Effects of the bond dilution on the phase diagrams of a spin-1 transverse Ising model with crystal field interaction on a honeycomb lattice

A bond diluted spin-1 Ising model with crystal and transverse field interactions is examined for honeycomb lattice by introducing an effective field approximation that takes into account the correlations between different spins that emerge when expanding the identities. The effects of the crystal field as well as the transverse field and dilution on the phase diagrams and order parameter m_z are discussed in detail. A number of interesting and unusual phenomena such as reentrant phenomena and three successive phase transitions originating from the crystal field as well as the transverse field and bond dilution have been found.     

Understanding microscopic binding of human microsomal prostaglandin E synthase-1 with substrates and inhibitors by molecular modeling and dynamics simulation

Microsomal prostaglandin E synthase-1 (mPGES-1) is a promising target for development of next-generation anti-inflammatory drugs. It is crucial for rational design of the next-generation anti-inflammatory drugs to know the three-dimensional (3D) structure of mPGES-1 trimer and to understand how mPGES-1 binds with substrates and inhibitors. In the current work, a 3D structural model of human mPGES-1 trimer has been developed, for the first time, by performing combined homology modeling, molecular docking, and molecular dynamics simulation. The 3D structural model enables us to understand how mPGES-1 binds with its substrates/inhibitors, and the key amino acid residues for the mPGES-1 binding with ligands have been identified. The detailed 3D structures and calculated binding free energies for mPGES-1's binding with substrates and inhibitors are all consistent with available experimental data, suggesting that the 3D model of the mPGES-1 trimer and the enzyme-ligand binding modes are reasonable. The new structural insights obtained from this study should be valuable for rational design of next-generation anti-inflammatory drugs.     

KINETICS AND MECHANISM OF THE REACTION BETWEEN OLIGOSILOXANES AND P-TRICHLORO-N-DICHLOROPHOSPHORYL MONOPHOSPHAZENE (Cl3P[dbnd]N-POCl2)

Abstract

³¹P NMR investigation has been made of the action of Cl₃P[dbnd]N-POCl₂(I) first on hexamethyldisiloxane (Me₃Si)₂O and then on oligosiloxanes Me₃Si-(OSiMe₂)_n-OSiMe₃ n = 2 and n=3. The reactions were carried out in bulk or in solution with molar ratios siloxane/(I) varying from I to 5. It was demonstrated that only the monosubstitution of a chlorine atom by the -(OSiMe₂)_n,-OSiMe₃ species n = 0, 2, 3 with elimination of trimethylchlorosilane occurred leading to the derivatives Cl₂OP-N[dbnd]PCl₂O(SiMe₂-O)_nSiMe₃ (II). For n=2, 3 the siloxane redistribution reactions were observed by ²⁹Si NMR analysis. A two steps mechanism is proposed. consisting in a nucleophilic substitution, involving a tricoordinate phosphazenium intermediate, followed by the formation of an active ionic centre probably an oxonium ion, arising from the solvatation by the siloxane of this phosphazeniurn ion and /or of (II) leading to the redistribution reactions. The influences of the solvent, of trimethylchlorosilane, of the temperature, and of the addition of a protonated species (MDH) were investigated.     

Kinetics and mechanism of the reactions of Pd(II) complexes with azoles and diazines. Crystal structure of [Pd(bpma)(H2O)](ClO4)2.2H2O

Substitution reactions of the complexes [Pd(bpma)(H2O)]2+, [Pd(bpma)Cl]+, [Pd(dien)(H2O)]2+ and [Pd(dien)Cl]+, where bpma = bis(2-pyridylmethyl)amine and dien = diethylentriamine or 1,5-diamino-3-azapentane, with some nitrogen-donor ligands such as triazole, pyrazole, pyrimidine, pyrazine and pyridazine, were studied in an aqueous 0.10 M NaClO4 at pH 2.8 using variable-temperature and -pressure stopped-flow spectrophotometry. The second-order rate constants indicate that the Pd(II) complexes of bpma, viz. [Pd(bpma)(H2O)]2+ and [Pd(bpma)Cl]+, are more reactive than the complexes of dien, viz. [Pd(dien)(H2O)]2+ and [Pd(dien)Cl]+. Also, the aqua complexes, [Pd(bpma)(H2O)]2+ and [Pd(dien)(H2O)]2+, are much more reactive than the corresponding chloro complexes. The most reactive nucleophile of the five-membered rings is triazole and for the six-membered rings the most reactive one is pyridazine. Activation parameters were determined for all reactions and the negative entropies and volumes of activation (Delta S++, Delta V++) support an associative ligand substitution mechanism. The crystal structure of [Pd(bpma)(H2O)](ClO4)2.2H2O was determined by X-ray diffraction. Crystals are monoclinic with the space group P2(1)/c. The coordination geometry of [Pd(bpma)(H2O)]2+ is distorted square-planar. The Pd-N (central) bond distance, 1.958(5) A, is shorter than the other two Pd-N distances, 2.007(5) and 2.009(5) A. The Pd-O distance is 2.043(5) A.     

Investigation of the spectral content of a cw CO laser output using a high-resolution scanning Fabry-Perot interferometer

The use of a scanning Fabry-Perot interferometer of variable length (variable resolution) for investigating the output of a cw CO laser is reported. Under experimental conditions required to achieve maximum power it was found that the laser output consisted of two or more simultaneously occuring transitions due to the overlapping nature of the vibration- rotation bands. The frequency differences between these transitions were measured to an accuracy of 0.01 cm^-1. Operation of the CO laser on a single vibration-rotation transition was obtained by controlling the laser gain with the experimental variables of discharge pressure, gas temperature, and optical alignment. An alternative approach of obtaining monochromatic radiation, by using a Fabry-Perot interferometer as a frequency selective filter external to the CO laser, is reported.