水合作用与pH调控聚电解质刷的构象转变

我们基于Flory-Huggins理论,建立理论模型研究水合作用与pH调控聚电解质刷的构象转变.理论模型考虑聚电解质链与水分子间的作用(聚电解质链的水合作用)、体系中的静电作用.研究发现,随着水合作用的改变,聚电解质刷出现由溶胀到塌缩的构象转变.由此表明了水合作用可在很大程度调节聚电解质刷的相变.通过分析pH的调控效应我们还发现,在碱性环境中(pH=8),聚电解质链单体的解离度增大,静电排斥会使得聚电解质刷溶胀.由此表明,聚电解质刷内水合作用与静电效应的耦合,将会共同决定聚电解质刷的构象转变特性.理论结果深刻揭示了水合作用的改变,会使得聚电解质刷体系发生相变,pH可在很大程度上改变其相变特性.     

The stoichiometry of the four linker subunits of Lumbricus terrestris hemoglobin suggests an asymmetric distribution

The extracellular, giant ( approximately 3.6 MDa) hexagonal bilayer hemoglobin of the earthworm Lumbricus terrestris consists of 12 dodecamers of globin chains tethered to a central complex of 36 non-globin, linker chains (24-32 kDa). Four types of linker chains L1-L4 have been detected by electrospray ionization (ESI) and by matrix-assisted laser desorption ionization (MALDI) mass spectrometry (MS) and isolated by reversed phase high pressure liquid chromatography (HPLC). Deconvolution of the HPLC elution profile and of the MS spectra provided the following individual linker contents, expressed as percent of the sum of the four linker peak areas: HPLC-21% L1, 37% L2, 23% L3 and 19% L4, MALDI-47% L1, 29% L2, 16% L3 and 8% L4; ESI-24% L1, 16% L2, 40% L3 and 20% L4; respectively. Comparison with electrophoretic results revealed a surprising lack of overall agreement between all the methods. The calculated mean values of the available linker contents were found to be 32+/-12% L1, 28+/-9% L2, 27+/-10% L3 and 13+/-7% L4, suggesting the following relative stoichiometry: L1: L2: L3: L4 approximately 1: 1: 1: 0.5. With a total of 36 linkers, a hexagonally symmetric distribution of each of the four linker chains is impossible. Thus, the asymmetric linker distribution provides an explanation for the existence of a large dipole moment of Lumbricus terrestris hemoglobin, 17,300+/-2300 Da (Takashima et al., 1999).     

Reduced Coulomb repulsion in NMP-TCNQ through intra- and interchain polarization

The “bare” Coulomb repulsion between two delocalized electrons in a one-dimensional poly (TCNQ^?) chain of the organic charge transfer crystal NMP-TCNQ is shown to be substantially reduced by attractive terms arising (1) from the polarization of the localized electronic system of the TCNQ chain itself and (2) from the polarization of the delocalized electrons in neighbouring NMP chains. The resulting effective repulsion is 0.33 eV at the Fermi level.     

Polyelectrolytes in the presence of multivalent ions: gelation versus segregation

We analyze solutions of strongly charged chains bridged by linkers such as multivalent ions. The gelation induced by the strong short range electrostatic attractions is dramatically suppressed by the long range electrostatic correlations due to the charge along the non-cross-linked monomers and ions. A modified Debye-Hückel approach of cross-linked clusters of charged chains is used to determine the mean field gelation transition self-consistently. Highly dilute polyelectrolyte solutions tend to segregate macroscopically. Semidilute solutions can form gels if the Bjerrum length l(B) and the distance between neighboring charged monomers along the chain b are both greater than the ion size a.     

