Laser-induced Fluorescence Spectroscopy Research Articles

BiPLS-RF: A hybrid wavelength selection strategy for laser induced fluorescence spectroscopy of power transformer oil

In this paper, a method for indirect diagnosis of transformer faults based on the fluorescence spectrum and characteristic wavelength screening of transformer oil has been proposed. Specifically, a hybrid strategy (BiPLS-RF) for establishing the fluorescence spectrum feature screening of transformer oil using backward interval partial least squares (BiPLS) and random forest (RF) has been proposed. Aiming at the problem of transformer fault diagnosis, the laser induced fluorescence (LIF) spectroscopy of transformer oil in different states was first collected, and it is found that the fluorescence spectrum intensity of normal transformer oil was stronger than that of faulty transformer oil. Then the characteristic bands of the original fluorescence spectra were screened by BiPLS. It is found that when the original fluorescence spectra were divided into 15 sub-intervals, the minimum root mean squares error of cross-validation can be obtained by selecting 3 sub-intervals (including 411 wavelengths). On this basis, RF was employed to further screen the characteristic wavelengths and realized the identification of the fluorescence spectrum. It is found that in the RF model composed of 54 trees, the selected 196 characteristic wavelengths of the fluorescence spectrum can minimize the analysis error (0.56%). In addition, the selected characteristic wavelength information was fed into other common classifiers to construct a fluorescence spectrum identification model, which further proved the effectiveness of BiPLS-RF for wavelength selection for LIF spectroscopy of power transformer oil. The results show that it is feasible to use BiPLS-RF to screen the characteristic wavelength of LIF spectroscopy and apply it to transformer fault diagnosis, which provides a new solution for transformer fault diagnosis.

Contribution of vibrational excited molecular nitrogen to ammonia synthesis using an atmospheric-pressure plasma jet

The contribution of atomic nitrogen is fairly possible in plasma-assisted catalytic synthesis of ammonia since it has high adsorption probabilities on solid surfaces. On the other hand, recently, the contribution of vibrational excited molecular nitrogen to ammonia synthesis has been discussed. In this work, we compared the fluxes of atomic nitrogen and vibrational excited molecular nitrogen with the rate of plasma-assisted ammonia synthesis. We employed an atmospheric-pressure nitrogen plasma jet, and the spatial afterglow of the plasma jet and a hydrogen flow irradiated the surface of a ruthenium catalyst. The fluxes of atomic nitrogen and vibrational excited molecular nitrogen were measured by two-photon absorption laser-induced fluorescence spectroscopy and laser Raman scattering, respectively. The synthesis rate of ammonia had a positive correlation with the flux of vibrational excited molecular nitrogen, while the variation of the synthesis rate with the gas flow rate was opposite to the flux of atomic nitrogen. The experimental results indicate the contribution of vibrational excited molecular nitrogen to the synthesis of ammonia using the atmospheric-pressure plasma, where the flux of vibrational excited molecular nitrogen is more than four orders of magnitude higher than that of atomic nitrogen.

New energy levels of atomic holmium discovered by laser spectroscopy in the near infrared spectral range

A combination of optogalvanic spectroscopy and laser-induced fluorescence spectroscopy with a continuous wave tunable single mode Ti-Sa laser was applied to find new energy levels of atomic holmium. Free and excited holmium atoms were produced in a liquid nitrogen-cooled hollow-cathode lamp. In this study, we examined 35 spectral lines of Ho I in the near-infrared wavelength range from 698 nm to 833 nm. Altogether, 16 new energy levels have been discovered, 5 levels of even parity and 11 levels of odd parity. Another four energy levels have been discovered but have already been published by another research group. Data on the hyperfine structure for the new levels are presented. Additionally, hyperfine structure data of three known levels of even parity were determined for the first time. The existence of the new energy levels was confirmed by analyzing 60 lines of previously measured Fourier transform spectra to precisely determine the energy of the levels.

Laser-induced fluorescence spectroscopy of certain essential oils by blue and violet diode laser excitation

Laser-induced fluorescence (LIF) spectroscopy of 8 essential oils (rosemary, basil, orange, lavender, peppermint, rose, pomegranate and tea tree oil) has been performed using compact blue and violet lasers operating at 447 nm and 405 nm respectively. The various features of the obtained spectra and their possible molecular origins have been discussed. Important constituents in these oils have been identified, such as two types of chlorophylls (A and B), in addition to a type of tocopherol (vitamin E). It may be possible to roughly estimate, qualitatively, the relative abundance of these constituents in these essential oils. To the best of our knowledge, the analysis of a significant number of essential oils by laser induced fluorescence (LIF) technique has not been performed before. As a future application, the technique can be used for the efficient and rapid detection adulterants in essential oils.

