Designing a Magnesium/Sodium Hybrid Battery Using Hierarchical Iron Selenide Architecture as Cathode Material and Modified Dual-Ion Salts in Ether as Electrolyte.

We developed a magnesium/sodium (Mg/Na) hybrid battery using a hierarchical disk-whisker FeSe2 architecture (HD-FeSe2) as the cathode material and a modified dual-ion electrolyte. The polarizable Se2- anion reduced the Mg2+ migration barrier, and the 3D configuration possessed a large surface area, which facilitated both Mg2+/Na+ cation diffusion and electron transport. The dual-ion salts with NaTFSI in ether reduced the Mg plating/stripping overvoltage in a symmetric cell. The hybrid battery exhibited an energy density of 260.9 Wh kg-1 and a power density of 600.8 W kg-1 at 0.2 A g-1. It showed a capacity retention of 154 mAh g-1 and a Coulombic efficiency of over 99.5% under 1.0 A g-1 after 800 long cycles. The battery also displayed outstanding temperature tolerance. The findings of 3D architecture as cathode material and hybrid electrolyte provide a pathway to design a highly reliable Mg/Na hybrid battery.

Orientational transitions of discotic columnar liquid crystals in cylindrical pores.

Confined in a cylindrical pore with homeotropic anchoring condition, the hexagonal columnar phase of discotic liquid crystals can form a "log-pile" configuration, in which the columns are perpendicular to the long axis of the pore. However, the {100} planes of the hexagonal lattice can orient either parallel (termed (100)‖ orientation) or perpendicular ((100)⊥) to pore axis. Here we experimentally show that the (100)‖ orientation is found in narrower cylindrical pores, and the (100)‖-(100)⊥ transition can be controlled by engineering the structure of the molecules. The (100)‖ orientation is destroyed in asymmetric discotics hepta(heptenyloxy)triphenylene (SATO7); replacing the oxygen linkage in hexa(hexyloxy)triphenylene (HATO6) by sulphur (HATS6) improves the (100)‖ orientation in small pores; adding a perfluorooctyl end to each alkyl chain of HATO6 (HATO6F8) moves the (100)‖-(100)⊥ transition to larger pores. We have provided a semi-quantitative explanation of the experimental observations, and discussed them in the context of previous findings on related materials in a wider pore size range from 60 nm to 100 µm. This allows us to produce a comprehensive picture of confined columnar liquid crystals whose applications critically depend on our ability to align them.

Assessment of the molecular mechanism in fish using eugenol as anesthesia based on network pharmacology.

Eugenol is a commonly used fish anesthetic, but its mechanism of action is not fully understood. This study employed network pharmacology, molecular docking, and molecular dynamics simulation to explore the anesthetic targets of eugenol in fish. Initially, 63 potential targets for eugenol anesthesia were identified using databases such as SwissTarget, TargetNet, GeneCards, OMIM, and TTD. The DAVID database was utilized to analyze the GO functions and KEGG pathways of these targets, revealing 384 GO enrichment terms and 43 KEGG pathways. These terms involved neuroactive ligand-receptor interaction, calcium signaling pathway, and synaptic transmission. Subsequently, AutodockTools software facilitated molecular docking with targets in the KEGG pathway for "neuroactive ligand-receptor interaction." The results showed that eugenol had a strong affinity with these proteins. Concurrently, molecular dynamics simulations were conducted on the proteins with the top four lowest binding energies (Cnr1, Oprk1, Nr3c1, and Chrm5a) in the presence of eugenol. The eugenol-protein complexes remained stable and equilibrated within the dynamic environment. The results indicated that eugenol-anesthesia might affect membrane receptors, neurotransmitters, and ion signaling. This study elucidates the anesthetic mechanism of eugenol, enriches the primary data on fish anesthesia, and offers new analytical tools for understanding the action mechanisms of fishery drugs.

Supertwisted Chiral Gyroid Mesophase in Chiral Rod-Like Compounds.

