Laser-induced Fluorescence Research Articles

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.

Laser-induced fluorescence spectroscopic investigation of Echium amoenum decoction

Herbs containing medicinal ingredients with nutritional value have recently gained attention as an alternative to synthetic drugs. Aside from their pharmaceutical worthiness, a variety of naturally occurring chromophores with specific optical properties have made them valuable sources of natural pigments for many biophotonic applications. Echium Amoenum (EA) is one of the colorful flowers that has been used in traditional medicine for a long time. To our knowledge, although several studies have been carried out on the characterization of EA ingredients and their chemical activities, information on EA fluorescence is still lacking. Here, laser induced fluorescence (LIF) features of the decoction of EA petals were evaluated and found to be highly dependent on the excitation wavelength, EA concentration, and detection geometry. The abundance of pigments, the boundaries of their absorption/emission spectral regions, and the corresponding energy transfer ascertain the contribution of certain chromophores to the cumulative fluorescence activity. Upon deconvolution of the LIF spectra, it was revealed that the different emission bands of rosmarinic acid (corresponding to its dissociated forms) and the luminescent activity of luteolin and β-carotene mainly determine the quantum distribution of the fluorescence of EA. Angular measurement of LIF in a symmetric cylindrical arrangement revealed the presence of the inner filters mainly due to the reabsorption of LIF photons by anthocyanins (flavone, pelargonidin, delphinidin and cyanidin) and carotenoids. We hope that the obtained results will be useful in various fields of photochemistry and biophotonics.

Biosensor development for diabetes diagnosis: Determining relevant miRNA using a newly developed N-annulated perylene fluorescent dye

MicroRNAs (miRNAs) have emerged as essential biomarkers for disease diagnosis, and several techniques are available to determine type 2 diabetes (T2D) relevant miRNAs. However, detecting circulating miRNAs can be challenging due to their small size, low abundance, and high sequence similarity, often requiring sensitive detection approaches combined with additional amplification processes. Laser-induced fluorescence (LIF) is a classic analytical method suitable for sensitively detecting trace amounts of nucleotide acid. Duplex-specific nuclease (DSN)-mediated amplification recently gained attention due to its catalytic activity based on target recycling, demonstrating a promising approach for miRNA amplification. This work developed a novel N-annulated perylene fluorescent dye to create a biosensor to analyze the miRNA (miR-223) relevant to T2D. The amine-reactive fluorescent dye assists the amidation reaction for nucleotide labeling, giving the oligonucleotide probe a high fluorescence quantum yield and sufficient water solubility. By combining the locked nucleic acid (LNA) modified oligonucleotide fluorescent probe to enhance the stability of LNA/RNA hybrids, thereby improving the DSN-mediated target miR-223 recycling for signal amplification, the proposed biosensor can highly selectively determine miR-223 with a limit of detection (LOD, S/N = 3) of 9.5 pM. When applied to real-world samples, the biosensor demonstrated its potential to distinguish between T2D patients and healthy controls.

Assessment of OH femtosecond thermally assisted fluorescence thermometry for hydrogen non-premixed flames

In this work, we further developed the planar temperature measurement method based on thermally assisted laser-induced fluorescence (TALF) with a single femtosecond (fs) laser and investigated the temperature distribution in the nitrogen-diluted oxygen–hydrogen cross-jet non-premixed flames at 1 kHz. Fs-TALF thermometry was firstly calibrated and assessed in a series of unconfined methane/air laminar flames at atmospheric pressure. In the calibration process, although the calibrated energy difference between OH v′ = 0 and 1 energy level was different from the theoretical value, the measured fluorescence ratio accurately reflected the temperature change from 1600 K to 2200 K in different methane flames. By comparing the calculated OH fluorescence spectrum, we believed that the main reason was the overlap of the OH (1-1) and (0-0) fluorescence bands. After the calibration, experiments were conducted with changing hydrogen flow velocity from 60 to 100 m/s and constant oxidizer flow velocity, where the dilution ratio, D varies from 0.46 to 0.7, and the equivalence ratio, ϕ, varies from 0.5 to 0.9. It is found, within the calibration range, fs-TALF thermometry can correctly measure the flame temperature. However, with ϕ further increases, the difference between the measured and theoretical temperatures gradually increases. At the same time, it was noted that the error in the measured temperature rises gradually as D decreases. In conclusion, fs-TALF thermometry can measure turbulent non-premixed hydrogen flames accurately in a range of temperature with acceptable temporal and partial resolution, while the errors within 200 K and spatial resolution is 170μm. The main error source should be the collisional effect due to the different local concentration of N2 and H2O. The results of this work will contribute to the further development the temperature measurement method hydrogen turbulent flames.

