Adsorption of organic molecules at the TiO2(110) surface: the effect of van der Waals interactions

Understanding the interaction of organic molecules with TiO2 surfaces is important for a wide range of technological applications. While density functional theory (DFT) calculations can provide valuable insight about these interactions, traditional DFT approaches with local exchange-correlation functionals suffer from a poor description of non-bonding van der Waals (vdW) interactions. We examine here the contribution of vdW forces to the interaction of small organic molecules (methane, methanol, formic acid and glycine) with the TiO2 (110) surface, based on DFT calculations with the optB88-vdW functional. The adsorption geometries and energies at different configurations were also obtained in the standard generalized gradient approximation (GGA-PBE) for comparison. We find that the optB88-vdW consistently gives shorter surface adsorbate-to-surface distances and slightly stronger interactions than PBE for the weak (physisorbed) modes of adsorption. In the case of strongly adsorbed (chemisorbed) molecules both functionals give similar results for the adsorption geometries, and also similar values of the relative energies between different chemisorption modes for each molecule. In particular both functionals predict that dissociative adsorption is more favourable than molecular adsorption for methanol, formic acid and glycine, in general agreement with experiment. The dissociation energies obtained from both functionals are also very similar, indicating that vdW interactions do not affect the thermodynamics of surface deprotonation. However, the optB88-vdW always predicts stronger adsorption than PBE. The comparison of the methanol adsorption energies with values obtained from a Redhead analysis of temperature programmed desorption data suggests that optB88-vdW significantly overestimates the adsorption strength, although we warn about the uncertainties involved in such comparisons.Comment: 32 pages, 8 figures; accepted in Surface Scienc

Estimating the risk of adverse birth outcomes in pregnant women undergoing non-obstetric surgery using routinely collected NHS data: an observational study

Background: Previous research suggests that non-obstetric surgery is carried out in 1 – 2% of all pregnancies. However, there is limited evidence quantifying the associated risks. Furthermore, of the evidence available, none relates directly to outcomes in the UK, and there are no current NHS guidelines regarding non-obstetric surgery in pregnant women. Objectives: To estimate the risk of adverse birth outcomes of pregnancies in which non-obstetric surgery was or was not carried out. To further analyse common procedure groups. Data Source: Hospital Episode Statistics (HES) maternity data collected between 2002 – 3 and 2011 – 12. Main outcomes: Spontaneous abortion, preterm delivery, maternal death, caesarean delivery, long inpatient stay, stillbirth and low birthweight. Methods: We utilised HES, an administrative database that includes records of all patient admissions and day cases in all English NHS hospitals. We analysed HES maternity data collected between 2002 – 3 and 2011 – 12, and identified pregnancies in which non-obstetric surgery was carried out. We used logistic regression models to determine the adjusted relative risk and attributable risk of non-obstetric surgical procedures for adverse birth outcomes and the number needed to harm. Results: We identified 6,486,280 pregnancies, in 47,628 of which non-obstetric surgery was carried out. In comparison with pregnancies in which surgery was not carried out, we found that non-obstetric surgery was associated with a higher risk of adverse birth outcomes, although the attributable risk was generally low. We estimated that for every 287 pregnancies in which a surgical operation was carried out there was one additional stillbirth; for every 31 operations there was one additional preterm delivery; for every 25 operations there was one additional caesarean section; for every 50 operations there was one additional long inpatient stay; and for every 39 operations there was one additional low-birthweight baby. Limitations: We have no means of disentangling the effect of the surgery from the effect of the underlying condition itself. Many spontaneous abortions will not be associated with a hospital admission and, therefore, will not be included in our analysis. A spontaneous abortion may be more likely to be reported if it occurs during the same hospital admission as the procedure, and this could account for the associated increased risk with surgery during pregnancy. There are missing values of key data items to determine parity, gestational age, birthweight and stillbirth. Conclusions: This is the first study to report the risk of adverse birth outcomes following non-obstetric surgery during pregnancy across NHS hospitals in England. We have no means of disentangling the effect of the surgery from the effect of the underlying condition itself. Our observational study can never attribute a causal relationship between surgery and adverse birth outcomes, and we were unable to determine the risk of not undergoing surgery where surgery was clinically indicated. We have some reservations over associations of risk factors with spontaneous abortion because of potential ascertainment bias. However, we believe that our findings and, in particular, the numbers needed to harm improve on previous research, utilise a more recent and larger data set based on UK practices, and are useful reference points for any discussion of risk with prospective patients. The risk of adverse birth outcomes in pregnant women undergoing non-obstetric surgery is relatively low, confirming that surgical procedures during pregnancy are generally safe. Future work: Further evaluation of the association of non-obstetric surgery and spontaneous abortion. Evaluation of the impact of non-obstetric surgery on the newborn (e.g. neonatal intensive care unit admission, prolonged length of neonatal stay, neonatal death). Funding: The National Institute for Health Research Health Services and Delivery Research programme

