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1.
Planta ; 259(5): 104, 2024 Mar 29.
Article in English | MEDLINE | ID: mdl-38551672

ABSTRACT

MAIN CONCLUSION: The post-transcriptional gene regulatory pathway and small RNA pathway play important roles in regulating the rapid and long-term response of Rhododendron moulmainense to high-temperature stress. The Rhododendron plays an important role in maintaining ecological balance. However, it is difficult to domesticate for use in urban ecosystems due to their strict optimum growth temperature condition, and its evolution and adaptation are little known. Here, we combined transcriptome and small RNAome to reveal the rapid response and long-term adaptability regulation strategies in Rhododendron moulmainense under high-temperature stress. The post-transcriptional gene regulatory pathway plays important roles in stress response, in which the protein folding pathway is rapidly induced at 4 h after heat stress, and alternative splicing plays an important role in regulating gene expression at 7 days after heat stress. The chloroplasts oxidative damage is the main factor inhibiting photosynthesis efficiency. Through WGCNA analysis, we identified gene association patterns and potential key regulatory genes responsible for maintaining the ROS steady-state under heat stress. Finally, we found that the sRNA synthesis pathway is induced under heat stress. Combined with small RNAome, we found that more miRNAs are significantly changed under long-term heat stress. Furthermore, MYBs might play a central role in target gene interaction network of differentially expressed miRNAs in R. moulmainense under heat stress. MYBs are closely related to ABA, consistently, ABA synthesis and signaling pathways are significantly inhibited, and the change in stomatal aperture is not obvious under heat stress. Taken together, we gained valuable insights into the transplantation and long-term conservation domestication of Rhododendron, and provide genetic resources for genetic modification and molecular breeding to improve heat resistance in Rhododendron.


Subject(s)
MicroRNAs , Rhododendron , Transcriptome/genetics , Rhododendron/genetics , Rhododendron/metabolism , Ecosystem , Heat-Shock Response/genetics , MicroRNAs/genetics , Gene Expression Profiling
2.
Nat Commun ; 15(1): 1108, 2024 Feb 06.
Article in English | MEDLINE | ID: mdl-38321000

ABSTRACT

The next generation of high-capacity, multi-task optical informatics requires sophisticated manipulation of multiple degrees of freedom (DoFs) of light, especially when they are coupled in a non-separable way. Vector beam, as a typical non-separable state between the spin and orbital angular momentum DoFs, mathematically akin to entangled qubits, has inspired multifarious theories and applications in both quantum and classical regimes. Although qubit rotation is a vital and ubiquitous operation in quantum informatics, its classical analogue is rarely studied. Here, we demonstrate the logical rotation of vectorial non-separable states via the uniform self-assembled chiral superstructures, with favorable controllability, high compactness and exemption from formidable alignment. Photonic band engineering of such 1D chiral photonic crystal renders the incident-angle-dependent evolution of the spatially-variant polarizations. The logical rotation angle of a non-separable state can be tuned in a wide range over 4π by this single homogeneous device, flexibly providing a set of distinguished logic gates. Potential applications, including angular motion tracking and proof-of-principle logic network, are demonstrated by specific configuration. This work brings important insight into soft matter photonics and present an elegant strategy to harness high-dimensional photonic states.

3.
Nat Commun ; 15(1): 197, 2024 Jan 03.
Article in English | MEDLINE | ID: mdl-38172091

ABSTRACT

Branched flows occur ubiquitously in various wave systems, when the propagating waves encounter weak correlated scattering potentials. Here we report the experimental realization of electrical tuning of the branched flow of light using a nematic liquid crystal (NLC) system. We create the physical realization of the weakly correlated disordered potentials of light via the inhomogeneous orientations of the NLC. We demonstrate that the branched flow of light can be switched on and off as well as tuned continuously through the electro-optical properties of NLC film. We further show that the branched flow can be manipulated by the polarization of the incident light due to the optical anisotropy of the NLC film. The nature of the branched flow of light is revealed via the unconventional intensity statistics and the rapid fidelity decay along the light propagation. Our study unveils an excellent platform for the tuning of the branched flow of light which creates a testbed for fundamental physics and offers a new way for steering light.

