Cyclic perfluorocarbon radicals and anions having high global warming potentials (GWPs): structures, electron affinities, and vibrational frequencies

Adiabatic electron affinities, optimized molecular geometries, and IR-active vibrational frequencies have been predicted for small cyclic hydrocarbon radicals C(n)H(2)(n)(-)(1) (n = 3-6) and their perfluoro counterparts C(n)F(2)(n)(-)(1) (n = 3-6). Total energies and optimized geometries of the radicals and corresponding anions have been obtained using carefully calibrated (Chem. Rev. 2002, 102, 231) density functional methods, namely, the B3LYP, BLYP, and BP86 functionals in conjunction with the DZP++ basis set. The predicted electron affinities show that only the cyclopropyl radical tends to bind electrons among the hydrocarbon radicals studied. The trend for the perfluorocarbon (PFC) radicals is quite different. The electron affinities increase with expanding ring size until n = 5 and then slightly decrease at n = 6. Predicted electron affinities of the hydrocarbon radicals using the B3LYP hybrid functional are 0.24 eV (C(3)H(5)/C(3)H(5)(-)), -0.19 eV (C(4)H(7)/C(4)H(7)(-)), -0.15 eV (C(5)H(9)/C(5)H(9)(-)), and -0.11 eV (C(6)H(11)/C(6)H(11)(-)). Analogous electron affinities of the perflurocarbon radicals are 2.81 eV (C(3)F(5)/C(3)F(5)(-)), 3.18 eV (C(4)F(7)/C(4)F(7)(-)), 3.34 eV (C(5)F(9)/C(5)F(9)(-)), and 3.21 eV (C(6)F(11)/C(6)F(11)(-)).     

Hypervalency avoided: simple substituted BrF3 and BrF5 molecules. Structures, thermochemistry, and electron affinities of the bromine hydrogen fluorides HBrF2 and HBrF4

Five different pure density functional theory (DFT) and hybrid Hartree-Fock/DFT methods have been used to search for the molecular structures, thermochemistry, and electron affinities of the bromine hydrogen fluorides HBrF(n)/HBrF(n)(-) (n = 2, 4). The basis sets used in this work are of double-zeta plus polarization quality in conjunction with s- and p-type diffuse functions, labeled as DZP++. Structures with Br-F and Br-H normal bonds, that is, HBrF(2)/HBrF(2)(-) with C(2v) or C(s) symmetry and HBrF(4)/HBrF(4)(-) with C(4v) or C(s) symmetry, are genuine minima. However, unlike the original BrF(3) and BrF(5) molecules, the global minima for HBrF(n)/HBrF(n)(-) (n = 2, 4) species are predicted to be complexes, some of which contain hydrogen bonds. The demise of the hypervalent structures is due to the availability of favorable dissociation products involving HF, which has a much larger dissociation energy than F(2). Similar reasoning suggests that PF(4)H, SF(3)H, SF(5)H, ClF(2)H, ClF(4)H, AsF(4)H, SeF(3)H, and SeF(5)H will all be hydrogen bond structures incorporating diatomic HF. The most reasonable theoretical values of the adiabatic electron affinities (EA(ad)) are 3.69 (HBrF(2)) and 4.38 eV (HBrF(4)) with the BHLYP method. These electron affinities are comparable to those of the analogous molecules: Br(2)F(n), ClBrF(n), and BrF(n)(+1) systems. The first F-atom dissociation energies for the neutral global minima are 60 (HBrF(2)) and 49 kcal/mol (HBrF(4)) with the B3LYP method. The first H-atom dissociation energies for the same systems are 109 (HBrF(2)) and 116 kcal/mol (HBrF(4)). The large Br-H bond energies are not sufficient to render the hypervalent structures energetically tenable. The dissociation energies for the complexes to their fragments are relatively small.     

Dosage de traces de fer total dans les vins

Résumé Le dosage électrophotocolorimétrique des traces de fer total dans les vins au moyen de l'orthophénanthroline a été peu étudié jusqu'à présent. Sous un titre général le mémoire expose les conclusions auxquelles ont abouti diverses recherches consacrées à l'étude du dosage en question. L'application raisonnée de la méthode deBencze a permis d'établir une technique d'évaluation photocolorimétrique du fer dans les vins et les jus de fruits. Intéressante par sa simplicité et sa rapidité d'exécution, la technique en question indique le moyen de doser cet élément directement dans les liquides obtenus à partir des vins, suivant le procédé du traitement oxydatif au perhydrol. Ce traitement a permis de revaloriser le dosage du fer au point de vue de la rapidité par rapport à la minéralisation sèche, sans apporter en même temps des complications dans les manipulations analytiques et sans affecter la sensibilité et la précision de la réaction colorimétrique.

