Stabilization of Carbocation Intermediate by Cucurbit[7]uril Enables High Photolysis Efficiency DOI
Shan Mei, Qi Ou,

Xingchen Tang

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(28), P. 5291 - 5296

Published: July 10, 2023

A cucurbit[7]uril-based host-guest strategy is employed to enhance the efficiency of photolysis reactions that release caged molecules from photoremovable protecting groups. The benzyl acetate follows a heterolytic bond cleavage mechanism, thereby leading formation contact ion pair as key reactive intermediate. Gibbs free energy lowered by 3.06 kcal/mol through stabilization cucurbit[7]uril, revealed DFT calculations, which results in 40-fold increase quantum yield reaction. This methodology also applicable chloride leaving group and diphenyl group. We anticipate this research presents novel improve involving active cationics, enriching field supramolecular catalysis.

Language: Английский

Rejuvenating old fluorophores with new chemistry DOI
Martin J. Schnermann, Luke D. Lavis

Current Opinion in Chemical Biology, Journal Year: 2023, Volume and Issue: 75, P. 102335 - 102335

Published: June 1, 2023

Language: Английский

Citations

18
Triplet‐Triplet Energy Transfer: A Simple Strategy for an Efficient Visible Light‐Induced Photoclick Reaction DOI Creative Commons
Youxin Fu, Georgios Alachouzos, Nadja A. Simeth

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(21)

Published: March 21, 2024

Abstract Photoclick reactions combine the advantages offered by light‐driven processes and classical click chemistry have found applications ranging from surface functionalization, polymer conjugation, photo‐crosslinking, protein labeling. Despite these advances, dependency of most photoclick on UV light poses a severe obstacle for their general implementation, as this can be absorbed other molecules in system resulting degradation or unwanted reactivity. However, development simple efficient to achieve bathochromically shifted transformations remains challenging. Here, we introduce triplet‐triplet energy transfer fast selective way enable visible light‐induced reactions. Specifically, show that 9,10‐phenanthrenequinones ( PQ s) efficiently react with electron‐rich alkenes ERA presence catalytic amount (as little 5 mol %) photosensitizers. The photocycloaddition reaction achieved under green (530 nm) orange (590 irradiation, representing bathochromic shift over 100 nm compared PQ‐ERA s system. Furthermore, combining appropriate reactants, establish an orthogonal, blue which product distribution precisely controlled choice color light.

Language: Английский

Citations

6
Red/near-infrared light triggered photorelease via sensitized photolysis DOI
Donghao Lu,

Shu Yang,

Qiyu Yu

et al.

Coordination Chemistry Reviews, Journal Year: 2024, Volume and Issue: 518, P. 216117 - 216117

Published: July 27, 2024

Language: Английский

Citations

6
Deuteration of heptamethine cyanine dyes enhances their emission efficacy DOI Creative Commons
Hana Janeková, Hannah C. Friedman, Marina Russo

et al.

Chemical Communications, Journal Year: 2023, Volume and Issue: 60(8), P. 1000 - 1003

Published: Dec. 18, 2023

The design of bright short-wave infrared fluorophores remains a grand challenge. Here we investigate the impact deuteration on properties in series heptamethine dyes, absorption which spans near-infrared and SWIR regions. We demonstrate that it is generally applicable strategy leads to enhanced quantum yields fluorescence, longer-lived singlet excited states suppressed rates non-radiative deactivation processes.

Language: Английский

Citations

13
The emerging tools for precisely manipulating microtubules DOI Creative Commons

Yen-Ling Lian,

Yu‐Chun Lin

Current Opinion in Cell Biology, Journal Year: 2024, Volume and Issue: 88, P. 102360 - 102360

Published: April 18, 2024

Cells generate a highly diverse microtubule network to carry out different activities. This is comprised of distinct tubulin isotypes, tubulins with post-translational modifications, and many microtubule-based structures. Defects in this complex system cause numerous human disorders. However, how subtypes regulate cellular architectures activities remains largely unexplored. Emerging tools such as photosensitive pharmaceuticals, chemogenetics, optogenetics enable the spatiotemporal manipulation structures, dynamics, cross-linking actin filaments target subtypes. review summarizes design rationale applications these new approaches aims provide roadmap for researchers navigating intricacies dynamics their modifications contexts, thereby opening avenues therapeutic interventions.

Language: Английский

Citations

4
Machine Learning for Reaction Performance Prediction in Allylic Substitution Enhanced by Automatic Extraction of a Substrate-Aware Descriptor DOI
Gufeng Yu, Xi Wang,

Yugong Luo

et al.

