Pnictogen-Bonding Catalysis and Transport Combined: Polyether Transporters Made In Situ

Humeniuk, Heorhii V.; Gini, Andrea; Hao, Xiaoyu; Coelho, Filipe Diogo De Sousa; Sakai, Naomi; Matile, Stefan

doi:10.1021/jacsau.1c00345

Cited by 47 publications

(51 citation statements)

References 74 publications

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“…Promising new perspectives with pnictogen relays include the involvement of pnictogen bonds 41 − 43 and hypervalent oxidized intermediates VIII , both known to provide new mechanisms in transport and catalysis. 44 − 50 Already in chalcogen-centered cascades, chalcogen bonding 42 , 51 − 55 accounts for exchange without activation energy. 56 The integration of pnictogen bonding increases the strength and versatility ( Figure 1 A, vide infra ).…”

Section: Resultsmentioning

confidence: 99%

Pnictogen-Centered Cascade Exchangers for Thiol-Mediated Uptake: As(III)-, Sb(III)-, and Bi(III)-Expanded Cyclic Disulfides as Inhibitors of Cytosolic Delivery and Viral Entry

Lim

Kato

Besnard

et al. 2022

JACS Au

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Dynamic covalent exchange cascades with cellular thiols are of interest to deliver substrates to the cytosol and to inhibit the entry of viruses. The best transporters and inhibitors known today are cyclic cascade exchangers (CAXs), producing a new exchanger with every exchange, mostly cyclic oligochalcogenides, particularly disulfides. The objective of this study was to expand the dynamic covalent chalcogen exchange cascades in thiol-mediated uptake by inserting pnictogen relays. A family of pnictogen-expanded cyclic disulfides covering As(III), Sb(III), and Bi(III) is introduced. Their ability to inhibit thiol-mediated cytosolic delivery is explored with fluorescently labeled CAXs as transporters. The promise of inhibiting viral entry is assessed with SARS-CoV-2 lentiviral vectors. Oxygen-bridged seven-membered 1,3,2-dithiabismepane rings are identified as privileged scaffolds. The same holds for six-membered 1,3,2-dithiarsinane rings made from asparagusic acid and para -aminophenylarsine oxide, which are inactive or toxic when used alone. These chemically complementary Bi(III) and As(III) cascade exchangers inhibit both thiol-mediated cytosolic delivery and SARS-CoV-2 lentivector uptake at concentrations of 10 μM or lower. Crystal structures, computational models, and exchange kinetics support that lentivector entry inhibition of the contracted dithiarsinane and the expanded dithiabismepane rings coincides with exchange cascades that occur without the release of the pnictogen relay and benefit from noncovalent pnictogen bonds. The identified leads open perspectives regarding drug delivery as well as unorthodox approaches toward dynamic covalent inhibition of cellular entry.

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Section: Resultsmentioning

confidence: 99%

Pnictogen-Centered Cascade Exchangers for Thiol-Mediated Uptake: As(III)-, Sb(III)-, and Bi(III)-Expanded Cyclic Disulfides as Inhibitors of Cytosolic Delivery and Viral Entry

Lim

Kato

Besnard

et al. 2022

JACS Au

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“…In the field of organocatalysis, the number of studies devoted to the development of new functional PnB-based catalysts has rapidly increased during recent years [93][94][95][96][97][98][99][100][101][102]. In this section, several selected examples involving PnB-based catalysts are discussed.…”

Section: Arsenic and Antimonymentioning

confidence: 99%

On the Importance of Pnictogen and Chalcogen Bonding Interactions in Supramolecular Catalysis

Frontera

Bauzá

2021

IJMS

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In this review, several examples of the application of pnictogen (Pn) (group 15) and chalcogen (Ch) bonding (group 16) interactions in organocatalytic processes are gathered, backed up with Molecular Electrostatic Potential surfaces of model systems. Despite the fact that the use of catalysts based on pnictogen and chalcogen bonding interactions is taking its first steps, it should be considered and used by the scientific community as a novel, promising tool in the field of organocatalysis.

