A pulsed (4.4 ns pulse length) frequency-doubled Nd:YAG laser operated at 10 Hz was used to generate Raman scattering of samples at a distance of 12 m. The scattered light was collected by a 6 in. telescope, and the Raman spectrum was recorded using an Acton SP-2750 spectrograph coupled to a gated intensified charge-coupled device (ICCD) detector. Applying a spatial offset between the point where the laser hit the sample and the focus of the telescope on the sample enabled collection of Raman photons that were predominantly generated inside the sample and not from its surface. This is especially effective when the content of concealed objects should be analyzed. High-quality Raman spectra could be recorded, within 10 s of data acquisition, from a solid (NaClO(3)) as well as a liquid (isopropyl alcohol) placed inside a 1.5 mm thick opaque low-density polyethylene (LDPE) plastic bottle. The applied spatial offset was also advantageous in cases where the surface of the container was highly fluorescent. In such a situation, Raman spectra of the sample could not be recorded when the sampling volume (telescope observation field) coincided with the focus of the excitation laser. However, with the use of a spatial offset of some millimeters, a clear Raman spectrum of the content (isopropyl alcohol) in a strongly fluorescent plastic container was obtained.

A compact multi-bounce attenuated total reflection (ATR) probe combined with a Fabry-Pérot filter spectrometer (FPFS) has been developed for detection of hydrogen peroxide used for oxidative gas scrubbing operating in the mid-infrared (MIR) spectral region. A novel MIR supercontinuum light source is employed to enhance the quantification capabilities of the sensor and is compared to a classical thermal emitter. An improvement of a factor of 4 in noise and approximately a factor of 3 in limit of detection is shown in this study allowing fast inline detection of aqueous hydrogen peroxide solutions around 0.1%.

On-line monitoring of key chemicals in an industrial production plant ensures economic operation, guarantees the desired product quality, and provides additional in-depth information on the involved chemical processes. For that purpose, rapid, rugged, and flexible measurement systems at reasonable cost are required. Here, we present the application of a flexible mid-IR filtometer for industrial gas sensing. The developed prototype consists of a modulated thermal infrared source, a temperature-controlled gas cell for absorption measurement and an integrated device consisting of a Fabry-Pérot interferometer and a pyroelectric mid-IR detector. The prototype was calibrated in the research laboratory at TU Wien for measuring methanol and methyl formate in the concentration ranges from 660 to 4390 and 747 to 4610 ppmV. Subsequently, the prototype was transferred and installed at the project partner Metadynea Austria GmbH and linked to their Process Control System via a dedicated micro-controller and used for on-line monitoring of the process off-gas. Up to five process streams were sequentially monitored in a fully automated manner. The obtained readings for methanol and methyl formate concentrations provided useful information on the efficiency and correct functioning of the process plant. Of special interest for industry is the now added capability to monitor the start-up phase and process irregularities with high time resolution (5 s).

Strong anion-exchange materials carry a positive charge that allows them to trap and concentrate anions while releasing other anions. Here, we introduced an ion exchange group into mesoporous silica films coated on attenuated total reflection (ATR) crystals to enrich nitrate from aqueous phase in the volume probed by the evanescent field. The ion-exchange and enrichment capabilities of the films were characterized using standard FTIR spectroscopy. Thereby fast analyte enrichment and full sensor recovery were observed. In addition, high enrichment factors of up to 1600 were achieved. After characterization, these coated ATR crystals were used in a dedicated ATR-IR filtometer comprising a Fabry-Pérot filter detector unit and a miniaturized thermal emitter with a footprint of only 80 mm × 120 mm × 70 mm. The filter covered the spectral region between 1250 -1800 cm -1 allowing for recording IR spectra of nitrate enriched into the mesoporous silica film. The sensor was calibrated using the Langmuir adsorption model as calibration function. From this, a limit of detection of 1.2 mg L -1 was derived for the ATR-IR filtometer.This emphasizes the high potential of functionalized mesoporous silica films combined with low-cost filtometers for portable water sensors.

