Lyotropic Solutions Research Articles

Nanotubes of a Different Kind: Stoichiometry and Geometry of the Orange II/γ-Cyclodextrin Complex in Water.

Orange II (O-II), a water-soluble ionic azo dye, aggregates and eventually forms needle-like crystals at concentrations greater than 0.15 M. However, when equimolar amounts of γ-cyclodextrin (γ-CD) are added to solutions containing O-II at 0.025 M or higher, the solution's appearance rapidly changes presenting a viscous, birefringent liquid, a lyotropic liquid crystalline solution. Birefringence is absent when viewing aqueous solutions of only O-II or γ-CD at concentrations greater than 0.03 M. Using ultraviolet-visible (UV-vis) and fluorescence spectroscopy, coupled with conductivity measurements, we postulate a structure for the basic "building block" of the self-assembly that eventually gives rise to a rodlike superstructure, leading to the formation of a lyotropic liquid crystalline phase.

Analysis of spinnable mesophase pitch in terms of lyotropic liquid crystalline solution

Analysis of spinnable mesophase pitch in terms of lyotropic liquid crystalline solution

Mechanochromic, Structurally Colored, and Edible Hydrogels Prepared from Hydroxypropyl Cellulose and Gelatin.

Hydroxypropyl cellulose (HPC) is an edible, cost-effective and widely used derivative of cellulose. Under lyotropic conditions in water, HPC forms a photonic, liquid crystalline mesophase with an exceptional mechanochromic response. However, due to insufficient physical cross-linking photonic HPC can flow freely as a viscous liquid, preventing the exploitation of this mechanochromic material in the absence of any external encapsulation or structural confinement. Here this challenge is addressed by mixing HPC and gelatin in water to form a self-supporting, viscoelastic, and edible supramolecular photonic hydrogel. It is demonstrated that the structural coloration, mechanochromism and non-Newtonian shear-thinning behavior of the lyotropic HPC solutions can all be retained into the gel state. Moreover, the rigidity of the HPC-gel provides a 69% shorter mechanochromic relaxation time back to its initial color when compared to the liquid HPC-water only system, broadening the dynamic color range of HPC by approximately 2.5× in response to a compressive pressure. Finally, the ability to formulate the HPC-gels in a scalable fashion from only water and "food-grade" constituents unlocks a wide range of potential applications, from response-tunable mechanochromic materials and colorant-free food decoration, to short-term sensors in, for example, biodegradable "smart labels" for food packaging.

Blends of Semiflexible Polymers: Interplay of Nematic Order and Phase Separation.

Mixtures of semiflexible polymers with a mismatch in either their persistence lengths or their contour lengths are studied by Density Functional Theory and Molecular Dynamics simulation. Considering lyotropic solutions under good solvent conditions, the mole fraction and pressure is systematically varied for several cases of bending stiffness (the normalized persistence length) and chain length N. For binary mixtures with different chain length (i.e., , or 64) but the same stiffness, isotropic-nematic phase coexistence is studied. For mixtures with the same chain length () and large stiffness disparity ( to 8), both isotropic-nematic and nematic-nematic unmixing occur. It is found that the phase diagrams may exhibit a triple point or a nematic-nematic critical point, and that coexisting phases differ appreciably in their monomer densities. The properties of the two types of chains (nematic order parameters, chain radii, etc.) in the various phases are studied in detail, and predictions on the (anisotropic) critical behavior near the critical point of nematic-nematic unmixing are made.

Phase Separation and Nematic Order in Lyotropic Solutions: Two Types of Polymers with Different Stiffnesses in a Common Solvent.

The interplay of the isotropic-nematic transition and phase separation in lyotropic solutions of two types of semiflexible macromolecules with pronounced difference in chain stiffness is studied by Density Functional Theory and Molecular Dynamics simulations. While the width of the isotropic-nematic two-phase coexistence region is narrow for solutions with a single type of semiflexible chain, the two-phase coexistence region widens for solutions containing two types of chains with rather disparate stiffness. In the nematic phase, both types of chains contribute to the nematic order, with intermediate values of the order parameter compared to the corresponding single component solutions. As the difference in bending stiffness is increased, the two chain types separate into two coexisting nematic phases. The phase behavior is rationalized by considering the chemical potentials of the two components and the Gibbs excess free energy. The geometric properties of the chain conformations under the various conditions are also discussed.

