On the application of Marcus-Hush theory to small polaron chemical dynamics in oxides: its relationship to the Holstein model and the importance of lattice-orbital symmetries.

The chemical dynamics of small polaron hopping within oxides is often interpreted through two-site variations on Marcus-Hush theory, while from a physics perspective small polaron hopping is more often approached from Holstein's solid-state formalism. Here we seek to provide a chemically oriented viewpoint, focusing on small polaron hopping in oxides, concerning these two phenomenological frameworks by employing both tight-binding modelling and first-principles calculations. First, within a semiclassical approach the Marcus-Hush relations are overviewed as a two-site reduction of Holstein's model. Within the single-band regime, similarities and differences between Holstein derived small polaron hopping and the Marcus-Hush model are also discussed. In this context the emergence of adiabaticity (or, conversely, diabaticity) is also explored within each framework both analytically and by directly evolving the system wavefunction. Then, through first-principles calculations of select oxides we explore how coupled lattice and orbital symmetries can impact on hopping properties - in a manner that is quite distinct typical chemical applications of Marcus-Hush theory. These results are then related back to the Holstein model to explore the relative applicability of the two frameworks towards interpreting small polaron hopping properties, where it is emphasized that the Holstein model offers an increasingly more appealing physicochemical interpretation of hopping processes as band and/or coupling interactions increase. Overall, this work aims to strengthen the physically oriented exploration of small polarons and their physicochemical properties in the growing oxide chemistry community.

Signal quality assessment of peripheral venous pressure.

Develop a signal quality index (SQI) for the widely available peripheral venous pressure waveform (PVP). We focus on the quality of the cardiac component in PVP. We model PVP by the adaptive non-harmonic model. When the cardiac component in PVP is stronger, the PVP is defined to have a higher quality. This signal quality is quantified by applying the synchrosqueezing transform to decompose the cardiac component out of PVP, and the SQI is defined as a value between 0 and 1. A database collected during the lower body negative pressure experiment is utilized to validate the developed SQI. All signals are labeled into categories of low and high qualities by experts. A support vector machine (SVM) learning model is trained for practical purpose. The developed signal quality index coincide with human experts' labels with the area under the curve 0.95. In a leave-one-subject-out cross validation (LOSOCV), the SQI achieves accuracy 0.89 and F1 0.88, which is consistently higher than other commonly used signal qualities, including entropy, power and mean venous pressure. The trained SVM model trained with SQI, entropy, power and mean venous pressure could achieve an accuracy 0.92 and F1 0.91 under LOSOCV. An exterior validation of SQI achieves accuracy 0.87 and F1 0.92; an exterior validation of the SVM model achieves accuracy 0.95 and F1 0.96. The developed SQI has a convincing potential to help identify high quality PVP segments for further hemodynamic study. This is the first work aiming to quantify the signal quality of the widely applied PVP waveform.

Interpopulation differences and temporal synchrony in rates of adult survival between two seabird colonies that differ in population size and distance to foraging grounds.

Understanding the processes that drive interpopulation differences in demography and population dynamics is central to metapopulation ecology. In colonial species, populations are limited by local resource availability. However, individuals from larger colonies will travel greater distances to overcome density-dependent competition. Consequently, these individuals may also experience greater carry-over effects and interpopulation differences in demography. To test this prediction, we use mark-recapture data collected over four decades from two breeding colonies of a seabird, the Manx shearwater (Puffinus puffinus), that exhibit strong spatial overlap throughout the annual cycle but differ in population size and maximum foraging distances. We quantify interpopulation differences and synchrony in rates of survival and assess whether local mean wind speeds act to strengthen or disrupt synchrony. In addition, we examine whether the imputed interpopulation differences in survival can generate population-level consequences. The colony where individuals travel further during the breeding season had slightly lower and more variable rates of survival, indicative of individuals experiencing greater carry-over effects. Fluctuations in survival were highly synchronous between the colonies, but neither synchronous, nor asynchronous, variation could be strongly attributed to fluctuations in local mean wind speeds. Finally, we demonstrate that the imputed interpopulation differences in rates of survival could lead to considerable differences in population growth. We hypothesise that the observed interpopulation differences in rates of adult survival reflect carry-over effects associated with foraging distances during the breeding season. More broadly, our results highlight that breeding season processes can be important for understanding interpopulation differences in the demographic rates and population dynamics of long-lived species, such as seabirds.

