Block copolymer–nanoparticle composites: Structure, functional properties, and processing

Sarkar, Biswajit; Alexandridis, Paschalis

doi:10.1016/j.progpolymsci.2014.10.009

Cited by 201 publications

(159 citation statements)

References 349 publications

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“…The successful navigation of nanoparticles (NPs) in a particular location of the block copolymer matrix and conferral of functional properties are governed by various enthalpic and entropic contributions to the total free energy [41]. This is the result of a balance between the polymer conformational entropy, NP translational entropy, and enthalpy of NP insertion caused by the creation of polymer-NP interfaces [41,[57][58][59][60].…”

Section: Discussionmentioning

confidence: 99%

“…This is the result of a balance between the polymer conformational entropy, NP translational entropy, and enthalpy of NP insertion caused by the creation of polymer-NP interfaces [41,[57][58][59][60]. The overall change in free energy resulting from the total change in enthalpy and entropy of the composite systems plays a critical role of NP dispersion in BCP volume and the overall morphology of the resulting composites [41,61,62]. Depending on the nature of polymer/particle interactions, particles can be located selectively at the interior of the domains formed by a particular block or localized at the interface, where different polymer blocks join [61].…”

Section: Discussionmentioning

confidence: 99%

“…Many reviews for various aspects of BCP nanocomposites have been published [4,5,8,12,15,16,18,19,[22][23][24][25][26][27][28][29][30][31][32][33][34][35][36][37][38][39][40][41]. To this end, considerable progress has been made in selectively controlling the distribution and location of QD/NP into the desired BCP domains [5,12,16,24,32,42,43].…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Enthalpy-driven selective loading of CdSe 0.75 S 0.25 nanoalloys in triblock copolymer polystyrene- b -polyisoprene- b -polystyrene

Aşkın¹,

Çeçen²,

Ünlütürk³

et al. 2016

Materials Today Communications

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a b s t r a c tCdSe 0.75 S 0.25 nanoalloys were blended with asymmetric triblock copolymer of polystyrene-bpolyisoprene-b-polystyrene(PS-SIS) in tetrahydrofuran. The fraction of styrene block varies from 14 to 22% with respect to isoprene by mass. The morphology of the copolymer cast film experiences a phase change from cylinder to lamella. CdSe 0.75 S 0.25 nanoalloys were prepared by two-phase method. The surface of the nanoalloys was capped by either oleic acid (OA) or n-tri-octylphosphonic acid (TOPO) in situ. The mean diameter of the alloyed particles is around 12 nm in both systems. The chemical nature of the nanoalloy surface was found to influence the dispersion of the particles over polymer volume. The size of the nanoalloy domains in PS is 50 nm, on average, consisting of approximately 0.7 wt% nanoalloys. However, the size of the nanoalloy domains is smaller when they are loaded into PS-SIS. The structure formation is predominantly determined by enthalpic compatibilization. Atomic force microscopy results suggest that the nanoalloys capped with TOPO sequester into PS-rich domains and enlarge the domain. On the other hand, the ones capped with OA prefer to locate in polyisoprene domains. The increase of particles over 1.0 wt% distorts the lamella structure.

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Section: Discussionmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Enthalpy-driven selective loading of CdSe 0.75 S 0.25 nanoalloys in triblock copolymer polystyrene- b -polyisoprene- b -polystyrene

Aşkın¹,

Çeçen²,

Ünlütürk³

et al. 2016

Materials Today Communications

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“…40 In NP-loaded micelles, BCPs suffer loss in conformational entropy during NP encapsulation resulting from NP rigidity, giving rise to phase transitions or surface defects. 41 PLGA copolymers are softer and more compressible than NPs, which may have enabled PLGA loading in the micelle core or micelle structure without affecting shape.…”

mentioning

confidence: 99%

Micelle-templated, poly(lactic-<em>co</em>-glycolic acid) nanoparticles for hydrophobic drug delivery

