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131.
Fernando Ribas Prado Claude Giessner-Prettre Alberte Pullman James F. Hinton Dennis Harpool Ken R. Metz 《Theoretical chemistry accounts》1981,59(1):55-69
The magnetic shielding constants of the different atoms of formamide, hydrated formamide and N-methylformamide are calculated by anab initio method. For the protons of formamide the measured differences between their chemical shifts are correctly reproduced by theory, provided that the molecular geometry used as input is carefully chosen. The differences between the values of the magnetic shielding constants calculated for formamide and hydrated formamide show that intermolecular hydrogen bonding produces variations of chemical shifts for all the atoms of the molecule except the formyl proton. The calculated chemical shift variations between formamide and N-methylformamide are compared to the experimental values and discussed in relation with different hydrogen bonding possibilities of the two molecules. The calculation of the contact term of the spin-spin coupling constants of formamide and hydrated formamide shows that in most cases the measured trends are satisfactorily reproduced and that the variations of these terms upon hydration are less than 3%. 相似文献
132.
Jacques Curély 《Monatshefte für Chemie / Chemical Monthly》2005,136(6):987-1011
Summary. The problem of direct exchange is examined in the simplest cases (formal coupling of two electrons initially isolated and hydrogen molecule). Then we consider the general case of a solid characterized by weak overlaps between the atomic orbitals of first-nearest neighbours so that the involved electrons are quasi-localized. We recall the physical origin of spin-orbit coupling. Its influence on direct exchange allows one to revisit Hunds rules and to express phenomenological Hamiltonians describing anisotropic couplings as well as the antisymmetrical Dzialoshinski-Moriya coupling. 相似文献
133.
An efficient method of photoaffinity labeling has been developed based on rationally designed multifunctional photoprobes. Photoaffinity techniques have been used to elucidate the protein structure at the interface of biomolecules by the photochemical labeling of interacting sites. However, the identification of labeled sites within target proteins is often difficult. Novel biotinyl bioprobes bearing a diazirine photophore have contributed significantly to the rapid elucidation of ligand binding sites within proteins, thereby extending conventional photoaffinity methods. This article discusses the synthesis and applications of various photoprobes bearing a biotin, including strategies using cleavable linkages between photophores. The combination of photoaffinity methods with chip technology is also described as a novel entry to rapid affinity-based screening of inhibitors. This review focuses on a rapid and reliable photoaffinity method utilizing diazirine-based multifunctional photoprobes with numerous potential applications in functional proteomics of biomolecular interactions. 相似文献
134.
NMR spectroscopy techniques for screening and identifying ligand binding to protein receptors 总被引:9,自引:0,他引:9
Binding events of ligands to receptors are the key for an understanding of biological processes. Gaining insight into protein-protein and protein-ligand interactions in solution has recently become possible on an atomic level by new NMR spectroscopic techniques. These experiments identify binding events either by looking at the resonance signals of the ligand or the protein. Ideally, both techniques together deliver a complete picture of ligand binding to a receptor. The approaches discussed in this review allow screening of compound libraries as well as a detailed identification of the groups involved in the binding events. Also, characterization of the binding strength and kinetics is possible, competitive binding as well as allosteric effects can be identified, and it has even been possible to identify ligand binding to intact viruses and membrane-bound proteins. 相似文献
135.
A study of carboxylic-modified mesoporous silica in controlled delivery for drug famotidine 总被引:2,自引:0,他引:2
A series of pure silica MSU and carboxylic-modified MSU materials were prepared. The formation of mesoporous silica materials with terminal carboxylic groups on pore surface was performed by the acid-catalyzed hydrolysis of cyano to carboxylic. Then their potential applications in controlled drug delivery carriers were investigated. Drug famotidine was selected as a model molecule out of the consideration of the terminal amino groups in its molecule. The adsorption experiments show significant adsorption of famotidine on the carboxylic-modified MSU materials. And, the functionalization level of carboxylic groups has been found to be the key factor affecting the adsorption capacities of the modified MSU materials for famotidine. Subsequently, three kinds of release fluids, including simulated gastric medium, simulated intestinal medium, and simulated body fluid, were used to test the famotidine release rate from the carboxylic-modified MSU material. Obvious delayed effect has been observed for the famotidine release from the carboxylic-modified mesoporous silica material under the in vitro assays. 相似文献
136.
The gold nanoprisms (GNPs) have exhibited special plasmonic properties for biomedical applications because of their unique shapes and dimensions. Based on their optical performance, the NIR dye IR780 not only enabled the GNPs-based nanosystem as SERRS nanoparticles for Raman-encoded molecular imaging, but also enhanced the plasmonic photothermal property by laser irradiation. Meanwhile, the GNPs/IR780-Lyp-1 by introduction of tumor-homing peptide segment LyP-1, which presents high affinity to p32 protein, demonstrated the increased enrichment in tumor region and enhanced photothermal therapy efficacy. 相似文献
137.
