Monodipserse Nanostructured Spheres of Block Copolymers and Nanoparticles via Cross-Flow Membrane Emulsification

Shin, Jae Man; Kim, Minsoo P.; Yang, Hyun-Seung; Ku, Kang Hee; Jang, Se Gyu; Youm, Kyung Ho; Yi, Gi‐Ra; Kim, Bumjoon J.

doi:10.1021/acs.chemmater.5b02020

Cited by 72 publications

(90 citation statements)

References 65 publications

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“…[43] As model system, we chose polystyrene-blockpolybutadiene-block-poly(tert-butyl methacrylate) (SBT) triblock terpolymers (Scheme 1a;s ee Supporting Information). [46][47][48][49][50] For our purposes,wefirst dissolved SBT in chloroform (CHCl 3 )at ac oncentration of c = 10 gL À1 ,f ollowed by emulsification in water containing cetyltrimethylammonium bromide (CTAB) (c = 10 gL À1 )a ss urfactant (Scheme 1b). Self-assembly in confinement has emerged as apowerful method to create functional block copolymer microparticles,y et, for triblock terpolymers the potential of confinement assembly is still largely unexplored.…”

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“…Self-assembly in confinement has emerged as apowerful method to create functional block copolymer microparticles,y et, for triblock terpolymers the potential of confinement assembly is still largely unexplored. [46][47][48][49][50] For our purposes,wefirst dissolved SBT in chloroform (CHCl 3 )at ac oncentration of c = 10 gL À1 ,f ollowed by emulsification in water containing cetyltrimethylammonium bromide (CTAB) (c = 10 gL À1 )a ss urfactant (Scheme 1b). CHCl 3 was allowed to evaporate over the course of 2days to give solid SBT Scheme 1.…”

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Template‐Free Synthesis and Selective Filling of Janus Nanocups

et al. 2019

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We report on the formation of shape-and surfaceanisotropic Janus nanocups (JNCs) by evaporation-induced confinement assembly (EICA) of ABC triblock terpolymers. During microphase separation in spherical confinement, the triblockt erpolymer spontaneously adopted ah emispherical shape with an inner concentric lamella-lamella (ll) morphology.C ross-linking and disassembly of the microparticles resulted in well-defined JNCs with different chemistry on the inside and outside.B ys ynthesizing polymers with increasing length of the cross-linkable block, we tuned the mechanical stability of the nanocups,w hichi sr elevant to control opening and closing of the cup cavity.Weutilize the Janus properties for selective uptake of cargo exemplified by the filling of JNCs with polymer or gold nanoparticles.The directional properties of JNCs suggest applications in locomotion, oil-spill recovery, storage and release,t emplating,a nd as nanoreactors with attoliter volume. Angewandte ChemieCommunications 7123

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Template‐Free Synthesis and Selective Filling of Janus Nanocups

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“…Okubo et al demonstrated poly(styrene‐ block ‐methylmethacrylate) (PS‐ b ‐PMMA) microspheres having a periodic onion‐like structure, prepared by the evaporation of solvent from droplets of an emulsion in toluene . Kim and co‐workers have developed a crossflow type membrane emulsification technology to control the size of block copolymer microspheres . Yabu and co‐workers also identified onion‐like structures in phase separated PS ‐b‐ PMMA microspheres produced using the SORP technique .…”

Section: Controlling the Structures Of Phase Separated Polymer Microsmentioning

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Fabrication of Nanostructured Composite Microspheres Based on the Self‐Assembly of Polymers and Functional Nanomaterials

