Absolute optical chiral analysis using cavity-enhanced polarimetry.

Chiral analysis is central for scientific advancement in the fields of chemistry, biology, and medicine. It is also indispensable in the development and quality control of chiral compounds in the chemical and pharmaceutical industries. Here, we present the concept of absolute optical chiral analysis, as enabled by cavity-enhanced polarimetry, which allows for accurate unambiguous enantiomeric characterization and enantiomeric excess determination of chiral compounds within complex mixtures at trace levels, without the need for calibration, even in the gas phase. Our approach and technology enable the absolute postchromatographic chiral analysis of complex gaseous mixtures, the rapid quality control of complex mixtures containing chiral volatile compounds, and the online in situ observation of chiral volatile emissions from a plant under stress.

Rapid parameter determination of discrete damped sinusoidal oscillations.

We present different computational approaches for the rapid extraction of the signal parameters of discretely sampled damped sinusoidal signals. We compare time- and frequency-domain-based computational approaches in terms of their accuracy and precision and computational time required in estimating the frequencies of such signals, and observe a general trade-off between precision and speed. Our motivation is precise and rapid analysis of damped sinusoidal signals as these become relevant in view of the recent experimental developments in cavity-enhanced polarimetry and ellipsometry, where the relevant time scales and frequencies are typically within the ∼1 - 10 µs and ∼1 - 100 MHz ranges, respectively. In such experimental efforts, single-shot analysis with high accuracy and precision becomes important when developing experiments that study dynamical effects and/or when developing portable instrumentations. Our results suggest that online, running-fashion, microsecond-resolved analysis of polarimetric/ellipsometric measurements with fractional uncertainties at the 10-6 levels, is possible, and using a proof-of-principle experimental demonstration we show that using a frequency-based analysis approach we can monitor and analyze signals at kHz rates and accurately detect signal changes at microsecond time-scales.

Action potentials induce biomagnetic fields in carnivorous Venus flytrap plants.

Upon stimulation, plants elicit electrical signals that can travel within a cellular network analogous to the animal nervous system. It is well-known that in the human brain, voltage changes in certain regions result from concerted electrical activity which, in the form of action potentials (APs), travels within nerve-cell arrays. Electro- and magnetophysiological techniques like electroencephalography, magnetoencephalography, and magnetic resonance imaging are used to record this activity and to diagnose disorders. Here we demonstrate that APs in a multicellular plant system produce measurable magnetic fields. Using atomic optically pumped magnetometers, biomagnetism associated with electrical activity in the carnivorous Venus flytrap, Dionaea muscipula, was recorded. Action potentials were induced by heat stimulation and detected both electrically and magnetically. Furthermore, the thermal properties of ion channels underlying the AP were studied. Beyond proof of principle, our findings pave the way to understanding the molecular basis of biomagnetism in living plants. In the future, magnetometry may be used to study long-distance electrical signaling in a variety of plant species, and to develop noninvasive diagnostics of plant stress and disease.

Absolute Chiral Sensing in Dielectric Metasurfaces Using Signal Reversals.

Sensing molecular chirality at the nanoscale has been a long-standing challenge due to the inherently weak nature of chiroptical signals, and nanophotonic approaches have proven fruitful in accessing these signals. However, in most cases, complete sensing of the chiral part of the molecule's refractive index (magnitude and sign of both its real and imaginary part) has not been possible, while the strong inherent signals from the nanostructures themselves obscure the weak chiroptical signals. Here, we propose a dielectric metamaterial system that overcomes these limitations and allows for complete measurements of the total chirality and discrimination of the effects of its real and imaginary part, possible also in an absolute manner via the application of a crucial signal reversal (excitation with reversed polarization) that enables chirality measurements without the need for sample removal. As proof of principle, we demonstrate signal enhancements by a factor of 200 for ultrathin, subwavelength, chiral samples over a uniform and accessible area.

Continuous-wave cavity ring-down polarimetry.

