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.

Should Current Laws Be Revised to Address Occupational Hazards Caused by Hand-Tool Size Mismatch Among Surgeons?

This Viewpoint discusses the challenges faced by surgeons with a smaller hand size­and women in particular­when using surgical tools designed for larger hands and explores potential legal remedies to address these challenges.

Correction: Velocity map images from surface-hopping; reactive scattering of OH (2Σ+) + H2 (1Σ+g).

Correction for 'Velocity map images from surface-hopping; reactive scattering of OH (2Σ+) + H2 (1Σ+g)' by Christopher Robertson and Martin J. Paterson, Chem. Commun., 2022, 58, 9092-9095, https://doi.org/10.1039/D2CC03368B.

"A ghost doesn't need insulin," Cotard's delusion leading to diabetic ketoacidosis and a body-mass index of 15: a case presentation.

BACKGROUND: Cotard's Syndrome (CS) is a rare clinical entity where patients can report nihilistic, delusional beliefs that they are already dead. Curiously, while weight loss, dehydration, and metabolic derangements have been described as discussed above, a review of the literature revealed neither a single case of a severely underweight patient nor a serious metabolic complication such as Diabetic Ketoacidosis. Further, a search on PubMed revealed no articles discussing the co-occurrence of Cotard's Delusion and eating disorders or comorbid metabolic illnesses such as diabetes mellitus. In order to better examine the association between Cotard's Delusion and comorbid eating disorders and metabolic illness, we will present and discuss a case where Cotard's delusion led to a severe metabolic outcome of DKA and a BMI of 15. CASE PRESENTATION: Mr. B is a 19 year old transgender man admitted to the hospital due to diabetic ketoacidosis secondary to Type 1 Diabetes Mellitus. Mr. B had a history of Obsessive-Compulsive Disorder, Major Depressive Disorder, and Post-Traumatic Stress Disorder. The primary pediatric team discovered that Mr. B had not been using his insulin appropriately and was severely underweight, and they believed this could be due to his underlying mental illness. The psychiatric consultation/liaison service found that Mr. B was suffering from Cotard's delusion leading him to be noncompliant with his insulin due to a belief that he was already dead. Cotard's delusion had in this case led to a severe metabolic outcome of DKA and a BMI of 15. CONCLUSIONS: This case provides clinical insight into the interactions of eating disorders and Cotard's delusion as well as the potential medical complications when Cotard's delusion is co-morbid with medical conditions such as Diabetes Mellitus. We recommend that clinicians routinely screen patients for Cotard's delusion and assess whether the presence of which could exacerbate any underlying medical illness. This includes clinicians taking special care in assessing patient's caloric and fluid intake as well as their adherence to medications both psychiatric and medical. Further research could be conducted to explore the potential overlap of Cotard's delusion and eating disorder phenomenology.

The effectiveness of financial incentives for COVID-19 vaccination: A systematic review.

Financial incentives are a controversial strategy for increasing vaccination. In this systematic review, we evaluated: 1) the effects of incentives on COVID-19 vaccinations; 2) whether effects differed based on study outcome, study design, incentive type and timing, or sample sociodemographic characteristics; and 3) the cost of incentives per additional vaccine administered. We searched PubMed, EMBASE, Scopus, and Econlit up to March 2022 for terms related to COVID, vaccines, and financial incentives, and identified 38 peer-reviewed, quantitative studies. Independent raters extracted study data and evaluated study quality. Studies examined the impact of financial incentives on COVID-19 vaccine uptake (k = 18), related psychological outcomes (e.g., vaccine intentions, k = 19), or both types of outcomes. For studies of vaccine uptake, none found that financial incentives had a negative effect on uptake, and most rigorous studies found that incentives had a positive effect on uptake. By contrast, studies of vaccine intentions were inconclusive. While three studies concluded that incentives may negatively impact vaccine intentions for some individuals, they had methodological limitations. Study outcomes (uptake versus intentions) and study design (experimental versus observational frameworks) appeared to influence results more than incentive type or timing. Additionally, income and political affiliation may moderate responses to incentives. Most studies evaluating cost per additional vaccine administered found that they ranged from $49-75. Overall, fears about financial incentives decreasing COVID-19 vaccine uptake are not supported by the evidence. Financial incentives likely increase COVID-19 vaccine uptake. While these increases appear to be small, they may be meaningful across populations. Registration: PROSPERO, CRD42022316086 (https://www.crd.york.ac.uk/prospero/display_record.php?ID=CRD42022316086).

