Laser-induced Fluorescence Spectroscopy Research Articles

Thermometry of Spatially Inhomogeneous Methane–Air Flame Using Two-Color Planar Laser-Induced Fluorescence and Coherent Anti-Stokes Raman Scattering Spectroscopy

Thermometry of Spatially Inhomogeneous Methane–Air Flame Using Two-Color Planar Laser-Induced Fluorescence and Coherent Anti-Stokes Raman Scattering Spectroscopy

Correlation between temperature distribution and changes in self-organized luminous pattern in an atmospheric pressure DC glow discharge with sheath gas flow

Abstract The self-organized luminous patterns observed above the anode surface in atmospheric-pressure DC glow discharges were changed by the composition of the gas flow. The patterns were observed not only with liquid anodes but also with metal anodes. Various pattern structures were observed by changing the helium gas flow rate in the core and the ambient oxygen gas flow rate supplied during the discharge. When the pattern formation was observed, the emission spectra and the radial spread of the positive column changed, and the voltage–current characteristic also changed. These results suggest that not only the anode surface but the entire discharge affects the pattern formation. Comparing the results for the liquid and metal anodes, the trends in the pattern formation and voltage–current characteristics were almost identical. The gas temperature in the discharge was also investigated in two different ways, by the laser-induced fluorescence spectroscopy of OH radicals and by Rayleigh scattering, showing in good agreement between both methods. Under the condition where the pattern formed, the gas temperature in the discharge was approximately 2500–3000 K and higher than that of the discharge without the pattern formation. Focusing on the gradient of the temperature distribution, the discharge with the pattern formation had a steeper gradient than that of the discharge without the pattern formation. It is suggested that not only the high temperature of the discharge but also the large gradient of the temperature change plays an important role in the pattern formation. The role of oxygen gas in the pattern formation may be the effect of increasing the temperature and altering the temperature gradient in the discharge rather than generating negative ions in the discharge.

LIFs-Based Fluorescent Analysis of Silver Ions in Water Using AIEgen-Embedded PVA Hydrogel.

The detection and quantification analysis of silver ions is important to protect human health and improve the level of wastewater treatment. In this work, a polyvinyl alcohol (PVA) hydrogel-based sensing material based on an aggregation-induced emission strategy was developed and combined with a portable laser-induced fluorescence spectroscopy (LIFs) device for the direct detection and quantification of silver ions in water. Considering the requirements of environmental water analysis regarding portability, reliability, and convenience, this fluorescence turn-on strategy was optimized accordingly to ensure the accuracy and stability of the analysis in complex natural water environmental. This sensing method showed operational excellence and good sensitivity (down to 1 ppb) and may provide a stable and convenient strategy for the on-site, real-time analysis of environmental water samples.

Multi-spectroscopic characterization system for cultural heritage materials analysis (SYSPECTRAL): Conception and example

A comprehensive understanding of chemical composition of cultural heritage materials usually requires several complementary analytical techniques. Given the fragility and value of artworks, minimizing or avoiding sampling and performing in situ analysis under ambient light is an important goal. This article outlines a novel prototype designed to merge LIBS, laser-induced fluorescence spectroscopy (LIF), Raman spectroscopy using a single pulsed laser, and reflectance spectroscopy in a multi-spectroscopic characterization system for cultural heritage analysis (SYSPECTRAL). The aim is to analyze cultural heritage materials in their original place, obtaining both elemental and molecular information at such same point that is not always insured with several separated experimental settings. The SYSPECTRAL system focuses on compactness, mobility, and ease of operation. Software designed for the prototype controls multi-spectroscopic measurements, allows for image capture, precise localization, and data acquisition. Reflectance spectra examined the material and colors at the surface, and the LIBS-LIF-Raman package examines the stratigraphic structure of a multi-layered painted sample.

Laser Spectroscopic Characterization of Supersonic Jet-Cooled 2,6-Diazaindole (26DAI).

