Mechanism and kinetics of dithiobenzoate‐mediated RAFT polymerization. I. The current situation

Investigations into the kinetics and mechanism of dithiobenzoate‐mediated Reversible Addition–Fragmentation Chain Transfer (RAFT) polymerizations, which exhibit nonideal kinetic behavior, such as induction periods and rate retardation, are comprehensively reviewed. The appreciable uncertainty in the rate coefficients associated with the RAFT equilibrium is discussed and methods for obtaining RAFT‐specific rate coefficients are detailed. In addition, mechanistic studies are presented, which target the elucidation of the fundamental cause of rate retarding effects. The experimental and theoretical data existing in the literature are critically evaluated and apparent discrepancies between the results of different studies into the kinetics of RAFT polymerizations are discussed. Finally, recommendations for further work are given. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5809–5831, 2006     

Constructive proposals for QFT based on the crossing property and on lightfront holography

The recent concept of modular localization of wedge algebras suggests two methods of classifying and constructing QFTs, one based on particle-like generators of wedge algebras using on-shell concepts (S-matrix, formfactors: crossing property) and the other using the off-shell simplification of lightfront holography (chiral theories). The lack of an operator interpretation of the crossing property is a serious obstacle in on-shell constructions. In special cases, one can define a “masterfield” whose connected formfactors constitute an auxiliary thermal QFT for which the KMS cyclicity equation is identical to the crossing property of the formfactors of the master field. Further progress is expected to result from a conceptual understanding of the role of on-shell concepts as particle states and the S-matrix within the holographic lightfront projection.     

Kinetics of the initial steps of G protein-coupled receptor-mediated cellular signaling revealed by single-molecule imaging.

We report on an in vivo single-molecule study of the signaling kinetics of G protein-coupled receptors (GPCR) performed using the neurokinin 1 receptor (NK1R) as a representative member. The NK1R signaling cascade is triggered by the specific binding of a fluorescently labeled agonist, substance P (SP). The diffusion of single receptor-ligand complexes in plasma membrane of living HEK 293 cells is imaged using fast single-molecule wide-field fluorescence microscopy at 100 ms time resolution. Diffusion trajectories are obtained which show intra- and intertrace heterogeneity in the diffusion mode. To investigate universal patterns in the diffusion trajectories we take the ligand-binding event as the common starting point. This synchronization allows us to observe changes in the character of the ligand-receptor-complex diffusion. Specifically, we find that the diffusion of ligand-receptor complexes is slowed down significantly and becomes more constrained as a function of time during the first 1000 ms. The decelerated and more constrained diffusion is attributed to an increasing interaction of the GPCR with cellular structures after the ligand-receptor complex is formed.     

(17) O NMR study of the intrinsic magnetic susceptibility and spin dynamics of the quantum kagome antiferromagnet ZnCu3(OH)(6)Cl(2)

We report, through 17O NMR, an unambiguous local determination of the intrinsic kagome lattice spin susceptibility as well as that created around nonmagnetic defects arising from natural Zn/Cu exchange in the S=1/2 (Cu2+) herbertsmithite ZnCu3(OH)6Cl2 compound. The issue of a singlet-triplet gap is addressed. The magnetic response around a defect is found to markedly differ from that observed in nonfrustrated antiferromagnets. Finally, we discuss our relaxation measurements in the light of Cu and Cl NMR data and suggest a flat q dependence of the excitations.     

Easy-axis kagome antiferromagnet: local-probe study of Nd3Ga5SiO14

We report a local-probe investigation of the magnetically anisotropic kagome compound Nd3Ga5SiO14. Our zero-field muon spin relaxation (muSR) results provide direct evidence of a fluctuating collective paramagnetic state down to 60 mK, supported by a wipeout of the Ga nuclear magnetic resonance (NMR) signal below 25 K. At 60 mK a dynamics crossover to a much more static state is observed by muSR in magnetic fields above 0.5 T. Accordingly, the NMR signal is recovered at low T above a threshold field, revealing a rapid temperature and field variation of the magnetic fluctuations.     

Structure and photoelectrical properties of SiO2/Si/SiO2 single quantum wells prepared under ultrahigh vacuum conditions

SiO₂/Si/SiO₂ single quantum wells (QWs) were prepared under ultrahigh vacuum conditions in order to study their structural, chemical and photoelectrical properties with respect to a possible application in photovoltaic devices. Amorphous silicon (a-Si) layers (thickness <10 nm) were deposited onto quartz glass (SiO₂) substrates and subsequently oxidized with neutral atomic oxygen at moderate temperatures of 600 °C. Under these conditions, the formation of suboxides is mostly suppressed and abrupt Si/SiO₂ interfaces are obtained. Crystallization of a-Si QWs requires temperatures as high as 1000 °C resulting in a nanocrystalline structure with a small amorphous fraction. The spectral dependence of the internal quantum efficiency of photoconductivity correlates well with the nanocrystalline structure and yields mobility lifetime products of <10^?7 cm² V^?1. This rather low value points towards a strong influence of Si/SiO₂ interface states on the carrier mobility and the carrier lifetime in Si QWs. Electronic passivation of interface states by subsequent hydrogen treatment in forming gas enhances the internal quantum efficiency by nearly one order of magnitude.     

Triplet-Induced Lesion Formation at CpT and TpC Sites in DNA

UV irradiation induces DNA lesions particularly at dipyrimidine sites. Using time-resolved UV pump (250 nm) and mid-IR probe spectroscopy the triplet pathway of cyclobutane pyrimidine dimer (CPD) formation within TpC and CpT sequences was studied. The triplet state is initially localized at the thymine base but decays with 30 ns under formation of a biradical state extending over both bases of the dipyrimidine. Subsequently this state either decays back to the electronic ground state on the 100 ns time scale or forms a cyclobutane pyrimidine dimer lesion (CPD). Stationary IR spectroscopy and triplet sensitization via 2′-methoxyacetophenone (2-M) in the UVA range shows that the lesions are formed with an efficiency of approximately 1.5 %. Deamination converts the cytosine moiety of the CPD lesions on the time scale of 10 hours into uracil which gives CPD(UpT) and CPD(TpU) lesions in which the coding potential of the initial cytosine base is vanished.