Estimating the risk of adverse birth outcomes in pregnant women undergoing non-obstetric surgery using routinely collected NHS data: an observational study

Background: Previous research suggests that non-obstetric surgery is carried out in 1 – 2% of all pregnancies. However, there is limited evidence quantifying the associated risks. Furthermore, of the evidence available, none relates directly to outcomes in the UK, and there are no current NHS guidelines regarding non-obstetric surgery in pregnant women. Objectives: To estimate the risk of adverse birth outcomes of pregnancies in which non-obstetric surgery was or was not carried out. To further analyse common procedure groups. Data Source: Hospital Episode Statistics (HES) maternity data collected between 2002 – 3 and 2011 – 12. Main outcomes: Spontaneous abortion, preterm delivery, maternal death, caesarean delivery, long inpatient stay, stillbirth and low birthweight. Methods: We utilised HES, an administrative database that includes records of all patient admissions and day cases in all English NHS hospitals. We analysed HES maternity data collected between 2002 – 3 and 2011 – 12, and identified pregnancies in which non-obstetric surgery was carried out. We used logistic regression models to determine the adjusted relative risk and attributable risk of non-obstetric surgical procedures for adverse birth outcomes and the number needed to harm. Results: We identified 6,486,280 pregnancies, in 47,628 of which non-obstetric surgery was carried out. In comparison with pregnancies in which surgery was not carried out, we found that non-obstetric surgery was associated with a higher risk of adverse birth outcomes, although the attributable risk was generally low. We estimated that for every 287 pregnancies in which a surgical operation was carried out there was one additional stillbirth; for every 31 operations there was one additional preterm delivery; for every 25 operations there was one additional caesarean section; for every 50 operations there was one additional long inpatient stay; and for every 39 operations there was one additional low-birthweight baby. Limitations: We have no means of disentangling the effect of the surgery from the effect of the underlying condition itself. Many spontaneous abortions will not be associated with a hospital admission and, therefore, will not be included in our analysis. A spontaneous abortion may be more likely to be reported if it occurs during the same hospital admission as the procedure, and this could account for the associated increased risk with surgery during pregnancy. There are missing values of key data items to determine parity, gestational age, birthweight and stillbirth. Conclusions: This is the first study to report the risk of adverse birth outcomes following non-obstetric surgery during pregnancy across NHS hospitals in England. We have no means of disentangling the effect of the surgery from the effect of the underlying condition itself. Our observational study can never attribute a causal relationship between surgery and adverse birth outcomes, and we were unable to determine the risk of not undergoing surgery where surgery was clinically indicated. We have some reservations over associations of risk factors with spontaneous abortion because of potential ascertainment bias. However, we believe that our findings and, in particular, the numbers needed to harm improve on previous research, utilise a more recent and larger data set based on UK practices, and are useful reference points for any discussion of risk with prospective patients. The risk of adverse birth outcomes in pregnant women undergoing non-obstetric surgery is relatively low, confirming that surgical procedures during pregnancy are generally safe. Future work: Further evaluation of the association of non-obstetric surgery and spontaneous abortion. Evaluation of the impact of non-obstetric surgery on the newborn (e.g. neonatal intensive care unit admission, prolonged length of neonatal stay, neonatal death). Funding: The National Institute for Health Research Health Services and Delivery Research programme

From pup to predator; generalized hidden Markov models reveal rapid development of movement strategies in a naïve long‐lived vertebrate

