Ab Initio Rotational and Vibrational Spectroscopy of CH Radicals at the Coupled Cluster Level.

Combustion and pyrolysis processes of allene and propyne are known to involve radicals with the structural formula CH, the most stable of which is the classic resonance-stabilized allyl radical. In addition to allyl, four other isomers of CH are possible: the propene derivatives -1-propenyl, -1-propenyl, and 2-propenyl, as well as the cyclopropane derivative cyclopropyl. Among these 5 species, the allyl radical has been extensively studied both theoretically and spectroscopically; however, little is known about the spectroscopy of the cyclopropyl radical, and virtually no experimental spectroscopic data are available for the remaining three.

Osteoradionecrosis in Pediatric Patients Treated with Proton Therapy for Head and Neck Malignancies.

Purpose: Osteoradionecrosis (ORN) is a feared complication after head and neck radiation, but the incidence and radiotherapy risk factors for ORN in children are unknown. In this retrospective analysis of a prospectively collected dataset, we evaluated the incidence and factors associated with development of ORN in children treated with proton therapy for head and neck malignancies.

Methods And Materials: We reviewed records from patients treated at a single institution between December 2006 and February 2020 including demographic data, tumor, and treatment details, ORN occurrence, and dosimetry.

K-Band Rotational Spectroscopy of Succinimide and N-Chlorosuccinimide.

Succinimide and its derivatives are cyclic five-membered rings that appear in a variety of natural products and are widely used in organic synthesis. From a structural standpoint, succinimide contains an NH group in the ring which interacts with two adjacent carbonyl groups, pushing the ring structure toward planarity at the expense of increasing ring strain and eclipsing interactions among the out-of-plane hydrogen atoms in the two CH groups. Previous quantum chemical calculations at different levels of theory have predicted both a nonplanar structure and a planar structure, the latter of which is the most consistent with gas-phase electron diffraction measurements.

Reactant Discovery with an Nanoreactor: Exploration of Astrophysical N-Heterocycle Precursors and Formation Pathways.

The incorporation of nitrogen atoms into cyclic compounds is essential for terrestrial life; nitrogen-containing (N-)heterocycles make up DNA and RNA nucleobases, several amino acids, B vitamins, porphyrins, and other components of biomolecules. The discovery of these molecules on meteorites with non-terrestrial isotopic abundances supports the hypothesis of exogenous delivery of prebiotic material to early Earth; however, there has been no detection of these species in interstellar environments, indicating that there is a need for greater knowledge of their astrochemical formation and destruction pathways. Here, we present results of simulations of gas-phase pyrrole and pyridine formation from an nanoreactor, a first-principles molecular dynamics simulation method that accelerates reaction discovery by applying non-equilibrium forces that are agnostic to individual reaction coordinates.

Reliable but multi-dimensional cognitive demand in operating partially automated vehicles: implications for real-world automation research.

The reliability of cognitive demand measures in controlled laboratory settings is well-documented; however, limited research has directly established their stability under real-life and high-stakes conditions, such as operating automated technology on actual highways. Partially automated vehicles have advanced to become an everyday mode of transportation, and research on driving these advanced vehicles requires reliable tools for evaluating the cognitive demand on motorists to sustain optimal engagement in the driving process. This study examined the reliability of five cognitive demand measures, while participants operated partially automated vehicles on real roads across four occasions.

Automated driving experiences, attention, and intentions following extensive on-road usage of a level 2 automation vehicle.

Introduction: An on-road study was conducted to examine the effects of level 2 automation on the stressfulness and enjoyment of driving and driving attention following prolonged usage. The study also examined the changes in the automated driving experience and attention over time as well as important predictors such as pre-driving trust in technology and attitudes toward automated systems.

Method: Motorists who had never used automated systems drove a level 2 automation vehicle for a 6-8 week period.

A Tale of Two Tails: Rotational Spectroscopy of -Ethyl Maleimide and -Ethyl Succinimide.

Broadband microwave spectra of -ethyl maleimide (NEM) and -ethyl succinimide (NES) have been recorded using chirped pulse Fourier transform microwave spectroscopy in the -band (26.5-40 GHz). The spectra for both molecules were fit to a Watson A-reduced Hamiltonian in the I representation to obtain best fit experimental rotational constants (NEM: = 2143.