The article presents a comprehensive laser spectroscopic characterization of a nitrogen-rich indole derivative, namely, 2,6-diazaindole (26DAI), in the gas phase. A supersonic jet-cooled molecular beam of 26DAI was characterized using two-color resonant two-photon ionization (2C-R2PI) and laser-induced fluorescence spectroscopy (LIF) to investigate the electronic excitation. The S1 ← S0 origin transition was obtained at 33915 cm-1, which was red-shifted from that of one (indole) and two (7-azaindole) nitrogen-containing indole derivatives by 1317 and 713 cm-1, respectively. The molecular orbital and energy analysis for the S1 ← S0 transition shows the significant stabilization of LUMO on subsequent N-insertion, resulting in the lowering of the S1 ← S0 (ππ*) transition energy. The single vibronic level fluorescence spectrum from the vibrationless S1 state of the molecule was recorded. The spectrum displayed an extensive Franck-Condon activity until 2500 cm-1 for the vibrational modes of the S0 state of the 26DAI molecule. The experimental ground state vibrational frequencies were compared to the calculated ones obtained at three different levels of theories. More accurate results were found at DFT B3LYP-D4 than those at the wave function-based MP2 and CCSD levels of theories. Further, the N-H stretching frequency of 26DAI in the S0 state was measured at 3524 cm-1 using fluorescence-dip infrared (FDIR) spectroscopy. The stability of 26DAI against ionization radiation was probed by measuring the two-color photoionization energy (IE2P) of 26DAI at 71866 cm-1. The IE2P value is significantly higher than those of N-poor counterparts (indole and 7-azaindole). The NBO charges and spin density (SD) values of the 26DAI molecule have shown that electronegative N(6) makes the cationic ground state less stable due to the position of the positive centers on the N atom. The results provided insights into the stability of N-rich biomolecules against photodamage. The current investigation can shed light on nature's way of stabilizing biomolecules with a possible N-insertion mechanism.

Interpretation of vertical migration and enrichment processes of rare earth elements (REEs) in ion-adsorption-type mineralization in Japan based on REE speciation analyses

Typical vertical profiles of ion-adsorption-type rare earth element (REE) deposits discovered in southwest Japan were studied by conducting speciation analyses, including X-ray absorption fine structure and laser-induced fluorescence spectroscopy combined with transmission electron microscopy and adsorption/desorption experiments. The results revealed that REE speciation, migration, and enrichment in weathered granite is largely controlled by soil pH, which in turn controls the variable charges of kaolinite, the REE host phase. Both the distribution coefficient Kd and the soil pH increase with depth. As a result, (i) REE dissolution and migration occur in the near-surface acidic environment of the upper layers, where hydroxyls of kaolinite basal surfaces and edges are deprotonated to a lesser degree, and (ii) REEs accumulate in the relatively high-pH environment below the surface, where hydroxyls of kaolinite basal surfaces and edges are deprotonated to a larger degree, producing REE adsorption sites with variable charges. An increase of soil pH to greater than 6 in deeper layers promotes inner-sphere complexation of REEs. Although inner-sphere complexation inhibits the ion-exchange extraction of REEs, the inner-sphere complexes can be still extracted by lowering the pH of the extraction solution. This fact, which indicates that the adsorption of both inner- and outer-sphere complexes is reversible, is important in terms of both (i) understanding vertical REE profiles in which the pH varies and (ii) the efficient recovery of REEs from REE-enriched layers at all depths in weathered granite.

Photopolymerization of Chlorpromazine-Loaded Gelatin Methacryloyl Hydrogels: Characterization and Antimicrobial Applications.

