An Endo-Selective Epoxide-Opening Cascade for the Fast Assembly of the Polycyclic Core Structure of Marine Ladder Polyethers

The rapid synthesis of marine ladder polyethers from polyepoxide precursors (in analogy with the biosynthetic pathway hypothesized by Nakanishi) is hampered by the fact that the exo-selective epoxide-opening cyclization cascade that gives THF-type polyethers is preferred over the endo-selective cascade that gives the desired products. We found that perfluoro-tert-butanol (PFTB) cooperating with 1-ethyl-3-methylimidazolium tetrafluoroborate ([EMIM]BF₄) can promote endo-selective epoxide-opening cyclization reactions of trisubstituted epoxy alcohols. Starting from readily accessible homochiral polyepoxy alcohols with a methyl group at all the endo-cyclization sites, we were able to construct polyethers up to five consecutive fused 6-, 7-, and/or 8-membered rings in one step. Notably, molecules with the 7/7/6/6 and 7/7/6/7/6 polyether frameworks of hemibrevetoxin B and brevenal, respectively, could be synthesized in 40 % and 17 % chemical yields.     

J-Aggregate-Based FRET Monitoring of Drug Release from Polymer Nanoparticles with High Drug Loading

Understanding drug-release kinetics is critical for the development of drug-loaded nanoparticles. We developed a J-aggregate-based Förster-resonance energy-transfer (FRET) method to investigate the release of novel high-drug-loading (50 wt %) nanoparticles in comparison with low-drug-loading (0.5 wt %) nanoparticles. Single-dye-loaded nanoparticles form J-aggregates because of the high dye-loading (50 wt %), resulting in a large red-shift (≈110 nm) in the fluorescence spectrum. Dual-dye-loaded nanoparticles with high dye-loading using FRET pairs exhibited not only FRET but also a J-aggregate red-shift (116 nm). Using this J-aggregate-based FRET method, dye-core–polymer-shell nanoparticles showed two release processes intracellularly: the dissolution of the dye aggregates into dye molecules and the release of the dye molecules from the polymer shell. Also, the high-dye-loading nanoparticles (50 wt %) exhibited a slow release kinetics in serum and relatively quick release in cells, demonstrating their great potential in drug delivery.     

In Situ Pyrolysis Tracking and Real-Time Phase Evolution: From a Binary Zinc Cluster to Supercapacitive Porous Carbon

The in situ tracking of the pyrolysis of a binary molecular cluster [Zn₇(μ₃-CH₃O)₆(L)₆][ZnLCl₂]₂ is presented with one brucite disk and two mononuclear fragments (L=mmimp: 2-methoxy-6-((methylimino)-methyl)phenolate) to porous carbon using TG-MS from 30 to 900 °C. Following up the spilled gas product during the decomposed reaction of zinc cluster along the temperature rising, and in conjunction with XRD, SEM, BET and other materials characterization, where three key steps were observed: 1) cleavage of the bulky external ligand; 2) reduction of ZnO and 3) volatilization of Zn. The real-time-dependent phase-sequential evolution of the remaining products and the processing of pore forming template transformation are proposed simultaneously. The porous carbon structure featuring a uniform nano-sized pore distribution synthesized at 900 °C with the highest surface area of 1644 m² g⁻¹ and pore volume of 0.926 cm³ g⁻¹ exhibits the best known capacitance of 662 F g⁻¹ at 0.5 A g⁻¹.     

Quantum Dots for Display Applications

This article offers a materials-chemistry perspective for colloidal quantum dots (QDs) in the field of display, including QD-enhanced liquid-crystal-display (QD-LCD) and QD-based light-emitting-diodes (QLEDs) display. The rapid successes of QDs for display in the past five years are not accidental but have a deep root in both maturity of their synthetic chemistry and their unique chemical, optical, and optoelectronic properties. This article intends to discuss the natural match of QD emitters for display and chemical means to eventually bring about their full potential.     

Rapid Capillary-Assisted Solution Printing of Perovskite Nanowire Arrays Enables Scalable Production of Photodetectors

Despite recent progress in producing perovskite nanowires (NWs) for optoelectronics, it remains challenging to solution-print an array of NWs with precisely controlled position and orientation. Herein, we report a robust capillary-assisted solution printing (CASP) strategy to rapidly access aligned and highly crystalline perovskite NW arrays. The key to the CASP approach lies in the integration of capillary-directed assembly through periodic nanochannels and solution printing through the programmably moving substrate to rapidly guide the deposition of perovskite NWs. The growth kinetics of perovskite NWs was closely examined by in situ optical microscopy. Intriguingly, the as-printed perovskite NWs array exhibit excellent optical and optoelectronic properties and can be conveniently implemented for the scalable fabrication of photodetectors.     

