Strong Visible-Light-Absorbing Cuprous Sensitizers for Dramatically Boosting Photocatalysis

Developing strong visible-light-absorbing (SVLA) earth-abundant photosensitizers (PSs) for significantly improving the utilization of solar energy is highly desirable, yet it remains a great challenge. Herein, we adopt a through-bond energy transfer (TBET) strategy by bridging boron dipyrromethene (Bodipy) and a Cu^I complex with an electronically conjugated bridge, resulting in the first SVLA Cu^I PSs ( Cu-2 and Cu-3 ). Cu-3 has an extremely high molar extinction coefficient of 162 260 m ⁻¹ cm⁻¹ at 518 nm, over 62 times higher than that of traditional Cu^I PS ( Cu-1 ). The photooxidation activity of Cu-3 is much greater than that of Cu-1 and noble-metal PSs (Ru(bpy)₃²⁺ and Ir(ppy)₃⁺) for both energy- and electron-transfer reactions. Femto- and nanosecond transient absorption and theoretical investigations demonstrate that a “ping-pong” energy-transfer process in Cu-3 involving a forward singlet TBET from Bodipy to the Cu^I complex and a backward triplet-triplet energy transfer greatly contribute to the long-lived and Bodipy-localized triplet excited state.     

Pressure-Suppressed Carrier Trapping Leads to Enhanced Emission in Two-Dimensional Perovskite (HA)2(GA)Pb2I7

A remarkable PL enhancement by 12 fold is achieved using pressure to modulate the structure of a recently developed 2D perovskite (HA)₂(GA)Pb₂I₇ (HA=n-hexylammonium, GA=guanidinium). This structure features a previously unattainable, extremely large cage. In situ structural, spectroscopic, and theoretical analyses reveal that lattice compression under a mild pressure within 1.6 GPa considerably suppresses the carrier trapping, leading to significantly enhanced emission. Further pressurization induces a non-luminescent amorphous yellow phase, which is retained and exhibits a continuously increasing band gap during decompression. When the pressure is released to 1.5 GPa, emission can be triggered by above-band gap laser irradiation, accompanied by a color change from yellow to orange. The obtained orange phase could be retained at ambient conditions and exhibits two-fold higher PL emission compared with the pristine (HA)₂(GA)Pb₂I₇.     

Machine-Driven Chemoenzymatic Synthesis of Glycopeptide

Historically, researchers have put considerable effort into developing automation systems to prepare natural biopolymers such as peptides and oligonucleotides. The availability of such mature systems has significantly advanced the development of natural science. Over the past twenty years, breakthroughs in automated synthesis of oligosaccharides have also been achieved. A machine-driven platform for glycopeptide synthesis by a reconstructed peptide synthesizer is described. The designed platform is based on the use of an amine-functionalized silica resin to facilitate the chemical synthesis of peptides in organic solvent as well as the enzymatic synthesis of glycan epitopes in the aqueous phase in a single reaction vessel. Both syntheses were performed by a peptide synthesizer in a semiautomated manner.     

Atomic-Scale Insight into Exsolution of CoFe Alloy Nanoparticles in La0.4Sr0.6Co0.2Fe0.7Mo0.1O3−δ with Efficient CO2 Electrolysis

In situ exsolution of metal nanoparticles in perovskite under reducing atmosphere is employed to generate a highly active metal–oxide interface for CO₂ electrolysis in a solid oxide electrolysis cell. Atomic-scale insight is provided into the exsolution of CoFe alloy nanoparticles in La_0.4Sr_0.6Co_0.2Fe_0.7Mo_0.1O_3−δ (LSCFM) by in situ scanning transmission electron microscopy (STEM) with energy-dispersive X-ray spectroscopy and DFT calculations. The doped Mo atoms occupy B sites of LSCFM, which increases the segregation energy of Co and Fe ions at B sites and improves the structural stability of LSCFM under a reducing atmosphere. In situ STEM measurements visualized sequential exsolution of Co and Fe ions, formation of CoFe alloy nanoparticles, and reversible exsolution and dissolution of CoFe alloy nanoparticles in LSCFM. The metal–oxide interface improves CO₂ adsorption and activation, showing a higher CO₂ electrolysis performance than the LSCFM counterparts.     

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.     

Asymmetric Coupling of Carbon-Centered Radicals Adjacent to Nitrogen: Copper-Catalyzed Cyanation and Etherification of Enamides

The first copper-catalyzed asymmetric cyanation and etherification reactions of enamides have been established, where a carbon-centered radical adjacent to a nitrogen atom (CRAN) is enantioselectively trapped by a chiral copper(II) species. Moreover, the asymmetric cyanation of vinyl esters was disclosed as well. These reactions feature very mild reaction conditions and high functional group tolerance, and give a series of chiral α-cyano amides, α-cyano esters and α-hemiaminals in good yields with excellent enantioselectivity. The chiral α-cyano amides can be easily converted into enantioenriched 1,2-diamines and amino acids.     

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.     

A Single-Atom Manipulation Approach for Synthesis of Atomically Mixed Nanoalloys as Efficient Catalysts

Synthesis of well-defined atomically mixed alloy nanoparticles on desired substrates is an ultimate goal for their practical application. Herein we report a general approach for preparing atomically mixed AuPt, AuPd, PtPd, AuPtPd NAs(nanoalloys) through single-atom level manipulation. By utilizing the ubiquitous tendency of aggregation of single atoms into nanoparticles at elevated temperatures, we have synthesized nanoalloys on a solid solvent with CeO₂ as a carrier and transition-metal single atoms as an intermediate state. The supported nanoalloys/CeO₂ with ultra-low noble metal content (containing 0.2 wt % Au and 0.2 wt % Pt) exhibit enhanced catalytic performance towards complete CO oxidation at room temperature and remarkable thermostability. This work provides a general strategy for facile and rapid synthesis of well-defined atomically mixed nanoalloys that can be applied for a range of emerging techniques.     

Rhombicuboctahedral Ag100: Four-Layered Octahedral Silver Nanocluster Adopting the Russian Nesting Doll Model

Precise atomic structure of metal nanoclusters (NCs) is fundamental for elucidating the structure–property relationships and the inherent size-evolution principles. Reported here is the largest known FCC-based (FCC=face centered cubic) silver nanocluster, [Ag₁₀₀(SC₆H₃^3,4F₂)₄₈(PPh₃)₈]⁻: the first all-octahedral symmetric nesting Ag nanocluster with a four-layered Ag₆@Ag₃₈@Ag₄₈S₂₄@Ag₈S₂₄P₈ structure, consistent symmetry elements, and a unique rhombicuboctahedral morphology distinct from theoretical predictions and previously reported FCC-based Ag clusters. DFT studies revealed extensive interlayer interactions and degenerate frontier orbitals. The FCC-based Russian nesting doll model constitutes a new platform for the study of the size-evolution principles of Ag NCs.