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1.
D2 ions produced in collisions of D ions with relative energies of 2.5–9.2 eV were detected for the first time. It is shown that the effective cross section for this reaction is no less than 1.5 × 10−14 cm2. Along with the theoretically predicted short-lived state of negative molecular deuterium ions, a state existing for more than 1 μs was observed.  相似文献   

2.
Ab initio (RHF, MP2) and Density Functional Theory (DFT) methods have been used to examine six isomers of the N15m cluster with the 6-31+G* basis set. Different from the known odd-numbered anionic N7m, N9m, and N11m clusters, in which the open-chain structures are the most stable species, the most stable N15m isomer is structure 1 (C1), which may be considered as a complex between the fragments cyclic N5m (D5h) and staggered N10 (D2d). The decomposition pathways of structure 2 (CS), containing two aromatic N5 rings connected by a N5 chain, and the open-chain structure 3 (C2v) were studied at the B3LYP/6-31+G* level of theory. Relative energies were refined at the level of B3LYP/6-311+G(3df,2p)//B3LYP/6-31+G*+ZPE (B3LYP/6-31+G*). The barriers for N2 and N5m (D5h) fission reactions for structure 2 are predicted to be 18.2 and 14.2 kcal x mol(-1), respectively. The corresponding N2+N3m fission barrier for structure 3 is predicted to be 11.2 kcal x mol(-1). Supplementary material is available for this article if you access the article at http://dx.doi.org/10.1007/s00894-003-0118-0. A link in the frame on the left on that page takes you directly to the supplementary material. Figure Structure 1 of the N15m cluster, showing bond distances in A and bond angles in degrees  相似文献   

3.
A method for determining the lifetime of unstable ions is described. The method is based on measuring the decrease in the ion beam current onto a fixed detector with increasing path length of the ion beam from the ion source to the detector. The measurements performed for D? 2 and HD? molecular ions have shown that their lifetimes are 3.5 ± 0.1 and 4.4 ± 0.1 μs, respectively.  相似文献   

4.
Abstract Sugar maple (Acer saccharum Marsh.)-dominated northern hardwood forests of the Great Lakes Region commonly receive elevated levels of atmospheric nitrate (NO3) deposition, which can alter belowground carbon (C) cycling. Past research has demonstrated that chronic experimental NO3 deposition (3 g N m−2 y−1 above ambient) elicits a threefold increase in the leaching loss of dissolved organic carbon (DOC). Here, we used DOC collected from tension-cup lysimeters to test whether increased DOC export under experimental NO3 deposition originated from forest floor or mineral soil organic matter (SOM). We used DOC radiocarbon dating to quantify C sources and colorimetric assays to measure DOC aromaticity and soluble polyphenolic content. Our results demonstrated that DOC exports are primarily derived from new C (<50-years-old) in the forest floor under both ambient and experimental NO3 deposition. Experimental NO3 deposition increased soluble polyphenolic content from 25.03 ± 4.26 to 49.19 ± 4.23 μg phenolic C mg DOC−1, and increased total aromatic content as measured by specific UV absorbance. However, increased aromatic compounds represented a small fraction (<10%) of the total observed increased DOC leaching. In combination, these findings suggest that experimental NO3 deposition has altered the production or retention as well as phenolic content of DOC formed in forest floor, however exact mechanisms are uncertain. Further elucidation of the mechanism(s) controlling enhanced DOC leaching is important for understanding long-term responses of Great Lakes forests to anthropogenic N deposition and the consequences of those responses for aquatic ecosystems.  相似文献   

5.
Sodium Nitroprusside (SNP) and S-Nitrosoglutathione (GSNO) differently affect mitochondrial H2O2 release at Complex-I. mM SNP increases while GSNO decreases the release induced by succinate alone or added on top of NAD-linked substrates. Stimulation likely depends on Nitric Oxide ( . NO) (released by SNP but not by GSNO) inhibiting cytochrome oxidase and mitochondrial respiration. Preincubations with SNP or high GSNO (10 mM plus DTE to increases its . NO release) induces an inhibition of the succinate dependent H2O2 production consistent with a . NO dependent covalent modification. However maximal inhibition of the succinate dependent H2O2 release is obtained in the presence of low GSNO (20–100 μM), but not with SNP. This inhibition appears independent of . NO release since μM GSNO does not affect mitochondrial respiration, or the H2O2 detection systems and its effect is very rapid. Inhibition may be partly due to an increased removal of O2.− since GSNO chemically competes with NBT and cytochrome C in O2.− detection.  相似文献   

