Fluorinated Copolymer-Oxide Hybrids

A fluorinated copolymer/metal oxide hybrid is fabricated by refluxing a high hydroxyl content fluorinated copolymer with tetraethoxysilane. The resulting organic-inorganic hybrids are transparent throughout the entire compositional range if processed with HCl as a catalyst. They exhibit a continuous variation in hardness, hydrophobicity, and abrasion resistance, intermediary between the properties of the pure polymer and that of a silica gel. The catalyst has a strong influence over the microstructure of the hybrid. ²⁹Si MAS-NMR indicates the presence of highly condensed silica clusters within the structure of the hybrid. If a Nd(III) alkoxide is used instead of TEOS, a Nd ³⁺-doped fluoropolymer is obtained. These results indicate that when a fluorinated copolymer contains groups amenable to hydrolysis and condensation, cross-linking with a metal alkoxide is possible, leading to an interesting families of hybrids.     

On the physical interpretation of Heywood and Redhead's algebraic impossibility theorem

Heywood and Redhead's 1983 algebraic (Kochen-Specker type) impossibility proof, which establishes the inconsistency of a broad class of contextualized local realistic theories, assumes two locality conditions and two auxiliary assumptions. One of those auxiliary conditions, FUNC^*, has been called a physically unmotivated,ad hoc formal constraint.In this paper, we derive Heywood and Redhead's auxiliary conditions from physical assumptions. This allows us to analyze which classes of hidden-variables theories escape the Heywood-Redhead contradiction. By doing so, we hope to clarify the physical and philosophical ramifications of the Heywood-Redhead proof. Most current hidden-variables theories, it turns out, violate Heywood and Redhead's auxiliary conditions.1. See Redhead [1], pp. 133–136, for a complete discussion.2. Arthur Fine first pointed out the implicit reliance on FUNC^*, and proved FUNC^* to be both consistent with and independent of the Value Rule.3. LetA=_ia_i P _i andB=_jb_j P_j be spectral resolutions ofA andB. Then <A,B> is the observable associated with maximal operatorR=_ijf_ij P _iP_j, where f_ij=F(a_i,b_j), and where function F is 1:1.4. Heywood and Redhead's versions of these conditions employ equivalence-class notation to specify the ontological context. {<D,E>}={R} refers to the equivalence class of all possible <D,E> formed by using different F functions (cf. Footnote 3). Clearly, such notation assumes that ifR andR are two distinct commuting maximal operators formed as described in Fn. 3 fromD andE using two different F(d_i,e_j) functions, then [Q]^t _(R)(R)=[Q]^t _(R)(R), so that [Q]^t _{R}(R) is uniquely defined.Heywood and Redhead never rely upon this assumption in their proof, however. It is easily checked that a Heywood-Redhead contradiction follows from my non-equivalence class versions of OLOC, ELOC, VR, and FUNC^*. Therefore, I will not use equivalence class notation.5. Here I denote by µ_R the composite state of all the apparatuses needed to measure R. So µ_R may represent the state of more than one device.6 This is because in a hidden-variables framework, quantum mechanical probabilities are a weighted average of the underlying hidden-variables probabilities.7. This argument resembles a proof given by Fine [8].8. Recall from theorem 1 that ifQ=f(R), then for all quantum states , P_(t)(Qf(r), R=r)=0.     

