The Ring-Closing Reaction of Cyclopentadiene Probed with Ultrafast X-ray Scattering.

The dynamics of cyclopentadiene (CP) following optical excitation at 243 nm was investigated by time-resolved pump-probe X-ray scattering using 16.2 keV X-rays at the Linac Coherent Light Source (LCLS). We present the first ultrafast structural evidence that the reaction leads directly to the formation of bicyclo[2.1.0]pentene (BP), a strained molecule with three- and four-membered rings. The bicyclic compound decays via a thermal backreaction to the vibrationally hot CP with a time constant of 21 ± 3 ps. A minor channel leads to ring-opened structures on a subpicosecond time scale.

Infrared spectra and fragmentation dynamics of isotopologue-selective mixed-ligand complexes.

Isolated mixed-ligand complexes provide tractable model systems in which to study competitive and cooperative binding effects as well as controlled energy flow. Here, we report spectroscopic and isotopologue-selective infrared photofragmentation dynamics of mixed gas-phase Au(12/13CO)n(N2O)m+ complexes. The rich infrared action spectra, which are reproduced well using simulations of calculated lowest energy structures, clarify previous ambiguities in the assignment of vibrational bands, especially accidental coincidence of CO and N2O bands. The fragmentation dynamics exhibit the same unexpected behaviour as reported previously in which, once CO loss channels are energetically accessible, these dominate the fragmentation branching ratios, despite the much lower binding energy of N2O. We have investigated the dynamics computationally by considering anharmonic couplings between a relevant subset of normal modes involving both ligand stretch and intermolecular modes. Discrepancies between correlated and uncorrelated model fit to the ab initio potential energy curves are quantified using a Boltzmann sampled root mean squared deviation providing insight into efficiency of vibrational energy transfer between high frequency ligand stretches and the softer intermolecular modes which break during fragmentation.

Investigation of risk factors for introduction of highly pathogenic avian influenza H5N1 infection among commercial turkey operations in the United States, 2022: a case-control study.

Introduction: The 2022-2023 highly pathogenic avian influenza (HPAI) H5N1 outbreak in the United States (U.S.) is the largest and most costly animal health event in U.S. history. Approximately 70% of commercial farms affected during this outbreak have been turkey farms. Methods: We conducted a case-control study to identify potential risk factors for introduction of HPAI virus onto commercial meat turkey operations. Data were collected from 66 case farms and 59 control farms in 12 states. Univariate and multivariable analyses were conducted to compare management and biosecurity factors on case and control farms. Results: Factors associated with increased risk of infection included being in an existing control zone, having both brooders and growers, having toms, seeing wild waterfowl or shorebirds in the closest field, and using rendering for dead bird disposal. Protective factors included having a restroom facility, including portable, available to crews that visit the farm and workers having access and using a shower at least some of the time when entering a specified barn. Discussion: Study results provide a better understanding of risk factors for HPAI infection and can be used to inform prevention and control measures for HPAI on U.S. turkey farms.

Investigation of risk factors for introduction of highly pathogenic avian influenza H5N1 virus onto table egg farms in the United States, 2022: a case-control study.

Introduction: The 2022-2023 highly pathogenic avian influenza (HPAI) H5N1 outbreak in the United States (U.S.) is the most geographically extensive and costly animal health event in U.S. history. In 2022 alone, over 57 million commercial and backyard poultry in 47 U.S. states were affected. Over 75% of affected poultry were part of the commercial table egg production sector. Methods: We conducted a case-control study to identify potential risk factors for introduction of HPAI virus onto commercial table egg operations. Univariate and multivariable analyses were conducted to compare farm characteristics, management, and biosecurity factors on case and control farms. Results: Factors associated with increased risk of infection included being in an existing control zone, sightings of wild waterfowl, mowing or bush hogging vegetation less than 4 times a month, having an off-site method of daily mortality disposal (off-site composting or burial, rendering, or landfill), and wild bird access to feed/feed ingredients at least some of the time. Protective factors included a high level of vehicle washing for trucks and trailers entering the farm (a composite variable that included having a permanent wash station), having designated personnel assigned to specific barns, having a farm entrance gate, and requiring a change of clothing for workers entering poultry barns. Discussion: Study results improve our understanding of risk factors for HPAI infection and control measures for preventing HPAI on commercial U.S. table egg farms.

