Liquid-crystalline Phase Transition Research Articles

Exploring the Physical Properties of Lipid Membranes with Polyhydroxy Oxanorbornane Head Group Using NBD-Conjugated and DPH Fluorescent Probes.

The present study focuses on exploring the physical properties of lipid membranes based on the polyhydroxy oxanorbornane (PH-ONB) headgroup, designed as synthetic analogues of naturally occurring archaeal lipid membranes. Specifically, we study two variants of PH-ONB headgroup-based lipids differing in the number of hydroxy groups present in the headgroup, with one having two hydroxy groups (ONB-2OH) and the other having three (ONB-3OH). These lipids form stable bilayer membranes. The study begins with a comprehensive analysis of the fluorescence characteristics of nitrobenzoxadiazole (NBD)-tagged ONB-based lipids in different solvent environments and within a model lipid membrane 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC). Subsequently, the physical properties of the ONB-based membranes were examined by using an NBD-tagged ONB-based probe and a commonly used extrinsic 1,6-diphenyl-1,3,5-hexatriene (DPH) fluorescent probe. The steady-state and time-resolved fluorescence properties of the NBD-tagged ONB-based probe and DPH were used to compare the physical properties of the ONB-based membranes, including polarity, fluidity, phase transition, order, hydration, location, heterogeneity, and rotational diffusion. The solid gel to liquid crystalline phase transition temperatures of ONB-2OH and ONB-3OH lipid membranes are found to be (68 ± 1) °C and (74 ± 1) °C, respectively. The variation in organization (size), fluidity, and phase transition temperature of ONB-based lipid membranes is explained by the extent of hydrogen bonding interactions between lipid head groups. ONB-based membranes exhibit characteristics similar to those of phospholipid membranes and possess a notably high phase transition temperature. These properties make them a promising and cost-effective synthetic alternative to archaeal lipid membranes with a wide range of potential applications.

Active Material‐Free Continuous Carbon Nanotube Fibers with Unprecedented Enhancement of Physicochemical Properties for Fiber‐Type Solid‐State Supercapacitors

AbstractFiber‐type solid‐state supercapacitors (FSSCs) are gaining traction as wearable energy storage devices, given their adaptability akin to traditional fibers. Carbon nanotube fibers (CNTFs) generated via a liquid crystalline (LC) wet‐spinning process demonstrate outstanding electrical conductivity, mechanical strength, and flexibility. However, their intrinsic “defect‐free” sp2 carbon surface restricts immediate FSSC application, limited by lower specific surface area and scant pseudocapacitive sites. This study develops LC‐spun CNTFs with inherent electrochemical activity, eliminating the need for post‐processing or additional active materials, a requirement typically essential in most previous research. This advancement arises from the wet‐spinning of functionalized CNTs from a LC solution with an exceptionally high concentration of 160 mg mL−1, facilitated by the manipulation of the LC phase transition range. The resultant CNTFs exhibit a refined internal structure, yielding an electrical conductivity of 1.9 MS m−1 and a mechanical strength of 0.93 GPa. Simultaneously, they demonstrate inherent electrical energy storage capabilities with a specific capacitance of 139.4 F g−1 and a volumetric capacitance of 192.4 F cm−3 at 0.5 A g−1. This innovation signifies a step forward in the potential for mass production without the burden of additional materials and steps.

Cardiolipin Strongly Inhibits the Leakage Activity of the Short Antimicrobial Peptide ATRA-1 in Comparison to LL-37, in Model Membranes Mimicking the Lipid Composition of Staphylococcus aureus