Enhancing selective production of atomic oxygen through nanosecond pulse-burst driven mode in a He/O2 dielectric barrier discharge

In this study, the temporal evolution of O atoms in a nanosecond burst-pulsed dielectric barrier discharge (DBD) is measured by two-photon absorption laser-induced fluorescence spectroscopy. The experiment is conducted at burst conditions of 50, 100, and 200 kHz pulse frequency, 10 Hz burst frequency, and 20–400 pulses in 0.1%–2% O2 + He mixtures. The accumulation effect of O atoms in the burst mode is observed and the density gradually saturates at around 100 pulses. Increasing the pulse frequency effectively enhances the O saturation density. The 0-dimensional kinetic model reveals that the saturation effect is primarily balanced by the formation and loss characteristics of O atoms. Similar saturation effect is also observed in the typical continuous periodic pulse mode (one pulse each cycle), but with a saturation density about one order of magnitude lower than that in the burst case, highlighting the burst excitation mode as an effective method for enhancing the instantaneous peak production of O atoms. Further investigations into the influence of O2 proportion on the selective production of O atoms are also performed. The results suggest that a low O2 proportion (<2%) and pulse-burst driven mode for the He/O2 DBD facilitates the selective production of O atoms while competing with O3 formation.

Time-resolved laser-induced fluorescence spectroscopy using CW diode laser for diagnostics of argon-ion velocity distribution near AC-biased electrode.

Controlling the ion velocity in an ion sheath by applying an alternating current (AC) voltage to an electrode and/or a substrate is critical in plasma material processes. To externally control the velocity distribution of incident ions on a substrate, the application of tailored-waveform AC voltages instead of sinusoidal voltages has garnered interest in recent years. In this study, to investigate temporal changes in ion-velocity distributions, we developed a time-resolved laser-induced fluorescence spectroscopy (LIF) system using a continuous-wave diode laser as an excitation-laser source. A time-resolved LIF system entails the capture of temporally continuous and spectrally discrete LIF spectra during an AC voltage cycle. By measuring temporal changes in the LIF signal intensity at various excitation-laser wavelengths, the argon-ion velocity distribution near the electrode following the AC voltage can be characterized. The results of applying sinusoidal, triangular, and rectangular bias waveforms indicate that the LIF measurement scheme proposed herein can be used to investigate the dynamic behavior of ion-velocity distributions controlled by tailored-waveform AC voltages.

Femtosecond laser-induced fluorescence spectroscopy for the rapid detection of pathogenic bacteria

Femtosecond laser-induced fluorescence spectroscopy for the rapid detection of pathogenic bacteria

Spectroscopic Characterization of the Biochemical Profile of Mung Seedlings Following Treatment by Copper Oxide Nanoparticles

The present study aims to assess the physiological and biochemical changes in the mung plants (Vigna radiata L) due to the impact of copper oxide nanoparticles using laser-induced fluorescence, ultraviolet-visible and confocal micro-Raman spectroscopy. The mung seedlings were treated with copper oxide nanoparticles with concentrations of 0.2, 0.4, 0.6, 0.8, 1.0, 1.2, 1.4, 1.6 and 1.8 mM. The growth parameters of the mung seedlings show considerable decreases at higher concentrations of nanoparticles. The laser-induced fluorescence measurements showed a decrease in photosynthetic activity as indicated by the increase in the intensity ratio (I685/I732) with the nanoparticle concentration. Further, the ultraviolet-visible measurements show a decrease in the plant pigments chlorophyll a, chlorophyll b and carotenoids with the concentration of nanoparticles. Except for 0.2 mM, the Raman spectral signatures obtained from the leaves of mung-treated copper oxide nanoparticles reveal that the cell wall component proteins, lignin, pectin, carbohydrates, aliphatics and carotenoids declined with the treatment of nanoparticles. The decreasing intensity of carotenoids from the Raman measurements and the decreasing chlorophyll and carotenoid content in laser-induced fluorescence and ultraviolet-visible measurements suggest that copper oxide nanoparticles are toxic to mung plants. The spectroscopic techniques along with discriminatory and data processing approaches such as principal component analysis (PCA) are demonstrated to provide noninvasive, nondestructive, sensitive, rapid and effective screening of plants under various stresses.

