（-）-Tetrahydrolipstatin 1 was synthesized in three steps and 33.8% overall yield from aldehyde 6 by tandem Mukaiyama-aldol lactonization, which offered a concise, efficient and highly diastereoselective route to thi...（-）-Tetrahydrolipstatin 1 was synthesized in three steps and 33.8% overall yield from aldehyde 6 by tandem Mukaiyama-aldol lactonization, which offered a concise, efficient and highly diastereoselective route to this antiobesity drug. We also presented a resolution method for preparation of the crucial intermediate, β- （t-butyldimethylsilyloxy）tetradecanal.展开更多
From aerial parts of Austroeupatorium inulifolium was isolated the ent-nor-furano triol labdane austroeupatol 1.The compound 1 was treated with IBX showing an unexpected selectivity at the potentially oxidizable sites...From aerial parts of Austroeupatorium inulifolium was isolated the ent-nor-furano triol labdane austroeupatol 1.The compound 1 was treated with IBX showing an unexpected selectivity at the potentially oxidizable sites of the sub-strate yielding the 2-oxoaustroeupatol(2)and 2,19-dioxoaustroeupatol(3).The treatment of 2 with sodium periodate yields a heterocyclic derivative(ε-caprolactone derivate 4)formed by oxidative cleavage and unexpected intramo-lecular attack of the hydroxymethylene(C-19)oxygen to the ketonic carbon(C-2).A plausible mechanistic pathway for the obtention of compound 4 is proposed.展开更多
?-Phenyl－4－aroylfuran－3－carboxylic acids were reduced in aqueous alkaline solutions ofNaBH4 to afford hydroxy acids in excellent yields． Under the catalysis of boron trifluoride etherate，the hydroxy acids were c...?-Phenyl－4－aroylfuran－3－carboxylic acids were reduced in aqueous alkaline solutions ofNaBH4 to afford hydroxy acids in excellent yields． Under the catalysis of boron trifluoride etherate，the hydroxy acids were converted to lactones smoothly．展开更多
Herein, we report a novel synthesis of 1,3-oxazin-6-ones from enamides with CO2 through C--H carboxylation and one-pot cyclization. This transition-metal-free and redox-neutral process features broad substrate scope, ...Herein, we report a novel synthesis of 1,3-oxazin-6-ones from enamides with CO2 through C--H carboxylation and one-pot cyclization. This transition-metal-free and redox-neutral process features broad substrate scope, good functional group tolerance and facile product derivatization. The nucleophilic attack to CO2 from the electron-rich alkene is demonstrated for this reaction.展开更多
Direct functionalization of inert C(sp^(3))–H bonds in pharmaceutically significant compounds is very important in modern synthetic organic chemistry.In this article,we disclose a practical and efficient method for t...Direct functionalization of inert C(sp^(3))–H bonds in pharmaceutically significant compounds is very important in modern synthetic organic chemistry.In this article,we disclose a practical and efficient method for the oxidative lactonization of benzylic C(sp^(3))–H bonds enabled by the synergistic interactions of organic dye-type rose bengal,n-Bu_(4)N∙Br,O_(2) and Na_(2)HPO_(4) under visible light irradiation.This reaction does not require transition metal catalysts or strong oxidants.A range of structurally diverse phthalides has been synthesized with excellent selectivity and high functional group compatibility.The late-stage application of this reaction to the preparation of structurally complex phthalides demonstrates its synthetic utility.展开更多
The inhibitory effects of zinc oxide nanoparticles(ZnO NPs)and impacts of N-acylhomoserine lactone(AHL)-based quorum sensing(QS)on biological nitrogen removal(BNR)performance have beenwell-investigated.However,the eff...The inhibitory effects of zinc oxide nanoparticles(ZnO NPs)and impacts of N-acylhomoserine lactone(AHL)-based quorum sensing(QS)on biological nitrogen removal(BNR)performance have beenwell-investigated.However,the effects of ammonia nitrogen(NH_(4)^(+)-N)concentrations on NP toxicity and AHL regulation have seldom been addressed yet.This study consulted on the impacts of ZnO NPs on BNR systems when high NH_(4)^(+)-N concentrationwas available.The synergistic toxic effects of high-strength NH_(4)^(+)-N(200 mg/L)and ZnO NPs resulted in decreased ammonia oxidation rates and dropped the nitrogen removal efficiencies by 