首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 15 毫秒
1.
A parametric nonorthogonal tight-binding model (NTBM1) with the set of parameters for H–C–N–O systems is presented. This model compares well with widely used semi-empirical AM1 and PM3/PM7 models but contains less fitting parameters per atom. All NTBM1 parameters are derived based on a criterion of the best agreement between the calculated and experimental values of bond lengths, valence angles and binding energies for various H–C–N–O molecules. Results for more than 200 chemical compounds are reported. Parameters are currently available for hydrogen, carbon, nitrogen, oxygen atoms and corresponding interatomic interactions. The model has a good transferability and can be used for both relaxation of large molecular systems (e.g., high-molecular compounds or covalent cluster complexes) and long-timescale molecular dynamics simulation (e.g., modelling of thermal decomposition processes). The program package based on this model is available for download at no cost from http://ntbm.info.  相似文献   

2.
农业流域有机质流失造成水体富营养化和土地退化,不仅威胁水质和粮食安全,而且会导致温室气体排放等潜在环境问题。本研究用13C、15N和C/N作为指纹标志物,分析了南岳小流域出口沉积有机质的来源及其在林地、稻田和菜地等典型土地利用类型土壤的空间分布特征,并结合贝叶斯稳定同位素混合模型定量估算了各土地利用类型的贡献率。结果表明: δ13C具有显著的空间差异,沉积物有机质(-22.6‰±0.53‰)和林地土壤(-23.13‰±1.71‰)的δ13C显著高于稻田土壤(-25.24‰±1.4‰)。各土地利用类型土壤的δ15N差异不显著,沉积物的均值最大,为(4.37±0.83)‰,林地最小,为(2.38±1.97)‰;林地土壤的C/N均值最大,为16.66±7.18,稻田土壤的C/N均值最小,为11.95±0.92。贝叶斯稳定同位素混合模型结果显示,林地、稻田和菜地对流域出口沉积有机质的贡献率分别为19.6%、15.7%和64.7%;稻田和菜地作为农业用地的总贡献率为80.4%。说明农业用地土壤是南岳小流域沉积有机质的主要来源,可以通过优化农田管理措施有效控制流域养分流失。  相似文献   

3.
Thirteen X-ray crystal structures containing various non-covalent interactions such as halogen bonds, halogen–halogen contacts and hydrogen bonds (I?N, I?F, I?I, F?F, I?H and F?H) were considered and investigated using the DFT-D3 method (B97D/def2-QZVP). The interaction energies were calculated at MO62X/def2-QZVP and MP2/aug-cc-pvDZ level of theories. The higher interaction and dispersion energies (2nd crystal) of ?9.58 kcal mol?1 and ?7.10 kcal mol?1 observed for 1,4-di-iodotetrafluorobenzene bis [bis (2-phenylethyl) sulfoxide] structure indicates the most stable geometrical arrangement in the crystal packing. The electrostatic potential values calculated for all crystal structures have a positive σ-hole, which aids understanding of the nature of σ-hole bonds. The significance of the existence of halogen bonds in crystal packing environments was authenticated by replacing iodine atoms by bromine and chlorine atoms. Nucleus independent chemical shift analysis reported on the resonance contribution to the interaction energies of halogen bonds and halogen–halogen contacts. Hirshfeld surface analysis and topological analysis (atoms in molecules) were carried out to analyze the occurrence and strength of all non-covalent interactions. These analyses revealed that halogen bond interactions were more dominant than hydrogen bonding interactions in these crystal structures.
Graphical Abstract Molecluar structure of 1,4-Di-iodotetrafluorobenzene bis(thianthrene 5-oxide) moelcule and its corresponding molecular electrostatic potential map for the view of σ-hole.
  相似文献   

4.
5.
This paper describes a [15N,1H]/[13C,1H]-TROSY experiment for the simultaneous acquisition of the heteronuclear chemical shift correlations of backbone amide 15N–1H groups, side chain 15N–1H2 groups and aromatic 13C–1H groups in otherwise highly deuterated proteins. The 15N–1H and 13C–1H correlations are extracted from two subspectra of the same data set, thus preventing possible spectral overlap of aromatic and amide protons in the 1H dimension. The side-chain 15N–1H2 groups, which are suppressed in conventional [15N,1H)-TROSY, are observed with high sensitivity in the 15N–1H subspectrum. [15N,1H]/[13C,1H]-TROSY was used as the heteronuclear correlation block in a 3D [1H,1H]-NOESY-[15N,1H]/[13C,1H]-TROSY experiment with the membrane protein OmpA reconstituted in detergent micelles of molecular weight 80000 Da, which enabled the detection of numerous NOEs between backbone amide protons and both aromatic protons and side chain 15N–1H2 groups.  相似文献   