Uranium contamination of bivalve Mytilus galloprovincialis, speciation and localization

Uranium is a natural radioelement (also a model for heavier actinides), but may be released through anthropogenic activities. In order to assess its environmental impact in a given ecosystem, such as the marine system, it is essential to understand its distribution and speciation, and also to quantify its bioaccumulation. Our objective was to improve our understanding of the transfer and accumulation of uranium in marine biota with mussels taken here as sentinel species because of their sedentary nature and ability to filter seawater.We report here on the investigation of uranium accumulation, speciation, and localization in Mytilus galloprovincialis using a combination of several analytical (Inductively Coupled Plasma Mass Spectrometry, ICP-MS), spectroscopic (X ray Absorption Spectroscopy, XAS, Time Resolved Laser Induced Fluorescence Spectroscopy, TRLIFS), and imaging (Transmission Electron Microscopy, TEM, μ-XAS, Secondary Ion Mass Spectrometry, SIMS) techniques. Two cohorts of mussels from the Toulon Naval Base and the Villefranche-sur-Mer location were studied. The measurement of uranium Concentration Factor (CF) values show a clear trend in the organs of M. galloprovincialis: hepatopancreas ≫ gill > body ≥ mantle > foot. Although CF values for the entire mussel are comparable for TNB and VFM, hepatopancreas values show a significant increase in those from Toulon versus Villefranche-sur-Mer.Two organs of interest were selected for further spectroscopic investigations: the byssus and the hepatopancreas. In both cases, U(VI) (uranyl) is accumulated in a diffuse pattern, most probably linked to protein complexing functions, with the absence of a condensed phase.While such speciation studies on marine organisms can be challenging, they are an essential step for deciphering the impact of metallic radionuclides on the marine biota in the case of accidental release. Following our assumptions on uranyl speciation in both byssus and hepatopancreas, further steps will include the inventory and identification of the proteins or metabolites involved.

The Effects of Ozone Sterilization on the Chemical and Mechanical Properties of 3D-Printed Biocompatible PMMA.

Since ozone is highly corrosive, it can substantially affect the mechanical and chemical properties of the materials; consequently, it could affect the applicability of those materials in medical applications. The effect of ozone sterilization on the chemical and mechanical properties of additively manufactured specimens of biocompatible poly(methyl-methacrylate) was observed. FDM 3D-printed specimens of biocompatible PMMA in groups of five were exposed to high concentrations of ozone generated by corona discharge for different durations and at different ozone concentrations inside an enclosed chamber with embedded and calibrated ozone, temperature, and humidity sensors. A novel approach using laser-induced fluorescence (LIF) and spark-discharge optical emission spectrometry (SD-OES) was used to determine an eventual change in the chemical composition of specimens. Mechanical properties were determined by testing the tensile strength and Young's modulus. A calibrated digital microscope was used to observe the eventual degradation of material on the surface of the specimens. SD-OES and LIF analysis results do not show any detectable sterilization-caused chemical degradation, and no substantial difference in mechanical properties was detected. There was no detectable surface degradation observed under the digital microscope. The results obtained suggest that ozone sterilization appears to be a suitable technique for sterilizing PMMA medical devices.

Enhanced laser-induced fluorescence and Raman spectroscopy with gold nanoparticles for the diagnosis of oral squamous cell carcinoma

BackgroundThe incidence, mortality, and recurrence rates of oral cancer are high worldwide. It is a common and aggressive type of tumor. Owing to the challenges associated with early illness diagnosis, squamous cell carcinoma, a kind that is prevalent of oral cancer, has an unacceptably high fatality rate. The management of the condition and the prevention of cancer, on the other hand, depend greatly on early detection. Therefore, alternative methods for the treatment and early diagnosis are essential for oral cancer. The detection of tongue squamous cell carcinoma is aided by coupled surface plasmon resonance, which can occur in gold nanoparticles (AuNPs). Compared to the currently utilized imaging contrast chemicals, AuNPs are more biocompatible and capable of targeting specific surface molecules. In the current study, AuNPs were synthesized in one step via citrate reduction and applied to tongue samples of a Caucasian man's Homo sapiens (Squamous cell carcinoma from ATCC cell-lines) in order to improve early detection using and laser-induced fluorescence and Raman spectroscopy.ResultsUV–visible spectroscopy, Zeta potential, TEM, and FTIR spectroscopic technique were used to characterize the synthesized nanoparticles. The synthesized AuNPs measured 13 ± 3 nm with uniform size distribution and high stability. Results demonstrate the significance of AuNPs in improving the identification of tongue squamous cell carcinoma.ConclusionObtained results revealed that the use of AuNPs modifies the emitted spectra in the two employed spectroscopic techniques and provides more significant receiver operating characteristic curve parameters, hence a higher detection rate of cancer.

