Identification of a gene involved in the biosynthesis of cyclopropanated mycolic acids in Mycobacterium tuberculosis.

Mycolic acids represent a major constituent of the mycobacterial cell wall complex, which provides the first line of defense against potentially lethal environmental conditions. Slow-growing pathogenic mycobacteria such as Mycobacterium tuberculosis modify their mycolic acids by cyclopropanation, whereas fast-growing saprophytic species such as Mycobacterium smegmatis do not, suggesting that this modification may be associated with an increase in oxidative stress experienced by the slow-growing species. We have demonstrated the transformation of the distal cis double bond in the major mycolic acid of M. smegmatis to a cis-cyclopropane ring upon introduction of cosmid DNA from M. tuberculosis. This activity was localized to a single gene (cma1) encoding a protein that was 34% identical to the cyclopropane fatty acid synthase from Escherichia coli. Adjacent regions of the DNA sequence encode open reading frames that display homology to other fatty acid biosynthetic enzymes, indicating that some of the genes required for mycolic acid biosynthesis may be clustered in this region. M. smegmatis overexpressing the cma1 gene product significantly resist killing by hydrogen peroxide, suggesting that this modification may be an important adaptation of slow-growing mycobacteria to oxidative stress.

Enhanced electro-oxidation resistance of carbon electrodes induced by phosphorus surface groups

The electro-oxidation of carbon materials enormously degrades their performance and limits their wider utilization in multiple electrochemical applications. In this work, the positive influence of phosphorus functionalities on the overall electrochemical stability of carbon materials has been demonstrated under different conditions. We show that the extent and selectivity of electroxidation in P-containing carbons are completely different to those observed in conventional carbons without P. The electro-oxidation of P-containing carbons involves the active participation of phosphorus surface groups, which are gradually transformed at high potentials from less-to more-oxidized species to slow down the introduction of oxygen groups on the carbon surface (oxidation) and the subsequent generation of (C*OOH)-like unstable promoters of electro-gasification. The highest-oxidized P groups (–C–O–P-like species) seem to distribute the gained oxygen to neighboring carbon sites, which finally suffer oxidation and/or gasification. So it is thought that P-groups could act as mediators of carbon oxidation although including various steps and intermediates compared to electroxidation in P-free materials.

Towards the understanding of the interfacial pH scale at Pt(1 1 1) electrodes

The determination of the potentials of zero total and free charge, pztc and pzfc respectively, were made in a wide pH range by using the CO displacement method and the same calculation assumptions used previously for Pt(1 1 1) electrodes in contact with non-specifically adsorbing anions. Calculation of the pzfc involves, in occasions, long extrapolations that lead us to the introduction of the concept of potential of zero extrapolated charge (pzec). It was observed that the pztc changes with pH but the pzec is independent of this parameter. It was observed that the pztc > pzec at pH > 3.4 but the opposite is true for pH > 3.4. At the latter pH both pzec and pztc coincide. This defines two different pH regions and means that adsorbed hydrogen has to be corrected in the “acidic” solutions at the pztc while adsorbed OH is the species to be corrected in the “alkaline” range. The comparison of the overall picture suggests that neutral conditions at the interface are attained at significantly acidic solutions than those at the bulk.

THE DESIGN AND SYNTHESIS OF SILOXANE PRECURSORS FOR CHIRAL PERIODIC MESOPOROUS ORGANOSILICA MATERIALS

The development of cost-effective and reliable methods for the synthesis and separation of asymmetric compounds is paramount in helping to meet society’s ever-growing demand for chiral small molecules. Of these methods, chiral heterogeneous supports are particularly appealing as they allow for the reuse of the chiral source. One such support, based on the synergy between chiral organic units and structurally stable inorganic silicon scaffolds are periodic mesoporous organosilicas (PMOs). In the work described herein, I examine some of the factors governing the transmission of chirality between chiral dopants and prochiral bulk phases in chiral PMO materials. In particular, the exploration of 1,1’-binaphthalene-bridged chiral dopants with a focus on the point of attachment into the materials. Moreover, the effects of ordering in the materials are examined and reveal that chirality transfer is more facile in materials with molecular-scale order then those containing amorphous walls. Secondly, the issues surrounding the synthesis and purification of aryl-triethoxysilanes as siloxane precursors are addressed. Both the introduction of a two-carbon linker and the direct attachment of allyl and mixed allyldiethoxysilane species are explored. This work demonstrates that allyldiethoxysilanes are ideal, in that they are stable enough to permit facile synthesis, while still being able to hydrolyze completely to produce well-ordered materials. Lastly, the production of new bulk phases for chiral PMO materials is examined by introducing new prochiral nitrogen-containing siloxane precursors. Biphenyldiamine and bipyridine-bridged siloxane precursors are readily synthesized on reasonable scales. Their use as the bulk siloxane precursor in the production of PMO materials however, is precluded by insufficient gelation and additional siloxane precursors are necessary for the production of ordered materials. In addition to the research detailed above that forms the body of this thesis, two short works are appended. The first details the production of polythiophene assemblies mediated through coordination nanospaces, while the second explores the production of N-heterocyclic carbene functionalized gold nanoparticles through ligand exchange.

