The role of stable nitroxyl radical precursors as antioxidants in polyolefins

Various 2,2,6,6-tetramethyl piperidines and their N-alkyl derivatives of stable nitroxyl radical precursors containing acrylic(s) and methacrylic(s) groups were reactively processed in the presence of a peroxide as bound-antioxidant masterbatches for polyolefin stabilisation. It was found that grafting of the antioxidant monomers onto the polymer backbone was inevitably in competition with homopolymerisation of the monomers as well as melt degradation of the polymer and other side reactions. As previously reported, binding efficiency of bisacrylic nitroxyl precursor was maximum due to formation of unextractable homopolymer of the antioxidant. On the other hand, the binding efficiency of monoacrylic derivatives was low and the homopolymers were found extractable, which suggests that the bound monoacrylic derivatives are entirely grafted onto the polyolefin backbone. Application of bis and tri-functional coagents gave improved binding efficiency of the monoacrylic monomers. This may be due to copolymerisation of the antioxidants with the coagents and grafting of the copolymers onto the polymer backbone. Comparison of photostabilising activity of the fully extracted bound antioxidants to those of the corresponding unbound analogous showed lower results for the former. However, thermal stabilising activity of the bound antioxidants was higher than that of the unbound analogous due to better substantivity. Analysis using physical techniques and GPC for molecular weight distribution of masterbatches containing the bound monoacrylic antioxidants showed formation of high molecular weight products. Model reaction of a secondary amine derivative in liquid hydrocarbon and analysis of the product using FTIR and NMR spectroscopy indicated a possibility of side reaction, i.e. involvement of the amine active group (>N-H) of the antioxidant in the binding process to form the high molecular weight product. Implementation of various N-alkylated derivatives did not inhibit the side reaction. The photostabilising activity of the bound-antioxidants can be improved when applied in conjunction with small amounts of a benzophenone uv-stabiliser. The synergistic stabilising activity, however, was diminished when the uv-stabiliser was removed from the system during the service time. Nitroxyl precursors containing methacrylic group(s) gave lower binding efficiency than the corresponding acrylic derivatives. Reversible deploymerisation of the grafted methacrylic antioxidants may be responsible for this. Bis and tris-acrylic coagents improved the binding efficiency, and the presence of methacrylic group improved stabilising activity of the antioxidants. N-methyl derivatives were found to exhibit better stabilising activity than their parent secondary amine derivatives.

Approximating differentiable relationships between delay embedded dynamical systems with radical basis functions

This thesis is about the study of relationships between experimental dynamical systems. The basic approach is to fit radial basis function maps between time delay embeddings of manifolds. We have shown that under certain conditions these maps are generically diffeomorphisms, and can be analysed to determine whether or not the manifolds in question are diffeomorphically related to each other. If not, a study of the distribution of errors may provide information about the lack of equivalence between the two. The method has applications wherever two or more sensors are used to measure a single system, or where a single sensor can respond on more than one time scale: their respective time series can be tested to determine whether or not they are coupled, and to what degree. One application which we have explored is the determination of a minimum embedding dimension for dynamical system reconstruction. In this special case the diffeomorphism in question is closely related to the predictor for the time series itself. Linear transformations of delay embedded manifolds can also be shown to have nonlinear inverses under the right conditions, and we have used radial basis functions to approximate these inverse maps in a variety of contexts. This method is particularly useful when the linear transformation corresponds to the delay embedding of a finite impulse response filtered time series. One application of fitting an inverse to this linear map is the detection of periodic orbits in chaotic attractors, using suitably tuned filters. This method has also been used to separate signals with known bandwidths from deterministic noise, by tuning a filter to stop the signal and then recovering the chaos with the nonlinear inverse. The method may have applications to the cancellation of noise generated by mechanical or electrical systems. In the course of this research a sophisticated piece of software has been developed. The program allows the construction of a hierarchy of delay embeddings from scalar and multi-valued time series. The embedded objects can be analysed graphically, and radial basis function maps can be fitted between them asynchronously, in parallel, on a multi-processor machine. In addition to a graphical user interface, the program can be driven by a batch mode command language, incorporating the concept of parallel and sequential instruction groups and enabling complex sequences of experiments to be performed in parallel in a resource-efficient manner.

