Biomedical subjects

E M Terentjev

Publications and source records attributed to E M Terentjev.

At least 19 recordsLinked to original sources

PubMed2006

Fast relaxation of carbon nanotubes in polymer composite actuators.

Silicone elastomer composites containing multiwalled carbon nanotubes have been irradiated with near-infrared light to study their mechanical actuation response. We show that the speed of the stimulated response is faster than Debye relaxation, instead following a compressed-exponential law. However, the relaxation after switching off the light source follows the simple-exponential relaxation, as does the stimulated response at very low nanotube concentration. We discuss possible models and explanations to account for the fast photomechanical response.

Journal Article↗

PubMed2006

Spontaneous size selection in cholesteric and nematic emulsions.

We study the spontaneous size selection in lyotropic cholesteric (W/O) and thermotropic nematic (O/W) liquid crystal emulsions. The droplet sizes have been characterized by dynamic light scattering, which indicates a narrow monomodal distribution of droplets achieved spontaneously even without emulsion filtration. Anchoring of the director, provided by the chosen surfactant on the interface, may generate a topological defect inside the droplet. Below the critical radius R = K/W, determined by the ratio of Frank elastic and the surface anchoring constants, the effective anchoring strength is weak and droplets are not topologically charged; this allows them to coalesce freely, depleting the size distribution in this range. Large droplets possess a topological charge of +1 and present a high elastic energy barrier for pair coalescence; the resulting size distribution is skewed, with R > R, and effectively frozen.

Journal Article↗

PubMed2006

Chirality transfer and stereoselectivity of imprinted cholesteric networks.

Imprinting of cholesteric textures in a polymer network is a method of preserving a macroscopically chiral phase in a system with no molecular chirality. By modifying the elastic properties of the network, the resulting stored helical twist can be manipulated within a wide range since the imprinting efficiency depends on the balance between the elastic constants and twisting power at network formation. One spectacular property of phase chirality imprinting is the created ability of the network to adsorb preferentially one stereo component from a racemic mixture. In this paper we explore this property of chirality transfer from a macroscopic to a molecular scale. In particular, we focus on the competition between the phase chirality and the local nematic order. We demonstrate that it is possible to control the subsequent release of a chiral solvent component from the imprinting network and the reversibility of the stereo-selective swelling by racemic solvents.

Journal Article↗

PubMed2005

Stability of cellulose lyotropic liquid crystal emulsions.

We studied a new kind of W/O emulsions based on a lyotropic liquid crystal as the aqueous droplet phase. The cholesteric phase, a solution hydroxypropyl cellulose in water was dispersed in the continuous oil matrix, paraffin oil or heptane. We made a specific choice of surfactant in order to impose director anchoring conditions at the oil-water interface and orient the liquid crystal inside the droplet. The strong anchoring conditions resulted in a topological defect inside the droplets of size above the critical value R(*). The defect elastic energy creates a barrier against droplet coalescence, the effect of topological size selection. We have studied the orientation of the director inside the droplets and their size distribution.

Biophysical Phenomena↗

PubMed2005

Induced helicity in biopolymer networks under stress.

By combining dynamic mechanical and optical measurements in probing the internal structure of a biopolymer network (gelatin gel), we studied the quasi-equilibrium evolution of helical content as a function of the applied stress. Assuming that the net optical activity is proportional to the concentration of secondary helices of collagen chains, and assuming that affine mechanical deformation, we find a nonmonotonic relationship between the helical domains and an imposed deformation. The results are in qualitative agreement with theoretical predictions of alpha-helices induced by chain end-to-end stretching, and give a consistent picture of mechanically stimulated helix-coil transition in networks of denatured polypeptides.

Biopolymers↗

PubMed2005

Constrained Rouse model of rubber viscoelasticity.

In this work we use a new approach to investigate the equilibrium and linear dynamic-mechanical response of a polymer network. The classical Rouse model is extended to incorporate quenched constraints on its end-boundary conditions; a microscopic stress tensor for the network system is then derived in the affine deformation limit. To test the model we calculate the macroscopic stress in equilibrium, corresponding to the long-time limit of relaxation. Particular attention is paid to the treatment of compressibility and hydrostatic pressure in a sample with open boundaries. Although quite different in general, for small strains the model compares well with the classic equilibrium rubber-elasticity models. The dynamic shear modulus is obtained for a network relaxing after an instantaneous step strain by keeping track of relaxation of consecutive Rouse modes of constrained network strands. The results naturally cover the whole time range--from the dynamic glassy state down to the equilibrium incompressible rubber plateau.

