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1.
The 1H- and 13C-NMR spectra of dogoxin in solution in Me2So-d6 have been assigned completely. Measurement of the 3JC,H values has enabled estimation of the torsional angles involving the bonds linking the digitoxose residues, between the inner digitoxose and the genin unit, and for the unsaturated γ-lactone ring. These values have been supplemented by 1H---1H NOE data. In general, there is good agreement between the conformations in solution (NMR data) and the solid state (X-ray data), and that derived from theological modelling which shows evidence of conformational flexibility. The major difference occurs for the torsion between the genin and the innermost digitoxose residue where molecular dynamics predict the presence of two conformations, one similar to that seen by NMR and the other similar to the X-ray structure.  相似文献   

2.
The reaction of the monoalkyl complex trans-[Pt(DMSO)2Cl(CH3)] with a large variety of heterocyclic nitrogen bases L, in chloroform solution, leads to the formation of uncharged complexes of the type [Pt(DMSO)(L)Cl(CH3)], containing four different groups coordinated to the metal center. Only two out of the three different possible isomers were detected in solution. These two trans(C,N) and cis(C,N) species can be unambiguously identified through 1H NMR spectroscopy. For the trans(C,N) isomers, average values of 2JPtH=75±4 Hz and 3JPtH=36±4 Hz have been observed for the coordinated methyl and DMSO ligands, respectively. In the case of the cis(C,N) isomers, these values increase to 2JPtH=83±2 Hz, and decrease to 3JPtH=26±3 Hz due to the mutual exchange of ligands in trans position to CH3 and DMSO. In the case of bulky asymmetric ligands, such as quinoline, 2-quinolinecarboxaldehyde, 2-methylquinoline, 5-aminoquinoline, 2-phenylpyridine and 2-chloropyridine, slow rotation of the hindered group around the Pt---N bond makes the coordinated DMSO ligand prochiral. NMR experiments have shown that the first reaction product is the trans(C,N) isomer as a consequence of the very fast removal of one DMSO ligand by the nitrogen bases from the starting complex trans-[Pt(DMSO)2Cl(CH3)]. This trans kinetic product undergoes a geometrical conversion into the more stable cis(C,N) isomer through the intermediacy of fast exchanging aqua-species. The rate of isomerization and the relative stability of the two isomers depends essentially on the rate of aquation and on the steric congestion imposed by the new L ligand on the metal.  相似文献   

3.
The119Sn and 13C NMR spectra of ten trivinyltin(IV) compounds in solutions of non-coordinating (deuteriochloroform, trideuterionitromethane) and coordinating (hexadeuteriodimethyl sulphoxide) solvents have been studied. From δ(119Sn) chemical shifts and 1J(119Sn,13C) coupling constants an evaluation of the coordination number of the central tin atom and the shape of coordination polyhedra around the tin atom has been carried out. Various effects on the δ(13C) chemical shifts of both carbon atoms of the vinyl group are also discussed.  相似文献   

4.
Two simple experiments measuring the 13C linewidths ν1/2 and spin–lattice relaxation times T1 of each of the signals in the spectrum of trilinolein indicate that the ν1/2 and T1 values are consistent with the different degrees of motional freedom expected for the various 13C nuclei. However, for each chain, the ν1/2 and T1 measurements indicate a small reversal in mobility at C-10 relative to C-9 before motional freedom again steadily increases on each chain starting at C-11. The T1 experiment allows unambiguous assignments of the C-8 signal and C-14 signal, which differ by only 0.010 ppm. Measurements of 13C ν1/2 and T1 values on tripalmitin provide secure assignments for the C-5 and C-6 signals, for which conflicting assignments have been reported. The T1 measurements also show that among the tightly clustered C-8 through C-12 signals, the C-11 signals are the most downfield, while the C-12 signals are the most upfield, again contrary to a previous report. Similar measurements of 13C ν1/2 and T1 values on other triacylglycerols or related compounds may prove equally useful in making chemical shift assignments and detecting any discontinuities in motional freedom along a chain. The benefits and possible limitations of ultrahigh field NMR for studying triacylglycerols and related compounds are discussed.  相似文献   

