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An invisible, reversible catalytic reaction called enolization occurs consistently when carboxylic acid vapors contact metal oxide surfaces, a pathway widely invoked in mechanistic proposals for decarboxylative ketonization but not sufficiently examined experimentally. While the CO₂H group responsible for adsorption readily forms surface carboxylates, the weaker α-C–H acidity becomes evident only through reversible H/D exchange. The formation of an enolized surface carboxylate enables its subsequent condensation with a second carboxylate, a transformation widely regarded as the rate-determining step in the decarboxylative ketonization mechanism relevant to oxygen removal in biofuel upgrading. In our kinetic study, the rate of approaching equilibrium was measured for H/D isotopic exchange on alpha-carbon of isobutyric acid used in various concentrations in a vapor phase mixture with D2O as well as for reversed D/H exchange between alpha-deuterated isobutyric acid and H2O upon contact with monoclinic zirconia and anatase titania catalysts. Faster rate for H/D vs. D/H exchange points to alpha-deprotonation, i.e., enolization, as the rate determining step of the exchange mechanism. The intrinsic rate of enolization was deduced using McKay equation for equilibrium reactions. Kinetic activation parameters were obtained through temperature dependence of the rate constant for both exchange directions, H/D and D/H. KOH doping on ZrO2 changes the geometry of the transition state leading to higher rates of enolization and increasing H/D kinetic isotope effect from 1.4 to 5.8. The opposite effect of KOH doping is observed on anatase TiO2 – enolization rates are slightly decreased, kH/kD remains relatively constant at 2.6–2.8 indicating that the nature of basic centers on TiO2 is unaffected. These results confirm C–C coupling, not enolization, being the rate limiting step of the decarboxylative ketonization mechanism.more » « lessFree, publicly-accessible full text available January 1, 2027
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Free, publicly-accessible full text available June 15, 2026
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Free, publicly-accessible full text available June 21, 2026
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Rana, Karan Singh (Ed.)Despite the increasing number of racially and ethnically minoritized (REM) individuals earning PhDs and the substantial investment in diversity initiatives within higher education, the relative lack of diversity among faculty in tenure-track positions reveals a persistent systemic challenge. This study used an adaptation of the Community Readiness Tool to evaluate readiness for faculty diversification efforts in five biomedical departments. Interviews with 31 key informants were transcribed and coded manually and using NVIVO 12 in order to assign scores to each department in the six domains of readiness. The results revealed no meaningful differences in overall scores across institutional types, but did show differences within specific domains of readiness. These findings indicate that readiness is multi-faceted and academic departments can benefit by identifying priority areas in need of additional faculty buy-in and resources to enhance the success of diversification efforts.more » « lessFree, publicly-accessible full text available February 25, 2026
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The growing population of older adults emphasizes the need to develop interventions that prevent or delay some of the cognitive decline that accompanies aging. In particular, as memory impairment is the foremost cognitive deficit affecting older adults, it is vital to develop interventions that improve memory function. This study addressed the problem of false memories in aging by training older adults to use details of past events during memory retrieval to distinguish targets from related lures. We examined the neural basis of a retrieval-based monitoring strategy by assessing changes in univariate BOLD activity and discriminability of targets and lures pre and post training. Results showed training-related decreases in false memory rates with no alterations to hit rates. Both training and practice were associated with altered recruitment of a frontoparietal monitoring network as well as benefits to neural discriminability within network regions. Participants with lower baseline neural discriminability between target and lure items exhibited the largest changes in neural discriminability. Collectively, our results highlight the benefits of training for reductions of false memories in aging. They also provide an understanding of the neural mechanisms that support these reductions.more » « less
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Cognitive neuroscience is the interdisciplinary study of how cognitive and intellectual functions are processed and represented within the brain, which is critical to building understanding of core psychological and behavioural processes such as learning, memory, behaviour, perception, and consciousness. Understanding these processes not only offers relevant fundamental insights into brain-behavioural relations, but may also lead to actionable knowledge that can be applied in the clinical treatment of patients with various brain-related disabilities. This Handbook examines complex cognitive systems through the lens of neuroscience, as well as providing an overview of development and applications within cognitive and systems neuroscience research and beyond. Containing 35 original, state of the art contributions from leading experts in the field, this Handbook is essential reading for researchers and students of cognitive psychology, as well as scholars across the fields of neuroscientific, behavioural and health sciences. Part 1: Attention, Learning and Memory; Part 2: Language and Communication; Part 3: Emotion and Motivation; Part 4: Social Cognition; Part 5: Cognitive Control and Decision Making; and Part 6: Intelligence.more » « less