4.
Angew Chem Int Ed Engl ; 63(3): e202311053, 2024 Jan 15.
Article in English | MEDLINE | ID: mdl-37917574

ABSTRACT

With the rapid development of asymmetric catalysis, the demand for the enantioselective synthesis of complex and diverse molecules with different chiral elements is increasing. Owing to the unique features of atropisomerism, the catalytic asymmetric synthesis of atropisomers has attracted a considerable interest from the chemical science community. In particular, introducing additional chiral elements, such as carbon centered chirality, heteroatomic chirality, planar chirality, and helical chirality, into atropisomers provides an opportunity to incorporate new properties into axially chiral compounds, thus expanding the potential applications of atropisomers. Thus, it is important to perform catalytic asymmetric transformations to synthesize atropisomers bearing multiple chiral elements. In spite of challenges in such transformations, in recent years, chemists have devised powerful strategies under asymmetric organocatalysis or metal catalysis, synthesizing a wide range of enantioenriched atropisomers bearing multiple chiral elements. Therefore, the catalytic asymmetric synthesis of atropisomers bearing multiple chiral elements has become an emerging field. This review summarizes the rapid progress in this field and indicates challenges, thereby promoting this field to a new horizon.

5.
Cancer Rep (Hoboken) ; 7(1): e1921, 2024 01.
Article in English | MEDLINE | ID: mdl-37884351

ABSTRACT

Hepatocellular carcinoma (HCC) is the sixth most common malignant tumors and the third leading cause of cancer-related death worldwide. As an oncogene, Rab23 has been shown to be significantly related to the growth and migration of hepatocellular carcinoma in both in vitro and in vivo studies, but its underlying mechanism remains obscure. In the present study, we examined the effect of inhibiting Rab23 expression on the pathological progression of HCC. The correlation between liver Rab23 gene expression and survival probability in human HCC patients was analyzed using the TCGA database and CPTAC database. Rab23 knockdown hepatocellular carcinoma cell line was generated through lentiviral transduction, then we established a nude HCC xenograft model by subcutaneously implanting the transfected cells. The analysis of gene and protein expression was carried out using Western blot or RT-qPCR, respectively. Flow cytometry analysis was used to detect the level of apoptosis. The expression levels of key proteins involved in the Sonic Hedgehog (SHH) signaling pathway were assessed. The results showed that HCC patients with low levels of hepatic Rab23 mRNA and protein had a better survival tendency than those with higher levels of Rab23. Cell proliferations were reduced and apoptosis levels were increased after Knocking down Rab23 in HCC cell lines. Furthermore, in vivo studies have demonstrated that suppression of the Rab23 gene results in decreased tumor size, proliferation rate, and reduced levels of SHH-related proteins Smoothened and GLI-1. The above results suggest that Rab23 is involved in the pathological progression of HCC as an important regulator of the SHH signaling pathway, which also provides an important research basis for new therapeutic strategies for HCC.


Subject(s)
Carcinoma, Hepatocellular , Liver Neoplasms , Humans , Carcinoma, Hepatocellular/genetics , Liver Neoplasms/genetics , Down-Regulation , Cell Line, Tumor , Signal Transduction/physiology , Hedgehog Proteins/genetics , Hedgehog Proteins/metabolism
6.
Nano Lett ; 24(1): 140-147, 2024 Jan 10.
Article in English | MEDLINE | ID: mdl-37982545

ABSTRACT

Optical spatial differentiation is a typical operation of optical analog computing and can single out the edge to accelerate the subsequent image processing, but in some cases, overall information about the object needs to be presented synchronously. Here, we propose a multifunctional optical device based on structured chiral photonic crystals for the simultaneous realization of real-time dual-mode imaging. This optical differentiator is realized by self-organized large-birefringence cholesteric liquid crystals, which are photopatterned to encode with a special integrated geometric phase. Two highly spin-selective modes of second-order spatial differentiation and bright-field imaging are exhibited in the reflected and transmitted directions, respectively. Two-dimensional edges of both amplitude and phase objects have been efficiently enhanced in high contrast and the broadband spectrum. This work extends the ingenious building of hierarchical chiral nanostructures, enriches their applications in the emerging frontiers of optical computing, and boasts considerable potential in machine vision and microscopy.

