Laccases and Tyrosinases in Organic Synthesis

Laccases (Lac) and tyrosinases (TYR) are mild oxidants with a great potential in research and industry. In this work, we review recent advances in their use in organic synthesis. We summarize recent examples of Lac-catalyzed oxidation, homocoupling and heterocoupling, and TYR-catalyzed ortho-hydroxylation of phenols. We highlight the combination of Lac and TYR with other enzymes or chemical catalysts. We also point out the biological and pharmaceutical potential of the products, such as dimers of piceid, lignols, isorhamnetin, rutin, caffeic acid, 4-hydroxychalcones, thiols, hybrid antibiotics, benzimidazoles, benzothiazoles, pyrimidine derivatives, hydroxytyrosols, alkylcatechols, halocatechols, or dihydrocaffeoyl esters, etc. These products include radical scavengers; antibacterial, antiviral, and antitumor compounds; and building blocks for bioactive compounds and drugs. We summarize the available enzyme sources and discuss the scalability of their use in organic synthesis. In conclusion, we assume that the intensive use of laccases and tyrosinases in organic synthesis will yield new bioactive compounds and, in the long-term, reduce the environmental impact of industrial organic chemistry.     

Numerical Study of a Modified Time-Stepping θ-Scheme for Incompressible Flow Simulations

In [Turek (1996). Int. J. Numer. Meth. Fluids 22, 987–1011], we had performed numerical comparisons for different time stepping schemes for the incompressible Navier–Stokes equations. In this paper, we present the numerical analysis in the context of the Navier–Stokes equations for a modified time-stepping θ-scheme which has been recently proposed by Glowinski [Glowinski (2003). In: Ciarlet, P. G., and Lions, J. L. (eds.), Handbook of Numerical Analysis, Vol. IX, North-Holland, Amsterdam, pp. 3–1176]. Like the well-known classical Fractional-Step-θ-scheme which had been introduced by Glowinski [Glowinski (1985). In Murman, E. M. and Abarbanel, S. S. (eds.), Progress and Supercomputing in Computational Fluid Dynamics, Birkh?user, Boston MA; Bristeau et al. (1987). Comput. Phys. Rep. 6, 73–187], too, and which is still one of the most popular time stepping schemes, with or without operator splitting techniques, this new scheme consists of 3 substeps with nonequidistant substepping to build one macro time step. However, in contrast to the Fractional-Step-θ-scheme, the second substep can be formulated as an extrapolation step for previously computed data only, and the two remaining substeps look like a Backward Euler step so that no expensive operator evaluations for the right hand side vector with older solutions, as for instance in the Crank–Nicolson scheme, have to be performed. This modified scheme is implicit, strongly A-stable and second order accurate, too, which promises some advantageous behavior, particularly in implicit CFD simulations for the nonstationary Navier–Stokes equations. Representative numerical results, based on the software package FEATFLOW [Turek (2000). FEATFLOW Finite element software for the incompressible Navier–Stokes equations: User Manual, Release 1.2, University of Dortmund] are obtained for typical flow problems with benchmark character which provide a fair rating of the solution schemes, particularly in long time simulations.Dedicated to David Gottlieb on the occasion of his 60th anniversary     

Effect of acetylation on rheological properties of fish protein isolates during heating

Rheological properties of concentrated dispersions of muscle Pollack proteins acetylated to different degrees as a function of temperature have been studied. The character of viscosity changes of the partially acetylated isolates is almost identical with that of unacetylated protein. However, the temperatures corresponding to viscosity maxima increase proportionally to the degree of acetylation. A total acetylation of the free lysine ?-amino groups of Pollack protein results in a significant increase in the critical concentration and/or temperature of the sol-gel transition.     

Phase equilibria in the α-Ti-Al-Si region of the Ti-Si-Al system

An experimental investigation of the phase relations in the titanium (Ti)-aluminum (Al)-silicon (Si) system was undertaken by differential thermal analysis, x-ray diffraction, metallography, and microprobe analysis. The present measurements when combined with those from an earlier investigation at this laboratory provide data for 56 alloy compositions in the Ti-Al-Si system. The combined results allowed the construction of a solidus projection, a melting diagram including both solidus and liquidus, partial isothermal sections at 1270 °C and 1250 °C, three isopleths with a constant percentage of one or another component, and a reaction scheme.     