6.
The ability of an ecosystem to retain anthropogenic nitrogen (N) deposition is dependent upon plant and soil sinks for N, the strengths of which may be altered by chronic atmospheric N deposition. Sugar maple (Acer saccharum Marsh.), the dominant overstory tree in northern hardwood forests of the Lake States region, has a limited capacity to take up and assimilate NO3. However, it is uncertain whether long-term exposure to NO3 deposition might induce NO3 uptake by this ecologically important overstory tree. Here, we investigate whether 10 years of experimental NO3deposition (30 kg N ha−1 y−1) could induce NO3 uptake and assimilation in overstory sugar maple (approximately 90 years old), which would enable this species to function as a direct sink for atmospheric NO3 deposition. Kinetic parameters for NH4+ and NO3 uptake in fine roots, as well as leaf and root NO3 reductase activity, were measured under conditions of ambient and experimental NO3 deposition in four sugar maple-dominated stands spanning the geographic distribution of northern hardwood forests in the Upper Lake States. Chronic NO3 deposition did not alter the V max or K m for NO3 and NH4+ uptake nor did it influence NO3 reductase activity in leaves and fine roots. Moreover, the mean V max for NH4+ uptake (5.15 μmol 15N g−1 h−1) was eight times greater than the V max for NO3 uptake (0.63 μmol 15N g−1 h−1), indicating a much greater physiological capacity for NH4+ uptake in this species. Additionally, NO3 reductase activity was lower than most values for woody plants previously reported in the literature, further indicating a low physiological potential for NO3 assimilation in sugar maple. Our results demonstrate that chronic NO3 deposition has not induced the physiological capacity for NO3 uptake and assimilation by sugar maple, making this dominant species an unlikely direct sink for anthropogenic NO3 deposition.  相似文献   

7.
The structures and stabilities of eleven N13 + and N13 isomers have been investigated with second-order Møller–Plesset (MP2) and density functional theory (DFT) methods. Five N13 + isomers and six N13 isomers are all reasonable local minima on their potential energy hypersurfaces. The most stable N13 + cation is structure C-2 with C2v symmetry, which contains a pentazole ring and two N4 open chains. It is different from those of the N7 + and N9 + clusters, but similar to the N11 + cluster. Meanwhile, the most stable N13 structure A-2 is composed of a pentazole ring and a six-membered ring connected by two nitrogen atoms. It is not only different from those of the N7 and N9 clusters, but also from the N11 cluster. The decomposition pathways of structures C-2 and A-2 were investigated at the B3LYP/(aug)-cc-pVDZ level. From the barrier heights of the structures C-2 and A-2 decomposition processes, it is suggested that C-2 is difficult to observe experimentally and A-2 may be observed as a short-lived species. Figure Optimized geometrical parameters of N13 + isomer C-2   相似文献   

8.
A confined aquifer in the Malm Karst of the Franconian Alb, South Germany was investigated in order to understand the role of the vadose zone in denitrifiaction processes. The concentrations of chemical tracers Sr2+ and Cl and concentrations of stable isotope 18O were measured in spring water and precipitation during storm events. Based on these measurements a conceptual model for runoff was constructed. The results indicate that pre-event water, already stored in the system at the beginning of the event, flows downslope on vertical and lateral preferential flow paths. Chemical tracers used in a mixing model for hydrograph separation have shown that the pre-event water contribution is up to 30%. Applying this information to a conceptual runoff generation model, the values of 15N and 18O in nitrate could be calculated. Field observations showed the occurence of significant microbial denitrification processes above the soil/bedrock interface before nitrate percolates through to the deeper horizon of the vadose zone. The source of nitrate could be determined and denitrification processes were calculated. Assuming that the nitrate reduction follows a Rayleigh process one could approximate a nitrate input concentration of about 170 mg/l and a residual nitrate concentration of only about 15%. The results of the chemical and isotopic tracers postulate fertilizers as nitrate source with some influence of atmospheric nitrate. The combined application of hydrograph separation and determination of isotope values in 15N and 18O of nitrate lead to an improved understanding of microbial processes (nitrification, denitrification) in dynamic systems.  相似文献   

