Photo-PISA: Shedding Light on Polymerization-Induced Self-Assembly

Tan, Jianbo; Sun, Hao; Yu, Mingguang; Sumerlin, Brent S.; Zhang, Li

doi:10.1021/acsmacrolett.5b00748

Cited by 340 publications

(420 citation statements)

References 30 publications

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“…Indeed, significant progress toward this goal has just been reported by Zhang, Sumerlin, and co-workers. 172 Photoinitiated RAFT polymerization of HPMA was conducted using a PEG macro-CTA in the presence of an aqueous silica sol, with TEM studies providing reasonable evidence for nanoparticle encapsulation within the resulting PEG–PHPMA vesicles. Moreover, a model globular protein (bovine serum albumin, BSA) could also be incorporated within the same vesicles, although no direct visual evidence for this encapsulated species was possible.…”

Section: Potential Applications and Opportunities For Pisa Formulationsmentioning

confidence: 99%

A Critical Appraisal of RAFT-Mediated Polymerization-Induced Self-Assembly

2016

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Recently, polymerization-induced self-assembly (PISA) has become widely recognized as a robust and efficient route to produce block copolymer nanoparticles of controlled size, morphology, and surface chemistry. Several reviews of this field have been published since 2012, but a substantial number of new papers have been published in the last three years. In this Perspective, we provide a critical appraisal of the various advantages offered by this approach, while also pointing out some of its current drawbacks. Promising future research directions as well as remaining technical challenges and unresolved problems are briefly highlighted.

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Section: Potential Applications and Opportunities For Pisa Formulationsmentioning

confidence: 99%

A Critical Appraisal of RAFT-Mediated Polymerization-Induced Self-Assembly

2016

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“…[1][2][3][4][5][6][7][8][9][10][11][12][13] Recently, the so-called polymerization induced self-assembly (PISA) has been demonstrated to be a robust and efficient route for the direct in situ synthesis of block copolymer nano-objects of various morphologies at relatively high copolymer concentrations (up to 50 % solids). Styrene, 24-27 some common methacrylates (often benzyl methacrylate [28][29][30] and 2-hydroxypropyl methacrylate [31][32][33][34] ) and 18,19 In RAFT-mediated PISA systems, a soluble macromolecular chain transfer agent (macro-CTA) is chain-extended with a second monomer in a suitable solvent that is selected to be a nonsolvent for the growing second block.…”

Section: Introductionmentioning

confidence: 99%

Salicylaldehyde-functionalized block copolymer nano-objects: one-pot synthesis via polymerization-induced self-assembly and their simultaneous cross-linking and fluorescence modification