5.
为了探究锌对叶片光合产物向果实转移分配的影响机理,为苹果果实发育关键时期通过补锌措施提高果实品质奠定理论基础,以8年生‘寒富'/GM256/山定子为试材,采用13C同位素标记技术,研究苹果树叶片涂抹不同浓度锌(CK、Zn1、Zn2、Zn3、Zn4,分别代表浓度为0、0.1%、0.2%、0.3%和0.4%的ZnSO4·H2O溶液)对果实膨大期叶片13C同化能力及13C光合产物向果实运输的影响。结果表明: 随着锌浓度的增加,苹果树叶片Rubisco酶活性、净光合速率、山梨醇和蔗糖含量、6-磷酸山梨醇脱氢酶和蔗糖磷酸合酶活性,以及13C同化能力呈现先升高后降低的趋势,且均在Zn3处理下达到最高。与其他处理相比,Zn3处理的13C自留量(标记叶片+标记枝条)最低,为61.2%,而输出量最高,为38.8%。果实13C吸收量表现为Zn3>Zn2>Zn4>Zn1>CK。这说明叶片涂抹适宜浓度锌(0.3%ZnSO4·H2O溶液)处理增强了叶片的光合作用,提高了叶片光合产物的合成能力,促进了光合产物由叶片向果实的定向运输。  相似文献   

6.
化石燃料的大量使用和森林的过度砍伐,引起大气中CO2浓度的大幅度增加,同时由于Suess效应,大气CO2中的δ13C在不断地下降。植物中δ13C的变化是大气CO2浓度和同位素比值变化的敏感指示器。文中利用树木年轮δ13C序列和植物碳同位素分馏模型,尝试恢复了新疆阿勒泰地区近440年来大气δ13C的变化。结果表明,1850年之前,从树木年轮δ13C序列恢复的大气δ13C相对恒定在-6.60‰(R2=0.052),而1850年之后,该大气δ13C明显降低(R2=0.65),平均约为-7.04‰,平均年降低0.0084‰。这一结果高于从冰芯气泡所恢复的大气δ13C,1850年~1981年冰芯大气δ13C平均年降低约0.00657‰这可能与从树木年轮δ13C序列恢复的大气δ13C有更高的分辨率及树木生长点大气δ13C不同于全球大气δ13C值有关。  相似文献   

7.
植物凋落物碳输入显著影响陆地生态系统土壤CO2排放和有机碳(SOC)形成,然而,针对不同质地土壤添加不同化学结构外源碳去向依然不清楚。本研究将13C标记的葡萄糖、淀粉和纤维素添加至红壤和风沙土,比较2种质地土壤添加不同化学结构外源碳在土壤释放的CO2、SOC、可溶性有机碳(DOC)和微生物生物量碳(MBC)库的净累积量、回收率及贡献比例上的差异。结果表明: 添加外源有机碳显著提高了CO2、SOC、DOC和MBC的δ13C值,且随着外源有机碳化学结构复杂性的增加,CO2的δ13C峰值依次延迟出现;外源有机碳种类、土壤类型和培养时间均显著改变外源碳去向及其在各碳库的贡献比例;在风沙土中,外源有机碳更多被矿化为CO2,且CO2库的外源碳净累积量和回收率大小依次为葡萄糖>淀粉>纤维素;红壤添加外源碳转变为SOC的累积量和回收率显著高于风沙土,且红壤SOC库的外源碳净累积量和回收率大小顺序也为葡萄糖>淀粉>纤维素。可见,外源有机碳化学结构和土壤质地共同调控外源碳去向及累积贡献。  相似文献   

8.
采用13C-CO2进行连续标记,研究水稻分蘖期和孕穗期光合碳在植株-土壤系统中的分配及其对大气CO2浓度升高(800 μL·L-1)和施氮(100 mg·kg-1)的响应.结果表明: CO2浓度升高显著提高分蘖期根系生物量和孕穗期地上部生物量,并使生物量根冠比在分蘖期增加,而在孕穗期减小.CO2浓度升高条件下,施氮使水稻地上部分生物量增加,却显著降低了孕穗期水稻根系生物量.CO2浓度升高使光合13C在孕穗期向土壤的输入显著增加,然而施肥并没有促进由CO2浓度升高驱动的光合13C在土壤中的积累,而且还降低了土壤中的光合13C的分配比例.综上,CO2浓度升高显著提高了稻田土壤光合碳输入,促进稻田有机碳周转;施氮促进了水稻地上部的生长,却降低了光合碳向地下的分配比例.  相似文献   

9.
13C CP/MAS NMR spectroscopy has been shown to be a powerful tool to quantify the degree of acetylation of chitin and chitosan. In order to optimise the parameters which afford quantitative 13C cross-polarisation magic-angle spinning NMR spectra, a detailed relaxation study has been carried out on selected chitin and deacetylated chitin samples. A relaxation delay of 5 s and a contact time of 1 ms have been found to yield quantitative NMR spectra of samples with deacetylation degree values of 0.68 and 0.16. The measured spin-lattice relaxation times in the rotating frame, T1ρH, are in the range 6.4–8.9 ms for chitin and 4.3–7.3 ms for deacetylated chitin, while TCH values for both samples are very similar and range from 0.03 to 0.19 ms. Spin-counting experiments indicate that, within experimental error, all carbon is detected by NMR indicating that the samples studied contain no (or very few) paramagnetic centres.  相似文献   