Journal of Chemical Information and Modeling, Journal Year: 2025, Volume and Issue: 65(1), P. 312 - 325

Published: Jan. 2, 2025

Despite remarkable advancements in the organic synthesis field facilitated by use of machine learning (ML) techniques, prediction reaction outcomes, including yield estimation, catalyst optimization, and mechanism identification, continues to pose a significant challenge. This challenge arises primarily from lack appropriate descriptors capable retaining crucial molecular information for accurate while also ensuring computational efficiency. study presents successful application ML predicting performance Ir-catalyzed allylic substitution reactions. We introduce SubA, an innovative substrate-aware descriptor that is inspired fact specific atoms or motifs reactants drive outcomes. By employing graph matching algorithms backbone identification incorporating atomic properties derived density functional theory calculations, SubA extracts essential at both level level. Compared four mainstream descriptors, achieves reduced dimensionality enhanced accuracy with over 2% mean absolute error reduction random scaffold splitting evaluations. It demonstrates better generalization when confronted previously unreported substrate combinations extended experiments. Furthermore, interpretable analysis shows predictor focuses on key features, offering insights into mechanisms.

Language: Английский

Citations

0
Spatiotemporal Control Over Circadian Rhythms With Light DOI Creative Commons
Dušan Kolarski, Wiktor Szymański, Ben L. Feringa

et al.

Medicinal Research Reviews, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 5, 2025

Circadian rhythms are endogenous biological oscillators that synchronize internal physiological processes and behaviors with external environmental changes, sustaining homeostasis health. Disruption of circadian leads to numerous diseases, including cardiovascular metabolic cancer, diabetes, neurological disorders. Despite the potential restore healthy in organism, pharmacological chronotherapy lacks spatial temporal resolution. Addressing this challenge, chrono-photopharmacology, approach employs small molecules light-controlled activity, enables modulation when where needed. Two approaches-relying on irreversible reversible drug activation-have been proposed for purpose. These methodologies based photoremovable protecting groups photoswitches, respectively. Designing photoresponsive bioactive requires meticulous structural optimization obtain desired chemical photophysical properties, design principles, detailed guidelines challenges summarized here. In review, we also analyze all known modulators responsive light dissect rationale following their construction application control biology from protein level living organisms. Finally, present strength a allowing period phase.

Language: Английский

Citations

0
Precise photorelease in living cells by high-viscosity activatable coumarin-based photocages DOI Creative Commons
Xinyi Huang,

Yajie Shi,

Li Jiang

et al.

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

Published: Jan. 1, 2025

The first instance of utilizing high viscosity as a stimulus to activate photocages for the precise control cargo photorelease.

Language: Английский

Citations

0
A Structurally Compact Aqueous Soluble Oxypicolinium Photocage with High Photosensitivity DOI Creative Commons

Komadhie C. Dissanayake,

Mohammad K. I. Walid,

Madelyn Austin

et al.

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

Published: Jan. 1, 2025

Photocages are protecting groups that can be unmasked with light irradiation and provide spatiotemporal control over the activity of a biomolecule.

Language: Английский

Citations

0
The Quinoline Photoremovable Group (PPG) Platform—A Medicinal Chemist's Approach for Photocage Development and Applications DOI Creative Commons
Bence Kontra, Zoltán Mucsi, Janez Ilaš

et al.

Medicinal Research Reviews, Journal Year: 2025, Volume and Issue: unknown

Published: April 12, 2025

Photoremovable protecting groups (PPGs) offer a straightforward solution for the temporary inactivation of biologically active substrates and their subsequent controlled release by light irradiation. Their relatively easy design mode application have made them useful tools studying dynamic biological processes in vitro vivo. Recently, there has been growing body data investigating potential development drug delivery systems. Of various PPG scaffolds use, quinoline photocages history about 20 years. The structure-property relationships PPGs, as well alternative multibranch designs based on monomers thoroughly studied both experimentally theoretically. Therefore, PPGs serve representative study development, showing how applications followed chemical optimization or drove design. Since raison d'être lies light-activated performing structural changes materials, it is crucial to understand are selected utilized end-users, who often not chemists themselves. we discuss whether conclusions drawn from family could lead more general insights field whole. As PPG-related still rely heavily limited number scaffolds, worth considering, what be reasons slow uptake novel scaffolds.

Language: Английский

Citations

0