Atmospheric pressure chemical ionisation liquid chromatography/mass spectrometry of bacteriochlorophylls from Chlorobiaceae: characteristic fragmentations

Atmospheric pressure chemical ionisation liquid chromatography/mass spectrometry/mass spectrometry (APCI-LC/MS/MS) has been applied to the study of bacteriochlorophylls c, d, and e of phototrophic prokaryotes. Cultures of Chlorobiaceae containing bacteriochlorophyll c, d or e were examined using a high-resolution high-performance liquid chromatography (HPLC) method and APCI-LC/MS/MS employing post-column addition of formic acid. The results reveal complex distributions of bacteriochlorophyll homologues, with some closely eluting species giving isobaric protonated molecules. On-line LC/MS/MS studies reveal characteristic fragment ions for bacteriochlorophylls c, d, and e. Fragmentations involving loss of the extended alkyl substituents that are unique to bacteriochlorophylls c, d and e and their derivatives have been rationalised by studying the phaeophorbides and the results applied to the direct study of the bacteriochlorophylls.

An investigation into the structure and bioavailability of a-tocopherol dispersions in Gelucire 44/14

In this investigation we describe the preparation, physical characterisation and in vivo behaviour of solid dispersions of a liquid nutraceutical, ±-tocopherol, in Gelucire 44/14 with a view to establishing whether dispersion in this matrix may provide a means of formulating a liquid drug in a solid dosage form while also improving the oral bioavailability. Using Vitamin E Preparation USP as the source of ±-tocopherol, dispersions were prepared using a melt-fusion method with active loadings up to 50% (w/w) and characterised using differential scanning calorimetry and optical microscopy. Capsules containing 300 IU ±-tocopherol were manufactured and the absorption profiles compared to a commercial soft gelatin capsule preparation in healthy human volunteers. Confocal laser scanning microscopy (CLSM) studies were performed in order to elucidate the mechanism by which drug release may be occurring. Differential scanning calorimetry studies indicated that the presence of the active had a negligible effect on the melting profile of the carrier, indicating limited miscibility between the two components, a conclusion supported by the microscopy studies. Similarly, the dispersions were shown to exhibit a glass transition corresponding to the incorporated drug, indicating molecular cooperativity and hence phase separation from the lipid base. Despite the phase separation, it was noted that capsules stored for 18 months under ambient conditions showed no evidence of leakage. Bioavailability studies in six healthy male volunteers indicated that the Gelucire 44/14 formulation showed an approximately two-fold increase in total ±-tocopherol absorption compared to the commercial preparation. Confocal laser scanning microscopy studies indicated that, on contact with water, the dispersions formed two interfacial layers, from which the Gelucire 44/14 disperses in the liquid medium as small particles. Furthermore, evidence was obtained for the dispersed material becoming incorporated into the hydrated lipid. In conclusion, the dispersion of the liquid drug in Gelucire 44/14 appears to allow the dual advantages of the preparation of a solid formulation and improved bioavailability of this material.

Bereavement: A D.I.S.C. analysis

Theories of bereavement abound. The endeavour to understand this complex process has moved from intra-psychic explanations and stage theories to cognitive rationalizations and, most recently, process orientated explorations of bereavement. What has been missing in most of the literature to date is a detailed analysis of the context within which bereavement behaviours occur. This paper outlines a contingency analysis that includes consideration for the context of Death itself, Individual factors of the bereaved, Social factors, and influences of Cultural norms and systems (D.I.S.C.). The paper concludes by proposing that a comprehensive D.I.S.C. analysis might lead to whole person evidence-based practice in helping those who are experiencing bereavement.

Livelihood Strategies of Dock Workers in Durban, c. 1900-1959

This dissertation examines the livelihood strategies of African dock workers in Durban, South Africa, between the Anglo-Boer War and the 1959 strikes. These labourers did not conform to common conceptions of radical dock workers or conservative African migrant workers. While Marxist scholars have been correct to stress the working class consciousness of Durban’s dock workers, this consciousness was also more ambiguous. These workers and their leaders displayed a peculiar mix of concern for workers’ issues and defences of the rights and interests of African traders. Many of Durban’s dock workers were not only wage labourers. In fact, only a minority had wages as their only source of income. The Reserve economy played a role in sustaining the consumption levels of their households and, more importantly, more than half of the former dock workers interviewed for this research engaged in some form of commercial enterprise, often based on the pilferage and sale of cargoes. Some also teamed up with township women who sold pilfered goods while the men were at work. This combination of commercial strategies and wage labour has often been overlooked in the literature. By looking at these livelihood strategies, this dissertation considers how rural and urban economies interacted in households’ strategies and reinterprets the reproduction of labour and the household in order to move beyond dichotomies of proletarian versus rural consciousness. The dock workers’ households were neither proletarian households that were forced to reside in the countryside because of apartheid, nor traditional rural homesteads with a missing migrant member. The households were reproduced in three geographically separate spheres of production and consumption, none of which could reproduce the household on its own. These spheres were dependent on each other, but also separate, as physical distance gave the different household members some autonomy. Such multi-nodal households not only bridged the rural and the urban, but equally straddled the formal/informal divide. For many, their employment on the docks made their commercial enterprises possible, which allowed them to retire early from urban wage labour. Consequently, the interests of wage labourers could not be divorced from those of African small-scale entrepreneurs.

