Vesicular photothermal therapy agents (PTAs) are highly desirable in photothermal therapy (PTT) for their excellent light-harvesting ability and versatile hollow compartments. However, up to now, the reported vesicular PTAs are generally self-assembled from small molecules like liposomes, and polymer vesicles have seldom been used as PTAs due to the unsatisfactory photothermal conversion efficiency resulting from the irregular packing of chromophores in the vesicle membranes. Here we report a nano-sized polymer vesicle from hyperbranched polyporphyrins with favorable photothermal stability and extraordinarily high photothermal efficiency (44.1%), showing great potential in imaging-guided PTT for tumors through in vitro and in vivo experiments. These excellent properties are attributed to the in situ supramolecular polymerization of porphyrin units inside the vesicle membrane into well-organized 1D monofilaments driven by π-π stacking. We believe the supramolecular polymerization-enhanced self-assembly process reported here will shed a new light on the design of supramolecular materials with new structures and functions.

crosslinking [2,3] and metal ion chelation processes. [4,5] Thus, up to now, great efforts have been made to incorporate DOPA or catechol groups in a broad range of designed polymers to get mussel-inspired adhesives, which showed good bonding performances both at dry and underwater conditions. These polymers were generally named as "catecholfunctionalized polymers" (CFPs).Up to now, notable accomplishments have been achieved by using CFPs for high performance adhesion at atmospheric environment. Yu and Deming and co-workers reported the synthesis of DOPA-containing copolypeptides, exhibiting a bonding strength of 4.0 MPa on aluminum. [6] Wilker et al. synthesized poly[(3,4-dihydroxystyrene)-co-styrene] via anionic polymerization method, which achieved a bonding strength of 11 MPa on aluminum by using CaCO 3 particles as reinforcing materials. [7] Subsequently, they also incorporated the CFPs with poly(lactic acid) [8][9][10] or pendant oligo(ethylene glycol) moieties [4] to produce biodegradable/biocompatible adhesives with good dry-state bonding strength. Wan et al. synthesized catechol-functionalized poly(vinyl alcohol) via esterification reactions [11] and acetal formation reactions, [12] exhibiting bonding strengths of 4.0 MPa on glass and 14.9 MPa on stainless steel, respectively. Kaneko et al. synthesized a hyperbranched CFP via thermal polycondensation reaction between 3,4-dihydroxycinnamic acid and 4-hydroxycinnamic acid, which showed a bonding strength of ≈10 MPa on steel. [13] Then, they also prepared a similar hyperbranched polymer system with the bonding strength on steel up to 15 MPa. [14] However, despite great progress, the bonding strength of most reported CFPs on metal substrates is smaller than 15 MPa. Recently, Messersmith and co-workers [15] and Detrembleur and co-workers [16] separately reported the synthesis of catechol-functionalized polybenzoxazines and polyhydroxyurethanes, which were used to prepare thermoset adhesive materials with excellent bonding strength of 20.5 MPa on aluminum and 22.1 MPa on stainless steel, respectively. To our knowledge, these two polymers represent the best adhesive materials among CFPs for dry-state adhesion on metal Marine mussels have the ability to cling to various surfaces at wet or underwater conditions, which inspires the research of catechol-functionalized polymers (CFPs) to develop high-performance adhesive materials. However, these polymeric adhesives generally face the problems of complex synthetic route, and it is still high challenging to prepare CFPs with excellent adhesive performance both at dry and underwater conditions. Herein, a mussel-inspired alternating copolymer, poly(dopamine-alt-2,2-bis(4-glycidyloxyphenyl) propane) (P (DA-a-BGOP)), is synthesized in one step by using commercially available monomers through epoxy-amino click chemistry. The incorporation of polar groups and rigid bisphenol A structures into the polymer backbone enhances the cohesion energy of polymer matrix. The alternating polymer structure endows the polymers with high...

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A novel thermoresponsive hyperbranched multiarm copolymer with a hydrophobic hyperbranched poly[3-ethyl-3-(hydroxymethyl)oxetane] core and many poly(acrylamide- co-acrylonitrile) (P(AAm- co-AN)) arms was for the first time synthesized through a reversible addition-fragmentation chain-transfer polymerization. These copolymers show reversible, sharp, and controlled temperature-responsive phase transitions at the upper critical solution temperature (UCST) in water and electrolyte solution. It is the first report on the hyperbranched copolymers with a UCST transition. Two series copolymers with variable AN content (series A) and variable arm length (series B) were synthesized to study the influence of molecular structure on the UCST transition. It was found that the UCST of copolymers could be raised by increasing the AN content or decreasing the arm length. Most interestingly, the amplification effect of the hyperbranched topological structure leads to a broad change of the UCST from 33.2 to 65.2 °C with the little change of AN content (5.9%). On the basis of variable temperature nuclear magnetic resonance, dynamic light scattering, and transmission electron microscopy, a UCST transition mechanism, in combination with hydrophilic/hydrophobic balance and multimicelle aggregate (MMA), was proposed. This work enriches the UCST copolymer topology and may extend the knowledge on the structure-activity relationship as well as the mechanism of the UCST polymers.

Among the few available mRNA delivery vehicles, lipid nanoparticles (LNPs) are the most clinically advanced but they require cumbersome four components and suffer from inflammation‐related side effects that should be minimized for safety. Yet, a certain level of proinflammatory responses and innate immune activation are required to evoke T‐cell immunity for mRNA cancer vaccination. To address these issues and develop potent yet low‐inflammatory mRNA cancer vaccine vectors, a series of alternating copolymers “PHTA” featured with ortho‐hydroxy tertiary amine (HTA) repeating units for mRNA delivery is synthesized, which can play triple roles of condensing mRNA, enhancing the polymeric nanoparticle (PNP) stability, and prolonging circulation time. Unlike LNPs exhibiting high levels of inflammation, the PHTA‐based PNPs show negligible inflammatory side effects in vivo. Importantly, the top candidate PHTA‐C18 enables successful mRNA cancer vaccine delivery in vivo and leads to a robust CD8+ T cell mediated antitumor cellular immunity. Such PHTA‐based integrated PNP provides a potential approach for establishing mRNA cancer vaccines with good inflammatory safety profiles.