Interfacial electron transfer of perylenes: Influence of the anchor binding mode.

Interfacial electron transfer (IET) through saturated single-linker and dual-linker groups from a perylene chromophore into nanostructured TiO2 films was studied by ultrafast spectroscopy. Perylene chromophores with one and two propanoic acid linker groups in the peri and ortho positions were investigated. In comparison to previously studied perylenes bound via unsaturated acrylic acid linkers, the chromophores with saturated linkers showed bi-exponential IET dynamics.

Inequalities in the distribution of the general practice workforce in England: a practice-level longitudinal analysis.

Background: In England, demand for primary care services is increasing and GP shortages are widespread. Recently introduced primary care networks (PCNs) aim to expand the use of additional practice-based roles such as physician associates (PAs), pharmacists, paramedics, and others through financial incentives for recruitment of these roles. Inequalities in general practice, including additional roles, have not been examined in recent years, which is a meaningful gap in the literature.

A global-scale screening of non-native aquatic organisms to identify potentially invasive species under current and future climate conditions.

The threat posed by invasive non-native species worldwide requires a global approach to identify which introduced species are likely to pose an elevated risk of impact to native species and ecosystems. To inform policy, stakeholders and management decisions on global threats to aquatic ecosystems, 195 assessors representing 120 risk assessment areas across all six inhabited continents screened 819 non-native species from 15 groups of aquatic organisms (freshwater, brackish, marine plants and animals) using the Aquatic Species Invasiveness Screening Kit. This multi-lingual decision-support tool for the risk screening of aquatic organisms provides assessors with risk scores for a species under current and future climate change conditions that, following a statistically based calibration, permits the accurate classification of species into high-, medium- and low-risk categories under current and predicted climate conditions.

Meso- and microplastics monitoring in harbour environments: A case study for the Port of Durban, South Africa.

An investigation into the abundance and distribution of meso- and microplastics within the Port of Durban was conducted using a static immersible water pump and particle filtration system to collect meso- and microplastics from the water column, microplastics from sediment samples and corresponding CTD. Microplastics were detected in all samples under investigation. Results suggest that sewage overflow, stormwater drains, port operations, followed by rivers are input areas for mitigation to focus on.

Citizen science reveals microplastic hotspots within tidal estuaries and the remote Scilly Islands, United Kingdom.

The identification of microplastic hotspots is vital to our long-term understanding of their environmental fate and distribution. Although case studies have increased globally, sampling campaigns are often restricted geographically, with poor spatial resolution. Here, we use citizen science to increase our geographical reach, which improved our understanding of microplastic distribution in estuarine and beach sediment along the south-west coast of England.

Identification and characterisation of serotonin signalling in the potato cyst nematode Globodera pallida reveals new targets for crop protection.

Plant parasitic nematodes are microscopic pathogens that invade plant roots and cause extensive damage to crops. We have used a chemical biology approach to define mechanisms underpinning their parasitic behaviour: We discovered that reserpine, a plant alkaloid that inhibits the vesicular monoamine transporter (VMAT), potently impairs the ability of the potato cyst nematode Globodera pallida to enter the host plant root. We show this is due to an inhibition of serotonergic signalling that is essential for activation of the stylet which is used to access the host root.

Synthesis and Properties of Perylene-Bridge-Anchor Chromophoric Compounds.

The quest to control chromophore/semiconductor properties to enable new technologies in energy and information science requires detailed understanding of charge carrier dynamics at the atomistic level, which can often be attained through the use of model systems. Perylene-bridge-anchor compounds are successful models for studying fundamental charge transfer processes on TiO, which remains among the most commonly investigated and technologically important interfaces, mostly because of perylene's advantageous electronic and optical properties. Nonetheless, the ability to fully exploit synthetically the substitution pattern of perylene with linker (= bridge-anchor) units remains little explored.

Helical Peptides Design for Molecular Dipoles Functionalization of Wide Band Gap Oxides.

The use of helical hexapeptides to establish a surface dipole layer on a TiO substrate, with the goal of influencing the energy levels of a coadsorbed chromophore, is explored. Two helical hexapeptides, synthesized from 2-amino isobutyric acid (Aib) residues, were protected at the N-terminus with a carboxybenzyl group (Z) and at the C-terminus carried either a carboxylic acid or an isophthalic acid (Ipa) anchor group to form Z-(Aib)-COOH or Z-(Aib)-Ipa, respectively. Using a combination of vibrational and photoemission spectroscopies, bonding of the two peptides to TiO surfaces (either nanostructured or single-crystal TiO(110)) was found to be highly dependent on the anchor group, with Ipa establishing a monolayer much more efficiently than COOH.