Fundamental studies of mixed-gas inductively coupled plasmas

The effects of adding foreign gases to the central-gas flow or the intermediate-gas flow of an argon inductively coupled plasma are presented. In particular, the influence of up to 16.7% added helium, nitrogen or hydrogen on radially-resolved electron number density, electron temperature, gas-kinetic temperature and calcium ion emission profiles is examined. It is shown that these gases affect not only the fundamental parameters and bulk properties of the plasma, but also how energy is coupled and transported through the discharge and how that energy interacts with the sample. For example, added helium causes an increase in the gas-kinetic temperature, most likely due to the higher thermal conductivity of helium compared to argon but, in general, does not appear to affect significantly either the electron temperature or electron concentration. The shift in the calcium ion emission profile towards lower regions in the discharge with added helium may be attributable to higher droplet desolvation and particle vaporization rates. In contrast, the addition of nitrogen or hydrogen to an Inductively Coupled Argon Plasma (Ar ICP) results in dramatic changes in all three fundamental plasma parameters: electron number density, electron temperature, and gas-kinetic temperature. The net effect of these molecular gases (N₂ or H₂) on calcium ion emission and on the fundamental plasma parameters is shown to be dependent on the amount of gas added to the plasma and whether the gas is introduced as part of the central- or intermediate-gas flow. In general, nitrogen added to the central-gas flow causes a significant reduction in the number of electrons throughout most of the discharge (over an order of magnitude in certain regions), mainly in the central and upper zones of the ICP. A drop of 3000–5000 K in the central channel electron temperature and a smaller drop in the gas-kinetic temperature are also observed when N₂ is added to the central-gas flow. In contrast, the introduction of nitrogen in the intermediate flow causes about a 1 × 10¹⁵ electrons cm⁻³ increase in the electron concentration in the low, toroidal regions of the plasma and an increase in the gas-kinetic temperature of around 1000 K throughout most of the discharge. As seen with the addition of nitrogen to the central-gas flow, the electron temperature is found to increase in the toroidal zones of the plasma when N₂ is added to the intermediate flow. These combined effects cause a 20-fold depression in the calcium ion emission intensity only a 1.7-fold depression when N₂ is added to the central- or intermediate-gas flows, respectively. On the other hand, hydrogen causes a depression in the electron concentration in the upper areas of the plasma when this gas is added to the central flow but increases the number of electrons in the same region when added to the intermediate flow. Hydrogen also causes a dramatic effect on the electron and gas-kinetic temperatures, significantly increasing both of these parameters throughout the discharge. An increase in the calcium ion emission intensity, accompanied by a downward shift, elongation and broadening of the calcium ion emission profile is also observed with H₂ addition.     

Origin and development of the International Confederation for Thermal Analysis (ICTA)

The history of ICTA, from its conception at the First International Conference on Thermal Analysis in Aberdeen, Scotland, in 1965 through the subsequent eight Conferences to the 10th ICTA Congress in Hatfield, England, in 1992, is outlined. Brief biographies of Past-Presidents are appended.     

Pinkment: a synthetic platform for the development of fluorescent probes for diagnostic and theranostic applications

Reaction-based fluorescent-probes have proven successful for the visualisation of biological species in various cellular processes. Unfortunately, in order to tailor the design of a fluorescent probe to a specific application (i.e. organelle targeting, material and theranostic applications) often requires extensive synthetic efforts and the synthetic screening of a range of fluorophores to match the required synthetic needs. In this work, we have identified Pinkment-OH as a unique “plug-and-play” synthetic platform that can be used to develop a range of ONOO⁻ responsive fluorescent probes for a variety of applications. These include theranostic-based applications and potential material-based/bioconjugation applications. The as prepared probes displayed an excellent sensitivity and selectivity for ONOO⁻ over other ROS. In vitro studies using HeLa cells and RAW 264.7 macrophages demonstrated their ability to detect exogenously and endogenously produced ONOO⁻. Evaluation in an LPS-induced inflammation mouse model illustrated the ability to monitor ONOO⁻ production in acute inflammation. Lastly, theranostic-based probes enabled the simultaneous evaluation of indomethacin-based therapeutic effects combined with the visualisation of an inflammation biomarker in RAW 264.7 cells.

Pinkment, a resorufin based ONOO⁻ selective and sensitive ‘plug and play’ fluorescence-based platform for in vitro and in vivo use, enables facile functionalisation for various imaging and theranostic applications.     

Duality Functors for Triple Vector Bundles

We calculate the group of dualization operations for triple vector bundles, showing that it has order 96 and not 72 as given in Mackenzie’s original treatment. The group is a nonsplit extension of S ₄ by the Klein group. Dualization operations are interpreted as functors on appropriate categories and are said to be equal if they are naturally isomorphic. The method set out here will be applied in a subsequent paper to the case of n-fold vector bundles.     

Phosphinoferrocenylaminophosphines as novel and practical ligands for asymmetric catalysis

[structure: see text] A new series of ligands with a novel phosphine-aminophosphine ligation design as depicted in structure 1 has been prepared on a ferrocenylethyl backbone. These BoPhoz ligands of structure 2 have afforded exceedingly high activity and enantioselectivity in the rhodium-catalyzed asymmetric hydrogenation of dehydro-alpha-amino acid derivatives, itaconic acids, and alpha-ketoesters. These air-stable ligands are readily prepared from cost-effective and non-pyrophoric intermediates.