10.
本研究采用离轴积分腔输出光谱技术对北京山区侧柏人工林进行了大气CO2浓度及其δ13C值的原位观测,在半小时尺度上对比了林内不同高度处大气CO2浓度及其δ13C值的差异,并探究其对气象因子的响应.结果表明: 林内CO2浓度自日出后经历先降低后升高的变化趋势,最低值出现在16:00—16:30,浓度为352.5 μmol·mol-1,最大值出现在5:00左右,达到402.0 μmol·mol-1,其δ13C值变化趋势微弱且较为复杂,呈现出近地层先降低后升高、林冠层先升高后降低的趋势;研究日期内,林内CO2浓度随高度的升高而降低,林内0、2、5、8、12.5和18 m处的日均值为386.5、369.9、368.2、367.8、367.9和367.9 μmol·mol-113C值呈现出随高度升高而升高的趋势,林内0、2、5、8、12.5和18 m处的日均值为-16.0‰、-13.7‰、-13.5‰、-13.5‰、-13.1‰和-13.3‰;逐步回归分析表明,温度和湿度是影响林内大气CO2浓度及δ13C值的主要因子,饱和蒸汽压差(VPD)可以影响林内CO2浓度变化,风速可以影响林冠层CO2浓度变化,而土壤含水率、电导率和地面净辐射则是影响近地层CO2浓度及δ13C值的环境因子.这些环境因子通过增强或减弱生态系统内光合作用和呼吸作用来影响林内CO2浓度及其δ13C值的变化.  相似文献   

11.
本研究采用离轴积分腔输出光谱技术对北京山区侧柏人工林进行了大气CO2浓度及其δ13C值的原位观测,在半小时尺度上对比了林内不同高度处大气CO2浓度及其δ13C值的差异,并探究其对气象因子的响应.结果表明: 林内CO2浓度自日出后经历先降低后升高的变化趋势,最低值出现在16:00—16:30,浓度为352.5 μmol·mol-1,最大值出现在5:00左右,达到402.0 μmol·mol-1,其δ13C值变化趋势微弱且较为复杂,呈现出近地层先降低后升高、林冠层先升高后降低的趋势;研究日期内,林内CO2浓度随高度的升高而降低,林内0、2、5、8、12.5和18 m处的日均值为386.5、369.9、368.2、367.8、367.9和367.9 μmol·mol-113C值呈现出随高度升高而升高的趋势,林内0、2、5、8、12.5和18 m处的日均值为-16.0‰、-13.7‰、-13.5‰、-13.5‰、-13.1‰和-13.3‰;逐步回归分析表明,温度和湿度是影响林内大气CO2浓度及δ13C值的主要因子,饱和蒸汽压差(VPD)可以影响林内CO2浓度变化,风速可以影响林冠层CO2浓度变化,而土壤含水率、电导率和地面净辐射则是影响近地层CO2浓度及δ13C值的环境因子.这些环境因子通过增强或减弱生态系统内光合作用和呼吸作用来影响林内CO2浓度及其δ13C值的变化.  相似文献   

12.
Assessing petroleum biodegradation rates is an important part of predicting natural attenuation in subsurface sediments. Monitoring carbon dioxide (CO2) and methane (CH4) produced in situ, and their radiocarbon 14C), stable carbon (13C) and deuterium (D). signature provide a novel method to assess anaerobic microbial processes. Our objectives were to: (1) estimate the rate of anaerobic petroleum hydrocarbon (PH) mineralization by monitoring the production of soil gas CH4 and CO2 in the vadose zone of low-permeability sediment, (2) evaluate the dominant microbial processes using δ13C and δD, and (3) determine the proportion of CH4 and CO2 attributable to anaerobic mineralization of PH using 14C analysis. Argon was sparged into the subsurface to dilute existing CO2 and CH4 concentrations. Vadose zone CO2, CH4, oxygen, total combustible hydrocarbons, and argon concentrations were measured for 75 days. CO2 and CH4 samples were collected on day 86 and analyzed for 14C, δ13C, and δD. Based on CH4 soil gas production, the anaerobic biodegradation rate was estimated between 0.017 to 0.055 mg/kg soil-d. CH4 14C (2.6 pMC), δ13C (-45.64‰), and δD (-316‰) values indicated that fermentation of PH was the sale source of CH4 in the vadose zone. CO2 14C (62 pMC) indicated that approximately 47% of the total CO2 was from PH mineralization and 53% from plant root respiration. Although low-permeability sediment increases the difficulty of completely replacing in situ soil gas and assuring anaerobic conditions, this novel respiration method distinguished between anaerobic processes responsible for PH degradation.  相似文献   

