Amphiphilic polyether-based block copolymers as crosslinkable ligands for Au-nanoparticles

Hörenz, Christoph; Rudolph, Tobias; Barthel, Markus J.; Günther, Ulrike; Schacher, Felix H.

doi:10.1039/c4py01434k

Cited by 14 publications

(11 citation statements)

References 59 publications

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“…Dust-free solutions were obtained by filtration through hydrophobic fluoropore (PTFE) membrane filters with a pore size of 0.45 μm (Millipore, Millex-FH). DLS data evaluation was performed by using the CONTIN algorithm, which can be applied for the analysis of multiple decay processes as described in the literature. , A Philips EM420 transmission electron microscope (TEM) using a LaB 6 cathode at an acceleration voltage of 120 kV was used to obtain TEM images. TEM grids (carbon film on copper, 300 mesh) were purchased from Electron Microscopy Sciences (Hatfield, PA).…”

Section: Methodsmentioning

confidence: 99%

“…We take advantage of a recently developed strategy to place functional groups at the junction point of the block copolymers by combining carbanionic and oxyanionic polymerization and termination with a functional glycidyl ether (Scheme ). , In this case, a thin shell layer at the core of the micelles can be formed via a cross-linking reaction of the single functional group at the junction point.…”

Section: Introductionmentioning

confidence: 99%

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Polyvinylferrocene-Based Amphiphilic Block Copolymers Featuring Functional Junction Points for Cross-Linked Micelles

et al. 2016

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The synthesis of high-molecular-weight, welldefined poly(vinylferrocene)-block-poly(ethylene glycol) (PVFc-b-PEG) diblock copolymers (M n = 13 000−44 000 g mol −1 ; Đ = 1.29−1.34) with precisely one allyl group at the junction point is introduced. Allyl glycidyl ether (AGE) was used to end-functionalize PVFc, resulting in hydroxyl functional macroinitiators for the oxyanionic polymerization of ethylene oxide. The self-assembly behavior of the amphiphilic PVFc-b-PEG copolymers in water has been investigated in a detailed manner, using dynamic light scattering (DLS) and transmission electron microscopy (TEM). The redox activity of the PVFc block was confirmed by UV/vis spectroscopy, while cyclovoltammetry (CV) measurements were carried out to support the stability and full reversibility of the ferrocene/ferrocenium redox couple. Both formation and dissociation of the macromolecular self-assemblies in aqueous solution via oxidation and reduction of the PVFc segments were evidenced by TEM and DLS. The dye Nile Red was used as model compound to investigate the stabilization of a water-insoluble molecule in aqueous solution by the block copolymers via encapsulation inside micellar structures. Oxidation of the PVFc segments lead to instantaneous and quantitative release of the dye. Furthermore, incorporation of the allyl moiety at the block junction point was used to cross-link the shell of the compartments. By this strategy a stable incorporation of the dye was achieved while triggered release via oxidation led to quantitative liberation.

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Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Polyvinylferrocene-Based Amphiphilic Block Copolymers Featuring Functional Junction Points for Cross-Linked Micelles

et al. 2016

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“…The chemists have made a great deal of efforts in the exploration of more and better amphiphilic diblock polymers as the stabilizers of AuNPs. Thiol-derivatized poly(ε-caprolactone)b-poly(acrylic acid) (PCL-PAA), [39] folate-conjugated poly(laspartate-doxorubicin)-b-poly(ethylene glycol) (PAsp-PEG), [40] thermosensitive poly(N-isopropyl acrylamide)-b-poly(nbutylacrylate) (PNIPAM-PBA), [41] dithiol-functionalized poly(ethylene oxide)-b-poly(propylene oxide) (PEO-PPO), [42] polystyrene-b-polymethylbutylene (PS-PMB), [43] thiol terminated poly(ethyl oxide)-b-polystyrene (PEO-PS), [44,45] thiol-reactive poly(ethylene oxide)-b-poly(pyridyldisulfide ethylmethacrylate) (PEO-PPDSM), [46] thiol-terminated poly(ethylene oxide)-bpoly(furfuryl glycidyl ether) or poly(allyl glycidyl ether) (PEO-PFGE/PFGE), [47] PEG-PS with one pendant thiol group at the center point of blocks, [48] PEG-oleylamine, [49] and thermoresponsive poly(N-isopropylacrylamide-co-2,3-epithiopropyl methacrylate)-b-poly(poly(ethylene glycol) methyl ether methacrylate) P(NIPAM-ETMA)-P(PEGMA) bearing an episulfide moiety [50] were synthesized for stabilizing AuNPs. Taking an example, Nie and co-workers synthesized amphiphilic diblock polymers PEO-PS with a terminated thiol group, which were grafted onto the surface of AuNPs through AuS bonds, generating well-defined vesicles and tubules by selfassembly in selective solvents, as shown in Figure 2.…”

