Rod-like Molecules Research Articles

Clusters of B7 Fibers Reveal Origin of Blue Phase Stability in a Binary Mixture of Chiral Rod-like and Achiral Bent-Core Molecules.

Liquid crystal (LC) blue phases (BPs) have gained relevance because of their potential applicability as tunable photonic band gap materials. However, their narrow temperature range often restricts technical usage. Doping with an LC made of achiral bent-core (BC) molecules is one of the strategies employed to increase BP stability. It is now shown that mixing a BCLC exhibiting the polarization-modulated lamellar B7 phase, with a calamitic chiral LC made of rod-like (R) molecules, enhances the BP range considerably. The special feature in this system is the spontaneous expulsion of clusters of B7 fibers in the chiral nematic (N*) phase occurring below the BPs. This gives a clear indication that islands rich in BC molecules lie interspersed between the R molecules. Based on several experimental studies, it is shown that the BP stability may be attributed to an interplay of conformational and intrinsic chirality of the BC and R molecules across the interface of these islands. This study provides new insights from a molecular point of view and provides a novel technique for designing stable-induced BPs. The additional novelty is the occurrence of a phase transition within the fibers. Further, the electro-responsive fibers may also have a potential to form new materials.

Breaking Parallel Orientation of Rods via a Dendritic Architecture toward Diverse Supramolecular Structures.

Self-assembled nanostructures of rod-like molecules are commonly limited to nematic or layered smectic structures dominated by the parallel arrangement of the rod-like components. Distinct self-assembly behavior of four categories of dendritic rods constructed by placing a tri(hydroxy) group at the apex of dendritic oligo-fluorenes is observed. Designed hydrogen bonding and dendritic architecture break the parallel arrangement of the rods, resulting in molecules with specific (fan-like or cone-like) shapes. While the fan-shaped molecules tend to form hexagonal packing cylindrical phases, the cone-shaped molecules could form spherical motifs to pack into various ordered structures, including the Frank-Kasper A15 phase and dodecagonal quasicrystal. This study provides a model system to engineer diverse supramolecular structures by rod-like molecules and sheds new light into the mechanisms of the formation of unconventional spherical packing structures in soft matter.

Machine learning topological defects of confined liquid crystals in two dimensions.

Supervised machine learning can be used to classify images with spatially correlated physical features. We demonstrate the concept by using the coordinate files generated from an off-lattice computer simulation of rodlike molecules confined in a square box as an example. Because of the geometric frustrations at high number density, the nematic director field develops an inhomogeneous pattern containing various topological defects as the main physical feature. We describe two machine-learning procedures that can be used to effectively capture the correlation between the defect positions and the nematic directors around them and hence classify the topological defects. First is a feedforward neural network, which requires the aid of presorting the off-lattice simulation data in a coarse-grained fashion. Second is a recurrent neural network, which needs no such sorting and can be directly used for finding spatial correlations. The issues of when to presort a simulation data file and how the network structures affect such a decision are addressed.

Elastic colloidal monopoles and reconfigurable self-assembly in liquid crystals.

Monopole-like electrostatic interactions are ubiquitous in biology1 and condensed matter2-4, but they are often screened by counter-ions and cannot be switched from attractive to repulsive. In colloidal science, where the main goal is to develop colloidal particles2,3 that mimic and exceed the diversity and length scales of atomic and molecular assembly, electrostatically charged particles cannot change the sign of their surface charge or transform from monopoles to higher-order multipoles4. In liquid-crystal colloids5-7, elastic interactions between particles arise to minimize the free energy associated with elastic distortions in the long-range alignment of rod-like molecules around the particles5. In dipolar6,8, quadrupolar8-12 and hexadecapolar13 nematic colloids, the symmetries of such elastic distortions mimic both electrostatic multipoles14 and the outermost occupied electron shells of atoms7,15,16. Electric and magnetic switching17,18, spontaneous transformations19 and optical control20 of elastic multipoles, as well as their interactions with topological defects and surface boundary conditions, have been demonstrated in such colloids21-23. However, it has long been understood5,24 that elastic monopoles should relax to uniform or higher-order multipole states because of the elastic torques that they induce5,7. Here we develop nematic colloids with strong elastic monopole moments and with elastic torques balanced by the optical torques induced by ambient light. We demonstrate the monopole-to-quadrupole reconfiguration of these colloidal particles by unstructured light, which resembles the driving of atoms between the ground state and various excited states. We show that the sign of the elastic monopoles can be switched, and that like-charged monopoles attract whereas oppositely charged ones repel, unlike in electrostatics14. We also demonstrate the out-of-equilibrium dynamic assembly of these colloidal particles. This diverse and surprising behaviour is explained using a model that considers the balance of the optical and elastic torques that are responsible for the excited-state elastic monopoles and may lead to light-powered active-matter systems and self-assembled nanomachines.