Reducing incidence of postoperative acute kidney injury in trauma and orthopaedics patients: a quality improvement project.

BACKGROUND: Acute kidney injury (AKI) is a common postoperative complication which increases morbidity and mortality. This quality improvement project aimed to implement measures targeting known risk factors to decrease the incidence of postoperative AKI in trauma and orthopaedics (T&O) patients. METHODS: Data were collected across three six-month to 7-month cycles between 2017 and 2020, analysing all elective and emergency T&O operated patients within a single NHS Trust (n=714, 1008 and 928, respectively). Patients who developed a postoperative AKI were identified using biochemical criteria and data were collected on known AKI risk factors, including use of nephrotoxic medications, and patient outcomes. In the final cycle, the same variables were collected for patients without AKI. Between cycles, measures implemented included: preoperative and postoperative medication reconciliation aiming to stop nephrotoxic medications, orthogeriatrician review of high-risk patients and junior doctor teaching on fluid therapy. Statistical analysis was undertaken to determine the incidence of postoperative AKI across cycles, prevalence of risk factors and impact on length of hospital stay and postoperative mortality. RESULTS: There was a statistically significant decrease in postoperative AKI incidence from 4.27% (43 of 1008 patients) in cycle 2 to 2.05% (19 of 928) in cycle 3 (p=0.006), with a notable decrease in use of nephrotoxic medications. Significant predictors for the development of postoperative AKI included use of diuretics and receiving multiple nephrotoxic drug classes. Development of postoperative AKI significantly increased length of hospital stay by 7.11 days on average (95% CI: 4.84 to 9.38 days, p<0.001) and risk of 1-year postoperative mortality (OR 3.22, 95% CI: 1.03 to 10.55, p=0.046). CONCLUSION: This project demonstrates that a multifaceted approach targeting modifiable risk factors can reduce incidence of postoperative AKI in T&O patients, which may lead to reduced length of hospital stay and postoperative mortality.

Protecting pregnant people & infants against influenza: A landscape review of influenza vaccine hesitancy during pregnancy and strategies for vaccine promotion.

Before COVID-19, influenza vaccines were the most widely recommended vaccine during pregnancy worldwide. In response to immunization during pregnancy, maternal antibodies offer protection against potentially life-threatening disease in both pregnant people and their infants up to six months of age. Despite this, influenza vaccine hesitancy is common, with few countries reporting immunization rates in pregnant people above 50%. In this review, we highlight individual, institutional, and social factors associated with influenza vaccine hesitancy during pregnancy. In addition, we present an overview of the evidence evaluating interventions to address influenza vaccine hesitancy during pregnancy. While some studies have indicated promising results, no single intervention has consistently effectively increased influenza vaccine uptake during pregnancy. Using a social-ecological model of health framework, future strategies addressing multiple levels of vaccine hesitancy will be needed to realize the potential health benefits of prenatal immunization programs.

Pregnant people are a high priority group for influenza vaccination annually. Although vaccination can protect both mother and infant, vaccination rates are suboptimal during pregnancy. Previous research has suggested reasons for suboptimal vaccination rates, including concerns about the safety of vaccination during pregnancy and limited access to, and awareness of, influenza vaccines during pregnancy. Studies that have attempted to increase influenza vaccination rates during pregnancy have mostly shown no effect ­ with some exceptions. Public health professionals need to reevaluate strategies for improving vaccination rates during pregnancy.

An Infrared Study of Gas-Phase Metal Nitrosyl Ion-Molecule Complexes.

