共查询到19条相似文献,搜索用时 52 毫秒
1.
合成了对位取代的1-苯基-1,4-二氢烟酰胺和对位取代的1-苯基-1,2-二氢烟酰胺作为烟酰胺辅酶两种模型物, 分别测定了它们与N-甲基吖啶正离子反应热和活化吉布斯自由能. 通过对其热力学参数和动力学参数的比较发现, 虽然1,2-二氢烟酰胺辅酶模型物与吖啶正离子反应热力学驱动力大于相应的1,4-二氢烟酰胺辅酶模型物与吖啶正离子反应热力学驱动力, 但前者具有很高的活化熵, 从而导致其活化吉布斯自由能反而大于后者. 表明烟酰胺辅酶NADH反应中心结构在其氧化还原循环进化过程中选择1,4-二氢烟酰胺而不是1,2-二氢烟酰胺的根本原因是烟酰胺辅酶反应中心结构二氢吡啶环2位上的氢原子较4位上的氢原子有较大的空间位阻. 相似文献
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辅酶 NADH模型物还原反应机理研究长期以来一直是物理有机化学领域令人感兴趣的课题 [1~ 3 ] ,其中对于反应动力学的研究因其对推论反应机理的重要性而受到重视 .我们 [4 ,5] 曾报道过辅酶 NADH模型物 N -苄基 - 1 ,4-二氢烟酰胺 (BNAH)与 2 -溴 - 1 -苯基亚乙基丙二腈 (BPM)的还原脱溴环丙烷化反应 ,通过紫外 -可见光谱法测定了该反应的反应速率常数、同位素效应等动力学方面的结果 .然而紫外 -可见光谱法本身有一定的缺陷 ,例如 ,由于反应物在紫外 -可见光谱中的吸收峰可能互相重叠 ,有时会观察不到产物和中间体的形成 ;或者有时… 相似文献
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辅酶NADH模型物在有机合成中的应用一直是有机化学研究的一个热点.近来,辅酶NADH模型物结合一些手性催化剂在C=C、C=N和C=O键不对称氢化还原中的研究更是吸引了许多科学家的注意,本文综述这一领域的最近研究进展. 相似文献
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以烟酸为起始原料,设计并合成了一系列葡萄糖残基负载的水溶性NADH辅酶模型物,其结构经1H NMR表征. 相似文献
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合成了一系列3-酰胺基氮取代的NAD(P)H模型物,测定了其与5-硝基异喹啉正离子的二级反应速度常数,并一模型物的氧化还原电势进行了比较,实验结果表明,模型闰酰基氧-方面可离域二氢吡啶环上N的电子;另一方面负一的3-位酰基氧在反应过渡态中又可引起分子内和分子间的两种静电作用;3-位酰基的电子效应对模型物动力学反应性的影响是这两种效应综合作用的结果。 相似文献
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利用热力学循环方法,通过pK和有关电化学数据的测定,首次得到了NAD(P)H的辅酶模型物(BNAH)按不机理还原质子化N-芳基芴亚胺的各基元步骤的自由能变化,结合得到的同位素标纪结果,从热力学趋动力的角度区分了氢负离子的转移机理。 相似文献
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改进的缔合物模型中缔合平衡的求解过程被简化,使其能够同时优化更广范围的热力学数据,包括量热、emf和相图等等数据,将其应用于KCl-MgCl2和KCl-FeCl2熔盐体系,从已有的热力学数据优化出合理的溶液模型参数,由该模型推算溶液的热力学性质,结果显示改进的缔合物模型能够很好地描述熔盐体系的非理想性质. 相似文献
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钾长石矿热分解过程的研究 总被引:24,自引:0,他引:24
研究了钾长石矿热分解过程的反应行为和动力学.对6种钾长石体系进行了热力学分析,计算了各反应在800~1600K的△GT0,并以此指导实验.研究了焙烧温度、停留时间和助剂配比对钾长石体系热分解为水溶性钾的影响,得出最佳操作条件.添加0.9%添加剂Ⅰ能使适宜焙烧温度由1323K降至1223K,钾分解率可达84%.不加与加入添加剂Ⅰ的2种钾长石体系热分解过程皆符合克-金-布动力学方程,均受固膜扩散控制,表观活化能分别为184.84kJ/mol和158.9kJ/mol,并给出相应的动力学方程. 相似文献
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NADH/NAD^+是生物代谢过程中一种重要的辅酶。其氧化态在生物燃料分了降解过程中作为电子受体被还原;其还原态生物合成过程中作为一种绝妙的手性还原剂,为生物大分子 提供电子和自由能。 相似文献
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采用时间相关单光子计数技术, 结合紫外-可见吸收光谱和稳态荧光光谱, 对不同环境下的色氨酸和辅酶还原型烟酰胺腺嘌呤二核苷酸(NADH)之间的共振能量转移荧光动力学进行了研究. 单体色氨酸、 牛血清白蛋白以及乳酸脱氢酶蛋白与NADH之间相互作用的光谱数据表明, 只有存在NADH结合位点的乳酸脱氢酶和NADH之间发生了荧光共振能量转移. 进一步通过加入丙酮酸来阻断乳酸脱氢酶和NADH之间的荧光共振能量转移通道, 时间分辨荧光光谱和衰减相关光谱(DAS)证实, 蛋白结合位点的存在是NADH和色氨酸之间发生荧光共振能量转移的前提条件. DAS揭示了乳酸脱氢酶平均荧光寿命的减小主要是源于色氨酸中7.35 ns的荧光寿命成分与NADH之间的荧光共振能量转移, 同时给出了NADH和色氨酸之间的能量转移效率, 为研究NADH和蛋白之间的相互作用提供了新思路. 相似文献
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Summary. Computer simulation results for the Self-propagating High-temperature Synthesis (SHS) of the intermetallic compound NbSi2 are discussed in comparison with experiments for SHS of mechanically activated powders. The variation of wave speed of the
propagation front is considered while varying Nb grain size and thermal conductivity of the starting mixture. A co-operating
effect of these two parameters (due to the change in morphology of reactants after milling) is outlined. 相似文献
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Ulrik Gran 《Tetrahedron》2003,59(24):4303-4308
A new macrocyclic NADH model 1 has been designed and synthesised. The new model consists of the same subunits as previously reported models. However, the present model is designed as such that the pyridine nitrogen of the nicotinamide units are not incorporated in the macrocyclic framework. Thus, properties such as solubility can easily be varied by alkylation with an appropriate agent. The macrocyclic framework was prepared in 7 steps. Methylation of the pyridine nitrogens followed by reduction gave the desired model. This model compound was found to reduce methyl benzoylformate stereoselectively in good yield with 48% enantiomeric excess. 相似文献
