pKa values of aqua ligands of platinum (II) anticancer complexes: [1H, 15N] and 195Pt NMR Studies of cis- and trans- [PtCl2 (NH3) (Cyclohexylamine)]

Syntheses and NMR studies are reported of two 15N-labelled Pt(II) complexes of anticancer interest: cis-PtCl2(15NH3)(c-C6H1115NH2), a metabolite of the orally-active Pt(IV) complex cis,trans,cis-[PtCl2(acetate)2(c-C6H11NH2)(NH3), and trans-[PtCl2(15NH3)(c-C6H1115NH2), a reduction product of the active Pt(IV) complex trans,trans,trans-[PtCl2(OH)2(c-C6H11NH2). For cis-[PtCl2(15NH3)(c-C6H1115NH2), hydrolysis was faster for the chloride ligand trans to cyclohexylamine, and the pKa values determined by [1H, 15N NMR spectroscopy for the two cis monoaqua isomers were the same (6.73). The trans monoaqua complex was a stronger acid with pKa of 5.4 (determined by 195Pt NMR). For the cis diaqua complex, pKa values of 5.68 and 7.68 were determined.

Convenient synthetic routes to bidentate and monodentate 2-, 3- and 4-pyridyl phosphines: potentially useful ligands for water-soluble complex catalysts

The monodentate and bidentate pyridyl phosphines, PR3 and R2P(CH2)2PR2, where R=3- or 4-pyridyl can be prepared in high yields by treatment of butyllithium/TMEDA/3- or 4-bromopyridine with PCl3 or Cl2P(CH2)2PCl2 at low temperature. 1,2-Bis(di-2-pyridylphosphino)ethane is conveniently synthesised by an alternative route involving reaction of 1,2-dibromoethane with lithium di-2-pyridylphosphide.

[1H,15N] N.M.R. Kinetic Studies of Reactions of cis- and trans-[PtCl2(15NH3)(c-C6H1115NH2)] with Guanosine 5'-Monophosphate

cis-[PtCl2(15NH3)(c-C6H11NH2)] is an active metabolite of the oral platinum(IV) anticancer drug cis,trans,cis-[PtCl2(CH3CO2)2(NH2)(c-C6H11NH2)]. Since it is likely that guanine bases on DNA are targets for this drug, we have analysed the kinetics of reaction of this platinum(II) metabolite with guanosine 5′-monophosphate (5′-GMP) at 310 K, pH 7, using [1H, 15N] n.m.r. methods. Reactions of the trans isomer are reported for comparison. The reactions proceed via aquated intermediates, and, for the cis isomer, the rates of aquation and substitution of H2O by 5′-GMP are 2-5 times faster trans to the amine ligand (c-C6H11NH2) compared to trans to NH3 for both the first and second steps. For the trans complex, the first aquation step is c. 3 times faster than for the cis complex, as expected from the higher trans influence of Cl¯, whereas the rate of the second aquation step (trans to N7 of 5′-GMP) is comparable to that trans to NH3. These findings have implications for the courses of reactions with DNA.

The thermal desulfination of allylic sulfonyl halides

Allylic sulfonyl halides can be generated by halogenolysis of the corresponding triorganotin sulfinates. Allylic sulfonyl bromides and iodides undergo a first order, thermal desulfination with allylic rearrangement to yield the corresponding allylic halides. The desulfination of a cyclic allylic sulfonyl bromide is stereospecific, proceeding with T-syn bromine migration.

The assassination of time (ζeta-philosophy)

The Digital Art Weeks PROGRAM (DAW06) is concerned with the application of digital technology in the arts. Consisting again this year of symposium, workshops and performances, the program offers insight into current research and innovations in art and technology as well as illustrating resulting synergies in a series of performances, making artists aware of impulses in technology and scientists aware of the possibilities of the application of technology in the arts.

Duty to mitigate in leasehold law

Discusses by reference to case law, including Commonwealth authorities, the rights and duties of landlords where demised premises are abandoned by a tenant who has defaulted on the rent, including the remedies available to the landlord, the limitations on his right to sue for loss of rent due between abandonment and expiration of the term, and the applicability of the contractual doctrine of mitigation of damages in leasehold law. Examines the Court of Appeal decision in Reichman v Beveridge on the duty of mitigate loss in an action merely seeking recovery of rent as it accrues due.

Trembling the plane of immanence: media arts philosophy and the re-vision of art (or what’s acoustics got to do with the visual?)

Invited lecture at the Royal Academy of Art.

