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1.
The organotin complex [Ph3SnS(CH2)3SSnPh3] (1) was synthesized by PdCl2 catalyzed reaction between Ph3SnCl and disodium-1,3-propanedithiolate which in turn was prepared from 1,2-propanedithiol and sodium in refluxing THF. Reaction of 1 with Ru3(CO)12 in refluxing THF affords the mononuclear complex trans-[Ru(CO)4(SnPh3)2] (2) and the dinuclear complex [Ru2(CO)6(μ-κ2-SCH2CH2CH2S)] (3) in 20 and 11% yields, respectively, formed by cleavage of Sn-S bond of the ligand and Ru-Ru bonds of the cluster. Treatment of pymSSnPPh3 (pymS = pyrimidine-2-thiolate) with Ru3(CO)12 at 55-60 °C also gives 2 in 38% yield. Both 1 and 2 have been characterized by a combination of spectroscopic data and single crystal X-ray diffraction analysis.  相似文献   

2.
The flux of a trace gas between soil and atmosphere is usually the result of simultaneously operating production and consumption processes. The compensation concentration is the concentration at which the rate of production equals the rate of consumption so that the net flux between soil and atmosphere is zero. Production and uptake may be due to different processes, which are at least partially known for some of the trace gases, and which may be differently regulated. The direction and the magnitude of the flux between soil and atmosphere is a function of both the compensation concentration and the trace gas concentration in the ambient atmosphere. Compensation and/or ambient concentrations may fluctuate and thus may have a strong impact on the flux of CO, NO and NO2, and to a smaller extent also on that of H2. Compensation concentrations also exist for N2O and OCS, but are too high to affect the flux under field conditions. Compensation concentrations have so far not been demonstrated for the flux of CH4. However, the uptake of CH4 by soil exhibits a threshold concentration below which no uptake occurs.Article invited in celebration of tenth anniversary ofBiogeochemistry.  相似文献   

3.
Three widely used methods for measuring total soil CO2 evolution are evaluated, including the dynamic CO2 absorption method, the static CO2 absorption method and the closed chamber method. The study covers laboratory experiments. numerical experiments with a simulation model and field measurements. The results are used to perform an error analysis. The aim of this error analysis is to indicate the impact of each method on the CO2 dynamics during the measurement, and to select the most suitable method for frequent field usage.Laboratory experiments and simulation results show that the dynamic CO2 absorption method has the potential to absorb all CO2 evolving at the soil surface. The results also prove that the method has only a minor impact on the CO2 concentration-depth gradient and the CO2 efflux. The static CO2 absorption method underestimates the soil CO2 evolution, because the absorption velocity is too low, due to slow diffusion processes. Measurements with the closed-chamber method are based on an increasing concentration with time under a closed cover. However, the accumulation of gas alters the concentration gradient in the soil profile and thus causes a rapidly decreasing efflux during the measurement. A commonly used mathematical procedure, which corrects for the altered concentration gradient, does not yield the exact surface efflux, because the effect of increasing storage in the soil profile is not incorporated. Field measurements of CO2 evolution, using the closed-chamber method and the dynamic CO2 absorption method confirm the trends that have been predicted by the simulation model. The results of this study indicate that the dynamic CO2 absorption method is accurate. As it is cheap and simple, it is suitable for the study of temporal and spatial dynamics of CO2 evolution from the soil.  相似文献   

4.
Kästle M  Grune T 《Biochimie》2011,93(6):1076-1079
A substantial part of soluble, oxidized proteins are degraded by the proteasome. However, it is still under debate whether these oxidized proteins are degraded by the 26S proteasome in an ubiquitin-dependent way or in an ubiquitin-independent way by the 20S proteasome. Therefore, we treated cells with H2O2 and UV-A irradiation and detected protein carbonyls and ubiquitination by immunoblotting. Separation of ubiquitinated proteins from non-ubiquitinated reveals that most oxidized proteins are not ubiquitinated.  相似文献   

