Bis-pyridiumaldoxime reactivators connected with CH2O(CH2)n OCH2 linkers between pyridinium rings and their reactivity against VX

New bis-pyridinium oxime reactivators connected with CH2O(CH2)n OCH2 linkers between two pyridinium rings were designed and synthesized, and their reactivation potency was evaluated for AChE inhibited by organophosphorus VX agent. Among the prepared compounds, 1,2-dimethoxy-ethylene-bis-N,N'-4-pyridiumaldoxime dichloride 5a was the most potent and appeared to be the most promising compound as a potential reactivator for AChE inhibited by organophosphorus VX agent.     

New oxime reactivators connected with CH2O(CH2)nOCH2 linker and their reactivation potency for organophosphorus agents-inhibited acetylcholinesterase

New bis-pyridinium oxime reactivators 6 with CH₂O(CH₂)₂OCH₂ and CH₂O(CH₂)₄OCH₂ linkers between the two pyridinium rings were designed and synthesized. In the in vitro test of their potency to reactivate AChE inhibited by organophosphorus agents at 5 × 10⁻³ M concentration, the reactivation ability of 1,2-dimethoxy-ethylene-bis-N,N′-4-pyridiumaldoxime dichloride (6a) was 63% for housefly (HF) AChE inhibited by diisopropyl fluorophosphates (DFP), 51% for bovine red blood cell (RBC) AChE inhibited by DFP, 67% for HF-AChE inhibited by paraoxon, and 81% for RBC-AChE inhibited by paraoxon. Except in the case of DFP-inhibited HF AChE test of 2-PAM, the activities of 6a are much higher than the activities of 2-PAM and HI-6 which are AChE reactivators currently in use.     

Fluxes of N2O,CH4 and CO2 on afforested boreal agricultural soils

After drainage of natural boreal peatlands, the decomposition of organic matter increases and peat soil may turn into a net source of CO₂ and N₂O, whereas CH₄ emission is known to decrease. Afforestation is a potential mitigation strategy to reduce greenhouse gas emission from organic agricultural soils. A static chamber technique was used to evaluate the fluxes of CH₄, N₂O and CO₂ from three boreal organic agricultural soils in western Finland, afforested 1, 6 or 23 years before this study. The mean emissions of CH₄ and N₂O during the growing seasons did not correlate with the age of the tree stand. All sites were sources of N₂O. The highest daily N₂O emission during the growing season, measured in the oldest site, was as high as 29 mg N₂O m^–2d^–1. In general, organic agricultural soils are sinks for methane. Here, the oldest site acted as a small sink for methane, whereas the two youngest afforested organic soils were sources for methane with maximum emission rates (up to 154 mg m^–2d^–1) similar to those reported for minerogenous natural peatlands. Soil respiration rates decreased with the age of the forest. The high soil respiration in the younger sites, probably resulted from the high biomass production of herbs, could create soil anaerobiosis and increase methane production. Our results show that afforestation of agricultural peat soils does not abruptly terminate the N₂O emissions during the first two decades, and afforestation can even enhance methane emission for a few years. The carbon accumulation in the developing tree stand can partly compensate the carbon loss from soil.     

Dynamics of dissolved O2, CO2, CH4, and N2O in a tropical coastal swamp in southern Thailand

We studied the distribution of dissolved O₂, CO₂, CH₄, and N₂O in a coastal swamp system in Thailand with the goal to characterize the dynamics of these gases within the system. The gas concentrations varied spatially and seasonally in both surface and ground waters. The entire system was a strong sourcefor CO₂ and CH₄, and a possible sink for atmospheric N₂O. Seasonal variation in precipitation primarily regulated the redox conditions in the system. However, distributions of CO₂, CH₄, and N₂O in the river that received swamp waters were not always in agreement with redox conditions indicated by dissolvedO₂ concentrations. Sulfate production through pyriteoxidation occurred in the swamp with thin peat layerunder aerobic conditions and was reflected by elevatedSO ₄ ^2– /Cl^– in the river water. When SO ₄ ^2– /Cl^– was high, CO₂ and CH₄ concentrations decreased, whereas the N₂O concentration increased. The excess SO ₄ ^2– in the river water was thus identified as a potential indicator for gas dynamics in this coastal swamp system.     

Vibrational analysis of nucleic acids. I. The phosphodiester group in dimethyl phosphate model compounds: (CH3O)2PO2-, (CD3O)2PO2-, and (13CH3O)2PO2-.

