Macroscopic Chirality Research Articles

Self-Assembling and Luminescent Properties of Chiral Bisoxadiazole Derivatives in Solution and Liquid-Crystalline Phases.

Herein, we report the synthesis, self-assembly, and electroluminescence characteristics of a new green-emitting, pseudodiscoid chiral molecule, OXDC, containing an electron-donating stilbene core and an electron-accepting oxadiazole substituent. The helical organization and specific interaction of the chiral pseudodiscoid molecule resulted in the formation of self-assembled nanofibers with a columnar superstructure. Macroscopic chirality was observed in both the liquid-crystalline phases and the self-assembled nanofibers of OXDC, a feature which was absent in the analogous achiral oxadiazole derivative reported earlier [ Sivadas , A. P. ; Supergelation via Purely Aromatic π-π Driven Self-Assembly of Pseudodiscotic Oxadiazole Mesogens . J. Am. Chem. Soc. 2014 , 136 , 5416 - 5423 ]. A high-performance organic light-emitting device was demonstrated using OXDC as the emitting material, with a luminous intensity of 10 115 cd m-2 at 5 V and chromaticity coordinates of (0.32, 0.51).

Fast determination of three-dimensional fibril orientation of type-I collagen via macroscopic chirality

Polarization-resolved second harmonic generation (SHG) microscopy is appealing for studying structural proteins and well-organized biophotonic nanostructures, due to its highly sensitized structural specificity. In recent years, it has been used to investigate the chiroptical effect, particularly SHG circular dichroism (SHG-CD) in biological tissues. Although SHG-CD attributed to macromolecular structures has been demonstrated, the corresponding quantitative analysis and interpretation on how SHG correlates with second-order susceptibility χ(2) under circularly polarized excitations remains unclear. In this study, we demonstrate a method based on macroscopic chirality to elucidate the correlation between SHG-CD and the orientation angle of the molecular structure. By exploiting this approach, three-dimensional (3D) molecular orientation of type-I collagen is revealed with only two cross polarized SHG images (i.e., interactions of left and right circular polarizations) without acquiring an image stack of varying polarization.

Macroscopic behavior of polar nematic gels and elastomers.

We present the derivation of the macroscopic equations for uniaxial polar nematic gels and elastomers. We include the strain field as well as relative rotations as independent dynamic macroscopic degrees of freedom. As a consequence, special emphasis is laid on possible static and dynamic cross-couplings between these macroscopic degrees of freedom associated with the network, and the other macroscopic degrees of freedom including reorientations of the macroscopic polarization. In particular, we find static and dissipative dynamic cross-couplings between strain fields and relative rotations on one hand and the macroscopic polarization on the other that allow for new possibilities to manipulate polar nematics. To give one example each for the effects of a static and a dissipative cross-coupling: we find that a static electric field applied perpendicularly to the polar preferred direction leads to relative rotations while dynamically relative rotations can lead to transverse electric currents. In addition to a permanent network, we also consider the effect of a transient network, which is particularly important for the case of gels, melts and concentrated polymer solutions. A section on the influence of macroscopic chirality is included as well.

Supramolecular aggregates with macroscopic chirality by self-assembly of helical small molecules

In this work, we investigated the self-assembly of helical small molecules and found that the formed micrometer-sized supramolecular structures represented macroscopic chirality. Our observation will provide useful information for exploring the factors which are able to essentially control the chiral expression from molecular details to high-level chirality occurred in nature.

Hierarchical Propagation of Chirality through Reversible Polymerization: The Cholesteric Phase of DNA Oligomers.

Unveiling the subtle rules that control the buildup of macroscopic chirality starting from chiral molecular elements is a challenge for theory and computations. In this context, a remarkable phenomenon is the formation of helically twisted nematic (cholesteric) phases, with pitch in the micrometer range, driven by self-assembly of relatively small chiral species into supramolecular semiflexible polymers. We have developed a theoretical framework to connect the cholesteric organization to the shape and chirality of the constituents, described with molecular detail, in this kind of system. The theory has been tested against new accurate measurements for solutions of short DNA duplexes. We show that the cholesteric organization is determined by steric repulsion between duplexes, and we identify distinctive features of linear self-assembly in the temperature and concentration dependence of the pitch.