We present a combined experimental and quantum chemical study of gas-phase group 9 metal nitrosyl complexes, M(NO)n+ (M = Co, Rh, Ir). Experimental infrared photodissociation spectra of mass-selected ion-molecule complexes are presented in the region 1600 cm-1 to 2000 cm-1 which includes the NO stretch. These are interpreted by comparison with the simulated spectra of energetically low-lying structures calculated using density functional theory. A mix of linear and nonlinear ligand binding is observed, often within the same complex, and clear evidence of coordination shell closing is observed at n = 4 for Co(NO)n+ and Ir(NO)n+. Calculations of Rh(NO)n+ complexes suggest additional low-lying five-coordinate structures. In all cases, once a second coordination shell is occupied, new spectral features appear which are assigned to (NO)2 dimer moieties. Further evidence of such motifs comes from differences in the spectra recorded in the dissociation channels corresponding to single and double ligand loss.

An infrared study of CO2 activation by holmium ions, Ho+ and HoO.

We report a combined experimental and computational study of carbon dioxide activation at gas-phase Ho+ and HoO+ centres. Infrared action spectra of Ho(CO2)n+ and [HoO(CO2)n]+ ion-molecule complexes have been recorded in the spectral region 1700-2400 cm-1 and assigned by comparison with simulated spectra of energetically low-lying structures determined by density functional theory. Little by way of activation is observed in Ho(CO2)n+ complexes with CO2 binding end-on to the Ho+ ion. By contrast, all [HoO(CO2)n]+ complexes n ≥ 3 show unambiguous evidence for formation of a carbonate radical anion moiety, . The signature of this structure, a new vibrational band observed around 1840 cm-1 for n = 3, continues to red-shift monotonically with each successive CO2 ligand binding with net charge transfer from the ligand rather than the metal centre.

Women-Reported Barriers and Facilitators of Continued Engagement with Medications for Opioid Use Disorder.

Opioid-related fatalities increased exponentially during the COVID-19 pandemic and show little sign of abating. Despite decades of scientific evidence that sustained engagement with medications for opioid use disorders (MOUD) yields positive psychosocial outcomes, less than 30% of people with OUD engage in MOUD. Treatment rates are lowest for women. The aim of this project was to identify women-specific barriers and facilitators to treatment engagement, drawing from the lived experience of women in treatment. Data are provided from a parent study that used a community-partnered participatory research approach to adapt an evidence-based digital storytelling intervention for supporting continued MOUD treatment engagement. The parent study collected qualitative data between August and December 2018 from 20 women in Western Massachusetts who had received MOUD for at least 90 days. Using constructivist grounded theory, we identified major themes and selected illustrative quotations. Key barriers identified in this project include: (1) MOUD-specific discrimination encountered via social media, and in workplace and treatment/recovery settings; and (2) fear, perceptions, and experiences with MOUD, including mental health medication synergies, internalization of MOUD-related stigma, expectations of treatment duration, and opioid-specific mistrust of providers. Women identified two key facilitators to MOUD engagement: (1) feeling "safe" within treatment settings and (2) online communities as a source of positive reinforcement. We conclude with women-specific recommendations for research and interventions to improve MOUD engagement and provide human-centered care for this historically marginalized population.

The use of digital stories as a health promotion intervention: a scoping review.

BACKGROUND: It is challenging to develop health promotion interventions created in collaboration with communities affected by inequities that focus beyond individual behavior change. One potential solution is interventions that use digital stories (DS). Digital storytelling (DST) is an opportunity for reflection, connection with others, and the elevation of voices often absent from daily discourse. Consequently, public health researchers and practitioners frequently employ the DST workshop process to develop messaging that promotes health and highlights concerns in partnership with historically marginalized communities. With participants' permission, DS can reach beyond the storytellers through behavior or attitude change interventions for health promotion among communities who share the targeted health concern. Our goal was to synthesize the literature describing interventions that use DS for health promotion to identify gaps. METHODS: We conducted a scoping review. Our inclusion criteria were articles that: 1) described empirical research; 2) used DS that were developed using the StoryCenter DST method; 3) assessed an intervention that used DS to address the health promotion of viewers (individuals, families, community, and/or society) impacted by the targeted health issue 4) were written in English or Spanish. To synthesize the results of the included studies, we mapped them to the health determinants in the National Institute of Minority Health and Health Disparities (NIMHD) research framework. We assessed the number of occurrences of each determinant described in the results of each article. RESULTS: Ten articles met the eligibility criteria. All the included articles highlighted health equity issues. Our mapping of the articles with definitive results to the NIMHD research framework indicates that interventions that use DS addressed 17 out of 20 health determinants. All mapped interventions influenced intentions to change health behaviors (NIMHD level/domain: Individual/Behavioral), increased health literacy (Individual/Health Care System), and/or stimulated conversations that addressed community norms (Community/Sociocultural Environment). CONCLUSIONS: Interventions that use DS appear to positively affect the health promotion of participants across a range of health issues and determinants. Future research is needed in the Interpersonal, Community, and Societal levels and within the Biological, Physical/Built Environment, and Sociocultural Environment domains.