Rotational spectroscopy of methyl -butyl ether with a new band chirped-pulse Fourier transform microwave spectrometer.

Chirped-pulse Fourier transform microwave (CP-FTMW) spectroscopy is a powerful tool for performing broadband gas-phase rotational spectroscopy, and its applications include discovery of new molecules, complex mixture analysis, and exploration of fundamental molecular physics. Here we report the development of a new band (26.5-40 GHz) CP-FTMW spectrometer that is equipped with a pulsed supersonic expansion source and a heated reservoir for low-volatility samples.

Driver behavior while using Level 2 vehicle automation: a hybrid naturalistic study.

Vehicle automation is becoming more prevalent. Understanding how drivers use this technology and its safety implications is crucial. In a 6-8 week naturalistic study, we leveraged a hybrid naturalistic driving research design to evaluate driver behavior with Level 2 vehicle automation, incorporating unique naturalistic and experimental control conditions.

This Is Your Brain on Autopilot 2.0: The Influence of Practice on Driver Workload and Engagement During On-Road, Partially Automated Driving.

Objective: This on-road study employed behavioral and neurophysiological measurement techniques to assess the influence of six weeks of practice driving a Level 2 partially automated vehicle on driver workload and engagement.

Background: Level 2 partial automation requires a driver to maintain supervisory control of the vehicle to detect "edge cases" that the automation is not equipped to handle. There is mixed evidence regarding whether drivers can do so effectively.

Measuring affect and complex working memory in natural and urban environments.

Introduction: Research suggests that spending time in natural environments is associated with cognitive and affective benefits, while increased use of technology and time spent in urban environments are associated with depletion of cognitive resources and an increasing prevalence of mental illness. Attention Restoration Theory suggests that exposure to natural environments can restore depleted attentional resources and thereby improve cognitive functioning and mood. Specifically, recent meta-analyses have revealed that the most improved cognitive abilities after nature exposure include selective attention, working memory, and cognitive flexibility.

COVID-19 in Patients with a Primary Refugee-Associated Language in a Kentucky Emergency Department During 2020.

COVID-19 has heavily impacted the refugee population in the United States due to exposure risks, living and working conditions, and healthcare access, but little is known about outcomes. We reviewed emergency department visits to a Kentucky hospital among 2163 patients from March-December 2020, studying incidence of COVID-19 diagnosis for patients with a primary refugee-associated language compared to English speakers, and outcomes after diagnosis including hospitalization, length of stay, and in-hospital mortality. Patients in the population of interest had higher odds of COVID-19 diagnosis in the hospital (OR = 12.

Multireference configuration interaction study of the predissociation of C via its FΠ state.

Photodissociation is one of the main destruction pathways for dicarbon (C) in astronomical environments, such as diffuse interstellar clouds, yet the accuracy of modern astrochemical models is limited by a lack of accurate photodissociation cross sections in the vacuum ultraviolet range. C features a strong predissociative FΠ-XΣ electronic transition near 130 nm originally measured in 1969; however, no experimental studies of this transition have been carried out since, and theoretical studies of the FΠ state are limited. In this work, potential energy curves of excited electronic states of C are calculated with the aim of describing the predissociative nature of the FΠ state and providing new ab initio photodissociation cross sections for astrochemical applications.

Rotational and Vibrational Spectra of the Pyridyl Radicals: A Coupled-Cluster Study.

Pyridyl is a prototypical nitrogen-containing aromatic radical that may be a key intermediate in the formation of nitrogen-containing aromatic molecules under astrophysical conditions. On meteorites, a variety of complex molecules with nitrogen-containing rings have been detected with nonterrestrial isotopic abundances, and larger nitrogen-containing polycyclic aromatic hydrocarbons (PANHs) have been proposed to be responsible for certain unidentified infrared emission bands in the interstellar medium. In this work, the three isomers of pyridyl (2-, 3-, and 4-pyridyl) have been investigated with coupled cluster methods.

