Rapid Semiconducting Supramolecular Mg(II)-Metallohydrogel: Exploring Its Potential in Nonvolatile Resistive Switching Applications and Antiseptic Wound Healing Properties.

An effective strategy was employed for the rapid development of a supramolecular metallohydrogel of Mg(II) ion (i.e., Mg@PEHA) using pentaethylenehexamine (PEHA) as a low-molecular-weight gelator in aqueous medium under ambient conditions. The mechanical stability of the synthesized Mg@PEHA metallohydrogel was characterized by using rheological analysis, which showed its robustness across different angular frequencies and oscillator stress levels. The metallohydrogel exhibited excellent thixotropic behavior, which signifies that Mg@PEHA has a self-healing nature. Field emission scanning electron microscopy and transmission electron microscopy images were utilized to explore the rectangular pebble-like hierarchical network of the Mg@PEHA metallohydrogel. Elemental mapping through energy-dispersive X-ray spectroscopy analysis confirmed the presence of primary chemical constituents in the metallohydrogel. Fourier transform infrared spectroscopy spectroscopy provided insights into the possible formation strategy of the metallohydrogel. In this work, Schottky diode structures in a metal-semiconductor-metal geometry based on a magnesium(II) metallohydrogel (Mg@PEHA) were constructed, and the charge transport behavior was observed. Additionally, a resistive random access memory (RRAM) device was developed using Mg@PEHA, which displayed bipolar resistive switching behavior at room temperature. The researchers investigated the switching mechanism, which involved the formation or rupture of conduction filaments, to gain insights into the resistive switching process. The RRAM device demonstrated excellent performance with a high ON/OFF ratio of approximately 100 and remarkable endurance of over 5000 switching cycles. RRAM devices exhibit good endurance, meaning they can endure a large number of read and write cycles without significant degradation in performance. RRAM devices have shown promising reliability in terms of long-term performance and stability, making them suitable for critical applications that require reliable memory solutions. Significant inhibitory activity against the drug-resistant Klebsiella pneumonia strain and its biofilm formation ability was demonstrated by Mg@PEHA. The minimum inhibitory concentration value of the metallohydrogel was determined to be 3 mg/mL when it was dissolved in 1% DMSO. To study the antibiofilm activity, an MTT assay was performed, revealing that biofilm inhibition (60%) commenced at 1 mg/mL of Mg@PEHA when dissolved in 1% DMSO. Moreover, in the mouse excisional wound model, Mg@PEHA played a crucial role in preventing postoperative wound infections and promoting wound healing.

Concentration- and Solvent-Induced Chiral Tuning by Manipulating Non-Proteinogenic Amino Acids in Glycoconjugate Supra-Scaffolds: Interaction with Protein, and Streptomycin Delivery.

We showed solvent- and concentration-triggered chiral tuning of the fibrous assemblies of two novel glycoconjugates Z-P(Gly)-Glu and Z-F(4-N)-Glu made by chemical attachment of Cbz-protected [short as Z)] non-proteinogenic amino acids L-phenylglycine [short as P(Gly)] and 4-Nitro-L-phenylalanine [short as F(4-N)] with D-glucosamine [short as Glu]. Both biomimetic gelators can form self-healing and shape-persistent gels with a very low critical gelator concentration in water as well as in various organic solvents, indicating they are ambidextrous supergelators. Detailed spectroscopic studies suggested ß-sheet secondary structure formation during anisotropic self-aggregation of the gelators which resulted in the formation of hierarchical left-handed helical fibers in acetone with an interlayer spacing of 2.4 nm. After the physical characterization of the gels, serum protein interaction with the gelators was assessed, indicating they may be ideal for biomedical applications. Further, both gelators are benign, non-immunogenic, non-allergenic, and non-toxic in nature, which was confirmed by performing the blood parameters and liver function tests on Wister rats. Streptomycin-loaded hydrogels showed efficacious antibacterial activity in vitro and in vivo as well. Finally, cell attachment and biocompatibility of the hydrogels were demonstrated which opens a newer avenue for promising biomedical and therapeutic applications.

Solvent- and Substrate-Induced Chiroptical Inversion in Amphiphilic, Biocompatible Glycoconjugate Supramolecules: Shape-Persistent Gelation, Self-Healing, and Antibacterial Activity.

