Rate constants for aqueous‐phase reactions of SO4− with C2F5C(O)O− and C3F7C(O)O− at 298 K

Perfluorocarboxylic acids and their anions (PFCAs), such as perfluorooctanate (C₇F₁₅C(O)O^?), have been generally recognized to be global pollutants and are believed to persist in the environment. Kinetic data for reactions of sulfate anion radicals (SO₄^?) with PFCAs are needed to evaluate the residence times of PFCAs in the environment, but no kinetic data have been reported, except for the rate constant for the reaction of SO₄^? with trifluoroacetate (CF₃C(O)O^?) (k₁). In this study, using the fact that PFCAs react with SO₄^? to form shorter chain PFCAs, we determined rates relative to k₁ of the reactions of photolytically generated SO₄^? with two short‐chain PFCAs, pentafluoropropionate (C₂F₅C(O)O^?; k₂) and heptafluorobutyrate (C₃F₇C(O)O^?; k₃), along with conversion ratios for conversion of C₂F₅C(O)O^? into CF₃C(O)O^? (α) and conversion of C₃F₇C(O)O^? into C₂F₅C(O)O^? (β) and CF₃C(O)O^? (γ) at 298 K. Values of k₁, k₂, or k₃ might change over the course of reaction with increasing ionic strength. Nevertheless, if the values of k₁/k₂, k₂/k₃, α, β, and γ remain almost constant during the reaction, a simple equation involving relative rates, such as k₁/k₂, can be used to relate the concentrations of C₃F₇C(O)O^?, C₂F₅C(O)O^?, and CF₃C(O)O^?. We compared the relative rates, such as k₁/k₂, and the conversion ratios determined from various experimental runs with different initial conditions to check whether relative rates and conversion ratios remained almost constant during each experimental run. The values of k₁/k₂, k₂/k₃, α, β, and γ seemed to remain almost constant, which facilitated determination of k₂/k₁ = 0.89 ± 0.07, k₃/k₁ = 0.84 ± 0.08, α = 0.88 ± 0.05, β = 0.75 ± 0.05, and γ = 0.17 ± 0.02. © 2007 Wiley Periodicals, Inc. Int J Chem Kinet 39: 276–288, 2007     

Ionic products in ground polymer. IV. Anions in poly(vinylidene fluoride)

When poly(vinylidene fluoride) (PVDF) was ground with tetracyanoethylene (TCNE) powder in a vibration glass ball mill in vacuum in the dark at 77 K, the TCNE anion radical (TCNE-) was detected in the mixture by ESR spectroscopy. The TCNE.- is formed by the abstraction of electrons by TCNE from the anion that is produced by a heterogeneous bond scission of carbon-carbon bonds in the polymer main chain. The assignment of TCNE.- was carried out by the ESR spectral simulation on the basis of an anisotropic effective hyperfine tensor that includes a forbidden transition term. At least 85% of the bond scission of the PVDF main chain is induced by a heterogeneous process to produce ionic products. The yield of these mechanions seems to increase with the polarity of carbon-carbon bond owing to a substituent group bonded to the carbon in the polymer main chain.     

Activation analysis of vanadium in the egg of ascidian

Vanadium content of the eggs and embryos of ascidian, Halocynthia roretzi was determined by activation analysis. The determination was performed by the comparison of the activity around 1.434 MeV peak of⁵²V in the sample to that of the standard. The concentration of vanadium in the eggs remained unchanged during the cleavage stage and the animal accumulated it progressively in the early embryogenesis. The content in the larvae after metamorphosis amounted to nearly fifteen times of that of the unfertilized eggs.     

Measurement of Fluorescence Quantum Yield of Ultraviolet-Absorbing Substance Extracted from Red Alga: Porphyra yezoensis and its Photothermal Spectroscopy

Optical properties of an ultraviolet-absorbing substance (UVAS) extracted from the marine red alga, Porphyra yezoensis, have been investigated. The substance is excited by UV light, and the emitted fluorescence is detected using an intelligent fluorescence detector. The fluorescence of UVAS is weaker by four orders of magnitude than the fluorescence intensity emitted by anthracene in the same optical system. The absorbed energy is apparently not transferred to the photosynthesis process and is believed to be consumed as heat. Using photothermal spectroscopy, a signal is observed indicating that the absorbed photon energy has transferred to the heat. The waveform of the photothermal signal of UVAS is similar to that of quinoxaline, whose fluorescence quantum yield is known to be zero. It is determined that the fluorescence quantum yield and the energy of the triplet state of UVAS are 1.7 ± 0.7 ± 10⁻⁴ and 21000 ± 1000 cm ⁻¹, respectively. The conclusion is that the excited molecules of UVAS decay by passing through the triplet state and dissipate all absorbed energy as heat.     

Stereoisomers of selenilimines: isolation and reactions of 9-phenylselenoxanthene-N-arylsulfonylselenilimines

The isolates cis- and trans-9phenylselenoxanthene-N-arylsulfonylselenilimines were not interconverted thermally. cis-Isomers were converted to trans-isomers by chloramine-T or -B in a fashion of S_N2 type substitution. cis-Isomers did not rearrange but trans-isomers rearranged thermally to 9-arylsulfonamido-9-phenylselenoxanthenes, whereas both isomers underwent the base-catalyzed intermolecular rearrangement.     

Non-stereospecific ring expansions of benzothiazoline sulfoxides

Non-stereospecific ring expansions of 3-acetylbenzothiazoline sulfoxides to benzothiazines from the reaction with acetic anhydride are reported.     

Water molecules in a protein cavity detected by a statistical-mechanical theory

Four water molecules confined in a small cavity of hen egg-white lysozyme were detected by means of the three-dimensional (3D) RISM theory, a statistical-mechanical theory of molecular solutions. This is the first theoretical realization of confined molecules in a protein without making nonsense tricks, such as placing the molecules in the space a priori. Possible impacts which the result may have on biochemistry and biophysics, including the molecular recognition, enzymatic reactions, etc., are discussed.