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Pumping ions against a concentration gradient through protein-based transporters is a cornerstone of numerous biological processes. Mimicking this function by using artificial receptors remains a daunting challenge, mainly because of the difficulties in balancing between the requirement for high binding affinities and precise and on-demand ion capture and release properties. We report a trimeric hydrazone photoswitch-based receptor that converts light energy into work by actively transporting chloride anion against a gradient through a dichloromethane liquid membrane, functioning as a molecular pump. The system manifests ease of synthesis, bistability, excellent photoswitching properties, and superb ON-OFF binding properties (difference of up to six orders of magnitude). 

The spatiotemporal control over the structure of nanoparticles while monitoring their localization in tumor cells can improve the precision of controlled drug release, thus enhancing the efficiency of drug delivery. Here, we report on a photochromic nanoparticle system ( LSNP ), assembled from fluorescent bistable hydrazone photoswitch-modified amphiphilic copolymers. The intrinsic emission of the hydrazone switch allows for the visualization of particle uptake, as well as their intracellular distribution. The Z → E photoswitching of the hydrazone switch within the nanoparticle leads to the expansion of the nanoparticles ( i.e. , drug release) accompanied by emission quenching, the degree of which can function as an internal indicator for the amount of drug released. The bistability of the switch enables the kinetic trapping of particles of different sizes as a function of irradiation time, and allows for the exhibition of light-dependent cell cytotoxicity in MDA-MB-231 cells using LSNP loaded with doxorubicin. 

Abstract The development of large pore single‐crystalline covalently linked organic frameworks is critical in revealing the detailed structure‐property relationship with substrates. One emergent approach is to photo‐crosslink hydrogen‐bonded molecular crystals. Introducing complementary hydrogen‐bonded carboxylic acid building blocks is promising to construct large pore networks, but these molecules often form interpenetrated networks or non‐porous solids. Herein, we introduced heteromeric carboxylic acid dimers to construct a non‐interpenetrated molecular crystal. Crosslinking this crystal precursor with dithiols afforded a large pore single‐crystalline hydrogen‐bonded crosslinked organic framework H_COF‐101. X‐ray diffraction analysis revealed H_COF‐101 as an interlayer connected hexagonal network, which possesses flexible linkages and large porous channels to host a hydrazone photoswitch. Multicycle Z/E‐isomerization of the hydrazone took place reversibly within H_COF‐101, showcasing the potential use of H_COF‐101 for optical information storage.