Facile synthesis of nanocrystalline LiFePO4/graphene composite as cathode material for high power lithium ion batteries

We describe a simple strategy, which is based on the idea of space confinement, for the synthesis of carbon coating on LiFePO₄ nanoparticles/graphene nanosheets composites in a water-in-oil emulsion system. The prepared composite displayed high performance as a cathode material for lithium-ion battery, such as high reversible lithium storage capacity (158 mA h g^-1 after 100 cycles), high coulombic efficiency (over 97%), excellent cycling stability and high rate capability (as high as 83 mA h g ^-1 at 60 C). Very significantly, the preparation method employed can be easily adapted and be extended as a general approach to sophisticated compositions and structures for the preparation of highly dispersed nanosized structure on graphene. 

Super suburbia: developing resilience by closing resource cycles in North Belfast

Sustainability can be described as having three interlinked strands, known as the ‘trias energetica’, without which resilience is difficult to achieve. These strands are environmental, social and economic: and if taken as indicators, the suburbs of North Belfast are very poorly performing indeed. Places such as Ligoneal and Glen Cairn have poor housing stock energetically, and also little economic activity. This paper describes propositional work completed by Queens University and Belfast City Council as part of the UK’s Technology Strategy Board’s Future Cities Programme, which aimed to develop new synergies in these neighbourhoods by the insertion of closed cycle economies.

By utilising a research by design methodology, the paper develops a process-based and phased design to develop a new emergent form to these neighbourhoods, one in which new productive systems are embedded into the city, at a small-scales. These include a peak-load hydro-electric project in Ligoneal; a productive landscape in Glen Cairn and a city-wide energy refurbishment utilising neighbourhood waste streams.

These designs allow for a roadmap for development to be created that could change the modus operandi of an area over a relatively short period of time, and show that even modest investments of productive technologies at a local scale could fundamentally change the form and the economic and environmental operation of the city in the future, and create a new resilient city, one that can be less externally dependent and more socially just.

New suburbia: designing in urban resilience by closing resource cycles

By utilising a research by design methodology, the paper develops a process-based and phased design to develop a new emergent form to these neighbourhoods, one in which new productive systems are embedded into the city, at a small-scales. These include a peak-load hydro-electric project in Ligoneal; a productive landscape in Glen Cairn and a city-wide energy refurbishment utilising neighbourhood waste streams.

The three projects illustrate different ways in which place-based solutions can enact urban transformation through a process of rigorous visualisation of process, and its attendant changes in content and form of the neighbourhood, These designs, based around a process-based strategy plan, allow for a roadmap for development to be created that could change the modus operandi of an area over a relatively short period of time,. The paper demonstrates that even modest investments of productive technologies at a local scale can fundamentally change the form and the economic and environmental operation of the city in the future, and create a new resilient city, one that can have resilience built-in. This resilience allows the neighbourhood to be less externally dependent on resources, economically active and more socially just.

Progress towards improving chronologies for marine sediment records.

The North Atlantic has played a key role in abrupt climate changes due to the sensitivity of the Atlantic Meridional Overturning Circulation (AMOC) to the location and strength of deep water formation. It is crucial for modelling future climate change to understand the role of the AMOC in the rapid warming and gradual cooling cycles known as Dansgaard-Oescher (DO) events which are recorded in the Greenland ice cores. However, palaeoceanographic research into DO events has been hampered by the uncertainty in timing due largely to the lack of a precise chronological time frame for marine records. While tephrochronology provides links to the Greenland ice core records at a few points, radiocarbon remains the primary dating method for most marine cores. Due to variations in the atmospheric and oceanic 14C concentration, radiocarbon ages must be calibrated to provide calendric ages. The IntCal Working Group provides a global estimate of ocean 14C ages for calibration of marine radiocarbon dates, but the variability of the surface marine reservoir age in the North Atlantic particularly during Heinrich or DO events, makes calibration uncertain. In addition, the current Marine09 radiocarbon calibration beyond around 15 ka BP is largely based on 'tuning' to the Hulu Cave isotope record, so that the timing of events may not be entirely synchronous with the Greenland ice cores. The use of event-stratigraphy and independent chronological markers such as tephra provide the scope to improve marine radiocarbon reservoir age estimates particularly in the North Atlantic where a number of tephra horizons have been identified in both marine sediments and the Greenland ice cores. Quantification of timescale uncertainties is critical but statistical techniques which can take into account the differential dating between events can improve the precision. Such techniques should make it possible to develop specific marine calibration curves for selected regions.

