Chiral surfaces are of growing interest for enantioselective adsorption and reactions. While metal surfaces can be prepared with a wide range of chiral surface orientations, chiral oxide surface preparation is much more challenging. Herein, we demonstrate that the chirality of a metal surface can be used to direct the homochiral growth of a thin film chiral oxide. Specifically, we study the chiral ‘29’ copper oxide, formed by oxidizing a Cu(111) single crystal at 650 K. Surface structure spread single crystals which expose a continuous distribution of surface orientations as a function of position on the crystal, enabled us to systematically investigate the mechanism of chirality transfer between metal and oxide with high-resolution scanning tunneling microscopy. We discovered that the local underlying metal facet directs the orientation and chirality of the oxide overlayer. Importantly, single homochiral domains of the ‘29’ oxide were found in areas where the Cu step edges that templated growth were ≤20 nm apart. We used this information to select a Cu(239 241 246) oriented single crystal and demonstrate that a ‘29’ oxide surface can be grown in homochiral domains by templating from the subtle chirality of the underlying metal crystal. This work demonstrates how a small degree of chirality induced by very slight misorientation of a metal surface (~1 sites/ 20 nm2) can be amplified by oxidation to yield a homochiral oxide with a regular array of chiral oxide pores (~75 sites/ 20 nm2). This offers a general approach for making chiral oxide surfaces via oxidation of an appropriately miscut metal surface.
more »
« less
Nonlinear chiral rheology of phospholipid monolayers
Microbutton rheometry reveals that the chiral morphology of dipalmitoylphosphatidylcholine (DPPC) monolayers imparts a chiral nonlinear rheological response. The nonlinear elastic modulus and yield stress of DPPC monolayers are greater when sheared clockwise (C), against the natural winding direction of DPPC domains, than counter-clockwise (CC). Under strong CC shear strains, domains deform plastically; by contrast, domains appear to fracture under strong C shearing. After CC shearing, extended LC domains develop regular patterns of new invaginations as they recoil, which we hypothesize reflect the nucleation and growth of new defect lines across which the tilt direction undergoes a step change in orientation. The regular spacing of these twist-gradient defects is likely set by a competition between the molecular chirality and the correlation length of the DPPC lattice. The macroscopic mechanical consequences of DPPC's underlying molecular chirality are remarkable, given the single-component, non-cross-linked nature of the monolayers they form.
more »
« less
- Award ID(s):
- 1706378
- PAR ID:
- 10057718
- Date Published:
- Journal Name:
- Soft Matter
- Volume:
- 14
- Issue:
- 13
- ISSN:
- 1744-683X
- Page Range / eLocation ID:
- 2476 to 2483
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Abstract Supramolecular chirality typically originates from either chiral molecular building blocks or external chiral stimuli. Generating chirality in achiral systems in the absence of a chiral input, however, is non-trivial and necessitates spontaneous mirror symmetry breaking. Achiral nematic lyotropic chromonic liquid crystals have been reported to break mirror symmetry under strong surface or geometric constraints. Here we describe a previously unrecognised mechanism for creating chiral structures by subjecting the material to a pressure-driven flow in a microfluidic cell. The chirality arises from a periodic double-twist configuration of the liquid crystal and manifests as a striking stripe pattern. We show that the mirror symmetry breaking is triggered at regions of flow-induced biaxial-splay configurations of the director field, which are unstable to small perturbations and evolve into lower energy structures. The simplicity of this unique pathway to mirror symmetry breaking can shed light on the requirements for forming macroscopic chiral structures.more » « less
-
Supramolecular chirality typically originates from either chiral molecular building blocks or external chiral stimuli. Generating chirality in achiral systems in the absence of a chiral input, however, is non-trivial and necessitates spontaneous mirror symmetry breaking. Achiral nematic lyotropic chromonic liquid crystals have been reported to break mirror symmetry under strong surface or geometric constraints. Here we describe a previously unrecognised mechanism for creating chiral structures by subjecting the material to a pressure-driven flow in a microfluidic cell. The chirality arises from a periodic double-twist configuration of the liquid crystal and manifests as a striking stripe pattern. We show that the mirror symmetry breaking is triggered at regions of flow-induced biaxial-splay configurations of the director field, which are unstable to small perturbations and evolve into lower energy structures. The simplicity of this unique pathway to mirror symmetry breaking can shed light on the requirements for forming macroscopic chiral structures.more » « less
-
Achiral metasurfaces with near-field optical chirality have attracted great attention in molecular sensing and chiral emission control. Here, the circular dichroism (CD) response of an achiral metasurface induced by spatially selective coupling with polymethyl methacrylate (PMMA) molecules is demonstrated. A designed achiral metasurface with a V-shaped resonator exhibits large optical chirality with a strongly dissymmetric distribution under circular polarization. By introducing a PMMA molecule layer on top of the metasurface, which covers the area with large optical chirality, CD in absorption of 0.38 and a dissymmetric factor of optical chiralitygcof 0.16 are obtained. Furthermore, an analysis of the coupled harmonic oscillator model reveals stronger coupling strength between the PMMA layer and the metasurface under RCP incidence, compared to the LCP case. Moreover, it is shown that the far-field CD response of the metasurface is linearly correlated with the dissymmetric near-field optical chirality distribution. The demonstrated results present the potential for advancing applications in chiral molecule vibrational sensing, thermal emission control, and infrared chiral imaging.more » « less
-
Surface tension, surface-specific vibrational spectroscopy and differential scanning calorimetry measurements were all used to test cooperative adsorption of glucuronic acid (GU) to DPPC monolayers adsorbed to the aqueous/vapor interface. Experiments were performed using GU solutions prepared in Millipore water and in carbonate/bicarbonate solutions buffered to a pH of 9.0. The effects of GU on DPPC monolayer structure and organization were carried out with tightly packed monolayers (40 Å2/DPPC) and monolayers in their liquid condensed phase (55 Å2/molecule). Surface tension data show that GU concentrations of 50 mM lead to expanded DPPC monolayers with diminished surface tensions (or higher surface pressures) at a given DPPC coverage relative to monolayers on pure water. With unbuffered solutions, GU induces significant ordering within liquid condensed monolayers although the effects of GU on tightly packed DPPC monolayers are less pronounced. GU also induces a second, higher melting temperature in DPPC vesicles implying that GU (at sufficiently high concentrations) strengthens lipid-lipid cohesion, possibly by replacing water solvating the DPPC headgroups. Together, these observations all support a cooperative adsorption mechanism. In buffer solutions, the effects of dissolved GU on DPPC structure and organization are muted. Only at sufficiently high GU concentrations (when the solution’s buffering capacity has been exceeded) do the data again show evidence of cooperative adsorption. These findings place limits on cooperative adsorption’s ability to enrich interfacial organic content in alkaline environmental systems such as oceans.more » « less
An official website of the United States government

