Electrostatic Force-Enabled Microneedle Patches that Exploit Photoredox Catalysis for Transdermal Phototherapy.

Microneedle patches for topical administration of photodynamic therapy (PDT) sensitizers are attractive owing to their safety, selectivity, and noninvasiveness. However, low-efficiency photosensitizer delivery coupled with the limitations of the hypoxic tumor microenvironment remains challenging. To overcome these issues, we developed an effective microneedle patch based on intermolecular electrostatic interactions within a photosensitizer matrix containing a zinc-containing porphyrin analogue, .

Internally diketopyrrolopyrrole-bridged bis-anthracene macrocycle: a multifunctional fluorescent platform.

A covalently bridged macrocycle (5) comprising two anthracene strands connected at the lactam positions of a diketopyrrolopyrrole (DPP) chromophore has been constructed. The crystal structure reveals that the central DPP chromophore is wrapped with the externally twisted bis-anthracene macrocycle. The internally bridged macrocycle architecture endows 5 with multifunctional properties.

Correction: Ion pair extractant selective for LiCl and LiBr.

[This corrects the article DOI: 10.1039/D4SC03760J.].

Superresolution imaging of antibiotic-induced structural disruption of bacteria enabled by photochromic glycomicelles.

Bacterial evolution, particularly in hospital settings, is leading to an increase in multidrug resistance. Understanding the basis for this resistance is critical as it can drive discovery of new antibiotics while allowing the clinical use of known antibiotics to be optimized. Here, we report a photoactive chemical probe for superresolution microscopy that allows for the in situ probing of antibiotic-induced structural disruption of bacteria.

Diphenylacetylene-Incorporating Octaphyrin: A Rigid Macrocycle with Readily Separable Conformational Isomers.

An expanded carbaporphyrinoid analogue, octaphyrin(2,1,1,1,2,1,1,1), containing two rigid diphenylacetylene moieties is reported. In contrast to traditional pyrrolic macrocycles where flexible conformers coexist in dynamic equilibrium, this macrocycle exists as two separable, conformationally stable stereoisomers, denoted as 1A and 1B. The conformational effect of both conformers, as well as their protonated forms, were thoroughly studied using NMR spectroscopy, UV/Vis, and single crystal X-ray diffraction analyses.

Thermally Driven Catch-and-Release of CoCl.

A heat-driven catch-and-release strategy for CoCl capture is described. It is based on the use of an immobilized neutral dicyclohexylacetamide-based receptor supported on polystyrene (PS-). An X-ray diffraction analysis of a single crystal of ·CoCl revealed an ion-pair complex comprising a hexacoordinated cobalt cation [·Co] and a tetrachlorocobaltate anion [CoCl].

Lutetium Texaphyrin-Celecoxib Conjugate as a Potential Immuno-Photodynamic Therapy Agent.

Immuno-photodynamic therapy (IPDT) has emerged as a new modality for cancer treatment. Novel photosensitizers can help achieve the promise inherent in IPDT, namely, the complete eradication of a tumor without recurrence. We report here a small molecule photosensitizer conjugate, LuCXB.

Chemically Mediated Artificial Electron Transport Chain.

Electron transport chains (ETCs) are ubiquitous in nearly all living systems. Replicating the complexity and control inherent in these multicomponent systems using ensembles of small molecules opens up promising avenues for molecular therapeutics, catalyst design, and the development of innovative energy conversion and storage systems. Here, we present a noncovalent, multistep artificial electron transport chains comprising cyclo[8]pyrrole (), a -aryl hexaphyrin(1.

1,3,5-2,4,6-Functionalized Benzene Molecular Cage: An Environmentally Responsive Scaffold that Supports Hierarchical Superstructures.

New stimulus-responsive scaffolds are of interest as constituents of hierarchical supramolecular ensembles. 1,3,5-2,4,6-Functionalized, facially segregated benzene moieties have a time-honored role as building blocks for host molecules. However, their user as switchable motifs in the construction of multi-component supramolecular structures remains poorly explored.

Cu(II) complex that synergistically potentiates cytotoxicity and an antitumor immune response by targeting cellular redox homeostasis.

Developing anticancer drugs with low side effects is an ongoing challenge. Immunogenic cell death (ICD) has received extensive attention as a potential synergistic modality for cancer immunotherapy. However, only a limited set of drugs or treatment modalities can trigger an ICD response and none of them have cytotoxic selectivity.

Photochemical and biological dual-effects enhance the inhibition of photosensitizers for tumour growth.

Photosensitizers typically rely on a singular photochemical reaction to generate reactive oxygen species, which can then inhibit or eradicate lesions. However, photosensitizers often exhibit limited therapeutic efficiency due to their reliance on a single photochemical effect. Herein, we propose a new strategy that integrates the photochemical effect (type-I photochemical effect) with a biological effect (proton sponge effect).

Three-Dimensional Crystalline Organic Framework Stabilized by Molecular Mortise-and-Tenon Jointing.

