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81.
Beate Hager Bettina Schwarzinger Heinz Falk 《Monatshefte für Chemie / Chemical Monthly》2006,137(2):163-168
Summary. Two model compounds for the green fluorescent protein chromophore were prepared. One of them incorporates the natural 4-hydroxybenzylidene
group of the natural tyrosin derived chromophore, the other one bears a methyl group instead of the hydroxy group. Whereas
the photochemically prepared (E)-diastereomer of the first compound very effectively reverted thermally (room temperature) to the thermodynamically stable
(Z)-diastereomer, the (E)-diastereomer of the second derivative proved to be stable even at elevated temperatures for more than a day. This finding
can be rationalized by constructing the appropriate resonance structures showing that only in the first case an effective
delocalization enables partial single bond character of the benzylidene double bond. From the standpoint of chemical etiology,
only Nature’s choice of the tyrosin derived chromophore of the green fluorescent protein provides an efficient radiationless
thermal relaxation channel for the unwanted photo-diastereomerization product formed after excitation besides the dominating
fluorescence channel of its chromophore. 相似文献
82.
Two-dimensional infrared (2D IR) correlation spectroscopy was applied to study the structural changes occurring in the decomposition of PHEA-co-MMA/SiO2. Complicated absorption spectral changes were observed in the heating process. 2D IR analysis indicates that during heating, covalent bonds, (Si-O-C), between the polymer and the inorganic moiety were formed, which was the main factor in the improvement in thermal properties of the hybrids such as the decomposition temperatures (Td). The thermal stability of the hybrids was also studied by solid-state 29Si MAS NMR spectroscopy and TGA tests. Their results complemented each other well. 相似文献
83.
设计合成了两种新型的以聚吡唑硼酸盐、氨基酸为配体的钒氧配合物VO[phCH2CH(NH2)COO][HB(pz)3](1)和VO(3,5-Me2pz)[HB(3,5-Me2pz)3](CH3COO)(2). 通过元素分析、红外光谱对配合物进行了表征, 并利用单晶X射线衍射技术解析了它们的结构. 非等温热分解动力学研究表明, 配合物1和2的热分解反应都是分两步进行的. 通过计算, 配合物1热分解的第一步反应的可能机理为成核与生长(n=1/4); 第二步反应的可能机理为化学反应. 其非等温动力学方程分别为, dα/dT=(A/β)e-E/RT(1/4)(1-α)[-ln(1-α)]-3 和dα/dT=(A/β)e-E/RT(1-α)2. 分解反应的表观活化能分别是223.52 和331.94 kJ·mol-1; 指前因子ln(A/s-1)分别是49.67 和57.50. 配合物2 热分解的第一步反应的可能机理为化学反应; 第二步反应的可能机理为成核与生长(n=1/2). 其非等温动力学方程分别为, dα/dT=(A/β)e-E/RT(1-α)2, 和dα/dT=(A/β)e-E/RT(1/2)(1-α)[-ln(1-α)]-1. 分解反应的表观活化能分别是300.56 和444.72 kJ·mol-1; 指前因子ln(A/s-1)分别是75.53 和92.50. 相似文献
84.
85.
增容剂对聚丙烯/粘土纳米复合材料热分解动力学的影响 总被引:12,自引:0,他引:12
采用三单体固相接枝聚丙烯作为增容剂制备了聚丙烯粘土纳米复合材料.通过XRD和TEM表征了其纳米结构.利用动态TGA方法研究了聚丙烯和纳米复合材料的热稳定性.分别采用Flynn Wall Ozawa和Kissinger法研究了聚丙烯及其纳米复合材料的热分解动力学.结果都表明,蒙脱土的加入明显提高了聚丙烯的起始热分解温度,纳米复合材料热失重10%时的温度比聚丙烯提高40K左右;纳米复合材料的热分解温度区间明显比聚丙烯的窄;纳米复合材料热分解表观活化能明显增大,与聚丙烯相比提高50%以上. 相似文献
86.
