Nucleoside Azide-Alkyne Cycloaddition Reactions Under Solvothermal Conditions or Using Copper Vials in a Ball Mill

Novel nucleoside analogues containing photoswitchable moieties were prepared using 'click' cycloaddition reactions between 5 '-azido-5 '-deoxythymidine and mono- or bis-N-propargylamide-substituted azobenzenes. In solution, high to quantitative yields were achieved using 5mol% Cu(I) in the presence of a stabilizing ligand. 'Click' reactions using the monopropargylamides were also effected in the absence of added cuprous salts by the application of liquid assisted grinding (LAG) in metallic copper reaction vials. Specifically, high speed vibration ball milling (HSVBM) using a 3/32('') (2.38mm) diameter copper ball (62mg) at 60Hz overnight in the presence of ethyl acetate lead to complete consumption of the 5 '-azido nucleoside with clean conversion to the corresponding 1,3-triazole.

Density functional theory study on the activation of molecular oxygen on a stepped gold surface in an aqueous environment: a new approach for simulating reactions in solution

The activation of oxygen molecules is an important issue in the gold-catalyzed partial oxidation of alcohols in aqueous solution. The complexity of the solution arising from a large number of solvent molecules makes it difficult to study the reaction in the system. In this work, O-2 activation on an Au catalyst is investigated using an effective approach to estimate the reaction barriers in the presence of solvent. Our calculations show that O-2 can be activated, undergoing OOH* in the presence of water molecules. The OOH* can readily be formed on Au(211) via four possible pathways with almost equivalent free energy barriers at the aqueous-solid interface: the direct or indirect activation of O-2 by surface hydrogen or the hydrolysis of O-2 following a Langmuir-Hinshelwood mechanism or an Eley-Rideal mechanism. Among them, the Eley-Rideal mechanism may be slightly more favorable due to the restriction of the low coverage of surface H on Au(211) in the other mechanisms. The results shed light on the importance of water molecules on the activation of oxygen in gold-catalyzed systems. Solvent is found to facilitate the oxygen activation process mainly by offering extra electrons and stabilizing the transition states. A correlation between the energy barrier and the negative charge of the reaction center is found. The activation barrier is substantially reduced by the aqueous environment, in which the first solvation shell plays the most important role in the barrier reduction. Our approach may be useful for estimating the reaction barriers in aqueous systems.

Riots and Reactions: Hypocrisy and Disaffiliation?

The August 2011 riots in England occasioned widespread condemnation from government and the media. Here, we apply the concepts of hypocrisy and affiliation to explore reactions to these riots. Initially acknowledging that politics necessitates a degree of hypocrisy, we note that some forms of hypocrisy are indefensible: they compromise injavascript:void(0);tegrity. With rioters condemned as thugs and members of a feral underclass, some reactions exemplified forms of corrosive hypocrisy that deflected attention away from economic, social and cultural problems. Moreover, such reactions omitted to attend to the concept of [dis]affiliation amongst young rioters. Accordingly, we look to the role that education might play in re-affiliating those who do not feel they belong to, or have a sufficient stake in, society. Whilst our focus is on the riots in England, the exploration of hypocrisy and affiliation, and discussion of education for re-affiliation, transcends that national context.

Deflagrations in hybrid CONe white dwarfs: a route to explain the faint Type Iax supernova 2008ha

Stellar evolution models predict the existence of hybrid white dwarfs (WDs) with a carbon-oxygen core surrounded by an oxygen-neon mantle. Being born with masses similar to 1.1 M-aS (TM), hybrid WDs in a binary system may easily approach the Chandrasekhar mass (M-Ch) by accretion and give rise to a thermonuclear explosion. Here, we investigate an off-centre deflagration in a near-M-Ch hybrid WD under the assumption that nuclear burning only occurs in carbon-rich material. Performing hydrodynamics simulations of the explosion and detailed nucleosynthesis post-processing calculations, we find that only 0.014 M-aS (TM) of material is ejected while the remainder of the mass stays bound. The ejecta consist predominantly of iron-group elements, O, C, Si and S. We also calculate synthetic observables for our model and find reasonable agreement with the faint Type Iax SN 2008ha. This shows for the first time that deflagrations in near-M-Ch WDs can in principle explain the observed diversity of Type Iax supernovae. Leaving behind a near-M-Ch bound remnant opens the possibility for recurrent explosions or a subsequent accretion-induced collapse in faint Type Iax SNe, if further accretion episodes occur. From binary population synthesis calculations, we find the rate of hybrid WDs approaching M-Ch to be of the order of 1 per cent of the Galactic SN Ia rate.

