Total Fluorescence Yield Research Articles

Measurement of the ultraviolet-induced fluorescence yield from integrating spheres

We report theory and measurements of a simple and absolute technique for the determination of the total emitted spectral fluorescence yield inside an integrating sphere from the sphere coating under irradiation with a monochromatic beam. This technique measures the spectral response of a monochromator–detector system to the radiation exiting from an integrating sphere. The total spectral fluorescence yield can be calculated from the response measurement and an overall responsivity function that is obtained by calibrating the system with a standard source. This technique provides quantitative fluorescence analysis of the coating of an integrating sphere wall.

Chemical analysis for optimal synthesis of ferrihydrite-modified diatomite using soft X-ray absorption near-edge structure spectroscopy

Effects of process parameters such as concentrations of FeCl2, NaOH, and drying temperature on the formation mechanism and chemical characteristics of ferrihydrite-modified diatomite are studied by using X-ray absorption near-edge structure spectroscopy. The spectra were recorded in total electron yield mode and/or fluorescence yield mode to investigate the chemical nature of Fe and Si on the surface and/or in the bulk of ferrihydrite-modified diatomite, respectively. It was found that only the surface SiO2 was partially dissolved in the NaOH solution with stirring and heating, whereas the bulk of diatomite seemed to be preserved. The dissolved Si was incorporated into the structure of ferrihydrite to form the 2-line Si-containing ferrihydrite on the surface of diatomite. The crystalline degree of ferrihydrite increased with the increasing FeCl2 concentration and the Brunauer–Emmett–Teller specific surface area of ferrihydrite-modified diatomite decreased with the increasing FeCl2 concentration. The crystalline degree of ferrihydrite decreased with the increase of NaOH concentration. The high temperature calcination caused an energy shift in the Si L-edge spectra to the high energy side and a transformation of Si-containing ferrihydrite to crystallized hematite might occur when ferrihydrite-modified diatomite is calcined at 900°C. In this study, the optimal synthesis conditions for the ferrihydrite-modified diatomite with the least crystalline Si-containing ferrihydrite and the highest surface area were found to be as the follows: 0.5 M FeCl2 solution, 6 M NaOH solution and drying temperature of 50°C.

Addition of carboxylic acids modifies phosphate sorption on soil and boehmite surfaces: A solution chemistry and XANES spectroscopy study

Soil acidification is a globally significant agricultural issue, as the plant availability of phosphorus (P) is decreased through increased P sorption onto aluminium (Al) hydroxides and other solid phase binding sites. X-ray absorption near edge structure (XANES) spectroscopy generated new information on the speciation of Al and P in the presence of carboxylic acids on soil and boehmite ( γ-AlOOH) surfaces. XANES spectra were acquired in the soft X-ray regime at the P and Al L 2 , 3 -edges, and the Al K-edge, respectively. Adding oxalic acid to soil enhanced Al dissolution and exposed previously occluded soil P, while hydroxybenzoic and coumaric acids did not compete with P for surface binding sites. Boehmite strongly adsorbed carboxylic acids in the absence of applied phosphorus. However, when P was applied with carboxylic acids, the carboxylics were unable to compete with P for binding, especially hydroxybenzoic and coumaric acids. Using XANES in both total electron yield and fluorescence yield modes provided valuable information on both surface and near-surface processes of P and Al due to different information depths. The Al K-edge XANES provided baseline information on the solid-phase matrix. XANES in total electron yield mode and at the P L-edge shows promise for speciation of elements on soil surfaces due to enhanced sensitivity for speciation of surface-adsorbed species compared to the commonly used P K-edge XANES.

Investigation of the amorphous to crystalline phase transition of chemical solution deposited Pb(Zr0.3Ti0.7)O3 thin films by soft X-ray absorption and soft X-ray emission spectroscopy

