Ordered clustering of single atomic Te vacancies in atomically thin PtTe2 promotes hydrogen evolution catalysis.

Exposing and stabilizing undercoordinated platinum (Pt) sites and therefore optimizing their adsorption to reactive intermediates offers a desirable strategy to develop highly efficient Pt-based electrocatalysts. However, preparation of atomically controllable Pt-based model catalysts to understand the correlation between electronic structure, adsorption energy, and catalytic properties of atomic Pt sites is still challenging. Herein we report the atomically thin two-dimensional PtTe2 nanosheets with well-dispersed single atomic Te vacancies (Te-SAVs) and atomically well-defined undercoordinated Pt sites as a model electrocatalyst. A controlled thermal treatment drives the migration of the Te-SAVs to form thermodynamically stabilized, ordered Te-SAV clusters, which decreases both the density of states of undercoordinated Pt sites around the Fermi level and the interacting orbital volume of Pt sites. As a result, the binding strength of atomically defined Pt active sites to H intermediates is effectively reduced, which renders PtTe2 nanosheets highly active and stable in hydrogen evolution reaction.

Towards isolated attosecond electron bunches using ultrashort-pulse laser-solid interactions.

We investigate MeV-level attosecond electron bunches from ultrashort-pulse laser-solid interactions through similarities between experimental and simulated electron energy spectra. We show measurements of the bunch duration and temporal structure from particle-in-cell simulations. The experimental observation of such bunches favors specular reflection direction when focusing the laser pulse onto a subwavelength boundary of thick overdense plasmas at grazing incidence. Particle-in-cell simulation further reveals that the attosecond duration is a result of ultra-thin ([Formula: see text]tenth of a micron) gaps of zero electromagnetic energy density in the modulated reflected radiation, while the bunching (locally peaked electron concentration) comes from the highly-directional electron angular distribution acquired by the electrons in a grazing incidence setup. To isolate a single electron bunch, we perform simulations using 1-cycle laser pulses and analyze the effect of carrier-envelop phase with particle tracking. The duration of the electron bunch can be further decreased by increasing the laser intensity and the focal spot size, while its direction can be changed by tuning the preplasma density gradient.

An evaluation of the mid-ventilation method for the planning of stereotactic lung plans.

BACKGROUND AND PURPOSE: Stereotactic ablative body radiotherapy for lung plans requires 4DCT. Most radiotherapy centres use this to determine an internal target volume (ITV), despite studies suggesting that planning on a mid-ventilation (Mid-V) phase can reduce target volumes. The purpose of this study is two-fold: to determine whether the Mid-V approach provides adequate coverage and to discuss methods to enable the Mid-V approach to be applied more widely. METHOD: 4D scans of 79 patients were outlined on every phase. The mid-V phase was identified. Margins were determined from the range of motion, and plans generated with a 55 Gy prescription. A grid-based method was used to get the probability of tumour coverage in the presence of systematic and random uncertainties, with and without blurring for breathing motion. RESULTS: For the Mid-V plans with the margins calculated from the van-Herk formula, after blurring doses for breathing, the coverage (dose covering 95% of the CTV 95% of the time) was greater than for plans with isotropic 5 mm margins uncorrected for breathing (58.2 Gy v 57.3 Gy). Similar results were obtained for a linear margin chosen as 0.15 of the breathing range. Deformable contour propagation in a commercial outlining system (ProSoma) identified the same mid-V phase in the majority of cases. CONCLUSION: Our results confirm that a mid-V approach can be used to reduce the PTV size, with no loss of tumour coverage. We propose the use of a simplified margin formula equal to the margin ignoring breathing plus 0.15 of the range of motion.

Platinum Nanoparticle Inclusion into a Carbonized Polymer of Intrinsic Microporosity: Electrochemical Characteristics of a Catalyst for Electroless Hydrogen Peroxide Production.