Treating anisotropic artefacts in circular dichroism spectroscopy enables investigation of lyotropic liquid crystalline polyaspartate solutions.

Circular dichroism (CD) spectroscopy is commonly used for investigation of the secondary structure of biomolecular compounds as well as polymers in isotropic solution. In anisotropic solution, the usage of the apparent CD is prone to misinterpretations due to artefacts from contributions of e.g. linear dichroism (LD). Herein, a method for the complete cancelation of anisotropic artefacts in the apparent CD is developed and its validity proven. The approach is further used for investigation of the conformation and the lyotropic liquid crystalline (LLC) structure of a copolyaspartate. For this system, a temperature-dependent change of the polymer's helical conformation (helix reversal) is known. Furthermore, a rotation of the aligned polymer helices inside a magnetic field (helix realignment) is independently present, occurring at a lower temperature compared to the helix reversal. In the current study, the helix reversal is confirmed and found to be accompanied by a change of the LLC structure. A cholesteric structure is detected and revealed to change its sense (cholesteric reversal) at the temperature at which the helix realigns in the magnetic field. The determination of the cholesteric sense is enabled by measuring the induced CD of an achiral dye, dissolved in the anisotropic polymer solution. Investigation of the anisotropic polymer solution is, thus, only made possible by cancellation of the aforementioned anisotropic artefacts. This allows the observation of changes of the liquid crystal structure from right-handed cholesteric, through left-handed cholesteric, to nematic with increasing temperature.

Entropic Unmixing in Nematic Blends of Semiflexible Polymers.

Binary mixtures of semiflexible polymers with the same chain length, but different persistence lengths, separate into two coexisting different nematic phases when the osmotic pressure of the lyotropic solution is varied. Molecular Dynamics simulations and Density Functional Theory predict phase diagrams either with a triple point, where the isotropic phase coexists with two nematic phases or a critical point of unmixing within the nematic mixture. The difference in locally preferred bond angles between the constituents drives this unmixing without any attractive interactions between monomers.

Playing the blues, the greens and the reds with cellulose-based structural colours.

Structural vivid colours can arise from the interference of light reflected from structures exhibiting periodicity on scales in the range of visible wavelengths. This effect is observed with light reflected from cell-walls of some plants and exoskeletons of certain insects. Sometimes the colour sequence observed for these structures consists of nearly circular concentric rings that vary in colour from Red, Orange, Yellow, Green, Cyan to Blue, from the periphery to the centre, similarly to the colour scheme sequence observed for the rainbow (ROYGB). The sequence of colours has been found for solid films obtained from droplets of aqueous cellulose nanocrystals (CNCs) suspensions and attributed to a "coffee ring" effect. In this work, coloured lyotropic solutions and solid films obtained from a cellulose derivative in the presence of trifluoroacetic acid (TFA), which acts as a "reactive solvent", are revisited. The systems were investigated with spectroscopy, using circularly and linearly polarised light, coupled with a polarised optical microscope (POM) and scanning electron microscopy (SEM). The lyotropic cholesteric liquid crystalline solutions were confined in capillaries to simplify 1D molecular diffusion along the capillary where an unexpected sequence of the structural colours was observed. The development and reappearance of the sequence of vivid colours seem consistent with the reaction-diffusion of the "reactive solvent" in the presence of the cellulosic chains. The strong TFA acts as an auto-catalyst for the chemical reaction between TFA and the hydroxyl groups, existing along the cellulosic chain, and diffuses to the top and bottom along the capillaries, carrying dissolved cellulosic chains. Uncovering the precise mechanism of colour sequence and evolution over time in cellulosic lyotropic solutions has important implications for future optical/sensors applications and for the understanding of the development of cellulose-based structures in nature.

