Showing papers by "Xudong Xu published in 2022"

Supramolecular assemblies based on natural small molecules: Union would be effective

Abstract: Natural products have been used to prevent and treat human diseases for thousands of years, especially the extensive natural small molecules (NSMs) such as terpenoids, steroids and glycosides. A quantity of studies are confined to concern about their chemical structures and pharmacological activities at the monomolecular level, whereas the spontaneous assemblies of them in liquids yielding supramolecular structures have not been clearly understood deeply. Compared to the macromolecules or synthetic small molecular compounds, NSMs have the inherent advantages of lower toxicity, better biocompatibility, biodegradability and biological activity. Self-assembly of single component and multicomponent co-assembly are unique techniques for designing supramolecular entities. Assemblies are of special significance due to their range of applications in the areas of drug delivery systems, pollutants capture, materials synthesis, etc. The assembled mechanism of supramolecular NSMs which are mainly driven by multiple non-covalent interactions are summarized. Furthermore, a new hypothesis aimed to interpret the integration effects of multi-components of traditional Chinese medicines (TCMs) inspired on the theory of supramolecular assembly is proposed. Generally, this review can enlighten us to achieve the qualitative leap for understanding natural products from monomolecule to supramolecular structures and multi-component interactions, which is valuable for the intensive research and application.

Tuning the Cyclopropane Ring-Opening Reaction over Electronic Bias by Fusion to a Pre-Aromatic Ring: TfOH-Promoted Aromatization of Dibenzonorcaradienes to Dibenzo[f,h]isocoumarins.

Abstract: Fusion of the cyclopropane ring bearing two vicinal acceptors to the pre-aromatic dihydrophenanthrene ring, which is constructed by the Pd-catalyzed cross-coupling between the vicinal aromatic rings, is found to effectively direct the cleavage of the electronically unfavored cyclopropane bond between the vicinal acceptors. Consequently, a modular method for the rapid synthesis of dibenzo[f,h]isocoumarins from methyl ketones, aryl aldehydes, and α-keto esters via a reaction cascade of aldol condensation, Kukhtin-Ramirez cyclopropanation, Pd-catalyzed direct arylation, and acid-promoted aromatization has been realized.

A novel DPP‐4 inhibitor Gramcyclin A attenuates cognitive deficits in APP/PS1/tau triple transgenic mice via enhancing brain GLP‐1‐dependent glucose uptake

Abstract: Enhancing glucagon‐like peptide 1 (GLP‐1) signaling with a dipeptidyl peptidase IV (DPP‐4) inhibitor might exert protective effects on Alzheimer's disease (AD). We found that intragastric administration of Gramcyclin A (10, 20 and 40 mg/kg), a novel DPP‐4 inhibitor, for 3 months significantly reversed cognitive decline in APP/PS1/tau triple transgenic mice in a dose‐dependent manner. Gramcyclin A treatment markedly reduced Aβ plaques as well as the insoluble and soluble forms of Aβ40 and Aβ42 in the hippocampus of APP/PS1/tau mice. Treatment with Gramcyclin A remarkedly decreased the level of microglia and suppressed neuroinflammation in the hippocampus of APP/PS1/tau mice. Moreover, Gramcyclin A treatment could increase brain glucose uptake in APP/PS1/tau mice, as detected by 18‐fluoro‐2‐deoxyglucose (18F‐FDG) micro‐positron emission tomography (micro‐PET) imaging. Furthermore, Gramcyclin A significantly increased expression of glucagon‐like peptide‐1 (GLP‐1), GLP‐1R, proliferator‐activated receptor gamma coactivator (PGC)‐1α and glucose transporter 4 (GLUT4), and inhibited insulin receptor (IRS)‐1 phosphorylation and tau hyperphosphorylation in the hippocampus of APP/PS1/tau mice. Collectively, Gramcyclin A conferred protective effects against AD via enhancing brain GLP‐1‐dependent glucose uptake. The DPP‐4 inhibitor Gramcyclin A might be a potential therapeutic drug for AD.

