A portable absorption-fluorometer for detection of organic substances in fluids

Using the method of multipath-saturation fluorescence, which considers both fluorescent as well as nonfluorescent substances, the total absorption coefficient can be determined with high sensitivity. This new fluorescence method is appropriate, e.g. for in-situ applications. Thus a portable absorption-fluorometer has been constructed. The main part of the device is a multireflection cell based on a design of Herriott with a 1 cm quartz-cuvette. Two pairs of spherical dielectric mirrors are used to realize the multireflection of the excitation radiation in the UV and blue spectral range. The combination of a cylindrical and a convace mirror leads to a long pathway of the excitation radiation and, thus, to a full absorption by the fluid. A first experiment has been performed with drinking water samples defined polluted by non-fluorescent p-nitrophenol and 2-nitroaniline. Based on the method of multipath-saturation fluorescence a good correlation to the substance concentration was achieved, whereas the conventional absorption failed.     

Metal ion sensing novel calix[4]crown fluoroionophore with a two-photon absorption property

1,3-Alternate calix[4]arene-based fluorescent chemosensors bearing two-photon absorbing chromophores have been synthesized, and their sensing behaviors toward metal ions were investigated via absorption band shifts as well as one- and two-photon fluorescence changes. Free ligands absorb the light at 461 nm and weakly emit their fluorescence at 600 nm when excited by UV-vis radiation at 461 nm, but no two-photon excited fluorescence is emitted by excitation at 780 nm. Addition of an Al(3+) or Pb(2+) ion to a solution of the ligand causes a blue-shifted absorption and enhanced fluorescence due to a declined resonance energy transfer (RET) upon excitation by one- and two-photon processes. Addition of a Pb(2+) ion to a solution of 1.K(+) results in a higher fluorescence intensity than the original 1.Pb(2+) complex regardless of one- or two-photon excitation, due to the allosteric effect induced by the complexation of K(+) with a crown loop.     

Correction for Inner Filter Effects in Fluorescence Spectroscopy

A method is proposed for correcting experimental fluorescence readings for inner filter effects, i.e. the absorption of the exciting light and/or the absorption of the emitted radiation, which cause the non-linearity between fluorescence intensity and fluorophor concentration. Basically the method consists of measuring the fluorescence intensity at two different points along the diagonal in the cell. Unlike similar methods proposed in the literature, the two points are corrected simultaneously for both absorption of excitation and of emission radiation without the necessity of reading the optical density of the solution, and with a very simple data elaboration.     

Toward on-chip X-ray analysis

The possibility of performing chemical analysis and structure determinations with the use of X-rays in a microfluidic chip environment is explored. Externally generated radiation, radioisotope irradiation and on-chip generated X-rays were considered as excitation means for the performance of sample analysis with the techniques of X-ray fluorescence and diffraction. The absorption properties of chip-building materials by different radiation sources are reviewed and data on absorption coefficients calculated, upon which recommendations for optimisations with the use of various X-ray sources may be made. The capabilities and limitations of on-chip X-ray analysis are placed in perspective by preliminary experimental results of diffraction, fluorescence and on-chip X-ray generation experiments.     

Effect of the excitation source on the quantum-yield measurements of rhodamine B laser dye studied using thermal-lens technique.

A dual-beam transient thermal-lens technique was employed for the determination of absolute fluorescence quantum-yield measurements of Rhodamine B laser dye in different solvents. We investigated the effect of excitation on the absolute fluorescence quantum yield of Rhodamine B. 514 nm radiation from an argon ion laser was used as a cw excitation source and 532 nm pulses from a Q-switched Nd:YAG laser were used as a pulsed excitation source. The fluorescence quantum-yield values were found to be strongly influenced by environmental effects as well as the transient nature of the excitation beam. Our results also indicate that parameters, like the concentration of the dye solution, aggregate formation and excited state absorption, affect the absolute values of the fluorescence yield significantly.     