We present a new cavity-based polarimetric scheme for highly sensitive and time-resolved measurements of birefringence and dichroism, linear and circular, that employs rapidly pulsed single-frequency continuous wave (CW) laser sources and extends current cavity-based spectropolarimetric techniques. We demonstrate how the use of a CW laser source allows for gains in spectral resolution, signal intensity, and data acquisition rate compared to traditional pulsed-based cavity ring-down polarimetry (CRDP). We discuss a particular CW-CRDP modality that is different from intensity-based cavity-enhanced polarimetric schemes as it relies on the determination of the polarization rotation frequency during a ring-down event generated by large intracavity polarization anisotropies. We present the principles of CW-CRDP and validate the applicability of this technique for the measurement of the non-resonant Faraday effect in solid SiO2 and CeF3 and gaseous butane. We give a general analysis of the fundamental sensitivity limits for CRDP techniques and show how the presented frequency-based methodology alleviates the requirement for high finesse cavities to achieve high polarimetric sensitivities and, thus, allows for the extension of cavity-based polarimetric schemes into different spectral regimes, but most importantly renders the CW-CRDP methodology particularly suitable for robust portable polarimetric instrumentations.

Diamond Magnetic Microscopy of Malarial Hemozoin Nanocrystals.

Magnetic microscopy of malarial hemozoin nanocrystals is performed by optically detected magnetic resonance imaging of near-surface diamond nitrogen-vacancy centers. Hemozoin crystals are extracted from Plasmodium falciparum-infected human blood cells and studied alongside synthetic hemozoin crystals. The stray magnetic fields produced by individual crystals are imaged at room temperature as a function of the applied field up to 350 mT. More than 100 nanocrystals are analyzed, revealing the distribution of their magnetic properties. Most crystals (96%) exhibit a linear dependence of the stray-field magnitude on the applied field, confirming hemozoin's paramagnetic nature. A volume magnetic susceptibility of 3.4 × 10-4 is inferred with use of a magnetostatic model informed by correlated scanning-electron-microscopy measurements of crystal dimensions. A small fraction of nanoparticles (4/82 for Plasmodium falciparum-produced nanoparticles and 1/41 for synthetic nanoparticles) exhibit a saturation behavior consistent with superparamagnetism. Translation of this platform to the study of living Plasmodium-infected cells may shed new light on hemozoin formation dynamics and their interaction with antimalarial drugs.

Infrared laser threshold magnetometry with a NV doped diamond intracavity etalon.

We propose a hybrid laser system consisting of a semiconductor external cavity laser associated to an intra-cavity diamond etalon doped with nitrogen-vacancy color centers. We consider laser emission tuned to the infrared absorption line that is enhanced under the magnetic field dependent nitrogen-vacancy electron spin resonance and show that this architecture leads to a compact solid-state magnetometer that can be operated at room-temperature. The sensitivity to the magnetic field limited by the photonshot-noise of the output laser beam is estimated to be less than 1 pT/Hz. Unlike usual NV center infrared magnetometry, this method would not require an external frequency stabilized laser. Since the proposed system relies on the competition between the laser threshold and an intracavity absorption, such laser-based optical sensor could be easily adapted to a broad variety of sensing applications based on absorption spectroscopy.

On the Possibility of Miniature Diamond-Based Magnetometers Using Waveguide Geometries.

We propose the use of a diamond waveguide structure to enhance the sensitivity of magnetometers relying on the detection of the spin state of nitrogen-vacancy ensembles in diamond by infrared optical absorption. An optical waveguide structure allows for enhanced optical path-lengths avoiding the use of optical cavities and complicated setups. The presented design for diamond-based magnetometers enables miniaturization while maintaining high sensitivity and forms the basis for magnetic field sensors applicable in biomedical, industrial and space-related applications.

Nondestructive in-line sub-picomolar detection of magnetic nanoparticles in flowing complex fluids.

