Porphyrinoid–Cyclodextrin Assemblies in Biomedical Research: An Update

Abstract

Porphyrinoids, well-known cofactors in fundamental processes of life, have stimulated interest as synthetic models of natural systems and integral components of photodynamic therapy, but their utilization is compromised by self-aggregation in aqueous media. The capacity of cyclodextrins to include hydrophobic molecules in their cavity provides porphyrinoids with a protective environment against oxidation and the ability to disperse efficiently in biological fluids. Moreover, engineered cyclodextrin−porphyrinoid assemblies enhance the photodynamic abilities of porphyrinoids, can carry chemotherapeutics for synergistic modalities, and can be enriched with functions including cell recognition, tissue penetration, and imaging. This Perspective includes synthetic porphyrinoid−cyclodextrin models of proteins participating in fundamental processes, such as enzymatic catalysis, respiration, and electron transfer. In addition, since porphyrinoid− cyclodextrin systems comprise third generation photosensitizers, recent developments for their utilization in photomedicine, that is, multimodal therapy for cancer (e.g., PDT, PTT) and antimicrobial treatment, and eventually in biocompatible therapeutic or diagnostic platforms for next-generation nanomedicine and theranostics are discussed. Perspective pubs.acs.org/jmc

Structural Deformation to β‐Cyclodextrin Due to Strong π‐Stacking in the Self‐Assembly of Inclusion Complex

“…The distortions are not transitory in nature and lead to formation of assemblies which are stable even at high temperatures. The structure and properties of cyclodextrins continue to inspire chemists [39–46] . In this context the understanding that CD structures are not inflexible may lead to design of novel molecular architectures in the future.…”

“…The structure and properties of cyclodextrins continue to inspire chemists. [39][40][41][42][43][44][45][46] In this context the understanding that CD structures are not inflexible may lead to design of novel molecular architectures in the future. Structural deformation of cyclodextrin is subject to several theoretical studies, but none of the studies have considered large deformations to its structure.…”

Structural Insights into the Host–Guest Complexation between β-Cyclodextrin and Bio-Conjugatable Adamantane Derivatives

“…Compared to other synthetic host systems, e.g., crown ethers [ 7 , 8 , 9 ], calixarenes [ 10 , 11 , 12 ], cucurbiturils [ 9 , 13 , 14 ], and pillararenes [ 15 , 16 , 17 ], CDs are less toxic and/or exhibit good water solubility and biocompatibility [ 11 , 18 ]. Their facile covalent modification also renders them highly promising candidates as functional delivery systems [ 19 , 20 , 21 , 22 ].…”

FRET‐Based In‐Cell Detection of Highly Selective Supramolecular Complexes of meso‐Tetraarylporphyrin with Peptide/BODIPY‐Modified Per‐O‐Methyl‐β‐Cyclodextrins

“…The biomedical applications of the supramolecular Por/CD Me system have been demonstrated by us and other research groups and reviewed in recent papers. [13][14][15][16][17] We recently investigated selective detection with the Por/CD Me complex in biological media, including serum, blood, and urine, using 5,10,15,20-tetrakis(4-sulfonatophenyl) porphyrin (TPPS) and 13 C-labeled heptakis(2,3,6-tri-O-methyl-13 C)-β-cyclodextrin ( 13 C-CD Me ). [18] Several NMR techniques revealed that the supramolecular 1 : 2 TPPS/ 13 C-CD Me complex is quite stable and detectable in these biologically crowded media, that contain many biocomponents, including proteins and lipids.…”