Normal coordinate analyses and vibrational assignments are presented for the dimethyl phosphate anion [(CH3O)2PO2-] and its deuteriomethyl [(CD3O)2PO2-] and carbon-13 [(13CH3O)2PO2-] derivatives in the gauche-gauche conformation. The dimethyl phosphate anion, which is the simplest model for the nucleic acid phosphodiester moiety, exhibits many of the spectral complexities of DNA and RNA and has previously resisted a complete and consistent vibrational analysis. In the present study we make use of new experimental data on the dimethyl phosphate isotopomers, including Raman depolarization measurements, to develop a consistent valence force field for normal modes of the C--O--P--O--C phosphodiester network and its hydrogenic substituents, as well as for stretching and bending modes of the O--P--O network of the anionic phosphodioxy group (PO2-). The force field established for dimethyl phosphate incorporates one significant nonbonded force constant, introduced from ab initio calculations, to account for interaction between the two ester C--O bonds. This study resolves previous problematic assignments for conformation-sensitive symmetric (in-phase) and asymmetric (out-of-phase) skeletal stretching modes of the ester linkages and demonstrates substantial anharmonicity in the hydrogen-stretching vibrations of the methyl substituents. New assignments are proposed for Raman bands of the phosphodioxy group, which may serve as potential indicators of structure and interaction of the DNA phosphates.     

反刍家畜及其排泄物对N2O和CH4排放的贡献

了解反刍动物及其排泄物对温室气体的贡献以及主要影响因素对于认识全球气候变化及寻找减缓措施都具有重要的社会、经济和生态学意义.本文在综述了大量国内外相关文献的基础上,提出提高家畜营养水平和均衡营养,特别是在天然草原上增加豆科牧草的比例,并通过在饲料中适量添加中链脂肪酸等添加剂,是提高家畜的生产性能、降低CH4排放量的有效措施.同时指出,由于在家畜排泄物处理和利用过程中,降低一种温室气体的排放可能会增加另一种气体的排放,因此,应该根据它们对大气增温潜值的差异,将各种处理下温室气体换算成CO2-C,从而进行比较分析,通过调整综合措施以达到二者总释放量的最低水平;同时还应该考虑到所产生的NH3和亚硝酸盐/硝酸盐对大气和环境的污染.因此,如何提高反刍家畜的饲养与营养、调整放牧管理制度、改善草原群落结构,从而在提高个体生产性能的基础上达到降低家畜总饲养量,最终实现草原生态保护、家畜生产和温室气体排放综合考虑的折衷管理方案,是今后所要解决的科学问题.任何减缓温室气体排放的措施都应该以整个生产系统为基础,从而综合评价所采取措施的有效性.     

Stereoselective synthesis of Psi[CH(2)O] pseudodipeptides and conformational analysis of a PhePsi[CH(2)O]Ala containing analogue of the drug desmopressin

A method for synthesis of XaaPsi[CH(2)O]Ala/Gly pseudodipeptides in good yields and excellent diastereoselectivity from azido alcohols and (R)-2-chloropropionic acid or tert-butyl bromoacetate has been developed. Insertion of one of the pseudodipeptide building blocks in the peptide drug desmopressin revealed that methylene ether isosteres may have only a minor influence on the secondary structure of peptides.     

开放式空气CO2增高对稻田CH4和N2O排放的影响

在FACE(free aircarbondioxideenrichment)平台上 ,采用静态暗箱 气相色谱法观测研究了大气CO2 浓度增加对稻田CH4和N2 O排放的影响 .结果表明 ,在 15 0和 2 5 0kgN·hm-2 两种氮肥水平下大气CO2 浓度增加 2 0 0 μmol·mol-1均明显促进水稻生长 ,水稻生物量积累 .大气CO2 浓度增加对 15 0和 2 5 0kgN·hm-2 两种氮肥水平下稻田CH4排放均无显著影响 ,并简要分析了与现有文献报道结果不一致的原因 .大气CO2 浓度增加也未导致 15 0和 2 5 0kgN·hm-2 两种氮肥水平下稻田N2 O排放的明显变化 ,与大多数研究结果一致 .     

CH...O hydrogen bonds at protein-protein interfaces

For the first time, a statistical potential has been developed to quantitatively describe the CH.O hydrogen bonding interaction at the protein-protein interface. The calculated energies of the CH.O pair interaction show a favorable valley at approximately 3.3 A, exhibiting a feature typical of an H-bond and similar to the ab initio quantum calculation result (Scheiner, S., Kar, T., and Gu, Y. (2001) J. Biol. Chem. 276, 9832-9837). The potentials have been applied to a set of 469 protein-protein complexes to calculate the contribution of different types of interactions to each protein complex: the average energy contribution of a conventional H-bond is approximately 30%; that of a CH.O H-bond is 17%; and that of a hydrophobic interaction is 50%. In some protein-protein complexes, the contribution of the CH.O H-bond can reach as high as approximately 40-50%, indicating the importance of the CH.O H-bond at the protein interface. At the interfaces of these complexes, C(alpha)H.O H-bonds frequently occur between adjacent strands in both parallel and antiparallel orientations, having the obvious structural motif of bifurcated H-bonds. Our study suggests that the weak CH.O H-bond makes an important contribution to the association and stability of protein complexes and needs more attention in protein-protein interaction studies.     