Among the intriguing bicontinuous self-assembled structures, the gyroid cubic is the most ubiquitous. It is found in block and star polymers, surfactants with or without solvent, in thermotropic liquid crystals with end- or side-chains, and in biosystems providing structural color and modelling cell mitosis. It contains two interpenetrating networks of opposite chirality and is thus achiral if, as usual, the content of the two nets is the same. However, we now find that this is not the case for strongly chiral compounds. While achiral molecules follow the opposite twists of nets 1 and 2, molecules with a chiral center in their rod-like core fail to follow the 70° twist between junctions in net 2 and instead wind against it by -110° to still match the junction orientation. The metastable chiral gyroid is a high-entropy high-heat-capacity mesophase. The homochirality of its nets makes the CD signal of the thienofluorenone compounds close to that in the stable I23 phase with 3 isochiral nets.

Enantiomers Self-Sort into Separate Counter-Twisted Ribbons of the Fddd Liquid Crystal─Antiferrochirality and Parachirality.

The recently discovered orthorhombic liquid crystal (LC) phase of symmetry Fddd is proving to be widespread. In this work, a chiral hydroxybutyrate linkage is inserted into the molecular core of hexacatenar rodlike compounds, containing a thienylfluorenone fluorophore. In addition to more usual tools, the methods used include grazing-incidence X-ray scattering, modulated differential scanning calorimetry (DSC), flash DSC with rates up to 6000 K/s, and chiro-optical spectroscopies using Mueller matrix method, plus conformational mapping. Although pure R and S enantiomers form only a strongly chiral hexagonal columnar LC phase (Colh*), the racemic mixture forms a highly ordered Fddd phase with 4 right- and 4 left-handed twisted ribbon-like columns traversing its large unit cell. In that structure, the two enantiomers locally deracemize and self-sort into the columns of their preferred chirality. The twisted ribbons in Fddd, with a 7.54 nm pitch, consist of stacked rafts, each containing ∼2 side-by-side molecules, the successive rafts rotated by 17°. In contrast, an analogous achiral compound forms only the columnar phase. The multiple methods used gave a comprehensive picture and helped in-depth understanding not only of the Fddd phase but also of the "parachiral" Colh* in pure enantiomers with irregular helicity, whose chirality is compared to the magnetization of a paramagnet in a field. Unusual short-range ordering effects are also described. An explanation of these phenomena is proposed based on conformational analysis. Surprisingly, the isotropic-columnar transition is extremely fast, completing within ∼20 ms. A clear effect of phase on UV-vis absorption and emission is observed.

Rational engineering NiMoO4nanosheets or Mn3O4nanowires on Fe2O3microdiscs as novel hierarchical anodes for high-performance lithium-ion batteries.

Since current graphite-based lithium-ion battery anode has a low theoretical capacity, the development of high-performance lithium-ion battery is severely restricted. Here, novel hierarchical composites composing of microdisc and the secondarily grown nanosheets and nanowires are developed, taking NiMoO4nanosheets and Mn3O4nanowires growing on Fe2O3microdiscs as demonstrating examples. The growth processes of the hierarchical structures have been investigated by adjusting a series of preparation conditions. The morphologies and structures have been characterized by using scanning electron microscopy, transmission electron microscope and x-ray diffraction. Fe2O3@Mn3O4composite-based anode displays a capacity of 713 mAh g-1after 100 cycles at 0.5 A g-1with a high Coulombic efficiency. A good rate-performance is also achieved. Fe2O3@NiMoO4anode delivers 539 mAh g-1after 100 cycles at 0.5 A g-1, which is obviously higher than that of pure Fe2O3. The hierarchical structure is conducive to improve the transport of electrons and ions, and provide numerous active sites, thus significantly enhancing the electrochemical performance. Moreover, the electron transfer performance is investigated by using density functional theory calculations. It is expected the findings presented here and the rational engineering of nanosheets/nanowires on microdiscs would be applicable for developing many other high-performance energy-storage composites.

Essential oil of Magnolia denudata is an effective anesthetic for spotted seabass (Lateolabrax maculatus): a test of its effect on blood biochemistry, physiology, and gill morphology.

