Aryl trifluoromethyl ethers (ArOCF3) are prevalent in pharmaceuticals, agrochemicals, and materials. However, methods for the general and efficient synthesis of these compounds are extremely ...underdeveloped and limited. Herein, we describe a highly efficient and general procedure for the direct O‐trifluoromethylation of unprotected phenols through a silver‐mediated cross‐coupling reaction using CF3SiMe3 as the CF3 source and exogenous oxidants. This novel oxidative trifluoromethylation provides access to a wide range of aryl trifluoromethyl ethers from simple phenols. The mild process was also applied to the late‐stage trifluoromethylation of a medicinally relevant compound.
Combining two nucleophiles: The direct oxidative O‐trifluoromethylation of phenols with CF3SiMe3 provides a general and practical method for the preparation of aryl trifluoromethyl ethers. A wide variety of functional groups are tolerated under these conditions, and the method can also be employed for the late‐stage trifluoromethylation of complex pharmaceutically relevant molecules (NFSI= N‐fluorobenzenesulfonimide).
An unprecedented reaction for the direct trifluoromethylthiolation and fluorination of alkyl alcohols using AgSCF3 and nBu4NI has been developed. The trifluoromethylthiolated compounds and alkyl ...fluorides were selectively formed by changing the ratio of AgSCF3/nBu4NI. This protocol is tolerant of different functional groups and might be applicable to late‐stage trifluoromethylthiolation of alcohols.
Silver bullet: A new strategy has been developed for the direct trifluoromethylthiolation of alkyl alcohols using AgSCF3 and nBu4NI. This protocol does not require the activation of alcohols in advance. A variety of alkyl alcohols bearing different functional groups were transformed into the corresponding alkyl trifluoromethyl sulfides in moderate to good yields.
Up to 10–20% of patients with coronavirus disease 2019 (COVID‐19) develop a severe pulmonary disease due to immune dysfunction and cytokine dysregulation. However, the extracellular proteomic ...characteristics in respiratory tract of these critical COVID‐19 patients still remain to be investigated. In the present study, we performed a quantitative proteomic analysis of the bronchoalveolar lavage fluid (BALF) from patients with critical COVID‐19 and from non‐COVID‐19 controls. Our study identified 358 differentially expressed BALF proteins (P < 0.05), among which 41 were significantly changed after using the Benjamini–Hochberg correction (q < 0.05). The up‐regulated signaling was found to be mainly involved in inflammatory signaling and response to oxidative stress. A series of increased extracellular factors including Tenascin‐C (TNC), Mucin‐1 (KL‐6 or MUC1), Lipocalin‐2 (LCN2), periostin (POSTN), Chitinase 3‐like 1 (CHI3L1 or YKL40), and S100A12, and the antigens including lymphocyte antigen 6D/E48 antigen (LY6D), CD9 antigen, CD177 antigen, and prostate stem cell antigen (PSCA) were identified, among which the proinflammatory factors TNC and KL‐6 were further validated in serum of another thirty‐nine COVID‐19 patients and healthy controls, showing high potentials of being biomarkers or therapeutic candidates for COVID‐19. This BALF proteome associated with COVID‐19 would also be a valuable resource for researches on anti‐inflammatory medication and understanding the molecular mechanisms of host response.
Database
Proteomic raw data are available in ProteomeXchange (http://proteomecentral.proteomexchange.org) under the accession number PXD022085, and in iProX (www.iprox.org) under the accession number IPX0002429000.
Here, we use quantitative proteomics to analyze alterations in the bronchoalveolar lavage fluid of patients with critical COVID‐19 relative to non‐COVID‐19 controls. We find that up‐regulated signaling mainly involves inflammatory signaling and response to oxidative stress and identify increases in extracellular factors and in their related interaction networks. The bronchoalveolar proteome of COVID‐19 patients provides a valuable resource for future research.
Herein, we report near‐infrared (NIR) light‐driven shape‐morphing of programmable MXene‐containing anisotropic hydrogel actuators that are fabricated through in situ free‐radical copolymerization of ...a judiciously designed MXene nanomonomer with thermosensitive hydrogel network. A low electric field (few V mm−1) was found to enable a spatial distribution of MXene nanosheets and hence introduce anisotropy into the hydrogel network. Programmable anisotropic hydrogel actuators were developed by controlling ITO electrode pattern, direct‐current (DC) electric field direction and mask‐assisted photopolymerization. As a proof‐of‐concept, we demonstrate NIR light‐driven shape morphing of the MXene‐containing anisotropic hydrogel into various shapes and devise a four‐arm soft gripper that can perform distinct photomechanical functions such as grasping, lifting/lowering down and releasing an object upon sequential NIR light exposure.
Programmable anisotropic hydrogel actuators with near‐infrared (NIR) light‐driven shape morphing properties were fabricated through in situ free‐radical copolymerization of a judiciously designed photopolymerizable MXene nanomonomer with thermosensitive PNIPAM‐based smart hydrogels. A shape‐programmed four‐arm soft gripper was demonstrated to perform distinct photomechanical functions under sequential exposure to spatiotemporal NIR light.
