No abstract

Broken symmetries induce strong even-order nonlinear optical responses in materials and at interfaces. Unlike conventional covalently bonded nonlinear crystals, van der Waals (vdW) heterostructures feature layers that can be stacked at arbitrary angles, giving complete control over the presence or lack of inversion symmetry at a crystal interface. Here, we report highly tunable second harmonic generation (SHG) from nanomechanically rotatable stacks of bulk hexagonal boron nitride (BN) crystals and introduce the term twistoptics to describe studies of optical properties in twistable vdW systems. By suppressing residual bulk effects, we observe SHG intensity modulated by a factor of more than 50, and polarization patterns determined by moiré interface symmetry. Last, we demonstrate greatly enhanced conversion efficiency in vdW vertical superlattice structures with multiple symmetry-broken interfaces. Our study paves the way for compact twistoptics architectures aimed at efficient tunable frequency conversion and demonstrates SHG as a robust probe of buried vdW interfaces.

Twisted two-dimensional van der Waals (vdW) heterostructures have unlocked a new means for manipulating the properties of quantum materials. The resulting mesoscopic moiré superlattices are accessible to a wide variety of scanning probes. To date, spatially-resolved techniques have prioritized electronic structure visualization, with lattice response experiments only in their infancy. Here, we therefore investigate lattice dynamics in twisted layers of hexagonal boron nitride (hBN), formed by a minute twist angle between two hBN monolayers assembled on a graphite substrate. Nano-infrared (nano-IR) spectroscopy reveals systematic variations of the in-plane optical phonon frequencies amongst the triangular domains and domain walls in the hBN moiré superlattices. Our first-principles calculations unveil a local and stacking-dependent interaction with the underlying graphite, prompting symmetry-breaking between the otherwise identical neighboring moiré domains of twisted hBN.

Previous studies with group C meningococcal polysaccharide-tetanus toxoid (GCMP-TT) conjugates had suggested that the GCMP O-acetyl group masked the protective epitope for group C meningococci through steric hindrance or altered conformations. For this report, we confirmed this phenomenon and performed comparative studies with group Y meningococcal polysaccharide (GYMP)-TT to determine whether it might extend to other serogroups. The de-O-acetylated (dOA) polysaccharides (PSs) resulted in higher serum bactericidal activities (SBA) towards the O-acetylated (OA) meningococcal strains from the respective serogroups. High-resolution H-nuclear magnetic resonance spectroscopy at 500 MHz and competitive inhibition serum bactericidal assays were used to characterize the nature of the protective epitope. In head-to-head comparisons with OA PSs as SBA inhibitors, the dOA PSs provided 10 to 1,000 times better inhibition for GCMP in human and mouse antisera and 6 to 13 times better inhibition for GYMP in mouse antisera, using OA strains in all assays. In addition, the SBA for OA strains was highly correlated with dOA PS-specific immunoglobulin G (r ‫؍‬ 0.72 to 0.98) for both GCMP and GYMP. The results suggest that there may be a generalized role for the O-acetyl group to provide an epitope of misdirected immunogenicity for meningococcal PS capsules, enabling escape from immune surveillance. In addition to greater chemical consistency, the dOA forms of GCMP and GYMP conjugate vaccines endow greater immunologic competence to the PSs, rendering them capable of eliciting higher levels of functional antibodies toward the protective epitopes.

Natural hyperbolic materials with dielectric permittivities of opposite sign along different principal axes can confine long-wavelength electromagnetic waves down to the nanoscale, well below the diffraction limit. This has been demonstrated using hyperbolic phonon polaritons (HPP) in hexagonal boron nitride (hBN) and -MoO 3 , among other materials. However, HPP dissipation at ambient conditions is substantial and its fundamental limits remain unexplored 1,2 . Here, we exploit cryogenic nano-infrared imaging to investigate propagating HPP in isotopically pure hBN and naturally abundant -MoO 3 crystals. Close to liquid-nitrogen temperatures, the losses for HPP in isotopic hBN drop significantly, resulting in propagation lengths in excess of 25 micrometers, with lifetimes exceeding 5 picoseconds, thereby surpassing prior reports on such highly-confined polaritonic modes.Our nanoscale, temperature-dependent imaging reveals the relevance of acoustic phonons in hyperbolic polariton damping and will be instrumental in mitigating such losses for miniaturized middle infrared technologies operating at the liquid-nitrogen temperatures.