Theoretical investigation of the ground and excited state of silylated coumarin

We present ground and excited state properties of silylated coumarin dyes. We have calculated the energies and dipole moments of ground and excited states of silylated coumarins and some coumarin derivatives. Using CIS we find a good agreement with experimental S₀→S₁ excitation energies. Silylation of dye molecules had minor effect on the transition energies. On the basis of theoretical results, we conclude that silylated dye will have improved long-term photostability compared to its unsilylated counterpart due to its covalent bonding with the host matrix.     

Laser Raman Spectrum of Triglycine Sulfate

Abstract

The laser Raman spectrum of ferroelectric triglycine sulfate has been determined by the use of an argon ion gas laser. The observed Raman lines are compared with reported assignments in the literature by Taurel¹ and Krishnan², Determination of depolarization ratio of the sulfate line at 980 cm^?1 shows that the Raman band is highly polarizable and the molecular vibration is totally symmetrical v₁.

The role played by the glycine groups in the spontaneous polarization and its reversal can be indirectly confirmed by Raman spectrum of TGS. Interpretation of the Raman spectrum indicates that the SO₄ groups do not have tetrahedral symmetry at roan temperature. Ferroelectric behavior of TGS is attributed to the glycine groups.     

Laser Raman Spectra of Crystalline Chloromercurate(II) Complexes

Abstract

The laser Raman spectra of crystalline [(CH₃)₄N] HgCl₃ and [(CH₃)₄N]₂HgCl₄ have been studied in the 400–20 cm^?1 region. All expected Raman active modes for the HgCl₃ ^? and HgCl₄ ^?2 ions are observed and assignments of the vibrational frequencies are made in relation to the structure of the anions.     

RECENT DEVELOPMENTS IN INSTRUMENTATION FOR LASER INDUCED BREAKDOWN SPECTROSCOPY

ABSTRACT

This review describes, in detail, the most recent developments in instrumentation for laser induced breakdown spectroscopy (LIBS). The paper focuses on various laser systems, including excimer, CO₂, and Nd: YAG and their performance in LIBS. The coupling of fiber-optics to LIBS and development of portable LIBS systems and their performance is presented. New approaches such as dual pulse operation, multi-fiber, resonant ablation, and combination with laser induced fluorescence are further described. Finally the use of the Echelle spectrometer in which it has been combined with various charge coupled devices.     

A novel time-integral type laser energy meter based on anisotropic Seebeck effect

We have posed the design of a time-integral type laser energy meter based on anisotropic Seebeck effect for the first time. Anisotropic Seebeck effect is responsible for the laser-induced thermoelectric voltage effect in high temperature superconductor (HTSC) cuprates and colossal magnetoresistance (CMR) manganites thin films grown on tilted single crystal substrates. In this study, for an example, an epitaxial La_2/3Ca_1/3MnO₃ thin film prepared on a tilted LaAlO₃ substrate by standard pulsed-laser deposition (PLD) method is tested with a 1064-nm Q-switched Nd:YAG laser and its 2nd (532 nm), 3rd (355 nm), and 4th (266 nm) harmonics from room temperature to 16 K. The integral of the voltage signal with time shows a good linear relation with the laser energy per pulse in the measured wavelength and temperature range, which confirms the theoretical analysis given in this letter and can be used to design a time-integral type laser energy meter. The sensitivity increases as the film thickness increases or as the thermal diffusion constant decreases, which makes the time-integral type laser energy meter low cost as compared with the peak-voltage type. It operates with fast (nanosecond range) and broad-spectrum (from infrared to ultraviolet) response in wide temperature range (from room temperature to 10s K), and can be useful replacements for pyroelectric power/energy meters.     

Investigation into CO2 laser cleaning of titanium alloys for gas-turbine component manufacture

This paper reports results of the investigation into the feasibility of using a CO₂ laser technology to perform critical cleaning of gas-turbine aero-engine components for manufacture. It reports the results of recent trials and relates these to a thermal model of the cleaning mechanisms, and describes resultant component integrity. The paper defines the experimental conditions for the laser cleaning of various aerospace-grade contaminated titanium alloys, using a continuous wave CO₂ laser. Laser cleaning of Ti64 proved successful for electron beam welding, but not for the more sensitive Ti6246. For diffusion bonding the trials produced a defective standard of joint. Effects of oxide formation is modelled and examined experimentally.     