CO2 capture and electrochemical conversion using superbasic [P66614][124Triz]

The ionic liquid trihexyltetradecylphosphonium 1,2,4-triazolide, [P66614][124Triz], has been shown to chemisorb CO2 through equimolar binding of the carbon dioxide with the 1,2,4-triazolide anion. This leads to a possible new, low energy pathway for the electrochemical reduction of carbon dioxide to formate and syngas at low overpotentials, utilizing this reactive ionic liquid media. Herein, an electrochemical investigation of water and carbon dioxide addition to the [P66614][124Triz] on gold and platinum working electrodes is reported. Electrolysis measurements have been performed using CO2 saturated [P66614][124Triz] based solutions at −0.9 V and −1.9 V on gold and platinum electrodes. The effects of the electrode material on the formation of formate and syngas using these solutions are presented and discussed.

Constraints on explosive silicon burning in core-collapse supernovae from measured Ni/Fe ratios

Measurements of explosive nucleosynthesis yields in core-collapse supernovae provide tests for explosion models. We investigate constraints on explosive conditions derivable from measured amounts of nickel and iron after radioactive decays using nucleosynthesis networks with parameterized thermodynamic trajectories. The Ni/Fe ratio is for most regimes dominated by the production ratio of Ni-58/(Fe-54 + Ni-56), which tends to grow with higher neutron excess and with higher entropy. For SN 2012ec, a supernova (SN) that produced a Ni/Fe ratio of 3.4 +/- 1.2 times solar, we find that burning of a fuel with neutron excess eta approximate to 6 x 10(-3) is required. Unless the progenitor metallicity is over five times solar, the only layer in the progenitor with such a neutron excess is the silicon shell. SNe producing large amounts of stable nickel thus suggest that this deep-lying layer can be, at least partially, ejected in the explosion. We find that common spherically symmetric models of M-ZAMS less than or similar to 13 M-circle dot stars exploding with a delay time of less than one second (M-cut < 1.5 M-circle dot) are able to achieve such silicon-shell ejection. SNe that produce solar or subsolar Ni/Fe ratios, such as SN 1987A, must instead have burnt and ejected only oxygen-shell material, which allows a lower limit to the mass cut to be set. Finally, we find that the extreme Ni/Fe value of 60-75 times solar derived for the Crab cannot be reproduced by any realistic entropy burning outside the iron core, and neutrino-neutronization obtained in electron capture models remains the only viable explanation.

How Video Lecture Capture affects Student Engagement in a University Computer Programming Course: Attendance, Video Viewing Behaviours and Student Attitudes

