Facile synthesis of guanidine functionalised building blocks

Three useful developments in the preparation of guanidines are presented herein. A collection of bis(Boc)aminoalkylguanidines (n=2, 3, 4 and 6; Boc=tert-butoxycarbonyl), known to be prone to cyclisation, have been synthesised and isolated without chromatography as shelf-stable sulfonate salts in good yield (up to 94%). Secondly, a selection of guanidines tethered to a range of other functional groups, including alkyne, alkene, alcohol, and azide, have been prepared in good yields with no requirement for a purification step, and thirdly an inexpensive, high-yielding (93%), and facile synthesis of N,N'-bis(Boc)guanidine, a key precursor for N,N'-bis(Boc)-N'-triflylguanidine, is described in which the need for chromatographic purification is again obviated.

Graphene and graphitic derivative filled polymer composites as potential sensors

Graphite and numerous graphitic-derived micro- and nano-particles have gained importance in current materials science research. These two-dimensional sheets of sp(2)-hybridized carbon atoms remarkably influence the properties of polymers. Graphene mono-layers, graphene oxides, graphite oxides, exfoliated graphite, and other related materials are derived from a parental graphite structure. In this review, we focus primarily on the role of these fillers in regulating the electrical and sensing properties of polymer composites. It has been demonstrated that the addition of an optimized mixture of graphene and or its derivatives to various polymers produces a record-high enhancement of the electrical conductivity and achieved semiconducting characteristics at small filler loading, making it suitable for sensor manufacture. Promising sensing characteristics are observed in graphite-derived composite films compared with those of micro-sized composites and the properties are explained mainly based on the filler volume fraction, nature and rate of dispersion and the filler polymer interactions at the interface. In short, this critical review aims to provide a thorough understanding of the recent advances in the area of graphitic-based polymer composites in advanced electronics. Future perspectives in this rapidly developing field are also discussed.

An alternative clustering scheme in WSN

Despite significant advancements in wireless sensor networks (WSNs), energy conservation in the networks remains one of the most important research challenges. One approach commonly used to prolong the network lifetime is through aggregating data at the cluster heads (CHs). However, there is possibility that the CHs may fail and function incorrectly due to a number of reasons such as power instability. During the failure, the CHs are unable to collect and transfer data correctly. This affects the performance of the WSN. Early detection of failure of CHs will reduce the data loss and provide possible minimal recovery efforts. This paper proposes a self-configurable clustering mechanism to detect the disordered CHs and replace them with other nodes. Simulation results verify the effectiveness of the proposed approach.

Self-assembled V2O5 interconnected microspheres produced in a fish-water electrolyte medium as a high-performance lithium-ion-battery cathode

Interconnected microspheres of V2O5 composed of ultra-long nanobelts are synthesized in an environmental friendly way by adopting a conventional anodization process combined with annealing. The synthesis process is simple and low-cost because it does not require any additional chemicals or reagents. Commercial fish-water is used as an electrolyte medium to anodize vanadium foil for the first time. Electron microscopy investigation reveals that each belt consists of numerous nanofibers with free space between them. Therefore, this novel nanostructure demonstrates many outstanding features during electrochemical operation. This structure prevents self-aggregation of active materials and fully utilizes the advantage of active materials by maintaining a large effective contact area between active materials, conductive additives, and electrolyte, which is a key challenge for most nanomaterials. The electrodes exhibit promising electrochemical performance with a stable discharge capacity of 227 mAh·g–1 at 1C after 200 cycles. The rate capability of the electrode is outstanding, and the obtained capacity is as high as 278 at 0.5C, 259 at 1C, 240 at 2C, 206 at 5C, and 166 mAh·g–1 at 10C. Overall, this novel structure could be one of the most favorable nanostructures of vanadium oxide-based cathodes for Li-ion batteries. [Figure not available: see fulltext.]

