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31.
Graeme Cooke Hugues A de Cremiers Florence M.A DuclairoirJulie Leonardi Georgina RosairVincent M Rotello 《Tetrahedron》2003,59(18):3341-3347
We describe the electrochemically controlled hydrogen bonding interactions between the isobutyl flavin/2,6-diferrocenylamidopyridine (2·5) and 9,10-phenanthrenequinone/1-ferrocenyl-3-hexylurea (4·6) dyads. Cyclic and square wave voltammetry studies have shown that the binding efficiencies between these moieties can be electrochemically actuated in non-polar (CH2Cl2 for 2·5) or polar (DMF for 4·6) organic solvents between three distinct states. 相似文献
32.
Linder DP Rodgers KR Banister J Wyllie GR Ellison MK Scheidt WR 《Journal of the American Chemical Society》2004,126(43):14136-14148
Recent years have seen dramatic growth in our understanding of the biological roles of nitric oxide (NO). Yet, the fundamental underpinnings of its reactivities with transition metal centers in proteins and enzymes, the stabilities of their structures, and the relationships between structure and reactivity remains, to a significant extent, elusive. This is especially true for the so-called ferric heme nitrosyls ([FeNO](6) in the Enemark-Feltham scheme). The Fe-CO and C-O bond strengths in the isoelectronic ferrous carbonyl complexes are widely recognized to be inversely correlated and sensitive to structural, environmental, and electronic factors. On the other hand, the Fe-NO and N-O bonds in [FeNO](6) heme complexes exhibit seemingly inconsistent behavior in response to varying structure and environment. This report contains resonance Raman and density functional theory results that suggest a new model for FeNO bonding in five-coordinate [FeNO](6) complexes. On the basis of resonance Raman and FTIR data, a direct correlation between the nu(Fe)(-)(NO) and nu(N)(-)(O) frequencies of [Fe(OEP)NO](ClO(4)) and [Fe(OEP)NO](ClO(4)).CHCl(3) (two crystal forms of the same complex) has been established. Density functional theory calculations show that the relationship between Fe-NO and N-O bond strengths is responsive to FeNO electron density in three molecular orbitals. The highest energy orbital of the three is sigma-antibonding with respect to the entire FeNO unit. The other two comprise a lower-energy, degenerate, or nearly degenerate pair that is pi-bonding with respect to Fe-NO and pi-antibonding with respect to N-O. The relative sensitivities of the electron density distributions in these orbitals are shown to be consistent with all published indicators of Fe-N-O bond strengths and angles, including the examples reported here. 相似文献
33.
Gray M Cuello AO Cooke G Rotello VM 《Journal of the American Chemical Society》2003,125(26):7882-7888
Two receptors, a diaminotriazine derivative (DAT) and diamidopyridine (DAP), are complementary to the electroactive naphthalimide (N) through three-point hydrogen bonding. The association constants of the two receptors were evaluated for both the fully oxidized and the radical anion forms of N. In the oxidized state, the two receptors displayed identical binding constants. Diamidopyridine, however, lowers the reduction potential of naphthalimide to a far greater extent than does diaminotriazine, indicating a greater affinity for diamidopyridine by naphthalimide in the radical anion form. This behavior was mirrored by EPR experiments that showed small deviations from the hyperfine coupling pattern of N(red) in the presence of DAT, with greater effects seen for the N(red).DAP complex. Computational simulations using the UB3LYP/6-311+G(d,p)//UHF/6-31G(d) hybrid gave theoretical hyperfine constants in good quantitative agreement with the experimental results. Using this correlation, we determined that electrostatics and hydrogen bond polarizability play key roles in controlling redox-modulated molecular recognition. 相似文献
34.
Lilian F. J. Noël Ian A. Maxwell Willy J. M. Van Well Anton L. German 《Journal of polymer science. Part A, Polymer chemistry》1994,32(11):2161-2168
Recently a model has been developed capable of predicting absolute monomer concentrations and their ratios in the polymer, aqueous, and monomer droplet phases as a function of conversion in batch emulsion copolymerizations without using any adjustable parameters. In this article the sensitivity of model predictions of composition drift toward deviations of 10% in all model parameters (maximum swellabilities of monomer in the polymer phase, water solubilities, reactivity ratios, and monomer and polymer densities) was estimated using the monomer combination methyl methacrylate-styrene as an example. From the sensitivity analysis it can be concluded that the reactivity ratios are the most important parameters affecting composition drift. The effects of deviations in maximum swellabilities and monomer and polymer densities on composition drift can be neglected, while the water solubility is important only in those cases where the amount of monomer in the aqueous phase cannot be neglected as compared with the total monomer amount. © 1994 John Wiley & Sons, Inc. 相似文献
35.
