Energy yield of fluorescence of complex organic compounds upon electron excitation

With use of electron energy loss spectra for vapors of anthracene, perylene, 1,4[di(2,5-phenyloxazolyl)] benzene, and paratherphenyl the energy yields of fluorescence are calculated for electron collision. It is shown that they are considerably smaller than those for optical excitation conditions. Deceased Institute of Molecular and Atomic Physics of the National Academy of Sciences of Belarus, 70, F. Skorina Ave., Minsk, 220072, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 65, No. 1, pp. 146–148, January–February, 1998.     

An accurate determination of the K‐shell X‐ray fluorescence yield of silicon

A measurement of the K‐shell fluorescence yield of silicon is undertaken in which identified sources of systematic errors in previous measurements are reduced or eliminated. This enables a stringent test of the only two sets of theoretical predictions available for atomic numbers less than 18. Our result ω_K = 0.0495 ± 0.0015 is very slightly lower than the non‐relativistic Hartree‐Fock‐Slater (HFS) prediction of 0.0514. This stringent test of the HFS predictions helps to refine the fundamental parameter database of the X‐ray fluorescence analysis technique, whose importance for light elements is increasing. Our work indicates the need for new theoretical calculations of K‐shell fluorescence yields for these elements. Copyright © 2012 John Wiley & Sons, Ltd.     

Average 2p subshells fluorescence yield values of some elements in the atomic number range 60 ≤ Z ≤ 90

The average 2p (L_2,3) subshells fluorescence yield (?_2,3) in 11 elements with Z ranging from 60 to 90 were measured with corporation of total L_2,3 X-ray production cross-sections. Measurements were carried out exciting L₂ and L₃ subshells of relevant elements that were exposed to beam of selected K X-rays from secondary sources. The measured values were compared with theoretical and semi-empirical values. It is clear that the present values of experimental ?_2,3 are generally smaller than the calculated and semi-empirical values for some elements in the atomic number range 60–90.     

Determination of experimental K-shell fluorescence yield for potassium and calcium compounds

K-shell fluorescence yields were experimentally determined for potassium and calcium compounds using a Si(Li) X-ray detector system (FWHM=5.96 keV at 160 eV). The samples were excited by 5.96 keV photons produced by a ⁵⁵Fe radioisotope source. The experimental values are systematically lower than the theoretical values.      

Temperature chamber for measurement of fluorescence yield and nitrogen spectrum in the project AIRFLY

This paper refers to the construction and utilization of the chamber that has been used for measurement of fluorescence yield within the frame of the project AIRFLY. The chamber was designed to simulate some physical conditions in high levels of the atmosphere, particularly pressure, temperature and humidity. The aim of the AIRFLY (AIR FLuorescence Yield) project is to simulate and to measure the process of the fluorescence and Cherenkov emission produced by impact of high-energy cosmic rays (UHECR) on molecules of nitrogen in high levels of the atmosphere. This is required for calibration of fluorescence detectors (FDs) dedicated for monitoring particles of these energies by means of fluorescence measurements.     

Total electron yield mode for XANES measurements in the energy region of 2.1-6.0 keV

The total electron yield (TEY)mode has been developed successfully for XANES measurements at Beamline 4B7A of BSRF (Beijing Synchrotron Radiation Facility).Its performance was studied by measuring sulphur K-edge XANES of three CdS samples (mixed with graphite powder as an electric conductor)with different concentration:75%,50% and 25%.The data are collected in TEY mode and fluorescence yield (FY)mode respectively for comparison.The results demonstrate that the TEY spectra of three samples agree well with each other after the background is subtracted and normalized.The measured XANES spectra by TEY mode without bias and with 100V bias are almost identical to one another,but the signal-to-noise ratio of spectra measured without bias is better than that with 100V bias.The consistency of the self-absorption corrected FY spectra and TEY spectra are within 10% for the three samples.     

Fluorescence quantum yield of rhodamine 6G using pulsed photoacoustic technique

Experimental method for measuring photoacoustic(PA) signals generated by a pulsed laser beam in liquids is described. The pulsed PA technique is found to be a convenient and accurate method for determination of quantum yield in fluorescent dye solutions. Concentration dependence of quantum yield of rhodamine 6G in water is studied using the above method. The results indicate that the quantum yield decreases with increase in concentration in the quenching region in agreement with the existing reports based on radiometric measurements.     

Total electron yield mode for XANES measurements in the energy region of 2.1——6.0 keV

The total electron yield (TEY) mode has been developed successfully for XANES measurements at Beamline 4B7A of BSRF (Beijing Synchrotron Radiation Facility). Its performance was studied by measuring sulphur K-edge XANES of three CdS samples (mixed with graphite powder as an electric conductor) with different concentration: 75%, 50% and 25%. The data are collected in TEY mode and fluorescence yield (FY) mode respectively for comparison. The results demonstrate that the TEY spectra of three samples agree well with each other after the background is subtracted and normalized. The measured XANES spectra by TEY mode without bias and with 100V bias are almost identical to one another, but the signal-to-noise ratio of spectra measured without bias is better than that with 100V bias. The consistency of the self-absorption corrected FY spectra and TEY spectra are within 10% for the three samples.     