6.
Several β-amidodehydroaminobutyric acid derivatives were prepared from N,C-diprotected β-bromodehydroaminobutyric acids and amides by a copper catalyzed C–N coupling reaction. The best reaction conditions include the use of a catalytic amount of CuI, N,N′-dimethylethylenediamine as ligand and K2CO3 as base in toluene at 110 °C. The stereochemistry of the products was determined using NOE difference experiments and the results obtained are in agreement with an E-stereochemistry. Thus, the stereochemistry is maintained in the case of the E-isomers of β-bromodehydroaminobutyric acid derivatives, but when the Z-isomers were used as substrates the reaction proceeds with inversion of configuration. The use of β-bromodehydrodipeptides as substrates was also tested. It was found that the reaction outcome depend on the stereochemistry of the β-bromodehydrodipeptide and on the nature of the first amino acid residue. The products isolated were the β-amidodehydrodipeptide derivatives and/or the corresponding dihydropyrazines. The same catalytic system (CuI/N,N′-dimethylethylene diamine) was used in the C–O coupling reactions between a tyrosine derivative and aryl bromides. The new O-aryltyrosine derivatives were isolated in moderate to good yields. The photophysical properties of two of these compounds were studied in four solvents of different polarity. The results show that these compounds after deprotection can be used as fluorescence markers.  相似文献   

7.
We describe here, adaptation of the HNN pulse sequence for multiple nuclei detection using two independent receivers by utilizing the detectable 13Cα transverse magnetization which was otherwise dephased out in the conventional HNN experiment. It enables acquisition of 2D 13Cα15N sequential correlations along with the standard 3D 15N–15N–1H correlations, which provides directionality to sequential walk in HNN, on one hand, and enhances the speed of backbone assignment, on the other. We foresee that the implementation of dual direct detection opens up new avenues for a wide variety of modifications that would further enhance the value and applications of the experiment, and enable derivation of hitherto impossible information.  相似文献   

8.
We present two time-shared experiments that enable the characterization of all nOes in 1H–13C-ILV methyl-labelled proteins that are otherwise uniformly deuterated and 15N enriched and possibly selectively protonated for distinct residue types. A 3D experiment simultaneously provides the spectra of a 3D NOESY-HN-TROSY and of a 3D NOESY-HC-PEP-HSQC. Thus, nOes from any protons to methyl or amide protons are dispersed with respect to 15N and 13C chemical shifts, respectively. The single 4D experiment presented here yields simultaneously the four 4D experiments HC-HSQC-NOESY-HC-PEP-HSQC, HC-HSQC-NOESY-HN-TROSY, HN-HSQC-NOESY-HN-TROSY and HN-HSQC-NOESY-HC-PEP-HSQC. This allows for the unambiguous determination of all nOes involving amide and methyl protons. The method was applied to a (1H,13C)-ILV−(1H)-FY-(U−2H,15N) sample of a 37 kDa di-domain of the E. coli enterobactin synthetase module EntF.  相似文献   

9.
Climate change has consequences for terrestrial functioning, but predictions of plant responses remain uncertain because of the gaps in the representation of nutrient cycles and C–N–P interactions in ecosystem models. Here, we review the processes that are included in ecosystem models, but focus on coupled C–N–P cycle models. We highlight important plant adjustments to climate change, elevated atmospheric CO2, and/or nutrient limitations that are currently not—or only partially—incorporated in ecosystem models by reviewing experimental studies and compiling data. Plant adjustments concern C:N:P stoichiometry, photosynthetic capacity, nutrient resorption rates, allocation patterns, symbiotic N2 fixation and root exudation (phosphatases, carboxylates) and the effect of root exudation on nutrient mobilization in the soil rhizosphere (P solubilization, biochemical mineralization of organic P and priming effect). We showed that several plant adjustments could be formulated and calibrated using existing experimental data in the literature. Finally, we proposed a roadmap for future research because improving ecosystem models necessitate specific data and collaborations between modelers and empiricists.  相似文献   

