S K-edge XAS and DFT calculations on SAM dependent pyruvate formate-lyase activating enzyme: nature of interaction between the Fe4S4 cluster and SAM and its role in reactivity

S K-edge X-ray absorption spectroscopy on the resting oxidized and the S-adenosyl-l-methionine (SAM) bound forms of pyruvate formate-lyase activating enzyme are reported. The data show an increase in pre-edge intensity, which is due to additional contributions from sulfide and thiolate of the Fe(4)S(4) cluster into the C-S σ* orbital. This experimentally demonstrates that there is a backbonding interaction between the Fe(4)S(4) cluster and C-S σ* orbitals of SAM in this inner sphere complex. DFT calculations that reproduce the data indicate that this backbonding is enhanced in the reduced form and that this configurational interaction between the donor and acceptor orbitals facilitates the electron transfer from the cluster to the SAM, which otherwise has a large outer sphere electron transfer barrier. The energy of the reductive cleavage of the C-S bond is sensitive to the dielectric of the protein in the immediate vicinity of the site as a high dielectric stabilizes the more charge separated reactant increasing the reaction barrier. This may provide a mechanism for generation of the 5'-deoxyadenosyl radical upon substrate binding.     

Vibrational spectroscopy and ionic conductivity of polyethylene oxide-NaClO4-CuO nanocomposite

Structure, morphology and thermal properties of polyethylene oxide (PEO) with sodium perchlorate (NaClO(4)) as electrolytic salt have been investigated by incorporating cupric monoxide (CuO) nanoparticles. Monoclinic CuO affects melting and glass transition temperatures of PEO-NaClO(4). Crystallinity and free ion concentration change with the variation of CuO concentration. The maximum ionic conductivity is observed for 10 wt.% CuO. Ionic conductivity follows Arrhenius type behavior as a function of temperature.     

Optimal non-linear dimension reduction scheme for classical molecular dynamics

The optimal creation of a reduced space that effectively captures the long timescale dynamics of a non-linear molecular system over a range of frequencies is described. The technique builds on a previously developed subspace method based on linear constant projective transformation of the original full space. The present work attempts to propose transformation that are spatially dependent thereby leading to an effective subspace for better representing the dynamics of interests. The algorithm seeks out an optimal transformation consistent with desired low frequency motion in a rather general way. The method is demonstrated for a six-dimensional nonlinear system reduced to two-dimensions. Superior performance is found in evaluating ensemble-averaged classical dynamical properties.     

High-spin [2 x 2] [Fe(III)2Ni(II)2] heterometallic square grid with an S = 3 ground state

A [2 x 2] heterometallic [Fe(III)2Ni(II)2] ferrimagnetic, square-grid complex has been synthesized by the self-assembly reaction of a mononuclear Fe(III) precursor with Ni(NO3)2. Intramolecular antiferromagnetic exchange through the resulting hydrazone O-bridging framework (M-O-M 133.3-136.4 degrees) leads to an S = 3 ground state. Structural and magnetic properties are discussed.     

The disorder of perfluoroalkyl chains in crystals: Two case histories of interpretation and refinement

Perfluoroalkyl chains in solids are highly disordered in a wide range of temperatures. Poor attention is typically given to this problem in crystallographic studies to the point that no attempt is frequently made in order to model the collected data and disorder remains even unmentioned in a large number of single crystal reports. This paper presents a short analysis of the problems related with this disorder. Two simple crystal structures, namely the halogen bonded adducts between N,N,N′,N′-tetramethyl-1,4-phenylendiamine and α,ω-diiodoperfluorobutane or α,ω-diiodoperfluorohexane are discussed in details in order to suggest some simple and basic principles for the refinement of perfluoroalkyl chains in single crystal structural studies.     

Ultrafast photoinduced electron transfer in the micelle and the gel phase of a PEO-PPO-PEO triblock copolymer

Ultrafast photoinduced electron transfer (PET) from N,N-dimethylaniline (DMA) to coumarin dyes is studied in the micelle and the gel phase of a triblock copolymer, (PEO)(20)-(PPO)(70)-(PEO)(20) (Pluronic P123) by picosecond and femtosecond emission spectroscopies. The rate of PET in a P123 micelle and gel is found to be nonexponential and faster than the slow components of solvation dynamics. In a P123 micelle and gel, PET occurs on multiple time scales ranging from a subpicosecond time scale to a few nanoseconds. In the gel phase, the highest rate constant (9.3 x 10(9) M(-1) s(-1)) of ET for C152 is about two times higher than that (3.8 x 10(9) M(-1) s(-1)) observed in micelle phase. The ultrafast components of electron transfer (ET) exhibits a bell shaped dependence with the free energy change which is similar to the Marcus inversion. Possible reasons for slower PET in P123 micelle compared to other micelles and relative to P123 gel are discussed.     

Improvement in nanoscale contact resistance of alumina

In all contact-related applications such as the wear-resistant inserts, biomedical implants, high strain rate impact-resistant plates, etc., nanohardness, i.e. the intrinsic contact resistance at the nano scale, plays a major role. In spite of the wealth of literature, the studies on nanohardness of dense, coarse-grain alumina ceramics which represent many commercial varieties; have reasonably good hardness at the macro scale and characteristically exhibit R-curve behaviour, are far from significant. Here, to the best of our knowledge, we report for the first time the experimental observations of the increase in intrinsic contact resistance at the nano scale with the loading rate applied to a high-density (～95?% of theoretical) coarse-grain (～20?μm) alumina ceramics. These observations were explained in terms of the initiation of nanoscale plasticity and maximum shear stress generated just underneath the nanoindenter.     

Non-linearity parameter B/A of binary liquid mixtures at elevated pressures

When sound waves of high amplitude propagate, several non-linear effects occur. Ultrasonic studies in liquid mixtures provide valuable information about structure and interaction in such systems. The present investigation comprises of theoretical evaluation of the acoustic non-linearity parameter B/A of four binary liquid mixtures using Tong and Dong equation at high pressures and T=303.15 K. Thermodynamic method has also been used to calculate the non-linearity parameter after making certain approximations.     

Ultrasonic velocity of binary systems at elevated pressures

Various empirical theories of ultrasonic velocity have been applied to three binary liquid mixtures, under pressures up to 200 MPa and their validity have been tested. A pressure dependent study of ultrasonic velocities has been made at 303.15 K. The agreement between theory and experiment is found to be quite satisfactory.     

Current gain and external quantum efficiency modeling of GeSn based direct bandgap multiple quantum well heterojunction phototransistor

This paper aims to provide the performance characteristics of proposed, strain balanced direct band gap multiple quantum wells (MQWs) hetero phototransistor (HPT) made of SiGeSn/GeSn alloys grown on Si substrate which is compatible with recent CMOS fabrication technology. This also presents a comprehensive comparison of this proposed structure with the existing HPT structure made of indirect gap Ge/SiGe MQWs. Alloys of Ge and Sn grown on Si platform shows about tenfold increase in absorption over Ge at C and L-bands due to direct nature of band gap in GeSn. Initial work begins the solution of continuity equation to solve the different terminal current densities and optical gain of the multiple quantum well structure. Main analysis was concentrated on finding the external quantum efficiency depending on the doping variations of emitter and base, base width etc. Finally the photocurrent density variations are estimated for the structure and compared with existing indirect band gap HPT. The calculated values for direct band gap GeSn HPT device are found to be comparable with those for indirect band gap SiGe device to flourish as a potential candidate of photo detectors for the present day telecommunication network.