Cascade C-H-Activated Polyannulations toward Ring-Fused Heteroaromatic Polymers for Intracellular pH Mapping and Cancer Cell Killing.

The development of straightforward and efficient synthetic methods toward ring-fused heteroaromatic polymers with attractive functionalities has great significance in both chemistry and materials science. Herein, we develop a facile cascade C-H-activated polyannulation route that can in situ generate multiple ring-fused aza-heteroaromatic polymers from readily available monomers in an atom-economical manner. A series of complex polybenzimidazole derivatives with high absolute molecular weights of up to 24 000 are efficiently produced in high yields within 2 h. Benefiting from their unique imidazole-containing ring-fused structures with multiple aryl pendants, the obtained polymers show excellent thermal and morphological stability, good solution processability, high refractive index, small chromic dispersion, as well as remarkable acid-base-responsive fluorescence. Taking advantage of the ratiometric fluorescence response of the triphenylamine-substituted heteroaromatic polymer to pH variations, we successfully apply it as a sensitive fluorescence probe for the mapping and quantitative analysis of intracellular pH in live cells. Furthermore, through the simple N-methylation reaction of the ring-fused polybenzimidazoles, diverse azonia-containing polyelectrolytes are readily produced, which can efficiently kill cancer cells via the synergistic effects of dark toxicity and phototoxicity.

A wearable microneedle patch incorporating reversible FRET-based hydrogel sensors for continuous glucose monitoring.

Continuous glucose monitors are crucial for diabetes management, but invasive sampling, signal drift and frequent calibrations restrict their widespread usage. Microneedle sensors are emerging as a minimally-invasive platform for real-time monitoring of clinical parameters in interstitial fluid. Herein, a painless and flexible microneedle sensing patch is constructed by a mechanically-strong microneedle base and a thin layer of fluorescent hydrogel sensor for on-site, accurate, and continuous glucose monitoring. The Förster resonance energy transfer (FRET)-based hydrogel sensors are fabricated by facile photopolymerizations of acryloylated FRET pairs and glucose-specific phenylboronic acid. The optimized hydrogel sensor enables quantification of glucose with reversibility, high selectivity, and signal stability against photobleaching. Poly (ethylene glycol diacrylate)-co-polyacrylamide hydrogel is utilized as the microneedle base, facilitating effective skin piercing and biofluid extraction. The integrated microneedle sensor patch displays a sensitivity of 0.029 mM-1 in the (patho)physiological range, a low detection limit of 0.193 mM, and a response time of 7.7 min in human serum. Hypoglycemia, euglycemia and hyperglycemia are continuously monitored over 6 h simulated meal and rest activities in a porcine skin model. This microneedle sensor with high transdermal analytical performance offers a powerful tool for continuous diabetes monitoring at point-of-care settings.

Cell Cycle Control of Nanoplastics Internalization in Phytoplankton.

Nanoparticles (NPs) for delivering chemotherapeutic drugs are now in clinical trials, and cellular uptake of NPs plays an important role in determining the drug delivery efficiency. Herein, we reported that the bioaccumulation and internalization of NPs were governed by the cell cycle. Specifically, we found that the bioaccumulation of NPs was more favored in the G2/M stages, followed by the S and G0/G1 stages. We demonstrated that three key parameters-clathrin-mediated endocytosis capacity, algal cell membrane permeability, and exopolymer substance (EPS) thickness-were critical in the bioaccumulation of NPs during the cell cycling process. Over the 24-h average duration of cell cycle, clathrin-mediated endocytosis capacity was much higher at the S stage than that at the G0/G1 and G2/M stages. Besides, cell membrane permeability was measured to be higher in S and G2/M stages while the lowest in G0/G1 stage. We have also identified the change of EPS thickness during the 24-h cell cycle. Transition from G0/G1 to S and G2/M induced the attenuation in EPS thickness, and the thinnest EPS was found at the end of mitosis. The cell cycle control NPs internalization were further verified by exposing Ag nanoparticles to algae at different cell cycle stages, confirming the important roles of EPS thickness and cell cycle control in the dynamic internalization processes. The present study highlights the important roles of cell cycle controlling the NPs bioaccumulation and internalization, with possible implications in maximizing NPs internalization efficiency while reducing the cost.