Polycrystalline Diamond Micro-Hotplates.

Micro-hotplate structures are increasingly being investigated for use in a host of applications ranging from broadband infra-red sources within absorption-based gas sensors to in situ heater stages for ultra-high-resolution imaging. With devices usually fabricated from a conductive electrode placed on top of a freestanding radiator element, coefficient of thermal expansion (CTE) mismatches between layers and electro-migration within the heating element typically lead to failure upon exceeding temperatures of 1600 K. In an attempt to mitigate such issues, a series of hotplates of varying geometry have been fabricated from a single layer of mechanically robust, high thermal conductivity, and low CTE boron-doped polycrystalline diamond. Upon testing under high vacuum conditions and characterization of the emission spectra, the resulting devices are shown to exhibit a grey-body like emission response and reach temperatures vastly in excess of conventional geometries of up to 2731 K at applied powers of ⩽100 mW. Characterization of the thermalization time meanwhile demonstrates rapid millisecond response times, while Raman spectroscopy reveals the performance of the devices is dictated by cumulative graphitization at elevated temperatures. As such, both diamond and sp2 carbon are shown to be promising materials for the fabrication of next-generation micro-hotplates.

Practical and General Alcohol Deoxygenation Protocol.

Herein, we describe a practical protocol for the removal of alcohol functional groups through reductive cleavage of their benzoate ester analogs. This transformation requires a strong single electron transfer (SET) reductant and a means to accelerate slow fragmentation following substrate reduction. To accomplish this, we developed a photocatalytic system that generates a potent reductant from formate salts alongside Brønsted or Lewis acids that promote fragmentation of the reduced intermediate. This deoxygenation procedure is effective across structurally and electronically diverse alcohols and enables a variety of difficult net transformations. This protocol requires no precautions to exclude air or moisture and remains efficient on multigram scale. Finally, the system can be adapted to a one-pot benzoylation-deoxygenation sequence to enable direct alcohol deletion. Mechanistic studies validate that the role of acidic additives is to promote the key C(sp3 )-O bond fragmentation step.

Unveiling Potent Photooxidation Behavior of Catalytic Photoreductants.

We describe a photocatalytic system that reveals latent photooxidant behavior from one of the most reducing conventional photoredox catalysts, N-phenylphenothiazine (PTH). This aerobic photochemical reaction engages difficult to oxidize feedstocks, such as benzene, in C(sp2)-N coupling reactions through direct oxidation. Mechanistic studies are consistent with activation of PTH via photooxidation and with Lewis acid cocatalysts scavenging inhibitors inextricably formed in this process.

Non-innocent Radical Ion Intermediates in Photoredox Catalysis: Parallel Reduction Modes Enable Coupling of Diverse Aryl Chlorides.

We describe a photocatalytic system that elicits potent photoreductant activity from conventional photocatalysts by leveraging radical anion intermediates generated in situ. The combination of an isophthalonitrile photocatalyst and sodium formate promotes diverse aryl radical coupling reactions from abundant but difficult to reduce aryl chloride substrates. Mechanistic studies reveal two parallel pathways for substrate reduction both enabled by a key terminal reductant byproduct, carbon dioxide radical anion.

Potent Reductants via Electron-Primed Photoredox Catalysis: Unlocking Aryl Chlorides for Radical Coupling.

We describe a new catalytic strategy to transcend the energetic limitations of visible light by electrochemically priming a photocatalyst prior to excitation. This new catalytic system is able to productively engage aryl chlorides with reduction potentials hundreds of millivolts beyond the potential of Na0 in productive radical coupling reactions. The aryl radicals produced via this strategy can be leveraged for both carbon-carbon and carbon-heteroatom bond-forming reactions. Through direct comparison, we illustrate the reactivity and selectivity advantages of this approach relative to electrolysis and photoredox catalysis.

