CuZn-based catalyst is an attractive catalyst for methanol synthesis from CO_(2)hydrogenation,but it early deactivates and its methanol yield still needs to improve.In this study,Y_(2)O_(3)was introduced to Cu/ZnO usi...CuZn-based catalyst is an attractive catalyst for methanol synthesis from CO_(2)hydrogenation,but it early deactivates and its methanol yield still needs to improve.In this study,Y_(2)O_(3)was introduced to Cu/ZnO using a one-pot hydrothermal method,and exhibits a synergistic effect of ZnO and Y_(2)O_(3)on enhancing methanol yield and the stability.We found that the interaction between Y_(2)O_(3)and ZnO results in abundant oxygen vacancies formation,thereby enhancing CO_(2)adsorption and activation.Kinetic analysis and in situ DRIFTS suggest that RWGS forming CO and methanol formation compete for a mutual intermediate HCOO^(*),and the introduction of Y_(2)O_(3)to Cu/ZnO raises the energy barrier for the CO formation but lowers that for methanol formation,thus enhancing the methanol yield on Cu/ZnO/Y_(2)O_(3).展开更多
Theσ-bond activation by main group element has received enormous attention from theoretical and experimental chemists.Here,the reaction of C-X(X=Cl,Br,I)bonds in benzyl and allyl halides with a pincer-type phosphorus...Theσ-bond activation by main group element has received enormous attention from theoretical and experimental chemists.Here,the reaction of C-X(X=Cl,Br,I)bonds in benzyl and allyl halides with a pincer-type phosphorus(Ⅲ)species was reported.A series of structurally robust phosphorus(Ⅴ)compounds were formed via the formal oxidative addition reactions of C-X bonds to the phosphorus(Ⅲ)center.Density functional theory calculations show that the nucleophilic addition process is more favorable than the direct oxidative addition mechanism.Isomerization of bent structures of phosphorus(Ⅲ)compound to poorly nucleophilic compounds to undergo further C-X bond activation can be rationalized by frontier molecule orbital analysis.This study not only provides a deep understanding of the reactivity of phosphorus(Ⅲ)species but also demonstrates a potential of main group elements for the small-molecule activation.展开更多
Since the initial discovery of alane AlH3in 1942 by Stecher and Wiberg[1],as well as lithium aluminum hydride LiAlH4in 1947 by Finholt,Bond and Schlesinger[2],aluminum hydrides have been ubiquitously utilized in diver...Since the initial discovery of alane AlH3in 1942 by Stecher and Wiberg[1],as well as lithium aluminum hydride LiAlH4in 1947 by Finholt,Bond and Schlesinger[2],aluminum hydrides have been ubiquitously utilized in diverse chemical reactions.They serve as the powerful functional group-reducing reagents,hydrogen sources,and bases[3].展开更多
Rheumatoid arthritis(RA)is a chronic inflammatory autoimmune disease that affects millions of people worldwide.Current therapeutic drugs for RA are often limited by poor solubility,unresponsive to monotherapy,low bioa...Rheumatoid arthritis(RA)is a chronic inflammatory autoimmune disease that affects millions of people worldwide.Current therapeutic drugs for RA are often limited by poor solubility,unresponsive to monotherapy,low bioavailability,and severe side effects.To address these challenges,we developed a pH-responsive,biodegradable,and multifunctional oral hydrogel delivery system(GTPM Gel)based on the major active ingredients(glycyrrhizic acid(GA),total alkaloids of FZ(TAC),pseudoephedrine(PE),Mg^(2+))from Mahuang Fuzi decoction for the treatment of RA in clinic.In this system,all four components synergistically contributed to gel formation and pharmacodynamics,making each component indispensable.Notably,Mg2+in GTPM Gel promoted the gelation of GA via coordination bonds while exhibiting anti-inflammatory properties and facilitating osteochondral regeneration.Moreover,GTPM Gel enhanced the solubility of TAC and reduced its toxicity,leading to improved anti-RA effects.In vitro and In vivo studies demonstrated that GTPM Gel effectively inhibited the polarization of inflammatory macrophages,reduced pannus formation,and inhibited bone and cartilage erosion by downregulating the PI3K/AKT/NF-κB signaling pathway.This study suggested that the magnesium ion-mediated natural multi-component hydrogel,with its remarkable efficacy and biocompatibility,holds promise as a potential therapeutic candidate for RA treatment.展开更多
The application of nanotechnology for antimicrobial delivery has capacity to improve anti-bacterial efficacy.Currently,the usage of various inorganic and organic carriers,such as metal ions,nano-silicon and surfactant...The application of nanotechnology for antimicrobial delivery has capacity to improve anti-bacterial efficacy.Currently,the usage of various inorganic and organic carriers,such as metal ions,nano-silicon and surfactants,might increase the potential toxicity of nanoparticles and make their clinical transformation more difficult.Herein,a nano-delivery system was constructed by direct self-assembly of antibacterial phytochemicals(berberine and rhein)originated from traditional Chinese medicine Coptis chinensis Franch.and Rheum palmatum L.,respectively.Combining X-ray single