Correlation of TACC3, FGFR3, MMSET and p21 expression with the t(4;14)(p16.3;q32) in multiple myeloma

The t(4;14)(p16;q32) translocation seen in c. 18% of newly diagnosed multiple myeloma (MM) cases, results in FGFR3 activation and creation of an IGH/MMSET fusion transcript. We have recently shown that FGFR3 is activated in only 75% of t(4;14)(+) cases, suggesting that alternative genes near the breakpoint may be involved in the transforming event. The gene, TACC3, located just 50 kb telomeric of FGFR3, with transforming capacity, therefore represented a candidate gene. Using a real-time quantitative polymerase chain reaction-based approach on a cohort of 54 patients, we found a statistically significant, twofold increase in TACC3 expression in t(4;14)(+) cases. TACC3, MMSET and p21 values were positively correlated in all cases and, of particular interest, six patient samples [three t(4;14)(-), three t(4;14)(+)] samples showed a joint up-regulation of TACC3, MMSET and p21. Although a poor prognosis is linked with elevated MMSET expression, an extended follow-up period will be required to evaluate the significance of elevated TACC3 and p21 expression in this subgroup of MM.

Positive and negative contractile effects of somatostatin-14 on rat ventricular cardiomyocytes.

Somatostatin-14 elicits negative inotropic and chronotropic actions in atrial myocardium. Less is known about the effects of somatostatin-14 in ventricular myocardium. The direct contractile effects of somatostatin-14 were assessed using ventricular cardiomyocytes isolated from the hearts of adult rats. Cells were stimulated at 0.5 Hz with CaCl2 (2 mM) under basal conditions and in the presence of the -adrenoceptor agonist, isoprenaline (1 nM), or the selective inhibitor of the transient outward current (Ito), 4-aminopyridine (500 M). Somatostatin-14 did not alter basal contractile response but it did inhibit (IC50 13 nM) the response to isoprenaline (1 nM). In the presence of 4-aminopyridine (500 M), somatostatin-14 stimulated a positive contractile response (EC50 118 fM) that was attenuated markedly by diltiazem (100 nM). These data indicate that somatostatin-14 exerts dual effects directly in rat ventricular cardiomyocytes: (1) a negative contractile effect, observed in the presence of isoprenaline (1 nM), coupled to activation of Ito; and (2) a previously unreported and very potent positive contractile effect, unmasked by 4-aminopyridine (500 M), coupled to the influx of calcium ions via L-type calcium channels. The greater potency of somatostatin-14 for producing the positive contractile effect indicates that the peptide may exert a predominantly stimulatory influence on the resting contractility of ventricular myocardium in vivo, whereas the negative contractile effect, observed at much higher concentrations, could indicate that localized elevations in the concentration of the peptide may serve as a negative regulatory influence to limit the detrimental effects of excessive stimulation of cardiomyocyte contractility.

Understanding B-type supergiants in the low metallicity environment of the SMC

Spectroscopic analyses of 7 SMC B-type supergiants and 1 giant have been undertaken using high resolution optical data obtained on the VLT with UVES. FASTWIND, a non-LTE, spherical, line-blanketed model atmosphere code was used to derive atmospheric and wind parameters of these stars as well as their absolute abundances. Mass-loss rates, derived from H-alpha profiles, are in poor agreement with metallicity dependent theoretical predictions. Indeed the wind-momenta of the SMC stars appear to be in good agreement with the wind-momentum luminosity relationship (WLR) of Galactic B-type stars, a puzzling result given that line-driven wind theory predicts a metallicity dependence. However the galactic stars were analysed using unblanketed model atmospheres which may mask any dependence on metallicity. A mean nitrogen enhancement of a factor of 14 is observed in the supergiants whilst only an enrichment of a factor of 4 is present in the giant, AV216. Similar excesses in nitrogen are observed in O-type dwarfs and supergiants in the same mass range, suggesting that the additional nitrogen is produced while the stars are still on the main-sequence. These nitrogen enrichments can be reproduced by current stellar evolution models, which include rotationally induced mixing, only if large initial rotational velocities of 300 kin s(-1) are invoked. Such large rotational velocities appear to be inconsistent with observed v sin i distributions for O-type stars and B-type supergiants. Hence it is suggested that the currently available stellar evolution models require more efficient mixing for lower rotational velocities.

Measurements of helium metastable density in an atmospheric pressure glow discharge

The density of metastable helium atoms in a dielectric barrier discharge operating in helium with some impurities present has been measured using laser-collisional-induced fluorescence and absorption techniques. Time-resolved measurements indicate that helium metastables contribute to the production of impurity ions, in this case N-2(+), in the postdischarge current phase of a glow discharge. In our particular discharge environment, the helium metastable density is (1.5+/-1.4)x10(10) cm(-3), a result consistent with failure to observe absorption by metastables in a multipass absorption measurement. (C) 2004 American Institute of Physics.

Collision mechanisms in one-electron capture by slow H and He- like ions of C, N and O in H and H-2

Translational energy spectroscopy (TES) has been used to study state-selective one-electron capture by H and He-like ions of C, N and O in both H and H-2 within the range 250-900 eV amu(- 1). The main collision mechanisms leading to state-selective electron capture have been identified, their relative importance assessed and compared, where possible, with theoretical predictions and with any previous measurements based on photon emission spectroscopy. For one-electron capture in H-2, the relative importance of contributions from non- dissociative and dissociative capture as well as from two- electron capture into autoionizing states is found to be strikingly different for the cases considered. Our TES measurements in atomic hydrogen provide an important extension of previous measurements to energies below 1000 eV amu(-1) and show that, as the impact energy decreases, electron capture becomes more selective until only a single n product channel is significant. These product main channels are well described by reaction windows calculated using a Landau-Zener approach. However, the same approach applied to the more complex energy- change spectra observed in H-2 is found to be less successful.