A new method of quench monitoring in liquid scintillation counting: The H number concept

The quench level of different liquid scintillation counting samples is measured by comparison of the responses (pulse heights) produced by the same energy electrons in each sample. The electrons utilized in the measurements are those of the maximum energy (E_max) which are produced by the single Compton scattering process for the same energy gamma-rays in each sample. The relation of the E_max response produced in any sample is related to the E_max response produced in an unquenched, sealed standard. The relation, difference in response on a logarithm response scale, is defined as the “H Number,” H#. The H# is related to the counting efficiency of the desired radionuclide by measurement of a set of standards of known amounts of the radionuclide and different amounts of quench (standard quench curve). This report presents the theory of the H# concept. Several of the unique features of the H# method are discussed. Quench curves based upon the H# are compared to other previously used methods of quench monitoring. D. L. Horrocks, US Patent No. 4,075,480.     

Simultaneous time- and wavelength-resolved fluorescence microscopy of single molecules

Single fluorophores and single-pair fluorescence resonance energy transfer were studied with a new confocal fluorescence microscope that allows, for the first time, the wavelength and emission time of each detected photon to be simultaneously measured with single molecule sensitivity. In this apparatus, the photons collected from the sample are imaged through a dispersive optical system onto a time and position sensitive photon detector. For each detected photon the detection system records its wavelength, its emission time relative to the excitation pulse, and its absolute emission time. A histogram over many photons can generate a full fluorescence spectrum and correlated decay plot for a single molecule for any time interval. At the single molecule level, this approach makes possible entirely new types of temporal and spectral correlation spectroscopies. This paper presents our initial results on simultaneous time- and wavelength-resolved fluorescence measurements of single rhodamine 6G (R6G), tetramethylrhodamine (TMR), and Cy3 molecules embedded in thin films of poly(methyl methacrylate) (PMMA), and of single-pair fluorescence resonance energy transfer between two Alexa fluorophores spaced apart by a short polyproline peptide.     

Experimental investigation of multiple scattering of 662 keV gamma rays in zinc at 90°

Compton scattering investigations usually examine the case when photon has undergone only one Compton collision in the sample. The probability of a photon being scattered several times may be significant for a target of finite dimensions both in depth and lateral dimensions. The present experiment is undertaken to study the intensity and energy distributions of 662 keV gamma rays multiply scattered from a zinc target of various thicknesses at a scattering angle of 90° with the scattered photons being detected by an HPGe gamma detector. We observe that with an increase in target thickness, the number of multiply scattered photons also increases and saturates at a particular value of the target thickness (saturation depth). This supports the work of Paramesh, L., Venkataramaih, L., Gopala, K., Sanjeevaih, H. [1983. Z-dependence of saturation depth for multiple scattering of 662 keV photons from thick samples. Nucl. Instrum. Methods 206, 327–230]. The double Compton scattered peak is also observed in the experimental spectra, with a position in agreement with the predictions of Fernandez, J.E. [1991. Compton and Rayleigh double scattering of unpolarized radiation. Phys. Rev. A44, 4232–4248] and Barnea, G., Dick. C.E., Ginzburg. A.E., Seltzer. S.M. [1995. A study of multiple scattering background in Compton scatter imaging. NDT E Int. 28. 155–162].     

Interaction between the water soluble poly{1,4-phenylene-[9,9-bis(4-phenoxy butylsulfonate)]fluorene-2,7-diyl} copolymer and ionic surfactants followed by spectroscopic and conductivity measurements

