Size, shape, overall composition, and surface functionality largely determine the properties and applications of metal nanoparticles. Aside from well-defined metal clusters, their composition is ...often estimated assuming a quasi-spherical shape of the nanoparticle core. With decreasing diameter of the assumed circumscribed sphere, particularly in the range of only a few nanometers, the estimated nanoparticle composition increasingly deviates from the real composition, leading to significant discrepancies between anticipated and experimentally observed composition, properties, and characteristics. We here assembled a compendium of tables, models, and equations for thiol-protected gold nanoparticles that will allow experimental scientists to more accurately estimate the composition of their gold nanoparticles using TEM image analysis data. The estimates obtained from following the routines described here will then serve as a guide for further analytical characterization of as-synthesized gold nanoparticles by other bulk (thermal, structural, chemical, and compositional) and surface characterization techniques. While the tables, models, and equations are dedicated to gold nanoparticles, the composition of other metal nanoparticle cores with face-centered cubic lattices can easily be estimated simply by substituting the value for the radius of the metal atom of interest.
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Chirality is a fundamental scientific concept best described by the absence of mirror symmetry and the inability to superimpose an object onto its mirror image by translation and rotation. Chirality ...is expressed at almost all molecular levels, from single molecules to supramolecular systems, and present virtually everywhere in nature. Here, to explore how chirality propagates from a chiral nanoscale surface, we study gold nanoparticles functionalized with axially chiral binaphthyl molecules. In particular, we synthesized three enantiomeric pairs of chiral ligand-capped gold nanoparticles differing in size, curvature, and ligand density to tune the chirality transfer from nanoscale solid surfaces to a bulk anisotropic liquid crystal medium. Ultimately, we are examining how far the chirality from a nanoparticle surface reaches into a bulk material. Circular dichroism spectra of the gold nanoparticles decorated with binaphthyl thiols confirmed that the binaphthyl moieties form a cisoid conformation in isotropic organic solvents. In the chiral nematic liquid crystal phase, induced by dispersing the gold nanoparticles into an achiral anisotropic nematic liquid crystal solvent, the binaphthyl moieties on the nanoparticle surface form a transoid conformation as determined by imaging the helical twist direction of the induced cholesteric phase. This suggests that the ligand density on the nanoscale metal surfaces provides a dynamic space to alter and adjust the helicity of binaphthyl derivatives in response to the ordering of the surrounding medium. The helical pitch values of the induced chiral nematic phase were determined, and the helical twisting power (HTP) of the chiral gold nanoparticles calculated to elucidate the chirality transfer efficiency of the binaphthyl ligand capped gold nanoparticles. Remarkably, the HTP increases with increasing diameter of the particles, that is, the efficiency of the chirality transfer of the binaphthyl units bound to the nanoparticle surface is diminished as the size of the particle is reduced. However, in comparison to the free ligands, per chiral molecule all tested gold nanoparticles induce helical distortions in a 10- to 50-fold larger number of liquid crystal host molecules surrounding each particle, indicating a significantly enhanced chiral correlation length. We propose that both the helicity and the chirality transfer efficiency of axially chiral binaphthyl derivatives can be controlled at metal nanoparticle surfaces by adjusting the particle size and curvature as well as the number and density of the chiral ligands to ultimately measure and tune the chiral correlation length.
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In this work, we demonstrate control of the handedness of semicrystalline modulated helical nanofilaments (HNFmods) formed by achiral bent-core liquid crystal molecules by axially chiral ...binaphthyl-based additives as guest molecules solely under spatial nanoconfinement in anodic aluminum oxide nanochannels. The molecules of the same chiral additives are expelled from the HNFmods in the bulk, and as a result thereof do not affect the handedness or helical pitch of bulk HNFmods, resulting in an HNFmod conglomerate with chirality-preserving growth within each domain. However, under confinement these axially chiral guest molecules, likely embedded in the HNFmod host, do affect the helicity of the HNFmods. The configuration of the axially chiral molecules decides the HNFmod helix handedness and their concentration, and the helix angle is related to the helical pitch of the HNFmods. In addition to local imaging data obtained by scanning electron microscopy, global studies by thin-film circular dichroism spectropolarimetry support the imaging results.
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Fascinating nematic‐ and smectic‐like self‐assembled arrays are observed for gold nanorods partially capped with either laterally or terminally attached nematic liquid crystals upon slow evaporation ...of an organic solvent on TEM grids. These arrays can be manipulated and reoriented by applying an external magnetic field from quasi‐planar to vertical similar to a Fréedericksz transition of common organic nematic liquid crystals. Birefringence and thin film textures of these self‐assembled gold nanorod arrays observed by polarized optical microscopy are strongly reminiscent of common organic nematic liquid crystal textures between crossed polarizers and, additionally, support the formation of ordered liquid crystal‐like anisotropic superstructures. The ordering within these arrays is also confirmed in bulk samples using small angle X‐ray scattering (SAXS).
Fascinating nematic‐ and smectic‐like self‐assembled arrays are observed for gold nanorods partially capped with either laterally or terminally substituted nematic liquid crystals upon slow evaporation of an organic solvent on transmission electron microscopy (TEM) grids. These arrays can be manipulated and reoriented by applying an external magnetic field from quasi‐planar to vertical similar to a Fréedericksz transition of common organic nematic liquid crystals.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
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.