No Difference in Arousal or Cognitive Demands Between Manual and Partially Automated Driving: A Multi-Method On-Road Study.

Introduction: Partial driving automation is not always reliable and requires that drivers maintain readiness to take over control and manually operate the vehicle. Little is known about differences in drivers' arousal and cognitive demands under partial automation and how it may make it difficult for drivers to transition from automated to manual modes. This research examined whether there are differences in drivers' arousal and cognitive demands during manual versus partial automation driving.

Effects of the Kentucky Hepatitis Academic Mentorship Program on Hepatitis C Treatment in a Federally Qualified Health Center.

Background: Hepatitis C virus (HCV) infection is prevalent in Kentucky, and treatment in primary care clinics is being implemented through collaborations such as the Kentucky Hepatitis Academic Mentorship Program (KHAMP) to meet Medicaid requirements.

Methods: We completed a retrospective review of 375 HCV patients seen from 2018-2019, comparing outcomes pre- and post- KHAMP implementation.

Results: Post-KHAMP implementation in 2019, 191 patients were diagnosed with HCV.

Axillary Thermometry Demonstrates Greater Reliability Compared With Rectal Thermometry in Healthy Neonates.

Rectal thermometry (RT) is considered the gold standard for measuring temperature in newborns, despite increasing use of temporal artery thermometry (TT) and axillary thermometry (AT) methods. Few prospective studies compare RT, TT, and AT in a newborn nursery setting. To determine the accuracy and reliability of these methods, we enrolled 205 healthy, full-term newborns.

Coupled Cluster Characterization of 1-, 2-, and 3-Pyrrolyl: Parameters for Vibrational and Rotational Spectroscopy.

Pyrrolyl (CHN) is a nitrogen-containing aromatic radical that is a derivative of pyrrole (CHN) and is an important intermediate in the combustion of biomass. It is also relevant for chemistry in Titan's atmosphere and may be present in the interstellar medium. The lowest-energy isomer, 1-pyrrolyl, has been involved in many experimental and theoretical studies of the N-H photodissociation of pyrrole, yet it has only been directly spectroscopically detected via electron paramagnetic resonance and through the photoelectron spectrum of the pyrrolide anion, yielding three vibrational frequencies.

Rotational Spectrum of the β-Cyanovinyl Radical: A Possible Astrophysical N-Heterocycle Precursor.

A fundamental question in the field of astrochemistry is whether the molecules essential to life originated in the interstellar medium (ISM), and, if so, how they were formed. Nitrogen-containing heterocycles are of particular interest because of their role in biology; however, to date, no N-heterocycle has been detected in the ISM, and it is unclear how and where such species might form. Recently, the β-cyanovinyl radical (HCCHCN) was implicated in the low-temperature gas-phase formation of pyridine.

Blueberries Improve Pain, Gait Performance, and Inflammation in Individuals with Symptomatic Knee Osteoarthritis.

Osteoarthritis (OA) is the most common joint disorder in the world and is the most frequent cause of walking related disability among older adults in the US, which brings a significant economic burden and reduces quality of life. The initiation and development of OA typically involves degeneration or progressive loss of the structure and function of articular cartilage. Inflammation is one of the major drives of the progression of OA.

At-a-glance - Concurrent monitoring of opioid prescribing practices and opioid-related deaths: the context in Nova Scotia, Canada.

Timely public health surveillance is required to understand trends in opioid use and harms. Here, opioid dispensing data from the Nova Scotia Prescription Monitoring Program are presented alongside fatality data from the Nova Scotia Medical Examiner Service. Concurrent monitoring of trends in these data sources is essential to detect population-level effects (whether intended or unintended) of interventions related to opioid prescribing.

Assessment of attitudes and targeted educational needs for refugee care providers in a Ugandan hospital.

Objectives: To evaluate medical trainees' attitudes toward refugee patients in a refugee host country, and to identify educational needs.

Methods: A 54-question cross-sectional questionnaire was administered to a convenience sample of 81 post-graduate medical trainees at Mbarara Regional Referral Hospital, Uganda, in 2016. Descriptive statistics on medical trainees' attitudes and educational needs regarding care for refugees were calculated.