Cross-linked Polymersome Membranes:  Vesicles with Broadly Adjustable Properties

Discher, Bohdana M.; Bermudez, Harry; Hammer, Daniel A.; Discher, Dennis E.; Won, You Yeon; Bates, Frank S.

doi:10.1021/jp011958z

Cited by 251 publications

(288 citation statements)

References 37 publications

(56 reference statements)

Supporting

Mentioning

276

Contrasting

Unclassified

Order By: Relevance

“…The polymersomes and nanotubes were cross-linked by free radical polymerization (17). A mixture of 90 l of potassium persulfate (12.5 mg͞ml), 8 l of 9 mg͞ml sodium metabisulfite solution, and 8 l of 130 mg͞300 l ferrous sulfate heptahydrate solution was applied to the polymer structures by using a flow cell.…”

Section: Methodsmentioning

confidence: 99%

“…Conversely, supramolecular structures from the self-assembly of higher-molecular-weight amphiphiles, such as block copolymers, are more amenable to stabilization by cross-linking. Polymersomes (polymer vesicles) (16) have been chemically cross-linked to form structures that are stable indefinitely (17). Worm-like micelles of diblock copolymers with diameters as small as 10 nm and lengths exceeding 1 m were cross-linked without any disruption of the cylindrical morphology (18).…”

mentioning

confidence: 99%

“…We stabilize our pulled polymer nanotubes by free radical polymerization of the hydrophobic butadiene tails (17). We introduce the cross-linking reagents using a flow-cell device.…”

mentioning

confidence: 99%

See 2 more Smart Citations

Stable and robust polymer nanotubes stretched from polymersomes

Reiner

Wells

Kishore

et al. 2006

Proc. Natl. Acad. Sci. U.S.A.

View full text Add to dashboard Cite

We create long polymer nanotubes by directly pulling on the membrane of polymersomes using either optical tweezers or a micropipette. The polymersomes are composed of amphiphilic diblock copolymers, and the nanotubes formed have an aqueous core connected to the aqueous interior of the polymersome. We stabilize the pulled nanotubes by subsequent chemical crosslinking. The cross-linked nanotubes are extremely robust and can be moved to another medium for use elsewhere. We demonstrate the ability to form networks of polymer nanotubes and polymersomes by optical manipulation. The aqueous core of the polymer nanotubes together with their robust character makes them interesting candidates for nanofluidics and other applications in biotechnology.cross-link ͉ optical tweezers ͉ nanofluidics ͉ vesicles N anotubes are among the most promising structures in nanotechnology. Carbon nanotubes are already finding applications in composite materials requiring high strength-to-weight ratio, and many more applications are expected in the near future (1). Nanotubes also can naturally occur in biology. Transport of genetic material from phage viruses to bacteria can occur via protein nanotubes (2), and phospholipid nanotubes between live cells, purported to be a conduit for intercellular organelle transport, were recently observed (3). The use of nanotubes for transport of biological molecules is particularly exciting, with potentially significant applications in biotechnology. Gold nanotubules in polymer membranes have been used to separate small biological molecules on the basis of molecular size (4) and DNA fragments according to base recognition. Experiments on the movement of DNA in nanofabricated structures (5, 6) showed that new transport mechanisms occur when spatial confinement in one or more dimensions is less than the radius of gyration. Similar effects also have been observed with DNA fragments passing through multiwalled carbon nanotubes (7). All of these nanotubular structures have an interior aqueous environment suitable for biological molecules, but with the exception of ref. 6, the length of an individual channel is only on the order of 1 m.Extremely long, water-filled nanotubes can be formed from self-assembling amphiphilic molecules. For example, phospholipids can spontaneously form nanotubes under appropriate conditions (8). Vesicle membranes composed of self-assembled amphiphilic molecules can exhibit both elastic and viscoelastic properties, which, under the application of a localized force, can result in the formation of a nanotube. Pioneering work by Evans et al. (9) demonstrated the formation of phospholipid nanotubes by using a micropipette to pull on phospholipid vesicle (liposome) membranes. More recently, Orwar and coworkers (10) adopted the technique of Evans to create elaborate networks of liposomes interconnected by phospholipid nanotubes and demonstrated transport through these networks. Similarly, optical tweezers have been used to create phospholipid nanotubes by pulling directly on membranes of ...

show abstract

Section: Methodsmentioning

confidence: 99%

mentioning

confidence: 99%

See 1 more Smart Citation

Stable and robust polymer nanotubes stretched from polymersomes

Reiner

Wells

Kishore

et al. 2006

Proc. Natl. Acad. Sci. U.S.A.

