scholarly journals The contribution of intermolecular forces to phototropic actuation of liquid crystalline elastomers

2021 ◽  
Vol 12 (10) ◽  
pp. 1581-1587
Author(s):  
Tayler S. Hebner ◽  
Christopher N. Bowman ◽  
Timothy J. White

Azobenzene-functionalized crystalline elastomers containing a monomer with reduced aromatic content exhibits enhanced phototropic response.

2000 ◽  
Vol 55 (11-12) ◽  
pp. 918-922 ◽  
Author(s):  
Durga Prasad Ojha

Abstract The molecular ordering of some biphenyl derivatives like 4-acetyl-2'-nitrobiphenyl (ANBP), 4-nitro-2-biphenylamine (NBPA) and 4-acetyl-3'-chlorobiphenyl (ACBP) has been examined using basic con-cepts of quantum mechanics and intermolecular forces. The CNDO/2 method has been employed to compute the net atomic charge and atomic dipole components at each atomic centre. The modified Ray-leigh-Schrödinger perturbation theory along with the multicentred-multipole expansion method has been employed to evaluate long-range interactions while a '6-exp' potential function has been assumed for short-range interactions. Accuracies upto 0.1 A in translation and 1° in rotation have been achieved. Probability of occurrence of a particular configuration has been calculated using MB-statistics. On the basis of stacking and in-plane interaction energy calculations, all possible geometrical arrangements between molecular pairs have been considered and a most favorable configuration of pairing has been obtained. A comparative picture of molecular parameters like total energy, binding energy, total dipole moment etc. has been given. An attempt has been made to develop a molecular model correlated with the liquid crystalline property exhibited by this class of molecules.


Author(s):  
Antony N. Beris ◽  
Brian J. Edwards

Liquid crystals (LCs) present a state of matter with properties—as the name suggests—intermediate between those of liquids and crystalline solids. Liquid-crystalline materials, as all liquids, cannot support shear stresses at static equilibrium. Their molecules are characterized by an anisotropy in the shape and/or intermolecular forces. Thus, there is the potential for the formation of a separate phase(s), called a “mesophase(s),” where a partial order arises in the molecular orientation and/or location, which extends over macroscopic distances. This partial long-range molecular order, reminiscent of (but not equivalent to) the perfect order of solid crystals, in addition to the material fluidity, is primarily responsible for the many properties which are inherent characteristics of liquid-crystalline phases, such as a rapid response to electric and magnetic fields, anisotropic optical and rheological properties, etc.—see, for examples, the reviews by Stephen and Straley [1974] and Jackson and Shaw [1991], the monographs by de Gennes [1974], Chandrasekhar [1977], and Vertogen and de Jeu [1988], and the edited volumes by Ciferri et al. [1982] and Ciferri [1991]. The variety of the liquid-crystalline macroscopic properties is such that trying to derive a theory capable of describing the principal liquid-crystalline dynamic characteristics can be a very frustrating task if one does not approach the issue in a systematic fashion. Characteristically, the main two theories that have been advanced over the last thirty years for the description of the liquid-crystalline flow behavior—the Leslie/ Ericksen (LE) theory and the Doi theory—are essentially models developed from a set theoretical frame work—continuum mechanics and molecular theory, respectively. Nevertheless, each one of these theories has a limited domain of application. The description of the dynamic liquid-crystalline behavior through the bracket formalism, as seen in this chapter, leads naturally to a single conformation tensor theory with an extended domain of validity. This conformation theory consistently generalizes both previous theories, which can be recovered from it as particular cases. This offers additional evidence that the wealth of inherent information in LCs can only be appropriately handled when pursued in a systematic, fundamental manner.


Author(s):  
Joseph A. Zasadzinski

At low weight fractions, many surfactant and biological amphiphiles form dispersions of lamellar liquid crystalline liposomes in water. Amphiphile molecules tend to align themselves in parallel bilayers which are free to bend. Bilayers must form closed surfaces to separate hydrophobic and hydrophilic domains completely. Continuum theory of liquid crystals requires that the constant spacing of bilayer surfaces be maintained except at singularities of no more than line extent. Maxwell demonstrated that only two types of closed surfaces can satisfy this constraint: concentric spheres and Dupin cyclides. Dupin cyclides (Figure 1) are parallel closed surfaces which have a conjugate ellipse (r1) and hyperbola (r2) as singularities in the bilayer spacing. Any straight line drawn from a point on the ellipse to a point on the hyperbola is normal to every surface it intersects (broken lines in Figure 1). A simple example, and limiting case, is a family of concentric tori (Figure 1b).To distinguish between the allowable arrangements, freeze fracture TEM micrographs of representative biological (L-α phosphotidylcholine: L-α PC) and surfactant (sodium heptylnonyl benzenesulfonate: SHBS)liposomes are compared to mathematically derived sections of Dupin cyclides and concentric spheres.


Author(s):  
Afzana Anwer ◽  
S. Eilidh Bedford ◽  
Richard J. Spontak ◽  
Alan H. Windle

Random copolyesters composed of wholly aromatic monomers such as p-oxybenzoate (B) and 2,6-oxynaphthoate (N) are known to exhibit liquid crystalline characteristics at elevated temperatures and over a broad composition range. Previous studies employing techniques such as X-ray diffractometry (XRD) and differential scanning calorimetry (DSC) have conclusively proven that these thermotropic copolymers can possess a significant crystalline fraction, depending on molecular characteristics and processing history, despite the fact that the copolymer chains possess random intramolecular sequencing. Consequently, the nature of the crystalline structure that develops when these materials are processed in their mesophases and subsequently annealed has recently received considerable attention. A model that has been consistent with all experimental observations involves the Non-Periodic Layer (NPL) crystallite, which occurs when identical monomer sequences enter into register between adjacent chains. The objective of this work is to employ electron microscopy to identify and characterize these crystallites.


