An unexpected P-cluster like intermediate en route to the nitrogenase FeMo-co

The nitrogenase MoFe protein contains two different FeS centers, the P-cluster and the iron–molybdenum cofactor (FeMo-co). The former is a [Fe₈S₇] center responsible for conveying electrons to the latter, a [MoFe₇S₉C-(R)-homocitrate] species, where N₂ reduction takes place. NifB is arguably the key enzyme in FeMo-co assembly as it catalyzes the fusion of two [Fe₄S₄] clusters and the insertion of carbide and sulfide ions to build NifB-co, a [Fe₈S₉C] precursor to FeMo-co. Recently, two crystal structures of NifB proteins were reported, one containing two out of three [Fe₄S₄] clusters coordinated by the protein which is likely to correspond to an early stage of the reaction mechanism. The other one was fully complemented with the three [Fe₄S₄] clusters (RS, K1 and K2), but was obtained at lower resolution and a satisfactory model was not obtained. Here we report improved processing of this crystallographic data. At odds with what was previously reported, this structure contains a unique [Fe₈S₈] cluster, likely to be a NifB-co precursor resulting from the fusion of K1- and K2-clusters. Strikingly, this new [Fe₈S₈] cluster has both a structure and coordination sphere geometry reminiscent of the fully reduced P-cluster (P^N-state) with an additional μ²-bridging sulfide ion pointing toward the RS cluster. Comparison of available NifB structures further unveils the plasticity of this protein and suggests how ligand reorganization would accommodate cluster loading and fusion in the time-course of NifB-co synthesis.

The K-cluster of NifB as a key intermediate in the synthesis of the nitrogenase active site supports [Fe₄S₄] cluster fusion occurs before carbide and sulfide insertion and displays ligand spatial arrangement reminiscent to that of the P-cluster.     

Study of polycrystalline bulk CuIn1-xGaxTe2

Polycrystalline CuIn_1−xGa_xTe₂ bulk films were synthesized by reacting, in stoichiometric proportions, high purity Cu, In, Ga and Te in a vacuum sealed quartz ampoule. The phase structure and composition of the bulk films were analysed by X-ray diffraction and energy-dispersive X-ray analysis, respectively. The bulk samples, of p-type conductivity, are found to be near-stoichiometric, polycrystalline, with tetragonal chalcopyrite structure, predominantly oriented along a direction perpendicular to the (1 1 2) plane. Photoluminescence spectra were recorded at 7 K and 700 mW to characterize the defects and the structural quality. The main peak as a function of composition has been studied.     

Crack Tip Opening Angle as a Fracture Resistance Parameter to Describe Ductile Crack Extension and Arrest in Steel Pipes under Service Pressure

The angle between two element sides representing the crack tip is defined as the crack tip opening angle (CTOA). Its critical value is used as a criterion of fracture resistance for characterizing stable tearing in thin metallic materials. Various methods are used for determination of the CTOA. Optical microscopy is one of the most common methods as well as fitting of experimental load-displacement diagrams by the finite element method (DIC). Additionally, analytical analysis using the experimental load-displacement curve method (SSM) derived from the plastic hinge model of deflection in three-point bending of a ductile specimen is applied. This approach assumes a constant rotation centre distance. Values of CTOA for API 5L X65 pipe steel found by three methods—DIC, CNM, and SSM—are given. Values of CTOA given by these three methods are similar and close to 20°. A discussion on the different parameters used to characterize the fracture resistance of running cracks in a pipe under service pressure is presented. The energy of fracture at impact determined by Charpy or drop-weight tear test (DWTT) tests and the critical J energy parameter are considered as well as the yield locus after damage, cohesive zone energy, and CTOA is another approach. One notes that CTOA is assumed to be constant during stable crack extension and decreases linearly with crack length during the instable and primary phase. A numerical technique to describe a ductile running crack using the node release technique and using CTOA as the fracture resistance criterion is presented. This method is compared with three different two-curve methods (TCMs): the Battelle, high strength line pipe (HLP), and HLP-Sumitomo methods. The Batelle TCM, as the oldest method, based on Charpy energy, gives a strongly conservative prediction. Predictions by the CTOA method are close to those obtained by the HLP-Sumitomo one.     

The development and validation of a novel LC–MS/MS method for the quantification of cenicriviroc in human plasma and cerebrospinal fluid

A high-performance liquid chromatography tandem mass spectrometric method was developed and validated for cenicriviroc (CVC) quantification in human plasma and cerebrospinal fluid (CSF). The method involved precipitation with acetonitrile and injecting supernatants onto the column. Separation was achieved on an XBridge C₁₈ column with a gradient elution of 0.1% formic acid in water and acetonitrile. Analyte detection was conducted in positive ion mode using selected reaction monitoring. The m/z transitions were: CVC (697.3 → 574.3) and CVC-d7 (704.4 → 574.3). Calibration curve ranged from 5 to 1000 ng/mL for plasma and from 0.241 to 15.0 ng/mL for CSF. The intra- and inter-day precision and accuracy were <15% for both plasma and CSF across four different concentrations. CVC recovery from plasma and artificial CSF was >90%. The method was utilized for the measurement of patients’ plasma and CSF samples taking a dose of 50, 150 and 300 mg q.d.     

