Assessment of LIBS for Spectrochemical Analysis: A Review

Abstract

This review assesses the applications of laser-induced breakdown spectroscopy (LIBS) for the analysis of a variety of samples, including biomaterials (teeth, nail, hair, gallstones, and kidney stones, etc.), food materials (fruits and vegetables, milk, salt, nutritional supplements, etc.), medicinal plants, industrial waste, liquid samples, etc. In addition, for the first time the identification of cholesterol and pigment stones was performed on the basis of atomic lines of different elements and molecular bands of C₂ molecules present in the LIBS spectra of gallstones. Chemometric techniques such as principal component analysis (PCA) was also applied to LIBS data for rapid identification/classification of different gallstone samples. LIBS analysis of toxic/heavy elements present in vegetables (spinach, tomato) and rice is also presented in this review. It was observed that vegetables grown near industrial areas are rich in several toxic metals like Pb and Cr. The wastewater samples from different industries were also analyzed by recording their spectra using a liquid jet. These results clearly demonstrate the ability of LIBS technique as an instant monitoring device to detect heavy metals present in liquid samples. Finally, this review shows that LIBS is a versatile analytical technique with unlimited applications.     

Spectral-Kinetic Characteristics of Pyrene Fluorescence in Model Systems and Membranes of Etioplasts

The decay kinetics parameters of monomer and excimer fluorescence of pyrene in artificial galactolipid protein-free micelles and membranes of prolamellar bodies (PLB) of etioplasts have been determined. A complex law of probe fluorescence decay in artificial and native membranes has been discovered. It has been found that the addition of protochlorophyllide (Pd) to lipid micelles led to a considerable reduction in the lifetime of the long-lived component of the fluorescence-decay kinetics of the monomer form of pyrene (₂) and to the appearance of luminescence in the region of 640 nm in the stationary spectra of fluorescence at excitation of the pyrene molecules present in the bilayer. In native membranes of etioplasts, the monomer duration ₂ did not depend on the pigment content and the Pd fluorescence upon excitation through pyrene was absent. The membranes of etioplasts and the pigment-containing artificial micelles did not differ in the ₂ value of the excimer. They only differed in the contribution of the long-lived component to the total fluorescence (low in native membranes). The pigment-protein interaction in the etioplast membranes and the absence from them of pigment directly associated with lipids are discussed.     

Spectral Properties of Bacteriochlorophyll c in Organisms and in Model Systems

Polarized absorption and fluorescence spectra of bacteriochlorophyll c and green photosynthetic bacterium Prostheecochloris aestuarii cells and cell fragments embedded in stretched polymer film were measured. In pigment samples the artificial oligomers of bacteriochlorophyll c (with absorption about 750 nm) and other forms of this pigment and bacteriopheophytin (with absorption at 670 nm) were present. In bacteria samples, embedded in polymer, oligomers were in high degree disaggregated and as a result the absorption about 670 nm was observed. Previously for similar sets of samples the decay of fluorescence excited only at one wavelength was analyzed on three exponential components, but exact lifetime values of these components for various samples were different. The aim of present paper was to check if these differences occur because of various contributions to decay from three well defined forms or if they were related to the existence of several pigment forms with slightly different lifetimes. The global analysis of data obtained for various excitation and observation wavelengths of fluorescence were done. From this analysis it follows that the second situation occurs. For a model system containing artificial oligomers the largest component of decay has a ⁴ of about 0.183 ns or 0.136 ns depending on observation wavelength. For the bacteria sample, in which the emission at 680 nm is the superposition from various pigments, global analysis done for various excitation wavelengths shows also that the values differ depending on the regions of fluorescence observation. From polarized spectra, it follows that in the model system the pigments absorbing at 670 nm are randomly distributed whereas oligomers are highly oriented. In bacteria fragments absorbing at 670 nm pigment molecules can be divided into two groups: one oriented along the axis of film stretching and the second practically randomly distributed. In living organisms, under some conditions, small amount of 670 nm pigments can be present and can work as excitation energy traps or as antenna transferring the excitation. Present results show that the role of various pools of 670 nm absorbing pigments can be different because of their differing orientation.     

Two‐Color Laser Photodynamic Therapy of Tumors

A method of photodynamic therapy of tumors (neoplasms) based on simultaneous action of radiation from two lasers with different generation wavelengths is proposed and implemented in an experiment on animals. The antineoplastic effect was evaluated by the dimensions of the necrosis region determined using the method of vital staining of tissues. The effect of photodynamic therapy in the case of simultaneous use of the two lasers (₁ = 627.8 nm and ₂ = 671 nm) turned out to be higher than in the case of their separate application. The hypothetical reason for the phenomenon is oxyhemoglobin photodissociation that leads to the enrichment of blood with free oxygen.     

