantiogriseum URM4622 was carried using a PEG/phosphate aqueous two-phase system (ATPS). A 2(3)-full experimental design was used to investigate the influence of PEG molar mass, PEG concentration and phosphate concentration on the selected responses, namely partition coefficient, activity yield and purification factor. The ATPS was composed of PEG (molar mass of 550, 1500 and 4000 g/mol) at concentrations of 15.0, 17.5 and 20.0% (w/w) and phosphate at concentrations of 12.5, 15.0 and 17.5% (w/w). The best results of one-step extraction of collagenase from the fermentation broth (partition coefficient of 1.01, activity yield of 242% and purification factor of 23.5) were obtained at pH 6.0 using 20.0% (w/w) PEG 550 and 17.5% (w/w) phosphate. The results of this preliminary study demonstrate that the selected ATPS is satisfactorily selective for the extraction of such a collagenase. (C) 2012 Elsevier B.V. All rights reserved.

Liquid-liquid equilibria for systems composed of rice bran oil and alcohol-rich solvents: Application to extraction and deacidification of oil

The liquid-liquid equilibria of systems composed of rice bran oil, free fatty acids, ethanol and water were investigated at temperatures ranging from 10 to 60 degrees C. The results of the present study indicated that the mutual solubility of the compounds decreased with an increase in the water content of the solvent and a decrease in the temperature of the solution. The experimental data set was correlated by applying the UNIQUAC model. The average variance between the experimental and calculated compositions was 0.35%, indicating that the model can accurately predict behavior of the compounds at different temperatures and degrees of hydration. The adjustment of interaction parameters enables both the simulation of liquid-liquid extractors for deacidification of vegetable oil and the prediction of phase compositions for the oil and alcohol-rich phases that are generated during cooling of the stream exiting the extractor (when using ethanol as the solvent). (C) 2012 Elsevier Ltd. All rights reserved.

Solid phase microextraction and LC-MS/MS for the determination of paliperidone after stereoselective fungal biotransformation of risperidone

The present work describes for the first time the use of SPME coupled to LC-MS/MS employing the polar organic mode in a stereoselective fungal biotransformation study to investigate the fungi ability to biotransform the drug risperidone into its chiral and active metabolite 9-hydroxyrisperidone (9-RispOH). The chromatographic separation was performed on a Chiralcel OJ-H column using methanol:ethanol (50:50, v/v) plus 0.2% triethylamine as the mobile phase at a flow rate of 0.8 mL min(-1). The SPME process was performed using a C18 fiber, 30 min of extraction time and 5 min of desorption time in the mobile phase. The method was completely validated and all parameters were in agreement with the literature recommendations. The Cunninghamella echinulata fungus was able to biotransform risperidone into the active metabolite, (+)-9-RispOH, resulting in 100% of enantiomeric excess. The Cunninghamella elegans fungus was also able to stereoselectively biotransform risperidone into (+)- and (-)-9-RispOH enantiomers at different rates. (C) 2012 Elsevier B.V. All rights reserved.

Study of photorespiration in marine microalgae through the determination of glycolic acid using hydrophilic interaction liquid chromatography

Determination of organic acids in intracellular extracts and in the cultivation media of marine microalgae aid investigations about metabolic routes related to assimilation of atmospheric carbon by these organisms, which are known by their role in the carbon dioxide sink. The separation of these acids was investigated by hydrophilic interaction liquid chromatography (HILIC) using isocratic elution with a mobile phase composed of 70: 30 v/v acetonitrile/20 mmol/L ammonium acetate buffer (pH 6.8) and detection at 220 nm. HILIC allowed the determinations of glycolic acid, the most important metabolite for the evaluation of the photorespiration process in algae, to be made with better selectivity than that achieved by reversed phase liquid chromatography, but with less detectability. The concentration of glycolic acid was determined in the cultivation media and in intracellular extracts of the algae Tetraselmis gracilis and Phaeodactylum tricornutum submitted to different conditions of aeration: (i) without forced aeration, (ii) aeration with atmospheric air, and (iii) bubbling with N(2). The concentration of glycolic acid had a higher increase as the cultures were aerated with nitrogen, showing higher photorespiratory flux than that occurring in the cultures aerated with atmospheric air.