7.
Environ Technol ; : 1-11, 2023 Aug 08.
Article in English | MEDLINE | ID: mdl-37553118

ABSTRACT

The present work investigates the performance of a biofilm reactor filled with a new type of combined packing used to treat wastewater and explores a new technology approach for the application of coral sand and waste non-woven fabric. The combined packing was made of coral sand and waste non-woven fabric, which was used as a biofilm carrier to treat sewage. The experimental results showed that the removal efficiencies of COD, NH4+-N and TN in the biofilm reactor containing the combined packing were 92.9%, 72.9% and 63.2%, respectively. The maximum removal efficiencies of COD, NH4+-N and TN in the biofilm reactor containing single packing were 89.0%, 63.4% and 55.2%, respectively. The properties of the combined packing were characterized by Fourier Transform Infrared (FTIR), specific surface area, SEM and dehydrogenase activity. Infrared analysis showed that there were hydroxyl, carboxyl and carbonyl groups on the surface of coral sand and non-woven fabric which were beneficial for biofilm growth and wastewater treatment. The large pores in the interior of coral sand and non-woven fabric could provide a comfortable environment for microbes to grow and reproduce. The dehydrogenase activity of the biofilm on the surface of coral sand in the third biofilm reactor was 49.91 µgTF·g-1·h-1, which was significantly higher than that of the other two biofilm reactors. The new type of combined packing is suitable for biofilm carriers with low cost, which can be applied to actual sewage treatment projects. This study provides a reference for the practical application of the technique.

8.
Adv Mater ; 35(33): e2301714, 2023 Aug.
Article in English | MEDLINE | ID: mdl-37158735

ABSTRACT

Chiral nanostructures featuring the unique optical activity have attracted broad interests from scientists. The typical polarization rotation of transmitted light is usually wavelength dependent, namely the optical rotatory dispersion. However, its dynamic tunability and intriguing collaboration with other optical degrees of freedom, especially the highly desired spatial phase, remain elusive. Herein, a bi-chiral liquid crystalline nanostructure is proposed to induce an effect called reflective optical rotatory dispersion. Thanks to the independent manipulation of opposite-handed self-assembled helices, spin-decoupled geometric phases are induced simultaneously. These naturally unite multi-dimensions of light and versatile stimuli-responsiveness of soft matter. Dynamic holography driven by heat and electric field is demonstrated with a fast response. For polychromatic light, the hybrid multiplexed holographic painting is exhibited with fruitful tunable colors. This study extends the ingenious construction of soft chiral superstructures, presents an open-ended strategy for on-demand light control, and enlightens advanced applications of display, optical computing, and communication.

9.
Zhen Ci Yan Jiu ; 48(4): 311-6, 2023 Apr 25.
Article in Chinese | MEDLINE | ID: mdl-37186193

ABSTRACT

OBJECTIVE: To observe the effect of electroacupuncture (EA) pretreatment at "Quchi "(LI11) and "Xuehai "(SP10) on expression of interleukin (IL)-33, suppression of tumorigenicity 2 (ST2) and mast cell degranulation in sensitive area of skin tissue in rats with urticaria, so as to explore its mechanisms underlying prevention of urticaria. METHODS: A total of 32 male SD rats were randomly divided into blank control, model, EA preconditioning and medication groups, with 8 rats in each group. The urticaria model was established by topical injection of the prepared anti-ovalbumin serum (foreign serum, 0.1 mL/spot) along the bilateral sides of the spinal column on the back, followed by injection of mixture solution of ovalbumin, 0.5% evans blue and normal saline via the tail vein 48 h later. EA intervention (2 Hz/15 Hz, 1 mA) was applied to bilateral LI11 and SP10 for 20 min, once daily for 7 d before modeling.Back sensitization was started from the 5th day on. Rats of the medication group received gavage of loratadine, and those of the model group received gavage of the same volume of normal saline. The diameter of evans blue spots at the back skin tissue was measured; the histopathological changes of the blue spot tissues were observed by light microscope after H.E. staining. The state of degranulation of mast cells in the subcutaneous loose connective tissue was observed by using toluidine blue staining. Serum IgE and histamine contents were detected by ELISA, and the immunoactivity of IL-33 and ST2 in the skin and subcutaneous tissues of the sensitized spots (evans blue exudation spots) was observed by immunohistochemistry. RESULTS: Compared with the blank control group, the diameter of evans blue spot, degranulation rate of mast cells, serum IgE and histamine contents, and the immunoactivity of IL-33 and ST2 in the evans blue exudation spot tissues were significantly increased in the model group (P<0.01). In comparison with the model group, the increase of the above-mentioned indexes was reversed in both EA and medication groups (P<0.01,P<0.05). No significant differences were found between the EA and medication groups in down-regulating the levels of the 6 indexes. H.E. staining of the blue spot tissues of rats in the model group showed incomplete structure of the epidermal layer of the skin, unclear interface of tissues, incomplete keratinization, chaotic epidermal cells, disorderly arrangement of fibers in the dermis, and infiltration of inflammatory cells and edema, which was relatively milder in the EA and medication groups. CONCLUSION: EA preconditioning can prevent urticaria (reduce size and sensitive reactions) in rats, which may be associated with its functions in lowering the level of IgE through inhibiting IL-33 and ST2.