Calibration techniques for quantitative NO measurement using Laser-Induced Fluorescence

Laser-Induced Fluorescence (LIF) is an essential optical diagnostic technique for the high-resolution and low-uncertainty measurement of combustion species concentration in a variety of applications and conditions. Two different calibration techniques are explored in this study to obtain quantitative Nitric Oxide (NO) concentration measurements in flames. The first technique, the most employed in the literature, uses the extrapolation of the fluorescence signal from seeded to nascent NO and is only valid under negligible NO reburn conditions. The second technique uses the optical calibration of the experimental setup to relate it to a modelled LIF signal and can be applied regardless of NO reburn. Both of these techniques are explored under two different assumptions: constant and non-constant interfering LIF signal on the NO absorption spectrum. While the former is most often used in the literature, the latter is necessary when the LIF signal from interfering species cannot be distinguished from the NO-LIF signal, especially in high pressure conditions. Hence, a total of four techniques are presented in this work and are found to be in excellent agreement when performed in different flame conditions. The calibration techniques are applied to three lean, atmospheric, laminar, premixed, methane-air flames to explore their field of applicability. Specifically, the study explores the relevance of the techniques in reburn conditions, which occur mostly in high pressure, rich, highly-seeded, or NH3-containing flames. This study aims to offer the reader a portfolio of calibration techniques to use according to the conditions in which they need to be applied. While this study was carried out measuring NO concentration in a stagnation flame burner, the concepts and equations presented can be transposed to the measurement of other species and to other experimental configurations.

In-capillary magnetic separation and enrichment coupled with laser-induced fluorescence for rapid determination of biomolecules

Biomolecules are indispensable in the life activities and metabolism of various organisms, and their highly sensitive detection is of great significance for disease diagnosis and food safety. Due to the complexity of the matrix and the low concentration of the target, separation and enrichment of biomolecules prior to detection are necessary and time-consuming. Herein, a novel approach combining in-capillary magnetic separation and enrichment with laser-induced fluorescence detection method was proposed for qualitative and quantitative analysis of biomolecules. Two different sequence aptamers modified with magnetic nanoparticles and labeled with fluorescence were used as capture probes and signal probes to form sandwich structures with target molecules for detection. Under the combined influence of magnetic field force and fluid drag force, the integration of separation, enrichment and on-line detection were finished within 5min. Under optimal conditions, the developed method provided a low limit of detection as 2.7 fmol/L, 0.57 nmol/L, 3 CFU/mL for DNA, thrombin and Staphylococcus aureus, respectively. This proposed method offers a promising platform for the sensitive and rapid determination of biomolecules. It holds significant potential for future applications in fields of environmental and biochemical analysis.

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.

Study on the flame structure and flow field of hydrogen-enriched combustion in array micro-tube

Addressing climate change and reducing greenhouse gas emissions are critical priorities. Utilizing hydrogen-rich methane or pure hydrogen as fuels within gas turbines, facilitated by array micro-tube premixed combustion technology, is anticipated to markedly accelerate the decarbonization process of the energy sector. In this study, the flame structure of the array micro-tube premixed burner under various fuel compositions was examined using OH-Planar Laser-Induced Fluorescence and Particle Image Velocimetry measurement techniques. The effects of the equivalence ratio (φ) and the hydrogen power ratio (HPR) on the characteristics of the flame front, including its curvature, density, volume, and the associated flow field properties, were discussed. As φ and HPR increase, the wrinkled structure of the flame front is significantly enhanced, with a more pronounced effect on smaller scales. This enhancement leads to the separation of the unburned pockets from the main flame. Concurrently, both the flame length and the flame area decrease with the augmentation of φ and HPR, indicating a more concentrated combustion process and increased combustion intensity under hydrogen-enriched and pure hydrogen conditions. The study also observed a slight increase in both the negative and positive curvatures of the flame front, with a more notable increase in the negative curvature. The increased negative curvature results in an elevated degree of wrinkling and a higher value of Σ (flame surface density), reaching a maximum of 0.876 mm−1 under the conditions where φ is 0.8 and ⟨c⟩ (mean progress variable) is 0.5, resulting in the smallest observed flame volume of 100.6 mm3. Upon coupling the flame with the flow field, it was discovered that the exit flow field of the array micro-tube exhibits symmetry and a characteristic conical flame shape. The burning velocity of the side flame brushes increases, and the velocity peak shifts upstream. The aforementioned findings confirm that the addition of hydrogen increases the laminar flame velocity, enabling the flame to stably anchor to the microtube outlet and thereby enhance the flame's robustness and stability.

