共查询到20条相似文献,搜索用时 15 毫秒
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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
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Cui Y Karunasekara Y Harvey PJ Board PG Dulhunty AF Casarotto MG 《Journal of biomolecular NMR》2005,32(1):89-90
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Presence of Ornithine in the Urate-binding α<Subscript>1</Subscript>—<Subscript>2</Subscript>Globulin 总被引:1,自引:0,他引:1
THE urate-binding α1–α2 globulin has been isolated from human plasma in a highly purified state1. The protein was purified by DEAE-‘Sephadex’, ammonium sulphate precipitation and semi-preparative Polyacrylamide gel electrophoresis. The urate-binding α1–α2 globulin is a rod-shaped glycoprotein, containing 12.1% carbohydrate, with an isoelectric point of 4.6 and a molecular weight of 67,000 ± 4,000. Amino-acid analysis indicated an unknown basic compound which appeared as an extra peak just in front of lysine1. To identify this compound, high voltage paper electrophoresis has been carried out on a plate electrophoresis apparatus in pyridine-acetate buffer pH 3.5. A spot separated out corresponding to ornithine. Amino-acid analysis on a BC-200 automatic analyser (Bio-Cal Instruments Co., West Germany), with a 54 cm column at 55° C and with 0.35 M sodium citrate buffer, pH 5.28, as elution buffer at a flow-rate of 150 ml./h, showed that ornithine was present. The presence of ornithine in the protein hydrolysate was also verified by gas chromatography/mass spectrometry2. 相似文献
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V. A. Belyaev D. A. Kozlov A. A. Terent’ev A. E. Trenin 《Plasma Physics Reports》2017,43(10):1039-1041
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
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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
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While ~30% of the human genome encodes membrane proteins, only a handful of structures of membrane proteins have been resolved to high resolution. Here, we studied the structure of a member of the Cys-loop ligand gated ion channel protein superfamily of receptors, human type A γ2α1β2α1β2 gamma amino butyric acid receptor complex in a lipid bilayer environment. Studying the correlation between the structure and function of the gamma amino butyric acid receptor may enhance our understanding of the molecular basis of ion channel dysfunctions linked with epilepsy, ataxia, migraine, schizophrenia and other neurodegenerative diseases. The structure of human γ2α1β2α1β2 has been modeled based on the X-ray structure of the Caenorhabditis elegans glutamate-gated chloride channel via homology modeling. The template provided the first inhibitory channel structure for the Cys-loop superfamily of ligand-gated ion channels. The only available template structure before this glutamate-gated chloride channel was a cation selective channel which had very low sequence identity with gamma aminobutyric acid receptor. Here, our aim was to study the effect of structural corrections originating from modeling on a more reliable template structure. The homology model was analyzed for structural properties via a 100 ns molecular dynamics (MD) study. Due to the structural shifts and the removal of an open channel potentiator molecule, ivermectin, from the template structure, helical packing changes were observed in the transmembrane segment. Namely removal of ivermectin molecule caused a closure around the Leu 9 position along the ion channel. In terms of the structural shifts, there are three potential disulfide bridges between the M1 and M3 helices of the γ2 and 2 α1 subunits in the model. The effect of these disulfide bridges was investigated via monitoring the differences in root mean square fluctuations (RMSF) of individual amino acids and principal component analysis of the MD trajectory of the two homology models—one with the disulfide bridge and one with protonated Cys residues. In all subunit types, RMSF of the transmembrane domain helices are reduced in the presence of disulfide bridges. Additionally, loop A, loop F and loop C fluctuations were affected in the extracellular domain. In cross-correlation analysis of the trajectory, the two model structures displayed different coupling in between the M2–M3 linker region, protruding from the membrane, and the β1-β2/D loop and cys-loop regions in the extracellular domain. Correlations of the C loop, which collapses directly over the bound ligand molecule, were also affected by differences in the packing of transmembrane helices. Finally, more localized correlations were observed in the transmembrane helices when disulfide bridges were present in the model. The differences observed in this study suggest that dynamic coupling at the interface of extracellular and ion channel domains differs from the coupling introduced by disulfide bridges in the transmembrane region. We hope that this hypothesis will be tested experimentally in the near future. 相似文献