Subject(s)
Acupuncture Therapy , Electroacupuncture , Urticaria , Rats , Male , Animals , Rats, Sprague-Dawley , Mast Cells , Interleukin-1 Receptor-Like 1 Protein , Histamine , Evans Blue , Interleukin-33/genetics , Saline Solution , Urticaria/genetics , Urticaria/therapy , Immunoglobulin E , Acupuncture Points , Receptors, Interleukin-1
10.
Lupus ; 32(2): 239-251, 2023 Feb.
Article in English | MEDLINE | ID: mdl-36480924

ABSTRACT

OBJECTIVE: Despite widespread recognition, the mechanisms underlying the relationship between systemic lupus erythematosus (SLE) and atherosclerosis (AS) are still unclear. Our study aimed to explore the shared genetic signature and molecular mechanisms of SLE and AS using a bioinformatics approach. METHODS: Gene expression profiles of GSE50772 (contains peripheral blood mononuclear cells from 61 SLE patients and 20 normal samples) and GSE100927 (contains 69 AS plaque tissue samples and 35 control samples) were downloaded from the Gene Expression Database (GEO) before the differentially expressed genes were obtained using the "limma" package in R. The differential genes were then subjected to gene ontology (GO) and Kyoto Encyclopedia of Genes and Genomes (KEGG) pathway analysis using the DAVID online platform to annotate their functions. The intersection targets of PPI and WGCNA were used as key shared genes for SLE and AS with their diagnostic value as shared genes being verified through ROC curves. Finally, Cytoscape 3.7.2 software was used to construct a miRNA-mRNA network map associated with the shared genes. RESULTS: A total of 246 DEGs were identified, including 189 upregulated genes and 57 downregulated genes, which were mainly enriched in signaling pathways such as TNF signaling pathway, IL-17 signaling pathway, and NF-kB signaling pathway. The molecular basis for the relationship between SLE and AS may be the aforementioned signaling pathways. Following ROC curve validation, the intersection of PPI and WGCNA, as well as AQP9, CCR1, CD83, CXCL1, and FCGR2A, resulted in the identification of 15 shared genes. CONCLUSION: The study provided a new perspective on the common molecular mechanisms between SLE and AS, and the key genes and pathways that were identified as being part of these pathways may offer fresh perspectives and suggestions for further experimental research.


Subject(s)
Atherosclerosis , Lupus Erythematosus, Systemic , MicroRNAs , Humans , Leukocytes, Mononuclear , Lupus Erythematosus, Systemic/genetics , Transcriptome , Atherosclerosis/genetics , Computational Biology/methods , Gene Expression Profiling
11.
Int J Mol Sci ; 23(19)2022 Sep 22.
Article in English | MEDLINE | ID: mdl-36232461

ABSTRACT

Quercetin and kaempferol are flavonoids widely present in fruits, vegetables, and medicinal plants. They have attracted much attention due to their antioxidant, anti-inflammatory, anticancer, antibacterial, and neuroprotective properties. As the guarantee cells in direct contact with germ cells, Sertoli cells exert the role of support, nutrition, and protection in spermatogenesis. In the current study, network pharmacology was used to explore the targets and signaling pathways of quercetin and kaempferol in treating spermatogenic disorders. In vitro experiments were integrated to verify the results of quercetin and kaempferol against heat stress-induced Sertoli cell injury. The online platform was used to analyze the GO biological pathway and KEGG pathway. The results of the network pharmacology showed that quercetin and kaempferol intervention in spermatogenesis disorders were mostly targeting the oxidative response to oxidative stress, the ROS metabolic process and the NFκB pathway. The results of the cell experiment showed that Quercetin and kaempferol can prevent the decline of cell viability induced by heat stress, reduce the expression levels of HSP70 and ROS in Sertoli cells, reduce p-NF-κB-p65 and p-IκB levels, up-regulate the expression of occludin, vimentin and F-actin in Sertoli cells, and protect cell structure. Our research is the first to demonstrate that quercetin and kaempferol may exert effects in resisting the injury of cell viability and structure under heat stress.


