Anion binding studies of tris(2-aminoethyl)amine based amide receptors with nitro functionalized aryl substitutions: A positional isomeric effect

Syntheses and crystal structures of tren-based amide, L¹, N,N′,N″-tris[(2-amino-ethyl)-4-nitro-benzamide] and L², N,N′,N″-tris[(2-amino-ethyl)-2-nitro-benzamide] are reported and compared with previously published tripodal amide receptor L³, N,N′,N″-tris[(2-amino-ethyl)-3-nitro-benzamide]. The crystallographic results show intramolecular and intermolecular hydrogen-bonding interactions between two arms of the tripodal receptor and two other adjacent molecules in cases of L¹ and L² whereas in addition to the above interactions an aromatic π···π stacking among tripodal arms is also observed in L³. Receptors L¹, L² and L³ having electron withdrawing -NO₂ substituted (para, ortho and meta, respectively) phenyl moieties are explored toward their solution state anion binding properties and selectivity studies. The substantial changes in chemical shifts are observed for the amide protons (-NH) and aromatic protons (-CH) with F⁻ and Cl⁻ in cases of L¹ and L³, and only with F⁻ for L², indicating the participation of -NH and -CH protons in the solution state binding events. Binding constants for the above cases are calculated by ¹H NMR titration upon monitoring the -NH signal. Receptor L² shows exclusive selectivity toward F⁻ in dimethyl sulfoxide (DMSO). The structural aspects of binding I⁻, ClO₄⁻ and SiF₆²⁻ with the monoprotonated L¹, L¹H⁺·I⁻·DMF (1), L¹H⁺·ClO₄⁻·DMF (2) and L¹H⁺·0.5SiF₆²⁻·H₂O (3), respectively are examined crystallographically. Anion binding with multiple receptor units is observed via amide N-H···anion as well as aryl C-H···anion hydrogen-bonding interactions in all the complexes as observed in cases of previously reported crystal structures of anionic complexes of protonated L³. The aryl group having nitro functionality that contributes to solution state anion binding with the neutral receptor and solid state coordination in complexes 1-3 through CH···anion interactions is noteworthy.     

黄土高原丘陵沟壑小流域土壤水分垂直分布变异特征及影响因子

以地统计学的半变异函数为分析工具,分析了黄土高原丘陵沟壑区小流域土壤水分在垂直方向的空间变异特征以及土地利用类型和地形等因子对其的影响.结果表明:1)球状模型可以很好地拟合土壤水分在垂直方向的半变异函数曲线,其存在强烈或中等程度的空间自相关,变程范围从2～5 m不等;2)果园对土壤水分含量的影响主要表现在1～2 m深度,5月份含量最高,且分布均匀,8月份由于气温和叶面蒸腾作用,水分含量最低.坡耕地和梯田的水分含量都较高,垂直变化不明显,梯田的土壤水分含量最低月份是9月,比坡耕地晚1个月,这是因为所种作物的主要生长季节为9月份,这期间消耗水分较多而造成的.林地由于根系发达,对土壤水分垂直方向的变化的影响比较大,变化为先增大、再减小、最后再增大且分布趋于平缓.灌木林的土壤水分含量整体较低,主要变化深度范围集中在0～2 m;草地的土壤水分含量较高,垂直变化的深度范围集中在1 m以内;3)坡度、坡向地形因子和土壤水分的垂直方向变异特征没有呈现明显的相关性.     

森林生态系统土壤CO2释放随海拔梯度的变化及其影响因子

联合国气候框架公约的签署提升了人们对全球变暖、碳循环的关注。土壤CO₂释放作为土壤-大气CO₂交换的主要途径之一,成为了各国生态学家研究的重点内容。通过对1800~2155m海拔梯度上森林生态系统土壤CO₂释放进行研究,揭示了较小空间尺度上土壤CO₂释放的变化规律及其控制机制。在研究区域内,随着海拔梯度的增加,森林土壤CO₂释放由(1.94±006) μmol m^-2 s^-1逐渐增加至(2.22±0.07) μ mol m^-2 s^-1。土壤温度、土壤水分、土壤有机碳（SOC）、全N、全P与土壤CO₂释放呈显著正相关（n=14, P<0.05）;土壤容重与土壤CO₂释放速率呈显著负相关（n=14,P<0.05）;土壤pH对土壤CO₂释放影响不显著。作为一个复杂的生态学过程,环境因子及其交互作用对土壤CO₂释放产生影响,为了减少因子共线性影响,逐步降低因子维数,采用主成分分析（PCA）揭示了土壤温度、土壤水分、SOC、全N、全P、容重6个因子的联合作用,其累积贡献率达到了57％以上;进一步运用逐步回归分析方法,探讨了影响土壤CO₂释放沿海拔梯度分布的主导因子,结果表明土壤水分是研究区域森林生态系统土壤CO₂释放沿海拔梯度变化的主导因子。     