Improving safety by developing trust with a just culture.

This article presents a simple conceptual road map for implementing a just culture in healthcare settings. The concept of just culture was developed as one of five fundamental elements of a safety culture by psychology professor James Reason in 1997. A just culture requires an unbiased method of judging human error and is designed to develop organisational trust so that adverse medical events (errors) are reported and corrected before they combine with other errors to cause injury or death. To implement a just culture properly so as to increase organisational safety, practitioners must understand its role in enabling the error reporting needed to develop a safety culture. This article reviews these foundational concepts and explores the human causes of errors that a just culture addresses, the psychological importance of a just culture in enabling error reporting and how to implement a just culture in organisations.

Critical Narrative Intervention for Health Equity Research and Practice: Editorial Commentary Introducing the Health Promotion Practice Critical Narrative Intervention Special Collection.

This special collection of Health Promotion Practice introduces critical narrative intervention (CNI) as a key theoretical framing for an asset-based, narrative, and participatory approach to promoting health and addressing social inequality. Innovative digital and visual methodologies highlighted in this special collection-comics and graphic novels, cellphilms and other participatory film, story booths, digital storytelling, and photovoice-are changing the way critical public health researchers and practitioners forge new knowledge, creating new possibilities for interdisciplinary and activist-based inquiry. Public health research and engagement efforts that critically contend with historically repressive structures and intervene through narrative and participatory processes to enact change with and for disenfranchised communities are long overdue. This special collection showcases six CNI projects that promote equity and justice in the context of LGBTQ, nonbinary, and other gender-diverse young people; people who inject drugs living with hepatitis C virus; young women who trade sex; undocumented and formerly undocumented immigrants; and people living with HIV/AIDS. It is our intent that this collection of exemplars can serve as a guidepost for practitioners and researchers interested in expanding the scope of critical public health praxis. Individually and collectively, the special collection illustrates how CNI can create space for the increased representation of historically silenced populations, redress stigma, and provoke important questions to guide a new era of health equity research.

Spectroscopy and Infrared Photofragmentation Dynamics of Mixed Ligand Ion-Molecule Complexes: Au(CO)x(N2O)y.

We report a combined experimental and computational study of the structure and fragmentation dynamics of mixed ligand gas-phase ion-molecule complexes. Specifically, we have studied the infrared spectroscopy and vibrationally induced photofragmentation dynamics of mass-selected Au(CO)x(N2O)y+ complexes. The structures can be understood on the basis of local CO and N2O chromophores in different solvation shells with CO found preferentially in the core. Rich fragmentation dynamics are observed as a function of complex composition and the vibrational mode excited. The dynamics are characterized in terms of branching ratios for different ligand loss channels in light of calculated internal energy distributions. Intramolecular vibrational redistribution appears to be rapid, and dissociation is observed into all energetically accessible channels with little or no evidence for preferential breaking of the weakest intermolecular interactions.