Lyotropic mixture made of potassium laurate/1-undecanol/K2SO4/water presenting high birefringences and large biaxial nematic phase domain: a laser conoscopy study

The lyotropic liquid crystalline quaternary mixture made of potassium laurate (KL), potassium sulphate, 1-undecanol and water was investigated by experimental optical methods (optical microscopy and laser conoscopy). In a particular temperature and relative concentrations range, the three nematic phases (two uniaxial and one biaxial) were identified. The biaxial domain in the temperature/KL concentration surface is larger when compared to other lyotropic mixtures. Moreover, this new mixture gives nematic phases with higher birefringence than similar systems. The behavior of the symmetric tensor order parameter invariants sigma(3) and sigma(2) calculated from the measured optical birefringences supports that the uniaxial-to-biaxial transitions are of second order, described by a mean-field theory.

Biaxial nematic phase in the Maier-Saupe model for a mixture of discs and cylinders

We analyze the global phase diagram of a Maier-Saupe lattice model with the inclusion of shape-disordered degrees of freedom to mimic a mixture of oblate and prolate molecules (discs and cylinders). In the neighborhood of a Landau multicritical point, solutions of the statistical problem can be written as a Landau-de Gennes expansion for the free energy. If the shape-disordered degrees of freedom are quenched, we confirm the existence of a biaxial nematic structure. If orientational and disorder degrees of freedom are allowed to thermalize, this biaxial solution becomes thermodynamically unstable. Also, we use a two-temperature formalism to mimic the presence of two distinct relaxation times, and show that a slight departure from complete thermalization is enough to stabilize a biaxial nematic phase.

Determination of anticonvulsants in human plasma using SPME in a heated interface coupled online to liquid chromatography (SPME-LC)

A simple and sensitive method using solid phase microextraction (SPME) and liquid chromatography (LC) with heated online desorption (SPME-LC) was developed and validated to analyze anticonvulsants (AEDs) in human plasma samples. A heated lab-made interface chamber was used in the desorption procedure, which allowed the transference of the whole extracted sample. The SPME conditions were optimized by applying an experimental design. Important factors are discussed such as fiber coating types, pH, extraction time and desorption conditions. The drugs were analyzed by LC, using a C18 column (150 mm x 4.6 mm x 5 mm); and 50 mmol L-1, pH 5.50 ammonium acetate buffer : acetonitrile : methanol (55 : 22 : 23 v/v) as the mobile phase with a flow rate of 0.8 mL min(-1). The suggested method presented precision (intra-assay and inter-assay), linearity and limit of quantification (LOQ) all adequate for the therapeutic drug monitoring (TDM) of AEDs in plasma.

Thermal Analysis and Raman Spectra of Different Phases of the Ionic Liquid Butyltrimethylammonium Bis(trifluoromethylsulfonyl)imide

The ionic liquid butyltrimethylammonium bis(trifluoromethylsulfonyl)imide, [C4C1C1C1N][Tf2N], is a glass-forming liquid that exhibits partial crystallization depending on the cooling rate. Differential scanning calorimetry (DSC) indicates crystallization at T-c = 227 K, melting at T-m = 258 K, glass transition at T-g similar to 191 K, and also cold crystallization at T-cc similar to 219 K. Raman spectroscopy shows that the crystalline structure obtained by slow cooling is formed with [Tf2N](-) in cisoid conformation, whereas [Tf2N](-) in transoid conformation results from fast cooling. No preferred conformation of the butyl chain of the [C4C1C1C1N](+) cation is favored by slow or fast cooling of [C4C1C1C1N][Tf2N]. Low-frequency Raman spectroscopy shows that crystalline domains developing in the supercooled liquid result in a glacial state made of a mixture of crystallites and amorphous phase. However, these crystalline structures obtained by slow cooling or cold crystallization are not the same because anion-cation interactions promote local structures with distinct conformations of the [Tf2N](-) anion.

