990 resultados para Basic mechanism
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Water film can serve as a sliding surface and cause landslides on gentle slopes. The development of "water film" in saturated sand is analyzed numerically and theoretically based on a quasi-three-phase model. It is shown that stable water films initiate and grow if the choking state (where the fluid velocity decreases to near zero) remains steady in a liquefied sand column. Discontinuity can occur in pore water velocity, grain velocity and pore pressure after the initiation of a water film. However, the discontinuity and water film can disappear once the choking state is changed. The key to the formation of water film is the choking in the sand column caused by eroded fine grains.
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The mechanism of energy balance in an open-channel flow with submerged vegetation was investigated. The energy borrowed from the local flow, energy spending caused by vegetation drag and flow resistance, and energy transition along the water depth were calculated on the basis of the computational results of velocity and Reynolds stress. Further analysis showed that the energy spending in a cross-section was a maximum around the top of the vegetation, and its value decreased progressively until reaching zero at the flume bed or water surface. The energy borrowed from the local flow in the vegetated region could not provide for spending; therefore, surplus borrowed energy in the non-vegetated region was transmitted to the vegetated region. In addition, the total energy transition in the cross-section was zero; therefore, the total energy borrowed from the flow balanced the energy loss in the whole cross-section. At the same time, we found that there were three effects of vegetation on the flow: turbulence restriction due to vegetation, turbulence source due to vegetation and energy transference due to vegetation, where the second effect was the strongest one. Crown Copyright (C) 2010 Published by Elsevier Ltd. All rights reserved.
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手性胺是合成天然产物和手性药物的重要中间体,亚胺和烯胺的不对称催化还原是制备手性胺最直接有效的方式之一。手性有机小分子催化的亚胺不对称还原已取得了可喜的进展,但到目前为止,有机小分子催化的烯胺不对称还原,尤其是环状烯胺的不对称还原还少有报道。 本研究从手性叔丁基亚磺酰胺出发,设计并合成了一系列含有叔丁基亚磺酰基的新型脲类及硫脲类催化剂,并将其用于催化三氯硅烷对烯胺的不对称还原,尤其是1, 4-二氢吡啶酯类环状烯胺的不对称还原。通过对催化反应条件的优化,发现当添加1eq H2O时,反应收率和对映选择性明显提高,获得高达99% 的收率和88% ee,同时也取得了很好的非对映选择性(dr = 8:92)。首次实现了三氯硅烷对1, 4-二氢吡啶酯类环状烯胺的高立体选择性还原。 通过机理方面的研究,我们推测反应过程中可能是:首先,底物1, 4-二氢吡啶酯与催化剂形成氢键而被活化,当加入添加剂后,添加剂与三氯硅烷反应释放出一个质子,然后受活化的1, 4-二氢吡啶酯捕获该质子转变成更活泼的亚胺正离子的中间体。随后,在催化剂上的手性硫氧的活化下,三氯硅烷的负氢加成到受活化的亚胺正离子的中间体上,最后生成比较有利的反式产物1, 4, 5, 6-四氢吡啶乙酯。 Calalytic enantioselective reduction of imines and enamines represents one of the most straightforward and efficient methods for the preparation of chiral amines, which is an important class of intermediates for the synthesis of natural products and chiral drugs. Significant progresses have been made in organocatalytic enantioselective reduction of imines. However, asymmetric reduction of enamines, especially of cyclic enamines catalyzed by small organocatalysts has scarcely been reported. In this study, starting from chiral tert-butanesulfinamide, a series of structurally simple tert-butanesulfinyl urea and thiourea organocatalysts were developed and employed in asymmetric reduction of enamines by triclorosilane, particularly in the reduction of cyclic enamines such as Hantzsch 1, 4-dihydropyridines. During the optimization of reaction condictions, we found that the addition of one equivalent of H2O could significantly improve the yields and enatioselectivities. Under optimal condictions, 99% yield, up to 88% ee, and 8:92 diastereomeric ratio were obtained. Thus, we have for the first time realized the highly stereoselective reduction of Hantzsch 1, 4-dihydropyridines catalyzed by triclorosilane. As for the mechanism, we speculate that the Hantzsch 1, 4-dihydropyridine was firstly engaged with the catalyst through hydrogen bond. The proton released from the reaction of the additive and triclorosilane next added to one of the C=C bond to make an active iminium intermediate, which was then attacked by the nucleophlic hydrogen of HSiCl3 activated by the Lewis basic sulfinyl function of the catalyst to provide superior trans-1, 4, 5, 6-tetrahydropyridine products.
