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.

Dynamic analysis of Flip-Chip Self-Alignment

Self-alignment of soldered electronic components such as flip-chips (FC), ball grid arrays (BGA) and optoelectronic devices during solder reflow is important as it ensures good alignment between components and substrates. Two uncoupled analytical models are presented which provide estimates of the dynamic time scales of both the chip and the solder in the self-alignment process. These predicted time scales can be used to decide whether a coupled dynamic analysis is required for the analysis of the chip motion. In this paper, we will show that for flip-chips, the alignment dynamics can be described accurately only when the chip motion is coupled with the solder motion because the two have similar time-scale values. To study this coupled phenomenon, a dynamic modeling method has been developed. The modeling results show that the uncoupled and coupled calculations result in significantly different predictions. The calculations based on the coupled model predict much faster rates of alignment than those predicted using the uncoupled approach.

Case based adaptation using interpolation over nominal values

In this paper we propose a method for interpolation over a set of retrieved cases in the adaptation phase of the case-based reasoning cycle. The method has two advantages over traditional systems: the first is that it can predict “new” instances, not yet present in the case base; the second is that it can predict solutions not present in the retrieval set. The method is a generalisation of Shepard’s Interpolation method, formulated as the minimisation of an error function defined in terms of distance metrics in the solution and problem spaces. We term the retrieval algorithm the Generalised Shepard Nearest Neighbour (GSNN) method. A novel aspect of GSNN is that it provides a general method for interpolation over nominal solution domains. The method is illustrated in the paper with reference to the Irises classification problem. It is evaluated with reference to a simulated nominal value test problem, and to a benchmark case base from the travel domain. The algorithm is shown to out-perform conventional nearest neighbour methods on these problems. Finally, GSNN is shown to improve in efficiency when used in conjunction with a diverse retrieval algorithm.

Predicting HCl concentrations in fire enclosures using an HCl decay model coupled to a CFD-based fire field model

The amount of atmospheric hydrogen chloride (HCl) within fire enclosures produced from the combustion of chloride-based materials tends to decay as the fire effluent is transported through the enclosure due to mixing with fresh air and absorption by solids. This paper describes an HCl decay model, typically used in zone models, which has been modified and applied to a computational fluid dynamics (CFD)-based fire field model. While the modified model still makes use of some empirical formulations to represent the deposition mechanisms, these have been reduced from the original three to two through the use of the CFD framework. Furthermore, the effect of HCl flow to the wall surfaces on the time to reach equilibrium between HCl in the boundary layer and on wall surfaces is addressed by the modified model. Simulation results using the modified HCl decay model are compared with data from three experiments. The model is found to be able to reproduce the experimental trends and the predicted HCl levels are in good agreement with measured values

Individual crisis episodes and cultural transition: finding the macrocosm in the microcosm

According to dialogical self theory (Hermans, 2001), individual identities reflect cultural and subcultural values, and appropriate voices and discourses from the social environment. Bronfenbrenner’s (1979) systemic theory of human development similarly postulates that individual and social development occur in a symbiotic and interdependent fashion. It would therefore be predicted that individual changes in identity reflect macrocosmic changes in cultural values and social structures. The current study investigated narratives of crisis transitions within adults aged 25-40, by way of interviews with 22 participants. An intensive qualitative analysis showed that the narratives of crisis could indeed be viewed as individual manifestations of contemporary cultural changes. National statistics and academic research have documented in the UK substantial cultural shifts over the last twenty years including the lessening popularity of marriage, the rise of freelance and portfolio careers and the growth of accepted alternative gender roles. In individual crises, changes made over the course of the episode were invariably in the same direction as these social changes; towards flexible work patterns, non-marital relationships and redefined gender identities. Before the crisis, participants described their identity as bound into an established discourse of conventionality, a traditional sense of masculinity or feminitity and a singular career role, while after the crisis alternative and fluid identities are explored, and identity is less defined by role and institution. These findings show that changes in the social macrocosm can be found in the individual microcosm, and therefore support dialogical self theory.