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Fluorescent polymersomes with both aggregation‐induced emission (AIE) and CO2‐responsive properties were developed from amphiphilic block copolymer PEG‐b‐P(DEAEMA‐co‐TPEMA) in which the hydrophobic block was a copolymer made of tetraphenylethene functionalized methacrylate (TPEMA) and 2‐(diethylamino)ethyl methacrylate (DEAEMA) with unspecified sequence arrangement. Four block copolymers with different DEAEMA/TPEMA and hydrophilic/hydrophobic ratios were synthesized, and bright AIE polymersomes were prepared by nanoprecipitation in THF/water and dioxane/water systems. Polymersomes of PEG45‐b‐P(DEAEMA36‐co‐TPEMA6) were chosen to study the CO2‐responsive property. Upon CO2 bubbling vesicles transformed to small spherical micelles, and upon Ar bubbling micelles returned to vesicles with the presence of a few intermediate morphologies. These polymersomes might have promising applications as sensors, nanoreactors, or controlled release systems. [ABSTRACT FROM AUTHOR]

Next-generation therapeutic approaches are expected to rely on the engineering of biomimetic cellular systems that can mimic specific cellular functions. Herein, we demonstrate a highly effective route for constructing structural and functional eukaryotic cell mimics by loading pH-sensitive polymersomes as membrane-associated and free-floating organelle mimics inside the multifunctional cell membrane. Metabolism mimicry has been validated by performing successive enzymatic cascade reactions spatially separated at specific sites of cell mimics in the presence and absence of extracellular organelle mimics. These enzymatic reactions take place in a highly controllable, reproducible, efficient, and successive manner. Our biomimetic approach to material design for establishing functional principles brings considerable enrichment to the fields of biomedicine, biocatalysis, biotechnology, and systems biology. [ABSTRACT FROM AUTHOR]

Polymeric nanoreactors (NRs) have distinct advantages to improve chemical reaction efficiency, but the in vivo applications are limited by lack of tissue-specificity. Herein, novel glucose oxidase (GOD)-loaded therapeutic vesicular NRs ( theraNR) are constructed based on a diblock copolymer containing poly(ethylene glycol) (PEG) and copolymerized phenylboronic ester or piperidine-functionalized methacrylate (P(PBEM- co-PEM)). Upon systemic injection, theraNR are inactive in normal tissues. At a tumor site, theraNR are specifically activated by the tumor acidity via improved permeability of the membranes. Hydrogen peroxide (H2O2) production by the catalysis of GOD in theraNR increases tumor oxidative stress significantly. Meanwhile, high levels of H2O2 induce self-destruction of theraNR releasing quinone methide (QM) to deplete glutathione and suppress the antioxidant ability of cancer cells. Finally, theraNR efficiently kill cancer cells and ablate tumors via the synergistic effect. [ABSTRACT FROM AUTHOR]

We report molecular interaction-driven self-assembly of supramolecularly engineered amphiphilic macromolecules (SEAM) containing a single supramolecular structure-directing unit (SSDU) consisting of an H-bonding group connected to a naphthalene diimide chromophore. Two such SEAMs, P1-50 and P2-50, having the identical chemical structure and hydrophobic/hydrophilic balance, exhibit distinct self-assembled structures (polymersome and cylindrical micelle, respectively) due to a difference in the H-bonding group (hydrazide or amide, respectively) of the single SSDU. When mixed together, P1-50 and P2-50 adopted self-sorted assembly. For either series of polymers, variation in the hydrophobic/hydrophilic balance does not alter the morphology reconfirming that self-assembly is primarily driven by directional molecular interaction which is capable of overruling the existing norms in packing parameter-dependent morphology control in an immiscibility-driven block copolymer assembly. [ABSTRACT FROM AUTHOR]