Scalar mixing and entrainment in an axisymmetric jet subjected to external turbulence

The present study aims to understand the process of turbulent entrainment into a jet, as affected by background turbulence, using scalar statistics. Planar laser-induced fluorescence was employed to capture the orthogonal cross sections of the jet at a fixed downstream station with varying background turbulence intensities and length scales. The conditional scalar profiles revealed that the thickness of the scalar turbulent/turbulent interface is greater than that of the traditional turbulent/non-turbulent interface, and the interfacial thickness is an increasing function of the background turbulence intensity. Although nibbling remains the primary entrainment mechanism in the far field, increased occurrence of concentration “holes” within the interfacial layer in the presence of ambient turbulence suggests a more significant role of large-scale engulfment in the turbulent/turbulent entrainment process (although still below 1% of the total mass flux). Enhanced contribution of the area of detached jet patches (i.e., “islands”) to that of the main jet is hypothesized to be evidence of intense detrainment events in the background turbulence. This can potentially contribute to a reduced net entrainment into the jet, which manifests as less negative values of scalar skewness within the jet core.

Immiscible non-Newtonian displacement flows in stationary and axially rotating pipes

We examine immiscible displacement flows in stationary and rotating pipes, at a fixed inclination angle in a density-unstable configuration, using a viscoplastic fluid to displace a less viscous Newtonian fluid. We employ non-intrusive experimental methods, such as camera imaging, planar laser-induced fluorescence (PLIF), and ultrasound Doppler velocimetry (UDV). We analyze the impact of key dimensionless numbers, including the imposed Reynolds numbers (Re, Re*), rotational Reynolds number (Rer), capillary number (Ca), and viscosity ratio (M), on flow patterns, regime classifications, regime transition boundaries, interfacial instabilities, and displacement efficiency. Our experiments demonstrate distinct immiscible displacement flow patterns in stationary and rotating pipes. In stationary pipes, heavier fluids slump underneath lighter ones, resulting in lift-head and wavy interface stratified flows, driven by gravity. Decreasing M slows the interface evolution and reduces its front velocity, while increasing Re* shortens the thin layer of the interface tail. In rotating pipes, the interplay between viscous, rotational, and capillary forces generates swirling slug flows with stable, elongated, and chaotic sub-regimes. Progressively, decreasing M leads to swirling dispersed droplet flow, swirling fragmented flow, and, eventually, swirling bulk flow. The interface dynamics, such as wave formations and velocity profiles, is influenced by rotational forces and inertial effects, with Fourier analysis showing the dependence of the interfacial front velocity's dominant frequency on Re and Rer. Finally, UDV measurements reveal the existence/absence of countercurrent flows in stationary/rotating pipes, while PLIF results provide further insight into droplet formation and concentration field behavior at the pipe center plane.

Fluorescence imaging of plume-surface interaction in large-scale reduced pressure environments

Planar laser-induced fluorescence (PLIF) was applied for the first time in the 20-ft vacuum chamber at the Marshall Space Flight Center to visualize the plume-surface interaction (PSI) of a nitrogen jet seeded with nitric oxide (NO). A Mach 5.3 nozzle was used to simulate the exhaust of a landing spacecraft for two different jet stagnation pressures and one jet stagnation temperature. A flat plate was used to simulate the landing surface, and two different dimensionless altitudes were investigated. The chamber pressure was reduced such that both lunar-relevant environments at 0.01–28 Pa and Martian-relevant environments at ∼600 Pa were investigated. PLIF flow visualization was performed using a pulsed, tunable, ultraviolet laser, which entered the vacuum chamber through a window, and was directed to the test article using remote-controlled mirrors. Fluorescence at ultraviolet wavelengths was imaged using an intensified camera, which was placed inside a pressurized enclosure located inside the vacuum chamber. For the Martian-relevant condition, a Mach disk and stagnation bubble were observed at h/De = 10, whereas a pair of oblique stagnation shocks were observed at h/De = 3. Significantly complex flows, such as different stagnation shock behaviors, were observed for the lunar-relevant conditions based on the h/De and Reynolds number. The results presented here are the first NO-PLIF measurements of the PSI flowfield within rarefied environments. The unique information on jet expansion and plume structure will be useful to aid researchers in validating complex computational simulations and to inform engineering designs of extraterrestrial landing systems.

