The individual and mean activity coefficients of an electrolyte from the inverse GCMC simulation

The grand-canonical Monte Carlo (GCMC) technique, which is primarily used to calculate the concentration of a solute for a given activity coefficient, can be inverted and applied to calculate the activity coefficients corresponding to a given concentration of a solute. The changes needed to be introduced in the GCMC algorithm are discussed in the paper. The new method called the inverse GCMC (IGCMC) technique is applied to calculate the mean activity coefficient of 1:1, 2:2, 2:1, 3:1 salts with equal and unequal ion sizes and over a wide range of the electrolyte concentrations. The results for equal ion sizes are compared with the corresponding data obtained from the GCMC of Valleau and Cohen. It is shown that the IGCMC technique, after some extensions, can be used to compute the individual ionic activity coefficients. A comparison is made with the Sloth and Sørensen individual activity results and with the theoretical predictions for the 1:1 electrolyte with unequal ion sizes.     

Imidazolium chloride‐based ionic liquid‐assisted improvement of lipase activity in organic solvents

The activity of a lipase from a newly isolated Pseudomonas sp. was investigated in the presence of organic solvents and imidazolium chloride‐based ionic liquids (IL) such as BMIM[Cl] and HMIM[Cl]. The lipase activity in the presence of IL was higher compared to that in common organic solvents such as methanol and 2‐propanol. A possible explanation for the enzyme activation might be the structural changes induced in the protein in organic systems. Since IL quench the intensity of fluorescence emission, it was not possible to investigate the major factor that influences the enzyme behavior in these new organic salts. Furthermore, the enzyme exhibited excellent activity in buffer mixtures containing both organic solvent and IL. The stability of the lipase at 50°C was considerably increased in the presence of 20% BMIM[Cl] compared with the untreated lipase in aqueous medium. The light scattering method clearly showed that prevention of aggregation could be the reason for thermal stabilization at 50°C in reactions containing IL. Kinetic analysis of the enzyme in the presence of different concentrations of IL showed that the K_m value increased from 0.45 mM in aqueous buffer to 2.4 mM in 50% v/v BMIM[Cl]/buffer. The increase in K_m indicates that IL can significantly reduce the binding affinity of the substrate to the enzyme. Also, a linear correlation was observed between the BMIM[Cl] concentration and V_max of the enzyme. As the concentration of BMIM[Cl] increased from 10 to 50% v/v, the V_max value increased from 1.8 to 46 μM/min.     

The effect of ionic liquid media on activity,selectivity and stability of Candida antarctica lipase B in transesterification reactions

Nineteen different 1,3-dialkylimidazolium-based ionic liquids (ILs) were used as reaction media for the synthesis of butyl butyrate by transesterification from vinyl butyrate and 1-butanol catalyzed by Candida antarctica lipase B (CaLB). The reaction was also carried out in hexane as a reference solvent. In all the water-immiscible ILs assayed, the enzymatic activity and selectivity were higher than that obtained in hexane. However, in water-miscible ILs, the activity was lower than in the reference solvent, although they showed >99.99% selectivity. Two solvent properties, hydrophobicity and nucleophilicity, were considered key parameters for analyzing the behavior of CaLB in ILs. In the case of ILs based on the same anion, the synthetic activity was gradually enhanced by increasing cation hydrophobicity. Furthermore, the activity of CaLB was greater in ILs containing anions of lower nucleophilicity. Stability studies indicate that CaLB exhibited greater stability in water-immiscible ILs than in water-miscible ILs.     

Ionic liquids for the production of insecticidal and microbicidal extracts of the fungus Cantharellus cibarius

Different ionic liquids were used as solvents for the effective extraction of the active metabolites of the fruit bodies of C. cibarius. The type of ionic liquid was found to play a significant role in this process. We found that the protic ionic liquid 1-[(nonyloxy)methyl]-1H-imidazol-3-ium salicylate (6) is a most-efficient extracting agent, being superior to classical solvents such as AcOEt or hexane. The obtained extracts generally revealed high insecticidal activities against both house fly and cockroach, with similar potencies as the standard pesticides bromfenvinphos or alphacypermethrin, as well as significant activities against bacteria, yeast, and moulds. Notably, the cidal activities against plant-pathogenic bacteria were stronger than against human bacterial strains.     

