Computational studies on the radiative and nonradiative processes of luminescent N-heteroleptic platinum(II) complexes

Three N-heteroleptic Pt(II) complexes, [Pt(C^C)(O^O)] [O^O = acetylacetonate, C^C = 1-phenyl-1,2,4-triazol-5-ylidene (1), C^C = 4-phenyl-1,2,4-triazol-5-ylidene (2), C^C = 2-phenylpyrazine (3)] have been investigated with density functional theory (DFT) and time-dependent density functional theory (TDDFT). The radiative decay rate constants of complexes 1–3 have been discussed with the oscillator strength (f_n), the strength of spin–orbit coupling (SOC) interaction between the lowest energy triplet excited state (T₁) and singlet excited states (S_n), and the energy gaps between E(T₁) and E(S_n). To illustrate the nonradiative decay processes, the transition states between triplet metal-centered (³MC) and T₁ states have been optimized and were verified with the calculations of vibrational frequencies and intrinsic reaction coordinate (IRC). In addition, the minimum energy crossing points (MECPs) between ³MC and ground states (S₀) were optimized. At last, the potential energy curves relevant to the nonradiative decay pathways are simulated. The results show that complex 3 has the biggest photoluminescence quantum yield because the complex 3 has the biggest radiative decay rate constant and the smallest nonradiative decay rate constant in complexes 1–3.     

Valorisation of waste fractions from autohydrolysis of selected lignocellulosic materials

Non‐isothermal processing of lignocellulosic materials in aqueous media (autohydrolysis reaction) under mild conditions leads to solutions containing valuable chemicals (oligosaccharides, sugars and acetic acid) and other, undesired, compounds (belonging to the extractive and acid‐soluble lignin fractions) which have to be removed in further purification treatments. Liquors obtained by non‐isothermal autohydrolysis of Eucalyptus globulus wood and corncobs under a variety of operational conditions were extracted with ethyl acetate in order to remove non‐saccharide components, and the suitability of the fraction dissolved in the organic phase was assayed for possible utilisation as an antioxidant. The yield and antioxidant activity of ethyl acetate extracts (measured by the α,α‐diphenyl‐β‐picrylhydrazyl (DPPH) radical scavenging capacity) showed a strong dependence on the autohydrolysis conditions. The antioxidant activity of extracts obtained under selected operational conditions compared well with synthetic antioxidants. © 2003 Society of Chemical Industry     

Immobilization and activation of vanadium(III) and titanium(III) single‐site catalysts for ethylene polymerization using MgCl2‐based supports

Significant increases in the activity of vanadium(III) amidinate catalysts for ethylene polymerization have been obtained by immobilization on a MgCl₂‐based support prepared by reaction of AlEt₃ with a MgCl₂/ethanol adduct. Catalyst immobilization and activation on this type of support prevents the rapid decay in activity observed under homogeneous polymerization conditions with unsupported catalysts. Stable polymerization activity is also observed with analogous titanium(III) complexes. Polyethylene with narrow molecular weight distribution and spherical particle morphology is obtained without reactor fouling. Copyright © 2005 Society of Chemical Industry     

Comparison of copper emission rates from wood treated with different preservatives to the environment

This study describes a laboratory method for the estimation of emission from preservative-treated wood in the different situations where emissions could enter the environment for use classes 3 (not in contact with ground) and 4 and 5 (in contact with the ground, fresh water or sea water) according to OECD Guidelines. Samples of scotch pine sapwood (Pinus sylvestris L.) were treated with CCA (1% and 2%), ACQ-1900 (3% and 7%), ACQ-2200 (2%), Tanalith E 3491 (2% and 2.8%), and Wolmanit CX-8 (2%).     

Studies of photoconductivity in β-Apo-8′ carotenal

The photoconductive properties of a carotenoid polyene,β-Apo-8′ carotenal in polycrystalline form has been studied. The growth of the photocurrent shows an overshoot in the growth-time curve before steady state value is attained. This behaviour of photocurrent is proposed to be due to higher value of recombination coefficient than trapping coefficient. From the temperature dependence study it is observed that the steady state photocurrent, at first increases with increase of temperature, attains a maximum at a particular temperatureT _max and then decreases with temperature. TheT _max value agrees with the temperature above and below which steady state photocurrent is attained differently. Monomolecular and bimolecular recombination processes at two temperature regimes are proposed to account for the observed behaviour. The dependence of photocurrent with excitation light intensity and wavelength study provide information on the carrier generation processes. The fast decay of photocurrent have been observed at different temperatures and from this study the decay constant is calculated and it is found to be temperature independent.     

