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21.
The emission Mössbauer spectra of 125I labeled iodobenzene, methyl iodide, and of their dilute solutions in benzene and hexane, were computer analyzed. Two species were observed, in one of which tellurium is presumably attached to two organic moieties, while in the other, tellurium is attached to a single organic moiety. 相似文献
22.
The change in optical properties of colloidal gold upon aggregation has been used to develop an experimentally convenient colorimetric method to study the interfacial phase transition of an elastin-like polypeptide (ELP), a thermally responsive biopolymer. Gold nanoparticles, functionalized with a self-assembled monolayer (SAM) of mercaptoundecanoic acid onto which an ELP was adsorbed, exhibit a characteristic red color due to the surface plasmon resonance (SPR) of individual colloids. Raising the solution temperature from 10 degrees C to 40 degrees C thermally triggered the hydrophilic-to-hydrophobic phase transition of the adsorbed ELP resulting in formation of large aggregates due to interparticle hydrophobic interaction. Formation of large aggregates caused a change in color of the colloidal suspension from red to violet due to coupling of surface plasmons in aggregated colloids. The surface phase transition of the ELP was reversible, as seen from the reversible change in color upon cooling the suspension to 10 degrees C. The formation of colloidal aggregates due to the interfacial phase transition of adsorbed ELP was independently verified by dynamic light scattering of ELP-modified gold colloids as a function of temperature. Colloidal SPR provides a simple and convenient colorimetric method to study the influence of the solution environment, interfacial properties, and grafting method on the transition properties of ELPs and other environmentally responsive polymers at the solid-water interface. 相似文献
23.
A brute-force numerical investigation has been carried out on the hopping of excitons in a three-dimensional molecular aggregate. Possibilities of vibronic decay, rapid chemical reactions of saturated species, radiative decay of overpopulated molecules, and cooperative chemical reactions involving saturated exciton populations on traps of two different types have been considered. Investigation have been performed with two types of initial distribution of excitons—facial and random—and for 10,000 or, sometimes, for 20,000 time steps each of duration 1ps. Several interesting observations have been made from this computer experiment: (1) The total number of occurrences of fast reactions depends upon the initial distribution of excitons. (2) It decreases if other exciton depleting processes are at work. (3) It also depends on the pattern of placement of traps. (4) The location of impurities also affects the rate of occurrence of these reactions. Thus, more reactions occur when the excitons are initially concentrated on one face and traps are suitably located on the path of flow of these excitons. A random initial distribution tends to equilibrate the excitons quickly over all the lattice points, thus giving rise to fewer reactions. (5) The number of reactions need not necessarily increase with the number of reaction centers; in fact, it decreases as more centers are added when the supply of excitons is severely limited. (6) A Complicated dynamics results when different types of additional processes, viz., enhanced fluorescence, radiative emissions, and cooperative chemical reactions are simultaneously allowed. The cooperative process has been clearly found to dominate. A first-order rate constant of about 108 s-1 has been calculated for the occurrence of the cooperative process. This rate is affected when other nonconserving processes are switched on. Observations (1), (4), and (5) are the most important conclusions of our work. They lie outside the scope of traditional models such as the random walk model, the diffusion model, and the lattice model for the migration of excitons in a molecular aggregate. © 1993 John Wiley & Sons, Inc. 相似文献
24.
Shefali Pal Sailendra Nath Poddar Gurucharan Mukherjee 《Transition Metal Chemistry》1994,19(4):449-452
Summary Nickel(II) and palladium(II) complexes of the 1,3-di(o-aminophenylthio) propane (H2L1) and 1,2-di(o-aminophenylthio)xylene (H2L2) ligands have been prepared and characterized. The hydrobromide salt of H2L1 gave a 12 ligand-metal complex of PdII, whereas free H2L1 formed the usual 1:1 species. The reaction of Na2PdCl4 with H2L2 resulted in S,S-dealkylation of the ligand and formation of a mononuclear complex of the corresponding thiol, i.e. 2-aminobenzenethiol. NiCl2, NiBr2 and Ni(ClO4)2 did not react directly with H2L2. NiII is a fairly hard ion and therefore does not coordinate to the soft thioether moiety in H2L2 in the absence of soft anions which symbiotically motivate NiII to act as a soft acceptor. It thus does not react with H2L2 in the presence of hard ions such as Cl–, Br- and ClO
4
–
, but, the in situ reaction of the constituents produced the tetrahedral NiII complex, contrary to earlier reports of similar types of octahedral species. 相似文献
25.