This study investigates the synthesis, characterization, and antimicrobial properties of hydrogels synthesized through the UV-pulsed laser photopolymerization of a polymer-photoinitiator-chlorpromazine mixture. Chlorpromazine was used for its known enhanced antimicrobial properties when exposed to UV laser radiation. The hydrogel was formed from a mixture containing 0.05% Irgacure 2959, 10% gelatin methacryloyl, and various concentrations of chlorpromazine (1, 2, and 4 mg/mL). Laser-induced fluorescence spectroscopy was employed to monitor the photoinduced changes of chlorpromazine and Irgacure 2959 during hydrogel formation, providing insight into the photodegradation dynamics. FTIR spectroscopy confirmed the incorporation of irradiated chlorpromazine within the hydrogel matrix, while the release profiles of chlorpromazine showed sustained release only in hydrogels containing 1 mg/mL of CPZ. The hydrogel showed significant antimicrobial activity against MRSA bacteria when compared to that of penicillin. These findings highlight the potential of CPZ loaded during the photopolymerization process into hydrogels as effective antimicrobial agents with sustained release properties, making them suitable for combating resistant bacterial strains.

Insight into the complexation of uranium with Bacillus sp. dwc-2 by multi-spectroscopic approaches: FT-IR, TRLF and XAFS spectroscopies

The micromechanisms of the interactions between uranium and microorganisms, especially chemical bonds and bonding numbers between uranium and microbe are not yet clear. In this work, uranium coordination with functional groups in/on Bacillus sp. dwc-2 has been rationally explored by X-ray absorption fine structure (XAFS), Fourier transform infrared (FT-IR), time-resolved laser-induced fluorescence (TRLF) spectroscopies. The results indicate that under acidic condition, 66.8 % of O atoms in coordination shell of U(VI) equatorial plane are provided by organic phosphoryl groups via monodentate coordination, 18.8 % and 15.5 % are provided by water molecules and carboxyl groups via monodentate and bidentate coordination, respectively. While under alkaline condition, these proportions change to 53.1 %, 34.4 % and 22.0 %, respectively. Under neutral condition, U(VI) is mainly deposited by complexing with inorganic phosphates released by microbial cells. Under anaerobic condition, partial U(VI) can be reduced to U(IV) which primarily complex with phosphorus containing groups via monodentate and bidentate coordination, existing as amorphous solids or coordination polymers. This is the first exploration of the binding mechanism between uranium and microorganisms at a semi-quantitative level under different conditions. Our studies will further enhance the contribute to the understanding of coordination mechanism of uranium with microorganism, and demonstrate the potential bioremediation value of this bacterium.

Laser induced fluorescence spectroscopy of the transition of jet cooled 14NO3 and 15NO3 II: the dispersed fluorescence spectrum from the 3rd E level of the ν4 mode (approximately the 2ν4 (e'), l = 0, level).

14NO3 and 15NO3 isotopomers were generated in a supersonic free jet expansion, and laser induced fluorescence (LIF) of the electronic transition was observed. Dispersed LIF spectra from the vibronic level at ∼770 cm-1 above the vibrationless level have been measured for each isotopomer. One remarkable characteristic of the dispersed fluorescence (DF) spectrum is that the ν2 fundamental is clearly observed, even though the transition 201 is forbidden in the electronic transition. Another is that two sets of vibrational structure are observed in the DF spectrum: one of the two sets is the structure with the origin at the excitation energy, and the other is that with the origin at the ν2 fundamental. These observations suggest that the fluorescent level has contribution from the ν2 mode. In part I (M. Fukushima, J. Mol. Spectrosc., 2022, 387, 111646), it has been reported that the ν4 progressions are one of the typical characteristics of the vibrational structure of the DF spectrum from the vibrationless level; the progressions have intensity gradually decreasing with increasing ν4 quantum number (named the "regular" distribution), and have members forbidden for the Δl = 0 selection rule. The intensity distribution of the ν4 progression with the origin at the ν2 fundamental is similar to that from the vibrationless level, while that with the origin at the excitation energy is drastically different from that from the vibrationless level. The Jahn-Teller (J-T) and Renner-Teller (R-T) interactions in the B̃2E' state enable us to interpret the intensity distributions of the ν4 progressions, in which relatively weak interactions are enough to reproduce the observed distributions. The spectral intensity distribution analyses adopting the two vibronic couplings suggest that the fluorescent level at ∼770 cm-1 above the vibrationless level is the 3rd E eigenstate of the ν4 mode. The major component of the ν4 3rd E state is the |Λ = ±1; v4 = 2, l4 = 0〉 level of the B̃2E' state, which is a vibrationally and a vibronically E' level, and it is therefore concluded that the major components of the fluorescent level are both of the ν2 = 1 level and ν4 = 2 level .

