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.

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.

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.

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.

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.

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.

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.

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.

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.

A multicenter audit of the use of bronchoscopy during open and thoracoscopic repair of esophageal atresia with tracheoesophageal fistula.

BACKGROUND: Esophageal atresia (EA) with tracheoesophageal fistula is usually repaired in the neonatal period. Preferential ventilation through the fistula can lead to gastric distension. Bronchoscopy has a role in defining the site and size of the fistula, and may be carried out by the surgeon or the anesthetist. The use of bronchoscopy varies across different institutions. METHODS: This is a multicenter case note review of infants with EA with tracheoesophageal fistula who underwent surgery between January 2010 and December 2015. This retrospective audit aims primarily to document the use of bronchoscopy during open and thoracoscopic repair at a selection of United Kingdom centers. Respiratory complications, that is relating to airway management, the respiratory system, and difficulty with ventilation, at induction and during surgery, are recorded. The range of techniques for anesthesia and analgesia in these centers is noted. RESULTS: Bronchoscopy was carried out in 52% of cases. The incidence of respiratory complications was 7% at induction and 21% during surgery. Thoracoscopic repair usually took longer. One center used high-frequency oscillatory ventilation, on an elective basis during thoracoscopic repair, to facilitate surgical access and address concerns about hypoxemia and hypercarbia. CONCLUSION: The use of bronchoscopy varies considerably between institutions. Infants undergoing tracheoesophageal fistula repair are at risk of perioperative respiratory morbidity. The advent of thoracoscopic repair has introduced further variation.

Meth Mouth, White Trash, and the Pseudo-Racialization of Methamphetamine Use in the U.S.

Drug scares have historically been created for a range of purposes and with a variety of effects in the United States. Moral panics evoked by these drug scares either support or challenge dominant American ideas about race, economics, and society. In the present study, we examined newspaper accounts of methamphetamine use in the Inland Pacific Northwest of the United States in an effort to understand how the "reality" of the "meth epidemic" is socially constructed in a "meth hotspot," and reflect upon the ways that the discourse of Whiteness intersects with this construction. For our analysis, we are cognizant of the "slipperiness" of the logic of Whiteness as a concept, and the ways that an alternative logic is articulated - one that strategically embraces or distances White drug users to support notions of White dominance. We focus on the possibility that individual meth users could then be portrayed pseudo-racially as "White trash," and thus rendered outside the logic of White racial order. Our findings center on two main themes: (1) the use of fear in the construction of the meth drug scare through the sensationalization of meth, its anthropomorphization, and the depiction of the threat of the White drug user; and (2) how the logic of Whiteness is discursively reconciled within this construction. Given current mediated discourses about drug use and health in the United States that center on the emergence of the White drug user as the face of the opioid crisis, we are well served to carefully consider the recent historical precedence of the "meth epidemic" in which the public was faced with reconciling their views about drug use and the intersection of race, class, and mainstream American identity.

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.

Restor(y)ing Health: A Conceptual Model of the Effects of Digital Storytelling.

We currently see an interdisciplinary shift toward a "participatory turn" in health research and promotion under which community engagement, shared decision making and planning, and the use of visual and digital methods have become paramount. Digital storytelling (DST) is one such innovative and engaging method increasingly used in applied health interventions, with a growing body of research identifying its value. Despite its increasing use, a standard approach to empirically assess the impacts on individuals participating in DST interventions does not currently exist. In this article, we define DST as a distinct narrative intervention, illustrate key elements that inform the methodology, and present a conceptual model to examine how DST may contribute to increased socioemotional well-being and bolster positive health outcomes. Our proposed model is informed by elements of narrative theory, Freirian conscientization, multimodality, and social cognitive theory and can serve as a guide for public health practitioners and researchers interested in assessing the potential benefits of DST as an applied health intervention. Recommendations for practice call for a rigorous methodological approach to apply and test this model across a range of health contexts and populations.

Intensified Sampling in Response to a Salmonella Heidelberg Outbreak Associated with Multiple Establishments Within a Single Poultry Corporation.

On June 28, 2013, the Food Safety and Inspection Service (FSIS) was notified by the Centers for Disease Control and Prevention (CDC) of an investigation of a multistate cluster of illnesses of Salmonella enterica serovar Heidelberg. Since case-patients in the cluster reported consumption of a variety of chicken products, FSIS used a simple likelihood-based approach using traceback information to focus on intensified sampling efforts. This article describes the multiphased product sampling approach taken by FSIS when epidemiologic evidence implicated chicken products from multiple establishments operating under one corporation. The objectives of sampling were to (1) assess process control of chicken slaughter and further processing and (2) determine whether outbreak strains were present in products from these implicated establishments. As part of the sample collection process, data collected by FSIS personnel to characterize product included category (whole chicken and type of chicken parts), brand, organic or conventional product, injection with salt solutions or flavorings, and whether product was skinless or skin-on. From the period September 9, 2013, through October 31, 2014, 3164 samples were taken as part of this effort. Salmonella percent positive declined from 19.7% to 5.3% during this timeframe as a result of regulatory and company efforts. The results of intensified sampling for this outbreak investigation informed an FSIS regulatory response and corrective actions taken by the implicated establishments. The company noted that a multihurdle approach to reduce Salmonella in products was taken, including on-farm efforts such as environmental testing, depopulation of affected flocks, disinfection of affected houses, vaccination, and use of various interventions within the establishments over the course of several months.