A spectroscope study of some semiquinone radical ions

The effect of substituents on the value of the oxidation potential of quinones is reviewed and attempts to prepare substituted diphenoquinones with high oxidation potentials are reported. Attempts to characterise the mechanism of addition and substitution in diphenoquinones by identifying the products of the Thiele acetylation of diphenoquinone are reported. The reaction proved most efficient when the incoming acetylinium ion is directed by substituents in the diphenoquinone. A 1,8-addition to diphenoquinone is reported and characterised by isolating the products of the reaction between acetyl chloride and diphenoquinone, with perchloric acid as catalyst. The alternating linewidth effects observed in e.s.r.spectra are discussed and applied to account for such effects observed in the e.s.r.spectra of diphenosemiquinone anion and cation radicals. The spectra are analysed and the intramolecular processes producing these effects are discussed. A dianion diradical where intramolecular rotation about the 1 - 1' bond is restricted is produced by the oxidation of 2,2' ,4,4' -tetra hydroxybiphenyl. Previous studies of diphenosemiquinone anions are reviewed and alkylated diphenosemiquinone anion are produced by the reduction of the parent quinone with potassium hydroxide solution, the resulting radical being stabilised by the presence of pyridine. A qualitative interpretation of the solvent-ion effect in alkylated diphenosemiquinone anions is given. Diphanosemiquinone cation radicals are reviewed and previous studies are re-examined.

Analysis of radicals and radical reaction products in cell signalling and biomolecular damage:the long hard road to gold-standard measures

The field of free radical biology and medicine continues to move at a tremendous pace, with a constant flow of ground-breaking discoveries. The following collection of papers in this issue of Biochemical Society Transactions highlights several key areas of topical interest, including the crucial role of validated measurements of radicals and reactive oxygen species in underpinning nearly all research in the field, the important advances being made as a result of the overlap of free radical research with the reinvigorated field of lipidomics (driven in part by innovations in MS-based analysis), the acceleration of new insights into the role of oxidative protein modifications (particularly to cysteine residues) in modulating cell signalling, and the effects of free radicals on the functions of mitochondria, extracellular matrix and the immune system. In the present article, we provide a brief overview of these research areas, but, throughout this discussion, it must be remembered that it is the availability of reliable analytical methodologies that will be a key factor in facilitating continuing developments in this exciting research area.

Radical or not so radical? Tactical variation in core policy formation by the Front National

Starting from a number of general tenets about radical political parties, this article examines the Front National (FN) in relation to its core policy issue of immigration. To what extent has FN immigration policy been defined from the outset by its radicalism? Has that radicalism been constant or variable over time? And how far can a reciprocal influence be detected between the FN and the center Right in immigration policy formulation? Focusing on election campaigns, manifestos, and key moments in the FN's evolution, the article assesses how the party has tailored its radicalism to contextual factors and tactical considerations. It reveals an FN less bound to a fixed policy and more ready to seek accommodation (with circumstance, public opinion, or the center Right) than is generally acknowledged. Conversely, it also assesses how the FN's mobilization of strong support on the immigration issue has had radicalizing effects on the center Right. The article concludes by considering whether the change of leadership in January 2011 might confine the FN to the radical Right or see it adopt a more center-oriented course.

Racing for radical innovation

How motorsport companies harness network diversity for discontinuous innovation.

Racing for radical innovation:how motorsport companies harness network diversity for discontinuous innovation

The motorsport industry is a significant part of the UK economy. According to industry estimates approximately 4,500 companies are involved in the UK Motorsport and Performance Engineering Industry and its wide-ranging support activities. The industry has an annual turnover of £6.0 billion, and contributes £3.6 billion worth of exports. The Motorsport Industry Association estimates that the support side of the sector alone "involving events management, public relations, marketing, sponsorship and a host of other support functions" accounts for approximately £1.7 billion of the yearly industry total. And in terms of employment, UK Motorsport supports 38,500 full and part-time jobs, including 25,000 engineers.