We have shown solvent- and substrate-dependent chiral inversion of a few glycoconjugate supramolecules. (Z)-F-Gluco, in which d-glucosamine has been attached chemically to Cbz-protected l-phenylalanine at the C terminus, forms a self-healing hydrogel through intertwining of the nanofibers wherein the gelators undergo lamellar packing in the ß-sheet secondary structures with a single chiral handedness. Dihybrid (Z)-F-gluco nanocomposite gel was prepared by in-situ formation of silver nanoparticles AgNPs in the gel; this enhances the mechanical properties of the composite gel through physical crosslinking without altering the packing pattern. In contrast, (Z)-L-gluco bearing an l-leucine moiety does not form a hydrogel but an organogel. Interestingly, the chiral handedness of the aggregates of (Z)-L-gluco can be reversed by choosing suitable solvents. In addition to self-healing behavior, (Z)-L-gluco gel revealed shape persistency. Further, (Z)-F-gluco hydrogel is benign, nontoxic, non-immunogenic, and non-allergenic in animal cells. AgNP-loaded (Z)-F-gluco hydrogel showed antibacterial activity against both Gram-positive and Gram-negative bacteria.

Suppressing depolarization by tail substitution in an organic supramolecular ferroelectric.

Despite being very well established in the field of electro-optics, ferroelectric liquid crystals so far lacked interest from a ferroelectric device perspective due to a typically high operating temperature, a modest remnant polarization and/or poor polarization retention. Here, we experimentally demonstrate how simple structural modification of a prototypical ferroelectric liquid-crystal benzene-1,3,5-trisamide (BTA) - introduction of branched-tail substituents - results in materials with a wide operating temperature range and a data retention time of more than 10 years in thin-film solution-processed capacitor devices at room temperature. The observed differences between linear- and branched-tail compounds are analyzed using density functional theory (DFT) and molecular dynamics (MD) simulations. We conclude that morphological factors like improved packing quality and reduced disorder, rather than electrostatic interactions or intra/inter-columnar steric hindrance, underlay the superior properties of the branched-tailed BTAs. Synergistic effects upon blending of compounds with branched and linear side-chains can be used to further improve the materials' characteristics.

Remarkable Role of C-I···N Halogen Bonding in Thixotropic 'Halo'gel Formation.

Halogen-bonding-induced self-assembly in the solution of equimolar mixtures of certain pyridyl-ended oligo p-phenylenevinylene (OPV)-derivatives with 1,4-diiodotetrafluorobenzene is reported. The mode of self-assembly, that is, cocrystallization, thixotropic gelation, or precipitation, depends strongly on the nature of chains (n-alkyl chains as a function of length or short oxyethylene chain) appended to the OPV-backbone as well as on the cooling rate of the corresponding hot solution. Single-crystal X-ray diffraction studies of the cocrystals reveal the "infinite" chain formation via C-I···N halogen-bonding interactions between the two components. In addition, multiple noncovalent interactions induce cross-links among these halogen-bonded "infinite" chains. Interestingly, the molecular packing in the "Cogel" bearing OPV-derivative with oxyethylene chains is found to be very similar to that of the cocrystal of the same.

Nanocomposite made of an oligo(p-phenylenevinylene)-based trihybrid thixotropic metallo(organo)gel comprising nanoscale metal-organic particles, carbon nanohorns, and silver nanoparticles.

A silver ion (Ag(+))-triggered thixotropic metallo(organo)gel of p-pyridyl-appended oligo(p-phenylenevinylene) derivatives (OPVs) is reported for the first time. Solubilization of single-walled carbon nanohorns (SWCNHs) in solutions of the pure OPVs as well as in the metallogels mediated by π-π interactions has also been achieved. In situ fabrication of silver nanoparticles (AgNPs) in the SWCNH-doped dihybrid gel leads to the formation of a trihybrid metallogel. The mechanical strength of the metallogels could be increased stepwise in the order: freshly prepared gel

Development of a novel self-healing Zn(II)-metallohydrogel with wide bandgap semiconducting properties for non-volatile memory device application.