Changes in nitrogen cycling and retention processes in soils under spruce forests along a nitrogen enrichment gradient in Germany

A network of long-term monitoring sites on nitrogen (N) input and output of forests across Germany showed that a number of Germany's forests are subject to or are experiencing N saturation and that spruce (Picea abies) stands have high risk. Our study was aimed at (1) quantifying the changes in gross rates of microbial N cycling and retention processes in forest soils along an N enrichment gradient and (2) relating the changes in soil N dynamics to N losses. We selected spruce sites representing an N enrichment gradient (indicated by leaching : throughfall N ratios) ranging from 0.04–0.13 (low N),≤0.26 (intermediate N enrichment) to≥0.42 (highly N enriched). To our knowledge, our study is the first to report on mechanistic changes in gross rates of soil N cycling and abiotic NO₃⁻ retention under ambient N enrichment gradient. Gross N mineralization, NH₄⁺ immobilization, gross nitrification, and NO₃⁻ immobilization rates increased up to intermediate N enrichment level and somewhat decreased at highly N-enriched condition. The turnover rates of NH₄⁺ and microbial N pools increased while the turnover rates of the NO₃⁻ pool decreased across the N enrichment gradient. Abiotic immobilization of NH₄⁺ did not differ across sites and was lower than that of NO₃⁻. Abiotic NO₃⁻ immobilization decreased across the N enrichment gradient. Microbial assimilation and turnover appeared to contribute largely to the retention of NH₄⁺. The increasing NO₃⁻ deposition and decreasing turnover rates of the NO₃⁻ pool, combined with decreasing abiotic NO₃⁻ retention, possibly contributed to increasing NO₃⁻ leaching and gaseous emissions across the N enrichment gradient. The empirical relationships of changes in microbial N cycling across the N enrichment gradient may be integrated in models used to predict responses of forest ecosystems (e.g. spruce) to increasing N deposition.     

Effect of Controlled Cold Storage on Recovery of Rotylenchulus reniformis from Naturally Infested Soil

Rotylenchulus reniformis is rapidly becoming the most economically important pest associated with cotton in the southeastern United States. Incentive programs have been implemented to support sampling of production fields to determine the presence and abundance of R. reniformis. These sampling programs have dramatically increased the number of soils samples submitted to nematology laboratories during autumn. The large numbers of samples overwhelm most labs and require placement in cold storage until extraction. Therefore, the objective of this study was to examine the length of time soils infested with R. reniformis can be stored before nematode extraction without compromising the accuracy of estimates of population densities. A sandy loam and a silty loam were the two cotton production soils used in this study. Rotylenchulus reniformis numbers decreased 61%during the first 180 days of storage in both soils. Rotylenchulus reniformis numbers from the initial sampling through 180 days decreased as a linear function. The decline of R. reniformis numbers during storage was estimated as 0.28% of the population lost daily from the maximum population through 180 days. The diminution of nematode numbers from 180 through 1,080 days in storage continued, but at a slower rate. Numbers of R. reniformis declined to less than 89%, 93%, and 99% of the initial population within 360, 720, and 1,080 days, respectively, of storage. The reduction of R. reniformis numbers over 180 days can be adjusted, allowing a more accurate estimation of R. reniformis levels in soil samples stored at 4 °C.     

A neutral model of edge effects

In this paper a spatially implicit neutral model for explaining the edge effects between habitats is proposed. To analyze this model we use two different approaches: a discrete approach that is based on the Master equation for a one step jump process and a continuous approach based on the approximation of the discrete jump process with the Kolmogorov-Fokker-Planck forward and backward equations. The discrete and continuous approaches are applied to analyze the species abundance distributions and the time to species extinction. Moreover, with the aid of the continuous approach a realistic classification of the behavior of species in local communities is developed. The species abundance dynamics at the edge between two distinct habitats is compared with those located in the homogeneous interior habitats using species abundance distributions and the first time to species extinction. We show that the structure of the links between local community and the metacommunity plays an important role on species persistence. Specifically, species at the edge between two distinct metacommunities have higher extinction rate than those in the interior habitats connected only to one metacommunity. Moreover, the same species might be persistent in the homogeneous interior habitat, but its probability of extinction from the edge local community could be very high.     

