Effect of hyperconjugation on ionization energies of hydroxyalkyl radicals

On the basis of electronic structure calculations and molecular orbital analysis, we offer a physical explanation of the observed large decrease (0.9 eV) in ionization energies (IE) in going from hydroxymethyl to hydroxyethyl radical. The effect is attributed to hyperconjugative interactions between the sigma CH orbitals of the methyl group in hydroxyethyl, the singly occupied p orbital of carbon, and the lone pair p orbital of oxygen. Analyses of vertical and adiabatic IEs and hyperconjugation energies computed by the natural bond orbital (NBO) procedure reveal that the decrease is due to the destabilization of the singly occupied molecular orbital in hydroxyethyl radical as well as structural relaxation of the cation maximizing the hyperconjugative interactions. The stabilization is achieved due to the contraction of the CO and CC bonds, whereas large changes in torsional angles bear little effect on the total hyperconjugation energies and, consequently, IEs.     

Ab initio comprehensive conformational analysis of 2'-deoxyuridine, the biologically significant DNA minor nucleoside, and reconstruction of its low-temperature matrix infrared spectrum

A comprehensive conformational analysis of isolated 2'-deoxyuridine (dU), a minor DNA nucleoside, has been performed by means of ab initio calculations at the MP2/6-311++G (d,p)//DFT B3LYP/6-31G (d,p) level of theory. At 298.15 and 420 K, all 94 allowed conformers of dU are within 8.96 and 7.91 kcal/mol Gibbs energy ranges, respectively. Syn orientation for the base and South (S) conformers for the sugar dominate at 298.15 K: syn/anti=62.3%:37.7% and S/N=77.2%:22.8%. At 420 K in the majority of conformers, the base is anti oriented and the population of North (N) sugars increases: syn/anti=39.3%:60.7% and S/N=63.0%:37.0%. Values of all conformational parameters and correlations between them, as well as their correlations with valence bonds, and also correlations between valence bonds and angles were estimated. In general, 14 types of intramolecular H-bonds were detected (1-3 H-bonds per conformer, the total number 175), namely, C1'H...O2 (16 H-bonds), C2'H1...O5' (9), C2'H2...O2 (21), C3'H...O2 (21), C5'H1...O2 (14), C5'H2...O2 (11), C6H...O4' (37), C6H...O5' (22), C3'H...HC6 (4), O5'H...HC6 (2), O3'H...O5' (5), O5'H...O4' (1), O5'H...O3' (4), and O5'H...O2 (8). Geometric, vibrational, structural-topological, and energetic features of the OH...O intramolecular H-bonds in dU conformers were determined. The close similarity between energetic and geometric characteristics of dU and thymidine DNA-like conformers in anti and relevant syn conformations and their transition states of the anti-->syn interconversion implies that mismatch DNA glycosylase discriminates between the two nucleosides, mainly because of the difference in the shapes of their bases. Convolution of calculated IR spectra of all the dU conformers within the limits 3400-3700 cm(-1) appears to be consistent with its low-temperature matrix IR spectrum (Ivanov et al. Spectrochim. Acta, Part A 2003, 59, 1959), wavenumber discrepancy not exceeding 1%. It was concluded that, for a reliable reproduction of the experimental spectrum, the whole set of conformers should be taken into consideration. The suggested method makes reconstruction of the isolated nucleoside IR spectrum at a physiological interval of temperature reasonably possible.     

Synthesis,in silico and in vitro Evaluation of Novel Oxazolopyrimidines as Promising Anticancer Agents

New potential bioactive oxazolopyrimidines have been synthesized using two main approaches: the pyrimidine ring annulation on a functionalized oxazole and the benzoyl bromide trimerization followed by rearrangement and formation of the oxazolo[5,4-d]pyrimidine scaffold. The docking analyzes have shown that 7-piperazine substituted oxazolo[4,5-d]pyrimidines 8a – 8c could be potential VEGFR2 inhibitors with high free energy of ligand–protein complex formation (ΔG: −10.1, −9.6, −9.8 kcal/mol, respectively). In vitro antitumor assays confirmed theoretical predictions that oxazolo[4,5-d]pyrimidines 8a – 8c containing positively charged piperazine moiety should demonstrate significantly higher cytotoxic effects. 4-[5-(4-Chlorophenyl)-2-phenyl[1,3]oxazolo[4,5-d]pyrimidin-7-yl]piperazin-1-ium trifluoroacetate ( 8c ) exhibited a slightly higher antiproliferative effect (IC₅₀=0.21 μm ) than doxorubicin (IC₅₀=0.36 μm ) on MDA-MB-231 cell line and has relatively good results on OVCAR-3 (IC₅₀=1.7 μm ) and HCT-116 (IC₅₀=0.24 μm ) cells.     

Reactivity of micellar systems based on supernucleophilic functional surfactants in processes of acyl group transfer

Processes of cleavage of 4-nitrophenyl esters of diethylphosphoric, diethylphosphonic, and 4-toluenesulfonic acids were investigated occurring in micelles of surfactants containing supernucleophilic oximate fragment and on their analogs not forming micelles in water. At transferring the reaction from water into the micelles of functional surfactants the reaction accelerates 10²?C10³ times. This acceleration is caused by the concentration of the substrate, for the nucleophilicity of the oximate fragment changes insignificantly. The reactivity of the functional surfactants is described by the Br?nsted dependence with a break, its character is analogous to the dependence of the oximes non-forming micelles.     

