Solution self-assembly of block copolymers (BCPs) typically generates spheres, rods, and vesicles. The reproducible bottom-up fabrication stable planar nanostructures remains elusive due to their tendency bend into closed bilayers. This morphological vacancy renders the study shape effects on BCP nanocarrier-cell interactions incomplete. Furthermore, single assemblies with built-in drug delivery functions geometry-optimized performance a major challenge. We demonstrate that PEG-b-PCPTM...

The past two decades have evidenced a tremendous growth in the field of responsive polymers, which can exhibit reversible or irreversible changes physical properties and/or chemical structures to an external stimulus such as pH, temperature, ionic strength, light irradiation, mechanical forces, electric and magnetic fields, specific analytes, additives (ions, bioactive molecules, etc.), combination them. Responsive polymers exist form solutions, gels, self-assembled nanoparticles,...

We report on the fabrication of photochromic polymersomes exhibiting photoswitchable and reversible bilayer permeability from newly designed poly(ethylene oxide)-b-PSPA (PEO-b-PSPA) diblock copolymers, where SPA is spiropyran (SP)-based monomer containing a unique carbamate linkage. Upon self-assembling into polymersomes, SP moieties within vesicle bilayers undergo phototriggered isomerization between hydrophobic (SP, λ2 > 450 nm irradiation) zwitterionic merocyanine (MC, λ1 < 420 states....

Reactive oxygen species (ROS) and oxidative stress are implicated in various physiological pathological processes, this feature provides a vital biochemical basis for designing novel therapeutic diagnostic nanomedicines. Among them, oxidation-responsive micelles vesicles (polymersomes) of amphiphilic block copolymers have been extensively explored; however, previous works, oxidation by ROS including H2O2 exclusively leads to microstructural destruction polymeric assemblies. For polymersomes,...

Antimicrobial resistance poses serious public health concerns and antibiotic misuse/abuse further complicates the situation; thus, it remains a considerable challenge to optimize/improve usage of currently available drugs. We report general strategy construct bacterial strain-selective delivery system for antibiotics based on responsive polymeric vesicles. In response enzymes including penicillin G amidase (PGA) β-lactamase (Bla), which are closely associated with drug-resistant strains,...

The development of a highly selective and fast responsive fluorogenic biosensor for diverse analytes ranging from bioactive small molecules to specific antigens is desirable but remains considerable challenge. We herein propose new approach by integrating substrate-selective enzymatic reactions with fluorogens exhibiting aggregation-induced emission feature. Tyrosine-functionalized tetraphenylethene, TPE-Tyr, molecularly dissolves in aqueous media negligible fluorescence emission; upon...

Stimuli-triggered disassembly of block copolymer vesicles or polymersomes has been conventionally achieved via solubility switching the bilayer-forming block, requiring cooperative changes most repeating units. Herein we report an alternative approach by incorporating hydrophobic blocks exhibiting stimuli-triggered head-to-tail cascade depolymerization features. Amphiphilic copolymers bearing this motif self-assemble into self-immolative (SIPsomes). By modular design terminal capping...

ConspectusAll living organisms and soft matter are intrinsically responsive adaptive to external stimuli. Inspired by this fact, tremendous effort aiming emulate subtle features exhibited nature has spurred the invention of a diverse range polymeric materials. Conventional stimuli-responsive polymers constructed via covalent bonds can undergo reversible or irreversible changes in chemical structures, physicochemical properties, both response variety They have been imparted with emerging...

The fabrication of block copolymer (BCP) vesicles (polymersomes) exhibiting synchronized covalent crosslinking and bilayer permeabilization remains a considerable challenge as typically leads to compromised membrane permeability. Herein it is demonstrated how solve this dilemma by employing stimuli-triggered strategy with amphiphilic BCPs containing photolabile carbamate-caged primary amines. Upon self-assembling into polymersomes, light-triggered self-immolative decaging reactions release...

The development of near-infrared (NIR) J-aggregates has received increasing attention due to their broad applications. Here, we report the nitrosation an amine-containing aza-BODIPY precursor (BDP-NH2 ), affording first nitric oxide (NO)-releasing NIR J-aggregate (BDP-NO). introduction N-nitrosamine moieties efficiently inhibits aromatic interactions BDP-NH2 , which instead promotes formation within micellar nanoparticles with a remarkable bathochromic shift ≈109 nm window (820 nm)....

The formation of biofilms is closely associated with persistent and chronic infections, physiological heterogeneity such as pH oxygen gradients renders highly resistant to conventional antibiotics. To date, effectively treating biofilm infections remains a significant challenge. Herein, we report the fabrication micellar nanoparticles adapted heterogeneous microenvironments, enabling nitric oxide (NO) release through two distinct photoredox catalysis mechanisms. key design feature involves...