9.
In two mountain ecosystems at the Alptal research site in central Switzerland, pulses of 15NO3 and 15NH4 were separately applied to trace deposited inorganic N. One forested and one litter meadow catchment, each approximately 1600 m2, were delimited by trenches in the Gleysols. K15NO3 was applied weekly or fortnightly over one year with a backpack sprayer, thus labelling the atmospheric nitrate deposition. After the sampling and a one-year break, 15NH4Cl was applied as a second one-year pulse, followed by a second sampling campaign. Trees (needles, branches and bole wood), ground vegetation, litter layer and soil (LF, A and B horizon) were sampled at the end of each labelling period. Extractable inorganic N, microbial N, and immobilised soil N were analysed in the LF and A horizons. During the whole labelling period, the runoff water was sampled as well. Most of the added tracer remained in both ecosystems. More NO3 than NH4+ tracer was retained, especially in the forest. The highest recovery was in the soil, mainly in the organic horizon, and in the ground vegetation, especially in the mosses. Event-based runoff analyses showed an immediate response of 15NO3 in runoff, with sharp 15N peaks corresponding to discharge peaks. NO3 leaching showed a clear seasonal pattern, being highest in spring during snowmelt. The high capacity of N retention in these ecosystems leads to the assumption that deposited N accumulates in the soil organic matter, causing a progressive decline of its C:N ratio.  相似文献   

10.
11.
12.
The molecular weight and subunit composition of Cl-,HCO3(-)- and picrotoxin-stimulated Mg2+-ATPase from rat brain plasma membrane solubilized in sodium deoxycholate were studied by gel filtration chromatography. The enzyme activity eluted from a Sephacryl S-300 column in a single peak associated with a protein of molecular weight approximately 300 kD and a Stokes radius of 5.4 nm. The enzyme-enriched fraction, concentrated and denatured by SDS, migrated through a Sephacryl S-200 column as three peaks with molecular weights of approximately 57, 53, and 45 kD. SDS-PAGE also showed three major protein bands with molecular weights of about 57, 53, and 48 kD. The molecular weight and subunit composition of the Cl- and HCO3(-)-stimulated Mg2+-ATPase from neuronal membrane of rat brain are similar with the molecular properties of GABA(A)-benzodiazepine receptor complex from mammalian brain but are different from those of P-type transport ATPases.  相似文献   

13.
Mitochondrial production of H2O2 is low with NAD substrates (glutamate/pyruvate, 3 and 2 mM) (G/P) and increases over ten times upon further addition of succinate, with the formation of a sigmoidal curve (semimaximal value at 290 μM, maximal H2O2 production at 600 μM succinate). Malate counteracts rapidly the succinate induced increased H2O2 release and moves the succinate dependent H2O2 production curve to the right. Nitric oxide (NO) and carbon monoxide (CO) are cytochrome c oxidase inhibitors which increase mitochondrial ROS production. Cyanide (CN) was used to mimic NO and CO. In the presence of G/P and succinate (300 μM), CN progressively increased the H2O2 release rate, starting at 1.5 μM. The succinate dependent H2O2 production curve was moved to the left by 30 μM CN. The Vmax was little modified. We conclude that succinate is the controller of mitochondrial H2O2 production, modulated by malate and CN. We propose that succinate promotes an interaction between Complex II and Complex I, which activates O2 production.  相似文献   

14.
Homology modeling of the complete structure of the large cytoplasmic loop between the fourth and fifth transmembrane segments (H4–H5 loop) of the subunit of Na+/K+-ATPase is reported. The deduced amino acid sequence shows high sequence identity and homology to the Ca2+-ATPase (32.8% identity and 53.3% similarity in our alignment), whose tertiary structure has been solved recently at 2.6-Å resolution by X-ray crystallography. This high homology allowed the construction of a model structure using the MODELLER program. Refinement was achieved through interactive visual and algorithmic analysis and minimization with the TRIPOS force field included in the SYBYL/MAXIMIN2 module. The docking of ATP as a substrate into the active site of the model was explored with the AUTODOCK program followed by molecular mechanics optimization of the most interesting complexes. Thus, the docking of ATP into the resulting model of the H4–H5 loop gave evidence for the existence of one ATP binding site only. We were able to specify Cys549, Phe548, Glu505, Lys501, Gln482, Lys480, Ser477, Phe475 and Glu446 as parts of the ATP binding site with Lys501 located in the depth of the positively charged binding pocket.Electronic Supplementary Material available.  相似文献   