Diverse patients' attitudes towards Artificial Intelligence (AI) in diagnosis.

Artificial intelligence (AI) has the potential to improve diagnostic accuracy. Yet people are often reluctant to trust automated systems, and some patient populations may be particularly distrusting. We sought to determine how diverse patient populations feel about the use of AI diagnostic tools, and whether framing and informing the choice affects uptake. To construct and pretest our materials, we conducted structured interviews with a diverse set of actual patients. We then conducted a pre-registered (osf.io/9y26x), randomized, blinded survey experiment in factorial design. A survey firm provided n = 2675 responses, oversampling minoritized populations. Clinical vignettes were randomly manipulated in eight variables with two levels each: disease severity (leukemia versus sleep apnea), whether AI is proven more accurate than human specialists, whether the AI clinic is personalized to the patient through listening and/or tailoring, whether the AI clinic avoids racial and/or financial biases, whether the Primary Care Physician (PCP) promises to explain and incorporate the advice, and whether the PCP nudges the patient towards AI as the established, recommended, and easy choice. Our main outcome measure was selection of AI clinic or human physician specialist clinic (binary, "AI uptake"). We found that with weighting representative to the U.S. population, respondents were almost evenly split (52.9% chose human doctor and 47.1% chose AI clinic). In unweighted experimental contrasts of respondents who met pre-registered criteria for engagement, a PCP's explanation that AI has proven superior accuracy increased uptake (OR = 1.48, CI 1.24-1.77, p < .001), as did a PCP's nudge towards AI as the established choice (OR = 1.25, CI: 1.05-1.50, p = .013), as did reassurance that the AI clinic had trained counselors to listen to the patient's unique perspectives (OR = 1.27, CI: 1.07-1.52, p = .008). Disease severity (leukemia versus sleep apnea) and other manipulations did not affect AI uptake significantly. Compared to White respondents, Black respondents selected AI less often (OR = .73, CI: .55-.96, p = .023) and Native Americans selected it more often (OR: 1.37, CI: 1.01-1.87, p = .041). Older respondents were less likely to choose AI (OR: .99, CI: .987-.999, p = .03), as were those who identified as politically conservative (OR: .65, CI: .52-.81, p < .001) or viewed religion as important (OR: .64, CI: .52-.77, p < .001). For each unit increase in education, the odds are 1.10 greater for selecting an AI provider (OR: 1.10, CI: 1.03-1.18, p = .004). While many patients appear resistant to the use of AI, accuracy information, nudges and a listening patient experience may help increase acceptance. To ensure that the benefits of AI are secured in clinical practice, future research on best methods of physician incorporation and patient decision making is required.

Pulse Oximeters and Violation of Federal Antidiscrimination Law.

This Viewpoint discusses how some pulse oximeters can provide incorrect oxygen saturation data for dark-skinned patients compared with light-skinned patients, describes the reasons that biased oximeters remained in use, and highlights why a rule recently proposed by the US Department of Health and Human Services may bring about needed change in the use of pulse oximetry for patients with dark skin.

Beyond "pains" and "gains": untangling the health consequences of probation.