Late-Pleistocene palaeoclimate and glacial activity recorded from lake sediments in the Eastern Alps

Greenland ice core data show that the last glaciation in the Northern Hemisphere was characterized by relatively short and rapid warming-cooling cycles. While the Last Glacial Maximum (LGM) and the following Late Glacial are well documented in the Eastern Alps, continuous and well dated records of the time period preceding the LGM are only known from stalagmites. Although most of the sediment that filled the Alpine valleys prior to the LGM was eroded, thick successions have been locally preserved as terraces along the flanks of large longitudinal valleys. The Inn valley in Tyrol (Austria) offers the most striking examples of Pleistocene terraces in the Eastern Alps. A large number of drill cores provides the opportunity to study these sediments for the first time in great detail. Our study focuses on the river terrace of Unterangerberg near Wörgl, where LGM gravel and till were deposited on top of (glacio)lacustrine sediments. The cores comprise mostly silty material, ranging from organic-rich to organic-poor and dropstone-rich beds. A diamictic layer classified as basal till is present at the bottom of the lake sediments. Radiocarbon ages of plant macro remains from the lake sequences indicate deposition between ~40 and >50 cal. ka BP. Luminescence ages obtained from fine-grain polymineral (4-11 μm) samples suggest an age of the lake deposits between ~40 to 60 ka and are consistent with the radiocarbon dates. Sedimentological analyses indicate that sedimentation in these palaeolakes was driven by local processes, but also by climatically induced changes in nearby glacier activity. These observations strongly hint towards a significant ice advance in the Eastern Alps during the early last glacial and subsequent mild interstadial conditions, supporting a local coniferous forest vegetation.

Fludarabine, Cyclophosphamide and Rituximab:an effective chemoimmunotherapy combination with high remission rates for chronic lymphocytic leukaemia

BACKGROUND: Combined Fludarabine and Cyclophosphamide is now standard first-line therapy in chronic lymphocytic leukaemia (CLL) and the addition of Rituximab improves outcome.

METHODS: We adopted a modified Fludarabine, Cyclophosphamide and Rituximab (FCR) protocol in treating 39 patients (median age 57 years) with progressive or advanced CLL. Depending on CR, treatment was given for four or six cycles.

RESULT: Twenty-six patients were treatment naïve and 13 were pre-treated. Twelve patients had progressive Binet stage A, 16 stage B and 11 stage C disease. The overall response rate (ORR) was 100%, with 75% achieving CR. Neutropenia was the major toxicity in 71/187 (38%) of the cycles. There were five deaths, two from infection and three from progressive disease. Twenty-six of 31 patients have maintained their post-treatment disease status for a median of 17 months (2-41).

CONCLUSION: We conclude that FCR is a feasible, well-tolerated and effective treatment for patients with CLL.

Circular polarisation frequency selective surface operating in Ku and Ka band

A double layer circular polarization (CP) frequency selective surface (FSS) for use as a dual-band quasi-optical diplexer suitable for deployment in reflector antenna systems is described. The FSS was designed to reflect Ku band signals (11.7–12.75 GHz) while transmitting Ka band signals (17.3–20.2 GHz) and conserving CP in each of these bands. The simulated/measured reflection loss over the Ku band was less than 0.05/0.1 dB for both TE and TM polarizations, while the simulated/measured axial ratio was less than 0.2/0.75 dB. Over the Ka band, the simulated/measured transmission loss for both polarizations was below 0.25/0.4 dB and the simulated/measured axial ratio was less than 0.25/0.75 dB. To the best of our knowledge, this is the first report of a metallo-dielectric FSS that simultaneously operates in CP for an oblique angle of incidence in both Ku and Ka bands.

A stacked Late Quaternary fluvio-periglacial sequence from the Axe valley, southern England with implications for landscape evolution and Palaeolithic archaeology

