Vibrational Spectroscopic Studies into Impurities in Ionic Liquids

Additional components present within an ionic liquid (IL) system have readily shown to alter the physiochemical properties and spectroscopic characteristics of the parent IL. Vibrational spectroscopy has been proven to be a powerful tool in probing these systems and identifying spectral changes as a result of the changing environment. This work presents a range of imidazolium-based ILs that have been probed with vibrational spectroscopy. The ILs investigated possess a 1-alkyl-3-methylimidazolium cation with corresponding anions ranging from [BF4] -, [Ac] -, Cl -, [DMP] -, and [MeSO4] -. Each IL investigated was doped with an array of impurities that may commonly be retained in an IL system due to preparation and or exposure to the environment. Contamination is a common problem, leading to the perturbation of many physical and chemical properties, which can impact the overall efficiency of an IL. Vibrational spectroscopy allows for the investigation into perturbations created by impurities and how varying concentrations ultimately affect the vibrational nature of the IL. These interactions have further been studied with the use of multivariate analysis to provide further insight into these changes. The combination of multiple vibrational spectroscopic techniques and analysis has allowed for an in-depth investigation into contaminated IL systems

Design synthesis and shape generation

If we are to capitalise on the potential that a design approach might bring to innovation in business and society, we need to build a better understanding of the evolving skill-sets that designers will need and the contexts within which design might operate. This demands more discourse between those involved in cutting edge practice, the researchers who help to uncover principles, codify knowledge and create theories and the educators who are nurturing future design talent. This book promotes such a discourse by reporting on the work of twenty research teams who explored different facets of future design activity as part of Phase 2 of the UK's research council supported Designing for the 21st Century Research Initiative. Each of these contributions describes the origins of the project, the research team and their project aims, the research methods used and the new knowledge and understanding generated. Editor and Initiative Director, Professor Tom Inns, provides an introductory chapter that suggests ways the reader might navigate these viewpoints. This chapter concludes with an overview of the key lessons that might be learnt from this collection of design research activity

Influence of body mass index and gender on physical activity in primary school children during PE and non-PE school days

The benefits of physical activity (PA) for children are well recognised. Children who display high levels of moderate to vigorous physical activity (MVPA) have a lower risk of becoming overweight/obese(1) or becoming inactive adults(2). Existing evidence suggests a potential interaction between gender and BMI in terms of PA, with low MVPA associated with those with greater BMI z-scores in 7–9 year old girls, but not boys(3). In 2014, the new National Curriculum for England was implemented across the UK for Physical Education (PE). The aim of this study was to compare objectively measured PA on PE and non-PE days and determine whether children’s BMI and gender influenced the differences found. PA was measured using tri-axial accelerometers (Actigraph GT3X-BT) worn at the hip in male (n 47) and female (n 39) children aged 6·8 (SD 0·6) years, height 123·2 (SD 5·6) cm and body mass 24·45 (SD 3·95) kg over four days at school (360 min per day). The duration of sedentary and MVPA in regular class time and structured PE classes (46 (SD 12) min duration) was measured using the previously validated Pulsford cut off points(4). BMI z-scores were calculated using WHO guidelines. Data were analysed using Pearson correlations, paired samples and independent samples t-tests, Cohen’s d for effect sizes (ES) and are presented as mean (SD). Children carried out more MVPA on PE days compared to non-PE days (ES = 0·78) and during PE lessons compared to corresponding non-PE time. Furthermore, children were significantly less sedentary in PE lessons compared to corresponding non-PE time. Consequently, children spent less overall time in the sedentary activity category on PE days compared to non-PE days(ES = 0·68). Childrens’ BMI z-scores correlated significantly with their quantity of sedentary and light activity (P < 0·001), but not MVPA (P = 0·60) and were very similar on both PE and non-PE days. Males were more active than their female peers, performing 8 and 6 min more MVPA (ES 0·89, 0·72) and 12 and 8 min less sedentary time on PE and non-PE days (ES −0·62, −0·42), respectively. In conclusion, PE lessons increased childrens’ daily MVPA and reduced their sedentary time. Although gender and BMI were associated with PA levels, the inclusion of PE lessons did not markedly increase their influence on overall energy expenditure. Overall, the study shows that PE lessons have a positive effect on childrens’ PA levels, likely resulting in positive effects on adiposity and overall health and wellbeing. 1. Bornstein D, Beets M, Byun W et al. (2011) J Sci Med Sport 14, 504–511. 2. Biddle SJH, Pearson N, Ross GM et al. (2010) Prev Med 51, 345–51. 3. Basterfield L, Adamson AJ, Pearce MS et al. (2011) J Phys Act Health 8, 543–547. 4. Pulsford RM, Cortina-Borja M, Rich C et al. (2011) PLoS One 6, 1–9

