Molecular approaches to the study of invasive seaweeds

A wide range of vectors is currently introducing a plethora of alien marine species into indigenous marine species assemblages. Over the past two decades, molecular studies of non-native seaweeds, including cryptic invaders, have successfully identified the species involved and their sources; we briefly review these studies. As yet, however, little research has been directed towards examining the genetic consequences of seaweed invasions. Here we provide an overview of seaweed invasions from a genetic perspective, focusing on invader species for which the greatest amount of information is available. We review invasion processes, and rationalize evolutionary and genetic consequences for the indigenous and invader species into two main groups: (1) changes in gene-pool composition, in population structure and allele frequencies; and (2) changes in genome organization at the species level through hybridization, and in individual gene expression profiles at the levels of expressed messenger RNA and the proteome (i.e., all proteins synthesized) and thus the phenotype. We draw on studies of better-known aquatic and terrestrial organisms to point the way forward in revealing the genetic consequences of seaweed invasions. We also highlight potential applications of more recent methodological and statistical approaches, such as microarray technology, assignment tests and mixed stock analysis.

Approaches to crystallization from ionic liquids: complex solvents-complex results, or, a strategy for controlled formation of new supramolecular architectures?

There are now more than 1200 papers a year describing research results using the 'neoteric' solvents, known as ionic liquids (ILs). If ILs are such highly studied solvents, why has there been so comparatively little research in their use in crystallization? Here we explore this question and discuss possible strategies for utilization of the mundane and the unique aspects of ILs for novel crystallization strategies including crystallization of high and low melting solids using thermal shifts; ''solvothermal'' techniques; slow diffusion; electrocrystallization; and use of a co-solvent. The results presented here and those appearing in the literature indicate both the complex nature of these solvents and their promise in delivering unique solvation, metal ion coordination numbers, coordination polymer motifs, and metal-anion interactions, to name but a few. These complex, but fascinating, results and the promise of much more intimate control over crystallization processes will drive a growing interest in using ILs as crystallization solvents.

Palladium catalysed formal 6-endo-trig approaches to pumiliotoxin alkaloids: interception of the elusive cyclopropyl intermediate

Intramolecular Heck cyclisation of (E)-vinyl bromides leads to indolizidines, related to pumiliotoxin alkaloids, in which the stereochemistry of the trisubstituted double bond undergoes inversion. A cyclopropyl intermediate, which is believed to be responsible for the double bond inversion, has been intercepted by forcing an 'early' beta-hydride elimination on this species. The relative stereochemistry of this cyclopropyl intermediate determines the regioselectivity of the final beta-hydride elimination. In this case all three beta-hydride eliminations were stereochemically permitted, giving rise to a mixture of three isomeric products, differing in the position of a double bond. (Z)-Vinyl bromides were found to be less reactive than (E)-vinyl bromides, but on cyclisation gave the required conjugated diene, with inversion of the vinyl bromide stereochemistry, as the sole reaction product. This methodology will allow rapid stereoselective access to the diene-based pumiliotoxin alkaloids.

Approaches to the Implementation of the Water Framework Directive: Targeting Mitigation Measures at Critical Source Areas of Diffuse Phosphorus in Irish Catchments

The Water Framework Directive (WFD) has initiated a shift towards a targeted approach to implementation through its focus on river basin districts as management units and the natural ecological characteristics of waterbodies. Due to its role in eutrophication, phosphorus (P) has received considerable attention, resulting in a significant body of research, which now forms the evidence base for the programme of measures (POMs) adopted in WFD River Basin Management Plans (RBMP). Targeting POMs at critical sources areas (CSAs) of P could significantly improve environmental efficiency and cost effectiveness of proposed mitigation strategies. This paper summarises the progress made towards targeting mitigation measures at CSAs in Irish catchments. A review of current research highlights that knowledge related to P export at field scale is relatively comprehensive however; the availability of site-specific data and tools limits widespread identification of CSA at this scale. Increasing complexity of hydrological processes at larger scales limits accurate identification of CSA at catchment scale. Implementation of a tiered approach, using catchment scale tools in conjunction with field-by-field surveys could decrease uncertainty and provide a more practical and cost effective method of delineating CSA in a range of catchments. Despite scientific and practical uncertainties, development of a tiered CSA-based approach to assist in the development of supplementary measures would provide a means of developing catchment-specific and cost-effective programmes of measures for diffuse P. The paper presents a conceptual framework for such an approach, which would have particular relevance for the development of supplementary measures in High Status Waterbodies (HSW). The cost and resources necessary for implementation are justified based on HSWs’ value as undisturbed reference condition ecosystems.

New Approaches to the Total Synthesis of the Bryostatin Antitumour Macrolides

In this Focus Review, we give an overview of various bryostatin total syntheses. We also discuss the synthesis of various bryostatin analogues and their biological activity. Work reviewed includes that of Masamune, Evans, Nishiyama and Yamamura, Hale and Manaviazar, Trost, Wender, Keck, Burke, Thomas, and Krische. Our coverage is primarily for the period 2001–2009, since detailed reviews already exist on bryostatin total synthesis work and biology up to this time.