The one-step vacuum carbonization synthesis of a platinum nano-catalyst embedded in a microporous heterocarbon (Pt@cPIM) is demonstrated. A nitrogen-rich polymer of an intrinsic microporosity (PIM) precursor is impregnated with PtCl62- to give (after vacuum carbonization at 700 °C) a nitrogen-containing heterocarbon with embedded Pt nanoparticles of typically 1⁻4 nm diameter (with some particles up to 20 nm diameter). The Brunauer-Emmett-Teller (BET) surface area of this hybrid material is 518 m² g-1 (with a cumulative pore volume of 1.1 cm³ g-1) consistent with the surface area of the corresponding platinum-free heterocarbon. In electrochemical experiments, the heterocarbon-embedded nano-platinum is observed as reactive towards hydrogen oxidation, but essentially non-reactive towards bigger molecules during methanol oxidation or during oxygen reduction. Therefore, oxygen reduction under electrochemical conditions is suggested to occur mainly via a 2-electron pathway on the outer carbon shell to give H2O2. Kinetic selectivity is confirmed in exploratory catalysis experiments in the presence of H2 gas (which is oxidized on Pt) and O2 gas (which is reduced on the heterocarbon surface) to result in the direct formation of H2O2.

One pot microwave synthesis of highly stable AuPd@Pd supported core-shell nanoparticles.

A series of 1 wt% supported Au, Pd and AuPd nanoalloy catalysts were prepared via microwave assisted reduction of PdCl2 and HAuCl4 in a facile, one pot process. The resulting materials showed excellent activity for the direct synthesis of hydrogen peroxide from hydrogen and oxygen, with a synergistic effect observed on the addition of Au into a Pd catalyst. Detailed electron microscopy showed that the bimetallic particles exhibited a core-shell morphology, with an Au core surrounded by an Au-Pd shell, with a size between 10-20 nm. The presence of Au in the shell was confirmed by EDX studies, with corroborating data from XPS measurements showing a significant contribution of both Au and Pd in the spectra, with the Au signal increasing as the total Au content of the catalyst increased. No PdO was observed, suggesting a complete reduction of the metal chloride nanoparticles. Unlike similar catalysts prepared by sol-immobilisation methodology, the core-shell structures showed excellent stability during the hydrogen peroxide synthesis reaction, and no catalyst deactivation was observed over 4 reuse cycles. This is the first time the preparation of stable core-shell particles have been reported using microwave assisted reduction. The observation that these particles are core-shell, without the need of a complicated synthesis or high thermal treatment and form in just 15 minutes presents an exciting opportunity for this experimental technique.

Momentum transport and nonlocality in heat-flux-driven magnetic reconnection in high-energy-density plasmas.

Recent theory has demonstrated a novel physics regime for magnetic reconnection in high-energy-density plasmas where the magnetic field is advected by heat flux via the Nernst effect. Here we elucidate the physics of the electron dissipation layer in this regime. Through fully kinetic simulation and a generalized Ohm's law derived from first principles, we show that momentum transport due to a nonlocal effect, the heat-flux-viscosity, provides the dissipation mechanism for magnetic reconnection. Scaling analysis, and simulations show that the reconnection process comprises a magnetic field compression stage and quasisteady reconnection stage, and the characteristic width of the current sheet in this regime is several electron mean-free paths. These results show the important interplay between nonlocal transport effects and generation of anisotropic components to the distribution function.

Control of the configuration of multiple femtosecond filaments in air by adaptive wavefront manipulation.

We demonstrate the ability to position single and multiple filaments arbitrarily within the energy reservoir of a high power femtosecond laser pulse. A deformable mirror controlled by a genetic algorithm finds the optimal phase profile for producing filaments at user-defined locations within the energy reservoir to within a quarter of the nominal filament size, on average. This proof-of-principle experiment demonstrates a potential technique for fast control of the configuration of the filaments.

Largest recorded non-invasive true intrathoracic desmoid tumour.

Intrathoracic desmoid tumours are rare soft-tissue neoplasms arising from fascial or musculo-aponeurotic structures, accounting for less than 0.03% of all neoplasms. Most cases in fact represent intrathoracic extension of chest wall tumours. This case report describes the largest recorded true intrathoracic desmoid tumour without mediastinal or chest wall invasion. The tumour was completely excised through a left thoracotomy with negative tumour margins. Management of the patient will involve radiological surveillance. Desmoids are benign tumours that do not metastasise but have a high rate of recurrence, especially if tumour margins are positive after surgical resection. Complete surgical resection is the treatment of choice. Other treatment options include radiotherapy; non-steroidal inflammatory drugs or antioestrogen therapy (tamoxifen) or a combination thereof; and chemotherapy or targeted drug therapy.