crystal diffraction,nuclear magnetic resonance and other spectra characterizations,the stacked structure of nanoparticles was profoundly demonstrated.Briefly,rhein acted as the layered backbone and berberine embedded in it.In vitro bacteriostasis experiment showed the minimum bactericidal concentration of nanoparticles was 0.1μmol/mL,which was lower than that of berberine and rhein.The results of confocal laser scanning microscope,biofilm quantitive assay and scanning electron microscopy indicated that nanoparticles had strong inhibitory effects on Staphylococcus aureus biofilm.More importantly,transmission electron microscopy and mass spectra indicated the further bacteriostatic mechanism of nanoparticles.Meanwhile,the nanoparticles had well biocompatibility and safety.Current study will open up new prospect that the design of self-assemblies between active phytochemicals can be originated from traditional Chinese medicine combination.展开更多
Tumor microenvironment (TME) plays an important role in the tumorigenesis, proliferation, invasion and metastasis. Thereby developing synergistic anticancer strategies with multiple mechanisms are urgent. Copper is wi...Tumor microenvironment (TME) plays an important role in the tumorigenesis, proliferation, invasion and metastasis. Thereby developing synergistic anticancer strategies with multiple mechanisms are urgent. Copper is widely used in the treatment of tumor chemodynamic therapy (CDT) due to its excellent laser-mediated photo- Fenton-like reaction. Additionally, copper can induce cell death through cuproptosis, which is a new modality different from the known death mechanisms and has great promise in tumor treatment. Herein, we report a natural small molecules carrier-free injectable hydrogel (NCTD Gel) consisted of Cu2+-mediated self-assembled glycyrrhizic acid (GA) and norcantharidin (NCTD), which are mainly governed by coordination and hydrogen bonds. Under 808 nm laser irradiation, NCTD Gel can produce reactive oxygen species (ROS), consume glutathione (GSH) and overcome hypoxia in TME, leading to synergistically regulate TME via apoptosis, cuproptosis and anti-inflammation. In addition, NCTD Gel’s CDT display high selectivity and good biocompatibility as it relies on the weak acidity and H2O2 overexpression of TME. Notably, NCTD Gel’s components are originated from clinical agents and its preparation process is easy, green and economical, without any excipients. This study provides a new carrier-free hydrogel synergistic antitumor strategy, which has a good prospect in industrial production and clinical transformation.展开更多
文摘CuZn-based catalyst is an attractive catalyst for methanol synthesis from CO_(2)hydrogenation,but it early deactivates and its methanol yield still needs to improve.In this study,Y_(2)O_(3)was introduced to Cu/ZnO using a one-pot hydrothermal method,and exhibits a synergistic effect of ZnO and Y_(2)O_(3)on enhancing methanol yield and the stability.We found that the interaction between Y_(2)O_(3)and ZnO results in abundant oxygen vacancies formation,thereby enhancing CO_(2)adsorption and activation.Kinetic analysis and in situ DRIFTS suggest that RWGS forming CO and methanol formation compete for a mutual intermediate HCOO^(*),and the introduction of Y_(2)O_(3)to Cu/ZnO raises the energy barrier for the CO formation but lowers that for methanol formation,thus enhancing the methanol yield on Cu/ZnO/Y_(2)O_(3).
基金supported by the National Natural Science Foundation of China(Nos.21772088 and 21573179)the Natural Science Foundation of Jiangsu Province(No.BK20170635)the Young Elite Scientist Sponsorship Program of China Association of Science and Technology,the program of Jiangsu SpeciallyAppointed Professor and Shuangchuang Talent Plan of Jiangsu Province。
文摘Theσ-bond activation by main group element has received enormous attention from theoretical and experimental chemists.Here,the reaction of C-X(X=Cl,Br,I)bonds in benzyl and allyl halides with a pincer-type phosphorus(Ⅲ)species was reported.A series of structurally robust phosphorus(Ⅴ)compounds were formed via the formal oxidative addition reactions of C-X bonds to the phosphorus(Ⅲ)center.Density functional theory calculations show that the nucleophilic addition process is more favorable than the direct oxidative addition mechanism.Isomerization of bent structures of phosphorus(Ⅲ)compound to poorly nucleophilic compounds to undergo further C-X bond activation can be rationalized by frontier molecule orbital analysis.This study not only provides a deep understanding of the reactivity of phosphorus(Ⅲ)species but also demonstrates a potential of main group elements for the small-molecule activation.
基金supported by the Nanyang Technological University(NTU),Nippon Shokubai and the Singapore Ministry of Education(MOET2EP10220-0002)。
文摘Since the initial discovery of alane AlH3in 1942 by Stecher and Wiberg[1],as well as lithium aluminum hydride LiAlH4in 1947 by Finholt,Bond and Schlesinger[2],aluminum hydrides have been ubiquitously utilized in diverse chemical reactions.They serve as the powerful functional group-reducing reagents,hydrogen sources,and bases[3].
