Polypropylene as a reductive agent for dehalogenation of brominated organic compounds

A new method for debromination of organics by a reductive medium like polypropylene is investigated. The reaction is carried out in inert atmosphere to avoid rapid oxidation of the polymer. Through this detoxification procedure, hydrogen bromide and small brominated alkanes are formed. Experiments in closed ampoules are carried out with tetrabromobisphenol A, dibromophenol, pentabromodiphenyl ether, dichlorophenol and an oil formed by pyrolysis of printed circuit boards in the Haloclean® process. The reaction is examined under isothermal conditions in a temperature range between 300 and 400°C and a residence time between 10 and 30 min. Optimal conditions were found at 350°C and at a residence time of 20 min. As chlorinated phenols are not destroyed under these conditions, the process may be a valuable procedure to gain hydrogen bromide out of mixtures of halogenated feed materials. Also, under atmospheric pressure, a reaction between polypropylene and brominated compounds takes place as could be proved by thermogravimetric analysis. Bromobenzene has an accelerating effect on the rate of weight loss of the polymer, but at higher concentrations, it can also be slowed down. © 2003 Elsevier Ltd. All rights reserved.

Inositol polyphosphate-mediated iron transport in Pseudomonas aeruginosa

It has previously been shown that myo-inositol hexakisphosphate (myo- InsP6) mediates iron transport into Pseudomonas aeruginosa and overcomes iron-dependent growth inhibition. In this study, the iron transport properties of myo-inositol trisphosphate and tetrakisphosphate regio-isomers were studied. Pseudomonas aeruginosa accumulated iron (III) at similar rates whether complexed with myo-Ins(1,2,3)P3 or myo-InsP6. Iron accumulation from other compounds, notably D/L myo-Ins(1,2,4,5)P4 and another inositol trisphosphate regio-isomer, D-myo-Ins(1,4,5)P3, was dramatically increased. Iron transport profiles from myo-InsP6 into mutants lacking the outer membrane porins oprF, oprD and oprP were similar to the wild-type, indicating that these porins are not involved in the transport process. The rates of reduction of iron (III) to iron (II) complexed to any of the compounds by a Ps. aeruginosa cell lysate were similar, suggesting that a reductive mechanism is not the rate-determining step.

Metaphor and translation:Some implications of a cognitive approach

Metaphor has been widely discussed within the discipline of Translation Studies, predominantly with respect to translatability and transfer methods. It has been argued that metaphors can become a translation problem, since transferring them from one language and culture to another one may be hampered by linguistic and cultural differences. A number of translation procedures for dealing with this problem have been suggested, e.g., substitution (metaphor into different metaphor), paraphrase (metaphor into sense), or deletion. Such procedures have been commented on both in normative models of translation (how to translate metaphors) and in descriptive models (how metaphors have been dealt with in actual translations). After a short overview of how metaphor has been dealt with in the discipline of Translation Studies, this paper discusses some implications of a cognitive approach to metaphors for translation theory and practice. Illustrations from authentic source and target texts (English and German, political discourse) show how translators handled metaphorical expressions, and what effects this had for the text itself, for text reception by the addressees, and for subsequent discursive developments. © 2004 Elsevier B.V. All right reserved.

Is it all tough talking at the top? A post-structuralist analysis of the construction of gendered speaker identities of British business leaders within interview narratives

This paper uses a feminist post-structuralist approach to examine the gendered identities of a sample of British business leaders in Britain. While recent national surveys offer many material reasons why women are acutely under-represented as business leaders, the role of language is rarely addressed. This paper explores the ways in which ten senior women and men construct their sense of leadership identities through the medium of interview narratives. Drawing upon two poststructuralist models of analysis (Derrida’s 1987 theory of deconstruction and Bakhtin’s 1927/1981 concept of double-voiced discourse), the paper shows how both females and males are able to shift pragmatically between interwoven corporate discourses, which demand competing cultural allegiances from one moment to the next, allegiances constantly tested by the rapid change and uncertainty that characterise global business. While male leaders experience a relative freedom of movement between different cultural discourses, female leaders are circumscribed by negative and reductive representations of female speech and behaviour. In sum, senior women are required constantly to observe, review, police and repair their use of leadership language, which potentially undermines their confidence and authority as leaders.