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川西北高寒草甸位于青藏高原东部地区,是我国四大牧区之一,也是长江和黄河等江河源区的重要水源涵养功能区。近几十年来,大量牦牛粪便被牧民作为生物能源、肥料或者食用菌产业的原料而利用,为草原生态系统的养分平衡增加了生态风险。鉴于在青藏高原地区针对牦牛粪便的相关研究尚未见报道,本文从粪便和土壤养分相互变化趋势的角度出发,研究了粪便在夏秋两季的分解状况和粪便其下及其周围土壤的养分变化。通过此研究,将有助于了解牦牛粪便在自然状态下的分解速率以及粪便对土壤养分及土壤微生物生物量的影响,为粪便对草地土壤生态系统的贡献提供概念性认识,同时也为高寒草甸草地这种脆弱生态系统的可持续管理提供理论依据。 针对牦牛粪便自身养分释放及其对土壤在时间和空间尺度上的影响,本文通过模拟牛粪堆积,在不同时间和固定区域内对牛粪和土壤进行了夏秋两季的采样测定,分析了牛粪及土壤NO3--N、NH4+-N、速效K、无机P、有机C、全N 和全P 含量随时间的变化趋势。得到如下结果: 1. 在研究区域内,牛粪对草地生态系统具有较强的养分(N、P)贡献能力。据初步统计,其估值大致为氮素699~932 kg ha-1,P 素为110~147 kg ha-1。牛粪(湿重、干重)在夏秋季节的分解速率具有较大差异,夏季显著快于秋季。夏季牛粪湿重、干重在2 个月左右之后分别降为初期的14%和24%,而秋季同期分别降为35%和52%。牛粪养分(NO3--N、NH4+-N、速效K、无机P、有机C、全N 和全P)的分解速率在夏季也要显著快于秋季。秋季经过2 个月左右的分解之后,牛粪以上含量分别降至初始态的32%、60%、36%、64%、58%、63%和43%,远高于夏季的同期水平。 2. 在不同季节,牛粪周围的土壤养分(NO3--N、NH4+-N、速效K 和无机P)含量变化随时间改变呈现相同的趋势。但是,牛粪周围不同远近下土壤养分随时间的动态变化幅度略有不同。粪下土壤养分含量随时间变化波动较大,距粪便越远,随时间变化的变幅越为平缓。总体来说,在夏季由于粪便分解较快,对土壤养分的持续作用时间不及秋季,秋季粪便分解变慢,表现出养分的缓释特征。其次,牛粪对粪下土壤影响的持续时间也长于对周围土壤的作用时间。 3. 粪便对土壤养分(NO3--N、NH4+-N、速效K、无机P)影响的范围在不同季节具有差异。夏季要高于秋季,但对周围土壤养分影响的持续时间低于秋季。在夏季短期内,牛粪对土壤NO3--N 和速效K 含量的影响范围能够超过30cm,而对NH4+-N 和无机P 的影响范围则介于10cm 和30cm 之间。在2 个月左右之后,牛粪对周围土壤养分的影响能力基本消失。在秋季,牛粪对周围土壤养分影响范围难以达到30cm 处。粪便在夏季对其下土壤和周围土壤的有机C、全N 和全P 含量并无显著影响,但在秋季能显著增加其下土壤有机C、全N 和全P 含量。 4. 牛粪在秋季对土壤SMB-C、SMB-N 和SMB-P 含量的影响能够持续2 个月以上,由于秋冬季节牛粪分解缓慢,因此推断这种效应持续时间至少能够1 年左右。另一方面,牛粪在秋季对土壤SMB-C、SMB-N 和SMB-P 含量的影响范围主要集中在其下土壤,而周围的影响效应并不明显。 The grassland on the eastern fringe of Qinghai-Tibetan Plateau was one of the four greatest pasture zones in our country and the main water conservation function zones in the hesastream of Yangtse River and Huanghe river. Rencent years, lots of dung in this area was used as biological energy, fertilizer or material of fungoid growing, leading to high risk of nutrient banlance in grassland ecosystem. In view of the researches on the impact of yak dung in this area are relatively rare, the present study focused on the relationship of dung and soil nutrient transformation in sunmer and autumn, which could profoundly illuminate the mechanism of dung decomposition and the effect of dung on soil chemical properties and soil microbe biomass. The present study also contributed to a basic understand and provided scientific management in the high-frigid ecosystem. Decomposition of yak dung and its effect on soil chemical properties in eastern grassland of Qinghai-Tibetan Plateau were