Atmospheric degradation mechanisms of a simulant organophosphorus pesticide isopropyl methyl methylphosphonate: A theoretical consideration

Calculations using density functional theory were performed to explore the mechanisms for atmospheric degradation of isopropyl methyl methylphosphonate (IMMP). The potential energy surface profiles for OH‐initiated reaction of IMMP were constructed, and all possible degradation channels were considered. Rate constants were further calculated using transition state theory. It was established from these calculations that H‐abstractions from alkyl groups have much lower energy barriers than substitutions of alkoxyl groups, and four possible H‐abstraction channels are competitive. Investigations into the secondary reactions under the presence of O₂/NO were also performed. It is shown that O₂ addition, reaction of peroxide radicals with NO to form RO radicals, and removal of ·RO are the major degradation pathways for alkyl radicals. Four selected products, CH₃OP(O)(CH₃)OC(O)CH₃, CH₃OP(O)(O)CH₃, (CH₃)₂CHOP(O)(CH₃)OH, and (CH₃)₂CHOP(O)(CH₃)OCH?O, are predicted to be the major products in this study. © 2013 Wiley Periodicals, Inc.     

Computational studies on the injection,transport, absorption,and phosphoresce properties of a series of cationic iridium (III) complexes [Ir(C∧N)2(L)2]+ (C∧N = ppy,tpy, dfppy,bzq)

Quantum chemistry methods are applied to investigate the electronic structures, injection and transport properties, absorption and phosphorescence mechanism of a series of Iridium (III) complexes [Ir(C∧N)₂(L)₂]⁺ (L = 4‐pyCO₂Et; C∧N = 2‐phenylpyridine, 1 ; 2‐(4‐tolyl)pyridine, 2 ; 2‐(4,6‐difluorophenyl)pyridimato, 3 ; benzoquinoline, 4 ), which may be used as emitters on organic light emitting diodes (OLEDs). Calculations of ionization potentials and electron affinities are used to evaluate the injection abilities of holes and electrons into these complexes. The reorganization energy (λ) calculations show that the four complexes are suitable as emitters in OLEDs. The absorptions and emissions can be tuned by adding substituent to the ppy ligand or extending the π‐conjugation effect of the C∧N ligand, and quantum yields of 1 – 4 are investigated. In addition, no solvent effect is observed in the absorption and emission spectra. © 2012 Wiley Periodicals, Inc.     

Calculations of dynamic dipole polarizabilities of Li and Na atoms in debye plasma using the model potential technique

The effects of Debye plasma on the frequency‐dependent polarizabilities of Li and Na atoms are investigated using symplectic algorithm within the framework of the pseudostate summation technique. Dynamic dipole polarizabilities of Li (2s ²S) and Na(3s ²S) as functions of scaled number density of the plasma electrons for arbitrary plasma temperature are presented. Screening effects on the resonance frequencies are also presented. In free‐atomic cases, our calculated results are comparable with the reported theoretical and experimental predictions. © 2012 Wiley Periodicals, Inc.     

H2S splitting on Cu(110): Insight from combined periodic density functional theory calculations and microkinetic simulation

Practical copper (Cu)‐based catalysts for the water–gas shift (WGS) reaction was long believed to expose a large proportion of Cu(110) planes. In this work, as an important first step toward addressing sulfur poisoning of these catalysts, the detailed mechanism for the splitting of hydrogen sulfide (H₂S) on the open Cu(110) facet has been investigated in the framework of periodic, self‐consistent density functional theory (DFT‐GGA). The microkinetic model based on the first‐principles calculations has also been developed to quantitatively evaluate the two considered decomposition routes for yielding surface atomic sulfur (S*): (1) H₂S → H₂S* → SH* → S* and (2) 2H₂S → 2H₂S* → 2SH* → S* + H₂S* → S* + H₂S. The first pathway proceeding through unimolecular SH* dissociation was identified to be feasible, whereas the second pathway involving bimolecular SH* disproportionation made no contribution to S* formation. The molecular adsorption of H₂S is the slowest elementary step of its full decomposition, being related with the large entropy term of the gas‐phase reactant under realistic reaction conditions. A comparison of thermodynamic and kinetic reactivity between the substrate and the close‐packed Cu(111) surface further shows that a loosely packed facet can promote the S* formation from H₂S on Cu, thus revealing that the reaction process is structure sensitive. The present DFT and microkinetic modeling results provide a reasonably complete picture for the chemistry of H₂S on the Cu(110) surface, which is a necessary basis for the design of new sulfur‐tolerant WGS catalysts. © 2013 Wiley Periodicals, Inc.     