13.
大气CO2浓度升高对土壤氮素转化过程产生重要影响,研究其变化有助于更好地预测陆地生态系统的固碳潜力.氮同位素自然丰度作为生态系统氮素循环过程的综合指标能够有效地指示CO2浓度升高对土壤氮素转化过程的影响.本研究采用开顶箱CO2 熏蒸法研究连续10年的大气CO2 浓度升高对我国东北地区蒙古栎及其土壤和微生物生物量碳、氮同位素自然丰度的影响.结果表明: 大气CO2浓度升高改变了土壤氮循环过程,增加了土壤微生物和植物叶片δ15N;促进了富13C土壤有机碳分解,中和了贫13C植物光合碳输入的效果,导致土壤可溶性有机碳和微生物碳δ13C在CO2升高条件下没有发生显著变化.这些结果表明,CO2浓度升高很可能促进了土壤有机质矿化过程,并加剧了系统氮限制的状态.  相似文献   

14.
以6年生‘烟富3’/M26/平邑甜茶苹果为试材,采用C、N双标记技术,研究在果实膨大后期用不同尿素浓度水溶液(N 0%、0.6%、1.2%、1.8%、2.4%,分别用CK、N1、N2、N3、N4表示)涂抹果实周围20 cm范围内叶片对叶片13C同化能力及13C光合产物、15N向果实转移分配的影响.结果表明: 随着尿素浓度的增加,叶片的叶绿素含量、氮含量、光合速率、山梨醇和蔗糖含量、6-磷酸山梨醇脱氢酶(S6PDH)和蔗糖磷酸合酶(SPS)活性及13C同化能力均先升高后降低,均以1.8%尿素涂抹处理最高,清水对照最低.13C自留量(自身叶片+自身新梢)以清水对照最高,为81.6%,1.8%尿素涂抹处理最低,为63.5%.向外输出的13C光合产物主要分布在标记果实,其次是未标记多年生枝,未标记叶片最低.果实13C吸收量随着尿素浓度增加呈先升高后降低趋势,以1.8%尿素涂抹处理最高(1.21 mg·g-1),清水对照最低(0.51 mg·g-1);果实15N吸收量随着尿素浓度增加呈持续升高趋势.表明尿素水溶液叶施可不同程度地提高叶片光合产物和氮素向果实转移分配的能力,以1.8%尿素涂抹处理叶片光合产物向果实转移分配能力最强,同时避免了过多的氮素向果实的输入.  相似文献   

15.
以6年生‘烟富3’/M26/平邑甜茶苹果为试材,采用C、N双标记技术,研究在果实膨大后期用不同尿素浓度水溶液(N 0%、0.6%、1.2%、1.8%、2.4%,分别用CK、N1、N2、N3、N4表示)涂抹果实周围20 cm范围内叶片对叶片13C同化能力及13C光合产物、15N向果实转移分配的影响.结果表明: 随着尿素浓度的增加,叶片的叶绿素含量、氮含量、光合速率、山梨醇和蔗糖含量、6-磷酸山梨醇脱氢酶(S6PDH)和蔗糖磷酸合酶(SPS)活性及13C同化能力均先升高后降低,均以1.8%尿素涂抹处理最高,清水对照最低.13C自留量(自身叶片+自身新梢)以清水对照最高,为81.6%,1.8%尿素涂抹处理最低,为63.5%.向外输出的13C光合产物主要分布在标记果实,其次是未标记多年生枝,未标记叶片最低.果实13C吸收量随着尿素浓度增加呈先升高后降低趋势,以1.8%尿素涂抹处理最高(1.21 mg·g-1),清水对照最低(0.51 mg·g-1);果实15N吸收量随着尿素浓度增加呈持续升高趋势.表明尿素水溶液叶施可不同程度地提高叶片光合产物和氮素向果实转移分配的能力,以1.8%尿素涂抹处理叶片光合产物向果实转移分配能力最强,同时避免了过多的氮素向果实的输入.  相似文献   

16.
The new organometallic cluster (η24-CO)2(CO)136-C6Me6) has been prepared by the thermolysis of Ru3(CO)12 with hexamethylbenzene in octane and characterised by a single crystal X-ray diffraction study. It is isostructural with the known cluster Ru624-CO)2(CO)136-C6H3Me3) and the metal core constitutnts the same tetrahedral Ru4 unit with two edge-bridging Ru atoms. The mesitylene derivative has been shown to undergo rearrangement to afford the octahedral carbido cluster Ru6C(CO)146-C6H3Me3), but this conversion is not observed for the new hexamethylbenzene derivative.  相似文献   

