Blue-light activated rapid polymerization for defect-free bulk Cu(<scp>i</scp>)-catalyzed azide–alkyne cycloaddition (CuAAC) crosslinked networks

Shete, Abhishek U.; El-Zaatari, Bassil M.; French, Jarrod B.; Kloxin, Christopher J.

doi:10.1039/c6cc05095f

Cited by 28 publications

(17 citation statements)

References 41 publications

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“…Many Type(I) photoinitiators absorb in the UV-region. Since azides can decompose under UV-irradiation, 32 Norrish Type(II) reactions have been employed in photoinitiating the CuAAC reaction using camphorquinone and a co-initiator such as a tertiary amine 44 . Mechanistically, the Norrish Type(II) reaction is an electron transfer reaction and typically abstracts a hydrogen intermolecularly in the presence of a co-initiator.…”

Section: Resultsmentioning

confidence: 99%

Copper ligand and anion effects: controlling the kinetics of the photoinitiated copper(i) catalyzed azide—alkyne cycloaddition polymerization

et al. 2018

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The kinetics of photoinduced copper(I) catalyzed azide-alkyne cycloaddition (CuAAC) polymerizations were assessed as a function of copper(II) amine-based ligands. Copper(II) bromide ligated with 1,1,4,7,10,10-hexamethylenetetramine (HMTETA) exhibited the fastest kinetics in both Norrish type(I) and type(II) photoinitiating systems. A characteristic induction period is observed with these polymerizations and is manipulated by adding an external tertiary amine in Norrish Type(II) photoinitating systems or by changing the anion of the copper(II) salt. Halides, specifically bromide and chloride, exhibit the fastest kinetics with the smallest induction period in comparison with organic anions, such as bistriflimide and triflate. The temporal control of the photo-CuAAC polymerization is affected by pre-ligation of the copper catalyst, by the presence of certain anions such as acetate, and by specific ligands such as tetramethylethylenediamine (TMEDA).

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Section: Resultsmentioning

confidence: 99%

Copper ligand and anion effects: controlling the kinetics of the photoinitiated copper(i) catalyzed azide—alkyne cycloaddition polymerization

et al. 2018

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“…The camphorquinone (CQ)/tertiary amine photoinitiation system is widely used to prepare in situ forming structures for the applications such as dental restorative resins [18][19][20][21]. The light curing mechanism of the CQ/amine system has been described previously by Teshima et al [22].…”

Section: Introductionmentioning

confidence: 99%

In situ forming hydrogels based on polyethylene glycol itaconate for tissue engineering application

et al. 2019

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Novel strategies have been proposed to enhance the quality of surgery by scheming noninvasive methods. For this reason, photo-curable in situ forming hydrogels have been well developed during advancements in the regenerative medicine. In this study, polyethylene glycol itaconate (PEGI) was synthesized by reacting polyethylene glycol (PEG) with different molecular weights (1000, 4000 and 8000 g mol −1) and itaconyl chloride. The synthesized PEGIs were fully characterized and employed as a macromonomer for the preparation of in situ forming hydrogels using a combination of camphorquinone and dimethylaminoethyl methacrylate as a reactive photoinitiator system, and hydroxyethyl methacrylate as a reactive diluent. The physical properties of the hydrogels including gel yield, equilibrium swelling and compressive strength were determined. The hydrogel based on PEG 4000 with a gel yield of 86%, a water uptake of 103%, a compressive modulus of 11.2 MPa, an elongation at break of 9% and a curing time of 4 min was selected for the encapsulation of rabbit articular chondrocyte cells. The cytocompatibility of the in situ formed hydrogels was evaluated using 3[4,5-dimethylthiazol-2-yl]-2,5-diphenyltetrazolium bromide, live-dead fluorescence assays and optical microscopy observations. Glycosaminoglycans were quantified by dimethylmethylene blue staining from the encapsulated chondrocytes after 14 days. The proposed in situ forming hydrogel can be considered as an injectable and photocurable carrier for cell delivery in cartilage tissue engineering.

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“…Indirect reduction by irradiation of a photoinitiator to generate a radical system that reduces copper(II) to copper(I) is the alternative approach that proceeds more quickly and offers wavelength tunability to make it appropriate for different systems [23,27]. This affords the ability to avoid photo-degradation of sensitive organic functionalities (such as the decomposition of azides [28] or oxidation/desorption of thiols [29] upon exposure to ultra-violet irradiation) and materials (such as those undergoing bioorthogonal processes) [30,31]. Furthermore, the use of this “click reaction,” which can proceed in a number of different solvents, makes it amenable to certain biological applications (such as biosensors), which may otherwise be impossible in specific solvent systems [32].…”

Section: Introductionmentioning

confidence: 99%

Indirect photopatterning of functionalized organic monolayers via copper-catalyzed “click chemistry”

Williams

Teplyakov

2018

Applied Surface Science

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Solution-based lithographic surface modification of an organic monolayer on a solid substrate is attained based on selective area photo-reduction of copper (II) to copper (I) to catalyze the azide-alkyne dipolar cycloaddition "click" reaction. X-ray photoelectron spectroscopy is used to confirm patterning, and spectroscopic results are analyzed and supplemented with computational models to confirm the surface chemistry. It is determined that this surface modification approach requires irradiation of the solid substrate with all necessary components present in solution. This method requires only minutes of irradiation to result in spatial and temporal control of the covalent surface functionalization of a monolayer and offers the potential for wavelength tunability that may be desirable in many applications utilizing organic monolayers.

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Blue-light activated rapid polymerization for defect-free bulk Cu(i)-catalyzed azide–alkyne cycloaddition (CuAAC) crosslinked networks

Cited by 28 publications

References 41 publications

Copper ligand and anion effects: controlling the kinetics of the photoinitiated copper(i) catalyzed azide—alkyne cycloaddition polymerization

Copper ligand and anion effects: controlling the kinetics of the photoinitiated copper(i) catalyzed azide—alkyne cycloaddition polymerization

In situ forming hydrogels based on polyethylene glycol itaconate for tissue engineering application

Indirect photopatterning of functionalized organic monolayers via copper-catalyzed “click chemistry”

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