基金funded by the National Natural Science Foundation of China(Nos.82274072 and 82474059)the Beijing Municipal Natural Science Foundation(Nos.7242221 and 7254503)+2 种基金Beijing Nova Programme Interdisciplinary Cooperation Project(No.20240484578)the Fundamental Research Funds for the Central Universities(China,Nos.2023-JYB-JBZD-049,2022-XJKYQD-008,and 2024-JYB-XJSJJ004)Beijing Key Laboratory for Basic and Development Research on Chinese Medicine(Beijing,No.100102).
文摘Rheumatoid arthritis(RA)is a chronic inflammatory autoimmune disease that affects millions of people worldwide.Current therapeutic drugs for RA are often limited by poor solubility,unresponsive to monotherapy,low bioavailability,and severe side effects.To address these challenges,we developed a pH-responsive,biodegradable,and multifunctional oral hydrogel delivery system(GTPM Gel)based on the major active ingredients(glycyrrhizic acid(GA),total alkaloids of FZ(TAC),pseudoephedrine(PE),Mg^(2+))from Mahuang Fuzi decoction for the treatment of RA in clinic.In this system,all four components synergistically contributed to gel formation and pharmacodynamics,making each component indispensable.Notably,Mg2+in GTPM Gel promoted the gelation of GA via coordination bonds while exhibiting anti-inflammatory properties and facilitating osteochondral regeneration.Moreover,GTPM Gel enhanced the solubility of TAC and reduced its toxicity,leading to improved anti-RA effects.In vitro and In vivo studies demonstrated that GTPM Gel effectively inhibited the polarization of inflammatory macrophages,reduced pannus formation,and inhibited bone and cartilage erosion by downregulating the PI3K/AKT/NF-κB signaling pathway.This study suggested that the magnesium ion-mediated natural multi-component hydrogel,with its remarkable efficacy and biocompatibility,holds promise as a potential therapeutic candidate for RA treatment.
基金funded by the Beijing Municipal Natural Science Foundation(No.7202116,China)National Natural Science Foundation of China(No.81603256)+2 种基金project of China Association of Chinese Medicine(CACM-2018-QNRC2-B08)the Fundamental Research Funds for the Central Universities(BUCM-2019-JCRC002,BUCM-2018-2020 and 2019-JYBTD005,China)Beijing Key Laboratory for Basic and Development Research on Chinese Medicine(Beijing,China)
文摘The application of nanotechnology for antimicrobial delivery has capacity to improve anti-bacterial efficacy.Currently,the usage of various inorganic and organic carriers,such as metal ions,nano-silicon and surfactants,might increase the potential toxicity of nanoparticles and make their clinical transformation more difficult.Herein,a nano-delivery system was constructed by direct self-assembly of antibacterial phytochemicals(berberine and rhein)originated from traditional Chinese medicine Coptis chinensis Franch.and Rheum palmatum L.,respectively.Combining X-ray single crystal diffraction,nuclear magnetic resonance and other spectra characterizations,the stacked structure of nanoparticles was profoundly demonstrated.Briefly,rhein acted as the layered backbone and berberine embedded in it.In vitro bacteriostasis experiment showed the minimum bactericidal concentration of nanoparticles was 0.1μmol/mL,which was lower than that of berberine and rhein.The results of confocal laser scanning microscope,biofilm quantitive assay and scanning electron microscopy indicated that nanoparticles had strong inhibitory effects on Staphylococcus aureus biofilm.More importantly,transmission electron microscopy and mass spectra indicated the further bacteriostatic mechanism of nanoparticles.Meanwhile,the nanoparticles had well biocompatibility and safety.Current study will open up new prospect that the design of self-assemblies between active phytochemicals can be originated from traditional Chinese medicine combination.
基金National Natural Science Foundation of China(No.82274072)the Beijing Municipal Natural Science Foundation(No.L222015),Beijing Nova program(No.Z201100006820026)+1 种基金the Fundamental Research Funds for the Central Universities(2022-XJ-KYQD-008,China)Beijing Key Laboratory for Basic and Development Research on Chinese Medicine(Beijing,100102).
文摘Tumor microenvironment (TME) plays an important role in the tumorigenesis, proliferation, invasion and metastasis. Thereby developing synergistic anticancer strategies with multiple mechanisms are urgent. Copper is widely used in the treatment of tumor chemodynamic therapy (CDT) due to its excellent laser-mediated photo- Fenton-like reaction. Additionally, copper can induce cell death through cuproptosis, which is a new modality different from the known death mechanisms and has great promise in tumor treatment. Herein, we report a natural small molecules carrier-free injectable hydrogel (NCTD Gel) consisted of Cu2+-mediated self-assembled glycyrrhizic acid (GA) and norcantharidin (NCTD), which are mainly governed by coordination and hydrogen bonds. Under 808 nm laser irradiation, NCTD Gel can produce reactive oxygen species (ROS), consume glutathione (GSH) and overcome hypoxia in TME, leading to synergistically regulate TME via apoptosis, cuproptosis and anti-inflammation. In addition, NCTD Gel’s CDT display high selectivity and good biocompatibility as it relies on the weak acidity and H2O2 overexpression of TME. Notably, NCTD Gel’s components are originated from clinical agents and its preparation process is easy, green and economical, without any excipients. This study provides a new carrier-free hydrogel synergistic antitumor strategy, which has a good prospect in industrial production and clinical transformation.
