A hydrophobic photouncaging reaction to profile the lipid droplet interactome in tissues DOI Creative Commons
Di Shen, Qun Zhao,

Huaiyue Zhang

et al.

Proceedings of the National Academy of Sciences, Journal Year: 2025, Volume and Issue: 122(16)

Published: April 16, 2025

Most bioorthogonal photouncaging reactions preferentially occur in polar environments to accommodate biological applications the aqueous cellular milieu. However, they are not precisely designed chemically adapt diverse microenvironments of cell. Herein, we report a hydrophobic reaction with tailored photolytic kinetics toward solvent polarity. Structural modulations aminobenzoquinone-based photocage reveal impact cyclic ring size, steric substituent, and electronic substituent on individual uncaging ( k H2O dioxane ) polarity preference / ). Rational incorporation optimized moieties leads up 20.2-fold nonpolar kinetic selectivity Further photochemical spectroscopic characterizations theoretical calculations together uncover mechanism underlying polarity-dependent kinetics. The uncaged ortho-quinone methide product bears covalent reactivity nucleophiles protein revealed by tandem mass spectrometry. Finally, demonstrate application such lipophilic chemistry selective labeling profiling proteins proximity lipid droplets inside human fatty liver tissues. Together, this work studies effects adapts it suborganelle-targeted profiling.

Language: Английский

meso-Methyl BODIPY Photocages: Mechanisms, Photochemical Properties, and Applications DOI
Pradeep Shrestha, Dnyaneshwar Kand, Roy Weinstain

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(32), P. 17497 - 17514

Published: Aug. 3, 2023

meso-methyl BODIPY photocages have recently emerged as an exciting new class of photoremovable protecting groups (PPGs) that release leaving upon absorption visible to near-infrared light. In this Perspective, we summarize the development these PPGs and highlight their critical photochemical properties applications. We discuss PPGs, structure–photoreactivity studies, insights into photoreaction mechanism, scope functional can be caged, chemical synthesis structures, how substituents alter water solubility PPG direct specific subcellular compartments. Applications exploit unique optical are also discussed, from wavelength-selective photoactivation biological studies photoresponsive organic materials photomedicine.

Language: Английский

Citations

64
Engineering a Green Fluorescent Protein-Core-Inspired NIR-Photocage: Exploring meso-GFP-PRPG toward Alzheimer’s Disease Therapeutics DOI Creative Commons

Saugat Mondal,

Jusung An,

Tapas Bera

et al.

ACS Central Science, Journal Year: 2025, Volume and Issue: unknown

Published: March 19, 2025

Language: Английский

Citations

2
Photouncaging of Carboxylic Acids from Cyanine Dyes with Near‐Infrared Light** DOI Creative Commons
Hana Janeková, Marina Russo, Urs Ziegler

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(33)

Published: May 17, 2022

Near-infrared light (NIR; 650-900 nm) offers unparalleled advantages as a biocompatible stimulus. The development of photocages that operate in this region represents fundamental challenge due to the low energy excitation light. Herein, we repurpose cyanine dyes into are available on multigram scale three steps and efficiently release carboxylic acids aqueous media upon irradiation with NIR up 820 nm. photouncaging process is examined using several techniques, providing evidence it proceeds via photooxidative pathway. We demonstrate practical utility live HeLa cells by delivery acid cargo, was otherwise not uptaken its free form. In combination modularity scaffold, realization these accessible will fully unleash potential emerging field NIR-photoactivation facilitate widespread adoption outside photochemistry community.

Language: Английский

Citations

47
Photo-controllable biochemistry: Exploiting the photocages in phototherapeutic window DOI Creative Commons
Hao Xiong, Yunjie Xu,

Byungkook Kim

et al.

Chem, Journal Year: 2022, Volume and Issue: 9(1), P. 29 - 64

Published: Dec. 1, 2022

Language: Английский

Citations

44
Sensitizer-controlled photochemical reactivityviaupconversion of red light DOI Creative Commons
Felix Glaser, Oliver S. Wenger

Chemical Science, Journal Year: 2022, Volume and Issue: 14(1), P. 149 - 161

Published: Dec. 1, 2022

By combining the energy input from two red photons, chemical reactions that would normally require blue or ultraviolet irradiation become accessible. Key advantages of this biphotonic excitation strategy are light usually penetrates deeper into complex reaction mixtures and causes less photo-damage than direct illumination in ultraviolet. Here, we demonstrate primary light-absorber a dual photocatalytic system comprised transition metal-based photosensitizer an organic co-catalyst can completely alter outcome. Photochemical reductions achieved with copper(i) presence sacrificial electron donor, whereas oxidative substrate activation occurs osmium(ii) photosensitizer. Based on time-resolved laser spectroscopy, changeover photochemical reactivity is due to different underlying mechanisms. Following triplet transfer 9,10-dicyanoanthracene (DCA) subsequent triplet-triplet annihilation upconversion, fluorescent singlet excited state DCA triggers activation, which initiates