Nanopatterning and electrical tuning of MoS2 layers with a subnanometer helium ion beam

We report subnanometer modification enabled by an ultrafine helium ion beam. By adjusting ion dose and the beam profile, structural defects were controllably introduced in a few-layer molybdenum disulfide (MoS2) sample and its stoichiometry was modified by preferential sputtering of sulfur at a few-nanometer scale. Localized tuning of the resistivity of MoS2 was demonstrated and semiconducting, metallic-like, or insulating material was obtained by irradiation with different doses of He(+). Amorphous MoSx with metallic behavior has been demonstrated for the first time. Fabrication of MoS2 nanostructures with 7 nm dimensions and pristine crystal structure was also achieved. The damage at the edges of these nanostructures was typically confined to within 1 nm. Nanoribbons with widths as small as 1 nm were reproducibly fabricated. This nanoscale modification technique is a generalized approach that can be applied to various two-dimensional (2D) materials to produce a new range of 2D metamaterials.

Mechanism of a green graphene oxide reduction with reusable potassium carbonate

 A green method for the deoxygenation of graphene oxide (GO) was developed using K2CO3 as a reusable reduction agent. The size and thickness of the reduced GO are less than 1 μm and around 0.85 nm, respectively. Carbon dioxide is the only byproduct during this process. The reduction mechanism of the graphene oxide includes two reduction steps. On the one hand, ionic oxygen generated from the electrochemical reaction between hydroxyl ions and oxygen in the presence of K2CO3 reacts with carbonyl groups attached to the GO layers at 50°C. On the other hand, ionic oxygen attacks hydroxyl and epoxide groups, which become carbonyl groups and then are converted to carbon dioxide by K2CO3 at 90°C. These oxygenous groups are finally converted to CO2 from graphene layers, leading to the formation of graphene sheets. Headspace solid-phase microextraction and gas chromatography-mass spectrometry detected the existence of n-dodecanal and 4-ethylbenzoic acid cyclopentyl ester during the reduction, suggesting that oxygen functional groups on the GO layers are not only aligned, but randomly dispersed in some areas based on the proposed mechanism.

Patterns of connectivity and population structure of the southern calamary Sepioteuthis australis in southern Australia

The southern calamary, Sepioteuthis australis, is a commercially and recreationally important inshore cephalopod endemic to southern Australia and New Zealand. Typical of other cephalopods, S. australis has a short life span, form nearshore spawning aggregations and undergo direct development. Such life history traits may restrict connectivity between spawning grounds creating highly structured and genetically differentiated populations that are susceptible to population crashes. Here we use seven polymorphic microsatellite markers to assess connectivity and population structure of S. australis across a large part of its geographic range in Australia. Little genetic differentiation was found between sampling locations. Overall, FST was low (0.005, 95% CI≤<0.001-0.011) and we detected no significant genetic differentiation between any of the locations sampled. There was no strong relationship between genetic and geographical distance, and our neighbour joining analysis did not show clustering of clades based on geographical locations. Similarly, network analysis showed strong connectivity amongst most locations, in particular, Tasmania appears to be well connected with several other locations and may act as an important source population. High levels of gene flow and connectivity between S. australis sampling sites across Australia are important for this short-lived species, ensuring resilience against spatial and temporal mortality fluctuations.

Novel imidazolinium ionic liquids and organic salts

The preparation and physical properties of a novel family of ionic liquids and organic salts based on the imidazolinium cation are described, and compared with their imidazolium analogues in some cases. Ionic liquids were obtained with the triflate, formate and salicylate anions, while > 100 °C melting points were observed with acetate and several other benzoate derivatives. The triflate salt was less ion-conductive than the corresponding imidazolium salt, but less so than expected on the basis of its viscosity, suggesting a contribution from proton conductivity. The electrochemical window of the imidazolinium was slightly extended in the reductive direction, due to the lower proton activity produced by the cation in this case. Imidazolinium salts are also known to exhibit anti-corrosion properties and hence a preliminary study of this property is also reported; 2-methylimidazolinium 4-hydroxycinnamate was found to show strong anodic corrosion inhibition on mild steel.