When cost-efficient technologies meet politics:a case study of radical wireless network implementation

Cost efficiency has been a dominant perspective in the traditional IT literature. However, in complex technology and business environment, the widely recognized cost efficient assumption of information technology has been increasingly challenged. Drawing from a case study of wireless network implementation situated in a politically sensitive workplace, this paper provided practice insights for IT managers in today’s networked economy. More specifically, stories experienced in the case study illustrated that despite well-calculated cost efficiency of wireless network infrastructure, the radical implementation process in the case organization encountered enormous challenges and opposition due to the fact that administrators failed to consider various stakeholders’ positions and interests. Eventually, the implementation objectives and outcome were considerably undermined. Implications from this empirical case research reemphasized the significance of understanding political forces situated in any business environment where different stakeholders hold conflicting interests. Lessons learned from the case story further encouraged IT managers and policy makers to better strategize emerging information technology in general and wireless networks in particular as the whole global society and business environment are increasingly facing an emerging wireless world.

Managing radical ICT implementation and politics: A case study of cost-efficient wireless networks

This paper analyzes a case study of wireless network implementation in a politically sensitive environment and seeks to gain practical insights for IT managers in today’s networked economy. The case evolved around an urgent decision to implement wireless networks that were a radical replacement for the existing wired network infrastructure. Although the wireless network infrastructure was well calculated as being considerably cost-efficient, inexperienced administrators and IT department failed to consult various involved stakeholders. Consequently, unintended results of wireless network implementation entangled with the cost efficiency of technology outcome and in turn undermined the objectives and achievement of the initial project plan. Drawing from social perspectives, this case study challenges traditionally dominant perspectives of technology efficiency and summarizes several lessons that could help IT managers and policy makers to better strategize ICT in general, and wireless networks in particular.

Fuzzy assessment of performance of a decision making units using DEA:a non-radical approach

Data Envelopment Analysis (DEA) is recognized as a modern approach to the assessment of performance of a set of homogeneous Decision Making Units (DMUs) that use similar sources to produce similar outputs. While DEA commonly is used with precise data, recently several approaches are introduced for evaluating DMUs with uncertain data. In the existing approaches many information on uncertainties are lost. For example in the defuzzification, the a-level and fuzzy ranking approaches are not considered. In the tolerance approach the inequality or equality signs are fuzzified but the fuzzy coefficients (inputs and outputs) are not treated directly. The purpose of this paper is to develop a new model to evaluate DMUs under uncertainty using Fuzzy DEA and to include a-level to the model under fuzzy environment. An example is given to illustrate this method in details.

Detection of phosphatidylserine with a modified polar head group in human keratinocytes exposed to the radical generator AAPH

Phosphatidylserine (PS) is preferentially located in the inner leaflet of the cell membrane, and translocation of PS oxidized in fatty acyl chains to the outside of membrane has been reported as signaling to macrophage receptors to clear apoptotic cells. It was recently shown that PS can be oxidized in serine moiety of polar head-group. In the present work, a targeted lipidomic approach was applied to detecting OxPS modified at the polar head-group in keratinocytes that were exposed to the radical generator AAPH. Glycerophosphoacetic acid derivatives (GPAA) were found to be the major oxidation products of OxPS modified at the polar head-group during oxidation induced by AAPH-generated radicals, similarly to previous observations for the oxidation induced by OH radical. The neutral loss scan of 58Da and a novel precursor ion scan of m/z 137.1 (HOPO3CH2COOH) allowed the recognition of GPAA derivatives in the total lipid extracts obtained from HaCaT cells treated with AAPH. The positive identification of serine head group oxidation products in cells under controlled oxidative conditions opens new perspectives and justifies further studies in other cellular environments in order to understand fully the role of PS polar head-group oxidation in cell homeostasis and disease.