Extreme catalysts from low-temperature environments

Cold-loving or psychrophilic organisms are widely distributed in nature as a large part of the earth's surface is at temperatures around 0 degrees C. To maintain metabolic rates and to prosper in cold environments, these extremophilic organisms have developed a vast array of adaptations. One main adaptive strategy developed in order to cope with the reduction of chemical reaction rates induced by low temperatures is the synthesis of cold-adapted or psychrophilic enzymes. These enzymes are characterized by a high catalytic activity at low temperatures associated with a low thermal stability. A study of protein adaptation strategies suggests that the high activity of psychrophilic enzymes could be achieved by the destabilization of the active site, allowing the catalytic center to be more flexible at low temperatures, whereas other protein regions may be destabilized or as rigid as their mesophilic counterparts. Due to these particular properties, psychrophilic enzymes offer a high potential not only for fundamental research but also for biotechnological applications.     

Selection and properties of alpha-acetolactate decarboxylase-deficient spontaneous mutants of Streptococcus thermophilus

Many lactic acid bacteria produce diacetyl, which is a desirable aroma compound in some fermented dairy products. Strains or mutants of Lactococcus lactis subsp. lactis biovar. diacetylactis that are deficient in alpha-acetolactate decarboxylase are used in some food processes for their ability to produce large amounts of diacetyl. However, up until now, the use of alpha-acetolactate decarboxylase-deficient mutants of Streptococcus thermophilus for increased diacetyl production has not been evaluated. The objective of the present study was to devise a procedure for selecting spontaneous alpha-acetolactate decarboxylase-deficient mutants of S. thermophilus. We observed that in a chemically defined medium (CDM) containing alpha-ketobutyrate plus leucine, or alpha-ketobutyrate plus leucine plus isoleucine, the alpha-acetolactate decarboxylase-deficient mutant TIL865, obtained by directed mutagenesis, grew faster than its parent strain. This property was used for selecting spontaneous alpha-acetolactate decarboxylase-deficient mutants on agar plates. The resulting mutants were able to grow in milk, and their acidifying activity was slightly lower than that of the parent strain. Under partial anaerobic or aerobic conditions, they produced approximately three times more diacetyl than the parent strain. Such spontaneous mutants may be useful for increasing the diacetyl content of fermented milks whose production involves S. thermophilus strains.     

Olfactory Responses to Aphid and Host Plant Volatile Releases: (E)-β-Farnesene an Effective Kairomone for the Predator Adalia bipunctata

The volatiles released from several aphid and host plant species, alone or associated, were studied for their infochemical role in prey location. Using a four-arm olfactometer, the attraction of several combinations of three aphid (Myzus persicae, Acyrthosiphon pisum, and Brevicoryne brassicae) and three plant (Vicia faba, Brassica napus, and Sinapis alba) species toward Adalia bipunctata larvae and adults was observed. Both predatory larvae and adults were attracted only by A. pisum and M. persicae when they were crushed, whatever the host plant. (E)-beta-farnesene, the aphid alarm pheromone, was the effective kairomone for the ladybird. Plant leaves alone (V. faba, B. napus, and S. alba) or in association with nonstressed whole aphids (the three species) did not have any attraction for the predator. The B. brassicae specialist aphid is the only prey that was not attracted to A. bipunctata larvae and adults, even if they were crushed. Release of B. brassicae molecules similar to the host plant allelochemicals was demonstrated by GC-MS analysis. The lack of behavioral response of the ladybird at short distance toward the cruciferous specialist aphid was related only to the absence of (E)-beta-farnesene in the aphid prey volatile pattern.     