5.
Abstract

Molecular simulation methods were applied to study the effect of hydrophilicity on CO2/CH4 separation using carbon nanotube (CNT) membranes. CNTs with a diameter of ~1 nm were functionalised by varying amounts of carbonyl groups, in order to achieve various hydrophilicity. The presence of –CO groups inside the CNT allow a significant gain in the diffusion selectivity of CO2, while in contrast the adsorption selectivity is hardly changed. The corresponding permeation selectivity increases as the hydrophilicity of the CNT-based membrane increases. However, the permeability of CO2 decreases due to a combination of the intermolecular interactions between the gas and functional groups and the steric effects of the added functional groups. Considering both the permeation selectivity and permeability, it was found that the maximum separation performance is achieved in a certain hydrophilic CNT membrane. Moreover, the separation performance of hydrophilic CNTs for CO2/CH4 mixtures breaks the Robeson upper bound.  相似文献   

6.
余普  罗蓝  何佳忆  李西 《西北植物学报》2015,35(9):1791-1799
以一年生曼地亚红豆杉(Taxus media cv.hicksii)扦插苗为材料,采用密闭箱静态熏气法,研究不同甲醛(CH2O)浓度(0、5、10、20和40 mg·m-3)和熏气时间(1、3、5、7 d)对曼地亚红豆杉的生理响应。结果显示:(1)在5~20 mg·m-3CH2O浓度下,曼地亚红豆杉叶片均无受害症状,在40 mg·m-3CH2O熏气1 d时,叶片开始出现受害症状,并随时间的延长逐渐加重;(2)随着CH2O浓度的增加和熏气时间的延长,叶片MDA、Pro含量和相对电导率皆呈增加趋势,SS含量表现为先升后降,但仍显著高于对照;(3)在5 mg·m-3CH2O处理下,叶片SOD、CAT、PPO和GR作为第一道防线共同作用以清除过多的活性氧,其中PPO最为敏感;在10、20 mg·m-3CH2O处理下,SOD、POD、CAT、PPO、APX和GR共同作用加快对活性氧的清理;在40 mg·m-3CH2O浓度下,各酶的活性均受到抑制,其中APX、PPO和GR活性显著低于对照,而SOD、POD和CAT活性仍显著高于对照。研究表明,在中低CH2O浓度(5~20 mg·m-3)处理下,曼地亚红豆杉主要通过合成渗透调节物质和活性氧自由基的酶促清除机制共同作用来适应逆境,在40 mg·m-3CH2O浓度下,APX、PPO、GR活性受到显著抑制,细胞膜过氧化程度加剧,植物叶片受到伤害;在CH2O浓度低于20 mg·m-3时,曼地亚红豆杉通过自身的应激保护系统来维持正常的生理活动,表现出较强的CH2O耐受性。  相似文献   

7.
Treatment of liquid manure can result in the production of ammonia, nitrous oxide and methane. Earthworms mix and transform nitrogen and carbon without consuming additional energy. The objective of this paper is to analyse whether earthworms modify the emissions of NH3, N2O, CH4 and CO2 during vermifiltration of pig slurry.The experiment used mesocosms of around 50 L, made from a vermifilter treating the diluted manure of a swine house. Three levels of slurry were added to the mesocosms, with or without earthworms, during one month, in triplicate. Earthworm abundance and gas emissions were measured three and five times, respectively.There was a decrease in emissions of ammonia and nitrous oxide and a sink of methane in treatments with earthworms. We suggest that earthworm abundance can be used as a bioindicator of low energy input, and low greenhouse gas and ammonia output in systems using fresh slurry with water recycling.  相似文献   

8.
免耕施肥对稻田甲烷与氧化亚氮排放及其温室效应的影响   总被引:12,自引:0,他引:12  
2008年采用静态箱-气相色谱法对鄂东南免耕不施肥(NT0)、翻耕不施肥(CT0)、免耕施肥(NTC)和翻耕施肥(CTC) 4种处理下稻田CH4和N2O的排放进行测定.结果表明:各处理CH4排放均呈先升高后降低的季节性规律,而N2O排放的季节性规律不明显;施肥显著提高了稻田CH4和N2O的排放.与翻耕不施肥相比,免耕不施肥显著提高了CH4的排放量,并显著降低了N2O的排放量;与翻耕施肥相比,免耕施肥仅略降低了CH4的排放量和略提高了N2O的排放量.对稻田CH4和N2O两种气体的综合温室效应分析表明,与翻耕不施肥相比,免耕不施肥的综合温室效应提高了25.9%,与翻耕施肥相比,免耕施肥的综合温室效应降低了10.1%.因此,合理的肥料运筹和稻田免耕技术可降低两种气体的综合温室效应.  相似文献   