Journal Article↗

PubMed2005

Stretching globular polymers. I. Single chains.

We review the force-extension behavior of polymers collapsed in poor solvent, modified to include the effects of semiflexibility and considered for globules with "ordered" and "disordered" internal structures. A series of ordered globules is used as a model for the unbinding of a disordered globule beneath its glass transition and for multiple-repeat proteins such as the poly-Ig-domain titin used in atomic force microscopy studies. These single-chain results form the foundation for the treatment of cross-linked networks of globular polymers.

Journal Article↗

PubMed2005

Stretching globular polymers. II. Macroscopic cross-linked networks.

We expand upon the results for the force-extension behavior of single-collapsed polymer chains to consider the mechanical response of networks of cross-linked globular polymers in poor solvent. Force-strain curves are obtained under the affine deformation approximation for networked globules with both disordered and ordered globule conformations. Due to their large stored lengths, these networks would be capable of reaching extremely large strains. They also show anomalous nonmonotonic force-strain response, as a consequence of the nonmonotonic force-extension curves of their constituent globules. Finally, we consider the stability of ordered and disordered globules in these networks and propose means taken from biological and colloid science to stabilize networked globules.

Journal Article↗

PubMed2005

Viscoelasticity of a protein monolayer from anisotropic surface pressure measurements.

We present a method to completely characterize the viscoelasticity of Langmuir monolayers. In contrast to existing techniques, both the compression and shear moduli are determined at the same time, in a single experiment and with a standard apparatus. This approach relies on the measurement of anisotropy in the surface pressure: the tension is measured in orientations perpendicular and parallel to the compression direction. We apply this technique to the study of beta-lactoglobulin spread monolayers, a system that has been shown to develop a shear modulus at high concentration. Beta-lactoglobulin monolayers are interesting both because of their importance in food science and because they exhibit universally slow dynamical behavior that is not fully understood. Our results confirm that the compressional modulus dominates the total viscoelastic response and also provide a complex shear modulus, emerging above a critical concentration. We are able to describe how each of the dynamical response moduli is related to the surface concentration and to the equilibrium osmotic pressure.

Algorithms↗

PubMed2004

Photonic gaps in cholesteric elastomers under deformation.

Cholesteric liquid crystal elastomers have interesting and potentially very useful photonic properties. In an ideal monodomain configuration of these materials, one finds a Bragg reflection of light in a narrow wavelength range and a particular circular polarization. This is due to the periodic structure of the material along one dimension. In many practical cases, the cholesteric rubber possesses a sufficient degree of quenched disorder, which makes the selective reflection broadband. We investigate experimentally the problem of how the transmittance of light is affected by mechanical deformation of the elastomer, and the relation to changes in liquid crystalline structure. We explore a series of samples which have been synthesized with photonic stop gaps across the visible range. This allows us to compare results with detailed theoretical predictions regarding the evolution of stop gaps in cholesteric elastomers.

Journal Article↗

PubMed2004

Commentary on "Mechanical properties of monodomain side-chain nematic elastomers" by P. Martinoty, P. Stein, H. Finkelmann, H. Pleiner and H.R. Brand.

We discuss the background to static and dynamic soft elasticity. The evidence in the static case and the symmetry basis for soft and semi-soft elasticity is well understood. By contrast the dynamic analogy is less clear. Lack of clean time scale separation clouds the interpretation of director relaxation keeping up, or not, with imposed strains. However, the reduction in modulus between geometries obtaining at low frequencies and being lost at high frequencies confirms that director reaction indeed determines dynamical semi-softness.

Anisotropy↗

PubMed2003

Stereo-selective swelling of imprinted cholesteric networks.

Molecular chirality, and the chiral symmetry breaking of resulting macroscopic phases, can be topologically imprinted and manipulated by cross-linking and swelling of polymer networks. We present a new experimental approach to stereo-specific separation of chiral isomers by using a cholesteric elastomer in which a helical director distribution has been topologically imprinted by cross-linking. This makes the material unusual in that is has a strong phase chirality, but no molecular chirality at all; we study the nature and parameters controlling the twist-untwist transition. Adding a racemic mixture to the imprinted network results in selective swelling by only the component of "correct" handedness. We investigate the capacity of demixing in a racemic environment, which depends on network parameters and the underlying nematic order.

Models, Chemical↗

PubMed2003

Liquid crystalline elastomers: dynamics and relaxation of microstructure.