The cultivation of Castanea sativa (Mill.) in Europe, from its origin to its diffusion on a continental scale

The history of Castanea sativa (sweet chestnut) cultivation since medieval times has been well described on the basis of the very rich documentation available. Far fewer attempts have been made to give a historical synthesis of the events that led to the cultivation of sweet chestnut in much earlier times. In this article we attempt to reconstruct this part of the European history of chestnut cultivation and its early diffusion by use of different sources of information, such as pollen studies, archaeology, history and literature. Using this multidisciplinary approach, we have tried to identify the roles of the Greek and Roman civilizations in the dissemination of chestnut cultivation on a European scale. In particular, we show that use of the chestnut for food was not the primary driving force behind the introduction of the tree into Europe by the Romans. Apart from the Insubrian Region in the north of the Italian peninsula, no other centre of chestnut cultivation existed in Europe during the Roman period. The Romans may have introduced the idea of systematically cultivating and using chestnut. In certain cases they introduced the species itself; however no evidence of systematic planting of chestnut exists. The greatest interest in the management of chestnut for fruit production most probably developed after the Roman period and can be associated with the socio-economic structures of medieval times. It was then that self-sufficient cultures based on the cultivation of chestnut as a source of subsistence were formed.

(Tables 1,2) Viability of Poa trivialis seeds transported to Antarctica from different locations

Antarctic ecosystems are at risk from the introduction of invasive species. The first step in the process of invasion is the transportation of alien species to Antarctic in a viable state. However, the effect of long-distance human-mediated dispersal, over different time-scales, on propagule viability is not well known. We assessed the viability of Poa trivialis seeds transported to Antarctica from the UK, South Africa and Australia by ship or by ship and aircraft. Following transportation to the Antarctic Treaty area, no reduction in seed viability was found, despite journey times lasting up to 284 days and seeds experiencing temperatures as low as -1.5°C. This work confirms that human-mediated transport may overcome the dispersal barrier for some propagules, and highlights the need for effective pre-departure biosecurity measures.

(Table 1) Number of invertebrate species per bottom trawl haul in the Kapp Norvegia to Halley Bay area on cruise EASIZ I (ANT-XIII/3) and in the Kapp Norvegia - Austasen area on cruise EASIZ III (ANT-XVII/3)

Ecological work carried out on the Antarctic and Magellan shelves since the first IBMANT conference held at the UMAG, Punta Arenas in 1997 is summarized to identify areas where progress has been made and others, where impor- tant gaps have remained in understanding past and present interaction between the Antarctic and the southern tip of South America. This information is complementary to a review on shallow-water work along the Scotia Arc (Barnes, 2005) and recent work done in the deep sea (Brandt and Hilbig, 2004). While principally referring to shipboard work in deeper water, above all during the recent international EASIZ and LAMPOS campaigns, relevant work from shore stations is also included. Six years after the first IBMANT symposium, significant progress has been made along the latitudinal gradient from the Magellan region to the high Antarctic in the fields of biodiversity, biogeography and community structure, life strategies and adaptations, the role of disturbance and its significance for biodiversity, and trophic coupling of the benthic realm with the water column and sea ice. A better understanding has developed of the role of evolutionary and ecological factors in shaping past and present-day environmental conditions, species composition and distribution, and ecosystem functioning. Furthermore, the science community engaged in unravelling Antarctic-Magellan interactions has advanced in methodological aspects such as new analytical approaches for comparing biodiversity derived from visual methods, growth and age determination, trophic modelling using stable isotope ratios, and molecular approaches for taxonomic and phylogenetic purposes. At the same time, much effort has been invested to complement the species inventory of the two adjacent regions. However, much work remains to be done to fill the numerous gaps. Some perspectives are outlined in this review, and sug- gestions are made where particular emphasis should be placed in future work, much of which will be developed in the frame of SCAR's EBA (Evolution and Biodiversity in the Antarctic) programme.

Table 1. - Estimated numbers of marine zooplnaktonic species for the World Oceanand for the South Atlantic

In total, ca. 7000 zooplanktonic species have been described for the World Ocean. This figure represents less than 4% of the total number of known marine organisms. Of the 7000 zooplanktonic species world-wide, some 60% are present in the South Atlantic; about one third of the latter have been recorded in its Subantarctic waters, and ca. 20% south of the Polar Front. When compared with those of benthic animals, these figures indicate that proportions of the overall inventories that are present in the cold waters are almost two times higher among the zooplankton. In agreement with this pattern, the proportions of Antarctic endemics in the benthos are very significantly higher than those in the plankton. For the water-column dwelling animals, the Polar Front boundary is more important than the Tropical-Subtropical limit, but almost equivalent to the Subtropical-Transitional limit, and weaker in biogeographic terms than the Transitional-Subantarctic boundary. Some of the implications of these dissimilarities, both for ecological theory and for resource allocation strategies, are discussed.

