Solvent‐Free Self‐Assembly for Scalable Preparation of Highly Crystalline Mesoporous Metal Oxides

Mesoporous metal oxides (MMOs) have been demonstrated great potential in various applications. Up to now, the direct synthesis of MMOs is still limited to the solvent induced inorganic‐organic self‐assembly process. Here, we develop a facile, general, and high throughput solvent‐free self‐assembly strategy to synthesize a series of MMOs including single‐component MMOs and multi‐component MMOs (e.g., doped MMOs, composite MMOs, and polymetallic oxide) with high crystallinity and remarkable porous properties by grinding and heating raw materials. Compared with the traditional solution self‐assembly process, the avoidance of solvents in this method not only greatly increases the yield of target products and synthesis efficiency, but also reduces the environmental pollution and the consumption of cost and energy. We believe the presented approach will pave a new avenue for scalable production of advanced mesoporous materials for various applications.     

Systematic Research and Evaluation Models of Nanomotors for Cancer Combined Therapy

Limited tumor permeability of therapeutic agents is a great challenge faced by current cancer therapy methods. Herein, a kind of near infrared light (NIR)‐driven nanomotor with autonomous movement, targeted ability, hierarchical porous structure, multi‐drugs for cancer chemo/photothermal therapy is designed, prepared and characterized. Further, we establish a method to study the interaction between nanomotors and cells, along with their tumor permeability mechanism, including 2D cellular models, 3D multicellular tumor spheroids and in vivo models. In vivo tumor elimination results verify that the movement behaviour of the nanomotors can greatly facilitate them to eliminate tumor through multiple therapeutic methods. This work tries to establish systematic research and evaluation models, providing strategies to understand the relationship between motion behaviour and tumor permeation efficiency of nanomotors in depth.     

Preparative isolation of arylbutanoid‐type phenol [(‐)‐rhododendrin] with peak tailing on conventional C18 column using middle chromatogram isolated gel column coupled with reversed‐phase liquid chromatography

Reversed‐phase liquid chromatography coupled with middle chromatogram isolated gel column was employed for the efficient preparative separation of the arylbutanoid‐type phenol [(‐)‐rhododendrin] from Saxifraga tangutica. Universal C18 (XTerra C18) and XCharge C18 columns were compared for (‐)‐rhododendrin fraction analysis and preparation. Although tailing and overloading occurred on the XTerra C18 column, the positively charged reversed‐phase C18 column (XCharge C18) overcame these drawbacks, allowing for favorable separation resolution, even when loading at a on a preparative scale (3.69 mg per injection). The general separation process was as follows. First, 365.0 mg of crude (‐)‐rhododendrin was enriched from 165 g Saxifraga tangutica extract via a middle chromatogram isolated gel column. Second, separation was performed on an XTerra C18 preparative column, from which 73.8 mg of the target fraction was easily obtained. Finally, the 24.0 mg tailing peak of (‐)‐rhododendrin on XTerra C18 column was selectively purified on the XCharge C18 analytical column. These results demonstrate that the tailing nonalkaloid peaks can be effectively used for preparative isolation on XCharge C18 columns.     

Dual‐Mode Antibacterial Conjugated Polymer Nanoparticles for Photothermal and Photodynamic Therapy

In this work, dual‐mode antibacterial conjugated polymer nanoparticles (DMCPNs) combined with photothermal therapy (PTT) and photodynamic therapy (PDT) are designed and explored for efficient killing of ampicillin‐resistant Escherichia coli (Amp^r E. coli). The DMCPNs are self‐assembled into nanoparticles with a size of 50.4 ± 0.6 nm by co‐precipitation method using the photothermal agent poly(diketopyrrolopyrrole‐thienothiophene) (PDPPTT) and the photosensitizer poly[2‐methoxy‐5‐((2‐ethylhexyl)oxy)‐p‐phenylenevinylene] (MEH‐PPV) in the presence of poly(styrene‐co‐maleic anhydride) which makes nanoparticles disperse well in water via hydrophobic interactions. Thus, DMCPNs simultaneously possess photothermal effect and the ability of sensitizing oxygen in the surrounding to generate reactive oxygen species upon the illumination of light, which could easily damage resistant bacteria. Under combined irradiation of near‐infrared light (550 mW cm^?2, 5 min) and white light (65 mW cm^?2, 5 min), DMCPNs with a concentration of 9.6 × 10^?4 µm could reach a 93% inhibition rate against Amp^r E. coli, which is higher than the efficiency treated by PTT or PDT alone. The dual‐mode nanoparticles provide potential for treating pathogenic infections induced by resistant microorganisms in clinic.     