Polymorphism is a remarkable concept in chemistry, materials science, computer science, and biology. Whether it is the ability of a material to exist in two or more crystal structures, a single ...interface connecting to two different entities, or alternative phenotypes of an organism, polymorphism determines function and properties. In materials science, polymorphism can be found in an impressively wide range of materials, including crystalline materials, minerals, metals, alloys, and polymers. Here we report on polymorphism in a liquid crystal. A bent-core liquid crystal with a single chiral side chain forms two structurally and morphologically significantly different liquid crystal phases solely depending on the cooling rate from the isotropic liquid state. On slow cooling, the thermodynamically more stable oblique columnar phase forms, and on rapid cooling, a not heretofore reported helical microfilament phase. Since structure determines function and properties, the structural color for these phases also differs.
Revolutionary developments in the fabrication of nanosized particles have created enormous expectations in the last few years for the use of such materials in areas such as medical diagnostics and ...drug-delivery, and in high-tech devices. By its very nature, nanotechnology is of immense academic and industrial interest as it involves the creation and exploitation of materials with structural features in between those of atoms and bulk materials, with at least one dimension limited to between 1 and 100 nm. Most importantly, the properties of materials with nanometric dimensions are, in most instances, significantly different from those of atoms or bulk materials. Research efforts geared towards new synthetic procedures for shape and size-uniform nanoscale building blocks as well as efficient self-assembly protocols for manipulation of these building blocks into functional materials has created enormous excitement in the field of liquid crystal research. Liquid crystals (LCs) by their very nature are suitable candidates for matrix-guided synthesis and self-assembly of nanoscale materials, since the liquid crystalline state combines order and mobility at the molecular (nanoscale) level. Based on selected relevant examples, this review attempts to give a short overview of current research efforts in LC-nanoscience. The areas addressed in this review include the synthesis of nanomaterials using LCs as templates, the design of LC nanomaterials, self-assembly of nanomaterials using LC phases, defect formation in LC-nanoparticle suspensions, and potential applications. Despite the seeming diversity of these research topics, this review will make an effort to establish logical links between these different research areas.
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EMUNI, FIS, FZAB, GEOZS, GIS, IJS, IMTLJ, KILJ, KISLJ, MFDPS, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, SBMB, SBNM, UKNU, UL, UM, UPUK, VKSCE, ZAGLJ
We report that liquid crystal elastomers (LCEs), often portrayed as artificial muscles, serve as scaffolds for skeletal muscle cell. A simultaneous microemulsion photopolymerization and cross-linking ...results in nematic LCE microspheres 10–30 μm in diameter that when conjoined form a LCE construct that serves as the first proof-of-concept for responsive LCE muscle cell scaffolds. Confocal microscopy experiments clearly established that LCEs with a globular, porous morphology permit both attachment and proliferation of C2C12 myoblasts, while the nonporous elastomer morphology, prepared in the absence of a microemulsion, does not. In addition, cytotoxicity and proliferation assays confirm that the liquid crystal elastomer materials are biocompatible promoting cellular proliferation without any inherent cytotoxicity.
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Chirality at the nanoscale, or more precisely, the chirality or chiroptical effects of chiral ligand-capped metal nanoparticles (NPs) is an intriguing and rapidly evolving field in nanomaterial ...research with promising applications in catalysis, metamaterials, and chiral sensing. The aim of this work was to seek out a system that not only allows the detection and understanding of NP chirality but also permits visualization of the extent of chirality transfer to a surrounding medium. The nematic liquid crystal phase is an ideal candidate, displaying characteristic defect texture changes upon doping with chiral additives. To test this, we synthesized chiral cholesterol-capped gold NPs and prepared well-dispersed mixtures in two nematic liquid crystal hosts. Induced circular dichroism spectropolarimetry and polarized light optical microscopy revealed that all three gold NPs induce chiral nematic phases, and that those synthesized in the presence of a chiral bias (disulfide) are more powerful chiral inducers than those where the NP was formed in the absence of a chiral bias (prepared by conjugation of a chiral silane to preformed NPs). Helical pitch data here visually show a clear dependence on the NP size and the number of chiral ligands bound to the NP surface, thereby supporting earlier experimental and theoretical data that smaller metal NPs made in the presence of a chiral bias are stronger chiral inducers.
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In this Highlight article we will describe the current impact of nanoscale materials (nanoparticles and carbon nanotubes) in liquid crystal nanocomposites on the improvement of LC display (LCD) ...applications, an industry currently worth more than $60 billion per year. First tendencies clearly demonstrate the potential of nanomaterials to improve upon current LCD technologies with the discovery of new or modified switching modes, lower operating voltages, faster switching speeds, and higher contrast ratios-enormous advantages in a world with more LCDs than people (see ref. : D. W. Bruce, J. W. Goodby, J. R. Sambles and H. J. Coles, Introduction: New directions in liquid crystal science, Philos. Trans. R. Soc. London, Ser. A, 2006, 364, 2567-2571).
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