9.
Soil from a pulse cultivated farmers land of Odisha, India, have been subjected to incubation studies for 40 consecutive days, to establish the impact of various nitrogenous fertilizers and water filled pore space (WFPS) on green house gas emission (N2O & CH4). C2H2 inhibition technique was followed to have a comprehensive understanding about the individual contribution of nitrifiers and denitrifiers towards the emission of N2O. Nevertheless, low concentration of C2H2 (5 ml: flow rate 0.1 kg/cm2) is hypothesized to partially impede the metabolic pathways of denitrifying bacterial population, thus reducing the overall N2O emission rate. Different soil parameters of the experimental soil such as moisture, total organic carbon, ammonium content and nitrate–nitrogen contents were measured at regular intervals. Application of external N-sources under different WFPS conditions revealed the diverse role played by the indigenous soil microorganism towards green house gas emission. Isolation of heterotrophic microorganisms (Pseudomonas) from the soil samples, further supported the fact that denitrification might be prevailing during specific conditions thus contributing to N2O emission. Statistical analysis showed that WFPS was the most influential parameter affecting N2O formation in soil in absence of an inhibitor like C2H2.  相似文献   

10.
东北温带次生林和落叶松人工林土壤CH4吸收和N2O排放通量   总被引:2,自引:0,他引:2  
孙海龙  张彦东  吴世义 《生态学报》2013,33(17):5320-5328
2007年6月-2008年6月,在帽儿山用静态箱/气相色谱法测定了相邻次生林和落叶松人工林土壤CH4和N2O通量,结果表明:次生林转变为落叶松人工林后土壤年CH4吸收和年N2O排放通量均显著增加,分别为次生林的1.2倍和3.6倍.两林分CH4和N2O通量表现相似的季节动态,生长季土壤CH4吸收通量和N2O排放通量均高于非生长季.次生林和落叶松人工林土壤CH4吸收通量与土壤温度均呈正相关关系,而与土壤含水量呈负相关关系.土壤N2O排放通量与土壤温度和土壤铵态氮含量均呈正相关关系,而与土壤含水量没有明显相关性.次生林转变为落叶松人工林后,落叶松林地较厚的凋落物层改变了林地土壤水分的格局,影响了土壤的CH4和N2O通量.  相似文献   

11.
The small molecules already existing on the earth can be assembled to biological macromolecules in the presence of the suitable tool. A workman must sharpen his tools if he is to do his work well. The tool must be specific, delicate and automatic. Obviously, it is enzyme. Therefore, to explore the origin of life we must understand the origin of the manufacturing tool of biological macromolecules—the origin of enzymes. We can understand more about the origin and evolution procedures of enzymes from the NO2. NO2 can easily form the dimmer, N2O4. Four N2O4 molecules can coordinate with a suitable metal ion and form a plane super molecule with four N2O4 molecules. This supramolecule provides the basis for the appearance of enzymes: (1) It is the template for producing enzymes. (2) It provides the active centers for enzymes. (3) It provides for the enzymes with specific function of chiral selection. This supramolecule reacts with formaldehyde and porphyrin compound is gradually formed. Once suitable function groups are substituted on the porphyrin ring, enzymes are formed. The primitive environment of earth can easily produce NO2 and CH2O. Therefore, this might be one clue to the origin of life.
Xiangchen YinEmail:
  相似文献   