A strategy for tuning achiral main-chain polymers into helical assemblies and chiral memory systems.

A general strategy to tune the achiral main chain polymers into helical nanoassemblies was proposed based on the co-gelation approach. As an example, two achiral main chain polymers, PCz8 and PSi8, were selected, and their co-assembly with an amphiphilic l- or d-glutamide gelator was investigated. Although the polymers could not form gels individually, they could form co-gels with the gelator and the resultant gels exhibited macroscopic supramolecular chirality, which could be confirmed by CD spectra and SEM observations. Moreover, the supramolecular chirality can be memorized even after the gelator molecules were removed. Remarkably, either the gelator-containing or gelator-free chiral polymer assemblies showed circularly polarized luminescence (CPL), which is usually inherent to intrinsic chiral polymers. It was suggested that during the co-gelation, the chirality of the gelator was transferred to and memorized by the achiral polymers. The approach seems to be general and we provided the first example to tune the achiral polymers into helical assemblies through the co-gelation.

Dimethyl Sulfoxide Induced Destabilization and Disassembly of Various Structural Variants of Insulin Fibrils Monitored by Vibrational Circular Dichroism.

Dimethyl sulfoxide (DMSO) induced destabilization of insulin fibrils has been previously studied by Fourier transform infrared spectroscopy and interpreted in terms of secondary structural changes. The variation of this process for fibrils with different types of higher-order morphological structures remained unclear. Here, we utilize vibrational circular dichroism (VCD), which has been reported to provide a useful biophysical probe of the supramolecular chirality of amyloid fibrils, to characterize changes in the macroscopic chirality following DMSO-induced disassembly for two types of insulin fibrils formed under different conditions, at different reduced pH values with and without added salt and agitation. We confirm that very high concentrations of DMSO can disaggregate both types of insulin fibrils, which initially maintained a β-sheet conformation and eventually changed their secondary structure to a disordered form. The two types responded to varying concentrations of DMSO, and disaggregation followed different mechanisms. Interconversion of specific insulin fibril morphological types also occurred during the destabilization process as monitored by VCD. With transmission electron microscopy, we were able to correlate the changes in VCD sign patterns to alteration of morphology of the insulin fibrils.

Macroscopic behavior of ferrocholesteric liquid crystals and ferrocholesteric gels and elastomers.

We study the influence of macroscopic chirality on the macroscopic properties of superparamagnetic liquid crystals and gels. Specifically we derive macroscopic dynamic equations for ferrocholesteric low molecular weight (LMW) liquid crystals and for ferrocholesteric gels and elastomers in the local description using the director field as macroscopic variable. The magnetization is treated as a macroscopic dynamic degree of freedom and its coupling to all other macroscopic variables is examined in detail. We incorporate into our dynamic analysis terms that are linear in a magnetic field giving rise to a number of cross-coupling terms not possible otherwise. A number of properties that are unique to the class of systems studied arise. As an example for a static property we find a term in the generalized energy which is linear in the electric field and quadratic in the magnetic field. We find that applying a magnetic field to a ferrocholesteric can lead to reversible electric currents, heat currents and concentration currents, which change their sign with a sign change of macroscopic chirality. As an example of a rather intriguing dissipative dynamic contribution we point out that for ferrocholesterics and for ferrocholesteric gels and elastomers in a magnetic field extensional flow leads to electric and heat currents.

Electrostatic and aromatic interaction-directed supramolecular self-assembly of a designed Fmoc-tripeptide into helical nanoribbons.

