SearcharxivSearch

arXiv · 1405.7060

Evanescent-wave and open-air chiral sensing via signal-reversing cavity-enhanced polarimetry

Abstract

Sensing chirality is of fundamental importance to many fields, including analytical and biological chemistry, pharmacology, and fundamental physics. Recent developments have extended optical chiral sensing using microwaves, fs pulses, superchiral light, and photoionization. The most widely used methods are the traditional methods of circular dichroism and optical rotation (OR). However, chiral signals are typically very weak, and their measurement is limited by larger time-dependent backgrounds and by imperfect and slow subtraction procedures. Here, we demonstrate a pulsed-laser bowtie-cavity-enhanced polarimeter with counter-propagating beams, which solves these background problems: the chiral signals are enhanced by the number of cavity passes; the effects of linear birefringence are suppressed by a large induced intracavity Faraday rotation; and rapid signal reversals are effected by reversing the Faraday rotation and subtracting signals from the counter-propagating beams. These advantages allow measurements of absolute chiral signals in environments where background subtractions are not feasible: we measure optical rotation from chiral vapour in open air, and from chiral liquids in the evanescent wave (EW) produced by total internal reflection at a prism surface. EW-OR of (+)-maltodextrin and (-)-fructose solutions confirm the Drude-Condon model for Maxwell's equations in isotropic optically active media. In particular, the effective optical rotation path length, near index matching, is equal to the Goos-H\"anchen shift of the EW. The limits of this polarimeter, when using a continuous-wave laser locked to a stable high-finesse cavity, should match sensitivity measurements for linear birefringence ($3\times 10^{-13}$ rad), which is several orders of magnitude more sensitive than current chiral detection limits, transforming the power of chiral sensing in many fields.

Explore related subjects

Keep this discovery

BibTeXRIS

Dimitris Sofikitis, Lykourgos Bougas, Georgios E. Katsoprinakis, Alexandros K. Spiliotis, Benoit Loppinet, T. Peter Rakitzis. 2014-05-27. Evanescent-wave and open-air chiral sensing via signal-reversing cavity-enhanced polarimetry. https://doi.org/10.1038/nature13680

Cite the original work for its findings. Save a collection to share your selection of sources.

KEEP EXPLORING

Related papers

Breaking Water at Graphene Defects

Water dissociation at solid surfaces underpins processes ranging from corrosion and catalysis to electrochemistry and photovoltaics. Defects often serve as reactive sites for dissociation, yet how solvation influences water dissociation at such sites remains poorly understood. Here, we use state-of-the-art machine-learned interatomic potentials to explore water dissociation at defective graphene-water interfaces. We show that solvation qualitatively changes the reaction mechanism at a graphene single vacancy (SV), opening pathways that are absent for an isolated water molecule. Whereas the gas-phase process proceeds via a single concerted channel, the solvated SV splits water through two competing pathways: a basic route forming SV-H and OH-(aq), and an acidic route forming SV-OH and H3O+(aq). These lower-barrier pathways produce distinct chemisorbed intermediates that enhance graphene-water adsorption. Accordingly, even a simple carbon vacancy gives rise to unexpectedly rich interfacial chemistry, coupling surface chemistry to interfacial charge and wettability, with implications for carbon functionalization and nanofluidic transport.

physics.chem-ph

Comprehensive Study of L-Menthol and Octanoic Acid as a Hydrophobic Eutectic Solvent

Hydrophobic eutectic solvents (HES) based on natural compounds represent promising green alternatives to conventional solvents. In this work, we investigate the physicochemical, structural, and dynamical properties of an ES formed by L-menthol and octanoic acid using a combined experimental and molecular dynamics simulation approach. Five compositions with molar ratios from 1:3 to 3:1 were studied with molecular dynamics simulation in the temperature range 15 degrees C to 35 degrees C. Experimental measurements of density and viscosity in the temperature range from 5 degrees C to 35 degrees C were complemented with results obtained from MD simulations employing the OPLS force field. Structural analyses based on radial distribution functions and Kirkwood-Buff integrals reveal that the dominant interactions in the mixture are hydrogen bonds between L-menthol and octanoic acid molecules. Dynamic properties, including self-diffusion coefficients and hydrogen-bond lifetimes, indicate that intermolecular hydrogen bonds between the two components are stronger and longer-lived than bonds between identical species. These findings provide molecular-level insight into the structure and transport properties of menthol-based ESs relevant for green solvent applications.

physics.chem-ph

More is not always better: Dissociative photoionization limits the EUV absorbing photacid generator pentafluorophenyl triflate in photolithography

Pentafluorophenyl triflate has been explored as a highly absorbing neutral photoacid generator (PAG) candidate for next generation chemically amplified resists used in extreme ultraviolet (EUV) lithography. Although increased fluorination enhances EUV absorption, this study demonstrates that such an approach does not necessarily improve photoacid generation efficiency. Using photoelectron-photoion coincidence (PEPICO) spectroscopy at the 92 eV photon energy of the EUV scanners in combination with quantum chemical calculations, the dissociative photoionization of pentafluorophenyl triflate was systematically investigated. The photoionization mass spectrum reveals extensive fragmentation, with the parent ion contributing only 3.1 % of the total signal and CF$_3^+$ representing the dominant product ion. Computed appearance energies align well with experimental trends and support a sequential fragmentation pathway involving loss of SO$_2$, CF$_3$, and CO. Crucially, none of the major dissociation channels yield precursors capable of forming triflic acid, the strong photoacid required for efficient deprotection reactions in chemically amplified resists. Combined with previous dissociative electron attachment studies indicating similarly unfavorable fragmentation, the results demonstrate that despite its high EUV absorption cross section, pentafluorophenyl triflate is unsuitable as a PAG for EUV lithography. The findings highlight the importance of understanding fundamental photoionization and electron interaction mechanisms to guide the rational design of next generation high performance EUV photoresists.

physics.chem-ph