et al. 2016

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Salicylaldehyde-functional diblock copolymer nano-objects were synthesized by polymerization induced self-assembly (PISA) via RAFT dispersion polymerization of a newly designed core-forming monomer, 3-formyl-4-hydroxybenzyl methacrylate (FHMA), using poly(2-hydroxypropyl methacrylate) (PHPMA) macromolecular chain transfer agent as a steric stabilizer in methanol at 65 o C. A range of PHPMA-b-PFHMA block copolymer morphologies including sphere, worm and vesicle could be accessed by adjusting the degree of polymerization of core forming block PFHMA. Since the salicylaldehyde groups of core-forming PFHMA blocks could react with hydrazine in a 2:1 stoichiometry to form salicylaldazines with aggregation-induced emission, one-step post-modification of the PISA nano-objects using hydrazine enabled their inherent nanostructures to be stabilized via covalent cross-linking and simultaneously conferred luminescent features on the resulting stabilized nanoparticles. Solid nano-objects, obtained easily via precipitation into diethyl ether, could be re-dispersed well in methanol and THF. The nano-objects could also be re-dispersed in water to form colloidal dispersions at a low concentration (≤ 1% w/w). Thanks to the stability imparted by the cross-linking, the morphologies of the preformed PISA nano-objects remained intact even after re-dispersing these cross-linked nano-objects in THF (a good solvent for both blocks). The stabilized nano-objects displayed strong orange fluorescence in water, organic solvents or solid states. This work opens the possibility for simultaneous functionlization and stabilization of PISA-generated block copolymer nano-objects. Materials 2-Hydroxypropyl methacrylate (HPMA; J&K, 97%) was passed through a column of basic alumina to remove inhibitor and then stored at -20 °C prior to use. 2, 2′-Azobis(isobutyronitrile) (AIBN; Sinopharm Chemical Reagent, 99%) was purified by recrystallization from ethanol. 4-Cyano-4-(propylthiocarbonothioylthio)pentanoic acid (CPPA) 53 and 5-(chloromethyl)-2-hydroxybenzaldehyde 54 were synthesized according to literature procedures. Other reagents were all analytical grade and used as received. Synthesis of 3-formyl-4-hydroxybenzyl methacrylate (FHMA)A mixture of methacrylic acid (25.8 g, 0.3 mol), sodium hydroxide (12.0 g, 0.3 accelerating voltage of 120 kV. For preparation of TEM samples, a drop of diluted dispersion (0.15 % w/w) solution was deposited onto a carbon-coated copper grid and dried under ambient conditions. All samples were not stained. Results and discussion Synthesis of monomer 3-formyl-4-hydroxybenzyl methacrylate (FHMA)A novel salicylaldehyde functionalized methacrylate monomer FHMA was designed and synthesized readily by the reaction of methacrylic acid with 5-(chloromethyl)-2-hydroxybenzaldehyde (Scheme 1). The structure of FHMA was confirmed on the base of the elemental analysis, MS, and 1 H NMR spectroscopy. The 1 H NMR spectrum (Fig. 1) exhibits the characteristic signals corresponding to methacrylic vinyl (a,b), aldehyde (i) and hydroxyl (h) mo...

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“…A relevant example, although at laboratory scale, is the synthesis of polyacrylamide with a well-defined branched structure for applications in chemical enhanced oil recovery, as developed within our Groningen University Product Technology group by Wever [44] and more recently by v. Mastrigt [45]. Other recent examples illustrate the possibility of using photo-initiated RAFT polymerization in emulsion, further expanding its scope [46,47].…”

Section: Future Prospects Of Crp-methods In Industrial Settingsmentioning

confidence: 99%

Free-Radical Graft Polymerization onto Starch as a Tool to Tune Properties in Relation to Potential Applications. A Review

2018

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Abstract:Grafting of acrylic monomers onto the renewable feedstock starch via free radical polymerizations has been investigated for many years. Many potential applications have been studied, such as superabsorbents, flocculants, thickening agents and so forth. It is expected that size and spacing of the grafts have a large influence on the performance of such polymers. Yet, information upon the structure-property relationships is only scarcely found in literature. Moreover, there is no clear overview of how reaction variables can be used to influence the grafted structure. In this review, an assessment has been made of the relation between the architecture of the grafts and potential applications. Then, from a selection of relevant literature data it is demonstrated that reaction variables such as the relative concentrations of initiator and monomer, have a large impact on the average size and spacing of the grafts. The emergence of controlled radical polymerizations, like Atom Transfer Radical Polymerization (ATRP) and Reversible Addition-Fragmentation chain Transfer (RAFT), is discussed, both the current status and future prospects. These methods are promising in the future of starch grafting, especially for systems where homopolymer formation may be a problem. Nevertheless, higher costs and other related issues make these advanced methods more suitable in high added-value products.

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Photo-PISA: Shedding Light on Polymerization-Induced Self-Assembly

Cited by 340 publications

References 30 publications

A Critical Appraisal of RAFT-Mediated Polymerization-Induced Self-Assembly

A Critical Appraisal of RAFT-Mediated Polymerization-Induced Self-Assembly

Salicylaldehyde-functionalized block copolymer nano-objects: one-pot synthesis via polymerization-induced self-assembly and their simultaneous cross-linking and fluorescence modification

Free-Radical Graft Polymerization onto Starch as a Tool to Tune Properties in Relation to Potential Applications. A Review

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