Chemical solution deposited (CSD) complex oxide thin films attract considerable interest in various emerging fields as for example, fuel cells, ferroelectric random access memories or coated conductors. In the present paper the results of soft-X-ray spectroscopy between 280 and 560 eV on the amorphous to crystalline phase transition of ferroelectric Pb(Zr0.3Ti0.7)O3 (PZT) thin films are presented. Five CSD samples derived from the same wafer coated with a PZT film pyrolyzed at 350 °C were heat treated at different temperatures between 400 and 700 °C. At first the samples were morphologically and electrically characterized. Subsequently the soft-X-ray absorption and emission experiments were performed at the undulator beamline 8.0 of the Advanced Light Source of the Lawrence Berkeley National Laboratory. Soft-X-ray absorption spectra were acquired for the Ti L 2,3-, O K-, and C K-edge thresholds by using simultaneously the total electron yield (TEY) and total fluorescence yield (TFY) detection methods. For two samples, annealed at 400 and 700 °C, respectively, the resonant inelastic soft-X-ray spectroscopy (RIXS) was applied for various excitation energies near the Ti L-, O K-edges. We observed clear evidence of a rutile phase at untypically low temperatures. This rutile phase transforms into the perovskite phase upon increasing annealing temperature. These results are discussed in the framework of current microscopic models of the PZT (111) texture selection.

Unoccupied electronic states in graphite oxides

Unoccupied electronic states of graphite oxides with different oxidation times have been investigated using X-ray absorption spectroscopy (XAS) in total electron yield (TEY) and total fluorescence yield (TFY) modes. The graphite oxides exhibit graphite-like sp 2 states with additional electronic states originating from functional groups. The intensity of the π * state decreases as the atomic ratio O:C increases. The intensity ratio of carboxyl to π * states in XAS TEY mode corresponds to the area ratio of carboxyl to sp 2 carbon in X-ray photoelectron spectroscopy. In addition, the two modes in XAS can identify electronic states of functional groups originating from surface or bulk regions.

XMCD studies on Co and Li doped ZnO magnetic semiconductors

ZnO doped with a few per cent (<10%) of magnetic ions such as Co exhibit room temperature (RT) ferromagnetism, transforming it into a very promising candidate for future spin electronic applications. We present x-ray magnetic circular dichroism (XMCD) spectroscopy, which has been used in total electron yield, total fluorescence yield, and reflection mode to investigate the origin of ferromagnetism in such diluted magnetic semiconductor materials in a surface, bulk and interface sensitive way, respectively. We investigated three different types of samples: ZnO doped with 5% Co, artificially layered films, and layered films with additional co-doping of 10% Li. These films are prepared by pulsed laser deposition (PLD) and characterized by superconducting quantum interference device (SQUID) magnetometry. Extensive XMCD measurements at the CoL2,3 and the O K edges, done with a very good signal-to-noise ratio, have revealed only cobalt paramagnetism and non magnetic oxygen signatures at low and high temperatures. We do not see any element specific signature for ferromagnetism at all. By exclusion, our results suggest oxygen vacancies as the intrinsic origin for RT ferromagnetism in doped ZnO.

Fast electron generation in cones with ultraintense laser pulses

Experimental results from copper cones irradiated with ultraintense laser light are presented. Spatial images and total yields of CuKα fluorescence were measured as a function of the laser focusing properties. The fluorescence emission extends into the cone approximately 300μm from the cone tip and cannot be explained by ray tracing including cone wall absorption. In addition, the total fluorescence yield from cones is an order of magnitude higher than for equivalent mass foil targets. Indications are that the physics of the laser-cone interaction is dominated by preplasma created from the long duration, low-energy prepulse from the laser.

Molecular properties of R-phycocyanin subunits from Polysiphonia urceolata in potassium phosphate buffer

The two subunits of R-phycocyanin from Polysiphonia urceolata were isolated and renatured. The renatured subunits were characterized by electrophoresis, molecular weights and spectra. The blue-shifted spectra, fluorescence recovery and restoring of the energy transfer suggested correct refolding of the subunits. The molecular properties of the subunits in potassium phosphate buffer (KPB) were investigated in detail. The total fluorescence yields (Q(T)) of the beta subunit declined while the energy transfer efficiency (E(T)) in the beta subunit was promoted with the increase of KPB concentration. On the other hand, both Q(T) and E(T) were enhanced with the increasing of the subunit concentrations. Based on the structural information, the fluorescence quenching in high concentrations of KPB was ascribed to less rigid chromophores caused by the weakening of the hydrogen-bond interaction network, while the enhancement of the fluorescence and E(T) was due to the aggregation of the subunits in the ionic solvent. Aggregation was confirmed by cysteine-assisted promotion of renaturation yield and stability, as well as equilibrium unfolding tests. Optimal conditions were proposed for the refolding/unfolding studies, under which the subunits were mainly monomeric. Compared to that in C-PC, the blue-shifted spectrum of PCB in R-PC is suggested to bring larger energy transfer efficiency, probably due to the necessity of the light harvesting for P. urceolata living in deep water.

