Search for: All records

ABSTRACT Biomimetic designs are inspired by the complex and unique behavior of naturally occurring materials, and can be applied to many systems, including polymers. ZIPer polymers (Zwitter arene‐ion like polymer) are inspired by byssal threads found on mussels, and their physical state is highly sensitive to various environmental conditions. Specifically, the ZIPer polymer undergoes chemospecific phase transitions, exhibiting potential for its use as an ionic responsive technology. Though this phenomenon has been observed with Raman spectroscopy, little is known about how salt identity or concentration affect polymer inter‐ and intra‐chain interactions. Previous studies have used Raman spectroscopy to analyze ZIPer polymer behavior in the presence of salt; however, the effect is typically only observed with sodium chloride and often only compares spectra at two concentrations. Additionally, studies have mainly focused on the spectral evidence of cation–π interactions, significantly narrowing their spectral range. In order to develop a more predictive framework for ZIPer polymer behavior, a range of salt identities and concentrations need to be tested. This study uses Raman spectroscopy to investigate ZIPer polymer behavior in the presence of a series of salts, namely NaCl, NaOTFA, NaBr, NaBF₄, and NaPF₆, each at 0.1 M, 0.5 M, 1.0 M, and 1.5 M concentrations. Moreover, we observe spectral changes in a range from 550 to 2000 cm⁻¹. Spectral evidence suggests that the cation–π interactions previously hypothesized to be the driver of ZIPer polymer behavior are not the only mechanism determining the chemoresponsive phase transitions. We hypothesize that cation–π interactions and dispersion forces are competing mechanisms controlling ZIPer polymer behavior. Furthermore, we suggest that at certain concentrations the dominating mechanism transitions, and this inflection point is salt identity dependent. 

Background: COVID-19 vaccines have been approved and made available. While questions of vaccine allocation strategies have received significant attention, important questions remain regarding the potential impact of the vaccine given uncertainties regarding efficacy against transmission, availability, timing, and durability. Methods: We adapted a susceptible-exposed-infectious-recovered (SEIR) model to examine the potential impact on hospitalization and mortality assuming increasing rates of vaccine efficacy, coverage, and administration. We also evaluated the uncertainty of the vaccine to prevent infectiousness as well as the impact on outcomes based on the timing of distribution and the potential effects of waning immunity. Findings: Increased vaccine efficacy against disease reduces hospitalizations and deaths from COVID-19; however, the relative benefit of transmission blocking varied depending on the timing of vaccine distribution. Early in an outbreak, a vaccine that reduces transmission will be relatively more effective than one introduced later in the outbreak. In addition, earlier and accelerated implementation of a less effective vaccine is more impactful than later implementation of a more effective vaccine. These findings are magnified when considering the durability of the vaccine. Vaccination in the spring will be less impactful when immunity is less durable. Interpretation: Policy choices regarding non-pharmaceutical interventions, such as social distancing and face mask use, will need to remain in place longer if the vaccine is less effective at reducing transmission or distributed slower. In addition, the stage of the local outbreak greatly impacts the overall effectiveness of the vaccine in a region and should be considered when allocating vaccines. 

Abstract Non‐growing season CO₂emissions from Arctic tundra remain a major uncertainty in forecasting climate change consequences of permafrost thaw. We present the first time series of soil and microbial CO₂emissions from a graminoid tundra based on year‐round in situ measurements of the radiocarbon content of soil CO₂(Δ¹⁴CO₂) and of bulk soil C (Δ¹⁴C), microbial activity, and temperature. Combining these data with land‐atmosphere CO₂exchange allows estimates of the proportion and mean age of microbial CO₂emissions year‐round. We observe a seasonal shift in emission sources from fresh carbon during the growing season (August Δ¹⁴CO₂ = 74 ± 4.7‰, 37% ± 3.4% microbial, mean ± se) to increasingly older soil carbon in fall and winter (March Δ¹⁴CO₂ = 22 ± 1.3‰, 47% ± 8% microbial). Thus, rising soil temperatures and emissions during fall and winter are depleting aged soil carbon pools in the active layer and thawing permafrost and further accelerating climate change.