Comparison of Optogalvanic and Laser-Induced Fluorescence Spectroscopy

When investigating complex atomic spectra, it may happen accidentally that two or even several transitions between different pairs of combining energy levels have nearly the same wavenumber, and the observed spectral lines are overlapping (blend situations). In such cases, investigations of hyperfine structures can be very helpful in the identification of the involved transitions. In this paper, two complicated blend situations within the spectra of lanthanide atoms (Praseodymium and Lanthanum) are discussed as examples. The experimental methods applied are optogalvanic and laser-induced fluorescence spectroscopy, combined with emission spectra gained via Fourier transform spectroscopy. It is shown that, in such cases, a combination of optogalvanic and laser-induced fluorescence detection is necessary to find all transitions contributing to the observed spectral signatures.

A perturbed energy level of the holmium atom

This study focuses on two lines of atomic holmium for which standard hyperfine structure analysis could not be performed. The lines were studied by laser-induced fluorescence spectroscopy using a Ti-sapphire laser. Usually, the hyperfine structure of spectral lines is described by the well-known Casimir formula. However, this was not possible in the analysis of these two lines. The common feature of these two lines is that their upper energy levels are identical. In this study, hyperfine structure analyses were performed by considering a perturbation in the hyperfine splitting of the upper energy level of both lines. Shifts were introduced for the hyperfine sub-levels with F = 4 to 7 of the perturbed level, with the help of which the positions of all components of both laser lines could be satisfactorily explained. The same behaviour was found for three other spectral lines present in the Fourier transform spectrum, which are connected to the same perturbed upper energy level. The perturbation must be caused by a hitherto unknown energy level of odd parity with small J -value. The energy, J - quantum number and hyperfine constant A of this level were estimated.

Three-dimensional flow velocity determination using laser-induced fluorescence method with asymmetric optical vortex beams

Laser-induced fluorescence (LIF) Doppler spectroscopy using an optical vortex beam with an asymmetric intensity distribution, referred to as aOVLIF, is proposed as a new method to measure plasma flow velocity. LIF spectra were calculated numerically using typical laboratory low-temperature plasma parameters, and it was revealed that an ion flow across the beam produces a frequency shift of the spectra. This method also has the capability of temperature measurements. The propagation effects of asymmetric optical vortex beams are discussed assuming an actual experiment, and it is found that the sensitivity to the transverse flow velocity is approximately unchanged. The aOVLIF method, which exploits the inhomogeneous phase structure of optical vortices, can be applied to the determination of three-dimensional velocity vectors and promises to enhance the usefulness of conventional LIF spectroscopy using plane waves.

Extending the Large Molecule Limit: The Role of Fermi Resonance in Developing a Quantum Functional Group.

Polyatomic molecules equipped with optical cycling centers (OCCs), enabling continuous photon scattering during optical excitation, are exciting candidates for advancing quantum information science. However, as these molecules grow in size and complexity, the interplay of complex vibronic couplings on optical cycling becomes a critical but relatively unexplored consideration. Here, we present an extensive exploration of Fermi resonances in large-scale OCC-containing molecules using high-resolution dispersed laser-induced fluorescence and excitation spectroscopy. These resonances manifest as vibrational coupling leading to intensity borrowing by combination bands near optically active harmonic bands, which require additional repumping lasers for effective optical cycling. To mitigate these effects, we explore altering the vibrational energy level spacing through substitutions on the phenyl ring or changes in the OCC itself. While the complete elimination of vibrational coupling in complex molecules remains challenging, our findings highlight significant mitigation possibilities, opening new avenues for optimizing optical cycling in large polyatomic molecules.

Spectroscopic detection of the gallium methylene (GaCH2 and GaCD2) free radical in the gas phase by laser-induced fluorescence and emission spectroscopy.

GaCH2, a free radical thought to play a role in the chemical vapor deposition of gallium-containing thin films and semiconductors, has been spectroscopically detected for the first time. The radical was produced in a pulsed discharge jet using a precursor mixture of trimethylgallium vapor in high pressure argon and studied by laser-induced fluorescence and wavelength resolved emission techniques. Partially rotationally resolved spectra of the hydrogenated and deuterated species were obtained, and they exhibit the nuclear statistical weight variations and subband structure expected for a 2A2-2B1 electronic transition. The measured spectroscopic quantities have been compared to our own abinitio calculations of the ground and excited state properties. The electronic spectrum of gallium methylene is similar to the corresponding spectrum of the aluminum methylene radical, which we reported in 2022.

