Two-Color Spatially Resolved Tuning of Polymer-Coated Metasurfaces.

For the realization of truly reconfigurable metasurface technologies, dynamic spatial tuning of the metasurface resonance is required. Here we report the use of organic photoswitches as a means for the light-induced spatial tuning of metasurface resonances. Coating of a dielectric metasurface, hosting high-quality-factor resonances, with a spiropyran (SPA)-containing polymer enabled dynamic resonance tuning up to 4 times the resonance full-width at half-maximum with arbitrary spatial precision.

Visible light-induced switching of soft matter materials properties based on thioindigo photoswitches.

Thioindigos are visible light responsive photoswitches with excellent spatial control over the conformational change between their trans- and cis- isomers. However, they possess limited solubility in all conventional organic solvents and polymers, hindering their application in soft matter materials. Herein, we introduce a strategy for the covalent insertion of thioindigo units into polymer main chains, enabling thioindigos to function within crosslinked polymeric hydrogels.

Photochemical Action Plots Reveal the Fundamental Mismatch Between Absorptivity and Photochemical Reactivity.

Over the last years, the authors' laboratory has employed monochromatic tuneable laser systems to reveal a fundamental mismatch between the absorptivity of a chromophore and its photochemical reactivity for the vast majority of covalent bond forming reactions as well as specific bond cleavage reactions. In the general chemistry community, however, the long-held assumption pervades that effective photochemical reactions are obtained in situations where there is strong overlap between the absorption spectrum and the excitation wavelength. The current Perspective illustrates that the absorption spectrum of a molecule only provides information about electronic excitations and remains entirely silent on other energy redistribution mechanisms that follow, which critically influence photochemical reactivity.

Association between Religious Beliefs and HPV Vaccination Attitudes among College Students.

Objective And Participants: The authors sought an updated examination of attitudes toward Human Papillomavirus (HPV) catch-up vaccination among college students at a private religious university.

Methods: A total of 1557 college students completed a 62-question survey of religious and HPV vaccination attitudes during the fall of 2021. Students' willingness to receive catch-up HPV vaccination and willingness to vaccinate a future child against HPV were recorded.

A Machine-Vision Approach to Transmission Electron Microscopy Workflows, Results Analysis and Data Management.

Transmission electron microscopy (TEM) enables users to study materials at their fundamental, atomic scale. Complex experiments routinely generate thousands of images with numerous parameters that require time-consuming and complicated analysis. AXON synchronicity is a machine-vision synchronization (MVS) software solution designed to address the pain points inherent to TEM studies.

Income level and treatment selection in prostate cancer: analysis of a North Carolina population-based cohort.

Background: Disparities in treatment selection based on socioeconomic status for prostate cancer exist. However, the association between patient-level income with treatment selection priorities and treatment received has not been studied.

Methods: A population-based cohort of 1382 individuals with newly diagnosed prostate cancer was enrolled throughout North Carolina prior to treatment.

Quantifying microcracks on fractured bone surfaces - Potential use in forensic anthropology.

Bone fracture surface morphology (FSM) can provide valuable information on the cause of failure in forensic and archaeological applications and it depends primarily on three factors, the loading conditions (like strain rate), the ambient conditions (wet or dry bone material) and the quality of bone material itself. The quality of bone material evidently changes in taphonomy as a result of the decomposition process and that in turn is expected to affect FSM. Porcine bones were fractured by a standardised impact during the course of soft tissue decomposition, at 28-day intervals, over 140 days (equivalent to 638 cooling degree days).

Two Photon Induced Pulsed Laser Polymerization with Near Infrared Light.

We introduce two-photon (2P) pulsed laser polymerization (PLP) at 800 nm, demonstrating its working principle even through biological tissue. We show that 2P PLP is reliable in determining propagation rate coefficients on the example of the free radical polymerization of methyl methacrylate (MMA) at frequencies ranging from 10 to 100 Hz.

Near Infrared Light Induced Radical Polymerization in Water.

