Macroporous carbon aerogel as a novel adsorbent for immobilized enzymes and a support for the lipase-active heterogeneous biocatalysts for conversion of triglycerides and fatty acids

A macroporous carbon aerogel (MCA) was produced by in situ synthesis of multi-walled carbon nanotubes (CNTs) via catalytic high-temperature decomposition of ethylene over the supported Fe:Co catalyst. A three-dimensional framework of ball-shaped MCA granules was formed by chaotic interlacing of growing CNTs and mechanical strength of the granules was high enough for their promising application in heterogeneous processes, in particular, bioconversion of fatty acids. The macroporous carbon aerogel was investigated as a novel support for adsorptive immobilization of an enzyme—Thermomyces lanuginosus lipase, followed by preparation of the lipase-active heterogeneous biocatalysts. It was found that the efficient and tight adsorption of the lipase on MCA occurred due to hydrophobic interactions. The amount of the lipase adsorbed in one dense adsorptive layer was equal to 110 mg per 1 g of the carbon aerogel. The lipase adsorbed in the 1st adsorptive layer possessed the maximum activity, 700–800 U/mg. The lipase-active heterogeneous biocatalysts were studied in the periodic processes of hydrolysis of emulsified triglycerides (tributyrin), interesterification of vegetable oil with ethyl acetate, and esterification of fatty acids (butyric C4:0, capric C10:0, and stearic C18:0) with isopentanol. It was found that T. lanuginosus lipase lost significantly its enzymatic activity during adsorption on the carbon aerogel; possible causes of the negative effect of such immobilization were discussed. The specific activity of the adsorbed lipase, as well as activity and stability of the biocatalysts depended foremost on the type of the reaction performed. The maximum activities of the biocatalysts were determined to be approximately 75·10³ and 2.5 U/g in tributyrin hydrolysis (aqueous media) and esterification of fatty acid (non-aqueous media), respectively. Stability of the biocatalysts was very high in the esterification reaction due to accumulation of essential water inside MCA. The lipase-active biocatalysts carried out the synthesis of isopentyl caprinate in organic solvents (hexane?+?diethyl ether) for several 100 h at 40 °C.     

An application of the recreation level of service approach to forests in Israel

Due to the limitations of the carrying capacity approach a level of service approach is advanced for recreation planning in outdoor settings. This paper is the first to apply this approach to a concerete realworld setting, picnics in two forests in Israel. To this end a survey was conducted among visitors to the two forests. The survey serves to elicit the factors that determine the level of satisfaction visitors derive from picnics in these sites, and the relative importance of these factors. On this basis the tolerance range of visitors for the various dimensions is elicited, using the site based method to identify the upper level of the range and the generic method to identify the lower extremity of the range. By relating the perceived level in each site to the tolerance range the level of service for each site is computed. The results show that the level of service approach is indeed applicable to concrete cases, and that it provides practical insights to planners at both the site level and the regional level, where it can serve as a tool for prioritizing resource allocation among sites. However, there is a need for further extensive experimentation with this method, both to assess whether it can be used to prioritize among sites where different activities take place, and to further substantiate the methodology used to elicit and calculate the levels of service.     

Understanding the Role of Alumina (Al2O3), Pentalithium Aluminate (Li5AlO4), and Pentasodium Aluminate (Na5AlO4) Coatings on the Li and Mn-Rich NCM Cathode Material 0.33Li2MnO3·0.67Li(Ni0.4Co0.2Mn0.4)O2 for Enhanced Electrochemical Performance

The active role of alumina, pentalithium aluminate (Li₅AlO₄, Li-aluminate), and pentasodium aluminate (Na₅AlO₄, Na-aluminate) as the surface protection coatings produced via atomic layer deposition on Li and Mn-rich NCM cathode materials 0.33Li₂MnO₃·0.67LiNi_0.4Co_0.2Mn_0.4O₂ is discussed. A notable improvement in the electrochemical behavior of the coated cathodes has been found while tested in Li-coin cells at 30 °C. Though all the coated cathodes demonstrate enhanced electrochemical cycling and rate performances, Na-aluminate coated cathodes exhibit exemplary behavior. Prolonged cycling and rate capability testing demonstrate that after more than 400 cycles at 1 C rate, the uncoated cathode delivers only 63 mAh g⁻¹, while those with alumina, Li-aluminate, and Na-aluminate coatings exhibit approximately two times higher specific capacities. The coated cathodes display steady average discharge potential and lower evolution of the voltage hysteresis during prolonged cycling compared to the uncoated cathode. Importantly, Na-aluminate coated cathode shows a lowering in gases (O₂, CO₂, H₂, etc.) evolution. Post-cycling analysis of the electrodes demonstrates higher morphological integrity of the coated cathode materials and lower transition metals dissolution from them. The coatings mitigate undesirable side reactions between the electrodes and the electrolyte solution in the cells.     

