High‐Density Display of Protein Ligands on Self‐Assembled Capsules via Noncovalent Fluorous Interactions

Harano, Koji; Yamada, Junya; Mizuno, Shinichiro; Nakamura, Eiichi

doi:10.1002/asia.201403144

Cited by 6 publications

(6 citation statements)

References 44 publications

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“…We examined the surface morphology of the vesicles after ROMP by low-landing voltage SEM equipped with a monochromator, which we have recently shown to be useful for the structural analysis of organic molecular aggregates placed on a conductive substrate such as IZO. − As illustrated in Figure a, polymerization of the diethyl ester monomer 5a on the catalyst-doped fluorous vesicle V1 yielded the polymer 6a seen as bulges of several nanometers in diameter, suggesting that the polymer product was phase-segregated from the fluorous membrane as ROMP of 5a progresses.…”

Section: Resultsmentioning

confidence: 99%

Nanoscale Control of Polymer Assembly on a Synthetic Catalyst–Bilayer System

2016

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The use of the interior of self-assembled membrane as a template for polymer synthesis and assembly has long attracted the interest of chemists. However, it is difficult to utilize a lipid membrane as a chemical reactor for controlled assembly for polymers because lipid membrane is easily destabilized by loading of extraneous molecules. We found that a several-nanometer-thick bilayer vesicle made by self-assembly of an organic fullerene amphiphile doped with a metathesis catalyst serves as a nanosized chemical reactor in water, where a polymer is synthesized and assembled, depending on the affinity of the growing polymer to the organic groups on the amphiphile. This catalyst-bilayer system can thus control supramolecular assembly of the ester-functionalized polymer product into different nanoscale structures: a nanoparticle made of a single polymer chain and a nanocapsule made of several tens of polymer chains.

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Section: Resultsmentioning

confidence: 99%

Nanoscale Control of Polymer Assembly on a Synthetic Catalyst–Bilayer System

2016

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“…Among all our vesicles, F8K has the most hydrophobic surface; therefore, it was chosen as a model for the study. We added sequentially an aqueous solution of fluorous-tagged mannose (FT-Man) and a solution of mannose-binding protein concanavalin A (ConA) (Figure a and b), and ConA became densely bound on the fluorous surface . In a concentrated solution, the binding caused the cross-linking of many vesicles to increase the turbidity.…”

Section: Functional Cfa Vesiclesmentioning

confidence: 99%

“…We added sequentially an aqueous solution of fluorous-tagged mannose (FT-Man) and a solution of mannose-binding protein concanavalin A (ConA) (Figure 12a and b), and ConA became densely bound on the fluorous surface. 45 In a concentrated solution, the binding caused the cross-linking of many vesicles to increase the turbidity. Similarly, fluoroustagged galactose (Gal)-binding peanut agglutinin A (FT-Gal) and biotin-binding avidin (FT-biotin) (Figure 12b) were bound to the vesicle.…”

Section: Noncovalent Surface Functionalizationmentioning

confidence: 99%

Interfacial Chemistry of Conical Fullerene Amphiphiles in Water

Harano

Nakamura

2019

Acc. Chem. Res.

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Conspectus Amphiphiles are used for a variety of applications in our daily life and in industrial processes. They typically possess hydrophobic and hydrophilic moieties within the molecule, thereby performing a myriad of functions through the formation of two- and three-dimensional assemblies in water, such as Gibbs monolayers and micelles. However, these functions are often inseparable because they emerge from the same structural feature of the molecule, and are difficult to control because the structural diversity is limited to either long-chain hydrocarbons bearing a polar end group(s) or polymers bearing polar groups exposed to the exterior surface. In this Account, we describe the chemistry of a new class of amphiphiles, conical fullerene amphiphiles (CFAs), utilizing a superhydrophobic [60]fullerene group as a nonpolar apex with added structural features to make it soluble in water. By selective functionalization of only one side of the fullerene molecule, the CFA molecules spontaneously assemble in water through strong hydrophobic interactions among the fullerene apexes and exhibit unusual supramolecular and interfacial behavior. They form unilamellar micelles and vesicles at a critical aggregation concentration as low as micromolar, not showing any air–water and oil–water interfacial activity. The strong preference for self-assembly in water over monolayer formation at an air–water interface makes CFAs unique among conventional nonpolymeric surfactants. The CFA assemblies are often so mechanically robust that they can be transferred to the surface of a solid substrate and analyzed by high-resolution microscopy. Because of this rigid conical structure of a few nanometers in size, CFA molecules aggregate readily in water to form a hierarchical assembly with biomolecules and nanomaterials while maintaining the structural integrity of the CFA aggregate to form multicomponent agglomerates of controllable structural features. For instance, tissue-selective in vivo transport of DNA and siRNA has been achieved. Hybridization of a CFA vesicle with a transition metal catalyst enables the construction of a structurally defined nanospace and an interface for precise control of the nanoscale morphology of polymers. Solubilization of hydrophobic nanocarbons and nanoparticles is also achieved through hemimicelle formation on solid surfaces. The examples reported here illustrate the potential of the conical fullerene motif for the design of amphiphiles as well as supramolecular structures at molecular and tens of nanometers scale.

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“…Unlike lipid vesicles, which are irregular in size, mechanically unstable, and leaky against water permeation, a nanometer-sized bilayer vesicle spontaneously made from perfluoroalkylated [60]fullerene ( F8K , R = C 8 F 17 , Figure a,b) is mechanically robust and watertight, − and their radius can be precisely tuned between 10 and 30 nm by changing the molecular structure and preparation conditions. Although it possibly contains free water in its interior, no information has thus far been available on the internal structure, or on the characteristics, of water in the vesicle.…”

Section: Introductionmentioning

confidence: 99%

Neutron Scattering Reveals Water Confined in a Watertight Bilayer Vesicle

et al. 2018

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Water molecules confined in a nanocavity possess distinctly different characteristics from those in bulk, yet the preparation of such nanocavities is still a major experimental challenge. We report here a self-assembled vesicle of an anionic perfluoroalkylated [60]fullerene, unique for its outstanding stability and water tightness, containing water not bound to the membranes. Small-angle neutron scattering revealed that a vesicle of 14 nm outer radius contains a 2 nm thick fullerene bilayer, inside of which is a 3 nm thick membrane-bound water and unbound water in the 4 nm innermost cavity. The vesicle shows astonishingly low water permeability that is 6 to 9 orders of magnitude smaller than that of a lipid vesicle. As a result, a single vesicle isolated on a substrate can retain the interior water in air or even under high vacuum, indicating that the vesicle cavity provides a new tool for physicochemical studies of confined water as well as ions and molecules dissolved in it.

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High‐Density Display of Protein Ligands on Self‐Assembled Capsules via Noncovalent Fluorous Interactions

Cited by 6 publications

References 44 publications

Nanoscale Control of Polymer Assembly on a Synthetic Catalyst–Bilayer System

Nanoscale Control of Polymer Assembly on a Synthetic Catalyst–Bilayer System

Interfacial Chemistry of Conical Fullerene Amphiphiles in Water

Neutron Scattering Reveals Water Confined in a Watertight Bilayer Vesicle

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