Cardiolipin is one of the main phospholipid components of Staphylococcus aureus membranes. This lipid is found at varying concentrations in the bilayer, depending on the growth stage of the bacteria, and as a response to environmental stress. Cardiolipin is an anionic phospholipid with four acyl chains, which modulates the bending properties of the membrane due to its inverted conical shape. It has been shown to inhibit the pore forming activity of several antimicrobial peptides, in general doubling the peptide concentration needed to induce leakage. Here we find that the short snake-derived antimicrobial peptide ATRA-1 is inhibited by several orders of magnitude in the presence of cardiolipin in saturated membranes (DMPG) compared to the human cathelicidin LL-37, which is only inhibited two-fold in its leakage-inducing concentration. The ATRA-1 is too short to span the membrane and its leakage activity is likely related to detergent-like alterations of bilayer structure. Fluorescence spectroscopy shows only a minor effect on ATRA-1 binding to DMPG membranes due to the presence of cardiolipin. However, FTIR spectroscopy shows that the acyl chain structure of DMPG membranes, containing cardiolipin, become more organized in the presence of ATRA-1, as reflected by an increase in the gel to liquid-crystalline phase transition temperature. Instead, a depression in the melting temperature is induced by ATRA-1 in DMPG in the absence of cardiolipin. In comparison, LL-37 induces a depression of the main phase transition of DMPG even in the presence of cardiolipin. These data suggest that cardiolipin inhibits the penetration of ATRA-1 into the membrane core, impeding its capacity to disrupt lipid packing.

A Thermo-Responsive Polymer Micelle with a Liquid Crystalline Core.

An amphiphilic diblock copolymer (PChM-PNIPAM), composed of poly(cholesteryl 6-methacryloyloxy hexanoate) (PChM) and poly(N-isopropyl acrylamide) (PNIPAM) blocks, was prepared via reversible addition-fragmentation chain transfer radical polymerization. The PChM and PNIPAM blocks exhibited liquid crystalline behavior and a lower critical solution temperature (LCST), respectively. PChM-PNIPAM formed water-soluble polymer micelles in water below the LCST because of hydrophobic interactions of the PChM blocks. The PChM and PNIPAM blocks formed the core and hydrophilic shell of the micelles, respectively. With increasing temperature, the molecular motion of the pendant cholesteryl groups increased, and a liquid crystalline phase transition occurred from an amorphous state in the core. With further increases in temperature, the PNIPAM block in the shell exhibited the LCST and dehydrated. Hydrophobic interactions of the PNIPAM shells resulted in inter-micellar aggregation above the LCST.

Cardiolipin induces strong inhibition of the short antimicrobial peptide Atra-1, but only weak inhibition of LL-37 in saturated model membranes.

Cardiolipin (CL) is an anionic tetra-acyl chained glycerophospholipid that increases lipid packing levels and induces intrinsic negative curvature in membranes. Cardiolipin is one of the main components in Staphylococcus aureus membranes, where increased levels of this lipid are induced at the expense of diacyl phosphatidylglycerol in response to stress. We investigate cardiolipin as an inhibitor of the lytic activity of the cationic antimicrobial peptides Atra-1 and LL-37 in model systems with varying phosphatidylglycerol/cardiolipin ratios. One of the characteristic difference between these two antimicrobial peptides is their length. While Atra-1 is a short peptides with only 11 residues, LL-37 is 37 residues in length. We observe that the presence of cardiolipin increases the leakage-inducing concentration of Atra-1 by several orders of magnitude, while only doubling that for LL-37. We find that cardiolipin does not affect peptide binding to phosphatidylglycerol/cardiolipin liposomes significantly for either peptide, measured by shifts in Laurdan GP, so it is likely that CL affects the insertion into the membrane. We measure by FTIR the thermotropic behavior of the model systems in the presence of the peptides. In the absence of CL, both peptides induce shifts in the gel to liquid-crystalline phase transition temperature, but in the presence of CL this shift was strongly reduced in the case of Atra-1. These results suggest that CL can inhibit cAMP activity drastically depending on the antimicrobial peptide structure.