Author(s):  
Linda C. Sawyer

Recent liquid crystalline polymer (LCP) research has sought to define structure-property relationships of these complex new materials. The two major types of LCPs, thermotropic and lyotropic LCPs, both exhibit effects of process history on the microstructure frozen into the solid state. The high mechanical anisotropy of the molecules favors formation of complex structures. Microscopy has been used to develop an understanding of these microstructures and to describe them in a fundamental structural model. Preparation methods used include microtomy, etching, fracture and sonication for study by optical and electron microscopy techniques, which have been described for polymers. The model accounts for the macrostructures and microstructures observed in highly oriented fibers and films.Rod-like liquid crystalline polymers produce oriented materials because they have extended chain structures in the solid state. These polymers have found application as high modulus fibers and films with unique properties due to the formation of ordered solutions (lyotropic) or melts (thermotropic) which transform easily into highly oriented, extended chain structures in the solid state.


Author(s):  
D.F. Clapin ◽  
V.J.A. Montpetit

Alzheimer's disease is characterized by the accumulation of abnormal filamentous proteins. The most important of these are amyloid fibrils and paired helical filaments (PHF). PHF are located intraneuronally forming bundles called neurofibrillary tangles. The designation of these structures as "tangles" is appropriate at the light microscopic level. However, localized domains within individual tangles appear to demonstrate a regular spacing which may indicate a liquid crystalline phase. The purpose of this paper is to present a statistical geometric analysis of PHF packing.


Author(s):  
Christopher Viney

Light microscopy is a convenient technique for characterizing molecular order in fluid liquid crystalline materials. Microstructures can usually be observed under the actual conditions that promote the formation of liquid crystalline phases, whether or not a solvent is required, and at temperatures that can range from the boiling point of nitrogen to 600°C. It is relatively easy to produce specimens that are sufficiently thin and flat, simply by confining a droplet between glass cover slides. Specimens do not need to be conducting, and they do not have to be maintained in a vacuum. Drybox or other controlled environmental conditions can be maintained in a sealed chamber equipped with transparent windows; some heating/ freezing stages can be used for this purpose. It is relatively easy to construct a modified stage so that the generation and relaxation of global molecular order can be observed while specimens are being sheared, simulating flow conditions that exist during processing. Also, light only rarely affects the chemical composition or molecular weight distribution of the sample. Because little or no processing is required after collecting the sample, one can be confident that biologically derived materials will reveal many of their in vivo structural characteristics, even though microscopy is performed in vitro.


Author(s):  
E. Naranjo

Equilibrium vesicles, those which are the stable form of aggregation and form spontaneously on mixing surfactant with water, have never been demonstrated in single component bilayers and only rarely in lipid or surfactant mixtures. Designing a simple and general method for producing spontaneous and stable vesicles depends on a better understanding of the thermodynamics of aggregation, the interplay of intermolecular forces in surfactants, and an efficient way of doing structural characterization in dynamic systems.


Author(s):  
Christine M. Dannels ◽  
Christopher Viney

Processing polymers from the liquid crystalline state offers several advantages compared to processing from conventional fluids. These include: better axial strength and stiffness in fibers, better planar orientation in films, lower viscosity during processing, low solidification shrinkage of injection moldings (thermotropic processing), and low thermal expansion coefficients. However, the compressive strength of the solid is disappointing. Previous efforts to improve this property have focussed on synthesizing stiffer molecules. The effect of microstructural scale has been overlooked, even though its relevance to the mechanical and physical properties of more traditional materials is well established. By analogy with the behavior of metals and ceramics, one would expect a fine microstructure (i..e. a high density of orientational defects) to be desirable.Also, because much microstructural detail in liquid crystalline polymers occurs on a scale close to the wavelength of light, light is scattered on passing through these materials.


Author(s):  
David M. Anderson ◽  
Tomas Landh

First discovered in surfactant-water liquid crystalline systems, so-called ‘bicontinuous cubic phases’ have the property that hydropnilic and lipophilic microdomains form interpenetrating networks conforming to cubic lattices on the scale of nanometers. Later these same structures were found in star diblock copolymers, where the simultaneous continuity of elastomeric and glassy domains gives rise to unique physical properties. Today it is well-established that the symmetry and topology of such a morphology are accurately described by one of several triply-periodic minimal surfaces, and that the interface between hydrophilic and hydrophobic, or immiscible polymer, domains is described by a triply-periodic surface of constant, nonzero mean curvature. One example of such a dividing surface is shown in figure 5.The study of these structures has become of increasing importance in the past five years for two reasons:1)Bicontinuous cubic phase liquid crystals are now being polymerized to create microporous materials with monodispersed pores and readily functionalizable porewalls; figure 3 shows a TEM from a polymerized surfactant / methylmethacrylate / water cubic phase; and2)Compelling evidence has been found that these same morphologies describe biomembrane systems in a wide range of cells.


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