Planktonic foraminifer abundance and estimated sea surface temperatures and salinities of DSDP Leg 74 holes

Two hydraulic piston cores containing the total Quaternary suite were analyzed quantitatively in their planktonic foraminiferal contents. For the Early Pleistocene, the Caribbean standard zonation (BOLLI & PREMOLI-SILVA) can be adopted and refined by the introduction of an additional subzone at its base (the Globorotalia triangula subzone). Local substages are proposed for the Late Pleistocene because index fossils are missing. The use of the transfer-function technique resulted in paleotemperature and paleosalinity curves with a time resolution of cycles of about 4-68,000 years duration. The Early Pleistocene paleoenvironment is characterized by low oscillations of the surface water temperatures, followed by a distinct cooling trend during the Globorotalia viola subzone, a period of smoothed cycles during the Globorotalia hessi subzone and distinctly developed cycles during the late Pleistocene since the oxygen isotope termination III. Grainsize distribution and several dissolution indices gave evidence for current activities on the top of the Walvis Ridge, where the amount of fine grained components in the sediment is reduced in comparison with that of the flanks.

(Table 2) Species composition of agglutinated foraminifers from the abyssal zone of the Pacific Ocean

The quantitative study of distribution and taxonomic composition of recent living and dead (without plasma) benthic foraminifers revealed three foraminiferal assemblages in bottom sediments of the Pacific Ocean at depths of 3350 to 4981 m. The assemblage dominated by epibenthic Lagenammina difflugiformis, Reophax dentaliniformis, and Saccorhiza ramose occupies slopes of underwater hills. The assemblage with a high share of infaunal Cribrostomoides subglobosum, C. nitidum, and Ammobaculites agglutinans is registered on an abyssal plateau. The assemblage with a significant proportion of large Astrorhiza and Reophax species, which are characterized by active way of life, populates gentle slopes and narrow depressions with potentially strong bottom currents.

(Table 1) Distribution of Lower Cretaceous calcareous nannofossils at DSDP Hole 93-603B

Upper Berriasian to lower Aptian calcareous nannofossil assemblages have been studied from a siliciclastic deep-sea fan complex and a subjacent limestone sequence drilled beneath the lower continental rise in the western North American Basin, 270 miles (435 km) off Cape Hatteras, North Carolina (USA). Sharp lithologic facies changes and reworking by turbidites complicate the biostratigraphic interpretation, but provide an excellent opportunity to better distinguish "nearshore" from open-ocean nannofossil species, and to investigate the introduction of neritic taxa into the deep-see environment, a phenomenon that appears to have been widespread within the circum-North Atlantic during Neocomian times. Well-preserved assemblages in dark, carbonaceous claystones were probably displaced from the oxygen minimum zone along the upper slope or outer shelf. Neritic, continental margin species prevalent in this facies include the holococcolith Zebrashapka vanhintei n. gen., n. sp., Lithraphidites alatus magnus n. spp., Pickelhaube furtiva n. gen., and a host of nannoconids and micrantholiths. A qualitative evaluation of widely used guide fossils suggests that the triad of proposed markers for the base of Roth's Zone NC3 make their first appearances in the following (ascending) order: Diadorhombus rectus, TUbodiscus verenae, Calcicalathina oblongata. Of these, we chose the nominative species for the zone, T. verenae, to mark its base and to approximate the Berriasian/Valangian boundary. Cyclagelosphaera deflandrei is strongly affected by diagenesis and is therefore not a reliable index species for the base of Zone NC4 near the Valanginian/Hauterivian boundary (the last occurrence of T. verenae is also not suitable there). In addition, Lithraphidites bollii, a form apparently confined to the low latitudes of the Tethyan region, was absent at the more temperate Site 603 and not available as a subzonal marker for the upper Hautervian-lower Barremian (mid-NC4 and mid-NC5, respectively). Cruciellipsis cuvillieri, however, provides a reliable datum just below the Hauterivian/Barremian boundary (base of NC5), despite the potential for reworking in this section. Nannoconids tend to be reworked in this section, and do not provide trustworthy forms to mark the Barremian/Aptian boundary (base of NC6). Hayesites irregularis n. comb, probably does provide a useful first appearance datum within the lower Aptian, if it is not confused with a more birefringent and globular form, Rucinolithus terebrodentarius n. sp. Rhagodiscus angustus is mimicked by a similar form (Zeughrabdotusl pseudoangustus n. sp.), which apparently ranges down to the Hauterivian, thus Lithastrinus floralis provides a more useful first appearance datum for the base of the middle-upper Aptian Rhagodiscus angustus Zone (NC7). Aside from the new taxa mentioned above, the following are also described: Cretarhabdusl delicatus n. sp. and Cyclagelosphaera jiangii n. sp.