Angew Chem Int Ed Engl
December 2024
Macrocycles represent one important class of functional molecules, and dynamic macrocycles with the potential of cleavability, adaptability, and topological conversion are challenging. Herein we report photoswitchable allosteric and topological control of dynamic covalent macrocycles and further the use in guest binding and mechanically interlocked molecules. The manipulation of competing ring-chain equilibria and bond formation/scission within reaction systems enabled light-induced structural regulation over dithioacetal and thioacetal dynamic bonds, accordingly realizing bidirectional switching between crown ether-like covalent macrocycles and their linear counterparts.
View Article and Find Full Text PDFStudies of complex systems and emerging properties to mimic biosystems are at the forefront of chemical research. Dynamic multistep cascades, especially those exhibiting allosteric regulation, are challenging. Herein, we demonstrate a versatile platform of photoswitchable covalent cascades toward remote and bidirectional control of reversible covalent bonds and ensuing assemblies.
View Article and Find Full Text PDFPurpose: This study aimed to explore the prevalence of Toxoplasma gondii (T. gondii) among patients in Guangzhou city, South China, and to identify susceptible patient populations and analyze the causes of infection differences.
Methods: From May 2020 to May 2022, a total of 637 sera were collected from patients, and 205 sera were collected from health participants as health control.
Phototriggered click and clip reactions can endow chemical processes with high spatiotemporal resolution and sustainability, but are challenging with a limited scope. Herein we report photoswitchable reversible covalent conjugate addition-elimination reactions toward light-addressed modular covalent connection and disconnection. By coupling between photochromic dithienylethene switch and Michael acceptors, the reactivity of Michael reactions was tuned through closed-ring and open-ring forms of dithienylethene, allowing switching on and off dynamic exchange of a wide scope of thiol and amine nucleophiles.
View Article and Find Full Text PDFDouble →π* interactions between one common electron donor of the carbonyl oxygen and two individual acceptor aldehyde/imine units are presented. The structural and mechanistic insights were revealed through a collection of experimental and computational evidence. The orientation and further energetic dependence of orbital interactions were facilely regulated by the size of cyclic urea scaffolds, the bulkiness of aldehydes/imines, and the flexibility of imine macrocycles.
View Article and Find Full Text PDFThe bidirectional interconversion between ketone and enol structures of 4-cyclopentene-1,3-dione derivatives was realized by photoswitching of fused dithienylethene using UV and visible light. A loss of antiaromaticity offered the driving force for light-triggered enolization and was supported by theoretical studies. Solvent and substituent effects provided additional means for regulating photoswitchable keto-enol tautomerism.
View Article and Find Full Text PDFThe manipulation of covalent bonds could be directed toward degradable, recyclable, and sustainable materials. However, there is an intrinsic conflict between properties of stability and degradability. Here we report light-controlled formation/scission of three types of covalent bonds (C-N, C-O, and C-S) through photoswitching between equilibrium and nonequilibrium states of dynamic covalent systems, achieving dual benefits of photoaddressable stability and cleavability.
View Article and Find Full Text PDFLiver cancer is associated with high mortality, particularly in patients infected with the hepatitis B virus. Treatment methods remain very limited. Here, we explored the effects of 17β-estradiol (E2) on apoptosis of various liver cell lines (LO2, HepG2, and HepG2.
View Article and Find Full Text PDFA new protocol for C-S bond formation was developed by selective cross-coupling between a thiyl radical and an isobutyronitrile radical. Using this strategy, a series of valuable α-alkylthionitrile derivatives were synthesized from basic starting materials. Preliminary mechanistic investigation was performed by EPR and XAFS, revealing that the transient thiyl radical could be stabilized by a copper catalyst to a persistent one.
View Article and Find Full Text PDFSelective C-H bond activation and functionalization is an invaluable and eco-friendly tool for new chemical bond construction. Recently, great progress has been made in the highly selective ortho- and meta-C-H bond functionalization of arene derivatives. In contrast, the remote para-C-H bond functionalization still remains a challenge.
View Article and Find Full Text PDFIn this study, a CMOS compatible capacitive humidity sensor structure was designed and fabricated on a 200 mm CMOS BEOL Line. A top Al interconnect layer was used as an electrode with a comb/serpent structure, and graphene oxide (GO) was used as sensing material. XRD analysis was done which shows that GO sensing material has a strong and sharp (002) peak at about 10.
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