Climate warming and the potential extinction of fig wasps, the obligate pollinators of figs.

Figs (Ficus) have a reciprocally obligate mutualism with tiny, short-lived (1-2 days) fig wasps (Agaonidae). The small size and short life of these pollinators is expected to make them more vulnerable to climate change than their larger and longer-lived hosts. We experimentally tested the thermal tolerances of four species of adult female fig wasp from equatorial Singapore. The results suggest that an increase of 3°C or more above the current temperatures experienced across much of the equatorial tropics would markedly decrease the active adult lifespan of all four species. Fig plants are the centre of an intricate web of specialist and generalist animals. Unless fig wasps can acclimate or adapt to warmer temperatures in time, these responses may disrupt the mutualism, potentially affecting multiple trophic levels.

Using free text information to explore how and when GPs code a diagnosis of ovarian cancer: an observational study using primary care records of patients with ovarian cancer.

BACKGROUND: Primary care databases provide a unique resource for healthcare research, but most researchers currently use only the Read codes for their studies, ignoring information in the free text, which is much harder to access. OBJECTIVES: To investigate how much information on ovarian cancer diagnosis is 'hidden' in the free text and the time lag between a diagnosis being described in the text or in a hospital letter and the patient being given a Read code for that diagnosis. DESIGN: Anonymised free text records from the General Practice Research Database of 344 women with a Read code indicating ovarian cancer between 1 June 2002 and 31 May 2007 were used to compare the date at which the diagnosis was first coded with the date at which the diagnosis was recorded in the free text. Free text relating to a diagnosis was identified (a) from the date of coded diagnosis and (b) by searching for words relating to the ovary. RESULTS: 90% of cases had information relating to their ovary in the free text. 45% had text indicating a definite diagnosis of ovarian cancer. 22% had text confirming a diagnosis before the coded date; 10% over 4 weeks previously. Four patients did not have ovarian cancer and 10% had only ambiguous or suspected diagnoses associated with the ovarian cancer code. CONCLUSIONS: There was a vast amount of extra information relating to diagnoses in the free text. Although in most cases text confirmed the coded diagnosis, it also showed that in some cases GPs do not code a definite diagnosis on the date that it is confirmed. For diseases which rely on hospital consultants for diagnosis, free text (particularly letters) is invaluable for accurate dating of diagnosis and referrals and also for identifying misclassified cases.

High-order harmonic generation from solid targets with 2 mJ pulses.

Harmonics up to the 18th order are generated from solid targets by focusing 2 mJ, 50 fs pulses at 800 nm to a spot size of 1.7 µm (FWHM). To our knowledge, this is the first demonstration of high-harmonic generation with a very short focal length paraboloid (f/1.4) and kilohertz laser system. The harmonics have a low divergence (<4°) compared to the driving beam and conversion efficiencies (>10(-7) per harmonic) comparable to gas harmonics. No contrast enhancement techniques are employed, and the system is capable of operating at 500 Hz.

Generation of GeV protons from 1 PW laser interaction with near critical density targets.

The propagation of ultraintense laser pulses through matter is connected with the generation of strong moving magnetic fields in the propagation channel as well as the formation of a thin ion filament along the axis of the channel. Upon exiting the plasma the magnetic field displaces the electrons at the back of the target, generating a quasistatic electric field that accelerates and collimates ions from the filament. Two dimensional particle-in-cell simulations show that a 1 PW laser pulse tightly focused on a near-critical density target is able to accelerate protons up to an energy of 1.3 GeV. Scaling laws and optimal conditions for proton acceleration are established considering the energy depletion of the laser pulse.

Schwinger limit attainability with extreme power lasers.