Divergent Synthesis of Monosubstituted and Unsymmetrical 3,6‐Disubstituted Tetrazines from Carboxylic Ester Precursors

Since tetrazines are important tools to the field of bioorthogonal chemistry, there is a need for new approaches to synthesize unsymmetrical and 3‐monosubstituted tetrazines. Described here is a general, one‐pot method for converting (3‐methyloxetan‐3‐yl)methyl carboxylic esters into 3‐thiomethyltetrazines. These versatile intermediates were applied to the synthesis of unsymmetrical tetrazines through Pd‐catalyzed cross‐coupling and in the first catalytic thioether reduction to access monosubstituted tetrazines. This method enables the development of new tetrazine compounds possessing a favorable combination of kinetics, small size, and hydrophilicity. It was applied to a broad range of aliphatic and aromatic ester precursors and to the synthesis of heterocycles including BODIPY fluorophores and biotin. In addition, a series of tetrazine probes for monoacylglycerol lipase (MAGL) were synthesized and the most reactive one was applied to the labeling of endogenous MAGL in live cells.     

Ordered Solid‐State Microstructures of Conjugated Polymers Arising from Solution‐State Aggregation

Controlling the solution‐state aggregation of conjugated polymers for producing specific microstructures remains challenging. Herein, a practical approach is developed to finely tune the solid‐state microstructures through temperature‐controlled solution‐state aggregation and polymer crystallization. High temperature generates significant conformation fluctuation of conjugated backbones in solution, which facilitates the polymer crystallization from solvated aggregates to orderly packed structures. The polymer films deposited at high temperatures exhibit less structural disorders and higher electron mobilities (up to two orders of magnitude) in field‐effect transistors, compared to those deposited at low temperatures. This work provides an effective strategy to tune the solution‐state aggregation to reveal the relationship between solution‐state aggregation and solid‐state microstructures of conjugated polymers.     

Three‐Dimensional Cuprous Lead Bromide Framework with Highly Efficient and Stable Blue Photoluminescence Emission

Considering the instability and low photoluminescence quantum yield (PLQY) of blue‐emitting perovskites, it is still challenging and attractive to construct single crystalline hybrid lead halides with highly stable and efficient blue light emission. Herein, by rationally introducing d¹⁰ transition metal into single lead halide as new structural building unit and optical emitting center, we prepared a bimetallic halide of [(NH₄)₂]CuPbBr₅ with new type of three‐dimensional (3D) anionic framework. [(NH₄)₂]CuPbBr₅ exhibits strong band‐edge blue emission (441 nm) with a high PLQY of 32 % upon excitation with UV light. Detailed photophysical studies indicate [(NH₄)₂]CuPbBr₅ also displays broadband red light emissions derived from self‐trapped states. Furthermore, the 3D framework features high structural and optical stabilities at extreme environments during at least three years. To our best knowledge, this work represents the first 3D non‐perovskite bimetallic halide with highly efficient and stable blue light emission.     

Non‐Lithography Hydrodynamic Printing of Micro/Nanostructures on Curved Surfaces

A key issue of micro/nano devices is how to integrate micro/nanostructures with specified chemical components onto various curved surfaces. Hydrodynamic printing of micro/nanostructures on three‐dimensional curved surfaces is achieved with a strategy that combines template‐induced hydrodynamic printing and self‐assembly of nanoparticles (NPs). Non‐lithography flexible wall‐shaped templates are replicated with microscale features by dicing a trench‐shaped silicon wafer. Arising from the capillary pumped function between the template and curved substrates, NPs in the colloidal suspension self‐assemble into close‐packed micro/nanostructures without a gravity effect. Theoretical analysis with the lattice Boltzmann model reveals the fundamental principles of the hydrodynamic assembly process. Spiral linear structures achieved by two kinds of fluorescent NPs show non‐interfering photoluminescence properties, while the waveguide and photoluminescence are confirmed in 3D curved space. The printed multiconstituent micro/nanostructures with single‐NP resolution may serve as a general platform for optoelectronics beyond flat surfaces.     

Multimode Self‐Oscillating Vesicle Transformers

Engineering synthetic materials that mimic the complex rhythmic oscillatory behavior of living cells is a fundamental challenge in science and technology. Up to now, the reported synthetic model system still cannot compete with nature in oscillatory modes and amplitudes. Presented here is a novel alternating copolymer vesicle that exhibits drastic and multimode shape oscillations in real time, which are controlled by polymer concentrations and driven by the Belousov—Zhabotinsky oscillatory reaction, including swelling/deswelling, twisting/detwisting, stretching/shrinking, fusion/fission, and multiple division. Some of them, especially the fission oscillation, have not been observed before. In addition, the oscillation magnitude with regard to diameter is much larger than that of previously reported self‐oscillating vesicles. Such a self‐oscillating vesicle transformer would extend the complexity and capacity of membrane deformations in synthetic systems, approaching those of natural cells.