The chemistry of British bituminous coals : an assessment of phase transfer catalysed reactions in the determination of coal structure

Three British bituminous coals, (Gedling, Cresswell, and Cortonwood Silkstone) were selected for study. Procedures were developed, using phase transfer catalysts (PTC's), to degrade the solvent insoluble fractions of the coals. PTC's are of interest because they have the potential to bring about selective high conversion reactions, under mild conditions, (often in the past, severe reaction conditions have had to be used to degrade the coals, this in turn resulted in the loss of much of the structural information). We have applied a variety of physical and chemical techniques to maximise the amount of structural information, these include, elemental analysis, 1H-NMR, 13C-CPMAS-NMR, GPC, GC-MS, FTIR spectroscopy, DRIFT spectroscopy, and gas adsorption measurements. The main conclusions from the work are listed below:- ( 1 ) PTC O-methylation; This reaction removes hydrogen bonds within the coal matrix by 'capping' the phenolic groups. It was found that the polymer-like matrix could be made more flexible, but not significantly more soluble, by O-methylation. I.E. the trapped or 'mobile' phase of the coals could be removed at a faster rate after this reaction had been carried out. ( 2 ) PTC Reductive and Acidic Ether Cleavage; The three coals were found to contain insignificant amounts of dialkyl and alkyl aryl ethers. The number of diaryl ethers could not be estimated, by reductive ether cleavage, (even though a high proportion of all three coals was solublised). The majority of the ethers present in the coals were inert to both cleavage methods, and are therefore assumed to be heterocyclic ethers. ( 3 ) Trif!uoroperacetic Acid Oxidation; This oxidant was used to study the aliphatic portions of the polymer-like macromolecular matrix of the coals. Normally this reagent will only solublise low rank coals, we however have developed a method whereby trifluoroperacetic acid can be used to degrade high rank bituminous coals. ( 4 ) PTC/Permanganate Oxidation; This reagent has been found to be much more selective than the traditional alkaline permanganate oxidation, with a lot more structural information being retained within the various fractions. This degradative method therefore has the potential of yielding new information about the molecular structure of coals.

The 'hard problem' and the quantum physicists. Part 2: modern times

This is the second part of a review of the work of quantum physicists on the ‘hard part’ of the problem of mind. After an introduction which sets the scene and a brief review of contemporary work on the neural correlates of consciousness (NCC) the work of four prominent modern investigators is examined: J.C. Eccles/Friedrich Beck; Henry Stapp; Stuart Hameroff/Roger Penrose; David Bohm. With the exception of David Bohm, all attempt to show where in the brain’s microstructure quantum affects could make themselves felt. It is reluctantly concluded that none have neurobiological plausibility. They are all instances, to paraphrase T.H. Huxley, of a beautiful hypothesis destroyed by ugly facts. David Bohm does not attempt to fit his new quantum physics to contemporary neurobiology but instead asks for a radical rethink of our conventional scientific paradigm. He suggests that we should look towards developing a ‘pan-experientialism’ or ‘dual-aspect monism’ where consciousness goes ‘all the way down’ and that the ‘hard problem’ is not soluble within the framework of ideas provided by ‘classical’ natural science.

The chemistry of some organotellurium compounds

Tbe formation of Pd(TeR)n and (CuTeR)n from the reaction between telluroesters and Pd(II)or Cu(II) suggested that these organa­tellurium reagents may be useful precursors of RTe- ligands in reactions with transition-metal substrates. Also the formation of telluronium salts Me2RTeI- from the reaction between telluroesters and methyl iodide, together with the above, confirm the cleavage of -cõ-Te bonds rather than -C-Te bonds. The formation of a carboxylic acid from the toluene solution of a ditelluride d palladium(O) complex in the presence of light oxygen (from air) is demonstrated. When the solvent employed is p-xylene an aldehyde is formed.The reaction proceeds via the free radical, RTeO, with Pd(PPh3)4 as a catalyst.It has also been shown that the oxidation of aldehydes to carboxylic acids is catalysed by ditelluride. Spin trapping experiments with PhCH=N(O)But (phenyl-t-butyl-nitrone) have provided evidence that the oxidative addition of an alkyl halide (RX=Mei, BunBr, BusecBr, ButBr, BrCH2-CH=CHCH2Br, and Br(CH2)4Br) to diphenyltelluride and reductive elimination of CH3SCN from Ph2(CH3)Te(NCS) proceeds via radical pathways. A mechanism is proposed for oxidative addition which involves the preformation of a charge transfer complex of alkyl halide and diphenyltelluride.The first step is the formation of a charge transfer complex, and the initial product of the oxidative addition is a "covalent" form of the tellurium(IV)compound. When the radical R is more stable, Ph2TeX2 may be the major tellurium(IV)product. The reaction of RTeNa (R=p-EtOC6H4, Ph) with organic dihalides X2(CH2)n (n=1,2,3,4) affords telluronium salts (n=3,4; X=Cl, Br) the nature of which is discussed.For n=l (X=Br, I)the products are formulated as charge transfer complexes of stoichiometry (RTe)2(CH2).CH2X2• For n=2, elimination of ditelluride occurs with the formation of an alkene. Some 125’Te Mõssbauer data are discussed and it is suggested that the unusually low value of 6 (7.58 mm.s-1 ) for  p-EtO.C6H4.Te)2(cH2)cH2Br2 relates to removal of 5's electronsfrom the spare pair orbltal via the charge transfer interaction. 125Te Mossbauer data for (p-EtO.C6H4)Te(CH2)4Br are typical of a tellurium (IV) compound and in particular ∇ is in the expected range for a telluronium salt. The product of the reaction of Na Te (C6H4.OEt), with 1,3-dibromopropane is, from the Mössbauer data, also a telluronium salt.

