Emulsion Solvent Evaporation-Induced Self-Assembly of Block Copolymers Containing pH-Sensitive Block

Wu, Yuqing; Wang, Ke; Tan, Haiying; Xu, Jiangping; Zhu, Jintao

doi:10.1021/acs.langmuir.7b02330

Cited by 51 publications

(63 citation statements)

References 57 publications

(83 reference statements)

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“…Interfacial instability is a contemporary topic that is extensively studied in polymer science to develop novel morphologies, with one example being hierarchically structured microparticles during solvent removal from oil‐in‐water emulsions . The fundamental principle is that the interface is full of fluctuations and the undulation amplitude is controlled by the interfacial tension.…”

Section: Resultsmentioning

confidence: 99%

A Cast Net Thrown onto an Interface: Wrapping 3D Objects with an Interfacially Jammed Amphiphilic Sheet

Cui

Gao

Bowland

et al. 2020

Adv Materials Inter

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with the encapsulant being either solid elastic films [12][13][14][15][16] or solid-like jammed films of functional particles. [17][18][19][20][21] These films are rigid enough to stabilize nonequilibrium morphologies of the wrapped liquid, thus breaking the limit of equilibrium morphologies and further creating new shapes of wrapped, encapsulated fluids with inimitable functionalities.For traditional liquid-phase technologies, a liquid-like layer of surfactant or particles is usually used for wrapping and stabilizing liquid droplets. [22][23][24] Recent studies show that sufficiently thin elastic sheets offer a novel path to spontaneously wrap liquid droplets using capillary forces, where the elastic energy of curving sheets is balanced by the reduction of interfacial energy. [15,16,25,26] Although negligible at macroscopic scales, capillary forces become dominant and are able to bend the elastic sheets when the bending rigidity of elastic sheets is vanishingly small. [12,15,25] The robust elastic sheets allow the liquid drops to be trapped in nonequilibrium 3D shapes via a process that is usually referred to as capillary origami. [12,16,26] In previous wrapping studies, the final encapsulated 3D geometry was almost solely determined by the initial geometry of the flat thin elastic sheets, which made the process complicated and lacked versatility. The elastic sheets in previous reports were often conventional polymer thin films whose interfacial activities were too weak to manipulate the interfacial tension and participate in morphology evolution. [12,15,16] A large-scale elastic sheet [27] with a significant interfacial activity is desired to manipulate the interface that can adapt to various nonequilibrium shapes by external influence-a stimulant for evolved morphologies at the interface.Here, we report in situ formation of a large-scale surfactant sheet with strong interfacial activities by interfacial jamming of poorly soluble amphiphilic lignin macromolecules in particulate form at an oil/water interface. The amphiphilic nature of the surfactant sheet enables wrapping of either water or oil droplets, while its rigidity allows it to hold the liquid phases in various nonequilibrium morphologies. The surfactant sheet is physically networked by reversible hydrogen bonding and π-π interaction, which endows it with transforming and self-healing ability. The strong interfacial activity of the surfactant sheet results in an interfacial instability, which drives evolution of interfacial morphology and novel wrapped microstructures.Wrapping a 3D object with a 2D sheet is not uncommon, but the wrapping behavior becomes complex and interesting when the sheet is bestowed with strong interfacial activities. Amphiphilic lignin macromolecules, isolated from biomass, form a scalable thin surfactant sheet at an oil/water interface through the interfacial jamming process. The process marks three distinct stages of interfacial behavior: a) diffusive assembly, b) viscous assembly with retarded mobility, and c) flexible yet irre...

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Section: Resultsmentioning

confidence: 99%

A Cast Net Thrown onto an Interface: Wrapping 3D Objects with an Interfacially Jammed Amphiphilic Sheet

Cui

Gao

Bowland

et al. 2020

Adv Materials Inter

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“…Yellow (and their corresponding bars) represents our and commonly used stabilizers, while red (and their corresponding bars) is denoted as commonly reported materials in synthesizing biodegradable and/or nonspherical nanoparticles for drug delivery and targeting. Abbreviations and further details of referred material–nanoparticles: SDS (sodium dodecyl sulfate), (2) Docusate‐Na, (3) Triton X‐100, (4) Na‐Cholate & ‐Deoxycholate, (5) PVP (poly(vinylpyrrolidone)), (6) PEG (poly(ethylene glycol)) 6000, (7) Dextran, (8) Poloxamer 188, (9) HSA (human serum albumin), (10) Chitosan, (11) Cyanoacrylate, (12) PS‐COOH (carboxylated poly(styrene)), (13) PS (poly(styrene)), (14) PDMS (poy(dimethylsiloxane)), (15) PMMA (poly(methyl methacrylate)), (16) PHEA (poly(hydroxyethyl acrylate)), (17) PHEMA (poly(hydroxyethyl methacrylate)), (18) PEGDA (poly(ethylene glycol) diacrylate)‐PHEMA (poly(hydroxyethyl methacrylate)), (19) CEA (2‐carboxyethyl acrylate), (20) PBLG (poly(γ‐benzyl l ‐glutamate)), (21) Triglyceride (cocoa butter), (22) P4VP (poly(4‐vinyl pyridine)), (23) Au (gold), and (24) SWCNT (single‐walled carbon nanotubes) …”