Functional Analysis of Photosystem II in a PsbO-1-Deficient Mutant in Arabidopsis thaliana

The Arabidopsis thaliana mutant psbo1 (formerly the mutant LE18-30), which contains a point mutation in the psbO-1 gene leading to defective expression of the PsbO-1 protein, has recently been described [Murakami, R. et al. (2002) FEBS Lett. 523, 138-142]. This mutant completely lacks the PsbO-1 protein and overexpresses the PsbO-2 protein. To further study the effect of PsbO-1 deficiency on the function of photosystem II, the polyphasic chlorophyll a fluorescence rise and flash fluorescence induction and decay of the relative fluorescence quantum yield were measured in whole leaves from wild type and the psbo1 mutant. Additionally, flash oxygen yield experiments were performed on thylakoid membranes isolated from wild type and the psbo1 mutant. The results obtained indicate that during fluorescence induction the psbo1 gene exhibited an enhanced O to P transition. Additionally, while the J to I transition in wild type accounted for more than 30% of the total fluorescence yield, in the mutant it accounted for less than 2% rise in the total. Analysis of the flash-induced fluorescence rise in the presence of DCMU indicated that in wild type the ratio of PS IIalpha to PS IIbeta reaction centers was approximately 1.2 while in the mutant the ratio was approximately 0.3. Fluorescence decay kinetics in the absence of DCMU indicated that electron transfer to QB was significantly altered in the mutant. Fluorescence decay kinetics in the presence of DCMU indicated that the charge recombination between QA- and the S2 state of the oxygen-evolving complex was retarded. Furthermore, flash oxygen yield analysis indicated that both the S2 and S3 states exhibited significantly longer lifetimes in the psbo1 mutant than in wild type. Our data indicate that while PsbO-1-deficient plants can grow photoautotrophically (although at a reduced growth rate) the photochemistry of PS II is significantly altered.

Surface characterization ofMnxGe1−xandCryMnxGe1−x−ydilute magnetic semiconductors

We have used x-ray photoemission electron microscopy (XPEEM) and x-ray absorption spectroscopy (XAS) to characterize MnxGe1-x and CryMnxGe1-x-y films grown by molecular beam epitaxy. The surface layers of the as-grown films probed by XPEEM present segregation of Mn-rich phases. XAS using both total electron yield and fluorescence yield detection shows that the films are heavily oxidized after exposure to air. Etching in HF and HCl can be used to reduce oxidation, but inhomogeneities in the surface composition might not be completely eliminated depending on the Mn concentration. X-ray magnetic circular dichroism (XMCD) measurements reveal that neither the etched nor the as-grown films present remanent ferromagnetic behavior down to a temperature of 5 K within the probing depth of the fluorescence yield (similar to 20 nm). Mn is paramagnetic in both the oxidized and etched samples, with an increased tendency to order magnetically toward the interior of the films. Cr in CryMnxGe1-x-y possesses a paramagnetic moment only in the oxidized form. A comparison of the XAS line shapes obtained in the present study with those of Mn impurities deposited on Ge and GaAs surfaces demonstrates that the interpretation of XAS spectra of Mn-doped dilute magnetic semiconductors in the literature is often affected by residual oxidation.

Lyman and Balmer emission following core excitations in methane and ammonia molecules

The intensities of hydrogen Lyman-α and Balmer series emission lines as a result of photoexcitation of free CH4 and NH3 molecules at the C 1s and N 1s edges have been measured. For methane, the total fluorescence yield in the visible region (300–650 nm) was also recorded. Excitation functions of the Balmer lines show relative intensity enhancement of Balmer-β emission in comparison with Balmer-α at higher core-to-Rydberg excitations. The Lyman-α emission intensity, in general, follows the relations observed in the corresponding total ion yield measurements. Additionally, the Balmer-γ and -δ yields were measured for ammonia molecules and they show intensity maxima at photon energies shifted closer to the N 1s threshold than Balmer-α and -β. A quantum defect analysis is performed to find out which core excitations are responsible for this enhanced intensity. Dissociation pathways leading to the emission in H atoms are discussed.