Cyclic and acyclic modifications of 5-aminoimidazole-4-carboxamide

The Introduction gives a brief resume' of the biologically important aspects of 5 -aminoimidazole -4 -carbozamide (1) and explores., in-depth, the synthetic routes to this imidazole. All documented reactions of 5 -aninoimidanole-4 -carboxamide are reviewed in detail, with particular emphasis on the preparation and subsequent coupling reactions of 5 –diazo-imidazole-4 -carboxamide (6). A series of thirteen novel amide 5-amino-2-arylazoimidazole-4-carboxamide derivatives (117-129) were prepared by the coupling of aryldiazonium salts with 5-aminoimidazole-4-carboxamide. Chemical modification of these azo-dyes resulted in the preparation of eight previously unknown acyl derivatives (136-143) Interaction of 5-amino-2-arylazoimidazole-4-carboxides with ethyl formate in sodium ethoxide effected pyrimidine ring closure to the novel 8-arylazohypoxanthines (144 and 145). Several reductive techniques were employed in an effort to obtain the elusive 2,5-diaminoimidazole-4-carboxamide (71),a candidate chemotherapeutic agent, from the arylazoiridazoles. No success can be reported although 5-amino-2-(3-aminoindazol-2-yl) imidazole-4-carboxamide (151) was isolated due to a partial reduction and intramolecular cyclisation of 5-amino72-(2-cyanaphenylazo)imidazole-4-carboxamide (122) .Further possible synthetic approaches to the diaminoimidazole are discussed in Chapter 4. An interesting degradation of a known unstable nitrohydrazone is described in Chapter 5.This resulted in formation of 1, 1-bis(pyrazol--3-ylazo)-1-nitroethane (164) instead of the expected cyclisation to a bicyclic tetrazine N-oxide. An improved preparation of 5-diazoinidazole-4-carboxamide has been achieved, and the diazo-azole formed cycloadducts with isocyanates to yield the hitherto unknown imidazo[5,1-d][1,2,3,5]tetrazin-7(6H)-ones. Eleven derivatives (167-177) of this new ring-system were prepared and characterised. Chemical and spectroscopic investigation showed this ring-system to be unstable under certain conditions, and a comparative study of stability within the group has been made. "Retro-cycloaddition" under protic and photolytic conditions was an unexpected property of 6-substituted imidazo[5,1-d][1,2,3,5]tetrazin--7(0)-ones.Selected examples of the imidazotetrazinone ring-system were tested for antitumour activity. The results of biological evaluation are given in Chapter 7, and have culminated in a Patent application by the collaborating body, May and Baker Ltd. One compound,3-carbamoyl-6-(2-chloro-ethyl)imidazo[5,1-d][1,2,3,5jtetrazin-7(6H)-one (175),shows striking anti-tumour activity in rodent test systems.

