Dynamic Copper Site Redispersion through Atom Trapping in Zeolite Defects.

Single-site copper-based catalysts have shown remarkable activity and selectivity for a variety of reactions. However, deactivation by sintering in high-temperature reducing environments remains a challenge and often limits their use due to irreversible structural changes to the catalyst. Here, we report zeolite-based copper catalysts in which copper oxide agglomerates formed after reaction can be repeatedly redispersed back to single sites using an oxidative treatment in air at 550 °C. Under different environments, single-site copper in Cu-Zn-Y/deAlBeta undergoes dynamic changes in structure and oxidation state that can be tuned to promote the formation of key active sites while minimizing deactivation through Cu sintering. For example, single-site Cu2+ reduces to Cu1+ after catalyst pretreatment (270 °C, 101 kPa H2) and further to Cu0 nanoparticles under reaction conditions (270-350 °C, 7 kPa EtOH, 94 kPa H2) or accelerated aging (400-450 °C, 101 kPa H2). After regeneration at 550 °C in air, agglomerated CuO was dispersed back to single sites in the presence and absence of Zn and Y, which was verified by imaging, in situ spectroscopy, and catalytic rate measurements. Ab initio molecular dynamics simulations show that solvation of CuO monomers by water facilitates their transport through the zeolite pore, and condensation of the CuO monomer with a fully protonated silanol nest entraps copper and reforms the single-site structure. The capability of silanol nests to trap and stabilize copper single sites under oxidizing conditions could extend the use of single-site copper catalysts to a wider variety of reactions and allows for a simple regeneration strategy for copper single-site catalysts.

Optical penetration models for practical prediction of femtosecond laser ablation of dental hard tissue.

OBJECTIVES: To develop and practically test high-precision femtosecond laser ablation models for dental hard tissue that are useful for detailed planning of automated laser dental restorative treatment. METHODS: Analytical models are proposed, derived, and demonstrated for practical calculation of ablation rates, ablation efficiency and ablated morphology of human dental enamel and dentin using femtosecond lasers. The models assume an effective optical attenuation coefficient for the irradiated material. To achieve ablation, it is necessary for the local energy density of the attenuated pulse in the hard tissue to surpass a predefined threshold that signifies the minimum energy density required for material ionization. A 1029 nm, 40 W carbide 275 fs laser was used to ablate sliced adult human teeth and generate the data necessary for testing the models. The volume of material removed, and the shape of the ablated channel were measured using optical profilometry. RESULTS: The models fit with the measured ablation efficiency curve against laser fluence for both enamel and dentin, correctly capturing the fluence for optimum ablation and the volume of ablated material per pulse. The detailed shapes of a 400-micrometer wide channel and a single-pulse width channel are accurately predicted using the superposition of the analytical result for a single pulse. CONCLUSIONS: The findings have value for planning automated dental restorative treatment using femtosecond lasers. The measurements and analysis give estimates of the optical properties of enamel and dentin irradiated with an infrared femtosecond laser at above-threshold fluence and the proposed models give insight into the physics of femtosecond laser processing of dental hard tissue.

Subfemtowatt Laser Phase Tracking.

Low power optical phase tracking is an enabling capability for intersatellite laser interferometry, as minimum trackable power places significant constraints on mission design. Through the combination of laser stabilization and control-loop parameter optimization, we have demonstrated continuous tracking of a subfemtowatt optical field with a mean time between slips of more than 1000 s. Comparison with analytical models and numerical simulations verified that the observed experimental performance was limited by photon shot noise and unsuppressed laser frequency fluctuations. Furthermore, with two stabilized lasers, we have demonstrated 100 min of continuous phase tracking of Gravity Recovery and Climate Experiment (GRACE)-like signal dynamics with an optical carrier ranging in power between 1-7 fW with zero cycle slips. These results indicate the feasibility of future interspacecraft laser links operating with significantly reduced received optical power.

Symmetry Breaking for Voting Mechanisms.