A rapid and effective strategy has been devised for the swift development of a Zn(II)-ion-based supramolecular metallohydrogel, termed Zn@PEH, using pentaethylenehexamine as a low molecular weight gelator. This process occurs in an aqueous medium at room temperature and atmospheric pressure. The mechanical strength of the synthesized Zn@PEH metallohydrogel has been assessed through rheological analysis, considering angular frequency and oscillator stress dependencies. Notably, the Zn@PEH metallohydrogel exhibits exceptional self-healing abilities and can bear substantial loads, which have been characterized through thixotropic analysis. Additionally, this metallohydrogel displays injectable properties. The structural arrangement resembling pebbles within the hierarchical network of the supramolecular Zn@PEH metallohydrogel has been explored using FESEM and TEM measurements. EDX elemental mapping has confirmed the primary chemical constituents of the metallohydrogel. The formation mechanism of the metallohydrogel has been analyzed via FT-IR spectroscopy. Furthermore, zinc(II) metallohydrogel (Zn@PEH)-based Schottky diode structure has been fabricated in a lateral metal-semiconductor-metal configuration and  it's charge transport behavior has also been studied. Notably, the zinc(II) metallohydrogel-based resistive random access memory (RRAM) device (Zn@PEH) demonstrates bipolar resistive switching behavior at room temperature. This RRAM device showcases remarkable switching endurance over 1000 consecutive cycles and a high ON/OFF ratio of approximately 270. Further, 2 × 2 crossbar array of the RRAM devices were designed to demonstrate OR and NOT logic circuit operations, which can be extended for performing higher order computing operations. These structures hold promise for applications in non-volatile memory design, neuromorphic and in-memory computing, flexible electronics, and optoelectronic devices due to their straightforward fabrication process, robust resistive switching behavior, and overall system stability.

Novel supramolecular luminescent metallogels containing Tb(iii) and Eu(iii) ions with benzene-1,3,5-tricarboxylic acid gelator: advancing semiconductor applications in microelectronic devices.

A novel strategy was employed to create supramolecular metallogels incorporating Tb(iii) and Eu(iii) ions using benzene-1,3,5-tricarboxylic acid (TA) as a gelator in N,N-dimethylformamide (DMF). Rheological analysis demonstrated their mechanical robustness under varying stress levels and angular frequencies. FESEM imaging revealed a flake-like hierarchical network for Tb-TA and a rod-shaped architecture for Eu-TA. EDX analysis confirmed essential chemical constituents within the metallogels. FT-IR, PXRD, Raman spectroscopy, and thermogravimetric analysis assessed their gelation process and material properties, showing semiconducting characteristics, validated by optical band-gap measurements. Metal-semiconductor junction-based devices integrating Al metal with Tb(iii)- and Eu(iii)-metallogels exhibited non-linear charge transport akin to a Schottky diode, indicating potential for advanced electronic device development. Direct utilization of benzene-1,3,5-tricarboxylic acid and Tb(iii)/Eu(iii) sources underscores their suitability as semiconducting materials for device fabrication. This study explores the versatile applications of Tb-TA and Eu-TA metallogels, offering insights for material science researchers.

Remarkable regioisomer control in the hydrogel formation from a two-component mixture of pyridine-end oligo(p-phenylenevinylene)s and N-decanoyl-L-alanine.

N-Decanoyl-L-alanine (DA) was mixed with either colorless 4,4'-bipyridine (BP) or various derivatives such as chromogenic oligo(p-phenylenevinylene) (OPV) functionalized with isomeric pyridine termini in specific molar ratios. This mixtures form salt-type gels in a water/ethanol (2:1, v/v) mixture. The gelation properties of these two-component mixtures could be modulated by variation of the position of the ''N'' atom of the end pyridyl groups in OPVs. The presence of acid-base interactions in the self-assembly of these two-component systems leading to gelation was probed in detail by using stoichiometry-dependent UV/Vis and FTIR spectroscopy. Furthermore, temperature-dependent UV/Vis and fluorescence spectroscopy clearly demonstrated a J-type aggregation mode of these gelator molecules during the sol-to-gel transition process. Morphological features and the arrangement of the molecules in the gels were examined by using scanning electron microscopy (SEM), atomic force microscopy (AFM), and X-ray diffraction (XRD) techniques. Calculation of the length of each molecular system by energy minimization in its extended conformation and comparison with the XRD patterns revealed that this class of gelator molecules adopts lamellar organizations. Rheological properties of these two-component systems provided clear evidence that the flow behavior could be modulated by varying the acid/amine ratio. Polarized optical microscopy (POM), differential scanning calorimetry (DSC), and XRD results revealed that the solid-phase behavior of such two-component mixtures (acid/base=2:1) varied significantly upon changing the proton-acceptor part from BP to OPV. Interestingly, the XRD pattern of these acid/base mixtures after annealing at their associated isotropic temperature was significantly different from that of their xerogels.

