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101.
Xiu Hui Lu Hai Bin Yu Wei Rong Wu Yue Hua Xu 《International journal of quantum chemistry》2007,107(2):451-457
Mechanisms of the cycloaddition reaction between singlet difluoromethylene carbene and acetone have been investigated with the second‐order Møller–Plesset (MP2)/6‐31G* method, including geometry optimization and vibrational analysis. Energies for the involved stationary points on the potential energy surface (PES) are corrected by zero‐point energy (ZPE) and CCSD(T)/6‐31G* single‐point calculations. From the PES obtained with the CCSD(T)//MP2/6‐31G* method for the cycloaddition reaction between singlet difluoromethylene carbene and acetone, it can be predicted that path B of reactions 2 and 3 should be two competitive leading channels of the cycloaddition reaction between difluoromethylene carbene and acetone. The former consists of two steps: (i) the two reactants first form a four‐membered ring intermediate, INT2, which is a barrier‐free exothermic reaction of 97.8 kJ/mol; (ii) the intermediate INT2 isomerizes to a four‐membered product P2b via a transition state TS2b with an energy barrier of 24.9 kJ/mol, which results from the methyl group transfer. The latter proceeds in three steps: (i) the two reactants first form an intermediate, INT1c, through a barrier‐free exothermic reaction of 199.4 kJ/mol; (ii) the intermediate INT1c further reacts with acetone to form a polycyclic intermediate, INT3, which is also a barrier‐free exothermic reaction of 27.4 kJ/mol; and (iii) INT3 isomerizes to a polycyclic product P3 via a transition state TS3 with an energy barrier of 25.8 kJ/mol. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 相似文献
102.
二甲基甲酰胺中四种钕盐的电导 总被引:3,自引:0,他引:3
通过电导测量研究了四种钕盐:Nd(CF3SO3)3、Nd(ClO4)3、Nd(NO3)3和NdCl3在极性非质子溶剂DMF中的电导性质.利用线性拟合方法求得在25 ℃下Nd(CF3SO3)3和Nd(ClO4)3的极限摩尔电导率分别为278.8和 280.7 S•cm2•mol-1.用间接方法求得Nd(NO3)3 与NdCl3 的极限摩尔电导率分别为297.2和287.3 S•cm2 •mol-1.在25~65 ℃温度范围内,Nd(CF3SO3)3和Nd(ClO4)3的电导率随温度呈线性变化. Nd(NO3)3和NdCl3的电导行为表现出明显的离子缔合. 相似文献
103.
In aqueous H2SO4, Ce(IV) ion oxidizes rapidly Arnold's base((p-Me2NC6H4)2CH2, Ar2CH2) to the protonated species of Michler's hydrol((p-Me2NC6H4)2CHOH, Ar2CHOH) and Michler's hydrol blue((p-Me2NC6H4)2CH+, Ar2CH+). With Ar2CH2 in excess, the rate law of the Ce(IV)-Ar2CH2 reaction in 0.100 M H2SO4 is expressed -d[Ce(IV)]/dt = kapp[Ar2CH2]0[Ce(IV)] with kapp = 199 ± 8M?1s?1 at25°C. When the consumption of Ce(IV) ion is nearly complete, the characteristic blue color of Ar2CH+ ion starts to appear; later it fades relatively slowly. The electron transfer of this reaction takes place on the nitrogen atom rather than on the methylene carbon atom. The dissociation of the binuclear complex [Ce(III)ArCHAr-Ce(III)] is responsible for the appearance of the Ar2CH+ dye whereas the protonation reaction causes the dye to fade. In highly acidic solution, the rate law of the protonation reaction of Michler's hydrol blue is -d[Ar2CH+]/dt = kobs[Ar2CH+] where Kobs = ((ac + 1)[H*] + bc[H+]2)/(a + b[H+]) (in HClO4) and kobs= ((ac + 1 + e[HSO4?])[H+] + bc[H+]2 + d[HSO4?] + q[HSO4?]2/[H+])/(a + b[H+] + f[HSO4?] + g[HSO4?]/[H+]) (in H2SO4), and at 25°C and μ = 0.1 M, a = 0.0870 M s, b = 0.655 s, c = 0.202 M?1s?1, d = 0.110, e = 0.0070 M?1, f = 0.156 s, g = 0.156 s, and q = 0.124. In highly basic solution, the rate law of the hydroxylation reaction of Michler's hydrol blue is -d[Ar2CH+]/dt = kOH[OH?]0[Ar2CH+] with kOH = 174 ± 1 M?1s?1 at 25°C and μ = 0.1 M. The protonation reaction of Michler's hydrol blue takes place predominantly via hydrolysis whereas its hydroxylation occurs predominantly via the path of direct OH attack. 相似文献
104.