Identifying potentially invasive non-native marine and brackish water species for the Arabian Gulf and Sea of Oman.

Invasive non-native species (NNS) are internationally recognized as posing a serious threat to global biodiversity, economies and human health. The identification of invasive NNS is already established, those that may arrive in the future, their vectors and pathways of introduction and spread, and hotspots of invasion are important for a targeted approach to managing introductions and impacts at local, regional and global scales. The aim of this study was to identify which marine and brackish NNS are already present in marine systems of the northeastern Arabia area (Arabian Gulf and Sea of Oman) and of these which ones are potentially invasive, and which species have a high likelihood of being introduced in the future and negatively affect biodiversity.

Bio-Curation for Cellular Signalling: The KAMI Project.

The general question of what constitutes bio-curation for rule-based modelling of cellular signalling is posed. A general approach to the problem is presented, based on rewriting in hierarchies of graphs, together with a specific instantiation of the methodology that addresses our particular bio-curation problem. The current state of the ongoing development of the KAMI bio-curation tool, based on this approach, is outlined along with our plans for future development.

Morphology-Preserving Sensitization of ZnO Nanorod Surfaces via Click-Chemistry.

Films of ZnO nanorods grown by chemical vapor deposition were functionalized with a chromophore in a stepwise process that preserves the surface morphology. In the first step, the ZnO nanorods were functionalized by exposure to prop-2-ynoic acid (propiolic acid) in vacuum, which did bind through the COOH group leading to a ZnO surface functionalized with ethyne moieties (ethyne/ZnO). In the second step, 9-(4-azidophenyl)-2,5-di-tert-butylperylene (DTBPe-Ph-N) was reacted with the ethyne/ZnO surface via copper-catalyzed azide-alkyne click reaction (CuAAC) in solution to form the DTBPe-functionalized surface (DTBPe/ZnO).

Community fluctuations and local extinction in a planktonic food web.

Determining statistical patterns irrespective of interacting agents (i.e. macroecology) is useful to explore the mechanisms driving population fluctuations and extinctions in natural food webs.

Ocean net heat flux influences seasonal to interannual patterns of plankton abundance.

Changes in the net heat flux (NHF) into the ocean have profound impacts on global climate. We analyse a long-term plankton time-series and show that the NHF is a critical indicator of ecosystem dynamics. We show that phytoplankton abundance and diversity patterns are tightly bounded by the switches between negative and positive NHF over an annual cycle.

Next generation sequencing reveals the hidden diversity of zooplankton assemblages.

Background: Zooplankton play an important role in our oceans, in biogeochemical cycling and providing a food source for commercially important fish larvae. However, difficulties in correctly identifying zooplankton hinder our understanding of their roles in marine ecosystem functioning, and can prevent detection of long term changes in their community structure. The advent of massively parallel next generation sequencing technology allows DNA sequence data to be recovered directly from whole community samples.

Intrinsic information carriers in combinatorial dynamical systems.

Many proteins are composed of structural and chemical features--"sites" for short--characterized by definite interaction capabilities, such as noncovalent binding or covalent modification of other proteins. This modularity allows for varying degrees of independence, as the behavior of a site might be controlled by the state of some but not all sites of the ambient protein. Independence quickly generates a startling combinatorial complexity that shapes most biological networks, such as mammalian signaling systems, and effectively prevents their study in terms of kinetic equations-unless the complexity is radically trimmed.

Internal coarse-graining of molecular systems.

Modelers of molecular signaling networks must cope with the combinatorial explosion of protein states generated by posttranslational modifications and complex formation. Rule-based models provide a powerful alternative to approaches that require explicit enumeration of all possible molecular species of a system. Such models consist of formal rules stipulating the (partial) contexts wherein specific protein-protein interactions occur.

Root and shoot growth, assimilate partitioning and cell proliferation in roots of Sitka spruce (Picea sitchensis) grown in filtered and unfiltered chambers.

Rooted cuttings of clonal Sitka spruce (Picea sitchensis (Bong.) Carr.) were grown from April to October in 1 m long tubes sunk into the ground inside open top chambers.

An evaluation of the effectiveness, safety and acceptability of a nurse practitioner in a rheumatology outpatient clinic.

Seventy patients with RA were randomly allocated to either a Rheumatology Nurse Practitioner (RNP) or Consultant Rheumatologist (CR) clinic. They were seen on six occasions in 1 year. Effectiveness and safety were assessed by biochemical, clinical, psychological and functional variables; patient knowledge and satisfaction were measured by questionnaire.