The interaction has been studied in aqueous solutions between a negatively charged conjugated polyelectrolyte poly{1,4-phenylene-[9,9-bis(4-phenoxybutylsulfonate)]fluorene-2,7-diyl} copolymer (PBS-PFP) and several cationic tetraalkylammonium surfactants with different structures (alkyl chain length, counterion, or double alkyl chain), with tetramethylammonium cations and with the anionic surfactant sodium dodecyl sulfate (SDS) by electronic absorption and emission spectroscopy and by conductivity measurements. The results are compared with those previously obtained on the interaction of the same polymer with the nonionic surfactant C12E5. The nature of the electrostatic or hydrophobic polymer-surfactant interactions leads to very different behavior. The polymer induces the aggregation with the cationic surfactants at concentrations well below the critical micelle concentration, while this is inhibited with the anionic SDS, as demonstrated from conductivity measurements. The interaction with cationic surfactants only shows a small dependence on alkyl chain length or counterion and is suggested to be dominated by electrostatic interactions. In contrast to previous studies with the nonionic C12E5, both the cationic and the anionic surfactants quench the PBS-PFP emission intensity, leading also to a decrease in the polymer emission lifetime. However, the interaction with these cationic surfactants leads to the appearance of a new emission band (approximately 525 nm), which may be due to energy hopping to defect sites due to the increase of PBS-PFP interchain interaction favored by charge neutralization of the anionic polymer by cationic surfactant and by hydrophobic interactions involving the surfactant alkyl chains, since the same green band is not observed by adding either tetramethylammonium hydroxide or chloride. This effect suggests that the cationic surfactants are changing the nature of PBS-PFP aggregates. The nature of the polymer and surfactant interactions can, thus, be used to control the spectroscopic and conductivity properties of the polymer, which may have implications in its applications.     

Photoluminescence emission spectroscopic study of molybdenum-based heteropolyacid catalysts

Summary Photoluminescence emission spectroscopy studies of heteropolyacid (HPA) catalysts have been carried out. All the HPA samples gave rise to violet emission peak (emission peak I) at the same wavelength of 418 nm. However, a shoulder peak in the visible region (emission peak II) appeared at different wavelengths depending on the identity of the HPA sample. Photoluminescence emission peak (II) energies could be correlated with the negative differential resistance (NDR) peak voltages of nanostructured HPA monolayers measured using scanning tunneling microscopy (STM).     

Effects of fluorination on iridium(III) complex phosphorescence: magnetic circular dichroism and relativistic time-dependent density functional theory

We use a combination of low temperature, high field magnetic circular dichroism, absorption, and emission spectroscopy with relativistic time-dependent density functional calculations to reveal a subtle interplay between the effects of chemical substitution and spin-orbit coupling (SOC) in a family of iridium(III) complexes. Fluorination at the ortho and para positions of the phenyl group of fac-tris(1-methyl-5-phenyl-3-n-propyl-[1,2,4]triazolyl)iridium(III) cause changes that are independent of whether the other position is fluorinated or protonated. This is demonstrated by a simple linear relationship found for a range of measured and calculated properties of these complexes. Further, we show that the phosphorescent radiative rate, k(r), is determined by the degree to which SOC is able to hybridize T(1) to S(3) and that k(r) is proportional to the inverse fourth power of the energy gap between these excitations. We show that fluorination in the para position leads to a much larger increase of the energy gap than fluorination at the ortho position. Theory is used to trace this back to the fact that fluorination at the para position increases the difference in electron density between the phenyl and triazolyl groups, which distorts the complex further from octahedral symmetry, and increases the energy separation between the highest occupied molecular orbital (HOMO) and the HOMO-1. This provides a new design criterion for phosphorescent iridium(III) complexes for organic optoelectronic applications. In contrast, the nonradiative rate is greatly enhanced by fluorination at the ortho position. This may be connected to a significant redistribution of spectral weight. We also show that the lowest energy excitation, 1A, has almost no oscillator strength; therefore, the second lowest excitation, 2E, is the dominant emissive state at room temperature. Nevertheless the mirror image rule between absorption and emission is obeyed, as 2E is responsible for both absorption and emission at all but very low (<10 K) temperatures.     