12.
Bovine α1,3galactosyltransferase (α1,3GalT) transfers galactose from UDP-α-galactose to terminal β-linked galactosyl residues with retention of configuration of the incoming galactose residue. The epitope synthesized has been shown to be critical for xenotransplantation. According to a proposed double-displacement reaction mechanism, glutamate-317 (E317) is thought to be the catalytic nucleophile. The proposed catalytic role of E317 involves an initial nucleophilic attack with inversion of configuration and formation of a covalent sugar–enzyme intermediate between E317 and galactose from the donor substrate, followed by a second nucleophilic attack performed by the acceptor substrate with a second inversion of configuration. To determine whether E317 of α1,3GalT is critical for enzyme activity, site-directed mutagenesis was used to substitute alanine, aspartic acid, cysteine and histidine for E317. If the proposed reaction mechanism for the α1,3GalT enzyme is correct, E317D and E317H would produce active enzymes since they can act as nucleophiles. The non-conservative mutation E317A and conservative mutation E317C are predicted to produce inactive or very low activity enzymes since the E317A mutant cannot engage in a nucleophilic attack, and the E317C mutant would trap the galactose residue. The results obtained demonstrate that E317D and E317H mutants retained activity, albeit significantly less than the wild-type enzyme. Additionally, both E317A and E317C mutant also retained enzyme activity, suggesting that E317 is not the catalytic nucleophile proposed in the double-displacement mechanism. Therefore, either a different amino acid may act as the catalytic nucleophile or the reaction must proceed by a different mechanism.  相似文献   

13.
The maximum quantum yields (a,c) for CO2 uptake in low-oxygen atmospheres were determined for 11 species of C3 vascular plants of diverse taxa, habitat and life form using an Ulbricht-sphere leaf chamber. Comparisons were also made between tissues of varied age within species. The species examined were Psilotum nudum (L.) P. Beauv., Davallia bullata Wall. ex Hook., Cycas revoluta Thunb., Araucaria heterophylla (Salisb.) Franco, Picea abies (L.) Karst., Nerium oleander L., Ruellia humilis Nutt., Pilea microphylla (L.) Karst., Beaucarnea stricta Lem., Oplismenus hirtellus (L.) P. Beauv. and Poa annua L. Quantum yields were calculated from the initial slopes of the response of CO2 uptake to the quantity of photons absorbed in conditions of diffuse lighting. Regression analysis of variance of the initial slopes of the response of CO2 uptake to photon absorption failed to show any statistically significant differences between age classes within species or between the mature photosynthetic organs of different species. The constancy of a,c was apparent despite marked variation in the light-saturated rates of CO2 uptake within and between species. The mean a,c was 0.093±0.003 for 11 species. By contrast, surface absorptance varied markedly between species from 0.90 to 0.60, producing proportional variation in the quantum yield calculated on an incidentlight basis. The ratio of variable to maximum fluorescence emission at 695 nm for the same tissues also failed to show any statistically significant variation between species, with a mean of 0.838±0.008. Mean values of a,c reported here for C3 species, in the absence of photorespiration, are higher than reported in previous surveys of vascular plants, but consistent with recent estimates of the quantum yields of O2 evolution.Abbreviations and Symbols A rate of CO2 uptake per unit projected area (mol · m–2 · s–1) - Fm the maximum fluorescence emission at 695 nm in saturating excitation light when closure of PSII reaction centres is maximal (relative units) - Fo the ground fluorescence at 695 nm when all PSII reaction centres are assumed open (relative units) - Fv the difference between Fm and Fo - JQ rate of CO2 uptake by the sample (nmol · s–1) - JQ rate of photon absorption by the sample (nmol · s–1) - Q absorbed photon flux per unit of projected area (nmol · m–2 · s–1) - 1 the light absorptance of photosynthetic organs (dimensionless) - s1 and s'1 the total and projected surface areas of the photosynthetic organs examined (m2) - a,c and i,c the quantum yields for CO2 uptake on an absorbed- and incident-light basis, respectively (dimensionless) - a,o the quantum yield for O2 evolution on an absorbed-light basis (dimensionless) This work was supported by grant PI7179-BIO, FWF, Austria to H.B-N. and by a British Council travel award to S.P.L. This work was completed under the auspices of U.S. Department of Energy under Contract No. DE-AC02-76CH00016. We also thank Dr. K.J. Parkinson of PP Systems, Hitchin, UK for the loan of a prototype of a commercial integrating-sphere leaf chamber developed from our design.  相似文献   