Language: Английский

Citations

41
Ligand-Directed Photocatalysts and Far-Red Light Enable Catalytic Bioorthogonal Uncaging inside Live Cells DOI

Julia E. Rosenberger,

Yixin Xie, Yinzhi Fang

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(11), P. 6067 - 6078

Published: March 7, 2023

Described are ligand-directed catalysts for live-cell, photocatalytic activation of bioorthogonal chemistry. Catalytic groups localized via a tethered ligand either to DNA or tubulin, and red light (660 nm) photocatalysis is used initiate cascade DHTz oxidation, intramolecular Diels–Alder reaction, elimination release phenolic compounds. Silarhodamine (SiR) dyes, more conventionally as biological fluorophores, serve photocatalysts that have high cytocompatibility produce minimal singlet oxygen. Commercially available conjugates Hoechst dye (SiR-H) docetaxel (SiR-T) localize SiR the nucleus microtubules, respectively. Computation was assist design new class redox-activated photocage phenol n-CA4, microtubule-destabilizing agent. In model studies, uncaging complete within 5 min using only 2 μM 40 photocage. situ spectroscopic studies support mechanism involving rapid reaction rate-determining step. cellular this process successful at low concentrations both (25 nM) SiR-H (500 nM). Uncaging n-CA4 causes microtubule depolymerization an accompanying reduction in cell area. Control demonstrate catalyzes inside cell, not extracellular environment. With SiR-T, same serves photocatalyst fluorescent reporter depolymerization, with confocal microscopy, it possible visualize real time result live cells.

Language: Английский

Citations

35
Turning Red without Feeling Embarrassed─Xanthenium-Based Photocages for Red-Light-Activated Phototherapeutics DOI Creative Commons

Alexandra Egyed,

Krisztina Németh,

Tibor Á. Molnár

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(7), P. 4026 - 4034

Published: Feb. 8, 2023

Herein, we present high-yielding, concise access to a set of xanthenium-derived, water-soluble, low-molecular-weight photocages allowing light-controlled cargo release in the green red region. Very importantly, these new allow installation various payloads through ester, carbamate, or carbonate linkages even at last stage synthesis. Payloads were uncaged with high efficiency upon green, orange, light irradiation, leading carboxylic acids, phenols, and amines. The near-ideal properties carboxanthenium derivative further evaluated context drug using camptothecin-derived chemotherapeutic drug, SN38. Notably, caged showed orders magnitude lower cellulo, which was reinstated after irradiation. presented offer that facilitate translation photoactivated chemotherapy toward clinical applications.

Language: Английский

Citations

32
The fate of the contact ion pair determines the photochemistry of coumarin-based photocleavable protecting groups DOI Creative Commons
Albert M. Schulte, Georgios Alachouzos, Wiktor Szymański

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(6), P. 2062 - 2073

Published: Jan. 1, 2024

Improving the efficiency of photocleavable protecting groups is crucial for their application. Here we reveal how fate contact ion pair intermediate plays a key role in defining this efficiency.

Language: Английский

Citations

12
Light in a Heartbeat: Bond Scission by a Single Photon above 800 nm DOI Creative Commons
Marina Russo, Hana Janeková, Debora Meier

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(12), P. 8417 - 8424

Published: March 18, 2024

Photocages enable scientists to take full control over the activity of molecules using light as a biocompatible stimulus. Their emerging applications in photoactivated therapies call for efficient uncaging near-infrared (NIR) window, which represents fundamental challenge. Here, we report synthetically accessible cyanine photocages that liberate alcohol, phenol, amine, and thiol payloads upon irradiation with NIR up 820 nm aqueous media. The display unique chameleon-like behavior operate via two distinct mechanisms: photooxidation heterolytic bond cleavage. latter process constitutes first example direct scission by single photon ever observed dyes or at wavelengths exceeding 800 nm. Modulation beating rates human cardiomyocytes achieved light-actuated release adrenergic agonist etilefrine submicromolar concentrations low doses (∼12 J cm

Language: Английский

Citations

10
Specific and Long‐Term Luminescent Monitoring of Hydrogen Peroxide in Tumor Metastasis DOI
Xindong Wang,

Fu Ji,

Jiang Chang

et al.

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(20)

Published: Feb. 27, 2023

Luminescent monitoring of endogenous hydrogen peroxide (H2 O2 ) in tumors is conducive to understanding metastasis and developing novel therapeutics. The clinical transformation obstructed by the limited light penetration depth, toxicity nano-probes, lack long-term modes up days or months. New are introduced via specific probes implantable devices, which can achieve real-time with a readout frequency 0.01 s for months years. Near-infrared dye-sensitized upconversion nanoparticles (UCNPs) fabricated as luminescent probes, specificity reactive oxygen species subtly regulated self-assembled monolayers on surfaces UCNPs. Combined passive implanted system, 20-day H2 rat model ovarian cancer peritoneal achieved, depth nano-probes circumvented. developed show great potential accelerating biochemical detection methods.

Language: Английский

Citations

19