Suppression of Deflecting Forces in Planar-Symmetric Dielectric Wakefield Accelerating Structures with Elliptical Bunches.

Wakefield based accelerators capable of accelerating gradients 2 orders of magnitude higher than present accelerators offer a path to compact high energy physics instruments and light sources. However, for high gradient accelerators, beam instabilities driven by commensurately high transverse wakefields limit beam quality. Previously, it has been theoretically shown that transverse wakefields can be reduced by elliptically shaping the transverse sizes of beams in dielectric structures with planar symmetry. Here, we report experimental measurements that demonstrate reduced transverse wakefields for elliptical beams in planar symmetric structures which are consistent with theoretical models. These results may enable the design of gigavolt-per-meter gradient wakefield based accelerators that produce and stably accelerate high quality beams.

Air-clad suspended nanocrystalline diamond ridge waveguides.

A hybrid group IV ridge waveguide platform is demonstrated, with potential application across the optical spectrum from ultraviolet to the far infrared wavelengths. The waveguides are fabricated by partial etching of sub-micron ridges in a nanocrystalline diamond thin film grown on top of a silicon wafer. To create vertical confinement, the diamond film is locally undercut by exposing the chip to an isotropic fluorine plasma etch via etch holes surrounding the waveguides, resulting in a mechanically stable suspended air-clad waveguide platform. Optical characterization of the waveguides at 1550 nm yields an average optical loss of 4.67 ± 0.47 dB/mm. Further improvement to the fabrication process is expected to significantly reduce this waveguide loss.

Superconductivity in planarised nanocrystalline diamond films.

Chemical vapour deposition (CVD) grown boron-doped nanocrystalline diamond (B-NCD) is an attractive material for the fabrication of high frequency superconducting nanoelectromechanical systems (NEMS) due to its high Young's modulus. The as-grown films have a surface roughness that increases with film thickness due to the columnar growth mechanism. To reduce intrinsic losses in B-NCD NEMS it is crucial to correct for this surface roughness by polishing. In this paper, in contrast to conventional polishing, it is demonstrated that the root-mean-square (RMS) roughness of a 520 nm thick B-NCD film can be reduced by chemical mechanical polishing (CMP) from 44.0 nm to 1.5 nm in 14 hours without damaging the sample or introducing significant changes to the superconducting transition temperature, [Formula: see text], thus enabling the use of B-NCD films in the fabrication of high quality superconducting NEMS.

Effect of slurry composition on the chemical mechanical polishing of thin diamond films.

Nanocrystalline diamond (NCD) thin films grown by chemical vapour deposition have an intrinsic surface roughness, which hinders the development and performance of the films' various applications. Traditional methods of diamond polishing are not effective on NCD thin films. Films either shatter due to the combination of wafer bow and high mechanical pressures or produce uneven surfaces, which has led to the adaptation of the chemical mechanical polishing (CMP) technique for NCD films. This process is poorly understood and in need of optimisation. To compare the effect of slurry composition and pH upon polishing rates, a series of NCD thin films have been polished for three hours using a Logitech Ltd. Tribo CMP System in conjunction with a polyester/polyurethane polishing cloth and six different slurries. The reduction in surface roughness was measured hourly using an atomic force microscope. The final surface chemistry was examined using X-ray photoelectron spectroscopy and a scanning electron microscope. It was found that of all the various properties of the slurries, including pH and composition, the particle size was the determining factor for the polishing rate. The smaller particles polishing at a greater rate than the larger ones.

Palladium-Catalyzed, Multicomponent Approach to ß-Lactams via Aryl Halide Carbonylation.

A palladium-catalyzed multicomponent method for the synthesis of ß-lactams from imines, aryl halides, and CO has been developed. This transformation proceeds via two tandem catalytic carbonylation reactions mediated by Pd(PtBu3)2 and provides a route to prepare these products from five separate reagents. A diverse range of polysubstituted ß-lactams can be generated by systematic variation of the substrates. This methodology can also be extended to the use of iodo-substituted imines to produce novel spirocyclic ß-lactams in good yields and selectivity.