Three-dimensional (3D) crystalline organic frameworks with complex topologies, high surface area, and low densities afford a variety of application prospects. However, the design and construction of these frameworks have been largely limited to systems containing polyhedron-shaped building blocks or those relying on component interpenetration. Here, we report the synthesis of a 3D crystalline organic framework based on molecular mortise-and-tenon jointing.

A Janus carbaporphyrin pseudo-dimer.

Carbaporphyrin dimers, investigated for their distinctive electronic structures and exceptional properties, have predominantly consisted of systems containing identical subunits. This study addresses the associated knowledge gap by focusing on asymmetric carbaporphyrin dimers with Janus-like characteristics. The synthesis of a Janus-type carbaporphyrin pseudo-dimer 5 is presented.

Columnar liquid crystals based on antiaromatic expanded porphyrins.

Three naphthorosarins, antiaromatic expanded porphyrins bearing different substituents (NRos 1-3), designed to self-assemble into columnar liquid crystalline (LC) structures, were synthesized and characterized using polarized optical microscopy (POM), differential scanning calorimetry (DSC), X-ray diffraction (XRD), as well as supporting computational calculations. The substituents were found to play a crucial role in modulating the LC behaviour.

Theranostic Fluorescent Probes.

The ability to gain spatiotemporal information, and in some cases achieve spatiotemporal control, in the context of drug delivery makes theranostic fluorescent probes an attractive and intensely investigated research topic. This interest is reflected in the steep rise in publications on the topic that have appeared over the past decade. Theranostic fluorescent probes, in their various incarnations, generally comprise a fluorophore linked to a masked drug, in which the drug is released as the result of certain stimuli, with both intrinsic and extrinsic stimuli being reported.

Fluorinated Nonporous Adaptive Cages for the Efficient Removal of Perfluorooctanoic Acid from Aqueous Source Phases.

Per- and polyfluoroalkyl substances (PFAS) accumulate in water resources and pose serious environmental and health threats due to their nonbiodegradable nature and long environmental persistence times. Strategies for the efficient removal of PFAS from contaminated water are needed to address this concern. Here, we report a fluorinated nonporous adaptive crystalline cage () that exploits electrostatic interaction, hydrogen bonding, and F-F interactions to achieve the efficient removal of perfluorooctanoic acid (PFOA) from aqueous source phases.

Lutetium texaphyrin: A photocatalyst that triggers pyroptosis via biomolecular photoredox catalysis.

Photon-controlled pyroptosis activation (PhotoPyro) is a promising technique for cancer immunotherapy due to its noninvasive nature, precise control, and ease of operation. Here, we report that biomolecular photoredox catalysis in cells might be an important mechanism underlying PhotoPyro. Our findings reveal that the photocatalyst lutetium texaphyrin () facilitates rapid and direct photoredox oxidation of nicotinamide adenine dinucleotide, nicotinamide adenine dinucleotide phosphate, and various amino acids, thereby triggering pyroptosis through the caspase 3/GSDME pathway.

Targeted Cyclo[8]pyrrole-Based NIR-II Photoacoustic Tomography Probe for Suppression of Orthotopic Pancreatic Tumor Growth and Intra-abdominal Metastases.

Pancreatic cancer is highly lethal. New diagnostic and treatment modalities are desperately needed. We report here that an expanded porphyrin, cyclo[8]pyrrole (CP), with a high extinction coefficient (89.

Cyclo[2]pyridine[8]pyrrole: An Expanded Porphyrinoid with Three Closed-Shell Oxidation States.

We report here an expanded porphyrinoid, cyclo[2]pyridine[8]pyrrole, , that can exist at three closed-shell oxidation levels. Macrocycle was synthesized via the oxidative coupling of two open chain precursors and fully characterized by means of NMR and UV-vis spectroscopies, MS, and X-ray crystallography. Reduction of the fully oxidized form (, blue) with NaBH produced either the half-oxidized (, teal) or fully reduced forms (, pale yellow), depending on the amount of reducing agent used and the presence or absence of air.

3D-Printed Porous Supramolecular Sorbents for Cobalt Recycling.

Electronic waste recycling is a recognized global challenge that requires new strategies to bind and release critical materials selectively, such as cobalt present in lithium-ion batteries. To address this challenge, hierarchical 3D-printed porous polymer scaffolds bearing supramolecular receptors were prepared using vat photopolymerization and their cobalt binding profiles were examined as a function of matrix polarity. By combining high-resolution digital light processing (DLP) with polymerization-induced phase separation (PIPS), functional acrylic copolymer networks with micrometer-level precision of geometry and nanometer-level pores were generated.

High-nuclearity Luminescent Lanthanide Nanocages for Tumor Drug Delivery.

There is an unmet need for easy-to-visualize drug carriers that can deliver therapeutic cargoes deep into solid tumors. Herein, we report the preparation of ultrasmall luminescent imine-based lanthanide nanocages, Eu and Tb (collectively Ln ), designed to encapsulate anticancer chemotherapeutics for tumor therapy. The as-prepared nanocages possess large cavities suitable for the encapsulation of doxorubicin (DOX), yielding DOX@Ln nanocages with diameters around 5 nm.