Recent Progress and Applications of Thermal Lens Spectrometry and Photothermal Beam Deflection Techniques in Environmental Sensing.

This paper presents recent development and applications of thermal lens microscopy (TLM) and beam deflection spectrometry (BDS) for the analysis of water samples and sea ice. Coupling of TLM detection to a microfluidic system for flow injection analysis (µFIA) enables the detection of microcystin-LR in waters with a four samples/min throughput (in triplicate injections) and provides an LOD of 0.08 µg/L which is 12-times lower than the MCL for microcystin-LR in water. µFIA-TLM was also applied for the determination of total Fe and Fe(II) in 3 µL samples of synthetic cloudwater. The LODs were found to be 100 nM for Fe(II) and 70 nM for total Fe. The application of µFIA-TLM for the determination of ammonium in water resulted in an LOD of 2.3 µM for injection of a 5 µL sample and TLM detection in a 100 µm deep microfluidic channel. For the determination of iron species in sea ice, the BDS was coupled to a diffusive gradient in the thin film technique (DGT). The 2D distribution of Fe(II) and total Fe on DGT gels provided by the BDS (LOD of 50 nM) reflected the distribution of Fe species in sea ice put in contact with DGT gels.

The influence of selected indigenous yeasts on Pinot Noir wine colour properties.

BACKGROUND: The use of indigenous selected starters in winemaking is gaining interest due to certain advantages for the sensory quality of the wine. The present work shows the results of a laboratory experiment in which the influence of selected indigenous yeasts on the colour characteristics of Pinot Noir was studied with the use of high hydroxycinnamate decarboxylase activity yeasts. Pichia guilliermondii ZIM624 and Wickerhamomyces anomalus S138 yeasts were used in sequential fermentation with two strains of Saccharomyces cerevisiae, the native ZIM2180 strain and commercial Fermol Premier Cru (FPC). RESULTS: In co-inoculation fermentations, non-Saccharomyces yeasts decreased colour intensity (on average by 25.5%). In wines fermented with ZIM624, the concentration of vinylphenolic pyranoanthocyanins increased (average concentration 1.5 mg L-1 ). However, vitisin concentration was significantly higher in S138 + FPC fermentation (1.3 mg L-1 and an average of 0.9 mg L-1 , respectively). Pinot Noir wines fermented with only ZIM2180 and sequential inoculation of ZIM624 + ZIM2180 resulted in significantly higher colour intensity (6.1 ± 0.0 AU and 4.4 ± 0.0 AU, respectively) and lower wine hue parameters compared to other wines. Sensory evaluation also showed that both wines had the highest perceived colour intensity and purple colour suggesting improvement in wine quality parameters. CONCLUSIONS: The results confirmed that selected indigenous starters made out of Saccharomyces and non-Saccharomyces yeasts can alter Pinot Noir wine colour parameters and improve wine colour properties. Those yeasts properties should be investigated prior to the development of new commercial starters but also be considered in large scale spontaneous fermentations of low colour intensity red wines like Pinot Noir. © 2021 Society of Chemical Industry.

Application of complex geometrical optics to determination of thermal, transport, and optical parameters of thin films by the photothermal beam deflection technique.

In this work, complex geometrical optics is, for what we believe is the first time, applied instead of geometrical or wave optics to describe the probe beam interaction with the field of the thermal wave in photothermal beam deflection (photothermal deflection spectroscopy) experiments on thin films. On the basis of this approach the thermal (thermal diffusivity and conductivity), optical (energy band gap), and transport (carrier lifetime) parameters of the semiconductor thin films (pure TiO2, N- and C-doped TiO2, or TiO2/SiO2 composites deposited on a glass or aluminum support) were determined with better accuracy and simultaneously during one measurement. The results are in good agreement with results obtained by the use of other methods and reported in the literature.

Characterization of sustainable biocompatible materials based on chitosan: cellulose composites containing sporopollenin exine capsules.

