Exploring the Condensation Reaction between Aromatic Nitriles and Amino Thiols To Optimize In Situ Nanoparticle Formation for the Imaging of Proteases and Glycosidases in Cells

The condensation reaction between 6-hydroxy-2-cyanobenzothiazole (CBT) and cysteine has been shown for various applications such as site-specific protein labelling and in vivo cancer imaging. This report further expands the substrate scope of this reaction by varying the substituents on aromatic nitriles and amino thiols and testing their reactivity and ability to form nanoparticles for cell imaging. The structure–activity relationship study leads to the identification of the minimum structural requirement for the macrocyclization and assembly process in forming nanoparticles. One of the scaffolds made of 2-pyrimidinecarbonitrile and cysteine joined by a benzyl linker was applied to design fluorescent probes for imaging caspase-3/7 and β-galactosidase activity in live cells. These results demonstrate the generality of this system for imaging hydrolytic enzymes.     

Sequence-Dependent DNA Functionalization of Upconversion Nanoparticles and Their Programmable Assemblies

DNA-modified lanthanide-doped upconversion nanoparticles (DNA-UCNPs) that combine the functions of DNA and the optical features of UCNPs have shown great promise in a wide range of fields. However, challenges remain in precisely tethering and orienting the DNA strands on the UCNP surface. Herein, we systematically investigate the sequence dependence of DNAs in their interactions with UCNPs, and reveal that poly-cytosine (poly-C) has high affinity for the UCNP surface. A general approach to synthesize monodispersed DNA-UCNP conjugates is developed using poly-C-containing diblock DNA strands. The poly-C segment of the DNA strand binds to the surfaces of UCNPs and the second segment is oriented perpendicularly on the UCNP surface, making the DNA-UCNPs highly stable and monodispersed in aqueous solution. The dense layer of DNA on the UCNP surface enables the programmable assembly of UCNPs with other DNA-functionalized nanoparticles or DNA origamis through hybridization, resulting in the formation of well-organized complex structures.     

Substrate-Induced Dimerization Assembly of Chiral Macrocycle Catalysts toward Cooperative Asymmetric Catalysis

An artificial system of substrate-induced dimerization assembly of chiral macrocycle catalysts enables a highly cooperative hydrogen-bonding activation network for efficient enantioselective transformation. These macrocycles contain two thiourea and two chiral diamine moieties and dimerize with sulfate to form a sandwich-like assembly. The macrocycles then adopt an extended conformation and reciprocally complement the hydrogen-bonding interaction sites. Inspired by the guest-induced dynamic assembly, these macrocycles catalyze the decarboxylative Mannich reaction of cyclic aldimines containing a sulfamate heading group. The imine substrate can be activated toward nucleophilic attack of β-ketoacid by a cooperative hydrogen-bonding network enabled by sulfamate-induced dimerization assembly of the macrocycle catalysts. Highly efficient (>95 % yield in most cases) and enantioselective (up to 97.5:2.5 er) transformation of a variety of substrates using only 5 mol % macrocycle was achieved.     

Modular Design of Noble‐Metal‐Free Mixed Metal Oxide Electrocatalysts for Complete Water Splitting

Electrocatalytic water splitting into H₂ and O₂ is a key technology for carbon‐neutral energy. Here, we report a modular materials design leading to noble metal‐free composite electrocatalysts, which combine high electrical conductivity, high OER and HER reactivity and high durability. The scalable bottom‐up fabrication allows the stable deposition of mixed metal oxide nanostructures with different functionalities on copper foam electrodes. The composite catalyst shows sustained OER and HER activity in 0.1 m aqueous KOH over prolonged periods (t>10 h) at low overpotentials (OER: ≈300 mV; HER: ≈100 mV) and high faradaic efficiencies (OER: ≈100 %, HER: ≈98 %). The new synthetic concept will enable the development of multifunctional, mixed metal oxide composites as high‐performance electrocatalysts for challenging energy conversion and storage reactions.     

Ion‐Specific Assembly of Strong,Tough, and Stiff Biofibers

Designing engineering materials with high stiffness and high toughness is challenging as stiff materials tend to be brittle. Many biological materials realize this objective through multiscale (i.e., atomic‐ to macroscale) mechanisms that are extremely difficult to replicate in synthetic materials. Inspired from the architecture of such biological structures, we here present flow‐assisted organization and assembly of renewable native cellulose nanofibrils (CNFs), which yields highly anisotropic biofibers characterized by a unique combination of high strength (1010 MPa), high toughness (62 MJ m^?3) and high stiffness (57 GPa). We observed that properties of the fibers are primarily governed by specific ion characteristics such as hydration enthalpy and polarizability. A fundamental facet of this study is thus to elucidate the role of specific anion binding following the Hofmeister series on the mechanical properties of wet fibrillar networks, and link this to the differences in properties of dry nanostructured fibers. This knowledge is useful for rational design of nanomaterials and is critical for validation of specific ion effect theories. The bioinspired assembly demonstrated here is relevant example for designing high‐performance materials with absolute structural control.     

Small-Molecule Modulation of Soft-Matter Frank–Kasper Phases: A Method for Adding Function to Form

Incorporation of small amounts of α-tocopherol (vitamin E) in blends with the cellobiose–triazole-linked atactic poly(4-methyl-1-pentene) (CB-aPMP) sugar–polyolefin conjugate can be used to exert external control over thermotropic phase behavior and provide access to non-canonical soft matter Frank–Kasper A15 and σ phases. These results establish a paradigm that can be used for the further design and development of scalable quantities of soft matter FK phases of increased structural complexity and functional capability.     

Singlet Fission in Carbene-Derived Diradicaloids

Herein, we present a new class of singlet fission (SF) materials based on diradicaloids of carbene scaffolds, namely cyclic (alkyl)(amino)carbenes (CAACs). Our modular approach allows the tuning of two key SF criteria: the steric factor and the diradical character. In turn, we modified the energy landscapes of excited states in a systematic manner to accommodate the needs for SF. We report the first example of intermolecular SF in solution by dimer self-assembly at cryogenic temperatures.