Recently, Rowe and Aishwaryaprajna (2019) introduced a simple majority vote technique that efficiently solves Jump with large gaps, OneMax with large noise, and any monotone function with a polynomial-size image. In this paper, we identify a pathological condition for this algorithm: the presence of spin-flip symmetry in the problem instance. Spin-flip symmetry is the invariance of a pseudo-Boolean function to complementation. Many important combinatorial optimization problems admit objective functions that exhibit this pathology, such as graph problems, Ising models, and variants of propositional satisfiability. We prove that no population size exists that allows the majority vote technique to solve spin-flip symmetric functions of unitation with reasonable probability. To remedy this, we introduce a symmetry-breaking technique that allows the majority vote algorithm to overcome this issue for many landscapes. This technique requires only a minor modification to the original majority vote algorithm to force it to sample strings in {0,1}n from a dimension n-1 hyperplane. We prove a sufficient condition for a spin-flip symmetric function to possess in order for the symmetry-breaking voting algorithm to succeed, and prove its efficiency on generalized TwoMax, a spin-flip symmetric variant of Jump, and families of constructed 3-NAE-SAT and 2-XOR-SAT formulas. We also prove that the algorithm fails on the one-dimensional Ising model, and suggest different techniques for overcoming this. Finally, we present empirical results that explore the tightness of the runtime bounds and the performance of the technique on randomized satisfiability variants.

Complete Revascularization with Multivessel PCI for Myocardial Infarction.

BACKGROUND: In patients with ST-segment elevation myocardial infarction (STEMI), percutaneous coronary intervention (PCI) of the culprit lesion reduces the risk of cardiovascular death or myocardial infarction. Whether PCI of nonculprit lesions further reduces the risk of such events is unclear. METHODS: We randomly assigned patients with STEMI and multivessel coronary artery disease who had undergone successful culprit-lesion PCI to a strategy of either complete revascularization with PCI of angiographically significant nonculprit lesions or no further revascularization. Randomization was stratified according to the intended timing of nonculprit-lesion PCI (either during or after the index hospitalization). The first coprimary outcome was the composite of cardiovascular death or myocardial infarction; the second coprimary outcome was the composite of cardiovascular death, myocardial infarction, or ischemia-driven revascularization. RESULTS: At a median follow-up of 3 years, the first coprimary outcome had occurred in 158 of the 2016 patients (7.8%) in the complete-revascularization group as compared with 213 of the 2025 patients (10.5%) in the culprit-lesion-only PCI group (hazard ratio, 0.74; 95% confidence interval [CI], 0.60 to 0.91; P = 0.004). The second coprimary outcome had occurred in 179 patients (8.9%) in the complete-revascularization group as compared with 339 patients (16.7%) in the culprit-lesion-only PCI group (hazard ratio, 0.51; 95% CI, 0.43 to 0.61; P<0.001). For both coprimary outcomes, the benefit of complete revascularization was consistently observed regardless of the intended timing of nonculprit-lesion PCI (P = 0.62 and P = 0.27 for interaction for the first and second coprimary outcomes, respectively). CONCLUSIONS: Among patients with STEMI and multivessel coronary artery disease, complete revascularization was superior to culprit-lesion-only PCI in reducing the risk of cardiovascular death or myocardial infarction, as well as the risk of cardiovascular death, myocardial infarction, or ischemia-driven revascularization. (Funded by the Canadian Institutes of Health Research and others; COMPLETE ClinicalTrials.gov number, NCT01740479.).

Absolute frequency readout derived from ULE cavity for next generation geodesy missions: erratum.

We found a calculation error affecting the scaling of results presented in Figure 7 of our article "Absolute frequency readout derived from ULE cavity for next generation geodesy missions" [Opt. Express2926014 (2021)10.1364/OE.434483] . The corrected Figure 7 is published here.

A Multicenter Randomized Controlled Trial Comparing Safety, Efficacy, and Cost-effectiveness of the Surgisis Anal Fistula Plug Versus Surgeon's Preference for Transsphincteric Fistula-in-Ano: The FIAT Trial.

OBJECTIVE: To undertake a randomized comparison of the Biodesign Surgisis anal fistula plug against surgeon's preference in treating cryptoglandular transsphincteric fistula-in-ano. SUMMARY BACKGROUND DATA: The efficacy of the Biodesign Surgisis anal fistula plug in healing anal fistulae is uncertain. METHODS: Participants were randomized to the fistula plug with surgeon's preference (advancement flap, cutting seton, fistulotomy, Ligation of the Intersphincteric Fistula Tract procedure). The primary outcome was faecal incontinence quality of life (FIQoL) at 12-months. Secondary outcomes were fistula healing, incontinence rates, and complication and reintervention rates. RESULTS: Between May 2011 and March 2016, 304 participants were randomized to fistula plug or surgeon's preference. No differences were seen in FIQoL between the 2 groups at 12 months. Clinical fistula healing was reported in 66/122 (54%) of the fistula plug and 66/119 (55%) of the surgeon's preference groups at 12 months. Fecal incontinence rates improved marginally in both the groups. Complications and reinterventions were frequent, with significantly more complications in the fistula plug group at 6-weeks (49/142, 35% vs 25/137, 18%; P=0.002). The mean total costs were £2738 (s.d. £1151) for the fistula plug and £2308 (s.d. £1228) for the surgeon's preference group (mean difference +£430, P=0.0174). The average total quality adjusted life years (QALYs) gained was marginally higher in the fistula plug group. The fistula plug was 35% to 45% likely to be cost-effective across a willingness to pay threshold of £20,000 to £30,000 / QALY. CONCLUSIONS: The Biodesign Surgisis anal fistula plug is associated with similar FIQoL and healing rates to surgeon's preference at 12 months. Higher costs and highly uncertain gains in QALYs mean that the fistula plug may not be considered as a cost-effective treatment in the UK NHS.