15.
Although field studies have demonstrated an ecosystem-specific effect of experimental atmospheric nitrogen (N) deposition on litter decomposition, a mechanistic understanding of how ligninolytic microbial communities respond to atmospheric deposition is lacking. Because high levels of inorganic N suppress lignin decomposition by some basidiomycetes, it is plausible that the abundance and activity of these key microorganisms underlies differential ecosystem responses of decomposition to atmospheric N deposition. We hypothesize that: (a) atmospheric N deposition will cause an ecosystem-specific reduction in basidiomycete activity and abundance with greatest decreases in ecosystems with lignin-rich forest litter and (b) the abundance of lignin degrading basidiomycetes will be positively correlated with ligninolytic enzyme activity. To test these hypotheses, we measured the effects of experimental N deposition on the potential activity of phenol oxidase enzymes, and the abundance of basidiomycete genes encoding laccase, a primary phenol oxidase enzyme, in three hardwood forests spanning a range of leaf litter lignin content. The black oak-white oak (BOWO) contains high lignin litter, the sugar maple-basswood (SMBW) has low lignin litter, and the sugar maple-red oak (SMRO) is intermediate. An ecosystem by N deposition interaction significantly influenced phenol oxidase activity in the surface soil (P = 0.05), where phenol oxidase activity decreased with increasing experimental N deposition in the BOWO ecosystem. No consistent response to N deposition was evident for surface soil phenol oxidase activity within either the SMRO or SMBW ecosystem. This interaction did not influence laccase gene abundance. Instead, basidiomycete laccase gene abundance was reduced by experimental N deposition (main effect) in surface soil. There was only a weak correlation between basidiomycete laccase gene abundance and potential phenol oxidase enzyme activity, suggesting that the abundance of organisms possessing laccase genes may not control phenol oxidase activity in soil. Our results suggest that the regulation of laccase gene expression may mediate the decomposition response to atmospheric N deposition.  相似文献   

16.
The cystine/glutamate exchanger (antiporter xc) is a membrane transporter involved in the uptake of cystine, the rate-limiting amino acid in the synthesis of glutathione. Recent studies suggest that the antiporter plays a role in the slow oxidative excitotoxity and in the pathological effects of β-N-oxalylamino-l-alanine, the molecule responsible for neurolathyrism, a neurotoxic upper motor neuron disease. The mouse cystine/glutamate exchanger has been cloned and showed to be composed of two distinct proteins, one of which being a novel protein, named xCT, of 502 amino acids and 12 putative trans-membrane domains. We have generated and purified a polyclonal antibody to mouse xCT and studied its expression in rat brain and in different cultured cells (astrocytes, fibroblasts and neurons) using Western blot and immunocytochemical techniques. Expression of xCT was also studied in rat brain and muscle at different developmental stages. Parallel experiments were carried out with antibodies to the heavy chain of 4F2 surface antigen, the non-specific subunit of the antiporter xc. xCT antibody detected in all cell and tissue extracts a specific band of about 40 kDa. Subcellular fractionation demonstrated that xCT is concentrated mainly in the microsomal-mitochondrial fraction, in accord with its structure as transmembrane protein. Immunocytochemical analysis showed a strong staining in all cells examined, included neurons. Furthermore, both xCT and the heavy chain of 4F2 surface antigen increased in the brain during development, reaching the highest expression in adulthood. The study of the expression and developmental profile of xCT represents a first step towards a better characterization of its biochemical properties and function, which in turn may help to understand the relative contribution of the xc antiporter in the pathogenesis of certain neurodegenerative diseases.  相似文献   