利用扫描隧道显微镜研究了荧光液晶分子2, 5-二-[2-(3, 4-二-十二烷氧基-苯基)-乙烯基]-3, 6-二甲基吡嗪(BPDP12)在石墨表面上自组装单层膜的结构. 实验结果表明, 该化合物在石墨表面形成两种自组装结构:一种是稳定的, 分子的共轭中心相互平行, 烷基链相互交错的密排结构;另一种是不稳定的, 分子的共轭中心彼此为烷基链所分隔的非密排结构. 分子之间较强的π-π作用和分子烷基链之间的范德华作用力对分子组装的取向形成竞争, 是产生两种不同组装结构的根本原因. 相似文献
105.
本报道用了2,6-二氯-4-溴偶氮胂作显色剂测定微量铀(Ⅵ)的光度法。在H2SO4介质中,铀(Ⅵ与)2,6-二氯-4-溴偶氮胂形成1:2络合物,其λmax=640nm;表观摩尔吸光系数为1.1×10^5L.mol^-^1.cm^-^1;铀的浓度在0.0-22.0μg/ml内符合比耳定律。方法具有灵敏度高,选择性好,操作方便等特点并已用于废水及矿样中微量铀(Ⅵ)的测定。 相似文献
106.
The hydrothermal reaction of YbCl(3) small middle dot6H(2)O with 1,2,4,5-benzenetetracarboxylic dianhydride resulted in [[Yb((b)btec)(1/4)((d)btec)(3/6)(H(2)O)(2)](4).6H(2)O](n)() (1) (H(4)btec = 1,2,4,5-benzenetetracarboxylic acid), and the solvothermal reaction of Er(NO(3))(3) small middle dot6H(2)O or TbCl(3).6H(2)O with 1,2,4,5-benzenetetracarboxylic dianhydride in H(2)O/acetic acid gave rise to [[Er(2)((c)btec)(2/4)((e)btec)(2/4)((f)btec)(2/4)(H(2)O)(4)].4H(2)O](n)() (2) and [[Tb(H(2)btec)(2/4)((f)btec)(3/6)(H(2)O)].2H(2)O](n)() (3), respectively. Complex 1 crystallizes in monoclinic space group C2/m with a = 20.8119(5) A, b = 17.6174(1) A, c = 5.7252(2) A, beta = 92.324(1) degrees, and Z = 1. 1 possesses a three-dimensional framework consisting of eight-coordinate ytterbium centers and two kinds of channels along the c axis. Complex 2 crystallizes in triclinic space group P with a = 9.6739(5) A, b = 11.0039(5) A, c = 11.5523 A, alpha = 104.8330(10) degrees, beta = 91.0000(10) degrees, gamma = 114.2570(10) degrees, and Z = 2. 2 has a three-dimensional framework comprising both eight- and nine-coordinate erbium centers and channels along the a axis. Complex 3 crystallizes in monoclinic space group P2(1)/n with a = 10.7246(12) A, b = 7.1693(9) A, c = 17.158(2) A, beta = 97.109(2) degrees, and Z = 4. 3 shows a three-dimensional framework containing nine-coordinate terbium centers and channels along the b axis. Uncoordinated water molecules occupy the channels in the three complexes. TGA and XRPD were determined for the three complexes, and the results illustrate that the framework of 1 is retained upon removal of uncoordinated and coordinated water molecules. 相似文献
107.