Introduction
The use of video capture of lectures in Higher Education is not a recent occurrence with web based learning technologies including digital recording of live lectures becoming increasing commonly offered by universities throughout the world (Holliman and Scanlon, 2004). However in the past decade the increase in technical infrastructural provision including the availability of high speed broadband has increased the potential and use of videoed lecture capture. This had led to a variety of lecture capture formats including pod casting, live streaming or delayed broadcasting of whole or part of lectures.
Additionally in the past five years there has been a significant increase in the popularity of online learning, specifically via Massive Open Online Courses (MOOCs) (Vardi, 2014). One of the key aspects of MOOCs is the simulated recording of lecture like activities. There has been and continues to be much debate on the consequences of the popularity of MOOCs, especially in relation to its potential uses within established University programmes.
There have been a number of studies dedicated to the effects of videoing lectures.
The clustered areas of research in video lecture capture have the following main themes:
• Staff perceptions including attendance, performance of students and staff workload
• Reinforcement versus replacement of lectures
• Improved flexibility of learning
• Facilitating engaging and effective learning experiences
• Student usage, perception and satisfaction
• Facilitating students learning at their own pace
Most of the body of the research has concentrated on student and faculty perceptions, including academic achievement, student attendance and engagement (Johnston et al, 2012).
Generally the research has been positive in review of the benefits of lecture capture for both students and faculty. This perception coupled with technical infrastructure improvements and student demand may well mean that the use of video lecture capture will continue to increase in frequency in the next number of years in tertiary education. However there is a relatively limited amount of research in the effects of lecture capture specifically in the area of computer programming with Watkins 2007 being one of few studies . Video delivery of programming solutions is particularly useful for enabling a lecturer to illustrate the complex decision making processes and iterative nature of the actual code development process (Watkins et al 2007). As such research in this area would appear to be particularly appropriate to help inform debate and future decisions made by policy makers.
Research questions and objectives
The purpose of the research was to investigate how a series of lecture captures (in which the audio of lectures and video of on-screen projected content were recorded) impacted on the delivery and learning of a programme of study in an MSc Software Development course in Queen’s University, Belfast, Northern Ireland. The MSc is conversion programme, intended to take graduates from non-computing primary degrees and upskill them in this area. The research specifically targeted the Java programming module within the course. It also analyses and reports on the empirical data from attendances and various video viewing statistics. In addition, qualitative data was collected from staff and student feedback to help contextualise the quantitative results.
Methodology, Methods and Research Instruments Used
The study was conducted with a cohort of 85 post graduate students taking a compulsory module in Java programming in the first semester of a one year MSc in Software Development. A pre-course survey of students found that 58% preferred to have available videos of “key moments” of lectures rather than whole lectures. A large scale study carried out by Guo concluded that “shorter videos are much more engaging” (Guo 2013). Of concern was the potential for low audience retention for videos of whole lectures.
The lecturers recorded snippets of the lecture directly before or after the actual physical delivery of the lecture, in a quiet environment and then upload the video directly to a closed YouTube channel. These snippets generally concentrated on significant parts of the theory followed by theory related coding demonstration activities and were faithful in replication of the face to face lecture. Generally each lecture was supported by two to three videos of durations ranging from 20 – 30 minutes.
Attendance
The MSc programme has several attendance based modules of which Java Programming was one element. In order to assess the consequence on attendance for the Programming module a control was established. The control used was a Database module which is taken by the same students and runs in the same semester.
Access engagement
The videos were hosted on a closed YouTube channel made available only to the students in the class. The channel had enabled analytics which reported on the following areas for all and for each individual video; views (hits), audience retention, viewing devices / operating systems used and minutes watched.
Student attitudes
Three surveys were taken in regard to investigating student attitudes towards the videoing of lectures. The first was before the start of the programming module, then at the mid-point and subsequently after the programme was complete.
The questions in the first survey were targeted at eliciting student attitudes towards lecture capture before they had experienced it in the programme. The midpoint survey gathered data in relation to how the students were individually using the system up to that point. This included feedback on how many videos an individual had watched, viewing duration, primary reasons for watching and the result on attendance, in addition to probing for comments or suggestions. The final survey on course completion contained questions similar to the midpoint survey but in summative view of the whole video programme.
Conclusions and Outcomes
The study confirmed findings of other such investigations illustrating that there is little or no effect on attendance at lectures. The use of the videos appears to help promote continual learning but they are particularly accessed by students at assessment periods. Students respond positively to the ability to access lectures digitally, as a means of reinforcing learning experiences rather than replacing them. Feedback from students was overwhelmingly positive indicating that the videos benefited their learning. Also there are significant benefits to part recording of lectures rather than recording whole lectures. The behaviour viewing trends analytics suggest that despite the increase in the popularity of online learning via MOOCs and the promotion of video learning on mobile devices in fact in this study the vast majority of students accessed the online videos at home on laptops or desktops However, in part, this is likely due to the nature of the taught subject, that being programming.
The research involved prerecording the lecture in smaller timed units and then uploading for distribution to counteract existing quality issues with recording entire live lectures. However the advancement and consequential improvement in quality of in situ lecture capture equipment may well help negate the need to record elsewhere. The research has also highlighted an area of potentially very significant use for performance analysis and improvement that could have major implications for the quality of teaching. A study of the analytics of the viewings of the videos could well provide a quick response formative feedback mechanism for the lecturer. If a videoed lecture either recorded live or later is a true reflection of the face to face lecture an analysis of the viewing patterns for the video may well reveal trends that correspond with the live delivery.

