Induced neodymium luminescence in sol–gel derived layered double hydroxides

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Phase stability of Crn+ 1GaCn MAX phases from first principles and Cr2GaC thin‐film synthesis using magnetron sputtering from elemental targets

Ab‐initio calculations have been used to investigate the phase stability and magnetic state of Cr_{n+ 1}GaC_n MAX phase. Cr₂GaC (n = 1) was predicted to be stable, with a ground state corresponding to an antiferromagnetic spin configuration. Thin‐film synthesis by magnetron sputtering from elemental targets, including liquid Ga, shows the formation of Cr₂GaC, previously only attained from bulk synthesis methods. The films were deposited at 650 °C on MgO(111) substrates. X‐ray diffraction and high‐resolution transmission electron microscopy show epitaxial growth of (000?) MAX phase. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Switching the Inhibitor-Enzyme Recognition Profile via Chimeric Carbonic Anhydrase XII

A key part of the optimization of small molecules in pharmaceutical inhibitor development is to vary the molecular design to enhance complementarity of chemical features of the compound with the positioning of amino acids in the active site of a target enzyme. Typically this involves iterations of synthesis, to modify the compound, and biophysical assay, to assess the outcomes. Selective targeting of the anti-cancer carbonic anhydrase isoform XII (CA XII), this process is challenging because the overall fold is very similar across the twelve CA isoforms. To enhance drug development for CA XII we used a reverse engineering approach where mutation of the key six amino acids in the active site of human CA XII into the CA II isoform was performed to provide a protein chimera (chCA XII) which is amenable to structure-based compound optimization. Through determination of structural detail and affinity measurement of the interaction with over 60 compounds we observed that the compounds that bound CA XII more strongly than CA II, switched their preference and bound more strongly to the engineered chimera, chCA XII, based on CA II, but containing the 6 key amino acids from CA XII, behaved as CA XII in its compound recognition profile. The structures of the compounds in the chimeric active site also resembled those determined for complexes with CA XII, hence validating this protein engineering approach in the development of new inhibitors.     

Asymptotic Expansion for the Distribution Density Function of the Compound Poisson Process in Large Deviations

The paper is devoted to obtaining the asymptotic expansion and determination of the structure of the remainder term taking into consideration large deviations in the Cramér zone for the distribution density function of the standardized compound Poisson process. Following Deltuvien? and Saulis (Acta Appl Math 78:87–97, 2003. doi: 10.1023/A:1025783905023; Lith Math J 41:620–625, 2001) and Saulis and Statulevi?ius [Limit theorems for large deviations. Mathematics and its applications (Soviet Series), vol 73, pp 154–187, Kluwer, Dordrecht, 1991], the solution to the problem is achieved by first using a general lemma presented by Saulis (see Lemma 6.1 in Saulis and Statulevi?ius 1991, p. 154) on the asymptotic expansion for the density function of an arbitrary random variable with zero mean and unit variance and combining methods for cumulants and characteristic functions. By taking into consideration the large deviations in the Cramér zone for the density function of the standardized compound Poisson process, the result for the asymptotic expansion extends the asymptotic expansions for the density function of the sums of non-random number of summands (Deltuvien? and Saulis 2003, 2001).     

Theorems on Large Deviations for Randomly Indexed Sum of Weighted Random Variables

In this paper, we consider a random variable \(Z_{t}=\sum_{i=1}^{N_{t}}a_{i}X_{i}\), where \(X, X_{1}, X_{2}, \ldots\) are independent identically distributed random variables with mean E X=μ and variance D X=σ ²>0. It is assumed that Z ₀=0, 0≤a _i <∞, and N _t , t≥0 is a non-negative integer-valued random variable independent of X _i , i=1,2,…?. The paper is devoted to the analysis of accuracy of the standard normal approximation to the sum \(\tilde{Z}_{t}=(\mathbf{D}Z_{t})^{-1/2}(Z_{t}-\mathbf{E}Z_{t})\), large deviation theorems in the Cramer and power Linnik zones, and exponential inequalities for \(\mathbf{P}(\tilde{Z}_{t}\geq x)\).     

Sea Buckthorn Leaf Powders: The Impact of Cultivar and Drying Mode on Antioxidant,Phytochemical, and Chromatic Profile of Valuable Resource

Sea buckthorn (Hippophae rhamnoides L. (HR)) leaf powders are the underutilized, promising resource of valuable compounds. Genotype and processing methods are key factors in the preparation of homogenous, stable, and quantified ingredients. The aim of this study was to evaluate the phenolic, triterpenic, antioxidant profiles, carotenoid and chlorophyll content, and chromatic characteristics of convection-dried and freeze-dried HR leaf powders obtained from ten different female cultivars, namely ‘Avgustinka’, ‘Botaniceskaja Liubitelskaja’, ‘Botaniceskaja’, ‘Hibrid Percika’, ‘Julia’, ‘Nivelena’, ‘Otradnaja’, ‘Podarok Sadu’, ‘Trofimovskaja’, and ‘Vorobjovskaja’. The chromatic characteristics were determined using the CIELAB scale. The phytochemical profiles were determined using HPLC-PDA (high performance liquid chromatography with photodiode array detector) analysis; spectrophotometric assays and antioxidant activities were investigated using ABTS (2,2′-Azino-bis(3-ethylbenzothiazoline-6-sulfonic acid)) and FRAP (ferric ion reducing antioxidant power) assays. The sea buckthorn leaf powders had a yellowish-green appearance. The drying mode had a significant impact on the total antioxidant activity, chlorophyll content, and chromatic characteristics of the samples; the freeze-dried samples were superior in antioxidant activity, chlorophyll, carotenoid content, and chromatic profile, compared to convection-dried leaf powder samples. The determined triterpenic and phenolic profiles strongly depend on the cultivar, and the drying technique had no impact on qualitative and quantitative composition. Catechin, epigallocatechin, procyanidin B3, ursolic acid, α-amyrin, and β-sitosterol could be used as quantitative markers in the phenolic and triterpenic profiles. The cultivars ‘Avgustinka’, ‘Nivelena’, and ‘Botaniceskaja’ were superior to other tested cultivars, with the phytochemical composition and antioxidant activity.     

Effect of Chloride Ions on the Behavior of Saccharin, N-Methylsaccharin, and 2-Butyne-1,4-diol during Electrodeposition of Nickel from Acid Electrolytes

Rates of transformation of organic additives (saccharin, N-methylsaccharin, 2-butyne-1,4-diol) and accumulation of products of their cathodic reactions are studied during nickel electrodeposition from the chloride and Watts electrolytes. A large concentration of chloride ions accelerates the saccharine and N-methylsaccharin consumption due accelerated synthesis of o-toluenesulfamide, N-methyl-o-toluenesulfamide, and N-methylbenzylsultam, thus facilitating adsorption of additives on the nickel cathode via the carbonyl group. An inhibition of adsorption via the sulfonyl group is accompanied by a decrease in the accumulation of corresponding benzamides. An increase in the concentration of chloride ions in electrolytes containing 2-butyne-1,4-diol promotes accumulation of 2-buten-1,4-diol and inhibits hydrogenation of the double bond to a saturated bond. Differences in the behavior of the additives are due to (i) competition of chloride ions with the additives in the electrolyte or with their electroreduction products during adsorption on the nickel cathode, (ii) a change in the deposit potential, and (iii) a change in the concentration of inclusions in the deposits, which determine the catalytic activity of the cathode.