Die wichtige Rolle von Vesikeln in vielen Bereichen der Zellfunktion ist gut bekannt, aber erst seit kurzem offenbart sich mithilfe neuer, komplexerer Bildgebungsverfahren ihre Allgegenwart in der Natur. Während die biologischen Eigenschaften von Vesikeln und ihre physiologischen Funktionen immer besser verstanden werden, werden auch vermehrt sehr elegante, künstliche Vesikel für eine Reihe technischer Anwendungen und die Grundlagenforschung entwickelt. Hier wollen wir den Stand der Technik von biologischen und synthetischen Vesikeln darstellen und ihre biologischen Eigenschaften in Zusammenhang mit aktuellen Syntheseentwicklungen bringen, um so einen Überblick über diese komplexen, rasch aufstrebenden Fachgebiete zu geben. Darüber hinaus werden die Herausforderungen und Möglichkeiten für die zukünftige biologische und präparative Entwicklung von Vesikeln präsentiert. Natürliche und künstliche Vesikel: Parallel zur Aufklärung der biologischen Eigenschaften und physiologischen Funktion von Vesikeln werden immer elegantere künstliche Vesikel beschrieben. In diesem Aufsatz soll ein Überblick über biologische und präparative Fortschritte gegeben und gezeigt werden, wie beide Forschungsgebiete voneinander profitieren können. [ABSTRACT FROM AUTHOR]

Simple cyclic disulfides under high tension mediate the uptake of giant substrates, that is, liposomes and polymersomes with diameters of up to 400 nm, into HeLa Kyoto cells. To place them at the surface of the vesicles, the strained disulfides were attached to the head-group of cationic amphiphiles. Bell-shaped dose response curves revealed self-activation of the strained amphiphiles by self-assembly into microdomains at low concentrations and self-inhibition by micelle formation at high concentrations. Poor colocalization of internalized vesicles with endosomes, lysosomes, and mitochondria indicate substantial release into the cytosol. The increasing activity with disulfide ring tension, inhibition with Ellman's reagent, and inactivity of maleimide and guanidinium controls outline a distinct mode of action that deserves further investigation and is promising for practical applications. [ABSTRACT FROM AUTHOR]

The light-triggered, programmable rupture of cell-sized vesicles is described, with particular emphasis on self-assembled polymersome capsules. The mechanism involves a hypotonic osmotic imbalance created by the accumulation of photogenerated species inside the lumen, which cannot be compensated owing to the low water permeability of the membrane. This simple and versatile mechanism can be adapted to a wealth of hydrosoluble molecules, which are either able to generate reactive oxygen species or undergo photocleavage. Ultimately, in a multi-compartmentalized and cell-like system, the possibility to selectively burst polymersomes with high specificity and temporal precision and to consequently deliver small encapsulated vesicles (both polymersomes and liposomes) is demonstrated. [ABSTRACT FROM AUTHOR]

Chemistry plays a crucial role in creating synthetic analogues of biomacromolecular structures. Of particular scientific and technological interest are biomimetic vesicles that are inspired by natural membrane compartments and organelles but avoid their drawbacks, such as membrane instability and limited control over cargo transport across the boundaries. In this study, completely synthetic vesicles were developed from stable polymeric walls and easy-to-engineer membrane DNA nanopores. The hybrid nanocontainers feature selective permeability and permit the transport of organic molecules of 1.5 nm size. Larger enzymes (ca. 5 nm) can be encapsulated and retained within the vesicles yet remain catalytically active. The hybrid structures constitute a new type of enzymatic nanoreactor. The high tunability of the polymeric vesicles and DNA pores will be key in tailoring the nanocontainers for applications in drug delivery, bioimaging, biocatalysis, and cell mimicry. [ABSTRACT FROM AUTHOR]

Polymersomes provide a good platform for targeted drug delivery and the creation of complex (bio)catalytically active systems for research in synthetic biology. To realize these applications requires both spatial control over the encapsulation components in these polymersomes and a means to report where the components are in the polymersomes. To address these twin challenges, we synthesized the protein-polymer bioconjugate PNIPAM- b-amilFP497 composed of thermoresponsive poly( N-isopropylacrylamide) (PNIPAM) and a green-fluorescent protein variant (amilFP497). Above 37 °C, this bioconjugate forms polymersomes that can (co-)encapsulate the fluorescent drug doxorubicin and the fluorescent light-harvesting protein phycoerythrin 545 (PE545). Using fluorescence lifetime imaging microscopy and Förster resonance energy transfer (FLIM-FRET), we can distinguish the co-encapsulated PE545 protein inside the polymersome membrane while doxorubicin is found both in the polymersome core and membrane. [ABSTRACT FROM AUTHOR]

