Oxygen diffusion in SrCe<Subscript>0.95</Subscript>Yb<Subscript>0.05</Subscript>O<Subscript>3−δ</Subscript>

¹⁸O/¹⁶O isotope exchange depth profiling (IEDP) combined with secondary ion mass spectrometry (SIMS) has been used to measure the oxygen tracer diffusivity of SrCe_0.95Yb_0.05O_3– between 800 °C and 500 °C at a nominal pressure of 200 mbar. The values of D* (oxygen tracer diffusion coefficient) and k (surface exchange coefficient) increase steadily with increasing temperature, and the activation energies are 1.13 eV and 0.96 eV, respectively. Oxygen ion conductivities have been calculated using the Nernst–Einstein equation. The transport number for oxide ions at 769 °C, the highest temperature studied, is only ~0.05. Moreover, SrCe_0.95Yb_0.05O_3– has been studied using impedance spectroscopy under dry O₂, wet O₂ and wet H₂ (N₂/10% H₂) atmospheres, over the range 850–300 °C. Above ~550 °C, SrCe_0.95Yb_0.05O_3– shows higher conductivity in dry O₂ than in wet O₂ or wet H₂; below that temperature the results obtained for the three atmospheres are comparable. Dry O₂ shows the highest activation energy (0.77 eV); the activation energies for wet O₂ and wet H₂ are identical (0.62 eV).Abbreviations HTPC high-temperature proton conductor - IEDP isotope exchange depth profiling - SIMS secondary ion mass spectrometryPresented at the OSSEP Workshop Ionic and Mixed Conductors: Methods and Processes, Aveiro, Portugal, 10–12 April 2003     

J-aggregation and its characterization in Langmuir-Blodgett films of merocyanine dyes

Langmuir-Blodgett (LB) films are constructed by successively transferring monomolecular layers formed at the air-water interface onto solid substrates. One of the advantages of the LB technique in fabricating molecular aggregates lies in the fact that it can employ various kinds of molecules by mixing them at the air-water interface. The mixed system may exhibit new properties that are not observed for individual components. This method would be useful, for example, in the studies of the formation and control of the J-aggregates of functional dyes that attract attention both in science and technology. In this paper, I review this subject mainly based on our recent results in merocyanines. LB films of merocyanine dyes, mixed with arachidic acid (C(20)), exhibit J-aggregate formation and have been serving as typical systems in revealing the physical and structural aspects of nanosized molecular aggregates constructed as monolayers. In the case of LB films of a merocyanine dye having benzothiazole as donor nucleus (abbreviated as DS), electron spin resonance (ESR) spectroscopy has been successful in determining the characteristic in-plane orientation of dye molecules with respect to the dipping direction, which led to the discovery of the flow orientation effect during the dipping process of LB films as the origin of optical dichroism often observed in LB films. In this article, after an introduction of ESR spectroscopy, three major topics on the merocyanine J-aggregation and its characterization in mixed films are discussed. The first topic is the observation and control of the size of J-aggregates in the dilution limit of dyes in arachidic acid matrix for a methyl-substituted DS (6-Me-DS). Dependence of atomic force microscopy (AFM) patterns on the molar ratio allows the identification of dye domains. J-band optical peak analysis based on the Kuhn's extended dipole model, supplemented by a novel application of femtosecond pump-probe optical spectroscopy, yields the size of the J-aggregates of 10(3). The second topic is the control of the J-band peak wavelengths by mixing two different kinds of dye molecules. The first case is the mixture of a J-forming 6-Me-DS and non-J-forming merocyanine analog, DO with benzo-oxazole instead of benzothiazole of DS. The second case is the mixture of both J-forming dyes but with different J-band peak positions, 6-Me-DS and another analog of 5-Cl-DS. The optical peak shifts depending on the molar mixing ratio will be presented. The last topic is related to the elucidation of electronic states of dye molecules in the J-aggregates. Light-induced ESR (LESR) of DS films with stable isotope ((15)N or (13)C)-substituted dyes provide clear evidence for the photoinduced charge transfer by the detection of hyperfine structures. Moreover, infrared (IR) spectroscopy of (13)C-enriched dye identifies the IR absorption peak of the relevant carbon in the chromophore. The results give evidence for the enhanced intramolecular charge transfer of dyes in the J-aggregates compared with an isolated merocyanine composed of donor and acceptor moiety. Lastly, the Cl attachment in 5-Cl-DS leads to a significant enhancement of the nitrogen hyperfine coupling in the LESR spectra. These examples and others demonstrate the potential of LB films of merocyanines in the studies of the nanosized molecular aggregates in monolayer assemblies.     

