Reentrant condensation of proteins in solution induced by multivalent counterions

Negatively charged globular proteins in solution undergo a condensation upon adding trivalent counterions between two critical concentrations C and C, C 相似文献   

Collapse of spherical polyelectrolyte brushes in the presence of multivalent counterions

We consider the interaction of multivalent counterions with spherical polyelectrolyte brushes (SPB). The SPB result if linear polyelectrolyte (PE) chains (contour length: 60 nm) are densely grafted to colloidal spheres of 116 nm in diameter. Dispersed in water, the surface layer consisting of chains of the strong PE poly(styrene sulfonic acid) (PSS) will swell. We demonstrate that successive addition of trivalent ions (La3+) leads to a collapse in which the surface layer is shrinking drastically. All findings are discussed on the base of a theoretical mean-field approach using the Donnan equilibrium. The ion exchange and a strong binding of trivalent ions by PE chains is followed up by a drop in the osmotic pressure inside the brush. This reduction is the driving force for the collapse. The strong ion-chain correlation is discussed with results obtained from molecular dynamics simulations.     

同种电荷能相互吸引吗?

许多生物大分子 (如DNA等 )常常会出现一些违反物理学中基本规律的现象 ,例如它们虽然具有相同符号的电荷 ,但却能相互吸引并在水中聚集成团 ,称为丛生现象 .科学家们认为这种丛生现象的产生一定是由于某些溶于水中的离子或带电小分子抵消了大分子的电荷所形成的 ,但却不能破解其中的机理与细节 .最近美国Illinois大学的生物物理学家G .Wong和他的同事们对这个问题开展了研究 ,他们对同种电荷相互吸引进行了一些简单的实验后发现 ,想使同种电荷发生相互吸引必需要在离子大小的范围内才有可能 .在许多年以前 ,生化学家们早就发现要使带电…     

When,why, and how does like like like?: Electrostatic attraction between similarly charged species

In the Derjaguin-Landau-Verwey-Overbeek (DLVO) framework of the past 60 years, colloidal interaction between similarly charged particles has been claimed to be simply repulsive, and an attraction such as the van der Waals interaction is attached to the Coulombic repulsion. Statistical-thermodynamic considerations show that the electrostatic Helmholtz free energy ΔF^el is generally not equal to the electrostatic Gibbs free energy ΔG^el for simple ionic solutions, and the difference ΔG^el–ΔF^el (corresponding to the electrostatic osmotic pressure p^el) becomes larger with increasing charge number. Thus, it is expected that ΔG^el–ΔF^el be large for highly charged macroions. In the DLVO framework, however, ΔG^el = ΔF^el was postulated. Sogami showed that a mean field approach reproduced repulsion at the level of ΔF^el but resulted in (repulsion and) attraction at the level of ΔG^el. Overbeek’s critique of Sogami theory is shown to be in error. If this criticism were correct, then not only the Sogami theory but also the Debye-Hückel theory would be wrong. The attraction is thus confirmed to exist not only for multi-valent but also mono-valent counterions.     

Quasiparticles in the theory of fermion condensation

It is shown that Landau’s quasiparticle formalism continues to work in systems with a fermion condensate. In the case of a finite system this formalism is suitable for describing the restructuring of states at the Fermi surface. It also works in an infinite system, and the idea of quasiparticles at low temperature as well-defined excitations at the Fermi surface remains valid. The quasiparticle lifetime is directly proportional to the temperature, and the density of states is inversely proportional to the temperature. Pis’ma Zh. éksp. Teor. Fiz. 63, No. 9, 719–723 (10 May 1996)     

Toward the theory of fermionic condensation

The diagrammatic technique elaborated by Belyaev for the theory of a Fermi liquid has been implemented to analyze the behavior of Fermi systems beyond the topological phase transition point, where the fermionic condensate appears. It has been shown that the inclusion of the interaction between the condensate and above-condensate particles leads to the emergence of a gap in the single-particle excitation spectrum of these particles even in the absence of Cooper pairing. Hence, the emergence of this gap in homogeneous electron systems of silicon field-effect structures leads to a metal–insulator phase transition rather than to superconductivity. It has been shown that the same interaction explains the nature of the Fermi arc structure in twodimensional electron systems of cuprates.     

Counterion condensation in ionic micelles as studied by a combined use of SANS and SAXS

We report a combined use of small-angle neutron scattering (SANS) and small-angle X-ray scattering (SAXS) to the study of counterion condensation in ionic micelles. Small-angle neutron and X-ray scattering measurements have been carried out on two surfactants cetyltrimethylammonium bromide (CTABr) and cetyltrimethylammonium chloride (CTACl), which are similar but having different counterions. SANS measurements show that CTABr surfactant forms much larger micelles than CTACl. This is explained in terms of higher condensation of Br⁻ counterions than Cl⁻ counterions. SAXS data on these systems suggest that the Br⁻ counterions are condensed around the micelles over smaller thickness than those of Cl⁻ counterions.     

