Colour switching with photochromic vinylidene-naphthofurans

A series of novel photochromic vinylidene-naphthofurans with extended conjugation, and a free hydroxyl function, were easily prepared using the Suzuki reaction. After silanization, these dyes were embedded in ormosil matrices affording solid and transparent materials that acquire different colourations (violet, green, bluish), reversibly, when exposed to the UV (Sun) light, for 2?min, at room temperature. The presence of an extra phenyl ring in some positions affects both the λ_max of absorption of the photochromic compounds in the uncoloured closed and open coloured form. After removal of the light source the materials lose progressively their colouration returning to the initial uncoloured state in less than 15?min?at room temperature.     

Experimental and molecular dynamics simulation study of the sublimation energetics of cyclopentadienyltricarbonylmanganese (Cymantrene)

The standard molar enthalpy of sublimation of monoclinic cyclopentadienyltricarbonylmanganese, Mn(eta (5)-C 5H 5)(CO) 3, at 298.15 K, was determined as Delta sub H m (o)[Mn(eta (5)-C 5H 5)(CO) 3] = 75.97 +/- 0.37 kJ x mol (-1) from Knudsen effusion and Calvet-drop microcalorimetry measurements, thus considerably improving the very large inaccuracy (>10 kJ x mol (-1)) of the published data. The obtained value was used to assess the extension of the OPLS-based all-atom force field we previously developed for iron metallocenes to manganese organometallic compounds. The modified force field was able to reproduce the volumetric properties (density and unit-cell volume) of crystalline Mn(eta (5)-C 5H 5)(CO) 3 with a deviation of 0.6% and the experimentally determined enthalpy of sublimation with an accuracy of 1 kJ x mol (-1). The interaction (epsilon) and atomic-diameter (sigma) parameters of the Lennard-Jones (12-6) potential function used to calculate dispersion contributions within the framework of the force field were found to be transferable from iron to manganese.     

High-Spin and Reactive Fe13 Cluster with Exposed Metal Sites

Atomically defined large metal clusters have applications in new reaction development and preparation of materials with tailored properties. Expanding the synthetic toolbox for reactive high nuclearity metal complexes, we report a new class of Fe clusters, Tp*₄W₄Fe₁₃S₁₂ , displaying a Fe₁₃ core with M−M bonds that has precedent only in main group and late metal chemistry. M₁₃ clusters with closed shell electron configurations can show significant stability and have been classified as superatoms. In contrast, Tp*₄W₄Fe₁₃S₁₂ displays a large spin ground state of S=13. This compound performs small molecule activations involving the transfer of up to 12 electrons resulting in significant cluster rearrangements.     

Interaction with specific HSP90 residues as a scoring function: validation in the D3R Grand Challenge 2015

Here is reported the development of a novel scoring function that performs remarkably well at identifying the native binding pose of a subset of HSP90 inhibitors containing aminopyrimidine or resorcinol based scaffolds. This scoring function is called PocketScore, and consists of the interaction energy between a ligand and three residues in the binding pocket: Asp93, Thr184 and a water molecule. We integrated PocketScore into a molecular docking workflow, and used it to participate in the Drug Design Data Resource (D3R) Grand Challenge 2015 (GC2015). PocketScore was able to rank 180 molecules of the GC2015 according to their binding affinity with satisfactory performance. These results indicate that the specific residues considered by PocketScore are determinant to properly model the interaction between HSP90 and its subset of inhibitors containing aminopyrimidine or resorcinol based scaffolds. Moreover, the development of PocketScore aimed at improving docking power while neglecting the prediction of binding affinities, suggesting that accurate identification of native binding poses is a determinant factor for the performance of virtual screens.     

Hydrophobic interaction chromatography of Chromobacterium viscosum lipase on polypropylene glycol immobilised on Sepharose.

The fractionation of Chromobacterium viscosum lipase was performed using a polypropylene glycol-Sepharose gel. The influence of mobile phase composition on the adsorption of lipase on the gel was studied and it was found that the retention of lipase depends on the salt used and increased with increasing the ionic strength. The retention was not strongly affected by changing the pH value of the mobile phase. By using 20% (w/v) ammonium sulphate in phosphate buffer a total retention of lipase on the column was obtained and by simply decreasing the ionic strength of the buffer, desorption of lipase could be achieved. The chromatographic purification of Chromobacterium viscosum lipase by hydrophobic interaction chromatography on Sepharose CL-6B modified by covalent immobilisation of 1,4-butanediol diglycidyl ether, polyethylene glycol and polypropylene glycol was also compared.     

Influence of pre-shearing on rheometric measurements of an oil-based drilling fluid

Drilling fluids are suspensions of solid particles and present thixotropic and elastoviscoplastic behaviors simultaneously, which turn their rheological characterization into a challenging task. Rotational rheometers are widely employed to determine the properties of these fluids, and one major challenge in rheometric tests carried out with thixotropic fluids is to obtain repeatable results. Submitting the fluid specimen to a known shear history by performing a pre-shear procedure is commonly used to achieve repeatable results with thixotropic fluids. In this paper, the effect of different pre-shearing conditions on the rheological measurements of an oil-based drilling fluid was investigated using cross-hatched parallel plates. Firstly, an adequate aging time to ensure complete fluid restructuring was determined by monitoring the storage modulus, G′, over an oscillatory time sweep experiment. Shear-rate controlled start-up tests were then conducted to evaluate the gel strength and the steady-state shear stress. Nine different pre-shearing conditions were evaluated, and each experiment was performed three times. Finally, the results were analyzed by using two statistical tools: a two-way analysis of variance (ANOVA) and the Tukey’s range test. The analysis shows that despite the good repeatability achieved when the same pre-shear condition is applied, the pre-shearing affects not only the gel strength but also the steady-state shear stress. The ANOVA also revealed that the effect of the pre-shearing shear rate on the fluid rheological behavior is statistically more significant than the effect of the pre-shearing time. The same analysis was performed after 10 s and 10 min of aging, and similar results were obtained.     

Evaluation of recombinant invasive, non-pathogenic Eschericia coli as a vaccine vector against the intracellular pathogen, Brucella

Background  

There is no safe, effective human vaccine against brucellosis. Live attenuated Brucella strains are widely used to vaccinate animals. However these live Brucella vaccines can cause disease and are unsafe for humans. Killed Brucella or subunit vaccines are not effective in eliciting long term protection. In this study, we evaluate an approach using a live, non-pathogenic bacteria (E. coli) genetically engineered to mimic the brucellae pathway of infection and present antigens for an appropriate cytolitic T cell response.     

Collocation and iterated collocation methods for a class of weakly singular Volterra integral equations

We discuss the convergence properties of spline collocation and iterated collocation methods for a weakly singular Volterra integral equation associated with certain heat conduction problems. This work completes the previous studies of numerical methods for this type of equations with noncompact kernel. In particular, a global convergence result is obtained and it is shown that discrete superconvergence can be achieved with the iterated collocation if the exact solution belongs to some appropriate spaces. Some numerical examples illustrate the theoretical results.