Selective Protein (Post-)modifications through Dynamic Covalent Chemistry: Self-activated S_NAr Reactions

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 2, 2025

SNAr reactions were remarkably accelerated using a pretargeting and activating unit based on dynamic covalent chemistry (DCvC). A Cys attack at the C–F bond aromatic ring of salicylaldehyde derivatives was only observed upon iminium formation with neighboring Lys residue model small peptides. Such self-activation ascribed to stronger electron-withdrawing capability respect that parent aldehyde stabilized transition state reaction, together higher preorganization reactive groups in cationic aldiminium species. This approach further applied for functionalization two antibodies. In both cases, presence group close proximity resulted noteworthy increase bioconjugation yields, excellent chemo-selectivity. Whereas modification an IgG1 antibody led stochastic product distributions, microenvironment selectivity noted when employing IgG4, line lower number residues hinge region latter. Additionally, postfunctionalization modified antibodies attained through exchange tethered derivative hydrazides, representing unprecedented "tag modify" selective strategy DCvC.

Language: Английский

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Supramolecular and molecular capsules, cages and containers

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(21), P. 10380 - 10408

Published: Jan. 1, 2024

Stemming from early seminal notions of molecular recognition and encapsulation, three-dimensional, cavity-containing capsular compounds assemblies have attracted intense interest due to the ability modulate chemical physical properties species encapsulated within these confined spaces compared bulk environments. With such a diverse range covalent motifs non-covalent (supramolecular) interactions available assemble building blocks, an incredibly wide-range capsular-type architectures been developed. Furthermore, synthetic tunability internal environments gives chemists opportunity engineer systems for uses in sensing, sequestration, catalysis transport molecules, just name few. In this tutorial review, overview is provided into design principles, synthesis, characterisation, structural facets coordination cages, porous organic supramolecular capsules, foldamers mechanically interlocked molecules. Using recent examples, advantages limitations each system are explored, highlighting their application various tasks functions.

Language: Английский

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Precise Assembly/Disassembly of Homo-Type and Hetero-Type Macrocycles with Photoresponsive and Non-Photoresponsive Dynamic Covalent Bonds

Organic & Biomolecular Chemistry, Journal Year: 2025, Volume and Issue: 23(10), P. 2498 - 2509

Published: Jan. 1, 2025

Dynamic covalent macrocycles offer the advantage of tunable ring-opening/ring-closure and structural transformation, but their control with precision remains a daunting task due to labile nature reversible bonds. Herein we demonstrate precise formation/scission varied sizes by contrasting reactivity, stability, degradability light-active light-inactive dynamic The incorporation photoswitchable non-photoresponsive aldehyde sites into one single dialdehyde component afforded creation [1 + 1] type primary diamines suitable lengths. manipulation light acid/base stimuli allowed on-demand breaking/remaking macrocycles, achieving interconversion between macrocyclic linear skeletons. Moreover, combination dialdehyde, diamines, secondary enabled construction hetero-type [2 1 1'] via enhanced discrimination hierarchical assembly. Light-induced kinetic locking/unlocking bonds further macrocycle-to-macrocycle conversion when needed. Through leveraging controllable connection/disconnection, switchable formation/disintegration mechanically interlocked catenanes was accomplished. results described showcase potential photoinduced chemistry for preparing complex architectures should set stage molecular recognition, assemblies, synthetic motors, responsive materials.

Language: Английский

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Self-Assembly of Azulene-Based Imine Cages: Synthesis and Supramolecular Organization

Crystal Growth & Design, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 5, 2025

Language: Английский

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Template-directed self-assembly of porphyrin nanorings through imine condensation reaction

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Template-directed self-assembly has proven to be an extremely effective method for the precise fabrication of biomacromolecules in natural systems, while artificial template-directed systems preparation highly intricate molecules remain a great challenge. In this article, we report porphyrin nanorings with different cavity sizes from tetraaldehyde-derived Zn(ii) and diamine precursor through imine condensation reaction. Up 9 or 18 self-assemble together produce triporphyrin nanoring hexaporphyrin one step, assistance tripyridine hexapyridine template, respectively. The imine-linked are further modified by reduction acylation reactions obtain more stable nanorings. open cavities rings enable them act as hosts encapsulate fullerenes (C60 C70). This work presents efficient strategy construction complicated using dynamic covalent chemistry bond formation.