We introduce a gold nanorod (AuNR) driven methodology to induce free radical polymerization in water with near infrared light (800 nm). The process exploits photothermal conversion in AuNR and subsequent heat transfer to a radical initiator (here azobisisobutyronitrile) for primary radical generation. A broad range of reaction conditions were investigated, demonstrating control over molecular weight and reaction conversion of dimethylacrylamide polymers, using nuclear magnetic resonance spectroscopy.

Regioisomerism in Symmetric Dimethyl Dialdehydes Dictates their Photochemical Reactivity.

We herein report the first light-driven selective monoderivatization (desymmetrization) of two chemically equivalent carbonyl groups in a single chromophore. By comparing of four symmetric regioisomers, featuring two equivalent -methylbenzaldehyde units, we identify dimethyltherephtalaldehydes (DMTAs) which can be activated in a dual wavelength-selective fashion. Under visible light and UV-light irradiation, DMTAs undergo two consecutive Diels-Alder reactions exhibiting near-quantitative -selectivity (>99%) and provide excellent yields (96-98%).

Two-colour light activated covalent bond formation.

We introduce a photochemical bond forming system, where two colours of light are required to trigger covalent bond formation. Specifically, we exploit a visible light cis/trans isomerization of chlorinated azobenzene, which can only undergo reaction with a photochemically generated ketene in its cis state. Detailed photophysical mapping of the reaction efficiencies at a wide range of monochromatic wavelengths revealed the optimum irradiation conditions.

Two Sides of the Same Coin: Light as a Tool to Control and Map Microsphere Design.

Herein, we establish the effect of intensity and wavelength on the size of microparticles formed via precipitation polymerization, employing photocrosslinkable prepolymers. Simultaneous measurement of backscattered laser irradiation enabled real-time tracking of particle growth and provides the ability to vary the LED intensity (λ = 415 nm) during various stages of particle growth. Critically, particle diameters can be controlled between 200 and 700 nm by varying the LED power from 73 to 0.

An Evaluation of Docusate Monotherapy and the Prevention of Opioid-Induced Constipation after Surgery.

Our purpose was to determine if docusate monotherapy is effective in preventing opioid-induced constipation in patients receiving opioids following orthopedic surgery. Our single-center, retrospective, cohort study evaluated 212 orthopedic patients who received opioids between May 1, 2018, and December 31, 2018. All patients were aged 18 years and older, hospitalized for more than 48 hours, and received docusate for primary prevention of constipation post-operatively.

Treg tissue stability depends on lymphotoxin beta-receptor- and adenosine-receptor-driven lymphatic endothelial cell responses.

Regulatory T cell (Treg) lymphatic migration is required for resolving inflammation and prolonging allograft survival. Focusing on Treg interactions with lymphatic endothelial cells (LECs), we dissect mechanisms and functional consequences of Treg transendothelial migration (TEM). Using three genetic mouse models of pancreatic islet transplantation, we show that Treg lymphotoxin (LT) αβ and LEC LTβ receptor (LTβR) signaling are required for efficient Treg migration and suppressive function to prolong allograft survival.

Orange-Light-Induced Photochemistry Gated by pH and Confined Environments.

We introduce a new photochemically active compound, i.e., pyridinepyrene (PyPy), entailing a pH-active moiety that effects a significant halochromic shift into orange-light (λ = 590 nm) activatable photoreactivity while concomitantly exerting control over its reaction pathways.

Sequence-independent activation of photocycloadditions using two colours of light.

We exploit two reactive chromophores to establish sequence-independent photochemical activation, employing -methyl benzaldehyde (MBA) and ,-(dimethylamino)pyrene aryl tetrazole (APAT) with -(2-hydroxy)ethyl maleimide (HEM), without any additives. Critically, the order of the irradiation sequence is irrelevant, as the shorter wavelength does not activate the higher wavelength activated species. Therefore, full sequence-independent λ-orthogonality is achieved through differences in both the reaction quantum yields ( and ) and wavelength-dependent reactivity profiles of the employed chromophores.