Section: Resultsmentioning

confidence: 99%

“…First, beside well‐defined amorphous aliphatic polyesters and PS‐COOH studied here, another best example for the aforementioned hypothesis is poly(4‐vinyl pyridine) (P4VP), an amorphous and a weakly hydrophilic polymer (Figure e). Likewise the aliphatic polyesters, P4VP (grafted by PS) exhibits shape‐memory properties depending on media pH . In contrast to aliphatic polyesters, the P4VP hydrophobicity becomes lesser at pH lower than its p K a (5.5) and reaches maximum at higher pH .…”

Section: Discussionmentioning

confidence: 99%

“…Likewise the aliphatic polyesters, P4VP (grafted by PS) exhibits shape‐memory properties depending on media pH . In contrast to aliphatic polyesters, the P4VP hydrophobicity becomes lesser at pH lower than its p K a (5.5) and reaches maximum at higher pH . Therefore, these findings are recently employed to produce a pH‐sensitive block copolymer with polystyrene (PS‐ b ‐P4VP) .…”

Section: Discussionmentioning

confidence: 99%

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Nonspherical Nanoparticle Shape Stability Is Affected by Complex Manufacturing Aspects: Its Implications for Drug Delivery and Targeting

Haryadi

Hafner

Amin

et al. 2019

Adv Healthcare Materials

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The shape of nanoparticles is known recently as an important design parameter influencing considerably the fate of nanoparticles with and in biological systems. Several manufacturing techniques to generate nonspherical nanoparticles as well as studies on in vitro and in vivo effects thereof have been described. However, nonspherical nanoparticle shape stability in physiological‐related conditions and the impact of formulation parameters on nonspherical nanoparticle resistance still need to be investigated. To address these issues, different nanoparticle fabrication methods using biodegradable polymers are explored to produce nonspherical nanoparticles via the prevailing film‐stretching method. In addition, systematic comparisons to other nanoparticle systems prepared by different manufacturing techniques and less biodegradable materials (but still commonly utilized for drug delivery and targeting) are conducted. The study evinces that the strong interplay from multiple nanoparticle properties (i.e., internal structure, Young's modulus, surface roughness, liquefaction temperature [glass transition (Tg) or melting (Tm)], porosity, and surface hydrophobicity) is present. It is not possible to predict the nonsphericity longevity by merely one or two factor(s). The most influential features in preserving the nonsphericity of nanoparticles are existence of internal structure and low surface hydrophobicity (i.e., surface‐free energy (SFE) > ≈55 mN m−1, material–water interfacial tension <6 mN m−1), especially if the nanoparticles are soft (<1 GPa), rough (Rrms > 10 nm), porous (>1 m2 g−1), and in possession of low bulk liquefaction temperature (<100 °C). Interestingly, low surface hydrophobicity of nanoparticles can be obtained indirectly by the significant presence of residual stabilizers. Therefore, it is strongly suggested that nonsphericity of particle systems is highly dependent on surface chemistry but cannot be appraised separately from other factors. These results and reviews allot valuable guidelines for the design and manufacturing of nonspherical nanoparticles having adequate shape stability, thereby appropriate with their usage purposes. Furthermore, they can assist in understanding and explaining the possible mechanisms of nonspherical nanoparticles effectivity loss and distinctive material behavior at the nanoscale.

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“…With the deepening of the research and the improvement of the experimental technique, the researchers find that the onion‐like vesicles with different layers can be obtained through the self‐assembly of the polymer systems . For example, Kang et al studied the self‐assembly of the comb‐like amphiphilic copolymers in aqueous media and observed that the number of wall layers is dependent on the concentration of polymers in the aqueous media .…”

Section: Introductionmentioning

confidence: 99%

Multilayer onion‐like vesicles self‐assembled from amphiphilic hyperbranched multiarm copolymers via simulation

Hao

Tan

et al. 2020

Journal of Polymer Science

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Multilayer onion‐like vesicles are valuable in cell mimics and biomedicine fields. However, as an excellent self‐assembly precursor, the formation of multilayer onion‐like vesicles by the self‐assembly of hyperbranched multiarm copolymers (HMCs) were not reported due to the complex self‐assembly dynamics. In this article, the self‐assembly behavior of multilayer onion‐like vesicles from HMCs was systematically investigated using dissipative particle dynamics simulation. The formation conditions for different kinds of vesicles were disclosed through the construction of the morphological phase diagram. Moreover, the formation mechanisms of the onion‐like vesicles with different layers were revealed. We observed that it is the fusion mechanism in low concentrations and the molecular rearrangement mechanism in high concentrations. For low concentration, the law between the number of the membrane layers and the morphology of the aggregates in the fusion process was disclosed. Meanwhile, the membrane of the onion‐like vesicles self‐assembled from HMCs is monolayer structure and the thickness of each layer is decreased in sequence from inside to outside. The current observations have important guiding significance for its application in drug delivery systems.

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Emulsion Solvent Evaporation-Induced Self-Assembly of Block Copolymers Containing pH-Sensitive Block

Cited by 51 publications

References 57 publications

A Cast Net Thrown onto an Interface: Wrapping 3D Objects with an Interfacially Jammed Amphiphilic Sheet

A Cast Net Thrown onto an Interface: Wrapping 3D Objects with an Interfacially Jammed Amphiphilic Sheet

Nonspherical Nanoparticle Shape Stability Is Affected by Complex Manufacturing Aspects: Its Implications for Drug Delivery and Targeting

Multilayer onion‐like vesicles self‐assembled from amphiphilic hyperbranched multiarm copolymers via simulation

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