Synthesis of N-substituted 4-hydroxynaphthalimides using palladium-catalysed hydroxylation

Successful implementation of a palladium-mediated hydroxylation of N-substituted 4-chloro-1,8-naphthalimides has been achieved. The methodology detailed herein utilises 4-chloro-1,8-naphthalic anhydride as a starting point and implements the catalyst/ligand combination of Pd(OAc)2/t-BuXPhos; all of which are relatively inexpensive. A range of imide substituents tolerated the reaction conditions, including acid sensitive substrates which are not compatible with other existing methodology. As such this approach is not only complimentary to existing procedures, it presents a more direct alternative to accessing 4-hydroxy-1,8-naphthalimides.

Novel Na+ Ion diffusion mechanism in mixed organic-inorganic ionic liquid electrolyte leading to high Na+ transference number and stable, high rate electrochemical cycling of sodium cells

Ambient temperature sodium batteries hold the promise of a new generation of high energy density, low-cost energy storage technologies. Particularly challenging in sodium electrochemistry is achieving high stability at high charge/discharge rates. We report here mixtures of inorganic/organic cation fluorosulfonamide (FSI) ionic liquids that exhibit unexpectedly high Na+ transference numbers due to a structural diffusion mechanism not previously observed in this type of electrolyte. The electrolyte can therefore support high current density cycling of sodium. We investigate the effect of NaFSI salt concentration in methylpropylpyrrolidinium (C3mpyr) FSI ionic liquid (IL) on the reversible plating and dissolution of sodium metal, both on a copper electrode and in a symmetric Na/Na metal cell. NaFSI is highly soluble in the IL allowing the preparation of mixtures that contain very high Na contents, greater than 3.2 mol/kg (50 mol %) at room temperature. Despite the fact that overall ion diffusivity decreases substantially with increasing alkali salt concentration, we have found that these high Na+ content electrolytes can support higher current densities (1 mA/cm2) and greater stability upon continued cycling. EIS measurements indicate that the interfacial impedance is decreased in the high concentration systems, which provides for a particularly low-resistance solid-electrolyte interphase (SEI), resulting in faster charge transfer at the interface. Na+ transference numbers determined by the Bruce-Vincent method increased substantially with increasing NaFSI content, approaching >0.3 at the saturation concentration limit which may explain the improved performance. NMR spectroscopy, PFG diffusion measurements, and molecular dynamics simulations reveal a changeover to a facile structural diffusion mechanism for sodium ion transport at high concentrations in these electrolytes.

A multiobjective state transition algorithm for single machine scheduling

In this paper, a discrete state transition algorithm is introduced to solve a multiobjective single machine job shop scheduling problem. In the proposed approach, a non-dominated sort technique is used to select the best from a candidate state set, and a Pareto archived strategy is adopted to keep all the non-dominated solutions. Compared with the enumeration and other heuristics, experimental results have demonstrated the effectiveness of the multiobjective state transition algorithm.

Flood Risk Management In Small Urban River Using A Sustainable Urban Drainage System: Wortley Beck, Leeds, Uk

In the UK, urban river basins are particularly vulnerable to flash floods due to short and intense rainfall. This paper presents potential flood resilience approaches for the highly urbanised Wortley Beck river basin, south west of the Leeds city centre. The reach of Wortley Beck is approximately 6km long with contributing catchment area of 30km2 that drain into the River Aire. Lower Wortley has experienced regular flooding over the last few years from a range of sources, including Wortley Beck and surface and ground water, that affects properties both upstream and downstream of Farnley Lake as well as Wortley Ring Road. This has serious implications for society, the environment and economy activity in the City of Leeds. The first stage of the study involves systematically incorporating Wortley Beck’s land scape features on an Arc-GIS platform to identify existing green features in the region. This process also enables the exploration of potential blue green features: green spaces, green roofs, water retention ponds and swales at appropriate locations and connect them with existing green corridors to maximize their productivity. The next stage is involved in developing a detailed 2D urban flood inundation model for the Wortley Beck region using the CityCat model. CityCat is capable to model the effects of permeable/impermeable ground surfaces and buildings/roofs to generate flood depth and velocity maps at 1m caused by design storm events. The final stage of the study is involved in simulation of range of rainfall and flood event scenarios through CityCat model with different blue green features. Installation of other hard engineering individual property protection measures through water butts and flood walls are also incorporated in the CityCat model. This enables an integrated sustainable flood resilience strategy for this region.

