Stability of clavulanic acid under variable pH, ionic strength and temperature conditions. A new kinetic approach

Clavulanic acid (CA) is a beta-lactam antibiotic that alone exhibits only weak antibacterial activity, but is a potent inhibitor of beta-lactamases enzymes. For this reason it is used as a therapeutic in conjunction with penicillins and cephalosporins. However, it is a well-known fact that it is unstable not only during its production phase, but also during downstream processing. Therefore, the main objective of this study was the evaluation of CA long-term stability under different conditions of pH and temperature, in the presence of variable levels of different salts, so as to suggest the best conditions to perform its simultaneous production and recovery by two-phase polymer/salt liquid-liquid extractive fermentation. To this purpose, the CA stability was investigated at different values of pH (4.0-8.0) and temperature (20-45 degrees C), and the best conditions were met at a pH 6.0-7.2 and 20 degrees C. Its stability was also investigated at 30 degrees C in the presence of NaCl, Na(2)SO(4), CaCl(2) and MgSO(4) at concentrations of 0.1 and 0.5 M in Mcllvaine buffer (pH 6.5). All salts led to increased CA instability with respect to the buffer alone, and this effect decreased in following sequence: Na(2)SO(4) > MgSO(4) > CaCl(2) > NaCl. Kinetic and thermodynamic parameters of CA degradation were calculated adopting a new model that took into consideration the equilibrium between the active and a reversibly inactivated form of CA after long-time degradation. (C) 2009 Elsevier B.V. All rights reserved.

Thermal Cycling Stability of Silica Membranes for Gas Separation

Hydrogen is being seen as an alternative energy carrier to conventional hydrocarbons to reduce greenhouse gas emissions. High efficiency separation technologies to remove hydrogen from the greenhouse gas, carbon dioxide, are therefore in growing demand. Traditional thermodynamic separation systems utilise distillation, absorption and adsorption, but are limited in efficiency at compact scales. Molecular sieve silica (MSS) membranes can perform this separation as they have high permselectivity of hydrogen to carbon dioxide, but their stability under thermal cycling is not well reported. In this work we exposed a standard MSS membrane and a carbonised template MSS (CTMSS) membrane to thermal cycling from 100 to 450°C. The standard MSS and carbonised template CTMSS membranes both showed permselectivity of helium to nitrogen dropping from around 10 to 6 in the first set of cycles, remaining stable until the last test. The permselectivity drop was due to small micropore collapse, which occurred via structure movement during cycling. Simulating single stage membrane separation with a 50:50 molar feed of H2:CO2, H2 exiting the permeate stream would start at 79% and stabilise at 67%. Higher selectivity membranes showed less of a purity drop, indicating the margin at which to design a stable membrane separation unit for CO2 capture.

Structural stability of adenylate kinase from the sulfate-reducing bacteria Desulfovibrio gigas

Biophysical Chemistry 110 (2004) 83–92

Entropy Production In Thermodynamic Climate Models

We present a non-equilibrium theory in a system with heat and radiative fluxes. The obtained expression for the entropy production is applied to a simple one-dimensional climate model based on the first law of thermodynamics. In the model, the dissipative fluxes are assumed to be independent variables, following the criteria of the Extended Irreversible Thermodynamics (BIT) that enlarges, in reference to the classical expression, the applicability of a macroscopic thermodynamic theory for systems far from equilibrium. We analyze the second differential of the classical and the generalized entropy as a criteria of stability of the steady states. Finally, the extreme state is obtained using variational techniques and observing that the system is close to the maximum dissipation rate

Second differential of the entropy as a criterion for the stability in low-dimensional climate models

