A Short Review of Cavity-Enhanced Raman Spectroscopy for Gas Analysis.

The market of gas sensors is mainly governed by electrochemical, semiconductor, and non-dispersive infrared absorption (NDIR)-based optical sensors. Despite offering a wide range of detectable gases, unknown gas mixtures can be challenging to these sensor types, as appropriate combinations of sensors need to be chosen beforehand, also reducing cross-talk between them. As an optical alternative, Raman spectroscopy can be used, as, in principle, no prior knowledge is needed, covering nearly all gas compounds. Yet, it has the disadvantage of a low quantum yield through a low scattering cross section for gases. There have been various efforts to circumvent this issue by enhancing the Raman yield through different methods. For gases, in particular, cavity-enhanced Raman spectroscopy shows promising results. Here, cavities can be used to enhance the laser beam power, allowing higher laser beam-analyte interaction lengths, while also providing the opportunity to utilize lower cost equipment. In this work, we review cavity-enhanced Raman spectroscopy, particularly the general research interest into this topic, common setups, and already achieved resolutions.

Optimal all-optical switching of a microcavity resonance in the telecom range using the electronic Kerr effect.

We have switched GaAs/AlAs and AlGaAs/AlAs planar microcavities that operate in the "Original" (O) telecom band by exploiting the instantaneous electronic Kerr effect. We observe that the resonance frequency reversibly shifts within one picosecond when the nanostructure is pumped with low-energy photons. We investigate experimentally and theoretically the role of several parameters: the material backbone and its electronic bandgap, the quality factor, and the duration of the switch pulse. The magnitude of the frequency shift is reduced when the backbone of the central λ-layer has a greater electronic bandgap compared to the cavity resonance frequency and the frequency of the pump. This observation is caused by the fact that pumping with photon energies near the bandgap resonantly enhances the switched magnitude. We thus find that cavities operating in the telecom O-band are more amenable to ultrafast Kerr switching than those operating at lower frequencies, such as the C-band. Our results indicate that the large bandgap of AlGaAs/AlAs cavity allows to tune both the pump and the probe to the telecom range to perform Kerr switching without detrimental two-photon absorption. We observe that the magnitude of the resonance frequency shift decreases with increasing quality factor of the cavity. Our model shows that the magnitude of the resonance frequency shift depends on the pump pulse duration and is maximized when the duration matches the cavity storage time to within a factor two. In our experiments, we obtain a maximum shift of the cavity resonance relative to the cavity linewidth of 20%. We project that the shift of the cavity resonance can be increased twofold with a pump pulse duration that better matches the cavity storage time. We provide the essential parameter settings for different materials so that the frequency shift of the cavity resonance can be maximized using the electronic Kerr effect.

All-optical switching of a microcavity repeated at terahertz rates.

We have repeatedly and reproducibly switched a GaAs-AlAs planar microcavity operating in the "original" telecom band by exploiting the virtually instantaneous electronic Kerr effect. We achieve repetition times as fast as 300 fs, thereby breaking the terahertz modulation barrier. The rate of the switching in our experiments is only determined by optics and not by material-related relaxation. Our results offer opportunities for fundamental studies of cavity quantum electrodynamics and optical information processing in the subpicosecond time scale.

Exploration of an Alarm Sensor to Detect Infusion Failure Administered by Syringe Pumps.

Incorrect medication administration causes millions of undesirable complications worldwide every year. The problem is severe and there are many control systems in the market, yet the exact molecular composition of the solution is not monitored. Here, we propose an alarm sensor based on UV-Vis spectroscopy and refractometry. Both methods are non-invasive and non-destructive as they utilize visible light for the analysis. Moreover, they can be used for on-site or point-of-care diagnosis. UV-Vis-spectrometer detect the absorption of light caused by an electronic transition in an atom or molecule. In contrast a refractometer measures the extent of light refraction as part of a refractive index of transparent substances. Both methods can be used for quantification of dissolved analytes in transparent substances. We show that a sensor combining both methods is capable to discern most standard medications that are used in intensive care medicine. Furthermore, an integration of the alarm sensor in already existing monitoring systems is possible.

Surface plasmons and magneto-optic activity in hexagonal Ni anti-dot arrays.

The influence of surface plasmons on the magneto-optic activity in a two-dimensional hexagonal array is addressed. The experiments were performed using hexagonal array of circular holes in a ferromagnetic Ni film. Well pronounced troughs are observed in the optical reflectivity, resulting from the presence of surface plasmons. The surface plasmons are found to strongly enhance the magneto-optic response (Kerr rotation), as compared to a continuous film of the same composition. The influence of the hexagonal symmetry of the pattern on the coupling between the plasmonic excitations is demonstrated, using optical diffraction measurements and theoretical calculations of the magneto-optic and of the angular dependence of the optical activity.