Subject(s)
Burns , Quercetin , Actins , Anti-Bacterial Agents/therapeutic use , Antioxidants/pharmacology , Burns/drug therapy , Flavonoids , Heat-Shock Response , Humans , Kaempferols/pharmacology , Kaempferols/therapeutic use , Male , NF-kappa B/metabolism , Network Pharmacology , Occludin , Quercetin/pharmacology , Quercetin/therapeutic use , Reactive Oxygen Species/metabolism , Sertoli Cells/metabolism , Vimentin
12.
Light Sci Appl ; 11(1): 135, 2022 May 12.
Article in English | MEDLINE | ID: mdl-35551179

ABSTRACT

Recently discovered reflective Pancharatnam-Berry phase (PB phase) from chiral anisotropic media (e.g., cholesteric liquid crystal, CLC) has aroused great interest in the emerging frontier of planar optics. However, the single chirality of common CLCs results in the intrinsic limitation of the same spin-selective PB phase manipulation, which means the reversal of the input spin cannot realize the conjugated PB phase. In this work, an innovative scheme based on opposite-chirality-coexisted superstructures is proposed to simultaneously modulate orthogonal circular polarization and get PB phase reversal. Through refilling CLC into a washed-out polymer network with opposite chirality and delicate photo-patterned structures, reflective optical vortex (OV) with opposite topological charges and vector beams with conjugated spiral PB phases are efficiently generated depending on the incident polarization. Furthermore, OV holograms are encoded to reconstruct polarization-selective OV arrays, indicating the strong capability of such opposite-chirality-coexisted anisotropic media. This work provides a new compact platform for planar optics, and sheds light on the architectures and functionalities of chiral superstructures.

13.
Sci Total Environ ; 833: 155024, 2022 Aug 10.
Article in English | MEDLINE | ID: mdl-35390374

ABSTRACT

Microplastic (MPs) pollution is increasingly becoming a global environmental problem. MPs entering the environment are subjected to various aging processes, among which photoaging is the most important process leading to MPs oxidation. Persistent free radicals (EPFRs) are formed on the surface of MPs during photoaging, but it is not clear whether EPFRs on the surface of MPs can produce reactive oxygen species (ROS) and thus degrade organic pollutants. In this study, with polystyrene (PS) as the representative plastic and sulfamethazine (SMT) degradation as the target pollutant, the effect and mechanism of light-induced PS on SMT degradation were investigated by experiment and theoretical calculation. It was found that PS can stimulate the production of ROS under sunlight, which can significantly improve the degradation rate of SMT. Through quenching experiment and free radical trapping experiment, it was found that the mechanism of PS promoting the degradation of SMT was mainly due to the production of hydroxyl radical (·OH) in the system, and ·OH was the main ROS species affecting the oxidative degradation of SMT. The characterization results show that the high reactive oxygen generation ability of PS under solar irradiation was due to the abundant photoactive oxidation functional groups on its surface. In addition, the key reaction sites of SMT were predicted by density functional theory (DFT) calculation. The results of different calculations consistently showed that the sulfonamide group of SMT, the pyrimidine heterocycle and the amino group of aniline are the reaction sites of ·OH priority attack. The main intermediates were determined by UHPLC-HRMS/MS. Combined with theoretical calculation, it was proposed that the oxidative degradation pathway of SMT mainly includes SN bond cleavage, SMILES rearrangement and SO2 group removal. This study clarified the effect of PS on the degradation of organic pollutants under light, and provided theoretical guidance for the degradation mechanism.