In this work, photothermal beam deflection spectrometric technique (BDS) is applied for non-contact and non-destructive characterization of chitosan (CS): cellulose (CEL) biocomposites with incorporated sporopollenin exine capsules (SEC). The objective was to determine the structural and thermal properties of synthesized CS:CEL:SEC composites with varying amounts of SEC, and to validate the BDS by photopyroelectric calorimetry (PPE) as an independent technique. It was found that CS:CEL biocomposites without SEC exhibit low porosities, which are on the order of 0.005 %, but can be increased by augmenting the content of CEL in the composite and/or by incorporation of SEC. By increasing the SEC content of CS:CEL composites to 50 % (w/w), the porosity increased up to 0.17 %. SEC also increases the surface roughness of biocomposite by over 2000-times to reach the roughness amplitude of 6 µm in composites with 50 % SEC. The thermal conductivities of investigated biocomposites were in the range of 40-80 mWm-1 K-1, while the thermal diffusivities were on the order of fractions of mm2s-1. With first validation of BDS results for thermal properties of CS:CEL-based composites, which show agreement with PPE results to within 5 %, this study confirms BDS technique as a perspectives tool for non-destructive characterization of CS:CEL:SEC biocomposites.

Reflecting the Quality Degradation of Engine Oil by the Thermal Diffusivity: Radiative and Nonradiative Analyses.

Ageing of engine oil is an important issue determining the engine life and performance. The present work attempts to delineate the ageing-induced changes in engine oil through the mode-mismatched dual-beam thermal lens (MMDBTL) technique and other conventional spectroscopic techniques. For the analyses, engine oil samples were collected after every 200 km of runtime. As the thermal diffusivity is related to the nonradiative deexcitation upon optical absorption, comprehensive radiative and nonradiative analyses were carried out. The Ultraviolet-Visible, Fourier transform infrared, and Nuclear magnetic resonance spectroscopic analyses point to the structural modification as a result of the breaking of the long-chain hydrocarbons into ketones, aldehydes, esters, and other compounds. This modifies the absorption pattern, which can also be understood from the nonlinear refractive index study using the Z-scan technique. The compositional variations associated with the degradation upon ageing, the length of the hydrocarbon chain, and the formation of newer molecules account for the enhancement of the thermal diffusivity revealed through the MMBDTL techniques. The complementary nature of the radiative and nonradiative emission is understood from the fluorescence study. Thus, the study reveals the possibility of thermal diffusivity measurement as an effective tool for the quality monitoring of engine oil.

Non-Contact and Self-Calibrated Photopyroelectric Method for Complete Thermal Characterization of Porous Materials.

A general theory of a photopyroelectric (PPE) configuration, based on an opaque sample and transparent pyroelectric sensor, backing and coupling fluids is developed. A combined back-front detection investigation, based on a frequency scan of the phase of the PPE signals, followed by a self-normalization of the phases' behavior, leads to the possibility of simultaneously measuring both thermal effusivity and diffusivity of a solid sample. A particular case of this configuration, with no coupling fluid at the sample/backing interface and air instead of coupling fluid at the sample/sensor interface (non-contact method) is suitable for simultaneous measurement ofboth thermal diffusivity and effusivity (in fact complete thermal characterization) of porous solids. Compared with the already proposed configurations for investigations of porous materials, this novel configuration makes use of a fitting procedure with only one fitting parameter, in order to guarantee the uniqueness of the solution. The porous solids belong to a class of materials which are by far not easy to be investigated using PPE. To the best of our knowledge, porous materials represent the only type of compounds, belonging to condensed matter, which were not taken into consideration (until recently) as potential samples for PPE calorimetric investigations. Consequently, the method proposed in this paper complete the area of applications of the PPE method. Applications on some porous building materials and cellulose-based samples validate the theory.

Measuring Thermal Diffusivity of Azoheteroarene Thin Layers by Photothermal Beam Deflection and Photothermal Lens Methods.

