Probing hyperbolic and surface phonon-polaritons in 2D materials using Raman spectroscopy.

The hyperbolic dispersion relation of phonon-polaritons (PhPols) in anisotropic van der Waals materials provides high-momentum states, directional propagation, subdiffractional confinement, large optical density of states, and enhanced light-matter interactions. In this work, we use Raman spectroscopy in the convenient backscattering configuration to probe PhPol in GaSe, a 2D material presenting two hyperbolic regions separated by a double reststrahlen band. By varying the incidence angle, dispersion relations are revealed for samples with thicknesses between 200 and 750 nm. Raman spectra simulations confirm the observation of one surface and two extraordinary guided polaritons and match the evolution of PhPol frequency as a function of vertical confinement. GaSe appears to provide relatively low propagation losses and supports confinement factors matching or exceeding those reported for other 2D materials. Resonant excitation close to the 1s exciton singularly exalts the scattering efficiency of PhPols, providing enhanced scattering signals and means to probe the coupling of PhPols to other solid-state excitations.

Restoring the Coherence of Quantum Emitters through Optically Driven Motional Narrowing Forces.

Motional narrowing is a phenomenon by which a quantum state can be entangled with a noisy environment and still retain its intrinsic coherence. Using two optically induced motional forces driving the environmental electrical field amplitude and fluctuations, we present a compelling illustration of the effects of motional narrowing on the energy, line shape, and line width of a single quantum emitter, a Te2 molecule embedded in ZnSe, subject to spectral diffusion. Motional narrowing is achieved in several regimes, irrespectively of the inhomogeneous disorder initially present and the charge reservoir state sourcing the field. The optimal coherence limit set by the radiative rate can be approached by accelerating spectral diffusion into the THz regime. Motional narrowing applies to any quantum systems for which environmental fluctuations can be deliberately accelerated and alleviates the need for perfected materials and devices.

Mid-infrared Polarized Emission from Black Phosphorus Light-Emitting Diodes.

We demonstrate a mid-infrared light-emitting diode based on the 2D semiconductor black phosphorus (BP). The device is composed of a mechanically exfoliated BP/molybdenum disulfide heterojunction. Under forward bias, it emits polarized electroluminescence at λ = 3.68 µm, with room-temperature internal and external quantum efficiencies of ∼1% and ∼0.03%, respectively. In our structure, outcoupling losses are dominated by radiation toward the high refractive index substrate. The ability to tune the bandgap of BP and consequently its emission wavelength with layer number, strain, and electric field make these LEDs particularly attractive for heterointegration into mid-infrared photonic platforms.

Second-Order Raman Scattering in Exfoliated Black Phosphorus.

Second-order Raman scattering has been extensively studied in carbon-based nanomaterials, for example, nanotube and graphene, because it activates normally forbidden Raman modes that are sensitive to crystal disorder, such as defects, dopants, strain, and so forth. The sp2-hybridized carbon systems are, however, the exception among nanomaterials, where first-order Raman processes usually dominate. Here we report the identification of four second-order Raman modes, named D1, D1', D2 and D2', in exfoliated black phosphorus (P(black)), an elemental direct-gap semiconductor exhibiting strong mechanical and electronic anisotropies. Located in close proximity to the Ag1 and Ag2 modes, these new modes dominate at an excitation wavelength of 633 nm. Their evolutions as a function of sample thickness, excitation wavelength, and defect density indicate that they are defect-activated and involve high-momentum phonons in a doubly resonant Raman process. Ab initio simulations of a monolayer reveal that the D' and D modes occur through intravalley scatterings with split contributions in the armchair and zigzag directions, respectively. The high sensitivity of these D modes to disorder helps explaining several discrepancies found in the literature.

Polarization-Resolved Raman Study of Bulk-like and Davydov-Induced Vibrational Modes of Exfoliated Black Phosphorus.