In this work, we introduce a system combining an acoustic trap for bead injection with attenuated total reflection (ATR) infrared (IR) spectroscopy. By mounting an acoustofluidic cell hosting an ultrasound source on top of a custom-built ATR fixture, we were able to trap beads labeled with the enzyme alkaline phosphatase without requiring any mechanical retention elements. Sequential injection analysis was employed for reproducible sample handling and bead injection into the acoustic trap. To showcase potential applications of the presented setup for kinetic studies, we monitored the conversion of p-nitrophenylphosphate into p-nitrophenol and phosphate via beads carrying the immobilized enzyme using ATR-IR spectroscopy. Retaining the labeled beads via ultrasound particle manipulation resulted in excellent experimental reproducibility (relative standard deviation, 3.91%). It was demonstrated that trapped beads remained stably restrained with up to eight changes of liquid passing through the acoustofluidic cell. Beads could be discarded in a straightforward manner by switching off the ultrasound, in contrast to systems containing mechanical retention elements, which require backflushing. Multiple experiments were performed by employing different substrate concentrations with the same batch of trapped beads as well as varying the amount of enzyme present in the cell, enabling enzyme kinetic studies and emphasizing the application of the proposed setup in studies where enzymatic reuse is desired. This proves the potential of the acoustic trap combined with ATR-IR spectroscopy to monitor the activity of immobilized enzymes and its ability to perform complex bead-based assays.

No abstract

Time-resolved stand-off Raman spectroscopy was used to determine both the position and identity of substances relative to each other at remote distances (up to tens of meters). Spectral information of three xylene isomers, toluene, and sodium chlorate was obtained at a distance of 12 m from the setup. Pairs and triplets of these samples were placed at varying distances (10-60 cm) relative to each other. Via the photon time of flight the distance between the individual samples was determined to an accuracy of 7% (corresponding to a few cm) of the physically measured distance. Furthermore, at a distance of 40 m, time-resolved Raman depth profiling was used to detect sodium chlorate in a white plastic container that was non-transparent to the human eye. The combination of the ranging capabilities of Raman LIDAR (sample location usually determined using prior knowledge of the analyte of interest) with stand-off Raman spectroscopy (analyte detection at remote distances) provides the capability for depth profile identification of unknown substances and analysis of concealed content in distant objects. To achieve these results, a 532 nm laser with a pulse length of 4.4 ns was synchronized to an intensified charge-coupled device camera with a minimum gate width of 500 ps. For automated data analysis a multivariate curve resolution algorithm was employed.

Raman spectroscopy is a nondestructive characterization method offering chemical-specific information. However, the cross-section of inelastically (Raman) scattered light is very low compared to elastically (Rayleigh) scattered light, resulting in weak signal intensities in Raman spectroscopy. Despite providing crucial information in off-line measurements, it usually is not sensitive enough for efficient, in-line process control in conjunction with low particle concentrations. To overcome this limitation, two custom-made 1.4404 stainless-steel prototype add-ons were developed for in-line Raman probes that enable ultrasound particle manipulation and thus concentration of particles in suspensions in the focus of the Raman excitation laser. Depending on size and density differences between particles and the carrier medium, particles are typically caught in the nodal planes of a quasi-standing wave field formed in an acoustic resonator in front of the sensor. Two arrangements were realized with regard to the propagation direction of the ultrasonic wave relative to the propagation direction of the laser. The parallel arrangement improved the limit of detection (LOD) by a factor of ≈30. In addition to increased sensitivity, the perpendicular arrangement offers increased selectivity: modifying the frequency of the ultrasonic wave field allows the liquid or solid phase to be moved into the focus of the Raman laser. The combination of in-line Raman spectroscopy with ultrasound particle manipulation holds promise to push the limits of conventional Raman spectroscopy, hence broadening its field of application to areas where previously Raman spectroscopy has not had sufficient sensitivity for accurate, in-line detection.