Detection statistics for coherent RMCW LiDAR.

This paper presents an analytical model and experimental validation for the detection performance and false-alarm rates for phase-encoded random modulation continuous-wave (RMCW) LiDAR. Derivation of the model focuses on propagating the effects of relevant noise sources through the system to determine an analytical expression for the detection rate, expressed by the probability of detection. The model demonstrates that probability of detection depends only on three factors: i) the mean signal-to-noise ratio (SNR) of the measurement; ii) the measurement integration time; and iii) speckle-induced intensity noise. The predicted analytical relationship between measurement SNR and probability of detection was validated by numerical simulations and experimental demonstrations in both a controlled fiber channel and under fully-developed speckle conditions in an uncontrolled free-space channel.

Absolute frequency readout derived from ULE cavity for next generation geodesy missions.

The next generation of Gravity Recovery and Climate Experiment (GRACE)-like dual-satellite geodesy missions proposals will rely on inter-spacecraft laser interferometry as the primary instrument to recover geodesy signals. Laser frequency stability is one of the main limits of this measurement and is important at two distinct timescales: short timescales over 10-1000 seconds to measure the local gravity below the satellites, and at the month to year timescales, where the subsequent gravity measurements are compared to indicate loss or gain of mass (or water and ice) over that period. This paper demonstrates a simple phase modulation scheme to directly measure laser frequency change over long timescales by comparing an on-board Ultra-Stable Oscillator (USO) clocked frequency reference to the Free Spectral Range (FSR) of the on-board optical cavity. By recording the fractional frequency variations the scale correction factor may be computed for a laser locked to a known longitudinal mode of the optical cavity. The experimental results demonstrate a fractional absolute laser frequency stability at the 10 ppb level (10-8) at time scales greater than 10 000 seconds, likely sufficient for next generation mission requirements.

High stability laser locking to an optical cavity using tilt locking.

This paper describes, to our knowledge, the first demonstration of high performance tilt locking, a method of stabilizing laser frequency to an optical reference cavity using a spatial-mode readout technique. The experiment utilized a traveling wave cavity with a finesse of approximately 10,000, housed in a thermally controlled vacuum chamber. The tilt locking method in a double pass configuration has promising performance in the 100 µHz-1 Hz band, including surpassing the Gravity Recovery and Climate Experiment (GRACE) Follow-On laser ranging interferometer requirement. Tilt locking offers a number of benefits such as high sensitivity, low cost, and simple implementation and therefore should be considered for future applications requiring high performance laser locking, such as future laser-based satellite geodesy missions and the Laser Interferometer Space Antenna.

Engineering Challenges of Solution and Slurry-Phase Chemical Hydrogen Storage Materials for Automotive Fuel Cell Applications.

We present the research findings of the DOE-funded Hydrogen Storage Engineering Center of Excellence (HSECoE) related to liquid-phase and slurry-phase chemical hydrogen storage media and their potential as future hydrogen storage media for automotive applications. Chemical hydrogen storage media other than neat liquid compositions will prove difficult to meet the DOE system level targets. Solid- and slurry-phase chemical hydrogen storage media requiring off-board regeneration are impractical and highly unlikely to be implemented for automotive applications because of the formidable task of developing solid- or slurry-phase transport systems that are commercially reliable and economical throughout the entire life cycle of the fuel. Additionally, the regeneration cost and efficiency of chemical hydrogen storage media is currently the single most prohibitive barrier to implementing chemical hydrogen storage media. Ideally, neat liquid-phase chemical hydrogen storage media with net-usable gravimetric hydrogen capacities of greater than 7.8 wt% are projected to meet the 2017 DOE system level gravimetric and volumetric targets. The research presented herein is a collection of research findings that do not in and of themselves warrant a dedicated manuscript. However, the collection of results do, in fact, highlight the engineering challenges and short-comings in scaling up and demonstrating fluid-phase ammonia borane and alane compositions that all future materials researchers working in hydrogen storage should be aware of.

Biological variation of measured and estimated glomerular filtration rate in patients with chronic kidney disease.

