Expanding the range of healable materials is an important challenge for sustainable societies. Noncrystalline, high-molecular-weight polymers generally form mechanically robust materials, which, however, are difficult to repair once they fractured. This because their polymer chains heavily entangled and diffuse too sluggishly unite fractured surfaces within reasonable time scales. Here we report that low-molecular-weight polymers, when cross-linked by dense hydrogen bonds, yield yet readily...

Abstract Although chirality has been recognized as an essential entity for life, it still remains a big mystery how the homochirality in nature emerged biomolecules. Certain achiral motifs are known to assemble into chiral nanostructures. In rare cases, their absolute geometries enantiomerically biased by mirror symmetry breaking. Here we report first example of asymmetric catalysis using symmetry-broken helical nanoribbon ligand. We obtain this from benzoic acid appended...

Symmetry is an important factor in material design. Generally, it difficult to quantitively discuss symmetry-property relations. Two materials only with symmetry differences are requisite verify whether polar or nonpolar chiral systems advantageous for a specific property/phenomenon, such as chirality-induced spin selectivity. However, selectively prepare having different symmetries without changing other physical properties. The current study successfully prepared seven exceptionally...

A series of water-soluble telechelic dithiol monomers bearing multiple guanidinium ion (Gu+) units in their main chains were synthesized for packaging siRNA by template-assisted oxidative polymerization at thiol termini. In the presence siRNA, TEGGu4 affords a uniform-sized (7 ± 2 nm) nanocaplet containing (PTEGGu4⊃siRNA; PTEGGu4 = polymerized TEGGu4). When this small conjugate is incubated with live cells, cellular uptake occurs, and undergoes depolymerization reductive cytosolic...

Water-soluble linear polymers GumBAn (m/n = 18/6, 12/12, and 6/18) with multiple guanidinium ion (Gu(+)) boronic acid (BA) pendants in their side chains were synthesized as ATP-responsive modulators for enzyme activity. strongly bind to the phosphate (PO4(-)) 1,2-diol units of ATP via Gu(+) BA pendants, respectively. As only can be used proteins, is able modulate activity enzymes response ATP. a proof-of-concept study, we demonstrated that trypsin (Trp) deactivated by hybridization GumBAn....

Dendron G1(Gu+)9R and linear peptide oligomer Asn(TEG-Gu+)9, decorated with multiple guanidinium (Gu+) ions as sticky pendants via an oligo(oxyethylene) spacer, adhere to BSA protein assemblies such microtubules in aqueous buffers. Using fluorescently labeled pyrenyl rhodamine focal cores, the adhesion process can be visualized by FRET or confocal laser scanning microscopy. The leads their stabilization against depolymerization into α/β-tubulin heterodimer components, where effects of...

Polar interactions such as electrostatic forces and hydrogen bonds play an essential role in biological molecular recognition. On a protein surface, polar occur mostly hydrophobic environment because nonpolar amino acid residues cover ~75% of the surface. We report that ionic on surface are modulated by their subnanoscale distance to developed series head groups-appended self-assembled monolayers with C2, C6, C8, C12 space-filling alkyl chains, which capture dendritic guest via formation...

We developed a water-soluble adhesive photoswitch (Gluen-Azo-SA, average n = 5) that selectively binds to target enzyme and photochemically modulates its enzymatic activity even in cell lysates. Its design strategy features photochromic azobenzene unit (Azo), which carries on one side an inhibitory motif for the other glue part (Gluen) utilizes multiple guanidinium ion (Gu+) pendants adhering onto surface. The of Gluen-Azo-SA is carbonic anhydrase (CA) because sulfonamide (SA) derivatives,...

Transferrin (Tf) is known to induce transcytosis, which a consecutive endocytosis/exocytosis event. We developed Tf-appended nanocaplet (TfNC⊃siRNA) for the purpose of realizing siRNA delivery into deep tissues and RNA interference (RNAi) subsequently. For obtaining TfNC⊃siRNA, macromonomer (AzGu) bearing multiple guanidinium (Gu+) ion units, azide (N3) groups, trityl (Trt)-protected thiol groups in main chain, side chains, termini, respectively, was newly designed. Because multivalent...

Caspase-3 (Casp-3) is an enzyme that efficiently induces apoptosis, a form of programmed cell death. We report dendritic molecular glue PCGlue enables intracellular delivery Casp-3 and its photoactivation. carrying multiple guanidinium (Gu+) ion pendants via photocleavable linkages can tightly adhere to deliver it into the cytoplasm mainly by direct penetration through plasma membrane. Casp-3, whose surface covered PCGlue, unable interact with cellular substrates therefore not induce...