Synthesis and Self-Assembly of Silicon-Containing Azobenzene Liquid Crystalline Block Copolymers

The synthesis and self-assembly of a high interaction parameter silicon-containing liquid crystalline block copolymer (Si-LCBCP) are reported, containing thermally and photo-responsive azobenzene mesogens in the side chains which undergo molecular structural transitions, influencing phase transitions and orientation in the block copolymer. A series of the azobenzene-containing Si-LCBCPs, poly{dimethylsiloxane-b-11-[4-(4-cyanophenylazo)phenoxy]undecane methacrylate}, were synthesized through atom transfer radical polymerization, and the bulk self-assembly as well as the influence of the liquid-crystalline (LC) phase transition of the LC block on the microphase-separated nanostructure of the BCPs is described. As the volume fraction of the PMAAzo block (fPMAAzo) changes from 41 to 71%, lamellar, double gyroid (GYR), orthorhombic Fddd network, hexagonally packed cylindrical (HEX), and body centered cubic nanostructures were obtained. When fPMAAzo = 55–57%, a thermally reversible HEX-GYR-Fddd phase transition induced by the temperature change and LC phase transition was observed. Bulk morphologies are compared with thin-film self-assembly, and pattern transfer into silica nanostructures is demonstrated.

Effects of a Semisynthetic Catechin on Phosphatidylglycerol Membranes: A Mixed Experimental and Simulation Study.

Catechins have been shown to display a great variety of biological activities, prominent among them are their chemo preventive and chemotherapeutic properties against several types of cancer. The amphiphilic nature of catechins points to the membrane as a potential target for their actions. 3,4,5-Trimethoxybenzoate of catechin (TMBC) is a modified structural analog of catechin that shows significant antiproliferative activity against melanoma and breast cancer cells. Phosphatidylglycerol is an anionic membrane phospholipid with important physical and biochemical characteristics that make it biologically relevant. In addition, phosphatidylglycerol is a preeminent component of bacterial membranes. Using biomimetic membranes, we examined the effects of TMBC on the structural and dynamic properties of phosphatidylglycerol bilayers by means of biophysical techniques such as differential scanning calorimetry, X-ray diffraction and infrared spectroscopy, together with an analysis through molecular dynamics simulation. We found that TMBC perturbs the thermotropic gel to liquid-crystalline phase transition and promotes immiscibility in both phospholipid phases. The modified catechin decreases the thickness of the bilayer and is able to form hydrogen bonds with the carbonyl groups of the phospholipid. Experimental data support the simulated data that locate TMBC as mostly forming clusters in the middle region of each monolayer approaching the carbonyl moiety of the phospholipid. The presence of TMBC modifies the structural and dynamic properties of the phosphatidylglycerol bilayer. The decrease in membrane thickness and the change of the hydrogen bonding pattern in the interfacial region of the bilayer elicited by the catechin might contribute to the alteration of the events taking place in the membrane and might help to understand the mechanism of action of the diverse effects displayed by catechins.

Long chain ceramides raise the main phase transition of monounsaturated phospholipids to physiological temperature

Little is known about the molecular mechanisms of ceramide-mediated cellular signaling. We examined the effects of palmitoyl ceramide (C16-ceramide) and stearoyl ceramide (C18-ceramide) on the phase behavior of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) and 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphoethanolamine (POPE) using differential scanning calorimetry (DSC) and small- and wide-angle X-ray scattering (SAXS, WAXS). As previously published, the presence of ceramides increased the lamellar gel-to-lamellar liquid crystalline (Lβ–Lα) phase transition temperature of POPC and POPE and decreased the Lα-to-inverted hexagonal (Lα–HII) phase transition temperature of POPE. Interestingly, despite an ~ 30° difference in the main phase transition temperatures of POPC and POPE, the Lβ–Lα phase transition temperatures were very close between POPC/C18-ceramide and POPE/C18-ceramide and were near physiological temperature. A comparison of the results of C16-ceramide in published and our own results with those of C18-ceramide indicates that increase of the carbon chain length of ceramide from 16 to 18 and/or the small difference of ceramide content in the membrane dramatically change the phase transition temperature of POPC and POPE to near physiological temperature. Our results support the idea that ceramide signaling is mediated by the alteration of lipid phase-dependent partitioning of signaling proteins.