Improving pulse oximetry accuracy in dark-skinned patients: technical aspects and current regulations.

Recent concerns regarding the clinical accuracy of pulse oximetry in dark-skinned patients, specifically in detecting occult hypoxaemia, have motivated research on this topic and recently reported in this journal. We provide an overview of the technical aspects of the issue, the sources of inaccuracy, and the current regulations and limitations. These insights offer perspectives on how pulse oximetry can be improved to address these potential limitations.

Using the ear photoplethysmographic waveform as an early indicator of central hypovolemia in healthy volunteers utilizing LBNP induced hypovolemia model.

Objective. To study the photoplethysmographic (PPG) waveforms of different locations (ear and finger) during lower body negative pressure (LBNP) induced hypovolemia. Then, to determine whether the PPG waveform can be used to detect hypovolemia during the early stage of LBNP.Approach. 36 healthy volunteers were recruited for progressive LBNP induced hypovolemia, with an endpoint of -60 mmHg or development of hypoperfusion symptoms, whichever comes first. Subjects tolerating the entire protocol without symptoms were designated as high tolerance (HT), while symptomatic subjects were designated as low tolerance (LT). Subjects were monitored with an electrocardiogram, continuous noninvasive blood pressure monitor, and two pulse oximetry probes, one on the ear (Xhale) and one the finger (Nellcor). Stroke volume was measured non-invasively utilizing Non-Invasive Cardiac Output Monitor (NICOM, Cheetah Medical). The waveform morphology was analyzed using novel PPG waveforms indices, including phase hemodynamic index (PHI) and amplitude hemodyamaic index and were evaluated from the ear PPG and finger PPG at different LBNP stages.Main results. The PHI, particularly the phase relationship between the second harmonic and the fundamental component of the ear PPG denoted as∇φ2,during the early stage of LBNP (-15 mmHg) in the HT and LT groups is statistically significantly different (pvalue = 0.0033) with the area under curve 0.81 (CI: 0.616-0.926). The other indices are not significantly different. The 5 fold cross validation shows that∇φ2during the early stage of LBNP (-15 mmHg) as the single index could predict the tolerance of the subject with the sensitivity, specificity, accuracy andF1 as 0.771 ± 0.192, 0.71 ± 0.107, 0.7 ± 0.1 and 0.771 ± 0.192 respectively.Significance. The ear's PPG PHI which compares the phases of the fundamental and second harmonic has the potential to be used as an early predictor of central hypovolemia.

Inaccuracy of pulse oximetry with dark skin pigmentation: clinical implications and need for improvement.

Recent reports highlight potential inaccuracies of pulse oximetry in patients with various degrees of skin pigmentation. We summarise the literature, provide an overview of potential clinical implications, and provide insights into how pulse oximetry could be improved to mitigate against such potential shortcomings.

First-principles redox energy estimates under the condition of satisfying the general form of Koopmans' theorem: An atomistic study of aqueous iron.

In this work, we explore the relative accuracy to which a hybrid functional, in the context of density functional theory, may predict redox properties under the constraint of satisfying the general form of Koopmans' theorem. Taking aqueous iron as our model system within the framework of first-principles molecular dynamics, direct comparison between computed single-particle energies and experimental ionization data is assessed by both (1) tuning the degree of hybrid exchange, to satisfy the general form of Koopmans' theorem, and (2) ensuring the application of finite-size corrections. These finite-size corrections are benchmarked through classical molecular dynamics calculations, extended to large atomic ensembles, for which good convergence is obtained in the large supercell limit. Our first-principles findings indicate that while precise quantitative agreement with experimental ionization data cannot always be attained for solvated systems, when satisfying the general form of Koopmans' theorem via hybrid functionals, theoretically robust estimates of single-particle redox energies are most often arrived at by employing a total energy difference approach. That is, when seeking to employ a value of exact exchange that does not satisfy the general form of Koopmans' theorem, but some other physical metric, the single-particle energy estimate that would most closely align with the general form of Koopmans' theorem is obtained from a total energy difference approach. In this respect, these findings provide important guidance for the more general comparison of redox energies computed via hybrid functionals with experimental data.