Resolving X-Ray Photoelectron Spectra of Ionic Liquids with Difference Spectroscopy

X-ray photoelectron spectroscopy (XPS) is a powerful element-specific technique to determine the composition and chemical state of all elements in an involatile sample. However, for elements such as carbon, the wide variety of chemical states produce complex spectra that are difficult to interpret, consequently concealing important information due to the uncertainty in signal identity. Here we report a process whereby chemical modification of carbon structures with electron withdrawing groups can reveal this information, providing accurate, highly refined fitting models far more complex than previously possible. This method is demonstrated with functionalised ionic liquids bearing chlorine or trifluoromethane groups that shift electron density from targeted locations. By comparing the C 1s spectra of non-functional ionic liquids to their functional analogues, a series of difference spectra can be produced to identify exact binding energies of carbon photoemissions, which can be used to improve the C 1s peak fitting of both samples. Importantly, ionic liquids possess ideal chemical and physical properties, which enhance this methodology to enable significant progress in XPS peak fitting and data interpretation

Satellite-based model detection of recent climate-driven changes in northern high-latitude vegetation productivity

We applied a satellite remote sensing based production efficiency model (PEM) using an integrated AVHRR and MODIS FPAR/LAI time series with a regionally corrected NCEP/NCAR reanalysis daily surface meteorology and NASA/GEWEX Surface Radiation Budget shortwave solar radiation inputs to assess annual terrestrial net primary productivity (NPP) for the pan-Arctic basin and Alaska from 1983 to 2005. Our results show that low temperature constraints on Boreal-Arctic NPP are decreasing by 0.43% per year (P \u3c 0.001), whereas a positive trend in vegetation moisture constraints of 0.49% per year (P = 0.04) are offsetting the potential benefits of longer growing seasons and contributing to recent disturbances in NPP. The PEM simulations of NPP seasonality, annual anomalies and trends are similar to stand inventory network measurements of boreal aspen stem growth (r = 0.56; P = 0.007) and atmospheric CO2 measurement based estimates of the timing of growing season onset (r = 0.78; P \u3c 0.001). Our results indicate that summer drought led to marked NPP decreases in much of the boreal forest region after the late-1990s. However, seasonal low temperatures are still a dominant limitation on regional NPP. Despite recent drought events, mean annual NPP for the pan-Arctic region showed a positive growth trend of 0.34% per year (20.27 TgC/a; P = 0.002) from 1983 to 2005. Drought induced NPP decreases may become more frequent and widespread as regional ecosystems adjust to a warmer, drier atmosphere, though the occurrence and severity of drought events will depend on future patterns of plant-available moisture

Chemical tagging can work: Identification of stellar phase-space structures purely by chemical-abundance similarity

Chemical tagging promises to use detailed abundance measurements to identify spatially separated stars that were in fact born together (in the same molecular cloud), long ago. This idea has not yielded much practical success, presumably because of the noise and incompleteness in chemical-abundance measurements. We have succeeded in substantially improving spectroscopic measurements with The Cannon, which has now delivered 15 individual abundances for ~100,000 stars observed as part of the APOGEE spectroscopic survey, with precisions around 0.04 dex. We test the chemical-tagging hypothesis by looking at clusters in abundance space and confirming that they are clustered in phase space. We identify (by the k-means algorithm) overdensities of stars in the 15-dimensional chemical-abundance space delivered by The Cannon, and plot the associated stars in phase space. We use only abundance-space information (no positional information) to identify stellar groups. We find that clusters in abundance space are indeed clusters in phase space. We recover some known phase-space clusters and find other interesting structures. This is the first-ever project to identify phase-space structures at survey-scale by blind search purely in abundance space; it verifies the precision of the abundance measurements delivered by The Cannon; the prospects for future data sets appear very good.Comment: accepted for publication in the Ap