determined. The study simulated the real dung pats, took dung and soil samples at different time and fixed-point in summer and autumn. The samples were analysed for NO3--N, NH4+-N, available K, inorganic P, total organic C (TOC), total N (TN), total P (TP). It was concluded that: 1. In study area, the yak dung supplied to ecosystem substantial nutrient. It is estimated that the N contribution of dung was approximately 699~932 kg ha-1, P contribution was approximately 110~147 kg ha-1. The rate of yak decomposition was more rapid in summer than autumn, the wet and dry weight of yak decreased to 14% and 24% respectively after 2 months when dung excreted in summer, with 35% and 52% in autumn. The content of NO3--N、NH4+-N、available K、inorganic P、TOC、TN and TP in dung decomposed more rapid in summer too. After 2 months when dung excreted in autumn, the content of above nutrient decreased to 32%、60%、36%、64%、58%、63% and 43% respectively,which were significantly higher than summer. 2. The content of NO3--N、NH4+-N、available K and inorganic P in soil around dung had the same transformation trend in each season, whereas it was distinguishing at different gradient of distance from dung, the nutrient in soil below dung had the most significant change while the more far from dung, the less change in soil. It was concluded that the yak dung had prolong impacts on soil in autumn compared with summer, besides, it aslo showed that the yak dung had protract effect on soil below dung compared with soil around dung. 3. The yak dung had expansive impact on soil around dung in summer whereas had relatively short effect compared with autumn. In short-term at summer, there was a significant increase about the content of NO3--N and available K around 30cm radius from dung pat while the content of NH4+-N and inorganic P between 10cm to 30cm. After 2 months, the impact almost disappeared. In autumn, the effect was hard to reach 30cm. The yak dung had no significant effects on the content of TOC、TN and TP in soil below or around dung in summer whereas there was a obvious increase in soil below dung pat in autumn. 4. The duration of effect of yak dung on soil microbial biomass(SMB) C、N and P was at least 2 months, maybe even more than 1 year. On the other hand, the impact of dung on SMB-C、SMB-N and SMB-P mainly acted on soil below dung while no obious effect on soil around dung.