The discourse of biology lectures : aspects of its mode and text structure

The present thesis investigates mode related aspects in biology lecture discourse and attempts to identify the position of this variety along the spontaneous spoken versus planned written language continuum. Nine lectures (of 43,000 words) consisting of three sets of three lectures each, given by the three lecturers at Aston University, make up the corpus. The indeterminacy of the results obtained from the investigation of grammatical complexity as measured in subordination motivates the need to take the analysis beyond sentence level to the study of mode related aspects in the use of sentence-initial connectives, sub-topic shifting and paraphrase. It is found that biology lecture discourse combines features typical of speech and writing at sentence as well as discourse level: thus, subordination is more used than co-ordination, but one degree complexity sentence is favoured; some sentence initial connectives are only found in uses typical of spoken language but sub-topic shift signalling (generally introduced by a connective) typical of planned written language is a major feature of the lectures; syntactic and lexical revision and repetition, interrupted structures are found in the sub-topic shift signalling utterance and paraphrase, but the text is also amenable to analysis into sentence like units. On the other hand, it is also found that: (1) while there are some differences in the use of a given feature, inter-speaker variation is on the whole not significant; (2) mode related aspects are often motivated by the didactic function of the variety; and (3) the structuring of the text follows a sequencing whose boundaries are marked by sub-topic shifting and the summary paraphrase. This study enables us to draw four theoretical conclusions: (1) mode related aspects cannot be approached as a simple dichotomy since a combination of aspects of both speech and writing are found in a given feature. It is necessary to go to the level of textual features to identify mode related aspects; (2) homogeneity is dominant in this sample of lectures which suggests that there is a high level of standardization in this variety; (3) the didactic function of the variety is manifested in some mode related aspects; (4) the features studied play a role in the structuring of the text.

The synthesis and properties of some hydrazines

A new synthetic method, applicable to the preparation of a wide range of hydrazine derivatives, is described. This involves the diborane reduction of a hydrazone, or, more conveniently, the reductive-condensation of a hydrazine and the appropriate aldehyde (or ketone). The method gives high yields and provides a particularly simple route to the relatively inaccessible 1,2-disubstituted hydrazines bearing a different group on each nitrogen. The new method has also been applied to the preparation of 1,2-disubstituted hydrazines with the same group on both nitrogens (via the azine), the very rare 1 ,2-disubstituted hydrazines bearing a tert-butyl group, trisubstituted hydrazines and monosubstituted hydrazines. Application of the reaction to the preparation of diaziridines has also been investigated. A mechanism for the reduction, supported by the isolation of a boron-containing intermediate, is suggested. Some limitations of the procedure are discussed. A general i.r. method of distinguishing the isomeric disubstituted hydrazines, as stable salts, has been developed. This has the advantages of speed and simplicity over previous methods. The mass spectra of a series of monosubstituted hydrazines, a series of 1,2-disubstituted hydrazines and some 1-benzoyl 2-alkylhydrazines have been examined in detail. The spectra are generally dominated byα -cleavage processes and the compounds show a variety of interesting rearrangement reactions. The mass spectra of some 1, 1-disubstituted hydrazines and some trisubstituted hydrazines have also been examined. Rearrangement processes occurring in the mass spectrum of tropylium fluoroborate have been examined. Similar rearrangements have been found in the spectrum of trityl fluoroborate and may be of general occurrence in the mass spectra of aromatic fluoroborates. Chemical shift values for some groups on hydrazine nitrogen are recorded and the results of tumour inhibitory tests on some hydrazines are also given.

Servitization of the manufacturing firm:exploring the operations practices and technologies that deliver advanced services

Purpose: This paper aims to explore practices and technologies successfully servitised manufacturers employ in the delivery of advanced services. Design/methodology/approach: A case study methodology is applied across four manufacturing organisations successful in servitization. Through interviews with personnel across host manufacturers, their partners, and key customers, extensive data are collected about service delivery systems. Analyses identify convergence in their practices and technologies. Findings: Six distinct technologies and practices are revealed: facilities and their location, micro-vertical integration and supplier relationships, information and communication technologies (ICTs), performance measurement and value demonstration, people deployment and their skills, and business processes and customer relationships. These are then combined in an integrative framework that illustrates how operations are configured to successfully deliver advanced services. Research limitations/implications: The analyses are reductive and rationalising. Future studies could identify other technologies and practices. Case study as a method is inherently limited in the extent to which findings can be generalised. Practical implications: Awareness and interest in servitization is growing, yet adoption of a servitization strategy requires particular organisational capabilities on the part of the manufacturer. This study identifies technologies and practices that underpin these capabilities. Originality/value: This paper contributes to the understanding of the servitization process and, in particular, the implications to broader operations of the firm. © Emerald Group Publishing Limited.

