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.     

Extraction-chromatographic properties and radiation resistance of a solid extractant based on di-2-ethylhexyl hydrogen phosphate

Extraction-chromatographic properties of LN-B200-S sorbent based on di-2-ethylhexyl hydrogen phosphate were studied. The equilibrium distribution coefficients of Am in the sorbent–HNO₃ system, the total exchange capacity, and the capacity to breakthrough were determined. The influence of the absorbed dose on the above parameters was examined. The suggested extraction-chromatographic system was tested with a real solution of spent nuclear fuel from an RBMK-1000 reactor as applied to the recovery of the Am–Cm–Nd fraction.     

Poly(hydroxybutyrate‐co‐hydroxyvalerate) and bovine serum albumin blend prepared by electrospinning

Electrospinning is a method for the preparation of nanosized polymer fibers. Here, electrospinning is used to prepare a blend of a polyester, poly(hydroxybutyrate‐co‐hydroxyvalerate) (PHBV), and a globular protein, bovine serum albumin (BSA). The electrospun blend film is compared with a solution‐cast blend film and with single‐component electrospun films made of PHBV and BSA. In the electrospun blend films, BSA manifests itself as flat ribbons and a fine network formed from fibers less than 50 nm in diameter. The dissolution rate of BSA from the electrospun blended film is lower than from the solution‐cast one. The films are characterized using scanning electron microscopy, differential scanning calorimetry, and contact‐angle measurements. The obtained PHBV+BSA blend films have several emergent properties: a slow BSA dissolution rate, a fine BSA network, and unusual thermal behavior. Thus, the PHBV+BSA blend films introduce a new class of polymer–protein blends. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45090.     

A Sol–Gel Derived CuOx/Al2O3–ZrO2 Catalyst for the Selective Reduction of NO by Propane in the Presence of Excess Oxygen

Copper catalysts supported on alumina-doped zirconia were prepared by sol–gel processing followed by supercritical drying or aging in the mother solution at 100°C. After drying and calcination, the catalyst supports were impregnated with a copper(II) nitrate aqueous solution by the incipient wetness method to achieve a Cu loading of about 2%. The samples showed 90% NO conversion at 350–400°C. The catalytic performance of these systems appears to be determined by the degree of clustering of copper cations as probed by FTIR spectroscopy of adsorbed CO.     

Competitive hydrogen bonding mechanisms underlying phase behavior of triple poly(N‐vinyl pyrrolidone)–poly(ethylene glycol)–poly(methacrylic acid‐co‐ethylacrylate) blends

Differential scanning calorimetry (DSC) of triple blends of high molecular weight poly(N‐vinyl pyrrolidone) (PVP) with oligomeric poly(ethylene glycol) (PEG) of molecular weight 400 g/mol and copolymer of methacrylic acid with ethylacrylate (PMAA‐co‐EA) demonstrates partial miscibility of polymer components, which is due to formation of interpolymer hydrogen bonds (reversible crosslinking). Because both PVP and PMAA‐co‐EA are amorphous polymers and PEG exhibits crystalline phase, the DSC examination is informative on the phase state of PEG in the triple blends and reveals a strong competition between PEG and PMAA‐co‐EA for interaction with PVP. The hydrogen bonding in the triple PVP–PEG–PMAA‐co‐EA blends has been established with FTIR Spectroscopy. To evaluate the relative strengths of hydrogen bonded complexes in PVP–PEG–PMAA‐co‐EA blends, quantum‐chemical calculations were performed. According to this analysis, the energy of H‐bonding has been found to diminish in the order: PVP–PMAA‐co‐EA–PEG(OH) > PVP–(OH)PEG(OH)–PVP > PVP–H₂O > PVP–PEG(OH) > PMAA‐co‐EA–PEG(? O? ) > PVP–PMAA‐co‐EA > PMAA‐co‐EA–PEG(OH). Thus, most stable complexes are the triple PVP–PMAA‐co‐EA–PEG(OH) complex and the complex wherein comparatively short PEG chains form simultaneously two hydrogen bonds to PVP carbonyl groups through both terminal OH‐groups, acting as H‐bonding crosslinks between longer PVP backbones. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Experience of the forecast of water and power resources changes at warming of the 21st century