白色麝香霉挥发性有机化合物的抗菌活性和组成分析

采用核糖体RNA转录间隔区(internal transcribed spacer of ribosomal RNA,ITS r RNA)、RNA聚合酶II(RNA polymerase II,rpb2)和β-维管蛋白(beta-tubulin,tub1)基因系统发育分析法,鉴定了一株分离自浙江庆元的麝香霉ZJQY709,鉴定结果表明该菌为白色麝香霉Muscodor albus。生长速率法测定结果显示该菌株最适生长温度为22–28℃。二分格培养皿对峙培养法测定该菌挥发性有机化合物的抑菌活性,结果表明其挥发性有机化合物对灰葡萄孢菌和立枯丝核菌的生长抑制作用较强,而对尖孢镰刀菌和终极腐霉的抑制作用较弱。固相微萃取/气质联用法分析该菌产生的挥发性有机化合物,结果显示其挥发性有机化合物成分复杂,主要气体成分为2-甲基丙酸、乙酸-2-甲基丙酯和1-丁醇-2-甲基乙酸。     

Power analysis of statistical methods for comparing treatment differences from limiting dilution assays

Summary Six different statistical methods for comparing limiting dilution assays were evaluated, using both real data and a power analysis of simulated data. Simulated data consisted of a series of 12 dilutions for two treatment groups with 24 cultures per dilution and 1,000 independent replications of each experiment. Data within each replication were generated by Monte Carlo simulation, based on a probability model of the experiment. Analyses of the simulated data revealed that the type I error rates for the six methods differed substantially, with only likelihood ratio and Taswell's weighted mean methods approximating the nominal 5% significance level. Of the six methods, likelihood ratio and Taswell's minimum Chi-square exhibited the best power (least probability of type II errors). Taswell's weighted mean test yielded acceptable type I and type II error rates, whereas the regression method was judged unacceptable for scientific work.     

Impact of enzyme concentration and residence time on apparent activity recovery in jump dilution analysis

Jump dilution analysis is commonly used to evaluate the reversibility of inhibition and to quantify the residence time of the inhibitor–enzyme complex. During hit and lead characterization, one sometimes observes apparently linear progress curves after jump dilution that display activity recoveries that are intermediate between those expected for fully reversible and irreversible inhibition. Computer simulations of progress curves after jump dilution indicate that seemingly linear progress curves can result when dealing with tight-binding inhibitors if substoichiometric concentrations of inhibitor are preincubated with enzyme. In this situation, the activity recovered is comparable to that expected for instantaneously reversible inhibitors. In addition, simulations demonstrate that intermediate values of activity recovery may be observed for compounds with modestly slow dissociation rates (i.e., residence times >0 min but ?20 min) when the attending curvature of the data is not accounted for. The observation of intermediate values of recovery can, thus, serve as an indication of either modest residence time or a contaminating inactivator within an inhibitor sample, in either case prompting greater scrutiny of the test compound.     

Extending the diffuse layer model of surface acidity behaviour: III. Estimating bound site activity coefficients

Abstract

Although detailed thermodynamic analyses of the 2-pK diffuse layer surface complexation model generally specify bound site activity coefficients for the purpose of accounting for those non-ideal excess free energies contributing to bound site electrochemical potentials, in application these terms are ignored based on one or more of the following assumptions: (1) bound site activity coefficients cancel out in the mass action quotients; (2) bound sites display ideal behaviour; and/or (3) these energies are already included in the exponential Boltzmann terms. In this work it is demonstrated that the bound site charging energy terms discussed in the two previous papers in this series have both conceptual and computational analogies to the charging energy contribution to the activity coefficients obtained from the Debye–Huckel Limiting Law. On high charge density colloidal particles at constant counterion condensation (τ), these charging energies can be related to the surface potential (ψ) by: ΔG_charging = (1 – τ)Fψ (where F is the Faraday constant). If one assumes a maximum practical accuracy of ± 10% in experimental estimates of ψ, then it is suggested that charging energies are likely to be experimentally indiscernible under conditions where τ > 0.9. These findings support the historical practice of ignoring bound site activity coefficients with the 2-pK diffuse layer surface complexation model in the following situations: for spherical particles with a radius ≥ 0.1 μm at ionic strengths ≥ 0.001 M (1 : 1), and for spherical particles with a radius >0.01 μm at an ionic strength >0.1 M (1 : 1). In contrast, charging energies (and non-ideal behaviour) are predicted to be significant at all charge densities and ionic strengths for spherical particles with a radius of 0.001 μm.     

