CO disrupts the reduced H-cluster of FeFe hydrogenase. A combined DFT and protein film voltammetry study

Carbon monoxide is often described as a competitive inhibitor of FeFe hydrogenases, and it is used for probing H(2) binding to synthetic or in silico models of the active site H-cluster. Yet it does not always behave as a simple inhibitor. Using an original approach which combines accurate electrochemical measurements and theoretical calculations, we elucidate the mechanism by which, under certain conditions, CO binding can cause permanent damage to the H-cluster. Like in the case of oxygen inhibition, the reaction with CO engages the entire H-cluster, rather than only the Fe(2) subsite.     

Periodic boundary value problems for higher‐order fractional differential systems

Approximation of solutions of fractional differential systems (FDS) of higher orders is studied for periodic boundary value problem (PBVP). We propose a numerical‐analytic technique to construct a sequence of functions convergent to the limit function, which is a solution of the given PBVP, if the corresponding determined equation has a root. We also study scalar fractional differential equations (FDE) with asymptotically constant nonlinearities leading to Landesman‐Lazer–type conditions.     

Electrical Properties Investigation in PA12/PANI Composites

Summary: Volume conducting PA-12 based composites powders were chemically prepared by in situ polymerization and aniline doping at room temperature. These kinds of polyamide / PANI composites were investigated regarding their electrical properties. Their ac and dc electrical properties measured in the frequency range of 10⁻²–10⁷ Hz are reported and the frequency dependence of electrical conductivity was investigated as a function of PANI concentration leading to the determination of the conductivity. The experimental conductivity was found to increase continuously with PANI content and explained by percolation theory with a relatively low percolation threshold of about 0.4 wt.%. The dielectric behavior of various PANI polymer composites has been characterized by the critical frequency ω_c (denoting the crossover from the dc plateau of the conductivity to its frequency dependent ac behaviour). Modelling the conductivity behavior versus volume fraction using Slupkowski approach has revealed that the considered parameters are not sufficient to describe the electrical conductivity behavior.     

New Method for Covalent Fluorescent Biomolecule Labeling with Hemicyanine Dye

Fluorescent chromophore, alkylamino-(tetra-hydronaphthalenylidene)- benzothiazolium derivatives (HBTN dyes), are proposed as covalent labels for proteins via aliphatic amino groups. Spectral-luminescent properties of 3-methyl-2-{(E)-[7-(methylamino)-4,4a,5,6-tetra-hydronaphthalen-2(3H)-ylidene]methyl}-1,3-benzothiazol-3-ium chloride (HBTN, R=Me) and its predecessor, 2-[(E)-(7-methoxy-4,4a,5,6-tetrahydronaphthalen-2(3H)-ylidene)methyl]-3-methyl-1,3-benzothia-zol-3-ium chloride (ABTN), are studied for free dyes and in the presence of DNA and BSA. Considerable spectral-luminescent changes accompany the transformation of ABTN into HBTN that allows monitoring conjugation reaction. In presence of DNA and BSA the HBTN increases its emission in 15 and 4 times respectively and becomes strongly fluorescent. The conditions for labeling are developed and a model conjugate of HBTN dye with BSA is synthesized. It was shown that using of HBTN dye as a fluorescent label allows detection by eye of about 3 μg/band of BSA on polyacrylamide gel upon UV-irradiation.     

Nanomechanical testing of ODS steels irradiated with 1 MeV/amu heavy ions

Development of oxide dispersion strengthened (ODS) steels, as candidates for fuel claddings for Gen IV nuclear reactors, requires a comprehensive study of their behaviour under operating conditions. In this work, 1.2 MeV/amu Kr and Xe irradiation was used to simulate fission fragment impact. New irradiation approaches with respect to a non-homogeneous damage profile under ion irradiation were proposed. Hardness profiles of irradiated ODS steels were obtained by continuous stiffness measurements with subsequent analysis of size effects according to the Nix–Gao model. It was found, that heavy ion irradiation leads to hardness saturation in ODS steels in a damage dose range of 0.1–1 dpa. Observed hardening is about 20% and is not connected with the radiation stability of Y–Ti–O and Y–Al–O oxide particles in ODS steels as it was studied by TEM.     

Authentication of Rhodiola rosea,Rhodiola quadrifida and Rhodiola rosea liquid extract from the Ukrainian market using HPTLC chromatographic profiles

Abstract

Rhodiola rosea and Rhodiola quadrifida are widely distributed and sold in Eastern Europe. The purpose of this paper was to identify R.rosea, R.quadrifida and Rhodiola rosea liquid extract (RRLE) in the Ukrainian market and bring out adulteration cases using chromatographic characterisation by HPTLC. The multiple samples of R.rosea, R.quadrifida and RRLE were compared; the optimal chromatographic conditions for identification of R.rosea and RRLE based on the presence of rosavins and salidroside as well as for identification of R.quadrifida based on the presence of salidroside were proposed; the specific HPTLC fingerprints were obtained; the acceptance criteria for each product were set. The adulteration cases for R.rosea and RRLE samples were established. The dependence on handling R.rosea and presence of rosavins was determined. It was assumed that low-quality raw materials or inefficient technology process were used for RRLE. The consistency of HPTLC fingerprints for R.quadrifida samples was established.     

Reversible control of free energy and topography of nanostructured surfaces

We describe a facile method for the formation of dynamic nanostructured surfaces based on the modification of porous anodic aluminum oxide with poly(N-isopropyl acrylamide) (PNIPAAm) via surface-initiated atom transfer radical polymerization. The dynamic structure of these surfaces was investigated by atomic force microscopy (AFM), which showed dramatic changes in the surface nanostructure above and below the aqueous lower critical solution temperature of PNIPAAm. These changes in surface structure are correlated with changes in the macroscopic wettability of the surfaces, which was probed by water contact angle measurements. Principal component analysis was used to develop a quantitative correlation between AFM image intensity histograms and macroscopic wettability. Such correlations and dynamic nanostructured surfaces may have a variety of uses.     

Polynomial Time Approximation Scheme for Two Parallel Machines Scheduling with a Common Due Date to Maximize Early Work

We study the scheduling problem with a common due date on two parallel identical machines and the total early work criterion. The problem is known to be NP-hard. We prove a few dominance properties of optimal solutions of this problem. Their proposal was inspired by the results of some auxiliary computational experiments. Test were performed with the dynamic programming algorithm and list algorithms. Then, we propose the polynomial time approximation scheme, based on structuring problem input. Moreover, we discuss the relationship between the early work criterion and the related late work criterion. We compare the computational complexity and approximability of scheduling problems with both mentioned objective functions.     

Synthesis of α-CF3- and α-CCl3 substituted nitrogen heterocycles by aza Diels-Alder and cyclocondensation reactions

Convenient synthetic approaches for α-CF₃- and α-CCl₃ substituted pyridines, hydrogenated pyridines, azanorbornenes, 4H-1,2,4-thiadiazine- and 2H-1,2,6-thiadiazine-1,1-dioxides were developed on the basis of cycloaddition and cyclocondensation reactions of trihaloethaneimines and imidoyl chlorides.