Hydropower Energy Simulation Using Mike 11 Model; A Case Study In South Germany's Small Run-Of-River Hydropower Plants

Renewable energy production is a basic supplement to stabilize rapidly increasing global energy demand and skyrocketing energy price as well as to balance the fluctuation of supply from non-renewable energy sources at electrical grid hubs. The European energy traders, government and private company energy providers and other stakeholders have been, since recently, a major beneficiary, customer and clients of Hydropower simulation solutions. The relationship between rainfall-runoff model outputs and energy productions of hydropower plants has not been clearly studied. In this research, association of rainfall, catchment characteristics, river network and runoff with energy production of a particular hydropower station is examined. The essence of this study is to justify the correspondence between runoff extracted from calibrated catchment and energy production of hydropower plant located at a catchment outlet; to employ a unique technique to convert runoff to energy based on statistical and graphical trend analysis of the two, and to provide environment for energy forecast. For rainfall-runoff model setup and calibration, MIKE 11 NAM model is applied, meanwhile MIKE 11 SO model is used to track, adopt and set a control strategy at hydropower location for runoff-energy correlation. The model is tested at two selected micro run-of-river hydropower plants located in South Germany. Two consecutive calibration is compromised to test the model; one for rainfall-runoff model and other for energy simulation. Calibration results and supporting verification plots of two case studies indicated that simulated discharge and energy production is comparable with the measured discharge and energy production respectively.

Evaluating And Optimizing Sustainable Drainage Design To Maximize Multiple Benefits: Case Studies In China

In the past, the focus of drainage design was on sizing pipes and storages in order to provide sufficient network capacity. This traditional approach, together with computer software and technical guidance, had been successful for many years. However, due to rapid population growth and urbanisation, the requirements of a “good” drainage design have also changed significantly. In addition to water management, other aspects such as environmental impacts, amenity values and carbon footprint have to be considered during the design process. Going forward, we need to address the key sustainability issues carefully and practically. The key challenge of moving from simple objectives (e.g. capacity and costs) to complicated objectives (e.g. capacity, flood risk, environment, amenity etc) is the difficulty to strike a balance between various objectives and to justify potential benefits and compromises. In order to assist decision makers, we developed a new decision support system for drainage design. The system consists of two main components – a multi-criteria evaluation framework for drainage systems and a multi-objective optimisation tool. The evaluation framework is used for the quantification of performance, life-cycle costs and benefits of different drainage systems. The optimisation tool can search for feasible combinations of design parameters such as the sizes, order and type of drainage components that maximise multiple benefits. In this paper, we will discuss real-world application of the decision support system. A number of case studies have been developed based on recent drainage projects in China. We will use the case studies to illustrate how the evaluation framework highlights and compares the pros and cons of various design options. We will also discuss how the design parameters can be optimised based on the preferences of decision makers. The work described here is the output of an EngD project funded by EPSRC and XP Solutions.

SESAME: Finding Ways Of Promoting SME Adaptation To Flood Risk

Small and medium-sized companies and other enterprises (SMEs) around the world are exposed to flood risk and many of the 4.5 million in the UK are at risk. As SMEs represent almost half of total business turnover in the UK, their protection is a vital part of the drive for greater climate change resilience. However, few have measures in place to ensure the continuity of their activities during a flood and its aftermath. The SESAME project aims to develop tools that encourage businesses to discover ways of becoming more resilient to floods and to appreciate how much better off they will be once they have adapted to the ongoing risk. By taking some of the mystery out of flooding and flood risk, it aims to make it susceptible to the same business acumen that enables the UK’s SMEs to deal with the many other challenges they face. In this paper we will report on the different aspects of the research in the project Understanding behaviour Changing behaviour Modelling impacts Economic impacts Through the above the project will advise government, local authorities and other public bodies on how to improve their responses to floods and will enable them to recommend ways to improve the guidelines provided to SMEs in flood risk areas.