Over the last decades, the use of magnetic nanoparticles in research and commercial applications has increased dramatically. However, direct detection of trace quantities remains a challenge in terms of equipment cost, operating conditions and data acquisition times, especially in flowing conditions within complex media. Here we present the in-line, non-destructive detection of magnetic nanoparticles using high performance atomic magnetometers at ambient conditions in flowing media. We achieve sub-picomolar sensitivities measuring ~30 nm ferromagnetic iron and cobalt nanoparticles that are suitable for biomedical and industrial applications, under flowing conditions in water and whole blood. Additionally, we demonstrate real-time surveillance of the magnetic separation of nanoparticles from water and whole blood. Overall our system has the merit of in-line direct measurement of trace quantities of ferromagnetic nanoparticles with so far unreached sensitivities and could be applied in the biomedical field (diagnostics and therapeutics) but also in the industrial sector.

Highly Nuclear-Spin-Polarized Deuterium Atoms from the UV Photodissociation of Deuterium Iodide.

We report a novel highly spin-polarized deuterium (SPD) source, via the photodissociation of deuterium iodide at 270 nm. I(^{2}P_{3/2}) photofragments are ionized with m-state selectivity, and their velocity distribution measured via velocity-map slice imaging, from which the D polarization is determined. The process produces ∼100% electronically polarized D at the time of dissociation, which is then converted to ∼60% nuclear D polarization after ∼1.6 ns. These production times for SPD allow collision-limited densities of ∼10^{18} cm^{-3} and at production rates of ∼10^{21} s^{-1} which are 10^{6} and 10^{4} times higher than conventional (Stern-Gerlach separation) methods, respectively. We discuss the production of SPD beams, and combining high-density SPD with laser fusion, to investigate polarized D-T, D-^{3}He, and D-D fusion.

Chiral cavity ring down polarimetry: Chirality and magnetometry measurements using signal reversals.

We present the theory and experimental details for chiral-cavity-ring-down polarimetry and magnetometry, based on ring cavities supporting counterpropagating laser beams. The optical-rotation symmetry is broken by the presence of both chiral and Faraday birefringence, giving rise to signal reversals which allow rapid background subtractions. We present the measurement of the specific rotation at 800 nm of vapors of α-pinene, 2-butanol, and α-phellandrene, the measurement of optical rotation of sucrose solutions in a flow cell, the measurement of the Verdet constant of fused silica, and measurements and theoretical treatment of evanescent-wave optical rotation at a prism surface. Therefore, these signal-enhancing and signal-reversing methods open the way for ultrasensitive polarimetry measurements in gases, liquids and solids, and at surfaces.

Search for Ultralight Scalar Dark Matter with Atomic Spectroscopy.

We report new limits on ultralight scalar dark matter (DM) with dilatonlike couplings to photons that can induce oscillations in the fine-structure constant α. Atomic dysprosium exhibits an electronic structure with two nearly degenerate levels whose energy splitting is sensitive to changes in α. Spectroscopy data for two isotopes of dysprosium over a two-year span are analyzed for coherent oscillations with angular frequencies below 1 rad s-1. No signal consistent with a DM coupling is identified, leading to new constraints on dilatonlike photon couplings over a wide mass range. Under the assumption that the scalar field comprises all of the DM, our limits on the coupling exceed those from equivalence-principle tests by up to 4 orders of magnitude for masses below 3×10(-18) eV. Excess oscillatory power, inconsistent with fine-structure variation, is detected in a control channel, and is likely due to a systematic effect. Our atomic spectroscopy limits on DM are the first of their kind, and leave substantial room for improvement with state-of-the-art atomic clocks.

Evanescent-wave and ambient chiral sensing by signal-reversing cavity ringdown polarimetry.

