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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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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Light, Switch, Action! The Influence of Geometrical Photoisomerization in an Adaptive Self-Assembled System

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(46), P. 31892 - 31900

Published: Nov. 5, 2024

The ubiquitous ability of natural dynamic nanostructures to adapt environmental changes is a highly desirable property for chemical systems, particularly in the development complex matter, molecular machines, and life-like materials. Designing such systems challenging due generation mixtures with responses that are difficult predict, characterize, diversify. Here, we navigate between self-assembled architectures using light by operating an intrinsic photoswitchable building block governs state system. When complementary units present, photoswitch determines predominant architecture, reversibly adapting cage macrocycles, including (otherwise inaccessible) higher-energy assemblies. Our study showcases this concept seven different transformations, offering unprecedented degree control, diversification, adaptation self-selecting units. These findings could enable applications on-demand dissipative macrocycles based on bonds. We also envision transient nanostructures, e.g., reticular polymeric materials, being explored fine-tuning nature unit.

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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Electrochemical switching in mechanically interlocked molecules (MIMs)

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(10), P. 2954 - 2980

Published: Jan. 1, 2024

Mechanically interlocked molecules (MIMs) which include rotaxanes and catenanes are formed by the mechanical linking of two or more components has ability to switch between different states in presence an external stimuli.

Language: Английский

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Mechanically Interlocked Water-Soluble Pd₆ Host for the Selective Separation of Coal Tar-Based Planar Aromatic Molecules

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(32), P. 14924 - 14932

Published: June 19, 2024

Research on the synthesis of catenated cages has been a growing field interest in past few years. While multiple types with different structures have synthesized, application such systems much less explored. Specifically, use separation industrially relevant molecules that are present coal tar not explored before. Herein, we demonstrate newly synthesized interlocked cage 1 [C184H240N76O48Pd6] (M6L4), formed through self-assembly ligand L.HNO3 (tris(4-(1H-imidazole-1-yl)benzylidene)hydrazine-1-carbohydrazonhydrazide) acceptor cis-[(tmchda)Pd(NO3)2] [tmchda = ±N,N,N′,N′-tetramethylcyclohexane-1,2-diamine] (M). The was able to separate isomers (anthracene and phenanthrene) using simple solvent extraction technique. Using same technique, more difficult structurally physiochemically similar compounds acenaphthene acenaphthylene performed for first time as host. Other noninterlocked hexanuclear Pd6 having wider cavity proved inefficient separation, demonstrating uniqueness challenging separation.

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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