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组特殊自养氨氧化混合种群,表现:无机环境种群生长迅速、生物量高;在一个完全无机的自养生长环境中,不仅保持高氨氧化速率,并出现丰富的异养微生物种群;该种群置于异养、厌氧环境中,迅速表现出产氢特征。对于这样一个特殊的生态体系,研究其共生机理,以及联接这些种群之间的碳源和能源问题,将具有非常重要意义。我们拟从种群特征、细胞表面分泌产物、游离体系产物多糖、蛋白和脂肪酸方面开展研究。 第一部分,自养氨氧化混合种群的基本特征。采用氨氧化培养基,进行种群氨氧化特征研究;采用扫描电镜观察自养混合种群的微观特征;沉降、离心去除微生物种群,分析水相中的总有机碳、糖类等物质;利用LB培养基进行种群的分离、纯化,并采用DGGE手段对微生物种群结构进行分析。结果表明,接入菌种后(2/5000(V/V)),培养液中氨(200mg/L)在3-5天内快速降解;亚硝酸盐与氨氮变化呈负相关趋势,仅有少量硝酸盐含量(< 30mg/L)。氨氧化种群的生物量增长与氨氧化趋势一致,初始生物量7.75 mg/L(蛋白含量),3-5天后生物量快速增长,并达到最高63.06 mg/L(蛋白含量)。电镜图片显示,种群外包裹一层粘液。离心除去菌体后,检测培养液总有机碳和糖的含量,同样表现出与生物量增长相似的特征,分别由初始的3.73、2.35 mg/L,3-5内天迅速增加,并分别达到最大值35.19、27.45 mg/L。经初步分离、纯化并对纯化菌株进行测序,获得了10株异养微生物分别为布鲁氏菌科苍白杆菌属、纤维单孢菌、类芽孢菌属、黄杆菌属、无色杆菌、鞘脂单胞菌、嗜麦芽寡养单胞菌、噬氢菌属、硫红球菌、假单胞菌;DGGE显示,约有20分条离带,我们对其中的两条优势条带进行切割回收测序,鉴定为欧洲亚硝化单胞菌(Nitrosomonas eur)。 第二部分:混合种群自养-异养菌共生的可能机制。在对微生物种群特征初步分析基础上,针对胞外糖类组分可能被微生物代谢分解,我们重点对微生物细胞蛋白质与糖类进行分析。采用超声结合RIPA裂解液裂解,SDS-PAGE电泳分析混合种群总蛋白种类,并通过氨基酸分析仪及红外光谱法分析氨基酸组成及蛋白红外特征。采用超声破碎结合反复冻融对细胞样品进行处理,提取液采用醇沉、Sevage脱氮白,凝胶过滤方法脱盐和分级分离。对提取物的糖分析包括:紫外扫描,红外光谱,核磁共振,单糖组成分析;扫描电镜观察菌群破裂现象。SDS-PAGE分析结果表明:氨氧化种群不同生长阶段都显示出42kD蛋白表达量很高,d4时42kD蛋白表达已经很强,4-7d内一直持续这种过量表达,直到d8后表达开始减弱。说明42kD蛋白可能与氨氧化密切相关。红外光谱分析显示:细胞提取物的特征峰分布在3427.42cm-1、1718.18 cm-1和1681.72 cm-1、1160.07和1086.74 cm-1,分别对应为OH、 C=O、C-O-C基团,表明具有蛋白的典型特征;氨基酸分析显示蛋白中的Gly,Asp,Ala,Glu含量相对较高。 提取物中胞外多糖分离谱图得到不均一组分,共得到6个收集峰;紫外扫描在201-213 nm处有多糖吸收峰,同样表明多糖成分不均一性;多糖红外光谱特征峰主要分别在3400.49 cm-1、2920.28 cm-1、1154.54和1087.52 cm-1,对应OH、-CH2- or CH 、C-O-H or C-O-C等多糖特征基团;多糖提取物核磁共振1H d4.3~5.9之间出现强吸收峰,这是1H中,多糖存在的明显证据,1H NMR中,其中O-乙酰基的甲基上的氢信号为d1.1~1.3之间。糖肟全苯甲酸酯衍生物的HPLC测定中,得到单一的单糖峰,由于时间问题,还未进行更深入的试验;电镜图片显示,种群中的细胞有大量的破裂现象。 实验表明,自养氨氧化混合种群显示出快速的氨氧化速率,氨氧化过程生物量和有机质的增加明显。微生物种群包裹粘液层,并分离纯化出大量的异养菌;去除菌体后的游离培养液中存在有机质(包括多糖)说明无机自养生长体系中存在异养菌生长、繁殖的二次碳源;细胞提取物中蛋白条带数目多、种类丰富;细胞多糖提取物具有明显的多糖特征,以及单糖的存在。结合种群的显微特征和游离体系中的有机质的检测结果,我们认为,无机自养生长体系中,种群细胞生长过程中发生的破裂现象可能是导致大量的蛋白、多糖释放到游离胞外,并成为其他异养菌生长的碳源和氮源。这可能是自养体系中,大量异养菌共生的可能机制,至于是什么原因引起种群生长过程中产生的破裂现象,还有待下一步深入研究。 A group of mixed autotrophic ammonia oxidizing populations, having much biological characteristic tested by concerned personnel for pilot test: Performed rapid population growth and obtained high biomass in inorganic environment; Not only maintained a high rate of ammoxidation, promoted a wealth of heterotrophic microbial populations growth in a totally inorganic and autotrophic growth environment; Placed in heterotrophic and anaerobic environment,had the performance characteristics that could rapidly produce hydrogen.For such a special ecological system, Study its symbiotic mechanism and the connection between these populations of carbon and energy issues, will have a very important significance. We intended from the characteristics of the population, the secretion product of cell surface, free substance in the liquid medium like polysaccharide, protein and fatty acids carrying out research. Part I: The basic features of mixed autotrophic ammonia oxidizing populations . Use inorganic liquid medium, processed study for ammonia oxidation characteristics of the population; we used scanning electron microscopy to get micro-features of autotrophic ammonia oxidizing populations .The medium was carried out settlement and centrifugal then removed the microbial populations, after all of that we analysis the water phase for total organic carbon(TOC), carbohydrate and other substances; Solid ammonia oxidizing medium was adopted to separation and purification of population, DGGE means was for structure analysis of microbial population. The results showed that after the inoculum of bacteria (2 / 5000 (V / V)), ammonia in the culture medium (200 mg / L) was rapid degradation in 3-5 days; ammonia and nitrite have the negative correlation between changes in the trend, then only a small amount of nitrate content (<30mg / L). The biomass growth