胆结石的FT－Raman光谱研究

胆结石的ＦＴ－Ｒａｍａｎ光谱研究徐智勇，李维红，王立波，许振华，吴瑾光（北京大学化学与分子工程学院，稀土材料化学与应用国家重点实验室北京１００８７１）ＴｈｅＩｄｅｎｔｉｆｉｃａｔｉｏｎｏｆＴｈｒｅｅＤｉｆｆｅｒｅｎｔＴｙｐｅｓｏｆＧａｌｌｓｔｏｎｅｓ...     

Threshold conditions for 800 nm pumping of 2 μm Tm : Ho lasers

Pumping requirements of pulsed and continuous wave (CW) 2 m Tm : Ho lasers are investigated experimentally and theoretically for excitation at 800 nm. The influence of the pulse duration on threshold is measured using a chopped Ti : Al₂O₃ laser. Based on the experimental and simulated results the spatial and temporal pump requirements in future quasi-CW high-power diode-pumped 2 m Tm : Ho lasers are determined. The experiments and the model allow the evaluation of different loss mechanisms and indicate significant 540 nm emitting loss mechanisms.     

Identification and imaging of hot O2 (v″=2, 3, or 4) in hydrogen flames using 193 nm- and 210 nm-range light

Some simple molecules can be excited by light within the tuning ranges of ArF (193–194 nm) and KrF (247.8–248.8 nm) excimer lasers and their fluorescence has been previously used for imaging. Additional wavelength ranges should become available by Raman shifting. As a demonstration, we present excitation and fluorescence spectra from hot O₂ obtained (a) with tunable 193 nm-range light and (b) with that light shifted into the 210 nm range. All measurements are via predissociative upper states. In the 193 nm range, results are compared with those of Andresen's group. In the 210 nm range, the light is tuned to various excitation wavelengths in the (5 3), (8 4), and (7 4) bands of the B–X transition. The (7 4) excitations are well separated and the (7 v) fluoresence spectrum is in accord with Franck-Condon calculations. The wavelengths tend to overlap for the (5 3) and (8 4) excitations and the fluorescence is weaker. State-specific two-dimensional fluorescence images of an H₂-O₂ flame are obtained in both wavelength ranges to illustrate the use of the method.We acknowledge the National Science Foundation and the Donors of the Petroleum Research Fund, administered by the American Chemical Society, for support of this research     

Optical studies of pulsed-laser fragmentation of biliary calculi

The fragmentation of gallstones and kidney stones using pulsed visible laser radiation has recently been demonstrated; however, the fragmentation mechanism is not well understood. The temporal and spectral characteristics of the bright flash of light accompanying fragmentation of gallstones were studied using 0.8 and 360-s-long, 690-nm-wavelength, dye-laser pulses. Time-resolved visible emission spectra show a broad continuum upon which line spectra are superimposed. The continuum emission is due to free-free and free-bound electron transitions indicative of a plasma and the line spectra are due to neutral and ionized calcium. Initiation of this plasma is fluence rather than intensity dependent. A model is proposed in which laser energy is coupled to the plasma, which then impulsively expands, generating intense acoustic transients which fracture the stone.     

Simultaneous determination of benomyl and morestan residues in waters by synchronous solid-phase spectrofluorimetry

In this paper a new, sensitive, and simple method for simultaneous determination of pesticides morestan and benomyl at trace levels in waters is reported. Both chemicals, showing native fluorescence in solution at neutral medium, were fixed on C-18 silica gel at pH 1, giving a fluorescent system. The benomyl-morestan-silica gel system, after dry, was packed in a 1-mm silica cell and its synchronous fluorescence spectra were recorded at =80 nm for determination of benomyl and =25 nm for determination of morestan. Measurements of fluorescence were performed at ₁=289 nm and ₂=367 nm for benomyl and morestan analysis, respectively. The applicable concentration ranges were from 0.5 to 15.0 ng·ml^–1 for benomyl and from 0.6 to 15.0 ng·ml^–1 for morestan, with relative standard deviations of 1.2 and 1.5% for benomyl and morestan, respectively, being 0.15 and 0.18 ng·ml^–1 its respective detection limits. The method was applied to the simultaneous determination of residues of both pesticides in water of different provenances.     