Responsive supramolecular gels were constructed from crown ether terminated four-arm star poly(epsilon-caprolactone) (PCL-DB24C8) and dibenzylammonium-terminated two-arm PCL-DBAS (see scheme), exploiting the formation of pseudorotaxane linkages between ammonium moieties. The resultant exhibit thermo- pH-induced reversible gel-sol transition.

Micellar traffic lights: The title FRET system (FRET=fluorescence resonance energy transfer) consists of one type donor dye and two types acceptor dyes. On/off fluorescence switching the latter dyes can be controlled by pH changes light, respectively. This novel multicolor luminescent polymeric assembly act as a ratiometric probe for temperature with tunable sensitivity. Detailed facts importance to specialist readers are published "Supporting Information". Such documents peer-reviewed, but...

We report on the fabrication of hybrid silica nanoparticles densely grafted with thermoresponsive poly(N-isopropylacrylamide) (PNIPAM) brushes inner and outer layers selectively labeled fluorescence resonance energy transfer (FRET) donors, 4-(2-acryloyloxyethylamino)-7-nitro-2,1,3-benzoxadiazole (NBDAE), photoswitchable acceptors, 1′-(2-methacryloxyethyl)-3′,3′-dimethyl-6-nitro-spiro(2H-1-benzo-pyran-2,2′-indoline) (SPMA), respectively, via surface-initiated sequential atom radical...

We report on a robust approach to the size-selective and template-free synthesis of asymmetrically functionalized ultrasmall (<4 nm) gold nanoparticles (AuNPs) stably anchored with single amphiphilic triblock copolymer chain per NP. Directed NP self-assembly in aqueous solution can be facilely accomplished afford organic/inorganic hybrid micelles, vesicles, rods, large compound micelles by taking advantage rich microphase separation behavior as-synthesized AuNP copolymers, PEO-AuNP-PS, which...

Upon stimuli-triggered single cleavage of capping moieties at the focal point and chain terminal, self-immolative dendrimers (SIDs) linear polymers (l-SIPs) undergo spontaneous domino-like radial fragmentation cascade head-to-tail depolymerization, respectively. The nature response selectivity signal amplification has rendered them a unique type stimuli-responsive materials. Moreover, novel design principles are required for further advancement in field (SIPs). Herein, we report facile...

Four-arm star-shaped copolymers, TPE-star-P(DMA-co-BMA-co-Gd), containing TPE cores with an aggregation-induced emission (AIE) feature, a T 1-type magnetic resonance (MR) contrast agent, and amphiphilic cationic arms, are synthesized. By taking advantage of non-covalent interactions between star copolymers bacteria surfaces, bimodal fluorometric/MR detection concomitant inhibition both Gram-positive Gram-negative strains in aqueous media explored. As service to our authors readers, this...

We report on the fabrication of organic/inorganic hybrid micelles amphiphilic block copolymers physically encapsulated with hydrophobic drugs within micellar cores and stably embedded superparamagnetic iron oxide (SPIO) nanoparticles hydrophilic coronas, which possess integrated functions chemotherapeutic drug delivery magnetic resonance (MR) imaging contrast enhancement. Poly(ε-caprolactone)-b-poly(glycerol monomethacrylate), PCL-b-PGMA, PCL-b-P(OEGMA-co-FA) were synthesized at first by...

In this work, we integrated the concept of aggregation-induced emission (AIE) with specific supramolecular recognition between K+ ions and crown ether moieties to develop more effective fluorometric probes. We synthesized a novel ether-functionalized tetraphenylethene (TPE) derivative, TPE-(B15C5)4, via thiol-ene click reaction thiol-derivatized TPE, TPE-(SH)4, maleimide-functionalized benzo-15-crown-5 (B15C5). TPE core four outer B15C5 serve as AIE-active motif K+-recognizing...

Supramolecular vesicles, also referred to as polymersomes, self-assembled from amphiphilic polymers capable of synchronically loading with both hydrophilic and hydrophobic payloads have shown promising potential in drug delivery application. Herein, we report the fabrication pH-responsive polymersomes via supramolecular self-assembly diblock copolymers, poly(ethylene oxide)-b-poly(2-((((5-methyl-2-(2,4,6-trimethoxyphenyl)-1,3-dioxan-5-yl)methoxy)carbonyl)amino)ethyl methacrylate)...

The local delivery of gaseous signaling molecules (GSMs) has shown promising therapeutic potential. However, although GSMs have a subtle interplay in physiological and pathological conditions, the co-delivery different for purposes remains unexplored. Herein, we covalently graft nitric oxide (NO)-releasing N-nitrosamine moiety onto carbon monoxide (CO)-releasing 3-hydroxyflavone (3-HF) antenna, resulting first NO/CO-releasing donor. Under visible light irradiation, photo-mediated co-release...