Search for: All records

Abstract Plasmonic rulers (PRs) linking nanoscale distance dependence spectral shifts are important for studying cellular microenvironments and biomarker detection. The traditional PR design employs tethering metal nanoparticle pairs using synthetic and biopolymers that severely suffer from reproducibility issues, as well as lack reversibility. Here, the fabrication of novel PRs is reported through the formation of self‐assembled monolayers (SAMs) of photoswitchable molecular machines chemically tethered onto sharp‐tip gold nanostructures (Au NSs). This unique and highly sensitive PR utilizes localized surface plasmon resonance (LSPR) properties of Au NSs to spectroscopically evaluate dipole–dipole coupling between NSs and photoisomerizable spiropyran (SP)‐merocyanine (MC) conjugates in the solid‐state. It is observed that the SAM‐modified NSs are extremely sensitive to the photoisomerization of SP‐to‐MC, resulting in LSPR shifts as large as 5.6 nm for every 1.0 Å change in distance. The highly dipolar MC changes the NS‐SAM interfacial polarizability and alters the dipole–dipole coupling leading to the ultrasensitive PR is hypothesized. The hypothesis is supported theoretically by calculating dipole polarizability of an inorganic‐organic heterodimer model and experimentally by determining work function and interfacial dipole values. Taken together, this work represents the fabrication of next‐generation PRs, which hold great promise for advanced, plasmonic‐based sensors and optoelectronic device fabrication. 

This work presents a new granular hydrogel preparation workflow using gelatin-norbornene-carbohydrazide, a macromer amenable to three orthogonal click chemistries for microgel crosslinking, stiffening, and annealing into granular hydrogels 

Abstract The merging of photocatalysis with halogen‐atom transfer (XAT) processes has proven to be a versatile tool for the generation of carbon‐centered radicals in organic synthesis. XAT processes are unique in that they generate radicals without requiring the use of strong reductants necessary for the traditional single electron transfer (SET) activation of halides. Pathways to achieve XAT in synthetic applications can be categorized into three major sections: i) heteroatom‐based activators, ii) metal‐based activators, and iii) carbon‐based activators among which α‐aminoalkyl radicals have taken the center stage. Access to these α‐aminoalkyl radicals as XAT reagents has gained significant attention in the past few years due to the robustness of the reactions, the simplicity of the reagents required, and the broadness of their applications. Generation of these α‐aminoalkyl radicals is simply achieved through the single electron oxidation of tertiary amines, which after deprotonation at the α‐position generates the α‐aminoalkyl radicals. Due to the wide scope of tertiary amines available and the tunable nucleophilicity of α‐aminoalkyl radical formed, this strategy has become an attractive alternative to heteroatom/metal‐based radicals for XAT. In this minireview, we focus our attention on recent (2020–2023) developments and uses of this robust technology to mediate XAT processes. 

Research has shown that police officer involved shootings, misconduct and excessive use of force complaints exhibit network effects, where officers are at greater risk of being involved in these incidents when they socialize with officers who have a history of use of force and misconduct. In this work, we first construct a network survival model for the time-to-event of use of force incidents involving new police trainees. The model includes network effects of the diffusion of risk from field training officer (FTO) to trainee. We then introduce a network rewiring algorithm to maximize the expected time to use of force events upon completion of field training. We study several versions of the algorithm, including constraints that encourage demographic diversity of FTOs. Using data from Indianapolis, we show that rewiring the network can increase the expected time (in days) of a recruit's first use of force incident by 8%. We then discuss the potential benefits and challenges associated with implementing such an algorithm in practice. 

Abstract ObjectiveAn improved understanding of the role of the leptomeningeal collateral circulation in blood flow compensation following middle cerebral artery (MCA) occlusion can contribute to more effective treatment development for ischemic stroke. The present study introduces a model of the cerebral circulation to predict cerebral blood flow and tissue oxygenation following MCA occlusion. MethodsThe model incorporates flow regulation mechanisms based on changes in pressure, shear stress, and metabolic demand. Oxygen saturation in cerebral vessels and tissue is calculated using a Krogh cylinder model. The model is used to assess the effects of changes in oxygen demand and arterial pressure on cerebral blood flow and oxygenation after MCA occlusion. ResultsAn increase from five to 11 leptomeningeal collateral vessels was shown to increase the oxygen saturation in the region distal to the occlusion by nearly 100%. Post‐occlusion, the model also predicted a loss of autoregulation and a decrease in flow to the ischemic territory as oxygen demand was increased; these results were consistent with data from experiments that induced cerebral ischemia. ConclusionsThis study highlights the importance of leptomeningeal collaterals following MCA occlusion and reinforces the idea that lower oxygen demand and higher arterial pressure improve conditions of flow and oxygenation. 