Experimental and computational evidence of U(VI)–OH–Si(OH)4 complexes under alkaline conditions: Implications for cement systems

The complexation of uranyl hydroxides with orthosilicic acid was investigated by experimental and theoretical methods. Spectroluminescence titration was performed in a glovebox under argon atmosphere at pH 9.2, 10.5 and 11.5, with [U(VI)] = 10−6 and 5 × 10−6 mol kgw−1. The polymerization effects of silicic acid were minimized by ruling out samples with less than 90 % monomeric silicic acid present, identified via UV–Vis spectrometry using the molybdate blue method. Linear regression analysis based on time-resolved laser-induced fluorescence spectroscopy (TRLFS) results yielded the conditional stepwise formation constants of U(VI)–OH–Si(OH)4 complexes at 0.05 mol kgw−1 NaNO3. The main spectroscopic features – characteristic peak positions and decay-time – are reported for the first time for the UO2(OH)2SiO(OH)3− species observed at pH 9.2 and 10.5 and UO2(OH)2SiO2(OH)22− predominant at pH 11.5. Quantum chemical calculations successfully computed the theoretical luminescence spectrum of the complex UO2(OH)2SiO(OH)3− species, thus underpinning the proposed chemical model for weakly alkaline systems. The conditional stability constants were extrapolated to infinite dilution using the Davies equation, resulting in log10β°(UO2(OH)2SiO(OH)3−) and log10β°(UO2(OH)2SiO2(OH)22−). Implications for U(VI) speciation in the presence and absence of competing carbonate are discussed for silicate-rich environments expected in certain repository concepts for nuclear waste disposal.

Spectroscopic characterization of the complexes of 2-(2'-pyridyl)-benzimidazole and (H2O)1,2, (CH3OH)1,2, and (NH3)1,2 isolated in the gas phase.

The hydrogen-bonded docking preferences of small solvent molecules on 2-(2'-pyridyl)-benzimidazole (PBI) were studied experimentally aided by computational findings. The PBI-S1,2 complexes (S = H2O, CH3OH, and NH3) were produced in a supersonically jet-cooled molecular beam and probed using resonant two-photon ionization and laser-induced fluorescence spectroscopy, with multiple isomers confirmed by UV-UV hole-burning spectroscopy. Two distinct isomers of PBI-H2O and PBI-(H2O)2 complexes were identified, while PBI-CH3OH and PBI-NH3 each formed a single 1 : 1 and 1 : 2 complex. Computational results with experimental findings revealed PBI-S-a as the most stable structure, with a solvent molecule forming a hydrogen-bonded bridge between imidazolyl-NH (NIH) and pyridyl-N (NP) at site-a. The site-a isomers exhibit higher S1 state stability compared to the S0 state, resulting in red-shifted S0 → S1 band origin for PBI-S-a and a further red-shift for the PBI-(S)2-aa isomers. In contrast, the PBI-S-b isomer, with a hydrogen bond between imidazolyl-N (NI) and pyridyl-CH (CPH) at site-b opposite to site-a, showed a blue-shifted band origin transition. A unique PBI-(H2O)2-ab isomer was detected with solvent molecules bound at both sites a and b, displaying a smaller red-shift in the band origin transition than the aa-isomer. The energy barrier for solvent-to-chromophore proton transfer varies with isomeric configuration. PBI-H2O-b isomers show significantly higher barriers (>800 cm-1), while PBI-(H2O)-aa has a slightly increased barrier (>436 cm-1) compared to the PBI-H2O-a (420 ± 10 cm-1) isomer. This study explores the potential landscape of PBI, enhancing our understanding of stabilization effects, spectral shifts, and their impact on chromophore excited-state dynamics in various environments.

Combined Use of Laser-Induced Breakdown and X-Ray Fluorescence Spectroscopies for Elemental Analysis of Aquatic Organisms

Combined Use of Laser-Induced Breakdown and X-Ray Fluorescence Spectroscopies for Elemental Analysis of Aquatic Organisms

Experimental determination of the partitioning of representative organic pollutants to the air-water interface.

Using glancing-angle laser-induced fluorescence (GALIF) spectroscopy as a probe, the partitioning of naphthalene, fluoranthene, pyrene, umbelliferone, phenol red, and bisphenol A from bulk solution to the air-water interface was examined in both pure water and aqueous solutions of 6 mM octanol. Previous studies provided similar Langmuir adsorption isotherms for anthracene and imidazole 2-carboxaldehyde. The surface partitioning behaviour of each compound in both environments was well described using a Langmuir adsorption model; partitioning coefficients were derived from the fits to such isotherms. Only the PAH molecules, naphthalene, fluoranthene and pyrene, saw an enhancement in the surface partitioning in octanol solution compared to pure water. The surface partitioning to pure water surfaces could be fairly well described using a one parameter linear free energy relationship based on either solubility or KOW.