The second differential of the entropy is used for analysing the stability of a thermodynamic climatic model. A delay time for the heat flux is introduced whereby it becomes an independent variable. Two different expressions for the second differential of the entropy are used: one follows classical irreversible thermodynamics theory; the second is related to the introduction of response time and is due to the extended irreversible thermodynamics theory. the second differential of the classical entropy leads to unstable solutions for high values of delay times. the extended expression always implies stable states for an ice-free earth. When the ice-albedo feedback is included, a discontinuous distribution of stable states is found for high response times. Following the thermodynamic analysis of the model, the maximum rates of entropy production at the steady state are obtained. A latitudinally isothermal earth produces the extremum in global entropy production. the material contribution to entropy production (by which we mean the production of entropy by material transport of heat) is a maximum when the latitudinal distribution of temperatures becomes less homogeneous than present values

Assessment of Convective Activity Using Stability Indices as Inferred from Radiosonde and MODIS Data

The combined use of both radiosonde data and three-dimensional satellite derived data over ocean and land is useful for a better understanding of atmospheric thermodynamics. Here, an attempt is made to study the ther-modynamic structure of convective atmosphere during pre-monsoon season over southwest peninsular India utilizing satellite derived data and radiosonde data. The stability indices were computed for the selected stations over southwest peninsular India viz: Thiruvananthapuram and Cochin, using the radiosonde data for five pre- monsoon seasons. The stability indices studied for the region are Showalter Index (SI), K Index (KI), Lifted In-dex (LI), Total Totals Index (TTI), Humidity Index (HI), Deep Convective Index (DCI) and thermodynamic pa-rameters such as Convective Available Potential Energy (CAPE) and Convective Inhibition Energy (CINE). The traditional Showalter Index has been modified to incorporate the thermodynamics over tropical region. MODIS data over South Peninsular India is also used for the study. When there is a convective system over south penin-sular India, the value of LI over the region is less than −4. On the other hand, the region where LI is more than 2 is comparatively stable without any convection. Similarly, when KI values are in the range 35 to 40, there is a possibility for convection. The threshold value for TTI is found to be between 50 and 55. Further, we found that prior to convection, dry bulb temperature at 1000, 850, 700 and 500 hPa is minimum and the dew point tem-perature is a maximum, which leads to increase in relative humidity. The total column water vapor is maximum in the convective region and minimum in the stable region. The threshold values for the different stability indices are found to be agreeing with that reported in literature.

Structural stability and reversible unfolding of recombinant porcine S100A12

Porcine S100A12 is a member of the S100 proteins, family of small acidic calcium-binding proteins characterized by the presence of two EF-hand motifs. These proteins are involved in many cellular events such as the regulation of protein phosphorylation, enzymatic activity, protein-protein interaction, Ca(2+) homeostasis, inflammatory processes and intermediate filament polymerization. In addition, members of this family bind Zn(2+) or Ca(2+) with cooperative effect on binding. In this study, the gene sequence encoding porcine S100A12 was obtained by the synthetic gene approach using E. coli codon bias. Additionally, we report a thermodynamic study of the recombinant S100A12 using circular dichroism, fluorescence and isothermal titration calorimetry. The results of urea and temperature induced unfolding and refolding processes indicated a reversible two-state process. Also, the ANS fluorescence studies showed that in presence of divalent ions the protein exposes hydrophobic sites which could facilitate the interaction with other proteins and trigger the physiological responses. (c) 2008 Elsevier B.V. All rights reserved.

Theoretical study of the structure and stability of NbxOy, and NbxOy+ (x = 1-3; y = 2-5, 7, 8) clusters

Geometric, thermodynamic and electronic properties of cluster neutrals NbxOy and cations NbxOy+ (x = 1-3; y = 2-5, 7, 8) have been characterized theoretically. A DFT calculation using a hybrid combination of B3LYP with contracted Huzinaga basis sets. Numerical results of the relative stabilities, ionization potentials and band gaps of different clusters are in agreement with experiment. Analysis of dissociation channels supports the more stable building blocks as formed by NbO2, NbO2+ NbO3 and NbO3+ stoichiometries. The net atomic charges suggest that oxygen donor molecules can interact more favorably on central niobium atoms of cluster cations, while the interaction with oxygen acceptor molecules is more favorable on the terminal oxygen atoms of neutral clusters. A topological analysis of the electron localization function gradient field indicates that the clusters may be described as having a strong ionic interaction between Nb and O atoms. Published by Elsevier B.V. B.V.