The smectic phase in semiflexible polymer materials: A large scale molecular dynamics study

Semiflexible polymers in concentrated lyotropic solution are studied within a bead-spring model by molecular dynamics simulations, focusing on the emergence of a smectic A phase and its properties. We systematically vary the density of the monomeric units for several contour lengths that are taken smaller than the chain persistence length. The difficulties concerning the equilibration of such systems and the choice of appropriate ensemble (constant volume versus constant pressure, where all three linear dimensions of the simulation box can fluctuate independently) are carefully discussed. Using HOOMD-blue on graphics processing units, systems containing more than a million monomeric units are accessible, making it possible to distinguish the order of the phase transitions that occur. While in this model the nematic-smectic transition is continuous, the transition from the smectic phase to a related crystalline structure with true three-dimensional long-range order is clearly of first order. Further, both orientational and positional correlations of monomeric units are studied as well as the order parameters characterizing the nematic, smectic A, and crystalline phases. The analogy between smectic order and one-dimensional harmonic crystals with respect to the behavior of the structure factor is also explored. Finally, the results are put in perspective with pertinent theoretical predictions and possible experiments.

Nematic order in solutions of semiflexible polymers: Hairpins, elastic constants, and the nematic-smectic transition.

Coarse-grained models of lyotropic solutions of semiflexible polymers are studied by both molecular dynamics simulations and density functional theory calculations, using an implicit solvent bead-spring model with a bond-angle potential. We systematically vary the monomer density, persistence length, and contour length over a wide range and explore the full range from the isotropic-nematic transition to the nematic-smectic transition. In the nematic regime, we span the entire regime from rigid-rod like polymers to thin wormlike chains, confined in effective straight tubes caused by the collective nematic effective ordering field. We show that the distribution of bond angles relative to the director is well described by a Gaussian, irrespective of whether the chains are rod-like or rather flexible. However, the related concept of "deflection length" is shown to make sense only in the latter case for rather dilute solutions since otherwise the deflection length is of the order of about two bond lengths only. When the solution is semi-dilute, a substantial renormalization of the persistence length occurs, while this effect is absent in the isotropic phase even at rather high monomer densities. The effective radii of the "tubes" confining the chains in the related description of orientational ordering are significantly larger than the distances between neighboring chains, providing evidence for a pronounced collective character of orientational fluctuations. Hairpins can be identified close to the isotropic-nematic transition, and their probability of occurrence agrees qualitatively with the Vroege-Odijk theory. The corresponding theoretical predictions for the elastic constants, however, are not in good agreement with the simulations. We attribute the shortcomings of the theories to their neglect of the coupling between local density and orientational fluctuations. Finally, we detected for this model a transition to a smectic phase for reduced monomer densities near 0.7.

Densely Packed Semiflexible Macromolecules in a Rigid Spherical Capsule

The ordering of semiflexible polymers with persistence length lp and contour length L confined in a sphere of radius R is studied by molecular dynamics simulations of a coarse-grained model. Monomer densities are chosen where the corresponding bulk lyotropic solution or melt is a well-ordered nematic, and purely repulsive walls of the rigid confining sphere are considered. It is found that polymers close to the walls are bent according to the curvature of the confining spheres with all their monomers in a few layers parallel to the sphere surface, whereas the remaining macromolecules closer to the sphere center have one chain end and their center of mass far from the surface. The latter chains are responsible for the average nematic order of the system for sufficiently stiff chains. If L exceeds R, a single transition from isotropic to nematic states is found when lp increases. However, if R is close to an even multiple of L, a second transition occurs where chain ends are enriched near the equatorial plane (and two further planes parallel to it, if R ≈ 2L); i.e., the system develops a distorted smectic structure. The order in the surface shell then is characterized by topological defects.

Conformations and orientational ordering of semiflexible polymers in spherical confinement.

Semiflexible polymers in lyotropic solution confined inside spherical nanoscopic "containers" with repulsive walls are studied by molecular dynamics simulations and density functional theory, as a first step to model confinement effects on stiff polymers inside of miniemulsions, vesicles, and cells. It is shown that the depletion effects caused by the monomer-wall repulsion depend distinctly on the radius R of the sphere. Further, nontrivial orientational effects occur when R, the persistence length ℓp, and the contour length L of the polymers are of similar magnitude. At intermediate densities, a "shell" of wall-attached chains is forming, such that the monomers belonging to those chains are in a layer at about the distance of one monomer from the container wall. At the same time, the density of the centers of mass of these chains is peaked somewhat further inside, but still near the wall. However, the arrangement of chains is such that the total monomer density is almost uniform in the sphere, apart from a small layering peak at the wall. It is shown that excluded volume effects among the monomers are crucial to account for this behavior, although they are negligible for comparable isolated single semiflexible chains of the same length.