Measurement of thermal properties of thin films is challenging. In particular, thermal characterization is very difficult in semi-transparent samples. Here, we use two photothermal methods to obtain information about the thermal diffusivity as well as thermal conductivity of azoheteroarene functionalized polymer thin layers. The photothermal beam deflection (PBD) method is employed to gather data directly on thermal conductivity and thermal diffusivity, while the thermal lens (TL) method is employed to measure the effective thermal diffusivity. Consequently, the thermal diffusivity of the layers is indirectly estimated from the effective thermal diffusivity using a well-established theoretical relationship. Despite the utilization of distinct methods, our study reveals a remarkable consistency in the highly accurate results obtained from both approaches. This remarkable agreement reaffirms the reliability and mutual compatibility of the employed methods, highlighting their shared ability to provide accurate and congruent outcomes.

Influence of P3HT:PCBM Ratio on Thermal and Transport Properties of Bulk Heterojunction Solar Cells.

The influence of P3HT:PCBM ratio on thermal and transport properties of solar cells were determined by photothermal beam deflection spectrometry, which is advantageous tool for non-destructively study of bulk heterojunction layers of organic solar cells. P3HT:PCBM layers of different P3HT:PCBM ratios were deposited on top of PEDOT:PSS/ITO layers which were included in organic bulk-heterojunction solar cells. The thermal diffusivity, energy gap and charge carrier lifetime were measured at different illumination conditions and with a different P3HT:PCBM ratios. As expected, it was found that the energy band gap depends on the P3HT:PCBM ratio. Thermal diffusivity is decreasing, while charge carrier lifetime is increasing with PCBM concentration. Energy band gap was found to be independent on illumination intensity, while thermal diffusivity was increasing and carrier lifetime was decreasing with illumination intensity. The carrier lifetime exhibits qualitatively similar dependence on the PCBM concentration when compared to the open-circuit voltage of operating solar cells under AM1.5 illumination. BDS and standard I-V measurement yielded comparable results arguing that the former is suitable for characterization of organic solar cells.

Improved Photopyroelectric (PPE) Configuration for Thermal Effusivity Investigations of Porous Solids.

A new photopyroelectric detection configuration is proposed in order to measure the thermal effusivity of porous solids. Compared with the previously reported detection scheme this configuration makes use of a transparent window in front of the pyroelectric sensor. In such a way, the heat losses by convection at the sensor's irradiated surface are eliminated, and consequently, the conduction remains the only process responsible for the heat propagation in the whole detection cell. In the paper, the mathematical model for this new configuration is developed, with the main conclusion that the sample's thermal effusivity can be finally obtained via a fitting procedure with only two fitting parameters (instead of three as previously reported); in such a way, the possible degeneracy of the results is eliminated. The suitability of the method is demonstrated with application on some porous building materials and cellulose-based pressed powders.

Synthesis and Characterization of MWCNT-COOH/Fe3O4 and CNT-COOH/Fe3O4/NiO Nanocomposites: Assessment of Adsorption and Photocatalytic Performance.

In this study the adsorption and photodegradation capabilities of modified multi-walled carbon nanotubes (MWCNTs), using tartrazine as a model pollutant, is demonstrated. MWCNT-COOH/Fe3O4 and MWCNT-COOH/Fe3O4/NiO nanocomposites were prepared by precipitation of metal oxides in the presence of MWCNTs. Their properties were examined by X-ray diffraction in powder (XRD), Fourier-transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), scanning electron microscopy (SEM), Raman spectroscopy, synchrotron-based Scanning PhotoElectron Microscopy (SPEM), and Brunauer-Emmett-Teller (BET) analysis. It was found that the optimal adsorption conditions were pH 4 for MWCNT-COOH/Fe3O4 and pH 3 for MWCNT-COOH/Fe3O4/NiO, temperature 25 °C, adsorbent dose 1 g L-1, initial concentration of tartrazine 5 mg L-1 for MWCNT-COOH/Fe3O4 and 10 mg L-1 for MWCNT-COOH/Fe3O4/NiO and contact time 5 min for MWCNT-COOH/Fe3O4/NiO and 15 min for MWCNT-COOH/Fe3O4. Moreover, the predominant degradation process was elucidated simultaneously, with and without simulated sunlight irradiation, using thermal lens spectrometry (TLS) and UV-Vis absorption spectrophotometry. The results indicated the prevalence of the photodegradation mechanism over adsorption from the beginning of the degradation process.