Direct Electron Transfer from Upconversion Graphene Quantum Dots to TiO2 Enabling Infrared Light-Driven Overall Water Splitting

Abstract: Utilization of infrared light in photocatalytic water splitting is highly important yet challenging given its large proportion in sunlight. Although upconversion material may photogenerate electrons with sufficient energy, the electron transfer between upconversion material and semiconductor is inefficient limiting overall photocatalytic performance. In this work, a TiO2/graphene quantum dot (GQD) hybrid system has been designed with intimate interface, which enables highly efficient transfer of photogenerated electrons from GQDs to TiO2. The designed hybrid material with high photogenerated electron density displays photocatalytic activity under infrared light (20 mW cm−2) for overall water splitting (H2: 60.4 μmol gcat.−1 h−1 and O2: 30.0 μmol gcat.−1 h−1). With infrared light well harnessed, the system offers a solar-to-hydrogen (STH) efficiency of 0.80% in full solar spectrum. This work provides new insight into harnessing charge transfer between upconversion materials and semiconductor photocatalysts and opens a new avenue for designing photocatalysts toward working under infrared light.

Regulating Interfacial Water Structure by Tensile Strain to Boost Electrochemical Semi-hydrogenation of Alkynes

Abstract: Electrochemical semi-hydrogenation (ECSH) of alkynes to produce alkenes is an ideal alternative to traditional thermal semi-hydrogenation (TSH), and yet is limited by low conversion yield and product selectivity. Here, we...

Efficient interlayer confined nitrate reduction reaction and oxygen generation enabled by interlayer expansion.

Abstract: Electrochemically converting nitrate ions back to ammonia can not only eliminate water pollution but also obtain valuable ammonia without a serious carbon footprint, and is thus deemed as an efficient supplement to the traditional Haber-Bosch process. Currently reported catalysts can achieve a single electrode reaction in the electrochemical nitrate reduction reaction. However, the bifunctionality of a single catalyst for both cathodic and anodic reactions has not yet been reported. Herein, we report Fe-doped layered α-Ni(OH)2 with expanded interlayer spacing as an efficient bifunctional catalyst for the nitrate reduction reaction and oxygen evolution reaction. The expanded interlayer spacing facilitates in situ electrochemical potassium ion intercalation between layers. In situ Raman spectroscopy characterization confirms that both the nitrate reduction reaction and oxygen evolution reaction are confined between layers and are triggered by the accumulation of potassium ions. The obtained α-Ni0.881Fe0.119(OH)2 nanosheets deliver an ammonia yield rate of 8.1 mol gcat.-1 h-1 with a NO3--to-NH3 faradaic efficiency of 97.5% at the cathode. The overpotential of oxygen generation at 10 mA cm-2 is reduced to 254 mV at the anode. As a bifunctional catalyst in overall electrolysis, the current density of α-Ni0.881Fe0.119(OH)2 reaches 24.8 mA cm-2 at a voltage of 2.0 V and performs continuously for 50 h with a current retention of 80.2%.

Self-assembled glycyrrhetinic acid derivatives for functional applications: a review.

Abstract: Glycyrrhetinic acid (GA), a famous natural product, has been attracting more attention recently because of its remarkable biological activity, natural sweetness, and good biocompatibility. In the past few years, a considerable amount of literature has grown up around the theme of GA-based chemical modification to broaden its functional applications. Promising structures including gels, micelles, nanoparticles, liposomes, and so forth have been constantly reported. On the one hand, the assembly mechanisms of various materials based on GA derivatives have been elucidated via modern analytical techniques. On the other hand, their potential application prospects in edible additives, intelligent drug delivery, and other fields have been investigated fully due to availability, biocompatibility, and controllable degradability. Inspired by these findings, a systematic summary and classification of the materials formed by GA derivatives seems necessary and meaningful. This review sums up the new functional applications of GA derivatives for the first time and provides better prospects for their application and development.

The Biosynthesis Related Enzyme, Structure Diversity and Bioactivity Abundance of Indole-Diterpenes: A Review

Abstract: Indole diterpenes are a large class of secondary metabolites produced by fungi, possessing a cyclic diterpenoid backbone and an indole moiety. Novel structures and important biological activity have made indole diterpenes one of the focuses of synthetic chemists. Although the discovery, identification, structural diversity, biological activity and especially structure–activity relationship of indole diterpenes have been reported in some papers in recent years, they are absent of a systematic and comprehensive analysis, and there is no elucidation of enzymes related to this kind of natural product. Therefore, it is necessary to summarize the relevant reports to provide new perspectives for the following research. In this review, for the first time, the function of related synthases and the structure–activity relationship of indole diterpenes are expounded, and the recent research advances of them are emphasized.