Detecting and quantifying chirality is important in fields ranging from analytical and biological chemistry to pharmacology and fundamental physics: it can aid drug design and synthesis, contribute to protein structure determination, and help detect parity violation of the weak force. Recent developments employ microwaves, femtosecond pulses, superchiral light or photoionization to determine chirality, yet the most widely used methods remain the traditional methods of measuring circular dichroism and optical rotation. However, these signals are typically very weak against larger time-dependent backgrounds. Cavity-enhanced optical methods can be used to amplify weak signals by passing them repeatedly through an optical cavity, and two-mirror cavities achieving up to 10(5) cavity passes have enabled absorption and birefringence measurements with record sensitivities. But chiral signals cancel when passing back and forth through a cavity, while the ubiquitous spurious linear birefringence background is enhanced. Even when intracavity optics overcome these problems, absolute chirality measurements remain difficult and sometimes impossible. Here we use a pulsed-laser bowtie cavity ringdown polarimeter with counter-propagating beams to enhance chiral signals by a factor equal to the number of cavity passes (typically >10(3)); to suppress the effects of linear birefringence by means of a large induced intracavity Faraday rotation; and to effect rapid signal reversals by reversing the Faraday rotation and subtracting signals from the counter-propagating beams. These features allow absolute chiral signal measurements in environments where background subtraction is not feasible: we determine optical rotation from α-pinene vapour in open air, and from maltodextrin and fructose solutions in the evanescent wave produced by total internal reflection at a prism surface. The limits of the present polarimeter, when using a continuous-wave laser locked to a stable, high-finesse cavity, should match the sensitivity of linear birefringence measurements (3 × 10(-13) radians), which is several orders of magnitude more sensitive than current chiral detection limits and is expected to transform chiral sensing in many fields.

Parent-molecule rotational depolarization of photofragment angular momentum distributions: diatomic and polyatomic molecules.

We extend the A(q)(k) polarization-parameter model, which describes product angular momentum polarization from one photon photodissociation of polyatomic molecules in the molecular frame [J. Chem. Phys., 2010, 132, 224310], to the case of rotating parent molecules. The depolarization of the A(q)(k) is described by a set of rotational depolarization factors that depend on the angle of rotation of the molecular axis γ. We evaluate these rotational depolarization factors for the case of dissociating diatomic molecules and demonstrate that they are in complete agreement with the results of Kuznetsov and Vasyutinskii [J. Chem. Phys., 2005, 123, 034307] obtained from a fully quantum mechanical approach of the same problem, showing the effective equivalence of the two approaches. We further evaluate the set of rotational depolarization factors for the case of dissociating polyatomic molecules that have three (near) equal moments of inertia, thus extending these calculations to polyatomic systems. This ideal case yields insights for the dissociation of polyatomic molecules of various symmetries when we compare the long lifetime limit with the results obtained for the diatomic case. In particular, in the long lifetime limit the depolarization factors of the A(0)(k) (odd k), Re(A(1)(k)) (even k) and Im(A(1)(k)) (odd k) for diatomic molecules vanish; in contrast, for polyatomic molecules the depolarization factors for the A(0)(k) (odd k) reduce to a value of 1/3, whereas for the Re(A(1)(k)) (even k) and Im(A(1)(k)) (odd k) they reduce to 1/5.

(2+1) laser-induced fluorescence of spin-polarized hydrogen atoms.

We report the measurement of the spin polarization of hydrogen (SPH) atoms by (2+1) laser-induced fluorescence, produced via the photodissociation of thermal HBr molecules with circularly polarized 193 nm light. This scheme, which involves two-photon laser excitation at 205 nm and fluorescence at 656 nm, offers an experimentally simpler polarization-detection method than the previously reported vacuum ultraviolet detection scheme, allowing the detection of SPH atoms to be performed more straightforwardly, from the photodissociation of a wide range of molecules and from a variety of collision experiments.

Laser detection of spin-polarized hydrogen from HCl and HBr photodissociation: comparison of H- and halogen-atom polarizations.

Thermal HCl and HBr molecules were photodissociated using circularly polarized 193 nm light, and the speed-dependent spin polarization of the H-atom photofragments was measured using polarized fluorescence at 121.6 nm. Both polarization components, described by the a(0)(1)(perpendicular) and Re[a(1)(1)(parallel, perpendicular)] parameters which arise from incoherent and coherent dissociation mechanisms, are measured. The values of the a(0)(1)(perpendicular) parameter, for both HCl and HBr photodissociation, are within experimental error of the predictions of both ab initio calculations and of previous measurements of the polarization of the halide cofragments. The experimental and ab initio theoretical values of the Re[a(1)(1)(parallel, perpendicular)] parameter show some disagreement, suggesting that further theoretical investigations are required. Overall, good agreement occurs despite the fact that the current experiments photodissociate molecules at 295 K, whereas previous measurements were conducted at rotational temperatures of about 15 K.