Vukadin M. Leovac Vladimir Divjaković Ana F. Petrović Nikolai V. Gerbeleu 《Monatshefte für Chemie / Chemical Monthly》1989,120(3):181-186
Summary The reaction of warmDMF solutions of Cu(II) perchlorate, 5-nitrosalicylaldehyde S-methylisothiosemicarbazone (H2
L) and piperidine (Pip) yielded the paramagnetic (eff=2.19 B.M.) Cu(L)Pip complex, whereL is the dianionic form of H2
L, formed as a result of deprotonation of the phenolic hydroxyl and NH2 group. Crystal data of the complex are: monoclinic P21,a=11.902(4),b=6.765(3),c=11.343(4)Å; =112.92°,V=841.20(8)Å3,M=400.9,Z=2,d
0=1.60 gcm–3,d
c
=1.58 gcm–3,F(000)=424. The structure was refined to a residualR=0.047. The copper(II) ion is coordinated in a square-planar arrangement by the piperidine nitrogen and the NNO set of donor atoms ofL.
Komplexe der Übergangsmetalle mit Thiosemicarbazid-Liganden, IV. Synthese und molekulare Struktur von 5-Nitrosalicylaldehyd-S-methylisothiosemicarbazonato-piperidin-kupfer(II)
Zusammenfassung Durch die Reaktion in warmenDMF-Lösungen von Cu(II) Perchlorat, 5-Nitrosalicylaldehyd-S-methylisothiosemicarbazon (H2 L) und Piperidin (Pip) wurde ein paramagnetischer Komplex (eff=2.19 B.M.) Cu(L)Pip erhalten, wobeiL nach doppelter Deprotonierung (NH2- und Phenolhydroxyl-Gruppe) als dianionische Form von H2 L vorliegt. Die kristallographischen Daten des Komplexes sind: monokline Raumgruppe P21,a=11.902(4),b=6.765(3),c=11.343(4)Å, =112.92°;V=841.20Å3,M=400.9,Z=2,d 0=1.60 gcm–3,d c =1.58 gcm–3,F(000)=424. Die struktur wurde bis zu einemR-Wert von 0.047 verfeinert. Die Koordination des Kupfers wird quadratisch-planar über den Piperidin-Stickstoff und die NNO-Donorhülle der Chelatliganden gebildet.相似文献
138.
Rudnev AV Aleksenko SS Semenova O Hartinger CG Timerbaev AR Keppler BK 《Journal of separation science》2005,28(2):121-127
A CE method has been developed to evidence and quantitatively characterize the interaction between platinum-based antitumor drugs and human serum proteins. This method is a variant of affinity CE modified regarding both experimental setup and data treatment so as to measure the peaks (or vacancies) that correspond to the bound drug when it slowly binds to the protein. Using the formalism of the Hummel-Dreyer method and cisplatin and oxaliplatin as test compounds, a protocol for determining albumin and transferrin binding constants and stoichiometries, including (and distinguished by) 48 hours of incubation of the reaction mixture, was elaborated. Relative affinities of drugs toward different proteins in aqueous solution at physiological pH, chloride concentration, and temperature were compared in terms of overall binding constants and numbers of drug molecules attached to the protein. The results indicate that both platinum drugs bind to albumin more strongly than to transferrin, supporting the concept that the albumin fraction is a major drug supply route for chemotherapeutical needs. From a comparison with the binding parameters measured previously for cisplatin by other methods, conclusions were drawn about the validity of CE as a simple and convenient method for assaying protein-drug reactions with slow kinetics. 相似文献
139.
A method to analyze human plasma proteins without fractionation, directly applying a plasma-matrix mixture on the target plate of a matrix-assisted laser desorption/ionization-time of flight-mass spectrometer (MALDI-TOF-MS), has been described. Peaks of ionized plasma proteins could not be detected applying a mixture of an undiluted plasma sample and a matrix solution, but they appeared when the plasma was diluted before mixing with the matrix. Tenfold diluted plasma provided well-resolved protein peaks in the m/z range from 4000 to 30,000. The addition of a simple post-crystallization washing procedure performed on the target plate further improved the quality of mass spectra. We numbered 58 peaks in the range of 4-160 kDa and 32 out of which were assigned to the plasma protein species which have been reported. Especially high sensitivity and resolution were obtained in the region < 30 kDa, where multiple isoforms of apolipoprotein A-I, apolipoprotein A-II, apolipoprotein C-I, apolipoprotein C-II, apolipoprotein C-III, and transthyretin could be assigned. Various post-translational modifications are involved in the isoforms, e.g., proteolytic cleavage, glycosylation and chemical modifications. This method will become complementary with the present electrophoretic techniques, especially for the analysis of low-molecular-mass proteins. 相似文献
140.
The electrical and magnetic properties of the tetragonal phase SmCuOSe are reported as a function of the temperature. The optical properties were studied by means of diffuse reflectance spectrum in the UV-Vis range. The electrical resistivity measurements as well as diffuse reflectance spectrum show that SmCuOSe is a semiconductor with an optical band gap (Eg) of 2.6 eV. In this phase, Cu is at its monovalent oxidation state and, as such, it does not contribute to the total magnetic moment, whereas Sm is in its 3+ oxidation state, with a large VanVleck contribution due to the admixture of the fundamental state with higher energy levels. 相似文献