Bifunctional and Self-Supported NiFeP-Layer-Coated NiP Rods for Electrochemical Water Splitting in Alkaline Solution.

Designing efficient and robust nonprecious metal-based electrocatalysts for overall water electrolysis, which is mainly limited by the oxygen evolution reaction (OER), for hydrogen production remains a major challenge for the hydrogen economy. In this work, a bimetallic NiFeP catalyst is coated on nickel phosphide rods grown on nickel foam (NiFeP@NiP@NF). This self-supported and interfacially connected electrode structure is favorable for mass transfer and reducing electrical resistance during electrocatalysis. The preparation of NiFeP@NiP@NF is optimized in terms of (i) the coprecipitation time of the NiFe Prussian blue analogue layer that serves as phosphides precursor and (ii) the phosphidation temperature. The optimized sample exhibits excellent OER performance delivering current densities of 10 and 100 mA cm-2 at low overpotentials of 227 and 252 mV in 1.0 M KOH, respectively, and maintaining 10 mA cm-2 for more than 120 h without obvious degradation. Moreover, it can also be operated as a hydrogen evolution electrocatalyst, requiring an overpotential of 105 mV at 10 mA cm-2 in the same medium. Thus, the as-prepared material was tentatively utilized as a bifunctional electrocatalyst in a symmetric electrolyzer, requiring a voltage bias of 1.57 V to afford 10 mA cm-2 in 1.0 M KOH, while exhibiting outstanding stability.

Evaluation of an on-site surface enhanced Raman scattering sensor for benzotriazole.

Benzotriazole (BTAH) has been used for decades as corrosion inhibitor and antifreeze. Since it is fairly soluble in water but very stable and can only be partly removed from wastewater treatment plants, it represents a threat to the environment and thus also to human health. Therefore, it is of uttermost importance to have a detection method capable of monitoring the concentration of BTAH at trace level on-site. Here, we demonstrate that a sensor based on surface-enhanced Raman spectroscopy is capable of detecting trace-level concentrations of BTAH. We carefully studied the concentration dependency and the time dependent coverage. Moreover, we could not only perform the measurements with clean solution but also with real samples from a wastewater treatment plant, ensuring that our method proposed works in a complex environment.

Nanoparticular surface-bound PCBs, PCDDs, and PCDFs-a novel class of potentially higher toxic POPs.

In a previous study, Env Sci Poll Res:1-7, 2015 showed that polychlorinated biphenyls (PCBs), polychlorinated dibenzo dioxins (PCDDs), and polychlorinated dibenzo furanes (PCDFs) are found in commercially available (nano) particular titanium dioxide as a result of the fabrication. Here, we give a brief perspective and reason the toxicity of these new classes of persistent organic pollutants (POPs) by reviewing also their nanoparticular properties, such as surface-to-volume ratio, photocatalytic activity, polarity shifts, and stealth effect. These insights point towards a new class of POPs and toxicologic effects, which are related to the size but not a result of nanotechnology itself. We pave the way to the understanding of until now unresolved very complex phenomena, such as the indoor exposure, formation, and transformation of POP and sick-building syndrome. This is a fundamental message for nanotoxicology and kinetics and should be taken into account when determining the toxicity of nanomaterials and POPs separately and as a combination.

PCDDs, PCDFs, and PCBs co-occurrence in TiO2 nanoparticles.

In the present study, we report on the co-occurrence of persistent organic pollutants (POPs) adsorbed on nanoparticular titanium dioxide (TiO2). We report on the finding of polychlorinated dibenzodioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and polychlorinated biphenyls (PCBs) on the surface of commercially available TiO2 nanoparticles, being formed during the fabrication process of the TiO2. Thereby, the samples comprise PCBs with higher congener numbers or, in the absence of PCBs, a high concentration of PCDDs and PCDFs. This new class of POPs on an active catalytic surface and the great range of applications of nanoparticular TiO2, such as in color pigments, cosmetics, and inks, give rise to great concern due to their potential toxicity.

Spectroscopy of the shear force interaction in scanning near-field optical microscopy.

Shear force detection is a common method of tip-sample distance control in scanning near-field optical microscopy. Shear force is the force acting on a laterally oscillating probe tip near a surface. Despite its frequent use, the nature of the interaction between tip and sample surface is a matter of debate. In order to investigate the problem, approach curves, i.e. amplitude and phase of the tip oscillation as a function of the tip-sample distance, are studied in terms of a harmonic oscillator model. The extracted force and damping constants are influenced by the substrate material. The character of the interaction ranges from elastic to dissipative. The interaction range is of atomic dimensions with a sharp onset. Between a metal-coated tip and a Cu sample, a power law for the force-distance curve is observed.