Cytoplasm-enriched fragments ofChara: structure and electrophysiology

Summary Cytoplasm-enriched fragments prepared from internodal cells ofChara corallina by centrifugation contain membrane bound vesicles ranging in size from a few m to hundreds of m. If the fragments are incubated in artificial pond water (APW) of pH₀ above 6.5, neutral red stains the inside of many vesicles bright crimson, suggesting the presence of inward proton-pumping. In APW of pH₀ below 6 crimson vesicles are found less frequently. Under such conditions most vesicles remain unstained inside and some develop indistinct pink halos. After a few days most fragments form a central vacuole, which stains red, regardless of the pH₀. The cytoplasmic layer still contains vesicles after vacuole formation.In order to identify the membrane bounding the vesicles various fluorescent probes were applied either by injection into the fragment or directly onto the vesicles released into artificial cytoplasm. Lucifer yellow or 6 COOH-F move readily across the tonoplast in intact cells, but did not enter any vesicles. On the other hand, the fluorescent cationic stain DIOC, which is used to highlight mitochondria and especially endoplasmic reticulum, stained the vesicle membrane. Numerous elliptical or kidney shaped nuclei in the flowing cytoplasm were highlighted with DAPI. In some fragments the nuclei formed large agreggates sometimes filling the width of the fragment.Patch-clamping the vesicles in artificial cytoplasm showed the presence of several kinds of channels, some displaying similar behaviour to the K⁺ channels observed in cytoplasmic droplets.Analogous to the plasmalemma of intact cells, the fragments without vacuoles displayed electrophysiological states dominated by either K⁺ conduction, H⁺ (or OH^–) conduction or the proton pump. On the other hand, excitation transients in fragments were of low amplitude or absent altogether. Detailed comparisons of data from fragments and intact cells are shown. The effect of vacuole formation on fragment electrophysiology was also explored.     

Mineral control of organic carbon mineralization in a range of temperate conifer forest soils

Coupled climate–ecosystem models predict significant alteration of temperate forest biome distribution in response to climate warming. Temperate forest biomes contain approximately 10% of global soil carbon (C) stocks and therefore any change in their distribution may have significant impacts on terrestrial C budgets. Using the Sierra Nevada as a model system for temperate forest soils, we examined the effects of temperature and soil mineralogy on soil C mineralization. We incubated soils from three conifer biomes dominated by ponderosa pine (PP), white fir (WF), and red fir (RF) tree species, on granite (GR), basalt (BS), and andesite (AN) parent materials, at three temperatures (12.5°C, 7.5°C, 5.0°C). AN soils were dominated by noncrystalline materials (allophane, Al‐humus complexes), GR soils by crystalline minerals (kaolinite, vermiculite), and BS soils by a mix of crystalline and noncrystalline materials. Soil C mineralization (ranging from 1.9 to 34.6 [mg C (g soil C)^?1] or 0.1 to 2.3 [mg C (g soil)^?1]) differed significantly between parent materials in all biomes with a general pattern of ANδ¹³C values of respired CO₂ suggest greater decomposition of recalcitrant soil C compounds with increasing temperature, indicating a shift in primary C source utilization with temperature. Our results demonstrate that soil mineralogy moderates soil C mineralization and that soil C response to temperature includes shifts in decomposition rates, mineralizable pool size, and primary C source utilization.     

镍污染对土壤微生物的生态效应

镍是高等植物和某些微生物必需的微量营养元素之一,在它们的生命活动中起着重要作用;但浓度较高时,也是一种极毒元素。大量的研究表明,镍污染土壤中微生物的生长、代谢、群落结构和种群多样性会受到不同程度的影响;微生物在长期受重金属威迫的环境中形成其适应性。利用微生物形成的这种适应机制,采用微生物技术治理重金属污染的土壤是可能的。本文还对镍污染土壤的微生物评价指标体系、土壤环境容量、微生物技术开发和综合治理技术开发等的进一步研究作了展望。