The development of sustainable synthetic methodologies remains a central goal in modern chemistry. Recent advances in photocatalysis, mechanochemistry, and electrochemistry have each provided unique advantages. Magnetic fields offer distinctive opportunities for organic synthesis as a complementary approach. This review summarizes recent advances in organic transformations enabled by rotating magnetic fields and metal rods from two perspectives: (1) magnetoredox reactions via electromagnetic induction, and (2) mechanochemical milling reactions.
We developed a light-mediated, surface modification technique to encapsulate hydrogels in covalently bound, hydrophobic polymer coatings. Poly(acrylic acid) (PAA) hydrogel surfaces were photocatalytically decarboxylated and subsequently decorated with hydrophobic polyacrylates. These shell-encapsulated hydrogels exhibited excellent hydrophobicities and anti-swelling behaviors relative to unmodified PAA hydrogels.
Peroxymonosulfate (PMS)-based advanced oxidation technology has been proven to be a viable option for the decontamination of organic pollutants from water bodies. Advanced catalyst design is essential to this technology. Herein, a vanadium-doped LaFeO3 perovskite (LFO-V) featuring asymmetric Fe-O-V sites was rationally designed. Thanks to orbital electron interaction between Fe and V atoms, the modified electronic structure elevated electron density near the Fermi energy level while reducing the energy barrier toward effective PMS activation. This facilitated concurrent PMS reduction at the Fe sites to generate SO4 ' and ' OH (57.7 %), and PMS oxidation at V sites to produce 1 O2 (42.3 %). The LFO-V/PMS system demonstrated excellent tetracycline (TC) degradation performance with a 2-fold enhancement in rate constant compared to that of pristine LFO. Further, the LFO-V maintained long-term stability, and the toxicity of degradation intermediates was evaluated through microbial metabolomics. This work establishes an effective route to regulate the PMS activation pathways through precise electronic structure modulation, advancing the rational design of advanced Fenton-like catalysts. (c) 2025 Published by Elsevier B.V. on behalf of Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.
Herein, a photoexcited-state palladium-catalyzed 6-endo selective annulation reaction of aryl-halide-tethered enamides has been developed, allowing various isoquinolinone motifs synthesized under mild conditions. This approach features operational simplicity, broad substrate scope, good functional group tolerance, and high chemo- and regioselectivity. The synthetic versatility of this methodology is underscored by scalable synthesis and downstream derivatization. Mechanistic studies reveal that this protocol involves a hybrid Pd-radical pathway and that the nitrogen atom is crucial for the observed endo selectivity.
Herein, we describe a straightforward, thiol-free palladium-catalyzed umpolung protocol that uses mild conditions to stitch together readily available dibromoolefins and disulfides, yielding a diverse array of 2-sulfenyl benzofused heterocycles. Upon insertion of Zn into disulfide, in situ generated zinc thiolate engaged in a tandem cyclization/functionalization squence as a viable thiolation agent. In contrast to the existing methods that rely on sophisticated manipulations to prepare starting materials, this technique features high efficiency, synthesis simplicity, commercial availability of reagents, and a broad substrate scope.
Transition-metal-catalyzed C-H aminocarbonylation represents a pivotal route to amides, which are key structural motifs in natural products, pharmaceuticals and functional molecules. Conventional direct C-H carbonylation methods, however, often require organic solvents, excess gaseous CO, and show limited compatibility with isotopic labeling. Herein, we report a palladium-catalyzed aminocarbonylation protocol facilitated by electromagnetic milling (EMM). Unlike traditional approaches, this strategy leverages external fields, notably magnetic, to achieve precise control over amide synthesis. Operating under solvent-free conditions with only 2.0 equivalents of CO, the reaction employs aryl sulfonium salts, displays broad substrate scope and excellent functional group tolerance, and is scalable to the gram level. Furthermore, it provides a unique platform for the late-stage 13C-labeling of pharmaceuticals. Mechanistic studies highlight the essential role of EMM in promoting acyl palladium formation and subsequent amine transfer. The biological efficacy of the synthesized 13C-labeled benzocaine, which promotes collagen repair in a tumor ulcer microenvironment, further demonstrates the practical utility of this strategy.