A novel supramolecular Zn(ii)-metallogel: an efficient microelectronic semiconducting device application.

A unique strategy for the synthesis of a supramolecular metallogel employing zinc ions and adipic acid in DMF medium has been established at room temperature. Rheological analysis was used to investigate the mechanical characteristics of the supramolecular Zn(ii)-metallogel. Field emission scanning electron microscopy and transmission electron microscopy were used to analyse the hexagonal shape morphological features of the Zn(ii)-metallogel. Interestingly, the electrical conductivity is observed in the electronic device with Zn(ii)-metallogel based metal-semiconductor (MS) junctions. All aspects of the metallogel's electrical properties were investigated. The electrical conductivity of the metallogel-based thin film device was 7.38 × 10-5 S m-1. The synthesised Zn(ii)-metallogel based device was investigated for its semi-conductive properties, such as its Schottky barrier diode nature.

A 5-aminoisophthalic acid low molecular weight gelator based novel semiconducting supramolecular Zn(ii)-metallogel: unlocking an efficient Schottky barrier diode for microelectronics.

A novel method has been successfully developed for creating supramolecular metallogels using zinc(ii) ions and 5-aminoisophthalic acid as the gelator (low molecular weight gelator) in a dimethylformamide (DMF) solvent at room temperature. Comprehensive rheological investigations confirm the robust mechanical strength of the resulting zinc(ii)-metallogel. Microstructural analysis conducted through field-emission scanning electron microscopy (FESEM) unveils a unique flake-like morphology, with energy-dispersive X-ray (EDX) elemental mapping confirming the prevalence of zinc as the primary constituent of the metallogel. To understand the formation mechanism of this metallogel, Fourier-transform infrared (FT-IR) spectroscopy was employed. Notably, these supramolecular zinc(ii)-metallogel assemblies exhibit electrical conductivity reminiscent of metal-semiconductor (MS) junction electronic components. Surprisingly, the metallogel-based thin film device showcases an impressive electrical conductivity of 1.34 × 10-5 S m-1. The semiconductor characteristics of the synthesized zinc(ii)-metallogel devices, including their Schottky barrier diode properties, have been extensively investigated. This multifaceted study opens up a promising avenue for designing functional materials tailored for electronic applications. It harnesses the synergistic properties of supramolecular metallogels and highlights their significant potential in the development of semiconductor devices. This work represents a novel approach to the creation of advanced materials with unique electronic properties, offering exciting prospects for future innovations in electronic and semiconductor technologies.

Two novel low molecular weight gelator-driven supramolecular metallogels efficient in antimicrobial activity applications.

A remarkable ultrasonication technique was successfully employed to create two novel metallogels using citric acid as a low molecular weight gelator, in combination with cadmium(ii)-acetate and mercury(ii)-acetate dissolved in N,N-dimethyl formamide at room temperature and under ambient conditions. The mechanical properties of the resulting Cd(ii)- and Hg(ii)-metallogels were rigorously examined through rheological analyses, which revealed their robust mechanical stability under varying angular frequencies and shear strains. Detailed characterization of the chemical constituents within these metallogels was accomplished through EDX mapping experiments, while microstructural features were visualized using field emission scanning electron microscope (FESEM) images. Additionally, FT-IR spectroscopic analysis was employed to elucidate the metallogel formation mechanism. Significantly, the antimicrobial efficacy of these novel metallogels was assessed against a panel of bacteria, including Gram-positive strains such as Bacillus subtilis and Staphylococcus epidermidis, as well as Gram-negative species like Escherichia coli and Pseudomonas aeruginosa. The results demonstrated substantial antibacterial activity, highlighting the potential of Cd(ii) and Hg(ii)-based citric acid-mediated metallogels as effective agents against a broad spectrum of bacteria. In conclusion, this study provides a comprehensive exploration of the synthesis, characterization, and antimicrobial properties of Cd(ii) and Hg(ii)-based citric acid-mediated metallogels, shedding light on their promising applications in combating both Gram-positive and Gram-negative bacterial infections. These findings open up exciting prospects for the development of advanced materials with multifaceted industrial and biomedical uses.