High intensity colliding laser pulses can create abundant electron-positron pair plasma [A. R. Bell and J. G. Kirk, Phys. Rev. Lett. 101, 200403 (2008)], which can scatter the incoming electromagnetic waves. This process can prevent one from reaching the critical field of quantum electrodynamics at which vacuum breakdown and polarization occur. Considering the pairs are seeded by the Schwinger mechanism, it is shown that the effects of radiation friction and the electron-positron avalanche development in vacuum depend on the electromagnetic wave polarization. For circularly polarized colliding pulses, these effects dominate not only the particle motion but also the evolution of the pulses. For linearly polarized pulses, these effects are not as strong. There is an apparent analogy of these cases with circular and linear electron accelerators to the corresponding constraining and reduced roles of synchrotron radiation losses.

Determining the date of diagnosis--is it a simple matter? The impact of different approaches to dating diagnosis on estimates of delayed care for ovarian cancer in UK primary care.

BACKGROUND: Studies of cancer incidence and early management will increasingly draw on routine electronic patient records. However, data may be incomplete or inaccurate. We developed a generalizable strategy for investigating presenting symptoms and delays in diagnosis using ovarian cancer as an example. METHODS: The General Practice Research Database was used to investigate the time between first report of symptom and diagnosis of 344 women diagnosed with ovarian cancer between 01/06/2002 and 31/05/2008. Effects of possible inaccuracies in dating of diagnosis on the frequencies and timing of the most commonly reported symptoms were investigated using four increasingly inclusive definitions of first diagnosis/suspicion: 1. "Definite diagnosis" 2. "Ambiguous diagnosis" 3. "First treatment or complication suggesting pre-existing diagnosis", 4 "First relevant test or referral". RESULTS: The most commonly coded symptoms before a definite diagnosis of ovarian cancer, were abdominal pain (41%), urogenital problems(25%), abdominal distension (24%), constipation/change in bowel habits (23%) with 70% of cases reporting at least one of these. The median time between first reporting each of these symptoms and diagnosis was 13, 21, 9.5 and 8.5 weeks respectively. 19% had a code for definitions 2 or 3 prior to definite diagnosis and 73% a code for 4. However, the proportion with symptoms and the delays were similar for all four definitions except 4, where the median delay was 8, 8, 3, 10 and 0 weeks respectively. CONCLUSION: Symptoms recorded in the General Practice Research Database are similar to those reported in the literature, although their frequency is lower than in studies based on self-report. Generalizable strategies for exploring the impact of recording practice on date of diagnosis in electronic patient records are recommended, and studies which date diagnoses in GP records need to present sensitivity analyses based on investigation, referral and diagnosis data. Free text information may be essential in obtaining accurate estimates of incidence, and for accurate dating of diagnoses.

Birth outcomes of Asian-Indian-Americans.

OBJECTIVE: This study examines the maternal characteristics and birth outcomes of infants of U.S. resident Asian-Indian-American (AIA) mothers and compares those to infants of U.S. resident Whites and African-American (AA) mothers. METHODS: Single live births to U.S. resident mothers with race/ethnicity coded on birth certificate as AIA, non-Hispanic White, or non-Hispanic AA were drawn from NCHS 1995 to 2000 U.S. Linked Live Birth/Infant Death files. RESULTS: Compared to AAs or Whites, AIAs have the lowest percentage of births to teen or unmarried mothers and mothers with high parity for age or with low educational attainment. After taking these factors into account, AIA had the highest risk of LBW, small-for-gestational age and term SGA births but a risk of infant death only slightly higher than Whites and far less than AAs. CONCLUSIONS: The birth outcomes of AIAs do not follow the paradigm that more impoverished minority populations should have greater proportions of low birth weight and preterm births and accordingly greater infant mortality rates.

Clinical findings, diagnosis, prevalence and predisposing factors for lameness localised to the middle carpal joint in young Standardbred racehorses.