Self-Assembly of Diacetylene-Bridged Phenylenevinylene Oligomers in Water and Organic Solvents.

Rodlike π-conjugated molecules in which two OPV fragments are connected through a diacetylene bond self-assemble in aqueous and organic media. Optical spectroscopy and AFM measurements indicated that, in water, strong hydrophobic interactions between π-cores promote aggregation into robust, uniform micellar structures. In contrast, in apolar solvents, a fibrilar morphology is obtained by coiling of columnar stacks. These stacks are formed in a nucleation-elongation process with degrees of cooperativity of 0.006, that is influenced by the low rotation barriers around the σ-bonds in the diacetylene linker.

Does Introduction of a Bent Tail Stabilize Biaxiality and Lateral Switching Behavior of Smectic A Liquid Crystal Phases of Rodlike Molecules?

By introducing an oleyl group at the end of the straight rodlike molecule, the effect of the tail shape on the liquid crystallinity, biaxiality, and lateral switching behavior of the smectic A phase was investigated. Three types of molecules possessing a fluorinated phenyl (pentafluorophenyl, 2,3,4-trifluorophenyl, or 2,3-difluorophenyl) group and a cis-octadec-9-enyl group were synthesized, and their liquid crystallinities were compared with the corresponding molecules with a straight alkyl ( trans-octadec-9-enyl or n-octadecanyl) group. In switching experiments, the molecules with a bent terminal chain showed higher spontaneous polarization ( Ps) values than those with a straight terminal chain. Further, the directional changes of the long molecular axes were suppressed for the molecules possessing a bent terminal chain. These results show that the introduction of a bent terminal chain is highly effective for stabilizing ferroelectric switching behaviors.

Wide temperature range of an electrically tunable selective reflection of light by oblique helicoidal cholesteric

ABSTRACTOblique helicoidal cholesteric liquid crystals (ChOH) offer an unprecedented opportunity to tune selective reflection of light in a broad spectral range from ultraviolet to infrared by an electric field. The major problem is that the temperature range of stable ChOH is typically above the room temperature and is relatively narrow, a few degrees. In this work, we demonstrate that by using a mixture of flexible dimeric and rod-like molecules, one can significantly expand the temperature range of intense Bragg reflection, from 16°C to 27°C. We demonstrate that the selective reflection peak, reflection intensity, bandwidth and threshold electric field are all temperature dependent and discuss the associated mechanisms. The results show that both the electric field and temperature can be used to tune the structural colour of oblique helicoidal cholesteric structures. The proposed material can be used in switchable optical devices based on liquid crystals, such as light modulators, indoor smart windows, and filters.

Tunable Twisting Motion of Organic Linkers via Concentration and Hydrogen-Bond Formation

Benzothiadiazole dibenzoic acid (BTDB) derivative is a well-known organic linker in various metal–organic framework structures as well as a fluorescent probe in biological systems. Here, we demonstrate that the radiative and nonradiative decay channels of BTDB can be interplayed and precisely controlled through concentration and hydrogen-bond interactions as directly evidenced experimentally and theoretically. This leads to excited-state structural changes that significantly suppress the torsional motion around the benzothiadiazole moiety, leading to an enormous increase in the emission quantum yields from ∼1 to 70%. These changes are associated with the existence of two equilibria, where dimers and small oligomers form in dimethylformamide (DMF), with high formation constants of 18 000 M–1 and 1.2 × 1013 M–3, respectively. These evolving species, i.e., the dimers and oligomers, are formed via hydrogen bonds between carboxylic acid groups present at the far edge of the rodlike BTDB molecules. The estimated repeating number for this small-oligomer formation via bonded monomers is eight in DMF, as shown by emission spectra analysis. With deprotonation as a control experiment, these associated species can easily collapse with the initial monomer species, confirming the role of the hydrogen-bond formation in the observed phenomena. Theoretical studies and NMR experiments not only confirm the existence of the dimers, but also demonstrate the important role of the hydrogen bonds in the excited-state dynamics. These new findings provide a better understanding of the photophysical behaviors of organic linkers used in a wide range of chemical and biological applications.

