Influence of added salts on the cage escape yields in the photoredox quenching of Ru(bpy)2+3 excited states

The influence of electrolytes on the photoredox kinetics and cage escape yields of redox products (π_redox) in the quenching of Ru(bpy)^2+*₃ by methylviologen (MV²⁺), Tl^III and Hg^II have been investigated. For all three quenchers π_redox appears to be strongly dependent on the nature of the anion. Photoelectrochemical cells based on the latter systems are described.     

Visible Light Induced Water Cleavage in CdS Dispersions Loaded with Pt and RuO2, Hole Scavenging by RuO2

Illumination of aqueous CdS dispersions loaded with Pt and RuO₂ by visible light produces hydrogen and oxygen in stoichiometric proportion. No degradation of the photocatalyst is noted after 60 h of irradiation time. The RuO₂ deposit on the particle surface greatly accelerates the transfer of holes from the semiconductor valence band to the aqueous solution thus inhibiting photocorrosion.     

Characterization of colloidal hematite particle shape and dispersion behavior

An elliptically polarized light scattering (EPLS) technique for the size and shape characterization of ellipsoidal hematite particles is presented. The hematite particles are synthesized by aging aqueous FeCl(3) or Fe(NO(3))(3) solutions at 100 degrees C. Different reaction conditions create particles of aspect ratios between 1 (spherical) and 8 (elongated). Cross-sectional diameter and aspect ratio are observed as a function of reaction (aging) time. Growth of the elongated particles, as well as their fractal aggregation behavior, is characterized using EPLS and comparisons are made with photon correlation spectroscopy and TEM measurements.     

Biomimetic pH/redox dual stimuli‐responsive zwitterionic polymer block poly(L‐histidine) micelles for intracellular delivery of doxorubicin into tumor cells

A series of pH/redox dual stimuli‐responsive poly(2‐methacryloyloxyethyl phosphorylcholine)₂₅‐block‐poly(l ‐histidine)_n (p[MPC])₂₅‐b‐p[His]_n, n = 20, 35, 50, and 75) copolymers consisting of a pH‐responsive p(His)_n block and a biocompatible phospholipid analog p(MPC) block connected by a redox‐responsive disulfide linker have been synthesized. The block copolymers are self‐assembled into uniform micelles (～100 nm) in which doxorubicin (Dox) is efficiently encapsulated. The in vitro release profile shows an enhanced release of Dox at low pH (5.0) in 10 mM glutathione (GSH). The in vitro cell viability assays performed using various cell lines show that the blank hybrid micelles have no acute or intrinsic toxicity. A pH‐dependent cytotoxicity is observed with the Dox‐loaded micelles, especially at pH 5.0. Moreover, confocal microscopy images and flow cytometry results show the pH‐dependent cellular uptake of Dox‐loaded micelles. Therefore, the Dox‐loaded micelles can be considered a good candidate for cancer therapy. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2061–2070     

Stretching and collapse of neutral polymer layers under association with ionic surfactants

We provide experimental evidence for stretching and collapse of neutral polymer layers, already adsorbed at an oil-in-water interface, due to its interaction with surfactants. Upon stretching, the first interaction length (2L(0)) follows a power law dependence on surfactant concentration ( proportional, variant C(x)(s), where x approximately 0.5 for cationic surfactants) and collapses in the presence of salt, as a relatively weak power law (C(-y)(s), where y=0.17), in good agreement with brush length decay for polyelectrolyte brushes.     

Base catalyzed rearrangement of some bicyclic ketol acetates.

The ketol $\text{3a}$ and its acetate $\text{3b}$ when refluxed in methanolic potassium hydroxide (5%) were found to rearrange to 4-methyl-8-acetyl-5,6,7,8-tetrahydro-1-naphthol $\text{4}$. The epimeric acetate $\text{3c}$ also behaved likewise. A mechanism is suggested for the rearrangement.     

Effect of addition of a non-equidiffusional reactant to an equidiffusional diffusion flame

A Burke–Schumann (flame-sheet) formulation is developed for diffusion flames between a fuel and oxidiser with Lewis numbers of unity, subject to addition to the fuel and/or oxidiser stream of a different reactant for which the Lewis number differs from unity. This formulation is applied to laminar counterflow diffusion-flame experiments, reported here, in which hydrogen was added to either methane–nitrogen mixtures or oxygen–nitrogen mixtures at normal atmospheric pressure, with both feed streams at normal room temperature. Experimental conditions were adjusted to fix selected values of the stoichiometric mixture fraction and the adiabatic flame temperature, and the strain rate was increased gradually, maintaining the momentum balance of the two streams, until extinction occurred. At the selected sets of values, the strain rate at extinction was measured as a function of the hydrogen concentration in the fuel or oxidiser stream. The ratio of the fraction of the oxidiser flux that consumes hydrogen to the fraction that consumes fuel was calculated from the new Burke–Schumann formulation, and it was found that, within experimental uncertainty, the ratio of the extinction strain rate with hydrogen addition to that without was the same at any given value of this oxygen flux ratio, irrespective of whether the hydrogen was added on the fuel or oxidiser side. This experimental result was also in close agreement with computational predictions employing detailed chemistry. These results imply that differences in detailed hydrogen concentration profiles within the reaction zone have little or no influence on the chemical kinetics of extinction when the stoichiometric mixture fraction, the adiabatic flame temperature, and the proportion of oxygen that consumes the added fuel are fixed. This same correspondence may be expected to apply for other fuels and additives.     

On the power of white pebbles

We construct a family (G _p |p) of directed acyclic graphs such that any black pebble strategy forG _p requiresp ² pebbles whereas 3p+1 pebbles are sufficient when white pebbles are allowed.Supported by the National Science Foundation under contract no. DCR-8407256 and by the office of Naval Research under contract no. N0014-80-0517.