Theoretical study on the ClO/ClO- system electron-transfer reactivity by the golden-rule

The structures, properties and electron transfer reactivity of the ClO/ClO- coupling system are studied in this paper at ab initio (UHF and UMP2) levels and the Density Functional Theory (DFT: UB3LYP, UB3P86, UB3PW91) levels employing 6311 + G(3df) basis set and on the basis of the Golden-rule of the time-dependent perturbation theory. Investigations indicate that the results obtained using the UB3LYP method employing 6-311 + G(3df) basis set is in excellent agreement with the experiment. For this coupling system, six stable coupling modes have been found which correspond to six different encounter complexes and denote six different electron transfer mechanism: four O-O directly linked structures (one collinear: D-h, one anti-parallel: C-s, two twist: C-2) and two Cl-O linked structures (cis- and anti- C-s structures). The activation energies, the stabilization energies and the electronic coupling matrix elements have also been calculated for the electron transfer reactions via these six different mechanism at the UB3LYP/6-311 + G(3df) level, and then the electron transfer rates are determined at the same level. The most favorable coupling mode to the electron transfer is the anti-parallel mechanism. The averaged electron transfer rate is about 5.58 X 10(11) M-1 s(-1). It is also implied that the B3LYP method can give more reasonable results for the electron transfer reactivity of this system. (C) 2003 Elsevier B.V. All rights reserved.

Determination of peptides and amino acids from wool and beer with sensitive fluorescent reagent 2-(9-carbazole)-ethyl chloroformate by reverse phase high-performance liquid chromotography and liquid chromotography mass spectrometry

A new method for the sensitive determination of amino acids and peptides using the tagging reagent 2-(9-carbazole)-ethyl chloroformate (CEOC) with fluorescence (FL) detection has been developed. Identification of derivatives was carried out by liquid chromotography mass spectrometry. The chromophore in the 2-(9-fluorenyl)-ethyl chloroformate (FMOC) reagent was replaced by carbazole, which resulted in a sensitive fluorescence lerivatizing agent CEOC. CEOC can easily and quickly label peptides and amino acids. Derivatives are stable enough to be efficiently analyzed by high-performance liquid chromatography. Studies on derivatization demonstrate excellent derivative yields over the pH range 8.8-10.0. Maximal yields close to 100% are observed with three- to fourfold molar reagent excess. Derivatives exhibit strong fluorescence and allow direct injection of the reaction mixture with no significant disturbance from the major fluorescent reagent degradation by-products, such as 2(9-carbazole)-ethanol and bis-(2-(9-carbazole)-ethyl) carbonate. In addition, the detection responses for CEOC derivatives are compared to those obtained with FMOC. The ratios AC(CEOC)/AC(FMOC) = 1.00-1.82 for fluorescence (FL) response and AC'(CEOC)/AC'(FMOC) = 1.00-1.21 for ultraviolet (UV) response are observed (here, AC and AC' are, respectively, FL and UV F response). Separation of the derivatized peptides and amino acids has been optimized on a Hypersil BDS C18 column. Excellent linear responses are observed. This method was used successfully to analyze protein hydrolysates from wool and from direct-derivatized beer. (C) 2003 Elsevier Science (USA). All rights reserved.

On the induction period of methane aromatization over Mo-based catalysts

The behavior of different species during the temperature-programmed surface reaction (TPSR) of methane over various catalysts is traced by an online mass spectrometer, It is demonstrated that the transformation of MoO3 to molybdenum carbide hinders the activation of methane as well as the succeeding aromatization in the TPSR, If this transformation process is done before the reaction, the temperature needed for methane activation and benzene formation will be greatly lowered (760 and 847 K, respectively). On the basis of comparison of the catalytic behavior of molybdenum supported on different zeolites, it is suggested that the initial activation of methane is the rate-determining step of this reaction. For the cobalt catalysts supported on HMCM-22 or Mo catalysts supported on TiO2, no benzene formation could be observed during the TPSR, However, the prohibition of benzene formation is different in nature over these two catalysts: the former lacks the special properties exhibited by molybdenum carbide, which can continuously activate methane even when multiple layers of carbonaceous species are formed on its surface, while the latter cannot accomplish the aromatization reaction since there are no Bronsted acid sites to which the activated intermediates can migrate, although the activation of methane can be achieved on it. Only for the catalysts that possess both of these properties, together with the special channel structure of zeolite, can efficient methane aromatization be accomplished. (C) 2000 Academic Press.

冬小麦播种密度和施肥方式对麦田杂草群落组成及生长的影响

在半湿润地区的土垫旱耕人为土上,以冬小麦品种小偃22为指示作物,通过田间小区试验研究了不同施肥条件下冬小麦田间杂草种群的组成以及在4个生育期(越冬期、返青期、拔节期、成熟期)田间杂草密度和生物量的变化.结果表明:(1)在冬小麦全生育期内共发现以猪殃殃、麦家公、婆婆纳、播娘蒿、泽漆、荠菜等为主的17种杂草,不同生育期杂草的优势种群不同,而且杂草总密度表现为越冬期>返青期>拔节期,生物量表现为拔节期>返青期>越冬期;(2)与不施肥处理(P0N0)比较,单施氮肥增加了杂草密度和生物量,在氮磷配施条件下,氮肥对生物量有极显著影响且随施氮量增加表现为减小趋势,其中PN45处理的杂草生物量最大并比P0N0增加51.8%;施磷对杂草生物量有极显著影响,其中单施磷比P0N0处理增加44.0%,PN135处理比P0N135处理增加24.0%.(3)低密度播种比正常密度播种能显著增加杂草生物量,平均增加幅度达82.9%.结果表明,通过增施氮肥和适当增加种植密度,可在一定程度上控制杂草发生,促进作物良好生长