Air Filtration and Radon Decay Product Mitigation

Air cleaning as a means of mitigating the risks arising from exposure to indoor radon progeny has been evaluated in a single-family house in the north eastem US. using an automated, semi-continuous activity-weighted size distribution measurement system. The measurements included radon concentration, condensation nuclei count, and activity-weighted size distribution of radon decay products. Measurements were made in the house with and without an operating air filtration system and with various particle sources common to normal indoor activities operating. Aerosols were generated by running water in a shower, candle burning, cigarette smoking, vacuuming, opening doors, and cooking. Using a room model, the changes in attachment rates, average attachment diameters, and deposition rates of the unattached fraction with and without the air cleaning system were calculated. In the presence of active aerosol sources, the air filtration unit typically reduced the concentration of particles within the hour following the end of particle generation. After candle burning, cigarette smoking, and vacuuming in the bedroom, the reductions of PAEC by air filtration are about 60% with the air filtration system operating in the bedroom. During cooking in the kitchen, the reductions of PAEC in the bedroom with the air filtration system were about 40%. However, for all cases the dose reductions were smaller than the particle and PAEC reductions. For those particles that were generated within the bedroom, there was a 20% to 50% reduction in dose. In the case of cooking where the door was open and particles infiltrated from the rest of the house, the dose reduction was only 5% on average and appears to be insignificant. Thus, the dose reductions were h e r than the reductions in activity concentration, but there were no cases where the estimated dose actually increased.     

住宅隔热的影响因素及设计对策

夏季 ,室外气候诸因素经过不同途径 ,对室内的影响会有差异。了解这些差异有助于在设计时把握主要问题。讨论在住宅隔热设计中 ,针对不同的室内条件 ,应优先考虑的因素及相应的设计对策。     

Influence of wood extractives on the photo‐discoloration of wood surfaces exposed to artificial weathering

Extracted and unextracted black cherry (Prunus serotina), red oak (Quercus rubra), and red pine (Pinus resinosa) wood specimens were exposed to artificial weathering, and their discoloration process was investigated to obtain basic understanding on the role of wood extractives in the weathering of hardwoods and softwoods. Color measurements were made with a spectrometer according to ISO 2470 standards, using the CIELAB system. Results obtained showed that the rate of whiteness was not significantly affected by extractives removed with organic solvents, but were significantly affected when organic solvent extraction was followed by water extraction. The total discoloration rate had the same pattern, and chromaticity coordinates were less affected by wood extractives. These results confirm the hypothesis that some extractives contained in wood act as antioxidants and are able to provide some protection to wood surfaces against weathering degradation. However, more work is needed to understand the chemistry and mechanism of action of these extractives so as to develop any practical use for this property. © 2006 Wiley Periodicals, Inc. Col Res Appl, 31, 425–434, 2006; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/col.20248     

Effect of olive residue benzylation on the thermal and mechanical properties of poly(vinyl chloride)/olive residue composites

The changes in mechanical properties, the thermal stability, and the water absorption capacity of poly (vinyl chloride)/olive residue flour composites were studied as a function of various residue olive flour ratios, i.e., 0, 5, 15, and 25% by weight taking into account the effect of benzylation chemical treatment of the filler. The study showed that composite samples prepared with the untreated filler exhibited higher tensile modulus and hardness compared with the neat resin, whereas elongation and tensile strength were observed to decline. On the other hand, the PVC hardness was found to increase with addition of the untreated olive residue flour (ORF), however the composite samples prepared with the benzylated flour exhibited lower hardness than those prepared with untreated olive residue. Moreover, the amount of absorbed water depends on the amount of filler in the composite. The comparison of the results obtained from the samples of F5, F20, and F30 formulations between the untreated and treated ORF indicated a reduction in absorbed water for the composite samples containing treated ORF with benzyl chloride. As a result, the mechanical properties of the treated composites were improved. Furthermore, the thermal characterization of the different samples carried out by color change test and thermogravimetric analysis revealed an increase in the onset temperatures of decomposition for the treated composites. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

伴随内转换电子发射的俄歇电子能量及强度计算

简要介绍了伴随内转换电子发射产生的俄歇电子能量与强度的计算方法、计算程序及工作流程，并以^129Iβ^-衰变为例说明其具体应用。