Fluorescence and Laser Emission from Coumarin-Acridine Orange Mixtures

The sensitized fluorescence and laser emissions of dye mixtures; (I) coumarin 102 (donor) and acridine orange (acceptor) and (II) coumarin 47 (donor) and acridine orange (acceptor) with Hg-lamp and N₂ laser, have been measured as a function of dye concentration and of the pump power (N₂ laser). Acridine orange which does not lase by itself on excitation with N₂ laser, lases efficiently in the presence of 7-amino-coumarins via singlet-singlet energy transfer. Energy transfer rate constants and critical distances have been estimated from fluorescence intensity and lifetime measurements. The performance of energy transfer dye lasers (ETDLs) are discussed in terms of spectral characteristics of the dyes and their penetration depths.     

Biscoumarins - New Laser Dyes in Coumarin Series

With a view to extend the tunability range using new derivatives in the coumarin series of dyes, a novel series have been synthesized, viz. the biscoumarins where two coumarin nuclei are coupled. These are studied for their lasing characteristics, optical spectra and quantum efficiencies. Laser spectra of these dyes in various solvents are also studied. Tunability range of these dyes have been found to cover blue green region of the spectrum and though there is shift to longer wavelength as compared to monocoumarins, extending the tunability range, it is not as much as would be normally expected with extended conjugation involving two coumarin nucled.     

Corticospinal interaction during isometric compensation for modulated forces with different frequencies

Background

The zebrafish visual system is a good research model because the zebrafish retina is very similar to that of humans in terms of the morphologies and functions. Studies of the retina have been facilitated by improvements in imaging techniques. In vitro techniques such as immunohistochemistry and in vivo imaging using transgenic zebrafish have been proven useful for visualizing specific subtypes of retinal cells. In contrast, in vivo imaging using organic fluorescent molecules such as fluorescent sphingolipids allows non-invasive staining and visualization of retinal cells en masse. However, these fluorescent molecules also localize to the interstitial fluid and stain whole larvae.

Results

We screened fluorescent coumarin derivatives that might preferentially stain neuronal cells including retinal cells. We identified four coumarin derivatives that could be used for in vivo imaging of zebrafish retinal cells. The retinas of living zebrafish could be stained by simply immersing larvae in water containing 1 μg/ml of a coumarin derivative for 30 min. By using confocal laser scanning microscopy, the lamination of the zebrafish retina was clearly visualized. Using these coumarin derivatives, we were able to assess the development of the zebrafish retina and the morphological abnormalities induced by genetic or chemical interventions. The coumarin derivatives were also suitable for counter-staining of transgenic zebrafish expressing fluorescent proteins in specific subtypes of retinal cells.

Conclusions

The coumarin derivatives identified in this study can stain zebrafish retinal cells in a relatively short time and at low concentrations, making them suitable for in vivo imaging of the zebrafish retina. Therefore, they will be useful tools in genetic and chemical screenings using zebrafish to identify genes and chemicals that may have crucial functions in the retina.     

Efficient quasi-three-level Nd:YAG laser at 946 nm pumped by a tunable external cavity tapered diode laser

Using a tunable external cavity tapered diode laser (ECDL) pumped quasi-three-level Nd:YAG laser, a fivefold reduction in threshold and twofold increase in slope efficiency is demonstrated when compared to a traditional broad area diode laser pump source. A TEM₀₀ power of 800 mW with 65% slope efficiency is obtained, the highest reported TEM₀₀ power from any 946 nm Nd:YAG laser pumped by a single emitter diode laser pump source. A quantum efficiency of 0.85 has been estimated from experimental data using a simple quasi-three-level model. The reported value is in good agreement with published values, suggesting that the model is adequate. Improvement of the 946 nm laser due to the ECDL's narrow spectrum proves to be less significant when compared to its spatial quality, inferring a broad spectrum tapered diode laser pump source may be most practical. Experimental confirmation of such setup is given.     

Comparison of mechanisms and effects of Nd:YAG and CO2 laser cleaning of titanium alloys

The paper compares laser cleaning trials performed using a Q-switched Nd:YAG laser, λ = 1.064 μm and a continuous wave (CW) CO₂ laser, λ = 10.6 μm, applied to aerospace-grade, contaminated titanium alloys. The mechanisms for cleaning using each laser system are modelled to determine the mode and extent of contaminant removal. The model results are then compared with the surface chemistry and micro-structural results from the cleaning trials performed. The results show the dominant cleaning process for Nd:YAG cleaning to be by evaporation of the contaminant via conduction through surface heating, while for CO₂ laser cleaning the small fraction of the beam coupling directly with the contaminant is sufficient for direct heating and selective evaporation. The results for experimental cleaning, electron beam (EB) welding and diffusion bonding align well with the model, particularly when secondary reactions are taken into account.     