Identification of adulterants in açaí pulp samples using laser-induced fluorescence spectroscopy combined with linear discriminant analysis (LDA) method: A demonstration of the potential applicability of the technique

Identification of adulterants in açaí pulp samples using laser-induced fluorescence spectroscopy combined with linear discriminant analysis (LDA) method: A demonstration of the potential applicability of the technique

Investigating the interaction of uranium(VI) with diatoms and their bacterial community: A microscopic and spectroscopic study

Diatoms and bacteria play a vital role in investigating the ecological effects of heavy metals in the environment. Despite separate studies on metal interactions with diatoms and bacteria, there is a significant gap in research regarding heavy metal interactions within a diatom-bacterium system, which closely mirrors natural conditions. In this study, we aim to address this gap by examining the interaction of uranium(VI) (U(VI)) with Achnanthidium saprophilum freshwater diatoms and their natural bacterial community, primarily consisting of four successfully isolated bacterial strains (Acidovorax facilis, Agrobacterium fabrum, Brevundimonas mediterranea, and Pseudomonas peli) from the diatom culture. Uranium (U) bio-association experiments were performed both on the xenic A. saprophilum culture and on the four bacterial isolates. Scanning electron microscopy and transmission electron microscopy coupled with spectrum imaging analysis based on energy-dispersive X-ray spectroscopy revealed a clear co-localization of U and phosphorus both on the surface and inside A. saprophilum diatoms and the associated bacterial cells. Time-resolved laser-induced fluorescence spectroscopy with parallel factor analysis identified similar U(VI) binding motifs both on A. saprophilum diatoms and the four bacterial isolates. This is the first work providing valuable microscopic and spectroscopic data on U localization and speciation within a diatom-bacterium system, demonstrating the contribution of the co-occurring bacteria to the overall interaction with U, a factor non-negligible for future modeling and assessment of radiological effects on living microorganisms.

Two-dye two-color laser-induced fluorescence spectroscopy on droplets of green solvent water/ethanol mixtures for thermometry and mixture composition

This work shows new insights on the application of two-color laser-induced-fluorescence (2c-LIF) thermometry in a droplet chain. A two-dye mixture is used in ethanol, water and ethanol/water mixtures in order to reach a high-temperature sensitivity and avoid the detection of lasing effects in the droplets. Various droplet sizes are recorded in regard to the limitation of the detection system for very small micrometric droplets. The breakup of a droplet chain is measured to assess the spectral detection system in applications with liquid structures of different sizes. Additionally, a proposal to expand the 2c-LIF application for studying ethanol/water droplets regarding mixture composition with a third color channel is presented. Forming two intensity ratios, the spectra can be used to obtain information on the mixture composition of the solvent. Measurements in different ethanol/water mixtures containing 0–100 vol% water are evaluated to show this possibility.

Spontaneous Production of I2 at the Surface of Aqueous Iodide Solutions.

Several groups have recently reported spontaneous production of atmospherically reactive species, including molecular iodine (I2) at the air-water interface of droplets. In this study, glancing angle laser-induced fluorescence spectroscopy was used to track the luminol fluorescence at the surface of sodium iodide (NaI) and sodium chloride (NaCl) solutions. Although luminol fluorescence is hardly quenched by halide anions, even up to fairly high concentrations, it is effectively quenched by I2. We observe luminol fluorescence quenching at the surface of NaI solutions but not at the surface of NaCl solutions, pointing to the formation of I2 at the surface of NaI solutions. This provides further support for the proposal that the strong electric field or the reduction solvation present at the air-water interface can initiate spontaneous iodide activation and other chemistry there. The spontaneous production of I2 at the surface of aqueous iodide solutions presents a previously unconsidered source of iodine in the atmosphere.