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Summary There has been little study of the electrophotocolorometric determination of the total iron content of wines by means of orthophenanthroline. Under a general title, the paper gives the general conclusions reached as a result of various studies of this determination. An intelligent application of theBencze method has resulted in a photocolorimetric evaluation of iron in wines and fruit juices. Characterized by simplicity and rapidity, this technique provides a means of determining this element directly in the liquids obtained from wines after oxidative treatment with perhydrol. This procedure compares, favorably with respect to speed with mineralization by the dry method, but is free from the complications in the analytical manipulations and there is no adverse effect on the sensitivity and the precision of the colorimetric reaction.

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Zusammenfassung Die elektrokolorimetrische Bestimmung der geringen Gesamtmengen an Eisen in Wein mit Hilfe von o-Phenanthrolin wurde bisher nur wenig untersucht. Die beim Studium dieses Verfahrens gesammelten Erfahrungen werden in Form eines allgemeinen Überblicks mitgeteilt. Die Anwendung der Methode vonBencze führte zur Ausarbeitung einer Arbeitsvorschrift zur kolorimetrischen Bestimmung des Eisens in Wein und Fruchtsäften. Diese ist wegen der Einfachheit und Geschwindigkeit ihrer Durchführung von praktischem Interesse. In der durch Oxydation des Weines mit Wasserstoffperoxyd erhaltenen Lösung kann das Eisen unmittelbar bestimmt werden. Diese Art des Aufschlusses ist besser geeignet als die trockene Veraschung, ohne die Empfindlichkeit oder die Genauigkeit der Farbreaktion zu beeinträchtigen.

     

SENSITIVITY OF Porphyromonas AND Prevotella SPECIES IN LIQUID MEDIA TO ARGON LASER

Abstract— The phototoxicity of argon laser irradiation was studied in aqueous suspensions of Porphyromonas endodontalis (American Type Culture Collection [ATCC] 35406), Porphyromonas gingivalis (ATCC 33277), Prevotella denticola (ATCC 33184) and two strains of Prevotella intermedia (ATCC 15033 and 49046), all "black-pigmented bacteria," BPB, that accumulate cellular porphyrins. Several of these species have been implicated in the etiology of Periodontol disease. Non-black-pigmented bacteria were also studied to test the specificity of irradiation as a potential photodynamic treatment for Periodontol infections. Cell suspensions were irradiated with an argon laser at fluences of 20–200 J/cm². When cultured in hemin-supplemented media, ATCC 15033 was the most sensitive to irradiation. However, a second strain of the same species (ATCC 49046) was resistant. The photosensitivity of other species ranked ATCC 33277 > 35406 = 33184 = 35496. When hemin was replaced in media by hemoglobin, ATCC 33277 became resistant to irradiation. Protoporphyrin IX content in BPB cells was shown not to be a major factor determining photosensitivity. Oxygen was required during irradiation for BPB species to be affected. Non-black-pigmented bacteria were much less sensitive to irradiation than BPB.     

Diffraction dissociation of nuclei in 450 GeV/c proton-nucleus collisions

Diffractive dissociation of nuclei (Be, Al, W) in collisions with 450 GeV/c protons,pApX, has been measured with the HELIOS spectrometer at the CERN Super Proton synchrotron. The dependence of the single-diffraction cross-section on the nuclear massA can be parametrized as _SD mb×A ^0.35±0.02, showing the peripheral nature of the process. The differential cross-section d_SD=(3.8±0.3)mb ×A ^0.35±0.02, is exponential with the slope parameter, increasing from 6.2±0.4 (GeV/c)^–2 for beryllium to 7.9±0.5 (GeV/c)^–2 for tungsten. The slope parameter also increases with increasing massM _X of the diffractively produced state. The rapidity, multiplicity, and transverse-momentum distributions of the particles of the diffractively produced stateX show a longitudinal phase-space population and are remarkably insensitive to the nuclear mass. This, together with theA ^1/3 dependence of _SD, suggests that the dominant process of nuclear diffractive excitation is the dissociation of single nucleons.Deceased     

Superdeformed bands in195Tl

Two superdeformed (SD) bands have been found and assigned to¹⁹⁵Tl on the basis of excitation function and cross bombardment results. The two bands are almost identical in transition energies to those observed in¹⁹³Tl. They are signature partners with a splitting, presumably due to the proton i_13/2 (=5/2) orbital, characteristic of all known SD bands in the thallium isotopes. Their alignments relative to the¹⁹³Tl bands were found to be zero.On leave from Comision National de Energia Atomica 1429 Buenos Aires, Argentina.     