Study on quench effects in liquid scintillation counting during tritium measurements

Quench effects can cause a serious reduction in counting efficiency for a given sample/cocktail mixture in liquid scintillation counting (LSC) experiments. This paper presents a simple experiment performed in order to test the influence of quenching on the LSC efficiency of ³H. The aim of this study was to investigate the behavior of several quench agents with different quench strengths (nitromethane, nitric acid, acetone, dimethyl-sulfoxide) added in different amounts to tritiated water in order to obtain standard sets for quench calibration curves. The OptiPhase HiSafe 2 and OptiPhase HiSafe 3 scintillation cocktails were used in this study in order to compare their quench resistance. Measurements were performed using a low-level LS counter (Wallac, Quantulus 1220).     

Photochemical Grafting of Organic Alkenes to Single-Crystal TiO(2) Surfaces: A Mechanistic Study

The UV-induced photochemical grafting of terminal alkenes has emerged as a versatile way to form molecular layers on semiconductor surfaces. Recent studies have shown that grafting reactions can be initiated by photoelectron emission into the reactant liquid as well as by excitation across the semiconductor band gap, but the relative importance of these two processes is expected to depend on the nature of the semiconductors, the reactant alkene and the excitation wavelength. Here we report a study of the wavelength-dependent photochemical grafting of alkenes onto single-crystal TiO(2) samples. Trifluoroacetamide-protected 10-aminododec-1-ene (TFAAD), 10-N-BOC-aminodec-1-ene (t-BOC), and 1-dodecene were used as model alkenes. On rutile (110), photons with energy above the band gap but below the expected work function are not effective at inducing grafting, while photons with energy sufficient to induce electronic transitions from the TiO(2) Fermi level to electronic acceptor states of the reactant molecules induce grafting. A comparison of rutile (110), rutile (001), anatase (001), and anatase (101) samples shows slightly enhanced grafting for rutile but no difference between crystal faces for a given crystal phase. Hydroxylation of the surface increases the reaction rate by lowering the work function and thereby facilitating photoelectron ejection into the adjacent alkene. These results demonstrate that photoelectron emission is the dominant mechanism responsible for grafting when using short-wavelength (～254 nm) light and suggest that photoemission events beginning on mid-gap states may play a crucial role.     

Vibrational spectroscopy and relaxation of an anharmonic oscillator coupled to harmonic bath

The vibrational spectroscopy and relaxation of an anharmonic oscillator coupled to a harmonic bath are examined to assess the applicability of the time correlation function (TCF), the response function, and the semiclassical frequency modulation (SFM) model to the calculation of infrared (IR) spectra. These three approaches are often used in connection with the molecular dynamics simulations but have not been compared in detail. We also analyze the vibrational energy relaxation (VER), which determines the line shape and is itself a pivotal process in energy transport. The IR spectra and VER are calculated using the generalized Langevin equation (GLE), the Gaussian wavepacket (GWP) method, and the quantum master equation (QME). By calculating the vibrational frequency TCF, a detailed analysis of the frequency fluctuation and correlation time of the model is provided. The peak amplitude and width in the IR spectra calculated by the GLE with the harmonic quantum correction are shown to agree well with those by the QME though the vibrational frequency is generally overestimated. The GWP method improves the peak position by considering the zero-point energy and the anharmonicity although the red-shift slightly overshoots the QME reference. The GWP also yields an extra peak in the higher-frequency region than the fundamental transition arising from the difference frequency of the center and width oscillations of a wavepacket. The SFM approach underestimates the peak amplitude of the IR spectra but well reproduces the peak width. Further, the dependence of the VER rate on the strength of an excitation pulse is discussed.     

Photon, Electron and Secondary Ion Emission from Single C(60) keV Impacts

This paper presents the first observation of coincidental emission of photons, electrons and secondary ions from individual C(60) keV impacts. An increase in photon, electron and secondary ion yields is observed as a function of C(60) projectile energy. The effect of target structure/composition on photon and electron emissions at the nanometer level is shown for a CsI target. The time-resolved photon emission may be characterized by a fast component emission in the UV-Vis range with a short decay time, while the electron and secondary ion emission follow a Poisson distribution.     