Wettability-dependent dissolution dynamics of oxygen bubbles on Ti64 substrates

In this study, the dissolution of a single oxygen bubble on a solid surface, here Titanium alloy Ti64, in ultrapure water with different oxygen undersaturation levels is investigated. For that purpose, a combination of shadowgraph technique and planar laser-induced fluorescence is used to measure simultaneously the changes in bubble geometry and in the dissolved oxygen concentration around the bubble. Two different wettabilities of the Ti64 surface are adjusted by using plasma-enhanced chemical vapor deposition. The dissolution process on the solid surface involves two distinct phases, namely bouncing of the oxygen bubble at the Ti64 surface and the subsequent dissolution of the bubble, primarily by diffusion. By investigating the features of oxygen bubbles bouncing, it was found that the boundary layer of dissolved oxygen surrounding the bubble surface is redistributed by the vortices emerging during bouncing. This establishes the initial conditions for the subsequent second dissolution phase of the oxygen bubbles on the Ti64 surfaces. In this phase, the mass transfer of O2 proceeds non-homogeneously across the bubble surface, leading to an oxygen accumulation close to the Ti64 surface. We further show that the main factor influencing the differences in the dynamics of O2 bubble dissolution is the variation in the surface area of the bubbles available for mass transfer, which is determined by the substrate wettability. As a result, dissolution proceeds faster at the hydrophilic Ti64 surface due to the smaller contact angle, which provokes a larger surface area.

Rydberg-State Double-Well Potentials of Van der Waals Molecules

Recent progress in studies of Rydberg double-well electronic energy states of MeNg (Me = 12-group atom, Ng = noble gas atom) van der Waals (vdW) molecules is presented and analysed. The presentation covers approaches in experimental studies as well as ab initio-calculations of potential energy curves (PECs). The analysis is shown in a broader context of Rydberg states of hetero- and homo-diatomic molecules with PECs possessing complex ‘exotic’ structure. Laser induced fluorescence (LIF) excitation spectra and dispersed emission spectra employed in the spectroscopical characterization of Rydberg states are presented on the background of the diverse spectroscopic methods for their investigations such as laser vaporization–optical resonance (LV-OR), pump-and-probe methods, and polarization labelling spectroscopy. Important and current state-of-the-art applications of Rydberg states with irregular potentials in photoassociation (PA), vibrational and rotational cooling, molecular clocks, frequency standards, and molecular wave-packet interferometry are highlighted.

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.

Detection of Nickel Atoms Released from Electrodes in Spark Discharges Using Laser-Induced Fluorescence.

The reduction of greenhouse gas emissions and the effort of carbon neutrality require the improvement of spark-ignition engines in terms of efficiency and capability to operate on renewable fuels. The electrode wear of spark plugs, used for ignition of novel fuels and lean mixtures, emerges as a significant challenge in this transition. Understanding the physical mechanism and influence of spark operation parameters of the wear process is thus important. Compared to the conventional methodology of performing long-term wear tests, laser-based optical diagnostics methods are capable of assessing electrode wear during one single or a few spark discharges. In this work, the necessary initial steps required for performing optical investigations using laser-induced fluorescence (LIF) are presented. Several excitation pathways of nickel atoms were investigated, and 336.96 nm was identified as the optimal one. This excitation approach yielded emissions between 338.75 and 353.58 nm, effectively avoiding the major interference from N2 plasma emission in spark discharges. Additionally, a linear relationship in fluorescence signal intensity with excitation energy up to 400 µJ was observed. These findings indicate the potential of LIF for in situ diagnostics of electrode wear, contributing to engine development in both efficiency and compatibility with sustainable fuels.

Compact Laser-Induced Fluorescence Detector with Adjustable Laser Focal Spot for Multiple Purposes.