Anticarcinogenic trimethoxybenzoate of catechin stabilizes the liquid crystalline bilayer phase in phosphatidylethanolamine membranes

The anticarcinogenic properties of catechins stand out among the great variety of biological actions attributed to these compounds. The capacity of catechins to interact with lipids and their participation in membrane related processes points out to the membrane as their potential site of action. Phosphatidylethanolamine is an abundant phospholipid in mammalian membranes that has tendency to form non lamellar phases, it is associated with important cellular processes, and it has been related to cancer. In order to shed light into the molecular effect of the anticarcinogenic 3,4,5-trimethoxybenzoate of catechin (TMBC) on lipid polymorphism and membrane structure and dynamics, we present a combined experimental and computational study of the interaction between this semisynthetic catechin and biomimetic membranes composed of unsaturated phosphatidylethanolamine. Our experimental evidence reveals that TMBC is readily incorporated into unsaturated phosphatidylethanolamine system where it is able to shift the gel to liquid crystalline phase transition temperature to lower values, decreasing the cooperativity and the enthalpy change of the transition. The presence of TMBC is able to promote the formation of gel phase immiscibility and to block the formation of the inverted hexagonal phase. In the bilayer liquid crystalline phase, the catechin decreases the interlamellar repeat distance, it increases the fluidity of the membrane, and it alters the hydrogen bond pattern of the interfacial region of the bilayer. Our molecular dynamics results concur with the experimental data and locate TMBC forming different domains near the interfacial region of the bilayer where it modifies the lateral pressure profile of the membrane leading to a stabilization of the bilayer in the liquid crystalline phase and to a potential alteration of the function of the membrane.

Nanolattice-Forming Hybrid Collagens in Protective Shark Egg Cases.

Nanoscopic structural control with long-range ordering remains a profound challenge in nanomaterial fabrication. The nanoarchitectured egg cases of elasmobranchs rely on a hierarchically ordered latticework for their protective function─serving as an exemplary system for nanoscale self-assembly. Although the proteinaceous precursors are known to undergo intermediate liquid crystalline phase transitions before being structurally arrested in the final nanolattice architecture, their sequences have so far remained unknown. By leveraging RNA-seq and proteomic techniques, we identified a cohort of nanolattice-forming proteins comprising a collagenous midblock flanked by domains typically associated with innate immunity and network-forming collagens. Structurally homologous proteins were found in the genomes of other egg-case-producing cartilaginous fishes, suggesting a conserved molecular self-assembly strategy. The identity and stabilizing role of cross-links were subsequently elucidated using mass spectrometry and in situ small-angle X-ray scattering. Our findings provide a new design approach for protein-based liquid crystalline elastomers and the self-assembly of nanolattices.

3,4,5-Trimethoxybenzoate of Catechin, an Anticarcinogenic Semisynthetic Catechin, Modulates the Physical Properties of Anionic Phospholipid Membranes

3,4,5-Trimethoxybenzoate of catechin (TMBC) is a semisynthetic catechin which shows strong antiproliferative activity against malignant melanoma cells. The amphiphilic nature of the molecule suggests that the membrane could be a potential site of action, hence the study of its interaction with lipid bilayers is mandatory in order to gain information on the effect of the catechin on the membrane properties and dynamics. Anionic phospholipids, though being minor components of the membrane, possess singular physical and biochemical properties that make them physiologically essential. Utilizing phosphatidylserine biomimetic membranes, we study the interaction between the catechin and anionic bilayers, bringing together a variety of experimental techniques and molecular dynamics simulation. The experimental data suggest that the molecule is embedded into the phosphatidylserine bilayers, where it perturbs the thermotropic gel to liquid crystalline phase transition. In the gel phase, the catechin promotes the formation of interdigitation, and in the liquid crystalline phase, it decreases the bilayer thickness and increases the hydrogen bonding pattern of the interfacial region of the bilayer. The simulation data agree with the experimental ones and indicate that the molecule is located in the interior of the anionic bilayer as monomer and small clusters reaching the carbonyl region of the phospholipid, where it also disturbs the intermolecular hydrogen bonding between neighboring lipids. Our observations suggest that the catechin incorporates well into phosphatidylserine bilayers, where it produces structural changes that could affect the functioning of the membrane.

