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991.
本实验采用金属有机化学方法成功地将富勒烯分子引入到PNVC侧链形成CBP(CharmBraceletPolymer)型共聚功能材料,研究了其UV-VIs谱行为。结果表明,C_(60)或C_(60)/C_(70)混合物化学修饰的产物其紫外可见谱明显向长波方向移动,谱峰范围由280nm扩展至870nm。C_(60)含量增加,红移程度增大,在可见区域的吸收程度亦增加。产物主要存在5个特征峰,分别位于215nm、265nm、298nm、335nm、345nm处,其中215nm峰为C_(60)仅存的特征峰。最后讨论了不同合成条件与产物硝化处理对其UV-VIS谱行为的影响。 相似文献
992.
Yang G Miao R Jin C Mei Y Tang H Hong J Guo Z Zhu L 《Journal of mass spectrometry : JMS》2005,40(8):1005-1016
Interaction of carboplatin with cytochrome c (Cyt. c) has been investigated by electrospray ionization mass spectrometry (ESI-MS) and tandem mass spectrometry (MS/MS). ESI-MS studies revealed that the ring-opened adducts of carboplatin with Cyt. c were formed in the stoichiometric ratio of 1:1 and 2:1 at pH 5.0 and 37 degrees C and in the stoichiometric ratio of 1:1 only at pH 7.0 and 37 degrees C. It was also found that Cyt. c could be cleaved by carboplatin at pH 2.5 and 50 degrees C. The cleaved fragments of Cyt. c were determined by ESI-MS and MS/MS analysis to be Glu66 approximately Met80, Ac-Gly01 approximately Met65, Glu66 approximately Glu104, Ac-Gly01 approximately Met80 and Ile81 approximately Glu104. The carboplatin prefers to anchor to Met65 first, then to Met80. To further confirm the binding site of Met, AcMet-Gly was used as the model molecule to investigate its interaction with carboplatin and its hydrolysis reaction. On the basis of species detected during the reaction monitored by ESI-MS, a possible pathway of the cleavage reaction was proposed. 相似文献
993.
995.
996.
A CASPT2/CASSCF study has been carried out to investigate the mechanism of the photolysis of 2,3-diazabicyclo[2.2.2]oct-2-ene (DBO) under direct and triplet-sensitized irradiation. By exploring the detailed potential energy surfaces including intermediates, transition states, conical intersections, and singlet/triplet crossing points, for the first excited singlet (S(1)) and the low-lying triplet states (T(1), T(2), and T(3)), we provide satisfactory explanations of many experimental findings associated with the photophysical and photochemical processes of DBO. A key finding of this work is the existence of a significantly twisted S(1) minimum, which can satisfactorily explain the envelope of the broad emission band of DBO. It is demonstrated that the S(1) (n-pi*) intermediate can decay to the T(1) (n-pi*) state by undergoing intersystem crossing (rather inefficient) to the T(2) (pi-pi*) state followed by internal conversion to the T(1) state. The high fluorescence yield and the extraordinarily long lifetime of the singlet excited DBO are due to the presence of relatively high barriers, both for intersystem crossing and for C-N cleavage. The short lifetime of the triplet DBO is caused by fast radiationless decay to the ground state. 相似文献
997.
Yong-Jiang Xu Weitao Pan Xin Chen Wai C. Wong Marc Labelle 《Tetrahedron letters》2005,46(44):7523-7526
Novel synthetic approaches toward 5,6-dihydro-pyrimido[4,5-b][1,4]oxazepines were reported that led to successful introduction of poorly reactive anilines and various 2-hydroxybenzaldehydes to this therapeutically relevant scaffold. More extensive SAR studies on this scaffold hence became possible. 相似文献
998.
Liang Hong Chen Zhen-Feng Hu Rui-Xiang Yu Qing Zhou Zhong-Yuan Zhou Xiang-Ge 《Transition Metal Chemistry》2002,27(1):102-104
(n-Bu4N)4[Mo8O26] reacts with the Na salt of 2-mercaptopyridine N-oxide (NaPT) in MeCN to give the complex (n-Bu4N)2[MoO2(PT)2·Mo4O8(-O)2(3-O)2(PT)2] (1) which contains two metal centres: one being mononuclear molybdenum chelating to two PT ligands, and the other a tetranuclear oxomolybdenum cluster with two PT ligands at the terminal point. The i.r. spectrum of the title complex exhibits absorption bands at 911.5 and 881.9 cm–1, characteristic of the [cis-MoO2]2+ fragment. 相似文献
999.
Zhao Y Kan ZY Zeng ZX Hao YH Chen H Tan Z 《Journal of the American Chemical Society》2004,126(41):13255-13264
Nucleic acid molecules may fold into secondary structures, and the formation of such structures is involved in many biological processes and technical applications. The folding and unfolding rate constants define the kinetics of conformation interconversion and the stability of these structures and is important in realizing their functions. We developed a method to determine these kinetic parameters using an optical biosensor based on surface plasmon resonance. The folding and unfolding of a nucleic acid is coupled with a hybridization reaction by immobilization of the target nucleic acid on a sensor chip surface and injection of a complementary probe nucleic acid over the sensor chip surface. By monitoring the time course of duplex formation, both the folding and unfolding rate constants for the target nucleic acid and the association and dissociation rate constants for the target-probe duplex can all be derived from the same measurement. We applied this method to determine the folding and unfolding rate constants of the G-quadruplex of human telomere sequence (TTAGGG)(4) and its association and dissociation rate constants with the complementary strand (CCCTAA)(4). The results show that both the folding and unfolding occur on the time scale of minutes at physiological concentration of K(+). We speculate that this property might be important for telomere elongation. A complete set of the kinetic parameters for both of the structures allows us to study the competition between the formation of the quadruplex and the duplex. Calculations indicate that the formation of both the quadruplex and the duplex is strand concentration-dependent, and the quadruplex can be efficiently formed at low strand concentration. This property may provide the basis for the formation of the quadruplex in vivo in the presence of a complementary strand. 相似文献
1000.
Yuan LF Yang J Wang H Zeng C Li Q Wang B Hou JG Zhu Q Chen DM 《Journal of the American Chemical Society》2003,125(1):169-172
Orientationally ordered structures of two-dimensional (2D) C(60) at low temperature have been investigated theoretically and experimentally. Using total energy optimization with a phenomenological potential, we find the ground state is a close packed hexagonal lattice in which all the molecules have the same orientation. Several local minima of the potential energy surface are found to be associated with other 1 x 1 lattices as well as 2 x 2 lattices. The energies of the orientational domain boundaries of the 1x1 lattices are also computed, and two kinds of which yield negative values. A majority of these theoretical findings are confirmed by our low-temperature scanning tunneling microscopy study of a 2D C(60) array supported on a self-assembled monolayer. 相似文献