CuO nanoparticles' effect on the photosynthetic performance in seed tissues of Inga laurina (Fabaceae).

Copper oxide nanoparticles (CuONPs) have been produced on a large scale because they can be applied across various fields, especially in nano-enabled healthcare and agricultural products. However, the increasing use of CuONPs leads to their release and accumulation into the environment. The CuONPs uptaken by seeds and their implications on germination behavior have been reported, but little is known or understood about their impact on photosynthesis in seed tissues. To fill knowledge gaps, this study evaluated the effects of CuONP concentrations (0-300mg L-1) on the photosynthetic activity of Inga laurina seeds. The microscopy data showed that CuONPs had an average size distribution of 57.5 ± 0.7nm. Copper ion release and production of reactive oxygen species (ROS) by CuONPs were also evaluated by dialysis and spectroscopy experiments, respectively. CuONPs were not able to intrinsically generate ROS and released a low content of Cu2⁺ ions (4.5%, w/w). Time evolution of chlorophyll fluorescence imaging and laser-induced fluorescence spectroscopy were used to monitor the seeds subjected to nanoparticles during 168h. The data demonstrate that CuONPs affected the steady-state maximum chlorophyll fluorescence ( ), the photochemical efficiency of photosystem II ( ), and non-photochemical quenching ( ) of Inga laurina seeds over time. Besides, the significantly increased at the seed development stage, near the root protrusion stage, probably due to energy dissipation at this germination step. Additionally, the results indicated that CuONPs can change the oscillatory rhythms of energy dissipation of the seeds, disturbing the circadian clock. In conclusion, the results indicate that CuONPs can affect the photosynthetic behavior of I. laurina seeds. These findings open opportunities for using chlorophyll fluorescence as a non-destructive tool to evaluate nanoparticle impact on photosynthetic activity in seed tissues.

Postfilament-Induced Two-Photon Fluorescence of Dyed Liquid Aerosol Enhanced by Structured Femtosecond Laser Pulse

Laser-induced fluorescence spectroscopy (LIFS) is actively used for remote sensing of atmospheric aerosols and is currently one of the most sensitive and selective techniques for determining small concentrations of substances inside particles. The use of high-power femtosecond laser sources for LIFS-based remote sensing of aerosols contributes to the development of new-generation fluorescence atmospheric lidars since it makes it possible to overcome the energy threshold for the nonlinear-optical effects of multiphoton absorption in particles and receive the emission signal at long distances in the atmosphere. Our study is aimed at the development and experimental demonstration of the technique of nonlinear laser-induced fluorescence spectroscopy (NLIFS) based on the remote excitation of aerosol fluorescent emission stimulated by a spatially structured high-power femtosecond laser pulse. Importantly, for the first time to our knowledge, we demonstrate the advances in using stochastically structured plasma-free intense light channels (postfilaments) specially formed by the propagation of femtosecond laser radiation through a turbulent air layer to improve NLIFS efficiency. A multiple increase in the received signal of two-photon-excited fluorescence of polydisperse-dyed aqueous aerosols by the structured postfilaments is reported.

