Regulating HS release from self-assembled peptide HS-donor conjugates using cysteine derivatives.

Self-assembled peptides provide a modular and diverse platform for drug delivery, and innovative delivery methods are needed for delivery of hydrogen sulfide (HS), an endogenous signaling molecule (gasotransmitter) with significant therapeutic potential. Of the available types of HS donors, peptide/protein HS donor conjugates (PHDCs) offer significant versatility. Here we discuss the design, synthesis, and in-depth study of a PHDC containing three covalently linked components: a thiol-triggered HS donor based on an -aroylthiooxime (SATO), a GFFF tetrapeptide, and a tetraethylene glycol (TEG) dendron.

Stimuli-Responsive Polymers at the Interface with Biology.

There has been growing interest in polymeric systems that break down or undergo property changes in response to stimuli. Such polymers can play important roles in biological systems, where they can be used to control the release of therapeutics, modulate imaging signals, actuate movement, or direct the growth of cells. In this Perspective, after discussing the most important stimuli relevant to biological applications, we will present a selection of recent exciting developments.

NO- and HS- releasing nanomaterials: A crosstalk signaling pathway in cancer.

The gasotransmitters nitric oxide (NO) and hydrogen sulfide (HS) play important roles not only in maintaining physiological functions, but also in pathological conditions and events. Importantly, these molecules show a complex interplay in cancer biology, demonstrating both tumor-promoting and anti-tumor activities depending on their concentration, flux, and the environmental redox state. Additionally, various cell types respond differently to NO and HS.

Polymer Characterization by Size-Exclusion Chromatography with Multi-Angle Light Scattering (SEC-MALS): A Tutorial Review.

This tutorial review presents the theory and application of SEC-MALS with minimal equations and a focus on synthetic polymer characterization, serving as an entry point for polymer scientists who want to learn more about SEC-MALS. We discuss the principles of static light scattering, outline its capability to generate absolute weight-average molar mass values, and extend its application to SEC-MALS. Practical elements are emphasized, enabling researchers to appreciate how values for , and are determined in an SEC-MALS experiment and how experimental conditions and input values, such as the specific refractive index increment ( ), influence the results.

Synthesis and real-time characterization of self-healing, injectable, fast-gelling hydrogels based on alginate multi-reducing end polysaccharides (MREPs).

Polysaccharide-based hydrogels are promising for many biomedical applications including drug delivery, wound healing, and tissue engineering. We illustrate herein self-healing, injectable, fast-gelling hydrogels prepared from multi-reducing end polysaccharides, recently introduced by the Edgar group. Simple condensation of reducing ends from multi-reducing end alginate (M-Alg) with amines from polyethylene imine (PEI) in water affords a dynamic, hydrophilic polysaccharide network.

Observation of naturally canalized phonon polaritons in LiVO thin layers.

Polariton canalization is characterized by intrinsic collimation of energy flow along a single crystalline axis. This optical phenomenon has been experimentally demonstrated at the nanoscale by stacking and twisting van der Waals (vdW) layers of α-MoO, by combining α-MoO and graphene, or by fabricating an h-BN metasurface. However, these material platforms have significant drawbacks, such as complex fabrication and high optical losses in the case of metasurfaces.

Design, Synthesis, and Antifungal Activity of 3-Substituted-2()-Oxaboroles.

Next generation antimicrobial therapeutics are desperately needed as new pathogens with multiple resistance mechanisms continually emerge. Two oxaboroles, tavaborole and crisaborole, were recently approved as topical treatments for onychomycosis and atopic dermatitis, respectively, warranting further studies into this privileged structural class. Herein, we report the antimicrobial properties of 3-substituted-2()-oxaboroles, an unstudied family of medicinally relevant oxaboroles.

In Vitro and In Vivo Testing of Microbe Growth on Antimicrobial Nursing Scrubs.

Around 5% to 10% of hospitalized patients develop a hospital-acquired infection (HAI). Scrubs are a potential vector of HAIs. To compare the antimicrobial characteristics of scrubs with and without an antimicrobial fabric coating, as tested in the laboratory (in vitro) and hospital (in vivo) environments.

Using Redox-Switchable Polymerization Catalysis to Synthesize a Chemically Recyclable Thermoplastic Elastomer.

In an effort to synthesize chemically recyclable thermoplastic elastomers, a redox-switchable catalytic system was developed to synthesize triblock copolymers containing stiff poly(lactic acid) (PLA) end blocks and a flexible poly(tetrahydrofuran-co-cyclohexene oxide) (poly(THF-co-CHO) copolymer as the mid-block. The orthogonal reactivity induced by changing the oxidation state of the iron-based catalyst enabled the synthesis of the triblock copolymers in a single reaction flask from a mixture of monomers. The triblock copolymers demonstrated improved flexibility compared to poly(l-lactic acid) (PLLA) and thermomechanical properties that resemble thermoplastic elastomers, including a rubbery plateau in the range of -60 to 40 °C.

Polariton design and modulation via van der Waals/doped semiconductor heterostructures.