17.
A new room-temperature molten salt, 1:2 LiCl-ethylaluminum dichloride (LiCl-EtAlCl2, f.p. about 178 K), is examined using 13C relaxation methods at 7.05 T (−25 to + 80 °C). The methylene carbon undergoes scalar relaxation of the ‘second kind’ as it is coupled to a faster relaxing (quadrupolar) nucleus. LiCl-EtAlCl2 undergoes a significant liquid-state phase change between 5 and 15 °C as evidenced by observed changes in the relaxation properties of the methylene and methyl carbons and J(13C−27Al). The J(13C−27Al) coupling constants are 75 (− 10 to + 5 °C) and 11 Hz (15–65 °C), indicating a change in structure between 5 and 15 °C. Chemical shift anisotropies of 56 and 48 ppm are obtained for the methylene and methyl carbons in the EtAlCl2 dimer part of the 1:2 LiCl-EtAlCl2 solution.  相似文献   

18.
2010年在四川卧龙自然保护区选择海拔为2350、2700、3150和3530 m的4个分布地点,研究了巴郎山海拔梯度对奇花柳叶片13C、光合、CO2扩散导度、氮含量、光合氮利用效率(PNUE)和比叶面积(SLA)的影响.结果表明: 随着海拔的升高,目标树种叶片氮含量(尤其是单位面积氮含量)及PNUE增加,叶片13C值也随之显著增加,且海拔每升高1000 m,13C增加1.4‰;CO2扩散导度(气孔导度和叶肉细胞导度)的增加,在一定程度上阻碍了叶片13C值随海拔升高,但不足以改变13C值随海拔升高的趋势;羧化能力是羧化位点与外界CO2分压比(Pc/Pa),甚至13C的限制因子.在海拔2350~2700 m,奇花柳光合系统内部氮素分配主要受温度的影响,而2700~3530 m的光照作用可能更大.奇花柳的SLA随海拔无显著变化.  相似文献   

19.
为探究黄淮冬麦区测墒补灌节水条件下协同提高小麦产量和水氮利用效率的氮肥管理措施,以小麦品种‘烟农1212'为材料,在拔节期和开花期将各处理0~40 cm土层土壤相对含水量均补灌至70%条件下,设置3个施氮水平,即150(N1)、210(N2)和270 kg·hm-2(黄淮冬麦区常规施氮量,N3),研究施氮量对小麦开花后旗叶光合特性、13C同化物积累与转运及水氮利用效率的影响。结果表明: N2和N3处理开花后14~35 d旗叶光合能力显著高于N1处理,N2与N3处理间差异不显著。13C同位素示踪结果显示,N2处理开花后营养器官13C同化物转运量比N1和N3处理分别高12.1%和7.1%,成熟期13C同化物在籽粒中的分配量比N1和N3处理分别高10.1%和5.3%。施氮量亦调节了小麦不同生育阶段的耗水量、耗水模系数和总耗水量,小麦全生育期耗水量表现为N2与N3处理无显著差异,但均显著高于N1处理,N2处理拔节至成熟期阶段耗水量和耗水模系数均较高。N2处理水分利用效率比N3和N1处理分别高7.5%和4.8%,籽粒产量比N3和N1处理分别高4.7%和10.9%,氮肥偏生产力比N3处理高34.6%。综合考虑小麦籽粒产量和水氮利用效率,施氮量为210 kg·hm-2处理为研究区测墒补灌节水条件下的最佳施氮量。  相似文献   

20.
本试验以131个沙棘属植物种群为研究对象,通过测定其叶片碳稳定同位素(δ13C)值,分析了碳稳定同位素特征与环境因子之间的关系。结果表明: 沙棘属植物叶片的δ13C值介于-24.65‰~-29.11‰,平均值为-26.97‰,属于C3植物,叶片δ13C值变异系数为种内大于种间,表明环境因子是影响沙棘属植物叶片δ13C含量变化的主导因素。沙棘属植物叶片的δ13C值与经纬度的变化无显著相关,与海拔呈显著负相关。通过建立回归方程: δ13C(‰)=0.118VAP-0.007GST-0.000028RDA-20.721(R2=0.212,P<0.0001),说明影响沙棘属叶片δ13C值最主要的因素是水蒸气压(VAP)、生长季温度(GST)和太阳辐射(RDA)。研究结果可为沙棘属植物对全球气候变化的响应提供理论依据。  相似文献   

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