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“…Pnictogen bonding, unlike other noncovalent interactions, is among the least theoretically and computationally studied chemical interactions [ 1 , 2 , 3 , 4 , 5 , 6 ], yet has been featured in applications in many areas such as catalysis [ 7 , 8 , 9 , 10 ], coordination chemistry [ 3 , 11 , 12 , 13 , 14 , 15 ], photovoltaics [ 16 , 17 ], and supramolecular chemistry [ 4 , 5 ]. There are relatively few reviews [ 3 , 18 , 19 , 20 , 21 , 22 ], original papers (for example [ 1 , 5 , 23 , 24 , 25 , 26 , 27 , 28 , 29 ]), overviews [ 30 ], and comments on the strength [ 31 ], nature [ 32 , 33 ], and propensity of elements of the pnictogen family (Group 15) to engage in pnictogen bonding [ 34 , 35 , 36 ].…”

Section: Introductionmentioning

confidence: 99%

“…A pnictogen bond features geometric and electronic characteristics akin to those of the hydrogen bond, triel bond (Group 13), tetrel bond (Group 14), chalcogen bond (Group 16), halogen bond (Group 17), arogen bond (Group 18), and other noncovalent interactions, and is therefore regarded as a sister interaction. The importance of pnictogen bonds emerges from its implication in the design and discovery of several functional materials [ 16 , 17 ], such as organic-inorganic halide perovskite semiconductors and in many other areas of materials science [ 3 , 4 , 5 , 6 , 7 , 8 , 9 , 10 , 11 , 12 , 13 , 14 , 15 ].…”

Section: Introductionmentioning

confidence: 99%

The Pnictogen Bond: The Covalently Bound Arsenic Atom in Molecular Entities in Crystals as a Pnictogen Bond Donor

Varadwaj

Marques

et al. 2022

Molecules

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In chemical systems, the arsenic-centered pnictogen bond, or simply the arsenic bond, occurs when there is evidence of a net attractive interaction between the electrophilic region associated with a covalently or coordinately bound arsenic atom in a molecular entity and a nucleophile in another or the same molecular entity. It is the third member of the family of pnictogen bonds formed by the third atom of the pnictogen family, Group 15 of the periodic table, and is an inter- or intramolecular noncovalent interaction. In this overview, we present several illustrative crystal structures deposited into the Cambridge Structure Database (CSD) and the Inorganic Chemistry Structural Database (ICSD) during the last and current centuries to demonstrate that the arsenic atom in molecular entities has a significant ability to act as an electrophilic agent to make an attractive engagement with nucleophiles when in close vicinity, thereby forming σ-hole or π-hole interactions, and hence driving (in part, at least) the overall stability of the system’s crystalline phase. This overview does not include results from theoretical simulations reported by others as none of them address the signatory details of As-centered pnictogen bonds. Rather, we aimed at highlighting the interaction modes of arsenic-centered σ- and π-holes in the rationale design of crystal lattices to demonstrate that such interactions are abundant in crystalline materials, but care has to be taken to identify them as is usually done with the much more widely known noncovalent interactions in chemical systems, halogen bonding and hydrogen bonding. We also demonstrate that As-centered pnictogen bonds are usually accompanied by other primary and secondary interactions, which reinforce their occurrence and strength in most of the crystal structures illustrated. A statistical analysis of structures deposited into the CSD was performed for each interaction type As···D (D = N, O, S, Se, Te, F, Cl, Br, I, arene’s π system), thus providing insight into the typical nature of As···D interaction distances and ∠R–As···D bond angles of these interactions in crystals, where R is the remainder of the molecular entity.

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Pnictogen-Bonding Catalysis and Transport Combined: Polyether Transporters Made In Situ

Cited by 47 publications

References 74 publications

Pnictogen-Centered Cascade Exchangers for Thiol-Mediated Uptake: As(III)-, Sb(III)-, and Bi(III)-Expanded Cyclic Disulfides as Inhibitors of Cytosolic Delivery and Viral Entry

Pnictogen-Centered Cascade Exchangers for Thiol-Mediated Uptake: As(III)-, Sb(III)-, and Bi(III)-Expanded Cyclic Disulfides as Inhibitors of Cytosolic Delivery and Viral Entry

On the Importance of Pnictogen and Chalcogen Bonding Interactions in Supramolecular Catalysis

The Pnictogen Bond: The Covalently Bound Arsenic Atom in Molecular Entities in Crystals as a Pnictogen Bond Donor

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