Carbon mineralization from composts and food industry wastes added to soil

We have studied the short term C mineralization of six wastes from important food industries, one sludge from a biogas plant and three composts. All the wastes were characterized chemically and fractionated according to the Van Soest method. The fresh wastes were incubated under controlled environment conditions to determine the C mineralization rate. Based on first order mineralization kinetics, we calculated the hypothetical amount of stable C in the wastes as the amount of C that would not be mineralized within one year under field conditions. The percentage of stable organic C in the organic matter was in general much larger in the composts than in the other wastes, but when expressed on dry matter, the non-composted wastes had comparable or larger amounts of stable organic C than the composts and have a considerable potential for supplying organic matter to soils, and hence for C sequestration. The amount of stable organic C could best be predicted by the total N content of the wastes (R _a ² = 0.855), whereas the results of the fractionation had very little predictive power, probably due to problems related to the high ash content of some of the wastes. An index that combined stable organic C and N and P content in the wastes was calculated to assess possible limitations for applying these wastes in agriculture. Under current nutrient legislation in Western Europe, a number of these wastes will only be usable in small amounts, but these and other food industry wastes could still prove to be valuable soil amendments in nutrient poor situations, for increasing soil organic C content and supplying nutrients.     

Application of the general rate model with the Maxwell-Stefan equations for the prediction of the band profiles of the 1-indanol enantiomers

The adsorption isotherm data of R- and S-1-indanol and of their racemic mixture on cellulose tribenzoate were measured by frontal analysis. These experimental data were fitted to the single-component and the modified competitive Bilangmuir isotherms. The overloaded elution profiles of bands of the pure enantiomers and of the racemic mixture were calculated for different sample sizes, using the best competitive isotherm model and the General Rate Model of chromatography coupled with the generalized Maxwell-Stefan equation that describes the surface diffusion flux. The calculated and the experimental profiles were found to be in excellent agreement in all cases. The parameters of the model of the mass transfer kinetics were derived from the band profiles obtained for the pure enantiomers. The same values of these parameters give an excellent prediction of the profiles of multicomponent bands. The new model described here allows a satisfactory interpretation of the competitive mass transfer kinetics.     

Effect of Ion Concentration Changes in the Limited Extracellular Spaces on Sarcolemmal Ion Transport and Ca2+ Turnover in a Model of Human Ventricular Cardiomyocyte

We have developed a computer model of human cardiac ventricular myocyte (CVM), including t-tubular and cleft spaces with the aim of evaluating the impact of accumulation-depletion of ions in restricted extracellular spaces on transmembrane ion transport and ionic homeostasis in human CVM. The model was based on available data from human CVMs. Under steady state, the effect of ion concentration changes in extracellular spaces on [Ca²⁺]_i-transient was explored as a function of critical fractions of ion transporters in t-tubular membrane (not documented for human CVM). Depletion of Ca²⁺ and accumulation of K⁺ occurring in extracellular spaces slightly affected the transmembrane Ca²⁺ flux, but not the action potential duration (APD₉₀). The [Ca²⁺]_i-transient was reduced (by 2%–9%), depending on the stimulation frequency, the rate of ion exchange between t-tubules and clefts and fractions of ion-transfer proteins in the t-tubular membrane. Under non-steady state, the responses of the model to changes of stimulation frequency were analyzed. A sudden increase of frequency (1–2.5 Hz) caused a temporal decrease of [Ca²⁺] in both extracellular spaces, a reduction of [Ca²⁺]_i-transient (by 15%) and APD₉₀ (by 13 ms). The results reveal different effects of activity-related ion concentration changes in human cardiac t-tubules (steady-state effects) and intercellular clefts (transient effects) in the modulation of membrane ion transport and Ca²⁺ turnover.     

Relationship Between Structure and Glass Transition Temperature in Low-silica Calcium Aluminosilicate Glasses: the Origin of the Anomaly at Low Silica Content

The anomalous behavior of the glass transition temperature ( T _g) in low silica calcium aluminosilicate glasses has been related to the structural modifications observed by neutron and X-ray diffraction. The diffraction data indicate that Al and Si are in tetrahedral sites and that Ca atoms are in distorted octahedral sites. By subtracting the correlation functions for glasses at constant SiO₂ or constant Al₂O₃ content, we have shown that Si and Al atoms are introduced in a different way within the glass structure. Si is present in various Q ⁿ sites, while Al resides in Q³ and Q⁴ sites for glasses with high CaO content and enters fully polymerized Q⁴ sites with increasing SiO₂ or Al₂O₃ content. The higher proportion of Al in Q³ positions at high CaO content yields a depolymerization of the network. The lower connectivity will contribute to a decrease of the viscosity, which may be at the origin of the decrease of T _g for glasses at low silica content.     