Language: Английский

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One-Pot Synthesis of Tridentate Bicyclocalixarene Cage Molecules

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 18, 2025

Efficient one-pot synthesis of tridentate bicyclocalixarenes was developed by condensing phloroglucinol with dechlorinated pyrimidine or triazine a yield up to 58%. These cage-like molecules adopt symmetric three-blade propeller structure different terminal function groups and arm spans ranging from 7.5 15.8 Å. Due the 1,3-alternate configuration intermediate heterocalixarenes, cage can be prepared only benzene rings as upper lower caps. They will an ideal scaffold for preparation ultrathin two-dimensional materials.

Language: Английский

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Paramagnetic Cage-Type Co(II) Complexes of Chiral Macrocycles: Enantio- and Size-Selective Binding of Guest Molecules

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 23, 2025

Two enantiomers of the cage-type complex, [Co3LR2] and [Co3LS2] a large hexaazatriphenolic [3 + 3] macrocyclic imine L, have been synthesized characterized on basis NMR, CD, ESI MS spectra. The X-ray crystal structures [Co3L2] crystalline forms reveal two macrocycles cone shape stitched together by three Co(II) ions, forming barrel-shaped molecule with central void. Because limited size cavity enantiopure nature these enantiomeric complexes, both size-selective enantioselective binding guest molecules are observed. In case chiral guests, interaction paramagnetic centers leads to an effective NMR enantiodifferentiation signals molecules, even at host:guest ratios as low 1:200. tight prochiral such ethanol isopropanol within results in splitting enantiotopic methylene methyl signals. dc magnetic data for accord presence high-spin ac susceptibility this complex indicate field-induced single magnet (SMM) behavior. contrast reaction Co(II), ligand H3L Ni(II) or Cu(II) salts contraction macrocycle formation complexes smaller [2 2] macrocycle.

Language: Английский

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Temperature-dependent molecular assembly governs the selective convergent dynamic covalent reactions on surface

Chemical Communications, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

The temperature-dependent assembly of condensed products leads to selective convergent dynamic covalent reactions on surfaces.

Language: Английский

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Triple Adaptation of Constitutional Dynamic Networks of Imines in Response to Micellar Agents: Internal Uptake–Interfacial Localization–Shape Transition

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(13), P. 9096 - 9111

Published: March 25, 2024

Understanding the behavior of complex chemical reaction networks and how environmental conditions can modulate their organization as well associated outcomes may take advantage design related artificial systems. Microenvironments with defined boundaries are particular interest for unique properties prebiotic significance. Dynamic covalent libraries (DCvLs) underlying constitutional dynamic (CDNs) have been shown to be appropriate studying adaptation several processes, including compartmentalization. However, microcompartments (e.g., micelles) provide specific environments selective protection from interfering reactions such hydrolysis an enhanced promiscuity due interface, governing different processes network modulation. Different interactions between micelles library constituents lead sensing, resulting in expressions through pattern generation. The integrated into protected hence preferentially expressed composition at cost constitutionally linked members. In present work, micellar integration was observed two processes: internal uptake based on hydrophobic forces interfacial localization relying attractive electrostatic interactions. latter drives a triple feedback shape self-assembled entity. Our results demonstrate enforce expression CDNs by reducing uptaken members, unravelling that govern response networks. Such studies open way toward using DCvLs understand emergence complexity within microenvironments.

Language: Английский

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Chirality Sensing in Coordination-driven Supramolecular Assemblies

Current Organic Chemistry, Journal Year: 2024, Volume and Issue: 28(12), P. 941 - 958

Published: March 28, 2024

Abstract: Chirality is a widespread structural characteristic found in nature and plays vital role the structure functioning of almost all biological systems. Nevertheless, translation chirality into synthetic systems highly intricate yet captivating, as it not only applies fundamental understanding but also has potential to tackle significant difficulties biochemistry medicine. Structurally, process coordination-driven selfassembly involves organization basic molecular components well-defined porous homochiral metal-organic cages (MOCs). This allows for systematic investigation enantioselective processes occurring within nanocavities, which have limited space specific chiral microenvironments. article aims provide comprehensive summary recent advancements supramolecular generated fascinating class MOCs. It will cover synthesis characterization these materials, well implications their stereochemical information terms recognition enantio-separation. Subsequently, subjective viewpoint be presented regarding potential, possibilities, challenges future advancement this domain, aiming expand progress creating novel functional materials realm chemistry beyond.

Language: Английский

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