A setup for synchrotron‐radiation‐induced total reflection X‐ray fluorescence and X‐ray absorption near‐edge structure recently commissioned at BESSY II BAMline

An automatic sample changer chamber for total reflection X‐ray fluorescence (TXRF) and X‐ray absorption near‐edge structure (XANES) analysis in TXRF geometry was successfully set up at the BAMline at BESSY II. TXRF and TXRF‐XANES are valuable tools for elemental determination and speciation, especially where sample amounts are limited (<1 mg) and concentrations are low (ng ml^?1 to µg ml^?1). TXRF requires a well defined geometry regarding the reflecting surface of a sample carrier and the synchrotron beam. The newly installed chamber allows for reliable sample positioning, remote sample changing and evacuation of the fluorescence beam path. The chamber was successfully used showing accurate determination of elemental amounts in the certified reference material NIST water 1640. Low limits of detection of less than 100 fg absolute (10 pg ml^?1) for Ni were found. TXRF‐XANES on different Re species was applied. An unknown species of Re was found to be Re in the +7 oxidation state.     

X-ray fluorescence in some rare earth and high Z elements excited by 661.6 keV γ-rays

The K-shell X-ray fluorescence cross sections are determined experimentally for 10 elements such as Pb, Hg, Ir, W, Lu, Tm, Dy, Tb, Gd and Nd at excitation energy of 661.6 keV associated with γ-rays of ¹³⁷Cs radioisotope. The technique employed involves the measurement of total intensity of fluorescent K X-rays that follow the photoeffect absorption of a known flux of γ-rays using a well type Nal(Tl) detector. The obtained results are compared with the available theoretical values and other measured values.     

Alignment of low‐dose X‐ray fluorescence tomography images using differential phase contrast

X‐ray fluorescence nanotomography provides unprecedented sensitivity for studies of trace metal distributions in whole biological cells. Dose fractionation, in which one acquires very low dose individual projections and then obtains high statistics reconstructions as signal from a voxel is brought together (Hegerl & Hoppe, 1976), requires accurate alignment of these individual projections so as to correct for rotation stage runout. It is shown here that differential phase contrast at 10.2 keV beam energy offers the potential for accurate cross‐correlation alignment of successive projections, by demonstrating that successive low dose, 3 ms per pixel, images acquired at the same specimen position and rotation angle have a narrower and smoother cross‐correlation function (1.5 pixels FWHM at 300 nm pixel size) than that obtained from zinc fluorescence images (25 pixels FWHM). The differential phase contrast alignment resolution is thus well below the 700 nm × 500 nm beam spot size used in this demonstration, so that dose fractionation should be possible for reduced‐dose, more rapidly acquired, fluorescence nanotomography experiments.     

Unravelling overlaps and torsion-facilitated coupling using two-dimensional laser-induced fluorescence

Two-dimensional laser-induced fluorescence (2D-LIF) spectroscopy is employed to identify contributions to fluorescence excitation spectra that arise from both overlapping bands and coupling between zero-order states (ZOSs). Evidence is found for the role of torsional motion in facilitating the coupling between vibrations that particularly involves the lowest-wavenumber out-of-plane vibrational modes. The experiments are carried out on jet-cooled p-fluorotoluene, where the molecules are initially in the lowest two torsional levels. Here we concentrate on the 390–420?cm^?1 features in the S₁?←?S₀ excitation spectrum, assigning the features seen in the 2D-LIF spectrum, aided by separate dispersed fluorescence spectra. The 2D-LIF spectra allow the overlapping contributions to be cleanly separated, including some that arise from vibrational-torsional coupling. Various coupling routes open up because of the different symmetries of the lowest two torsional modes; these combine with the vibrational symmetry to provide new symmetry-allowed vibration-torsion (‘vibtor’) interactions, and the role of the excited m?=?1 torsional level is found to be significant.     

Surface EXAFS via differential electron yield

Surface‐sensitive analysis via extended X‐ray absorption fine‐structure (EXAFS) spectroscopy is demonstrated using a thickness‐defined SiO₂ (12.4 nm)/Si sample. The proposed method exploits the differential electron yield (DEY) method wherein Auger electrons escaping from a sample surface are detected by an electron analyzer. The DEY method removes local intensity changes in the EXAFS spectra caused by photoelectrons crossing the Auger peak during X‐ray energy sweeps, enabling EXAFS analysis through Fourier transformation of wide‐energy‐range spectral oscillations. The Si K‐edge DEY X‐ray absorption near‐edge structure (XANES) spectrum appears to comprise high amounts of SiO₂ and low Si content, suggesting an analysis depth, as expressed using the inelastic mean free path of electrons in general electron spectroscopy, of approximately 4.2 nm. The first nearest neighbor (Si—O) distance derived from the Fourier transform of the Si K‐edge DEY‐EXAFS oscillation is 1.63 Å. This value is within the reported values of bulk SiO₂, showing that DEY can be used to detect a surface layer of 12.4 nm thickness with an analysis depth of approximately 4.2 nm and enable `surface EXAFS' analysis using Fourier transformation.     