Alkylation of Hydroquinone with tert-butanol over Silica-immobilized Triflate Derivatives

Friedel-Crafts alkylations of α-methylnaphthalene with various alkylating agents were first carried out in the presence of methanesulfonic acid (MeSA). The Brønsted acid catalyst MeSA exhibited outstanding catalytic performance, and was found to be excellent catalyst and solvent for alkylation reaction of aromatic hydrocarbon. It’s found that alkenes can be used as excellent alkylating agent for alkylation of α-methylnaphthalene. The effects of various reaction parameters like type of alkylating agent, dosages of catalysts, reaction temperature and reaction time were investigated in detail. Moreover, the performance of reuse for catalysts was also studied. It’s found that, under the optimal reaction conditions, more than 90% of conversion for olefins and 100% of selectivity for the desired products were obtained. Compared with traditional catalysis technology, the reaction, catalyzed by MeSA catalyst, no volatile solvents needed, good selectivity for desired products could be obtained. The catalyst can be isolated easily from the reaction mixtures by decantation, and was successfully reused. The methanesulfonic acid could be considered as environmentally friendly novel catalyst and solvent for long-chain alkylation of α-methylnaphthalene with alkenes. The catalytic reaction mechanism for alkylation in the presence of MeSA was proposed as well.     

Effect of B2O3 addition on structure and properties of Yb3+/Al3+/B3+-co-doped silica glasses

The homogeneous Yb³⁺/Al³⁺/B³⁺-co-doped silica glasses were prepared via a sol-gel method. The impact of B₂O₃ addition on the physical and optical properties and network structure was systematically studied. The network structure was investigated by the Fourier Transform Infrared (FT-IR), Raman spectra, and Solid State Nuclear Magnetic Resonance (SSNMR). Herein, B₂O₃ addition can continuously decrease the refractive index and density. When B₂O₃ is lower than 2 mol%, B₂O₃ addition can obviously decrease the scalar crystal field parameters, Yb³⁺ asymmetry degree, Yb³⁺ cross-sections, due to the generation of Yb–O–B bonds at the cost of partial Yb–O–Al/Si ones. When B₂O₃ is more than 2 mol%, FT-IR, Raman spectra, and SSNMR results indicate that further increased B atoms prefer to connect with Si and Al rather than Yb. Consequently, the above parameters are basically unchanged. Based on the results, an intuitive model of structure and properties evolution during the substitution of SiO₂ by B₂O₃ has been established.     

Development of blown film linear low-density polyethylene–clay nanocomposites: Part A: Manufacturing process and morphology

In this study, linear low-density polyethylene (LLDPE)/clay nanocomposites with different clay contents were prepared by melt intercalation using two different compatibilizers: maleic anhydride grafted styrene–ethylene–butylene–styrene and maleic anhydride grafted polyethylene (PE-g-MA). Melt intercalation was achieved by twin extrusion and nanocomposite films were produced by blown film extrusion. Effects of clay and compatibilizer fractions and type of compatibilizer on the structure, permeability, and the barrier properties of the nanocomposite films were investigated. PE-g-MA was shown to notably improve the dispersion of clay layers in the polyethylene matrix, and this was examined by atomic force microscopy and X-ray diffraction. The latter tests have also highlighted the importance of the screw configuration: the presence of mixing elements favors the dispersion and distribution of nanoclay. Moreover, differential scanning calorimetry results have shown no significant effect of the clay on the crystallinity of the composite while thermogravimetric analysis tests have demonstrated a decrease of onset and peak of decomposition temperatures. Finally, barrier properties toward water vapor transmission were measured. It was proven that not also clay, but the compatibilizer participated in decreasing the permeability of the film. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48589.