Boosting the interlayer-confined nitrate reduction reaction by in situ electrochemical potassium ion intercalation

Abstract: Electrochemically converting nitrate ions back to valuable ammonia (NH3) represents a sustainable alternative to the traditional Haber-Bosch process. However, NH3 electrosynthesis is currently restricted by the low catalytic activities and Faradaic efficiency (FE) of NO3−-to-NH3. Here we report an interlayer-confined nitrate reduction reaction (NTRR) in a two-dimensional layered structure. The results indicate that in situ electrochemical K+ intercalation expands the interlayer spacing, which triggers the NTRR between layers. The obtained α-Ni0.902Cu0.098(OH)2 ultrathin nanosheets deliver high NTRR performance with an NH3 yield rate of 13.4 mol gcat.−1 h−1 and NO3−-to-NH3 FE of 98.9% at −0.6 V, far exceeding those of Cu-based electrocatalysts. Moreover, the catalyst exhibits good cycling stability, which can sustain 20 successive cycles without obvious decay of activity and NH3 FE. Meanwhile, in situ electrochemical Raman spectroscopy results unravel the NO3−-to-NH3 pathway.

Daphnane-Type Diterpenes from Stelleropsis tianschanica and Their Antitumor Activity

Abstract: Four new daphnane-type diterpenes named tianchaterpenes C-F (1–4) and six known ones were isolated from Stelleropsis tianschanica. Their structures were elucidated based on chemical and spectral analyses. The comparisons of calculated and experimental electronic circular dichroism (ECD) methods were used to determine the absolute configurations of new compounds. Additionally, compounds 1–10 were evaluated for their cytotoxic activities against HGC-27 cell lines; the results demonstrate that compound 2 had strong cytotoxic activities with IC50 values of 8.8 µM, for which activity was better than that of cisplatin (13.2 ± 0.67 µM).

Direct Electron Transfer from Upconversion Graphene Quantum Dots to TiO 2 Enabling Infrared Light-Driven Overall Water Splitting

Abstract: , Utilization of infrared light in photocatalytic water splitting is highly important yet challenging given its large proportion in sunlight. Although upconversion material may photogenerate electrons with su ffi cient energy, the electron transfer between upconversion material and semiconductor is ine ffi cient limiting overall photocatalytic performance. In this work, a TiO 2 / graphene quantum dot (GQD) hybrid system has been designed with intimate interface, which enables highly e ffi cient transfer of photogenerated electrons from GQDs to TiO 2 . The designed hybrid material with high photogenerated electron density displays photocatalytic activity under infrared light (20 mWcm -2 ) for overall water splitting (H 2 : 60.4 μ mol g cat.-1 h -1 and O 2 : 30.0 μ mol g cat.-1 h -1 ). With infrared light well harnessed, the system o ff ers a solar-to-hydrogen (STH) e ffi ciency of 0.80% in full solar spectrum. This work provides new insight into harnessing charge transfer between upconversion materials and semiconductor photocatalysts and opens a new avenue for designing photocatalysts toward working under infrared light.

Five New Polyoxypregnane Glycosides from the Vines of Aspidopterys obcordata and Their Antinephrolithiasis Activity

Abstract: From the dried vines of Aspidopterys obcordata Hemsl, five new polyoxypregnane glycosides, named obcordatas J–N (1–5), were obtained. Their structures were fully elucidated and characterized by HRESIMS and extensive spectroscopic data. In addition, all of the new compounds were screened for their antinephrolithiasis activity in vitro. The results showed that compounds 1–3 have prominent protective effects on calcium oxalate crystal-induced human kidney 2 (HK-2) cells, with EC50 values ranging from 6.72 to 14.00 μM, which is consistent with the application value of A. obcordata in folk medicine for kidney stones.