Insight in NO synthesis in a gliding arc plasma via gas temperature and density mapping by laser-induced fluorescence

A gliding arc (GA) plasma, operating at atmospheric pressure in a gas mixture of 50% N2 and 50% O2, is studied using laser-induced fluorescence spectroscopy. The main goal is to determine the two-dimensional distribution of both the gas temperature and the NO ground state density in the afterglow. As GA plasma discharges at atmospheric pressure normally produce rather high NO x densities, the high concentration of relevant absorbers, such as NO, may impose essential restrictions for the use of ‘classical’ laser-induced fluorescence methods (dealing with excitation in the bandhead vicinity), as the laser beam would be strongly absorbed along its propagation in the afterglow. Since this was indeed the case for the studied discharge, an approach dealing with laser-based excitation of separate rotational lines is proposed. In this case, due to a non-saturated absorption regime, simultaneous and reliable measurements of both the NO density and the gas temperature (using a reference fitting spectrum) are possible. The proposed method is applied to provide a two-dimensional map for both the NO density and the gas temperature at different plasma conditions. The results show that the input gas flow rate strongly alters the plasma shape, which appears as an elongated column at low input gas flow rate and spreads laterally as the flow rate increases. Finally, based on temperature map analysis, a clear correlation between the gas temperature and NO concentration is found. The proposed method may be interesting for the plasma-chemical analysis of discharges with high molecular production yields, where knowledge of both molecular concentration and gas temperature is required.

Wavelength modulation laser-induced fluorescence for plasma characterization.

Laser-Induced Fluorescence (LIF) spectroscopy is an essential tool for probing ion and atom velocity distribution functions (VDFs) in complex plasmas. VDFs carry information about the kinetic properties of species that is critical for plasma characterization. Accurate interpretation of these functions is challenging due to factors such as multicomponent distributions, broadening effects, and background emissions. Our research investigates the use of Wavelength Modulation (WM) LIF to enhance the sensitivity of VDF measurements. Unlike standard Amplitude Modulation (AM) methods, WM-LIF measures the derivative of the LIF signal. This approach makes variations in VDF shape more pronounced. VDF measurements with WM-LIF were investigated with both numerical modeling and experimental measurements. The developed model enables the generation of both WM and AM signals, facilitating comparative analysis of fitting outcomes. Experiments were conducted in a weakly collisional argon plasma with magnetized electrons and non-magnetized ions. Measurements of the argon ion VDFs employed a narrow-band tunable diode laser, which scanned the 4p4D7/2-3d4F9/2 transition centered at 664.553nm in vacuum. A lock-in amplifier detected the second harmonic WM signal, which was generated by modulating the laser wavelength with an externally controlled piezo-driven mirror of the diode laser. Our findings indicate that the WM-LIF signal is more sensitive to fitting parameters, allowing for better identification of VDF parameters such as the number of distribution components, their temperatures, and velocities. In addition, WM-LIF can serve as an independent method to verify AM measurements and is particularly beneficial in environments with substantial light noise or background emissions, such as those involving thermionic cathodes and reflective surfaces.

Research on a deconvolution algorithm for laser-induced fluorescence diagnosis based on the maximum entropy principle

Laser-induced fluorescence (LIF) spectroscopy is employed for plasma diagnosis, necessitating the utilization of deconvolution algorithms to isolate the Doppler effect from the raw spectral signal. However, direct deconvolution becomes invalid in the presence of noise as it leads to infinite amplification of high-frequency noise components. To address this issue, we propose a deconvolution algorithm based on the maximum entropy principle. We validate the effectiveness of the proposed algorithm by utilizing simulated LIF spectra at various noise levels (signal-to-noise ratio, SNR = 20–80 dB) and measured LIF spectra with Xe as the working fluid. In the typical measured spectrum (SNR = 26.23 dB) experiment, compared with the Gaussian filter and the Richardson–Lucy (R-L) algorithm, the proposed algorithm demonstrates an increase in SNR of 1.39 dB and 4.66 dB, respectively, along with a reduction in the root-mean-square error (RMSE) of 35% and 64%, respectively. Additionally, there is a decrease in the spectral angle (SA) of 0.05 and 0.11, respectively. In the high-quality spectrum (SNR = 43.96 dB) experiment, the results show that the running time of the proposed algorithm is reduced by about 98% compared with the R-L iterative algorithm. Moreover, the maximum entropy algorithm avoids parameter optimization settings and is more suitable for automatic implementation. In conclusion, the proposed algorithm can accurately resolve Doppler spectrum details while effectively suppressing noise, thus highlighting its advantage in LIF spectral deconvolution applications.

