Surface-grafted polyacrylonitrile brushes with aggregation-induced emission properties

Kopeć, Maciej; Pikiel, Marcin; Vancso, G. Julius

doi:10.1039/c9py01213c

Cited by 21 publications

(18 citation statements)

References 54 publications

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“…The photoluminescent properties of PAN were largely ignored, since untreated isolated nitrile groups do not form photoactive conjugated structures. However, recent reports point out that PAN can generate photoluminescence when dissolved at high concentrations or densely grafted from flat silica surfaces ( Jang et al, 2006 ; Zhou et al, 2016 ; Kopeć et al, 2020 ). Additionally, there are recent reports of chemical conversion of PAN into photoactive species via microwave ( Go et al, 2017 ), pyrolysis ( Cao et al, 2020 ) and hydrothermal reactions ( Ermakov et al, 2000 ; Sun et al, 2020 ), which all can induce the crosslinking or the hydrolysis of -C≡N, resulting in photoluminescent crosslinked nanoparticles or polymers.…”

Section: Introductionmentioning

confidence: 99%

Assemblies of Polyacrylonitrile-Derived Photoactive Polymers as Blue and Green Light Photo-Cocatalysts for Cu-Catalyzed ATRP in Water and Organic Solvents

et al. 2021

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Photoluminescent nanosized quasi-spherical polymeric assemblies prepared by the hydrothermal reaction of polyacrylonitrile (PAN), ht-PLPPAN, were demonstrated to have the ability to photo-induce atom transfer radical polymerization (ATRP) catalyzed by low, parts per million concentrations of CuII complex with tris(2-pyridylmethyl)amine (TPMA). Such photo induced ATRP reactions of acrylate and methacrylate monomers were performed in water or organic solvents, using ht-PLPPAN as the photo-cocatalyst under blue or green light irradiation. Mechanistic studies indicate that ht-PLPPAN helps to sustain the polymerization by facilitating the activation of alkyl bromide species by two modes: 1) green or blue light-driven photoreduction of the CuII catalyst to the activating CuI form, and 2) direct activation of dormant alkyl bromide species which occurs only under blue light. The photoreduction of the CuII complex by ht-PLPPAN was confirmed by linear sweep voltammetry performed under illumination. Analysis of the polymerization kinetics in aqueous media indicated even though CuI complexes comprised only 1–1.4% of all Cu species at equilibrium, they exhibited high activation rate constant and activated the alkyl bromide initiators five to six orders of magnitude faster than ht-PLPPAN.

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Section: Introductionmentioning

confidence: 99%

Assemblies of Polyacrylonitrile-Derived Photoactive Polymers as Blue and Green Light Photo-Cocatalysts for Cu-Catalyzed ATRP in Water and Organic Solvents

et al. 2021

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“…Classical SI-ATRP requires the utilization of high amounts of copper-based catalyst, which is unfavorable in the case of biomedical and electronic applications of the brushes. In response to that, many researchers have moved their attention to SI-ATRP with a ppm concentration of copper catalyst [8,9] or SI-ATRP catalyzed by less harmful metal catalysts [10]. Moreover, recent progress in SI-RDRPs resulted in the development of photoinduced SI-ATRP, which may not only use low concentrations of metal-based catalyst [11,12] but also enables polymer brush synthesis using microliter volumes of reaction Polymers 2021, 13, 4458 2 of 16 mixture [13].…”

Section: Introductionmentioning

confidence: 99%

Preparation of Homopolymer, Block Copolymer, and Patterned Brushes Bearing Thiophene and Acetylene Groups Using Microliter Volumes of Reaction Mixtures

et al. 2021

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The synthesis of surface-grafted polymers with variable functionality requires the careful selection of polymerization methods that also enable spatially controlled grafting, which is crucial for the fabrication of, e.g., nano (micro) sensor or nanoelectronic devices. The development of versatile, simple, economical, and eco-friendly synthetic strategies is important for scaling up the production of such polymer brushes. We have recently shown that poly (3-methylthienyl methacrylate) (PMTM) and poly (3-trimethylsilyl-2-propynyl methacrylate) (PTPM) brushes with pendant thiophene and acetylene groups, respectively, could be used for the production of ladder-like conjugated brushes that are potentially useful in the mentioned applications. However, the previously developed syntheses of such brushes required the use of high volumes of reagents, elevated temperature, or high energy UV-B light. Therefore, we present here visible light-promoted metal-free surface-initiated ATRP (metal-free SI-ATRP) that allows the economical synthesis of PMTM and PTPM brushes utilizing only microliter volumes of reaction mixtures. The versatility of this approach was shown by the formation of homopolymers but also the block copolymer conjugated brushes (PMTM and PTPM blocks in both sequences) and patterned films using TEM grids serving as photomasks. A simple reaction setup with only a monomer, solvent, commercially available organic photocatalyst, and initiator decorated substrate makes the synthesis of these complex polymer structures achievable for non-experts and ready for scaling up.

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“…[ 10 ] AIE polymers could be prepared by coupling reactions (Suzuki coupling, [ 11,12 ] Wittig coupling, [ 11,13 ] Sonogashira coupling, [ 11,14 ] McMurry coupling, [ 15 ] Heck Coupling, [ 16 ] etc. ), free radical polymerization [ 17 ] (RAFT, [ 18,19 ] ATRP, [ 20,21 ] etc. ), condensation polymerization, [ 22,23 ] metathesis polymerization, [ 24,25 ] and click reaction.…”

Section: Introductionmentioning

confidence: 99%

An Olefin Copolymer with Aggregation‐Induced Emission Characteristics Synthesized by Using Metallocene Catalyst

Wang

Hou

et al. 2021

Macro Materials & Eng

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Copolymerization of ethylene with (2-(4-vinylphenyl)ethene-1,1,2-triyl) tribenzene is conducted by using a metallocene catalyst, giving an ethylene copolymer containing tetraphenylethene unit. The result of NMR shows that the tetraphenylethene unit is distributed in isolation in the polymer chain, and the melting point of the copolymer decreases linearly with the increase of the comonomer incorporation. The copolymer can emit blue fluorescence under ultraviolet light, and the intensity increases with the increase of the comonomer incorporation. The fluorescence of flakes made of the copolymer gradually becomes weaker when the temperature is raised. When the temperature is higher than the melting point of the copolymer, the fluorescence is almost invisible.

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Surface-grafted polyacrylonitrile brushes with aggregation-induced emission properties

Cited by 21 publications

References 54 publications

Assemblies of Polyacrylonitrile-Derived Photoactive Polymers as Blue and Green Light Photo-Cocatalysts for Cu-Catalyzed ATRP in Water and Organic Solvents

Assemblies of Polyacrylonitrile-Derived Photoactive Polymers as Blue and Green Light Photo-Cocatalysts for Cu-Catalyzed ATRP in Water and Organic Solvents

Preparation of Homopolymer, Block Copolymer, and Patterned Brushes Bearing Thiophene and Acetylene Groups Using Microliter Volumes of Reaction Mixtures

An Olefin Copolymer with Aggregation‐Induced Emission Characteristics Synthesized by Using Metallocene Catalyst

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