of ammoxidation population in line with the trend of ammonia oxidation, the initial volume of it was 7.75 mg / L (protein content), in 3-5 days upto 63.06 mg / L (protein content). Electron microscope image showed, the populations were wrapped in a layer of mucus, including the a large number ruptted micorbe , Centrifuge to remove bacteria, then detected the medium for total organic carbon and sugar content, result took on the same characteristics with biomass growth, that were from the initial 3.73、2.35 mg / L respectively, in 3-6 days achieved rapid increase in the maximum to 35.19、27.45 mg / L respectively. After initial separation、 purification ,then processed sequencing to strains purified and got the result that there were 10 heterotrophic microorganisms : Brucella Branch pale bacillus, Cellu lomonas, Bacillus species category, a Flavobacterium, colorless Bacteria, Aeromonas sheath fat, little support maltophilia Aeromonas, macrophages species hydrogen, sulphur-MI, Pseudomonas bacteria spores; DGGE display, there were 20 separation bands approximately. Part II: Mixed populations that autotrophic - heterotrophic bacteria symbiotic mechanism. On the basis of preliminary analysis of microbial population characteristics, aiming at extracellular carbohydrate components might be decomposition by microbial, we focused on microbial cell protein and carbohydrate analysis. Using ultrasound combined with RIPA lysis cracking the cells, SDS-PAGE electrophoresis analysis the total protein species of the population, and through the amino acid analyzer studied the compositions of amino acid and infrared spectroscopy analysis of a protein infrared characteristics. Using ultrasound combined with repeatedly freezing and thawing to treated the cell sample, then took the means that alcohol precipitation, deproteinization by Sevage, gel filtration aimed at desalination and grade separation to deal with the lysates . The extraction of sugar analysis included: UV scanning, IR, NMR, single-sugar composition analysis. SDS-PAGE analysis showed that: 42 kD protein expression was very high at different growth stages of mixed autotrophic ammonia oxidizing populations , on the fourth day, 42 kD protein expression had been very strong, 4-7d, it had continued this excessive expression, then started to weaken after 7 days. 42 kD protein that might be closely associated with ammonia oxidation. Infrared spectral analysis showed that: cell extracts with the characteristic that the peak distribution in 3427.42 cm-1、1718.18 cm-1 and 1681.72 cm-1、1160.07 cm-1 and 1086.74 cm-1 corresponding to OH、C = O、C-O-C Groups which had the typical characteristics of protein; and analysis showed that amino acids including Gly, Asp, Ala, Glu ,the content in the protein is relatively high. Exopolysaccharide in the extracts had the separation map that it was uneven, received a total of six collection peaks by the detection mode of phenol-sulphruic acid method ; ultraviolet scan in the 201-213 nm department had polysaccharide absorbing peak, the same ingredients that polysaccharide heterogeneity; infrared polysaccharide spectral characteristics of the main peak at 3400.49 cm-1, 2920.28 cm-1, 1154.54 and 1087.52 cm-1, corresponding OH,-CH2-or CH, C-O-H or C-O-C;and other characteristics of polysaccharide group; 1H NMR of polysaccharide extract appeared absorption peak between d4.3 ~5.9, which is the apparent evidence of polysaccharide, In 1H NMR, the hydrogen signal of one of O-acetyl was between 1.1 to 1.3. The determination of Sugar oxime whole benzoate derivatives by HPLC, there was a single-sugar peak, as a matter of time, yet more in-depth test. Summary: Mixed autotrophic ammonia oxidizing populations show us that it had the ability in ammonia oxidizing and it was great, organic