Chiral Supramolecular Structures Research Articles

Dispersive surface free energy of adsorbents modified by supramolecular structures of heterocyclic compounds

In the present work, the dispersive surface free energy was calculated by Dorris-Gray method for 30 samples of adsorbents modified with chiral supramolecular structures of uracil, 6-methyluracil, 5-hydroxy-6-methyluracil, 5-fluorouracil, thymine, melamine, cyanuric and barbirutic acids, and perylene-3,4,9,10-tetracarboxylic dianhydride. It was shown that the homologous series of n-alkanes is better suited for measuring dispersive surface free energy than the homologous series of alcohols. It was established that the classical Dorris-Gray method does not allow obtaining well interpretable data for the objects studied. This is due to a noticeable effect that inductive interactions of a polar surface as an inductor with nonpolar alkane molecules have on the calculated values. We suggested to modify the Dorris-Gray method, making it possible to obtain data on the dispersive component of the free energy of adsorption. It was shown that the changes in dispersive surface free energy as a result of the modification correlate well with data on the structure and properties of supramolecular ensembles of the modifiers used. The results obtained can be used to predict the enantioselectivity of chiral adsorbents.

Expression of chiral molecular and supramolecular structure on enantioselective catalytic activity

Understanding the structure-function relationships encoded on chiral catalysts is important for investigating the fundamental principles of catalytic enantioselectivity. Herein, the synthesis and self-assembly of naphthalene substituted bis-l/d-histidine amphiphiles (bis-l/d-NapHis) in DMF/water solution mixture is reported. The resulting supramolecular assemblies featuring well-defined P/M nanoribbons (NRs). With combination of the (P/M)-NR and metal ion catalytic centers (Mn+ = Co2+, Cu2+, Fe3+), the (P)-NR-Mn+ as chiral supramolecular catalysts show catalytic preference to 3,4-dihydroxy-S-phenylalanine (S-DOPA) oxidation while the (M)-NR-Mn+ show enantioselective bias to R-DOPA oxidation. In contrast, their monomeric counterparts bis-l/d-NapHis-Mn+ display an inverse and dramatically lower catalytic selectivity in the R/S-DOPA oxidation. Among them, the Co2+-coordinated supramolecular nanostructures show the highest catalytic efficiency and enantioselectivity (select factor up to 2.70), while the Fe3+-coordinated monomeric ones show nearly racemic products. Analysis of the kinetic results suggests that the synergistic effect between metal ions and the chiral supramolecular NRs can significantly regulate the enantioselective catalytic activity, while the metal ion-mediated monomeric bis-l/d-NapHis were less active. The studies on association constants and activation energies reveal the difference in catalytic efficiency and enantioselectivity resulting from the different energy barriers and binding affinities existed between the chiral molecular/supramolecular structures and R/S-DOPA enantiomers. This work clarifies the correlation between chiral molecular/supramolecular structures and enantioselective catalytic activity, shedding new light on the rational design of chiral catalysts with outstanding enantioselectivity.

Regulating the Chiroptical Expression of Aggregated Solvophobic Core by Solvophilic Segments.

The investigation of chiral supramolecular stacking is of essential significance for the understanding of the origin of homochirality in nature. Unlike structurally well-defined amphiphilic liposomes, it remains unclear whether the solvophilic segments of the amphiphilic block copolymer play a decisive role in the construction of asymmetric superstructures. Herein, insights are presented into the stacking patterns and morphological regulation in azobenzene-containing block copolymer assemblies solely by modulating the solvophilic chain length. The solvophilic poly(methacrylic acid) (PMAA) segments of different molecular weights could cause multi-mode chirality inversions involving stacking transitions between intra-chain π-π stacking, inter-chain H- and J-aggregation. Furthermore, the length of the solvophilic PMAA also affects the morphology of the chiral supramolecular assemblies; rice grain-like micelles, worms, nanofibers, floccules, and lamellae can be prepared at different solvophilic-solvophobic balance. The comprehensive mechanism is collectively revealed by utilizing various measurement methods, such as including circular dichroism (CD), small-angle X-ray scattering (SAXS), and wide-angle X-ray diffraction (WAXD). This study highlights the critical importance of fully dissolved solvophilic segments for the chiroptical regulation of the aggregated core, providing new insights into the arrangement of chiral supramolecular structures in polymer systems.