An Ising transition of chessboard tilings in a honeycomb liquid crystal

Rod-like molecules with two disparate side-chains self-assemble as square honeycomb undergoing a demixing Ising-type transition from single-coloured to two-coloured tiling.

A new member of a class of rod-like Mn12 single molecule magnets using 2-(pyridine-2-ly)propan-2-ol.

This paper reports on the synthesis, structure and magnetic properties of a new type of rod like Mn12 metal cluster, [Mn12O7(OH)2(OMe)2(dmhmp)4(O2CPh)11(H2O)] (6) where the ligand (dmhmpH) is 2-(pyridine-2-yl)propan-2-ol. Compound (6) was obtained by reacting MnCl2·4H2O with dmhmpH in the presence of benzoic salt and Et3N. The resulting crystalline material is assigned to the triclinic space group P1̄. Although compound (6) displays ferromagnetic and antiferromagnetic competition behavior, this does not prevent the molecule from functioning as a single-molecule magnet (SMM). The SMM behavior is evidenced by observing frequency dependent out-of-phase ac signals as well as magnetization hysteresis loops at low temperatures in a micro-SQUID study. A brief comparison between all rod-like Mn12 materials is also given in the manuscript.

Aggregation of Influenza A Virus Nuclear Export Protein.

Influenza A virus nuclear export protein (NEP) plays an important role in the viral life cycle. Recombinant NEP proteins containing (His)6-tag at either N- or C-terminus were obtained by heterologous expression in Escherichia coli cells and their high propensity for aggregation was demonstrated. Dynamic light scattering technique was used to study the kinetics and properties of NEP aggregation in solutions under different conditions (pH, ionic strength, presence of low-molecular-weight additives and organic solvents). Using atomic force microscopy, the predominance of spherical aggregates in all examined NEP preparations was shown, with some amyloid-like structures being observed in the case of NEP-C protein. A number of structure prediction programs were used to identify aggregation-prone regions in the NEP structure. All-atom molecular dynamics simulations indicate a high rate of NEP molecule aggregation and reveal the regions preferentially involved in the intermolecular contacts that are located at the edges of the rod-like protein molecule. Our results suggest that NEP aggregation is determined by different types of interactions and represents an intrinsic property of the protein that appears to be necessary for its functioning in vivo.

On the stationary solutions of Doi–Onsager model in general dimension

We give new results of the phase transition of dilute colloidal solutions of rod-like molecules in dimension D≥3. For the low concentration of particles in a carrier fluid, we prove that the isotropic phase is the unique solution to the Doi–Onsager model with the general potential kernel. In addition, we present the regime of the bifurcation of nematic phases in the class of axially symmetric solutions. Our method is based on a generalization of the classical Leray–Schauder degree we developed for this problem.

Tunable colloid trajectories in nematic liquid crystals near wavy walls

The ability to dictate the motion of microscopic objects is an important challenge in fields ranging from materials science to biology. Field-directed assembly drives microparticles along paths defined by energy gradients. Nematic liquid crystals, consisting of rod-like molecules, provide new opportunities in this domain. Deviations of nematic liquid crystal molecules from uniform orientation cost elastic energy, and such deviations can be molded by bounding vessel shape. Here, by placing a wavy wall in a nematic liquid crystal, we impose alternating splay and bend distortions, and define a smoothly varying elastic energy field. A microparticle in this field displays a rich set of behaviors, as this system has multiple stable states, repulsive and attractive loci, and interaction strengths that can be tuned to allow reconfigurable states. Microparticles can transition between defect configurations, move along distinct paths, and select sites for preferred docking. Such tailored landscapes have promise in reconfigurable systems and in microrobotics applications.

Electric switching of visible and infrared transmission using liquid crystals co-doped with plasmonic gold nanorods and dichroic dyes.

Smart windows and many other applications require synchronous or alternating facile electric switching of transmitted light intensity in visible and near infrared spectral ranges, but most electrochromic devices suffer from slow, nonuniform switching, high power consumption and limited options for designing spectral characteristics. Here we develop a guest-host mesostructured composite with rod-like dye molecules and plasmonic nanorods spontaneously aligned either parallel or orthogonally to the director of the liquid crystal host. This composite material enables fast, low-voltage electric switching of electromagnetic radiation in visible and infrared ranges, which can be customized depending on the needs of applications, like climate-dependent optimal solar gain control in smart windows.