Abstract Ion mobility spectrometry coupled to mass spectrometry (IMS/MS) is a widely used tool for biomolecular separations and structural elucidation. The application of IMS/MS has resulted in exciting developments in structural proteomics and genomics. This perspective gives a brief background of the field, addresses some of the important issues in making structural measurements, and introduces complementary techniques. 

Abstract To advance the MXene field, it is crucial to optimize each step of the synthesis process and create a detailed, systematic guide for synthesizing high‐quality MXene that can be consistently reproduced. In this study, a detailed guide is provided for an optimized synthesis of titanium carbide (Ti₃C₂T_x) MXene using a mixture of hydrofluoric and hydrochloric acids for the selective etching of the stoichimetric‐Ti₃AlC₂MAX phase and delamination of the etched multilayered Ti₃C₂T_xMXene using lithium chloride at 65 °C for 1 h with argon bubbling. The effect of different synthesis variables is investigated, including the stoichiometry of the mixed powders to synthesize Ti₃AlC₂, pre‐etch impurity removal conditions, selective etching, storage, and drying of MXene multilayer powder, and the subsequent delamination conditions. The synthesis yield and the MXene film electrical conductivity are used as the two parameters to evaluate the MXene quality. Also the MXenes are characterized with scanning electron microscopy, x‐ray diffraction, atomic force microscopy, and ellipsometry. The Ti₃C₂T_xfilm made via the optimized method shows electrical conductivity as high as ≈21,000 S/cm with a synthesis yield of up to 38 %. A detailed protocol is also provided for the Ti₃C₂T_xMXene synthesis as the supporting information for this study. 

Abstract PurposeThis study aims to characterize the dependence of measured retinal arterial and venous saturation on vessel diameter and central reflex in retinal oximetry, with an ultimate goal of identifying potential causes and suggesting approaches to improve measurement accuracy. MethodsIn 10 subjects, oxygen saturation, vessel diameter and optical density are obtained using Oxymap Analyzer software without diameter correction. Diameter dependence of saturation is characterized using linear regression between measured values of saturation and diameter. Occurrences of negative values of vessel optical densities (ODs) associated with central vessel reflex are acquired from Oxymap Analyzer. A conceptual model is used to calculate the ratio of optical densities (ODRs) according to retinal reflectance properties and single and double‐pass light transmission across fixed path lengths. Model‐predicted values are compared with measured oximetry values at different vessel diameters. ResultsVenous saturation shows an inverse relationship with vessel diameter (D) across subjects, with a mean slope of −0.180 (SE = 0.022) %/μm (20 < D < 180 μm) and a more rapid saturation increase at small vessel diameters reaching to over 80%. Arterial saturation yields smaller positive and negative slopes in individual subjects, with an average of −0.007 (SE = 0.021) %/μm (20 < D < 200 μm) across all subjects. Measurements where vessel brightness exceeds that of the retinal background result in negative values of optical density, causing an artifactual increase in saturation. Optimization of model reflectance values produces a good fit of the conceptual model to measured ODRs. ConclusionMeasurement artefacts in retinal oximetry are caused by strong central vessel reflections, and apparent diameter sensitivity may result from single and double‐pass transmission in vessels. Improvement in correction for vessel diameter is indicated for arteries however further study is necessary for venous corrections. 

Even when they are able to secure employment, people with cognitive disabilities typically encounter significant difficulties in the workplace. In this paper, we focus on Mixed-Ability workplaces: work settings in which people without disabilities and with different types of disabilities collaborate on a daily basis. The case study for our exploratory research is a university library that has been able to support a mixed-ability work setting for over four years. We describe how a theory from cognitive linguistics (Conceptual Metaphor Theory) can be used to explore the challenges that people encounter in mixed-ability workplaces, identify the cognitive processes that differ between neurotypical team leaders and workers with cognitive disabilities, and translate these findings into design recommendations for embodied technologies that support mixed-ability workplaces.