Magnolia denudata is a well-known ornamental tree in China due to its beautiful blossoms, and it has been used as an analgesic to treat human headaches. This study investigated the anesthetic potential and physiological response of the essential oil of M. denudata flowers on spotted seabass Lateolabrax maculatus. Fish (mean ± SD, 164.16 ± 15.40 g) were individually exposed to different concentrations of M. denudata essential oil (MDO, 10, 20, 40, 60, 80, 100, and 120 mg/L) and eugenol (10, 20, 30, 40, 50, 60, and 70 mg/L) to investigate anesthetic efficacy. Based on the ideal time criterion for anesthetic induction (< 3 min) and recovery (< 10 min), the lowest effective concentration for spotted seabass was 100 mg/L for MDO and 60 mg/L for eugenol. The physiological and histopathological damage in the gill of L. maculatus after using MDO and eugenol was also evaluated at the minimum dose inducing deep anesthesia, and at 0, 6, and 24 h after recovery. The results showed that MDO and eugenol anesthesia alleviated the levels of cortisol and glucose and the lactic dehydrogenase activity induced by handling. Compared with eugenol, MDO also caused secondary stress to the body, but MDO caused minor physiological responses and histological changes in the gills. This study suggests that MDO is an effective anesthetic for spotted seabass.

Gyroid-Nanostructured All-Solid Polymer Films Combining High H+ Conductivity with Low H2 Permeability.

Gyroid-nanostructured all-solid polymer films with exceedingly high proton conductivity and low H2 gas permeability have been created via crosslinking polymerization of mixtures of a zwitterionic amphiphilic monomer and a polymerizable imide-type acid that co-organize into bicontinuous cubic liquid-crystalline phases. The gyroid nanostructures are visualized by reconstructing a 3D electron map from the synchrotron X-ray diffraction patterns. These films exhibit high proton conductivity of the order of 10-1 S cm-1 and extremely low H2 gas permeability of the order of 10-15 mol m m-2 s-1 Pa-1 . These properties can be ascribed to the presence of the ionic liquid-like layer along the gyroid minimal surface. Since these two characteristics are required for improving the performance of proton-exchange membrane fuel cells, the present membrane design represents a promising strategy for the development of advanced devices, pertinent to establishing sustainable energy sources.

Liquid Organic Frameworks: The Single-Network "Plumber's Nightmare" Bicontinuous Cubic Liquid Crystal.

Novel bolapolyphiles, built of a p-terphenyl or bistolane core with polar glycerol end-groups and two laterally attached n-alkyl or semiperfluoroalkyl chains, form the first "single plumber's nightmare network", the simplest soft-matter cubic phase (Pm3̅m). Its cage-like grid comprises bundles of aromatic rods lying along the cubic unit cell edges, connected by six-way hydrogen-bonded junctions. Side-chains fill the remaining volume of this unique noninterpenetrating liquid-crystalline organic framework.

Extraordinary Acceleration of Cogwheel Helical Self-Organization of Dendronized Perylene Bisimides by the Dendron Sequence Encoding Their Tertiary Structure.

The cogwheel model of hierarchical self-organization provides a route to highly ordered crystalline helical columnar hexagonal arrays of perylene bisimides (PBIs) conjugated to (3,4,5)-dimethyloctyl (racemic dm8*, r) minidendrons. Cogwheel PBIs assemble with identical structural order irrespective of molecular chirality to generate helical columns jacketed with an alkyl coat with length equal to half the helical pitch, exhibiting helical deracemization in the crystal state. These assemblies were accessible only via annealing or cooling and reheating at 1 °C/min. Recently it was discovered that hybrid rr8 sequence-defined dendrons with r and linear n-octyl (8) chains enabled the formation of the cogwheel phase at 10 °C/min upon heating but not cooling. Here we report four libraries of hybrid PBIs with sequence-defined dendrons containing r and n-alkyl (CnH2n+1) chains with n = 6, 7, 9, and 10. Structural analysis of these libraries by fiber X-ray diffraction and differential scanning calorimetry reveals that the 9r9 sequence enables an extraordinary acceleration of cogwheel assembly at rates of up to 50 °C/min on heating and cooling, providing, to the best of our knowledge, the fastest crystallizing supramolecular or covalent macromolecule known. Solid-state NMR studies help to elucidate this unexpected and unprecedented extraordinary acceleration of hierarchical self-organization, which arises from a combination of crystal packing of the ideal tertiary structure and alkyl chain dynamics. This general model raises questions about the use of achiral motifs to achieve high structural order in chiral systems and the need for disorder to create order in complex biological and bioinspired synthetic systems.

Use of optical coherence tomography angiography for assessment of microvascular changes in the macula and optic nerve head in hypertensive patients without hypertensive retinopathy.