Disclinations without gradients: A nonlocal model for topological defects in liquid crystals

Nematic liquid crystals composed of rod-like molecules have an orientational elasticity that accounts for the energetics of the molecular orientation. This elasticity can be described by a unit vector field; the unit vector constraint interacts with even fairly simple boundary conditions to cause disclination defects. Disclinations are entirely a topological consequence of the kinematic constraint, and occur irrespective of the particular energetic model. Because disclinations are topological defects, they cannot be regularized by adding higher gradients, as in phase-field models of interface defects. On the contrary, the higher gradient terms would cause even greater singularities in the energy. In this paper, we formulate an integral-based nonlocal regularized energy for nematic liquid crystals. Our model penalizes disclination cores and thereby enforces a finite width, while the integral regularization ensures that the defect core energy is bounded and finite. The regularization at the same time tends to the standard gradient-based energies away from the disclination, as well as building in the head-tail symmetry. We characterize the formulation in its ability to describe disclinations of various strengths, and then apply it to examine: (1) the stability and decomposition of various disclinations, and the competition between bend and splay energies in determining the relative stability of integer and half-integer disclinations (2) the coalescence of a +12 and−12 disclination pair; we find the disclinations do not move at the same velocities towards each other, suggesting that the asymmetry of the director field plays a dominant role despite the equal-and-opposite topological strengths of the disclinations.

Electrochemical Properties of Li1.3Al0.3Ti1.7(PO4)3-Filled Composite Polymer Gel Electrolytes of Pvdf-HFP and Hydroxypropylcellulose

The composite polymer gel electrolytes (CPGE) for lithium-ion batteries are prepared by combining poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP) and hydroxypropylcellulose (HPC) as binary polymer components, Li1.3Al0.3Ti1.7(PO4)3 (LATP) as an inorganic filler, and 1 M LiPF6 dissolved in EC:PC:EMC as an electrolyte solution. The PVdF-HFP is included as a linear flexible polymer chain in the electrolyte medium, the rigid rod-like molecules of HPC has the lyotropic property between liquid crystalline and isotropic phases, and the LATP supports mechanical strength and also provides another conduction path in the gel medium [1] to increase ionic conductivity. The synergy among each component is expected to lead highly ionic conductive electrolytes with excellent mechanical strength. In this study, the electrochemical properties of LATP-filled CPGE are investigated and the charge-discharge performance of LiCoO2/graphite lithium-ion battery cell adopting the CPGE is also carried out. Through such the electrochemical investigations, the optimum amount of LATP showing the best performance would be mainly determined. Moreover, the low-temperature performance of the LiCoO2/CPGE/graphite cell would be particularly examined because the LATP(50 wt.)-filled CPGE (polymer 100 wt.) exhibits higher ionic conductivity (e.g., 4x10-3 S/cm) at low temperature (e.g., -10oC), compared with the CPGE without LATP (3.6x10-4 S/cm). In the presentation, how each component and its content contribute to the electrochemical performance of the cell would also be discussed in detail. Figure 1

Extended and Modulated Thienothiophenes for Thermally Durable and Solution-Processable Organic Semiconductors

Herein, we report the rational design of practical small-molecule organic semiconductors based on a π-electron skeleton of benzothieno[3,2-b]naphtho[2,3-b]thiophene (BTNT) whose layered herringbone (LHB) packing is intentionally modulated by the designated asymmetric substitutions with the phenyl group and normal alkyl chains. The thermal stability of the hybrid BTNT core is high enough, as it lies between those of dinaphtho[2,3-b:2′,3′-f]thieno[3,2-b]thiophene (DNTT) and benzothieno[3,2-b]benzothiophene (BTBT), although the solvent solubility for the substituted BTNT at ordinary 2,8-substituting positions by the alkyl chain and phenyl group remains extremely low. We show in the BTBT and BTNT derivatives that the tuning of the substituting position works to slightly bend the rodlike organic semiconductor molecules and thus to decrease the cohesive energy of the crystals with retention of the bilayer-type herringbone (b-LHB) packing for the asymmetric rodlike molecules. This modification eventually leads to an increase in solvent solubility, a decrease in phase transition temperature, and the suppression of liquid-crystalline phases at high temperatures. By using the substituting effect, we successfully achieve the organic semiconductors with modulated alkylated Ph-BTNT that exhibits both a sufficiently high solvent solubility and a sufficiently high thermal stability. The variation in the crystal packing also enhances the intermolecular transfer integrals along the T-shaped contacts within the intralayer herringbone packing. Spin coating of the material under ambient conditions affords high-performance bottom-gate, bottom-contact organic thin-film transistors, exhibiting high thermal durability in the device characteristics below 150 °C. The obtained devices also exhibit a higher mobility, a lower threshold voltage, and a smaller subthreshold swing, by initial thermal treatment at 140 °C, composed to those of the as-prepared films, because the thermal treatment stabilizes the b-LHB packing and thus suppresses the residual minority holes and shallow traps. These findings should be crucial in the design and development of organic semiconductor materials for practical printed electronics applications.