Development of a novel walkability index for London, United Kingdom: cross-sectional application to the Whitehall II Study.

BACKGROUND: Physical activity is essential for health; walking is the easiest way to incorporate activity into everyday life. Previous studies report positive associations between neighbourhood walkability and walking but most focused on cities in North America and Australasia. Urban form with respect to street connectivity, residential density and land use mix-common components of walkability indices-differs in European cities. The objective of this study was to develop a walkability index for London and test the index using walking data from the Whitehall II Study. METHODS: A neighbourhood walkability index for London was constructed, comprising factors associated with walking behaviours: residential dwelling density, street connectivity and land use mix. Three models were produced that differed in the land uses included. Neighbourhoods were operationalised at three levels of administrative geography: (i) 21,140 output areas, (ii) 633 wards and (iii) 33 local authorities. A neighbourhood walkability score was assigned to each London-dwelling Whitehall II Study participant (2003-04, N = 3020, mean ± SD age = 61.0 years ± 6.0) based on residential postcode. The effect of changing the model specification and the units of enumeration on spatial variation in walkability was examined. RESULTS: There was a radial decay in walkability from the centre to the periphery of London. There was high inter-model correlation in walkability scores for any given neighbourhood operationalisation (0.92-0.98), and moderate-high correlation between neighbourhood operationalisations for any given model (0.39-0.70). After adjustment for individual level factors and area deprivation, individuals in the most walkable neighbourhoods operationalised as wards were more likely to walk >6 h/week (OR = 1.4; 95 % CI: 1.1-1.9) than those in the least walkable. CONCLUSIONS: Walkability was associated with walking time in adults. This walkability index could help urban planners identify and design neighbourhoods in London with characteristics more supportive of walking, thereby promoting public health.

Virtual field trips as physically active lessons for children: a pilot study.

BACKGROUND: The modern classroom is an inherently sedentary environment. Virtual Field Trips (VFTs) using interactive whiteboards to explore virtual scenes are a potential method of converting sedentary class-time into physically active teaching. This pilot aimed to assess the effects of a developed VFT on physical activity and learning in primary-school children. METHODS: Participants (n = 85) were randomly assigned to a) a 30-minute physically active London 2012 Olympics-themed VFT, or b) a 30-minute sedentary version of the same VFT. Activity was measured using GT1M Actigraphs, content recall was assessed with a quiz and user evaluations were gained from teacher and pupil questionnaires. RESULTS: Pupils in the active VFT displayed significantly less sedentary time (p < 0.001), and significantly more light (p < 0.001), moderate (p = 0.01) and vigorous physical activity (p < 0.001) than sedentary VFT pupils. No differences in content recall were found between intervention groups: suggesting that adding physical activity into classroom teaching may not compromise attainment. High acceptability was found in teachers and active VFT students rated their session significantly higher than sedentary pupils (p < 0.002). CONCLUSIONS: This one-day pilot provides early evidence of the ability of VFTs to convert sedentary academic time into active time. Longitudinal research is needed to assess prolonged effects of active VFTs in reducing sedentary time.

Silica based polishing of {100} and {111} single crystal diamond.

Diamond is one of the hardest and most difficult to polish materials. In this paper, the polishing of {111} and {100} single crystal diamond surfaces by standard chemical mechanical polishing, as used in the silicon industry, is demonstrated. A Logitech Tribo Chemical Mechanical Polishing system with Logitech SF1 Syton and a polyurethane/polyester polishing pad was used. A reduction in roughness from 0.92 to 0.23 nm root mean square and 0.31 to 0.09 nm rms for {100} and {111} samples respectively was observed.

Observation of nonlinear dissipation in piezoresistive diamond nanomechanical resonators by heterodyne down-mixing.