Precise surface engineering of gold nanoclusters (Au NCs) is critical for electrocatalysis, but conventional strategies frequently fail to maintain atomic precision, owing to rapid reaction kinetics and parasitic etching reactions. Herein, we develop an electromagnetic multifield coupling strategy to enable the reproducible synthesis of previously inaccessible Au-25(SC18H37)(18)(-) nanoclusters, providing atomic-level insight into how ligand-induced surface microenvironments govern electrocatalytic CO2 reduction. Benchmarking their eCO(2)RR performance against the archetypal Au-25(PET)(18)(-) reveals a clear activity trend of Au-25(SC18H37)(18)(-) < Au-25(SC12H25)(18)(-) < Au-25(PET)(18)(-) < Au-25(SC6H13)(18)(-). In situ attenuated total reflection surface-enhanced infrared absorption spectroscopy demonstrates that ligand hydrophobicity, in concert with electrolyte anions, restructures interfacial water to suppress the competing HER while promoting *COOH formation, thereby dictating CO2 to CO selectivity. Density functional theory and ab initio molecular dynamics simulations reveal that ligand-dependent stabilization of the *COOH intermediate governs the rate-determining step, with Au-25(SC6H13)(18)(-) exhibiting optimal energetics that accelerate CO formation and desorption. Explicit solvation models show that more polarizable Br- and I- anions further stabilize *COOH and lower reaction barriers relative to Cl-. These findings identify ligand microenvironments and electrolyte anions as key regulators of eCO(2)RR kinetics.
A novel and efficient method has been developed for the synthesis of tert-butyl esters using (Boc)2O as the tert-butyl source, facilitated by electromagnetic milling. This green and sustainable approach is solvent-free, base-free, and operates without the need for additional heating, making it highly appealing for eco-friendly synthesis. The entirely neutral reaction environment proves particularly advantageous for synthesizing or modifying sensitive drug molecules, especially in late-stage functionalization. In this process, ferromagnetic rods, used as grinding media, become magnetized and charged under a high-speed rotating magnetic field. This magnetization plays a crucial role in bond activation by coordinating with the charged ferromagnetic rods, introducing a novel mechanism for bond activation that could inspire further research in this emerging field.
Fluorescent hydrogels constructed by integrating aggregation-induced emission (AIE) fluorophores have emerged as promising materials for information encryption. Due to the hydrophobic properties of AIEgens, they tend to aggregate in hydrophilic matrix of the hydrogel, which is beneficial for their fluorescent properties but detrimental to their uniform distribution within the gel network. To solve this problem, we have ingeniously developed a water-soluble aggregation-induced emission (AIE) fluorophore that can integrate with the hydrogel matrix, to deepen the application of hydrogel in information security by stimuli-responsiveness. The prepared AIE fluorophores not only possess high quantum yield, but also carry a remarkable ability to self-assemble in water, amplifying AIE emission. After combining with the hydrogel matrix composed of gelatin, carboxymethyl cellulose (CMC) and sodium tetraborate (Na2B4O7), the fluorophores still maintain the stimuli-responsiveness to metal ions, solvents and pH, endowing the hydrogel with tunable fluorescence properties. Additionally, the tailored multi-channel units allow for more secure information encryption and de-identification. This study may advance the expanded utilization of AIE fluorophores in the realm of hydrogel-based materials.
The pursuit of sustainable and environmentally benign methods and techniques continues to challenge organic chemists. Herein, we report the development of a novel approach in which electromagnetic induction could participate in the coupling of organic chlorides using a rotating magnetic field and metal rods. In particular, we describe the application of this strategy to the nickel-catalyzed cross-electrophile coupling of aryl chlorides with alkyl chlorides. Using these abundant and commercially available organochlorides, such a system allows reactions to proceed with a broader scope than the current protocols under mild conditions.
Herein, we demonstrate a robust palladium/norbornene-catalyzed deoxygenative ortho-benzylation of aryl iodides with non-derivatized benzyl alcohol, which enables the assembly of various diarylmethanes with high efficiency. Assisted by a carbodiimide, the alcohol is transiently converted into the corresponding isourea, which further polarizes the C-O bond and facilitates the reaction with the key aryl-NBE-palladacycle (ANP) intermediate through nitrogen atom coordination. The salient features of this methodology include operational simplicity, high chemoselectivity, and broad substrate scope. A preliminary mechanistic investigation indicated the higher reactivity of the isourea compared to the corresponding benzyl (pseudo)halide.
This article introduces a novel, eco-friendly, one-pot method for synthesizing imines via mechanochemistry. Using water as a hydrogen donor and iron as a reducing agent, nitroaromatics react with aldehydes in the presence of a palladium catalyst to form imines efficiently.
Synovial inflammation plays a crucial role in osteoarthritis (OA) development, leading to chronic inflammation and cartilage destruction. Although targeting synovitis can alleviate OA, clinical outcomes have been disappointing due to poor drug targeting and joint cavity heterogeneity. This study presents pH-responsive lipid nanoparticles (LNPs@UA), loaded with Urolithin A (UA), as a potential OA treatment. LNPs@UA showed uniform particle size, low zeta potential, and effective mitochondria-targeting and pH-responsive capabilities. In vitro, LNPs@UA reduced reactive oxygen species (ROS), pro-inflammatory factors (IL-1β, IL-6, TNF-α), and promoted M2 macrophage polarization. It improved mitochondrial structure, enhanced autophagy, and inhibited ferroptosis. In vivo, LNPs@UA alleviated OA progression in an ACLT-induced OA mouse model. Transcriptomic analysis revealed inhibition of NF-κB signaling and activation of repair pathways. These results suggest LNPs@UA could offer a promising therapeutic approach for OA.