Formation and Structure of Lyotropic Liquid Crystalline Mesophases in Donor–Acceptor Semiconducting Polymers

Design of side chains yielding highly amphiphilic conjugated polymers is proven to be an effective and general method to access lyotropic liquid crystalline mesophases, allowing greater control over crystalline morphology and improving transistor performance. The general strategy enables variations in structure and interactions that impact alignment and use of liquid crystalline alignment methods. Specifically, solvent-polymer interactions are harnessed to facilitate the formation of high quality polymer crystals in solution. Crystallinity developed in solution is then transferred to the solid state, and thin films of donor-acceptor copolymers cast from lyotropic solutions exhibit improved crystalline order in both the alkyl and π-stacking directions. Due to this improved crystallinity, transistors with active layers cast from lyotropic solutions exhibit a significant improvement in carrier mobility compared to those cast from isotropic solution. One or more embodiments of the present invention achieve a maximum carrier mobility of 0.61 cm 2 V −1 s −1 .

Bimodal form distribution from modelling biaxial lyotropic liquid crystal solutions through a polydisperse Maier–Saupe model

ABSTRACTBiaxial nematic phases have been the subject of a long list of studies. In particular, they were found for a few lyotropic micellar solutions. There is a debate in the literature on whether the micellar aggregates should be biaxial, or if biaxiality could be the result of perpendicular alignment of uniaxial particles of cylinder-like and disc-like geometry in a mixture. Based on recent studies on the phase stability of such mixtures, we have investigated a polydisperse distribution of uniaxial particles interacting through a Maier–Saupe potential. Our calculations were developed for a general distribution of micellar anisometries. The distribution was obtained from the fitting of our results to the experimental data of Yu and Saupe’s well-known 1980 paper, near the Landau point, yielding a bimodal distribution, with the presence of two quadrupoles referred to objects of opposite symmetry, that is to prolate and oblate micelles. This result lends support to the rationalization of the biaxial phase for lyotropic systems in terms of a polydisperse mixture of rod-like and disc-like micelles.

A new insight into the isotropic-nematic phase transition in lyotropic solutions of semiflexible polymers: density-functional theory tested by molecular dynamics.

Semiflexible polymers in solution are studied for a wide range of both contour length L and persistence length lp as a function of monomer concentration under good solvent conditions. Both density-functional theory (DFT) and molecular dynamics (MD) simulation methods are used, and a very good agreement between both techniques is observed for rather stiff polymers. Evidence for a new mechanism of order parameter fluctuations in the nematic phase is presented, namely collective deformations of bundles of wormlike chains twisted around each other, and the typical wavelengths and amplitudes of these modes are estimated. These long wavelength fluctuations cause a reduction of the order parameter in comparison with the DFT prediction. It is also found that DFT becomes unreliable for rather flexible polymers in predicting that the transition from the isotropic (I)-phase to the nematic (N)-phase still exists at very high monomer concentrations (which in reality does not occur). However, under conditions when DFT is accurate, it provides reliable predictions also for the width of the I-N two-phase coexistence region, which are difficult to obtain from MD in spite of the use of very large systems (up to 500 000 monomers) by means of graphics processing units (GPU). For short and not very stiff chains, a pre-transitional chain stretching is found in the isotropic phase near the I-N-transition, not predicted by theories. A comparison with theoretical predictions by Khokhlov-Semenov, Odijk, and Chen reveals that the scaled transition densities are not simply functions of L/lp only, as these theories predict, but depend on d/lp (where d is the chain diameter) as well. Chain properties in the nematically ordered phase are compared to those of chains confined in tubes, and the deflection length concept is tested. Eventually, some consequences for the interpretation of experiments are spelled out.

