Star polymers by photoinduced copper-catalyzed azide-alkyne cycloaddition click chemistry

Tinmaz, Hatice Busra; Arslan, Irem; Taşdelen, Mehmet Atilla

doi:10.1002/pola.27612

Cited by 42 publications

(43 citation statements)

References 71 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The 1 H-NMR spectra of PCL-alkyne and corresponding PP-g-PCL samples were also presented in Figure 4. As can be seen that the disappearances of characteristic alkyne and azide peaks; methine (c) 4.7 ppm and methylene (d) protons at 2.5 ppm of PCL-alkyne and methine (a) and methylene (b) as well as the appearance of triazole proton (c) at 8.12 ppm were great evidences for the successful formation of clicked product PP-g-PCL [54]. Also in Figure 5, the structure of another PPg-PEG copolymer was also analyzed by 1 H-NMR spectroscopy and the similar results were observed [45,[55][56][57][58].…”

Section: Resultsmentioning

confidence: 97%

Polypropylene-based graft copolymers via CuAAC click chemistry

Açık¹,

Sey²,

Taşdelen³

2018

Express Polym. Lett.

View full text Add to dashboard Cite

Abstract. Graft copolymers from commercial chlorinated polypropylene (PP-Cl) possessing either poly(ethylene glycol) (PEG) or poly(ɛ-caprolactone) (PCL) grafts are synthesized by copper (I)-catalyzed azide-alkyne cycloaddition 'click' reaction (CuAAC). For this purpose, azido-functional polypropylene is prepared by nucleophilic substitution of chlorine groups of PP-Cl with azidotrimethylsilane-tetrabutylammonium fluoride. Whereas, the clickable alkyne end-functional PEG and PCL are independently synthesized by esterification reaction of poly(ethylene glycol) methyl ether with 4-pentyonic acid at room temperature and ring-opening polymerization of ε-caprolactone using stannous octoate as catalyst and propargyl alcohol as initiator. Finally, the corresponding graft copolymers, PP-g-PEG and PP-g-PCL, with different surface properties were successfully synthesized by CuAAC 'click' reaction under mild condition. Spectral, chromatographic and thermal analyses at various stages prove the formation of desired polypropylene-based graft copolymers with well-defined properties. Furthermore, the water contact angle values of PP-Cl, PP-g-PEG and PP-g-PCL are found as 90±1°, 78±1.8° and 83±2.1°, respectively.

show abstract

Section: Resultsmentioning

confidence: 97%

Polypropylene-based graft copolymers via CuAAC click chemistry

Açık¹,

Sey²,

Taşdelen³

2018

Express Polym. Lett.

View full text Add to dashboard Cite

show abstract

“…The radicals generated upon irradiation reduce the Cu(II) complexes to Cu(I), which mediate the click reactions. 38,[43][44][45][46][47][48][49][50][51][52] In a previous study in our laboratory, we have shown the possibility of reducing Cu(II) complexes by Type I initiators such as 2, 2-dimethoxy-2-phenyl acetophenone, 2-benzyl-2dimethylamino-4′-morpholino butyrophenone, (2,4,6 trimethylbenzoyl)diphenylphosphine oxide and dicyclopentadienyl bis[2,6-difluoro-3-(1-pyrrolyl)phenyl] titanium (titanocene) as well as camphorquinone (CQ) as Type II visible light photoinitiator. 44,53 Type I initiators directly decompose upon irradiation to yield radicals capable of reducing Cu(II) to Cu(I).…”

Section: Introductionmentioning

confidence: 99%

Dibenzoyldiethylgermane as a visible light photo-reducing agent for CuAAC click reactions