Interaction of Docetaxel with Phosphatidylcholine Membranes: A Combined Experimental and Computational Study

The antineoplastic drug Docetaxel is a second generation taxane which is used against a great variety of cancers. The drug is highly lipophilic and produces a great array of severe toxic effects that limit its therapeutic effectiveness. The study of the interaction between Docetaxel and membranes is very scarce, however, it is required in order to get clues in relation with its function, mechanism of toxicity and possibilities of new formulations. Using phosphatidylcholine biomimetic membranes, we examine the interaction of Docetaxel with the phospholipid bilayer combining an experimental study, employing a series of biophysical techniques like Differential Scanning Calorimetry, X-Ray Diffraction and Infrared Spectroscopy, and a Molecular Dynamics simulation. Our experimental results indicated that Docetaxel incorporated into DPPC bilayer perturbing the gel to liquid crystalline phase transition and giving rise to immiscibility when the amount of the drug is increased. The drug promotes the gel ripple phase, increasing the bilayer thickness in the fluid phase, and is also able to alter the hydrogen-bonding interactions in the interfacial region of the bilayer producing a dehydration effect. The results from computational simulation agree with the experimental ones and located the Docetaxel molecule forming small clusters in the region of the carbon 8 of the acyl chain palisade overlapping with the carbonyl region of the phospholipid. Our results support the idea that the anticancer drug is embedded into the phospholipid bilayer to a limited amount and produces structural perturbations which might affect the function of the membrane.Graphical

Volatility Transition from Short‐Term to Long‐Term Photonic Transistor Memory by Using Smectic Liquid Crystalline Molecules as a Floating Gate

AbstractRod‐like molecules with liquid crystalline phase transitions show highly ordered stacking and orientation, which is promising as the floating gate electret in high‐performance photonic field‐effect transistor (FET) memory. In this work, a series of rod‐like molecules, alkyl‐dinaphtho[2,3‐b:2′,3′‐f]thieno[3,2‐b]thiophene (Cn‐DNTT), are investigated with a smectic liquid crystalline phase transition. The photonic FET memory featuring these rod‐like molecules is correlated with their morphology and crystallographic properties. A volatility transition from short−term to long−term memory behavior is found by utilizing the smectic liquid crystalline phase transitions (SmX, X = H, K, E) to orient the stacking in the floating gate. Accordingly, the annealed 2,9‐didecyldinaphtho[2,3‐b:2′,3′‐f]thieno[3,2‐b]thiophene (C10‐DNTT) polycrystalline film with the optimized alkyl chain length achieved preferential end‐on orientation associated with the herringbone‐type stacking to store charges during photowriting, along with effective charge tunneling for the trapped charges during electrical erasing. Therefore, the resultant photonic FET memory provided a superior ON/OFF current ratio of up to 105 with retention of 104 after 104 s. The results demonstrate that rod‐like molecules with smectic liquid crystalline phase and highly ordered orientation have great potentials for developing high‐performance photonic FET memory.

Influence of molecular architecture, hydrogen bonding, chemical moieties and flexible chain for smectic polymorphism in (4)EoBD(3)AmBA:nOBAs

A novel series of calamitic, complementary hydrogen-bonded (HB), meta-extended Schiff base core containing liquid crystalline (LC) complexes with ethoxy chain at one end and varied flexible chain at other end, viz., (4)EoBD(3)AmBA:nOBAs for n = 3–12 is reported. 1H, 13C NMR and FTIR spectroscopy confirm complex formation. LC phases, phase transition temperatures (T C) and enthalpy are characterized by polarizing optical microscopy and differential scanning calorimetry(DSC). SmA, SmC, SmBcryst,SmF, SmI, SmE, SmG and SmH phases are exhibited. Clearing and melting temperatures exhibit odd–even effect. Schiff base bridged by oxygen atom promoted of smectic phase occurrence. Complementary HB-induced and -enhanced tilted smectic phase range. Large LC phase variants, i.e., tetra, penta and hexa are observed. Hexa LC phase variant for n = 6 and 12. Unlike in p-n-alkoxy benzoic acids (nOBAs), Nematic phase is quenched. Quasi two-dimensional LC SmF and SmI phases identified. Lower (for n = 3,5), intermediate (for n = 6,7) and higher (n = 9) homologues exhibit 3D SmBcryst phase. Monotropic LC phase occurrence is also noticed. Apart from other LC phase transitions, SmA–SmC transition is mostly found to be second order or very weakly first order nature. Phase diagram by DSC infers existence of multi-critical points in the vicinity of SmF and SmI phase structures with psuedo hexagonal packing. Influence of meta-extended core, complementary HB and flexibility component are discussed for LC phase abundance. Role of orientational disorder induced by flexible component discussed. In comparison with LC phase occurrence in (4)MeoBD(3)AmBA:nOBAs, shielded inductomeric effect is argued for large thermal range of tilted smectic phases. Integrated and differential heat energies are estimated in successive heating and cooling scans to investigate optimized realization of LC phases. Results are discussed in the wake of contemporary reports in other LCs.