PURPOSE: To compare optical coherence tomography angiography (OCTA) screening parameters of the macula and optic nerve head (ONH) between healthy volunteers and chronic hypertensive patients without hypertensive retinopathy. METHODS: This was an observational, cross-sectional study. Fifty-seven chronic hypertensive patients without hypertensive retinopathy (22 men and 35 women) and 40 healthy volunteers (17 men and 23 women), ranging in age from 60 to 70 years, were included in this study. Patients and volunteers were divided into three groups and one eye was selected randomly from each participant. Group A comprised patients who had a history of hypertension for >10 years (n = 35); Group B comprised patients who had a history of hypertension for 5-10 years (n = 22); and Group C comprised 40 healthy volunteers who had no history of hypertension. A 3 × 3-mm macula scan and a 4.5 × 4.5-mm ONH scan were performed in each group by OCTA using prototype AngioVue software within the AngioVue device. Vessel density (VD), foveal avascular zone (FAZ) area, choriocapillaris flow area, ONH capillary density, retinal nerve fiber layer (RNFL) thickness, and demographic information were compared among the groups. RESULTS: Macula scans showed that superficial plexus VD was significantly lower in groups A and B than in group C (P < 0.05). In addition, FAZ area was significantly larger in group A than in group C (P < 0.05). Inner retinal layer thickness was significantly thinner in groups A and B than in group C (P < 0.05). In ONH scans, RNFL thickness was significantly thinner in group A than in groups B and C (P < 0.05); it was significantly thinner in group B than in group C (P < 0.05). Inside disc capillary density and peripapillary capillary density were significantly lower (P < 0.05) and greater (P < 0.05), respectively, in groups A and B than in group C. CONCLUSIONS: Superficial plexus VD, FAZ area, capillary density, and inner retinal thickness changed significantly in hypertensive patients without hypertensive retinopathy. However, only RNFL thickness was significantly thinner in patients who had >10 years of hypertension, compared to patients who had 5-10 years of hypertension. In addition, OCTA provided a method to prospectively assess changes in retinal microvasculature and thickness, thereby avoiding further long-term retinal damage in hypertensive patients.

Double-Gyroid Nanostructure Formation by Aggregation-Induced Atropisomerization and Co-Assembly of Ionic Liquid-Crystalline Amphiphiles.

We report a new molecular-design principle for creating double-gyroid nanostructured molecular assemblies based on atropisomerization. Ionic amphiphiles containing two imidazolium rings close to each other were designed and synthesized. NMR data revealed that the rotation of the imidazolium rings is restricted, with an activation energy as high as 63 kJ mol-1 in DMSO-d6 solution (DFT prediction for a model compound in the vacuum: 90-100 kJ mol-1 ). Due to the restricted rotation, the amphiphiles feature "double" atropisomeric axes in their ionic segments and form three stable atropisomers: meso, R, and S. These isomers co-organize into I a 3 ‾ d -type bicontinuous cubic liquid-crystalline mesophases through nanosegregation of the ionic and non-ionic parts. Considering the intrinsic characteristic of I a 3 ‾ d -type bicontinuous cubic structures that they are composed of intertwined right- and left-handed single gyroids, we propose that the simultaneous presence of both R- and S-atropisomers is an important contributor to the formation of double-gyroid structures.

Chirality Induction through Nano-Phase Separation: Alternating Network Gyroid Phase by Thermotropic Self-Assembly of X-Shaped Bolapolyphiles.

The single gyroid phase as well as the alternating double network gyroid, composed of two alternating single gyroid networks, hold a significant place in ordered nanoscale morphologies for their potential applications as photonic crystals, metamaterials and templates for porous ceramics and metals. Here, we report the first alternating network cubic liquid crystals. They form through self-assembly of X-shaped polyphiles, where glycerol-capped terphenyl rods lie on the gyroid surface while semiperfluorinated and aliphatic side-chains fill their respective separate channel networks. This new self-assembly mode can be considered as a two-color symmetry-broken double gyroid morphology, providing a tailored way to fabricate novel chiral structures with sub-10 nm periodicities using achiral compounds.

Sequence-Defined Dendrons Dictate Supramolecular Cogwheel Assembly of Dendronized Perylene Bisimides.

