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

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Янв. 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.

Язык: Английский

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Can Molecular Systems Learn?

ChemSystemsChem, Год журнала: 2025, Номер unknown

Опубликована: Янв. 24, 2025

Abstract Research across various disciplines shows the benefits of learning and memory for gaining functionality improving performance. It is increasingly clear that can be found in both physical virtual systems, from intelligent life forms to machines, simple organisms, even designed chemical systems. We are interested understanding what extent embodiments these processes synthesized engineered bottom up by using molecular components. In this perspective, we raise attempt answer conceptual questions about supramolecular systems as smallest units capable learning. define a process where complex system interacting components modifies itself response an applied stress or stimulus, resulting structural changes information gain. highlight potential chemistry networks design meet definition encoding, decoding, storing within system′s composition. Understanding basis could inform development materials autonomously acquire new properties their environment. This also provide insights next‐generation computing physical, rather than virtual,

Язык: 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, Год журнала: 2025, Номер 23(10), С. 2498 - 2509

Опубликована: Янв. 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.

Язык: Английский

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Kinetic Trapping of Rylene Diimide Covalent Organic Cages

The Journal of Organic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Март 17, 2025

Formation of imine organic cages relies on the error correction dynamic covalent chemistry. Here, we demonstrate kinetically trapped rylene diimide [2 + 3] formed in high yields, and investigate effect substituents their formation kinetics stability. Thereby, identified that alkoxy groups 2,4,6-trialkoxy-1,3,5-triformylbenzene, which are used to stabilize or COFs, act as stereoelectronic chameleons. They increase electrophilicity tritopic aldehyde rate bond but simultaneously diminish its kinetic stability solution. We also show aldehydes present solution may have a detrimental cage's In addition, observed 2] macrocycles intermediates cage decomposition. propose these represent interesting targets explore threshold at an assembly with rung structure turn from thermodynamic control. Generally, this work underscores critical factors governing chemistry assemblies, such steric bulk, (stereo)electronics, presence catalysts, water concentration.

Язык: 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, Год журнала: 2024, Номер 146(46), С. 31892 - 31900

Опубликована: Ноя. 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.

Язык: Английский

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Iminobispyrazole (IBP) Photoswitches: Two Pyrazole Rings Can Be Better Than One

Chemical Communications, Год журнала: 2024, Номер unknown

Опубликована: Янв. 1, 2024

We recently demonstrated that suitably functionalised aryliminopyrazoles can exhibit useful photoswitching properties. This study investigates the potential of iminobispyrazoles (IBPs). find regiochemistry IBPs strongly dictates their properties, most notably,

Язык: Английский

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