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20 result(s) for "Huang, Shenlin"
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BioAIEgens derived from rosin: how does molecular motion affect their photophysical processes in solid state?
The exploration of artificial luminogens with bright emission has been fully developed with the advancement of synthetic chemistry. However, many of them face problems like weakened emission in the aggregated state as well as poor renewability and sustainability. Therefore, the development of renewable and sustainable luminogens with anti-quenching function in the solid state, as well as to unveil the key factors that influence their luminescence behavior become highly significant. Herein, a new class of natural rosin-derived luminogens with aggregation-induced emission property (AIEgens) have been facilely obtained with good biocompatibility and targeted organelle imaging capability as well as photochromic behavior in the solid state. Mechanistic study indicates that the introduction of the alicyclic moiety helps suppress the excited-state molecular motion to enhance the solid-state emission. The current work fundamentally elucidates the role of alicyclic moiety in luminogen design and practically demonstrates a new source to large-scalely obtain biocompatible AIEgens. To date we have a myriad of luminogenes at our deposal but many of them face problems like weakened emission in the aggregated state as well as poor sustainability. Here, the authors develop a class of rosin-derived luminogens with aggregation induced emission properties providing good biocompatibility and demonstrate their application in organelle imaging.
Electroreductive hydroxy fluorosulfonylation of alkenes
An electroreductive strategy for radical hydroxyl fluorosulfonylation of alkenes with sulfuryl chlorofluoride and molecular oxygen from air is described. This mild protocol displays excellent functional group compatibility, broad scope, and good scalability, providing convenient access to diverse β-hydroxy sulfonyl fluorides. These β-hydroxy sulfonyl fluoride products can be further converted to valuable aliphatic sulfonyl fluorides, β-keto sulfonyl fluorides, and β-alkenyl sulfonyl fluorides. Further, some of these products showed excellent inhibitory activity against Botrytis cinerea or Bursaphelenchus xylophilus , which could be useful for potent agrochemical discovery. Preliminary mechanistic studies indicate that this transformation is achieved through rapid O 2 interception by the alkyl radical and subsequent reduction of the peroxy radical, which outcompete other side reactions such as chlorine atom transfer, hydrogen atom transfer, and Russell fragmentation. As sulfonyl fluorides have found wide applications, synthetic access to β-hydroxy sulfonyl fluorides is desirable. Here, the authors report an electroreductive strategy for radical hydroxyl fluorosulfonylation of alkenes with sulfuryl chlorofluoride and molecular oxygen from air.
LncRNA—UCA1 enhances cell proliferation and 5-fluorouracil resistance in colorectal cancer by inhibiting miR-204-5p
Recent preliminary studies reported the in vitro tumor-promoting effects of long non-coding RNA urothelial carcinoma associated 1 (UCA1) in colorectal cancer (CRC). However, the in vivo functions and molecular mechanism of UCA1 in CRC remain unclear. Therefore, we investigated the detailed role and mechanism of UCA1 in CRC. We found that UCA1 was up-regulated in CRCs and negatively correlated with survival time in two CRC cohorts. Functional assays revealed the in vitro and in vivo growth-promoting function of UCA1 and revealed that UCA1 can decrease the sensitivity of CRC cells to 5-FU by attenuating apoptosis. Further mechanistic studies revealed that UCA1 could sponge endogenous miR-204-5p and inhibit its activity. We also identified CREB1 as a new target of miR-204-5p. The protein levels of CREB1 were significantly up-regulated in CRCs, negatively associated with survival time and positively correlated with the UCA1 expression. The present work provides the first evidence of a UCA1-miR-204-5p- CREB1 / BCL2 / RAB22A regulatory network in CRC and reveals that UCA1 and CREB1 are potential new oncogenes and prognostic factors for CRC.
Organoelectrocatalytic cyclopropanation of alkenyl trifluoroborates with methylene compounds
Cyclopropanes are not only privileged motifs in many natural products, agrochemicals, and pharmaceuticals, but also highly versatile intermediates in synthetic chemistry. As such, great effort has been devoted to the cyclopropane construction. However, novel catalytic methods for cyclopropanation with two abundant substrates, mild conditions, high functional group tolerance, and broad scope are still highly desirable. Herein, we report an intermolecular electrocatalytic cyclopropanation of alkenyl trifluoroborates with methylene compounds. The reaction uses simple diphenyl sulfide as the electrocatalyst under base-free conditions. And thus, a broad scope of various methylene compounds as well as vinyltrifluoroborates is demonstrated, including styrenyl, 1,3-dienyl, fluorosulfonyl, and base-sensitive substrates. Preliminary mechanistic studies are presented, revealing the critical role of the boryl substituent to facilitate the desired pathway and the role of water as the hydrogen atom source. Although cyclopropanes are found in many natural products, agrochemicals, and pharmaceuticals, catalytic methods for cyclopropanation with two abundant substrates, mild conditions, high functional group tolerance, and broad scope are still highly desirable. Here, the authors report an intermolecular electrocatalytic cyclopropanation of alkenyl trifluoroborates with methylene compounds.
