Is [Co(4)(H(2)O)(2)(α-PW(9)O(34))(2)](10-) a genuine molecular catalyst in photochemical water oxidation? Answers from time-resolved hole scavenging experiments

Water oxidation catalysts: evolution of [Co(4)(H(2)O)(2)(α-PW(9)O(34))(2)](10-) to catalytically active species is assessed by laser flash photolysis in sacrificial photocatalytic cycles with Ru(bpy)(3)(2+) as a photosensitizer.     

Random perturbations effects on the stability of Tension Leg Platforms in offshore engineering and of other large structures

We analyze the stability of Tension Leg Platform offshore structures, as well as of some large flexible space structures, under random perturbations of their main parameters. An asymptotic theory and numerical methods are used as tools to study moment stability, and numerical simulations of the Monte Carlo type are also conducted for both purposes, of checking the results of the asymptotic theory and to handle cases when such a theory cannot be applied.     

Looking for some free energy? Call JEFREE (…)

In this communication, we present the Jarzynski's Equality FREe Energy (JEFREE) library, an efficient and easy‐to‐use C++ library targeted to the calculation of the free energy profile along a selected generalized coordinate of a system, within the framework of the nonequilibrium steered transformations as introduced by Jarzynski [Phys. Rev. E, 1997, 56, 5018]. JEFREE can be readily integrated into any code, since both C and FORTRAN wrappers have been developed, and easily customizable by a user thanks to the object‐oriented programming paradigm offered by the C++ language. Also, JEFREE implements the novel idea of making a total “morphing” of the system energy landscape before initiating the proper steering stage. This proves to be an efficient mean to overtake the problematic sampling of the initial equilibrium state when the number of degrees of freedom is high and the landscape owns many local minima separated by large energy barriers. The calculation of the free energy profile for the rotation along torsion angles in alkyl chains is presented as an example of application of our tool. © 2014 Wiley Periodicals, Inc.     

Explaining Fullerene Dispersion by using Micellar Solutions

An effective computational strategy to describe the dispersion of C₆₀ by surfactants is presented. The influence of parameters such as surfactant concentration and molecular length on the final morphology of the system is explored to explain the experimental results and to understand the incorporation of C₆₀ inside micelles. Both neutral and charged amphiphilic molecules are simulated. The long‐discussed problem of the location of fullerenes in micelles is addressed and C₆₀ is found in the hydrocarbon‐chain region of the micelles. If the available hydrophobic space increases, C₆₀ is localized in the inner part of the micellar core. Short, charged amphiphilic stabilizers are more efficient at dispersing fullerenes monomolecularly. Two different phases of C₆₀ are observed as the C₆₀/surfactant ratio varies. In the first, aggregates of C₆₀ are entrapped inside the micelles, whereas, in the second, colloidal nanoC₆₀ is formed with surfactants adsorbed on the surface.     

L−Lysine Amino Acid Adsorption on Zeolite L: a Combined Synchrotron,X-Ray and Neutron Diffraction Study

Combined neutron and X-ray powder diffraction techniques highlighted the sorption capacity of the acidic L zeolite towards the L-lysine amino acid. The role of zeolite channels in the stabilization of the lysine absorbed and the effect of water on protein structure are elucidated at atomistic level. The stabilization of the L α-helical conformation is related to strong H-bonds between the tail aminogroups of lysine molecules and the Brønsted acid site as well as to complex intermolecular H-bond system between water molecules, zeolite and amino acid. This finding is relevant in the catalytic synthesis of polypeptide, as well as in industrial biotechnology by qualitatively predicting binding behaviour     

Potential energy surface and kinetics of the helix–coil transition in a 33-peptide

The CHARMM force field is used to calculate 36 minima along the potential energy surface of the helix–coil conversion of Ac-A₁₄KG₃A₁₄K + 2H⁺ and to interconnect them through 35 transition states. The energy barriers are used to give the rate constants of interconversion between the conformers and the relevant kinetic equations are then solved. Fair to good agreement with the data obtained by drift time spectrometry experiments (D. T. Kaleta, M. F. Jarrold, J. Am. Chem. Soc. 125:7186, 2003) is obtained under a simple hypothesis of the initial conformer distribution. Contribution to the Fernando Bernardi Memorial Issue.     

12CH2F2 and13CH2F2far-infrared lasers: New lines and frequency measurements

We report here the discovery of 13 new far-infrared laser lines from¹²CH₂F₂ and seven new lines from¹³CH₂F₂. Most of the new lines were pumped by high-J lines of the 9R branch of a cw-CO₂ laser. Wavelengths range from 97.6 to 616.18 μm. Frequency, pump offset, relative polarization, and relative intensity were measured for most of the new lines.     

Influence of protease on dyeing of wool with acid dyes

The application of enzymes in the wool dyeing process is an important research goal in order to reduce the environmental impact and costs of this finishing process. The work has focused on the possibility of reducing the temperature of conventional dyeing, using an enzymatic pretreatment with a neutral protease to improve the diffusion of the dye into the fibers. After the identification of the optimal dyeing process, the study goes on transferring the method to an industrial application. For this reason the influence of a leveling agent added to the dyeing bath was considered and further tests with an industrial dyeing recipe were performed. In order to evaluate possible fiber damage, samples treated with enzyme were observed by scanning electron microscopy (SEM) and analyzed by gel electrophoresis (SDS-PAGE). Moreover, the variation of tensile strength and elongation of dyed samples were determined. In addition, color fastness to domestic laundering, perspiration and rubbing were carried out. Finally, color measurements and fiber section analysis were performed. The results show the possibility, thanks to the pretreatment with the investigated enzyme, to obtain a homogeneous and solid dyeing on fibers maintaining good mechanical properties, already working at 85°C instead of 98°C currently used in industry.