TY - JOUR

T1 - Rhenium(I) Block Copolymers based on Polyvinylpyrrolidone: A Successful Strategy to Water-Solubility and Biocompatibility

AU - Kisel, Kristina S.

AU - Baigildin, Vadim A.

AU - Solomatina , Anastasia I.

AU - Gostev, Alexey I.

AU - Sivtsov, Eugene V.

AU - Shakirova , Julia R.

AU - Tunik, Sergey P.

PY - 2023/1/1

Y1 - 2023/1/1

N2 - A series of diphosphine Re(I) complexes Re1–Re4 have been designed via decoration of the archetypal core {Re(CO)2(N^N)} through the installations of the phosphines P0 and P1 bearing the terminal double bond, where N^N = 2,2′-bipyridine (N^N1), 4,4′-di-tert-butyl-2,2′-bipyridine (N^N2) or 2,9-dimethyl-1,10-phenanthroline (N^N3) and P0 = diphenylvinylphosphine, and P1 = 4-(diphenylphosphino)styrene. These complexes were copolymerized with the corresponding N-vinylpyrrolidone-based Macro-RAFT agents of different polymer chain lengths to give water-soluble copolymers of low-molecular p(VP-l-Re) and high-molecular p(VP-h-Re) block-copolymers containing rhenium complexes. Compounds Re1–Re4, as well as the copolymers p(VP-l-Re) and p(VP-h-Re), demonstrate phosphorescence from a 3MLCT excited state typical for this type of chromophores. The copolymers p(VP-l-Re#) and p(VP-h-Re#) display weak sensitivity to molecular oxygen in aqueous and buffered media, which becomes almost negligible in the model physiological media. In cell experiments with CHO-K1 cell line, p(VP-l-Re2) and p(VP-h-Re2) displayed significantly reduced toxicity compared to the initial Re2 complex and internalized into cells presumably by endocytic pathways, being eventually accumulated in endosomes. The sensitivity of the copolymers to oxygen examined in CHO-K1 cells via phosphorescence lifetime imaging microscopy (PLIM) proved to be inessential.

AB - A series of diphosphine Re(I) complexes Re1–Re4 have been designed via decoration of the archetypal core {Re(CO)2(N^N)} through the installations of the phosphines P0 and P1 bearing the terminal double bond, where N^N = 2,2′-bipyridine (N^N1), 4,4′-di-tert-butyl-2,2′-bipyridine (N^N2) or 2,9-dimethyl-1,10-phenanthroline (N^N3) and P0 = diphenylvinylphosphine, and P1 = 4-(diphenylphosphino)styrene. These complexes were copolymerized with the corresponding N-vinylpyrrolidone-based Macro-RAFT agents of different polymer chain lengths to give water-soluble copolymers of low-molecular p(VP-l-Re) and high-molecular p(VP-h-Re) block-copolymers containing rhenium complexes. Compounds Re1–Re4, as well as the copolymers p(VP-l-Re) and p(VP-h-Re), demonstrate phosphorescence from a 3MLCT excited state typical for this type of chromophores. The copolymers p(VP-l-Re#) and p(VP-h-Re#) display weak sensitivity to molecular oxygen in aqueous and buffered media, which becomes almost negligible in the model physiological media. In cell experiments with CHO-K1 cell line, p(VP-l-Re2) and p(VP-h-Re2) displayed significantly reduced toxicity compared to the initial Re2 complex and internalized into cells presumably by endocytic pathways, being eventually accumulated in endosomes. The sensitivity of the copolymers to oxygen examined in CHO-K1 cells via phosphorescence lifetime imaging microscopy (PLIM) proved to be inessential.

KW - rhenium complexes

KW - Polyvinylpyrrolidone

KW - RAFT polymerization

KW - phosphorescence

KW - water-solubility

KW - biocompatibility

KW - Rhenium/chemistry

KW - Cricetinae

KW - Oxygen

KW - Solubility

KW - 2,2'-Dipyridyl

KW - Water/chemistry

KW - Polymers/chemistry

KW - Povidone

KW - Animals

KW - CHO Cells

KW - polyvinylpyrrolidone

UR - https://www.mendeley.com/catalogue/55934bc6-4678-3c0a-8d9a-abb8bc2bde7b/

U2 - 10.3390/molecules28010348

DO - 10.3390/molecules28010348

M3 - Article

C2 - 36615546

VL - 28

JO - Molecules

JF - Molecules

SN - 1420-3049

IS - 1

M1 - 348

ER -