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Nishit Goradia Amelie Wißbrock Christoph Wiedemann Frank Bordusa Ramadurai Ramachandran Diana Imhof Oliver Ohlenschläger 《Biomolecular NMR assignments》2016,10(2):329-333
Interleukin-36α (IL-36α) is a recently characterised member of the interleukin-1 superfamily. It is involved in the pathogenesis of inflammatory arthritis in one third of psoriasis patients. By binding of IL-36α to its receptor IL-36R via the NF-κB pathway other cytokines involved in inflammatory and apoptotic cascade are activated. The efficacy of complex formation is controlled by N-terminal processing. To obtain a more detailed view on the structure function relationship we performed a heteronuclear multidimensional NMR investigation and here report the 1H, 13C, and 15N resonance assignments for the backbone and side chain nuclei of the pro-inflammatory cytokine interleukin-36α. 相似文献
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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
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E. V. Navolotskaya V. B. Sadovnikov D. V. Zinchenko V. I. Vladimirov Y. A. Zolotarev 《Russian Journal of Bioorganic Chemistry》2017,43(6):673-677
The 125I-labeled B-subunit of the cholera toxin ([125I]CT-B, specific activity of 98 Ci/mmol) was prepared. This subunit was shown to be bound to the membranes which were isolated from epithelial cells of a mucous tunic of the rat thin intestine with high affinity (K d = 3.7 nM). The binding of the labeled protein was inhibited by the unlabeled α2-interferon (IFN-α2), α1-thymosin, (TM-α1), and the LKEKK synthetic peptide corresponding to the 16–20 sequence of TM-α1 and the 131–135 sequence of human IFN-α2 (Ki 1.0, 1.5, and 2.0 nM, respectively), whereas the KKEKL unlabeled synthetic peptide did not inhibit the binding (K i > 100 μМ). The LKEKK peptide and CT-B were shown to dose-dependently increase an activity of the soluble guanylate cyclase (sGC) in the concentration range from 10 to 1000 nM. Thus, the binding of TM- α1, IFN-α2, and the LKEKK peptide to the CT-B receptor on a surface of the epithelial cells of the mucous tunic of the rat thin intestine resulted in an increase in the intracellular level of cGMP. 相似文献
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E. Yu. Aleshina N. V. Pyndyk A. A. Moisa M. A. Sanzhakov O. N. Kharybin E. N. Nikolaev E. F. Kolesanova 《Biochemistry (Moscow) Supplemental Series B: Biomedical Chemistry》2008,2(3):288-292
The peptide RHDSGY, a fragment of the human β-amyloid Zn-binding site, and its isomers RH(D-Asp)SGY and RH(β-Asp)SGY have been obtained as amides by means of solid-phase synthesis and analyzed by HPLC and various mass spectrometric methods. The problem of low yield of the RHDSGY peptide and its isomers attributed to 9-fluorenylmethoxycarbonyl (Fmoc)-amino acids and/or formation of such side-products as RH(β-Asp)SGY (or RHDSGY during synthesis of RH(β-Asp)SGY) and RH(Asp-imide) SGY was solved via selection of individual reagents for removal of Fmoc groups from α-amino groups of the growing peptide chain. 相似文献
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Umitsu M Morishita H Murata Y Udaka K Akutsu H Yagi T Ikegami T 《Journal of biomolecular NMR》2005,31(4):365-366
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Daryl Codron Matt Sponheimer Jacqui Codron Sven Hammer Andreas Tschuor Ueli Braun Stefano M. Bernasconi Marcus Clauss 《European Journal of Wildlife Research》2012,58(1):303-313
Faecal stable isotope compositions reflect wildlife diets, if digestive processes along the gastrointestinal tract (GIT) do
not alter diet–faeces isotopic relationships in an unpredictable way. We investigated 13C and 15N compositions of digesta along the ruminant GIT, using Saanen dairy goats kept on pure grass hay or browse for >20 days.
