Harnessing Nanoreactors with Coupled Optical and Molecular Modalities for Photoenzymatic Modulation of Active Species in Cancer Photo‐Immunotherapy

Small, Journal Year: 2025, Volume and Issue: unknown

Published: March 10, 2025

The dynamic process in tumor ablation requires both the generation of reactive oxygen species (ROS) to elicit immunogenic cell death (ICD) and subsequent reduction ROS levels maintain stimulatory activity signaling proteins recover T cells' immune function. Inspired by regulation mechanism redox homeostasis myeloid-derived suppressor cells high-selectivity alcohols/aldehydes conversions 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) Fe(III) synergistic catalysis, photoenzymatic modulators with contradictory but functions are developed for adaptive photo-immunotherapy cancer. In particular, poly(caffeic acid) (PCA) nanospheres synthesized highly efficient oxidative polymerization CA. obtained π-conjugated structures have an extended absorbance near-infrared (NIR) region, narrow band energy (0.86 eV), low exciton binding (43.56 meV) that lead polymerization-enhanced type I photosensitization photostability. Meanwhile, abundant semiquinone radicals existing PCA bestow them superior antioxidant Under NIR irradiation, elevated superoxide radical yields (3.5-fold compared CA) heat stress robust ICD. When irradiation ceases, active downregulation infiltration lymphocytes increase 2.7-fold conventional photosensitizers. As envisaged, this work demonstrates a novel tactic remodel effective inhibition growth metastasis.

Language: Английский

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Machine Learning‐Based Prediction of Bond Dissociation Energies for Metal‐Trifluoromethyl Compounds^†

Chinese Journal of Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: March 22, 2025

Comprehensive Summary This study explores the application of machine learning to predict bond dissociation energies (BDEs) metal‐trifluoromethyl compounds. We constructed a dataset comprising 2219 BDEs using density functional theory (DFT). Through comparative analysis various algorithms and molecular fingerprints, we determined that XGBoost algorithm, when combined with MACCS Morgan exhibited superior performance. To further enhance predictive accuracy, integrated chemical descriptors alongside multiple achieving an R 2 value 0.951 on test set. The model demonstrated excellent generalization capabilities applied synthesized compounds, highlighting critical role in improving research not only establishes robust for but also underscores incorporating insights into workflows prediction properties.

Language: Английский

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Outcompeting Thermodynamics: Ion-Pairing and Coulombic Interactions to Trigger Perfluoroacetate Intra-Ionic Photooxidation for Perfluoroalkylation Reactions

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

Published: March 31, 2025

Trifluoromethylation is a key transformation in drug and agrochemical synthesis, yet current reagents often suffer from high cost, low atom economy, scalability. Trifluoroacetate derivatives represent ideal as they are highly abundant cheap, but their very positive one electron oxidation potential (∼2.3 V vs NHE) hampers widespread use photoredox catalysis. Indeed, at these potentials, selectively oxidizing trifluoroacetate over reaction solvent or partner substrates becomes challenging. Herein, we present novel approach that circumvents limitations through the of pentacationic Ir(III) photosensitizer forms strong 1:1 ion-pair with acetonitrile (Keq = 6 × 104 M–1). This formation enables rapid efficient photooxidation ∼90 ps without significant substrate oxidation, indicated by femtosecond nanosecond UV–visible transient absorption spectroscopy. The CF3• radicals so generated shown to trifluoromethylate range substrates, including aromatic compounds, heterocycles, natural products pharmaceutically relevant products, moderate yields (20–60%). Control experiments reveal ion-pairing crucial for successful generation photosensitizers oxidize forming ion pairs were ineffective trifluoromethylation. probably originates more thermodynamically accessible outcompeting diffusional oxidation. was further exemplified allow functionalization variety perfluoroalkyl groups different chain lengths. reported herein could also be used removal and/or substances (PFAS), called "forever chemicals", have recently raised environmental health concern.

Language: Английский

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Electrochemical Access to Difluoromethyl Groups: An Overview of Scope, Mechanisms, and Challenges

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 6826 - 6851

Published: April 14, 2025

Language: Английский

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Paired Chemical Upgrading in Photoelectrochemical Cells

JACS Au, Journal Year: 2025, Volume and Issue: 5(5), P. 2061 - 2075

Published: April 23, 2025

Photoelectrochemical (PEC) technology has emerged as a promising platform for sustainable energy conversion and chemical synthesis, utilizing solar to facilitate redox reactions. While PEC systems have been extensively studied water splitting, CO2 reduction, nitrogen reduction value-added compounds the sluggish oxygen evolution reaction (OER) on anode side less economic value of O2 limit system efficiency. To address this, researchers explored paired upgrading strategies, coupling selective anodic organic oxidation reactions (OORs) with cathodic This approach enabled simultaneous production high-value chemicals fuels, enhancing efficiency viability. In this Perspective, we highlight latest advancements milestones in OORs cathode within cells. Particular emphasis is placed key design principles, catalyst development, mechanisms, performance addition, challenges perspectives are provided future development emerging technology.