山杏幼苗水分生理生态特性及凋萎湿度的研究

对山杏幼苗进行 3种施水量的水分培养和干旱处理。结果表明 :随施水量的减少 ,叶片的净光合速率、蒸腾速率、气孔导度和水分利用效率等指标都随之下降 ,叶片温度提高。 40 9.2和 1 89.2 mm施水量对山杏幼苗各项指标的影响呈显著差异 ,而 40 9.2和 32 1 .2 mm之间与 32 1 .2和 1 89.2 mm之间均无差异。随土壤干旱的加剧 ,山杏幼苗叶片的蒸腾速率和水势与土壤含水量呈规律性变化 ;当干旱持续 39天时 ,1 .44%的土壤含水量可视为山杏幼苗的凋萎湿度

蔬菜温室土壤某些化学性质的演变特征

To explore the changes of soil chemical properties in vegetable greenhouse,a comparative study was carried out with the samples gathered from vegetable greenhouse fields and their adjacent upland fields in Damintun Town,Xinming County,Liaoning Province.The results showed that compared with upland fields,the contents of soil organic carbon and total nitrogen in greenhouse fields increased significantly.At the depth of 0～30 cm,soil organic carbon in greenhouses of 1-,4-and 10-year increased by 31.09%,35.44%,and 66.80%,respectively,compared with the upland soil.Soil nitrate content at the depth of 0～30 cm in greenhouse fields was 5.05～12.49 times as much as that in upland fields.The nitrate content in different soil layers increased with the increasing age of greenhouse field.,e.g.,at the depth of 20～30 cm,soil nitrate content was significantly higher in 10-year than in 1-and 4-year greenhouse field,with an increase of 65.73% and 50.89%,respectively,and 6.55 times as much as that in upland field,which indicated that soil nitrate transported downwards,and obviously enriched in deeper soil layers under heavy application of fertilizer.Also with the increasing age of greenhouse field,soil pH decreased,while soil soluble salts accumulated.

亚洲氮循环案例研究

以IPCC(Intergovernmental Panel on Climate Change)方法为基础,用IAP-N—1.0氮循环模型分析1961～2030年时间序列、亚洲各国家和地区的氮收支情况。农作物数据来源于联合国粮农组织(FAO)数据库。各参数及排放因子以亚洲国家检测出的数据为主,缺省值采用IPCC的默认值。本文主要讨论了活性氮产生及其不同的迁移和转化途径,以及环境对氮的富集作用和主要驱动因子。亚洲地区活性氮含量从1961年约14.4TgN/a迅速地增加到2000年约67.7TgN/a,预计到2030年可能达105.3TgN/a。人类对食物和能源需求的增长,以及缺乏提高氮肥利用率、降低矿物燃料燃烧释放NO_x的有效措施,使得由人类活动产生的大部分活性氮在环境中累积。解决这一问题还有待于用先进的生物技术,研制出新型高效氮源来代替目前的合成氮。

内蒙古鄂温克族牧民砖茶型氟铝联合中毒调查

目的调查鄂温克族牧民砖茶型氟铝联合中毒病情。方法随机对鄂温克族16~55岁男女均衡62名牧民进行发、血清、尿氟铝水平及血清电解质、生物化学检查,同时检测饮水、牛奶、砖茶、奶茶等氟铝水平,并进行临床检诊和拍摄前臂、骨盆正位X线片,不饮用砖茶的16~55岁男女均衡41名居民为对照组。结果发、血清、尿铝水平牧民组分别为(24.60±9.82)mg/Kg、(0.78±0.25)、(2.84±0.65)mg/L,对照组分别为(12.50±4.55)mg/kg、(0.18±0.11)、(2.09±0.64)mg/L;发、血清、尿氟水平牧民组分别为(1.00±0.52)mg/kg、(0.10±0.10)、(2.74±1.42)mg/L,对照组分别为(1.39±1.34)mg/kg、(0.04±0.03)、(0.87±0.43)mg/L;牧民发、血、尿铝及血、尿氟显著高于对照组(P<0.01)。牧民组血清AST、LDH、HBDH、ALP显著高于对照组(P<0.01)。X线摄片牧民组氟骨症检出率50.00%,关节退行性变检出率61.29%,骨间膜骨化33.87%,疏松型改变检出率29.03%,硬化型改变检出率8.06%;对照组氟骨症检出率2.44%,退行性变检出率34.15%,疏松型改变检出率21.95%,骨间膜骨化检出率2.44%,硬化型改变2.44%,X线氟骨症、关节退行性变、骨间膜骨化牧民组均高于对照组(P<0.01)。结论内蒙古鄂温克族牧民饮茶型氟中毒病情较为严重,其发病机理较为复杂,并导致多组织、器官损伤,可能为砖茶型氟铝联合中毒。