Exploration of a wide bandgap semiconducting supramolecular Mg(II)-metallohydrogel derived from an aliphatic amine: a robust resistive switching framework for brain-inspired computing.

A rapid metallohydrogelation strategy has been developed of magnesium(II)-ion using trimethylamine as a low molecular weight gelator in water medium at room temperature. The mechanical property of the synthesized metallohydrogel material is established through the rheological analysis. The nano-rose like morphological patterns of Mg(II)-metallohydrogel are characterized through field emission scanning electron microscopic study. The energy dispersive X-ray elemental mapping analysis confirms the primary gel forming elements of Mg(II)-metallohydrogel. The possible metallohydrogel formation strategy has been analyzed through FT-IR spectroscopic study. In this work, magnesium(II) metallohydrogel (Mg@TMA) based metal-semiconductor-metal structures have been developed and charge transport behaviour is studied. Here, it is confirmed that the magnesium(II) metallohydrogel (Mg@TMA) based resistive random access memory (RRAM) device is showing bipolar resistive switching behaviour at room temperature. We have also explored the mechanism of resistive switching behaviour using the formation (rupture) of conductive filaments between the metal electrodes. This RRAM devices exhibit excellent switching endurance over 10,000 switching cycles with a large ON/OFF ratio (~ 100). The easy fabrication techniques, robust resistive switching behaviour and stability of the present system makes these structures preferred candidate for applications in non-volatile memory design, neuromorphic computing, flexible electronics and optoelectronics etc.

Palladium-induced transformation of nematic liquid crystals to robust metallogel comprising self-assembled nanowires.

The formation of a nematic liquid-crystalline phase in the bulk along with gelation of a novel asymmetric bolaamphiphilic NDI scaffold has been demonstrated. Further, a discrete metal NDI complex that is capable of forming a robust metallogel through wrapping of the NDI core with the oxyethylene chains of the neighboring molecules has been synthesized.

Perfluoroarene induces a pentapeptidic hydrotrope into a pH-tolerant hydrogel allowing naked eye sensing of Ca2+ ions.

Self-assembly of a novel thermoresponsive, pyrene-appended oligopeptide sequence VPGKP (PyP) leads to the formation of spherical aggregates in water. The sizes of the globular aggregates of the peptide, PyP, strongly depend on the temperature of its suspension in water and decrease with the decrease in temperature showing a lower critical solution temperature (LCST) phenomenon. Furthermore, a pyrene-octafluoronaphthalene (OFN) 'pair' has been used as a supramolecular synthon to induce hydrogelation of PyP in the presence of an equimolar amount of OFN via complementary quadrupole-quadrupole interactions. The gel shows excellent pH tolerance and thixotropic behavior. Detailed studies suggest the existence of lamellar packing of the gelators in a right-handed helical fashion which yields globular aggregates. The globular aggregates are sticky in nature and form a gel via inter-globular interactions. Addition of Ca2+ ions reinforces the mechanical strength and also reduces the critical gelator concentration of the native gel through coordination with the free -COO- group of the gelator. Therefore, the present hydrogel system could further be used as a naked eye sensor of Ca2+ ions.

Pore size dependent cation adsorption in a nanoporous polymer film derived from a plastic columnar phase.

Self-supporting polymer thin films were obtained by the polymerization of an AB3-type hydrogen-bonded complex in the plastic columnar phase. Porous polymers with pore diameters of ≈1.1 and ≈1.6 nm lined with either -COOH or -COONa groups were fabricated from the polymer thin films. Both the pore size and pore collapse influence the adsorption of cations.

Homeotropic Self-Alignment of Discotic Liquid Crystals for Nanoporous Polymer Films.

Nanostructured polymer films with continuous, membrane-spanning pores from polymerizable hexagonal columnar discotic liquid crystals (LCs) were fabricated. A robust alignment method was developed to obtain homeotropic alignment of columns between glass surfaces by adding a small amount of a tri(ethylene glycol) modified analogue of the mesogen as a dopant that preferentially wets glass. The homeotropic LC alignment was fixated via a photoinitiated free radical copolymerization of a high-temperature tolerant trisallyl mesogen with a divinyl ester. Removal of the hydrogen-bonded template from the aligned columns afforded a nanoporous network with pores of nearly 1 nm in diameter perpendicular to the surface, and without noticeable collapse of the nanopores. The effect of pore orientation was demonstrated by an adsorption experiment in which homeotropic film showed a threefold increase in the initial uptake rate of methylene blue compared to planarly aligned films.