Laser excited atomic fluorescence of some transition elements in the nitrons oxide-acetylene flame

A pulsed, tunable dye laser, pumped with a nitrogen laser is used to excite the atomic fluorescence of Sc, V, Hf, Nb, Os, Zr, W, Rh and Ru. Except in the case of Rh, the nitrous oxide-acetylene flame has been used. The results obtained for Zr and W are due to scattering of the laser radiation from unvaporized particles in the flame. Since, for most elements, several fluorescence lines of comparable intensity have been observed after the primary excitation process, the usefulness of observing non-resonance fluorescence is stressed, particularly with regard to the possibility of minimizing spectral interferences. The experimental results demonstrate that the limits of detection obtained with the dye laser source are comparable or better than the best atomic absorption limits only when the same primary absorption line used for the atomic absorption measurements can be used for exciting the fluorescence.     

Study of spectral and fluorescent properties and isomerization of merocyanines containing nitrile groups as acceptors

The spectral, fluorescent, and photochemical properties of new merocyanines containing nitrile groups as acceptors have been studied. Positive solvatochromism is observed for most of these compounds; however, for the dye containing three nitrile groups as acceptors—polyenic aminotrinitrile—negative solvatochromism is observed: the absorption spectrum is shifted to shorter wavelengths with increasing the solvent polarity. In all solvents used, the fluorescence and fluorescence excitation spectra of the merocyanines almost do not depend on the excitation and fluorescence registration wavelengths, respectively. Using the flash photolysis method, the formation of photoisomers of the merocyanines has been detected and the kinetics of their decay in solvents of different polarity has been studied. Backward (dark) isomerization of the photoisomers has been shown to take place more slowly in nonpolar solvents.     

Rapid method of uranium determination in solutions based on X-ray fluorescence and absorption

A method of uranium determination in organic and aqueous solutions has been developed, based on fluorescence L X-ray excitation with a¹⁰⁹Cd source of several mCi activity and counting the excited L_α lines with a proportional counter. To eliminate uranium X-ray absorption by the accompanying elements the intensity of the source radiation (Ag K) transmitted through the analysed solution is measured. The ratio of these two intensities is independent of other elements present in the solution over a very broad range of concentration. The analysis time does not exceed 5 minutes. The precision and accuracy of this method in the range 0.5 to 100 g U/1 are comparable to those of the classical titrimetric method.     

Sub-picogram detection of lead by non-flame atomic fluorescence spectrometry with dye laser excitation

The frequency-doubled radiation of flashlamp-pumped dye laser has been compared with the radiation of an eleotrodeless discharge lamp (EDL) and a hollow cathode lamp (HCL) as excitation light sources in non-flame atomic fluorescence spectrometric (AFS) measurements. Detection limits and linear ranges of the analytical working curves have been studied. The aqueous Pb sample solutions used in this study were atomized in an electrically heated graphite rod. Direct line fluorescence at 405.8 nm has been observed. The limit of detection obtained with the laser as excitation source is about one order of magnitude lower than the detection limits obtained with the EDL and HCL. The absolute limit of detection of 0.2 pg is the lowest reported value to date attained in any atomic spectrometric method. The ultraviolet laser irradiance was found to be high enough to approach saturation conditions. As a result selfabsorption of the exciting laser beam is reduced and the linear range of the analytical working curve is extended to higher analyte concentrations.     

One-, two-, and three-photon absorption induced fluorescence of a novel chromophore in chloroform solution

One-, two-, and three-photon absorption induced fluorescence intensities of a novel nonlinear optical chromophore have been measured by using a tunable femtosecond pulsed laser as the excitation. Four resonance peaks are observed as the excitation wavelength is tuned from 600 to 2000 nm. These peaks correspond to the one-, two- and three-photon fluorescence resonance. Except for intensity difference, the lifetime and the fluorescence spectrum are found to be the same for the one-, two-, or three-photon resonance, hence suggesting that the same excited energy level is involved in emitting the fluorescence intensity. A three-level model is developed to account for the incident excitation laser intensity dependence of the one-photon and multiphoton fluorescence intensity. The model allows the multiphoton absorption cross sections to be extracted; it can also account for the deviation observed in the linear, square, and cubic intensity dependence of the one-, two-, and three-photon fluorescence intensity, respectively. To determine the absorption cross sections, the present method does not require the fluorescence quantum efficiency data, needed in the low intensity technique.     