Generalizations of Slater's constraint qualification for infinite convex programs

In this paper we study constraint qualifications and duality results for infinite convex programs (P) = inf{f(x): g(x) – S, x C}, whereg = (g ₁,g ₂) andS = S ₁ ×S ₂,S _i are convex cones,i = 1, 2,C is a convex subset of a vector spaceX, andf andg _i are, respectively, convex andS _i -convex,i = 1, 2. In particular, we consider the special case whenS ₂ is in afinite dimensional space,g ₂ is affine andS ₂ is polyhedral. We show that a recently introduced simple constraint qualification, and the so-called quasi relative interior constraint qualification both extend to (P), from the special case thatg = g ₂ is affine andS = S ₂ is polyhedral in a finite dimensional space (the so-called partially finite program). This provides generalized Slater type conditions for (P) which are much weaker than the standard Slater condition. We exhibit the relationship between these two constraint qualifications and show how to replace the affine assumption ong ₂ and the finite dimensionality assumption onS ₂, by a local compactness assumption. We then introduce the notion of strong quasi relative interior to get parallel results for more general infinite dimensional programs without the local compactness assumption. Our basic tool reduces to guaranteeing the closure of the sum of two closed convex cones.     

Analysis of natural flavonoids by microchip-micellar electrokinetic chromatography with pulsed amperometric detection

Catechins (catechin and other derivatives) are naturally occurring flavonoids present in a number of plants and foods. They are also part of numerous nutraceutical formulations because they are believed to have antioxidant, cancer chemo-preventative, anti-inflammatory and antimicrobial properties. The determination of catechins has traditionally been performed by HPLC. However, this methodology is both time and sample intensive and generates large amounts of organic solvent waste. In the current report, an application of MEKC using a PDMS microchip is presented for the analysis of catechins. The system uses pulsed amperometric detection for direct analysis of important naturally occurring catechins. The effect of pH, surfactant concentration, detection potential and signal stability were analyzed. Linear relationships were found between the concentration and peak current, with good stability and limits of detection of 8 [micro sign]M for catechin, epigallocatechin gallate and epicatechin, and 14 [micro sign]M for epicatechin gallate. Optimum conditions were applied to the detection of selected catechins in a commercially available green tea extract nutraceutical and the results were compared to HPLC analysis. The analysis using microchip micellar electrokinetic chromatography and pulsed amperometric detection was completed in 4.5 min, 10 times faster than the HPLC analysis.     

Plasma desorption mass spectrometry of transition metal complexes of thio- and selenosemicarbazones of 2-acetylpyridines

Summary Californium-252 plasma desorption mass spectra were recorded for complexes of the anions of various thio-and seleno-semicarbazones of 3-acetylpyridines(1–4) with the transition metal ions iron(III) and cobalt(II). Positive ion spectra gave clear evidence of the cation present and fragmentation with loss of ligands or parts of ligands was straightforward. Negative ion spectra likewise provided evidence of the intact anion except with tetracoordinate metal halide systems [MX₄]^– which lost one or more halide atoms. Evidence of fragmentation of the ligand and recombination of the fragments with the metal ion was also observed in the negative ion mode. Spectra were used to revise the structure of a complex previously reported as [FeLCl₂]⁽¹⁾ to [FeL₂]⁺[FeCl₄]^–.     

Visualization and characterization of electroactive defects in the native oxide film on aluminium

Spatial!y localized electrochemical activity at Al/Al2O3 electrodes has been investigated using scanning electrochemical microscopy (SECM) in order to establish the relationship between localized corrosion of Al (and Al alloys) with the defect structure of the native Al2O3 film. Local electron transfer at microscopic defects (2 to 50 microm radius) was visualized in acetonitrile solutions using the nitrobenzene/nitrobenzene radical anion (Eo approximately -1.6 V vs. Ag/Ag+) and tetracyanoquinodimethane/tetracyanoquinodimethane radical anion couples (Eo approximately -0.3 V) as redox mediators for imaging. SECM investigations revealed no significant differences in electrochemical activity at Al/AI203 electrodes in the two mediator solutions, indicating that electrical conduction at the defect sites is weakly dependent on interfacial potential and the electric field across the Al2O3 film. The density of electroactive defects observed by SECM varied by 2 to 3 orders of magnitude between electrodes prepared from the same source of Al (either 99.450% and 99.9995%) suggesting that electrical conduction in the native oxide is very sensitive to surface preparation. Defect densities as low as approximately 3 sites cm(-2) were readily measured by SECM.