A study of the ozonolysis of isoprene in a cryogenic buffer gas cell by high resolution microwave spectroscopy

We have developed a method to quantify reaction product ratios using high resolution microwave spectroscopy in a cryogenic buffer gas cell. We demonstrate the power of this method with the study of the ozonolysis of isoprene, CH2=C(CH3)-CH=CH2, the most abundant, non-methane hydrocarbon emitted into the atmosphere by vegetation. Isoprene is an asymmetric diene, and reacts with O3 at the 1,2 position to produce methyl vinyl ketone (MVK), formaldehyde, and a pair of carbonyl oxides: [CH3CO-CH=CH2 + CH2=OO] + [CH2=O + CH3COO-CH=CH2]. Alternatively, O3 could attack at the 3,4 position to produce methacrolein (MACR), formaldehyde, and two carbonyl oxides [CH2=C(CH3)-CHO + CH2=OO] + [CH2=O + CH2=C(CH3)-CHOO]. Purified O3 and isoprene were mixed for approximately 10 seconds under dilute (1.5-4% in argon) continuous flow conditions in an alumina tube held at 298 K and 5 Torr. Products exiting the tube were rapidly slowed and cooled within the buffer gas cell by collisions with cryogenic (4-7 K) He. High resolution chirped pulse microwave detection between 12 and 26 GHz was used to achieve highly sensitive (ppb scale), isomer-specific product quantification. We observed a ratio of MACR to MVK of 2.1 +/- 0.4 under 1:1 ozone to isoprene conditions and 2.1 +/- 0.2 under 2:1 ozone to isoprene conditions, a finding which is consistent with previous experimental results. Additionally, we discuss relative quantities of formic acid (HCOOH), an isomer of CH2=OO, and formaldehyde (CH2=O) under varying experimental conditions, and characterize the spectroscopic parameters of the singly-substituted 13C trans-isoprene and 13C anti-periplanar-methacrolein species. This work has the potential to be extended towards a complete branching ratio analysis, as well towards the ability to isolate, identify, and quantify new reactive intermediates in the ozonolysis of alkenes

Exploring the Experience of Dating as a Surviving Partner and Impact on Occupational Therapy

Background: Limited research has been conducted that explores the experience of dating as a member of the surviving partner community. This study aims to address this gap in literature by capturing the dating experience for those who are surviving partners. Method: A qualitative, phenomenological research design was used to gather data from thirteen surviving partners who have actively dated in the past, are currently dating, or are currently in a casual or serious relationship. Results: Interview data revealed that the participants\u27 dating experiences were impacted by their identity as a surviving partner. Participants reported experiencing pressure to engage in dating from their friends and family after losing their partner. Participants also experienced stigma from the general dating pool as well as judgment from inside and outside the surviving partner community. The importance of co-occupation to honor and remember their late partner with their current partner was a unique aspect of the surviving partner dating experience. Conclusion: This research adds to the body of knowledge regarding the surviving partner dating experience as well as the importance of co-occupation. Occupational therapists need to inquire about dating during evaluation and be aware of the impact of the surviving partner identity on occupation.https://soar.usa.edu/otdcapstones-spring2022/1010/thumbnail.jp

High Sensitivity Microwave Spectroscopy in a Cryogenic Buffer Gas Cell

We describe an instrument which can be used to analyze complex chemical mixtures at high resolution and high sensitivity. Molecules are collisionally cooled with helium gas at cryogenic temperatures (~ 4-7 K), and subsequently detected using chirped pulse microwave spectroscopy. Here we demonstrate three significant improvements to the apparatus relative to an earlier version: (1) extension of its operating range by more than a factor of two, from 12-18 GHz to 12-26 GHz, which allows a much wider range of species to be characterized; (2) improved detection sensitivity owing to use of cryogenically-cooled low-noise amplifiers and protection switches, and (3) a versatile method of sample input that enables analysis of solids, liquids, gases, and solutions, without the need for chemical separation (as demonstrated with a 12-16 GHz spectrum of lemon oil). This instrument can record broadband microwave spectra at comparable sensitivity to high Q cavity spectrometers which use pulsed supersonic jets, but up to 3000 times faster with a modest increase in sample consumption rate.Comment: 12 pages, 6 figure