多价抗衡离子诱导聚甲基丙烯酸N,N-二甲基氨基乙酯(PDMAEMA)刷构象转变的UCST行为

本文应用分子场理论,研究pH、[Fe(CN)_6]~(3-)诱导聚甲基丙烯酸N,N-二甲基氨基乙酯(PDMAEMA)刷的上临界溶解温度(UCST)构象转变与结构特性.理论模型考虑p H和[Fe(CN)_6]~(3-)对PDMAEMA刷体系的静电调控作用.研究发现,在不同[Fe(CN)_6]~(3-)浓度、不同p H条件下,PDMAEMA刷呈现了UCST构象转变行为.由于p H调节PDMAEMA单体质子化,[Fe(CN)_6]~(3-)通过与PDMAEMA带正电荷的单体结合,形成了在PDMAEMA链内以[Fe(CN)_6]~(3-)为中介的带电单体间的静电吸引结合.随着温度升高,[Fe(CN)_6]~(3-)与PDMAEMA带正电荷的单体结合被破坏,[Fe(CN)_6]~(3-)在链内凝聚导致的静电屏蔽效应减弱,PDMAEMA链内带电单体间的静电排斥增强,PDMAEMA刷的构象呈现了从塌缩到溶胀的UCST转变行为,并且在较高[Fe(CN)_6]~(3-)浓度条件下,PDMAEMA刷构象转变的UCST增高.在较低p H值条件下,较多的PDMAEMA单体被质子化,[Fe(CN)_6]~(3-)与PDMAEMA带正电单体的结合增强,PDMAEMA刷构象转变的UCST增大.基于pH和[Fe(CN)_6]~(3-)对PDMAEMA刷体系中的静电调控效应,可以预言,在较小p H和较大[Fe(CN)_6]~(3-)浓度条件下,PDMAEMA链在垂直培基表面沿着链方向形成结节状结构.这是由于以[Fe(CN)_6]~(3-)为中介的链内带电单体间的静电吸引作用增强,导致临近单体间汇聚结节.我们的理论结果符合实验观测,由此表明,pH调节PDMAEMA单体的带电状态,以及[Fe(CN)_6]~(3-)在PDMAEMA链内凝聚导致的静电屏蔽效应,决定着PDMAEMA刷的UCST构象转变和结构特性.     

A simple theory of condensation

A simple assumption of the emergence in gas of small atomic clusters consisting of c particles each leads to a phase separation (first-order transition). It reveals itself by the emergence of a “forbidden” density range starting at a certain temperature. Defining this latter value as the critical temperature predicts the existence of an interval with the anomalous heat capacity behavior c _p ∝ ΔT ^−1/c . The value c = 13 suggested in the literature yields the heat capacity exponent α = 0.077.     

Algebraic properties of the invariant charges of the Nambu-Goto theory

We analyse the infinite dimensional algebra of observable non-local integrals of motion of the Nambu-Goto string theory.Work supported by Deutsche Forschungsgemeinschaft     

The invariant charges of the Nambu-Goto theory in WKB-approximation: Renormalization

We discuss the one loop renormalization of the reparametrization invariant non-local conserved charges of the Nambu-Goto string theory. In addition we show the stability of a special well-known state under the corresponding infinitesimal symmetry transformations — at least in the WKB-approximation.Work supported by Deutsche Forschungsgemeinschaft     

Stochastic approach to the kinetic theory of condensation

The nonequilibrium statistical operator method in conjunction with the theory of physical FrenkelBand groups is used to derive a stochastic equation that describes the kinetics of nucleation.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 6, pp. 139–142, June, 1977.     

Density functional theory of fermion condensation

A density functional formulation of the fermion condensation is presented. It is demonstrated that the standard Kohn-Sham scheme is not valid beyond the fermion condensation phase transition since the functional starts to depend on the quasiparticle density matrix. Our consideration also furnishes an opportunity to calculate the real single particle excitation spectra of superconducting systems within the density functional theory.     

The origin of the attraction between like charged hydrophobic and hydrophilic walls confining a near-critical binary aqueous mixture with ions

The effect of ionic solute on a near-critical binary aqueous mixture confined between charged walls with different adsorption preferences is considered within a simple density functional theory. For the near-critical system containing small amounts of ions, a Landau-type functional is derived on the basis of the assumption that the correlation, ξ, and the Debye screening length, κ(-1), are both much larger than the molecular size. The corresponding approximate Euler-Lagrange equations are solved analytically for ions insoluble in the organic solvent. A nontrivial concentration profile of the solvent is found near the charged hydrophobic wall as a result of the competition between the short-range attraction of the organic solvent and the electrostatic attraction of the hydrated ions. An excess of water may be present near the hydrophobic surface for some range of the surface charge and ξκ. As a result, the effective potential between the hydrophilic and the hydrophobic surface can be repulsive far from the critical point, then attractive and again repulsive when the critical temperature is approached, in agreement with a recent experiment (Nellen et al 2011 Soft Matter 7 5360).     

“Conserved charges” of the Bondi-Metzner-Sachs algebra in the Brans-Dicke theory

The asymptotic symmetries in the Brans-Dicke theory are analyzed using Penrose's conformal completion method,which is independent of the coordinate system used.These symmetries,indeed,include supertranslations and Lorentz transformations for an asymptotically flat spacetime.With the Wald-Zoupas formalism,“conserved charges”and fluxes of the Bondi-Metzner-Sachs algebra are computed.The scalar degree of freedom contributes only to the Lorentz boost charge,even though it plays a role in various fluxes.The flux-balance laws are further applied to constrain the displacement memory,spin memory,and center-of-mass memory effects.     

The macroscopic theory of van der Waals attraction

The van der Waals energy between two films is calculated from the average quantum energy of the electromagnetic radiation field. All branch points and different Riemann surfaces appearing in earlier treatments vanish by applying finite boundary conditions. The final frequency integration runs over the full imaginary axis.     

Bose condensation of excitons in two-layer electronic systems in the absence of magnetic field

A high narrow peak of interlayer differential tunnel conductivity is observed at low temperatures in heterostructures with two closely located electronic layers in the absence of magnetic field. The analysis of experimental results suggests that this peak is due to the interlayer phase coherence that arises in the system as a result of the Bose condensation of interlayer excitons (electron-hole pairs) belonging to different layers, in accordance with the recent theoretical predictions.