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Kinzie, Jillian L; Wolf-Wendel, Lisa (Ed.)Though increasing numbers of racially and ethnically minoritized (REM) individuals earn PhDs and national initiatives focus on faculty diversity, challenges persist in recruiting, hiring, and retaining REM faculty. While a pervasive issue nationally, the literature predominantly focuses on faculty diversity at research‐intensive institutions. This exploratory case study pilots a readiness instrument to evaluate the commitment and willingness of a biomedical department at a primarily undergraduate institution to embrace faculty diversity before initiating a postdoctoral faculty conversion program. We introduce the Community Readiness Model (CRM) into an academic context, offering academic departments a robust framework and tool to evaluate readiness and capacity to recruit, retain, and support REM faculty. Practical Takeaways: Academic departments can be conceived of as a type of community. The adapted Department Readiness Tool can be a valuable method of evaluating a department's readiness to support the success of underrepresented minority faculty. Departments may score highly on some areas of readiness but relatively low on others, which provides insight into where time and resources should be invested to improve readiness.more » « less
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Abstract We present measurements of the neutral atomic hydrogen (Hi) mass function (HiMF) and cosmic Hidensity (ΩH I) at 0 ≤z≤ 0.088 from the Looking at the Distant Universe with MeerKAT Array (LADUMA) survey. Using LADUMA Data Release 1 (DR1), we analyze the HiMF via a new “recovery matrix” method that we benchmark against a more traditional modified maximum likelihood (MML) method. Our analysis, which implements a forward modeling approach, corrects for survey incompleteness and uses extensive synthetic source injections to ensure robust estimates of the HiMF parameters and their associated uncertainties. This new method tracks the recovery of sources in mass bins different from those in which they were injected and incorporates a Poisson likelihood in the forward modeling process, allowing it to correctly handle uncertainties in bins with few or no detections. The application of our analysis to a high-purity subsample of the LADUMA DR1 spectral line catalog in turn mitigates any possible biases that could result from the inconsistent treatment of synthetic and real sources. For the surveyed redshift range, the recovered Schechter function normalization, low-mass slope, and “knee” mass are Mpc−3dex−1, , and , respectively, which together imply a comoving cosmic Hidensity of . Our results show consistency between recovery matrix and MML methods and with previous low-redshift studies, giving confidence that the cosmic volume probed by LADUMA, even at low redshifts, is not an outlier in terms of its Hicontent.more » « lessFree, publicly-accessible full text available March 10, 2026
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Natural ventilation is used to cool buildings and cut energy costs by inducing airflow through building openings without the use of mechanical ventilation and cooling systems. However, prior research has documented increased introduction of particles into indoor environments that are naturally ventilated, with associated health consequences. The recently updated ASHRAE Standard 62.1–2019: Ventilation for Acceptable Indoor Air Quality Natural Ventilation Procedure (NVP) prescribes opening sizes as a function of occupant density and geometry for use as a ventilation strategy, a change from the previous standard. The current work quantifies the indoor air quality impacts of implementing the Standard 62.1–2019 Natural Ventilation Procedure in the United States and compares it to the 62.1-specified ventilation rate procedure. This is done via coupled transient simulation of CONTAM 3.4 and EnergyPlus 9.1. Three pollutant classes were identified to represent a broad range of contaminants: outdoor-generated pollutants, pollutants generated indoors by humans, and pollutants generated indoors by the building itself. With boundary conditions from measured weather and outdoor pollutant data for 13 representative locations throughout the U.S., our modeling first found 41%–185% annual average increase in ventilation rates over its mechanical counterpart if the NVP is used across the geometries and occupant densities in the Standard. Due to elevated ventilation rates, the Natural Ventilation Procedure reduced building-generated and occupant-generated contaminant concentrations during occupied hours by an average of 17%–61% compared to the ventilation rate procedure. Outdoor-generated fine particles averaged 2.1–2.5 times the concentrations indoors when using the NVP as compared to mechanical ventilation with a MERV-8 filter and 7.8–10.4 times the concentration of a mechanical system with a MERV-13 filter. Both ventilation rates and concentrations were substantially climate-specific and somewhat window geometry-specific. We further showed that increased filtration is needed in many cases to keep up with increased effective NVP rates in the 2019 Standard if acceptable levels of indoor particles are to be achieved, and we offer suggestions for improving the Standard.more » « less
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Zmuidzinas, Jonas; Gao, Jian-Rong (Ed.)
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