Hyperbolic phonon polaritons (HPhPs) can be supported in materials where the real parts of their permittivities along different directions are opposite in sign. HPhPs offer confinements of long-wavelength light to deeply subdiffractional scales, while the evanescent field allows for interactions with substrates, enabling the tuning of HPhPs by altering the underlying materials. Yet, conventionally used noble metal and dielectric substrates restrict the tunability of this approach.

The Role of Optical Phonon Confinement in the Infrared Dielectric Response of III-V Superlattices.

Polar dielectrics are key materials of interest for infrared (IR) nanophotonic applications due to their ability to host phonon-polaritons that allow for low-loss, subdiffractional control of light. The properties of phonon-polaritons are limited by the characteristics of optical phonons, which are nominally fixed for most "bulk" materials. Superlattices composed of alternating atomically thin materials offer control over crystal anisotropy through changes in composition, optical phonon confinement, and the emergence of new modes.

Case Bias Case Basis: Expanding Morbidity and Mortality Conference to Examine the Impact of Disparities in Surgical Care.

Introduction: Originally designed as a forum to discuss adverse patient events, Surgery Morbidity & Mortality Conference (M&M) has evolved into an integral tool within surgical education where trainees at all levels are taught to critically examine decision-making. Others have expanded the scope of subsets of M&M conferences to include additional factors that influence patient outcomes, such as social determinants of health, implicit bias and structural policies that contribute to health disparities. In this study, we implemented a disparities-based discussion into our surgical department's weekly M&M conference and examined the effect(s) on participants' understanding and perceptions of key disparities in access to surgical care.

Endothelial deletion of EPH receptor A4 alters single-cell profile and Tie2/Akap12 signaling to preserve blood-brain barrier integrity.

Neurobiological consequences of traumatic brain injury (TBI) result from a complex interplay of secondary injury responses and sequela that mediates chronic disability. Endothelial cells are important regulators of the cerebrovascular response to TBI. Our work demonstrates that genetic deletion of endothelial cell (EC)-specific EPH receptor A4 (EphA4) using conditional and knockout (KO) mice promotes blood-brain barrier (BBB) integrity and tissue protection, which correlates with improved motor function and cerebral blood flow recovery following controlled cortical impact (CCI) injury.

Development and delivery of a higher diploma in emergency medicine and critical care for clinical officers in Kenya.

The provision of emergency medicine and critical care in a cost-efficient manner has the potential to address many preventable deaths in low- and middle-income countries. Here, utilising Kern's framework for curriculum development, we describe the origins, development and implementation of the Emergency Medicine and Critical Care Clinical Officer training program; Kenya's first training programme for clinical officers in emergency medicine and critical care. Graduates are scattered across the country in diverse settings, ranging from national referral hospitals in the capital, Nairobi, to rural hospitals in northern Kenya.

Activating hidden signals by mimicking cryptic sites in a synthetic extracellular matrix.

Cryptic sites are short signaling peptides buried within the native extracellular matrix (ECM). Enzymatic cleavage of an ECM protein reveals these hidden peptide sequences, which interact with surface receptors to control cell behavior. Materials that mimic this dynamic interplay between cells and their surroundings via cryptic sites could enable application of this endogenous signaling phenomenon in synthetic ECM hydrogels.

Hydrogels for Gasotransmitter Delivery: Nitric Oxide, Carbon Monoxide, and Hydrogen Sulfide.

Gasotransmitters, gaseous signaling molecules including nitric oxide (NO), carbon monoxide (CO), and hydrogen sulfide (H S), maintain myriad physiological processes. Low levels of gasotransmitters are often associated with specific problems or diseases, so NO, CO, and H S hold potential in treating bacterial infections, chronic wounds, myocardial infarction, ischemia, and various other diseases. However, their clinical applications as therapeutic agents are limited due to their gaseous nature, short half-life, and broad physiological roles.

Supramolecular Peptide Nanostructures Regulate Catalytic Efficiency and Selectivity.

We report three constitutionally isomeric tetrapeptides, each comprising one glutamic acid (E) residue, one histidine (H) residue, and two lysine (K ) residues functionalized with side-chain hydrophobic S-aroylthiooxime (SATO) groups. Depending on the order of amino acids, these amphiphilic peptides self-assembled in aqueous solution into different nanostructures:nanoribbons, a mixture of nanotoroids and nanoribbons, or nanocoils. Each nanostructure catalyzed hydrolysis of a model substrate, with the nanocoils exhibiting the greatest rate enhancement and the highest enzymatic efficiency.

Tailored thermal emission in bulk calcite through optic axis reorientation.

The polar nature of calcite results in lattice vibrations that can be stimulated through gratings and nanostructures to design spatially and spectrally coherent thermal radiation patterns. In order to obtain optimal design control over such patterned materials, it is first necessary to understand the fundamental emissivity properties of the lattice vibrations themselves. Because calcite is a uniaxial material, when the optic axis (OA) is tilted with respect to the crystal surface, the surface wave solutions to Maxwell's equations and vibrational modes that are permitted will change due to the crystal's structural anisotropy.