Atomic Cluster Au_{10}

We report an intense broadband midinfrared absorption band in the Au_{10}^{+} cluster in a region in which only molecular vibrations would normally be expected. Observed in the infrared multiple photon dissociation spectra of Au_{10}Ar^{+}, Au_{10}(N_{2}O)^{+}, and Au_{10}(OCS)^{+}, the smooth feature stretches 700-3400 cm^{-1} (λ=14-2.9 µm). Calculations confirm unusually low-energy allowed electronic excitations consistent with the observed spectra. In Au_{10}(OCS)^{+}, IR absorption throughout the band drives OCS decomposition resulting in CO loss, providing an alternative method of bond activation or breaking.

Infrared action spectroscopy of nitrous oxide on cationic gold and cobalt clusters.

Understanding the catalytic decomposition of nitrous oxide on finely divided transition metals is an important environmental issue. In this study, we present the results of a combined infrared action spectroscopy and quantum chemical investigation of molecular N2O binding to isolated Aun+ (n ≤ 7) and Con+ (n ≤ 5) clusters. Infrared multiple-photon dissociation spectra have been recorded in the regions of both the N[double bond, length as m-dash]O (1000-1400 cm-1) and N[double bond, length as m-dash]N (2100-2450 cm-1) stretching modes of nitrous oxide. In the case of Aun+ clusters only the ground electronic state plays a role, while the involvement of energetically low-lying excited states in binding to the Con+ clusters cannot be ruled out. There is a clear preference for N-binding to clusters of both metals but some O-bound isomers are observed in the case of smaller Con(N2O)+ clusters.

Free electron laser infrared action spectroscopy of nitrous oxide binding to platinum clusters, Ptn(N2O).

Infrared multiple-photon dissociation spectroscopy has been applied to study Ptn(N2O)+ (n = 1-8) clusters which represent entrance-channel complexes on the reactive potential energy surface for nitrous oxide decomposition on platinum. Comparison of spectra recorded in the spectral region 950 cm-1 to 2400 cm-1 with those simulated for energetically low-lying structures from density functional theory shows a clear preference for molecular binding via the terminal N atom, though evidence of O-binding is observed for some cluster sizes. Enhanced reactivity of Ptn+n≥ 6 clusters towards N2O is reflected in the calculated reactive potential energy surfaces and, uniquely in the size range studied, Pt6(N2O)+ proved impossible to form in significant number density even with cryogenic cooling of the cluster source. Infrared-driven N2O decomposition, resulting in the formation of cluster oxides, PtnO+, is observed following vibrational excitation of several Ptn(N2O)+ complexes.

Infrared Study of OCS Binding and Size-Selective Reactivity with Gold Clusters, Aun+ (n = 1-10).

OCS binding to and reactivity with isolated gold cluster cations, Aun+ (n = 1-10), has been studied by infrared multiple photon dissociation (IR-MPD) spectroscopy in conjunction with quantum chemical calculations. The distribution of complexes AunSx(OCS)m+ formed reflects the relative reactivity of different cluster sizes with OCS, under the multiple collision conditions of our ablation source. The IR-MPD spectra of Aun(OCS)+ (n = 3-10) clusters are interpreted in terms of either µ1 or µ2 S binding motifs. Analysis of the fragmentation products following infrared excitation of parent Aun(OCS)+ clusters reveals strongly size-selective (odd-even) branching ratios for OCS and CO loss, respectively. CO loss signifies infrared-driven OCS decomposition on the cluster surface and is observed to occur predominantly on even n clusters (i.e., those with odd electron counts). The experimental data, including fragmentation branching ratios, are consistent with calculated potential energy landscapes, in which the initial species trapped are molecularly bound entrance channel complexes, rather than global minimum inserted structures. Attempts to generate Rhn(OCS)+ and Ptn(OCS)+ equivalents failed; only sulfide reaction products were observed in the mass spectrum, even after cooling the cluster source to -100 °C.

Extracellular Vesicles From Osteotropic Breast Cancer Cells Affect Bone Resident Cells.