Temperature effects in lamp and laser induced high resolution fluorescence spectra of tetracene in crystalline solutions: Analytical implications

Temperature effects on the highly specific high resolution fluorescence spectra of tetracene in crystalline solutions at cryogenic temperatures have been investigated with emphasis on analytical implications. A comparison has been made between conventional non-selective broad-band excitation and laser excitation with special attention to position, height, width and shape of the peaks in the fluorescence spectrum. When lamp excitation is employed, temperature increase invariably results in a height and intensity decrease of the narrow lines. However, upon laser excitation a maximum in intensity and peak height may he observed at elevated temperatures when excitation takes place in a region where a narrow banded absorption transition occurs. Peak shapes are Gaussian under lamp excitation; laser excitation yields narrower bands with more Lorentzian character. As the temperature increases the narrow bands undergo a shift, in a similar way for both lamp and laser excitation. An explanation for these observations is presented. It is crucial that in the laser excited methods also it is the absorption step which determines the emission that is obtained. The laser probes an area with narrow absorption bands so that the intensity of the emission light is strongly influenced by the degree of matching of laser line and molecular absorption bands.     

A new approach to absorption effects using radioisotope X-ray spectrometry

The quantitative interpretation of X-ray fluorescence /XRF/ data is often difficult because of matrix effects. The intensity of fluorescence measurement for a given element is not only dependent on the concentration of the element, but also on the mass absorption coefficients of the sample for both excitation and fluorescent radiation. In this paper, a new approach for the determination of absorption and transmission correction factors is described.     

Fluorescence resonance energy transfer in a novel two-photon absorbing system

A novel fluorescence resonance energy transfer (FRET) system containing a two-photon absorbing dye and a nile red chromophore has been synthesized. Upon two-photon excitation by laser at 815 nm this molecule displays efficient energy transfer from the two-photon absorbing dye to the nile red moiety, with an 8-fold increase in emission compared to the model compound. Similarly, single-photon excitation of the two-photon absorbing moiety at 405 nm results in >99% energy-transfer efficiency, along with a 3.4-fold increase in nile red emission compared to direct excitation of the nile red chromophore at 540 nm. This system provides an effective way to use IR radiation to excite molecules that, by themselves, have little or no two-photon absorption.     

Proton transfer in 3-hydroxyflavone: The influence of physical excitation conditions and dynamic quenching

The influence of excitation conditions, temperature, and fluorescence quencher on the properties of 3-hydoxyflavone excited states is considered. Two-band fluorescence spectra of 3-hydroxyflavone formed in excitation by electromagnetic radiation in the region of the S ₁ and S ₂ absorption bands over the temperature range 20–80°C were recorded and analyzed. The TEMPO spin quencher was used as an excited state quencher. An analysis of the fluorescence parameters showed that solution heating from room temperature to 60°C increased the rate of proton transfer by 1.24 times at standard excitation into the main absorption band. The rate increased still more rapidly (by 6.9 times) in excitation into the second absorption band. The presence of the quencher caused a decrease in the yields of both fluorescence bands according to the diffusion mechanism and a noticeable growth in the rate of proton transfer. The latter increased by 1.16 times at room temperature and by 1.25 times at 80°C. The corresponding changes were more substantial, especially at elevated temperatures, if the second singlet band was excited. They then amounted to 1.24 and 3.5 times over the same temperature range.     

Effect of ZnX (X=F2 and Cl2) as modifier on luminescence properties of Ho3+/Yb3+ doped tellurite glasses

Optical absorption and photoluminescent properties of Ho(3+)/Yb(3+) co-doped tellurite and zinc halide tellurite glasses are investigated. The effect of zinc halides as modifier on the luminescence properties of above mentioned samples has been explored. Two intense upconversion emission bands centered at 546 ((5)F(4), (5)S(2)→(5)I(8)) and 660 ((5)F(5)→(5)I(8)) nm are observed when samples are excited by 976 nm radiation. Zinc halides act as quencher when 976 nm excitation source is used. The up and downconversion emission spectra are recorded with 532 nm excitation source also. In this case also, zinc halides do not show any improvement. The dependence of upconversion intensities on excitation power and temperature is discussed. The power dependence study shows a quadratic dependence of fluorescence intensity on the excitation power while decrement in emission intensity of different transitions at different rates is observed in temperature dependence study. The possible upconversion mechanisms are also discussed in order to understand the energy transfer between Yb(3+) and Ho(3+) ions.     

