Near-Infrared Molecular Logic Gate for In Situ Construction and Quantification of Cell-Macromolecule Conjugates.

Engineering cell surfaces with macromolecules offers the potential to manipulate and control their phenotype and function for cell-based therapies. In situ construction and real-time evaluation of cell-macromolecule conjugates are vital for characterizing their dynamics, mobility, and function but remain a great challenge. Herein, we design a near-infrared (NIR) heptamethine cyanine (LS)-bearing dibenzocyclooctyne (DBCO) and norbornene (NB) in its structure for rapid and selective bioorthogonal "click" coupling to azide-labeled cells and tetrazine-functionalized macromolecular precursors. Specifically, only orthogonal dual "click" cell-macromolecule conjugates turn on NIR fluorescence, in which LS behaves as an AND logic gate, with azide- and tetrazine-derivatives being "input" and the emission intensity as the output. LS enables in situ construction and real-time evaluation of the process and functional effects that macromolecules "graft to" cells with high cytocompatibility. This probe is tailor-made for live-cell microscopy technologies, which may open new opportunities for promoting further developments in cell-tracking and cell-based therapies.

Intriguing H-Aggregates of Heptamethine Cyanine for Imaging-Guided Photothermal Cancer Therapy.

Organic small-molecule-based photothermal agents such as cyanine dyes have received increasing attention in developing novel cancer therapies with potential clinical utility but suffer from poor stability, low photothermal efficiency, and limited accumulation at tumor sites in molecular forms. Self-assembly of small-molecule dyes into supramolecular assemblies may address these concerns by controlling the molecular organization of dye monomers to form structures of a higher order. Among them, H-aggregates of dyes favor face-to-face contacts with strongly overlapping areas, which always have a negative connotation to exhibit low or no fluorescence in most cases but may emanate energy in nonradiative forms such as heat for photothermal cancer therapy applications. Here, the synergistic self-assembly of cyanine dyes into H-aggregates is developed as a new supramolecular strategy to fabricate small-molecule-based photothermal nanomaterials. Compared to the free cyanine dyes, the H-aggregates assembled from pyrene or tetraphenylethene (TPE) conjugating cyanine exhibit the expected absorption spectral blue shift and fluorescence self-quenching but unique photothermal properties. Remarkably, the obtained H-aggregates are saucer-shaped nanoparticles that exhibit passive tumor-targeting properties to induce imaging-guided photothermal tumor ablation under irradiation. This supramolecular strategy presented herein may open up new opportunities for constructing next-generation small-molecule-based self-assembly nanomaterials for PTT cancer therapy in clinics.

Tailor-Engineered POSS-Based Hybrid Gels for Bone Regeneration.

Organic-inorganic oligo(ethylene glycol)-polyhedral oligomeric silsesquioxanes (OEGn-POSS) hybrid materials are woven into macroscopically shaped entities by thiol-ene chemistry. The mechanical behavior and interfacial nature of the OEGn-POSS materials are easily tailored by changing the length of OEGn. The nanostructured OEGn-POSS materials exhibited excellent bioactivity to form hydroxyapatite, whose morphology was also dependent on the molecular weight of OEGn. Among them, OEG2-POSS materials enhanced the in vitro differentiation of adipose-derived stem cells to osteoblasts and promoted the in vivo bone formation within a femoral condyle defect site, but they could be limited by the mismatch rates between the degradation and new bone formation. Thus, OEG2-POSS could be practically applied for bone regeneration by optimizing the degradation rate based on its key structural features, which would be of great benefit to bone tissue engineering in the future.