Detoxification of brominated pyrolysis oils

The development of an innovative technology for the pyrolytic conversion of brominated phenols in a reductive medium aimed at product recovery for commercial use is discussed in this paper. Brominated phenols are toxic products, which contaminate pyrolysis oil of wastes from electronic and electrical equipment (WEEE). The pyrolysis experiments were carried out with 2,6-dibromophenol, tetrabromobisphenol A, WEEE pyrolysis oil and polypropylene or polyethylene in encapsulated ampoules under inert atmosphere in quasi-isothermal conditions (300-400 °C) with a different residence time (10-30 min). Optimal conditions were found to be the use of polypropylene at 350 °C with a residence time of 20 min. The main pyrolysis products were identified as HBr and phenol. A radical debromination mechanism for the pyrolytic destruction of brominated phenols is suggested. © 2003 Elsevier Science B.V. All rights reserved.

The fevered novel from Balzac to Bernanos:frenetic Catholicism in crisis, delirium and revolution

Book Review: The Fevered Novel from Balzac to Bernanos: Frenetic Catholicism in Crisis, Delirium and Revolution. By Francesco Manzini. (IGRS Books). London: Institute of Germanic and Romance Studies, 2011. 264 pp. Full text: This monograph is an important and compelling account of a novelistic tradition that stretches from Georges Bernanos back to Balzac, by way of Léon Bloy, Joris-Karl Huysmans, and Barbey d'Aurevilly. Depending on a master plot that evokes Maistrean themes of blood, sacrifice, and redemption, working in a feverish female body, this canon combines Romantic freneticism and anti-Enlightenment religion to create a compound that Francesco Manzini calls ‘frenetic Catholicism’. The theme of fever, Manzini tells us, was commented on by Huysmans in writing about Barbey d'Aurevilly. When André Gide read Bernanos's Sous le soleil de Satan, he dismissed it as a rehash of Bloy and Barbey. In this present work Manzini aims to make us aware once more of the gradually intensifying themacity of fever in writings more usually classed in theologo-literary categories. His analysis encompasses (though is not restricted to) Balzac's Ursule Mirouët, Barbey d'Aurevilly's Un prêtre marié, Huysmans's En rade, Bloy's Le Désespéré and La Femme pauvre, and Bernanos's Nouvelle histoire de Mouchette. Thus, as Manzini argues in his conclusion, between the freneticism of the Romantics and that of the surrealists this corpus represents an intermediary wave of freneticism, foregrounding fever, hyperconsciousness, dreamlike episodes, and female automatism. Manzini's knowledge of, and ease amidst, the sources is constantly impressive. Much like Richard Griffiths before him (The Reactionary Revolution: The Catholic Revival in French Literature, 1870–1914 (London: Constable, 1966)), he has read both the bad novels and the good ones. For that we are in his debt. His commentary thrives on the oddities of his subjects. He points quite rightly to the peculiar hubris of writers whose contempt for the secular excesses of scientism leads them down a cul-de-sac of primitive medical quackery. Likewise, he underlines how Zola's attempt to unwrite Barbey — exorcising the former's anti-Romantic animus, as much as scratching his anticlerical itch — leads him to recapitulate Barbey's religious authoritarianism in the secular vernacular of patriarchy. Les espèces qui se rapprochent se mangent, to paraphrase Bernanos (Les Grands Cimetières sous la lune). In spite of all Manzini's tightly organized analysis, however, this reader wonders whether the fevered novel ‘best allowed contemporaries — and now […] literary critics and historians — to imagine the issues at stake in the amorphous scientistic, religious, and political debates’ of the period (p. 17). Below the ideological clashes of nineteenth-century science and religion, the two contending dynamics of anthropocentrism and theocentrism are attested and, it can be argued, even more perfectly dramatized in other Catholic literature (Charles Péguy's poetry, for example). In these terms, what distinguishes the Catholic frenetics from their Romantic or surrealist counterparts is that their fevered subject represents an attempt to build a road out of what Canadian philosopher Charles Taylor calls ‘buffered’ individuality, and back towards the theocentric porous subject who is open to divine influence. By way of minor corrections, nuns do not take holy orders (p. 94) but make religious profession by taking vows. Also, the last Eucharistic host is not extreme unction (p. 119) but viaticum.