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101.
‘Head-to-head’ oligo-N-methylpyrrole peptide dimers linked by a methano[1,5]diazocin scaffold are presented in racemic as well as chiral fashion. Their DNA binding activities were assayed on calf thymus DNA, poly(dA-dT)2, and poly(dC-dG)2 by NMR and ECD spectroscopies, and fluorescence probe displacement assay. The presented dimers prefer AT sequences, but show higher affinity to poly(dC-dG)2 than distamycin A. The (4R,9R) configuration of methanodiazocin bridge was found to be better suited for interaction with ct-DNA and poly(dA-dT)2 than (4S,9S) configuration. 相似文献
102.
A new pulse sequence is proposed for the determination of scalar coupling correlation in small- and medium-sized organic compounds. The method uses a combination of the double pulsed field gradient spin-echo (DPFGSE) and the selective population transfer (SPT) techniques and is shown to be useful in the analysis of complex spectra with many overlapped signals. The usefulness of this method in the structural elucidation of natural substances is demonstrated using strychnine and digitoxin as examples. 相似文献
103.
104.
N-乙酸基取代四氮杂大环及其镧系配合物的热力学研究 总被引:2,自引:0,他引:2
用pH电位滴定法分别在25±0.1℃,40±0.1℃和80±0.1℃,0.5mol/LKNO3水溶液中测定了H_4L(5,7,12,14-四甲基-1,4,8,11-四氮杂环十四烷-N',n",N"',N""-四乙酸)的逐级质子化常数和焓值。又在40±0.1℃和80±0.1℃条件下测定了H4L与镧系金属离子(La~(3+),Nd~(3+),pr~(3+),Sm~(3+),Eu~(3+),Gd~(3+),Dy~(3+),Yb~(3+))配合物的稳定常数。结果表明:配合物稳定性高。 相似文献
105.
Inorganic-organic hybrids have been synthesized by incorporation of the inorganic component of Ti(OC2H5)4 into the organic polymer of ethyl cellulose. The inorganic-organic hybrids did not dissolve in toluene used as a solvent for the starting materials. The ethanol was formed as a by-product of the alcoholysis condensation reaction between Ti(OC2H5)4 and ethyl cellulose. These results suggest that ethoxy groups of Ti(OC2H5)4 react with hydroxy groups of ethyl cellulose to form cross-linking bonds of –O–Ti–O–. The reaction of Ti(OC2H5)4 with ethyl cellulose was further investigated by Fourier transform infrared (FT-IR) spectroscopy. The FT-IR spectroscopic experiments revealed that the Ti–O bond state of Ti(OC2H5)4 was changed by refluxing a toluene solution of Ti(OC2H5)4 with ethyl cellulose. The inorganic-organic hybrids have an interesting dielectric property; their dielectric constant is higher than that of ethyl cellulose and that of a simple mixture of TiO2 and ethyl cellulose. 相似文献
106.
Interactions between divalent alkali earth metal (DAEM) ions M (M?Be, Mg, Ca, Sr, Ba) and the second stable glycine conformer in the gas phase, which can transfer into the ground‐state glycine‐M2+ (except the glycine–Be2+) among each corresponding isomers when these divalent metal ions are bound, are studied at the hybrid three‐parameter B3LYP level with three different basis sets. Proton transfers from the hydroxyl to the amino nitrogen of the glycine without energy barriers have been first observed in the gas phase in these glycine–M2+ systems. The interaction between the glycine and these DAEM ions except beryllium and magnesium ion only create an amino hydrogen pointing to the original hydroxyl due to their weaker interaction relative to those divalent transition metal (DTM) ion‐bound glycine derivatives, being obviously different from that between the glycine and DTM ions, in which two amino hydrogens point to the original hydroxyl oxygen when these metal‐chelated glycine derivatives are produced. The interaction energy between the glycine and divalent magnesium would be the boundary of one or two amino hydrogens pointing to the hydrogyl oxygen, i.e., the ?170.3 kcal/mol of binding energy is a critical point. Similar intramolecular proton transfer has also been predicted for those DTM ion‐chelated glycine systems; however, that in the gas state has not been observed in the monovalent metal ion‐coordinated glycine systems. The binding energy between some monovalent TM ion and the glycine is similar to that of the glycine–Ba2+, which has the lowest binding strength among these DAEM–ion chelated glycine complexes. The difference among them only lies in the larger electrostatic and polarized effects in the latter, which favor the stability of the zwitterionic glycine form in the gas phase. According to these observations, we predict that the zwitterionic glycine would exist in the field of two positive charges in the gas phase. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem 94: 205–214, 2003 相似文献
107.
固定pH滴定法测定弱酸弱碱性药物 总被引:8,自引:0,他引:8
报道一种水溶液吕测定弱酸弱碱性药物的新型滴定分析方法-固定pH滴定法,其理论基础是弱酸弱碱在水溶液中各种存在形式的分布系数在pH值固定时为常数,对甲硝唑,盐酸美西律等离散常数在10^-8至10^-11范围内的7种弱酸弱碱性药物进行测定。结果与药典法吻合,回收率在99.4%~100.6%,方法简便,快速,准确,制剂中的赋形剂及色物不影响测定。 相似文献
108.
Organic sulfonyl fluorides are of interest owing to their insecticidal, germicidal and enzyme inhibitory properties. In the current work, synthesis of p-toluenesufonyl fluoride was accomplished by reacting p-toluenesulfonyl chloride with solid potassium fluoride using PEG-400 as a catalyst under solid-liquid phase transfer catalysis (S-L PTC) at 30 °C. p-Toluenesulfonyl fluoride is used as peroxygen bleach activator. It also finds use in the treatment of Alzheimer's disease. The mechanism is based on homogeneous solubilization of solid. PEG forms a complex with metal cation which associates with the nucleophile and it participates in SN2 type reactions. The reaction is intrinsically kinetically controlled. A complete theoretical analysis is done to determine both the rate constant and equilibrium constant from the same set of data. The activation energy and Gibbs free energy are also calculated. 相似文献
109.
V. E. Schneider E. E. Tornau A. A. Vlasova A. A. Gurskas 《Journal of inclusion phenomena and macrocyclic chemistry》1985,3(3):235-242
Clathrate thermodynamic stability conditions and the phase transitions associated with either the orientational ordering of the guest molecules or with the condensation of the guest molecules in the host lattice are investigated by means of the common microscopic model. The theory proposed describes the thermodynamic properties of -hydroquinone (Q
) clathrates. The dielectric constant (T) was measured experimentally inQ
·CH3OH andQ
·SO2 in the temperature range from 4.2 to 300 K and the phase transitions were found. It is shown that the theory qualitatively explains the experimental data obtained.Dedicated to Professor H. M. Powell. 相似文献
110.