The use of YouTube Analytics of Video Lecture Capture as a Teaching and Learning Performance Enhancer

Do patterns in the YouTube viewing analytics of Lecture Capture videos point to areas of potential teaching and learning performance enhancement? The goal of this action based research project was to capture and quantitatively analyse the viewing behaviours and patterns of a series of video lecture captures across several computing modules in Queen’s University, Belfast, Northern Ireland. The research sought to establish if a quantitative analysis of viewing behaviours coupled with a qualitative evaluation of the material provided from the students could be correlated to provide generalised patterns that could then be used to understand the learning experience of students during face to face lectures and, thereby, present opportunities to reflectively enhance lecturer performance and the students’ overall learning experience and, ultimately, their level of academic attainment.

Video Lecture Capture : Student Engagement

Video Capture of university lectures enables learners to be more flexible in their learning behaviour, for instance choosing to attend lectures in person or watch later. However attendance at lectures has been linked to academic success and is of concern for faculty staff contemplating the introduction of Video Lecture Capture. This research study was devised to assess the impact on learning of recording lectures in computer programming courses. The study also considered behavioural trends and attitudes of the students watching recorded lectures, such as when, where, frequency, duration and viewing devices used. The findings suggest there is no detrimental effect on attendance at lectures with video materials being used to support continual and reinforced learning with most access occurring at assessment periods. The analysis of the viewing behaviours provides a rich and accessible data source that could be potentially leveraged to improve lecture quality and enhance lecturer and learning performance.

Value capture: a valid means of funding PPPs?

This paper considers the use of value capture (VC) as a means of financing public-private partnerships (PPPs) in the United Kingdom (UK). Although some VC techniques are used in the UK, they are employed more widely in the United States of America. After considering the traditional approach to financing UK PPPs, this paper describes the main VC finance instruments. The findings of a series of case studies are then presented and conclusions drawn. While VC financing may prove unpopular with those bearing the cost of infrastructure improvements, it is recommended that such instruments are considered by UK policy makers.

Hydrogel antimicrobial capture coatings for endotracheal tubes; a pharmaceutical strategy designed to prevent ventilator-associated pneumonia.

This paper presents a novel strategy for the prevention of ventilator-associatedpneumonia that involves coating poly(vinyl chloride, PVC) endotracheal tubes (ET) withhydrogels that may be subsequently used to entrap nebulized antimicrobial solutions. Candidatehydrogels were prepared containing a range of ratios of hydroxyethyl methacrylate (HEMA) andmethacrylic acid (MAA) from 100:0 to 70:30 using free radical polymerization and, whenrequired, simultaneous attachment to PVC was performed. The mechanical properties, glasstransition temperatures, swelling kinetics, uptake of gentamicin from an aqueous medium, andgentamicin release were characterized. Increasing the MAA content of the hydrogels significantlydecreased the ultimate tensile strength, % elongation at break, Young’s modulus, and increasedthe glass transition temperature, the swelling ratio, and gentamicin uptake. Microbial(Staphylococcus aureus and Pseudomonas aeruginosa) adherence to control (drug-free) hydrogelswas observed; however, while adherence to gentamicin-containing p(HEMA) occurred, noadherence occurred to gentamicin-containing HEMA:MAA copolymers. Antimicrobialpersistence of gentamicin-containing hydrogels was examined by determining the zone ofinhibition against each microorganism on successive days. Hydrogel composition affected the observed antimicrobial persistence,with the hydrogel composed of 70:30 HEMA:MAA exhibiting >20 days persistence against S. aureus and P. aeruginosa,respectively. To simulate clinical use, the hydrogels (coated onto PVC) were first exposed to a nebulized solution of gentamicin(4 mL, 80 mg for 20 min), and then to nebulized bacteria (4 mL ca. 1 × 109 colony forming units mL−1, 30 min). Viable bacteriawere not observed on the gentamicin-treated p(HEMA: MAA) copolymers, whereas growth was observed on gentamicin-treatedp(HEMA). In light of the excellent antimicrobial activity and physicochemical properties, p(HEMA: MAA) copolymerscomposed of ratios of 80:20 or 70:30 HEMA: MAA were identified as potentially useful coatings of endotracheal tubes to be usedin conjunction with the clinical nebulization of gentamicin and designed for the prevention of ventilator-associated pneumonia