Study of first normal stress difference of poly(p-phenylene terephthalamide) in sulfuric acid

The first normal stress difference (N1) of lyotropic liquid crystalline solutions of poly(p-phenylene terephthalamide) (PPTA) in sulfuric acid was studied by rheometric measurements. For the first time, a negative value range of N1 was observed for the solutions in a high shear rate range. N1 showed a non-monotonic dependence on the shear rate when the PPTA/sulfuric-acid solution was in the nematic phase. The minimum value of the first normal stress difference (N1min) and the shear rate to achieve N1min (γ˙min) were observed to be closely correlated with temperature, concentration and molecular weight. Compared with some well-studied lyotropic LCP systems, the rheological behavior of PPTA/sulfuric-acid was more sensitively dependent on the concentration. Above observations indicate that the frustration of tumbling of average polymer orientation occurs in the high shear rate range and the influences of the factors are not exactly the same as those well-studied lyotropic LC polymer systems.

Orientation-Dependent Order-Disorder Transition of Block Copolymer Lamellae in Electric Fields.

Electric fields have been shown to stabilize the disordered phase of near-critical block copolymer solutions. Here, we use in situ synchrotron small-angle X-ray scattering to examine how the initial orientation of lamellar domains with respect to the external field (φ) affects the shift in the order-disorder transition temperature (TODT) of lyotropic solutions of poly(styrene-b-isoprene) in toluene. We find a downward shift of the transition temperature, which scales with lamellar orientation as ΔTODT ∼ cos2 φ, in accordance with theory.

Electric Field Induced Selective Disordering in Lamellar Block Copolymers

External electric fields align nanostructured block copolymers by either rotation of grains or nucleation and growth depending on how strongly the chemically distinct block copolymer components are segregated. In close vicinity to the order-disorder transition, theory and simulations suggest a third mechanism: selective disordering. We present a time-resolved small-angle X-ray scattering study that demonstrates how an electric field can indeed selectively disintegrate ill-aligned lamellae in a lyotropic block copolymer solution, while lamellae with interfaces oriented parallel to the applied field prevail. The present study adds an additional mechanism to the experimentally corroborated suite of mechanistic pathways, by which nanostructured block copolymers can align with an electric field. Our results further unveil the benefit of electric field assisted annealing for mitigating orientational disorder and topological defects in block copolymer mesophases, both in close vicinity to the order-disorder transition and well below it.

The influence of Hofmeister's effect on the osmotic behavior of erythrocytes and on the state of water in their suspension

AbstractThe bulk phase of water and its status in the cells play an important role in the management of metabolic processes. One of the little‐known universal phenomenon associated with the state of water is the Hofmeister effect which influences interfacial surfaces, the conformation of macromolecules, enzyme activity, and the growth of microorganisms. We investigated the influence of this effect on the change in the cell's ability to adapt to changing osmotic conditions, since understanding the mechanisms of osmotic behavior of the cells is an important step in the management of their activity (start of endo‐ and exocytosis, apoptosis). It is shown that specific properties of anions in the medium correlate with the osmotic sensitivity of red blood cells (RBC) and with indicators of free and bound water in suspension. The lyotropic series anion solution effect on the cell is a change of the hydration and structure of the membrane, which determines the osmotic behavior of the cell and the water environment properties.

The roles of betaine-ester analogues of 1-N-alkyl-3-N′-methyl imidazolium salts: as amphotropic ionic liquid crystals and organogelators

Betaine-ester analogues of 1-N-alkyl-3-N′-methyl imidazolium salts exhibiting both thermotropic and lyotropic liquid crystal behaviors are reported. Two typical compounds, structurally determined by single crystal X-ray diffraction exhibit an interdigitated bilayer packing. These compounds are gelators, which form gels in a variety of organic solvents such as chloroform, methanol, ethanol, tetrahydrofuran, while also exhibiting a lamellar mesophase. Results from IR and variable-temperature 1H NMR spectroscopy studies show that a trace amount of water (0.3–0.5% by volume) in CHCl3 plays a crucial role for developing the H-bonded network during gel formation. Ag-NPs (∼5–10 nm size) obtained from lyotropic LC solution and LC gel exhibit different morphologies ranging from spherical to truncated triangular plates.