Section: Amphiphilic Diblock Polymersmentioning

confidence: 99%

Recent Advances in Amphiphilic Polymers as the Stabilizers of Colloidal Gold Nanoparticles

Dai

Zhang

2018

Macro Materials & Eng

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Gold nanoparticles (AuNPs) exhibit high catalytic activity as catalysts and have potential applications in biomedicine. To prevent the aggregation of colloidal AuNPs, the stabilizers including organic small molecules, organic ligands, inorganic ligands, and polymers, are necessary to be added in the synthesis of colloidal AuNPs. Among these stabilizers, amphiphilic polymers have attracted significant attention from scientists in the development of polymerization and modification methods. To date, numerous efforts are employed to develop amphiphilic polymers as the stabilizers of colloidal AuNPs but are not well‐summarized yet. In this review, four parts (amphiphilic linear polymers, amphiphilic graft polymers, amphiphilic hyperbranched polymers, and amphiphilic dendrimers) according to the polymer architectures will be discussed. Comprehensive understanding of amphiphilic polymers that are used for stabilizing colloidal AuNPs is provided.

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“…A further aspect which in our opinion is of interest to interface design is the incorporation of reversibly cross-linkable segments into block copolymer materials, as e.g. recently shown for thiol-terminated block copolymer ligands on Au nanoparticles or PEO- block -poly(furfuryl glycidyl ether) (PEO- b -PFGE) block copolymer films . Both these approaches require external temperature input and thus still feature limited adaptivity.…”

Section: State-of-the-art: Selected Examplesmentioning

confidence: 99%

Polymer Interfaces: Synthetic Strategies Enabling Functionality, Adaptivity, and Spatial Control

2016

Self Cite

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Polymer interfaces are ubiquitous in Nature and technology. Equipping artificial polymer-based interfaces with highly defined functions requires advanced macromolecular chemistry and powerful chemical tools. In this Perspective, we explore the nature of anisotropici.e., spatially resolved polymer interfaces prepared via top-down and bottom-up approaches with selected examples from the recent literature. These range from self-assembly driven systems based on single polymer chains and block copolymers to lithographic encoding able to span wide spatial dimensions of patterning. Based thereon, we formulate the in our opinion required advances in polymer chemistry that will contribute significantly to preparing the next generation of structured interfaces. Among others, this includes the to-date limited orthogonality of parallelly executed ligation reactions as well as limits in λ-orthogonally addressable pericyclic ligation chemistry. Finally, we propose some long-term visions for not yet existinghowever currently soughttechnology that could drive interactive and adaptive polymer interface construction to new levels. These include the spatially resolved encoding of interfaces with molecular precision and the introduction of programmable properties to interfaces of varying shape and chemical complexity.

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Amphiphilic polyether-based block copolymers as crosslinkable ligands for Au-nanoparticles

Abstract: We report on the synthesis of thiol-terminated, polyether-based block copolymers featuring a crosslinkable block and their use as ligands for Au-nanoparticles in organic solvents.

Cited by 14 publications

References 59 publications

Polyvinylferrocene-Based Amphiphilic Block Copolymers Featuring Functional Junction Points for Cross-Linked Micelles

Polyvinylferrocene-Based Amphiphilic Block Copolymers Featuring Functional Junction Points for Cross-Linked Micelles

Recent Advances in Amphiphilic Polymers as the Stabilizers of Colloidal Gold Nanoparticles

Polymer Interfaces: Synthetic Strategies Enabling Functionality, Adaptivity, and Spatial Control

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