Mechanism of aziridination of styrene catalyzed by copper(I) bis(oxazoline)

Experimental studies show that copper complexes can be effectively anchored onto the pores of mesoporous solids, having a good catalytic performance in several reactions, among them the aziridination of olefins and in particular, styrene. In this work, the mechanism of the aziridination of styrene catalyzed by a bis(oxazoline) copper(I) complex was studied in detail by means of density functional theory (DFT) calculations. For such reactions in the homogeneous phase, our calculations revealed a wide diversity of reaction‐pathways, which have not been considered in previous studies, and should be taken into account due to the small energy differences between them. What is more, our results show that there is a strong dependence on the chosen DFT functional. This has profound implications on the way the heterogeneous reaction is studied. © 2013 Wiley Periodicals, Inc.     

Inactivation of Vaccinia Virus by Natural Sunlight and by Artificial UVB Radiation

This study determined the sensitivity of vaccinia virus, an orthopox virus commonly used as a surrogate for variola virus (etiological agent of smallpox), exposed to UVB radiation emitted by a solar simulator, or to direct natural sunlight. The data obtained indicate that: (1) the virucidal effect of natural sunlight can be mimicked adequately by an artificial light source with similar spectral characteristics in the UVB, (2) viral sensitivity to UVB or to solar radiation can be correlated with experimental data previously obtained with UVC, (3) the correlation factor between virus inactivation by solar radiation (measured at 300 ± 5 nm) and by UVC (254 nm) is between 33 and 60, and (4) the sensitivity of viruses either dry on glass surfaces or in liquid suspension is similar when in the presence of similar amounts of cellular debris and growth media. The findings reported in this study should assist in estimating the threat posed by the persistence of virus during epidemics or after an accidental or intentional release.     

Low‐level Laser Therapy Ameliorates CCl4‐induced Liver Cirrhosis in Rats

This study investigated the effects of low‐level laser therapy (LLLT) in the liver function, structure and inflammation in a experimental model of carbon tetrachloride (CCl₄)‐induced liver cirrhosis. Wistar rats were divided into Control, LLLT, CCl₄ and CCl₄+LLLT groups. CCl₄ groups received CCl₄ (0.4 g kg^?1; i.p.), three times a week, for 12 weeks. A 830 nm LLLT was performed with a continuous wave, 35 mW, 2.5 J cm^?2 per point, applied to four points of the liver (right and left upper and lower extremities, in the four lobes of the liver) for 2 weeks. Liver structure and inflammation (cirrhotic areas, collagen deposition, inflammation, density of Kupffer and hepatic stellate cells) and function (aspartate aminotransferase, alkaline phosphatase, gamma glutamyltransferase, lactate dehydrogenase, total proteins and globulins) were evaluated. LLLT significantly reduced CCl₄‐increased aspartate aminotransferase (P < 0.001), alkaline phosphatase (P < 0.001), gamma‐glutamyl transferase (P < 0.001) and lactate dehydrogenase (P < 0.01) activity, as well as total proteins (P < 0.05) and globulins (P < 0.01). LLLT also reduced the number of cirrhotic areas, the collagen accumulation and the hepatic inflammatory infiltrate. Of note, LLLT reduced CCl₄‐increased number of Kupffer cells (P < 0.05) and hepatic stellate cells (P < 0.05). We conclude that LLLT presents beneficial effects on liver function and structure in an experimental model of CCl₄‐induced cirrhosis.     

Low‐Level Laser Therapy Restores the Oxidative Stress Balance in Acute Lung Injury Induced by Gut Ischemia and Reperfusion

It remains unknown if the oxidative stress can be regulated by low‐level laser therapy (LLLT) in lung inflammation induced by intestinal reperfusion (i‐I/R). A study was developed in which rats were irradiated (660 nm, 30 mW, 5.4 J) on the skin over the bronchus and euthanized 2 h after the initial of intestinal reperfusion. Lung edema and bronchoalveolar lavage fluid neutrophils were measured by the Evans blue extravasation and myeloperoxidase (MPO) activity respectively. Lung histology was used for analyzing the injury score. Reactive oxygen species (ROS) was measured by fluorescence. Both expression intercellular adhesion molecule 1 (ICAM‐1) and peroxisome proliferator‐activated receptor‐y (PPARy) were measured by RT‐PCR. The lung immunohistochemical localization of ICAM‐1 was visualized as a brown stain. Both lung HSP70 and glutathione protein were evaluated by ELISA. LLLT reduced neatly the edema, neutrophils influx, MPO activity and ICAM‐1 mRNA expression. LLLT also reduced the ROS formation and oppositely increased GSH concentration in lung from i‐I/R groups. Both HSP70 and PPARy expression also were elevated after laser irradiation. Results indicate that laser effect in attenuating the acute lung inflammation is driven to restore the balance between the pro‐ and antioxidants mediators rising of PPARy expression and consequently the HSP70 production.