Telehealth and Allergy Services in Rural and Regional Locations That Lack Specialty Services.

Secondary to the coronavirus disease 2019 pandemic, telehealth quickly peaked as the dominant health care modality and its use still remains high. Although allergists and health care systems adapted quickly to adopt telehealth, its increased use has both highlighted its benefits for patients and allergists and demonstrated known concerns with delivering allergy specialty care to rural and regional patient populations. With increased concentration of both patients and allergists in urban areas, the ability to provide allergy specialty care to the rural and remote population continues to remain a challenge despite the advantages leveraged through telehealth. Herein, we review aspects specific to the rural patient population, tele-allergy outcomes with these patient cohorts, and efforts, both past and present, taken at different levels within the allergy community to promote our specialty through specific telehealth modalities to address and engage the rural and regional patient.

Tertiary Survey in the Days of Modern Imaging: Assessing the Detection Rate of Clinically Significant Injuries on Tertiary Survey in a Level 2 Trauma Centre.

AIM: To determine the utility of tertiary survey (TS) in patients subjected to whole-body CT (WBCT) or selective CT (SCT) following trauma. METHODS: A retrospective analysis was performed on trauma patients admitted to a level 2 trauma centre following the introduction of a standardised TS form in 2017. The initial imaging protocol (WBCT versus selective CT versus x-ray), subsequently requested imaging, standardised injury data, and length of stay (LOS) were recorded. Clinically significant injuries were defined as those with an Injury Severity Score (ISS) of 1 on the Abbreviated Injury Scale (AIS). RESULTS: Five hundred and seven patients were included. The rate of additional significant injuries at the time of TS was 1.18% (n=6), each requiring conservative management only. There was no significant difference in injury detection based on the initial imaging protocol; however, there were three near-misses identified. Of these patients, two underwent selective CT and one was subjected to a plain film series, with clinically significant injuries identified early upon completion of trauma imaging. Overall, 2.9% (n=15) of patients had completed trauma imaging during the same admission. WBCT was associated with higher ISS and length of stay (p<0.05). After controlling for ISS, there was no difference in length of stay between imaging modalities except in those patients with an ISS of 0 (no clinically significant injuries), who appeared to have longer admissions if subject to WBCT (p<0.001). CONCLUSION: The rate of missed injuries identified at TS is low. The imaging modality did not alter this. This may allow for the omission of the tertiary survey and earlier discharge in many trauma patients.

Modeling and multiobjective optimization of indoor airborne disease transmission risk and associated energy consumption for building HVAC systems.

The COVID-19 pandemic has renewed interest in assessing how the operation of HVAC systems influences the risk of airborne disease transmission in buildings. Various processes, such as ventilation and filtration, have been shown to reduce the probability of disease spread by removing or deactivating exhaled aerosols that potentially contain infectious material. However, such qualitative recommendations fail to specify how much of these or other disinfection techniques are needed to achieve acceptable risk levels in a particular space. An additional complication is that application of these techniques inevitably increases energy costs, the magnitude of which can vary significantly based on local weather. Moreover, the operational flexibility available to the HVAC system may be inherently limited by equipment capacities and occupant comfort requirements. Given this knowledge gap, we propose a set of dynamical models that can be used to estimate airborne transmission risk and energy consumption for building HVAC systems based on controller setpoints and a forecast of weather conditions. By combining physics-based material balances with phenomenological models of the HVAC control system, it is possible to predict time-varying airflows and other HVAC variables, which are then used to calculate key metrics. Through a variety of examples involving real and simulated commercial buildings, we show that our models can be used for monitoring purposes by applying them directly to transient building data as operated, or they may be embedded within a multi-objective optimization framework to evaluate the tradeoff between infection risk and energy consumption. By combining these applications, building managers can determine which spaces are in need of infection risk reduction and how to provide that reduction at the lowest energy cost. The key finding is that both the baseline infection risk and the most energy-efficient disinfection strategy can vary significantly from space to space and depend sensitively on the weather, thus underscoring the importance of the quantitative predictions provided by the models.