Soft robots that can move like living organisms and adapt to their surroundings are currently in the limelight from fundamental studies to technological applications, due to their advances in ...material flexibility, human-friendly interaction, and biological adaptation that surpass conventional rigid machines. Light-fueled smart actuators based on responsive soft materials are considered to be one of the most promising candidates to promote the field of untethered soft robotics, thereby attracting considerable attention amongst materials scientists and microroboticists to investigate photomechanics, photoswitch, bioinspired design, and actuation realization. In this review, we discuss the recent state-of-the-art advances in light-driven bimorph soft actuators, with the focus on bilayer strategy,
i.e.
, integration between photoactive and passive layers within a single material system. Bilayer structures can endow soft actuators with unprecedented features such as ultrasensitivity, programmability, superior compatibility, robustness, and sophistication in controllability. We begin with an explanation about the working principle of bimorph soft actuators and introduction of a synthesis pathway toward light-responsive materials for soft robotics. Then, photothermal and photochemical bimorph soft actuators are sequentially introduced, with an emphasis on the design strategy, actuation performance, underlying mechanism, and emerging applications. Finally, this review is concluded with a perspective on the existing challenges and future opportunities in this nascent research Frontier.
This review provides an account of the state-of-the-art light-driven bimorph soft actuators from their fundamentals to emerging applications, as well as new perspectives on the future scope, opportunities, and challenges.
Soft robots that can be remotely powered and controlled and mimic locomotion of living species open new perspectives in science and engineering. A natural‐scale monolithic caterpillar robot based on ...an optomechanical liquid crystalline elastomer with patterned molecular alignment is reported. The robot demonstrates different gaits and is capable of performing various tasks in complex environments.
Metabolic reprogramming is a hallmark of cancer. Herein we discover that the key glycolytic enzyme pyruvate kinase M2 isoform (PKM2), but not the related isoform PKM1, is methylated by ...co-activator-associated arginine methyltransferase 1 (CARM1). PKM2 methylation reversibly shifts the balance of metabolism from oxidative phosphorylation to aerobic glycolysis in breast cancer cells. Oxidative phosphorylation depends on mitochondrial calcium concentration, which becomes critical for cancer cell survival when PKM2 methylation is blocked. By interacting with and suppressing the expression of inositol-1,4,5-trisphosphate receptors (InsP
Rs), methylated PKM2 inhibits the influx of calcium from the endoplasmic reticulum to mitochondria. Inhibiting PKM2 methylation with a competitive peptide delivered by nanoparticles perturbs the metabolic energy balance in cancer cells, leading to a decrease in cell proliferation, migration and metastasis. Collectively, the CARM1-PKM2 axis serves as a metabolic reprogramming mechanism in tumorigenesis, and inhibiting PKM2 methylation generates metabolic vulnerability to InsP
R-dependent mitochondrial functions.
In order to obtain conductive concrete with good electrical conductivity and good mechanical properties, nanographite and magnetite sand excited by different activators and their combinations are ...added to ordinary concrete to obtain high quality and efficient conductive concrete. The optimal mixture ratio of alkali-excited conductive concrete and the effects of different activators and their combinations on the mechanics and electrical conductivity of concrete were studied. The microstructure of alkali-excited conductive concrete was analyzed by scanning electron microscope (SEM) to study its conductive mechanism. Results show that the conductive concrete obtained by compounding sodium hydroxide, sodium sulfate and calcium hydroxide has optimal mechanical and electrical properties when the graphite is 6% cement, and magnetite sand is 40% fine aggregate. The conductive concrete sample prepared by this method has a flexural strength of 6.84 MPa, a compressive strength of 47.79 MPa and a resistivity of 4805 Ω·cm (28 days). Compared with ordinary concrete (no nanographite and no magnetite sand), the compressive strength of conductive concrete is increased by 122.3%, the bending strength is increased by 116.5%, and the resistivity is reduced by 99.1%. SEM shows that the distribution of conductive materials in concrete is more uniform due to alkali excitation and calcium silicate hydrate (CSH) gel can be formed, which leads to better performance. The research in this paper is only a preliminary exploration of the characteristics of green conductive concrete, and the conductive heating characteristics and electromagnetic wave absorption properties of concrete, along with strength characteristics after adding conductive fillers, need to be further studied. It is suggested that further research should be carried out on the deicing characteristics of conductive concrete and the electromagnetic wave absorption properties used in stealth military engineering.
A bithiophene−alkyne‐based compound was synthesized and first utilized as a ligand for the selective hydrosilylation of allenes with primary and secondary phenylsilanes. It shows high selectivity ...towards the production of branched allylsilanes with a wide range of allenes. It is worth mentioning that the catalytic loading of the palladium can be reduced to 500 ppm. This work opens a new front of using bidentate thiophene ligand as a reaction promoter in transition‐metal‐catalyzed organic reaction.
...the identification of biomarkers and prognostic models to select patients for these combination therapies is a crucial issue in clinical practice. Compared to historical Meet-URO-related studies ...(Additional file 1), this small-size analysis explored the prognostic value of the Meet-URO score in similar disease status but with a different treatment type. ...the results about the positive effect of nephrectomy are consistent with a subgroup analysis of the Meet-URO 15 study (HR = 0.48, 95% CI 0.33 to 0.69, p < 0.001) 5. ...this study preliminarily illustrates that the Meet-URO score has the potential to present more accurate prognostic stratification than the IMDC score in mRCC patients receiving 2nd or 3rd-line TKIs-ICIs combination treatment.
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