Polymer dispersed cholesteric liquid crystals with combined photo- and mechanochromic response

The development of stimuli-sensitive systems is one of the newest and most promising directions in the field of modern materials science. The combination of various types of sensitivity in the same material opens the possibility of creating complex devices with a wide range of potential applications. This work deals with the design and preparation of new composite materials based on plasticized polyvinyl alcohol (PVA) films containing droplets of cholesteric liquid crystals (CLC). Mechanical stretching of elastic composite films results in a change in optical properties, namely selective light reflection (SLR), from CLC droplets. This in turn transforms the structure and optical properties of the entire polymer matrix. Such a process represents a certain mechano-optic response of the polymer matrix to the influence of mechanical deformation. The introduction of a chiral photochromic dopant into a composite film makes it possible to transform such a film into a photochromic material with the ability to control its optical properties using, for example, UV irradiation. Therefore, mechanical deformation of a polymer composite leads to a change in its optical properties (SLR) caused by a change chiral supramolecular structure of cholesteric mesophase. At the same time, UV irradiation of a polymer film induces E-Z isomerization process in the chiral photochromic dopant, altering its molecular shape and helical twisting power. This enables the using of this process for remote and contactless control of the composite optical properties. In addition, this feature allows one to implement the photopatterning and the recording of a latent image, which appears under the influence of a mechanical field.

Perovskite-Supramolecular Co-Assembly for Chiral Optoelectronics.

Hybrid inorganic-organic perovskites with chiral response and outstanding optoelectronic characteristics are promising materials for next-generation spin-optoelectronics. In particular, two-dimensional (2D) perovskites are promising chiroptical candidates due to their unique ability to incorporate chiral organic cations into their crystal structure, which imparts chirality. To enable their practical applications in chiral optoelectronic devices, it is essential to achieve an anisotropy factor (gCD ∼ 2) in chiral 2D perovskites. Currently, chiral 2D perovskites exhibit a relatively low gCD of 3.1 × 10-3. Several approaches have been explored to improve the chiral response of chiral 2D perovskites, including tailoring the molecular structure of chiral cations and increasing the degree of octahedral tilting in the perovskite lattice. However, current methods for chiral amplification have only achieved a moderate enhancement of gCD by 2-fold and are often accompanied by undesirable shifts or inversion in the circular dichroism spectra. There is a need for a more efficient approach to enhancing the chirality in 2D perovskites. Here, we report an innovative coassembly process that allows us to seamlessly grow chiral 2D perovskites on supramolecular helical structures. We discover that the interactions between perovskites and chiral supramolecular structures promote crystal lattice distortion in perovskites, which improves the chirality of 2D perovskites. Additionally, the obtained hierarchical coassembly can effectively harness the structural chirality of the supramolecular helices. The multilevel chiral enhancement leads to an enhancement in gCD by 2.7-fold without compromising the circular dichroism spectra of 2D perovskites.

Inverse chirality-induced spin selectivity effect in chiral assemblies of π-conjugated polymers.

Coupling of spin and charge currents to structural chirality in non-magnetic materials, known as chirality-induced spin selectivity, is promising for application in spintronic devices at room temperature. Although the chirality-induced spin selectivity effect has been identified in various chiral materials, its Onsager reciprocal process, the inverse chirality-induced spin selectivity effect, remains unexplored. Here we report the observation of the inverse chirality-induced spin selectivity effect in chiral assemblies of π-conjugated polymers. Using spin-pumping techniques, the inverse chirality-induced spin selectivity effect enables quantification of the magnitude of the longitudinal spin-to-charge conversion driven by chirality-induced spin selectivity in different chiral polymers. By widely tuning conductivities and supramolecular chiral structures via a printing method, we found a very long spin relaxation time of up to several nanoseconds parallel to the chiral axis. Our demonstration of the inverse chirality-induced spin selectivity effect suggests possibilities for elucidating the puzzling interplay between spin and chirality, and opens a route for spintronic applications using printable chiral assemblies.

Chirality Supramolecular Systems: Helical Assemblies, Structure Designs, and Functions.

