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  1. Abstract

    Singlet fission, a process that splits a singlet exciton into a biexciton, has promise in quantum information. We report time-resolved electron paramagnetic resonance measurements on a conformationally well-defined acene dimer molecule, TIPS-BP1', designed to exhibit strongly state-selective relaxation to specific magnetic spin sublevels. The resulting optically pumped spin polarization is a nearly pure initial state from the ensemble. The long-lived spin coherences modulate the signal intrinsically, allowing a measurement scheme that substantially removes noise and uncertainty in the magnetic resonance spectra. A nonadiabatic transition theory with a minimal number of spectroscopic parameters allows the quantitative assignment and interpretation of the spectra. In this work, we show that the rigid dimer TIPS-BP1' supports persistent spin coherences at temperatures far higher than those used in conventional superconducting quantum hardware.

  2. Free, publicly-accessible full text available November 15, 2023
  3. Abstract

    An accepted murine analogue for the environmental behavior of human SARS coronaviruses was aerosolized in microdroplets of its culture media and saliva to observe the decay of its airborne infectious potential under relative humidity (RH) conditions relevant to conditioned indoor air. Contained in a dark, 10 m3 chamber maintained at 22°C, murine hepatitis virus (MHV) was entrained in artificial saliva particles that were aerosolized in size distributions that mimic SARS-CoV-2 virus expelled from infected humans’ respiration. As judged by quantitative PCR, more than 95% of the airborne MHV aerosolized was recovered from microdroplets with mean aerodynamic diameters between 0.56 and 5.6 μm. As judged by its half-life, calculated from the median tissue culture infectious dose (TCID50), saliva was protective of airborne murine coronavirus through a RH range recommended for conditioned indoor air (60% < RH < 40%; average half-life = 60 minutes). However, its average half-life doubled to 120 minutes when RH was maintained at 25%. Saliva microaerosol was dominated by carbohydrates, which presented hallmarks of vitrification without efflorescence at low RH. These results suggest that dehydrating carbohydrates can affect the infectious potential coronaviruses exhibit while airborne, significantly extending their persistence under the drier humidity conditions encountered indoors.

  4. Equilibrium is a challenging concept for many, largely because developing a deep conceptual understanding of equilibrium requires someone to be able to connect the motions and interactions of particles that cannot be physically observed with macroscopic observations. Particle level chemistry animations and simulations can support student connections of particle motion with macroscopic observations, but for topics such as equilibrium additional visuals such as graphs are typically present which add additional complexity. Helping students make sense of such visuals requires careful scaffolding to draw their attention to important features and help them make connections between representations ( e.g. , particle motion and graphical representations). Further, as students enter our classrooms with varying levels of background understanding, they may require more or less time working with such simulations or animations to develop the desired level of conceptual understanding. This paper describes the development and testing of activities that use the PhET simulation “Reactions and Rates” to introduce the concept of equilibrium as a student preclass activity either in the form of directly using the simulation or guided by an instructor through a screencast. The pre-post analysis of the two most recent implementations of these activities indicates that students show improved understanding ofmore »the core ideas underlying equilibrium regardless of instructor, institution, or type of instructional environment (face to face or remote). We also observed that students were more readily able to provide particle level explanations of changes in equilibrium systems as they respond to stresses (such as changes to concentration and temperature) if they have had prior course instruction on collision theory. Lastly, we observed that student answers to explain how an equilibrium will respond to an applied stress more often focus on either initial responses or longer-term stability of concentrations, not on both key aspects.« less
    Free, publicly-accessible full text available July 1, 2023
  5. Abstract

    Among individuals with psychotic disorders, paranoid ideation is common and associated with increased impairment, decreased quality of life, and a more pessimistic prognosis. Although accumulating research indicates negative affect is a key precipitant of paranoid ideation, the possible protective role of positive affect has not been examined. Further, despite the interpersonal nature of paranoid ideation, there are limited and inconsistent findings regarding how social context, perceptions, and motivation influence paranoid ideation in real-world contexts. In this pilot study, we used smartphone ecological momentary assessment to understand the relevance of hour-by-hour fluctuations in mood and social experience for paranoid ideation in adults with psychotic disorders. Multilevel modeling results indicated that greater negative affect is associated with higher concurrent levels of paranoid ideation and that it is marginally related to elevated levels of future paranoid ideation. In contrast, positive affect was unrelated to momentary experiences of paranoid ideation. More severe momentary paranoid ideation was also associated with an elevated desire to withdraw from social encounters, irrespective of when with familiar or unfamiliar others. These observations underscore the role of negative affect in promoting paranoid ideation and highlight the contribution of paranoid ideation to the motivation to socially withdraw in psychotic disorders.

  6. Free, publicly-accessible full text available July 1, 2023
  7. Multi-stage fluidic reaction schemes for suspended particles (e.g., micro/nanospheres, cells, bacterial species, and extracellular vesicles) underly a diversity of chemical and biological applications. Conventional methods for executing such protocols can be exceedingly time, labor, and/or cost intensive. Microfluidic strategies can address these drawbacks; however, such technologies typically rely on clean room-based microfabrication that suffer from similar deficits for manufacturing the chips. To simultaneously overcome these challenges, here we explore the use of the submicron-scale additive manufacturing approach, “Two-Photon Direct Laser Writing (DLW)”, as a means for fabricating micro-fluidic “Deterministic Lateral Displacement (DLD)” arrays capable of passively guiding suspended particles across discrete, adjacent flow streams—the fundamental capability of continuous-flow multi-stage particle microreactors. Experimental results from microfluidic experimentation with 5 μm-in-diameter fluorescent particles revealed effective particle transport across flow streams, with 87.5% of fluorescent peaks detected in the designated, opposing outlet following the DLD array. These results suggest utility of the presented approach for micro- and nanoparticle-based microfluidic reactors targeting wide-ranging chemical and biological applications.
    Free, publicly-accessible full text available June 1, 2023
  8. Free, publicly-accessible full text available August 3, 2023
  9. We report a new method for regioselective aromatic bromination using lactic acid derivatives as halogen bond acceptors with N-bromosuccinimide (NBS). Several structural analogues of lactic acid affect the efficiency of aromatic brominations, presumably via Lewis acid/base halogen-bonding interactions. Rate comparisons of aromatic brominations demonstrate the reactivity enhancement available via catalytic additives capable of halogen bonding. Computational results demonstrate that Lewis basic additives interact with NBS to increase the electropositive character of bromine prior to electrophilic transfer. An optimized procedure using catalytic mandelic acid under aqueous conditions at room temperature was developed to promote aromatic bromination on a variety of arene substrates with complete regioselectivity.
    Free, publicly-accessible full text available June 16, 2023
  10. Surface-enhanced Raman scattering (SERS), a powerful technique for trace molecular detection, depends on chemical and electromagnetic enhancements. While recent advances in instrumentation and substrate design have expanded the utility, reproducibility, and quantitative capabilities of SERS, some challenges persist. In this review, advances in quantitative SERS detection are discussed as they relate to intermolecular interactions, surface selection rules, and target molecule solubility and accessibility. After a brief introduction to Raman scattering and SERS, impacts of surface selection rules and enhancement mechanisms are discussed as they relate to the observation of activation and deactivation of normal Raman modes in SERS. Next, experimental conditions that can be used to tune molecular affinity to and density near SERS substrates are summarized and considered while tuning these parameters is conveyed. Finally, successful examples of quantitative SERS detection are discussed, and future opportunities are outlined.
    Free, publicly-accessible full text available April 20, 2023