A Supramolecular Approach for Modulated Photoprotection, Lysosomal Delivery, and Photodynamic Activity of a Photosensitizer

Roy, Indranil; Bobbala, Sharan; Young, Ryan M.; Beldjoudi, Yassine; Nguyen, Minh T.; Cetin, M. Mustafa; Cooper, James A.; Allen, Shannon A.; Anamimoghadam, Ommid; Scott, Evan A.; Wasielewski, Michael R.; Stoddart, J. Fraser

doi:10.1021/jacs.9b03990

Cited by 65 publications

(69 citation statements)

References 37 publications

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“…Some, like 5,15-diphenylporphyrin 11, are commercially available and/or can be prepared on a large scale [ 26 , 27 ]. They typically serve as starting materials for post-cyclization modification of porphyrins [ 28 , 29 , 30 , 31 , 32 , 33 , 34 ] but have also found applications in their own right, e.g., as photosensitizers in photodynamic therapy [ 35 ].…”

Section: Introductionmentioning

confidence: 99%

Weak Interactions and Conformational Changes in Core-Protonated A2- and Ax-Type Porphyrin Dications

et al. 2020

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Individual chemical motifs are known to introduce structural distortions to the porphyrin macrocycle, be it in the core or at the periphery of the macrocycle. The interplay when introducing two or more of these known structural motifs has been scarcely explored and is not necessarily simply additive; these structural distortions have a chance to compound or negate to introduce new structural types. To this end, a series of compounds with complementary peripheral (5,15-disubstitution) and core (acidification) substitution patterns were investigated. The single-crystal X-ray structures of 18 5,15-diphenylporphyrin, 5,15-diphenylporphyrindi-ium diacid, and related compounds are reported, including the first example of a 5,15-dialkylporphyrindi-ium. Normal-coordinate structural decomposition (NSD) analysis is used for a detailed analysis of the conformation of the porphyrin subunit within the crystal structures. An elongation of porphyrin macrocycles along the C5,C15- axis (B2g symmetry) is observed in all of the free base porphyrins and porphyrin dications; distance across the core is around 0.3 Å in the free base and diacid compounds, and more than doubled in 5,15-dipentylporphyrin and 5,15-dipentylporphyrindi-ium diacid. While the free base porphyrins are largely planar, a large out-of-plane distortion can be observed in 5,15-diphenylporphyrin diacids, with the expected “projective saddle” shape characteristic for such systems. The combination of these two distortions (B2u and B2g) from regular porphyrin structure results in a macrocycle best characterized in the chiral point-group D2. A rare structural type of a cis-hydrogen bond chelate is observed for 5,15-dipentylporphyrindi-ium diacid, which adopts an achiral C2v symmetry. Crystallographic data indicate that the protonated porphyrin core forms hydrogen bonding chelates (N-H⋯X⋯H-N) to counter-anions. Weaker interactions, such as induced intramolecular C-H⋯O interactions from the porphyrin periphery are described, with distances characteristic of charge-assisted interactions. This paper offers a conceptual framework for accessing porphyrin macrocycles with designable distortion and symmetry, useful for the selective perturbation of electronic states and a design-for-application approach to solid state porphyrin materials.

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Section: Introductionmentioning

confidence: 99%

Weak Interactions and Conformational Changes in Core-Protonated A2- and Ax-Type Porphyrin Dications

et al. 2020

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“…One of the main objectives of developing water‐based hosts is for their use in biological systems. Some specific areas that have already been explored include the sequestering of compounds out of the bloodstream, [154] detection of biological compounds in human urine, [155] fluorescent cell imaging and sensing, [86] enzymatic assays, [156, 157] inhibition of amyloidosis, [111] and drug delivery and release [158, 159] . While these initial applications are impressive, as the field of water‐soluble hosts capable of sequestering hydrophilic compounds expands, the potential applications for them will follow suit.…”

Section: Discussionmentioning

confidence: 99%

Mimicking Biological Recognition: Lessons in Binding Hydrophilic Guests in Water

Johns

Harrison

Stingley

et al. 2021

Chemistry A European J

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Selective molecular recognition of hydrophilic guests in water plays a fundamental role in a vast number of biological processes, but synthetic mimicry of biomolecular recognition in water still proves challenging both in terms of achieving comparable affinities and selectivities. This Review highlights strategies that have been developed in the field of supramolecular chemistry to selectively and non‐covalently bind three classes of biologically relevant molecules: nucleotides, carbohydrates, and amino acids. As several groups have systematically modified receptors for a specific guest, an evolutionary perspective is also provided in some cases. Trends in the most effective binding forces for each class are described, providing insight into selectivity and potential directions for future work.

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“…[ 11 ] Compared with traditional PSs, these supramolecular PSs could greatly maximize their photodynamic effects and minimize side effects. For example, various macrocyclic molecules including cucurbit[ n ]uril, [ 12 ] pillar[ n ]arene, [ 13 ] boxlike synthetic receptor (ExBox·4Cl) [ 14 ] have been proposed to regulate the PDT efficiency of PSs through host–guest chemistry. However, these molecular sized supramolecular PSs are still limited by their poor tumor accumulation ability as they can be quickly cleared from the body.…”

Section: Introductionmentioning

confidence: 99%

Modular Design of Supramolecular Organic Frameworks for Image‐Guided Photodynamic Therapy

Wang

Xiang

et al. 2020

Adv Funct Materials

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Inspired by the efficient modular design of contemporary engineering, a design philosophy is proposed for the construction of molecular building blocks. Here, modular design of supramolecular organic frameworks (SOFs) for image-guided photodynamic therapy (PDT) in vivo is presented. The closo-dodecaborate cluster (B 12) can selectively bind with the convex exterior of cucurbit[8]uril (CB[8]) with a molar ratio of 1:3 through chaotropic effect, which enables the CB[8]-B 12 based SOFs with exchangeable units/ functions. After the B 12 is modified with polyethylene glycol (PEG) and RGD sequence as target ligand and the CB[8] is loaded with methylene blue (MB) as supramolecular photosensitizer, the SOFs can be easily prepared with wide engineering range. A uniform nanoshuttle (NanoSOF) with excellent water dispersibility and bioavailability can be prepared by simply mixing the B 12-PEG-RGD and MB@CB[8] in aqueous solution. As a proof of concept, the NanoSOF is applied as smart nanomedicine for targeted tumor imaging and PDT of tumor, and excellent tumor targeting ability as well as tumor ablation ability can be achieved in vivo. This work highlights the modular design of SOFs with exchangeable units/functions based on chaotropic effect, which may arouse research interests in many other fields.

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A Supramolecular Approach for Modulated Photoprotection, Lysosomal Delivery, and Photodynamic Activity of a Photosensitizer

Cited by 65 publications

References 37 publications

Weak Interactions and Conformational Changes in Core-Protonated A2- and Ax-Type Porphyrin Dications

Weak Interactions and Conformational Changes in Core-Protonated A2- and Ax-Type Porphyrin Dications

Mimicking Biological Recognition: Lessons in Binding Hydrophilic Guests in Water

Modular Design of Supramolecular Organic Frameworks for Image‐Guided Photodynamic Therapy

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