ACTIVE‐BAPO – A Versatile Transfer Agent for Photoactive Bis(acyl)phosphane Oxide Units

Abstract

A N-hydroxy succinimide (NHS) ester substituted bis(acyl)phosphane oxide (ACTIVE-BAPO) was prepared by phospha-Michael addition and used for an easy one-step BAPO ligation with substrates containing primary amino groups, such as amino acids, proteins, and poly(amidoamine) (PAMAM) dendrimers. Thereby, a range of new molecular and polymeric photoinitators was obtained. Real-time photorheology experiments demonstrated the outstanding effi-ciency of the PAMAM BAPOs as photoinitiators for free radical polymerization. Remarkably, it is found that PAMAM BAPOs also act as crosslinking agents to convert monofunctional methacrylate monomers into thermosetting networks without any further additives. Depending on the number of the attached BAPOs, thermosets with a different degree of crosslinking and swelling capability in water were obtained.

A General Strategy for Sustainable 3D Printing Based on A Multifunctional Photoinitiator

“…1 H NMR of γ‐CD‐ONB‐BAPO suggests the complete phosphorylation of vinyl groups originally present in γ‐CD‐ONB (Figure S6). The 31 P{ 1 H} NMR spectrum exhibits a single peak at 25.6 ppm (Figure S7), consistent with the chemical shift in previously reported BAPO derivatives [29,32–35] . Additionally, the 13 C{ 1 H} NMR spectrum (Figure S8) displays characteristic signals corresponding to the BAPO units, further supporting the successful incorporation of these moieties into the γ‐CD‐ONB .…”

A universal strategy to induce oxidative stress-mediated cell death in biological systems

“…NHS-BAPO was synthesized as previously reported. 17,22 NMR spectra were recorded on Bruker Avance 200, 250, 300, 400 and 500 spectrometers operating at room temperature if not otherwise speci ed. Chemical shifts δ were measured according to IUPAC and are given in parts per million (ppm) relative to TMS (1H-NMR and 13C-NMR) and 85% H3PO4 in D2O (31P-NMR).…”

A quest for stable phosphonyl radicals: limitations and possibilities of carbocyclic backbones and bulky substituents

“…The transient phosphonyl radicals are commonly obtained by lightinduced Norrish type 1 cleavage of the P-C(acyl) bond in monoacyl or bis(acyl) phosphine oxide photoinitiators (MAPOs or BAPOs, respectively). [31][32][33][34][35][36][37][38][39][40][41][42][43] The generated phosphonyl radical establishes a P-C bond with the olefin, and the arising C-centred radical acts as a chain carrier. 16,44 Importantly, phosphonyl radicals were experimentally proven to initiate the polymerisation with rate constants that are magnitudes larger compared to the parallelly formed C-centred acyl radicals.…”