θ-Solvent-Mediated Double-Shell Polyethylene Glycol Brushes on Nanoparticles for Improved Stealth Properties and Delivery Efficiency

Xue, Yao; Liu, Shuhan; An, Zixin; Li, Jia-Xuan; Wang, Chunyu; Wang, Xiaosong; Sun, Tianmeng; Liu, Kun

doi:10.1021/acs.jpclett.1c01291

Cited by 9 publications

(12 citation statements)

References 41 publications

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“…In many cases, self-assembly is driven by forces acting between the molecules capping the NP surface, rather than NPs themselves, and from this perspective, polymer ligands are particularly interesting and important. First, since macromolecular ligands and NPs can have similar dimensions, at a sufficiently high grafting density, a polymer corona can completely “disguise” the NP − and largely govern the self-assembly process. Second, polymers can be designed and synthesized with a variety of compositions, dimensions, and structures, all of which can be used individually or collectively to “program” NP assembly.…”

Section: Introductionmentioning

confidence: 99%

Polymer-Tethered Nanoparticles: From Surface Engineering to Directional Self-Assembly

et al. 2022

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Conspectus Current interest in nanoparticle ensembles is motivated by their collective synergetic properties that are distinct from or better than those of individual nanoparticles and their bulk counterparts. These new advanced optical, electronic, magnetic, and catalytic properties can find applications in advanced nanomaterials and functional devices, if control is achieved over nanoparticle organization. Self-assembly offers a cost-efficient approach to produce ensembles of nanoparticles with well-defined and predictable structures. Nanoparticles functionalized with polymer molecules are promising building blocks for self-assembled nanostructures, due to the comparable dimensions of macromolecules and nanoparticles, the ability to synthesize polymers with various compositions, degrees of polymerization, and structures, and the ability of polymers to self-assemble in their own right. Moreover, polymer ligands can endow additional functionalities to nanoparticle assemblies, thus broadening the range of their applications. In this Account, we describe recent progress of our research groups in the development of new strategies for the self-assembly of nanoparticles tethered to macromolecules. At the beginning of our journey, we developed a new approach to patchy nanoparticles and their self-assembly. In a thermodynamically driven strategy, we used poor solvency conditions to induce homopolymer surface segregation in pinned micelles (patches). Patchy nanoparticles underwent self-assembly in a well-defined and controlled manner. Following this work, we overcame the limitation of low yield of the generation of patchy nanoparticles, by using block copolymer ligands. For block copolymer-capped nanoparticles, patch formation and self-assembly were “staged” by using distinct stimuli for each process. We expanded this work to the generation of patchy nanoparticles via dynamic exchange of block copolymer molecules between the nanoparticle surface and micelles in the solution. The scope of our work was further extended to a series of strategies that utilized the change in the configuration of block copolymer ligands during nanoparticle interactions. To this end, we explored the amphiphilicity of block copolymer-tethered nanoparticles and complementary interactions between reactive block copolymer ligands. Both approaches enabled exquisite control over directional and self-limiting self-assembly of complex hierarchical nanostructures. Next, we focused on the self-assembly of chiral nanostructures. To enable this goal, we attached chiral molecules to the surface of nanoparticles and organized these hybrid building blocks in ensembles with excellent chiroptical properties. In summary, our work enables surface engineering of polymer-capped nanoparticles and their controllable and predictable self-assembly. Future research in the field of nanoparticle self-assembly will include the development of effective characterization techniques, the synthesis of new functional polymers, and the development of environmentally responsive se...