We report the observation of nonlinear dissipation in diamond nanomechanical resonators measured by an ultrasensitive heterodyne down-mixing piezoresistive detection technique. The combination of a hybrid structure as well as symmetry breaking clamps enables sensitive piezoresistive detection of multiple orthogonal modes in a diamond resonator over a wide frequency and temperature range. Using this detection method, we observe the transition from purely linear dissipation at room temperature to strongly nonlinear dissipation at cryogenic temperatures. At high drive powers and below liquid nitrogen temperatures, the resonant structure dynamics follows the Pol-Duffing equation of motion. Instead of using the broadening of the full width at half-maximum, we propose a nonlinear dissipation backbone curve as a method to characterize the strength of nonlinear dissipation in devices with a nonlinear spring constant.

Real-world evidence of epidemiology, patient characteristics, and mortality in people with drug-resistant epilepsy in the United Kingdom, 2011-2021.

BACKGROUND: A third of people with epilepsy are drug resistant. People with drug-resistant epilepsy (DRE) have a higher risk of mortality and physical injuries than those who respond to anti-seizure medication (ASM). This study describes patient characteristics, comorbidities, and mortality in people with DRE in the UK. METHODS: The Clinical Practice Research Datalink was utilised to select people with DRE prescribed a third ASM between 1 January 2011 and 31 March 2021. Annual incidence and prevalence of DRE, patient characteristics, comorbidities, and mortality rates were analysed. Subgroup analysis was performed by age, sex, presence of intellectual disabilities and time from epilepsy diagnosis to DRE. RESULTS: A total of 34,647 people with DRE were included (mean ± SD age 42.68 ± 23.59 years, 52.6% females). During the study period, annual DRE incidence ranged from 1.99% to 3.12%. As of 31 March 2021, DRE prevalence was 26.6% (95% confidence interval [CI] 26.3%-26.8%). A greater proportion of people with DRE resided in the most deprived regions, with 21.1% and 16.7% in the top two quintiles of the Index of Multiple Deprivation respectively, compared to < 15% in the three less deprived regions. All-cause mortality ranged from 3,687 to 4,802 per 100,000 persons with DRE, four times higher than that in the general population in the UK. Variations existed across subgroups. CONCLUSIONS: Considerable disease burden was observed in people with DRE in the UK. The findings emphasise the importance of early DRE diagnosis and appropriate disease management in people who develop DRE.

Levelling Up for health in towns? Development of a new deprivation index: the 'Stronger Towns Index' and its association with self-rated health and migration in England, between 2001 and 2011.

Aim: To develop the 'Stronger Towns Index': a deprivation index that took into account characteristics of areas encompassing towns that may be eligible for redevelopment funding and explore how this index was associated with self-rated health and migration within England between 2001 and 2011. Subject and methods: All members of the ONS Longitudinal Study in England aged 16 and over in 2001 whose records included a self-rated health response and a valid local authority code.Local authorities in England were ranked using a composite index developed using the five metrics set out in the Stronger Towns Funding: productivity, income, skills, deprivation measures, and the proportion of people living in towns.The index was split into deciles, and logistic regression carried out on the association between decile and self-rated health in 2001 in the main sample (n = 407,878) and decile change and self-rated health in 2011 in a subsample also present in 2011, with migration information (n = 299,008). Results: There were areas in the lowest deciles of Town Strength who did not receive funding. After multiple adjustment, LS members living in areas with higher deciles were significantly more likely (7% to 38%) to report good health than those in the lowest decile in 2001. Remaining in the same decile between 2001 and 2011 was associated with 7% lower odds of good self-rated health in 2011. Conclusion: It is important to consider health in towns when allocating funding. Areas in the Midlands may have missed out on funding which might help mitigate poor health.

Monitoring of the Initial Stages of Diamond Growth on Aluminum Nitride Using In Situ Spectroscopic Ellipsometry.

