Higher and lower supramolecular orders for the design of self-assembled heterochiral tripeptide hydrogel biomaterials

The self-assembly behaviour of the eight stereoisomers of Val\u2013Phe\u2013Phe tripeptides under physiological conditions is assessed by several spectroscopy and microscopy techniques. We report the first examples of self-organised hydrogels from tripeptides in the L\u2013D\u2013L or D\u2013L\u2013D configuration, besides the expected gels with the D\u2013L\u2013L or L\u2013D\u2013D configuration, thus widening the scope for using amino acid chirality as a tool to drive self-assembly. Importantly, the positions of D- and L-amino acids in the gelling tripeptides determine a higher or lower supramolecular order, which translates into macroscopic gels with different rheological properties and thermal behaviours. The more durable hydrogels perform well in cytotoxicity assays, and also as peptides in solution. An appropriate design of the chirality of self-assembling sequences thus allows for the fine-tuning of the properties of the gel biomaterials. In conclusion, this study adds key details of supramolecular organization that will assist in the ex novo design of assembling chiral small molecules for their use as biomaterials

Design of a hydrophobic tripeptide that self-assembles into amphiphilic superstructures forming a hydrogel biomaterial

We report the rational design of a heterochiral hydrophobic tripeptide self-assembling into amphiphilic D-superstructures that yield a self-supportive hydrogel at physiological pH. The material endures cell culture conditions and sustains fibroblast proliferation. Tripeptide superstructures are thoroughly analysed by several techniques

All at sea? Maritime dimensions of Europe's relations with Africa

The article examines three dimensions of Europe’s maritime relations with Africa: first, the notion that Europe’s strategic maritime frontiers are linked to Africa; second, the coherence or ‘actorness’ of the European Union’s (EU) anti-piracy force operating off the Horn of Africa; and third, the relationship between the EU’s own military and naval objectives and its wider regional policies in Africa. While the EU adopted a ‘Maritime Security Strategy’ in 2014, the article notes that, in practice, the EU’s strategy at sea has focused on two groups of ‘non-state actors’: the Africans who are ‘pirates’; and the migrants crossing the Mediterranean, who are the object of the EU’s Frontex patrols. As such, the initial question examined charts the somewhat fluid notion of the sea as a maritime frontier: where do Europe’s strategic interests in terms of its maritime frontiers lie? Is the EU’s anti-piracy mission defending them? Is this first-ever maritime mission a more tangible manifestation of EU’s common foreign and defence policy than some of the other shorter and smaller military and policing missions in Africa

Integration of environmental aspects in modelling and optimisation of water supply chains

Climate change becomes increasingly more relevant in the context of water systems planning. Tools are necessary to provide the most economic investment option considering the reliability of the infrastructure from technical and environmental perspectives. Accordingly, in this work, an optimisation approach, formulated as a spatially-explicit multi-period Mixed Integer Linear Programming (MILP) model, is proposed for the design of water supply chains at regional and national scales. The optimisation framework encompasses decisions such as installation of new purification plants, capacity expansion, and raw water trading schemes. The objective is to minimise the total cost incurring from capital and operating expenditures. Assessment of available resources for withdrawal is performed based on hydrological balances, governmental rules and sustainable limits. In the light of the increasing importance of reliability of water supply, a second objective, seeking to maximise the reliability of the supply chains, is introduced. The epsilon-constraint method is used as a solution procedure for the multi-objective formulation. Nash bargaining approach is applied to investigate the fair trade-offs between the two objectives and find the Pareto optimality. The models' capability is addressed through a case study based on Australia. The impact of variability in key input parameters is tackled through the implementation of a rigorous global sensitivity analysis (GSA). The findings suggest that variations in water demand can be more disruptive for the water supply chain than scenarios in which rainfalls are reduced. The frameworks can facilitate governmental multi-aspect decision making processes for the adequate and strategic investments of regional water supply infrastructure

Optimal design of water treatment processes

Predicted water shortages assign water treatment a leading role in improving water resources management. One of the main challenges associated with the processes remains early stage design of techno-economically optimised purification. This work addresses the current gap by undertaking a whole-system approach of flowsheet synthesis for the production of water at desired purity at minimum overall cost. The optimisation problem was formulated as a mixed-integer non-linear programming model. Two case studies were presented which incorporated the most common commercial technologies and the major pollution indicators, such as chemical oxygen demand, dissolved organic carbon, total suspended solids and total dissolved solids. The results were analysed and compared to existing guidelines in order to examine the applicability of the proposed approach

The Role of Kemeny's Constant in Properties of Markov Chains

In a finite state irreducible Markov chain with stationary probabilities \pi_i and mean first passage times m_(ij) (mean recurrence time when i = j) it was first shown by Kemeny and Snell (1960) that \sum_j \pi_j m_(ij) is a constant K, not depending on i. This constant has since become known as Kemeny's constant. A variety of techniques for finding expressions and various bounds for K are derived. The main interpretation focuses on its role as the expected time to mixing in a Markov chain. Various applications are considered including perturbation results, mixing on directed graphs and its relation to the Kirchhoff index of regular graphs.Comment: 13 page

Djibouti: small state strategy at a crossroads

Geography and politics indicate Djibouti would be a particularly weak and ineffectual ‘small state’. Located on a bridgehead between the poorest parts of Africa and Arabia, it is continental Africa’s smallest state by population and is devoid of natural resources. The text demonstrates that Djibouti has been able to transform weakness and liabilities stemming from its geo-strategic location, sandwiched between large neighbours and key maritime shipping lanes, into a lucrative ‘resource’. This has been achieved via creative diplomacy, fostering ties with a diverse range of states, translating acute dependence into economic and diplomatic capital. The text focusses primarily upon diplomatic strategies, while addressing broader concerns of small states’ energy, infrastructure and development policies

"Nested" cryptic diversity in a widespread marine ecosystem engineer: a challenge for detecting biological invasions

<p>Abstract</p> <p>Background</p> <p>Ecosystem engineers facilitate habitat formation and enhance biodiversity, but when they become invasive, they present a critical threat to native communities because they can drastically alter the receiving habitat. Management of such species thus needs to be a priority, but the poorly resolved taxonomy of many ecosystem engineers represents a major obstacle to correctly identifying them as being either native or introduced. We address this dilemma by studying the sea squirt <it>Pyura stolonifera</it>, an important ecosystem engineer that dominates coastal communities particularly in the southern hemisphere. Using DNA sequence data from four independently evolving loci, we aimed to determine levels of cryptic diversity, the invasive or native status of each regional population, and the most appropriate sampling design for identifying the geographic ranges of each evolutionary unit.</p> <p>Results</p> <p>Extensive sampling in Africa, Australasia and South America revealed the existence of "nested" levels of cryptic diversity, in which at least five distinct species can be further subdivided into smaller-scale genetic lineages. The ranges of several evolutionary units are limited by well-documented biogeographic disjunctions. Evidence for both cryptic native diversity and the existence of invasive populations allows us to considerably refine our view of the native versus introduced status of the evolutionary units within <it>Pyura stolonifera </it>in the different coastal communities they dominate.</p> <p>Conclusions</p> <p>This study illustrates the degree of taxonomic complexity that can exist within widespread species for which there is little taxonomic expertise, and it highlights the challenges involved in distinguishing between indigenous and introduced populations. The fact that multiple genetic lineages can be native to a single geographic region indicates that it is imperative to obtain samples from as many different habitat types and biotic zones as possible when attempting to identify the source region of a putative invader. "Nested" cryptic diversity, and the difficulties in correctly identifying invasive species that arise from it, represent a major challenge for managing biodiversity.</p