Winter CO2 CH4 and N2O fluxes on some natural and drained boreal peatlands

CO₂ and CH₄ fluxes during the winter were measured at natural and drained bog and fen sites in eastern Finland using both the closed chamber method and calculations of gas diffusion along a concentration gradient through the snowpack. The snow diffusion results were compared with those obtained by chamber, but the winter flux estimates were derived from chamber data only. CH₄ emissions from a poor bog were lower than those from an oligotrophic fen, while both CO₂ and CH₄ fluxes were higher in theCarex rostrata- occupied marginal (lagg) area of the fen than in the slightly less fertile centre. Average estimated winter CO₂-C losses from virgin and drained forested peatlands were 41 and 68 g CO₂-C m^–2, respectively, accounting for 23 and 21% of the annual total CO₂ release from the peat. The mean release of CH₄-C was 1.0 g in natural bogs and 3.4 g m^–2 in fens, giving rise to winter emissions averaging to 22% of the annual emission from the bogs and 10% of that from the fens. These wintertime carbon gas losses in Finnish natural peatlands were even greater than reported average long-term annual C accumulation values (less than 25g C m^–2). The narrow range of 10–30% of the proportion of winter CO₂ and CH₄ emissions from annual emissions found in Finnish peatlands suggest that a wider generalization in the boreal zone is possible. Drained forested bogs emitted 0.3 g CH₄-C m^–2 on the average, while the effectively drained fens consumed an average of 0.01 g CH₄-C m^–2. Reason for the low CH₄. efflux or net oxidation in drained peatlands probably lies in low substrate supply and thus low CH₄ production in the anoxic deep peat layers. N₂O release from a fertilized grassland site in November–May was 0.7 g N₂O m^–2, accounting for 38% of the total annual emission, while a forested bog released none and two efficiently drained forested fens 0.09 (28% of annual release) and 0.04 g N₂O m^–2 (27%) during the winter, respectively.     

黑土稻田CH4与N2O排放及减排措施研究

通过对黑土稻田CH₄和N₂O排放的观测,发现水稻生长季CH₄和N₂O排放量低于全国其它地区稻田CH₄和N₂O排放之间存在互为消长关系(r=-0．513,P<0．05),但在同样施肥水平条件下,间歇灌溉与长期淹灌相比,CH₄排放明显减少而N₂O略有增加,其相对综合温室效应被大大减少且水稻产量未受影响。为此,间歇灌溉可作为减少稻田温室气体排放的水分管理措施。另外,通过对CH₄和N₂O排放的相关微生物过程探讨,揭示产甲烷菌数与CH4排放问呈显著性正相关(R²=0．82,P<0．05),硝化菌数和反硝化菌数与N2O排放有重要关系。     

三江平原生长季沼泽湿地CH4、N2O排放及其影响因素

 2003年6～9月采用静态箱_气相色谱法,对三江平原生长季不同淹水条件下沼泽湿地CH₄、N₂O的排放进行了同步对比研究,并探讨了影响气体排放的主要影响因素。结果表明, 生长季沼泽湿地CH₄和N₂O排放具有明显的时空变化特征。长期淹水的毛果苔草（Carex lasiocarpa）和漂筏苔草(Carex pseudocuraica)植物带CH₄的平均排放强度分别为259.2和273.6 mg•m^-2•d^-1,高于季节性淹水的小叶章(Deyeuxia angustifolia)植物带的排放强度(38.16 mg•m^-2•d^-1)（p<0.00 0 1）;而生长季N₂O的平均排放强度分别为0.969、0.932 和0.983 mg•m^-2•d^-1, 植物带间无显著差异（p=0.967）。相关分析表明,气温和5 cm深地温对沼泽湿地CH₄生长季排放通量的影响较大,而水位则是影响长期淹水沼泽N₂O排放通量的主要因素;不同类型湿地间CH₄平均排放强度的差异主要受水位的控制,而强烈的还原环境可能是导致不同类型湿地具有近似的N₂O排放强度的原因。     