The high thermal conductivity of polycrystalline diamond makes it ideally suited for thermal management solutions for gallium nitride (GaN) devices, with a diamond layer grown on an aluminum nitride (AlN) interlayer atop the GaN stack. However, this application is limited by the thermal barrier at the interface between diamond and substrate, which has been associated with the transition region formed in the initial phases of growth. In this work, in situ spectroscopic ellipsometry (SE) is employed to monitor early-stage microwave plasma-enhanced chemical vapor deposition diamond growth on AlN. An optical model was developed from ex situ spectra and applied to spectra taken in situ during growth. Coalescence of separate islands into a single film was marked by a reduction in bulk void fraction prior to a spike in sp2 fraction due to grain boundary formation. Parameters determined by the SE model were corroborated using Raman spectroscopy and atomic force microscopy.

Implementation research for promoting access and rational use of antibiotics for children: lessons learnt from Tanzania.

Implementation research (IR) has proved to be a potential catalyst in facilitating the uptake of evidence-based innovations into routine practices and thereby maximizing public health outcomes. IR not only focuses on the effectiveness of the innovations but also identifies and addresses the barriers and facilitators to maximize their uptake into routine practices. This article describes the processes undertaken to implement a research project aimed at promoting access and rational use of antibiotics for children (PARAC). It also provides an overview of the lessons learnt during its implementation in Tanzanian hospital and community settings.

Non-Markovian temporal networks with auto- and cross-correlated link dynamics.

Many of the biological, social and man-made networks around us are inherently dynamic, with their links switching on and off over time. The evolution of these networks is often observed to be non-Markovian, and the dynamics of their links are often correlated. Hence, to accurately model these networks, predict their evolution, and understand how information and other relevant quantities propagate over them, the inclusion of both memory and dynamical dependencies between links is key. In this article we introduce a general class of models of temporal networks based on discrete autoregressive processes for link dynamics. As a concrete and useful case study, we then concentrate on a specific model within this class, which allows to generate temporal networks with a specified underlying structural backbone, and with precise control over the dynamical dependencies between links and the strength and length of their memories. In this network model the presence of each link is influenced not only by its past activity, but also by the past activities of other links, as specified by a coupling matrix, which directly controls the causal relations, and hence the correlations, among links. We propose a maximum likelihood method for estimating the model's parameters from data, showing how the model allows a more realistic description of real-world temporal networks and also to predict their evolution. Due to the flexibility of maximum likelihood inference, we illustrate how to deal with heterogeneity and time-varying patterns, possibly including also nonstationary network dynamics. We then use our network model to investigate the role that, both the features of memory and the type of correlations in the dynamics of links have on the properties of processes occurring over a temporal network. Namely, we study the speed of a spreading process, as measured by the time it takes for diffusion to reach equilibrium. Through both numerical simulations and analytical results, we are able to separate the roles of autocorrelations and neighborhood correlations in link dynamics, showing that not only is the speed of diffusion nonmonotonically dependent on the memory length, but also that correlations among neighboring links help to speed up the spreading process, while autocorrelations slow it back down. Our results have implications in the study of opinion formation, the modeling of social networks, and the spreading of epidemics through mobile populations.

The shape of memory in temporal networks.

How to best define, detect and characterize network memory, i.e. the dependence of a network's structure on its past, is currently a matter of debate. Here we show that the memory of a temporal network is inherently multidimensional, and we introduce a mathematical framework for defining and efficiently estimating the microscopic shape of memory, which characterises how the activity of each link intertwines with the activities of all other links. We validate our methodology on a range of synthetic models, and we then study the memory shape of real-world temporal networks spanning social, technological and biological systems, finding that these networks display heterogeneous memory shapes. In particular, online and offline social networks are markedly different, with the latter showing richer memory and memory scales. Our theory also elucidates the phenomenon of emergent virtual loops and provides a novel methodology for exploring the dynamically rich structure of complex systems.