10.
以虾夷扇贝(Mizuhopecten yessoensis)的生长性状、闭壳肌脂肪酸组成与含量、闭壳肌C、N元素含量及其比值为主要考察指标, 在对比选育家系的生长性状差异的基础上, 分析了不同生长速度的虾夷扇贝家系闭壳肌脂肪酸组成与含量差异, 研究了闭壳肌C、N元素含量及其C/N比值与脂肪酸含量的相关性。结果表明, 不同扇贝家系闭壳肌的主要脂肪酸含量差异较小而相对丰度差异明显, EPA (3.59—4.09 mg/g)和DHA (3.03—3.46 mg/g)之和占比扇贝闭壳肌脂肪酸总量的47.19%—49.32%; 不同家系的虾夷扇贝闭壳肌C、N元素稳态性较好, C元素和N元素的含量分别为(39.21±0.04)%和(10.62±0.16)%, C/N比值为3.70±0.06; 相关分析表明家系闭壳肌C/N比值与TFA、SFA、PUFA、EPA以及DHA等脂肪酸含量呈显著负相关。因此, 在进行虾夷扇贝生长相关选择育种时, 可以结合闭壳肌脂肪酸组成与含量、闭壳肌元素C/N比值开展复合性状选育, 从而为扇贝闭壳肌高品质脂肪酸家系选育提供科学依据。  相似文献   

11.
1. An organism utilizing benzonitrile as sole carbon and nitrogen source was isolated by the enrichment-culture technique and identified as a Nocardia sp. of the rhodochrous group. 2. Respiration studies indicate that nitrile degradation proceeds through benzoic acid and catechol. 3. Cell-free extracts of benzonitrile-grown cells contain an enzyme that catalyses the conversion of benzonitrile directly into benzoic acid without intermediate formation of benzamide. 4. This nitrilase enzyme was purified by DEAE-cellulose chromatography and gel filtration on Sephadex G-100 in the presence and absence of substrate. The purity of the enzyme was confirmed by sodium dodecyl sulphate/polyacrylamide-gel electrophoresis and isoelectric focusing on polyacrylamide gel. 5. The enzyme shows a time-dependent substrate-activation process in which the substrate catalyses the association of inactive subunits of mol.wt. 45000 to form the polymeric 12-unit active enzyme of mol.wt. 560000. The time required for complete association is highly dependent on the concentration of the enzyme, temperature and pH. 6. The associated enzyme has a pH optimum of 8.0 and K(m) with benzonitrile as substrate of 4mm. The activation energy of the reaction as deduced from the Arrhenius plot is 51.8kJ/mol. 7. Enzyme activity is inhibited by thiol-specific reagents and several metal ions. 8. Studies with different substrates indicate that the nitrilase is specific for nitrile groups directly attached to the benzene ring. Various substituents in the ring are compatible with activity, though ortho-substitution, except by fluorine, renders the nitrile invulnerable to attack. 9. The environmental implications of these findings and the possible significance of the enzyme in the regulation of metabolism are discussed.  相似文献   

12.
对细叶小羽藓(Haplocladium microphyllum)新老组织及其根际土壤的碳氮含量和同位素组成进行了分析,探讨了苔藓衰老过程控制元素和同位 素变化的机制以及苔藓对土壤的贡献。同种组织碳氮含量之间的相关性反映了苔藓固碳能力和氮需求的相互联系。新生组织碳氮含量明显高于 衰老组织且存在相关性,反映了苔藓衰老过程体内碳氮物质向新生组织迁移的生理特征。两种组织之间同位素组成(δ13C和δ15N)没有明显差 异,说明组织间的物质迁移没有产生明显的同位素分馏,其原因可能在于细叶小羽藓形态结构简单,体内物质迁移对碳氮同位素组成的影响较 小。相反,苔藓组织与根际土壤之间的有机碳/ 氮信息没有相关性,这可能与苔藓植物长期滞留营养物质、缓慢的分解和成土速度有关,反映了 该研究区苔藓层对土壤碳氮累积的贡献较小。  相似文献   

