Induction, transmission, and manipulation of chirality in molecular systems are well known, widely applied concepts. However, our understanding of how chirality of nanoscale entities can be controlled, measured, and transmitted to the environment is considerably lacking behind. Future discoveries of dynamic assemblies engineered from chiral nanomaterials, with a specific focus on shape and size effects, require exact methods to assess transmission and amplification of nanoscale chirality through space. Here we present a remarkably powerful chirality amplification approach by desymmetrization of plasmonic nanoparticles to nanorods. When bound to gold nanorods, a one order of magnitude lower number of chiral molecules induces a tighter helical distortion in the surrounding liquid crystal–a remarkable amplification of chirality through space. The change in helical distortion is consistent with a quantification of the change in overall chirality of the chiral ligand decorated nanomaterials differing in shape and size as calculated from a suitable pseudoscalar chirality indicator.
We describe the development and implementation of a new reversible coarse grained model where complex organic molecules are described in terms of a set of connected biaxial Gay–Berne ellipsoidal beads, decorated with point charges.
The creation and transmission of chirality in molecular systems is a well-known, widely applied notion. Our understanding of how the chirality of nanomaterials can be controlled, measured, transmitted through space, and applied is less well understood. Dynamic assemblies for chiral sensing or metamaterials engineered from chiral nanomaterials require exact methods to determine transmission and amplification of nanomaterial chirality through space. We report the synthesis of a series of gold nanorods (GNRs) with a constant aspect ratio of ∼4.3 capped with C 2 -symmetric, axially chiral binaphthyl thiols, preparation of dispersions in the nematic liquid crystal 5CB, measurements of the helical pitch, and the determination of the helical twisting power as well as the average distance between the chiral nanomaterial additives. By comparison to the neat organic chiral derivatives, we demonstrate how the amplification of chirality facilitated by GNRs decorated with chiral molecules can be used to clearly distinguish the chiral induction strength of a homologous series of binaphthyl derivatives, differing only in the length of the nontethered aliphatic chain, in the induced chiral nematic liquid crystal phase. Considering systematic errors in sample preparation and optical measurements, these chiral molecules would otherwise be deemed identical with respect to chiral induction. Notably, we find some of the highest ever-reported values of the helical twisting power. We further support our experimentally derived arguments of a more comprehensive understanding of chirality transfer by calculations of a suitable pseudoscalar chirality indicator.
Chirality, as a concept, is well understood at most length scales. However, quantitative models predicting the efficacy of the transmission of chirality across length scales are lacking. We propose here a modus operandi for a chiral nanoshape solute in an achiral nematic liquid crystal host showing that that chirality transfer may be understood by unusually simple geometric considerations. This mechanism is based on the product of a pseudoscalar chirality indicator and of a geometric shape compatibility factor based on the two-dimensional isoperimetric quotients for each nanoshape solute. The model is tested on an experimental set of precisely engineered gold nanoshapes. These libraries of calculated and in-parallel acquired experimental data among related nanoshapes pave the way for predictive calculations of chirality transfer in nanoscale, macromolecular, and biological systems, from designing chiral discriminators and enantioselective catalysts to developing chiral metamaterials and understanding nature’s innate ability to transfer homochirality across length scales.
Extending the range of existence of biaxial nematic phases is key to their use in applications. Here, we have investigated using extensive molecular dynamics (MD) simulations of a coarse-grained model the possible advantages of using mesogenic mixtures. We have studied the phase organisation of five thermotropic mixtures of biaxial Gay-Berne (GB) ellipsoidal particles having the same volume, but different shapes and interactions, with aspect ratios ranging from rod-like to disc-like and, choosing fractional compositions so as to model a Gaussian dispersity of shapes. The parameterisation is based on a previous GB model with biaxialities of opposite sign for steric and attractive interactions which was shown to exhibit a stable biaxial nematic phase. We found that mixing different biaxial GB particles has an overall stabilising effect on the biaxial nematic phase with respect to temperature, layering and, to some extent also demixing. The mixtures show a decrease of ordering transition temperatures, a widening of nematic temperature ranges, and the formation of smectic phases at lower temperatures.
We have investigated the possibility of extending the stability range of the biaxial nematic phase by adding an off-centre dipole of various strengths and orientations to elongated biaxial Gay-Berne (GB) mesogens yielding a relatively narrow biaxial nematic (N) phase, and a smectic (S) phase when dipole-less. The effect of dipoles is not easy to predict, and our previous investigations have shown the limited benefits of having a central dipole. Here we show, employing molecular dynamics (MD) simulations, that a not too strong off-centre dipole positioned along the longest axis of the nematogen can extend the temperature range of stability of the biaxial nematic phase, also shifting it towards lower temperatures.
Defined based on geometric concepts, the origin of biological homochirality including the single handedness of key building blocks, D-sugars and L-amino acids, is still heavily debated in many ongoing research...
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