Double proton transfer and one-electron oxidation behaviors in double H-bonded glycinamide-formamidine complex and comparison with biological base pair

The behaviors of double proton transfer (DPT) occurring in a representative glycinamide-formamidine complex have been investigated employing the B3LYP/6-311++G** level of theory. Computational results suggest that the participation of a formamidine molecule favors the proceeding of the proton transfer (PT) for glycinamide compared with that without mediator-assisted case. The DPT process proceeds with a concerted mechanism rather than a stepwise one since no zwitterionic complexes have been located during the DPT process. The barrier heights are 14.4 and 3.9 kcal/mol for the forward and reverse directions, respectively. However, both of them have been reduced by 3.1 and 2.9 kcal/mol to 11.3 and 1.0 kcal/mol with further inclusion of zero-point vibrational energy (ZPVE) corrections, where the lower reverse barrier height implies that the reverse reaction should proceed easily at any temperature of biological importance. Additionally, the one-electron oxidation process for the double H-bonded glycinamide-formamidine complex has also been investigated. The oxidated product is characterized by a distonic radical cation due to the fact that one-electron oxidation takes place on glycinamide fragment and a proton has been transferred from glycinamide to formamidine fragment spontaneously. As a result, the vertical and adiabatic ionization potentials for the neutral double H-bonded complex have been determined to be about 8.46 and 7.73 eV, respectively, where both of them have been reduced by about 0.79 and 0.87 eV relative to those of isolated glycinamide due to the formation of the intermolecular H-bond with formamidine. Finally, the differences between model system and adenine-thymine base pair have been discussed briefly.

长白山四种森林类型凋落物动态特征

2003年5月—2004年9月在长白山自然保护区北坡垂直植被带的4种森林群落——阔叶红松林、红松云冷杉林、岳桦云冷杉林和岳桦林内,利用凋落物收集器法对4种森林生态系统凋落物的凋落节律、年凋落物量进行了研究,同时通过凋落物养分含量分析,计算了凋落物的年养分归还量。结果表明:长白山不同的森林类型有不同的凋落节律及其组成,虽然4种森林凋落节律均是单峰型季节变化,但是其峰值出现的时间不同;不同森林类型之间,以及相同森林类型的不同时间之间,凋落物的年凋落量及其组成明显不同;阔叶红松林的年凋落物量最大,约为490g.m-2,其次为红松云冷杉林、岳桦云冷杉林和岳桦林;森林年凋落物量与海拔高度之间呈显著负相关;长白山4种类型森林的凋落物营养物质归还量都是C>灰分>N>K>P,且养分归还总量随海拔高度增加而减少。

城市地表径流人工湿地生态处理工程

以武汉市桃花岛塘和人工湿地组合生态处理系统为研究对象,探讨了该系统处理城市地表径流的初期调试运行,结果表明:塘和人工湿地组合生态系统可以有效的处理城市地表径流,该生态系统对各污染物的去除率分别为CODCr75.4%～79.1%、TP81.8%～84.3%、TN64.9%～69.8%、SS93.8%～94.7%;其中人工湿地对其进水中污染物CODCr、TP、TN、SS的去除率分别为60.7%～64.8%、73.4%～75.6%、43.2%～48.4%、60.3%～66.4%,污染去除负荷达到COD0.01kg/(m2d)。在无雨期该生态系统可以处理一部分城市生活污水,实现削减污染和保持系统稳定的双重功能。

Development of a precolumn derivatization method for the determination of free amines in wastewater by high-performance liquid chromatography via fluorescent detection with 9-(2-hydroxyethyl)acridone

A simple, sensitive, and mild method for the determination of amino compounds based on a condensation reaction with fluorescence detection has been developed. 9-(2-Hydroxyethyl)acridone reacts with coupling agent N,N-carbonyldiimidazole at ambient temperature to form activated amide intermediate 9-(2-acridone)oxyethylcarbonylimidazole (AOCD). The amide intermediate (AOCD) preferably reacts with amino compounds under mild reactions in the presence of 4-(dimethylamino)pyridine (base catalyst) in acetonitrile to give the corresponding sensitively fluorescent derivatives with an excitation maximum lambda(ex) 404 mn and an emission maximum at lambda(em) 440 nm. The labeled derivatives exhibit high stability under reversed-phase conditions. The fluorescence intensities of derivatives in various solvents or at different temperatures were investigated. The method, in conjunction with a gradient elution, offers a baseline resolution of the common amine derivatives on a reversed-phase C-18 column. The LC separation for the derivatized amines shows good reproducibility with acetonitrile-water including 2.5% DMF as mobile phase. The relative standard deviations (n = 6) for each amine derivative are <4.5%. The detection limits (at a signal-to-noise ratio of 3) per injection were 0.16-12.8 ng/mL. Further research for the field of application, based on the AOCD amide intermediate as derivatization reagent, for the determination of free amines in real water samples is achieved.

Analysis of aromatic amines by high-performance liquid chromatography with pre-column derivatization by 2-(9-carbazole)-ethyl-chloroformate

2-(9-Carbazole)-ethyl-chloroformate (CEOC), a novel pre-column fluorescence derivatization reagent, has been developed for the analysis of aromatic amines. Taking five monocyclic aromatic amines (o-toluidine, aniline, 3,4-dimethylaniline, N-ethyl-p-toluidine, and p-phenylenediamine) as testing compounds, derivatization conditions such as pH of borate buffer, reaction time and fluorescent tagging reagent concentration have been investigated. By a one-step procedure, CEOC reacts readily with the aromatic amines to form stable derivatives with excitation and emission wavelengths, respectively, at 293 and 360 nm. This derivatization reaction could be finished within 20 min even at room temperature. The peak shapes of the derivatized aromatic amines can be improved greatly without any addition of competition amines into the mobile phase. Furthermore, this method can offer excellent quantitative precision with high tolerance of the matrix of samples. (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.

辽西褐土施肥及养分循环再利用中长期试验Ⅰ.作物产量

在辽宁西部褐土上历时10 a的田间试验结果表明：氮肥对提高作物产量效果最好，平均增产率50%，平均每千克 N增产粮食21 kg。供试褐土富磷，试验前3 a施磷肥不显增产作用，之后增产明显，10 a平均增产率10.9%，平均每千克 P增产粮食47 kg。供试褐土富钾，连续10 a施钾肥不显增产作用。 在施用化肥基础上每年以60%收获产品直接堆腐回田，可比对应的化肥处理分别增产（10 a平均）40.6%（无肥对照）、19.5%（N肥基础）、12.1%（NP肥）和8.1%（NPK肥），平均年增产粮食（混合、烘干）分别为1.54、1.08、0.79、0.52 t/hm2。养分循环再利用的作物增产效益在试验的10 a中有着逐年增长的趋势，表明以堆肥形式循环回田养分的作物增产作用有着明显的残效叠加效应。

黄土旱塬小麦长期施肥的产量效应及土壤肥力变化

基于20 a长期施肥定位试验,研究了丰水年施肥对小麦产量和土壤肥力变化的影响。结果表明:各种肥料单施或配施对小麦产量的影响顺序为NPM>NM>NP>PM>M>N>P>CK,肥料配施有利于提高小麦产量并维持相对稳产;NP、NM、PM、NPM的交互作用明显,连应值均为正;氮磷配施能显著提高肥料对产量的贡献率和水分利用率,氮磷有机肥配施效果最佳,肥料对产量的贡献率为64.9%,水分利用率提高了103.5%,氮磷单施不如肥料配施;氮磷配施不利于土壤速效钾的积累,化肥和有机肥长期配施有利于土壤养分含量的增加,提高土壤肥力。