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Enzo Giannetti 《Journal of fluorine chemistry》2005,126(4):623-630
Intrinsic bond dissociation energies (BDEs) of selected fluorinated polymers are critically evaluated. Two distinctive approaches were followed. In the first one, according to Wu and Rodgers [E.-C. Wu, A.S. Rodgers, J. Am. Chem. Soc. 98 (1976) 6112-6115], starting from the gas-phase enthalpy of polymerization we obtained the polymer backbone BDE through appropriate thermodynamic cycles. Revised experimental results indicate that the CC BDEs of all the polymers taken into account fall within a limited energy interval, comparable to the average experimental uncertainty. Central to the second methodology adopted, is a model compound approach. Thanks to the large number of reliable thermodynamic data available in the scientific literature and to simple end-capping rules, C2 molecules were chosen as suitable models for infinite linear polymers and alternating copolymers between ethylene and fluorinated olefins. For partially fluorinated polymers, like polyvinylidene fluoride (PVDF), alternating ethylene-tertrafluoroethylene (ETFE) and alternating ethylene-chlorotrifluoroethylene (ECTFE), the weight loss due to HF and HCl evolution during heating experiments was successfully related to the threshold energy Eo(HX) for 1,2-elimination from chemically activated hydrofluoro and hydrofluorochlorocarbons according to the modified Rice-Rampsberger-Kassel (RRKM) unimolecular theory. 相似文献
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Xiu-Lin Zeng Wang-Hua Chen Jia-Cong Liu Jin-Lin Kan 《Journal of Molecular Structure》2007,810(1-3):47-51
Three density-functional methods (B3P86, B3PW91, and B3LYP) are employed to investigate the O–NO2 bond lengths, frontier orbital energies, and O–NO2 bond dissociation energies (BDEs) of n-propyl nitrate (NPN), isopropyl nitrate (IPN), 2-ethylhexyl nitrate (EHN), triethylene glycol dinitrate (Tri-EGDN), and tetraethylene glycol dinitrate (Tetra-EGDN). It is found that the O–NO2 bond lengthens (destabilizes) in the order of IPN, NPN, EHN, Tetra-EGDN, and Tri-EGDN. From the data of frontier orbital energies (EHOMO, ELUMO), and energy gaps (ΔE), we estimate the relative thermal stability ordering of five nitrates and their corresponding radicals. The predicted BDEs of O–NO2 bond in NPN, IPN, EHN, Tri-EGDN, and Tetra-EGDN, are 176.6, 174.5, 168.1, 156.1, and 159.3 kJ mol−1, respectively. Based on the finding that the present results of BDEs are well coincident with the experimental results of apparent activation energies from the literature, we can draw a conclusion that the experimental thermolysis of five nitrates is only unimolecular homolytical cleavage of the O–NO2 bonds. 相似文献
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The X(C,N,O)—NO2 bond dissociation energy (BDE) for CH3NO2, C2H3NO2, C2H5NO2, HONO2, CH3ONO2, C2H5ONO2, NH2NO2, (CH3)2NNO2 are computed using the DFT (B3LYP, B3PW91), the single and double-coupled cluster excited (CCSD), and the complete basis set (CBS-Q) methods, with the 6-311G** and cc-pVDZ basis sets. By comparing the computed energies and experimental results, we find that the DFT method can not give good results of BDE, but, the BDEs generated by the CCSD/cc-pVDZ, CBS-Q are in good agreement with experimental values. 相似文献