Nabar¹,

Mahajan²,

Calhoun³

et al. 2018

IJN

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Purpose Poly(lactic- co -glycolic acid) (PLGA) is widely used for drug delivery because of its biocompatibility, ability to solubilize a wide variety of drugs, and tunable degradation. However, achieving sub-100 nm nanoparticles (NPs), as might be desired for delivery via the enhanced permeability and retention effect, is extremely difficult via typical top-down emulsion approaches. Methods Here, we present a bottom-up synthesis method yielding PLGA/block copolymer hybrids (ie, “PolyDots”), consisting of hydrophobic PLGA chains entrapped within self-assembling poly(styrene- b -ethylene oxide) (PS- b -PEO) micelles. Results PolyDots exhibit average diameters <50 nm and lower polydispersity than conventional PLGA NPs. Drug encapsulation efficiencies of PolyDots match conventional PLGA NPs (ie, ~30%) and are greater than those obtained from PS- b -PEO micelles (ie, ~7%). Increasing the PLGA:PS- b -PEO weight ratio alters the drug release mechanism from chain relaxation to erosion controlled. PolyDots are taken up by model glioma cells via endocytotic mechanisms within 24 hours, providing a potential means for delivery to cytoplasm. PolyDots can be lyophilized with minimal change in morphology and encapsulant functionality, and can be produced at scale using electrospray. Conclusion Encapsulation of PLGA within micelles provides a bottom-up route for the synthesis of sub-100 nm PLGA-based nanocarriers with enhanced stability and drug-loading capacity, and tunable drug release, suitable for potential clinical applications.

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“…Therefore, "bottom-up" self-assembly approaches become alternative strategies to overcome these limitations, in particular block copolymer (BCP) templates are most widely used as scaffolds to direct the assemblies of NPs over macroscopic distances mirroring the BCP morphology. [ 1,[14][15][16][17][18][19][20] Generally, the fabrication of 2D single NP array applying BCPs thin fi lm as a template has been extensively reported. [14][15][16][17] Meanwhile based on the chemical difference of the blocks [21][22][23] or the nanocavities [ 24 ] provided by BCP template, metal NPs [ 21,[23][24] with suitable ligand and size control or metal precursors [ 22,23 ] can be introduced into each block, thus 2D dual NPs array can also be fabricated.…”

mentioning

confidence: 99%

Directed Self‐Assembly of Diblock Copolymer Thin Films on Prepatterned Metal Nanoarrays

Chang

Huang

2015

Macromol. Rapid Commun.

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The sequential layer by layer self-assembly of block copolymer (BCP) nanopatterns is an effective approach to construct 3D nanostructures. Here large-scale highly ordered metal nano-arrays prepared from solvent annealed thin films of polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP) diblock copolymer are used to direct the assembly of the same BCP. The influence of initial loading concentration of metal precursor, the type of metal nanoparticle (gold, platinum, and silver), and the nanoparticle-substrate interaction on the directed assembly behavior of the upper BCP layer have been focused. It is found that the upper BCP film can be completely directed by the gold nanoarray with P2VP domain exclusively located between two adjacent gold nanowires or nanodots, which behaves the same way as on the platinum nanoarray. While the silver nanoarray can be destroyed during the upper BCP self-assembly with the silver nanoparticles assembled into the P2VP domain. Based on the discussions of the surface energy of nanoparticles and the interplay between nanoparticle-substrate interaction and nanoparticle-polymer interaction, it is concluded that the effect of immobilization of nanoparticles on the substrate, together with entropy effect to minimize the energetically unfavorable chain stretching contributes to the most effective alignment between each layer.

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Block copolymer–nanoparticle composites: Structure, functional properties, and processing

Cited by 201 publications

References 349 publications

Enthalpy-driven selective loading of CdSe 0.75 S 0.25 nanoalloys in triblock copolymer polystyrene- b -polyisoprene- b -polystyrene

Enthalpy-driven selective loading of CdSe 0.75 S 0.25 nanoalloys in triblock copolymer polystyrene- b -polyisoprene- b -polystyrene

Micelle-templated, poly(lactic-<em>co</em>-glycolic acid) nanoparticles for hydrophobic drug delivery

Directed Self‐Assembly of Diblock Copolymer Thin Films on Prepatterned Metal Nanoarrays

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