The equilibrium mechanical response of nematic elastomers can be soft or hard depending on the relation between the imposed strains and the nematic director, in particular, if the local nematic director is able to respond by rotating. The dynamical response proves to be equally unusual. We examine the linear dynamic mechanical response of monodomain nematic elastomers under shear and the aspects of time-temperature superposition of the dynamical data across phase-transition regions. In the low-frequency region of the master curves, one finds a dramatic reduction of rubber plateau modulus and the rise in internal dissipation: in the shear geometries compatible with dynamic soft elasticity. Power-law variation of the storage modulus with frequency G' proportional, variant omega(a) agrees very well with the results of static stress relaxation, where each relaxation curve obeys the analogous power law G' proportional, variant t(-a) in the corresponding region of long times and temperatures.

Elastomers↗

PubMed2003

Phase chirality and stereo-selective swelling of cholesteric elastomers.

Cholesteric elastomers possess a macroscopic "phase chirality" as the director n rotates in a helical fashion along an optical axis z and can be described by a chiral order parameter alpha. This parameter can be tuned by changing the helix pitch p and the elastic properties of the network at formation. The cholesterics also possess a local nematic order, changing with temperature or during solvent swelling. In this paper, by measuring the power of optical rotation d upsilon /dz , we discover how these two parameters vary as functions of temperature or solvent adsorbed by the network. The main result is a finding of pronounced stereo-selectivity of cholesteric elastomers, demonstrating itself in the retention of the "correct" chirality component of a racemic solvent. It has been possible to quantify the amount of such stereo-separation, and the basic dynamics of the effect.

Calorimetry, Differential Scanning↗

PubMed2003

Dynamic soft elasticity in monodomain nematic elastomers.

We study the linear dynamic-mechanical response of monodomain nematic liquid crystalline elastomers under shear in the geometry that allows the director rotation. The aspects of time-temperature superposition are discussed at some length and Master Curves are obtained between the glassy state and the nematic transition temperature Tni. However, the time-temperature superposition did not work through the clearing point Tni, due to the transition from the "soft-elasticity" nematic regime to the ordinary isotropic rubber response. We focus on the low-frequency region of the Master Curves and establish the power law dependence of the modulus G' alpha w(a). This law agrees very well with the results of the static stress relaxation, where each relaxation curve obeys the analogous power law G' alpha t(-a) in the corresponding region of long times and temperatures.

Journal Article↗

PubMed2003

Stripe instability in thin films of smectic liquid-crystal polymers.

Two-dimensional nanostripes are formed in thin films of side-chain liquid-crystalline polymer films when the material enters the smectic phase. The structure is investigated using transmission electron microscopy. Electron diffraction patterns show that the chain molecules are mostly aligned in the film plane and the average molecular director is parallel to the direction of the stripes. We discuss factors affecting the stripe amplitude and periodicity, such as the film thickness and the temperature of annealing in the nematic phase, and suggest a possible mechanism for their formation. We propose that an equilibrium instability occurs due to a competition between the layer-aligning effect of the substrate and the planar director alignment, forcing smectic layers perpendicular to the film surface. The stripes decorate the overall patterns of nematic director in the polymer film and provide a means of high-resolution imaging for observation of textures and disclinations.

Journal Article↗

PubMed2002

Propagation of acoustic waves in nematic elastomers.

We develop a theory of elastic waves in oriented monodomain nematic elastomers. The effect of soft elasticity, combined with the Leslie-Ericksen version of dissipation function, results in an unusual dispersion and anomalous anisotropy of shear acoustic waves. A characteristic time scale of nematic rotation determines the crossover frequency, below which waves of some polarizations have a very strong attenuation while others experience no dissipation at all. We study the anisotropy of low-frequency Poynting vectors and wave fronts, and discuss a "squeeze" effect of energy transfer nonparallel to the wave vector. Based on these theoretical results, an application, the acoustic polarizer, is proposed.

Journal Article↗

PubMed2002

Evolution of photonic structure on deformation of cholesteric elastomers.

We subject a monodomain cholesteric liquid crystal elastomer to uniaxial strain perpendicular to its helical axis and study the response of its texture to deformation. A combination of mechanical, optical, and x-ray scattering measurements confirms the prediction for the director rotation, coarsening, and then unwinding the cholesteric helix. The study of optical absorption of circularly polarized light quantifies the complex dependence of the photonic band-gap structure on strain and directly relates to the microscopic deformation of elastomer. Agreement is found with the recently proposed theoretical prediction of the photonic structure of cholesteric elastomers.

Journal Article↗