Modular esterification of unstrained carbonyls through palladium-catalyzed alkyne bridging C-C bond activation
The insertion of an oxygen atom into carbon-carbon (C-C) σ-bonds of readily available ketones to form esters represents a fundamental transformation known as Baeyer-Villiger (BV) oxidation. While this classical reaction serves as a cornerstone in organic synthesis, its scope remains limited to single oxygen-atom insertion into ketone substrates. We herein report a versatile catalytic protocol that enables the insertion of alkynyl phenol analogues into unstrained C-C σ-bonds of diverse carbonyl compounds, including ketones, esters, and amides. This method provides modular access to an array of structurally varied products ranging from linear esters to medium- and macrocyclic lactones. This methodology displays broad substrate scope, excellent functional group tolerance, direct applicability to bioactive molecule modification with effective transfer of axial chirality. An in-depth computational study provides insights into the reaction mechanism. While Baeyer-Villiger oxidation reaction has served as a cornerstone in organic synthesis, its scope remains limited to single oxygen-atom insertion into ketone substrates. Here, the authors report a versatile protocol that enables the insertion of alkynyl phenol analogues into unstrained C-C σ-bonds of diverse carbonyl compounds, including ketones, esters, and amides.
An Early Warning Method Based on Transformer–Attention–LSTM Hybrid Framework for Landslides in the Red Bed Sedimentary Layers in Western Sichuan, China: Implications for Sustainable Hazard Mitigation
Global climate change and increasingly complex geological conditions have led to more frequent landslides in the red-bed sedimentary layers of western Sichuan, China, posing severe threats to human safety and hindering progress toward regional Sustainable Development Goals (SDGs), particularly those related to disaster risk reduction and ecological protection. To address this challenge and advance sustainable disaster management, this study proposes a lightweight hybrid model, termed Transformer–Attention–LSTM, which integrates the global attention mechanism of Transformers with the local time-series modeling capabilities of Long Short-Term Memory networks. Focusing on the Kuyaogou landslide, the model achieves an optimal balance between parameter scale, sequence length, and prediction accuracy. The mean Coefficient of Determination (R2) values for the test samples in the X, Y, and Z directions reached 0.948, representing enhancements of 9.9%, 4.2%, and 2.3%, respectively, compared to the suboptimal Attention–LSTM model. Concurrently, the Root Mean Square Error (RMSE) and Mean Absolute Error (MAE) were reduced to 9.23 mm and 7.17 mm, respectively. Based on these displacement predictions, the landslide evolution stage was determined by calculating the tangent angle, indicating that the Kuyaogou landslide will remain in a stable creep phase over the ensuing ten-day period with low overall risk of rapid movement, though localized instability requires continued monitoring. This research provides a ‘small, fast, and accurate’ paradigm for red-bed landslide displacement prediction, offering scientific support for disaster prevention and emergency decision-making. The framework demonstrates potential for broader application in monitoring other geological hazards, thereby contributing to the implementation of sustainable development strategies in geohazard-prone regions.
tLyP-1 Peptide Functionalized Human H Chain Ferritin for Targeted Delivery of Paclitaxel
The aims of this study were to test the feasibility, targeting specificity and anticancer therapeutic efficacy of CendR motif tLyP-1 functionalized at the N-terminal of ferritin for paclitaxel (PTX) delivery. A tumor homing and penetrating peptide tLyP-1 was fused to the N-terminal of human H chain ferritin (HFtn) to generate a dual-targeting nanoparticle delivery system. PTX molecules were encapsulated into the HFtn nanocage using the disassembly/assembly method by adjusting pHs. Cellular uptake was examined by confocal laser scanning microscopy (CLSM) and flow cytometry. The MTT assay was used to test the cytotoxicity of various PTX-loaded NPs against MDA-MB-231 and SMMC-7721 tumor cells. The wound healing and cell migration assays were conducted to assess the inhibitory effect on cell motility and metastasis. The inhibition effect on the SMMC-7721 tumor spheroids was studied and penetration ability was evaluated by CLSM. The antitumor efficacy of PTX-loaded NPs was assessed in MDA-MB-231 breast cancer xenografted in female BALB/c nude mice. Compared with HFtn-PTX, in vitro studies demonstrated that the tLyP-1-HFtn-PTX displayed enhanced intracellular delivery and better cytotoxicity and anti-invasion ability against both SMMC-7721 and MDA-MB-231 cells. The better penetrability and growth inhibitory effect on SMMC-7721 tumor spheroids were also testified. In vivo distribution and imaging demonstrated that the tLyP-1-HFtn-PTX NPs were selectively accumulated and penetrated at the tumor regions. Verified by the breast cancer cells model in BABL/c nude mice, tLyP-1-HFtn-PTX displayed higher in vivo therapeutic efficacy with lower systemic toxicity. Ferritin decorated with tumor-homing penetration peptide tLyP-1 at the N terminal could deliver PTX specifically inside the cell via receptor-mediated endocytosis with better efficacy. The peptide tLyP-1 which is supposed to work only at the C terminus showed enhanced tumor tissue penetration and antitumor efficacy, demonstrating that it also worked at the N-terminal of HFtn.
