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.     

非常规蛋白基木材胶黏剂研究现状及发展前景

介绍了动物和植物型非常规蛋白资源的种类及其制备蛋白基木材胶黏剂的研究现状和存在的问题,展望了非常规蛋白胶黏剂的发展前景。     

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     

马尾松木材中性脱脂工艺的研究

采用全因素试验法，对马尾松木材进行过热乙醇溶液脱脂处理，以获取马尾松木材高效脱脂工艺技术。试验结果显示：（1）脱脂温度对马尾松松脂溶出量的影响极显著，且溶出量随着脱脂温度的升高而增大；（2）脱脂时间对马尾松松脂溶出量的影响极显著，且溶出量随着脱脂时间的延长呈先增大后减小的趋势；（3）脱脂浴比对马尾松松脂溶出量的影响极显著，且溶出量随着脱脂浴比的延长呈先增大后减小的趋势；（4）利用过热乙醇溶液对马尾松木材进行脱脂，其最佳工艺是脱脂时间为130℃、脱脂时间为8h、浴比1：8。     

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%).     

Criteria and methodology for the evaluation of conservation interventions on treated porous stone susceptible to salt decay

Susceptibility of stone to salt decay is directly related to its microstructural and mechanical characteristics. In the present work, a porous stone from a quarry in Cyprus was examined. Samples of this stone were consolidated and protected with certain conservation materials. The modification of microstructural characteristics of the stone was evaluated by mercury intrusion porosimetry, while its mechanical characteristics were measured by compressive and bending strength tests. From these data, the susceptibility of Cyprus stone to salt (NaCl) decay was estimated. The values of crystallization pressure of NaCl were calculated and compared to the experimentally measured compressive and tensile strength of the stone, in order to examine the probability of stone disruption due to salt crystallization. The development of the phenomenon after coarse pores’ filling with crystals, i.e. crystallization of salts in capillaries or mechanical failure of the stone, was determined by thermodynamic analysis. Additionally, artificial weathering tests of marine salt spray were performed for the evaluation of stone’s durability after the conservation. The treated stone proved to be resistant to salt decay, as it presented ameliorated microstructural and mechanical characteristics, concerning decay due to soluble salt crystallization. The most possible thermodynamic scenario was small pores repletion with crystals, avoiding mechanical failure of the stone.     

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.     

Quantity,controls and functions of large woody debris in Midwestern USA streams

Large woody debris (LWD) can increase stream habitat heterogeneity by providing structure, altering flow patterns, enhancing sediment deposition, forming pools and retaining organic matter. In North America, the role of LWD has been studied extensively in streams of mature forests (e.g. Pacific Northwest), but few studies have assessed LWD in streams of younger forests (e.g. Midwestern USA). Our objectives were to: (1) quantify the volume and abundance of LWD in a set of Midwestern streams; (2) evaluate possible factors influencing LWD quantity; (3) identify the functional roles of LWD; and (4) compare LWD levels in the upper Midwest to those elsewhere in North America. In 2002 and 2003, we measured LWD and geomorphological variables in 15 low‐gradient streams draining previously logged watersheds in the Upper Peninsula of Michigan. Mean (±SE) LWD volume (0.77 ± 0.12 m³ 100 m⁻²) and abundance (33 ± 3 pieces 100 m⁻¹) were 71% and 10% lesser, respectively, than in streams of similar gradient elsewhere in North America. Channel shape (width:depth ratio) explained 30% of the variation in LWD volume (multiple stepwise regression, P = 0.015) while LWD length and length:channel width combined, explained 72% of the variation in LWD density (multiple stepwise regression, P < 0.0001). About 50% of the LWD either stored sediment or stabilized banks and 14% of the LWD formed pools, although pool density was not significantly related to LWD volume or density. LWD levels, overall, were low in upper Midwestern streams, but the relative importance of that LWD to ecosystem function may be magnified in these wood‐poor systems. Copyright © 2006 John Wiley & Sons, Ltd.