Attaining the wavelength range 189–197 nm by frequency mixing inβ-BaB2O4

Wavelengths in the range from 188.9 to 197 nm have been obtained by type-I sum frequency generation (SFG) in -BaB₂O₄. The fundamental beams were supplied by pulsed dye lasers one of which tuned between 780 and 950 nm and the other frequency-doubled at 497 nm. The possibility of shifting the excimer wavelength 248.5 nm to the excimer wavelength 193 nm has been demonstrated, replacing the frequency-doubled dye laser by KrF excimer lasers of different beam properties.     

Fluorescence of the C60-pyridine system in electrochemistry reduction processes

Three groups of strong fluorescence peaks of C₆₀, centered at 440, 575 and 700 nm, are observed in the supersaturated C₆₀-pyridine solution, and the onsite fluorescence spectra of this C₆₀-pyridine system in the first and second electrochemistry reduction processes are obtained for the first time. The results indicate that the fluorescence peaks centered at 440 nm originate from C₆₀ molecules dissolved in supersaturated C₆₀-pyridine solution, while fluorescence bands centered at 575 and 700 nm are emitted from undissolved C₆₀. It is also proved that a strong charge transfer interaction, which is significant for the symmetry increase of , as well as the formation of a transmission channel of energy, occurs between and pyridine, as is supported by surface-enhanced Raman scattering (SERS) spectra as well.     

Fluorescence and attenuation properties of Er3+ -doped phosphate-glass fibers and efficient infrared-to-visible up-conversion

Fluorescence spectra of phosphate glasses with different erbium doping have been measured. The flourescence intensity reaches its maximum at an Er³⁺-doping concentration of 0.75 mol%. When the Er³⁺ doping exceeds 0.75 mol%, the fluorescence intensity decreases due to concentration quenching. The attenuation at 1.53 µm of the fiber is 12.8 db/m. The fluorescence up-conversion of 1.064 µm Nd:YAG laser pulses into intense green 547 and 667 nm light in the fiber has been measured. The fluorescence output power of green (547 nm) and red (667 nm) light is 178 and 42 W, respectively with an excitation power of 1 W. The two signals are referred to as⁴ S _3/2 ⁴ I _{1 5/2} and⁴ F _9/2 ⁴ I _{1 5/2} transitions through two-photon absorption fluorescence.     

Solid state C NMR analysis of human gallstones from cancer and benign gall bladder diseases

Natural abundance ¹³C cross polarized (CP) magic angle spinning (MAS) nuclear magnetic resonance (NMR) analysis of human gall bladder stones collected from patients suffering from malignant and benign gall bladder disease was carried out which revealed different polymorphs of cholesterol in these stones. All gall bladder stones in present study had cholesterol as their main constituent. ¹³C CP-MAS NMR analysis revealed three forms of cholesterol molecules in these stones, which are anhydrous form, monohydrate crystalline with amorphous form and monohydrate crystalline form. Our study revealed that stones collected from patients associated with chronic cholecystitis (CC) disease have mostly different polymorph of cholesterol than stones collected from patients associated with gall bladder cancer (GBC). Such study will be helpful in understanding the mechanism of formation of gallstones which are associated with different gall bladder diseases. This is the first study by solid state NMR revealing different crystal polymorphism of cholesterol in human gallstones, extending the applicability of ¹³C CP-MAS NMR technique for the routine study of gallstones.     

An XeCl* Excimer Fluorescence Study on the Pulse Radiolysis of Xe–nCCl4 and Xe–SOCl2 Systems

The mechanism and kinetics of energy transfer from highly excited Xe states (E _ex > 9.5 eV), generated by a 12-ns electron beam, to chlorine donor molecules were deduced from time-resolved spectra of fluorescence in the region 240–340 nm. The emissions at 240–250 nm were assigned to Xe₂** excimers, and those at 308 and 340 nm to XeCl(B) and XeCl(C) states. Kinetic analysis of the recorded spectra for Xe–CCl₄ and Xe–SOCl₂ gas mixtures at constant xenon pressure and various pressures of molecular admixtures (0.1–1 Torr) allowed us to find the rate constants for the reactions (5) Xe** + RCI products, (6a) Xe** + RCl XeCl(B) + R*, and (6b) Xe** + RCl XeCl(C) + R*, where R is any radical.     

