In the current work, TiO 2 /Al 2 O 3 binary oxide photocatalysts were synthesized via two different sol-gel protocols (P1 and P2), where various TiO 2 to Al 2 O 3 mole ratios (0.5 and 1.0) and calcination temperatures (150-1000 • C) were utilized in the synthesis. Structural characterization of the synthesized binary oxide photocatalysts was also performed via BET surface area analysis, X-ray diffraction (XRD) and Raman spectroscopy. The photocatalytic NO(g) oxidation performances of these binary oxides were measured under UVA irradiation in a comparative fashion to that of a Degussa P25 industrial benchmark. TiO 2 /Al 2 O 3 binary oxide photocatalysts demonstrate a novel approach which is essentially a fusion of NSR (NO x storage reduction) and PCO (photocatalytic oxidation) technologies. In this approach, rather than attempting to perform complete NO x reduction, NO(g) is oxidized on a photocatalyst surface and stored in the solid state. Current results suggest that alumina domains can be utilized as active NO x capturing sites that can significantly eliminate the release of toxic NO 2 (g) into the atmosphere. Using either (P1) or (P2) protocols, structurally different binary oxide systems can be synthesized enabling much superior photocatalytic total NO x removal (i.e. up to 176% higher) than Degussa P25. Furthermore, such binary oxides can also simultaneously decrease the toxic NO 2 (g) emission to the atmosphere by 75% with respect to that of Degussa P25. There is a complex interplay between calcination temperature, crystal structure, composition and specific surface area, which dictate the ultimate photocatalytic activity in a coordinative manner. Two structurally different photocatalysts prepared via different preparation protocols reveal comparably high photocatalytic activities implying that the active sites responsible for the photocatalytic NO(g) oxidation and storage have a non-trivial nature.

A simple one-pot methodology provides easy access to amphiphilic PEG–pyrrole backbone polymers, which self-assemble into soft nanoparticles enabling efficient drug loading/sustained release and can be detected inside cells.

We describe here the development and structural characterization of a new type of mesoionic 1,3-dipole, which can be generated in the one-step reaction of imines with pyridine- or quinoline-based acid chlorides. Coupling the formation of these dipoles with alkyne cycloaddition can open a general and modular route to synthesize indolizines from combinations of available and diversifiable building blocks.

Dynamic covalent chemistryh as rapidlyb ecome an importanta pproacht oa ccess supramolecular structures. While the products generatedi nt hese reactions are heldt ogether by covalent bonds, the reversible nature of the transformations can limit the utility of many these systems in creating robust materials.W ed escribe herein am ethodt of orm stable andc ommonly employed amideb onds by exploiting the reversible coupling of imines and acyl chlorides.T he reactione mploys easilya ccessible reagents, is dynamic under ambientc onditions, without catalysts, and can be trapped with simple hydrolysis. Thiso ffers an approach to create broad families of amide products under thermodynamic control,i ncluding the selective formation of amide macrocycles or polymers.Supporting information and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

We describe here the development and structural characterization of an ew type of mesoionic 1,3-dipole,w hich can be generated in the one-step reaction of imines with pyridine-or quinoline-based acid chlorides.C oupling the formation of these dipoles with alkyne cycloaddition can open ag eneral and modular route to synthesize indolizines from combinations of available and diversifiable building blocks.

Peroxynitrite (ONOO−), a redox-active species generated under nitrosative stress conditions, can promote oxidative damage of lipids. Herein, we report the development and multifaceted utilization of a novel, activity-based phospholipid probe, PLP-ONOO–, for imaging lipid environments that are targeted by ONOO− in biomimetic and biological systems. Using PLP-ONOO– and the natural lipid 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine, we built synthetic protocell membranes in the form of giant vesicles (GVs). These GVs responded to ONOO− by lighting up and displayed excellent selectivity against other redox-active species, introducing an unprecedented function to biomimetic membrane architectures. Live HeLa cells containing PLP-ONOO– were investigated under cellular nitrosative stress induced by either external administration of peroxynitrite or endogenous stimulation with interferon-γ / lipopolysaccharide / phorbol myristate acetate. Both conditions enhanced the coumarin fluorescence within cells, providing insight into intracellular lipid environments potentially prone to peroxynitrite-mediated oxidative damage. This work offers a chemical reactivity-dependent function for synthetic vesicles and opens a possibility for investigating nitrosative stress at subcellular levels.

Laboratory models of protocells with the ability to sense and respond have the potential to serve as new-generation biosensing platforms in nanobiotechnology. While building such artificial cells often requires complex genetic engineering methods, bottom-up chemical approaches remain underdeveloped. Herein we describe the chemical construction, characterization, and utilization of biomimetic lipid vesicles capable of sensing environmental cues. These bilayer vesicles make use of phospholipid-enabled activity-based sensing to respond to either a reductive (presence of hydrogen sulfide) or an oxidative (presence of hydrogen peroxide) condition by lighting up at the membrane. Vesicle structures, 7–20 µm in diameter, remain intact throughout the process and display good-to-excellent selectivity against other redox conditions. This work opens up design opportunities for synthetic protocell architectures and enables a configurable molecular platform for engineering functional soft materials.

A new class of phosphorus-containing 1,3-dipole can be generated by the multicomponent reaction of aldehydes, acid chlorides and the phosphonite PhP(catechyl). These 1,3-dipoles are formally cyclic tautomers of simple Wittig-type...