Rapid development of a successful foraging strategy is critical for juvenile survival, especially for naïve animals that receive no parental guidance. However, this process is poorly understood for many species. Although observation of early‐life movements is increasingly possible with miniaturisation of animal‐borne telemetry devices, analytical limitations remain. Here, we tracked 29 recently‐weaned, grey seal Halichoerus grypus pups from colonies in two geographically distinct regions of the United Kingdom. We analysed at‐sea movements of pups throughout their initial months of nutritional independence to investigate the ontogeny of behaviour‐specific (foraging and travelling) movement patterns. Using generalized hidden Markov models (HMMs), we extended the conventional HMM framework to account for temporal changes in putative foraging and travelling movement characteristics, and investigate the effects of intrinsic (sex) and extrinsic (environment) factors on this process. Putative foraging behaviour became more tortuous with time, and travelling became faster and more directed, suggesting a reduction in search scale and an increase in travel efficiency as pups shifted from exploration to an adult‐like repeatable foraging strategy. Sex differences in movement characteristics were evident from colony departure, but sex‐specific activity budgets were only detected in one region. We show that sex‐specific behavioural strategies emerge before sexual size dimorphism in grey seals, and suggest that this phenomenon may occur in other long‐lived species. Our results also indicate that environmental variation may affect the emergence of sex‐specific foraging behaviour, highlighting the need to consider interacting intrinsic and extrinsic factors in shaping movement strategies of long‐lived vertebrates. Moreover, comparing the behavioural state estimations to those of a conventional HMM (no variation in state‐specific movement parameters) revealed differences in the amount and location of foraging activity, with implications for spatial conservation management. Overlooking intrinsic and extrinsic variation in movement processes could distort our understanding of foraging ecology, population dynamics, and conservation requirements

Sustaining the University of Johannesburg and Western Sydney University partnership in the time of COVID : a qualitative case study

Abstract: This article offers a qualitative case study of how COVID has changed an existing international education partnership between the University of Johannesburg (UJ) in South Africa and Western Sydney University (WSU) in Australia which involves collaboration with the not-for-profit Nsasani Trust and focuses on sustainability. Before COVID, both universities ran joint student mobility programs in the Kruger National Park (KNP) and were developing further plans for staff mobility and co-developed post- grad programs involving residency in both countries. These plans changed as a result of the COVID pandemic, which started in early 2020. Societal responses to the COVID pandemic, including national border closures, have forced academics, administrators and students to reconsider how internationalisation programs function during and after the pandemic. Using a qualitative case study based on personal experience, we argue that pre-existing university-to-university connections built before COVID will sustain linkages, but that the previous structure of engagement – based on physical mobility – can shift to new arrangements that can be run fully digitally or used to support limited mobility when international travel resumes in the future. We position the UJ-WSU relationship in the historical context of internationalisation to both highlight the enduring nature of international engagements and suggest that changes are required to make international education sustainable

Evaluation of pedometry as a patient-centered outcome in patients undergoing hematopoietic cell transplant (HCT): A comparison of pedometry and patient-reports of symptoms, health, and quality of life.

Aims We evaluated pedometry as a novel patient-centered outcome because it enables passive continuous assessment of activity and may provide information about the consequences of symptomatic toxicity complementary to self-report. Methods Adult patients undergoing hematopoietic cell transplant (HCT) wore pedometers and completed PRO assessments during transplant hospitalization (4 weeks) and 4 weeks post-discharge. Patient reports of symptomatic treatment toxicities (single items from PROCTCAE, http://healthcaredelivery.cancer.gov/pro-ctcae) and symptoms, physical health, mental health, and quality of life (PROMIS Global-10, http://nih.promis.org), assessed weekly with 7-day recall on Likert scales, were compared individually with pedometry data, summarized as average daily steps per week, using linear mixed models. Results Thirty-two patients [mean age 55 (SD = 14), 63 % male, 84 % white, 56 % autologous, 43 % allogeneic] completed a mean 4.6 (SD = 1.5, range 1–8) evaluable assessments. Regression model coefficients (β) indicated within-person decrements in average daily steps were associated with increases in pain (β = -852; 852 fewer steps per unit increase in pain score, p<0.001), fatigue (β = -886, p<0.001), vomiting (β = -518, p<0.01), shaking/chills (β = -587, p<0.01), diarrhea (β = -719, p<0.001), shortness of breath (β = -1018, p<0.05), reduction in carrying out social activities (β = 705, p<0.01) or physical activities (β = 618, p<0.01), and global physical health (β = 101, p<0.001), but not global mental health or quality of life. Conclusions In this small sample of HCT recipients, more severe symptoms, impaired physical health, and restrictions in the performance of usual daily activities were associated with statistically significant decrements in objectively measured daily steps. Pedometry may be a valuable outcome measure and validation anchor in clinical research

Pilot randomized trial of an electronic symptom monitoring and reporting intervention for hospitalized adults undergoing hematopoietic stem cell transplantation