13.
14.
潜流型菖蒲人工湿地不同C/N对污染物的去除效率   总被引:2,自引:0,他引:2  
选取炉渣和砾石为基质,以无植被为对照,分别设置低、中、高浓度的3个碳水平(C1、C2、C3)和3个氮水平(N1、N2、N3)处理,研究潜流型菖蒲人工湿地在不同C/N下净化生活污水中COD、总氮(TN)、总磷(TP)的效果。结果表明,在不同C/N下,菖蒲人工湿地对污水中COD、TN的去除效果显著高于无植被的人工湿地,菖蒲植被能增加人工湿地COD去除率10.53%,增加TN去除率6.73%;而对于TP的去除,有无植被无显著差异。随着进水N、P浓度及C/N的变化,菖蒲湿地对COD、TN和TP的去除率分别为67.57%~75.85%、20.91%~56.82%和7.15%~17.78%;同时,菖蒲植株对N、P的积累量也相应的变化,其地上部的N、P积累量为4.44~14.79和1.11~3.37g.m-2,平均占湿地N、P去除率的6.91%和10.67%;地下部的N、P积累量分别为2.35~5.20和0.74~1.41g.m-2,平均占湿地N、P去除率的2.69%和6.02%。植物地上器官对湿地N、P的积累量大于地下部,有利于通过收割作用去除湿地系统中的N、P。  相似文献   

15.
为了探究不同C/N(投入的总碳质量/投入的总氮质量)对生物絮凝硝化作用强度及微生物群落的影响,设置C/N为10∶、15∶1、20∶1、25∶1、30∶1进行相关研究.结果发现:C/N为10∶1和15∶1两组NO3-的积累量显著高于其他组的(P<0.05),且C/N为10∶1和15∶1两组NO3-的积累量存在显著性差异(P<0.05).5个处理组的氧化还原电位(ORP)在实验第一天迅速下降到负值,但5组间ORP变化均无显著性差异(P>0.05).从节约碳源的角度考虑,在第一批次实验筛选出的差异组间,即在C/N为10∶1和C/N为15∶1之间,设置C/N为10∶1、11∶1、12∶1、13∶1和14∶1,对照组不添加葡萄糖.结果显示,随着C/N的升高,各处理组NO3-的积累量逐渐下降.不添加碳源组NO3-的积累量明显高于其他组的(P>0.05).不添加碳源糖组与C/N为10∶1、11∶1组NO3-的积累量存在显著性差异(P<0.05),C/N为10∶1和15∶1组与C/N为12∶1、13∶1和14∶1组NO3-的积累量存在显著性差异(P<0.05).6个处理组ORP在实验第一天都迅速下降到负值,但6组间ORP变化均无显著性差异(P>0.05).将NO3-积累量有显著差异性的3个处理组(不添加碳源组,C/N=10、12组)进行高通量测序,发现3个处理组第一优势菌门和第一优势菌纲均为放线菌门和放线菌纲.在属水平中,芽孢杆菌属的丰度随着C/N的增加逐渐上升.综上所述,不添加碳源组的硝化作用强度最强,其余各处理组硝化作用强度随着C/N的升高逐渐降低.  相似文献   

16.
Amyloid fibrils are present in the extracellular space of various tissues in neurodegenerative and protein misfolding diseases. Amyloid fibrils may be used in nanotechnology applications, because of their self-assembly properties and stability, if their growth and orientation can be controlled. Recently, we have shown that amyloid beta 25-35 (A beta 25-35) forms a highly oriented, K(+)-dependent network on mica. Here, we analyzed the properties of A beta 25-35_N27C, the cysteine residue of which may be used for subsequent chemical modifications. We find that A beta 25-35_N27C forms epitaxially growing fibrils on mica, which evolve into a trigonally oriented branched network. The binding is apparently more sensitive to cation concentration than that of the wild-type peptide. By nanomanipulating A beta 25-35_N27C fibrils with a gold-coated AFM tip, we show that the sulfhydryl of Cys27 is reactive and accessible from the solution. The oriented network of A beta 25-35_N27C fibrils can therefore be specifically labeled and may be used for constructing nanobiotechnological devices.  相似文献   