Chirality, as one of the most striking characteristics, exists at various scales in nature. Originating from the interactions of host and guest molecules, supramolecular chirality possesses huge potential in the design of functional materials. Here, an overview of the recent progress in structure designs and functions of chiral supramolecular materials is present. First, three design routes of the chiral supramolecular structure are summarized. Compared with the template-induced and chemical synthesis strategies that depend on accurate molecular identification, the twisted-assembly technique creates chiral materials through the ordered stacking of the nanowire or films. Next, chirality inversion and amplification are reviewed to explain the chirality transfer from the molecular level to the macroscopic scale, where the available external stimuli on the chirality inversion are also given. Lastly, owing to the optical activity and the characteristics of the layer-by-layer stacking structure, the supramolecular chirality materials display various excellent performances, including smart response, shape-memorization, superior mechanical performance, and applications in biomedical fields. To sum up, this work provides a systematic review of the helical assemblies, structure design, and applications of supramolecular chirality systems.

Controlling Helical Asymmetry in Supramolecular Copolymers by In Situ Chemical Modification.

Amplification of asymmetry in complex molecular systems results from a delicate interplay of chiral supramolecular structures and their chemical reactivity. In this work, we show how the helicity of supramolecular assemblies can be controlled by performing a non-stereoselective methylation reaction on comonomers. By methylating chiral glutamic acid side chains in benzene-1,3,5-tricarboxamide (BTA) derivatives to form methyl esters, the assembly properties are modulated. As reacted comonomers, the methyl ester-BTAs induce a stronger bias in the screw-sense of helical fibers predominantly composed of stacked achiral alkyl-BTA monomers. Hence, applying the in situ methylation in a system with the glutamic acid-BTA comonomer induces asymmetry amplification. Moreover, mixing small quantities of enantiomers of glutamic acid-BTA and glutamate methyl ester-BTA in the presence of the achiral alkyl-BTAs leads to deracemization and inversion of the helical structures in solution via the in situ reaction toward a thermodynamic equilibrium. Theoretical modeling suggests that the observed effects are caused by enhanced comonomer interactions after the chemical modification. Our presented methodology enables on-demand control over asymmetry in ordered functional supramolecular materials.

Circularly Polarized Microscopy of Thin Films of Chiral Organic Dyes.

We introduce an optical microscopy technique, circularly polarized microscopy or CPM, able to afford spatially resolved electronic circular dichroism (ECD) of thin films of chiral organic semiconductors through a commercial microscope equipped with a camera and inexpensive optics. Provided the dichroic ratio is sufficiently large, the spatial resolution is on the order of the μm and is only limited by the magnification optics integrated in the microscope. We apply CPM to thin films of small chiral π-conjugated molecules, which gave rise to ordered aggregates in the thin layer. Primarily, conventional ECD can reveal and characterize chiral supramolecular structures and possible interferences between anisotropic properties of solid samples; however, it cannot generally account for the spatial distribution of such properties. CPM offers a characterization of supramolecular chirality and of commingling polarization anisotropies of the material, describing their local distribution. To validate CPM, we demonstrated that it can be adopted to quantify the local ECD of samples characterized by intense signals, virtually on any standard optical microscope.

Detecting Interplay of Chirality, Water, and Interfaces for Elucidating Biological Functions.