Isotopic changes occurred in the ventral rumen, and in the small intestine, where digesta had significantly higher δ13C and δ15N (associated with lower C or higher N content, respectively) values relative to other GIT sites. However, effects on isotope
fractionation were small (∼1.0‰ for δ13C and ∼ 2.0‰ for δ15N), and were reversed in the hindgut such that faecal isotope compositions did not differ from the foregut. No other substantial
isotopic changes occurred across GIT sites, despite the morphophysiological complexity of the ruminant GIT. We found similarly
small differences across GIT components of rheem gazelles (Gazella leptoceros) fed a mixture of C3 lucerne and C4 grass, although in this case faeces were 15N-depleted relative to other GIT components. Along with differences in δ15N between goats fed browse or grass, this result implies a systematic difference in diet–faeces δ15N relationships, contingent on the botanical composition of ruminant diets. Thus, while our results support faecal δ13C as a reliable proxy for wildlife diets, further work on factors influencing faecal 15N abundance is needed. Finally, we note high levels of isotopic variability between individuals fed the same diets, even accounting
for the relatively short duration of the experiments, suggesting an important influence of stochasticity on isotope fractionation. 相似文献
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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
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A TROSY-based NMR experiment is described for simultaneous measurement of the 15N longitudinal relaxation rate constant R1 and the {1H}–15N nuclear Overhauser enhancement. The experiment is based on the observation that the TROSY mixing pulse sequence element symmetrically exchanges 1H and 15N magnetizations. The accuracy of the proposed technique is validated by comparison to independent measurements of both relaxation parameters for the protein ubiquitin. The simultaneous experiment is approximately 20–33% shorter than conventional sequential measurements. 相似文献
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We have examined the effect of inorganic and organic carbon nutrition on the physiological expression of HCO3- transport and the CO2-concentrating mechanism (CCM) in the nutritionally versatile cyanobacterium Chlorogloeopsis sp. ATCC 27193. Cells grown under photoautotrophic conditions in the presence of limiting or replete levels of inorganic carbon (Ci), or grown under mixotrophic (light) or chemoheterotrophic (dark) conditions in the presence of sucrose retained both active CO2 and Na(+)-independent HCO3- transport activity. However, two distinct effects on the kinetic properties of HCO3- transport were observed, which segregated on the basis of phototrophic and chemoheterotrophic growth in the dark. In the former, the apparent substrate affinity of the HCO3- transport system (K0.5) varied (12-fold) in response to the growth Ci or mixotrophy while the maximum rate of HCO3- transport was approximately constant. In the latter case, the K0.5 value was unchanged from the starting value (35 microM) of Ci-limited photoautotrophic cells used to initiate the dark-grown cultures, but transport capacity declined 3-fold. Modulation of the K0.5 (HCO3- transport) value required light. Cellular carboxysome content was unaffected by growth under any of the regimes employed and these structures were the predominant location of ribulose-1,5-bisphosphate carboxylase/oxygenase, as indicated by immunogold electron microscopy. Mixotrophic and chemoheterotrophic growth resulted in a diminished ability to concentrate Ci internally and a reduction in Ci accumulation ratios at low external Ci concentrations. The relationship between photosynthetic carbon fixation and the internal Ci pool varied by 2-fold, with high-Ci-grown cells being the most efficient and mixotrophically grown cells the least, indicating that there was limited capacity to modulate this relationship in response to changes in carbon nutrition. Within broad limits this relationship appeared to be a fixed trait of the strain and an important factor in determining growth rate. 相似文献
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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 NO3− deposition (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