Supramolecular self-assembly offers an efficient pathway for creating macroscopically chiral structures in biology and materials science. Here, a new peptide consisting of an N-(9-fluorenylmethoxycarbonyl) headgroup connected to an aromatic phenylalanine-tryptophan dipeptide and terminated with zwitterionic lysine (Fmoc-FWK) and its cationic form (Fmoc-FWK-NH2) were designed for self-assembly into chiral structures. It was found that the Fmoc-FWK peptide self-assembled into left-handed helical nanoribbons at pH 11.2-11.8, whereas it formed nanofibers at pH 5 and 12 and large flat ribbons composed of many nanofibers in the pH range of 6-11. However, only nanofibers were observed in the cases of Fmoc-FWK-NH2 at different values. A series of structural characterizations based on CD, FTIR, UV-vis and fluorescence spectroscopy reveal that the electrostatic and aromatic interactions and the associated hydrogen bonding direct the self-assembly into various structures. The enhanced π-π stacking and hydrogen bonding were found in the helical nanoribbons. This difference in intermolecular interactions should be derived from the ionization of carboxyl and amino groups from lysine residues at different pH values. Furthermore, we performed molecular dynamics simulations to gain insight into the assembly mechanisms. The results imply that a relatively rigid molecular conformation and the strong intramolecular aromatic interaction between Trp and Fmoc groups favor chiral self-assembly. This study is the first attempt to design a Fmoc-tripeptide for the fabrication of helical structures with macroscopic chirality, which provides a successful example and allows us to create new peptide-based chiral assembly systems.

Cholesterics of colloidal helices: Predicting the macroscopic pitch from the particle shape and thermodynamic state

Building a general theoretical framework to describe the microscopic origin of macroscopic chirality in (colloidal) liquid crystals is a long-standing challenge. Here, we combine classical density functional theory with Monte Carlo calculations of virial-type coefficients to obtain the equilibrium cholesteric pitch as a function of thermodynamic state and microscopic details. Applying the theory to hard helices, we observe both right- and left-handed cholesteric phases that depend on a subtle combination of particle geometry and system density. In particular, we find that entropy alone can even lead to a (double) inversion in the cholesteric sense of twist upon changing the packing fraction. We show how the competition between single-particle properties (shape) and thermodynamics (local alignment) dictates the macroscopic chiral behavior. Moreover, by expanding our free-energy functional, we are able to assess, quantitatively, Straley's theory of weak chirality, which is used in several earlier studies. Furthermore, by extending our theory to different lyotropic and thermotropic liquid-crystal models, we analyze the effect of an additional soft interaction on the chiral behavior of the helices. Finally, we provide some guidelines for the description of more complex chiral phases, like twist-bend nematics. Our results provide new insights into the role of entropy in the microscopic origin of this state of matter.

Self-assembly and gelation of poly(aryl ether) dendrons containing hydrazide units: factors controlling the formation of helical structures.

Self-assembly of AB2 and AB3 type low molecular weight poly(aryl ether) dendrons that contain hydrazide units were used to investigate mechanistic aspects of helical structure formation during self-assembly. The results suggest that there are three important aspects that control helical structure formation in such systems with acyl hydrazide/hydrazone linkage: i) J-type aggregation, ii) the hydrogen-bond donor/acceptor ability of the solvent, and iii) the dielectric constant of the solvent. The monomer units self-assemble to form dimer structures through hydrogen-bonding and further assembly of the hydrogen-bonded dimers leads to macroscopic chirality in the present case. Dimer formation was confirmed by NMR spectroscopy and by mass spectrometry. The self-assembly in the system was driven by hydrogen-bonding and π-π stacking interactions. The morphology of the aggregates formed was examined by scanning electron microscopy, and the analysis suggests that aprotic solvent systems facilitate helical fibre formation, whereas introduction of protic solvents results in the formation of flat ribbons. This detailed mechanistic study suggests that the self-assembly follows a nucleation-elongation model to form helical structures, rather than the isodesmic model.

Cover Picture: Nanospheres, Nanotubes, Toroids, and Gels with Controlled Macroscopic Chirality (Angew. Chem. Int. Ed. 50/2014)

Cover Picture: Nanospheres, Nanotubes, Toroids, and Gels with Controlled Macroscopic Chirality (Angew. Chem. Int. Ed. 50/2014)

Macroscopic chirality of supramolecular gels formed from achiral tris(ethyl cinnamate) benzene-1,3,5-tricarboxamides.