matter and biomass increased significantly in the process of ammonia oxidation. Microbial populations was wrapped up slime layer, the phenomenon of cell breakdown obviously, and there were a lot of separation and purification of the heterotrophic bacteria; a lot of organic matter (including polysaccharides)remined in the medium that removal of cell indicated the inorganic system existed secondary carbon sources that could be used by the heterotrophic bacteria ; there were a large number proteins bands of cell extract, rich variety; cell extracts of polysaccharide had obvious characteristics of polysaccharide, and the existence evidence of single-sugar. Combined population of microscopic characteristics and free of organic matter in the test results, we believe that the health of inorganic system, population growth occurred in the course of the breakdown of the phenomenon is likely to lead to a lot of protein and polysaccharide released into the extracellular free, And other heterotrophic bacteria use them to the growth as carbon and nitrogen. This may be autotrophic system, the large number of heterotrophic bacteria symbiotic mechanism.
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Within the concept of the dinuclear system (DNS), a dynamical model is proposed for describing the formation of superheavy nuclei in complete fusion reactions by incorporating the coupling of the relative motion to the nucleon transfer process. The capture of two heavy colliding nuclei, the formation of the compound nucleus and the de-excitation process are calculated by using an empirical coupled channel model, solving a set of microscopically derived master equations numerically and applying statistical theory, respectively.Fusion-fission reactions and evaporation residue excitation functions of synthesizing superheavy nuclei (SHN)are investigated systematically and compared them with available experimental data. The possible factors that affecting the production cross sections of SHN are discussed in this workshop.
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IEECAS SKLLQG
Resumo:
The proton radioactivity half-lives of spherical proton emitters are investigated within a generalized liquid drop model (GLDM), including the proximity effects between nuclei in a neck and the mass and charge asymmetry. The penetrability is calculated in the WKB approximation and the assault frequency is estimated by the quantum mechanism method considering the structure of the parent nucleus. The spectroscopic factor is taken into account in half-life calculation, which is obtained by employing the relativistic mean field (RMF) theory. The half-lives within the GLDM are compared with the experimental data and other theoretical values. The results show that the GLDM works quite well for spherical proton emitters when the assault frequency is estimated by the quantum mechanical method and the spectroscopic factor is considered.
Resumo:
Oxidative damage is an important mechanism in X-ray-induced cell death. Radiolysis of water molecules is a source of reactive oxygen species (ROS) that contribute to X-ray-induced cell death. In this study, we showed by ROS detection and a cell survival assay that NADPH oxidase has a very important role in X-ray-induced cell death. Under X-ray irradiation, the upregulation of the expression of NADPH oxidase membrane Subunit gp91(phox) was dose-dependent. Meanwhile, the cytoplasmic subunit p47(phox) was translocated to the cell membrane and localized with p22(phox) and gp91(phox) to form reactive NADPH oxidase. Our data Suggest, for the first time, that NADPH oxidase-mediated generation of ROS is an important contributor to X-ray-induced cell death. This suggests a new target for combined gene transfer and radiotherapy.