Fluxes of CH4 and N2O in aspen stands grown under ambient and twice-ambient CO2

The objectives of this study were: (1) to quantify the effects of plant species' loss from designed calcareous grassland communities at a field site in northwestern Switzerland on the size and composition of earthworm communities, and (2) to evaluate how exposure of plant communities to elevated atmospheric CO2 might alter the effects of plant species' loss on earthworm communities. We non-destructively censused earthworm communities in each of 24 1.2 m2 experimental plots in autumn 1996 when soils were wet and earthworms were active. Each plot contained an experimental plant community with 31, 12 or 5 native plant species (eight plots each). Half of the plots in each species treatment were exposed to ambient CO2 concentrations (350 μL CO2 L-1) and half to elevated CO2 (600 μL CO2 L-1) using screen-aided CO2 control. The study was conducted in the fourth year after community establishment and the third year of CO2 treatment as part of a long-term study on the interactive effects of plant species' loss and elevated CO2 on grassland communities. The size (density and biomass) of earthworm communities declined linearly when the number of plant species in the community was reduced from 31 to 5 species (e.g. 32 ± 1 g m-2 to 23 ± 2 g m-2) due mainly to a decline in the endogeic worm species Allolobophora rosea which was the most abundant of nine earthworm species observed (nearly half of all worms in each plot). However, no changes in the relative contribution of individual species or the three main earthworm ecological groups (anecics, endogeics, epigeics) to the entire earthworm community were observed with declining number of plant species. The responses of earthworm communities to plant species'; loss appear to reflect changes in community fine root biomass in the topsoil (e.g. declining worm biomass with declining fine root biomass) observed in parallel studies conducted at this site. Further the results of this study demonstrate that a loss of plant species from these calcareous grassland communities may also alter the age structure of earthworm communities, but not significantly influence their diversity or composition. Our data also indicate that rising atmospheric CO2 may not greatly impact the size and composition of worm communities or alter the effects of plant species' loss on earthworm communities. Therefore, the disappearance of plant species from these native grasslands, as a result of ever increasing human activities, may be expected to lead to reductions in the size of earthworm communities and the ecosystem services they provide. This revised version was published online in July 2006 with corrections to the Cover Date.     

A gastrin-releasing peptide antagonist containing A psi (CH2O) amide bond surrogate

The [Leu26-psi(CH2O)Leu27] derivative of N-Ac-GRP20-27-peptide amide was prepared and evaluated as a gastrin-releasing peptide antagonist. This psi(CH2O) derivative was found to be a more potent inhibitor of [3H-Phe15]GRP15-24NH2 binding and N-Ac-GRP20-27NH2 induced mitogenesis in Swiss 3T3 fibroblasts than the related nitrogen analog [Leu13-psi(CH2NH)Leu14] bombesin. Possible reasons for the improved activity of the (CH2O) insert relative to the (CH2NH) group include increased hydrophobicity and a reduced tendency of the oxygen derivative to form hydrogen bonds.     

长白山阔叶红松林土壤氮化亚氮和甲烷的通量研究

采用静态箱／气相色谱分析方法对长白山阔叶红松林两个处理的N2O和CH4通量进行了研究．结果表明,凋落物对土壤N2O排放和CH4吸收的影响是显著的,影响程度分别是36．9％和23．4％．两个处理的N2O排放通量季节变化趋势相似：夏季(6～8月)的排放通量最高,春季(3～5月)次之,秋(9～11月)冬(12～1月)两季较低．其日变化趋势也相似：最大值都出现在18：00,最小值都出现在12：00和14：00．CH4吸收通量的季节变化趋势也很相似：夏秋两季的吸收通量明显高于春冬两季的吸收通量．其日变化趋势也相似：从14：00开始持续上升到18：00达到最大值,然后持续下降到早晨6：00达到通量的最小值．研究还发现,长白山阔叶红松林土壤的N2O排放和CH4吸收间存在着一种负线性相关关系．     

Regio and stereoselective oxidations of unsaturated steroidal compounds with H2O2 mediated by CH3ReO3

We have investigated the oxidative behavior of sterols such as cholesteryl acetate (1), 7-dehydrocholesteryl acetate (2), ergosteryl acetate (3), cholecalciferol acetate (Vitamin D(3) acetate) (4) and ergocalciferol acetate (Vitamin D(2) acetate) (5) with the oxidant system methyltrioxorhenium/H(2)O(2)/pyridine in order to check potential parameters controlling the selectivity. The reactions, performed in CH(2)Cl(2)/H(2)O at 25 degrees C, have shown good regio- and stereoselectivity. All oxidation products were isolated by high-performance liquid chromatography (HPLC) and characterized by MS(EI) or FAB, (1)H NMR, (13)C NMR, APT, COSY, HSQC, HMBC, ROESY and NOEDS measurements. Seven new oxygenated compounds were also obtained. Under the experimental conditions adopted in this work, only the diene steroids, i.e. 7-dehydrocholesteryl acetate and ergosteryl acetate, undergo hydrolytic oxirane ring opening, whereas Vitamin D(2) and D(3) acetates, containing the triene system and cholesteryl acetate yield only epoxides. The selectivity seems to be controlled by the nucleophilicity of double bonds and by stereoelectronic and steric effects.