Performance of quantitative analyses by liquid chromatography–electrospray ionisation tandem mass spectrometry: from external calibration to isotopomer-based exact matching

Liquid chromatography–tandem mass spectrometry (LC-MS/MS) is a versatile coupling system which combines both selectivity and sensitivity and certainty. Hence, it is generally considered as the most reliable technique to quantify chemical compounds in complex matrices. In the present paper, we evaluate the performance of LC-MS/MS methods for the quantification of 3-nitrotyrosine in human urine in order to point out its dependence on the design of the quantification method, and emphasize the role of matrix effects in the performance. We compare external and internal calibrations, isotope dilution and isotopomer-based exact matching. The role of both sample preparation and multiple transitions monitoring is particularly addressed.     

关于铀同位素标准物质的几个问题

讨论了铀同位素标准物质(UIRM)研制中的一些技术问题,如IRM中同位素丰度的定值,IRM不确定度的影响因素等,并介绍了国内外UIRM研制情况。     

Concerning the acidity and hydrogen bonding of hydroxyphenanthroperylene quinones like fringelite D,hypericin, and stentorin

Summary The strongly enhanced acidity of the bay hydroxyl group as compared to the respectiveperi hydroxyl groups of fringelite D, hypericin, and stentorin could be rationalized on the basis of a vinylogous carboxylic acid and was nicely corroborated by semiempirical calculations of the AM1 type. Experimental data obtained from several independent experimental methods, like polarized absorption spectroscopy, hole burning, and isotope effects, as well as from semiempirical AM1 and 6–31G levelab initio calculations conclusively pointed to dissymmetrical hydrogen bonding systems in both theperi andbay regions of the correspondingbay phenolate ions.

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Zu Acidität und Wasserstoffbrückenbindung von Hydroxyphenanthroperylenchinonen wie Fringelit D, Hypericin und Stentorin

Zusammenfassung Die stark erhöhte Acidität der bay-Hydroxylgruppen gegenüber jener derperi-Hydroxylgruppen von Fringelit D, Hypericin und Stentorin läßt sich auf der Basis einer vinylogen Carbonsäure verstehen und wurde auch durch semiempirische Rechnungen vom AM1-Typ erhärtet. Daten aus unabhängigen Experimenten wie Polarisationsspektroskopie, Lochbrennen und Isotopeneffekte sowie semiempirische AM1- undab initio-Rechnungen auf 6–31G Niveau belegen ein unsymmetrisches Wasserstoffbrückenbindungssystem sowohl für denperi-als auch denbay-Bereich der entsprechendenbay-Phenolationen.

     

Self-consistent-field – Hartree–Fock method with finite nuclear mass corrections

We have upgraded a Self-consistent-field – Hartree–Fock routine to include a finite nuclear mass correction for molecules developed in our laboratory. The new routine can handle isotopomers without calculating any nuclear kinetic energy matrix element. Tests on H₂, LiH, HF, F₂, and H₂O isotopomers indicate the equivalence of our correction to the standard diagonal adiabatic correction. A further original application to C₂H₆ illustrates the usefulness of the method for polyatomic molecules. The resulting molecular orbitals carry the nuclear mass signature, exemplified with Koopmans ionization potentials.From the Proceedings of the 28th Congreso de Químicos Teóricos de Expresión Latina (QUITEL 2002)     

Isotope‐Coded Affinity Tagging Technique Using Avidin Functional Affinity Electrophoresis: An Alternative to an Avidin Affinity Column

