Ultrafast laser flash photolysis (266 nm) of para- and ortho-biphenyl azide in acetonitrile produces azide excited states that have broad absorption bands centered at 480 nm. The para-biphenyl azide excited singlet state has a lifetime of 100 fs. The excited-state lifetime of the ortho-azide isomer is 450 +/- 150 fs. Decay of the azide excited states is accompanied by the formation of the corresponding known singlet nitrenes (para, lambdamax = 350 nm, ortho, lambdamax = 400 nm). Singlet para-biphenylnitrene is born with excess energy and undergoes vibrational cooling with a time constant of 11 ps to form the long-lived (tau approximately 9 ns) relaxed singlet nitrene. Singlet ortho-biphenylnitrene decays with a lifetime of 16 ps in acetonitrile at ambient temperature. 相似文献
The dissociation constants of fumaric acid were extracted from UV-vis spectra in the 10–90 ∘C range. These values were used to extract thermodynamic parameters that showed the temperature effects on the dissociations
reactions to be dominantly driven by the solvent. The molar absorption coefficients for the fumaric acid, the bifumarate and
fumarate species, can be accurately reproduced with the two-term Gauss–Lorentz equation. Deconvolution of these bands showed
strong π–π∗ transitions for all species and weaker charge-transfer-to-solvent transitions for the charged species. TD-DFT calculations
were used to identify the most important molecular orbitals involved in the vertical excitations of the fumaric acid species.
The electron population and their states of delocalization were also estimated with topological analyses of the electron density
and of the Becke–Edgecombe Electron Localization Function. 相似文献
This presentation deals with issues of comparability and traceability in food analysis in Australia from several perspectives. This includes the current national (Australian) and increasingly international (Codex) performance-based approach to food analysis. The Australian food regulatory process will be described, particularly those aspects that impact on the analysis of food in a regulatory sense. This section will also describe two areas where specific methods have been mandated in legislation and discuss two case studies where the analytical method has impacted on the elaboration of standards. Other areas to be covered include regulation/requirements relating to supply/availability of reference materials, the use of proficiency testing as a means of ensuring comparability, and, finally, some thoughts on what role BIPM/CCQM may play in the analysis of food.Electronic Supplementary Material Supplementary material is available for this article at
Terry SpencerEmail: Phone: +612-6213-6102Fax: +612-6213-6815
Liquid membrane emulsions were used to extract phenolic compounds and organic acids from their aqueous solutions. The emulsions contained caustic as the reactive agent. When the phenolic compounds and organic acids permeated through the liquid membranes into the emulsion droplets, they reacted with caustic and became ionized. The ionized species could not permeate through the liquid membranes and therefore were held in the emulsion droplets.
The conclusions of this recent investigation are:
(1) More than 99% of phenol and cresols can be extracted in less than 1 minute.
(2) Acetic and propionic acids can also be extracted but at much slower rates. However, if the amount of caustic is not sufficient to react with all the permeating compounds, the acids will be extracted preferentially to the phenols.
(3) The acids can only be extracted at low pH (acidic) whereas the phenolic compounds can be extracted at pH of 7.
(4) The extraction rates for phenol and acetic acid are the same in individual-compound and binary-mixture permeations.
