Heterograft copolymers of poly(ε‐caprolactone) prepared by combination of ATRA “grafting onto” and ATRP “grafting from” processes

This paper aims at reporting on the synthesis of a heterograft copolymer by combining the “grafting onto” process based on atom transfer radical addition (ATRA) and the “grafting from” process by atom transfer radical polymerization (ATRP). The statistical copolymerization of ε‐caprolactone (εCL) and α‐chloro‐ε‐caprolactone (αClεCL) was initiated by 2,2‐dibutyl‐2‐stanna‐1,3‐dioxepane (DSDOP), followed by ATRA of parts of the chlorinated units of poly(αClεCL‐co‐εCL) on the terminal double bond of α‐MeO,ω‐CH₂?CH? CH₂? CO₂‐poly(ethylene oxide) (PEO). The amphiphilic poly(εCL‐g‐EO) graft copolymer collected at this stage forms micelles as supported by dynamic light scattering (DLS) and transmission electron microscopy (TEM). The unreacted pendant chloro groups of poly(εCL‐g‐EO) were used to initiate the ATRP of styrene with formation of copolymer with two populations of randomly distributed grafts, that is PEO and polystyrene. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6015–6024, 2006     

Mass spectrometric investigation of bimolecular compounds

Two points involving molecular structure have been investigated using mass spectrometry. First, mass spectra have been obtained that indicate a rapid means for differentiating bimolecular compounds from other structural isomers. Second, the mass spectrometric method has been used to evaluate bonding within bimolecular compounds. Quinone compounds have been reacted with dhydroxybenzene compounds to produce quinhydrone products, and upon mass spectrometric analysis, the quinhydrones decompose to regenerate derivatives of the starting materials. Evaluation of the decomposition products suggests that the hydroxyl hydrogens are involved in a resonance structure, and while in symmetrical quinhydrones, the hydroxyl hydrogens are probably associated equally with each reactant, unsymmetrical quinhydrones generate an unbalanced electronic distribution that eliminates the complete equivalency of the hydrogens.     

Manipulations of listeners' echo perception are reflected in event-related potentials

To gain information from complex auditory scenes, it is necessary to determine which of the many loudness, pitch, and timbre changes originate from a single source. Grouping sound into sources based on spatial information is complicated by reverberant energy bouncing off multiple surfaces and reaching the ears from directions other than the source's location. The ability to localize sounds despite these echoes has been explored with the precedence effect: Identical sounds presented from two locations with a short stimulus onset asynchrony (e.g., 1-5 ms) are perceived as a single source with a location dominated by the lead sound. Importantly, echo thresholds, the shortest onset asynchrony at which a listener reports hearing the lag sound as a separate source about half of the time, can be manipulated by presenting sound pairs in contexts. Event-related brain potentials elicited by physically identical sounds in contexts that resulted in listeners reporting either one or two sources were compared. Sound pairs perceived as two sources elicited a larger anterior negativity 100-250 ms after onset, previously termed the object-related negativity, and a larger posterior positivity 250-500 ms. These results indicate that the models of room acoustics listeners form based on recent experience with the spatiotemporal properties of sound modulate perceptual as well as later higher-level processing.     

Negative thermal expansion in ZrW2O8: mechanisms, rigid unit modes, and neutron total scattering

The local structure of the low-temperature ordered phase of the negative thermal expansion (NTE) material has been investigated by reverse Monte Carlo (RMC) modeling of neutron total scattering data. We obtain, for the first time, quantitative measurements of the extent to which the and polyhedra move as rigid units, and we show that these values are consistent with the predictions of rigid unit mode theory. We suggest that rigid unit modes are associated with the NTE. Our results do not support a recent interpretation of x-ray-absorption fine structure spectroscopy data in terms of a larger rigid structural component involving the Zr-O-W linkage.     

Magnetic structure of MnO at 10 K from total neutron scattering data

Total neutron scattering data from a powdered sample of MnO collected at 10 K have been analyzed using the reverse Monte Carlo method to refine the nuclear and magnetic structure. The results give the first unambiguous assignment of the average magnetic structure. The magnetic moments are aligned ferromagnetically within (111) sheets with the magnetization vectors of alternate sheets along axes parallel and antiparallel to the <112> directions, albeit with a small modulated out-of-plane component. Small displacements of Mn and O (modulated with the same periodicity) accompany the magnetic ordering and both atomic and magnetic structures may be described in the monoclinic space group C2.     

From quantum disorder to magnetic order in an s=1/2 kagome lattice: a structural and magnetic study of herbertsmithite at high pressure

The structural and magnetic properties of deuterated herbertsmithite have been studied by means of neutron powder diffraction and magnetic susceptibility measurements in a wide range of temperatures and pressures. The experimental data demonstrate that a phase transition from the quantum-disordered spin-liquid phase to the long-range ordered antiferromagnetic phase with the Néel temperature T(N)=6 K is induced at P=2.5 GPa. The observed decrease of T(N) upon compression correlates with the anomalies in pressure behavior of Cu-O bond length and Cu-O-Cu bond angles. The reasons for the observed spin-freezing transition are discussed within the framework of the available theoretical models and the recent observation of the field-induced spin freezing.