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991.
(15)N CP/MAS solid state NMR should be a method of choice to obtain essential structural information on organic materials containing nitrogen atoms. However, the technique is generally not selected for the characterization of non-labelled chemical compounds, which represents the most common situation encountered by chemists. Actually, due to the poor sensitivity of (15)N the method is time-consuming and a very fine calibration is often a prerequisite to reach a sufficient signal/noise. The main drawback comes from the weakness of (15)N-(1)H dipolar couplings which leads to a splitting of the static Hartman Hahn condition into very narrow sideband conditions under MAS. Practically, it is more difficult to obtain a high enough CP transfer level on (15)N for the entire spectrum than on other more conventional nuclei like (13)C. An experimental investigation of the CP efficiency using the ramp and adiabatic CP transfer experiments is here proposed. Preliminary adjustments of experimental settings were first made on an (15)N-labeled substituted heterocyclic model system, and then applied to several other organic compounds. Particular attention was paid to the detection of non-protonated nitrogen atoms with a significant chemical shift anisotropy, which represented the least favourable case. It was experimentally demonstrated that, for these atoms, the adiabatic passage provided a much higher transfer level than the more conventional ramp sequence leading to an enhancement factor of up to 3.5 at a MAS frequency of 30 kHz. The resulting sensitivity rendered possible the detection of non-protonated nitrogen atoms at natural abundance with 2.5-mm rotors at 9.4 T. 相似文献
992.
Through SiP bond cleavage, the reaction of P7(SiMe3)3 with one equivalent of KOtBu or LiOtBu afforded different isomers of the heptaphosphanide anion [P7(SiMe3)2]−. With LiOtBu, concomitant inversion at an equatorial (silylated) phosphorus atom occurred and the Cs symmetric isomer characterized by a mirror plane formed. With KOtBu, inversion did not occur and the resulting asymmetric anion with C1 symmetry formed. With NaOtBu, a mixture of both isomers was obtained. The symmetries and structures of the anions were elucidated with 31P{1H} and 29Si{1H} NMR spectroscopy, and relative stabilities were calculated employing the B3LYP/6-31+G* method.The reaction of KP7(SiMe3)2 or LiP7(SiMe3)2 with 1,2-dichlorotetramethyldisilane led to (SiMe3)2P7SiMe2SiMe2P7(SiMe3)2, a molecule composed of two P7-cages connected by a disilane bridge. It can also be obtained through silyl exchange using P7(SiMe3)3 and ClMe2SiSiMe2Cl. The compound was characterized with 31P and 29Si-NMR spectroscopy and elemental analysis. Treatment of P7(SiMe3)3 with HypCl (Hyp = hypersilyl = Si(SiMe3)3) in DME led to the quantitative formation of Hyp2P7SiMe3. Single crystal X-ray diffraction as well as 31P and 29Si-NMR spectroscopy proves the presence of a heteroleptically substituted heptaphosphane cage.Quantum chemical HF and B3LYP/6-31G* calculations of equilibrium structures for the two possible isomers of P7(SiMe3)3 (sym and asym) reveal that asym is destabilized by about 30-40 kJ mol−1, which explains why its formation could not be observed. The phosphorus inversion barrier for the sym → asym transition is calculated as 60-70 kJ mol−1. 相似文献
993.
利用浮沉离心法得到了神东原煤的镜质组(SDV),并对其进行了固体13C-CP/MAS NMR测试和元素分析。由13C-NMR实验得到了SDV中碳原子的结构分布特征和12种结构参数。结果表明,在SDV的结构中芳香碳原子的存在形式主要是缩合程度为2的萘,其余则是以苯环和含杂原子的芳香环。利用结构参数和元素分析的结果构建了SDV的大分子结构模型, 并运用13C-NMR预测软件ACD/CNMR predictor计算了SDV大分子结构模型的13C 化学位移。根据计算结果对SDV的大分子结构模型进行了修正,获得了能和实验谱图吻合较好的大分子结构模型。 相似文献
994.
考虑煤中吡啶六元环与其他杂环的结合形式,对四种典型的吡啶型氮杂环结构及其热解中间产物中各键的Mayer键级进行了计算。通过对比Mayer键级的大小判断热解时最易发生断裂的键,进而对吡啶型氮热解时氮的逸出机理进行了分析。计算结果表明,吡啶型氮热解产生的含氮污染物主要是HCN;由于吡啶环与其他环结合方式的不同,氮的逸出过程也有差异。利用高频炉快速热解装置对吡啶和吖啶两种模型化合物进行了快速热解实验以验证计算结果。结果表明,吡啶和吖啶热解时虽有少量NH3生成,但含氮污染物仍以HCN为主,实验结果可为计算所得的结论提供一定支持。
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995.