Colloidal gold nanocrystals have been used to develop a new class of nanobiosensors that is able to recognize and detect specific DNA sequences and single-base mutations in a homogeneous format. At the core of this biosensor is a 2.5-nm gold nanoparticle that functions as both a nano-scaffold and a nano-quencher (efficient energy acceptor). Attached to this core are oligonucleotide molecules labeled with a thiol group at one end and a fluorophore at the other. This hybrid bio/inorganic construct is found to spontaneously assemble into a constrained arch-like conformation on the particle surface. Binding of target molecules results in a conformational change, which restores the fluorescence of the quenched fluorophore. Unlike conventional molecular beacons with a stem-and-loop structure, the nanoparticle probes do not require a stem, and their background fluorescence increases little with temperature. In comparison with the organic quencher Dabcyl (4,4'-dimethylaminophenyl azo benzoic acid), metal nanoparticles have unique structural and optical properties for new applications in biosensing and molecular engineering. 相似文献
36.
D Lathrop D Franke R Maxwell T Tepe R Flesher Z Zhang H Eckert 《Solid state nuclear magnetic resonance》1992,1(2):73-83
The ability of the 90 degrees-t1-180 degrees pulse sequence to produce accurate dipole-dipole coupling information in solids is investigated. To this end, the experimental 31P spin echo decays are measured for eighteen crystalline phosphides and phosphorus chalcogenides and compared with simulations, based on the known internuclear distances in these compounds. The experimental results are generally found accurate in compounds where the dominant contribution to the dipole-dipole coupling arises from nuclei in structurally inequivalent sites with large chemical shift anisotropies. For this situation, the quantum mechanical "flip-flop" term in the dipolar Hamiltonian is suppressed and the dipole-dipole coupling is entirely heteronuclear in character. All of those compounds that do not obey this condition show accelerated spin echo decays due to a fractional contribution of the flip-flop term and possibly incomplete refocusing of chemical shift terms on the time scale of the experiment. The results confirm on an empirical basis that the spin echo NMR technique can provide accurate dipole-dipole coupling information (and thus distance distributions) in disordered solids and glasses. 相似文献
37.
A range of new small bite-angle diphosphine complexes, [M(CO)4{X2PC(R1R2)PX2}] (M = Mo, W; X = Ph, Cy; R1 = H, Me, Et, Pr, allyl, R2 = Me, allyl), have been prepared via elaboration of the methylene backbones in [M(CO)4(X2PCH2PX2)] as a result of successive deprotonation and alkyl halide addition. When X = Ph it proved possible to replace both methylene protons but for X = Cy only one substitution proved possible. This is likely due to the electron-releasing nature of the cyclohexyl groups but may also be due to steric constraints. Attempts to prepare the bis(allyl) substituted complex [Mo(CO)4{Ph2PC(allyl)2PPh2}] were only moderately successful. The crystal structures of nine of these complexes are presented. 相似文献
38.
Maxwell A. Cairns Keith R. Dixon Martin A.R. Smith 《Journal of organometallic chemistry》1977,135(1):C33-C34
Syntheses of cis-[PtCl(CH2COCH3)(PEt3)2], cis-[PtCl(CH2NO2) (PEt3)2], and trans-[Pt(CCPh)2 (PEt3)2] are described. The procedure involves reaction of cis-[PtCl2(PEt3)2] with Ag2O and acidic CH bonds to precipitate AgC1 and generate a PtC bond. The method may represent a new general route to platinum—carbon bonds. 相似文献
39.
Small-angle static light scattering has been used to probe the evolution of aggregate size and structure in the shear-induced aggregation of latex particles. The size of aggregates obtained from the particle-sizing instrument (Coulter LS230) was compared with the size of those obtained with another approach utilizing the Guinier equation on the scattering data. Comparison of the two methods for studying the effects of mixing on the evolution of the aggregate size with time revealed similar trends. The aggregate structures were quantified in terms of their fractal dimensions on the grounds of the validity of Rayleigh-Gans-Debye scattering theory for the fractal aggregates. Analysis of the scattering patterns of aggregates verified that restructuring of the aggregates occurred as the aggregates were exposed to certain shear environments, resulting in a scale-dependent structure that could not be quantified by a fractal dimension. The effect of restructuring on aggregate size was particularly noticeable when the aggregates were exposed to average shear rates of 40 to 80 s(-1), whereas no significant restructuring occurred at lower shear rates. At 100 s(-1), the fragmentation of aggregates appeared to be more significant than aggregate compac-tion. Copyright 2001 Academic Press. 相似文献
40.
We investigate the effects of perturbative branching upon the accuracy with which one can determine the charge of the underlying QCD quantum from the charge structure of a given hadronic jet. We show explicitly how at asymptoticQ 2 we lose all such charge information. We investigate these effects at current PETRA energies using the Monte Carlo program of Fox and Wolfram; and find that a reasonably accurate charge determination is still possible at these energies. We suggest the variation of the jet charge structure with multiplicity, at a given energy, as a sensitive probe of the onset of perturbative branching inside jets. 相似文献