Thioacetylacetone: structural and vibrational assignments.

Thioacetylacetone and its variously deuterated isotopomers have been investigated using electronic and vibrational spectroscopy combined with quantum chemical calculations. Thioacetylacetone is known for its photochromic properties, but the structures of the initial and final forms have been the subject of a long debate. Analysis of the IR spectra recorded in low-temperature argon and xenon matrices, room-temperature solutions, and in the gas phase has allowed us to establish the nature of the photochromic species and of its precursor. Similar to the case of another beta-thioxoketone, monothiodibenzoylmethane, the photo-product has been assigned to the nonchelated SH exo-rotamer of the (Z)-enethiol tautomeric form, whereas the dominant ground-state species corresponds to the chelated (Z)-enol tautomeric form. Detailed vibrational assignments have been proposed for both forms based on quantum chemical calculations and polarization experiments. In the case of the chelated (Z)-enol species prevailing in the ground state, a second-order perturbative anharmonic analysis at the B3LYP/cc-pVTZ level indicated strong anharmonic effects associated with the intramolecular hydrogen bond, leading to a shift of more than 600 cm-1 of the wavenumber of the OH-stretching vibration. A small fraction of the SH endo-rotameric chelated (Z)-enethiol form was also detected under unperturbed conditions. The (Z)-enethiol form can be converted into the (Z)-enol form by irradiation at 290 nm.     

Experimental and Theoretical Investigation of the First‐Order Hyperpolarizability of Octupolar Merocyanine Dyes

Hyper‐Rayleigh scattering experiments and quantum chemical calculations are combined to investigate the second‐order nonlinear optical responses of a series of three‐arm merocyanine derivatives. They exhibit an octupolar hyperpolarizability response with lower amplitude than crystal violet due to a lower extent of the photoinduced charge transfer and reduced bond length alternation. Strong effects on the second‐order optical response measured close to the two‐photon absorption level are clearly evidenced; for example, the effective measured polarization ratio deviates below the ideal octupolar value of 3/2 even at very low excitation power. These effects are attributed to two‐photon absorption resonance, which we believe modifies dynamically the population of the ground state versus that of the excited state.     

Reactivity studies of carbon,phosphorus and sulfur‐based acyl sites with tertiary oximes in gemini surfactants

Kinetic studies of the reactions of tertiary oximes (monoisonitroso acetone; MINA and butane 2,3 dione monooxime; BDMO) with some carboxylate (p‐nitrophenyl acetate and p‐nitrophenyl benzoate), phosphate (p‐nitrophenyl diphenyl phosphate and bis (2,4‐dinitrophenyl) phosphate) and sulfonate (p‐nitrophenyl p‐toluene sulphonate) esters in gemini surfactants have been conducted. The observed first‐order rate constant versus surfactant profiles show micelle‐assisted bimolecular reactions involving interfacial ion exchange between bulk aqueous media and micellar pseudophase. Experimental results showed that MINA exhibited better nucleophilic activity towards ester cleavage than BDMO. Pseudophase model has been applied in order to determine micellar second‐order rate constants and binding constants. Copyright © 2013 John Wiley & Sons, Ltd.     

Substituting CF2 for O4′ in Components of Nucleic Acids: Towards Systems with Reduced Propensity to Form Abasic Lesions

Intrinsic structural features and energetics of nucleotides containing variously fluorinated sugars as potential building blocks of DNA duplexes and quadruplexes are explored systematically using the modern methods of density functional theory (DFT) and quantum chemical topology (QCT). Our results suggest that fluorination at the 2′‐β or 2′‐α,β positions somewhat stabilizes in vacuo the AI relative to the BI conformations. In contrast, substitution of the CF₂ group for the O4′ atom (O4′‐CF₂ modification) leads to a preference of the BI relative to AI DNA‐like conformers. All the studied modifications result in a noticeable increase in the stability of the glycosidic bond [estimated by the relaxed force constants (RFC) approach], with particularly encouraging results for the O4′‐CF₂ derivative. Consequently, the O4′‐CF₂ modified systems are suggested and explored as promising scaffolds for the development of duplex and quadruplex structures with reduced propensity to form abasic lesions and to undergo DNA damage.     

Creep-fatigue analysis of the steel AISI type 316 component failure

The purpose of this work is to extend a typical creep-damage model in order to describe material behavior under variable thermal and mechanical loading in wide stress range. The model basis is creep constitutive law in form of hyperbolic sine stress response function proposed by Nadai. The constitutive law is extended to assume the damage process under creep and fatigue by the introduction of scalar damage parameters and appropriate evolution equations according to Kachanov-Rabotnov concept. The material constants for model are identified by fitting the experimental creep and low-cycle fatigue data for the steel AISI type 316 at the range of temperatures 500°C – 750°C. The development of such model is motivated by the well described failure case study of high-temperature components at unit 1 of Eddystone power plant, which have operated during 130520 hours under creep-fatigue interaction conditions. The main steam piping (MSP) from this power plant is selected for thermo-mechanical creep-fatigue analysis applying the proposed material model. The estimated values of damage parameters comply with the real location of the component failure and a scatter of experimental data on creep-fatigue interaction diagram. (© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Modeling of primary and secondary creep for a wide stress range

Many materials exhibit a stress range dependent creep behavior. The power–law creep observed for a certain stress range changes to the viscous type creep if the stress value decreases. Recently published experimental data for advanced heat resistant steels indicate that the high creep exponent (in the range 5–12 for power–law behaviour) may decrease to the low value of approximately 1 within the stress range relevant for engineering structures. The aim of this paper is to confirm the necessity of the assumption of the stress range dependent power–law–viscous creep transition for the solution of stress relaxation problems affected by creep behavior at elevated temperatures. A constitutive model for the minimum creep rate is introduced to describe both the linear and the power law creep depending upon the stress level. The proposed constitutive model includes a strain hardening function to describe the primary creep stage. To demonstrate the existence of the linear creep behaviour in the low stress range of application area and the influence of the primary creep behaviour on relaxation, several solutions of a uniaxial stress relaxation problem are presented for the loading values relevant to engineering applications. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

How a Small Structural Difference Can Turn Optical Properties of π‐Extended Coumarins Upside Down: The Role of Non‐Innocent Saturated Rings

The fluorescence properties of two new families of heterocycles possessing either a seven‐ or five‐membered ring attached at the core molecule are entirely different in solution and in the solid state. Crystallization has the effect of inhibiting non‐radiative excited‐state deactivation pathways, operative in solution for the seven‐membered ring compounds, thus leading to significant fluorescence efficiency in the solid state, with quantum yields ranging from 0.10 to 0.36. Conversely, the five‐membered ring derivatives, which display notable emission properties in solution, are almost non‐emissive in the crystalline state, characterized by a long‐range π‐stacked arrangement. When embedded in polymeric films, both series show fluorescence features similar to the solution case, with remarkable fluorescence quantum yields ranging from 0.09 to 0.41. According to quantum chemical calculations, 3H‐chromeno[3,4‐c]pyridine‐4,5‐diones show the specific mechanism of fluorescence quenching. The derivatives bearing the seven‐membered ring undergo, in solution, a significant structural deformation in the excited state, resulting in a large decrease of the energy gap between S₁ and S₀ and hence to a substantial contribution of the internal conversion in the relaxation process. The fluorescence quenching of the five‐membered ring derivatives is in turn related to the intermolecular interaction between adjacent molecules prevailing to a greater extent in the crystal lattice.     

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.