Subject(s)
Microplastics , Water Pollutants, Chemical , Free Radicals , Plastics , Polystyrenes , Reactive Oxygen Species , Sulfamethazine , Water Pollutants, Chemical/analysis
14.
Ying Yong Sheng Tai Xue Bao ; 33(1): 141-148, 2022 Jan.
Article in Chinese | MEDLINE | ID: mdl-35224936

ABSTRACT

The measures of returning straw to the field can change soil environment in the field and affect crop growth. In order to explore the impacts of different straw returning measures on the preferential flow in the field, we investigated the movement characteristics of preferential flow in sugarcane fields under different straw returning measures [straw mulching (CM), straw burning mulching (BM), and non-straw mulching (CK)] in Guangxi by combining image analysis techniques with ecological landscape pattern analysis methods. The results showed that under the same external water supply environment, soil staining morphology of non-straw mulching sugarcane fields differentiated into finger-like and clump-like. Both straw mulching and straw burning mulching were mainly differentiated into clump-like. The mean total staining area ratio was significantly higher than that of non-straw mulching (26.0%). The ratio of surface staining area decreased rapidly under non-straw mulching. The water movement range decreased rapidly under straw mulching and straw burning mulching in the depth of 15-30 cm. The change rate of straw mulching staining area ratio was the lowest in the deep soil. The shape index of non-straw mulching was 15.54. The water flow movement was more concentrated. The average sub-circular index of straw mulching and straw burning mulching was 0.67 in the sugarcane field, with a higher degree of preferential flow bending, an average proximity index of 0.87, and better water flow connectivity. The average substrate flow depth (3.52 cm) and edge density index (11.51) were the smallest under non-straw mulching, but the priority flow ratio was the largest (73.2%), and the spatial development degree of preferential flow was the highest. The straw returning measures reduced the preferential flow in the sugarcane fields, with positive effects on water conservation.


Subject(s)
Saccharum , Soil , Agriculture/methods , China , Triticum , Water/analysis
15.
Front Microbiol ; 13: 1059262, 2022.
Article in English | MEDLINE | ID: mdl-36590395

ABSTRACT

Coral reef ecosystems are one of the most diverse and productive habitats on Earth. Microbes in the reef-overlying waters are key players in maintaining this ecosystem through regulating biogeochemical and ecological processes. However, the composition structure and assembly mechanism of microbial community in the reef-overlying waters remain largely unknown. In the present study, the bacterial communities from the overlying waters of atolls and fringing reefs as well as the surface waters of the adjacent open ocean of the Xisha Islands in the South China Sea were investigated using 16S rRNA high-throughput sequencing combined with a size-fractionation strategy. The results showed that environments of all sampling stations were similar, characterized by an almost complete lack of inorganic nutrients such as nitrogen and phosphorus. Proteobacteria, Cyanobacteria and Bacteroidetes were the dominant phyla, and Synechococcus was most abundant at the genus level in both large fraction (LF; 1.6-200 µm) and small fraction (SF; 0.2-1.6 µm) communities. Only a slight difference in community composition between LF and SF samples was observed. The bacterial communities among the three habitat types showed noticeable differences, and the bacterial composition among the atoll reefs was more varied than that among the fringing reefs. The similarity of bacterial communities significantly declined with the increasing geographic distance, and stochastic processes were more important than deterministic processes in bacterial community assembly. This study sheds lights on the bacterial biodiversity of coral reefs and the importance of stochastic process in structuring bacterial communities.

16.
Angew Chem Int Ed Engl ; 61(7): e202112226, 2022 Feb 07.
Article in English | MEDLINE | ID: mdl-34846087

ABSTRACT

A new class of axially chiral styrene-based thiourea tertiary amine catalysts, which have unique characteristics such as an efficient synthetic route, multiple chiral elements, and multiple activating groups, has been rationally designed. These new chiral catalysts have proven to be efficient organocatalysts, enabling the chemo-, diastereo-, and enantioselective (2+4) cyclization of 2-benzothiazolimines with homophthalic anhydrides in good yields (up to 96 %) with excellent stereoselectivities (all >95:5 dr, up to 98 % ee). More importantly, theoretical calculations elucidated the important role of an axially chiral styrene moiety in controlling both the reactivity and enantioselectivity. This work not only represents the first design of styrene-based chiral thiourea tertiary amine catalysts and the first catalytic asymmetric (2+4) cyclization of 2-benzothiazolimines, but also gives an in-depth understanding of axially chiral styrene-based organocatalysts.

17.
Molecules ; 26(21)2021 Nov 08.
Article in English | MEDLINE | ID: mdl-34771158

ABSTRACT

Catalytic asymmetric [2 + 4] cycloadditions of 3-vinylindoles with ortho-quinone methides and their precursors were carried out in the presence of chiral phosphoric acid to afford a series of indole-containing chroman derivatives with structural diversity in overall high yields (up to 98%), good diastereoselectivities (up to 93:7 dr) and moderate to excellent enantioselectivities (up to 98% ee). This approach not only enriches the chemistry of catalytic asymmetric cycloadditions involving 3-vinylindoles but is also useful for synthesizing chiral chroman derivatives.