14.
Coastal eutrophication by nutrient fluxes from agricultural land to marine recipients is presently combated by measures such as the implementation of watershed-scale wetland creation programs aimed at nitrogen removal. Such created agricultural wetlands - termed ‘nitrogen farming wetlands’ (NFWs) - receive nitrogen (N) loads predominantly as nitrate, facilitating N removal by denitrification. However, the conversion of agricultural soils into waterlogged wetland area is likely to increase climate gas emissions, particularly methane (CH4). There is thus a need to evaluate the benefits and risks of wetland creation at a large, watershed-scale.Here we investigate N retention and CH4 emission originating from watershed-scale wetland creation in South Sweden, the relation between both processes, and how CH4 emission depends on individual wetland parameters. We combine data from intensively studied reference wetlands with an extensive wetland survey to predict N retention and CH4 emission with simple models, to estimate the overall process rates (large-scale effects) as well as spatial variation among individual NFWs.We show that watershed-scale wetland creation serves targeted environmental objectives (N retention), and that CH4 emission is comparably low. Environmental benefit and risk of individual wetlands were not correlated, and may thus be managed independently. High cover of aquatic plants was the most important wetland property that suppressed CH4 net production, potentially facilitating N retention simultaneously. Further, differences between wetlands in water temperature and wetland age seemed to contribute to differences in CH4 net production. The nationally planned wetland creation (12,000 ha) could make a significant contribution to the targeted reduction of N fluxes (up to 27% of the Swedish environmental objective), at an environmental risk equaling 0.04% of the national anthropogenic climate gas emission.  相似文献   

15.
Butterbach-Bahl  K.  Papen  H. 《Plant and Soil》2002,240(1):77-90
In order to gain information about seasonal and interannual variations of CH4-fluxes at a spruce control site, a limed spruce site and a beech site of the Höglwald Forest, Bavaria, Germany, complete annual cycles of CH4-exchange between the soil and the atmosphere with 2-hourly resolution were followed for 4 consecutive years. The ranges of CH4 fluxes observed for the different sites were: +12.4 to –69.4 g CH4 m–2 h–1 (spruce control site), +11.7 to –51.4 g CH4 m–2 h–1 (limed spruce site), and –4.4 to –167.3 g CH4 m–2 h–1 (beech site). Lowest rates of atmospheric CH4-uptake or even a weak net-emission of CH4 by the soils were observed during winter/spring times, whereas highest rates of CH4-uptake were always found in summer/spring. Over the entire observation period of 4 years, mean CH4-uptake rates were –1.82 kg CH4-C ha–1 yr–1 at the spruce control site, –1.31 kg CH4-C ha–1 yr–1 at the limed spruce site, and –4.84 kg CH4-C ha–1 yr–1 at the beech site. The results obtained in this study demonstrate that in view of the huge interannual variations in CH4-fluxes of approx. 1 kg CH4-C ha–1 yr–1, multiple year measurements of CH4-fluxes are necessary to accurately characterize the sink strength of temperate forest for atmospheric CH4. By comparison of CH4-fluxes measured at the spruce control site and the limed spruce site, a significant negative effect of forest floor liming on CH4-uptake could be demonstrated. Compared to the spruce stand, the beech stand showed on average approx. 3 times higher rates of atmospheric CH4-uptake, most likely due to pronounced differences between both sites with regard to the organic layer structure and bulk density of the mineral soil. Regression analysis between CH4-fluxes and environmental parameters revealed that at all sites the dominating factors regulating temporal variations of CH4 fluxes were soil moisture and soil temperature. Field measurements of CH4 concentrations in the soil profile and laboratory measurements of CH4-oxidation and CH4-production activity on soil samples taken from different soil depths showed that the CH4-flux at the Höglwald Forest sites is the net-result of simultaneous occurring production and consumption of CH4 within the soil. Highest CH4-oxidation activity was found in the uppermost centimeters of the mineral soil, whereas highest potential CH4-production activity was found in the organic layer.  相似文献   

