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The intrinsic uncertainty of sensory information (i.e., evidence) does not necessarily deter an observer from making a reliable decision. Indeed, uncertainty can be reduced by integrating (accumulating) incoming sensory evidence. It is widely thought that this accumulation is instantiated via recurrent rate-code neural networks. Yet, these networks do not fully explain important aspects of perceptual decision-making, such as a subject’s ability to retain accumulated evidence during temporal gaps in the sensory evidence. Here, we utilized computational models to show that cortical circuits can switch flexibly between “retention” and “integration” modes during perceptual decision-making. Further, we found that, depending on how the sensory evidence was readout, we could simulate “stepping” and “ramping” activity patterns, which may be analogous to those seen in different studies of decision-making in the primate parietal cortex. This finding may reconcile these previous empirical studies because it suggests these two activity patterns emerge from the same mechanism. 

Hydrogen sulfide (H 2 S) is an endogenous gasotransmitter with potential therapeutic value for treating a range of disorders, such as ischemia-reperfusion injury resulting from a myocardial infarction or stroke. However, the medicinal delivery of H 2 S is hindered by its corrosive and toxic nature. In addition, small molecule H 2 S donors often generate other reactive and sulfur-containing species upon H 2 S release, leading to unwanted side effects. Here, we demonstrate that H 2 S release from biocompatible porous solids, namely metal–organic frameworks (MOFs), is a promising alternative strategy for H 2 S delivery under physiologically relevant conditions. In particular, through gas adsorption measurements and density functional theory calculations we establish that H 2 S binds strongly and reversibly within the tetrahedral pockets of the fumaric acid-derived framework MOF-801 and the mesaconic acid-derived framework Zr-mes, as well as the new itaconic acid-derived framework CORN-MOF-2. These features make all three frameworks among the best materials identified to date for the capture, storage, and delivery of H 2 S. In addition, these frameworks are non-toxic to HeLa cells and capable of releasing H 2 S under aqueous conditions, as confirmed by fluorescence assays. Last, a cellular ischemia-reperfusion injury model using H9c2 rat cardiomyoblast cells corroborates that H 2 S-loaded MOF-801 is capable of mitigating hypoxia-reoxygenation injury, likely due to the release of H 2 S. Overall, our findings suggest that H 2 S-loaded MOFs represent a new family of easily-handled solid sources of H 2 S that merit further investigation as therapeutic agents. In addition, our findings add Zr-mes and CORN-MOF-2 to the growing lexicon of biocompatible MOFs suitable for drug delivery. 

Diamine-appended variants of the metal–organic framework M2(dobpdc) (M = Mg, Mn, Fe, Co, Zn; dobpdc4– = 4,4′-dioxidobiphenyl-3,3′-dicarboxylate) exhibit exceptional CO2 capture properties owing to a unique cooperative adsorption mechanism, and thus hold promise for use in the development of energy- and cost-efficient CO2 separations. Understanding the nature of thermal transport in these materials is essential for such practical applications, however, as temperature rises resulting from exothermic CO2 uptake could potentially offset the energy savings offered by such cooperative adsorbents. Here, molecular dynamics (MD) simulations are employed in investigating thermal transport in bare and e-2-appended Zn2(dobpdc) (e-2 = N-ethylethylenediamine), both with and without CO2 as a guest. In the absence of CO2, the appended diamines function to enhance thermal conductivity in the ab-plane of e-2–Zn2(dobpdc) relative to the bare framework, as a result of noncovalent interactions between adjacent diamines that provide additional heat transfer pathways across the pore channel. Upon introduction of CO2, the thermal conductivity along the pore channel (the c-axis) increases due to the cooperative formation of metal-bound ammonium carbamates, which serve to create additional heat transfer pathways. In contrast, the thermal conductivity of the bare framework remains unchanged in the presence of zinc-bound CO2 but decreases in the presence of additional adsorbed CO2. 

Carbon capture and sequestration (CCS) from industrial point sources and direct air capture are necessary to combat global climate change. A particular challenge faced by amine‐based sorbents—the current leading technology—is poor stability towards O₂. Here, we demonstrate that CO₂chemisorption in γ‐cylodextrin‐based metal–organic frameworks (CD‐MOFs) occurs via HCO₃⁻formation at nucleophilic OH⁻sites within the framework pores, rather than via previously proposed pathways. The new framework KHCO₃CD‐MOF possesses rapid and high‐capacity CO₂uptake, good thermal, oxidative, and cycling stabilities, and selective CO₂capture under mixed gas conditions. Because of its low cost and performance under realistic conditions, KHCO₃CD‐MOF is a promising new platform for CCS. More broadly, our work demonstrates that the encapsulation of reactive OH⁻sites within a porous framework represents a potentially general strategy for the design of oxidation‐resistant adsorbents for CO₂capture.

 

Carbon capture and sequestration (CCS) from industrial point sources and direct air capture are necessary to combat global climate change. A particular challenge faced by amine‐based sorbents—the current leading technology—is poor stability towards O₂. Here, we demonstrate that CO₂chemisorption in γ‐cylodextrin‐based metal–organic frameworks (CD‐MOFs) occurs via HCO₃⁻formation at nucleophilic OH⁻sites within the framework pores, rather than via previously proposed pathways. The new framework KHCO₃CD‐MOF possesses rapid and high‐capacity CO₂uptake, good thermal, oxidative, and cycling stabilities, and selective CO₂capture under mixed gas conditions. Because of its low cost and performance under realistic conditions, KHCO₃CD‐MOF is a promising new platform for CCS. More broadly, our work demonstrates that the encapsulation of reactive OH⁻sites within a porous framework represents a potentially general strategy for the design of oxidation‐resistant adsorbents for CO₂capture.