18.
J Org Chem ; 86(15): 10427-10439, 2021 08 06.
Article in English | MEDLINE | ID: mdl-34313431

ABSTRACT

The first application of 3-alkyl-2-vinylindoles in catalytic asymmetric dearomative cycloadditions was established by chiral phosphoric acid (CPA)-catalyzed (2+3) cycloaddition with azoalkenes, leading to the generation of chiral pyrroloindolines bearing two tetrasubstituted stereogenic centers in good yields (61-96%) and excellent stereoselectivities (all >95:5 dr, 86-99% ee). This reaction has realized the first enantioselective dearomative cycloaddition of 3-alkyl-2-vinylindoles, which brings a new reactivity to this class of vinylindoles and will enrich the chemistry of 3-alkyl-2-vinylindoles. In addition, this approach has provided a useful strategy for the construction of enantioenriched pyrroloindoline skeletons bearing two tetrasubstituted stereogenic centers. More importantly, the bioassay of these chiral pyrroloindolines has revealed that some compounds exhibit strong anti-cancer activity against Hela and MCF-7 cell lines, which will be helpful for discovering anti-cancer drug candidates.


Subject(s)
Indoles , Catalysis , Cycloaddition Reaction , Stereoisomerism
19.
Angew Chem Int Ed Engl ; 60(5): 2355-2363, 2021 Feb 01.
Article in English | MEDLINE | ID: mdl-33089963

ABSTRACT

The regio- and enantioselective (3+3) cycloaddition of nitrones with 2-indolylmethanols was accomplished by the cooperative catalysis of hexafluoroisopropanol (HFIP) and chiral phosphoric acid (CPA). Using this approach, a series of indole-fused six-membered heterocycles were synthesized in high yields (up to 98 %), with excellent enantioselectivities (up to 96 % ee) and exclusive regiospecificity. This approach enabled not only the first organocatalytic asymmetric (3+3) cycloaddition of nitrones but also the first C3-nucleophilic asymmetric (3+3) cycloaddition of 2-indolylmethanols. More importantly, theoretical calculations elucidated the role of the cocatalyst HFIP in helping CPA control the reactivity and enantioselectivity of the reaction, demonstrating a new mode of cooperative catalysis.

20.
Sci Total Environ ; 760: 144122, 2021 Mar 15.
Article in English | MEDLINE | ID: mdl-33341612

ABSTRACT

Landfill refuse is a mixture of inorganic minerals and organic matter that is capable of undergoing complexation and redox reactions due to its active functional groups. Organic matter often combines with minerals in landfill refuse and it remains unclear whether this combination involves electron transfer. Therefore, the effects of landfill refuse composition on reductive dechlorination and speciation transformation of heavy metals were investigated in this study. Results show that landfill refuse comprises protein- and humic-like substances, aliphatic structures, and a large number of hydroxyl, carboxyl, quinoid and other active functional group. The electron donating capacity (0.09-0.26 µmol/g(C)) of landfill refuse was found to be higher than its electron accepting capacity (0.03-0.23 µmol/g(C)), indicating that electron donating groups (hydroxyl) were the main redox-active moieties, facilitating the reductive dechlorination of pentachlorophenol (PCP) by microorganism. Fe2O3, FeO and SiO2 were the main inorganic minerals affecting PCP dechlorination. The speciation distribution of heavy metals in landfill refuse was determined by the BCR sequential extraction method. Results showed that Zn and Ni have high potential migration capacity, poor stability and the highest bioavailability, while Cr, Cu and Pb are relatively stable and have weak migration potential. The oxygen- and nitrogen-containing functional groups, aliphatic structures and aromatic carbon in landfill refuse can promote the transformation of Ni and Cr from an unstable to stable state. Protein-like substances exhibit a strong Cu binding ability, allowing Cu to combine with organic matter more easily than other assessed heavy metals. Both Fe2O3 and FeO affected the stability of Cu. FeO promoted the stabilization of Zn, whereas Fe2O3 and SiO2 promoted Cu instability. These results could provide some references for the treatment of organic chlorides and the stabilization of heavy metals in landfill refuse in China.

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