On the orientational distribution functions in de Vries-type smectic liquid crystals

ABSTRACTIn de Vries smectic liquid crystals, the transition from the orthogonal smectic A (SmA) to the tilted smectic C (SmC) phase occurs with essentially no decrease in smectic layer thickness. This unusual behaviour is commonly explained assuming a ‘hollow-cone’ or ‘volcano-like’ orientational distribution function (ODF) of rod-like molecules in SmA and the transition to SmC being a pure disorder–order transition in the molecular tilt directions. However, even after 20 years of extensive investigations, the experimental confirmation of this ad hoc model is still inconclusive. While optical and electro-optic studies of many de Vries smectics can be readily explained with the hollow-cone model, X-ray diffraction (XRD) studies as well as many polarised Raman spectroscopy (PRS) studies support a broad Maier–Saupe distribution of a sugarloaf-like shape. We review and summarise X-ray, electro-optic and PRS results on the ODFs in the SmA phases of materials claimed to be of the de Vries type and discuss how seemingly contradicting findings can be true at the same time. In molecules where the core is far from collinear with the long molecular axis, the cores may exhibit a volcano ODF while the molecular axes exhibit a sugarloaf ODF.

Identification and characterization of GRIP domain Golgin PpImh1 from Pichia pastoris.

Budding yeast Pichia pastoris has highly advanced secretory pathways resembling mammalian systems, an advantage that makes it a suitable model system to study vesicular trafficking. Golgins are large Golgi-resident proteins, primarily reported to play role in cargo vesicle capture, but details of such mechanisms are yet to be deciphered. Golgins that localize to the Golgi via their GRIP domain, a C-terminal Golgi anchoring domain, are known as GRIP domain Golgins. In this present study, we have identified and functionally characterized a homologue of one such GRIP domain Golgin protein, Imh1, from the budding yeast P. pastoris. We have demonstrated that the GRIP domain present at the C-terminal of P. pastoris Imh1 (PpImh1) functions as its Golgi-targeting sequence. Using a combination of yeast two-hybrid analysis, dynamic light scattering and electron microscopy, we have shown that PpImh1 can self-associate and form a homodimer. Analysis of purified recombinant PpImh1 by CD spectroscopy indicates the presence of an 85% α-helical structure, a characteristic of high-content α-helical coiled-coil sequences normally present in other Golgin family proteins. Two-hybrid analysis indicated self-interaction between C-terminal fragments, yet N-terminal fragments do not mediate any such form of self-interaction, suggesting that PpImh1 may form a parallel dimer. Electron microscopy data indicates that PpImh1 forms extended rod-like homo-dimeric molecules with splayed N-terminal end which can act as a tether for capturing vesicles. Our study provides the first evidence in support of the dimeric Y-shaped structure for any Golgin in the budding yeast.

Stochastically pumped adaptation and directional motion of molecular machines

Recent developments in synthetic molecular motors and pumps have sprung from a remarkable confluence of experiment and theory. Synthetic accomplishments have facilitated the ability to design and create molecules, many of them featuring mechanically bonded components, to carry out specific functions in their environment—walking along a polymeric track, unidirectional circling of one ring about another, synthesizing stereoisomers according to an external protocol, or pumping rings onto a long rod-like molecule to form and maintain high-energy, complex, nonequilibrium structures from simpler antecedents. Progress in the theory of nanoscale stochastic thermodynamics, specifically the generalization and extension of the principle of microscopic reversibility to the single-molecule regime, has enhanced the understanding of the design requirements for achieving strong unidirectional motion and high efficiency of these synthetic molecular machines for harnessing energy from external fluctuations to carry out mechanical and/or chemical functions in their environment. A key insight is that the interaction between the fluctuations and the transition state energies plays a central role in determining the steady-state concentrations. Kinetic asymmetry, a requirement for stochastic adaptation, occurs when there is an imbalance in the effect of the fluctuations on the forward and reverse rate constants. Because of strong viscosity, the motions of the machine can be viewed as mechanical equilibrium processes where mechanical resonances are simply impossible but where the probability distributions for the state occupancies and trajectories are very different from those that would be expected at thermodynamic equilibrium.