Effects of Charge Location on the Absorptions and Lifetimes of Protonated Tyrosine Peptides in Vacuo

Nearby charges affect the electronic energy levels of chromophores, with the extent of the effect being determined by the magnitude of the charge and degree of charge-chromophore separation. The molecular configuration dictates the charge chromophore distance. Hence, in this study, we aim to assess how the location of the charge influences the absorption of a set of model protonated and diprotonated peptide ions, and whether spectral differences are large enough to be identified. The studied ions were the dipeptide YK, the tripeptide KYK (Y = tyrosine; K = lysine) and their complexes with 18-crown-6-ether (CE). The CE targets the ammonium group by forming internal ionic hydrogen bonds and limits the folding of the peptide. In the tripeptide, the distance between the chromophore and the backbone ammonium is enlarged relative to that in the dipeptide. Experiments were performed in an electrostatic ion storage ring using a tunable laser system, and action spectra based on lifetime measurements were obtained in the range from 210 to 310 nm. The spectra are all quite similar though there seems to be some changes in the absorption band between 210 and 250 nm, while in the lower energy band all ions had a maximum absorption at similar to 275 nm. Lifetimes after photoexcitation were found to shorten upon protonation and lengthen upon CE complexation, in accordance with the increased number of degrees of freedom and an increase in activation energies for dissociation as the mobile proton model is no longer operative.

Genetic analysis of the dTDP-rhamnose biosynthesis region of the Escherichia coli VW187 (O7:K1) rfb gene cluster:identification of functional homologs of rfbB and rfbA in the rff cluster and correct location of the rffE gene

The O-repeating unit of the Escherichia coli O7-specific lipopolysaccharide is made of galactose, mannose, rhamnose, 4-acetamido-4,6-dideoxyglucose, and N-acetyglucosamine. We have recently characterized the genes involved in the biosynthesis of the sugar precursor GDP-mannose occurring in the E. coli O7:K1 strain VW187 (C. L. Marolda and M. A. Valvano, J. Bacteriol. 175:148-158, 1993). In the present study, we identified and sequenced the rfbBDAC genes encoding the enzymes for the biosynthesis of another precursor, dTDP-rhamnose. These genes are localized on the upstream end of the rfbEcO7 region, and they are strongly conserved compared with similar genes found in various enteric and nonenteric bacteria. Upstream of rfbB we identified a DNA segment containing the rfb promoter and a highly conserved untranslated leader sequence also present in the promoter regions of other surface polysaccharide gene clusters. Also, we have determined that rfbB and rfbA have homologs, rffG (o355) and rffH (o292), respectively, located on the rff cluster, which is involved in the synthesis of enterobacterial common antigen. We provide biochemical evidence that rffG and rffH encode dTDP-glucose dehydratase and glucose-1-phosphate thymidylyltransferase activities, respectively, and we also show that rffG complemented the rfbB defect in the O7+ cosmid pJHCV32. We also demonstrate that rffG is distinct from rffE and map the rffE gene to the second gene of the rff cluster.

Moments of Recognition:The Four Semester Studio in QUB

It is a legitimate assertion that the common ground of work of worth in architecture, whether theoretical or built comes from a firmly held position on the part of the author. In addition to delivery key competencies architectural education should act to support the formation of such a position in the student, or to make students aware of the possibility of holding such a position.

It is with this in mind perhaps that intensive unit-based diploma and masters structures are increasingly becoming the standard structure for for schools of architecture across the UK. The strengths of such a structure are most evident when the school, either by virtue of financial strength or geographic location is able to attract a diverse range of contrasting positions to bear in the formation of these units. In effect the offering to the student is a short, intensive immersion into a clear line of thought based on the position of those running the unit. Research is channeled by those running the unit to the work of the students. A single cohort of students therefore is able to observe and understand a wide range of ways of thinking about the subject whether or not they are participants in a unit or not. It is axiomatic that where this structure is applied in the absence of these resources the result can be less helpful, individual units are differentiated not to reflect the interests of those running the unit but for the sake of difference as its own end.

In structuring the M.Arch programme in Queens University Belfast the reality of our somewhat peripheral location was placed at the forefront of our considerations. A single 4 semester studio is offered. The first three semesters are carefully structured to offer a range of directed and self directed projects to the students. By interrogation of these projects, and work undertaken at undergraduate level the aim is to assist the students to identify a personal position on architecture, which is then developed in the thesis in semester four. Research and design outputs are emergent from the interest of the student body, cultivated by staff who have the time over the four semesters to get to know all aspects of a students interests.

This paper will lay out this structure and some of the projects run within it. Now having delivered two graduating years the successes and challenges of the system will be laid out by reference to several case studies of individual student experiences of the structure.