Chemists have long been fascinated by chirality, water, and interfaces, making tremendous progress in each research area. However, the chemistry emerging from the interplay of chirality, water, and interfaces has been difficult to study due to technical challenges, creating a barrier to elucidating biological functions at interfaces. Most biopolymers (proteins, DNA, and RNA) fold into macroscopic chiral structures to perform biological functions. Their folding requires water, but water behaves differently at interfaces where the bulk water hydrogen-bonding network terminates. A question arises as to how water molecules rearrange to minimize free energy at interfaces while stabilizing the macroscopic folding of biopolymers to support biological function. This question is central to solving many research challenges, including the molecular origin of biological homochirality, folding and insertion of proteins into cell membranes, and the design of heterogeneous biocatalysts. Researchers can resolve these challenges if they have the theoretical tools to accurately predict molecular behaviors of water and biopolymers at various interfaces. However, developing such tools requires validation by the experimental data. These experimental data are scarce because few physical methods can simultaneously distinguish chiral folding of the biopolymers, separate signals of interfaces from the overwhelming background of bulk solvent, and differentiate water in hydration shells of the polymers from water elsewhere.We recently illustrated these very capacities of chirality-sensitive vibrational sum frequency generation spectroscopy (chiral SFG). While chiral SFG theory dictates that the method is surface-specific under the condition of electronic nonresonance, we show the method can distinguish chiral folding of proteins and DNA and probe water structures in the first hydration shell of proteins at interfaces. Using amide I signals, we observe protein folding into β-sheets without background signals from α-helices and disordered structures at interfaces, thereby demonstrating the effect of 2D crowding on protein folding. Also, chiral SFG signals of C-H stretches are silent from single-stranded DNA, but prominent for canonical antiparallel duplexes as well as noncanonical parallel duplexes at interfaces, allowing for sensing DNA secondary structures and hybridization. In establishing chiral SFG for detecting protein hydration structures, we observe an H218O isotopic shift that reveals water contribution to the chiral SFG spectra. Additionally, the phase of the O-H stretching bands flips when the protein chirality is switched from L to D. These experimental results agree with our simulated chiral SFG spectra of water hydrating the β-sheet protein at the vacuum-water interface. The simulations further reveal that over 90% of the total chiral SFG signal comes from water in the first hydration shell. We conclude that the chiral SFG signals originate from achiral water molecules that assemble around the protein into a chiral supramolecular structure with chirality transferred from the protein. As water O-H stretches can reveal hydrogen-bonding interactions, chiral SFG shows promise in probing the structures and dynamics of water-biopolymer interactions at interfaces. Altogether, our work has created an experimental and computational framework for chiral SFG to elucidate biological functions at interfaces, setting the stage for probing the intricate chemical interplay of chirality, water, and interfaces.

Anthracenemethyl Glycosides as Supramolecular Synthons for Chiral Self-Assembly and as Probes in Cell Imaging.

Chiral self-assembly of molecules warrants optimal structural features of synthons that promote formation of such self-assembled structures. A polyaromatic moiety coupled with hydrophilic, chiral-rich carbohydrates leads to segmentation of the regions and the self-assembly to supramolecular structures. Thermodynamic stability is augmented further through chiral self-assembly of the molecules, and formation of the desired chiral supramolecular structures is achieved. In the present study, we develop anthracene glycosides as efficient synthons that, in aqueous solutions, undergo facile self-assembly and lead to chiral supramolecular structures. Anthracenemethyl O-glycosides, installed with mono- and disaccharides, are studied for their self-assembly properties. Emerging chiral structures follow the configuration of the attached sugar moiety. Monosaccharide d- and l-glycopyranoside-containing derivatives alternate between left- and right-handed chiral structures, respectively. Disaccharide-containing derivatives do not exhibit chirality, even when self-assembly occurred. Photochemical [4π + 4π] cycloaddition occurs in the self-assembled structure in aqueous solution. Cell viability assay using HeLa cells shows above 80% viable cells at a concentration of 50 μM. Bioimaging assays reveal a significant imaging of HeLa cells for anthracenemethyl d-glucopyranoside; bright imaging was observed at the perinuclear region of the cells, suggestive of an active transport of the molecules through the cell membrane. d-Galactopyranoside and l-glucopyranoside-containing derivatives show weak imaging potencies.

Aggregation Modes of Chiral Diketopyrrolo[3,4-c]pyrrole Dyes in Solution and Thin Films.

The chiroptical features of chiral diketopyrrolo[3,4‐c]pyrrole (DPP) derivatives have been only marginally investigated to date. In this regard, we have synthesized ad hoc four chiral DPP dyes, functionalized with enantiopure alkyl groups from natural sources either on the lactam moieties or on the terminal positions of the π‐conjugated backbone, to promote an efficient self‐assembly into chiral supramolecular structures. For each of them, the aggregation modes has been investigated by absorbance and ECD spectroscopies in conditions of solution aggregation and on thin films, considering the effects of deposition technique (drop casting vs. spin coating) and post‐deposition operations (solvent and thermal annealing). The effect of the structure of lateral π‐conjugated units attached to the central DPP scaffold, as well as that of the position of the alkyl chiral group, has been assessed. ECD revealed superior capability, compared to absorbance spectroscopy, to provide information on the aggregation modes and to detect the possible co‐existence of multiple aggregation pathways.