Chromophore-Assisted Proximity Labeling of DNA Reveals Chromosomal Organization in Living Cells

The spatial arrangement of chromosome within the nucleus is linked to genome function and gene expression regulation. Existing genome-wide mapping methods often rely on chemically crosslinking DNA with protein baits, which raises concerns of artifacts being introduced during cell fixation. By genetically targeting a photosensitizer protein to specific subnuclear locations, we achieved blue-light-activated labeling of local DNA with a bioorthogonal functional handle for affinity purification and sequence identification through next-generation sequencing. When applied to the nuclear lamina in human embryonic kidney 293T cells, it revealed lamina-associated domains (LADs) that cover 37.6 % of the genome. These LADs overlap with heterochromatin hallmarks and are depleted with CpG islands. This simple labeling method avoids the harsh treatment of chemical crosslinking and is generally applicable to the genome-wide high-resolution mapping of the spatial chromosome organization in living cells.     

Chemically Programmable and Switchable CAR-T Therapy

Although macromolecules on cell surfaces are predominantly targeted and drugged with antibodies, they harbor pockets that are only accessible to small molecules and constitutes a rich subset of binding sites with immense potential diagnostic and therapeutic utility. Compared to antibodies, however, small molecules are disadvantaged by a less confined biodistribution, shorter circulatory half-life, and inability to communicate with the immune system. Presented herein is a method that endows small molecules with the ability to recruit and activate chimeric antigen receptor T cells (CAR-Ts). It is based on a CAR-T platform that uses a chemically programmed antibody fragment (cp-Fab) as on/off switch. In proof-of-concept studies, this cp-Fab/CAR-T system targeting folate binding proteins on the cell surface mediated potent and specific eradication of folate-receptor-expressing cancer cells in vitro and in vivo.     

A General Strategy for Hollow Metal-Phytate Coordination Complex Micropolyhedra Enabled by Cation Exchange

The ability to incorporate functional metal ions (Mⁿ⁺) into metal–organic coordination complexes adds remarkable flexibility in the synthesis of multifunctional organic–inorganic hybrid materials with tailorable electronic, optical, and magnetic properties. We report the cation-exchanged synthesis of a diverse range of hollow Mⁿ⁺-phytate (PA) micropolyhedra via the use of hollow Co²⁺-PA polyhedral networks as templates at room temperature. The attributes of the incoming Mⁿ⁺, namely Lewis acidity and ionic radius, control the exchange of the parent Co²⁺ ions and the degree of morphological deformation of the resulting hollow micropolyhedra. New functions can be obtained for both completely and partially exchanged products, as supported by the observation of Ln³⁺ (Ln³⁺=Tb³⁺, Eu³⁺, and Sm³⁺) luminescence from as-prepared hollow Ln³⁺-PA micropolyhedra after surface modification with dipicolinic acid as an antenna. Moreover, Fe³⁺- and Mn²⁺-PA polyhedral complexes were employed as magnetic contrast agents.     

N−H Bond Formation at a Diiron Bridging Nitride

Despite their connection to ammonia synthesis, little is known about the ability of iron-bound, bridging nitrides to form N−H bonds. Herein we report a linear diiron bridging nitride complex supported by a redox-active macrocycle. The unique ability of the ligand scaffold to adapt to the geometric preference of the bridging species was found to facilitate the formation of N−H bonds via proton-coupled electron transfer to generate a μ-amide product. The structurally analogous μ-silyl- and μ-borylamide complexes were shown to form from the net insertion of the nitride into the E−H bonds (E=B, Si). Protonation of the parent bridging amide produced ammonia in high yield, and treatment of the nitride with PhSH was found to liberate NH₃ in high yield through a reaction that engages the redox-activity of the ligand during PCET.     

Cationic Lipid-based Intracellular Delivery of Bacterial Effectors for Rewiring Malignant Cell Signaling

The abundance of bacterial effectors have inspired us to explore their potential in rewiring malignant cell signaling. Their incapability for entering cells, however, hinders such application. Herein we developed a cationic lipid-based high throughput library screening platform for effective intracellular delivery of bacterial effectors. As the misregulated MAPK signaling is a hallmark of many types of cancer, we turned to the Shigella effector OspF which irreversibly inactivates ERK, the terminal component of MAPK cascade. We created a function-based screening assay to obtain AMPA-O16B lipid nanoparticles for effective OspF intracellular delivery, which inhibited the malignant MAPK signaling and tumor growth in vitro and in vivo. Furthermore, the optimized lipid nanoparticle formulation can deliver OspF to modulate the immunosuppressive responses in macrophages. Our work is a general strategy to explore the therapeutic potentials of naturally evolved bacterial effectors.