Geometric features in lyotropic liquid crystalline phase transitions observed in aqueous surfactant systems

Lyotropic liquid crystalline phases are widely known to be formed in aqueous surfactant mixtures. Although the phase behavior of several surfactants has been elucidated in the past years, a striking absence of detailed discussion on how molecular geometric parameters vary as different liquid crystals are formed is consistently seen in literature. The current work aimed to partially fill this gap, by determining how several structural parameters changed in a variety of phase transitions previously observed in aqueous surfactant binary and ternary mixtures. The main findings reveal that the cell parameter dimensions are strongly correlated with the packing fraction of small aggregates in each phase; the folding and interpenetration of surfactant hydrocarbon chains are most likely to happen in phases with lower curvature, and can greatly affect other structural parameters; added components can alter the aqueous surfactant phase behavior at different extents; and highly ordered phases are favored by a substantial decrease in the cross-sectional areas per surfactant; among others. The obtained results enable important knowledge on lyotropic liquid crystal formation, in addition to providing detailed information on how to control and obtain such phases, thus prospecting new insights in areas where they are highly desired.

Annealing Process Dependence of the Self-Assembly of Rod–Coil Block Copolymer Thin Films

Thermal annealing, solvent vapor annealing, and a two-step solvent plus thermal annealing are applied to a series of silicon-containing rod–coil thermotropic liquid crystalline (LC) block copolymer thin films with LC volume fractions of 0.42–0.85. Solvent vapor annealing using selective solvents of acetone and heptane produced a wide range of ordered nanostructures with small feature sizes, such as sub-10 nm cylinders, gyroids, and spheres. Subsequent thermal annealing yields final morphologies that depend on the initial morphology and the thermotropic LC phase transition. Combined thermal and solvent annealing as well as design of the rod and coil volume fractions provides an effective way to control the morphologies of rod–coil block copolymers.

Studies on birefringence, order parameter and image analysis of liquid crystalline p-n butyloxy/butyl benzoic acid with dispersed ZnO nanoparticles

Abstract ZnO nanoparticles (nps) have wide range of applications and improve the optical parameters of molecules of soft liquid crystalline (LC) materials. The present paper mainly discusses the optical studies on LC materials regarding p-n-butyloxybenzoic acid (4oba) and p-n-butylbenzoic (4ba) compound along with homogeneous dispersion of ZnO nps in lower weight concentration, i.e., 1, 1.5, 2 and 2.5 wt%. The existence and size of ZnO nps in LC compounds are well determined through spectroscopic techniques such as scanning electron microscopy (SEM) and X-ray diffraction (XRD). The temperatures of LC compounds and phase transitions are determined by using polarizing optical microscopy (POM) and differential scanning calorimetry (DSC) which is found to decrease with increasing concentration of dispersed ZnO nps. Image enhancement with visual quality matrix method is used to improve the quality of the image. Specially designed wedge-shaped modified spectrometer is used to determine the refractive indices with different wavelengths (460, 500, 570 and 635 nm). The refractive indices measured are fitted with two and three coefficient Cauchy model. Further, the order parameter S of the molecules of 4ba and 4oba with dispersed ZnO nps are determined by molecular field models namely Kuczynski, Vuks and effective geometry model, respectively. From the data, it is found that the values of birefringence (δn) and order parameter (S) of the molecules of 4oba and 4ba are enhanced with the dispersion of ZnO nps with increasing weight concentrations in the stabilized nematic thermal region.