The Midlands LGBT Needs Assessment Community Report

Health disparities research seeks to understand specific health-related needs and outcomes for groups of people, particularly minority groups. In 2011, the Institutes of Medicine (IOM) released a report commissioned by the National Institutes of Health entitled The Health of Lesbian, Gay, Bisexual, and Transgender (LGBT) People: Building a Foundation for Understanding. For the first time, research on the health and well-being of LGBT persons has been prioritized by research funders at the highest levels

Use of Evidence-Based Practice Among Athletic Training Educators, Clinicians, and Students, Part 2: Attitudes, Beliefs, Accessibility, and Barriers

Context: Successful implementation of evidence-based practice (EBP) within athletic training is contingent upon understanding the attitudes and beliefs and perceived barriers toward EBP as well as the accessibility to EBP resources of athletic training educators, clinicians, and students. Objective: To assess the attitudes, beliefs, and perceived barriers toward EBP and accessibility to EBP resources among athletic training educators, clinicians, and students. Design: Cross-sectional study. Setting: Online survey instrument. Patients or Other Participants: A total of 1209 athletic trainers participated: professional athletic training education program directors (n = 132), clinical preceptors (n = 266), clinicians (n = 716), postprofessional athletic training educators (n = 24) and postprofessional students (n = 71). Main Outcome Measure(s):Likert-scale items (1 = strongly disagree, 4 = strongly agree) assessed attitudes and beliefs and perceived barriers, whereas multipart questions assessed accessibility to resources. Kruskal-Wallis H tests (P ≤ .05) and Mann-Whitney U tests with a Bonferroni adjustment (P ≤ .01) were used to determine differences among groups. Results:Athletic trainers agreed (3.27 ± 0.39 out of 4.0) that EBP has various benefits to clinical practice and disagreed (2.23 ± 0.42 out of 4.0) that negative perceptions are associated with EBP. Benefits to practice scores (P = .002) and negative perception scores (P \u3c .001) differed among groups. With respect to perceived barriers, athletic trainers disagreed that personal skills and attributes (2.29 ± 0.52 out of 4.0) as well as support and accessibility to resources (2.40 ± 0.40 out of 4.0) were barriers to EBP implementation. Differences were found among groups for personal skills and attributes scores (P \u3c .001) and support and accessibility to resources scores (P \u3c .001). Time (76.6%) and availability of EBP mentors (69.6%) were the 2 most prevalent barriers reported. Of the resources assessed, participants were most unfamiliar with clinical prediction rules (37.6%) and Cochrane databases (52.5%); direct access to these 2 resources varied among participants. Conclusions: Athletic trainers had positive attitudes toward the implementation of EBP within didactic education and clinical practice. However, accessibility and resource use remained low for some EBP-related resources. Although the perceived barriers to implementation are minimal, effective integration of EBP within athletic training will present challenges until these barriers dissolve

Design Teams as an Organizational Intervention to Improve Job Satisfaction and Worker Turnover in Public Child Welfare

This study focuses on the field test of a design team intervention in two rural and one urban site experiencing high workforce turnover. Hypothesis 1: Job satisfaction is significantly improved among public child welfare workers participating in the Design Team intervention. Hypothesis 2: Job satisfaction is significantly related to lower turnover in public child welfare workers participating in the Design Team intervention. The Design Team is an externally facilitated intervention in which team members consist of caseworkers and supervisors representing all services provided by the agency. The facilitator uses a formal logic model and team building expertise to guide the team. A pre-post design and structural equation modeling findings indicate a positive impact to overall worker job satisfaction and satisfaction with the nature of their work, and has strong potential to reduce turnover

Gaining an accurate reflection of the reality of palliative care through the use of free-text feedback in questionnaires: the AFTER study