(5) The extraction can be described by a mass transfer model. 相似文献
Comprehensive two-dimensional gas chromatography with isotope-dilution time-of-flight mass spectrometry (GC × GC-IDTOFMS) was used to measure polychlorinated dibenzo-p-dioxin (PCDD), polychlorinated dibenzofuran (PCDF), and coplanar polychlorinated biphenyl (cPCB) concentrations in ash, sediment, vegetation, and fish samples. The GC × GC capability was achieved by using a quad jet, dual stage, thermal modulator. Zone compression of the GC peaks from modulation resulted in a significant increase of the signal intensity over classical GC-IDTOFMS. The GC × GC column set used an Rtx-Dioxin 2 phase as the first dimension (1D) and an Rtx-500 as the second dimension (2D). The chromatographic separation of the 17 PCDD/Fs and the 4 cPCBs was attained in 1D except for 2,3,7,8-TCDD and CB126 for which deconvoluted ion currents (DIC) were required to be reported separately. The Rtx-500 phase separated the bulk matrix interfering compounds from the target analytes in 2D. The instrumental limit of detection (iLODs) was 0.5 pg for 2,3,7,8-TCDD. The calibration curves showed good correlation coefficients for all the compounds investigated in the concentration range of 0.5–200 pg. GC × GC-IDTOFMS results compared favorably to those from conventional isotope-dilution one-dimensional gas chromatography-high resolution mass spectrometry (GC-IDHRMS). The comprehensive mass analysis of the TOFMS further permitted the identification of other contaminants of concern in the samples. 相似文献
A scheme has been developed to eliminate virtually all signal intensity dependence on 1JCH in polarization transfers between 1H and 13C nuclei, reducing differences in signal intensity to only 1.5% over the entire natural 1JCH range. The scheme relies on the summation of time-domain data acquired with four suitably selected Delta delays so that the J dependence is essentially canceled in the final, signal-averaged free-induction decay. These Delta delays have been incorporated into the DEPT pulse sequence to create sensitivity-enhanced experiments for collecting quantitative 13C{1H} spectra. Four experiments, each with unique read pulse angles, give quantitative spectra with 200-300% more sensitivity than conventional 13C spectra acquired with inverse-gated 1H decoupling. The experiments are ideal for recording spectra with improved quantitative information or for substantially reducing the long acquisition times indicative of quantitative 13C experiments. The ability of the experiments to provide quantitative spectra was demonstrated with a simple ethylbenzene solution, however, they can easily be adapted to various applications for analysis of complex mixtures. 相似文献
The micro- and nanoarchitectures of water-swollen hydrogels were routinely analyzed in three dimensions at very high resolution by two cryopreparation methods that provide stable low-temperature specimens for in-lens high magnification recordings. Gemini surfactants (gS), poly-N-isopropylacrylamides (p-NIP Am), and elastin-mimetic di- (db-E) and triblock (tb-E) copolymer proteins that form hydrogels have been routinely analyzed to the sub-10-nm level in a single day. After they were quench or high pressure frozen, samples in bulk planchets were subsequently chromium coated and observed at low temperature in an in-lens field emission SEM. Pre-equilibrated planchets (4-40 degrees C) that hold 5-10 microl of hydrogel facilitate dynamic morphological studies above and below their transition temperatures. Rapidly frozen samples were fractured under liquid nitrogen, low-temperature metal coated, and observed in-lens to assess the dispersion characteristics of micelles and fragile colloidal assemblies within bulk frozen water. Utilizing the same planchet freezing system, the cryoetch-HRSEM technique removed bulk frozen water from the hydrogel matrix by low-temperature, high-vacuum sublimation. The remaining frozen solid-state sample faithfully represented the hydrogel matrix. Cryo- and cryoetch-HRSEM provided vast vistas of hydrogels at low and intermediate magnifications whereas high magnification recordings and anaglyphs (stereo images) provided a three-dimensional prospective and measurements on a molecular level. 相似文献
Summary A simple and fast method for the determination of fluorine in organic compounds is given. After closed-flask combustion, fluoride is measured by a solid state electrode. The procedure is applicable to organo-metallic compounds, but boron interferes.
Zusammenfassung Eine einfache Methode zur raschen Fluorbestimmung in organischen Verbindungen wurde angegeben. Nach Verbrennung im verschlossenen Kolben wird das Fluorid mit einer ionenspezifischen Elektrode gemessen. Das Verfahren ist für metallorganische Verbindungen anwendbar, aber Bor stört die Bestimmung.
An integrated analytical methodology has been developed for determining nitrogen-containing polycyclic aromatic hydrocarbons, which enables quantitation of individual contaminants as low as 1 μg/kg in sediment samples. A cross-sectional profile from the Hamilton Harbour sediment samples was analyzed for azaarenes. These contaminants were separated by Soxhlet extraction, and pH adjustment allowed their isolation from different classes of neutral and acidic components. Separation and identification of the organic bases in each sample were achieved by using open tubular column gas chromatography with thermionic detection and HRGC-mass spectrometry. Organic bases present in the samples included mostly azaarenes such as acridines, benzacridines, azafluorene, benzoquinolines, azapyrenes, etc. Quantitation and environmental significance of these compounds are discussed. Recoveries of individual azaarenes at two different levels were evaluated. Data presented indicate that detection limits of this method are between 1 and 10 μg/kg. Recovery azaarenes from bottom sediment samples at concentration levels between 1 to 100 μg/kg is 81 ± 17%. 相似文献
Johnny Mercer had a hit song a few decades ago in which he admonished us to accentuate the positive, eliminate the negative, hold on the affimative and to have nothing to do with in between. This seems like good advice, but as is the case with most good advice it is rather hard to follow and not always applicable. 相似文献