A parametric study on creep-fatigue endurance of welded joints

This work is devoted to parametric study on creep-fatigue endurance of the steel AISI type 316N(L) weldments defined as type 3 according to R5 Vol. 2/3 procedure at 550°C. The study is implemented using a novel direct method known as the Linear Matching Method (LMM) and based upon the creep-fatigue evaluation procedure considering time fraction rule for creep-damage assessment. Seven geometrical configurations of the weldment, which are characterised by individual values of a geometrical parameter ρ, are proposed. Parameter ρ, which represents different grades of TIG dressing, is a ratio between the radius of the fillet of the remelted metal on a weld toe and the thickness of welded plates. For each configuration, the total number of cycles to failure N^* in creep-fatigue conditions is assessed numerically for different loading cases including normalised bending moment and dwell period Δt. The obtained set of N^* is extrapolated by the analytic function dependent on , Δt and ρ. Proposed function for N^* shows good agreement with numerical results obtained by the LMM. It is used for the identification of Fatigue Strength Reduction Factors (FSRFs) effected by creep and dependent on Δt and ρ. (© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Temperature and composition dependence of magnetic properties of cobalt–chromium co-substituted magnesium ferrite nanomaterials

The temperature and composition dependence of magnetic properties of Co–Cr co-substituted magnesium ferrite, Mg_1−xCo_xCr_xFe_2−xO₄ (x=0.0–0.5), prepared by novel polyethylene glycol assisted microemulsion method, are studied. The synthesized materials are characterized by the Mössbauer spectrometer and standard magnetic measurements. Major hysteresis loops are measured up to the magnetic field of 50 kOe at 300, 200 and 100 K. The high field regimes of these loops are modeled using the Law of Approach to saturation to determine the first-order cubic anisotropy coefficient and saturation magnetization. Both the saturation magnetization and the anisotropy coefficient are observed to increase with the decrease in temperature for all Co–Cr co-substitution levels. Also, both the saturation magnetization and the anisotropy coefficient achieved maximum value at x=0.3 and x=0.2, respectively. Explanation of the observed behavior is proposed in terms of the site occupancy of the co-substituent, Co²⁺ and Cr³⁺ in the cubic spinel lattice.     

Bootstrap testing for discontinuities under long-range dependence

We consider testing for discontinuities in a trend function when the residual process exhibits long memory. Using a wavelet decomposition of the estimated trend function into a low-resolution and a high-resolution component, a test statistic is proposed based on blockwise resampling of estimated residual variances. Asymptotic validity of the test is derived. A simulation study illustrates finite sample properties.     

Octupolar merocyanine dyes: a new class of nonlinear optical chromophores

A set of new octupolar merocyanine chromophores was designed and synthesized. These compounds were prepared from the reaction of 1,3,5-triformyl-2,4,6-trihydroxybenzene with heterocyclic nucleophiles. Octupolar dyes were formed exclusively in their open-dye form. The one- and two-photon-absorption spectra of the dyes consist of two bands: The long-wavelength band in the two-photon absorption spectrum (a few hundreds GM above 1000?nm) matches well with the intense, long-wavelength-absorption band that is located in the visible region in the linear spectrum. Interestingly, an additional, much-more-intense TPA band in the NIR region is observed at higher energy, which corresponds to a weakly allowed one-photon electronic transition. Changing the peripheral heterocyclic moieties allows tuning of the optical properties to approach the cyanine limit (i.e., polymethine state), thus resulting in a red-shift of the low-energy one-photon-absorption band as well as to the rise of an intense two-photon-absorption band in the NIR region. To the best of our knowledge, this is the first synthesis and TPA characterization of octupolar merocyanine chromophores with typical low-bond-length alternation.     

Development of Functional Composite Cu(II)-Polyoxometalate/PLA with Antimicrobial Properties

Novel composite self-disinfecting films of polylactic acid (PLA) filled with nanosized particles of double sodium–copper(II) paratungstate B Na₂Cu₃(CuOH)₂[W₁₂O₄₀(OH)₂]·32H₂O (POM) were developed. The solvent casting (POM/PLA film) and solvent-free melt extrusion methods (Extr. POM/PLA film) were applied for film preparation. The copper (II) ion release to water from both types of the films after 10 days at different temperatures demonstrated that the PLA matrix acts as a diffusion barrier, and the resulting concentration of released copper in water at room temperature remained low, at 0.79% for POM/PLA film and 0.51% for Extr. POM/PLA film. The POM-containing films reveals a significant inhibitory effect against E. coli ATCC 25922 in the agar diffusion test. The numbers of CFUs in washes of the films after incubation for 24 h were found to be 3.6 log CFU mL^–1 (POM/PLA film) and 4.1 log CFU mL^–1 (Extr. POM/PLA film). The films combine the antibacterial properties of POM and a bio-based polymer matrix, which makes them a prospective coating material for applications in hospital indoor environments. Excellent thermal stability of POM gives a technological advantage for industrial manufacturing to allow the processing of novel composite material in the solvent free (molten) state.