17.
Carbon isotopic composition of soils subjected to C3–C4 vegetation change can be used to estimate C turnover in bulk soil and in soil organic matter (SOM) pools with fast and intermediate turnover rates. We hypothesized that the biological availability of SOM pools is inversely proportional to their thermal stability, so that thermogravimetry can be used to separate SOM pools with contrasting turnover rates. Soil samples from a field plot cultivated for 10.5 years with the perennial C4 plant Miscanthus×gigantheus were analyzed by thermogravimetry coupled with differential scanning calorimetry (DSC). Three SOM fractions were distinguished according to the differential weight losses and exothermic or endothermic reactions measured by DSC. The δ13C and δ15N values of these three fractions obtained by gradual soil heating were measured by IRMS. The weight losses up to 190 °C mainly reflected water evaporation because no significant C and N losses were detected and δ13C and δ15N values of the residual SOM remained unchanged. The δ13C values (−16.4‰) of SOM fraction decomposed between 190 and 390 °C (containing 79% of total soil C) were slightly closer to that of the Miscanthus plant tissues (δ13C = −11.8‰) compared to the δ13C values (−16.8‰) of SOM fraction decomposed above 390 °C containing the residual 21% of SOM. Thus, the C turnover in the thermally labile fraction was faster than that in thermally stable fractions, but the differences were not very strong. Therefore, in this first study combining TG-DSC with isotopic analysis, we conclude that the thermal stability of SOM was not very strongly related to biological availability of SOM fractions. In contrast to δ13C, the δ15N values strongly differed between SOM fractions, suggesting that N turnover in the soil was different from C turnover. More detailed fractionation of SOM by thermal analysis with subsequent isotopic analysis may improve the resolution for δ13C.  相似文献   

18.
Although several methods for determining erythrocyte lifespan are used in research studies that involve mice, all involve the alteration of RBC to allow for its tracking over time, which may affect overall RBC survival. The aims of this study were to determine 1) whether sex affects RBC survival; 2) whether RBC survival differs between the biotin method and an alternative method that uses GFP; and 3) whether repeat exposure of mice to biotin results in an antibiotin antibody response or decreased RBC survival. The results suggest no difference in the RBC half-life between male and female C57BL/6 mice (22.9 ± 1.2 and 22.4 ± 0.9 d, respectively). In addition, RBC half-life did not differ between the biotin- and GFP-based methods (20.5 ± 2.1 d and 22.7 ± 2.1 d, respectively). Finally, retransfusion of mice 90 d after an initial transfusion with biotin-labeled RBC did not induce detectable antibiotin antibodies nor alter the half-life of transfused biotin-labeled RBC (initial transfusion, 22.0 ± 1.2 d; subsequent transfusion, 23.4 ± 1.4 d, respectively).Abbreviations: T1/2, half-lifeRBC lifespan and senescence are important parameters used both clinically and in research studies of hereditary disorders of erythrocyte metabolism, transfusion medicine, and sepsis.8,21,27,32,35 Labeling RBC with a biotinylating reagent is a common method used to determine their circulating lifespan. Other methods involve using radioactive isotopes, such as 51Cr and 59Fe.7,20 Biotinylating reagents are preferred for various research applications with humans,8,23,24 and are used in a variety of animal models.1,25,33,34,37 Once biotin attaches to RBC surface proteins, streptavidin (a protein derived from Streptomyces avidinii) that is labeled with a fluorescent dye is used to form a strong and rapid complex with biotin, thereby allowing for its detection through flow cytometry. Blood samples analyzed sequentially over a period of weeks will show a linear decline in biotin–streptavidin signal as labeled cells age and are cleared from the circulation through the reticuloendothelial system.The characteristics of an ideal label for performing RBC survival studies include: 1) stable presence on or within the cell throughout its normal lifespan; 2) specificity for RBC; 3) inertness, such that the cell does not become prone to accelerated destruction; 4) nonrecycling (that is, the label does not reenter the circulation and bind to new cells after destruction of the labeled RBC); and 5) easy and accurate measurement by using available assays. Radioactive isotopes and other labels fulfill several of these criteria, but their limitations include elution from RBC as well as safety concerns.7,22 In contrast, biotin poses little to no risk of accumulation or toxicity. The sulfo- N-hydroxysuccinimide–biotin ester used for RBC tracking studies in humans and animals can be administered directly or through the transfusion of biotinylated RBC. Although it is generally accepted that biotinylation of RBC does not affect their function, antibodies to biotin have been demonstrated in some human studies, posing the question of whether repeated administration of biotin ester or biotinylated RBC could interfere with subsequent results within the same subject.4,20 Repeat transfusions of biotinylated RBC to mice have not been described in the literature. One aim of this study was to determine whether exposure to biotinylated RBC induces an antibiotin antibody response in mice. Furthermore, we tested whether the survival of biotinylated RBC changed after repeat exposure.Recently GFP-expressing RBC have been used to track the posttransfusion survival and recovery of stored RBC administered to nonGFP-expressing recipient mice.9,12,36 The C57BL/6-Tg(UBC–GFP)30Scha/J mouse strain is characterized by GFP expression under the control of a human ubiquitin C promoter. All tissues of these mice express GFP, including blood.26 GFP expression appears to be consistent throughout life and does not otherwise alter the normal structure, physiology, or function of RBC. In addition, GFP is unaffected by ambient light contamination or degradation, drawbacks that are associated with fluorescent dyes.15 In addition, GFP allows for the separation of cell populations through flow cytometry.9,11 Many qualities of GFP suggest that it may serve as a useful surrogate marker in place of other labeling techniques in mice. Therefore, we sought to evaluate the utility of UBC–GFP transgenic mice as an alternative to labeling RBC with biotin esters. Our aim for this work was to determine the survival of RBC in wild-type C57BL/6 mice and in the UBC–GFP strain and to compare methods for determining RBC half-life (T1/2).  相似文献   

