Liquid-crystalline ordering in the solution of semiflexible macromolecules

The solution of semiflexible polymer macromolecules with steric repulsion between the parts of the polymer chains is considered. The conditions for formation of the liquid-crystalline phase in this solution are determined by means of the Onsager method.     

Anomalous transport of macromolecules in solution

Based on a semi-phenomenological Fokker-Planck approach, we present and discuss a theoretical framework for studying the transport properties of macromolecules in solution. A formally exact expression for the diffusion of macromolecules is derived and utilized in order to show the anomalous character of the macromolecular diffusion, both at very short times, t→ 0, as well as in the asymptotic limit, t→∞. Numerical computations for 50- and 100-bead macromolecules demonstrate moreover a `superdiffusive' behaviour at short and intermediate times when compared with the data from the (Einstein's) phenomenological theory.     

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.     

Phase transitions in a solution of rodlike macromolecules of two different sizes

Phase equilibria for a solution of long rigid rods of diameters D_i and lengths L_i (i = 1,2) are studied analytically using Gaussian trial functions. The conditions on the molecular size parameters for a nematic—nematic phase transition to be possible are determined, and found to be satisfied everywhere except in a closed domain in the diameter ratio—length ratio plane. Information on the relative ordering of the two components is also provided.     

Self-diffusion of multiarm star polymers in solution far from and near the ordering transition

The self-diffusion of three 128-arm polybutadiene star solutions in toluene was investigated over a broad concentration range from dilute to the ordering region with pulsed field gradient NMR (PFG-NMR). The strong concentration dependence of the self-diffusion coefficient in the fluid state is distinguished clearly from that of linear chains and can be described by a non-Arrhenius VFT-like equation with the concentration playing the role of inverse temperature. In the concentrated regime, the observation of two dynamic phases reflects the coexistence of crystalline and liquid phases over a limited concentration region. The concentration dependences of both the ordinary (fluid-like) diffusion and the completely restricted in-cage motion of these hyper stars are in agreement with the behavior of concentrated colloidal suspensions.     

An equation of state for the isotropic phase of linear,partially flexible and fully flexible tangent hard-sphere chain fluids

A new equation of state is developed that accurately describes the isotropic phase behaviour of linear, partially flexible and fully flexible tangent hard-sphere chain fluids and their mixtures. The equation of state is based on the equation of state of Liu and Hu [H. Liu and Y. Hu, Fluid Phase Equilibr. 122, 75 (1996)] for fully flexible chain fluids. The effect of molecular flexibility is described by a pure-component parameter that is introduced in the theory at the level of the cavity correlation function of next-to-nearest neighbour segments in a chain molecule. The equation of state contains a total of three adjustable model constants. The extension to partially flexible- and linear chain fluids is based on a refitting of the first model constant to numerical data of the second virial coefficient of partially flexible and linear tangent hard-sphere chain fluids. The numerical data were obtained from an analytical approximation for the pair-excluded volume. The other two parameters were adjusted to molecular simulation data for the pressure of linear tangent hard-sphere chain fluids. For both, pure component systems and mixtures of chains of variable flexibility, the pressure and second virial coefficient obtained from the equation of state, are in excellent agreement with the results from Monte Carlo simulations. A significant improvement to TPT1, TPT2, generalised Flory-dimer theory and scaled particle theory is observed.     

Upgrade of MacCHESS facility for X‐ray scattering of biological macromolecules in solution

X‐ray scattering of biological macromolecules in solution is an increasingly popular tool for structural biology and benefits greatly from modern high‐brightness synchrotron sources. The upgraded MacCHESS BioSAXS station is now located at the 49‐pole wiggler beamline G1. The 20‐fold improved flux over the previous beamline F2 provides higher sample throughput and autonomous X‐ray scattering data collection using a unique SAXS/WAXS dual detectors configuration. This setup achieves a combined q‐range from 0.007 to 0.7 Å^?1, enabling better characterization of smaller molecules, while opening opportunities for emerging wide‐angle scattering methods. In addition, a facility upgrade of the positron storage ring to continuous top‐up mode has improved beam stability and eliminated beam drift over the course of typical BioSAXS experiments. Single exposure times have been reduced to 2 s for 3.560 mg ml^?1 lysozyme with an average quality factor I/σ of 20 in the Guinier region. A novel disposable plastic sample cell design that incorporates lower background X‐ray window material provides users with a more pristine sample environment than previously available. Systematic comparisons of common X‐ray window materials bonded to the cell have also been extended to the wide‐angle regime, offering new insight into best choices for various q‐space ranges. In addition, a quantitative assessment of signal‐to‐noise levels has been performed on the station to allow users to estimate necessary exposure times for obtaining usable signals in the Guinier regime. Users also have access to a new BioSAXS sample preparation laboratory which houses essential wet‐chemistry equipment and biophysical instrumentation. User experiments at the upgraded BioSAXS station have been on‐going since commissioning of the beamline in Summer 2013. A planned upgrade of the G1 insertion device to an undulator for the Winter 2014 cycle is expected to further improve flux by an order of magnitude.     