Extracellular vesicles (EVs) are emerging as mediators of a range of pathological processes, including cancer. However, their role in bone metastases has been poorly explored. We investigated EV-mediated effects of osteotropic breast cancer cells (MDA-MB-231) on bone resident cells and endothelial cells. Pretreatment of osteoblasts with conditioned medium (CM) of MDA-MB-231 (MDA) cells promoted pro-osteoclastogenic and pro-angiogenic effects by osteoblast EVs (OB-EVs), as well as an increase of RANKL-positive OB-EVs. Moreover, when treating osteoblasts with MDA-EVs, we observed a reduction of their number, metabolic activity, and alkaline phosphatase (Alp) activity. MDA-EVs also reduced transcription of Cyclin D1 and of the osteoblast-differentiating genes, while enhancing the expression of the pro-osteoclastogenic factors Rankl, Lcn2, Il1b, and Il6. Interestingly, a cytokine array on CM from osteoblasts treated with MDA-EVs showed an increase of the cytokines CCL3, CXCL2, Reg3G, and VEGF, while OPG and WISP1 were downregulated. MDA-EVs contained mRNAs of genes involved in bone metabolism, as well as cytokines, including PDGF-BB, CCL3, CCL27, VEGF, and Angiopoietin 2. In line with this profile, MDA-EVs increased osteoclastogenesis and in vivo angiogenesis. Finally, intraperitoneal injection of MDA-EVs in mice revealed their ability to reach the bone microenvironment and be integrated by osteoblasts and osteoclasts. In conclusion, we showed a role for osteoblast-derived EVs and tumor cell-derived EVs in the deregulation of bone and endothelial cell physiology, thus fueling the vicious cycle induced by bone tumors. © 2019 American Society for Bone and Mineral Research.

Digital storytelling as critical narrative intervention with adolescent women of Puerto Rican descent.

This article focuses on findings of a two-year pilot research study focused on addressing sexual and reproductive health inequities faced by adolescent women of Puerto Rican descent living on the mainland United States. Working with three groups of young women, in the pilot study we gathered ethnographic data in and around a group-based digital storytelling process to inform the development of a larger intervention. Digital stories are short (1-3 minute), participant produced videos that synthesize still and moving image, a voiceover recording of the participant telling her story, and background music and text to document personal experiences. Based on narrative analysis of digital stories and field notes written in and around the digital storytelling workshop process, as well as follow-up individual interviews with workshop participants, our findings center on the ways that trauma has specifically shaped participants' sexual and reproductive health experiences. We argue that digital storytelling serves as a critical narrative intervention, whereby participants' engagement in the storytelling process enables them to collaboratively interrogate and potentially address prior trauma, bolster a sense of social support and solidarity, and potentially recalibrate stigmatizing conversations about them. We introduce our project methodology, and then present key findings on trauma as it informs sexual and reproductive health practices, with digital storytelling showcased as a modality for critical narrative intervention. We conclude by discussing implications for critical public health research and practice.

Multidrug-Resistant Salmonella enterica Subspecies I Serovar 4,[5],12:i:- Isolates Recovered from Food Safety and Inspection Service-Regulated Products and Food Animal Ceca, 2007-2016.

Salmonella enterica subspecies I serovar 4,[5],12:i:- (Salmonella I 4,[5],12:i:-) is among the five most common serovars associated with human salmonellosis in the United States. In 2010, human infections with Salmonella I 4,[5],12:i:- which exhibited resistance to ampicillin, streptomycin, sulfonamides, and tetracycline (ASSuT) emerged as a public health concern. Outbreak investigations identified live animal settings, meat and poultry, and pets as confirmed and suspect sources of infection. To shed further light on possible sources of ASSuT-resistant Salmonella I 4,[5],12:i:- infections, we described isolates recovered from meat and poultry products regulated by the Food Safety and Inspection Service (FSIS) and from food animal ceca collected at FSIS-regulated slaughter establishments during 2007-2016. During the time period of interest, ASSuT-resistant Salmonella I 4,[5],12:i:- was found at low levels in multiple FSIS product classes including swine, turkey, cattle and chicken, which suggests this pathogen has a relatively wide host range. Monitoring trends in the various FSIS production classes over time and developing commodity profiles may help focus preventative strategies.