17.
The effect of NO3 ?:NH4 + ratio (14:1, 9:6, 7.5:7.5, 1:14, total 15 mmol/L N) in the nutrient solution on biomass, root morphology, and C and N metabolism parameter in hydroponically grown oilseed rape (Brassica napus L.) was evaluated. The dry weights of leaves and roots were significantly largest at the equal NO3 ?:NH4 + ratio (7.5:7.5) compared with those of high NO3 ?:NH4 + ratio (14:1) or low NO3 ?:NH4 + ratio (1:14). Additionally, low NO3 ?:NH4 + ratio (1:14) reduced total root length and root surface area compared with the equal NO3 ?:NH4 + ratio (7.5:7.5), while high NO3 ?:NH4 + ratio (14:1) did not show any significant effect on root morphology except average diameter. The maximum of chlorophyll a, chlorophyll b and carotenoid were obtained under 7.5:7.5 treatment, whereas the maximum of the leaf net photosynthetic (P n), stomatal conductance (G s) and transpiration rate (T r) were increased with increase in NH4 + concentration in the nutrient solution. The activity of nitrate reductase (NR) showed a significant difference at different NO3 ?:NH4 + ratios and ranged 9:6 > 7.5:7.5 > 14:1 > 1:14, whereas the range of soluble sugar and soluble protein was 7.5:7.5 > 1:14 > 9:6 > 14:1. Our study reveals that oilseed rape growth is greater under 7.5:7.5 treatment than that under three other treatments. Oilseed rape growth at high or low NO3 ?:NH4 + ratios was inhibited by decreased pigments, NR activity, soluble sugar, and soluble protein, whereas subdued root growth should be apprehended considerate under high NH4 + condition.  相似文献   

18.
MHC class I molecules are heterotrimeric complexes composed of heavy chain, 2-microglobulin (2m) and short peptide. This trimeric complex is generated in the endoplasmic reticulum (ER), where a peptide loading complex (PLC) facilitates transport from the cytosol and binding of the peptide to the preassembled ER resident heavy chain/2m dimers. Association of mouse MHC class I heavy chain with 2m is characterized by allelic differences in the number and/or positions of amino acid interactions. It is unclear, however, whether all alleles follow common binding patterns with minimal contributions by allele-specific contacts, or whether essential contacts with 2m are different for each allele. While searching for the PLC binding site in the 3 domain of the mouse MHC class I molecule H-2Db, we unexpectedly discovered a site critical for binding mouse, but not human, 2m. Interestingly, amino acids in the corresponding region of another MHC class I heavy chain allele do not make contacts with the mouse 2m. Thus, there are allelic differences in the modes of binding of 2m to the heavy chain of MHC class I.  相似文献   

19.
We report on the transformation and expression in sugar beet (Beta vulgaris) hairy roots of a Nicotiana alata NaPI gene encoding a serine proteinase inhibitor (PI) that has been shown to effectively reduce the population of a number of insect pests. Using in-gel analysis, two PI protein activities were detected at approximately 24- and/or 28-kDa in hairy roots generated via Agrobacterium rhizogenes-mediated gene transfer. Immunoblot analysis revealed the presence of the expected ~40 kDa precursor, and in some transformants, a ~20 kDa processing intermediate and the mature 6-kDa PIs. In general, processing of the precursor in the clonal lines was reduced or not detected. The reduced efficiency of post-translational processing of the N. alata PI precursor may be attributed to modification and/or altered folding of the recombinant protein or distinct post-translational machinery functioning in sugar beet hairy roots and Nicotiana. Disclaimer: Mention and/or use of a commercial or proprietary product to the exclusion of others does not constitute endorsement by the USDA.  相似文献   

20.
Trace elements have been recognized to play an important role in the development of Parkinson’s disease (PD). However, it is difficult to precisely identify the relationship between these elements and the progression of PD because of an insufficient number of patients. In this study, quantifications of selenium (Se), copper (Cu), iron (Fe) and zinc (Zn) by atomic absorption spectrophotometry were performed in plasma from 238 PD patients and 302 controls recruited from eastern China, which is so far the largest cohort of PD patients and controls for measuring plasma levels of these elements. We found that plasma Se and Fe concentrations were significantly increased whereas Cu and Zn concentrations decreased in PD patients as compared with controls. Meanwhile, these four elements displayed differential changes with regard to age. Linear and logistic regression analyses revealed that both Fe and Zn were negatively correlated with age in PD patients. Association analysis suggests that lower plasma Se and Fe levels may reduce the risk for PD, whereas lower plasma Zn is probably a PD risk factor. Finally, a model was generated to predict PD patients based on the plasma concentrations of these four trace elements as well as other features such as sex and age, which achieved an accuracy of 80.97±1.34% using 10-fold cross-validation. In summary, our data provide new insights into the roles of Se, Cu, Fe and Zn in PD progression.  相似文献   

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