BACKGROUND: Research on the health consequences of criminal legal system contact has increasingly looked beyond imprisonment to understand how more routine forms of surveillance and punishment shape wellbeing. One of these sites is probation, the largest form of supervision in the U.S. Drawing on an interview study with 162 adults on probation in Hennepin County, MN, in 2019, we map how adults on probation understand the consequences of supervision for their health and how these self-reported health changes correlate with individual, social, and structural circumstances. RESULTS: Roughly half of participants described their health as having improved since starting probation, while the remainder were split between no change and worsened health. Examining both closed-ended survey questions and open-ended interview prompts, we find that the "gains" of supervision were correlated with substance use treatment (often mandated), reduced drug and alcohol use, increased housing and food security, and perceptions of support from their probation officer. However, these potentially health-promoting mechanisms were attenuated for many participants by the significant "pains" of supervision, including the threat of revocation, which sometimes impacted mental health. In addition, participants in the most precarious circumstances were often unable to meet the demands of supervision, resulting in further punishment. CONCLUSIONS: Moving beyond the "pains" and "gains" framework, we argue that this analysis provides empirical evidence for the importance of moving social services outside of punishing criminal legal system interventions. People with criminal legal contact often come from deeply marginalized socio-economic contexts and are then expected to meet the rigorous demands of supervision with little state aid for redressing structural barriers. Access to essential services, including healthcare, food, and housing, without the threat of further criminal legal sanctions, can better prevent and respond to many of the behaviors that are currently criminalized in the U.S. legal system, including substance use.

Comparative effectiveness of mandates and financial policies targeting COVID-19 vaccine hesitancy: A randomized, controlled survey experiment.

Experts debate whether COVID-19 vaccine mandates or financial incentives will reduce, rather than increase, interest in vaccination. Among 3,698 unvaccinated U.S. residents, we conducted a randomized, controlled survey-embedded experiment to estimate the absolute and relative psychological effects of vaccine policies specifying: mandates by employers or airlines, bars, and restaurants; lotteries for $1 million, $200,000, or $100,000; guaranteed cash for $1000, $200, or $100; and $1,000 as either a tax credit or penalty. Vaccine intention -the study outcome- predicts uptake and provides insight into the psychological mechanism that is most proximal to behavior (i.e., vaccination). Compared to controls, those who learned about the $1,000 cash reward policy were 17.1 (±5.3)% more likely to want vaccination. Employer mandates are more promising than other mandate policies (8.6 [+/- 7.4]% vs. 1.4 [+/- 6.0]%). The full results suggest that neither mandates nor financial incentives are likely to have counterproductive psychological effects. These policies are not mutually exclusive and, if implemented well, they may increase vaccine uptake.

Velocity map images from surface-hopping; reactive scattering of OH (2Σ+) + H2 (1Σ+g).

We study OH(Σ) + H2 → H2O(X) + H reactive scattering using two potential energy models found in the literature. We analyze the quenching channels and generate velocity map images (VMI) by simulating quantum-classical trajectories of the quenched products. The initial conditions attempt to simulate supersonic jet, molecular beam scattering experiments which we compare against. The simulated results are able to elucidate the mechanisms behind some of these experimental observations.

What the harm principle says about vaccination and healthcare rationing.

Clinical ethicists hold near consensus on the view that healthcare should be provided regardless of patients' past behaviors. In classic cases, the consensus can be explained by two key rationales-a lack of acute scarcity and the intractability of the facts around those behaviors, which make discrimination on past behavior gratuitous and infeasible to do fairly. Healthcare providers have a duty to help those who can be helped. In contrast, the COVID-19 pandemic suggests the possible recurrence of a very different situation, where a foreseeable acute shortage of healthcare resources means that some cannot be helped. And that shortage is exacerbated by the discrete decision of some to decline a free, safe, and highly effective vaccine, where the facts are clear. In such a future case, if healthcare must be denied to some patients, rationers who ignore vaccination status will become complicit in externalizing the consequences of refusing vaccination onto those who did not refuse. I argue that giving the unvaccinated person healthcare resources that would have otherwise gone to other patients is to wrongfully set back the interests of, or harm, those patients. The article considers rejoinders around the voluntariness of the vaccination choice, which impinges both access and information, and how to scale this criterion proportionally with other rationing criteria that serve utility. Ultimately, the article speculates on why there will be some cognitive dissonance under this approach, while upholding a more general solidarity with and concern for all those seeking healthcare.