Owing to its crystallographic structure, black phosphorus is one of the few 2D materials expressing strongly anisotropic optical, transport, and mechanical properties. We report on the anisotropy of electron-phonon interactions through a polarization-resolved Raman study of the four vibrational modes of atomically thin black phosphorus (2D phosphane): the three bulk-like modes Ag1, B2g, and Ag2 and the Davydov-induced mode labeled Ag(B2u). The complex Raman tensor elements reveal that the relative variation in permittivity of all Ag modes is irrespective of the atomic motion involved lowest along the zigzag direction, the basal anisotropy of these variations is most pronounced for Ag2 and Ag(B2u), and interlayer interactions in multilayer samples lead to reduced anisotropy. The bulk-forbidden Ag(B2u) mode appears for n ≥ 2 and quickly subsides in thicker layers. It is assigned to a Davydov-induced IR to Raman conversion of the bulk IR mode B2u and exhibits characteristics similar to Ag2. Although this mode is expected to be weak, an electronic resonance significantly enhances its Raman efficiency such that it becomes a dominant mode in the spectrum of bilayer 2D phosphane.

Photooxidation and quantum confinement effects in exfoliated black phosphorus.

Thin layers of black phosphorus have recently raised interest owing to their two-dimensional (2D) semiconducting properties, such as tunable direct bandgap and high carrier mobilities. This lamellar crystal of phosphorus atoms can be exfoliated down to monolayer 2D-phosphane (also called phosphorene) using procedures similar to those used for graphene. Probing the properties has, however, been challenged by a fast degradation of the thinnest layers on exposure to ambient conditions. Herein, we investigate this chemistry using in situ Raman and transmission electron spectroscopies. The results highlight a thickness-dependent photoassisted oxidation reaction with oxygen dissolved in adsorbed water. The oxidation kinetics is consistent with a phenomenological model involving electron transfer and quantum confinement as key parameters. A procedure carried out in a glove box is used to prepare mono-, bi- and multilayer 2D-phosphane in their pristine states for further studies on the effect of layer thickness on the Raman modes. Controlled experiments in ambient conditions are shown to lower the A(g)(1)/A(g)(2) intensity ratio for ultrathin layers, a signature of oxidation.

Reducing the peptidyl features of caspase-3 inhibitors: a structural analysis.

Caspases are cysteine proteases that specifically cleave Asp-Xxx bonds. They are key agents in inflammation and apoptosis and are attractive targets for therapy against inflammation, neurodegeneration, ischemia, and cancer. Many caspase structures are known, but most involve either peptide or protein inhibitors, unattractive candidates for drug development. We present seven crystal structures of inhibited caspase-3 that illustrate several approaches to reducing the peptidyl characteristics of the inhibitors while maintaining their potency and selectivity. The inhibitors reduce the peptidyl nature of inhibitors while preserving binding potency by (1). exploiting a hydrophobic binding site C-terminal to the cleavage site, (2). replacing the negatively charged aspartyl residue at P4 with neutral groups, and (3). using a peptidomimetic 5,6,7-tricyclic system or a pyrazinone at P2-P3. In addition, we have found that two nicotinic acid aldehydes induce a significant conformational change in the S2 and S3 subsites of caspase-3, revealing an unexpected binding mode. These results advance the search for caspase-directed drugs by revealing how unacceptable molecular features can be removed without loss of potency.

Discovery of novel aspartyl ketone dipeptides as potent and selective caspase-3 inhibitors.

The discovery of a series of potent, selective and reversible dipeptidyl caspase-3 inhibitors are reported. The iterative discovery process of using combinatorial chemistry, parallel synthesis, moleculare modelling and structural biology will be discussed.

Photoinduced alkyl group exchange of ethylzinc alkoxides: X-ray crystal structure of an iodomethylzinc methoxide.

Irradiation of a solution of ethyl zinc alkoxides and CH2I2 leads to clean formation of iodomethylzinc alkoxides; these intermediates are important species generated in stereoselective cyclopropanation processes; no alkyl group exchange is observed in the absence of irradiation; the solid-state structure of (MeO)8Zn7(CH2I)6 is also reported.