Tailoring Pore Size and Chemical Interior of near 1 nm Sized Pores in a Nanoporous Polymer Based on a Discotic Liquid Crystal.

A triazine based disc shaped molecule with two hydrolyzable units, imine and ester groups, was polymerized via acyclic diene metathesis in the columnar hexagonal (Colhex) LC phase. Fabrication of a cationic nanoporous polymer (pore diameter ∼1.3 nm) lined with ammonium groups at the pore surface was achieved by hydrolysis of the imine linkage. Size selective aldehyde uptake by the cationic porous polymer was demonstrated. The anilinium groups in the pores were converted to azide as well as phenyl groups by further chemical treatment, leading to porous polymers with neutral functional groups in the pores. The pores were enlarged by further hydrolysis of the ester groups to create ∼2.6 nm pores lined with -COONa surface groups. The same pores could be obtained in a single step without first hydrolyzing the imine linkage. XRD studies demonstrated that the Colhex order of the monomer was preserved after polymerization as well as in both the nanoporous polymers. The porous anionic polymer lined with -COOH groups was further converted to the -COOLi, -COONa, -COOK, -COOCs, and -COONH4 salts. The porous polymer lined with -COONa groups selectively adsorbs a cationic dye, methylene blue, over an anionic dye.

First report of charge-transfer induced heat-set hydrogel. Structural insights and remarkable properties.

The remarkable ability of a charge-transfer (CT) complex prepared from a pyrene-based donor (Py-D) and a naphthalenediimide-based acceptor (NDI-A) led to the formation of a deep-violet in color, transparent hydrogel at room temperature (RT-gel). Simultaneously, the RT-gel was diluted beyond its critical gelator concentration (CGC) to obtain a transparent sol. Very interestingly, the resultant sol, on heating above 70 °C, transformed into a heat-set gel instantaneously with a hitherto unknown CGC value. Detailed studies revealed the smaller globular aggregates of the RT-gels fuse to form giant globules upon heating, which, in turn, resulted in heat-set gelation through further aggregation. The thermoresponsive property of Py-D alone and 1 : 1 Py-D : NDI-A CT complex was investigated in detail which revealed the hydrophobic collapse of the oxyethylene chains of the CT complex upon heating was mainly responsible for heat-set gelation. Thixotropy, injectability, as well as stimuli responsiveness of the RT-gels were also addressed. In contrast, heat-set gel did not show thixotropic behavior. The X-ray diffraction (XRD) patterns of the xerogel depicted lamellar packing of the CT stacks in the gel phase. Single crystal XRD studies further evidenced the 1 : 1 mixed CT stack formation in the lamellae and also ruled out orthogonal hydrogen bonding possibilities among the hydrazide unit in the CT gel although such interaction was observed in a single crystal of NDI-A alone. In addition, a Ag(+)-ion triggered metallogelation of NDI-A and nematic liquid-crystalline property of Py-D were also observed.

Charge transfer induces formation of stimuli-responsive, chiral, cohesive vesicles-on-a-string that eventually turn into a hydrogel.

A charge transfer (CT) mediated two-component, multistimuli responsive supergelation involving a L-histidine-appended pyrenyl derivative (PyHisOMe) as a donor and an asymmetric bolaamphiphilic naphthalene-diimide (Asym-NDI) derivative as an acceptor in a 2:1 mixture of H2O/MeOH was investigated. Asym-NDI alone self-assembled into pH-responsive vesicular nanostructures in water. Excellent selectivity in CT gel formation was achieved in terms of choosing amino acid appended pyrenyl donor scaffolds. Circular dichroism and morphological studies suggested formation of chiral, interconnected vesicular assemblies resembling "pearls-on-a-string" from these CT mixed stacks. XRD studies revealed the formation of monolayer lipid membranes from these CT mixed stacks that eventually led to the formation of individual vesicles. Strong cohesive forces among the interconnected vesicles originate from the protrusion of the oxyethylene chains from the surfaces of the chiral vesicles.