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81.
Reaction of COC12.6H20 with equimolar bis(3,5-dimethylpyrazolyl)methane (dmpzm) produced a mononuclear adduct [Co(dmpzm)Cl2] (1). Treatment of 1 with sodium dicyanamide (dca) afforded a polymeric complex [Co(dmpzm)(μ-dca)2]∞ (2). 1 and 2 were characterized by elemental analysis, IR spectra, thermogravimetric analysis and single-crystal X-ray diffraction. The cobalt atom in 1 adopts a distorted tetrahedral coordination geometry, bound to two N atoms of one dmpzm and two Cl atoms. Complex 2 has a 2D brick-wall network (extended along the bc plane) in which the { [Co(dmpzm)(μ-dca)]2} n^2n+ chains are interconnected by pairs of μ-dca anions along the c axis. The magnetic properties of 1 and 2 were also investigated. 相似文献
82.
Hongzhi Qiao Lei Zhang Dong Fang Zhenzhu Zhu Weijiang He Lihong Hu Liuqing Di Zijian Guo Xiaoyong Wang 《Chemical science》2021,12(12):4547
Copper complexes are promising anticancer agents widely studied to overcome tumor resistance to metal-based anticancer drugs. Nevertheless, copper complexes per se encounter drug resistance from time to time. Adenosine-5′-triphosphate (ATP)-responsive nanoparticles containing a copper complex CTND and B-cell lymphoma 2 (Bcl-2) small interfering RNA (siRNA) were constructed to cope with the resistance of cancer cells to the complex. CTND and siRNA can be released from the nanoparticles in cancer cells upon reacting with intracellular ATP. The resistance of B16F10 melanoma cells to CTND was terminated by silencing the cellular Bcl-2 gene via RNA interference, and the therapeutic efficacy was significantly enhanced. The nanoparticles triggered a cellular autophagy that amplified the apoptotic signals, thus revealing a novel mechanism for antagonizing the resistance of copper complexes. In view of the extensive association of Bcl-2 protein with cancer resistance to chemotherapeutics, this strategy may be universally applicable for overcoming the ubiquitous drug resistance to metallodrugs.Bcl-2-related tumor resistance to anticancer drugs can be overcome by silencing the cellular Bcl-2 gene via RNA interference. The realization of the goal is exemplified by delivering Bcl-2 siRNA and a tumor-resistant Cu complex to cancer cells with an ATP-responsive nanocarrier. 相似文献
83.
Two cobalt(II) coordination polymers formed from bte (bte = 1,2-bis(1,2,4-triazol-1-yl)ethane), namely [Co(bte)2(dca)2]n (1) and {[Co(bte)(dca)2] · H2O}n (2), have been synthesized and characterized by elementary analyses, IR, thermogravimetric analyses, X-ray diffraction analyses and magnetic measurements. Compound 1 is a double-chain with Co(II) centers bridged by bte, containing metallocycles of [Co2(bte)2] and trans dca as termination ligands. In 2, each Co(II) center is bonded by two bridging bte ligands and four dca as μ-1,5-dca in different orientations in the 3D network. 相似文献
84.
Catalytic Enantioselective Reduction of Prochiral Ketones with Chiral Ferrocenyl Amino Alcohols 总被引:1,自引:0,他引:1
The asymmetric reduction of prochiral ketones was catalyzed by a class of recoverable and highly stable chiral ferrocenyl amino alcohols derived from natural amino acids to yield optically active secondary alcohols in high chemical yields and moderate to good enantiomeric excesses. 相似文献
85.