An ensemble-based method for linear feature extraction for two-class problems

In this paper we propose three variants of a linear feature extraction technique based on Adaboost for two-class classification problems. Unlike other feature extraction techniques, we do not make any assumptions about the distribution of the data. At each boosting step we select from a pool of linear projections the one that minimizes the weighted error. We propose three different variants of the feature extraction algorithm, depending on the way the pool of individual projections is constructed. Using nine real and two artificial data sets of different original dimensionality and sample size we compare the performance of the three proposed techniques with three classical techniques for linear feature extraction: Fisher linear discriminant analysis (FLD), Nonparametric discriminant analysis (NDA) and a recently proposed feature extraction method for heteroscedastic data based on the Chernoff criterion. Our results show that for data sets of relatively low-original dimensionality FLD appears to be both the most accurate and the most economical feature extraction method (giving just one-dimension in the case of two classes). The techniques based on Adaboost fare better than the classical techniques for data sets of large original dimensionality.

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Inner estimation of the united solution set of interval linear algebraic system

It is shown that an algebraic interval solution of interval linear algebraic systems with matrix composed of “reverse” interval elements of the input matrix is a maximum inner estimation for the mited solution set in the sense of inclusion.     

Methods for correction of selectivity of N-(2-sulfoethyl)chitosan-based materials towards platinum(IV) and palladium(II) ions

In this paper, we report methods for correction of selectivity of sorbents based on N-(2-sulfoethyl)chitosan towards platinum(IV) and palladium(II) in HCl solutions. The common method for correction of selectivity of the sorbents is variation of their modification degree with complexing groups. An increase in the degree of sulfoethylation of the chitosan leads to the significant increase in selectivity of sorption of palladium(II) over platinum(IV). Application of the N-(2-sulfoethyl)chitosan with the highest degree of sulfoethylation allows for selective separation palladium(II) from platinum(IV) (рН = 5.0). Palladium is quantitatively desorbed from the surface of the N-(2-sulfoethyl)chitosans by 3.5 mol/dm³ solution of HCl.     

Crosslinking of addition copolymers from tricyclononenes bearing (CH3)3Si‐ and (C2H5O)3Si‐groups as a modification of membrane gas separation materials

Here, we report the synthesis and the study of gas‐transport properties of crosslinked highly permeable copolymers from Si‐containing norbornene derivatives. The initial high‐molecular‐weight copolymers were prepared via addition copolymerization of 3‐trimethylsilyltricyclo[4.2.1.0^2,5]non‐7‐ene (TCNSi1) with 3‐triethoxysilyltricyclo[4.2.1.0^2,5]non‐7‐ene (TCNSiOEt) in good or high yields using a Pd‐catalyst. The obtained copolymers included up to 10 mol% of TCNSiOEt units bearing reactive Si–O–C‐containing substituents. The crosslinking was readily realized by using simple sol–gel chemistry in the presence of Sn‐catalyst. The formed crosslinked copolymers were insoluble in common organic solvents. Permeability coefficients of various gases (He, H₂, O₂, N₂, CO₂, CH₄, C₂H₆, C₃H₈, n‐C₄H₁₀) in these copolymers before and after crosslinking were determined and the influence of the incorporated TCNSiOEt units as well as the crosslinking on gas transport properties were established. As a result, it was found that only a small reduction of gas‐permeability was observed when TNCSiOEt units were incorporated into the main chains, and the copolymers were crosslinked. At the same time, the selectivity for C₄H₁₀/CH₄ pair was increased. The suggested approach has allowed obtaining crosslinked polymers from Si‐containing monomers without a loss of the main membrane characteristics. POLYM. ENG. SCI., 59:2502–2507, 2019. © 2019 Society of Plastics Engineers