Spectroscopy of strongly correlated systems: Resonant x-ray scattering without energy resolution in the scattered beam

The total emission of photons excited by x rays (90\ifmmode^\circ\else\textdegree\fi{} between incident and detected photons) is measured vs the incident photon energy at the $\mathrm{Ce}\phantom{\rule{0.2em}{0ex}}{M}_{4,5}$ edges in $\mathrm{Ce}{\mathrm{In}}_{3}$, $\mathrm{Ce}\mathrm{Sn}{\mathrm{In}}_{2}$, $\mathrm{Ce}{\mathrm{Al}}_{2}$, $\mathrm{Ce}{\mathrm{Pd}}_{3}$, and $\mathrm{Ce}{\mathrm{Rh}}_{2}$, and at the $\mathrm{Ni}\phantom{\rule{0.2em}{0ex}}{L}_{2,3}$ edges in NiO. The results show the signature of a second-order process; these experiments must be interpreted as genuine resonant inelastic scattering (though without energy resolution of the emitted photons) and not as absorption spectroscopy measured by the total fluorescence yield. In Ce compounds, information on bulk hybridization can thus be obtained simply and with high sensitivity. The branching ratio between the different scattering channels is also measured. This approach opens innovative perspectives in resonant inelastic x-ray scattering.

X-ray absorption studies on cubic boron nitride thin films

Cubic boron nitride (c-BN) films synthesized by various energetic species assisted physical vapor deposition and chemical vapor deposition techniques on Si and diamond-coated Si substrates have been investigated by boron and nitrogen K-edge angle-resolved x-ray absorption near-edge structure in both total electron yield and fluorescence yield modes. X-ray absorption spectrum has been developed to study the film structure, the quantity and distribution of the partially ordered turbostratic (t-BN) and amorphous (a-BN) sp2-hybridized BN phases, and the t-BN∕a-BN ratios. The preferred direction of the t-BN basal planes at the interface between c-BN and substrate is found to be normal or nearly normal to the substrate. The content of the sp2-bonded BN in the c-BN films deposited on diamond-coated Si substrates reduces remarkably. The modifications of the electronic structure of the c-BN films with respect to bulk hexagonal BN and c-BN have been investigated and the crystallinity of c-BN films has also been evaluated from the x-ray absorption near edge structure results.

ＸＡＦＳによる微粒子の化学状態分析

The measurement of X-ray absorption fine structure (XAFS) spectra of fine particle samples using the total electron yield and X-ray fluorescence yield methods reveals the chemical state of surface and bulk, separately, of powder samples. For various particulate environmental samples (both standard samples and sampled in the fields) are measured and the chemical state analysis of sulphur has been performed in the present study. The difference among the samples collected at a same place/date and the similarity among the samples collected at the different places/date are discussed from the view point of the error introduced in the present experiment.

Fluorescence emission from photo-fragments after resonant S 2p excitations in H2S

Visible-UV fluorescence emission of gas-phase hydrogen sulfide, H(2)S, has been studied at the S 2p edge with synchrotron radiation excitation. Dispersed fluorescence measurements in the wavelength range 300-900 nm were taken at several photon energies corresponding to the excitations of the S 2p electrons to the unoccupied molecular and Rydberg orbitals. The spectra reveal fluorescence from the H, S, S(+), HS and HS(+) photo-fragments. H is found to be the strongest emitter at Rydberg excitations, while the emission from S(+) is dominant at the molecular resonances and above the S 2p ionization thresholds. The intensities of hydrogen Lyman-alpha (122 nm), Balmer-alpha (656 nm), Balmer-beta (486 nm) transitions as well as the visible-UV total fluorescence yield (300-900 nm) and the total ion yield were measured by scanning the photon energy in small steps across the S 2p edge. The different Balmer lines show some sensitivity to the specific core excitations, which is, however, not so strong as that recently observed in the water molecule [E. Melero García, A. Kivimäki, L. G. M. Pettersson, J. Alvarez Ruiz, M. Coreno, M. de Simone, R. Richter and K. C. Prince, Phys. Rev. Lett., 2006, 96, 063003].