When assessing changes in glomerular filtration rate (GFR) it is important to differentiate pathological change from intrinsic biological and analytical variation. GFR is measured using complex reference methods (e.g., iohexol clearance). In clinical practice measurement of creatinine and cystatin C are used in the Modification of Diet in Renal Disease [MDRD] or Chronic Kidney Disease Epidemiology Collaboration [CKD-EPI] equations to provide estimated GFR. Here we studied the biological variability of measured and estimated GFR in twenty nephrology outpatients (10 male, 10 female; median age 71, range 50-80 years) with moderate CKD (GFR 30-59 ml/min per 1.73 m2). Patients underwent weekly GFR measurement by iohexol clearance over four consecutive weeks. Simultaneously, GFR was estimated using the MDRD, CKD-EPIcreatinine, CKD-EPIcystatinC and CKD-EPIcreatinine+cystatinC equations. Within-subject biological variation expressed as a percentage [95% confidence interval] for the MDRD (5.0% [4.3-6.1]), CKD-EPIcreatinine (5.3% [4.5-6.4]), CKD-EPIcystatinC (5.3% [4.5-6.5]), and CKD-EPIcreatinine+cystatinC (5.0% [4.3-6.2]) equations were broadly equivalent. The within-subject biological variation for MDRD and CKD- EPIcreatinine+cystatinC estimated GFR were each significantly lower than that of the measured GFR (6.7% [5.6-8.2]). Reference change values, the point at which a true change in a biomarker in an individual can be inferred to have occurred with 95% probability were calculated. By the MDRD equation, positive and negative reference change values were 15.1% and 13.1% respectively. If an individual's baseline MDRD estimated GFR (ml/min per 1.73 m2) was 59, significant increases or decreases would be to values over 68 or under 51 respectively. Within-subject variability of estimated GFR was lower than measured GFR. Reference change values can be used to understand GFR changes in clinical practice. Thus, estimates of GFR are at least as reliable as measured GFR for monitoring patients over time.

The Importance of Model Structure in the Cost-Effectiveness Analysis of Primary Care Interventions for the Management of Hypertension.

BACKGROUND: Management of hypertension can lead to significant reductions in blood pressure, thereby reducing the risk of cardiovascular disease. Modeling the course of cardiovascular disease is not without complications, and uncertainty surrounding the structure of a model will almost always arise once a choice of a model structure is defined. OBJECTIVES: To provide a practical illustration of the impact on the results of cost-effectiveness of changing or adapting model structures in a previously published cost-utility analysis of a primary care intervention for the management of hypertension Targets and Self-Management for the Control of Blood Pressure in Stroke and at Risk Groups (TASMIN-SR). METHODS: The case study assessed the structural uncertainty arising from model structure and from the exclusion of secondary events. Four alternative model structures were implemented. Long-term cost-effectiveness was estimated and the results compared with those from the TASMIN-SR model. RESULTS: The main cost-effectiveness results obtained in the TASMIN-SR study did not change with the implementation of alternative model structures. Choice of model type was limited to a cohort Markov model, and because of the lack of epidemiological data, only model 4 captured structural uncertainty arising from the exclusion of secondary events in the case study model. CONCLUSIONS: The results of this study indicate that the main conclusions drawn from the TASMIN-SR model of cost-effectiveness were robust to changes in model structure and the inclusion of secondary events. Even though one of the models produced results that were different to those of TASMIN-SR, the fact that the main conclusions were identical suggests that a more parsimonious model may have sufficed.

High power compatible internally sensed optical phased array.

The technical embodiment of the Huygens-Fresnel principle, an optical phased array (OPA) is an arrangement of optical emitters with relative phases controlled to create a desired beam profile after propagation. One important application of an OPA is coherent beam combining (CBC), which can be used to create beams of higher power than is possible with a single laser source, especially for narrow linewidth sources. Here we present an all-fiber architecture that stabilizes the relative output phase by inferring the relative path length differences between lasers using the small fraction of light that is back-reflected into the fiber at the OPA's glass-air interface, without the need for any external sampling optics. This architecture is compatible with high power continuous wave laser sources (e.g., fiber amplifiers) up to 100 W per channel. The high-power compatible internally sensed OPA was implemented experimentally using commercial 15 W fiber amplifiers, demonstrating an output RMS phase stability of λ/194, and the ability to steer the beam at up to 10 kHz.

Methods Used in Economic Evaluations of Tuberculin Skin Tests and Interferon Gamma Release Assays for the Screening of Latent Tuberculosis Infection: A Systematic Review.