Through-Plane and In-Plane Thermal Diffusivity Determination of Graphene Nanoplatelets by Photothermal Beam Deflection Spectrometry.

In this work, in-plane and through-plane thermal diffusivities and conductivities of a freestanding sheet of graphene nanoplatelets are determined using photothermal beam deflection spectrometry. Two experimental methods were employed in order to observe the effect of load pressures on the thermal diffusivity and conductivity of the materials. The in-plane thermal diffusivity was determined by the use of a slope method supported by a new theoretical model, whereas the through-plane thermal diffusivity was determined by a frequency scan method in which the obtained data were processed with a specifically developed least-squares data processing algorithm. On the basis of the determined values, the in-plane and through-plane thermal conductivities and their dependences on the values of thermal diffusivity were found. The results show a significant difference in the character of thermal parameter dependence between the two methods. In the case of the in-plane configuration of the experimental setup, the thermal conductivity decreases with the increase in thermal diffusivity, whereas with the through-plane variant, the thermal conductivity increases with an increase in thermal diffusivity for the whole range of the loading pressure used. This behavior is due to the dependence of heat propagation on changes introduced in the graphene nano-platelets structure by compression.

Nanobody-Dependent Detection of Microcystis aeruginosa by ELISA and Thermal Lens Spectrometry.

Nanobodies against cell surface antigens of toxic cyanobacteria Microcystis aeruginosa were recovered by whole-cell biopanning of a naïve phage display library of nanobodies. Six unique sequences were identified and three sub-cloned and purified as fusion immunoreagents together with either green fluorescent protein or AviTag to be used for diagnostics. The yields of nanobody constructs were in the range of 5-10 mg/l and their specificity and sensitivity was initially evaluated by immunofluorescence and by fluorescent enzyme-linked immunosorbent assay (ELISA) using fluorescent nanobodies. The ELISA data confirmed the nanobody specificity but showed that the saturation of the fluorescence signal already in the presence of few hundreds of cells limited the dynamic range of the method. As an alternative, Avi-tagged nanobodies were used in combination with streptavidin-linked horseradish peroxidase for developing a diagnostic colorimetric cell ELISA, the limit-of-detection of which was 3.2 and 4.5 cells/ml for the two tested cyanobacteria strains, whereas the linear range of the assay was expanded from 10 to 10,000 cells. The fluorescent nanobodies were finally exploited for quantifying cyanobacteria by thermal lens spectrometry (TLS) that enabled to reach a limit-of-detection of 1.2 cells/ml and provided a linear range of measurement between 0 and 10,000 cells. No cross-reactivity with unrelated microalgae was detected and both colorimetric ELISA and TLS provided a linear range of detection of few logs. The data indicate that nanobodies are suitable capture reagents and that both TLS and colorimetric ELISA are reliable to monitor variations of cyanobacteria populations.

Photodegradation mechanisms of reactive blue 19 dye under UV and simulated solar light irradiation.