Accuracy control of three-dimensional Nd:YAG laser shaping by ablation

Improving the dimensional accuracy along the optical axis without decreasing the materials removing rate is a key issue in three-dimensional laser shaping. This paper presents a concept for performing three-dimensional laser shaping by directly using machining laser as the photo source of the non-contacting measuring device. Due to the high power measuring photo source and a 1.06 μm bandpass filter, the interference caused by the emission light of ablated surface can be effectively avoided, the delay time is not needed to be inserted between the laser pulse and the measurement. So the measurement will not decrease the material removal rate and productivity. By using this system, the shaping accuracy of 30 μm can be achieved at the removing rate of about 4.0×10⁻² mm³/sec for Si₃N₄ ceramic, both are much better than the results obtained before.     

Inversion analysis of K 2 coupled electronic states with the Fourier grid method

We present a new determination of the potential curves and interactions of the coupled electronic states A ¹ Σ ⁺ _u and b ³ Π _u of the potassium dimer, based on new laser spectroscopy measurements within a molecular beam, combined with data available in the literature. We used a new global deperturbation approach, involving the Fourier Grid Hamiltonian method for energy level calculation. A standard deviation of 1.2 is obtained corresponding to a variance of 7.5×10 ^-3 cm^-1, representing a significant improvement compared to the standard deviation of 4 yielded by the traditional local deperturbation approach. Received 12 June 2001 and Received in final form 3 September 2001     

Hyperfine structure and isotope shift measurements on 4d10 1S0 → 4d9 5p J=1 transitions in Pd I using deep-UV cw laser spectroscopy

The 4 d ^{10 1} S₀ ground-state transitions to the 4 d ⁹ 5 p configuration of palladium (Pd) have been studied. For this purpose, a tunable, single-mode, deep-UV cw laser has been built to generate the sum frequency of a frequency-doubled Ti:S laser with a second Ti:S laser. The produced wavelengths range from 244 to 276 nm. From the measured spectra the frequency splitting due to hyperfine structure and isotope shift, the hyperfine structure A and B constants and the lifetimes of the states have been extracted. Received 3 October 2001     

Laser dye stability. Part 5

Photodegradation parameters that relate bleaching and absorption at the lasing wavelength λ_l have been examined for over 30 different coumarin and quinolone laser dyes in a number of solvents. Quinolone dyes were found to bleach faster than the coumarin dyes. The effect of chemical substituents was found to affect bleaching of the coumarin dyes only to a small (20%) extent in ethanol. The major effect of chemical substituents was in the conversion of a dye to products absorbing at λ_l. Effects of solvent, cover gas, and changes in fluorescent quantum yields are discussed. Of particular interest is the photodegradation parameterA, the ratio of the percent absorption at λ_l to the total input energy per dm³. Combined with τ, the total input energy per dm³ required for a laser to reach half its original intensity, it was found thatAτ=1.2±0.9 for all of the dyes independent of dye concentration in all of the solvents tested. It appears that where bleaching of the dye is only of the order of 10–20%, the absorption at λ_l is 1.2% when our dye laser has reached one-half of its initial output. It is consequently possible to estimate τ values of new dyes by the use ofA terms through the relationshipA ₁τ₁=A ₂τ₂ where τ₁ of Dye 1 has been calibrated in the same dye laser system.     

Design and synthesis of novel (Z)-5-((1,3-diphenyl-1H-pyrazol-4-yl)methylene)-3-((1-substituted phenyl-1H-1,2,3-triazol-4-yl)methyl)thiazolidine-2,4-diones: a potential cytotoxic scaffolds and their molecular modeling studies

In an effort to discover potential cytotoxic agents, a series of novel (Z)-5-((1,3-diphenyl-1H-pyrazol-4-yl)methylene)-3-((1-substituted phenyl-1H-1,2,3-triazol-4-yl)methyl)thiazolidine-2,4-dione derivatives (8a–n) were designed and synthesized in various steps with acceptable reaction procedures with quantitative yields and characterized by ¹H NMR, ¹³C NMR, IR, HRMS and ESI–MS spectra. These newly synthesized novel derivatives were screened for their in vitro cell viability/cytotoxic studies against human breast cancer cell line (MCF-7) with various concentrations of 0.625 µM, 1.25 µM, 2.5 µM, 5 µM and 10 µM, respectively. The biological interpretation assay outcome was demonstrated in terms of cell viability percentage reduction and IC₅₀ values against standard reference drug cisplatin. Based on these results, most of the derivatives exhibited promising cytotoxic activity. Among them, particularly compounds 8j (R₁?=?OMe and R₃?=?NO₂) and 8e (R₃?=?CF₃) demonstrate remarkable cytotoxic activity with IC₅₀ values 0.426 µM?±?0.455 and 0.608 µM?±?0.408, which are even better than the standard drug cisplatin 0.636 µM?±?0.458 and compounds 8m (R₂?=?OMe and R₃?=?OMe) and 8c (R₃?=?OMe) exhibited closely equivalent IC₅₀ values to the standard drug with IC₅₀ values 0.95 µM?±?0.32 and 0.976 µM?±?0.313 and rest of the compounds exhibits moderate cytotoxic activity. Moreover, molecular modeling studies and ADME calculations of the novel synthesized derivatives are in adequate consent with the pharmacological screening results.