In many research fields, the demand for miniaturized laser-induced fluorescence (LIF) detection systems has been increasing. This work has developed a compact LIF detector, employing a laser diode as the excitation source and a photodiode as the photodetector with an adjustable laser focal spot, to meet the diverse requirements of various observation targets, such as capillaries, PCR tubes, and microfluidic chips. It features the functionalities of background fluorescence correction, the adaptive adjustment of the dynamic range, and constant power control for the laser. The influence of the excitation power on the detection limit was studied through experiments, and the configuration results for LED/LD as light sources and 487/450 nm wavelengths were compared and optimized. A fully integrated, compact, modular epifluorescence LIF detector was subsequently constructed, measuring 40 × 22 × 38 mm3 in total size, with a cost of USD 320, and achieving a detection limit of 0.4 nM for fluorescein sodium. Finally, the detector was integrated into a nucleic acid detection system with a microfluidic chip on the Chinese Space Station (CSS) and was also tested with PCR tubes and capillaries, proving its broad practicality and adaptability to various analytical systems.

Multi-Technique Approach for the Sustainable Characterisation and the Digital Documentation of Painted Surfaces in the Hypogeum Environment of the Priscilla Catacombs in Rome

The purpose of this paper is to identify an efficient, sustainable, and “green” approach to address the challenges of the preservation of hypogeum heritage, focusing on the problem of moisture, a recurring cause of degradation in porous materials, especially in catacombs. Conventional and novel technologies have been used to address this issue with a completely non-destructive approach. The article provides a multidisciplinary investigation making use of advanced technologies and analysis to quantify the extent and distribution of water infiltration in masonry before damage starts to be visible or irreversibly causes damage. Four different technologies, namely Portable Nuclear Magnetic Resonance (NMR), Audio Frequency–Acoustic Imaging (AF–AI), Laser-Induced Fluorescence (LIF), Infrared Thermography (IRT), and 3D Laser Scanning (RGB-ITR), were applied in the Priscilla catacombs in Rome (Italy). These imaging techniques allow the characterisation of the deterioration of painted surfaces within the delicate environment of the Greek chapel in the Priscilla catacombs. The resulting high-detailed 3D coloured model allowed for easily referencing the data collected by the other techniques aimed also at the study of the potential presence of salt efflorescence and/or microorganisms. The results supply an efficient and sustainable tool aimed at cultural heritage conservation but also at the creation of digital documentation obtained with green methodologies for a wider sharing, ensuring its preservation for future generations.

High spatiotemporal resolution optical measurements of two-stage ignition and combustion in Engine Combustion Network Spray D flames

This study explores flame structures and combustion dynamics in high-pressure n-dodecane fuel sprays, focusing on the formation and consumption of formaldehyde (CH2O) during autoignition and the development of poly-aromatic hydrocarbons (PAH) as soot precursors. These processes are crucial for optimizing combustion efficiency and reducing emissions. However, traditional approaches, which rely on single-shot measurements or ensemble-averaged visualizations, often overlook critical early-stage processes during low-temperature ignition. To overcome these challenges, we employed an innovative high-speed planar laser-induced fluorescence (PLIF) technique at 50 kHz using a pulse-burst Nd:YAG laser system with an excitation wavelength of 355 nm. This approach, applied for the first time to Engine Combustion Network (ECN) Spray D flames, provides unprecedented insights into the combustion processes at varying ambient temperatures and oxygen concentrations. Additionally, simultaneous high-speed schlieren imaging at 100 kHz was used to visualize spray penetration, first-stage ignition, and thermal expansion zones. Our findings reveal that, similar to Spray A flames, CH2O forms in cold, fuel-rich zones well upstream of the combustion zone. However, in Spray D flames, the schlieren signal softening observed in the jet's head does not lead to complete disappearance, and the CH2O signal is absent from the full head of the spray. During the second-stage ignition, CH2O consumption accelerates due to high-temperature reactions, leading to a significant reduction in its signal. Unlike the mushroom-shaped structure seen in Spray A flames, Spray D flames exhibit a quasi-steady PAH phase structure, with lean peripheral mixtures insufficient for soot precursor formation. Notably, reducing ambient oxygen concentration to 13 % while maintaining or increasing temperature prolongs the presence of CH2O, highlighting its influence on ignition dynamics and oxidation processes in dodecane spray flames. This study provides new insights into the combustion mechanisms of high-pressure sprays and offers valuable data for developing next-generation combustion technologies, including models, aimed at improving efficiency and reducing emissions.

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.