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     

Thermoelectric power of transition solutes in liquid tin

Thermoelectric powers of Fe, Ni and Co dissolved in liquid Sn are measured and discussed in relation to resistivity and susceptibility by reference to the concept of virtual bound state.     

Sound attenuation in one-dimensional magnetic systems at finite temperatures

Sound attenuattion constants are calculated for the one-dimensional ferro- and antiferromagnetic systems at finite temperatures. Their frequency dependences, in both cases, turn out to be $\text{ω}{}^{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}{}_{\mathrm{<mtext>k</mtext>}}\text{if}\text{ω}{}_{\mathrm{<mtext>k</mtext>}}\text{? ω}{}_{\mathrm{c}}\text{and}\text{ω}{}^2{}_{\mathrm{<mtext>k</mtext>}}\text{if}\text{ω}{}_{\mathrm{<mtext>k</mtext>}}\text{?ω}{}_{\mathrm{c}}$, where ω_c is a “cut-off” frequency related to the three-dimensional anisotropic interactions.     

POSSIBLE ROLE OF METALLOTHIONEIN IN THE CELLULAR DEFENSE MECHANISM AGAINST UVB IRRADIATION IN NEONATAL HUMAN SKIN FIBROBLASTS

Abstract: The role of metallothionein (MT) in protecting skin cells against UVB irradiation was investigated. Fibroblast strains from normal adult (HS-K) and neonatal (NB1RGB) human skins as well as keratinocyte strains from human skin (SV40-HSK) and newborn Balb/c mouse skin (Pam 212) were exposed to UVB irradiation.
The sensitivity of HS-K and NB1RGB cells to UVB irradiation was similar; those of SV40-HSK and Pam 212 cells were two- and six-fold as sensitive to UVB irradiation as HS-K cells, respectively. The HS-K cells contained the greatest cellular reduced form of glutathione (GSH) levels compared to the three other skin cells: the levels were 13-, 7- and 6-fold of those in NB1RGB, SV40-HSK and Pam 212 cells, respectively. These results indicated that the sensitivity of skin cells to UVB irradiation was not always associated with their endogenous GSH levels. In particular, despite the fact that NB1RGB cells contained a relatively small amount of GSH, they were less sensitive to UVB irradiation.
NB1RGB cells contained 4–30 times more MT than those in other skin cells examined. The sulfhydryl residues of MT molecules in the NB1RGB cells were estimated to be mostly unoccupied by metals, suggesting they act in a similar way to those of GSH. Moreover, NB1RGB cells in which the MT content was elevated by dexamethasone (1 μ M ) or Zn²⁺ (7 μg/mL) treatment were more resistant to UVB irradiation than nontreated ones.
These results suggest that, at least in neonatal human skin fibroblasts, MT may play a role in protection against UVB irradiation.     

Phase equilibria of AgI-AgBr system

The phase diagram and the heat of transition of AgI-AgBr system have been determined by using the differential scanning calorimetry (DSC) with the help of X-ray diffraction patterns. It has been verified that the miscibility gap between β-AgI-type solid solution and AgBr-type one depends on the thermal history of the sample. From the thermodynamic point of view, it is likely that the variation of transition temperature with composition suggests the change of correlation among silver ions in superionic conducting phase.     

The local time of self-intersections of Brownian motions as generalized Brownian functionals

In this Letter, we show that the local time of self-intersections ofd-dimensional Brownian motions is a generalized Brownian functional in the sense of Hida.     

1-Phosphacephalosporin. I. Synthesis of racemic 7-unsubstituted-1-phosphadethia-3-cephem 1-oxides

The novel unnatural ring system, 1-phosphacephalosporin, was synthesized for the first time from 4-acetoxy-2-azetidinone.