The current model of mid-latitude late Quaternary terrace sequences, is that they are uplift-driven but climatically controlled terrace staircases, relating to both regional-scale crustal and tectonic factors, and palaeohydrological variations forced by quasi-cyclic climatic conditions in the 100 K world (post Mid Pleistocene Transition). This model appears to hold for the majority of the river valleys draining into the English Channel which exhibit 8–15 terrace levels over approximately 60–100 m of altitudinal elevation. However, one valley, the Axe, has only one major morphological terrace and has long-been regarded as anomalous. This paper uses both conventional and novel stratigraphical methods (digital granulometry and terrestrial laser scanning) to show that this terrace is a stacked sedimentary sequence of 20–30 m thickness with a quasi-continuous (i.e. with hiatuses) pulsed, record of fluvial and periglacial sedimentation over at least the last 300–400 K yrs as determined principally by OSL dating of the upper two thirds of the sequence. Since uplift has been regional, there is no evidence of anomalous neotectonics, and climatic history must be comparable to the adjacent catchments (both of which have staircase sequences) a catchment-specific mechanism is required. The Axe is the only valley in North West Europe incised entirely into the near-horizontally bedded chert (crypto-crystalline quartz) and sand-rich Lower Cretaceous rocks creating a buried valley. Mapping of the valley slopes has identified many large landslide scars associated with past and present springs. It is proposed that these are thaw-slump scars and represent large hill-slope failures caused by Vauclausian water pressures and hydraulic fracturing of the chert during rapid permafrost melting. A simple 1D model of this thermokarstic process is used to explore this mechanism, and it is proposed that the resultant anomalously high input of chert and sand into the valley during terminations caused pulsed aggradation until the last termination. It is also proposed that interglacial and interstadial incision may have been prevented by the over-sized and interlocking nature of the sub-angular chert clasts until the Lateglacial when confinement of the river overcame this immobility threshold. One result of this hydrogeologically mediated valley evolution was to provide a sequence of proximal Palaeolithic archaeology over two MIS cycles. This study demonstrates that uplift tectonics and climate alone do not fully determine Quaternary valley evolution and that lithological and hydrogeological conditions are a fundamental cause of variation in terrestrial Quaternary records and landform evolution.

High temperature thermal stability of the HfO2/Ge (100) interface as a function of surface preparation studied by synchrotron radiation core level photo emission

High resolution soft x-ray photoemission spectroscopy (SXPS) have been used to study the high temperature thermal stability of ultra-thin atomic layer deposited (ALD) HfO2 layers (∼1 nm) on sulphur passivated and hydrofluoric acid (HF) treated germanium surfaces. The interfacial oxides which are detected for both surface preparations following HfO2 deposition can be effectively removed by annealing upto 700 °C without any evidence of chemical interaction at the HfO2/Ge interface. The estimated valence and conduction band offsets for the HfO2/Ge abrupt interface indicated that effective barriers exist to inhibit carrier injection.

Methodologic rigor of clinical trials on surgical management of eyes with coexisting cataract and glaucoma.

OBJECTIVE:

To assess the methodologic quality of published studies of the surgical management of coexisting cataract and glaucoma.

DESIGN:

Literature review and analysis.

METHOD:

We performed a systematic search of the literature to identify all English language articles pertaining to the surgical management of coexisting cataract and glaucoma in adults. Quality assessment was performed on all randomized controlled trials, nonrandomized controlled trials, and cohort studies. Overall quality scores and scores for individual methodologic domains were based on the evaluations of two experienced investigators who independently reviewed articles using an objective quality assessment form.

MAIN OUTCOME MEASURES:

Quality in each of five domains (representativeness, bias and confounding, intervention description, outcomes and follow-up, and statistical quality and interpretation) measured as the percentage of methodologic criteria met by each study.

RESULTS:

Thirty-six randomized controlled trials and 45 other studies were evaluated. The mean quality score for the randomized, controlled clinical trials was 63% (range, 11%-88%), and for the other studies the score was 45% (range, 3%-83%). The mean domain scores were 65% for description of therapy (range, 0%-100%), 62% for statistical analysis (range, 0%-100%), 58% for representativeness (range, 0%-94%), 49% for outcomes assessment (range, 0%-83%), and 30% for bias and confounding (range, 0%-83%). Twenty-five of the studies (31%) received a score of 0% in the bias and confounding domain for not randomizing patients, not masking the observers to treatment group, and not having equivalent groups at baseline.

CONCLUSIONS:

Greater methodologic rigor and more detailed reporting of study results, particularly in the area of bias and confounding, could improve the quality of published clinical studies assessing the surgical management of coexisting cataract and glaucoma.