C70X2(X=H,F, Cl)的稳定性和电子光谱

用INDO方法研究C70H2四种异构体的稳定性, 表明其最稳定异构体为1, 9-C70H2和7, 8-C70H2, 两者能量差为16.3KJ.mol^-^1, 与实验值及ab initio计算值接近; 光谱计算表明, 其特征吸收峰与实验值一致。在此基础上预测C70F2和C70Cl2的稳定性和电子光谱, 表明C70F2四种异构体的稳定性顺序与C70H2一致, 而C70Cl2则以21, 42-异构体最为稳定。二者的电子光谱与C70H2极其相似只是在500nm以上有细微差别。     

Antibacterial cotton fabrics with in situ generated silver and copper bimetallic nanoparticles using red sanders powder extract as reducing agent

Using aqueous extraction of red sanders powder as a reducing agent, silver and copper bimetallic nanoparticles were in situ generated in cotton fabrics. Silver and copper nanoparticles were also generated separately for comparison. The resulted nanocomposite cotton fabrics (NCFs) were characterized by Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), X-ray diffraction (XRD), thermogravimetric analysis (TGA), and antibacterial tests. SEM analysis indicated the generation of more number of nanoparticles when bimetallic source solutions were used. Further, the size range of the generated bimetallic nanoparticles was found to be lower than when individual metal nanoparticles were generated in NCFs. XRD analysis confirmed the in situ generation of silver and copper nanoparticles when equimolar bimetallic salt source solutions were utilized. The NCFs with bimetallic nanoparticles exhibited higher antibacterial activity against both Gram-negative and Gram-positive bacteria and hence can be considered for applications as antibacterial bed and dressing materials.     

Estimation of background radiation levels and associated health risks in mineral rich district Chiniot,Pakistan

The mineral extraction activities may disturb the natural radioactivity, therefore current study aims to generate baseline data of natural radionuclides and anthropogenic ¹³⁷Cs before the start of industrial activities. Gamma spectrometry and gross alpha and beta counting systems were used for activity measurement in environmental samples. In soil, the mean activity of ²³²Th, ²²⁶Ra, ⁴⁰K and ¹³⁷Cs were determined as 79 (66–117), 47 (34–80), 823 (602–1159) and 1.3 (1.1–4.5) Bq kg^?1, respectively. The average annual effective dose rate (128.7 µSv h^?1) in the study area was twice higher than world’s average value. Indoor hazard index was greater than unity at two places; therefore, proper ventilation is proposed during construction.

     

Comparative Study of Alkali-Cation-Based (Li+, Na+, K+) Electrolytes in Acetonitrile and Alkylcarbonates

The development of a suitable functional electrolyte is urgently required for fast-charging and high-voltage alkali-ion (Li, Na, K) batteries as well as next-generation hybrids supercapacitors. Many recent works focused on an optimal selection of electrolytes for alkali-ion based systems and their electrochemical performance but the understanding of the fundamental aspect that explains their different behaviour is rare. Herein, we report a comparative study of transport properties for LiPF₆, NaPF₆, KPF₆ in acetonitrile (AN) and a binary mixture of ethylene carbonate (EC), dimethyl carbonate (DMC): (EC/DMC : 1/1, weigh) through conductivities, densities and viscosities measurements in wide temperature domain. By application of the Stokes-Einstein, Nernst-Einstein, and Jones Dole equations, the effective ionic solvated radius of cation (r_eff), the ionic dissociation coefficient (α_D) and structuring Jones Dole's parameters (A, B) for salt are calculated and discussed according to solvent or cation nature as a function of temperature. From the results, we demonstrate that better mobility of potassium can be explained by the nature of the ion-ion and ion-solvent interactions due to its polarizability. In the same time, the predominance of triple ions in the case of K⁺, is a disadvantage at high concentration.     

Synthesis and characterization of ferromagnetic Fe3C/C composite nanoparticles as a catalyst for carbon nanotube growth

Polystyrene template microspheres of narrow size distribution were prepared by dispersion polymerization of styrene in a mixture of ethanol and 2-methoxy ethanol. These template particles dispersed in aqueous solution have been used for the entrapment of ferrocene by a swelling process of methylene chloride emulsion droplets containing ferrocene within these particles, followed by evaporation of methylene chloride. The effects of CH₂Cl₂ volume and the [CH₂Cl₂]/[FeC₁₀H₁₀] (w/w) ratio on the size and size distribution of the swollen template particles were elucidated. Air-stable Fe₃C nanoparticles embedded in amorphous carbon matrix (Fe₃C/C) have been prepared by thermal decomposition of the ferrocene-swollen template polystyrene particles at 500 °C for 2 h in a sealed cell. Decomposition of these swollen template particles for 2 h at higher temperatures led to the formation of carbon nanotubes (CNTs) in addition to the Fe₃C/C composite nanoparticles. The yield of the CNTs increased as the annealing temperature was raised. An opposite behavior was observed for the diameter of the formed CNTs. The size and size distribution, crystallinity, and magnetic properties of the different Fe₃C/C composite nanoparticles have also been controlled by the annealing temperature.