Spectroscopic and electronic structure studies of intermediate X in ribonucleotide reductase R2 and two variants: a description of the FeIV-oxo bond in the FeIII-O-FeIV dimer

Spectroscopic and electronic structure studies of the class I Escherichia coli ribonucleotide reductase (RNR) intermediate X and three computationally derived model complexes are presented, compared, and evaluated to determine the electronic and geometric structure of the FeIII-FeIV active site of intermediate X. Rapid freeze-quench (RFQ) EPR, absorption, and MCD were used to trap intermediate X in R2 wild-type (WT) and two variants, W48A and Y122F/Y356F. RFQ-EPR spin quantitation was used to determine the relative contributions of intermediate X and radicals present, while RFQ-MCD was used to specifically probe the FeIII/FeIV active site, which displayed three FeIV d-d transitions between 16,700 and 22,600 cm(-1), two FeIV d-d spin-flip transitions between 23,500 and 24,300 cm(-1), and five oxo to FeIV and FeIII charge transfer (CT) transitions between 25,000 and 32,000 cm(-1). The FeIV d-d transitions were perturbed in the two variants, confirming that all three d-d transitions derive from the d-pi manifold. Furthermore, the FeIV d-pi splittings in the WT are too large to correlate with a bis-mu-oxo structure. The assignment of the FeIV d-d transitions in WT intermediate X best correlates with a bridged mu-oxo/mu-hydroxo [FeIII(mu-O)(mu-OH)FeIV] structure. The mu-oxo/mu-hydroxo core structure provides an important sigma/pi superexchange pathway, which is not present in the bis-mu-oxo structure, to promote facile electron transfer from Y122 to the remote FeIV through the bent oxo bridge, thereby generating the tyrosyl radical for catalysis.     

Synthesis of ZnO2 nanoparticles by laser ablation in liquid and their annealing transformation into ZnO nanoparticles

A pulsed laser emitting UV radiations generated by the third harmonic of Nd:YAG was applied for the synthesis of nano-structured ZnO₂ and ZnO. For the synthesis of nanoparticles of ZnO₂, a high-purity metallic plate of Zn target was fixed at the bottom of a glass cell, in the presence of deionized water mixed with oxidizing agent H₂O₂, under repeated laser irradiation. The optical properties, size and the morphology of the synthesized ZnO₂ and ZnO by laser ablation was influenced strongly by post-annealing conditions which is not previously reported. By annealing ZnO₂ at 200 °C for 8 h, the product (ZnO₂) synthesized primarily was converted completely to ZnO. By variation of the annealing temperatures from 200 to 600 °C, the grain size of ZnO changes from 5 to 19 nm with a change in lattice parameters, the band gap and some other optical properties of nano-ZnO.     

The influence of boron concentrations on structural properties in disorder silicon films

In this work we present a detailed structural of a series of B-doped hydrogenated microcrystalline silicon (μc-Si:H) films deposited by plasma-enhanced chemical vapor deposition (PECVD) and B-doped polycrystalline silicon (poly-Si) films produced by step-by-step laser crystallization process from amorphous silicon. The influence of doping on the structural properties and structural changes during the sequential crystallization processes were monitored by Raman spectroscopy. Unlike μc-Si:H films, that consist of a two-phase mixture of amorphous and ordered Si, partially crystallized sample shows a stratified structure with polycrystalline silicon layer at the top of an amorphous layer. With increasing doping concentration the LO-TO phonon line in poly-Si shift to smaller wave numbers and broadens asymmetrically. The results are discussed in terms of resonant interaction between optical phonons and direct intraband transitions known as a Fano resonance. In μc-Si:H films, on the other hand, the Fano effect is not observed. The increase of doping in μc-Si:H films suppressed the crystalline volume fraction, which leads to an amorphization in the film structure. The structural variation in both μc-Si:H and poly-Si films leads to a change in hydrogen bonding configuration.     

Observation on Symmetry Properties of Sodium Zinc(II)-2,9,16,23-phthalocyanine Tetracarboxylate in Water:NaOH Solution

The shift of the Q-band of sodium zinc(II)-2,9,16,23-phthalocyanine tetracarboxylate (ZnPc(COONa)₄) to about 800 nm is attributed to the influence of the electron-donating property of the carboxylate groups substituted in the β–position. ZnPc(COONa)₄ which was found to have a symmetry of D _2h characterized by a splitting of the Q transition. This splitting was interpreted by the formation of dianionic symmetric ZnPc(COONa)₄ resulting from the dissociation of the pyrrole protons as well as the possibility of Na⁺ dissolution of ZnPc(COONa)₄ in the aqueous solution of NaOH.     

A novel method for non-destructive Compton scatter imaging based on the genetic algorithm

Compton scattering tomography is widely used in numerous applications such as biomedical imaging, nondestructive industrial testing and environmental survey, etc. This paper proposes the use of the genetic algorithm (GA), which utilizes bio-inspired mathematical models, to construct an image of the insides of a test object via the scattered photons, from a voxel within the object. A NaI(Tl) scintillation detector and a 185 MBq ¹³⁷Cs gamma ray source were used in the experimental measurements. The obtained results show that the proposed GA based method performs well in constructing images of objects.     