Language: Английский

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Advances in photocatalytic research on decarboxylative trifluoromethylation of trifluoroacetic acid and derivatives

Frontiers in Chemistry, Journal Year: 2025, Volume and Issue: 13

Published: May 14, 2025

Trifluoromethylation stands as a pivotal technology in modern synthetic chemistry, playing an indispensable role drug design, functional material development, and agrochemical innovation. With the growing emphasis on green chemistry principles, pursuit of environmentally benign trifluoromethylation strategies has emerged critical research frontier. Trifluoroacetic acid (TFA), characterized by its cost-effectiveness, stability, low toxicity, become promising alternative to conventional reagents. This review systematically summarizes advancements photocatalytic decarboxylative using TFA derivatives over past decade, focusing three key activation mechanisms: single-electron transfer (SET), electron donor-acceptor (EDA) complex-mediated pathways, ligand-to-metal charge (LMCT). paradigm shift is driven intrinsic limitations thermal decarboxylation, particularly reliance harsh conditions significant environmental burdens. In contrast, enable efficient C-CF3 bond construction under mild conditions, offering modular platform for synthesizing fluorinated molecules. Strategic priorities should focus overcoming fundamental challenges, including but not limited optimizing photosensitizer catalytic efficiency, establishing regioselective manipulation strategies, engineering multicomponent tandem reaction systems achieve methodologies conditions. Furthermore, integration mechanistic investigations with artificial intelligence-driven prediction will accelerate advancement precision technologies. progress anticipated provide sustainable solutions next-generation pharmaceuticals advanced materials, effectively bridging innovation gap between academic industrial implementation.

Language: Английский

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Visible-light-induced cascade radical cyclization of aryl alkynoates with fluoroalkyl carboxylic anhydrides to construct fluoroalkylated coumarins

Green Synthesis and Catalysis, Journal Year: 2025, Volume and Issue: unknown

Published: May 1, 2025

Language: Английский

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Selective photoelectrochemical synthesis of adipic acid using single-atom Ir decorated α-Fe2O3 photoanode

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: June 2, 2025

Photoelectrochemical (PEC) synthesis offers a sustainable route for fine chemicals production, yet comprehending and modulating the reaction processes at atomic level remains challenge. Herein, we develop single-atom Ir decorated Ti-doped α-Fe2O3 photoanode selective PEC of adipic acid from cyclohexanone using water as oxygen source. The system achieves 6.0 μmol cm-2 h-1 production with ~60% Faradaic efficiency ~88% selectivity. promotes photogenerated carrier separation transfer, while regulating electronic structure to optimize its adsorption strength OH- cyclohexanone. Mechanistic studies reveal non-free-radical pathway level, driven by holes through an adsorbed hydroxyl transfer. Notably, integrating amorphous silicon-based photocathode leads bias-free device that enables stable over 80 hours, underscoring potential light-driven synthesis.

Language: Английский

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Photoinduced Metal‐Free Decarboxylative Fluoroalkylation of Alkenes for the Synthesis of N‐Arylbutanamides and Oxindoles

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(68)

Published: Aug. 28, 2024

The visible light-induced decarboxylative cascade reaction of fluoroalkyl carboxylic acids has been achieved for the efficient synthesis fluorinated compounds. However, most transformations rely on noble iridium metal complex. Herein, a metal-free realized. This protocol features simple operation, transition free, and good functional group tolerance.

Language: Английский

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Recent Progress in Liquid Electrolytes for High‐Energy Lithium–Metal Batteries: From Molecular Engineering to Applications

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 25, 2024

Abstract Lithium–metal batteries (LMBs) have garnered significant interests for their promising high gravimetric energy density ( E g ) ∼ 750 Wh kg −1 . However, the practical application of LMBs is plagued by reactivity and large volume change during charging–discharging lithium–metal anode (LMA), seriously deteriorating battery safety cycle life. Great efforts been devoted to tailoring electrolytes favor Li–metal electroplating uniformizing deposition morphology suppressing side reactions between LMA. The aggressive chemistries both LMA its high‐voltage counterpart give new electrolyte components more opportunities, especially designing via molecular engineering. Here, a comprehensive in‐depth overview scientific challenges, fundamental mechanisms, particularly historical strategies molecules including solvents, salts, additives. Their important roles in tuning Li + solvation structure, interface composition, decomposition pathways, resultant electrochemical performance are also presented. Finally, novel insights research directions from viewpoints proposed future designs LMBs.

Language: Английский

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