Herein, we present a nickel-catalyzed C-S cross-coupling between aryl halides and ketene dithioacetals under "base-free" conditions without an exogenous ligand. By employing easily available ketene dithioacetals as sulfide donors, this reaction affords a broad range of unsymmetrical alkyl-aryl sulfides without using odorous and toxic thiols. The newly developed catalytic methodology features an excellent functional group tolerance, wide substrate scope, and diverse downstream synthesis. Preliminary mechanism investigations reveal that a Ni(I)/Ni(III) catalytic cycle might be involved.
Hydrogel-based soft materials have attracted significant attention in various fields due to their high water content, good biocompatibility, and variable mechanical strength. However, due to the hydrophilic properties of hydrogel networks, most of the hydrogel-based soft materials are easy to swell in water and have monotonous surface wettability. Here, taking advantage of the intrinsic hydrophobicity of siloxane, novel heteronetwork organohydrogels were synthesized by covalently integrating reactive siloxane monomers into the hydrophilic hydrogel networks via emulsion polymerization. The surface of the heteronetwork organohydrogels exhibited adaptive wettability owing to the rearrangement of the surface chemistry induced by varying solvent conditions. Moreover, the heterogeneous networks endowed organohydrogels with excellent anti-swelling abilities in water or oil (n-heptanes). The potential application of the prepared organohydrogels in the field of oil/water separation was also preliminarily explored. The idea and method of integrating polysiloxane into hydrogels in this study might provide a new insight to develop high-performance polysiloxane-based heteronetwork gel materials.
In recent years, redox reactions have harnessed light or mechanical energy to enable the formation of chemical bonds. We postulated a complementary approach that electromagnetic induction could promote the redox reaction of organic molecules using a rotating magnetic field and metal rods. Here, we report that electromotive force activates the redox-active trifluoromethylating reagents. This magnetoredox system can be applied to the trifluoromethylation of heteroarenes with high regioselectivity and hydrotrifluoromethylation of alkenes without the need for catalysts and organic additives.
EMM (electromagnetic mill)-promoted Pd-catalyzed solid state intramolecular Heck-type cyclization/boronation and Suzuki couplings are reported. Compared to previous mechanochemistry that constructed one chemical bond through a cross-coupling reaction, this strategy realizes cascade transformation along with multiple chemical bond formation. This conversion does not require organic solvents or additional heating, and it shows a good substrate scope and high functional group tolerance.
The reaction of chlorosilanes with organometallic reagents is an old and well‐developed approach to organosilicon compounds, however, its application was limited due to the sensitivity of organometallic reagents to air, water. Here we display a mechanochemical access to arylsilanes via Barbier‐type reaction of chlorosilanes with aryl halide with magnesium. By treatment of the two halides with Mg powder under electromagnetic milling, a series of arylsilanes are obtained within 15 minutes. Taking the advantages of the electromagnetic milling, this protocol features transition‐metal free, good functional group tolerance, air stable and mild conditions.
Herein, we present a Ni-catalyzed direct cross-coupling of heteroaromatic thioethers with aryl iodides via selective C(sp(2))-S bond cleavage under reductive conditions, thereby providing various biaryl frameworks with high efficiency. Mechanistic studies suggested Mo(CO)(6) played a crucial role in facilitating the activation of the C(sp(2))-S bond. This protocol demonstrated a wide substrate scope, operational simplicity, and good functional group compatibility. Furthermore, the utility of this reaction was highlighted by facile scale-up and sequential modification of heteroaryl frameworks.
Fluorescent gels are materials based on three-dimensional network structures, where fluorophores can be introduced into the gel networks through non-covalent or covalent interactions. This class of materials possesses unique properties derived from the gel structure, as well as specific light-emitting properties resulted from the fluorophores. Moreover, benefiting from the environmental sensitivity of fluorophores, the fluorescence behaviors of gels can be well tuned through environmental stimuli such as pH, light, temperature, and ionic strength. These properties make fluorescent gels potential in various areas including informatics, biomedicine, diagnosis, sensors, and so on. This review will first summarize the basic mechanism of fluorescence behaviors, and then outline the strategies to construct fluorescent gels as well as their associated applications. Furthermore, the current challenges and future prospects of fluorescent gels will also be recapitulated. This review is supposed to be appealing to scientists interested in fluorescent gels and other novel fluorescent materials.