Divergent reaction pathways for one-pot,three-component synthesis of novel 4H-pyrano[3,2-h]quinolines under ultrasound irradiation

The present paper deal with the multi-component condensation of 8-hydroxy quinoline, aromatic aldehydes, and sulfone derivatives catalyzed by p-toluenesulfonic acid for the synthesis of a series of 4H-pyrano[3,2-h]quinoline derivatives in ethanol under ultrasonic irradiations. We provide a series of quinoline derivatives containing sulfone moiety interesting for biological screening tests. The reactions were carried out under both conventional and ultrasonic irradiation conditions. In general, improvement in rates and yields were observed when reactions were carried out under sonication compared with classical silent conditions. Also, also, sonochemical reaction give different reaction pathway other than silent reaction. These remarkable effects appeared in sonicated reactions can be reasonably interpreted in terms of acoustic cavitation phenomenon. Structures of the products were established on analytical and spectral data.     

Infra-Red Study of Tautomerism in Some Schiff Bases.

Infra-Red spectra of a series of substituted salicylaldehyde and 2-hydroxy-naphthaldehyde Schiff bases were used to investigate enol-keto tautomeric equilibrium. Two model compounds, namely, salicylidinaniline and naphthylidinequinolineamine Schiff bases were used to represent the enol and keto forms, respectively. From the IR spectra of the model compounds it was possible to assign the IR absorption for the C=O and the C=N groups in both the keto and the enol form. It was also possible to assign other absorptions which were either specific to the keto or the enol forms. Specific pattern were observed for all the studied compounds.     

Charge-transfer complexes of barbiturates and phenytoin

Simple and sensitive spectrophotometric methods are described, for the first time, for the determination of sodium salts of phenobarbital (1), thiopental (2), methohexital (3) and phenytoin (4). The methods are based on the reaction of these drugs as n-electron donors with the sigma-acceptor iodine and various pi-acceptors: 7,7,8,8-tetracyanoquinodimethane; 2,3-dichloro-5,6-dicyano-1,4-benzoquinone; 2,3,5,6-tetrachloro-1,4-benzoquinone; 2,3,5,6-tetrafluoro-1,4-benzoquinone; 2,5-dichloro-3,6-dihydroxy-1,4-benzoquinone; tetracyanoethylene and 2,4,7-trinitro-9-fluorenon. Depending on the solvent polarity, different coloured charge-transfer complexes and radicals were developed. Different variables and parameters affecting the reactions were studied and optimized. The formed complexes were examined by UV/VIS, infrared and (1)H-NMR. Due to the rapid development of colours at ambient temperature, the obtained results were used on thin layer chromatograms for the detection of the investigated compounds. Beer's plots were obeyed in a general concentration range of 1-400 mug ml(-1) for the investigated compounds with different acceptors. Interference from some co-formulated drugs was also studied. No interference was observed due to additives commonly present in the pharmaceutical preparations. The proposed methods could be applied successfully to the determination of the investigated compounds in pure and pharmaceutical dosage forms with good accuracy and precision, the recoveries ranged from 98.7+/-0.5 to 101.1+/-0.5%. The results were compared favourably with the official methods.     

Variable coordination geometries at the diiron(II) active site of ribonucleotide reductase R2

The R2 subunit of Escherichia coli ribonucleotide reductase contains a dinuclear iron center that generates a catalytically essential stable tyrosyl radical by one electron oxidation of a nearby tyrosine residue. After acquisition of Fe(II) ions by the apo protein, the resulting diiron(II) center reacts with O(2) to initiate formation of the radical. Knowledge of the structure of the reactant diiron(II) form of R2 is a prerequisite for a detailed understanding of the O(2) activation mechanism. Whereas kinetic and spectroscopic studies of the reaction have generally been conducted at pH 7.6 with reactant produced by the addition of Fe(II) ions to the apo protein, the available crystal structures of diferrous R2 have been obtained by chemical or photoreduction of the oxidized diiron(III) protein at pH 5-6. To address this discrepancy, we have generated the diiron(II) states of wildtype R2 (R2-wt), R2-D84E, and R2-D84E/W48F by infusion of Fe(II) ions into crystals of the apo proteins at neutral pH. The structures of diferrous R2-wt and R2-D48E determined from these crystals reveal diiron(II) centers with active site geometries that differ significantly from those observed in either chemically or photoreduced crystals. Structures of R2-wt and R2-D48E/W48F determined at both neutral and low pH are very similar, suggesting that the differences are not due solely to pH effects. The structures of these "ferrous soaked" forms are more consistent with circular dichroism (CD) and magnetic circular dichroism (MCD) spectroscopic data and provide alternate starting points for consideration of possible O(2) activation mechanisms.