Thermodynamics of Dipolar Chain Systems

The thermodynamics of a quantum system of layers containing perpendicularly oriented dipolar molecules is studied within an oscillator approximation for both bosonic and fermionic species. The system is assumed to be built from chains with one molecule in each layer. We consider the effects of the intralayer repulsion and quantum statistical requirements in systems with more than one chain. Specifically, we consider the case of two chains and solve the problem analytically within the harmonic Hamiltonian approach which is accurate for large dipole moments. The case of three chains is calculated numerically. Our findings indicate that thermodynamic observables, such as the heat capacity, can be used to probe the signatures of the intralayer interaction between chains. This should be relevant for near future experiments on polar molecules with strong dipole moments.     

Partial crystallinity in alkyl side chain polymers dictates surface freezing

We have studied the structure of a novel crystalline surface monolayer on top of a disordered melt of the same material [poly(n-alkyl acrylate)s] using grazing incidence x-ray diffraction. The grazing incidence x-ray diffraction, surface tension, and bulk latent heat results show that side chains crystallize except the nine methylene units of the alkyl side chains closest to the polymer backbone. The partial crystallinity along with a thicker surface layer, due to the additional length of the linker group, explains why the difference between the surface order-to-disorder transition temperature and bulk melting temperature increases with a decrease in the length of the alkyl side chain.     

Microscale deformations in a two-dimensional lattice: Structural transitions and bifurcations at critical shear

A two-dimensional model of a crystal lattice with an essentially nonlinear interaction between atoms for arbitrary mutual displacements under shear conditions is considered. The energy of deformation contains a periodic term and gradient terms. The equilibrium equation in the sine-Helmholtz form (with two characteristic coherence lengths) is solved exactly. It is shown that a large uniform shear deformation is unstable and is accompanied by periodic modulations emerging in the plane of the layer and leading to nonuniform extensions and compressions of atomic chains, i.e., to a change in the long-range order. The chain slip by a lattice half-period or a larger value changes the long-range order as well. The obtained relations connecting the unit cell size and the amplitude of the displacement field determine the conditions for the existence of a modulated structure. A bifurcation transition from a purely elastic deformation of the lattice to its elastoplastic deformation, as well as a transition to its disordered (amorphous-type) state, is observed.     

Operator product expansion on a fractal: The short chain expansion for polymer networks

We prove to all orders of renormalized perturbative polymer field theory the existence of a short chain expansion applying to polymer solutions of long and short chains. For a general polymer network with long and short chains we show factorization of its partition sum by a short chain factor and a long chain factor in the short chain limit. This corresponds to an expansion for short distance along the fractal perimeter of the polymer chains connecting the network vertices and is related to a large mass expansion of field theory.

The scaling of the second virial coefficient for bimodal solutions is explained. Our method also applies to the correlations of the multifractal measure of harmonic diffusion onto an absorbing polymer. We give a result for expanding these correlations for short distance along the fractal carrier of the measure.     

Spectroscopic manifestations of nitrite group intermolecular repulsion in PAN

It has been found that methylene stretching bands in polyacrylonitrile (PAN) occur at higher frequencies and have a lower intensity than in other hydrocarbon compounds. This is a spectroscopic manifestation of nitrile group intermolecular repulsion in PAN, which leads to helical winding of the polymer chains. The distortion of the elementary unit geometry occurs on spiraiization, changing the methylene band parameters. On heating, the polymer spiral unwinds, which restores the normal geometry, band position, and intensity. The unwinding of a polymer chain represents a thermal transition, occurring in PAN at a temperature of about 180°C. This transition is a necessary prerequisite for initiation of cyclization.     

Exact bond ordered ground state for the transition between the band and the Mott insulator

We derive an effective Hamiltonian H(eff) for an ionic Hubbard chain, valid for tt) and the Mott insulator (MI) (U-Delta>t). Using spin-particle transformations [Phys. Rev. Lett. 86, 1082 (2001)]], we map H(eff)(U=Delta) into an SU(3) antiferromagnetic Heisenberg model whose exact ground state is known. In this way, we show rigorously that a spontaneously dimerized insulating ferroelectric phase appears in the transition region between the BI and the MI.     