Novel sorbents of ethanol “salt confined to porous matrix” for adsorptive cooling

In this paper a new family of sorbents, specifically designed for ethanol sorption, is presented. The composites were synthesized by a dry impregnation of matrices with an aqueous solution of various salts. The ethanol sorption capacity of the composites, under conditions typical for adsorptive air conditioning cycle, has been measured by using an express method based on the Polanyi principle of temperature invariance. Results obtained show that the best novel composites have the ethanol sorption ability which is higher than that of known ethanol sorbents. The composite LiBr(30 wt.%)/SiO₂ appears to show the highest sorption capacity and an uptake variation Δw = 0.56 and 0.40 g/g for air conditioning and ice making cycles, respectively. They are much larger than those obtained for conventional adsorbents. The correspondent cooling coefficient of performance (COP) was estimated to be 0.66 and 0.61, which is comparable with the COP of the best water sorbents.     

Effects of Aqueous Dispersions of C60, C70 and Gd@C82 Fullerenes on Genes Involved in Oxidative Stress and Anti-Inflammatory Pathways

Background: Fullerenes and metallofullerenes can be considered promising nanopharmaceuticals themselves and as a basis for chemical modification. As reactive oxygen species homeostasis plays a vital role in cells, the study of their effect on genes involved in oxidative stress and anti-inflammatory responses are of particular importance. Methods: Human fetal lung fibroblasts were incubated with aqueous dispersions of C₆₀, C₇₀, and Gd@C₈₂ in concentrations of 5 nM and 1.5 µM for 1, 3, 24, and 72 h. Cell viability, intracellular ROS, NOX4, NFκB, PRAR-γ, NRF2, heme oxygenase 1, and NAD(P)H quinone dehydrogenase 1 expression have been studied. Results & conclusion: The aqueous dispersions of C₆₀, C₇₀, and Gd@C₈₂ fullerenes are active participants in reactive oxygen species (ROS) homeostasis. Low and high concentrations of aqueous fullerene dispersions (AFD) have similar effects. C₇₀ was the most inert substance, C₆₀ was the most active substance. All AFDs have both “prooxidant” and “antioxidant” effects but with a different balance. Gd@C₈₂ was a substance with more pronounced antioxidant and anti-inflammatory properties, while C₇₀ had more pronounced “prooxidant” properties.     

Molecular mobility and physical ageing of plasticized poly(lactide)

Molecular mobility and physical ageing of amorphous plasticized polylactide (PLA) with two different contents of mesolactide are studied with the help of thermal analysis. Used plasticizers are acetyl tributyl citrate (ATBC) and triacetin (TA), two molecules with established miscibility and plasticizing efficiency. Lower plasticizer permanence of TA compared with ATBC is found. The plasticizer molecules decreased the size of the cooperativity domains at the glass transition temperature T_g and likely in the glassy state by decreasing intermacromolecular interactions and notwithstanding the mesolactide content of PLA and the chemical identity of the plasticizer. The recovery function is given and shows a significant effect of the plasticizer on the physical ageing. The supplementary free volume brought by the plasticizer enhances molecular mobility in the glassy state and increases structural relaxation at one order of magnitude. The comparison between different plasticizers reveals that the structural relaxation is however independent from the type of plasticizer and the percentage of mesolactide in PLA. POLYM. ENG. SCI., 55:858–865, 2015. © 2014 Society of Plastics Engineers     

Adsorption properties of composite materials (LiCl + LiBr)/silica

This paper presents experimental data on synthesis and the phase composition of novel composites “(LiCl + LiBr) confined to the silica gel pores” as well as their sorption equilibrium with water and methanol vapour. Phase transformation of the composites during methanol sorption was characterized in situ by an X-ray diffraction analysis. The isobars of sorption on the composites were measured in the temperature range T = 303–383 K at the methanol and water pressure P = 107 and 13 mbar, respectively, using a thermo-gravimetric technique. It was shown that the formation of solid solutions of LiCl and LiBr took place in limited ranges of LiBr (C_Br = 0–11 mol.%) and LiCl (C_Cl = 0–36 mol.%) content. These solutions absorbed water (methanol) at temperature that was intermediate between the individual solvation temperatures for confined LiCl and LiBr. In the composites with LiCl/LiBr molar ratio between the ranges of solubility a mixture of two solid solutions was formed. Each solution absorbed water (methanol) independently at a certain temperature. The use of the binary LiCl–LiBr system confined to the silica pores can be an effective tool for designing innovative materials with predetermined sorption properties.     

Segmentation modeling algorithm: a novel algorithm in data mining

Many enterprises have accumulated a large amount of data over time. To achieve competitive advantages, enterprises need to find effective ways to analyze and understand the vast amounts of raw data they have. Different methods and techniques have been used to reduce the data volume to a manageable level and to help enterprises identify the business value from the data sets. In particular, segmentation methods have been widely used in the area of data mining. In this paper, we present a new algorithm for data segmentation which can be used to build time-dependent customer behavior models. The proposed model has the potential to solve the optimization problem in data segmentation.