Yabu

2019

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Achieving the specific properties required for the applications discussed above necessitates control over the morphologies of the polymer particles as well as the precise alignment of functional nanoparticles at particle interiors and surfaces. Studies using seed polymerization and related so-called second generation particle preparation techniques have succeeded in preparing polymer microspheres having anisotropic morphologies. [10] These techniques for the synthesis of nonspherical polymer microparticles are both powerful and practical, although the particle shape has been found to be greatly affected by the preparation conditions employed. These conditions involve numerous parameters, and so controlling the particle morphology remains challenging. In addition to first and second generation particle preparation technologies employing emulsion polymerization, recent studies have demonstrated the fabrication of nanostructured microspheres based on the phase separation of polymers. [11,12] These methods can be considered as the third generation of progress in this field and allow the tuning of particle morphologies in association with phase separation theories developed during prior work with bulk polymer blends, alloys, and composites. The alignment of nanoparticles in phase separated polymer microspheres could lead to nanostructured particles with many practical applications. Figure 1 presents some of the many methods developed for the synthesis of polymer microspheres. This diagram indicates representative existing approaches used to obtain controlled particle sizes, as well as specific phases in the interior and at the surfaces of such microspheres, and can be divided into two main categories; top-down and bottom-up. These two types of procedures differ with regard to the process used to form internal and surface structures. The polymerization or crosslinking of uniformly sized oil/water (O/W) or water/oil (W/O) emulsion droplets formed by microfluidic devices is a well-known topdown fabrication technique used to produce structured polymer microspheres with sizes on the scale of tens of micrometers. [13] Taking advantage of the laminar flow inside narrow capillaries, multiple phases can be formed in the interiors of the emulsion droplets, resulting in the formation of multiphase polymer microspheres. [14] In contrast, in the case of bottom-up approaches, the phase separation of polymers is used to create internal and surface nanostructures. The latter methods have received considerable attention because they permit size control on a variety of size scales as well as morphological tuning. [15] This Review examines recent developments in the morphological control of polymer microspheres fabricated via the phase separation of polymers as well as the alignment of functional nanoparticles inside microspheres prepared by so-called bottom-up synthesis techniques. Several methods for adjusting the internal and surface morphologies of polymer microspheres based on the phase separation of polymer blends and block copoly...

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“…Stattdessen vereinen wir intrinsische Asymmetrie von ABC-Triblock-Terpolymeren mit der Selbstorganisation im beengten Raum unter Lçsungsmittel-Verdampfung (Schema 1). [46][47][48][49][50] In unserem Beispiel lçsen wir zunächst das SBT-Polymer in Chloroform (CHCl 3 )b ei c = 10 gL À1 und emulgieren die Polymerlçsung in Wasser mit Cetyltrimethylammoniumbromid (CTAB; c = 10 gL À1 )a ls Te nsid (Schema 1b). [44,45] Die Blocklängen wurden gewählt, um die Bildung einer Lamellen-Lamellen-(ll)-Morphologie zu begünstigen;d ie wichtigsten Details der Polymere sind in Tabelle 1aufgelistet.…”

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“…FürT riblock-Terpolymere ist das Potenzial dieser Methode jedoch bislang nahezu unerforscht. [46][47][48][49][50] In unserem Beispiel lçsen wir zunächst das SBT-Polymer in Chloroform (CHCl 3 )b ei c = 10 gL À1 und emulgieren die Polymerlçsung in Wasser mit Cetyltrimethylammoniumbromid (CTAB; c = 10 gL À1 )a ls Te nsid (Schema 1b). Anschließend verdampft CHCl 3 über einen Zeitraum von ca.…”

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Templat‐freie Synthese und selektive Befüllung von Janus‐Nanocups

et al. 2019

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Wirb erichten über die Herstellung von Janus-Nanocups (JNCs) mit anisotroper Form und Oberfläched urch Selbstorganisation von ABC-Triblock-Terpolymeren im beengten Raum, induziert durchL çsungsmittel-Verdampfung. Während der Mikrophasenseparation in sphärischer Begrenzung bildet das Triblock-Terpolymer spontan hemisphärische Mikropartikel mit einer inneren Lamellen-Lamellen(ll)-Morphologie.D urchV ernetzung und nachträgliches Zerlegen der Mikropartikel entstehen JNCs mit unterschiedlicher Chemie auf der Innen-und Außenseite.Die mechanische Stabilitätder JNCs lässt sich durch Variation der Länge des vernetzbaren Polymer-Blockskontrollieren. Die Stabilitätist dabei vor allem relevant, um das Öffnen/Schließen der Kavitätzusteuern. Wir nutzen die Janus-Eigenschaften zur selektiven Beladung, z. B. mit Polymeren oder Goldnanopartikeln. Dank ihrer gerichteten Eigenschaften kçnnten die JNCs als Mikroschwimmer,zur Wasserreinigung,a ls Wirkstofftransporter,a ls Template oder als Nanoreaktoren genutzt werden.

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Monodipserse Nanostructured Spheres of Block Copolymers and Nanoparticles via Cross-Flow Membrane Emulsification

Cited by 72 publications

References 65 publications

Template‐Free Synthesis and Selective Filling of Janus Nanocups

Template‐Free Synthesis and Selective Filling of Janus Nanocups

Fabrication of Nanostructured Composite Microspheres Based on the Self‐Assembly of Polymers and Functional Nanomaterials

Templat‐freie Synthese und selektive Befüllung von Janus‐Nanocups

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