Yangke Wanyan Xixi Xu Kehang Liu Huidan Zhang Junai Zhen Rong Zhang Jumei Wen Ping Liu Yuqing Chen 《Molecules (Basel, Switzerland)》2020,25(23)
Inhibition of the glycolytic pathway is a critical strategy in anticancer therapy because of the role of aerobic glycolysis in cancer cells. The glycolytic inhibitor 2-Deoxy-d-glucose (2-DG) has shown potential in combination with other anticancer agents. Buforin IIb is an effective antimicrobial peptide (AMP) with broad-spectrum anticancer activity and selectivity. The efficacy of combination treatment with 2-DG and buforin IIb in prostate cancer remains unknown. Here, we tested the efficacy of buforin IIb as a mitochondria-targeting AMP in the androgen-independent human prostate cancer cell line DU145. Combining 2-DG with buforin IIb had a synergistic toxic effect on DU145 cells and mouse xenograft tumors. Combination treatment with 2-DG and buforin IIb caused stronger proliferation inhibition, greater G1 cell cycle arrest, and higher apoptosis than either treatment alone. Combination treatment dramatically decreased L-lactate production and intracellular ATP levels, indicating severe inhibition of glycolysis and ATP production. Flow cytometry and confocal laser scanning microscopy results indicate that 2-DG may increase buforin IIb uptake by DU145 cells, thereby increasing the mitochondria-targeting capacity of buforin IIb. This may partly explain the effect of combination treatment on enhancing buforin IIb-induced apoptosis. Consistently, 2-DG increased mitochondrial dysfunction and upregulated Bax/Bcl-2, promoting cytochrome c release to initiate procaspase 3 cleavage induced by buforin IIb. These results suggest that 2-DG sensitizes prostate cancer DU145 cells to buforin IIb. Moreover, combination treatment caused minimal hemolysis and cytotoxicity to normal WPMY-1 cells. Collectively, the current study demonstrates that dual targeting of glycolysis and mitochondria by 2-DG and buforin IIb may be an effective anticancer strategy for the treatment of some advanced prostate cancer. 相似文献
108.
Synthesis,photophysical and electrochemical studies of di-2-pyridyl ketone complexes of rhodium(III)
Huang Wen Liang Lee Jen Rong Shi Sheu Yuan Tsai Cheng Yuan 《Transition Metal Chemistry》2003,28(4):381-387
Complexes of rhodium(III) with di-2-pyridyl ketone (dpk), Rh(dpk)(MeCN)Cl3
(1) and cis-[Rh(dpk)2Cl2]+
(2), have been successfully prepared and characterized. At low temperature (77 K), complex (2) in EtOH/MeOH (4:1, v/v) shows a broad, symmetric and structureless red emission with a microsecond lifetime and, hence, is assigned as the dd* phosphorescence. Electrochemical data, including cyclic voltammetry, normal pulse voltammetry, triple pulse voltammetry and controlled potential electrolysis, have been obtained for the two dpk complexes of rhodium(III) in MeCN. On the basis of analysis of the electrochemical (1,2) and luminescence data (2), electron transfer mechanisms are proposed. For complex (1), two reduction processes occur at the metal-localized orbitals with elimination of chlorides during the first reduction step. This is followed by a one-electron reduction at the metal. For complex (2), three electrons are transferred to the metal in two successive reduction steps accompanied by elimination of two chlorides. After these two reduction steps another one-electron reduction occurs at the dpk ligand. 相似文献
109.
手性液晶掺杂剂(S)┐4┐辛氧基┐4┐(2┐酰氧基┐丙氧基)联苯的合成马汝建李培荣国斌*(华东理工大学化学系上海200237)关键词铁电液晶材料,手性液晶掺杂剂,合成,手征性1997-02-03收稿,1997-08-07修回铁电液晶显示器所用的材料... 相似文献
110.
The geometries of the most stable isomers of gold telluride systems AuTe, Au2Te, and AuTe2 are determined using the MP2 method. The aspect of gold—telluride interaction, the electron correlation, and relativistic
effects on geometry and stability are investigated at the MP2 and CCSD(T) theoretical levels. The results show that the electron
correlation and relativistic effects are responsible not only for gold—gold attraction but also for additional gold—telluride
interaction. The gold—telluride interaction is strong enough to modify the known pattern of bare gold clusters. Both effects
are essential for determining the geometry and relative stability of this type of systems. 相似文献