Synthesis of multifunctional fluorescent magnetic graphene oxide hybrid materials

Fluorescent magnetic graphene oxide hybrid materials have been fabricated by a multistep method. X-ray diffraction, transmission and scanning electron microscopy, fluorescence spectroscopy, Fourier transform infrared spectroscopy, vibration sample magnetometry, and energy dispersive spectroscopy were used to characterize the resulting material. The results showed that the materials have a saturation magnetization value of 22.0 emu/g at room temperature and exhibit a symmetrical and narrow emission peak at 544 nm. The resultant materials are able to carry an anti-cancer drug, 5-fluorouracil, with a load capacity of 0.24 mg/mg.     

Optimization of collinear double-pulse femtosecond laser-induced breakdown spectroscopy of silicon

This paper investigates the optimization of double-pulse collinear femtosecond laser-induced breakdown spectroscopy (FLIBS) for silicon. Double-pulse FLIBS signal enhancements were observed over an extended range of sample focal plane position compared to single pulse FLIBS. The FLIBS signal intensity was studied as a function of pulse energy, inter-pulse delay (0 ps‑80 ps) and sample position. Correlation between crater volume and signal intensity was measured over a limited range of the sample focal plane position. It was found that double-pulse FLIBS is superior to single pulse for certain focal plane positions.     

Vibrational structure of complex compound emission spectra measured by dynamical photon flux fluctuations as predicted in quantum theory of irreversible processes

The 10 K emission spectrum of Cs₂TeBr₆ was measured by recording the fluctuating photon flux. Since this fluctuation, according to the theory, is due to the dynamic coupling of the molecular system to the environment controlling the dissipation of energy, it should depend on the frequency of the emitted photons. By this, the vibrational structure of the transition has been resolved which could not be obtained by usual emission spectroscopy.Dedicated to Professor Dr. H. Hartmann, Frankfurt am Main, on the occasion of his seventieth birthday     

Standardization of fluorescence excitation-emission-matrices in aquatic milieu

Fluorescence excitation-emission-matrices (EEM) are a useful tool for water quality monitoring. Recent publications show the potential of the method for real time drinking water control. However, in fluorescence measurements there is still a need for standardization to make data interpretation comparable. In this work a standardization procedure based on excitation and emission correction as well as normalization and optional inner filter effect correction is presented. By measurements of humic acid and tryptophan standards with two different spectrometers (LS 50 and LS 55 by PerkinElmer) the procedure application leads to comparable fluorescence intensities with relative standard deviations (median) of 6.6-8.4% and 10.6-12.0%, respectively. These small differences are not avoidable even if all possible correction methods are implemented and constant measurement conditions are given. The used BAM kit for emission correction induced good agreement in peak shape not only for single wavelengths but also for the whole EEM. As a consequence it is necessary to use identical equipment and identical experimental conditions in order to apply this method in fields of water quality control if small changes of fluorescence intensities are relevant for data assessment.     

Double‐Wall Carbon Nanotube–Porphyrin Supramolecular Hybrid: Synthesis and Photophysical Studies

Double‐wall carbon nanotubes (DWCNTs) with pyridyl units covalently attached to the external wall through isoxazolino linkers and carboxylic groups that have been esterified by pentyl chains are synthesized. The properties of these modified DWCNTs are then compared with an analogous sample based on single‐wall carbon nanotubes (SWCNTs). Raman spectroscopy shows the presence of characteristic radial breathing mode vibrations, confirming that the samples partly retain the integrity of the nanotubes in the case of DWCNTs, including the internal and external nanotubes. Quantification of the pyridyl content for both samples (DWCNT and SWCNT derivatives) is based on X‐ray photoelectron spectroscopy and thermogravimetric profiles, showing very similar substituent load. Both pyridyl‐containing nanotubes (DWCNTs and SWCNTs) form a complex with zinc porphyrin (ZnP), as evidenced by the presence of two isosbestic points in the absorption spectra of the porphyrin upon addition of the pyridyl‐functionalized nanotubes. Supramolecular complexes based on pyridyl‐substituted DWCNTs and SWCNTs quench the emission and the triplet excited state identically, through an energy‐transfer mechanism based on pre‐assembly of the ground state. Thus, the presence of the intact inner wall in DWCNTs does not influence the quenching behavior, with respect to SWCNTs, for energy‐transfer quenching with excited ZnP. These results sharply contrast with previous ones referring to electron‐transfer quenching, in which the double‐wall morphology of the nanotubes has been shown to considerably reduce the lifetime of charge separation, owing to faster electron mobility in DWCNTs compared to SWCNTs.     