The Kuroshio Extension northern recirculation gyre : profiling float measurements and forcing mechanism

Author Posting. © American Meteorological Society, 2008. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Physical Oceanography 38 (2008): 1764-1779, doi:10.1175/2008JPO3921.1.Middepth, time-mean circulation in the western North Pacific Ocean (28°–45°N, 140°–165°E) is investigated using drift information from the profiling floats deployed in the Kuroshio Extension System Study (KESS) and the International Argo programs. A well-defined, cyclonic recirculation gyre (RG) is found to exist north of the Kuroshio Extension jet, confined zonally between the Japan Trench (145°E) and the Shatsky Rise (156°E), and bordered to the north by the subarctic boundary along 40°N. This northern RG, which is simulated favorably in the eddy-resolving OGCM for the Earth Simulator (OFES) hindcast run model, has a maximum volume transport at 26.4 Sv across 159°E and its presence persists on the interannual and longer time scales. An examination of the time-mean x-momentum balance from the OFES hindcast run output reveals that horizontal convergence of Reynolds stresses works to accelerate both the eastward-flowing Kuroshio Extension jet and a westward mean flow north of the meandering jet. The fact that the northern RG is eddy driven is further confirmed by examining the turbulent Sverdrup balance, in which convergent eddy potential vorticity fluxes are found to induce the cyclonic RG across the background potential vorticity gradient field. For the strength of the simulated northern RG, the authors find the eddy dissipation effect to be important as well.This study was supported by NSF through Grant OCE-0220680 (UH) and OCE-0220161 (WHOI)

Systematic Review of Prognostic Factors for Return to Work in Workers with Sub Acute and Chronic Low Back Pain

Morgan, John (2012)Teaching Secondary Geography as if the Planet MattersLondres: Routledge, 165 p.ISBN 978-0-415-56387-1Morgan, John (2012)Teaching Secondary Geography as if the Planet MattersLondres: Routledge, 165 p.ISBN 978-0-415-56387-1Morgan, John (2012)Teaching Secondary Geography as if the Planet MattersLondres: Routledge, 165 p.ISBN 978-0-415-56387-1Morgan, John (2012)Teaching Secondary Geography as if the Planet MattersLondres: Routledge, 165 p.ISBN 978-0-415-56387-

Initial Results of a Prospective Study of Adjuvant Pancreatic Stereotactic Body Radiation Therapy for Close or Positive Margins

Purpose: Patients with close or positive margins after surgery for pancreatic carcinoma are at a high risk for recurrence. Stereotactic body radiation therapy (SBRT) allows for safe dose escalation with great conformity and short duration of treatment. Herein, we report the initial results of a prospective observational study that evaluated the efficacy and safety of this treatment option. Methods and Materials: Patients eligible for the study had pathologically proven T1-4N0-1M0 pancreatic adenocarcinoma with a positive margin (≤ 1 mm) or a close margin defined as \u3c 2.5 mm. Patients were treated with either neoadjuvant or adjuvant chemotherapy, if eligible for systemic therapy. All patients received 36 Gy in 3 fractions to the close or positive margin site. Results: From February 2013 to January 2018, 50 patients were enrolled with 49 patients treated on protocol and included in the analysis. The median age was 71 years. The median clinical target volume was 11.3 cc and median planning target volume 22.0 cc. The median overall survival was 23.7 months (95% confidence interval, 13.6-33.8). Local progression-free survival at 1 and 2 years was 85% and 77%, respectively. Regional progression-free survival at 1 and 2 years was 73% and 73%, respectively. Distant metastases-free survival was 57% and 49% at 1 and 2 years, respectively. Grade 3+ radiation toxicity was only 4.1% and occurred in 2 patients. Conclusions: Adjuvant pancreatic SBRT was shown to be a safe and feasible treatment option for patients with high-risk pancreatic adenocarcinoma and close or positive margins. This is the first prospective study of SBRT in high-risk postoperative pancreatic cancer. Our results yielded significant local and regional control with low rates of acute toxicity. This technique does not interrupt the administration of systemically dosed multiagent chemotherapy and can be safely interdigitated between cycles because SBRT is only 1 week of treatment