Self‐Assembled Polymeric Membranes and Nanoassemblies on Surfaces: Preparation, Characterization, and Current Applications

Polymersomes are a class of synthetic vesicles composed of a polymer membrane surrounding an aqueous inner cavity. In addition to their overall size, the thickness and composition of polymersome membranes determine the range of potential applications in which they can be employed. While synthetic polymer chemists have made great strides in controlling polymersome membrane parameters, measurement of their permeability to various analytes including gases, ions, organic molecules, and macromolecules remains a significant challenge. In this Outlook, we compare the general methods that have been developed to quantify polymersome membrane permeability, focusing in particular on their capability to accurately measure analyte flux. In addition, we briefly highlight strategies to control membrane permeability. Based on these learnings, we propose a set of criteria for designing future methods of quantifying membrane permeability such that the passage of a variety of molecules into and out of their lumens can be better understood.

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“… 71 While the majority of work in this domain has centered on liposomes, polymer-based studies have steadily gained interest. 11 , 72 − 75 …”

Section: Controlling Polymersome Permeabilitymentioning

confidence: 99%

“… Functional hybrid polymersomes containing membrane-spanning DNA nanopores display size-selective permeability, permitting the transport of substrates and products through the DNA nanopores but retaining bioactive encapsulated enzymes. Adapted with permission from ref ( 75 ). Copyright John Wiley & Sons 2016.…”

Section: Controlling Polymersome Permeabilitymentioning

confidence: 99%

Probing and Tuning the Permeability of Polymersomes

et al. 2020

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“… 4 − 12 From the initial stages of incorporating synthetic polymers into phospholipid vesicles, the present vesicle formulations with associated polymers have come a long way in terms of fine tuning their properties for drug delivery and applications in cosmetics, nutraceuticals, and food technology. 13 Polymer–liposome interactions could lead to (i) coating, (ii) insertion, (iii) disruption, and/or (iv) transforming the entire vesicle self-assembly. 14 These interactions are susceptible to experimental parameters such as solvent quality, temperature, ionic strength, and pressure and ultimately determine the liposome morphology, bilayer structure, and dynamics in the presence of polymers.…”

Section: Introductionmentioning

confidence: 99%

Manipulating Phospholipid Vesicles at the Nanoscale: A Transformation from Unilamellar to Multilamellar by an n-Alkyl-poly(ethylene oxide)

et al. 2021

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We investigated the influence of an n -alkyl-PEO polymer on the structure and dynamics of phospholipid vesicles. Multilayer formation and about a 9% increase in the size in vesicles were observed by cryogenic transmission electron microscopy (cryo-TEM), dynamic light scattering (DLS), and small-angle neutron/X-ray scattering (SANS/SAXS). The results indicate a change in the lamellar structure of the vesicles by a partial disruption caused by polymer chains, which seems to correlate with about a 30% reduction in bending rigidity per unit bilayer, as revealed by neutron spin echo (NSE) spectroscopy. Also, a strong change in lipid tail relaxation was observed. Our results point to opportunities using synthetic polymers to control the structure and dynamics of membranes, with possible applications in technical materials and also in drug and nutraceutical delivery.

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“…[37] At the same time, TPyCP can also generate a very small amount of superoxide radical. [37] At the same time, TPyCP can also generate a very small amount of superoxide radical.…”

Section: Ros Generation In Solutionmentioning

confidence: 99%

“…The mechanism involves the excitation of the PS, by illumination with an appropriate light source. [26,37,38] As a result, the toxic porphyrin [6,8] remains inside the polymersomes without any cytotoxic effect in the absence of irradiation. These reactive oxygen species, such as singlet dioxygen ( 1 O 2 ), are cytotoxic and result in the oxidative stress of the target cells, in solution and when encapsulated in polymersomes.…”

Section: Introductionmentioning

confidence: 99%

Porphyrin Containing Polymersomes with Enhanced ROS Generation Efficiency: In Vitro Evaluation

Kyropoulou

DiLeone

Lanzilotto

et al. 2019

Macromolecular Bioscience

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with subsequent damage to the cell components and consequent cell death. [1] PDT can be used to target tumor cells and is typically utilized in a combination therapy regime, together with other modalities such as radiotherapy, chemotherapy, and surgery. To optimize cell damage in the tumor and prevent significant collateral damage to healthy cells, the PS should be specifically localized in the pathogenic region. The lifetime and mean diffusion lengths of different ROS are very variable and localization will ensure that illumination generates ROS close to, at the surface of, or inside malignant tumor cells.Of particular interest for development of efficient PDT systems are porphyrins because the photochemical and photophysical properties may be tuned through modification of the central metal ion (if present) or through peripheral substituents. [2][3][4][5] However, despite the great potential of porphyrins as photosensitizers, these compounds possess crucial limitations in terms of biomedical application [6,7] such as a high dark toxicity, rather low activity under physiological conditions and typically poor water solubility. Efficient strategies to overcome these limitations and at the same time harness the beneficial properties of porphyrins are the (bio)-conjugation of the porphyrin to natural or synthetic polymers [8][9][10][11] or their incorporation in biocompatible nano carriers. Nanocarriers suitable for PDT materials include organic and inorganic nanoparticles, [12][13][14][15][16][17] liposomes, [18][19][20][21] and block copolymer-based vesicles or micelles. [22][23][24] Synthetic vesicles with sizes in the nanometer range, so-called polymersomes, are particularly appealing as carriers because they can be prepared with desired properties, [25] such as biocompatibility, possess an inner cavity where water-soluble photosensitizers can be encapsulated, [26] membranes allowing the entrapment of a hydrophobic photosensitizer and exhibit improved mechanical stability and robustness compared to liposomes. [27] There are a few examples of porphyrin-incorporating polymersomes, mostly concerning the non-covalent loading of the hydrophobic membrane with water insoluble porphyrins. [11,[28][29][30][31][32][33] The aim of those studies was to use the photophysical properties of the porphyrins to improve in vivo imaging. We have previously reported the synthesis and characterization of a water soluble tetra-N-alkylpyridinioporphyrin tetrabromide (TPyCP) (Scheme 1) which efficiently generates singlet oxygen both free Porphyrins are molecules possessing unique photophysical properties making them suitable for application in photodynamic therapy. The incorporation of porphyrins into natural or synthetic nano-assemblies such as polymersomes is a strategy to improve and prolong their therapeutic capacities and to overcome their limitations as therapeutic and diagnostic agents. Here, 5,10,15,20-tetrakis(1-(6-ethoxy-6-oxohexyl)-4-pyridin-1-io)-21H,23H-porphyrin tetrabromide porphyrin is inserted into polymersomes in order ...

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Self‐Assembled Polymeric Membranes and Nanoassemblies on Surfaces: Preparation, Characterization, and Current Applications

Cited by 21 publications

References 208 publications

Probing and Tuning the Permeability of Polymersomes

Probing and Tuning the Permeability of Polymersomes

Manipulating Phospholipid Vesicles at the Nanoscale: A Transformation from Unilamellar to Multilamellar by an n-Alkyl-poly(ethylene oxide)

Porphyrin Containing Polymersomes with Enhanced ROS Generation Efficiency: In Vitro Evaluation

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