The potential energy surface (PES) for the CF3CFHO2+HO2 reaction has been theoretically investigated using the DFT [B3LYP/6‐311G(d,p)] and B3LYP/6‐311++G(3df,3pd)//B3LYP/6‐311G(d,p) levels of theory. Both singlet and triplet PESs are investigated. The reaction mechanism on the triplet surface is simple. It is revealed that the formation of CF3CFHOOH+3O2 is the dominant channel on the triplet surface. On the basis of the ab initio data, the total rate constants for the reaction CF3CFHO2+HO2 in the T = 210–500 K range have been computed using conventional transition state theory with Wigner's tunneling correction and have been fitted by a rate constant expression as k = 1.04 ×10?12(cm3 molecule?1 s?1) exp (700.33/T). Calculated transition state rate constants with Wigner's tunneling correction for the reaction CF3CFHO2+HO2 are in good agreement with the available experimental values. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 相似文献
86.
This paper introducesa novel method for packing Capillary Electrochromatography Columns (CEC). Using vacuum packing methodology, silica particles as small as 1 microm were successfully packed into the capillary columns with 75 microm inner diameter. The columns are verystable and show no noticeable loss in efficiency after 200 sample injections. The performance of these vacuum packed capillary columns was evaluated with a mixture of aromatic and non-aromatic compounds. A 24 cm long capillary column can produce peak efficiencies of around 45,000 plates for benzene. 相似文献
87.
In this paper, we used bond-length equalization, aromatic stabilization energies (ASE) and nucleus-independent chemical shifts
(NICS), calculated with (density functional theory) B3LYP levels at the 6-311+G** basis set, to evaluate the aromaticity of a set of 38 five-member planar π-electron aromatic systems: sila-, aza- and phospha-
derivatives and their parent systems. The result revealed statistically significant correlations among the above three criteria,
and the order of aromaticity of the whole set was: Aza- derivatives rings > Phospha- derivatives rings > Sila- derivatives
rings > Carbon-containing rings; NICS(0.6) and NICS(0.8) had the same results in evaluating the order of aromaticity in our
case. 相似文献
88.
《Fluid Phase Equilibria》2006,244(2):137-152
The simultaneous solubility of sulfur dioxide and ammonia in aqueous solutions of (ammonium sulfate or sodium sulfate) was measured by a synthetic method in the temperature range from 313.6 to 373.2 K and at pressures up to 2.5 MPa. Furthermore, the enthalpy change upon diluting aqueous solutions of sulfur dioxide, ammonia and (ammonium sulfate or sodium sulfate) in aqueous solutions of the same salt was measured in a batch calorimeter at about 313 and 352 K. The experimental results are used for comparison with predictions from a thermodynamic model for the vapor–liquid equilibrium and the enthalpy of dilution of those chemical reacting systems. In that model, activity coefficients are calculated from Pitzer's molality-scale-based Gibbs excess energy model, where all interaction parameters are either adopted from previous investigations on the properties of the binary and ternary sub-systems (if available) or they are neglected (if they are not available). 相似文献
89.
《Electrochemistry communications》2007,9(3):469-474
The composite film based on Nafion and hydrophobic room-temperature ionic liquid (RTIL) 1-butyl-3-methyl-imidazolium hexafluorophosphate ([bmim] PF6) was explored. Here, Nafion was used as a binder to form Nafion-ionic liquids composite film and help [bmim] PF6 effectively adhered on glassy carbon (GC) electrode. X-ray photoelectron spectroscopy (XPS), cyclic voltammtery (CV) and electrochemical impedance spectroscopy (EIS) were used to characterize this composite film, showing that the composite film can effectively adhere on the GC electrode surface through Nafion interacting with [bmim] PF6 and GC electrode. Meanwhile, doping [bmim] PF6 in Nafion can also effectively reduce the electron transfer resistance of Nafion. The composite film can be readily used as an immobilization matrix to entrap horseradish peroxidase (HRP). A pair of well-defined redox peaks of HRP was obtained at the HRP/Nafion-[bmim] PF6 composite film-modified GC electrode through direct electron transfer between the protein and the underlying electrode. HRP can still retain its biological activity and enhance electrochemical reduction towards O2 and H2O2. It is expected that this composite film may find more potential applications in biosensors and biocatalysis. 相似文献
90.