Analytical Assessments of Gallstones and Urinary Stones: A Comprehensive Review of the Development from Laser to LIBS

Abstract

Laser-induced breakdown spectroscopy (LIBS) is a sensitive optical technique capable of fast multi-elemental analysis of various kinds of materials (solid, liquids, and gases) and its applications are growing rapidly and continue to extend to include a broad variety of biological materials. Its application is suited particularly for urinary stones and gallstones bulk analysis and microanalysis because investigation of the spatial distribution of matrix and trace elements can help to explain their emergence and growth. Therefore, we review the application of LIBS for the analysis of different kinds of gallstones and urinary stones. In brief, we also describe the history, fundamentals, advantages, and disadvantages of LIBS and its potential for spectrochemical analysis of gallstones and kidney stones. We also emphasize the applications of different kinds of lasers in urology, particularly the laser ablation of gallstones and urinary stones and its recent progress. We also summarize and compare the analytical figures of merits of analytical techniques that are commonly used to characterize and/or analyze stones.     

Modulation-free acetylene-stabilized lasers at 1542 nm using modulation transfer spectroscopy

We report frequency stabilization of diode lasers using modulation transfer spectroscopy of an acetylene transition (¹³C₂H₂, ₁+₃, P(16)) at 1542 nm. We realize modulation-free acetylene-stabilized lasers with a frequency stability of about 10^–11 and an absolute frequency accuracy of about 20 kHz.This revised version was published online in March 2005. In the previous version, the published online date was missing     

Nature of 2-Aminoxanthone Fluorescence

Absorption and fluorescence spectra of 2-aminoxanthone in solutions of different types at 77–350 K were studied. The existence of three bands (_{1 max} = 417 nm, ₁ = 14 ns; _{2 max} = 528 nm, ₂ = 13 ns; and _{3 max} = 565 nm, ₃ = 6 ns) in fluorescence of 2-aminoxanthone solutions has been established. It was shown that the first short-wave band was determined by deactivation of singlet excitation of an aminoxanthone molecule. The band with _{3 max} = 565 nm (depending on the concentration) is connected with excimer-type aggregates, which are formed by aminoxanthone molecules grouped with the help of dipole molecules of solvent or by weak hydrogen bonds between aminoxanthone molecules. The emission in band _{2 max} = 528 nm is caused by reversible changes in the 2-aminoxanthone molecule and probably is connected with an intramolecular proton transfer.     

Growth, spectroscopic characteristics and laser potential of Yb3+:Ca3La2(BO3)4 crystal

Crystal of Yb³⁺-doped Ca₃La₂(BO₃)₄ has been grown by the Czochralski technique. The room temperature absorption and fluorescence spectra of the crystal have been investigated. The result showed that this crystal exhibits broad absorption and emission with the FWHM of 11 nm at 978 nm and 66 nm FWHM at 1025 nm, respectively. The stimulated emission cross-section of Yb³⁺ ions were calculated using the reciprocity method and Fuchtbauer-Ladenburg method, respectively. The room temperature fluorescence decay curves of ² F _5/2 manifold of Yb³⁺ ions were recorded for both crystal and powder samples. The effect of radiation tapping on the spectroscopic properties is discussed. The result that the lifetime of the powder sample is shorter than that of the bulk sample demonstrates the existence of radiation trapping effect. The laser potentiality was also evaluated and the results show that this crystal is a good candidate for tunable and ultrashort pulse lasers.     

Laser scribing of polycrystalline thin films

We have investigated the use of several different types of lasers for scribing of the polycrystalline materials used for thin-film solar cells: CdTe, CuInGaSe₂ (CIGS), ZnO, SnO₂, Mo, Al, and Au. The lasers included four different neodymium–yttrium–aluminum garnet (Nd:YAG) (both 1064 and 532 nm wavelengths), a Cu vapor (511/578 nm), an XeCl excimer (308 nm), and a KrF excimer (248 nm). Pulse durations ranged from 0.1 to 250 ns. We found that the fundamental and frequency-doubled wavelengths of the Nd:YAG systems work well for almost all of the above materials except for the transparent conductor ZnO. The diode-laser-pumped Nd:YAG was particularly convenient to use. For ZnO the uv wavelengths of the two excimer lasers produced good results. Pulse duration was found generally not to be critical except for the case of CIGS on Mo where longer pulse durations (≥250 ns) are advantageous. The frequently observed problem of ridge formation along the edges of scribe lines in the semiconductor films can be eliminated by control of intensity gradients at the film through adjustment of the focus conditions.