A C3 -symmetric benzene-1,3,5-tricarboxamide substituted with ethyl cinnamate was found to self-assemble into supramolecular gels with macroscopic chirality in a DMF/H2 O mixture. The achiral compound simultaneously formed left- and right-handed twists in an unequal number, thus resulting in the macroscopic chirality of the gels without any chiral additives. Furthermore, ester-amide exchange reactions with chiral amines enabled the control of both the handedness of the twists and the macroscopic chirality of the gels, depending on the structures of the chiral amines. These results provide new prospects for understanding and regulating symmetry breaking in assemblies of supramolecular gels formed from achiral molecular building blocks.

Macroscopic Chirality of Supramolecular Gels Formed from Achiral Tris(ethyl cinnamate) Benzene‐1,3,5‐tricarboxamides

AbstractA C3‐symmetric benzene‐1,3,5‐tricarboxamide substituted with ethyl cinnamate was found to self‐assemble into supramolecular gels with macroscopic chirality in a DMF/H2O mixture. The achiral compound simultaneously formed left‐ and right‐handed twists in an unequal number, thus resulting in the macroscopic chirality of the gels without any chiral additives. Furthermore, ester–amide exchange reactions with chiral amines enabled the control of both the handedness of the twists and the macroscopic chirality of the gels, depending on the structures of the chiral amines. These results provide new prospects for understanding and regulating symmetry breaking in assemblies of supramolecular gels formed from achiral molecular building blocks.

Nanospheres, Nanotubes, Toroids, and Gels with Controlled Macroscopic Chirality

AbstractThe interaction of a highly dynamic poly(aryl acetylene) (poly‐1) with Li+, Na+, and Ag+ leads to macroscopically chiral supramolecular nanospheres, nanotubes, toroids, and gels. With Ag+, nanospheres with M helicity and tunable sizes are generated, which complement those obtained from the same polymer with divalent cations. With Li+ or Na+, poly‐1 yields chiral nanotubes, gels, or toroids with encapsulating properties and M helicity. Right‐handed supramolecular structures can be obtained by using the enantiomeric polymer. The interaction of poly‐1 with Na+ produces nanostructures whose helicity is highly dependent on the solvation state of the cation. Therefore, structures with either of the two helicities can be prepared from the same polymer by manipulation of the cosolvent. Such chiral nanotubes, toroids, and gels have previously not been obtained from helical polymer–metal complexes. Chiral nanospheres made of poly(aryl acetylene) that were previously assembled with metal(II) species can now be obtained with metal(I) species.

Nanospheres, nanotubes, toroids, and gels with controlled macroscopic chirality.

The interaction of a highly dynamic poly(aryl acetylene) (poly-1) with Li(+), Na(+), and Ag(+) leads to macroscopically chiral supramolecular nanospheres, nanotubes, toroids, and gels. With Ag(+), nanospheres with M helicity and tunable sizes are generated, which complement those obtained from the same polymer with divalent cations. With Li(+) or Na(+), poly-1 yields chiral nanotubes, gels, or toroids with encapsulating properties and M helicity. Right-handed supramolecular structures can be obtained by using the enantiomeric polymer. The interaction of poly-1 with Na(+) produces nanostructures whose helicity is highly dependent on the solvation state of the cation. Therefore, structures with either of the two helicities can be prepared from the same polymer by manipulation of the cosolvent. Such chiral nanotubes, toroids, and gels have previously not been obtained from helical polymer-metal complexes. Chiral nanospheres made of poly(aryl acetylene) that were previously assembled with metal(II) species can now be obtained with metal(I) species.