2015

View full text Add to dashboard Cite

show abstract

“…Only one synthetic approach towards peptidyl silsesquioxanes using click chemistry has been reported to date. [25][26][27][28][29][30] focussing on the synthesis of octa(3-azidopropyl)polyhedral oligomeric silsesquioxane POSS-(N 3 ) 8 ( Fig. 1) and its reaction with a variety of alkynes.…”

mentioning

confidence: 99%

“…1) and its reaction with a variety of alkynes. [25][26][27][28][29][30][31][32][33][34][35][36] The preparation of octa(3-azidopropyl)polyhedral oligomeric silsesquioxane POSS-(N 3 ) 8 requires a multi-step synthesis and suffers from a poor overall yield of 30-32%.…”

mentioning

confidence: 99%

Facile synthesis of novel hybrid POSS biomolecules via “Click” reactions

et al. 2017

View full text Add to dashboard Cite

A novel alkyne-terminated cubic-octameric POSS was synthesised in high yield (82-90%). The X-ray crystal structure revealed intra-and intermolecular hydrogen bonding between the amide groups of the arms.Hybrid biomaterials were synthesised in nearly quantitative yields via a click reaction with (i) azido-NFmoc-norleucine and (ii) 3 0 -azido-3 0 -deoxythymidine.Among the most commonly studied scaffolds for developing hybrid biomaterials 1-4 is polyhedral oligomeric silsesquioxane (POSS). POSS units are symmetrical, three-dimensional cubic molecules, which are unique nanometer-sized hybrid inorganicorganic materials 5,6 with the formula ( 'click' chemistry, is a simple method for coupling organic molecules containing azide and alkyne functional groups in high yields and its use in the elds of peptide and protein biomedical and material sciences is accelerating.22,23 The click reaction has been used to synthesise POSS biomaterials such as hybrid POSS-PEG hydrogels 24 that support chondrocyte attachment and proliferation. Only one synthetic approach towards peptidyl silsesquioxanes using click chemistry has been reported to date.25-30 focussing on the synthesis of octa(3-azidopropyl)polyhedral oligomeric silsesquioxane POSS-(N 3 ) 8 (Fig. 1) and its reaction with a variety of alkynes.25-36 The preparation of octa(3-azidopropyl)polyhedral oligomeric silsesquioxane POSS-(N 3 ) 8 requires a multi-step synthesis and suffers from a poor overall yield of 30-32%. 32The synthesis and click reaction of mono alkyneheptaisobutyl POSS were rst reported by Müller et al. 37 and Wu et al. 38 Müller et al. 37 have used aminopropylheptaisobutyl polyhedral oligomeric silsesquioxane (POSS) to produce monoalkyne-POSS in three steps and the click coupling occurred between the azido-terminated polystyrenes and alkyne-POSS to afford mono-, di-, and pentafunctional POSS-containing hybrid polystyrenes as star-shaped telechelic POSS-containing hybrid polymers. Wu et al.38 have prepared alkyne-functionalized-POSS in three steps from allyl-heptaisobutyl substituted-POSS and the product was linked to an azido-functionalized elastomer of poly(styrene-b-(ethylene-co-butylene)-b-styrene) (SEB-CH 2 N 3 ) via a click coupling reaction to form a novel hybrid copolymer. These approaches focused mostly on the preparation of a hybrid copolymer based on mono-alkyne-heptaisobutyl and azido polystyrene. However, the preparation of octa-alkyne-terminated POSS and their click coupling reactions with azido-biomolecules to produce hybrid biomaterials has not been investigated yet. We believe that this approach will open a wide range of biomedical applications that were not accessible in the past.Herein we report a novel synthetic approach to hybrid biomaterials based on octa-alkyne-terminated POSS and their reaction with (i) azido-N-Fmoc-L-norleucine and (ii) 3 0 -azido-3 0 -deoxythymidine, using the CuAAC reaction. Our approach Fig. 1 Octa(3-azidopropyl)POSS.

show abstract

Star polymers by photoinduced copper-catalyzed azide-alkyne cycloaddition click chemistry

Cited by 42 publications

References 71 publications

Polypropylene-based graft copolymers via CuAAC click chemistry

Polypropylene-based graft copolymers via CuAAC click chemistry

Dibenzoyldiethylgermane as a visible light photo-reducing agent for CuAAC click reactions

Facile synthesis of novel hybrid POSS biomolecules via “Click” reactions

Contact Info

Product

Resources

About