Physical-chemical and thermodynamic analyses of ethanol steam reforming for hydrogen production

Steam reforming is the most usual method of hydrogen production due to its high production efficiency and technological maturity the use of ethanol for this purpose is an interesting option because it is a renewable and environmentally friendly fuel. The objective of this article is to present the physical-chemical, thermodynamic, and exergetic analysis of a steam reformer of ethanol, in order to produce 0.7 Nm(3)/h of hydrogen as feedstock of a 1 kW PEMFC the global reaction of ethanol is considered. Superheated ethanol reacts with steam at high temperatures producing hydrogen and carbon dioxide, depending strongly on the thermodynamic conditions of reforming, as well as on the technical features of the reformer system and catalysts. The thermodynamic analysis shows the feasibility of this reaction in temperatures about 206 degrees C. Below this temperature, the reaction trends to the reactants. The advance degree increases with temperature and decreases with pressure. Optimal temperatures range between 600 and 700 degrees C. However, when the temperature attains 700 degrees C, the reaction stability occurs, that is, the hydrogen production attains the limit. For temperatures above 700 degrees C, the heat use is very high, involving high costs of production due to the higher volume of fuel or electricity used. The optimal pressure is 1 atm., e.g., at atmospheric pressure. The exergetic analysis shows that the lower irreversibility is attained for lower pressures. However the temperature changes do not affect significantly the irreversibilities. This analysis shows that the best thermodynamic conditions for steam reforming of ethanol are the same conditions suggested in the physical-chemical analysis.

On the stability of the extracellular hemoglobin of Glossoscolex paulistus, in two iron oxidation states, in the presence of urea

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Thermodynamic analysis of direct steam reforming of ethanol in molten carbonate fuel cell

Fuel cell as MCFC (molten carbonate fuel cell) operate at high temperatures, and due to this issue, cogeneration processes may be performed, sending heat for own process or other purposes as steam generation in an industry. The use of ethanol for this purpose is one of the best options because this is a renewable and less environmentally offensive fuel, and cheaper than oil-derived hydrocarbons (in the case of Brazil). In the same country, because of technical, environmental and economic advantages, the use of ethanol by steam reforming process have been the most investigated process. The objective of this study is to show a thermodynamic analysis of steam reforming of ethanol, to determine the best thermodynamic conditions where are produced the highest volumes of products, making possible a higher production of energy, that is, a most-efficient use of resources. To attain this objective, mass and energy balances are performed. Equilibrium constants and advance degrees are calculated to get the best thermodynamic conditions to attain higher reforming efficiency and, hence, higher electric efficiency, using the Nernst equation. The advance degree of reforming increases when the operation temperature also increases and when the operation pressure decreases. But at atmospheric pressure (1 atm), the advance degree tends to the stability in temperatures above 700°C, that is, the volume of supplemental production of reforming products is very small for the high use of energy resources necessary. Reactants and products of the steam-reforming of ethanol that weren't used may be used for the reforming. The use of non-used ethanol is also suggested for heating of reactants before reforming. The results show the behavior of MCFC. The current density, at same tension, is higher at 700°C than other studied temperatures as 600 and 650°C. This fact occurs due to smaller use of hydrogen at lower temperatures that varies between 46.8 and 58.9% in temperatures between 600 and 700°C. The higher calculated current density is 280 mA/cm 2. The power density increases when the volume of ethanol to be used also increases due to higher production of hydrogen. The highest produced power at 190 mW/cm 2 is 99.8, 109.8 and 113.7 mW/cm2 for 873, 923 and 973K, respectively. The thermodynamic efficiency has the objective to show the connection among operational conditions and energetic factors, which are some parameters that describes a process of internal steam reforming of ethanol.