A Phase I clinical trial of lodenafil carbonate, a new phosphodiesterase Type 5 (PDE5) inhibitor, in healthy male volunteers

Lodenafil carbonate is a new phosphodiesterase Type 5 (PDE5) inhibitor used in treatment of erectile dysfunction. Objective: The present study was conducted to evaluate the safety, tolerability, and pharmacokinetics of lodenafil carbonate after administering ascending (1 - 100 mg) single oral doses to healthy male volunteers (n = 33). Methods: The study was an open-label, dose-escalation, Phase I clinical trial involving the administration of single oral doses of lodenafil carbonate. Lodenafil carbonate was administered sequentially, escalating in single doses of 1 mg - 100 mg with a washout period of at least 1 week between each dose. The progression to the next dose was allowed after clinical and laboratory exams, Ambulatory Monitoring of Arterial Pressure (AMAP) without relevant clinical modifications and adverse events without clinical relevancy. Blood samples were collected at pre-dose, 0.25, 0.5, 0.75, 1, 1.25, 1.5, 1.75, 2, 2.5, 3, 3.5, 4, 4.5, 5, 6, 7, 8, 10, 12, 14, 16, 20 and 24 h post-dosing. Plasma samples for measurement of lodenafil carbonate and lodenafil were analyzed by liquid chromatography coupled to tandem mass spectrometry. Results: No serious adverse events were observed, and none of the subjects discontinued the study due to intolerance. The AMAP measurements, clinical and laboratory exams and ECG revealed no significant changes even at higher doses. Lodenafil carbonate was not detected in any samples, indicating that it acts as a prodrug. The mean lodenafil pharmacokinetic parameters for t(max) and t(1/2) were 1.6 (+/- 0.4) h and 3.3 (+/- 1.1) h, respectively. This study demonstrated that lodenafil carbonate was well tolerated and showed a good safety profile in healthy male volunteers.

Tricritical-like behavior of the nonlinear optical refraction at the nematic-isotropic transition in the E7 thermotropic liquid crystal

We use Z-scan technique to investigate the nonlinear optical response of the thermotropic liquid crystal E7 in the neighborhood of the nematic-isotropic phase transition. The analysis of the data for the nonlinear optical birefringence is compatible with an effective critical exponent of the order parameter, beta = 0.28 +/- 0.03, which is close to the classical value, beta = 0.25, for a tricritical point. The nonlinear optical absorption in the nematic range depends on the geometrical configuration of the nematic director with respect to the polarization beam, and vanishes in the isotropic phase.

Effect of alkyl chain length of alcohols on nematic uniaxial-to-biaxial phase transitions in a potassium laurate/alcohol/K2SO4/water lyotropic mixture

Lyotropic liquid crystalline quaternary mixtures of potassium laurate (KL), potassium sulphate (K2SO4)/alcohol (n-OH)/water, with the alcohols having different numbers of carbon atoms in the alkyl chain (n), from 1-octanol to 1-hexadecanol, were investigated by optical techniques (optical microscopy and laser conoscopy). The biaxial nematic phase domain is present in a window of values of n = n(KL) +/- 2, where n(KL) = 11 is the number of carbon atoms in the alkyl chain of KL. The biaxial phase domain became smaller and the uniaxial-to-biaxial phase transition temperatures shifted to relatively higher temperatures upon going from 1-nonanol to 1-tridecanol. Moreover, compared with other lyotropic mixtures these new mixtures present high birefringence values, which we expect to be related to the micellar shape anisotropy. Our results are interpreted assuming that alcohol molecules tend to segregate in the micelles in a way that depends on the relative value of n with respect to nKL. The larger the value of n, the more alcohol molecules tend to be located in the curved parts of the micelle, favoring the uniaxial nematic calamitic phase with respect to the biaxial and uniaxial discotic nematic phases.