Dirty theory: philosophical enactments after metaphysics

Modern forms of speculative philosophy continue to creep ‘unsuspectingly’ into our understanding of contemporary media/electronic arts, despite (or perhaps even because of) the attempts by Latour, Badiou, or Agamben especially when addressing the zero/one as if a contradictory ‘binary’ rather than as a kind of 'slice’ or (to use Deleuze and Guattari) an immanent plane of immanence. We argue that by playing with and against Neitzsche, Einstein, Godel, and Deleuze, a rather different story of art, not to mention philosophy, can be told. [From conference programme]

To tremble the zero: art in the age of algorithmic reproduction

'To Tremble the Zero: Art in the Age of Algorithmic Reproduction' is a philosophic, political and sensuous journey playing with (and against) Benjamin's 'Art in the Age of Mechanical Reproduction'. In an age inundated by the 'post-': postmodernity, posthuman, post art, postsexual, post-feminist, post-society, post-nation, etc, 'To Tremble the Zero' sets out to re/present the nature of what it means to do or make 'art', as well as what it means to be or have 'human/ity' when the ground is nothing other than the fractal, and algorithmically infinite, combinations of zero and one. The work will address also the unfortunate way in which modern forms of metaphysics continue to creep 'unsuspectingly' into our understanding of contemporary media/electronic arts, despite (or perhaps even because of) the attempts by Latour, Badiou, or Agamben especially when addressing the zero/one as if a contradictory 'binary' rather than as a kind of 'slice' or (to use Deleuze and Guattari) an immanent plane of immanence. This work argues that by retrieving Benjamin, Einstein, Gödel, and Haraway, a rather different story of art can be told.

Stakeholder engagement in sustainable housing refurbishment in the UK

The UK government is committed to effectively implement a viable sustainable agenda in the social housing sector. To this end housing associations and local authorities are being encouraged to improve the environmental performance of their new and existing homes. Whilst much attention has been focused on new housing (e.g. the Code for Sustainable Homes) little effort has been focussed on improving the 3.9 (approx) million homes maintained and managed by the public sector (in England), which, given the low rate of new build and demolition (<1% in England), will represent approximately 70% of the public housing stock in 2050. Thus, if UK is to achieve sustainable public housing the major effort will have to focus on the existing stock. However, interpreting the sustainability agenda for an existing housing portfolio is not a straight foreword activity. In addition to finding a ‘technical’ solution, landlords also haveto address the socio-economic issues that balance quality of expectations of tenants with the economic realities of funding social housing refurbishment. This paper will report the findings of a qualitative study (participatory approach) that examined the processes by which a large public landlord sought to develop a long-term sustainable housing strategy. Through a series of individual meetings and group workshops the research team identified: committed leadership; attitudes towards technology; social awareness; and collective understanding of the sustainability agenda as key issues that the organisation needed to address in developing a robust and defendable refurbishment strategy. The paper concludes that the challenges faced by the landlord in improving the sustainability of their existing stock are not primarily technical, but socio-economic. Further, while the economic challenges: initial capital cost; lack of funding; and pay-back periods can be overcome, if the political will exists, by fiscal measures; the social challenges: health & wellbeing; poverty; security; space needs; behaviour change; education; and trust; are much more complex in nature and will require a coordinated approach from all the stakeholders involved in the wider community if they are to be effectively addressed. The key challenge to public housing landlords is to develop mechanisms that can identify and interpret the complex nature of the social sustainability agenda in a way that reflects local aspirations (although the authors believe the factors will exist in all social housing communities, their relative importance is likely to vary between communities) whilst addressing Government agendas.

Investigating antecedents and consequences of brand identification

Purpose – This study aims to analyse the influences of prestige, satisfaction, and communication on brand identification and to show how brand identification influences word-of-mouth and brand repurchase. Design/methodology/approach – A theoretical model is developed and tested with a sample of car owners in the UK of two global car brands. Structural equation modelling was used with LISREL 8.54 and the maximum likelihood (ML) method. Findings – This paper draws mainly on the theory of social identity to provide a comprehensive understanding of conditions under which brand owners are likely to identify with their brand and the bases and consequences of such identification. It was shown that prestige, satisfaction, and communication effect brand identification. The study confirms that consumers' development of relationships via brand identification results in word of mouth about the brand and intentions to repurchase the brand. Furthermore, it was found that brand identification fully mediates the influences of prestige, satisfaction, and communication on word of mouth and brand repurchase. Research limitations/implications – The focus was on one country and one industry. Practical implications – Managers are provided with strategies that enhance the identification of their customers with their brand so that they can strengthen the customers' brand identification. Areas for future research are suggested. For instance, it could be interesting to test the model in a different industry and/or cultural context. Originality/value – Very few previous studies have looked at brand identification which is surprising considering it is such an important variable to influence word-of-mouth and brand repurchase. The study tests three antecedents to brand identification and two outcomes that have not been investigated previously. Overall, the study adds knowledge in this somewhat neglected area.