Slow energy relaxation of macromolecules and nanoclusters in solution

Many systems in the realm of nanophysics from both the living and the inorganic world display slow relaxation kinetics of energy fluctuations. In this Letter we propose a general explanation for such a phenomenon, based on the effects of interactions with the solvent. Within a simple harmonic model of the system fluctuations, we demonstrate that the inhomogeneity of coupling to the solvent of the bulk and surface atoms suffices to generate a complex spectrum of decay rates. We show for myoglobin and for a metal nanocluster that the result is a complex, nonexponential relaxation dynamics.     

Probing the Liquid-State Structure and Dynamics of Aqueous Solutions by Fluorescence Spectroscopy

Time-resolved fluorescence spectroscopy of the solvent-sensitive molecule 1,8-anilinonaphthalene sulfonate (ANS) is used to probe the structure and dynamics of an aqueous methanol solution (mole fraction = 0.5). The intensity decay of ANS in the mixed solvent displays single exponential kinetics under ambient conditions. At low temperature, a simple two-state solvent relaxation model describes the fluorescence decay for ANS in both methanol and the mixed solvent. The temperature dependence of ANS fluorescence in the mixed solvent is attributed to the onset of glassy dynamics in the aqueous component at higher temperature, implying a partial demixing of the water and methanol due to self-association. We discuss the absence of more complicated fluorescence decays in such a heterogeneous solvent system.     

Gels at interfaces

We discuss the adsorption of polymer gels on flat surfaces. Even in cases of complete wetting where the spreading power S is positive and where an equivalent liquid would spread, the elastic stresses due to the gel deformation upon adsorption oppose the spreading. The competition between elasticity characterized by the bulk shear modulus G and capillarity characterized by the spreading power S defines a typical length scale ℓ = S/G for the deformation in the gel. For loose gels ℓ can be of the order of 1 μm. Macroscopic gels larger than ℓ deform only at their edges over a region of size ℓ. Microscopic gels smaller than ℓ show a finite deformation despite the elastic stresses. The elastic stresses limit the spreading of the polymer, but solvent can be sucked out of a swollen gel by wetting the surface. The thin solvent film can extend rather far from the gel edge and carry solvent. We calculate the kinetics of the solvent film formation and of the solvent transfer from a more swollen gel to a less swollen gel. Received 16 July 2001     

DMF-H2O和DMF-D2O体系中13N弛豫的动态同位素效应的研究

本文测定了DMF-H₂O和DMF-D₂O体系在全部浓度范围内(摩尔分数为0~1) DMF分子中四极核¹⁴N的弛豫时间,讨论了弛豫的溶剂同位素效应和影响四极核弛豫的因素。研究结果表明,体系中¹⁴N的弛豫与溶剂水分子的动力学行为有着密切的联系,在无限稀释条件下溶质分子的运动完全受溶剂分子的控制.     

Spatial characterization of the laser-induced plasma plumes generated by IR CO2 pulsed laser on carbon targets

We have used ferrocene and paraffin wax as novel precursor and solvent for the growth of iron oxide nanoparticles. The proposed method of growth has several advantages over existing methods of growth using iron pentacarbonyl a precursor. Highly crystalline and monodispersed particles are obtained which assemble in two- and three-dimensional hexagonal closed packed superlattices. Growth kinetics has been studied by varying concentration of the precursor and time of growth. A phenomenological model has been proposed to explain the growth kinetics.     

The effective interaction for unbound nucleons and the optical potential

The effective interaction for an unbound nucleon in a complex nucleus is studied with particular emphasis upon the relationship of the unbound state interaction with the interaction for bound states. A successful unified treatment of unbound and bound states is given, and the unbound state effective interaction is related to the standard “optical model”. The attractive force for an unbound nucleon is shown to be of an exchange type and is best represented by a non-local, energy-independent potential which can be calculated, at least for not too high incident nucleon energy, from the attractive interaction between bound nucleons in a nucleus. We relate the unbound state potential to the bound state effective force as calculated by Negele using Hartree-Fock theory.

A non-local potential used by Elton, Webb, and Barrett in a successful analysis of electron scattering is shown, with minor modification, to work remarkably well in an analysis of elastic scattering of protons. Excellent agreement with experiment is obtained for the differential cross section and the polarization of protons with an incident energy up to 60 MeV scattered from ⁴⁰Ca, ⁵⁸Ni, ¹²⁰Sn and ²⁰⁸Pb. The real potential parameters are shown to be independent of the incident energy and physically reasonable; the imaginary potential parameters agree with expectations from Fermi gas and collective models. Bound state energy levels are also calculated with no readjustment of the real potential parameters in order to check the consistency of the interaction with the bound states, and the results are in good agreement with Negele.

The interaction of Skyrme as modified by Vautherin and Brink is also used in an analysis of elastic proton scattering. Good results are obtained for the differential cross section and the polarization for 20 MeV protons scattered from ⁵⁸Ni. At higher incident proton energy, and for larger nuclei, the results are poorer.     

