NMR-measurements for determination of local moisture content of coated wood

Local increased moisture content (MC) in wood constructions may result in different kinds of mechanical and, especially, biological degrading problems. Therefore, it is of great importance to control the MC of the material. However, there is at present no appropriate method for determining local MC in wood without destroying the product itself. Nondestructive measurements of local MC in wood is significant for the possibility of, for instance, monitoring the in situ MC in wood constructions over time, and thereby predicting potential problems. The nuclear magnetic resonance (NMR) technique has been shown to be valuable for the measurement of MC in wood. In this study, the possibility of utilizing this technique for local MC measurement in wood has been tested on wood samples exposed to water absorption for 72 h. The samples came from three different wood species treated with paint systems available on the market. In the wood samples an artificial “crack” had been created in the paint to introduce an area where the water could easily gain access to the wood. The results show the possibility of using the NMR technique for local MC measurements in wood. The measurement area, however, must be related to the properties of the material. In the case of wood, the measurement spot must be related to the early/latewood proportions. Further, a calibration of the NMR measurement must be made in relation to the expected density variations of the material.     

Differential Activity of Plasma and Vacuolar Membrane Transporters Contributes to Genotypic Differences in Salinity Tolerance in a Halophyte Species,Chenopodium quinoa

Halophytes species can be used as a highly convenient model system to reveal key ionic and molecular mechanisms that confer salinity tolerance in plants. Earlier, we reported that quinoa (Chenopodium quinoa Willd.), a facultative C3 halophyte species, can efficiently control the activity of slow (SV) and fast (FV) tonoplast channels to match specific growth conditions by ensuring that most of accumulated Na⁺ is safely locked in the vacuole (Bonales-Alatorre et al. (2013) Plant Physiology). This work extends these finding by comparing the properties of tonoplast FV and SV channels in two quinoa genotypes contrasting in their salinity tolerance. The work is complemented by studies of the kinetics of net ion fluxes across the plasma membrane of quinoa leaf mesophyll tissue. Our results suggest that multiple mechanisms contribute towards genotypic differences in salinity tolerance in quinoa. These include: (i) a higher rate of Na⁺ exclusion from leaf mesophyll; (ii) maintenance of low cytosolic Na⁺ levels; (iii) better K⁺ retention in the leaf mesophyll; (iv) a high rate of H⁺ pumping, which increases the ability of mesophyll cells to restore their membrane potential; and (v) the ability to reduce the activity of SV and FV channels under saline conditions. These mechanisms appear to be highly orchestrated, thus enabling the remarkable overall salinity tolerance of quinoa species.     

Peculiar electric properties of polarized layer in alkaline silicate glasses

Broadband dielectric spectroscopy (BDS) was applied to study polarization phenomena in alkaline silicate glasses, in particular, properties and structure of subsurface (anodic) polarized layers forming in poling with deposited film electrodes of different structures. A model of poled glasses which does not contradict experimental data is proposed. In accordance with the model, a poled glass is presented as two resistor-capacitor circuits in a series connection, one of which is the polarized layer and another is the rest of the sample. It is found that the electric properties of the layers essentially depend on the structure of the anodic electrode used in glass poling. It is also shown that the dielectric response of poled glass samples is mainly determined by the electric properties of the submicron polarized layers and this gives an opportunity to reveal specific properties of the layers rather than ones of the glass sample bulk. Revealed temperature dependence of DC conductivity of the polarized layers obeys Arrhenius's law, and determining activation energy does not depend on the electrode. Finally, it is noted that today above-mentioned information about polarized layers can be obtained only by BDS.     

Effects of mutations in the calcium-binding sites of recoverin on its calcium affinity: evidence for successive filling of the calcium binding sites

A molecule of the photoreceptor Ca²⁺-binding protein recoverincontains four potential EF-hand Ca²⁺-binding sites, of whichonly two, the second and the third, are capable of binding calciumions. We have studied the effects of substitutions in the second,third and fourth EF-hand sites of recoverin on its Ca²⁺-bindingproperties and some other characteristics, using intrinsic fluorescence,circular dichroism spectroscopy and differential scanning microcalorimetry.The interaction of the two operating binding sites of wild-typerecoverin with calcium increases the protein's thermal stability,but makes the environment around the tryptophan residues moreflexible. The amino acid substitution in the EF-hand 3 (E121Q)totally abolishes the high calcium affinity of recoverin, whilethe mutation in the EF-hand 2 (E85Q) causes only a moderatedecrease in calcium binding. Based on this evidence, we suggestthat the binding of calcium ions to recoverin is a sequentialprocess with the EF-hand 3 being filled first. Estimation ofCa²⁺-binding constants according to the sequential binding schemegave the values 3.7 x 10⁶ and 3.1 x 10⁵ M^–1 for thirdand second EF-hands, respectively. The substitutions in theEF-hand 2 or 3 (or in both the sites simultaneously) do notdisturb significantly either tertiary or secondary structureof the apo-protein. Amino acid substitutions, which have beendesigned to restore the calcium affinity of the EF-hand 4 (G160D,K161E, K162N, D165G and K166Q), increase the calcium capacityand affinity of recoverin but also perturb the protein structureand decrease the thermostability of its apo-form.     

