Rapidly self-deoxygenating controlled radical polymerization in water via in situ disproportionation of Cu(i)

Rapidly self-deoxygenating Cu-RDRP in aqueous media is investigated. The disproportionation of Cu(i)/Me₆Tren in water towards Cu(ii) and highly reactive Cu(0) leads to O₂-free reaction environments within the first seconds of the reaction, even when the reaction takes place in the open-air. By leveraging this significantly fast O₂-reducing activity of the disproportionation reaction, a range of well-defined water-soluble polymers with narrow dispersity are attained in a few minutes or less. This methodology provides the ability to prepare block copolymers via sequential monomer addition with little evidence for chain termination over the lifetime of the polymerization and allows for the synthesis of star-shaped polymers with the use of multi-functional initiators. The mechanism of self-deoxygenation is elucidated with the use of various characterization tools, and the species that participate in the rapid oxygen consumption is identified and discussed in detail.

The rapidly self-deoxygenating Cu-RDRP in aqueous media is investigated.     

Some symmetry-induced isotope effects in the kinetics of recombination reactions

Symmetry-induced isotope effects in recombination and collision-induced dissociation reactions are discussed. Progress on understanding the anomalous isotope effects in ozone is reviewed. Then, calculations are performed for the simpler reaction xNe+yNe+H<-->xNeyNe+H, where x and y label either identical or different isotopes. The atomic masses in the model are chosen so that symmetry is the only difference between the systems. Starting from a single potential energy surface, the properties of the bound, quasibound, and continuum states of the neon dimer are calculated. Then, the vibration rotation infinite order sudden approximation is used to calculate cross sections for all possible inelastic and dissociative processes. A rate constant matrix that exactly satisfies detailed balance is constructed. It allows recombination to occur both via direct three-body collisions and via tunneling into the quasibound states of the energy transfer mechanism. The eigenvalue rate coefficients are determined. Significant isotope effects are clearly found, and their behavior depends on the pressure, temperature, and mechanism of the reaction. Both spin statistics and symmetry breaking produce isotope effects. Under most conditions the breaking of symmetry enhances the rates, but a wide spectrum of effects is observed; they range from isotope effects with a normal mass dependence to huge, mass-independent isotope effects to cancellation and even to reversal of the isotope effects. This is the first calculation of symmetry-induced isotope effects in recombination rates from first principles. The relevance of the present effects to ozone recombination is discussed.     

A mathematical analysis of the bjerrum function for the stepwise equilibrium model

A mathematical analysis of the Bjerrum function is carried out. This function arises from the Stepwise Equilibrium Model, which is used to describe successive complex formation in systems consisting of free metal ion, free ligand, and all theML _i complexes that can form in solution. The appropriate root of the Bjerrum polynomial allows the determination of the concentrations of all species present in solution, given the initial concentrations of metal and of ligand, and the equilibrium constants governing the system. It is proved that there is only one positive root of the Bjerrum polynomial, and thus that only a single equilibrium state can exist. It is also shown that the positive root of the Bjerrum polynomial can be reliably obtained by Newton's method, but only if the initialization point is properly chosen, and that the initial concentrationL of ligand is the optimum such point. Finding this root is a calculation that typically must be carried out at each iteration in nonlinear least squares procedures for determining equilibrium constants. Finally, the necessary mathematical analysis is carried out to determine the optimum initial concentrations of metal and lgand which maximize the resulting concentration of a particularML _i complex.     

A microtiter plate assay for the detection of inhibitors of the Na +, K + -ATpase

A rapid microtiter plate assay for the detection of inhibitors of the Na⁺, K⁺-ATPase has been developed. The assay is based on the measurement of inorganic phosphate released from the substrate, ATP, and has been designed to be carried out in the individual wells of a microtiter plate. Since the production of inorganic phosphate is determined colorimetrically, multiple samples can be tested simultaneously using a microtiter plate reader. This microtiter plate assay is particularly useful for screening large numbers of samples, such as microbial culture supernatants.     

Recent contributions of high resolution gas chromatography to the analysis of environmental hydrocarbons

Analyses of hydrocarbon fractions from different areas of the marine environment are described to illustrate the possibilities and limitations of high resolution gas chromatography (HRGC) in the analysis of environmental samples. Examples are given of dissolved, particulate, and sedimentary hydrocarbons and organochlorine compounds; the importance of an adequate sampling of the marine environment is stressed. HR chromatographic profiles obtained in two columns of low and high polarity (SE-52 and PEG 20M) permit the sources and transport pathways of both natural and anthropogenic hydrocarbons to be traced. Analysis of tissues of marine mammals, which metabolize or excrete many of the biogenic and petrogenic hydrocarbons present in other areas of the marine environment, may provide an opportunity to obtain relatively clean profiles of many anthropogenic compounds of interest. The plotting of mass chromatograms from data compiled by COM-GC-MS remains the most appropriate method for the conclusive indentification of these compounds.     

Cucurbit[6]uril pseudorotaxanes: distinctive gas-phase dissociation and reactivity

Cucurbit[6]uril forms a doubly charged complex with 1,4-butanediammonium cation that is observed using electrospray ionization Fourier transform mass spectrometry. Such 1:1 complexes are not observed for the smaller cucurbit[5]uril, which forms a 2:1 ammonium:cucurbituril complex instead. The 1:1 complex with cucurbit[6]uril is difficult to fragment via collisional activation; when it does fragment, both breakup of the cucurbituril cage and loss of the amine are observed. Further, the complex reacts with tert-butylamine via slow adduction. In contrast, nonrotaxane analogues (such as doubly charged 2:1 complexes of either protonated 1,4-butanediamine or protonated ethylenediamine with cucurbit[6]uril) fragment via easy loss of the intact amine upon collisional activation and react with tert-butylamine via rapid displacement of the original amine. On the basis of stoichiometry, fragmentation behavior, and reactivity, we conclude that the doubly charged complex of cucurbit[6]uril with 1,4-butanediammonium is a gas-phase pseudorotaxane.     

Time-resolved spectroscopic studies of B(12) coenzymes: a comparison of the primary photolysis mechanism in methyl-, ethyl-, n-propyl-, and 5'-deoxyadenosylcobalamin.

An ultrafast transient absorption study of the primary photolysis of ethyl- and n-propylcobalamin in water is presented. Data have been obtained for two distinct excitation wavelengths, 400 nm at the edge of the UV gamma-band absorption, and 520 nm in the strong visible alphabeta-band absorption. These data are compared with results reported earlier for the B(12) coenzymes, methyl- and adenosylcobalamin. The data obtained for ethylcobalamin and n-propylcobalamin following excitation at 400 nm demonstrate the formation of one major photoproduct on a picosecond time scale. This photoproduct is spectroscopically identifiable as a cob(II)alamin species. Excitation of methyl-, ethyl-, and n-propylcobalamin at 520 nm in the low-lying alphabeta absorption band results in bond homolysis proceeding via a bound cob(III)alamin MLCT state. For all of the cobalamins studied here competition between geminate recombination of caged radical pairs and cage escape occurs on a time scale of 500 to 700 ps. The rate constants for geminate recombination in aqueous solution fall within a factor of 2 between 0.76 and 1.4 ns(-1). Intrinsic cage escape occurs on time scales ranging from 相似文献