Effect of continuum resonances on electronic transport in quantum wells

We investigate the influence of continuum resonances on the release of electrons by a quantum well. We find that the inclusion of resonance effects leads to a decrease in the rate of scattering by non-polar phonons from bound confined states to unbound continuum states.     

Detecting electronic coherence in excited-state electron transfer in fluorinated benzenes

Photoinduced electron transfer (ET) in heavily fluorinated benzenes in solution has been studied with broadband transient absorption spectroscopy. Spectrally resolved kinetics exhibit oscillations with amplitude up to 70% of the signal. The oscillation frequency is specific for each probe; in addition, for pentafluorobenzene it markedly depends on solvent, being 86 cm(-1) in hexane and 94 cm(-1) in acetonitrile. We argue that the observed behavior is not related to vibrational coherences, but originate from coherent electronic motion between an optically excited and an ET state.     

Conformational diffusion and helix formation kinetics

The time, temperature, and sequence dependences of helix formation kinetics of fully atomistic peptide models in explicit solvent are described quantitatively by a diffusive search within the coil state with barrierless transitions into the helical state. Conformational diffusion leads to nonexponential kinetics and jump-width dependences in temperature jump experiments.     

Solvent Exchange in Excited-State Relaxation in Mixed Solvents

The fluorescence of styrylthiazoloquinoxaline (STQ) in the solvent mixture methanol and dichloromethane (DCM) and 2-octanol have many common characteristics: biexponential fluorescence decay, wavelength-dependent amplitudes, a negative amplitude for the short-lifetime component at long emission wavelengths, and a time-dependent red shift of the emission spectrum. In octanol, the fluorescence lifetime decreases with increasing temperature, whereas the lifetime increases with temperature in the methanol/DCM mixture. The fluorescence characteristics in 2-octanol ( = 7.29 cP) are readily explained by the conventional model of excited-state relaxation kinetics by solvent reorientation. This model is not applicable for low-viscosity ( = 0.455 cP) solvent mixtures. A model of excited-state relaxation kinetics involving solvent exchange (versus solvent reorientation in pure solvents) in the excited state is proposed for the solvent mixture. The model assumes that the solvent compositions around the solute are different in the ground and excited states and the solvent composition is temperature dependent.     

Theory of microphase separation in crosslinked polymer blends immersed in a $ \theta$ -solvent

The aim of this work is a theoretical study of the effects of the solvent quality on the microphase separation in crosslinked polymer blends, from a static and kinetics point of view. More precisely, we assume that the crosslinked mixture is trapped in a q \theta -solvent. The static microphase properties are studied through the static structure factor. The latter is computed using an extended blob model, where the crosslinked unlike chains can be viewed as sequences of blobs. We demonstrate that the presence of the q \theta -solvent simply leads to a multiplicative renormalization of these properties, and the renormalization factors are powers of the overall monomer volume fraction. Second, we investigate the early kinetics of the microphase separation, via the relaxation rate, t_q \tau_{q}^{} , which is a function of the wave number q (at fixed temperature and monomer volume fraction). We first show that the kinetics is entirely controlled by local motions of Rouse type, since the slow motions are frozen out by the presence of crosslinks. Using the blob model, we find an explicit form for the growth rate W \Omega(q) = t_q^-1 \tau_{q}^{{-1}} , which depends, in addition to the wave number q , on the overall monomer volume fraction, F \Phi . Also, we discuss the effect of initial entanglements that are trapped when the system is crosslinked. In fact, these play the role of true reticulation points, and then, they quantitatively contribute to the microseparation phenomenon. Finally, the results are compared to their homologous relatively to the molten state and to the good solvent case. The main conclusion is that the quality of the solvent induces drastic changes of the microphase properties.     

Scaling and continuum percolation model for enzyme-catalyzed gel degradation

Enzyme-catalyzed gel degradation is inherently controlled by diffusion of enzymes in the gel. We report kinetics measurements on the gelatin-thermolysin system, varying solvent viscosity as well as gel and enzyme concentrations. Scaling relations and reduced variables are proposed which are shown to account for the experimental results. Finally, we argue that the nontrivial experimental dependence on enzyme concentration for the degradation time demonstrates that enzyme random walk is self-attracting, leading to a continuum percolation model for gel degradation.     

Repulsive Effect for Unbound High Energy Particles Along Rotation Axis in Kerr-Taub-NUT Spacetime

We have investigated the acceleration of the unbound high energy particles moving along the rotation axis in the Kerr-Taub-NUT spacetime, and then study the dependence of the repulsive effects on the NUT charge for the particles in the spacetime. Whether the repulsive effects with the NUT charge become stronger depends on the Carter constant, the position and velocity of the particles themselves. We also present numerically the changes of the observable velocity and acceleration with the NUT charge for the unbound particles in the Kerr-Taub-NUT spacetime.     

