Unsteady axisymmetric stagnation flow on a circular cylinder

Unsteady, axisymmetric stagnation flow about a circular cylinderis examined when the far-field flow is a periodic function oftime with a fixed time average and an oscillatory part of prescribedamplitude and frequency. Solutions are computed for arbitraryvalues of the Reynolds number, quantifying the effects of surfacecurvature, and a frequency parameter based on the period ofthe far-field flow. It is found that solutions remain regularand periodic provided that the far-field amplitude lies belowa critical value. Above this value, solutions terminate in afinite-time singularity. The blow-up time is delayed by increasingthe curvature of the surface. These results are corroboratedby asymptotic predictions valid in the limits of small and largeamplitude and frequency. For large Reynolds number, the problemreduces to the two-dimensional stagnation-point flow againsta plane wall studied by previous authors.     

Polyethylene glycol matrix reduces the rates of photochemical and thermal release of nitric oxide from S-nitroso-N-acetylcysteine

S -nitrosothiols have many biological activities and may act as nitric oxide (NO) carriers and donors, prolonging NO half-life in vivo. In spite of their great potential as therapeutic agents, most S -nitrosothiols are too unstable to isolate. We have shown that the S -nitroso adduct of N -acetylcysteine (SNAC) can be synthesized directly in aqueous and polyethylene glycol (PEG) 400 matrix by using a reactive gaseous (NO/O₂) mixture. Spectral monitoring of the S–N bond cleavage showed that SNAC, synthesized by this method, is relatively stable in nonbuf-fered aqueous solution at 25°C in the dark and that its stability is greatly increased in PEG matrix, resulting in a 28-fold decrease in its initial rate of thermal decomposition. Irradiation with UV light (λ= 333 nm) accelerated the rate of decomposition of SNAC to NO in both matrices, indicating that SNAC may find use for the photogeneration of NO. The quantum yield for SNAC decomposition decreased from 0.65 ± 0.15 in aqueous solution to 0.047 ± 0.005 in PEG 400 matrix. This increased stability in PEG matrix was assigned to a cage effect promoted by the PEG microenvironment that increases the rate of geminated radical pair recombination in the homolytic S–N bond cleavage process. This effect allowed for the storage of SNAC in PEG at −20°C in the dark for more than 10 weeks with negligible decomposition. Such stabilization may represent a viable option for the synthesis, storage and handling of S -nitrosothiol solutions for biomedical applications.     

Formation of nanodots on oblique ion sputtered InP surfaces

Using a field emission gun based scanning electron microscopy, we report the formation of nanodots on the InP surfaces after bombardment by 100 keV Ar⁺ ions under off-normal ion incidence (30° and 60° with respect to the surface normal) condition in the fluence range of 1 × 10¹⁶ to 1 × 10¹⁸ ions cm⁻². Nanodots start forming after a threshold fluence of about 1 × 10¹⁷ ions cm⁻². It is also seen that although the average dot diameter increases with fluence the average number of dots decreases with increasing fluence. Formation of such nanostructured features is attributed due to ion-beam sputtering. X-ray photoelectron spectroscopy analysis of the ion sputtered surface clearly shows In enrichment of the sputtered InP surface. The observation of growth of nanodots on the Ar⁺-ion sputtered InP surface under the present experimental condition matches well with the recent simulation results based on an atomistic model of sputter erosion.     

Picosecond fluorescence studies by intracavity gain spectroscopy in a modelocked dye laser

This article presents measurements which combine modelocking technique with intracavity spectroscopy. To test this approach, a sample (10^–5 m ethanolic solution of 1,4-dihydroxyanthranquinone) was inserted in a modelocked Ar⁺ ion laser and probed by intracavity pulses of a synchronously pumped dye laser. The probing of the sample results in an amplification of the dye laser output. Maximum output was measured if the pulses of the dye laser temporally overlapped with those of the Ar⁺ ion laser inside the sample. Under this condition, the spectral laser intensity was shaped by the spectrum of stimulated fluorescence which originated from a molecular vibronic state populated by pump laser excitation.Presented at LASERION '91, June 12–14, 1991, München (Germany)     