Purpose: Patients undergoing a hematopoietic stem cell transplantation (HCT) have varied symptoms during their hospitalization. This study examined whether daily symptom reporting (with electronic patient-reported outcomes [PROs]) in an inpatient bone marrow transplant clinic reduced symptom burden on post-transplant days +7, +10, and +14. Methods: A prospective, single-institution1:1 pilot randomized, two-arm study recruited HCT patients. HCT inpatients (N=76) reported daily on 16 common symptoms using the PRO version of the Common Terminology for Adverse Events (PRO-CTCAE). Fisher’s exact test was used to examine differences in the proportion of patients reporting individual symptoms. Multivariable linear regression modeling was used to examine group differences in peak symptom burden, while controlling for symptom burden at baseline, age, comorbidity, and transplantation type (autologous or allogeneic). Results: HCT patients receiving the PRO intervention also experienced lower peak symptom burden (average of 16 symptoms) at days +7, +10, and +14 (10.4 vs 14.5, p =0.03). Conclusions: Daily use of electronic symptom reporting to nurses in an inpatient bone marrow transplant clinic reduced peak symptom burden and improved individual symptoms during the two weeks post-transplant. A multi-site site trial is warranted to demonstrate the generalizability, efficacy, and value of this intervention

Evaluating Data Assimilation Algorithms

Data assimilation leads naturally to a Bayesian formulation in which the posterior probability distribution of the system state, given the observations, plays a central conceptual role. The aim of this paper is to use this Bayesian posterior probability distribution as a gold standard against which to evaluate various commonly used data assimilation algorithms. A key aspect of geophysical data assimilation is the high dimensionality and low predictability of the computational model. With this in mind, yet with the goal of allowing an explicit and accurate computation of the posterior distribution, we study the 2D Navier-Stokes equations in a periodic geometry. We compute the posterior probability distribution by state-of-the-art statistical sampling techniques. The commonly used algorithms that we evaluate against this accurate gold standard, as quantified by comparing the relative error in reproducing its moments, are 4DVAR and a variety of sequential filtering approximations based on 3DVAR and on extended and ensemble Kalman filters. The primary conclusions are that: (i) with appropriate parameter choices, approximate filters can perform well in reproducing the mean of the desired probability distribution; (ii) however they typically perform poorly when attempting to reproduce the covariance; (iii) this poor performance is compounded by the need to modify the covariance, in order to induce stability. Thus, whilst filters can be a useful tool in predicting mean behavior, they should be viewed with caution as predictors of uncertainty. These conclusions are intrinsic to the algorithms and will not change if the model complexity is increased, for example by employing a smaller viscosity, or by using a detailed NWP model

The Strong Energy Condition and the S-Brane Singularity Problem

Recently it has been argued that, because tachyonic matter satisfies the Strong Energy Condition [SEC], there is little hope of avoiding the singularities which plague S-Brane spacetimes. Meanwhile, however, Townsend and Wohlfarth have suggested an ingenious way of circumventing the SEC in such situations, and other suggestions for actually violating it in the S-Brane context have recently been proposed. Of course, the natural context for discussions of [effective or actual] violations of the SEC is the theory of asymptotically deSitter spacetimes, which tend to be less singular than ordinary FRW spacetimes. However, while violating or circumventing the SEC is necessary if singularities are to be avoided, it is not at all clear that it is sufficient. That is, we can ask: would an asymptotically deSitter S-brane spacetime be non-singular? We show that this is difficult to achieve; this result is in the spirit of the recently proved "S-brane singularity theorem". Essentially our results suggest that circumventing or violating the SEC may not suffice to solve the S-Brane singularity problem, though we do propose two ways of avoiding this conclusion.Comment: 13 pages, minor corrections and improvements, references adde

De Sitter and Schwarzschild-De Sitter According to Schwarzschild and De Sitter

When de Sitter first introduced his celebrated spacetime, he claimed, following Schwarzschild, that its spatial sections have the topology of the real projective space RP^3 (that is, the topology of the group manifold SO(3)) rather than, as is almost universally assumed today, that of the sphere S^3. (In modern language, Schwarzschild was disturbed by the non-local correlations enforced by S^3 geometry.) Thus, what we today call "de Sitter space" would not have been accepted as such by de Sitter. There is no real basis within classical cosmology for preferring S^3 to RP^3, but the general feeling appears to be that the distinction is in any case of little importance. We wish to argue that, in the light of current concerns about the nature of de Sitter space, this is a mistake. In particular, we argue that the difference between "dS(S^3)" and "dS(RP^3)" may be very important in attacking the problem of understanding horizon entropies. In the approach to de Sitter entropy via Schwarzschild-de Sitter spacetime, we find that the apparently trivial difference between RP^3 and S^3 actually leads to very different perspectives on this major question of quantum cosmology.Comment: 26 pages, 8 figures, typos fixed, references added, equation numbers finally fixed, JHEP versio