Avidin functional affinity electrophoresis (AFAEP) is substituted for an avidin affinity column (AAC) to capture biotinylated peptides in the Isotope‐Coded Affinity Tagging (ICAT) technique which is a valuable tool in quantitative proteomics. In this new technique, the AFAEP‐captured ICAT‐labeled biotinylated peptides are extracted with the biotin tag intact from the polyacrylamide gel piece with aqueous 95% formamide (pH 8.2) at 65 °C for 20 min, and then detected by a matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometer. Bovine serum albumin (BSA) and the ¹²C‐ and ¹³C‐ICAT reagents are used to test this AFAEP‐ICAT technique. The results show that both AFAEP and AAC methods provide quantitative information of the relative amounts of ¹²C‐ and ¹³C‐ICAT‐labeled biotinylated tryptic peptides of BSA in a sample. Compared with AAC, the AFAEP is cheaper to perform, more stringent in capturing the biotinylated peptides, and capable of simultaneously processing multiple samples.     

Trace lead measurement and on-line removal of matrix interference in seawater by isotope dilution coupled with flow injection and ICP-MS

Isotope dilution analysis method coupled with flow injection and inductively coupled plasma mass spectrometry (ID-FI-ICP-MS), enabled trace lead concentration in seawater to be determined and the high salt concentration in the matrix, such as Na⁺, Ca²⁺ and Mg²⁺, to be removed on-line. The operational parameters of the FI system including pH for the chelating reaction, concentration of 8-hydroxyquinoline-5-sulfonic acid (8-HQS), sample loading time and injection speed, washing time and speed, eluting acid concentration and eluting speed, and instrumental parameters for ICP-MS were optimized and selected. Accurate results could be achieved because the isotope ratios required can be precisely measured in the range of the eluting peak by means of ID-FI-ICP-MS. The 3σ detection limit was 0.204 ng ml⁻¹. The trace lead concentration of seawater in south Xiamen, China was 0.988 ± 0.039 ng ml⁻¹. The recoveries of spiked Pb standard in seawater and standard reference water (GBW 08607) were 97.9 and 101.0%, respectively, with a relative standard deviation of 0.98%. This method can be used to determine trace lead concentration in high salt matrix samples, and is especially useful when the eluting peaks do not have a Gaussian-distribution.     

F and C spectra of fluorinated and partially fluorinated vinyl alkyl ethers

Fluorine, hydrogen, and ¹³C NMR spectral data have been obtained for vinyl alkyl ethers containing fluorines. Some of the molecules are perfluorinated and others include hydrogen, bromine, and chlorine substituents. New generalizations regarding FF spin-spin coupling are developed and used, along with previously recognized correlations, in the confirmation of structures and the assignments of resonances. ¹³C spectroscopy, especially the analysis of ¹³C¹⁹F coupling, is critical in several of the structure determinations. Chlorine isotope effects on fluorine chemical shifts are observed when the chlorine and fluorine are attached to the same carbon, and are also used in the structure analyses. Long-range couplings between fluorines in the vinyl group and fluorines in the alkyl group are interpreted in terms of molecular geometry which allows certain of the alkyl fluorines to “touch” the fluorines cis and gem to the ether oxygen but not the fluorine trans to the oxygen. Two bond ¹³C¹⁹F coupling across the vinyl double bond is found to vary dramatically with the electronegativity of the vinyl substituents in the ethers, in accordance with previous observations for olefins.     

Determination of 19-norandrosterone in CCQM-P68. NIST results using an isotope dilution liquid chromatography/tandem mass spectrometry method

The US National Institute of Standards and Technology (NIST) participated in an international interlaboratory study under the auspices of the Consultative Committee for Amount of Substance (CCQM) for the determination of 19-norandrosterone (19-NA) in urine, the principal metabolite of nandrolone and certain other synthetic testosterone substitutes banned for use by the World Antidoping Agency (WADA). Prior to this study, NIST developed a candidate reference measurement procedure based upon isotope dilution liquid chromatography/tandem mass spectrometry. This method was applied to a urine sample distributed to the participants in the study by the Australian National Measurement Institute, Pymble, Australia (NMIA). The NIST results were in very good agreement with those from the other participants, all of whom used methods based upon gas chromatography/mass spectrometry. All known significant sources of uncertainty were evaluated, resulting in a relative expanded uncertainty of less than 5% (coverage factor k = 2).