Unusual winding of helices under tension

An unusual overwinding and a subsequently unwinding behavior of helix of filament with twisted microstructures under stretch is analyzed from the nonlinear variation of material chirality (i.e., chirality in material properties), motivated by recent single-molecule experiments for B-DNA. We establish a refined Cosserat rod model, which reproduces the deformation behaviors of filament incorporating its microscopic chirality. The helix of filament with twisted microstructures is found to exhibit a DNA-like nonlinear variation of material chirality under large elongation. The multiscale interactions between microscopic chirality of twisted microstructures and macroscopic chirality of helix determine the nonlinear coupling behaviors of hierarchically chiral structured materials. These results provide a fundamental principle for understanding the functions and mechanisms of chiral materials.

Three‐dimensional structural imaging of starch granules by second‐harmonic generation circular dichroism

Chirality is one of the most fundamental and essential structural properties of biological molecules. Many important biological molecules including amino acids and polysaccharides are intrinsically chiral. Conventionally, chiral species can be distinguished by interaction with circularly polarized light, and circular dichroism is one of the best-known approaches for chirality detection. As a linear optical process, circular dichroism suffers from very low signal contrast and lack of spatial resolution in the axial direction. It has been demonstrated that by incorporating nonlinear interaction with circularly polarized excitation, second-harmonic generation circular dichroism can provide much higher signal contrast. However, previous circular dichroism and second-harmonic generation circular dichroism studies are mostly limited to probe chiralities at surfaces and interfaces. It is known that second-harmonic generation, as a second-order nonlinear optical effect, provides excellent optical sectioning capability when combined with a laser-scanning microscope. In this work, we combine the axial resolving power of second-harmonic generation and chiral sensitivity of second-harmonic generation circular dichroism to realize three-dimensional chiral detection in biological tissues. Within the point spread function of a tight focus, second-harmonic generation circular dichroism could arise from the macroscopic supramolecular packing as well as the microscopic intramolecular chirality, so our aim is to clarify the origins of second-harmonic generation circular dichroism response in complicated three-dimensional biological systems. The sample we use is starch granules whose second-harmonic generation-active molecules are amylopectin with both microscopic chirality due to its helical structure and macroscopic chirality due to its crystallized packing. We found that in a starch granule, the second-harmonic generation for right-handed circularly polarized excitation is significantly different from second-harmonic generation for left-handed one, offering excellent second-harmonic generation circular dichroism contrast that approaches 100%. In addition, three-dimensional visualization of second-harmonic generation circular dichroism distribution with sub-micrometer spatial resolution is realized. We observed second-harmonic generation circular dichroism sign change across the starch granules, and the result suggests that in thick biological tissue, second-harmonic generation circular dichroism arises from macroscopic molecular packing. Our result provides a new method to visualize the organization of three-dimensional structures of starch granules. The second-harmonic generation circular dichroism imaging method expands the horizon of nonlinear chiroptical studies from simplified surface/solution environments to complicated biological tissues.

Lehmann effects and rotatoelectricity in liquid crystalline systems made of achiral molecules

We discuss Lehmann effects and rotato-electricity for liquid crystalline phases made of achiral molecules. We point out that for static and dynamic Lehmann effects to exist, it is not necessary to have chiral molecules provided the overall structure has macroscopic chirality. This question is of direct relevance for liquid crystalline phases formed by bent-core molecules provided they have a sufficiently low symmetry. This includes systems which break parity symmetry and have overall C(2) or C(1) symmetry. We point out that for liquid crystalline gels and elastomers one should be able to observe rotato-electricity for systems with macroscopic chirality. Rotatoelectricity is associated with the relative rotations between two subsystems, namely, between the network and the director, in an external electric field. Candidates include gels and even monolayers prepared from bent-core molecules with sufficiently low symmetry.

Self‐Assembly of Racemic Alanine Derivatives: Unexpected Chiral Twist and Enhanced Capacity for the Discrimination of Chiral Species

Twisted ribbons were formed by the self-assembly of racemic alanine derivatives (middle picture), whereas only flat nanostructures were obtained from the individual enantiomers (left). The twist was sensitive to a slight enantiomeric excess and showed remarkable macroscopic chirality. Moreover, it could discriminate various amino acid derivatives (right) and even enabled the determination of the ee value of a mixed system.