Double emulsions are valuable for the formation of multi-compartmental structures. A variety of pathways to prepare double emulsions have been developed, but heighthroughput routes to droplets of controlled size and architecture remain scarce. A new single-step process is introduced for preparation of water-in-oil-in-water double emulsions by a previously unexplained process of self-emulsification. We show that the origin of this process is the osmotic stress resulting from the presence of salt impurities within the amphiphilic block copolymers used for emulsion stabilization. Further, we utilize osmotically driven emulsification to tailor the structures of multiple emulsions, which upon solvent evaporation can yield multi-compartmental capsules or hierarchically structured porous films. [ABSTRACT FROM AUTHOR]

Large (200 nm) poly(ethylene oxide)-b-poly(butadiene) polymer vesicles fuse into giant (>1 μm) vesicles with mild agitation in dilute aqueous NaCl solutions. This unusual effect is attributed to the salt-induced contraction of the poly(ethylene oxide) corona, reducing steric resistance between vesicles and, with agitation, increasing the probability of contact between the hydrophobic cores of adjacent membranes. In addition, NaCl and agitation facilitated the creation of giant hybrid vesicles from much smaller homogeneous polymersomes and liposomes. Whereas lipid vesicles do not readily fuse with each other under the same circumstances, they did fuse with polymersomes to produce hybrid polymer/lipid vesicles. [ABSTRACT FROM AUTHOR]

The fabrication of block copolymer (BCP) vesicles (polymersomes) exhibiting synchronized covalent crosslinking and bilayer permeabilization remains a considerable challenge as crosslinking typically leads to compromised membrane permeability. Herein it is demonstrated how to solve this dilemma by employing a stimuli-triggered crosslinking strategy with amphiphilic BCPs containing photolabile carbamate-caged primary amines. Upon self-assembling into polymersomes, light-triggered self-immolative decaging reactions release primary amine moieties and extensive amidation reactions then occur due to suppressed amine p Ka within hydrophobic milieu. This leads to serendipitous vesicle crosslinking and the process is associated with bilayer hydrophobicity-to-hydrophilicity transition and membrane permeabilization. [ABSTRACT FROM AUTHOR]

Enzyme-filled polystyrene- b-poly(3-(isocyano- L-alanyl-aminoethyl)thiophene) (PS- b-PIAT) nanoreactors are encapsulated together with free enzymes and substrates in a larger polybutadiene- b-poly(ethylene oxide) (PB- b-PEO) polymersome, forming a multicompartmentalized structure, which shows structural resemblance to the cell and its organelles. An original cofactor-dependent three-enzyme cascade reaction is performed, using either compatible or incompatible enzymes, which takes place across multiple compartments. [ABSTRACT FROM AUTHOR]

Ein amphiphiles Triblockcopolymer, das durch einen säurelabilen β ‐ Thiopropionat ‐ Linker segmentiert wird, wurde aus einem Dithiol, einem Diacrylat und einem hydrophilen Polymer mit endständigem Acrylat in zwei Stufen in einem Gefäß synthetisiert. Es assemblierte spontan zu Vesikeln, die unter schwach sauren Bedingungen zerfallen und dabei nichtkovalent eingeschlossene Gastmoleküle freisetzen. [ABSTRACT FROM AUTHOR]

Polymersome zählen zu den stabilsten nichtkovalenten Vesikeln. Der Einschluss photoaktiver Moleküle im Innern dieser Aggregate sensibilisiert sie jedoch für ein lichtaktiviertes Aufbrechen unter kontrollierter Freisetzung ihres Inhalts. In der Zuschrift auf S. 1588 ff. stellen S. Lecommandoux, N. D. McClenaghan et al. zwei unterschiedliche Mechanismen vor, wie durch Bestrahlung ein plötzlicher Anstieg des osmotischen Drucks erzeugt werden kann, der diese Explosionen im Mikromaßstab auslöst. [ABSTRACT FROM AUTHOR]