View full text Add to dashboard Cite

show abstract

“…In addition, the vast number of available blocks make it possible to tune membrane properties, such as membrane thickness, polarity, toxicity or sensor-responsivity [15,16]. The membrane thickness plays an important role [17] in membrane-crossing biomolecules.…”

Section: Polymeric Membranesmentioning

confidence: 99%

Bio-Decorated Polymer Membranes: A New Approach in Diagnostics and Therapeutics

et al. 2011

View full text Add to dashboard Cite

Today, demand exists for new systems that can meet the challenges of identifying biological entities rapidly and specifically in diagnostics, developing stable and multifunctional membranes, and engineering devices at the nanometer scale. In this respect, bio-decorated membranes combine the specificity and efficacy of biological entities, such as peptides, proteins, and DNA, with stability and the opportunity to chemically tailor the properties of polymeric membranes. A smart strategy that serves to fulfill biological criteria is required, whereby polymer membranes come to mimic biological membranes and do not disturb but rather enhance the functioning and activity of a biological entity. Different approaches have been developed, exemplified by either planar or vesicular membranes, allowing insertion inside the polymer membrane or anchoring via functionalization of the membrane surface. Inspired by nature, but incorporating the strength provided by chemical design, bio-decorated polymer membranes represent a novel concept with great potential in diagnostics and therapeutics.

show abstract

“…[1][2][3][4][5] Especially interesting are peptide-and sugar-based biohybrid polymers and vesicles, which may inherit all the advantageous features of synthetic polymers (elasticity, solubility, etc.) and biological polymers (functionality, biocompatibility, etc.…”

mentioning

confidence: 99%

Glycopolymer vesicles with an asymmetric membrane

et al. 2009

View full text Add to dashboard Cite

Direct dissolution of glycosylated polybutadiene-poly(ethylene oxide) block copolymers can lead to the spontaneous formation of vesicles or membranes, which on the outside are coated with glucose and on the inside with poly(ethylene oxide).Polymer vesicles, also referred to as ''polymersomes, '' 1 are considered as model biomembranes for applications in life science and biomedicine.2 Block copolymer vesicles with broadly adjustable properties including stability, fluidity, and dynamics can have a better performance than the phospholipid membranes of biological cells. [1][2][3][4][5] Especially interesting are peptide-and sugar-based biohybrid polymers and vesicles, which may inherit all the advantageous features of synthetic polymers (elasticity, solubility, etc.) and biological polymers (functionality, biocompatibility, etc.).6,7 Glycopolymers are currently ''booming'' because of their easy availability 8 and potential use in cell sensing, therapeutics, and synthetic biology. 9Herein we describe the spontaneous formation of glycopolymer vesicles with an asymmetric membrane, 10-12 the outside of which is covered by glucose (Glc) and the inside by poly(ethylene oxide) (PEO) (see the illustrations in Fig. 1), in dilute aqueous solution. The vesicular structure of the aggregates was identified by light and X-ray scattering and electron microscopy. 2D-NOESY-NMR and surfaceenhanced Raman spectroscopy (SERS) were applied to demonstrate the asymmetric structure of the membrane.The glycopolymers 1 and 2 (see structure in Fig. 1A) used for this study were synthesized by photoaddition of 2,3,4,6-tetra-O-acetyl-1-thio-b-D-glucopyranose onto 1,2-polybutadieneblock-poly(ethylene oxide) (PB x -PEO y ; x = 65, y = 212 -1 and x = 68, y = 34 -2), as described earlier.13,14 The protected glycopolymers contained on average 33 (1) or 30 (2) glucose units per chain, and 6-9% of the double bonds remained unreacted (elemental analysis and 1 H NMR). The apparent polydispersity indexes of the samples were 1.1 and 1.2, respectively (size-exclusion chromatography, SEC). The deacetylation of the glucose units was achieved in a quantitative yield ( 1 H NMR and FT-IR).w Owing to the large weight fraction of hydrophilic units (Glc + PEO), w hydrophilic = 0.76 (1) and 0.58 (2), both glycopolymers could be directly dispersed in pure water. According to static and dynamic light scattering (SLS/DLS) (each series of measurements were done with four samples containing 0.025-0.1 wt% polymer at scattering angles between 121 and 1501), the dispersions contained very large aggregates with R g,0 = (550 AE 20) nm, R h,0 = (520 AE 20) nm (1) and R g,0 = (270 AE 40) nm, R h,0 = (280 AE 30) nm (2) (R g : radius of gyration, R h : hydrodynamic radius). The dimensions of the aggregates and the values of the characteristic ratio R g,0 /R h,0 B 1 suggest that the aggregates of 1 and 2 were vesicles.15 Combined SLS and DLS analysis 16 reveals a high softness of the particles, indicative for vesicles with a quite thin shell.w The existence of unilamellar vesicl...

show abstract

Cross-linked Polymersome Membranes: Vesicles with Broadly Adjustable Properties

Cited by 251 publications

References 37 publications

Stable and robust polymer nanotubes stretched from polymersomes

Stable and robust polymer nanotubes stretched from polymersomes

Bio-Decorated Polymer Membranes: A New Approach in Diagnostics and Therapeutics

Glycopolymer vesicles with an asymmetric membrane

Contact Info

Product

Resources

About