We developed a dendritic molecular glue PCGlue-NBD that can serve universally to "turn on" protein–protein interactions (PPIs) spatiotemporally. carrying multiple guanidinium ion (Gu+) pendants adhere strongly target proteins and cover their surfaces including the PPI interface regions, thereby suppressing PPIs with receptor proteins. Upon irradiation UV light, on protein is photocleaved at butyrate-substituted nitroveratryloxycarbonyl linkages in dendrimer framework, so multivalency for...

A sticky end: heterotropic conjugate of actin and myosin–actomysin–is stabilized by a water-soluble dendritic "molecular glue" bearing nine pendant guanidinium ions (see picture; ATP= adenosine triphosphate, ADP=adenosine diphosphate). The ATP-driven sliding motion filaments on myosin-functionalized coverslip is decelerated or totally arrested with higher-generation dendrimer, but not lower-generation one. Detailed facts importance to specialist readers are published as "Supporting...

The possibility to arrange biological molecules into ordered nanostructures is an important issue in nano- and biotechnology. Nature offers a wide range of molecular "bricks" (e.g., proteins, oligonucleotides, etc.) that spontaneously assemble more complex hierarchical systems with unique functionalities. Such building blocks can be also used for the construction nanomaterials peculiar properties DNA origami). In some cases, glues able bind biomolecules induce their assembly control final...

Symmetry is an important factor in material design. Generally, it difficult to quantitively discuss symmetry‐property relations. Two materials only with symmetry differences are requisite verify whether polar or nonpolar chiral systems advantageous for a specific property/phenomenon, such as chirality‐induced spin selectivity. However, selectively prepare having different symmetries without changing other physical properties. The current study successfully prepared seven exceptionally...

Abstract Mechanoluminescent materials serve as stress‐sensing platforms that emit light autonomously, featuring properties distinct from other mechanochromic for stress visualization. While these respond instantaneously to dynamic mechanical forces, visualization of distribution under static loads, where both and energetic equilibrium are established, remains a significant challenge in science, representing critical issue real‐time continuous monitoring. Here, an unprecedented...

The inhibitory effect of benzamidine as blocker on the protease activity trypsin is enhanced by covalent conjugation with bioadhesive molecular glue.

A water-soluble photoresponsive molecular glue, Azo-(18)Glue, consisting of a photochromic azobenzene core and two adhesive dendritic wedges with total 18 peripheral guanidinium ion (Gu(+)) pendants tightly adheres to the surface phospholipid membrane, even in buffer, via multivalent salt-bridge formation phosphate anions. photomechanical motion adhering Azo-(18)Glue possibly gives rise dynamic structural disordering membrane activates transmembrane permeation. In sharp contrast, no...

A water-soluble dendron with a fluorescein isothiocyanate (FITC) fluorescent label and bearing nine pendant guanidinium ion (Gu(+))/benzophenone (BP) pairs at its periphery (Glue(BP)-FITC) serves as "photoclickable molecular glue". By multivalent salt-bridge formation between Gu(+) ions oxyanions, Glue(BP)-FITC temporarily adheres to kinesin/microtubule hybrid. Upon subsequent exposure UV light, this noncovalent binding is made permanent via cross-linking reaction mediated by carbon radicals...

We developed dendritic caged molecular glues (CagedGlue-R) as tags for nucleus-targeted drug delivery, whose multiple guanidinium ion (Gu+) pendants are protected by an anionic photocleavable unit (butyrate-substituted nitroveratryloxycarbonyl; BANVOC). Negatively charged CagedGlue-R hardly binds to biomolecules because of their electrostatic repulsion. However, upon exposure UV light or near-infrared (NIR) light, the BANVOC groups rapidly detached yield uncaged glue (UncagedGlue-R) that...

Abstract PGlue PZ , a pyrazoline (PZ)‐based fluorescent adhesive which can be generated spatiotemporally in living systems, was developed. Since carries many guanidinium ion (Gu + ) pendants, it strongly adheres to various oxyanionic substrates through multivalent salt‐bridge interaction. is given by bioorthogonal photopolymerization of Gu ‐appended monomer (Glue TZ ), bearing tetrazole (TZ) and olefinic termini. Upon exposure UV light, Glue transforms into nitrileimine (NI) intermediate NI...

We developed a photoreactive molecular glue, BPGlue-N3, which can provide universal strategy to enhance the efficacy of DNA aptamers by temporary-to-permanent stepwise stabilization their conjugates with target proteins. As proof-of-concept study, we applied BPGlue-N3 SL1 (DNA aptamer)/c-Met (target protein) conjugate system. adhere and temporarily stabilize this aptamer/protein multivalently using its guanidinium ion (Gu+) pendants that form salt bridge oxyanionic moieties (e.g.,...