New method to measure the K-shell absorption jump factor in some rare-earth elements

The Compton scattering of 59.54 keV gamma rays by an Al scatterer has been used as a primer source at scattering angles from 48 to 118° by using a Si(Li) detector, and this primer gamma ray has been send to absorbers including Gd, Tb, Dy, Ho and Er. A new method has been developed to determine the K-shell absorption jump factor of elements and compounds. This method is based on simultaneous measurement of fluorescence radiation and scattered radiation, thus avoiding the problems with measuring the source strength and source-to-detector solid angle. In this method, the jump factor is effected from the scattering angle. Evident energies near to K-absorption edges of each lanthanide element have been determined for chosen angles, after the incident photon energy (59.5 keV) is exposed to Compton scattering from Al (secondary source). The experimental absorption jump factors are compared with the theoretical estimates and literature experimental values.     

Spectroscopy and upconversion of Dy3+ doped in sodium zinc phosphate glass

Optical absorption and fluorescence spectra of Dy3+ doped in sodium zinc phosphate glasses have been reported. Judd-Ofelt theory has been applied to analyze the spectra and determine the optical parameters such as transition probabilities, radiative lifetime, stimulated emission cross-section, etc. The fluorescence intensity of Dy3+ corresponding to 4F9/2-->6H13/2 transition increases with increasing concentration of Dy3+ but at higher concentrations, concentration quenching is observed. The radiative lifetime of the 4F9/2 level at 1 mol% concentration of Dy3+ in this host is found to be 541 micros. Emission corresponding to 4F9/2-->6H13/2 transition (570 nm) is observed on excitation with NIR radiation due to upconversion. An attempt is made to explain this observation.     

Photophysical Property of Photoactive Molecules with Multibranched Push-Pull Structures

The structure-property characteristics of a series of newly synthesized intramolecular charge-transfer (ICT) compounds, single-branch monomer with triphenylmethane as electron donor and 2,1,3-benzothiadiazole as acceptor, the corresponding two-branch dimer and three-branch trimer, have been investigated by means of steady-state and femtosecond time-resolved stimulated emission fluorescence depletion (FS TR-SEP FD) techniques in different polar solvents. The TD-DFT calculations are further performed to explain the observed ICT properties. The interpretation of the experimental results is based on the comparative stud-ies of the series of compounds which have increased amount of identical branch moiety. The similarity of the absorption and fluorescence spectra as well as strong solvent-dependence of the spectral properties for the three compounds reveal that the excited state of the dimer and trimer are nearly the same with that of the monomer, which may localize on one branch. It is found that polar excited state emerged through multidimensional intramolecular charge transfer from the donating moiety to the acceptor upon excitation, and quickly relaxed to one branch before emission. Even so, the red-shift in the absorption and emission spectra and decreased fluorescence radiative lifetime with respect to their monomer counterpart still suggest some extent delocalization of excited state in the dimer and trimer upon excitation. The similar behavior of their excited ICT state is demonstrated by FS TR-SEP FD mea-surements, and shows that the trimer has the largest charge-separate extent in all studied three samples. Finally, steady-state excitation anisotropy measurements has further been carried out to estimate the nature of the optical excitation and the mechanism of energy redistribution among the branches, where no plateau through the ICT band suggests the intramolecular excitation transfer process between the branches in dimer and trimer.     

Determination of yttrium in xenotime ore by energy dispersive X-ray fluorescence spectrometry

A radioisotope-excited X-ray fluorescence analysis is applied for the determination of yttrium in xenotime ore. An annular¹⁰⁹Cd source is employed for excitation of characteristic K X-rays of yttrium. The dilution method using pure starch as a diluent has been examined. Critical thickness of diluted ore sample has been determined. For the estimation of yttrium concentration in xenotime ore, the scattered radiation technique has been utilized. The validity and precision of the method have also been investigated.