16.
17.
温带针阔混交林土壤碳氮气体通量的主控因子与耦合关系   总被引:3,自引:0,他引:3  
中高纬度森林地区由于气候条件变化剧烈,土壤温室气体排放量的估算存在很大的不确定性,并且不同碳氮气体通量的主控因子与耦合关系尚不明确。以长白山温带针阔混交林为研究对象,采用静态箱-气相色谱法连续4a(2005—2009年)测定土壤二氧化碳(CO2)、甲烷(CH4)和氧化亚氮(N2O)净交换通量以及温度、水分等相关环境因子。研究结果表明:温带针阔混交林土壤整体上表现为CO2和N2O的排放源和CH4的吸收汇。土壤CH4、CO2和N2O通量的年均值分别为-1.3 kg CH4hm-2a-1、15102.2 kg CO2hm-2a-1和6.13 kg N2O hm-2a-1。土壤CO2通量呈现明显的季节性规律,主要受土壤温度的影响,水分次之;土壤CH4通量的季节变化不明显,与土壤水分显著正相关;土壤N2O通量季节变化与土壤CO2通量相似,与土壤水分、温度显著正相关。土壤CO2通量和CH4通量不存在任何类型的耦合关系,与N2O通量也不存在耦合关系;土壤CH4和N2O通量之间表现为消长型耦合关系。这项研究显示温带针阔混交林土壤碳氮气体通量主要受环境因子驱动,不同气体通量产生与消耗之间存在复杂的耦合关系,下一步研究需要深入探讨环境变化对其耦合关系的影响以及内在的生物驱动机制。  相似文献   

18.
Based on the HSQC scheme, we have designed a 2D heterocorrelated experiment which combines constant time (CT) 13C and variable time (VT) 15N chemical shift labelling. Although applicable to all carbons, this mode is particularly suitable for simultaneous recording of methyl-carbon and nitrogen chemical shifts at high digital resolution. The methyl carbon magnetisation is in the transverse plane during the whole CT period (1/JCC=28.6 ms). The magnetisation originating from NH protons is initially stored in the 2HzNz state, then prior to the VT chemical shift labelling period is converted into 2HzNy coherence. The VT -15N mode eliminates the effect of 1 J N,CO and 1,2 J N,CA coupling constants without the need for band-selective carbon pulses. An optional editing procedure is incorporated which eliminates signals from CH2 groups, thus removing any potential overlap with the CH3 signals. The CT-13CH3,VT-15N HSQC building block is used to construct two 3D experiments: 3D NOESY-CH3NH and 3D 13C,15N HSQC-NOESY-CH3NH. Combined use of these experiments yields proton and heteronuclear chemical shifts for moieties experiencing NOEs with CH3 and NH protons. These NOE interactions are resolved as a consequence of the high digital resolution in the carbon and nitrogen chemical shifts of CH3 and NH groups, respectively. The techniques are illustrated using a double labelled sample of the CH domain from calponin.  相似文献   

19.
Abstract

The Grand Canonical Monte Carlo (GCMC) and molecular dynamics (MD) simulation methods were used to investigate the adsorption and diffusion properties of CH4 and CO2 in montmorillonite slit-nanopores. It is found that, both CH4 and CO2 could adsorb closely onto the pore surface, while different adsorption states occur for CH4 and CO2, respectively, in montmorillonite slit-nanopores. Competitive adsorption of CO2 over CH4 exists in montmorillonite slit-nanopores, especially at the lower pressures, which is attributed to the different interaction intensity between the CH4–CO2 molecules and the pore surface. The diffusion coefficients of CH4 and CO2 both decrease with the enhanced pressures, while the CO2 has a relative weak diffusion coefficient comparing with CH4. A well displacement of the residual CH4 by CO2 in montmorillonite slit-nanopores was investigated, which is found that the displacement efficiency increases with the enhanced bulk pressures. It was determined that, the CO2 can be captured and reserved in the montmorillonite slit-nanopores during the displacement, and the sequestration amount of CO2 gets enhanced with the bulk pressure increasing. This study provides micro-behaviours of CH4 and CO2 in montmorillonite slit-nanopores, for the purpose to give out useful guidance for enhancing shale gas extraction by injecting CO2.  相似文献   

20.
A potential effect of climatic change was simulated by manipulating the water table height within intact peat monoliths. The treatment decreased methane flux (maximum –80%) and increased both carbon dioxide flux (maximum 146%) and nitrous oxide flux maximum 936%). Returning the water table height to its original level caused both nitrous oxide and carbon dioxide flux to rapidly return to control levels. However, methane flux remained at its experimentally induced low levels.  相似文献   

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