Catalytic activity of supported metal particles for sulfuric acid decomposition reaction

Production of hydrogen by splitting of water in the thermochemical sulfur-based cycles that employs the catalytic decomposition of sulfuric acid into SO₂ and O₂ is of considerable interest. However, all of the known catalytic systems studied to date that consist of metal particles on oxide substrates deactivate with time on stream. To develop an understanding of the factors that are responsible for catalyst activity, we investigate the fresh activity of several platinum group metals (PGM) catalysts, including Pd, Pt, Rh, Ir, and Ru supported on titania at 850 °C and perform an extensive theoretical study (density-functional-theory-based first-principles calculations and computer simulations) of the activity of the PGM nanoparticles of different size and shape positioned on TiO₂ (rutile and anatase) and Al₂O₃ (γ- and η-alumina) surfaces. The activity and deactivation of the catalytic systems are defined by (i) the energy barrier for the detachment of O atoms from the SO_n (n = 1, 2, 3) species, and (ii) the removal rate of the products of the sulfuric acid decomposition (atomic O, S, and the SO_n species) from metal nanoparticles. We show that these two nanoscale features collectively result in the observed experimental behavior. The removal rate of the reaction products is always lower than the SO_n decomposition rates. The relation between these two rates explains why the “softer” PGM nanoparticles (Pd and Pt) exhibit the highest initial catalytic activity.     

Novel Antitumor L‐Arabinose Derivative of Indolocarbazole with High Affinity to DNA

Novel indolocarbazole derivative 12‐(α‐L ‐arabinopyranosyl)indolo[2,3‐α]pyrrolo[3,4‐c]carbazole‐5,7‐dione (AIC) demonstrated high potency (at submicromolar concentrations) against the NCI panel of human tumor cell lines and transplanted tumors in vivo. In search of tentative targets for AIC, we found that the drug formed high affinity intercalative complexes with d(AT)₂₀, d(GC)₂₀ and calf thymus DNA (binding constants (1.6×10⁶) M ^?1≤K_a≤(3.3×10⁶) M ^?1). The drug intercalated preferentially into GC pairs of the duplex. Importantly, the concentrations at which AIC formed the intercalative complexes with DNA (C≤1 μM ) were identical to the concentrations that triggered p53‐dependent gene reporter transactivation, the replication block, the inhibition of topoisomerase I‐mediated DNA relaxation and death of HCT116 human colon carcinoma cells. We conclude that the formation of high affinity intercalative complexes with DNA is an important factor for anticancer efficacy of AIC.     

UV, Raman and XRD study of polymorphism of poly(methyl-n-propylsilane)

Raman, UV and XRD studies have been performed to characterize the structures of differently prepared samples of poly(methyl-n-propylsilane). The results demonstrate polymorphism of this polymer between T_c and T_g. At room temperature the polymer can exist in up to four modifications which comprise one amorphous disordered phase and three more ordered modifications, differing in the interchain organization and in the silicon backbone conformations. The latter are considered to be deviant, transoid and all-anti, respectively. The number of the modifications present and relative amount of each strongly depends on the preparation method and thermal history of the sample as well as on the molecular weight.     

Non-Enzymatic Template-Directed Recombination of RNAs

RNA non-enzymatic recombination reactions are of great interest within the hypothesis of the “RNA world”, which argues that at some stage of prebiotic life development proteins were not yet engaged in biochemical reactions and RNA carried out both the information storage task and the full range of catalytic roles necessary in primitive self-replicating systems. Here we report on the study of recombination reaction occuring between two 96 nucleotides (nts) fragments of RNAs under physiological conditions and governed by a short oligodeoxyribonucleotide template, partially complementary to sequences within each of the RNAs. Analysis of recombination products shows that ligation is predominantly template-directed, and occurs within the complementary complex with the template in “butt-to-butt” manner, in 1- or 3- nts bulges or in 2–3 nts internal loops. Minor recombination products formed in the template-independent manner are detected as well.