Research_9781453 1..9

Abstract: Utilization of infrared light in photocatalytic water splitting is highly important yet challenging given its large proportion in sunlight. Although upconversion material may photogenerate electrons with sufficient energy, the electron transfer between upconversion material and semiconductor is inefficient limiting overall photocatalytic performance. In this work, a TiO2/ graphene quantum dot (GQD) hybrid system has been designed with intimate interface, which enables highly efficient transfer of photogenerated electrons from GQDs to TiO2. The designed hybrid material with high photogenerated electron density displays photocatalytic activity under infrared light (20mWcm) for overall water splitting (H2: 60.4μmol gcat. -1 h and O2: 30.0 μmol gcat. -1 h). With infrared light well harnessed, the system offers a solar-to-hydrogen (STH) efficiency of 0.80% in full solar spectrum. This work provides new insight into harnessing charge transfer between upconversion materials and semiconductor photocatalysts and opens a new avenue for designing photocatalysts toward working under infrared light.

Two types of C-terminal regions of RNA-binding proteins play distinct roles in stress tolerance of Synechocystis sp. PCC 6803

Abstract: Abstract In the phylogenetic tree of RRM-type Rbps (RNA-binding proteins) in cyanobacteria, Rbp1 of Synechocystis 6803, with a single RRM (RNA recognition motif) region and a C-terminal glycine-rich region, and Rbp2, without the C-terminal region, both belong to the cluster I, whereas Rbp3 with a different type of C-terminal region is in the cluster II. Rbp1 is required for the cold adaptability of the cyanobacterium, and Rbp3 is for salt tolerance. Here, we report that the C-terminal region of Rbp1 is not required for the cold adaptability function but the C-terminal region of Rbp3 can direct the RRM of Rbp1 to the salt tolerance function. Bioinformatic and experimental analyses indicate that Rbps in cyanobacteria should be classified as two types. It is the first report for the distinct roles of C-terminal regions of Rbps in stress tolerance of cyanobacteria.

Abietane-Type Diterpenoids From Nepeta bracteata Benth. and Their Anti-Inflammatory Activity

Abstract: Terpenes possess a wide range of structural features and pharmaceutical activities and are promising for drug candidates. With the aim to find bioactive terpene molecules, eight new compounds were isolated from the medicinal plant Nepeta bracteata Benth., including seven new abietane-type diterpenoids (1–7), along with a new ursane-type triterpenoid (8). The structures of compounds 1–8 were elucidated through the detailed spectroscopic analyses of their 1D and 2D NMR and MS data, and the absolute configurations of compounds 1–7 were determined by comparing their experimental and calculated ECD spectra. Compound 1 was a novel degraded carbon diterpene with the disappearing of methyl signal at C-19, while compound 7 possessed a new norabietane-type diterpenoid carbon skeleton with the presence of five-membered lactone arising from ring rearrangement. The anti-inflammatory of all obtained isolates were evaluated on lipopolysaccharide (LPS)-stimulated RAW 264.7 cells and the results of anti-inflammatory activity screening showed that compared with the LPS model group, all compounds were significantly down-regulation the TNF-α inflammatory factor at the specific concentration, except for compound 6.

Interfacial Electronic Rearrangement and Synergistic Catalysis for Alkaline Water Splitting in Carbon Encapsulated Ni (111)/Ni3c (113) Heterostructure

Abstract: The realization of efficient water electrolysis is still blocked by the requirement for a high and stable driving potential above thermodynamic requirements. An Ni-based electrocatalyst, is a promising alternative for noble-metal-free electrocatalysts but tuning its surface electronic structure and exposing more active sites are the critical challenges to improving its intrinsic catalytic activity. Here, we tackle the challenge by tuning surface electronic structures synergistically with interfacial chemistry and crystal facet engineering, successfully designing and synthesizing the carbon-encapsulated Ni (111)/Ni3C (113) heterojunction electrocatalyst, demonstrating superior hydrogen evolution reaction (HER) activities, good stabilities with a small overpotential of −29 mV at 10 mA/cm2, and a low Tafel slope of 59.96 mV/dec in alkaline surroundings, approximating a commercial Pt/C catalyst and outperforming other reported Ni-based catalysts. The heterostructure electrocatalyst operates at 1.55 V and 1.26 V to reach 10 and 1 mA cm−2 in two-electrode measurements for overall alkaline water splitting, corresponding to 79% and 98% electricity-to-fuel conversion efficiency with respect to the lower heating value of hydrogen.