Global warming causes changes of those natural resources like power resources, water resources, agroclimatic and ecological resources etc. And these changes depend on climate. Dynamics of resources depends both on planned economic activities and on changes of a climate. In this work the climatic component of changes is discussed. Projecting results used in this paper are based on the data of the CMIP3 (coupled model intercomparison project) in the framework of Working Group on Coupled Modelling. This project includes the world’s best climate models. Results of modelling and the data of meteorological observations expressed by probability distribution functions (or empirical orthogonal functions) were compared. It was shown that the modelling data were much more reliable over flat territories. In result 11 most successful models were selected. They can be used for the forecast within the framework of known IPCC scenario A2 at the 21st century. Estimations of changes of volumes of a river runoff and conditions of humidity of territory have been allowed to determine that the serious reduction of resources is expected in the southern part of the East European plain. Its central and northern parts practically will not demonstrate changes.     

Object segmentation in cluttered and visually complex environments

Object segmentation is essential for systems that acquire object models online for robotic grasping. However, it remains a major technical challenge in visually complex and uncontrolled environments. Segmentation algorithms that rely on image features alone can perform poorly under certain lighting conditions, or if the object and the background have similar appearance. In parallel, known object segmentation algorithms that rely exclusively on three dimensional (3D) geometric data are derived under strong assumptions about the geometry of the scene. A promising approach to performing object segmentation is to use a combination of appearance and 3D features. In this paper, an object segmentation algorithm is presented that combines multiple appearance and geometric cues. The segmentation is formulated as a binary labeling problem. The Conditional Random Fields (CRF) framework is used to model the conditional probability of the labeling given the appearance and geometric data. The maximum a posteriori estimation of the labeling is obtained by minimizing the energy function corresponding to the CRF using graph cuts. A simple and efficient method for initializing the proposed algorithm is also presented. Experimental results have demonstrated the effectiveness of the proposed algorithm.     

Structural peculiarities of TiO2 and Pt/TiO2 catalysts for the photocatalytic oxidation of aqueous solution of Acid Orange 7 Dye upon ultraviolet light

TiO₂ (anatase) with different microstructure was synthesized by thermal hydrolysis of the titanyl sulfate and studied by X-ray powder diffraction, high resolution transmission electron microscopy and UV–vis diffuse reflectance spectroscopy. The effect of titanium dioxide structure, regular or distorted, on the photocatalytic degradation of Acid Orange 7 Dye (AO7) in water upon ultraviolet light was studied. It was found that synthesized TiO₂ possesses a relatively high reactivity when illuminated but also show different adsorption in the dark. The relationship between these behaviors depends on the real structure of the catalysts. Catalysts with a perfect structural ordering formed after heating at temperature higher than 500 °C show better photocatalytic performance. Small amount of Pt added into the TiO₂ structure was found to improve further the catalyst reactivity. Pt-modified titania catalysts oxidize AO7 more efficiently than P-25 Degussa TiO₂. Doping effect of Pt on the structural and photocatalytic properties of the samples is discussed.     

On the relationship between modulus of elasticity and microhardness

The correlation between the modulus of elasticity, on the one side, and Vickers microhardness and total microhardness, on the other side, was analyzed in the case of ultrahigh molecular weight polyethylenes. An extension of the application of the power relation between microhardness and the modulus (MH = aE^b) obtained by different methods was suggested. A linear dependence between constants obtained by Vickers and total microhardness measurements and other different techniques of modulus measurement was established, which signifies that both microhardness characteristics change their sensitivity toward the modulus in a similar way. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1794–1798, 2003