Action Plots in Action: In-Depth Insights into Photochemical Reactivity.

Predicting wavelength-dependent photochemical reactivity is challenging. Herein, we revive the well-established tool of measuring action spectra and adapt the technique to map wavelength-resolved covalent bond formation and cleavage in what we term "photochemical action plots". Underpinned by tunable lasers, which allow excitation of molecules with near-perfect wavelength precision, the photoinduced reactivity of several reaction classes have been mapped in detail.

On the phenology of protists: recurrent patterns reveal seasonal variation of protistan (Rhizaria: Cercozoa and Endomyxa) communities in tree canopies.

Tree canopies are colonized by billions of highly specialized microorganisms that are well adapted to the highly variable microclimatic conditions, caused by diurnal fluctuations and seasonal changes. In this study, we investigated seasonality patterns of protists in the tree canopies of a temperate floodplain forest via high-throughput sequencing with group-specific primers for the phyla Cercozoa and Endomyxa. We observed consistent seasonality, and identified divergent spring and autumn taxa.

To the canopy and beyond: Air dispersal as a mechanism of ubiquitous protistan pathogen assembly in tree canopies.

Cercozoa and Oomycota contain a huge biodiversity and important pathogens of forest trees and other vegetation. We analyzed air dispersal of these protistan phyla with an air sampler near-ground (~2 m) and in tree crowns (~25 m) of three tree species (oak, linden and ash) in a temperate floodplain forest in March (before leafing) and May (after leaf unfolding) 2019 with a cultivation-independent high-throughput metabarcoding approach. We found a high diversity of Cercozoa and Oomycota in air samples with 122 and 81 OTUs, respectively.

Chemiluminescent self-reported unfolding of single-chain nanoparticles.

We demonstrate the light-induced, crosslinker mediated collapse of linear polymer chains into single-chain nanoparticles (SCNPs) capable of self-reporting their unfolding. The crosslinker entails a phenyloxalate motif allowing for the targeted degradation of the SCNPs via addition of hydrogen peroxide that triggers chemiluminescence (CL). The time-dependant CL emission can serve as a guide to follow the time dependent unfolding of the SCNPs, allowing for a qualitative assessment of the underlying mechanism.

Wavelength-Gated Photochemical Synthesis of Phenalene Diimides.

Herein, we pioneer a wavelength-gated synthesis route to phenalene diimides. Consecutive Diels-Alder reactions of methylisophthalaldehydes and maleimides afford hexahydro-phenalene-1,6-diol diimides via 5-formyl-hexahydro-benzo[f]isoindoles as the intermediate. Both photoreactions are efficient (82-99 % yield) and exhibit excellent diastereoselectivity (62-98 % d.

From Forest Soil to the Canopy: Increased Habitat Diversity Does Not Increase Species Richness of Cercozoa and Oomycota in Tree Canopies.

Tree canopies provide habitats for diverse and until now, still poorly characterized communities of microbial eukaryotes. One of the most general patterns in community ecology is the increase in species richness with increasing habitat diversity. Thus, environmental heterogeneity of tree canopies should be an important factor governing community structure and diversity in this subsystem of forest ecosystems.

Mapping Photochemical Reactivity Profiles on Surfaces.

Herein, we introduce a comprehensive methodology to map the reactivity of photochemical systems on surfaces. The reactivity of photoreactive groups in solution often departs from their corresponding solution absorption spectra. On surfaces, the relationship between the surface absorption spectra and reactivity remains unexplored.

Broad sampling of monothalamids (Rhizaria, Foraminifera) gives further insight into diversity of non-marine Foraminifera.

Non-marine foraminifera are among the least known groups of protists and only a handful of species have been described since the 19th century. We collected one naked and five morphologically almost identical organic-walled monothalamid species from freshwater and terrestrial environments from Germany and Austria. One of the species was identified as Lieberkuehnia wageneriClaparède and Lachmann, 1859.