Moms Supporting Moms: Digital Storytelling With Peer Mentors in Recovery From Substance Use.

Substance use disorder (SUD) is a growing issue nationally, and SUD in pregnancy has significant consequences for mothers and their children. This article describes findings from a pilot project that used digital storytelling as a mechanism for understanding substance use and recovery from the perspective of women in recovery from SUD in pregnancy who worked as peer mentors with pregnant women currently experiencing SUD. Research on peer mentorship has primarily focused on outcomes for mentees but not the experience of the peer mentors themselves. In this qualitative study, a 3-day digital storytelling workshop was conducted with five women in recovery serving as peer mentors in their community. Each mentor also participated in an individual, in-depth interview. The digital storytelling workshop process helped peer mentors make linkages between their past substance use experiences to their present work of recovery, and fostered deep social connections between mentors through the shared experience. The workshop process also elicited a sense of hope among participants, which served as groundwork for developing advocacy-based efforts. Digital storytelling may be therapeutic for women in recovery and has the potential to be integrated into recovery programs to bolster hope and social support among participants.

IR Signature of Size-Selective CO2 Activation on Small Platinum Cluster Anions, Ptn - (n=4-7).

Infrared multiple photon dissociation spectroscopy (IR-MPD) has been employed to determine the nature of CO2 binding to size-selected platinum cluster anions, Ptn - (n=4-7). Interpreted in conjunction with density functional theory simulations, the results illustrate that the degree of CO2 activation can be controlled by the size of the metal cluster, with dissociative activation observed on all clusters n≥5. Of potential practical significance, in terms of the use of CO2 as a useful C1 feedstock, CO2 is observed molecularly-bound, but highly activated, on the Pt4 - cluster. It is trapped behind a barrier on the reactive potential energy surface which prevents dissociation.

Comparative Analysis of Extended-Spectrum-ß-Lactamase CTX-M-65-Producing Salmonella enterica Serovar Infantis Isolates from Humans, Food Animals, and Retail Chickens in the United States.

We sequenced the genomes of 10 Salmonella enterica serovar Infantis isolates containing blaCTX-M-65 obtained from chicken, cattle, and human sources collected between 2012 and 2015 in the United States through routine National Antimicrobial Resistance Monitoring System (NARMS) surveillance and product sampling programs. We also completely assembled the plasmids from four of the isolates. All isolates had a D87Y mutation in the gyrA gene and harbored between 7 and 10 resistance genes [aph(4)-Ia, aac(3)-IVa, aph(3')-Ic, blaCTX-M-65, fosA3, floR, dfrA14, sul1, tetA, aadA1] located in two distinct sites of a megaplasmid (∼316 to 323 kb) similar to that described in a blaCTX-M-65-positive S Infantis isolate from a patient in Italy. High-quality single nucleotide polymorphism (hqSNP) analysis revealed that all U.S. isolates were closely related, separated by only 1 to 38 pairwise high-quality SNPs, indicating a high likelihood that strains from humans, chickens, and cattle recently evolved from a common ancestor. The U.S. isolates were genetically similar to the blaCTX-M-65-positive S Infantis isolate from Italy, with a separation of 34 to 47 SNPs. This is the first report of the blaCTX-M-65 gene and the pESI (plasmid for emerging S Infantis)-like megaplasmid from S Infantis in the United States, and it illustrates the importance of applying a global One Health human and animal perspective to combat antimicrobial resistance.

Puerto Rican Latina Youth Coming Out to Talk About Sexuality and Identity.

Public health efforts focused on Latina youth sexuality are most commonly framed by the syndemic of teen pregnancy and sexually transmitted infections, a narrow and often heteronormative focus that perpetuates silences that contribute to health inequities and overlooks the growing need for increased education, awareness, and support for lesbian, gay, bisexual, transgender, and questioning (LGBTQ) youth. This article presents findings from the project Let's Talk About Sex: Digital Storytelling for Puerto Rican Latina Youth, which used a culturally centered, narrative-based approach for analyzing participants' own specifications of sexual values and practices. The strength of digital storytelling lies in its utility as an innovative tool for community-based and culturally situated research, as well as in its capacity to open up new spaces for health communication. Here we present two "coming out" case studies to illustrate the value of digital storytelling in supporting the development of meaningful and culturally relevant health promotion efforts for LGBTQ-identified Puerto Rican Latina youth across the life span.