Evolution of Surface Oxidation on Ta3N5 as Probed by a Photoelectrochemical Method.

In this work, we present an in situ method to probe the evolution of photoelectrochemically driven surface oxidation on photoanodes during active operation in aqueous solutions. A standard solution of K4Fe(CN)6-KPi was utilized to benchmark the photocurrent and assess progressive surface oxidation on Ta3N5 in various oxidizing solutions. In this manner, a proportional increase in the surface oxygen concentration was detected with respect to oxidation time and further correlated with a continuous decline in the photocurrent. To discern how surface oxidation alters the photocurrent, we experimentally and theoretically explored its impact on the surface carrier recombination and the interfacial hole transfer rates. Our results indicate that the sluggish photocurrent demonstrated by oxidized Ta3N5 arises because of changes in both rates. In particular, the results suggest that the N-O replacement present on the Ta3N5 surface primarily increases the carrier recombination rate near the surface and to a lesser degree reduces the interfacial hole transfer rate. More generally, this methodology is expected to further our understanding of surface oxidation atop other nonoxide semiconductor photoelectrodes and its impact on their operation.

Computational and infrared spectroscopic investigations of N-substituted carbazoles.

The carbazole moiety is a commonly identified structural motif in the high-molecular-weight components of petroleum, known as asphaltenes. Detailed characterization of carbazoles is important for understanding the structure of asphaltenes and addressing challenges in the areas of heavy oil recovery, transportation, upgrading, and oil spills, arising from asphaltene properties and composition. In this work we study carbazole and the four N-substituted carbazoles 9-methylcarbazole, 9-ethylcarbazole, 9-vinylcarbazole and 9-phenylcarbazole. Experimental far- and mid-infrared spectra of these five carbazoles are measured using transmission and photoacoustic techniques. The molecular structures of the monomers and the respective dimers, optimized at the ωB97X-D/6-311++G(d,p) level of the density functional theory (DFT), are subjected to harmonic vibrational frequency calculations. The effect of changing substituents on the N-H bond, π-π stacking distances, and angles between monomers within the dimers, in addition to intermolecular interactions, is investigated. Noncovalent interaction analysis is employed to highlight the areas of attractive and repulsive interactions in the dimers. Thermochemistry calculations show that the formation of dimers of all carbazoles is spontaneous at 298 K. Comparison of the calculated vibrational spectra of these compounds with experimental spectra indicates that the existence of both monomers and dimers must be invoked to account for the observed bands in the infrared spectra. Excellent correlations between the experimentally-determined and calculated harmonic vibrational energies are obtained, with an experimental-to-calculated scaling factor of 0.95-0.96. These findings highlight the coupled computational-experimental approach for the interpretation of vibrational spectra and are essential for improving the spectroscopic characterization of N-substituted carbazoles.

Photoacoustic Detection of Weak Absorption Bands in Infrared Spectra of Calcite.

Photoacoustic spectroscopic detection of infrared absorption often produces spectra with enhanced intensities for weaker peaks, enabling the detection of features due to overtones and combinations, as well as less-abundant isotopic species. To illustrate this phenomenon, we present and discuss photoacoustic infrared spectra of calcite. We use linearization of rapid-scan spectra, as well as comparing step-scan and rapid-scan spectra, to demonstrate that saturation is not the driving force behind these enhanced intensities. Our results point to a significant knowledge gap, since a theoretical basis for the enhancement of these weak bands has not yet been developed.