BACKGROUND: Latent tuberculosis infection (LTBI) provides a constant pool of new active tuberculosis cases; a third of the earth's population is estimated to be infected with LTBI. OBJECTIVE: The objective of this systematic review was to assess the quality and summarize the available evidence from published economic evaluations reporting on the cost-effectiveness of tuberculin skin tests (TSTs) compared with interferon gamma release assays (IGRAs) for the screening of LTBI. METHODS: An extensive systematic review of the published literature was conducted. A two-step process was adopted to identify relevant articles: information was extracted into evidence tables and then analyzed. The quality of the publications was assessed using a 10-item checklist specific for economic evaluations. RESULTS: Twenty-eight studies were identified for inclusion in this review. Most of the studies found IGRAs to be more cost-effective than TSTs; however, the conclusions from the studies varied significantly. Most studies scored highly on the checklist although only one fulfilled all the stipulated criteria. A wide variety of methodological approaches were documented; identified differences included the type of economic evaluation and model, time horizon, perspective, and outcomes measures. CONCLUSIONS: The lack of consistent methods across studies makes it difficult to draw any firm conclusions about the most cost-effective option between TSTs and IGRAs. This problem can be solved by improving the quality of economic evaluation studies in the field of LTBI screening, through adherence to quality checklists.

Methods Used in Economic Evaluations of Testing and Diagnosis for Ovarian Cancer: A Systematic Review.

OBJECTIVE: There are multiple tests available that can help diagnose ovarian cancer, and the cost-effective analysis of these diagnostic interventions is essential for making well-informed decisions regarding resource allocation. There are multiple factors that can impact on the conclusions drawn from economic evaluations including test accuracy, the impact of the testing pathway on patient costs and outcomes, and delays along the ovarian cancer test-treat pathway. The objective of this study was to evaluate how test accuracy, the choice of perspective, and delays along the testing and diagnostic pathway have been incorporated in economic evaluations of testing for ovarian cancer. METHODS: A systematic review of published literature was undertaken to identify economic evaluations (eg, cost-effectiveness, cost-utility analysis) focused on testing and diagnosis for ovarian cancer. RESULTS: Seven studies met the inclusion criteria. Six studies incorporated test accuracy and its impact on patients to some extent. Four studies adopted a societal perspective, but only one considered the costs incurred by patients on the testing and diagnosis pathway. Where delays on the testing pathway were incorporated into the analysis, these were frequently due to false-negative test results leading to delays in patients accessing treatment. Any anxiety that patients might experience as a result of a positive test was not considered in these studies. CONCLUSIONS: The impact on patients of receiving a positive test in terms of anxiety and the costs incurred by patients having to attend for testing and diagnosis are rarely considered. Delays along the testing and diagnosis pathway can have a major effect on patient outcomes, and it is important that these are acknowledged in economic evaluations focused on testing. Future economic analysis should incorporate these key determinants in order that diagnostic tests for ovarian cancer can be robustly evaluated.

EARLY COST-EFFECTIVENESS ANALYSIS OF NEW MEDICAL TESTS: RESPONSE.

As strong advocates and adopters of early cost-effectiveness modeling for test evaluation, we were excited to see the recent article "The Early Bird Catches the Worm: Early Cost-Effectiveness Analysis of New Medical Tests," in which Buisman and colleagues present a succinct and generalizable framework for conducting this type of analysis. The authors have done an excellent job in identifying and summarizing the key components of this methodology, as well as highlighting fundamental differences between early analyses versus the traditional late-stage approach. As the number of medical tests coming to market continues to grow, there is an ever growing need to develop rigorous methodology in this area, and we commend the authors for this timely work.

Robustness of Ant Colony Optimization to Noise.

Recently, ant colony optimization (ACO) algorithms have proven to be efficient in uncertain environments, such as noisy or dynamically changing fitness functions. Most of these analyses have focused on combinatorial problems such as path finding. We rigorously analyze an ACO algorithm optimizing linear pseudo-Boolean functions under additive posterior noise. We study noise distributions whose tails decay exponentially fast, including the classical case of additive Gaussian noise. Without noise, the classical [Formula: see text] EA outperforms any ACO algorithm, with smaller [Formula: see text] being better; however, in the case of large noise, the [Formula: see text] EA fails, even for high values of [Formula: see text] (which are known to help against small noise). In this article, we show that ACO is able to deal with arbitrarily large noise in a graceful manner; that is, as long as the evaporation factor [Formula: see text] is small enough, dependent on the variance [Formula: see text] of the noise and the dimension n of the search space, optimization will be successful. We also briefly consider the case of prior noise and prove that ACO can also efficiently optimize linear functions under this noise model.