Localization and Quantification of Platelet-Rich Thrombi in Large Blood Vessels With Near-Infrared Fluorescence Imaging

Imaging of thrombus formation in vivo has been limited by the inability to directly visualize and measure thrombi in large blood vessels in real time. Near-infrared light, with its superior tissue penetration and reduced scatter, could potentially solve this problem. Platelets were labeled with the near-infrared fluorophore IR-786. Optimal total fluorescence yield occurred at 6 attomoles of IR-786 per platelet. IR-786-labeled platelets were tested for their ability to detect thrombus formation in large animal model systems relevant to common human vascular procedures. Invisible near-infrared light did not distort the surgical field in any way, and even after optimization of per-platelet fluorescent yield, platelets remained fully functional. Intravenous infusion of just 3.6x10(10) labeled platelets into a 35-kg Yorkshire pig permitted thrombus visualization, with a signal-to-background ratio > or = 2, for at least 2 hours in coronary, carotid, and femoral vessels. Platelet-rich, actively growing clots were monitored in real time and quantified with respect to size and kinetics after injury to vessels, cutaneous incisions, intravascular stent insertion, or introduction of embolic coils. Similarly, formed clots were monitored in real time during thrombolysis with streptokinase and heparin. Vessel patency was assessed independently with a second near-infrared fluorescent blood pool agent. IR-786-labeled platelets provide sensitive, specific, and real-time visualization of thrombi in thick-walled blood vessels. In addition to immediate application in cardiac, transplant, and vascular surgery, the mechanisms that underlie thrombus formation in large blood vessels can now be investigated.

Major signal increase in fluorescence microscopy through dark-state relaxation

We report a substantial signal gain in fluorescence microscopy by ensuring that transient molecular dark states with lifetimes >1 micros, such as the triplet state relax between two molecular absorption events. For GFP and Rhodamine dye Atto532, we observed a 5-25-fold increase in total fluorescence yield before molecular bleaching when strong continuous-wave or high-repetition-rate pulsed illumination was replaced with pulses featuring temporal pulse separation >1 micros. The signal gain was observed both for one- and two-photon excitation. Obeying dark or triplet state relaxation in the illumination process signifies a major step toward imaging with low photobleaching and strong fluorescence fluxes.

Three-stage refolding/unfolding of the dual-color β-subunit in R-phycocyanin from Polysiphonia urceolata

The conformational changes during refolding and unfolding of the dual-color β-subunit in R-phycocyanin (R-PC) were monitored by the spectra, fluorescence anisotropy, and FRET. It was observed that both of the refolding and unfolding of the β-subunit would undergo a three-stage conformational change, but in a reverse order. During the refolding process, at the first stage, the configuration of the tetrapyrrole chromophores transformed from the cyclohelical to the extended one, suggested by the blue-shifted spectra. At the second stage, recovery of the hydrogen-bond and hydrophobic interaction network fixed the chromophore in a more rigid configuration, suggested by a linear increase in the total fluorescence yield. At the third stage, the increase of the FRET efficiency suggested a protein-framework movement that made the two chromophores closer or/and into a more parallel orientation. The fluorescence anisotropy further confirmed the three-stage model.

Silicate formation at the interface of Hf-oxide as a high- k dielectrics and Si(0 0 1) surfaces

The composition and chemical bonding of the first atoms across the interface between Si(0 0 1) and the gate dielectrics determine the quality of gate stacks. An analysis of that hidden interface is a challenge as it requires high sensitivity in both elemental and chemical state information. We used synchrotron radiation (SR) based photoelectron spectroscopy and, in particular, X-ray absorption spectroscopy in total electron yield and total fluorescence yield at the Si2p and the O1s edges to address this issue. We report on results for Hf oxide prepared by ALD and compare to Pr 2O 3/Si(0 0 1). For Hf oxide thin films we find evidence for the silicate formation at the interface as derived from the characteristic features in the X-ray absorption spectra at the Si2p and the O1s edges. Resonant photoelectron spectroscopy is used to analyze the absorption band in detail. Following the resonant profiles of initial and final states we deduce from the resonant behaviour a charge donation via a Si-induced charge transfer.

Orbital and bonding anisotropy in GaFeO 3

The polarization-dependent O K-edge X-ray absorption spectra on GaFeO 3 were simultaneously measured in the total electron yield and total fluorescence yield modes. The spectra measured in both modes display nearly identical polarization dependence, confirming that the polarization dependence is not due to extrinsic artifacts such as the oxygen non-stoichiometry or degradation at the surface but due to the intrinsic nature of this system. We also obtained identical magnetic hysteresis loops in both modes by using the X-ray magnetic circular dichroism at Fe L-edges.