Chiral, Magnetic, and Photosensitive Liquid Crystalline Nanocomposites Based on Multifunctional Nanoparticles and Achiral Liquid Crystals.

Nanoparticles serving as a multifunctional and multiaddressable dopant to modify the properties of liquid crystalline matrices are developed by combining cobalt ferrite nanocrystals with organic ligands featuring a robust photosensitive unit and a source of chirality from the natural pool. These nanoparticles provide a stable nanocomposite when dispersed in achiral liquid crystals, giving rise to chiral supramolecular structures that can respond to UV-light illumination, and, at the same time, the formed nanocomposite possesses strong magnetic response. We report on a nanocomposite that shows three additional functionalities (chirality and responsiveness to UV light and magnetic field) upon the introduction of a single dopant into achiral liquid crystals.

Optically active mesogenic triphenylenedicarboxyimides: Effects of axially connected aromatic ring at the stereogenic center on liquid crystal and self-assembly properties

We describe the synthesis and self-assembly behaviour of a series of ten optically active triphenylenedicarboxyimide (TDI) derivatives with a stereogenic center attached to the imide nitrogen carrying an end aromatic ring. All TDIs show an enantiotropic hexagonal columnar mesophase with high clearing temperatures up to 260 °C, which means that branching of the introduced stereocenter does not disrupt the columnar π−stacking of the TDI cores. Although all chiral TDIs in THF solution showed CD signal indicative of optical activity, chiral supramolecular structures were only observed in the columnar mesophase of three pairs of chiral TDIs (2, 4 and 5) having one end phenyl or naphthyl ring linked directly or close to the chiral center. DFT calculations suggests that the axially connected aromatic ring at the stereocenter provides steric repulsion upon stacking, thereby leading to the formation of chiral supramolecular structures. Besides, a small amount exclusively single-handed helical ribbons along with bundles of straight ribbons were simultaneously observed in SEM image of self-assembled R- or S-5 in mixed solution of ethyl acetate and ethanol, suggesting that the configuration of the stereogenic center is not the only factor responsible for inducing helical structures in solution.

Remotely controllable supramolecular rotor mounted inside a porphyrinic cage

Remotely controllable supramolecular rotor mounted inside a porphyrinic cage

Imaging deposition-dependent supramolecular chiral organisation.

Thin films of a chiral diketopyrrolopyrrole derivative were imaged with spatially-defined Mueller Matrix Polarimetry, focussing on the Circular Dichroism signal, giving unique insight into the impact that deposition techniques and thermal annealing can have on chiral supramolecular structures in the solid state, where homogeneity was observed for spun-coated films while drop-coating afforded chiroptical diversity in the material, a feature invisible to absorption spectroscopy or optical microscopy.

Reversible supramolecular chiral structures induced in azopolymers by elliptically polarized light: influence of the irradiation wavelength and intensity.

Photoinduced supramolecular chiral structures in azo materials have been extensively studied for the development of all-optical switches and because of their influence on the properties of certain types of polarization holographic gratings. Here, we investigate chiral structures induced by irradiation with elliptically polarized light in thin films of four azopolymers denoted as PAZO, P1, P1-2, which are amorphous, and P2, which is liquid crystalline. Their formation is characterized in real time by the kinetics of azimuth rotation. The influence of the irradiation wavelength and intensity is also analyzed. The largest azimuth rotation per unit thickness is achieved in PAZO (33°/µm) and P1-2 (25°/µm). Reversibility of the chiral structures is demonstrated by a tenfold change in the direction of rotation. Our results also indicate that chiral structures formation occurs significantly faster than the induction of linear birefringence.