Electric field light scattering by flexible linear polyelectrolytes in aqueous solution

Electric field light scattering results on aqueous solutions of linear, flexible NaPSS at minimal ionic strength are reported. Samples of molecular weights between 356 kg/mol and 2870 kg/mol were investigated. With increasing field strength the intensity as a function of wavenumber develops a pronounced oscillating behaviour. Besides the well-known first peak a second maximum is observed at the position at which a weak maximum for some samples already occurs at zero field. The overall intensity strongly depends on the frequency of the electric field. The electro-optical effect shows a maximum at 300 kHz. Increasing the particle concentration gives a large increase of the peak maximum, normalized to concentration. If plotted versus scattering angle the relative intensity increase is maximum for samples of medium molecular weight. The results strongly indicate a stretching and alignment of the chains, thus leading to or enlarging the short range order of the chains. Received 9 April 1999 and Received in final form 18 August 1999     

Liquid-crystalline phase behavior of a colloidal rod-plate mixture

The phase behavior of rod-plate mixtures was investigated using model systems containing unambiguously rod- and plate-shaped colloids. We find that the theoretically disputed biaxial nematic phase is unstable with respect to demixing into an isotropic and two uniaxial nematic phases. The phase behavior at very high densities is exceptionally rich and includes the coexistence of up to four different liquid crystalline phases, which stem from the coupling between the employed particle shapes and polydispersity.     

On the self-organization of linear macromolecules

The new unified context for crystallization of linear macromolecules from the melt, established by recent work, is expounded. The morphology of spherulites shows that they form because of a short-range force operative at the branch points of dominant lamellae that causes them to diverge at noncrystallographic angles of about 20°. Work on monodisperse n-alkanes has confirmed the identification of this short-range force with the pressure from dynamic cilia during growth. Accordingly, spherulites, like chain folding, are a direct consequence of molecular length. It is suggested that the tendency to form coarse spherulites even for extended-chain growth at lower temperatures may result from the increasing difference between the lengths of nucleus and molecule. Crystallization on linear nuclei has been used to maximize the concentration of segregants at the growth front and to demonstrate cellulation in undoped polymers for the first time. The behavior of branched polyethylenes differs from the uniform growth of the linear polymer in coarsening and developing protuberances at the growth front, all the while slowing continuously toward an asymptotic steady state; differences of detail may be useful in distinguishing polymers of different catalytic origin and branch content. Spherulitie growth is also nonlinear for these polymers, but is always faster than for rows. When there is sufficient segregation, spherulites themselves cellulate, increasingly so for higher branch content. Cellulation is thus an uncommon and secondary process may be superposed on regular spherulitie growth beyond a certain distance. Cell dimensions do not scale with the diffusion length; in so doing, the phenomenon displays new physics.     

Growth model for atomic ordering: the case for quadruple-period ordering in GaAsSb alloys

Quadruple-period ordering in GaAsSb alloys is studied both theoretically and experimentally. A growth model is proposed to account for the observed three-dimensional (3D) ordered structure. The model is qualitatively different from the widely accepted surface reconstruction and dimerization-induced ordering models that strictly speaking explain only the in-plane 2D patterns. Here, we show that the already ordered substrate will affect the reconstruction of the growth front with respect to the substrate to ensure a correct stacking of the individual 2D ordered layers into the observed 3D lattice.     

Thermodynamics of stiff macromolecules in the two-dimensional lattice model

The statistical-thermodynamic analysis of the compact structure (globule) of a flexural stiff macromolecule in the two-dimensional square lattice model is proposed. It is shown that the anisotropy of monomer direction distribution increases with increasing rigidity. The temperature dependence of the globule size turns out to be non-monotonic under fixed pressure.     

Superconductivity in ordering systems

We analyse the behaviour of 2-order parameter systems (where one subsystem is superconducting) in constant external ordering fields and find the spatial distribution of the order parameters.The authors would like to thank Prof. B. T.Matthias and Prof. T. L.Birman for useful discussions.     

Magnetic ordering in TmTe

Neutron diffraction experiments were performed on the divalent thulium compound TmTe. Magnetic structure determination leads to a type II antiferromagnet below the Néel temperature T_N = .43 K. No crystal field excitations were observed.