Long-range interactions in polymer melts: the anti-Casimir effect

It is well known that small neutral particles normally tend to aggregate due to the van der Waals forces. We discover a new universal long-range interaction between solid objects in polymer media that is directly opposite the van der Waals attraction. The new force could reverse the sign of the net interaction, possibly leading to the net repulsion. This universal repulsion comes from the subtracted soft fluctuation modes, which are not present in the real polymer system, but rather are in its ideal counterpart. The predicted effect has a deep relation to the classical Casimir interactions, providing an unusual example of fluctuation-induced repulsion instead of normal attraction. That is why it is referred to as the anti-Casimir effect. We also find that the correlation function of monomer units in a concentrated solution of infinite polymer chains follows a power-law rather than an exponential decay at large distances.     

Yangians and transition operators

Yangian has emerged as a underlying algebraic structure for quantum spin chains with inverse-square exchange interactions. Recently, it has also been found that the Yangian can be regarded as an extended dipole operator or transition operator connecting different highest weight states. In this report, we describe how Yangian can be used to construct the shift operators associated with the spin chain. Presented at the 9th Colloquium “Quantum Groups and Integrable Systems”, Prague, 22–24 June 2000. This work was supported by NUS Research Grant No. RP3982713.     

Dynamics of Random One-Dimensional ±J Systems

Finite chains of a two-state random Potts spin model with periodic boundary conditions are studied within Glauber dynamics. The spin exchange is assumed random with frustration between ferro and antiferromagnetic values (±J). Time-dependent fluctuations are induced by periodic temperature oscillations. Master type differential equations for spin correlation functions are solved within linear response theory. The spectrum of relaxation times are calculated at different temperatures. The ±J Potts glass chains undergo a zero temperature phase transition. The barriers against inversion of the spin chain take only two values; 0 and 2|J|. The temperature behaviour of specific heat is characterized by rounded peaks. The frequency dependence displays two plateaus for the real part of specific heat and two corresponding peaks for the imaginary part. The dynamic specific heat is not affected by the longest relaxing mode like susceptibility. The time separation of the modes is demonstrated by the Cole-Cole plots.     

Landau-Zener transition of a two-level system driven by spin chains near their critical points

The Landau-Zener (LZ) transition of a two-level system coupling to spin chains near their critical points is studied in this paper. Two kinds of spin chains, the Ising spin chain and XY spin chain, are considered. We calculate and analyze the effects of system-chain coupling on the LZ transition. A relation between the LZ transition and the critical points of the spin chain is established. These results suggest that LZ transitions may serve as the witnesses of criticality of the spin chain. This may provide a new way to study quantum phase transitions as well as LZ transitions.     

Propagation of spin information at the supramolecular scale through heteroaromatic linkers

We report an in-depth study on how spin information propagates at supramolecular scale through a family of heteroaromatic linkers. By density-functional theory calculations, we rationalize the behavior of a series of Cr7Ni dimers for which we are able to systematically change the aromatic linker thus tuning the strength of the magnetic interaction, as experimentally shown by low temperature micro-SQUID and specific heat measurements. We also predict a cos2 dependence of the magnetic coupling on the twisting angle between the aromatic cycles in bicyclic linkers, a mechanism parallel to charge transport on similar systems [L. Venkataraman et al., Nature (London) 442, 904 (2006)].     

梳型高分子聚合物向列相液晶的相变

本文根据Freiser关于向列相液晶分子相互作用模型,利用平均场理论,建立了梳型高分子聚合物向列相液晶分子的哈密顿量,导出序参数自洽方程,得到各向同性相至单轴向列相以及单轴至双轴向列相的相变,结果表明,当分子主、侧链耦合项中排斥作用及主、侧链中较强向列相场的场强增大时,单轴至双轴向列相相变温度升高,并从一级相变逐渐变为二级相变。 关键词：