Sambhu N. Datta 《International journal of quantum chemistry》2004,96(1):42-55
The solution of a unitarily transformed Dirac equation for the hydrogenic electron in zero magnetic field is investigated here. The momentum‐space representation is adopted as a natural recourse. The spinor part of the transformed wavefunction in momentum space can be easily prescribed for a central potential. Hence, for the Coulomb potential, a pair of equations is obtained for the radial components in momentum space. It is shown that starting from these radial equations, one can recover the equations previously derived by Rubinowicz, Lévy, and Lombardi for the problem of the Dirac hydrogen atom in momentum space. This establishes equivalence among different approaches based on the momentum representation, including the current treatment. The recovery of the equations due to Rubinowicz permits the exact eigenvalues to be written down and exact expressions to be derived for the radial components of the transformed wavefunction in momentum space. A new approach is adopted to carry out a reduction to the nonrelativistic regime and the nonrelativistic limit. At first the transformed momentum‐space equation for the hydrogen atom is rewritten in terms of the hyperspherical coordinates. The zeroth‐order solutions of the new equation are recovered in the limit c → ∞ where c is the speed of light. These are manifestly separable into positive‐ and negative‐energy forms. For positive energy, these solutions have nonvanishing upper components that are two‐component spinors. The latter exactly correspond to the single‐component, nonrelativistic, momentum‐space solutions derived by Fock. It is shown that when the upper component is corrected through first order in v2/c2 but the separability is still maintained for the transformed wavefunction, one retrieves the Pauli equation in momentum space. It is also shown that for a hydrogen atom placed in a uniform magnetic field, the nonvanishing momentum‐space matrix elements representing the anomalous Zeeman effect have a simple form, namely, the product of a radial integral and an angular integral. These integrals are equal to the well‐known radial and angular integrals in coordinate representation. The matrix elements can be easily evaluated. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem, 2003 相似文献
26.
Macrocyclization of bis-indole quinolines for selective stabilization of G-quadruplex DNA structures
The recognition of G-quadruplex (G4) DNA structures as important regulatory elements in biological mechanisms, and the connection between G4s and the evolvement of different diseases, has sparked interest in developing small organic molecules targeting G4s. However, such compounds often lack drug-like properties and selectivity. Here, we describe the design and synthesis of a novel class of macrocyclic bis-indole quinolines based on their non-macrocyclic lead compounds. The effects of the macrocyclization on the ability to interact with G4 DNA structures were investigated using biophysical assays and molecular dynamic simulations. Overall, this revealed compounds with potent abilities to interact with and stabilize G4 structures and a clear selectivity for both G4 DNA over dsDNA and for parallel/hybrid G4 topologies, which could be attributed to the macrocyclic structure. Moreover, we obtained knowledge about the structure–activity relationship of importance for the macrocyclic design and how structural modifications could be made to construct improved macrocyclic compounds. Thus, the macrocyclization of G4 ligands can serve as a basis for the optimization of research tools to study G4 biology and potential therapeutics targeting G4-related diseases.Macrocyclization improves the selectivity, affinity, and ability to stabilize G4 DNA structures. 相似文献
27.
A new series of N-substituted bis-(tetrahydropapaverine) ring systems have been synthesised in expectation of better antispasmodic activity in comparison with papaverine. The synthesis of the targeted heterocycles is described along with a discussion of their structure activity relationship. The general synthetic methods of bis-(tetrahydropapaverine) analogues involve tetrahydropapaverine, various piperazines, diisocyanates and diisothiocyanates as starting materials. Pharmacological evaluation involves the in vitro antispasmodic activity on a freshly removed guinea pig ileum using a force displacement transducer amplifier connected to a physiograph. Among the analogues synthesized in the present study, N,N'-bis-[2-carbamoyl-1-(3,4-dimethoxybenzyl)-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinolinyl]piperazine (22), was found to be the most potent muscle relaxant (IC(50): 0.31 microM). 相似文献
28.
Kundu S Pal A Ghosh SK Nath S Panigrahi S Praharaj S Pal T 《Inorganic chemistry》2004,43(18):5489-5491
Ligands with a beta-diketone skeleton have been employed for the first time as reductant to produce ligand stabilized gold nanoparticles of different shapes from aqueous HAuCl(4) solution. Evolution of stable gold nanoparticles follows first order (k approximately equal to 10(-2) min(-1)) kinetics with respect to Au(0) concentration. Growth of particles of different shapes (spherical or triangular or hexagonal) goes hand in hand under the influence of different beta-diketones, which have excellent capping and reducing properties. Chlorine insertion was observed to take place in the beta-diketone skeleton. 相似文献
29.
Sambhu N. Datta 《International journal of quantum chemistry》1995,56(2):91-95
Relativistic basis sets for first-row atoms have been constructed by using the near-Hartree–Fock (nonrelativistic) eigenvectors calculated by Partridge. These bases generate results of near-Dirac–Hartree–Fock quality. Relativistic total and orbital energies, relativistic corrections to the total energy, and magnetic interaction energies for the first-row atoms have been presented. The smallest Gaussian expansions (13s8 p expansions) yield Dirac–Hartree–Fock total energies accurate through six significant digits, while the largest expansions (18s13p expansions) give these energies accurate through seven significant digits. These results are more accurate than some of the results reported earlier, particularly for the open-shell atoms, indicating that the basis employed is reasonably economical for relativistic calculations. © 1995 John Wiley & Sons, Inc. 相似文献
30.
Satyendra Nath Gupta Uma Sankar Nandi 《Journal of polymer science. Part A, Polymer chemistry》1970,8(6):1493-1501
Dimethyl sulfoxide has been used as a solvent in the polymerization of methyl methacrylate and styrene. The chain-transfer coefficients of the solvent and the values of δ [i.e., (2kt)1/2/kp] in solvent-monomer mixtures of various compositions were determined. δ was observed to be dependent on the solvent concentration in the case of methyl methacrylate but remained constant in case of styrene. The lowering of the values of δ with increasing solvent concentration in case of methyl methacrylate has been attributed to an interaction between the solvent and poly(methyl methacrylate) radical resulting in lower termination rate. 相似文献