Simple One-Pot Syntheses of Water-Soluble Bis(acyl)phosphane Oxide Photoinitiators and Their Application in Surfactant-Free Emulsion Polymerization

Müller, Georgina; Zalibera, Michal; Gescheidt, Georg; Rosenthal, Amos J.; Santiso‐Quiñones, Gustavo; Dietliker, Kurt; Grützmacher, Hansjörg

doi:10.1002/marc.201400743

Cited by 69 publications

(58 citation statements)

References 34 publications

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“…Time-resolved (TR) EPR is the method of choice for studying spin-polarized intermediates in solutions. [35][36][37][38][39][40] So far, only one paper was 3 published reporting TR EPR study in ILs. 41 Using photoexcited triplet molecule of Zntetraphenylporphyrin (ZnTPP) authors clearly demonstrated that high viscosity of ILs suppresses electron spin relaxation caused by diffusional rotation of ZnTPP.…”

Section: Introductionmentioning

confidence: 99%

Probing Microenvironment in Ionic Liquids by Time-Resolved EPR of Photoexcited Triplets

et al. 2015

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Unusual physicochemical properties of ionic liquids (ILs) open vistas for a variety of new applications. Herewith, we investigate the influence of microviscosity and nanostructuring of ILs on spin dynamics of the dissolved photoexcited molecules. We use two most common ILs [Bmim]PF6 and [Bmim]BF4 (with its close analogue [C10mim]BF4) as solvents and photoexcited Zn tetraphenylporphyrin (ZnTPP) as a probe. Time-resolved electron paramagnetic resonance (TR EPR) is employed to investigate spectra and kinetics of spin-polarized triplet ZnTPP in the temperature range 100-270 K. TR EPR data clearly indicate the presence of two microenvironments of ZnTPP in frozen ILs at 100-200 K, being manifested in different spectral shapes and different spin relaxation rates. For one of these microenvironments TR EPR data is quite similar to those obtained in common frozen organic solvents (toluene, glycerol, N-methyl-2-pyrrolidone). However, the second one favors the remarkably slow relaxation of spin polarization, being much longer than in the case of common solvents. Additional experiments using continuous wave EPR and stable nitroxide as a probe confirmed the formation of heterogeneities upon freezing of ILs and complemented TR EPR results. Thus, TR EPR of photoexcited triplets can be effectively used for probing heterogeneities and nanostructuring in frozen ILs. In addition, the increase of polarization lifetime in frozen ILs is an interesting finding that might allow investigation of short-lived intermediates inaccessible otherwise.

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Section: Introductionmentioning

confidence: 99%

Probing Microenvironment in Ionic Liquids by Time-Resolved EPR of Photoexcited Triplets

et al. 2015

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“…58-60 Toward increasing the range of wavelengths available for photopolymerizations in water, Grutzmacher and coworkers recently reported the synthesis of highly efficient, water-soluble visible light photoinitiators using monoacylphosphineoxide and bisacylphosphineoxide salts that are promising for biological applications based on their response to low doses of blue light (465 nm LED for <30 min). 61-62 In addition, cyclic benzylidene ketone-based initiators that are water soluble and responsive to two-photon near infrared light (780 nm, ∼60 to 400 mW, 100 fs pulse) may prove useful for thiol–ene photopolymerizations in biomedical applications requiring increased light penetration in situ . 63 …”

Section: Thiol–ene Reactions For Hydrogel Formationmentioning

confidence: 99%

Thiol–ene Click Hydrogels for Therapeutic Delivery

Kharkar

Rehmann

Skeens

et al. 2016

ACS Biomater. Sci. Eng.

189

160

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Hydrogels are of growing interest for the delivery of therapeutics to specific sites in the body. For use as a delivery vehicle, hydrophilic precursors are usually laden with bioactive moieties and then directly injected to the site of interest for in situ gel formation and controlled release dictated by precursor design. Hydrogels formed by thiol–ene click reactions are attractive for local controlled release of therapeutics owing to their rapid reaction rate and efficiency under mild aqueous conditions, enabling in situ formation of gels with tunable properties often responsive to environmental cues. Herein, we will review the wide range of applications for thiol–ene hydrogels, from the prolonged release of anti-inflammatory drugs in the spine to the release of protein-based therapeutics in response to cell-secreted enzymes, with a focus on their clinical relevance. We will also provide a brief overview of thiol–ene click chemistry and discuss the available alkene chemistries pertinent to macromolecule functionalization and hydrogel formation. These chemistries include functional groups susceptible to Michael type reactions relevant for injection and radically-mediated reactions for greater temporal control of formation at sites of interest using light. Additionally, mechanisms for the encapsulation and controlled release of therapeutic cargoes are reviewed, including i) tuning the mesh size of the hydrogel initially and temporally for cargo entrapment and release and ii) covalent tethering of the cargo with degradable linkers or affinity binding sequences to mediate release. Finally, myriad thiol–ene hydrogels and their specific applications also are discussed to give a sampling of the current and future utilization of this chemistry for delivery of therapeutics, such as small molecule drugs, peptides, and biologics.

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“…[15] Fort his purpose 2 was dissolved in aqueous poly(ethylene glycol) methacrylate,which gives aclear solution (Figure 4a). [15] Fort his purpose 2 was dissolved in aqueous poly(ethylene glycol) methacrylate,which gives aclear solution (Figure 4a).…”

Section: Angewandte Chemiementioning

confidence: 99%

“…[10b, 11d,13] Furthermore,afew other copper(II) complexes were reported, and upon irradiation with light were converted into copper(I) compounds. [15] Remarkably, 1 serves as af our-electron-reducing agent and allows preparation of copper nanomaterials with high yields in aqueous systems. [15] Remarkably, 1 serves as af our-electron-reducing agent and allows preparation of copper nanomaterials with high yields in aqueous systems.…”

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confidence: 99%

Bismesitoylphosphinic Acid (BAPO‐OH): A Ligand for Copper Complexes and Four‐Electron Photoreductant for the Preparation of Copper Nanomaterials

et al. 2018

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Bismesitoylphosphinic acid, (HO)PO(COMes) 2 (BAPO-OH), is an efficient photoinitiator for free-radical polymerizations of olefins in aqueous phase.D escribed here are the structures of various copper(II) and copper(I) complexes with BAPO-OH as the ligand. The complex Cu II -(BAPO-O) 2 (H 2 O) 2 is photoactive,a nd under irradiation with UV light in aqueous phase,i ts erves as as ource of metallic copper in high purity and yield (> 80 %). Simultaneously,t he radical polymerization of acrylates can be initiated and allows the preparation of nanoparticle/polymer nanocomposites in which the metallic Cu nanoparticles are protected against oxidation. The determination of the stoichiometry of the photoreductions suggests an almost quantitative conversion from Cu II into Cu 0 with half an equivalent of BAPO-OH, which serves as afour-electron photoreductant.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

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Simple One-Pot Syntheses of Water-Soluble Bis(acyl)phosphane Oxide Photoinitiators and Their Application in Surfactant-Free Emulsion Polymerization

Cited by 69 publications

References 34 publications

Probing Microenvironment in Ionic Liquids by Time-Resolved EPR of Photoexcited Triplets

Probing Microenvironment in Ionic Liquids by Time-Resolved EPR of Photoexcited Triplets

Thiol–ene Click Hydrogels for Therapeutic Delivery

Bismesitoylphosphinic Acid (BAPO‐OH): A Ligand for Copper Complexes and Four‐Electron Photoreductant for the Preparation of Copper Nanomaterials

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