A dendronized perylene bisimide (PBI) that self-organizes into hexagonal arrays of supramolecular double helices with identical single-crystal-like order that disregards chirality was recently reported. A cogwheel model of self-assembly that explains this process was proposed. Accessing the highly ordered cogwheel phase required very slow heating and cooling or extended periods of annealing. Analogous PBIs with linear alkyl chains did not exhibit the cogwheel assembly. Here a library of sequence-defined dendrons containing all possible compositions of linear and racemic alkyl chains was employed to construct self-assembling PBIs. Thermal and structural analysis of their assemblies by differential scanning calorimetry (DSC) and fiber X-ray diffraction (XRD) revealed that the incorporation of n-alkyl chains accelerates the formation of the high order cogwheel phase, rendering the previously invisible phase accessible under standard heating and cooling rates. Small changes to the primary structure, as constitutional isomerism, result in significant changes to macroscopic properties such as melting of the periodic array. This study demonstrated how changes to the sequence-defined primary structure, including the relocation of methyl groups between two constitutional isomers, dictate tertiary and quaternary structure in hierarchical assemblies. This led to the discovery of a sequence that self-organizes the cogwheel assembly much faster than even the corresponding homochiral compounds and demonstrated that defined-sequence, which has long been recognized as a determinant for the complex structure of biomacromolecules including proteins and nucleic acids, plays the same role also in supramolecular synthetic systems.

New Type of Columnar Liquid Crystal Superlattice in Double-Taper Ionic Minidendrons.

Wedge-shaped molecules, such as dendrons, are among the most important building blocks for directed supramolecular self-assembly. Here we present a new approach aimed at widening the range and complexity of potential mesophases by introducing double-tapered mesogens. Two series of compounds are presented, both alkali metal salts (Li, Na, Cs) of 3,4,5-tris-alkoxybenzoic acid with a second tapered tris-alkoxyaryl group attached at the end of an alkoxy chain. The double-tapered compounds all display an unusual hexagonal columnar phase consisting of one ionic and three non-ionic columns per unit cell. The cation size has an unexpectedly drastic effect on unit cell size. Unlike most columnar phases, the current phases show unusually high dimensional stability on heating, and high stiffness in spite of being 80-85 % aliphatic, attributed to their molecular topology. The described approach may lead to co-assemblies of multifunctional materials, for example, parallel p- and n-semiconducting nanowires or parallel ionic and electronic conductors.

A Self-Assembled Bicontinuous Cubic Phase with a Single-Diamond Network.

The first single-diamond cubic phase in a liquid crystal is reported. This skeletal structure with the F d 3 ‾ m space group is formed by self-assembly of bolaamphiphiles with swallow-tailed lateral chains. It consists of bundles of π-conjugated p-terphenyl rods fused into an infinite network by hydrogen-bonded spheres at tetrahedral four-way junctions. We also present a quantitative model relating molecular architecture to the space-filling requirements of six possible bicontinuous cubic phases, that is, the single- and double-network versions of gyroid, diamond, and "plumber's nightmare".

Dendronized Poly(2-oxazoline) Displays within only Five Monomer Repeat Units Liquid Quasicrystal, A15 and σ Frank-Kasper Phases.

Liquid quasicrystals (LQC) have been discovered in self-assembling benzyl ether, biphenylmethyl ether, phenylpropyl ether, biphenylpropyl ether and some of their hybrid dendrons and subsequently in block copolymers, surfactants and other assemblies. These quasiperiodic arrays, which lack long-range translational periodicity, are approximated by two Frank-Kasper periodic arrays, Pm3̅ n cubic (Frank-Kasper A15) and P42/ mnm tetragonal (Frank-Kasper σ), which have been discovered in complex soft matter in the same order and compounds. Poly(2-oxazoline)s dendronized with (3,4) nG1 minidendrons (where n denotes an alkyl chain, C nH2 n+1) self-organize into the Pm3̅ n cubic phase ( n = 14 and 15) and, as reported recently, the P42/ mnm tetragonal phase ( n = 16). However, no LQC of a poly(2-oxazoline) is yet known. Here we report the synthesis, structural and retrostructural analysis of a dendronized poly(2-oxazoline) with n = 17 which self-organizes not only into the LQC but also in the above two Frank-Kasper approximants. All three phases are observed from the same polymer within a very narrow range of degree of polymerization that corresponds to only five monomer repeat units (5 ≤ DP ≤ 10). The formation of the Pm3̅ n cubic, P42/ mnm tetragonal and LQC phases from a single polymer chain within such a narrow range of DP raises the questions of how and why each of these phases is self-organized. This system may provide a model for theoretical investigations into the self-organization of soft matter into Frank-Kasper and related periodic and quasiperiodic arrays.