Insights into the Ligand Binding to Bromodomain-Containing Protein 9 (BRD9): A Guide to the Selection of Potential Binders by Computational Methods

The estimation of the binding of a set of molecules against BRD9 protein was carried out through an in silico molecular dynamics-driven exhaustive analysis to guide the identification of potential novel ligands. Starting from eight crystal structures of this protein co-complexed with known binders and one apo form, we conducted an exhaustive molecular docking/molecular dynamics (MD) investigation. To balance accuracy and an affordable calculation time, the systems were simulated for 100 ns in explicit solvent. Moreover, one complex was simulated for 1 µs to assess the influence of simulation time on the results. A set of MD-derived parameters was computed and compared with molecular docking-derived and experimental data. MM-GBSA and the per-residue interaction energy emerged as the main indicators for the good interaction between the specific binder and the protein counterpart. To assess the performance of the proposed analysis workflow, we tested six molecules featuring different binding affinities for BRD9, obtaining promising outcomes. Further insights were reported to highlight the influence of the starting structure on the molecular dynamics simulations evolution. The data confirmed that a ranking of BRD9 binders using key parameters arising from molecular dynamics is advisable to discard poor ligands before moving on with the synthesis and the biological tests.     

Computational models for the numerical simulation of voltage operated channels in nano–bio–electronics

In this article, we discuss the use of computational models in the study of voltage operated channels (VOCs) for bio-electronic applications. Electrochemical and fluid–mechanical ionic transport are described through the coupled use of systems of partial and ordinary differential equations (PDEs and ODEs). Functional iteration techniques for system decoupling and mixed–hybridized finite element discretization methods are proposed and validated in the simulation of realistic problems in Electrophysiology and Biochemistry. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Elucidating heteroatom influence on homonuclear 4J(H,H) coupling constants by DFT/NMR approach

We report the structural dependency of long range scalar J-coupling constant across four bonds as function of the dihedral angles Φ1 and Φ3. The calculated homonuclear coupling constants ⁴J(_H,H), obtained at a density functional theory level, were measured between C(1)─X(2) and X(2)─C(3) bonds in three-term models, where C, N, O, and S were systematically used as the second atom of the alkyl structures ( 1 - 4 ). The ⁴J_(H,H) calculated values, tabulated for variation of 30° for both Φ1 and Φ3, have disclosed an unexpected detectable coupling constant (⁴J(_H,H) ≥ 1 Hz) across heteroatoms, useful to provide valuable structural information. A 2-methyl-1,3-dithiane sulfide ( 5 ) was used as a case study to prove the applicability and reliability of the calculated values to real issues. The ⁴J(_H,H) values obtained at density functional theory for the system 4 have reproduced with good accuracy an unexpected experimental ⁴J(_H2ax-H4ax) = 1.01 Hz of sulfide molecule ( 5 ), suggesting these calculated coupling constant values as a new powerful tool for the organic synthesis and stereochemical analysis.     

Synthesis of the two enantiomers of the sex pheromone of Diabrotica Undecimpunct at a Howardi and of chiral precursors of other pheromones starting from enantiomerically pure methyl hydrogen (R)-3-methylglutarate

Readily available methyl hydrogen (R)-3-methylglutarate(2) is a useful chiral building block for the synthesis of several biologically active compounds. Enantiomerically pure (R)-2 has been employed to synthesize stereospecifically each of the two enantiomers, 1a and 1b, of 10-methyl-2-tridecanone, the sex pheromone of the southern corn rootworm, Diabrotica undecimpunctata howardi Barber. Compound (R)-2 has been also used to prepare 99% optically pure (R)-3-methyl-1-pentanol (6) and enantiomerically pure (R)-5-methyl-i-tricosyne (7). These compounds are useful building blocks suitable for the further elaboration to other chiral insect pheromones.