Insight into CO Activation over Cu(100) under Electrochemical Conditions

The reduction of CO₂ on copper electrodes has attracted great attentions in the last decades, since it provides a sustainable approach for energy restore. During the CO₂ reduction process, the electron transfer to CO_ads is experimentally suggested to be the crucial step. In this work, we examine two possible pathways in CO activation, i.e. to generate COH_ads and CHO_ads, respectively, by performing the state-of-the-art constrained ab initio molecular dynamics simulations on the charged Cu(100) electrode under aqueous conditions, which is close to the realistic electrochemical condition. The free energy profile in the formation of COH_ads via the coupled proton and electron transfer is plotted. Furthermore, by Bader charge analyses, a linear relationship between C-O bond distance and the negative charge in CO fragment is unveiled. The formation of CHO_ads is identified to be a surface catalytic reaction, which requires the adsorption of H atom on the surface first. By comparing these two pathways, we demonstrate that kinetically the formation of COH_ads is more favored than that of CHO_ads, while CHO_ads is thermodynamically more stable. This work reveals that CO activation via COH_ads intermediate is an important pathway in electrocatalysis, which could provide some insights into CO₂ electroreduction over Cu electrodes.

Síntese e aplicações catalíticas na funcionalização de alcanos de novos compostos com polioxometalatos e catiões orgânicos

A presente dissertação, que no seu conjunto se propõe apresentar o estudo de oxidação de compostos orgânicos com peróxido de hidrogénio na presença dos aniões do tipo Keggin, mono-substituídos por MnIII e FeIII, sob a forma de sais de tetra-n-butilamónio (TBA) e suportados em matriz de sílica funcionalizada, enquanto vital método de obtenção de importante precursores de síntese orgânica, tem na sua base o trabalho de Doutoramento desenvolvido no Departamento de Química da Universidade de Aveiro. Os compostos preparados e testados em sistema homogéneo foram os sais de TBA dos aniões de Keggin, de fórmula geral [XW11M(H2O)O39]n-, onde X = P, Si ou B e M = MnIII e FeIII. Em sistema heterogéneo foram testados diferentes materiais, que diferem entre si na matriz de sílica. Assim, fez-se a heterogeneização de [PW11Fe(H2O)O39]4- em sílica funcionalizada com catiões de césio e grupos propilamónio; [BW11Fe(H2O)O39]6- e [SiW11Fe(H2O)O39]5- foram imobilizados em sílica contendo grupos aminopropilo e o anião [PW11Mn(H2O)O39]4- foi suportado em sílica quimicamente modificada com grupos alquilamónio. Os substratos orgânicos estudados incluem o 1H-indeno, 1,2-di-hidronaftaleno, etilbenzeno, cumeno, p-cimeno, sec-butilbenzeno, 1- e 2-etilnaftaleno, cis-cicloocteno e ciclooctano. Paralelamente usaram-se alguns outros substratos, quando necessário obter esclarecimentos mecanísticos. A tese assenta numa estrutura composta por 7 capítulos. Na primeira, faz-se uma abordagem aos polioxometalatos e às reacções de oxidação de hidrocarbonetos, com particular destaque no uso de polioxometalatos em catálise oxidativa e também no uso de peróxido de hidrogénio como oxidante. A eficiência catalítica dos aniões de Keggin mono substituídos por MnIII e FeIII, em sistema homogéneo foi avaliada na oxidação de compostos orgânicos característicos, nomeadamente de ciclo-alcenilbenzenos, alquilbenzenos, ciclo-alquilbenzenos e hidrocarbonetos aromáticos policíclicos com H2O2, em acetonitrilo. Os resultados destes estudos encontram-se descritos nos capítulos dois, três e quatro desta tese. Estes compostos mostraram-se catalisadores eficientes e selectivos para a oxidação de alcanos e alcenos. O quinto capítulo da tese prossegue com a síntese, caracterização e eficiência catalítica dos polioxotungstatos referidos anteriormente imobilizados numa matriz de sílica funcionalizada com iões césio (SiO2-Cs), grupos aminopropilo (SiO2–(CH2)3NH2) ou trietilpropilamónio (SiO2-(CH2)3N(Et)3). A actividade catalítica destes compostos foi estudada utilizando o cis-cicloocteno e ciclooctano como substratos padrão. A oxidação de cis-clicoocteno originou o epóxido com 100% de selectividade e o catalisador foi reutilizado durante 4 ciclos com elevada eficiência. No sexto capítulo, são descritas as metodologias experimentais de síntese dos novos compostos, as condições catalíticas, a instrumentação e demais métodos e procedimentos usados. No sétimo e último capítulo, tecem-se as conclusões finais e apresentam-se algumas perspectivas de trabalho futuro utilizando o sistema, POM/H2O2, usado neste trabalho.