The thermal decomposition of ammonium vanadyl oxalate supported on La2O3, MgO, SiO2, Al2O3, ZrO2, TiO2, SAPO-5, and ZSM-5 oxides in a dynamic atmosphere of dry air was compared by thermal gravimetric analysis (TG) and differential thermal analysis (DTA). The calcined catalysts were characterized by X-ray diffractometry (XRD). The TG and DTA results demonstrate that the surface acid-base properties of the oxides play a significant role in the decomposition behaviour of the supported ammonium vanadyl oxalate, i.e. the basic oxides exhibit an endothermic effect and the acidic oxides show an exothermic effect. Two mechanisms are suggested for thermal decomposition of ammonium vanadyl oxalate on basic and acidic oxides, respectively. After transformation of the ammonium vanadyl oxalate to vanadia, subsequent rearrangement of the vanadia on the surface of the supports was also observed. During the thermal treatment or calcination in air, solid state reactions of vanadia with the surface of oxides such as La2O3, ZrO2 and TiO2 took place to form new phases. 相似文献
87.
Josef Ischtwan Peter Schwerdtfeger Sigrid D. Peyerimhoff Michael A. Collins Trygve Helgaker Poul Jørgensen Hans Jørgen Aa. Jensen 《Theoretical chemistry accounts》1994,89(2-3):157-168
Summary The intrinsic reaction-path, reactants, transition state and products for the reaction of NH (3–)+H2 (1
g
+
) NH2 (2B1)+H (2S) involving the lowest triplet electronic state of NH3 were calculated using multi-configuration (MC) SCF methods. The calculated change of internal energy for the reaction of 11.0 kcal mol–1 agrees with the experimental value within 2 kcal mol–1. The barrier to reaction is 23.4 kcal mol–1 high. The harmonic MCSCF reaction-path potential was calculated and canonical variational transition state theory calculations of the rate constants performed over a temperature range from 400 to 2500 K. The computed rate constants are generally two orders of magnitude smaller than those of the comparable reaction of OH with H2, whereas those of the reverse reaction are by a factor of 20 larger than those of OH2 with H. 相似文献
88.
《Journal of separation science》2003,26(11):1057-1062
The use of glass fiber as a support material for a surface compound serving to generate gaseous standard mixtures of ethene is described. The technique is based on the process of thermal decomposition of the surface compound in a desorber connected on‐line via a multi‐port valve to the calibrated device. The surface compound undergoes thermal decomposition at 245°C, yielding known amounts of ethene. The method enables on‐line preparation of a standard mixture immediately before the calibration step. Consequently, it can be also applied for the generation of standard mixtures containing volatile, malodorous, unstable, and toxic compounds. 相似文献
89.
A series of heat energy storage microcapsules was prepared using melamine-formaldehyde resin as the shell material and the mechanical properties of the shell were investigated. A phase change material whose melting point was 24 °C was used as core and the quantity of heat involved in phase transition was 225.5 J/g. Average diameter of the microcapsules varied from 5 to 10 μm, and the globular surface was smooth and compact. The mechanical properties of the shell were evaluated by observing the surface morphological structure change after application of pressure by means of scanning electron microscopy. When the mass ratio of the core and shell material is 3:1, a yield point of about 1.1×105 Pa was found and when the compression was increased beyond this point the microcapsules showed plastic behavior. This has been attributed to the cross-link density and to the high degree of reaction of the shell material. Different yield points subsequently reflected differences in the mechanical behavior. It was also found that the mechanical intensity of double-shell microcapsules was better than that of single shelled ones. 相似文献
90.
B. Pateyron M. F. Elchinger G. Delluc P. Fauchais 《Plasma Chemistry and Plasma Processing》1996,16(1):39-57
In most cases the energy dissipated in plasma jets used either,for heating or spraying is varied by changing the are current, the total gas floc+rate, and composition. However, when doing so, conditions are reached where the plasma jet may become supersonic. To predict such conditions or to characterize supersonic plasma jets the knowledge of the sound velocitya is mandatory The goal of this paper is to calculatea versus plasma forming gas composition, temperature, and pressure. Rigorous calculation would imply the knowledge of the chemical reaction kinetics, sound velocity depending strongly on this. Unfortunately such kinetics are generally lolknown for plasma jet floras and the only possibility is to determine the equilibrium sound velocitya calculated through the isentropic coefficient T. This coefficient has been calculated taking into account the dissociation and ionization reactions at equilibrium for temperatures ranging from 300 to 25,000 K and pressures between 0.1 and 1 Mpa for Ar, H2, He, Ar-He, Ar-H2, O2, N2, air, .steam, and methane.a often called the frozen sound velocity, was also calculated using (ratio of specific heats) instead of . 相似文献