Absolute Asymmetric Catalysis, from Concept to Experiment: A Narrative

AbstractThe generally accepted hypothesis to explain the origin of biological homochirality (that is to say, the fact that proteinogenic amino acids are left-handed, and carbohydrates right-handed, in all living beings) is to assume, in the course of prebiotic chemical evolution, the appearance of an initial enantiomeric excess in a set of chiral molecular entities by spontaneous mirror-symmetry breaking (SMSB), together with suitable amplification and replication mechanisms that overcome the thermodynamic drive to racemization. However, the achievement of SMSB in chemical reactions taking place in solution requires highly specific reaction networks showing nonlinear dynamics based on enantioselective autocatalysis, and examples of its experimental realization are very rare. On the other hand, emergence of net supramolecular chirality by SMSB in the self-assembly of achiral molecules has been seen to occur in several instances, and the chirality sign of the resulting supramolecular system can be controlled by the action of macroscopic chiral forces. These considerations led us to propose a new mechanism for the generation of net chirality in molecular systems, in which the SMSB takes place in the formation of chiral supramolecular dissipative structures from achiral monomers, leading to asymmetric imbalances in their composition that are subsequently transferred to a standard enantioselective catalytic reaction, dodging in this way the highly limiting requirement of finding suitable reactions in solution that show enantio­selective autocatalysis. We propose the name ‘absolute asymmetric catalysis’ for this approach, in which an achiral monomer is converted into a nonracemic chiral aggregate that is generated with SMSB and that is catalytically active.Our aim in this Account is to present a step-by-step narrative of the conceptual and experimental development of this hitherto unregarded, but prebiotically plausible, mechanism for the emergence of net chirality in molecular reactions.1 Introduction: The Origin of Biological Homochirality and Spontaneous Mirror-Symmetry Breaking2 Experimental Chemical Models for Spontaneous Mirror-Symmetry Breaking: The Soai Reaction and Beyond3 Spontaneous Mirror-Symmetry Breaking in Supramolecular Chemistry: Plenty of Room at the Top4 Absolute Asymmetric Catalysis: An Alternative Mechanism for the Emergence of Net Chirality in Molecular Systems 5 Experimental Realization of Top-Down Chirality Transfer to the Molecular Level6 Conclusions and Outlook

Multistate Switching of Spin Selectivity in Electron Transport through Light-Driven Molecular Motors.

It is established that electron transmission through chiral molecules depends on the electron's spin. This phenomenon, termed the chiral‐induced spin selectivity (CISS), effect has been observed in chiral molecules, supramolecular structures, polymers, and metal‐organic films. Which spin is preferred in the transmission depends on the handedness of the system and the tunneling direction of the electrons. Molecular motors based on overcrowded alkenes show multiple inversions of helical chirality under light irradiation and thermal relaxation. The authors found here multistate switching of spin selectivity in electron transfer through first generation molecular motors based on the four accessible distinct helical configurations, measured by magnetic‐conductive atomic force microscopy. It is shown that the helical state dictates the molecular organization on the surface. The efficient spin polarization observed in the photostationary state of the right‐handed motor coupled with the modulation of spin selectivity through the controlled sequence of helical states, opens opportunities to tune spin selectivity on‐demand with high spatio‐temporal precision. An energetic analysis correlates the spin injection barrier with the extent of spin polarization.

PH‐Controlled Supramolecular Self‐Assembly of Naphthalenediimide Appended l‐Alanine and Ethylenediamine Asymmetric Bolaamphiphile

AbstractDesign, synthesis and characterization of novel (2S)‐2‐[7‐(2‐aminoethyl)‐1,3,6,8‐tetraoxo‐3,6,7,8‐tetrahydrobenzo[lmn][3,8]phenanthrolin‐2(1H)‐yl]propanoic acid (1) bolaamphiphile, which combine naphthalene diimide (NDI) appended with l‐alanine at one end of imide and ethylenediamine at the other end. An l‐alanine bearing NDI‐based asymmetric bolaamphiphile self‐assembled at various pH ranging from 2 to 10 forms a variety of supramolecular nanostructures. The UV‐Vis and emission spectroscopic techniques employed for the optical and photophysical properties study of bolaamphiphile 1 at various pH values. It was revealed that the change in pH alters both the optical and photophysical properties of bolaamphiphile 1. Theoretical calculations used to investigate the electronic properties of the bolaamphiphile 1. Dynamic light scattering experiments displayed formation of aggregates in solution and scanning electron microscopy (SEM) was used to visualize the nanostructures formed on silicon wafers. Furthermore, the X‐ray diffraction was used to determine the nanostructure's packing properties i. e. crystalline/amorphous. Experimental circular dichroism (CD) spectroscopy results inferred and revealed the induction of chirality into the supramolecular systems, which was shown to be pH dependent. This study clearly demonstrates the manipulation of pH can control/tune chiral supramolecular structures and provide future methods for the development of chiral recognition and catalysis study.