The PITCH study: pitcher injuries during the first 30 days of the coronavirus disease 2019 halted Major League Baseball season.

Background: Major League Baseball (MLB) was among the first professional team sports leagues to resume play in the United States after public health measures related to the appearance of coronavirus disease 2019 caused interruptions to preseason training and major alterations to regular season play. There was a high level of concern that these athletes were ill-prepared for competition and would experience an increased risk of injury under the restricted play rules. Methods: The data in our study were compiled using publicly accessible records of players placed on injured lists from 2015 to 2020. These records came from 4 open access websites: rotoworld.com, fangraphs.com, foxsports.com, and spotrac.com. All injuries were confirmed using the transaction database found on the official MLB website (mlb.com). Results: A greater proportion of pitchers were injured during the first 30 days of the 2020 season compared to the first 30 days of any of the 5 prior seasons (29.74% vs. 11.72%, n=2190, P<.001). There was a demonstrated increase in injury risk in 2020 for the following anatomic locations: back and trunk, shoulder, upper arm and elbow, forearm and wrist, and hand and finger (P=.02; confidence interval [0.497-5.783]). When dividing the first month of play in 2020 into equal halves (15 days each), the number of relief pitcher injuries increased with time (60% vs. 78%, P=.04). Lastly, there was no proportional difference in placement on the short-term vs. long-term injured list. Conclusion: A significantly large increase in soft tissue injuries in 2020 compared to the prior 5 seasons predominantly affected the trunk and the upper extremity of pitchers in the first 30 days of play. Alterations to preseason training and regular season play in the 2020 MLB season due to coronavirus disease 2019 may have been particularly disadvantageous to professional pitchers who are positioned at baseline, the most injury prone position.

Interpreting interfacial semiconductor-liquid capacitive characteristics impacted by surface states: a theoretical and experimental study of CuGaS2.

Semiconductor-liquid interfaces are essential to the operation of many energy devices. Crucially, the operational characteristics of such devices are dependent upon both the flat band potential and doping concentration present in their solid-state semiconducting region. Traditionally, capacitive "linear" Mott-Schottky plots have often been utilized to extract these two parameters. However, significant concentrations of surface states within semiconductor-liquid junctions can give rise to strong non-linearities that prevent an effective linearity-based analysis. In this work, we detail a theoretical approach for estimating both the doping concentration and flat band potential from the capacitive characteristics of semiconductor-liquid junctions heavily impacted upon by surface states. Our theoretical approach is applied to CuGaS2 immersed in an aqueous electrolyte, for which excellent convergent values of the doping concentration and flat band potential are obtained across a wide range of impedance measurement frequencies. The results suggest a marked improvement over a linearity-based approach that could assist the analysis of many types of semiconductor-liquid junctions subject to high concentrations of surface states.

Ergodic and Nonergodic Dynamics of Oxygen Vacancy Migration at the Nanoscale in Inorganic Perovskites.

Perovskites are widely utilized either as a primary component or as a substrate in which the dynamics of charged oxygen vacancy defects play an important role. Current knowledge regarding the dynamics of vacancy mobility in perovskites is solely based upon volume- and/or time-averaged measurements. This impedes our understanding of the basic physical principles governing defect migration in inorganic materials. Here, we measure the ergodic and nonergodic dynamics of vacancy migration at the relevant spatial and temporal scales using time-resolved atomic force microscopy techniques. Our findings demonstrate that the time constant associated with oxygen vacancy migration is a local property and can change drastically on short length and time scales, such that nonergodic states lead to a dramatic increase in the migration barrier. This correlated spatial and temporal variation in oxygen vacancy dynamics can extend hundreds of nanometers across the surface in inorganic perovskites.

Infrared spectra of micro-structured samples with microPhotoacoustic spectroscopy and synchrotron radiation.