In this work we performed dye photodegradation experiments in presence of TiO2 and Cu/Zr modified TiO2. The changes in the shape of the spectra of RB19 caused by photocatalysts under the simulated solar or UV light were monitored. Since the predominant photocatalytic mechanism can only be observed in very dilute solution of RB19, UV-Vis absorption spectrometry for higher concentrations and thermal lens spectrometry for lower concentrations have been applied to elucidate the mechanistic details of degradation processes. Bleaching of the dye was a characteristic feature, that occurred under both simulated solar and UV lights. It was also evident, that the absorption peak with maximum centered at 592 nm undergoes a slight blue shift during irradiation. The experiments carried out using UV and simulated solar light demonstrated, that two different processes responsible for the RB19 dye degradation occurred. In the initial stage of irradiation one of the processes appears under the UV light and can be recognized by a characteristic blue shift in the absorption spectrum of the solution. The second process is characteristic for irradiation by the simulated solar light which involve a blue shift at longer periods (100 min). These phenomena were attributed to the photocatalytic and photosensitization mechanisms, respectively. However, photocatalytic mechanism was also observed under simulated solar radiation, when the initial dye concentration was decreased to 5 mgL-1, and was recognized by the increase of the thermal lens signal during the initial stages of degradation process. This was possible because the thermal lens spectroscopy technique provides a limit of quantification for RB19 at the concentration level of 0.12 mg L-1, while UV-Vis spectrometry enables quantification of RB19 only down to 4 mg L-1 levels.

A multi-thermal-lens approach to evaluation of multi-pass probe beam configuration in thermal lens spectrometry.

In this work, a recently proposed thermal lens instrument based on multi-pass probe beam concept is investigated and described as a multi-thermal-lens equivalent system. A simulation of the photothermal lens signal formation in a multi-thermal-lens equivalent configuration of the system is performed and validated by comparing the experimental signals of single, dual and ten-pass configurations to theoretically calculated values. The theoretically predicted enhancement of the signal is 9 to 10-fold for a weak thermal lens when comparing the ten-pass configuration with the conventional single-pass thermal lens system. Experimentally achieved signal enhancement in the ten-pass system is 8.3 for pure ethanol sample and between 8 and 9 for solutions with different concentrations of the Fe(II) - 1,10-Phenanthroline complex. Additionally, a value of 9.1 was calculated as the ratio of the slopes of the calibration lines obtained using the ten-pass and single-pass configurations. The achieved limit of detection for determination of Fe(II), in the ten-pass configuration, was 0.4 µgL-1, with a relative standard deviation around 4.5%, which compares favorably with previously reported results for TLS determination of Fe(II) in thin samples using low excitation power. For the multi-pass configuration the linear range of measurement is reduced when compared to the single-pass configuration. This is explained by the theoretical analysis of the photothermal signal under multi-pass condition, which shows the important contribution of nonlinear term in theoretical expression for the photothermal signal. The ten-pass configuration, which is presented and validated experimentally for the first time, offers important signal enhancement needed in recently developed TLS instruments with tunable, low power excitation sources.

Determination of Iron in Environmental Water Samples by FIA-TLS.

The determination of low concentration of iron in natural waters can be difficult due to the complexity of natural water, but primarily because it requires preconcentration of the sample with solvent extraction. In this work we report on results of thermal lens spectrometry (TLS) coupled to flow injection analysis (FIA) as a highly sensitive FIA-TLS method of iron detection. The concentration of iron redox species was determined using 1,10-phenanthroline (PHN), that forms stable complexes with Fe(II) ions which are characterized by an absorption maximum at 508 nm. The TLS system using a 633 nm probe laser and 530 nm pump laser beam was exploited for on-line detection in flow injection analysis, where a PHN solution was used as the carrier solution for FIA. The concentration of the complexing agent affects the quality of the TLS signal, and the optimal concentration was found at 1 mM PHN. The achieved limits of detection (LODs) for Fe(II) and total iron were 33 nM for Fe(II) and 21 nM for total iron concentration. The method was further validated by determining the linear concentration range, specificity in terms of analytical yield and by determining concentration of iron in a water sample from a local water stream.

Determination of Dissolved Iron Redox Species in Freshwater Sediment using DGT Technique Coupled to BDS.