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Section: Introductionmentioning

confidence: 99%

Polymer-Tethered Nanoparticles: From Surface Engineering to Directional Self-Assembly

et al. 2022

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“…Polyethylene glycol (PEG) is widely used for the surface modification of inorganic nanoparticles (NPs) to improve their stealth properties for in vitro and in vivo bioapplications. − PEG chains on NP surfaces not only provide a large steric hindrance due to their high conformational entropy but also can inhibit protein fouling by forming a physical and energetic hydration layer. − The steric hindrance and hydration layer of PEG chains minimize nonspecific protein binding, preventing the NPs from being recognized by the reticulo-endothelial system organs, and prolonging the blood circulation time of NPs, all of which are of importance for the in vitro and in vivo bioapplications of inorganic NPs. − …”

Section: Introductionmentioning

confidence: 99%

Physisorption of Poly(ethylene glycol) on Inorganic Nanoparticles

Xue

Gao

et al. 2022

ACS Nano

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Poly(ethylene glycol) (PEG) is the most widely used polymer to decorate inorganic nanoparticles (NPs) by the “grafting-to” method for antifouling properties. PEG also shows diverse supramolecular interactions with nanoparticle surfaces and polar molecules, suggesting that the physisorption between PEG chains and NPs cannot be ignored in the “grafting-to” process. However, the effect of physisorption of PEG to NPs on the process of chemisorption has been rarely studied. Herein, we report that unfunctionalized PEG is physically adsorbed on various NPs by polyvalent supramolecular interactions, adopting “loop-and-train-tail” conformations. We investigated the effect of molecular weight of PEG and ligands of the NPs on the conformation of PEG chains by experimental methods and simulation. It is demonstrated that the physisorption of PEG on NPs can facilitate the chemisorption in the initial stages but delays it in the later stages during the “grafting-to” process. This work provides a deeper understanding of the conformation of physisorbed PEG on NPs and the relationship between physisorption and chemisorption.

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“…[ 6 ] Owing to the effective chain conformation of PEG blocks, they can not only prevent particle aggregation via the antifouling effect, but also prolong the blood circulation time. [ 7 ] Despite these advantages, most surfactants used for the production of SLPs have low molecular weights or relatively weak intermolecular attractions. [ 8 ] Therefore, it remains difficult to maintain the molecular crystallinity of the lipid phase and form a mechanically strong interface simultaneously.…”

Section: Introductionmentioning

confidence: 99%

Hydrophobically Modified Cellulose Nanofibers‐Enveloped Solid Lipid Microparticles for Improved Antioxidant Cargo Retention

Bae

Seo

Shin

et al. 2022

Macromol. Rapid Commun.

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This study introduces a cellulose nanofiber surfactant system, in which the surface is hydrophobically modified with different alkyl chain structures for the effective envelopment of solid lipid microparticles (SLMs). To endow bacterial cellulose nanofibers (BCNFs) with excellent ability to assemble at the lipid-water interface, alkyl chains with designated molecular structures, such as decane, didecane, and eicosane, are covalently grafted onto the BCNF surface. Interfacial tension and interfacial rheology measurements indicate that dialkyl chain-grafted BCNFs (diC 10 BCNF) exhibit strong interfibrillar association at the interface. The formation of a dense and tough fibrillary membrane contributes significantly to the enveloping of the SLMs, regardless of the lipid type. Because the diC 10 BCNF-enveloped SLMs exhibit a core molecular crystalline phase at the microscale, they can immobilize an oil-soluble antioxidant while maintaining its long-term storage stability. These findings show that the cellulose-surfactant-based SLM technology is applicable to the stabilization and formulation of readily denatured active ingredients.

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θ-Solvent-Mediated Double-Shell Polyethylene Glycol Brushes on Nanoparticles for Improved Stealth Properties and Delivery Efficiency

Cited by 9 publications

References 41 publications

Polymer-Tethered Nanoparticles: From Surface Engineering to Directional Self-Assembly

Polymer-Tethered Nanoparticles: From Surface Engineering to Directional Self-Assembly

Physisorption of Poly(ethylene glycol) on Inorganic Nanoparticles

Hydrophobically Modified Cellulose Nanofibers‐Enveloped Solid Lipid Microparticles for Improved Antioxidant Cargo Retention

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