REASONS FOR PERFORMING STUDY: Lameness related to the middle carpal joint (MCJ) occurs in up to 30% of young Standardbred horses in race training and the incidence increase with radiographic severity of third carpal bone (C3) sclerosis on DPr-DDIO (skyline) view of the carpus. Factors predisposing horses to carpal injury have not been well investigated. OBJECTIVES: To determine the importance of MCJ lameness as a cause of wastage in young Standardbred racehorses, stage of training at which it occurs and predisposing factors, and to describe clinical findings and diagnosis. METHODS: Standardbred horses (n = 114) entering their first year of race training were examined at approximately 3-month intervals over 12-18 months. For 87 of the horses, a training diary was available and these horses were trained at 3 different stables, each using a different exercise regime. At each examination, forelimb conformation, MCJ effusion, MCJ lameness and radiographic findings were graded, and training history and reasons for lost training days recorded. Nuclear scintigraphy and exploratory arthroscopy were performed on a limited selection of horses. Results for horses that developed MCJ lameness during the study period were compared statistically with results for horses that did not. RESULTS: Carpal lameness occurred in 28% of horses and was present in 56% with forelimb lameness. In most cases lameness was mild, bilateral and with little or no MCJ effusion and was attributed to subchondral bone pain associated with radiographic evidence of C3 sclerosis. Carpal lameness was the most common reason for >1 month's rest during the study period. It occurred at any stage of training but, in most cases, some speed training had begun. Of the variables studied, poor forelimb conformation and more intense speed training were predisposing factors. CONCLUSIONS AND POTENTIAL RELEVANCE: The information gained should assist in making recommendations regarding training young Standardbreds to reduce the incidence of MCJ lameness. However, further investigations to determine the optimal training regime are warranted.

Intrauterine tobacco smoke exposure and hyaline membrane disease amongst triplets.

We assessed the association between prenatal smoking and respiratory distress syndrome (RDS) among triplets using a population-based retrospective cohort of 12,169 triplet live births in the United States between 1995 and 1997. Analysis was conducted using the generalised estimating equation framework to adjust for intra-cluster correlations. A total of 938 cases of RDS were reported comprising 35 among smoking (7.2%) and 903 among non-smoking gravidas (7.7%). The likelihood of RDS was comparable in both smoking categories [adjusted odds ratio (OR) = 0.93; 95% confidence interval (CI) = 0.65-1.32]. The risk for RDS due to smoking diminished with declining birth weight albeit non-significantly: low birth weight (OR = 0.99; 95% CI = 0.40-2.42), very low birth weight (OR = 0.85; 95% CI = 0.39-1.86), and extremely low birth weight (OR = 0.69; 95% CI = 0.30-1.58). In conclusion, among triplet neonates, smoking during pregnancy was not associated with respiratory distress syndrome.

Radiographic evaluation of sclerosis of the third carpal bone associated with exercise and the development of lameness in Standardbred racehorses.

REASONS FOR PERFORMING STUDY: Sclerosis of the third carpal bone is a common radiographic finding in both lame and sound racehorses, but there are no guidelines correlating degree of sclerosis and incidence of lameness. OBJECTIVES: To develop a protocol for describing subchondral bone sclerosis in C3 on dorsoproximal-dorsodistal oblique (DPr-DDiO) radiographs of the carpus and to correlate these changes with exercise history and carpal lameness. METHODS: One hundred and six Standardbreds entering their first year of training (exercise group) and 7 age-matched Standardbreds at pasture (controls) were examined at approximately 3 month intervals over 12-18 months. Examinations consisted of lameness evaluation and carpal radiographs (DPr-DDiO and flexed lateromedial projections). A grading system (very mild, mild, moderate and severe) for C3 sclerosis seen on the DPr-DDiO radiograph was developed that utilised a combination of the criteria of trabecular thickening (trabecular score; TS) and total percent area of the C3 radial facet affected (TAA). RESULTS: Exercise group horses showed significant increase in TS and TAA throughout training compared to control horses. Middle carpal joint lameness developed in 32/106 (30%) exercise group horses and none of the control horses. Incidence of middle carpal joint (MCJ) lameness was lower in horses with mild (2/30, 6.7%) than moderate (10/32, 31.2%) and severe (20/44, 45.4%) sclerosis throughout training. CONCLUSIONS: Horses with higher grades of sclerosis, as defined by this novel grading system, were more likely to develop MCJ lameness at some point of training. The proposed grading system gave a quantitative assessment of radiographic sclerosis that could then be used to correlate increasing severity of sclerosis with increasing incidences of lameness. POTENTIAL RELEVANCE: These results serve as a basis for further investigation into determining the degree of C3 sclerosis at which pathological changes and lameness can be expected.