Acceleration of Liquid-Crystalline Phase Transition Simulations Using Selectively Scaled and Returned Molecular Dynamics.

The molecular dynamics (MD) technique to accelerate simulation of phase transition to liquid-crystalline (LC) phases is demonstrated on the model LC system 4-octyl-4'-cyanobiphenyl (8CB) smectic A phase. Simulation of a phase transition to a smectic phase is challenging because an intrinsically long simulation time and large system size are required owing to the high order and low onset temperature. Acceleration of the simulated transition of 8CB to the smectic A phase was ultimately achieved by selectively weakening the intermolecular Lennard-Jones interaction of alkyl chains and then returning the scaled interaction to the unscaled one. The total time needed to form the smectic A phase using selectively scaled and returned molecular dynamics (ssrMD) was five times shorter than that when using unscaled MD. Formation of the smectic A phase occurred only when induced polarization from the antiparallel dipole dimer point charge was included in the simulation. The use of ssrMD presented herein is anticipated to accelerate the theoretical development of self-assembled organic materials containing both rigid and flexible moieties, including LC materials.

Investigation and Control of Charge Transport Anisotropy in Highly Oriented Friction-Transferred Polythiophene Thin Films.

Highly oriented thin films of poly[2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2-b]thiophene] (PBTTT) were prepared by friction-transfer technique followed by their characterization using polarized absorption spectroscopy, angle-dependent polarized Raman spectroscopy, and X-ray diffraction (XRD) techniques. Orientation in high-molecular-weight (MW) polymers is hampered by chain folding or entanglements, which limit their macromolecular orientation. Interestingly, utilizing high-molecular-weight PBTTT (MW > 50 kDa) and friction-transfer technique, successful fabrication of highly oriented thin films with very high dichroic ratio (∼30) was demonstrated. The role of the substrate's surface energy and its impact on the field-effect mobility (μ) of the oriented thin films were comprehensively investigated. The influence of annealing the thin films as prepared on the bare and self-assembled monolayer (SAM)-treated SiO2 surfaces exhibiting differential trends of μ was systematically investigated. This was explained by partial and complete conformational transformation of macromolecules on bare and SAM-treated SiO2 surfaces, respectively, after annealing them beyond liquid crystalline phase transition temperature, as revealed by in-plane and out-of-plane XRD results. On bare SiO2, optimum μ up to 0.03 cm2 V-1 s-1 along the backbone orientation was obtained for the thin films annealed to 120 °C; whereas, it reached up to 0.36 cm2 V-1 s-1 on SAM-treated SiO2 after annealing at 200 °C. Finally, a charge transport mechanism was proposed taking evidence from the anisotropic optical and electrical characteristics of the friction-transferred PBTTT films into consideration.

IMAGE ANALYSIS STUDIES IN RE-ENTRANT SMC PHASE ON HYDROGEN BONDED LIQUID CRYSTAL SA:10OBA

Ponte Academic JournalFeb 2020, Volume 76, Issue 2 IMAGE ANALYSIS STUDIES IN RE-ENTRANT SMC PHASE ON HYDROGEN BONDED LIQUID CRYSTAL SA:10OBAAuthor(s): K. Lakshmi Sarada ,A.V.N.Ashok Kumar, K. Mallika, S. Sreehari SastryJ. Ponte - Feb 2020 - Volume 76 - Issue 2 doi: 10.21506/j.ponte.2020.2.15 Abstract:Image analysis using MATLAB software for characterization of liquid crystalline (LC) phases and phase transition temperatures in hydrogen bonded liquid crystal dimer viz., Succinic acid (SA) (for n=10) with molecular formula nOBA:SA:nOBA is described. SmC, SmX, SmCRE and SmG phase variance is observed by optical textures through Polarized Optical Microscope and which are confirmed by Differential Scanning Calorimetry experimental technique. Influence of flexible end chain length and length of spacer moiety on the LC polymorphism is studied and the results are compared with reports on other HBLC dimers with similar type of molecular structure. Statistical parameters of LC textures based on gray scale intensity as a function of temperature are computed and discussed. Download full text:Check if you have access through your login credentials or your institution Username Password