Calcium imaging using fluorescence lifetimes and long-wavelength probes

We describe imaging of calcium concentrations using the long-wavelength Ca²⁺ indicators, Calcium Green, Orange, and Crimson. The lifetimes of these probes were measured using the frequency-domain method and were found to increase from 50% to severalfold in response to calcium. The two-dimensional images of the calcium concentration were obtained using a new apparatus for fluorescence lifetime imaging (FLIM). We also describe procedures to correct for the position-dependent frequency response of the gain-modulated image intensifier used in the FLIM apparatus. Importantly, the FLIM method does not require the probe to display shifts in the excitation or emission spectra. Using the FLIM method, calcium imaging is possible using probes which display changes in lifetime in response to calcium. Consequently, calcium imaging is possible with excitation wavelengths ranging from 488 to as long as 620 nm, where autofluorescence and/or photochemical damage is minimal. These probes are also suitable for calcium measurements of single cells using lifetime-based flow cytometry.     

应用高光谱仪探测叶片反射光谱中的荧光

介绍了一种利用光谱仪进行荧光测量的方法。采用LI 1800_12S积分球,耦合ASD地物光谱仪,在光源前面分别加载长波通、短波通截止滤光片,按照不同算法提取叶片表观反射光谱中的荧光。结果表明利用长波通滤光片测得的表观反射率差值光谱可以代表荧光光谱,在红光区和远红光区表现为明显的双峰特征,不同截止波长滤光片提取的荧光强度不同。采用短波通滤光片可直接获得荧光光谱,不同植物种类荧光光谱差异明显。此法对于植物被动荧光遥感探测及叶绿素荧光仪的研制和开发具有一定参考价值。     

基于单晶体的可调谐参量超荧光的产生

研究了一种基于单晶体的可调谐超荧光产生机理，在一个偏硼酸钡(BBO)晶体中实现了飞秒脉冲倍频过程和光参量产生过程.实验中采用kHz高功率钛宝石激光系统输出的飞秒脉冲光倍频后的蓝光作为抽运光，获得了可调谐范围为480—530 nm参量超荧光光谱输出.理论上分析了这种超荧光产生机理，并利用放大传递函数模拟出参量超荧光环的产生过程.结果表明，在一个BBO晶体中，当抽运光源输出光入射晶体角度同时满足倍频相位匹配角和非共线光参量产生相位匹配角时可产生参量超荧光环，通过微调相位匹配角可控制参量超荧光光谱调谐输出.该理论和实验研究为控制参量超荧光和量子纠缠态的产生提供了理论依据，对于量子成像和量子通讯等领域的发展具有重要意义.     

A laser-induced fluorescence biosensor by using ellipsoidal reflector

A new and compact fluorescence biosensor is constructed. The distinguished feature of this setup is the use of an ellipsoidal reflector as an optical collector of the fluorescence light. A traditional collecting lens with numerical aperture of 0.5 can only collect a few percent of the available signal, while the incorporation of the ellipsoidal reflector enables the apparatus to provide a signal increase of at least 66 times. A very good linear relationship between the concentration of fluorescent dye and the fluorescence intensity is achieved with correlation coefficient R=0.99979. The 3σ detection limit is 5 nM for microliter volume sample. Meanwhile, it is found that laser light scattering by dirts and scratches on the sample cell's windows and by turbidity in the sample solutions is the dominant limitation to increase the detection sensitivity. Approach to solve this problem is suggested.     

Coherent fluorescence emission by using hybrid photonic–plasmonic crystals

The spatial and temporal coherence of the fluorescence emission controlled by a quasi‐two‐dimensional hybrid photonic–plasmonic crystal structure covered with a thin fluorescent‐molecular‐doped dielectric film is investigated experimentally. A simple theoretical model to describe how a confined quasi‐two‐dimensional optical mode may induce coherent fluorescence emission is also presented. Concerning the spatial coherence, it is experimentally observed that the coherence area in the plane of the light source is in excess of 49 μm², which results in enhanced directional fluorescence emission. Concerning temporal coherence, the obtained coherence time is 4 times longer than that of the normal fluorescence emission in vacuum. Moreover, a Young's double‐slit interference experiment is performed to directly confirm the spatially coherent emission. This smoking gun proof of spatial coherence is reported here for the first time for the optical‐mode‐modified emission.