Hierarchical Self-Organization of Chiral Columns from Chiral Supramolecular Spheres.

The supramolecular column is an archetypal architecture in the field of periodic liquid crystalline and crystalline arrays. Columns are generated via self-assembly, coassembly, and polymerization of monomers containing molecules shaped as discs, tapered, twin- and Janus-tapered, crowns, hat-shaped crowns, and fragments thereof. These supramolecular columns can be helical and therefore exhibit chirality. In contrast, spheres represent a fundamentally distinct architecture, generated from conical and crown-like molecules, which self-organize into body-centered cubic, Pm3̅ n cubic (also known as Frank-Kasper A15), and tetragonal (also known as Frank-Kasper σ) phases. Supramolecular spherical aggregates are not known to further assemble into a columnar architecture, except as an intermediate state between a columnar periodic array and a cubic phase. In the present work, a chiral dendronized cyclotetraveratrylene (CTTV) derivative is demonstrated to self-organize into a supramolecular column unexpectedly constructed from supramolecular spheres, with no subsequent transition to a cubic phase. Structural and retrostructural analysis using a combination of differential scanning calorimetry, X-ray diffraction (XRD), molecular modeling, and simulation of XRD patterns reveals that this CTTV derivative, which is functionalized with eight chiral first-generation minidendrons, self-organizes via a column-from-spheres model. The transition from column to column-from-spheres was monitored by circular dichroism spectroscopy, which demonstrated that both the supramolecular column and supramolecular spheres are chiral. This column-from-spheres model, which unites two fundamentally distinct self-assembled architectures, provides a new mechanism to self-organize supramolecular columnar architectures.

Lamellar Liquid Crystals of In-Plane Lying Rod-Like Mesogens with Designer Side-Chains: The Case of Sliding versus Locked Layers.

The dimensionality of self-assembled nanostructures plays an essential role for their properties and applications. Herein, an understanding of the transition from weakly to strongly coupled layers in soft matter systems is provided involving in-plane organized π-conjugated rods. For this purpose, bolaamphiphilic triblock molecules consisting of a rigid biphenyl core, polar glycerol groups at the ends, and a branched (swallow-tail) or linear alkyl or semiperfluoroalkyl chain in lateral position have been synthesized and investigated. Besides weakly coupled lamellar isotropic (LamIso ), lamellar nematic (LamN ) and sliding lamellar smectic phases (LamSm ), a sequence of three distinct types of strongly coupled (correlated) lamellar smectic phases with either centered (c2mm) or non-centered rectangular (p2mm) lattice and an intermediate oblique lattices (p2) were observed depending on chain length, chain branching and degree of chain fluorination. This new sequence is explained by the strengthening of the layer coupling and the competition between energetic packing constraints and the entropic contribution of either longitudinal or tangential fluctuations. This example of directed side chain engineering of small generic model compounds provides general clues for morphological design of two-dimensional and three-dimensionally coupled lamellar systems involving larger π-conjugated molecular rods and molecular or supramolecular polymers, being of actual interest in organic electronics and nanotechnology.

Molecular ejection transition in liquid crystal columns self-assembled from wedge-shaped minidendrons.

Fan-shaped molecules with aromatic head-groups and two or more flexible pendant chains often self-assemble into columns that form columnar liquid crystals by packing on a 2d lattice. Such dendrons or minidendrons are essential building blocks in a large number of synthetic self-assembled systems and organic device materials. Here we report a new type of phase transition that occurs between two hexagonal columnar phases, Colh1 and Colh2, of Na-salt of 3,4,5-tris-dodecyloxy benzoic acid. Interestingly, the transition does not change the symmetry, which is p6mm in both phases, but on heating it involves a quantised drop in the number of molecules n in the cross-section of a column. The drop is from 4 to 3.5, with a further continuous decrease toward n = 3 as temperature increases further above Tc. The finding is based on evidence from X-ray diffraction. Using a transfer matrix formulation for the interactions within a column, with small additional mean field terms, we describe quantitatively the observed changes in terms of intermolecular forces responsible for the formation of supramolecular columns. The driving force behind temperature-induced molecular ejection from the columns is the increase in conformational disorder and the consequent lateral expansion of the alkyl chains. The asymmetry of the transition is due to the local order between 4-molecule discs giving extra stability to purely n = 4 columns.