19.
目的 为了获得白化的C57BL/6N小鼠,扩大其在皮肤移植和胚胎干细胞方面研究中的应用。方法 通过体外设计合成Cas9 mRNA和系列sgRNA(single guide RNAs),注射到小鼠的受精卵内,破坏合成C57BL/6N小鼠黑色素生成必须的酪氨酸酶(tyrosinase,TYR)基因序列的第1和第2外显子,产生基因突变,获得F0代白化的C57BL/6N小鼠,然后经过重复回交和自交,形成白化C57BL/6N小鼠近交系。结果 经过注射两对sgRNA,成功的获得了F0代的白化小鼠,在Tyr基因的第1和第2外显子中均发生了缺失突变,小鼠可以将突变基因传递给后代,并在其后代中产生了纯合的白色C57BL/6N小鼠,最后对白化小鼠突变类型进行了分析。结论 通过CRISPR-Cas9技术破坏了小鼠Tyr基因,成功地建立了白化C57BL/6N小鼠近交系,为将来的嵌合体制作、组织移植提供了新的研究工具。  相似文献   

20.
实验旨在探索不同C/N生物絮团对急性铜暴露洛氏鱥免疫抑制、炎症反应与氧化应激的保护作用。挑选480尾洛氏鱥(Rhynchocypris lagowskii Dybowski)幼鱼(10±0.15) g,随机分成4组,每组3个重复,每个重复40尾鱼。对照组饲喂商品料(C/N 10.8﹕1),实验组选择葡萄糖为外添碳源调节C/N 15﹕1(Ⅱ组)、C/N 20﹕1(Ⅲ组)和C/N 25﹕1(Ⅳ组),生长实验为56d,之后进行为期96h的急性铜暴露胁迫实验。结果表明,各实验组中免疫、抗氧化酶活性与炎症因子含量随着C/N的增加先升高后下降。其中,与对照组相比,Ⅲ和Ⅳ组血清碱性磷酸酶(AKP)、酸性磷酸酶(ACP)、溶菌酶(LSZ)、一氧化氮合酶(NOS)、补体C3、C4和免疫球蛋白M(IgM)水平显著升高(P<0.05),而Ⅲ和Ⅳ组之间补体C3和C4水平差异不显著(P>0.05);Ⅲ和Ⅳ组血清过氧化氢酶(CAT)、抗坏血酸(ASA)、超氧化物歧化酶(SOD)、总抗氧化能力(T-AOC)、谷胱甘肽过氧化物酶(GSHPX)与谷胱甘肽还原酶(GR)酶活性显著高于对照组(P<0.05...  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号