醌对卟啉荧光猝灭的溶剂效应

测定了在室温和未脱氧条件下不同浓度的苯醌(BQ)对卟啉衍生物四苯基卟吩(TPP),四苯基卟吩锌(ZnTPP)激发一重态的猝灭.由猝灭而引起的荧光强度的变化和荧光寿命的变化均可用Stern-Volmer关系式描述.由此根据寿命计算出的猝灭常数均比据荧光强度计算出的猝灭常数小.这是由于荧光强度测量中的自吸收效应引起的.实验结果表明;猝灭常数Kq与溶剂极性无关而只与粘度有关.说明这种猝灭是受扩散控制的动态猝灭.动力学分析表明,这是一种强猝灭,电荷转移猝灭速度比卟啉和醌的复合物的分解速度大或与之相近.比较实验结果和我们以前及其他作者发表的结果后,可以得出结论.苯醌对卟啉衍生物激发态电荷转移猝灭的溶剂效应随分子状态的不同而异:分子内的和通过三重态进行的分子间电荷转移猝灭受溶剂极性影响,但通过一重态进行的分子间电荷转移猝灭则与溶剂极性无关.     

Isotope Effects on the 17O, 1H Coupling Constant and the 17O-{1H} Nuclear Overhauser Effect in Water

The NMR spectra of solutions of 30% 17O-enriched H2O and D2O in nitromethane display the resonances of the three isotopomers H2O, HDO, and D2O. All 17O, 1H and 17O, 2H coupling constants and the primary and secondary isotope effects on J(17O, 1H) have been determined. The primary effect is -1.0 +/- 0.2 Hz and the secondary effect is -0.07 +/- 0.04 Hz. Using integrated intensities in the 17O NMR spectra, the equilibrium constant for the reaction H2O + D2O right harpoon over left harpoon 2HDO is found to be 3.68 +/- 0.2 at 343 K. From the relative integrated intensities of proton-coupled and -decoupled spectra the 17O-{1H} NOE is estimated for the first time, resulting in values of 0.908 and 0.945 for H2O and HDO, respectively. This means that dipole-dipole interactions contribute about 2.5% to the overall 17O relaxation rate in H2O dissolved in nitromethane. Copyright 1999 Academic Press.     

Critical microphase properties of crosslinked polymer blends with quenched random impurities

We extend published works dealing with microphase separation in crosslinked polymer blends to the case where these are surrounded by random impurities. To study their influence on critical microphase properties, from a static and kinetics point of view, we first assume that the (real) disorder caused by impurities is quenched. Second, the replica theory is used to study such critical properties, upon the impurities concentration and their interaction strength. More precisely, we compute the spinodal temperature and structure factor. We find that the spinodal temperature is shifted towards its lower and higher values, for attractive and repulsive impurities, respectively. The obtained expression for the static structure factor suggests that, contrarily to repulsive impurities, the crosslinked mixture scatters better in the presence of attractive ones. Thereafter, the study is extended to kinetics of microphase separation, when the mixture is impregnated by small random impurities. Kinetics is investigated through the growth rate, and in particular, we demonstrate that the latter is increased by the presence of repulsive impurities. This is natural, since these play a stabilizer role. Finally, the discussion is extended to crosslinked polymer blends immersed in a good solvent, which induces drastic changes of the critical microphase properties.     

溶剂气浮法分离水中的镍离子的动力学和热力学研究

以丁二酮肟为配件,十二烷基磺酸钠为捕集剂,对镍离子-丁二酮肟在水相中形成的 Ni-丁二酮肟-十二烷基磺酸钠体系的溶剂气浮进行了研究.研究表明表面活性剂与 Ni 离子的物质的量之比为20：1,约1h 水中的镍离子去除率可达90%.溶剂气浮的速率随着气流速率的增加而增加,共存溶剂乙醇、NaCl 存在会使去除率降低,有机溶剂的量对溶剂气浮影响较小,溶剂气浮过程遵从假一级动力学.考察了不同温度下溶剂气浮的回收速率,计算了该过程中的气浮表观活化能为8.99kJ/mol.而且将实验数据与理论模型进行了数值拟合.     

Significance of hydrophobic interactions in water–organic binary solvents

A LFE (Linear Free Energy) analysis of kinetic data for different organic reactions in various organic aqueous solutions was carried out. The rate constants of these reactions were compared with those for the solvolysis of tert-butyl chloride in the same solvents in terms of the LFE Relationships, and linear plots were observed in a wide range of the co-solvent content. This similarity points to a common nature of the solvent effect in these reactions in variety of water–organic mixtures, regardless of largely different reaction mechanisms. We explain these results by the prevalence of hydrophobic stabilization of the initial state of these reactions in water-rich solvent mixtures. Recently the same conclusion was also made on the basis of investigations into sonication effects in kinetics of organic reactions. A considerable contribution of hydrophobic effects to the Y scale by Grunwald and Winstein was deduced.