Comparison of statistical methods for the analysis of limiting dilution assays

Summary This study reports the results of a critical comparison of five statistical methods for estimating the density of viable cells in a limiting dilution assay (LDA). Artificial data were generated using Monte Carlo simulation. The performance of each statistical method was examined with respect to the accuracy of its estimator and, most importantly, the accuracy of its associated estimated standard error (SE). The regression method was found to perform at a level that is unacceptable for scientific research, due primarily to gross underestimation of the SE. The maximum likelihood method exhibited the best overall performance. A corrected version of Taswell's weighted-mean method, which provides the best performance among all noniterative methods examined, is also presented.     

A simpler analysis for the measurement of second virial coefficients by self-interaction chromatography

We describe a thermodynamic approach that supports the adoption of a simplified procedure for the determination of protein second virial coefficients (B(2)) by self-interaction chromatography. Its major advantage over the original method is a decrease in the number of parameters to which magnitudes must be assigned for the determination of B(2). Improved correlation of virial coefficients obtained by the chromatographic procedure with those obtained by light scattering is achieved by taking into account the twofold larger magnitudes of the former because of the experimental distinction between free and immobilized protein molecules in self-interaction chromatography.     

Effects of organic and inorganic nitrogen compounds on the activity of bacterial alkaline phosphatase

The stimulation of bacterial alkaline phosphatase activity (APA) by inorganic and organic nitrogen compounds was investigated in the southern Baltic Sea monthly between February and August 2001, by adding albumin, casein, leucine, ammonium, nitrate, ammonium + glucose or nitrate + glucose to 0.8 µm filtered seawater. The following questions were addressed: (1) Are there seasonal changes in the stimulation of APA by these substances?; (2) Does nitrogen alone stimulate this activity or only in combination with organic carbon?; (3) Is there a relationship between ambient nutrient concentrations and the degree of stimulation? The addition of the mentioned compounds stimulated the APA in bacteria to a high degree, however, there were seasonal variations. Stimulation was low in February and March but high from May to August when the stimulation, e.g., by ammonium + glucose, was up to 6000-fold higher compared with February. In most experiments, the addition of the amino acid leucine and of inorganic nitrogen alone resulted in an inhibition of the bacterial APA. A relationship between ambient nutrient concentrations and the stimulation of the bacterial APA was only observed for albumin, which correlated negatively with dissolved inorganic nitrogen (DIN) and phosphate concentrations and for casein, which correlated only with DIN. The results indicate that the regulation of bacterial APA and the DOP degradation can be significantly influenced by the availability of nitrogen and organic carbon.     

Cholinesterase inhibitory activity versus aromatic core multiplicity: A facile green synthesis and molecular docking study of novel piperidone embedded thiazolopyrimidines

Novel thiazolopyrimidine derivatives have been synthesized via microwave assisted, domino cascade methodology in ionic liquid and evaluated in vitro for their acetylcholinesterase (AChE) and butyrylcholinesterase (BChE) inhibitory activities. Among the newly synthesized compounds 6d, 6a, 6e and 6b displayed higher AChE inhibitory activity than standard drug, galanthamine, with IC₅₀ values of 0.53, 1.47, 1.62 and 2.05 μM, respectively. Interestingly, all the compounds except for 6m–r and 6x displayed higher BChE inhibitory potentials than galanthamine with IC₅₀ values ranging from 1.09 to 18.56 μM. Molecular docking simulations for 6d possessing the most potent AChE and BChE inhibitory activities, disclosed its binding interactions at the active site gorge of AChE and BChE enzymes.     