Background In healthcare, many service evaluation questionnaires use free-text boxes without formal mechanisms for analysis. Patients and carers spend time documenting concerns that are often ignored or managed locally in an ad hoc manner. Currently, palliative care experiences of patients and carers in Wales are measured using a service evaluation questionnaire, comprising both closed and open-ended questions. Previous research, exploring free-text responses from this questionnaire, suggests that questionnaire refinement should accommodate service users’ expressed priorities and concerns, and highlights the need to incorporate free-text data analysis strategies during study design. Methods Results from a previous analysis of 596 free-text responses provided the basis for an expert consensus day, where the current service evaluation questionnaire was refined. The refined version was tested during cognitive interviews with patients (n=10) and carers (n=7) receiving palliative care from 1 of 2 UK hospices. Data were analysed thematically. Results Interviews highlighted minor areas for change within the questionnaire and provided broader insight into patients’ experiences of palliative care services. Patients and carers place an emphasis on simplifying language, decreasing the numeric response range and reducing written instructions; relying instead on visual cues, including formatting and layout. Findings highlighted the importance patients attached to providing meaningful free-text contributions. Conclusions Questionnaire refinement should use the patient perspective to effectively facilitate respondent understanding, pertinence and usability. The importance of employing data analysis strategies during questionnaire design may reduce research waste, thus enabling a better interrogation of service provision

Improved PCR-Based Detection of Soil Transmitted Helminth Infections Using a Next-Generation Sequencing Approach to Assay Design

The soil transmitted helminths are a group of parasitic worms responsible for extensive mor- bidity in many of the world’s most economically depressed locations. With growing empha- sis on disease mapping and eradication, the availability of accurate and cost-effective diagnostic measures is of paramount importance to global control and elimination efforts. While real-time PCR-based molecular detection assays have shown great promise, to date, these assays have utilized sub-optimal targets. By performing next-generation sequencing- based repeat analyses, we have identified high copy-number, non-coding DNA sequences from a series of soil transmitted pathogens. We have used these repetitive DNA elements as targets in the development of novel, multi-parallel, PCR-based diagnostic assays

In Situ Forming, Enzyme-Responsive Peptoid-Peptide Hydrogels: An Advanced Long-Acting Injectable Drug Delivery System

Long-acting drug delivery systems are promising platforms to improve patient adherence to medication by delivering drugs over sustained periods and removing the need for patients to comply with oral regimens. This research paper provides a proof-of-concept for the development of a new optimized in situ forming injectable depot based on a tetrabenzylamine-tetraglycine-d-lysine-O-phospho-d-tyrosine peptoid-D-peptide formulation ((NPhe)4GGGGk(AZT)y(p)-OH). The chemical versatility of the peptoid-peptide motif allows low-molecular-weight drugs to be precisely and covalently conjugated. After subcutaneous injection, a hydrogel depot forms from the solubilized peptoid-peptide-drug formulation in response to phosphatase enzymes present within the skin space. This system is able to deliver clinically relevant concentrations of a model drug, the antiretroviral zidovudine (AZT), for 35 days in Sprague–Dawley rats. Oscillatory rheology demonstrated that hydrogel formation began within ∼30 s, an important characteristic of in situ systems for reducing initial drug bursts. Gel formation continued for up to ∼90 min. Small-angle neutron scattering data reveal narrow-radius fibers (∼0.78–1.8 nm) that closely fit formation via a flexible cylinder elliptical model. The inclusion of non-native peptoid monomers and D-variant amino acids confers protease resistance, enabling enhanced biostability to be demonstrated in vitro. Drug release proceeds via hydrolysis of an ester linkage under physiological conditions, releasing the drug in an unmodified form and further reducing the initial drug burst. Subcutaneous administration of (NPhe)4GGGGk(AZT)y(p)-OH to Sprague–Dawley rats resulted in zidovudine blood plasma concentrations within the 90% maximal inhibitory concentration (IC90) range (30–130 ng mL–1) for 35 days