Experimental study of nitric oxide distributions in non-premixed and premixed ammonia/hydrogen-air counterflow flames

This study reports an experimental investigation of quantitative Nitric Oxide (NO) distribution in both premixed and non-premixed NH3/H2-air flames using a counterflow burner at atmospheric pressure. One-dimensional (1D) NO laser-induced fluorescence (LIF) spectroscopy and Raman/Rayleigh spectroscopy were conducted to accurately resolve the quantitative 1D NO profile in terms of mixture fraction, temperature, and physical space. We calibrated a saturated NO-LIF model in 5 premixed lean H2/N2/NO-air flames with different seeded NO levels in a McKenna burner and validated its accuracy in three H2N2NO-air counterflow diffusion flames. The overall uncertainty of NO quantification was less than90 ppm. Our measurements were compared with simulations using different ammonia chemical kinetic models, revealing that current models have over 30% uncertainty in predicting peak NO concentrations (mole fraction) in 1D non-premixed and premixed flames and over 100% uncertainty in lower temperature regions. In premixed flames, measured NO concentrations fell within the intermediate range of current chemical kinetic models at lean and stoichiometric conditions, but were lower than the models at rich conditions. In non-premixed flames, all models overestimated the peak NO concentrations by more than 1000 ppm. It is noted that the measured peak NO concentrations increased with higher NH3/H2 ratios (from 4/6 to 8/2), strain rates (from 80 to 140 1/s), and N2 dilution ratios in a 1:1 NH3/H2 mixture (from 0 to 30%). Although most models could qualitatively predict the trends, they were inaccurate in quantifying NO. Additionally, the measured width of the NO profile in mixture fraction space expanded with increasing NH3/H2 ratio, N2 dilution ratio, and strain rate. While models could qualitatively predict this behavior, they consistently underestimated NO in the fuel-rich, lower-temperature region, resulting in a narrower NO profile width. The Manna model showed a better prediction of NO distribution in the fuel rich portion of non-premixed flames, accounting for NH3NO interactions at lower temperatures. These findings highlight the critical need to improve models to accurately predict NO concentrations in ammonia-containing flames and their behavior in fuel rich regions.

Non-invasive stratigraphic analyzes of gelatine-based modern painting materials with linear and nonlinear optical methods

Stratigraphic analyzes of polychrome surfaces, such as paintings, often need samples to offer consistent results regarding the sequence and composition of the layers. Non-invasive methodologies based on linear and nonlinear optical techniques limit material removal from the objects. Recently, optical coherence tomography (OCT) has become the preferred choice of heritage scientists because it is a safe and fast alternative for studying transparent or semi-transparent layers. Yet, nonlinear optical microscopy (NLOM)) technique in its modality of multiphoton excitation fluorescence (MPEF) has emerged as a promising tool for the same purpose. Here, we explored linear (OCT and confocal Raman microspectroscopy (CRM)) and nonlinear (NLOM-MPEF) optical methods’ capability to investigate gelatine-based layers in mock-up samples and a painting dated 1939 by an artist from the Surrealistic entourage. The optical behavior of mock-up samples that imitate the painting stratigraphy and of six painting fragments detached from the support was also investigated with fiber optics reflectance spectroscopy and laser induced fluorescence (LIF). Thickness values from the mock-ups obtained with OCT, CRM, and MPEF have provided evidence of the complementarity, from a millimetric to a micrometric scale, and the limitations (e.g. strong fluorescence emission in CRM) of the methods. Moreover, the presence of gelatine was ascertained by LIF spectroscopy applied to the painting fragments and NLOM-MPEF confirmed its suitability as a non-invasive technique for investigating gelatine-based stratigraphic systems.