Determinants for nasal trigeminal detection of volatile organic compounds

We explored the influence of methodological and chemical parameters on the detection of nasal chemesthesis (i.e., trigeminal stimulation) evoked by volatile organic compounds (VOCs). To avoid odor biases, chemesthesis was probed via nasal pungency detection in anosmics and via nasal localization (i.e., lateralization) in normosmics, in both cases using forced-choice procedures. In the experiments with anosmics, 12 neat VOCs were selected based on previous reports of lack of chemesthetic response. Although none of the VOCs reached 100% detection, detectability and confidence of detection were higher when using a glass vessel system adapted with nosepieces to fit the nostrils tightly than when using wide-mouth glass jars. Half the stimuli were detected well above chance and half were not. When the latter were tested again after being heated to 37 degrees C, that is, body temperature (from room temperature, 23 degrees C), to increase their vapor concentration, only one, octane, significantly increased its detectability. Chemesthesis gauged with normosmics mirrored that with anosmics. Gas chromatography measurements showed that, even at 23 degrees C, the saturated vapor concentrations of the undetected stimuli, except vanillin, were well above the respective calculated nasal pungency threshold (NPT) from an equation that, in the past, had accurately described and predicted NPTs. We conclude that, except for octane and perhaps vanillin, the failure of the other four VOCs to precipitate nasal chemesthesis rests on a chemical-structural limitation, for example, the molecules lack a key property to fit a receptor pocket, rather than on a concentration limitation, for example, the vapor concentration is too low to reach a threshold value.     

Fate coefficients for the toxicity assessment of air pollutants

The inclusion of fate and exposure is a central issue in Life Cycle Impact Assessment (LCIA). According to the framework developed by the Society of Environmental Toxicity and Chemistry (SETAC), fate and exposure route are included through a fate coefficient which makes the link between an emission and the related increase in concentration. In the Critical surface-time 95 methodology, fate factors of air pollutants are determined empirically at a world level as the ratio of measured concentration to the total estimated emission flow. Based on a detailed study performed for seventeen pollutants, a correlation is developed to predict fate factors from the residence time. Variation of a factor 10000 arc observed for the fate coefficient. Empirical fate factors are compared to modelled fate factors and are found to have a similar order of magnitude.     

Partition coefficients of substrates and products and solvent selection for biocatalysis under nearly anhydrous conditions

The effect of solvent on the activity of mushroom tyrosinase toward three substrates was studied at a constant water activity of either 0.74 or 0.86. No simple correlation was observed between enzyme activity and log P, but partition coefficients of substrate (P(s)) and product (P(p)) gave systematic relations with enzyme activity. When initial reaction rates were considered, there was a bellshaped relationship between enzyme activity and P(s) with an optimal P(s) for each substrate. This can be explained by assuming that the solvent affected the enzyme activity primarily by affecting the substrate concentration in the aqueous layer around the catalyst where the enzymic reaction occurs. When long-term reaction rates were considered, a high P(p)/P(s) ratio was consistent with preservation of enzyme activity. (c) 1994 John Wiley & Sons, Inc.     

The use of classification methods for modeling the antioxidant activity of flavonoid compounds

A study using two classification methods (SDA and SIMCA) was carried out in this work with the aim of investigating the relationship between the structure of flavonoid compounds and their free-radical-scavenging ability. In this work, we report the use of chemometric methods (SDA and SIMCA) able to select the most relevant variables (steric, electronic, and topological) responsible for this ability. The results obtained with the SDA and SIMCA methods agree perfectly with our previous model, in which we used other chemometric methods (PCA, HCA and KNN) and are also corroborated with experimental results from the literature. This is a strong indication of how reliable the selection of variables is. Three-dimensional projection of the hyperboxes for Classes 1 (right) and 2 (left)     

Combinatorial formulation of biocatalyst preparations for increased activity in organic solvents: salt activation of penicillin amidase

A combinatorial experimental technique was used to identify salts and salt mixtures capable of activating penicillin amidase in organic solvents for the transesterification of phenoxyacetate methyl ester with 1-propanol. Penicillin amidase was lyophilized in the presence of various chloride and acetate salts within 96-deep-well plates and catalytic rates measured to determine lead candidates for highly salt-activated preparations. The kinetics of the most active formulations were then further evaluated. These studies revealed that a formulation consisting of 98% (w/w) of a 1:1 KAc:CsCl salt mixture, 1% (w/w) enzyme, and 1% (w/w) potassium phosphate buffer was approximately 35,000-fold more active than the salt-free formulation in hexane, as reflected in values of V(max)/K(m). This extraordinary activation could be extended to more polar solvents, including tert-amyl alcohol, and to formulations with lower total salt contents. A correlation was found between the kosmotropic/chaotropic behavior of the salts (as measured by the Jones-Dole B coefficients) and the observed activation. Strongly chaotropic cations combined with strongly kosmotropic anions yielded the greatest activation, and this is likely due to the influence of the ions on protein-water and protein-salt interactions.