Wang Z Castellano S Kinderman SS Argueta CE Beshir AB Fenteany G Kwon O 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(2):649-654
A library of 91 heterocyclic compounds composed of 16 distinct scaffolds has been synthesized through a sequence of phosphine-catalyzed ring-forming reactions, Tebbe reactions, Diels-Alder reactions, and, in some cases, hydrolysis. This effort in diversity-oriented synthesis produced a collection of compounds that exhibited high levels of structural variation both in terms of stereochemistry and the range of scaffolds represented. A simple but powerful sequence of reactions thus led to a high-diversity library of relatively modest size with which to explore biologically relevant regions of chemical space. From this library, several molecules were identified that inhibit the migration and invasion of breast cancer cells and may serve as leads for the development of antimetastatic agents. 相似文献
996.
Banert K Meier B Penk E Saha B Würthwein EU Grimme S Rüffer T Schaarschmidt D Lang H 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(4):1128-1136
Substituted 1-azidocyclopentenes and 1-azidocyclohexenes were photolyzed to generate 2,3-bridged 2H-azirines. In the case of bridgehead azirines with a six-membered carbocycle, detection by NMR spectroscopic analysis was possible, whereas even kinetically stabilized bridgehead azirines with a five-membered ring could not be characterized by low-temperature NMR spectroscopic analysis. Thus, a recent report on the latter heterocycles was corrected. Depending on the substitution pattern, irradiation of 1-azidocyclopentenes either led to products that can be explained on the basis of short-lived 2,3-bridged 2H-azirines, or gave secondary products generated from triplet nitrenes. The diverse photoreactivity of 2,3-bridged 2H-azirines was also studied by quantum chemical methods (DFT, CCSD(T), CASSCF(6,6)) with respect to the singlet and triplet energy surfaces. The ring-opening processes leading to the corresponding vinyl nitrenes were identified as key steps for the observed reactivity. 相似文献
997.
998.
Kang IJ Khan NA Haque E Jhung SH 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(23):6437-6442
Chemical and thermal stabilities of isotypic metal-organic frameworks (MOFs) like Al-BDC (Al-benzenedicarboxylate called MIL-53-Al), Cr-BDC (MIL-53-Cr) and V-BDC (MIL-47-V), after purification to remove uncoordinated organic linkers, have been compared to understand the effect of the central metal ions on the stabilities of the porous MOF-type materials. Chemical stability to acids, bases, and water decreases in the order of Cr-BDC>Al-BDC>V-BDC, suggesting stability increases with increasing inertness of the central metal ions. However, thermal stability decreases in the order of Al-BDC>Cr-BDC> V-BDC, and this tendency may be explained by the strength of the metal-oxygen bond in common oxides like Al(2)O(3), Cr(2)O(3), and V(2)O(5). In order to evaluate precisely the stability of a MOF, it is necessary to remove uncoordinated organic linkers that are located in the pores of the MOF, because a filled MOF may be more stable than the same MOF after purification. 相似文献
999.
为考察溶质浓度对三碳多元醇水溶液氢键作用以及不同物质玻璃态形成能力的影响,采用1H NMR外标法研究不同浓度的1-丙醇(NPA),2-丙醇(IPA),1,2-丙二醇(PG),1,3-丙二醇(PD)和丙三醇(glycerol)的水溶液在室温常压下质子化学位移.结果表明:具有CH3CH(OH)一基团的PG烷基质子的化学位移变化趋势与其他几种醇相比有较大差异.醇羟基质子与水分子的氧形成较强O-H…O氢键.相同摩尔分数下,羟基数的增加导致水质子和羟基质子的化学位移降低,而且羟基位置不同也会导致水质子和羟基质子化学位移差异.这几种三碳多元醇碱性强弱的顺序和降低冰的均相成核温度能力的顺序一致,即glycerol>PG>PD>IPA>NPA,1H NMR技术表明glycerol和PG更适合用作低温保护剂. 相似文献
1000.
化学交联聚乙烯醇改性纤维素碱性阴离子交换复合膜的制备与性能 总被引:1,自引:0,他引:1
高稳定性碱性阴离子交换膜的制备已成为碱性固体电解质膜研究领域的一大热点.本文通过聚乙烯醇化学交联改性制备出了季铵化羟乙基乙氧基纤维素碱性阴离子交换膜(PVA/QHECE).采用傅里叶变换红外(FTIR)光谱、热重(TG)分析、交流(AC)阻抗等方法考察了复合膜的分子结构、热稳定性、耐碱稳定性及离子电导率等性能.详尽考察了交联时间、交联剂含量、聚合物组成对成膜力学强度、含水率以及OH-电导率的影响.实验结果表明:随着交联时间的增加,膜的溶胀率降低,力学强度随之增强,而离子电导率随膜含水率的降低没有发生明显变化,室温下OH-的电导率在3.26×10-4-4.44×10-4S·cm-1范围内变化.热重分析结果显示:掺入42.9%的QHECE时,膜的热分解温度达260℃.此外,将PVA/QHECE膜在6 mol·L-4 KOH浓碱溶液中80℃浸渍处理168 h,膜的电导率从4.90×10-4S·cm-1提高到9.68×10-4S·cm-1,而膜的外观和力学强度以及含水率未发生明显变化,这一结果表明该膜具有很好的耐碱化学稳定性,有望作为一种新型的碱性燃料电池用离子交换膜. 相似文献