Physical-chemical and thermodynamic analyses of steam reforming of ethanol to hydrogen production

The steam reforming is one of most utilized process of hydrogen production because of its high production efficiencies and its technological maturity. The use of ethanol for this purpose is a interesting option because this is a renewable and less environmentally offensive fuel. The objective of this study is evaluate the physical-chemical, thermodynamic and environmental analyses of steam reforming of ethanol. whose objective is to produce 0.7 Nm3/h of hydrogen to be used by a PEMFC of l kW. In this physical-chemical analysis, a global reaction of ethanol was considered. That is, the superheated ethanol and steam, at high temperatures, react to produce hydrogen and carbon dioxide. Beyond it's the simplest form to study the steam reforming of ethanol to hydrogen production, it's the case where occurs the highest production of hydrogen (the product to be used by fuel cells) and carbon dioxide, to be eliminated. But this reaction isn't real and depends greatly on the thermodynamic conditions of reforming, technical features of reformer system and catalysts. Other products generally formed (but not investigated in this study) are methane, carbon monoxide, among others. It was observed that the products is commonly produced in the moment when the reaction attains temperatures about 206°C (below this temperature, the reaction trend to the reaetants, that is, from hydrogen and carbon dioxide to steam and ethanol) and the advance degree of this reaction increases when the temperature of reaction also increases and when its pressure decreases. It's suggested reactions at about 600°C or higher. However, when the temperature attains 700°C, the stability of this reaction is occurred, that is, the production of reaction productions attains to the limit, that is the highest possible production. In temperatures above 700°C, the use of energy is very high for produce more products, having higher costs of production that the suggested temperature. The indicated pressure is 1 atm., a value that allows a desirable economy of energy that would also be used for pressurization or depressurization of steam reformer. In exergetic analysis, it's seem that the lower irreversibililies occur when the pressure of reactions are lower. However, the temperature changes don't affect significantly the irreversibilites. Utilizing the obtained results from this analysis, it was concluded that the best thermodynamic conditions for steam reforming of ethanol is the same conditions suggested in the physical-chemical analysis. The exergetic and first law efficiencies are high on the thermodynamie conditions studied.

Phenol oxidation by mushroom waste extracts: a kinetic and thermodynamic study

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Effect of the competition of Cu(II) and Ni(II) on the kinetic and thermodynamic stabilities of Cr(III)-organic ligand complexes using competitive ligand exchange (EDTA)

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

On the stability of the extracellular hemoglobin of Glossoscolex paulistus, in two iron oxidation states, in the presence of urea

The stability of the Glossoscolex paulistus hemoglobin (HbGp), in two iron oxidation states (and three forms), as monitored by optical absorption, fluorescence emission and circular dichroism (CD) spectroscopies, in the presence of the chaotropic agent urea, is studied. HbGp oligomeric dissociation, denaturation and iron oxidation are observed. CD data show that the cyanomet-HbGp is more stable than the oxy-form. Oxy- and cyanomet-HbGp show good fits on the basis of a two state model with critical urea concentrations at 220-222 nm of 5.1 +/- 0.2 and 6.1 +/- 0.1 mol/L, respectively. The three-state model was able to reveal a subtle second transition at lower urea concentration (1.0-2.0 mol/L) associated to partial oligomeric dissociation. The intermediate state for oxy- and cyanomet-HbGp is very similar to the native state. For met-HbGp, a different equilibrium, in the presence of urea, is observed. A sharp transition at 1.95 +/- 0.05 mol/L of denaturant is observed, associated to oligomeric dissociation and hemichrome formation. In this case, analysis by a three-state model reveals the great similarity between the intermediate and the unfolded states. Analysis of spectroscopic data, by two-state and three-state models, reveals consistency of obtained thermodynamic parameters for HbGp urea denaturation. (C) 2012 Elsevier Inc. All rights reserved.