In this work we have developed a novel method for determination of iron redox species by the use of diffusive gradients in thin-film (DGT) technique coupled to photothermal beam deflection spectroscopy (BDS). The combination of both methods achieved low limit of detection (LOD) of 0.14 µM for Fe (II) ions. The total Fe concentration determined in the Vrtojbica river sediment (Slovenia, Rozna Dolina, 5000 Nova Gorica) was 49.3 µgL-1. The Fe (II) and Fe (III) concentration amounted to 12.8 µgL-1 and 39.9 µgL-1, respectively. Such an approach opens new opportunities for monitoring the content of iron species in natural waters and sediments and provides highly sensitive chemical analysis and an accurate qualitative and quantitative characteristic of the materials under study.

Transparent Photocatalytic Thin Films on Flexible Polymer Substrates.

Self-cleaning and/or photocatalytic films on polymer substrates have found numerous applications during the past decades. However, the common demand for high-temperature post synthesis treatment limits the application to temperature resistant substrates only. Herein, we prepared self-cleaning photocatalytic films on four thermosensitive polymeric substrates: polyvinyl chloride (PVC), polymethyl methacrylate (PMMA), and acryl coated polyester (PES) fabric (D2) with poly(vinylidene fluoride) (PVDF) containing lacquer (D1). TiO2 was prepared via a low-temperature sol-gel process using titanium(IV) isopropoxide and zirconium(IV) butoxide as precursors with various loading levels of Zr; 0, 5, 10, and 20 mol.%, and deposited on the substrates by using a SiO2 binder in form of thin films (ca. 200 nm thick) via dip-coating. The films were characterized by SEM, hardness test, UV-Vis, photothermal beam deflection spectroscopy, and IR spectroscopy, while photocatalytic activity was measured by the fluorescence-based method of the terephthalic acid probe and wetting by contact angle measurements. Films containing 10 mol.% of Zr showed the best compromise regarding photocatalytic activity and mechanical stability while from substrates point of view PVC performed the best, followed by PMMA, D1, and D2. The beneficial role of SiO2 binder was not only guaranteeing excellent mechanical stability, but also to prevent the D1 polymer from deterioration; the latter was found to be labile to long-term solar-light exposure due to degradation of the top PVDF layer.

A combination of interdisciplinary analytical tools for evaluation of multi-layered coatings on medical grade stainless steel for biomedical applications.

In this comprehensive study several analytical techniques were used in order to evaluate multi-layered biomedical surface coatings composed of a drug (diclofenac) and a polymer (chitosan). Such a thorough examination is of paramount importance in order to assure safety and prove efficiency of potential biomedical materials already at the in vitro level, hence leading to their potentially faster introduction to clinical trials. For the first time a novel technique based on thermal diffusivity and conductivity measurements (photothermal beam deflection spectroscopy - BDS) was employed in order to analyse in a non-destructive way the thickness of respective layers, together with their thermal diffusivity and conductivity. In addition to attenuated total reflection Fourier-transform infrared spectroscopy (ATR-FTIR), BDS confirmed successive surface layers of the prepared coatings. Scanning electron microscopy and atomic force microscopy were used to examine structural information on the macro- and micro/nano-scale, respectively. Surface hydrophobicity was measured with the contact angle analysis, which clearly showed differences in hydrophobicity between coated and non-coated samples. Considering the targeted application of the prepared coatings (as implant in orthopaedic treatments), the in vitro drug release was analysed spectrophotometrically to examine the coatings potential for a controlled drug release. Furthermore, the material was also tested by electrochemical impedance spectroscopy and cyclic polarisation techniques, which were able to detect even minor differences between the performance of the coated and non-coated materials. As the final test, the biocompatibility of the coatings with human osteoblasts was determined.

Absorption Spectra of Ethanol and Water Using a Photothermal Lens Spectrophotometer.

In this work we report on the absorption spectra of ethanol and water in the region 430-700 nm using a homemade halogen lamp-based photothermal lens spectrophotometer with a multipass probe-beam configuration. The spectra also include well resolved, higher absorption overtones. The instrument achieves high sensitivity due to multiple reflections within the optical cavity containing the sample. Finally, an Arduino board was used for collecting and digitizing the signal, thus enabling a more compact device.