     

Development of a 2D dosimetry system based on the optically stimulated luminescence of Al2O3

A laser-scanning 2D dosimetry system based on the Optically Stimulated Luminescence (OSL) signal from Al₂O₃ films was built and demonstrated. The main challenge of using the OSL from Al₂O₃ for 2D dosimetry by laser scanning is the long lifetime (∼35 ms) of the main luminescence centers in this material (F-centers). In this work, we demonstrated the possibility of performing 2D dosimetry by laser scanning using a combination of the fast UV emission of F⁺-centers (lifetime <7 ns) and the slow F-center emission of Al₂O₃:C, and an algorithm to correct for the slow F-center luminescence lifetime. We also investigated the possibility of using Al₂O₃:C,Mg, to take advantage of its greater F⁺-center emission compared to Al₂O₃:C. Results from 6 MV photon beam irradiations from a clinical linear accelerator were compared to radiographic and radiochromic film profiles showing a good qualitative agreement.     

Dependence of Cm on the composition of solid binary propellants in ablative laser propulsion

Propulsion pellets of different metal/salt (Zn/CaCO₃) composition have been prepared. The impulse imparted to the pellet by the laser has been measured using two different methods: a torsion pendulum and a piezoelectric sensor. The dependence of the coupling coefficient, C_m, on the composition of the solid binary propellants in ablative laser propulsion has been investigated under different experimental conditions: in vacuum and at atmospheric pressure as well as with two different wavelengths, IR and UV. The composition of the Zn/CaCO₃ propellant mixture that optimizes the coupling coefficient, C_m, has been determined.     

A review of optically pumped far-infrared laser lines from methanol isotopes

The technique of optical pumping in polar molecules is the most efficient for Far-Infrared (FIR) laser generation, providing also a versatile and powerful tool for molecular spectroscopy in this spectral region. Methanol (CH₃OH) and its isotopic varieties are the best media for optically pumped FIR laser, with over thousand lines observed, and the most widely used for investigations and applications. In this sense, it is important organize and make available catalogues of FIR laser lines as complete as possible. Since the last critical reviews of 1984 [1] on methanol and its isotopic varieties [2,3,4], over hundred papers have been published dealing with hundreds of new FIR laser lines. In 1992 a review of FIR laser lines from CH₃OH was presented [5]. In this communication we extend this work to the other methanol isotopes, namely CH₃OD, CD₃OH, CD₃OD,¹³CH₃OH,¹³CD₃OH,¹³CD₃OD, CH₃ ¹⁸OH, CH₂DOH, CHD₂OH and CH₂DOD.Work supported by FAPESP, CNPq, FAEP-Brasil, and CNR-Italia     

Numerical solution of Boltzmann tranport equation for TEA CO2 laser having nitrogen-lean gas mixtures to predict laser characteristics and gas lifetime

Selective laser isotope separation by TEA CO₂ laser often needs short tail-free pulses. Using laser mixtures having very little nitrogen almost tail free laser pulses can be generated. The laser pulse characteristics and its gas lifetime is an important issue for long-term laser operation. Boltzmann transport equation is therefore solved numerically for TEA CO₂ laser gas mixtures having very little nitrogen to predict electron energy distribution function (EEDF). The distribution function is used to calculate various excitation and dissociation rate of CO₂ to predict laser pulse characteristics and laser gas lifetime, respectively.Laser rate equations have been solved with the calculated excitation rates for numerically evaluated discharge current and voltage profiles to calculate laser pulse shape. The calculated laser pulse shape and duration are in good agreement with the measured laser characteristics. The gas lifetime is estimated by integrating the equation governing the dissociation of CO₂. An experimental study of gas lifetime was carried out using quadrapole mass analyzer for such mixtures to estimate the O₂ being produced due to dissociation of CO₂ in the pulse discharge. The theoretically calculated O₂ concentration in the laser gas mixture matches with experimentally observed value. In the present TEA CO₂ laser system, for stable discharge the O₂ concentration should be below 0.2%.