Photoacoustic spectroscopy (PAS) measures the photon absorption spectrum of a sample through detection of the acoustic wave generated by the photothermal effect as one modulates the intensity of the incident radiation at each wavelength. We have recently demonstrated the implementation of PAS in a microscopy configuration with mid-infrared radiation (microPAS). In the present work, we describe the performance of microPAS using synchrotron radiation (SR) in diffraction-limited spectromicroscopy and imaging experiments. Spectra were obtained for polystyrene beads, polypropylene fibres, and single fibres of human hair. SR produced microPAS spectra of much higher intensity as compared with those obtained using conventional mid- and near-infrared sources. For hair samples, the penetration depth of mid-infrared light, even with bright SR, is significantly shorter than the probed sample thickness at very low modulation frequencies resulting in saturated PAS spectra. In contrast, microPAS spectra of polymer beads were in general of much better quality than those obtained with conventional sources. We also demonstrated the capability to collect line profiles and line spectra at diffraction limited spatial resolution. The microPAS spectra of beads appear free from appreciable bandshape distortions arising from the real part of the refractive index of the sample. This observation confirms microPAS as an absorption-only technique and establishes it as a valuable new tool in the microspectroscopic analysis of particulates and of samples with a complex topography.

Fully Quantized Electron Transfer Observed in a Single Redox Molecule at a Metal Interface.

Long-range electron transfer is a ubiquitous process that plays an important role in electrochemistry, biochemistry, organic electronics, and single molecule electronics. Fundamentally, quantum mechanical processes, at their core, manifest through both electron tunneling and the associated transition between quantized nuclear vibronic states (intramolecular vibrational relaxation) mediated by electron-nuclear coupling. Here, we report on measurements of long-range electron transfer at the interface between a single ferrocene molecule and a gold substrate separated by a hexadecanethiol quantum tunneling barrier. These redox measurements exhibit quantized nuclear transitions mediated by electron-nuclear coupling at 4.7 K in vacuum. By detecting the electric force associated with redox events by atomic force microscopy (AFM), with increasing AFM oscillation amplitude, the intensity of the observed  cantilever resonance frequency shift peak increases and then exhibits a series of discrete steps that are indicative of quantized nuclear transitions. The observed peak shapes agree well with a single-electron tunneling model with quantized nuclear state transitions associated with the conversion of the molecule between oxidized and reduced electronic states. This technique opens the door to simultaneously investigating quantized electron and nuclear dynamics in a diverse range of systems.

Section 718 (Telemedicine): Virtual Health Outcomes From Regional Health Command Europe.

BACKGROUND: Section 718 of the Fiscal Year 2017 (FY17) National Defense Authorization Act (NDAA) outlines many reportable telemedicine outcomes. While the Military Health System Data Repository (MDR) and the Management and Reporting Tool M2 provide some telemedicine analyses, there are many outcomes that neither the MDR nor M2 provide. Understanding patient and provider attitudes towards telehealth and specialty-specific usage may assist initial or ongoing telehealth lines of effort within Defense Health Agency Medical Treatment Facilities (DHA MTFs). METHODS: A retrospective descriptive analysis of synchronous virtual health (VH) encounters and results from three internally developed telehealth surveys for calendar year (CY) 2016 was conducted. RESULTS: Three thousand seven hundred and seventy-eight synchronous VH visits for 2,962 unique patients were completed by 142 providers located within 27 distinct specialty clinics. 89.8% of patients were adults and 75.9% were Active Duty. Skill type I and II medical providers conducted 1,827 new consultations, 1,187 follow-up visits, and 371 readiness exams. Overall, specialty-specific VH use ranged from less than 1% to 39.9%. Patient satisfaction was 98% while provider satisfaction ranged from 91% to 93%. Additionally, significant intangible savings were recognized. CONCLUSION: Regional medical centers conducting synchronous VH will require both internal and external data sources to report Section 718 outcomes required by Congress. As the anticipated demand for direct provider-to-patient telehealth increases, understanding these outcomes may aid initial and ongoing efforts in other military treatment facilities conducting synchronous VH.