Analytical Profiling of Proanthocyanidins from Acacia mearnsii Bark and In Vitro Assessment of Antioxidant and Antidiabetic Potential
The proanthocyanidins from ethanol extracts (80%, v/v) of Acacia mearnsii (A. mearnsii) bark on chemical-based and cellular antioxidant activity assays as well as carbolytic enzyme inhibitory activities were studied. About 77% of oligomeric proanthocyanidins in ethanol extracts of A. mearnsii bark were found by using normal-phase HPLC. In addition, HPLC-ESI-TOF/MS and MALDI-TOF/TOF MS analyses indicated that proanthocyanidins from A. mearnsii bark exhibited with a degree of polymerization ranging from 1 to 11. These results of combined antioxidant activity assays, as well as carbolytic enzyme inhibitory activities of proanthocyanidins from A. mearnsii bark, indicated an encouraging antioxidant capacity for the high polyphenol content and a potential for use as alternative drugs for lowering the glycemic response.
Cationic Pd(II)-catalyzed C–H activation/cross-coupling reactions at room temperature: synthetic and mechanistic studies
Cationic palladium(II) complexes have been found to be highly reactive towards aromatic C–H activation of arylureas at room temperature. A commercially available catalyst [Pd(MeCN) 4 ](BF 4 ) 2 or a nitrile-free cationic palladium(II) complex generated in situ from the reaction of Pd(OAc) 2 and HBF 4 , effectively catalyzes C–H activation/cross-coupling reactions between aryl iodides, arylboronic acids and acrylates under milder conditions than those previously reported. The nature of the directing group was found to be critical for achieving room temperature conditions, with the urea moiety the most effective in promoting facile coupling reactions at an ortho C–H position. This methodology has been utilized in a streamlined and efficient synthesis of boscalid, an agent produced on the kiloton scale annually and used to control a range of plant pathogens in broadacre and horticultural crops. Mechanistic investigations led to a proposed catalytic cycle involving three steps: (1) C–H activation to generate a cationic palladacycle; (2) reaction of the cationic palladacycle with an aryl iodide, arylboronic acid or acrylate, and (3) regeneration of the active cationic palladium catalyst. The reaction between a cationic palladium(II) complex and arylurea allowed the formation and isolation of the corresponding palladacycle intermediate, characterized by X-ray analysis. Roles of various additives in the stepwise process have also been studied.
Linker Regulation: Synthesis and Electrochemical Properties of Ferrocene-Decorated Cellulose
Ferrocene-decorated cellulosic materials are usually obtained via a couple of synthetic procedures, which might possibly affect their degree of substitution. In this work, two ferrocene-decorated cellulose esters, connected either by monocarboxylate or by dicarboxylate linkers, have been prepared via one-step reactions by means of esterifying microcrystalline cellulose (MCC) with ferrocenemonocarboxylic acid and 1,1’-ferrocenedicarboxylic acid (FcDA), respectively. Successful surface modification has been confirmed by elemental analysis, Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy, and thermogravimetric measurements. Large retention of the crystalline morphology can be revealed by powder X-ray diffraction, confirming its surface decoration as well. Cyclic voltammetry results of both esters have demonstrated that the winding of the cellulose chains in MCC-FcDA caused by its cross-linking structure might have unfavorable effect for electron transfer, resulting in weaker reversibility of its redox process. Therefore, exploration of a suitable linker might be of great importance to achieve ideal electrochemical properties. Graphic Abstract Two ferrocene-decorated cellulose esters connected either by mono or by dicarboxylate linkers have been synthesized via one-step reactions, exhibiting the more electrochemical reversibility of the monocarboxylate-linked ester.