Radiative relaxation quantum yields for synthetic eumelanin

We report absolute values for the radiative relaxation quantum yield of synthetic eumelanin as a function of excitation energy. These values were determined by correcting for pump beam attenuation and emission reabsorption in both eumelanin samples and fluorescein standards over a large range of concentrations. Our results confirm that eumelanins are capable of dissipating >99.9% of absorbed UV and visible radiation through nonradiative means. Furthermore, we have found that the radiative quantum yield of synthetic eumelanin is excitation energy dependent. This observation is supported by corrected emission spectra, which also show a clear dependence of both peak position and peak width on excitation energy. Our findings indicate that photoluminescence emission in eumelanins is derived from ensembles of small chemically distinct oligomeric units that can be selectively pumped. This hypothesis lends support to the theory that the basic structural unit of eumelanin is oligomeric rather than heteropolymeric.     

Fluorescence investigation of the recombinant cyanobacterial phytochrome (Cph1) and its C-terminally truncated monomeric species (Cph1Delta2): implication for holoprotein assembly,chromophore-apoprotein interaction and photochemistry

Recombinant dimeric full-length Cph1 holophytochrome and its C-terminally-truncated monomeric species [Cph1Delta2, comprising the chromophore-bearing N-terminal sensory module (residues 1 to 514)] from the cyanobacterium Synechocystis expressed in E. coli and reconstituted in vitro with phycocyanobilin (PCB) were investigated with the use of fluorescence spectroscopy and photochemistry in the temperature range from 85 to 293 K. Holoprotein assembly in Cph1 apparently proceeds via intermediate states with the emission maximum at 680-690 nm (I685) and 700 nm (I700) and a half-life time, at room temperature, of < or =5 s. Conversion of the putative I685 into mature Cph1 involves relaxation of the chromophore into a more flexible conformation. Cph1 and Cph1Delta2 were closely similar in their spectroscopic and photochemical characteristics (position of the emission band and its width, character of the temperature dependence of the fluorescence and activation energy of the fluorescence decay, kinetics and extent of the Pr conversion at low and ambient temperatures), suggesting that there is no immediate effect of the C-terminus on the photochemical properties of the chromophore in Cph1 and that chromophore-chromophore interactions in the dimer are not significant. The latter is also supported by the lack of energy transfer from the phycoerythrobilin (PEB) to PCB in the mixed PEB/PCB adduct of Cph1. At the same time, certain variations in the fluorescence and photochemical parameters of Cph1 with temperature of the sample and intensity of the excitation light and dependence of the emission spectra on excitation wavelength were observed. These variations are interpreted as a manifestation of the Cph1 heterogeneity which may be due to the existence of different conformers of the chromophore and photoproduct formation under excitation light.     

因子分析-电感耦合等离子体原子发射光谱分析中的峰位优化及光谱干扰校正

将目标因子分析用于电感耦合等离子体原子发射光谱分析(ICP-AES)对高纯氧化铥中稀土杂质的测定及光谱重叠干扰校正.数据矩阵由纯光谱矢量、混合物光谱矢量及模型背景矢量构成.提出利用各目标矢量的真误差的平方和为评价函数优化扫描光谱峰位,从而消除扫描式ICP光谱仪发射光谱线的峰位移动给测定带来的影响.