17.5%±0.2%.The increased extracellular polymeric substances(EPS)production was observed in response to the high NH_(4)^(+)-N and ZnO NP stress,which indicated the defensemechanism against the toxic effects in the BNR systemswas stimulated.Furthermore,the regulatory effects of exogenous N-decanoyl-homoserine lactone(C_(10)-HSL)-mediated QS system on NP-stressed BNR systems were revealed to improve the BNR performance under different NH_(4)^(+)-N concentrations.The C_(10)-HSL regulated the intracellular reactive oxygen species levels,denitrification functional enzyme activities,and antioxidant enzyme activities,respectively.This probably synergistically enhanced the defense mechanism against NP toxicity.However,compared to the low NH_(4)^(+)-N concentration of 60 mg/L,the efficacy of C_(10)-HSL was inhibited at high NH_(4)^(+)-N levels of 200 mg/L.The findings provided the significant application potential of QS system for BNR when facing toxic compound shock threats.展开更多
Direct converting carbon dioxide(CO_(2))and propane(C_(3)H_(8))into aromatics with high carbon utilization offers a desirable opportunity to simultaneously mitigate CO_(2)emission and adequately utilize C_(3)H_(8) in ...Direct converting carbon dioxide(CO_(2))and propane(C_(3)H_(8))into aromatics with high carbon utilization offers a desirable opportunity to simultaneously mitigate CO_(2)emission and adequately utilize C_(3)H_(8) in shale gas.Owing to their thermodynamic resistance,converting CO_(2)and C_(3)H_(8) respectively remains difficult.Here,we achieve 60.2%aromatics selectivity and 48.8%propane conversion over H-ZSM-5-25 via a zeolite-catalyzing the coupling of CO_(2)and C_(3)H_(8).Operando dual-beam FTIR spectroscopy combined with ^(13)C-labeled CO_(2)tracing experiments revealed that CO_(2)is directly involved in the generation of aromatics,with its carbon atoms selectively embedded into the aromatic ring,bypassing the reverse water-gas shift pathway.Accordingly,a cooperative aromatization mechanism is proposed.Thereinto,lactones,produced from CO_(2)and olefins,are proven to be the key intermediate.This work not only provides an opportunity for simultaneous conversion of CO_(2)and C_(3)H_(8),but also expends coupling strategy designing of CO_(2)and alkanes over acidic zeolites.展开更多
As a recently emerging wastewater treatment technology,Algal-bacterial granular sludge(ABGS)process shows significant advantages.However,current research on the ABGS system is a lack of a clear and complete understand...As a recently emerging wastewater treatment technology,Algal-bacterial granular sludge(ABGS)process shows significant advantages.However,current research on the ABGS system is a lack of a clear and complete understanding of the potential mechanism of signal molecules on the growth of ABGS.This study comprehensively explores the variations in the ABGS under different N-acyl-homoserine lactone(AHL)conditions by constructing three sequencing batch reactor(SBR)systems.The results indicate that N-hexanoyl-l-homoserine lactone(C6-HSL)accelerates the granulation process in the early stages by promoting the loosely bound extracellular polymeric substances(LB-EPS)secretion and filamentous bacteria growth,thereby shortening required time for initial granule formation.On the other hand,N-(3-oxodecanoyl)-l-homoserine lactone(3-oxo-C12-HSL)expedites the granulation process by promoting the tightly bound extracellular polymeric substances(TB-EPS)and aromatic protein secretion,benefiting structural stability and nitrogen and phosphorus removal efficiency of mature ABGS.展开更多
Traumatic axonal lesions of peripheral nerves disrupt neuronal connections with their targets,resulting in the loss of motor and sensory functions.Despite the peripheral nervous system’s capacity for axonal regrowth,...Traumatic axonal lesions of peripheral nerves disrupt neuronal connections with their targets,resulting in the loss of motor and sensory functions.Despite the peripheral nervous system’s capacity for axonal regrowth,this may lead to permanent impairements resulting in a loss of quality of life and a high socioeconomic burden.展开更多
Quorum quenching (QQ)-based strategies are efficient for biofouling control.However,the feasibility of using QQ bacteria in antibiotic-stressed membrane bioreactors (MBRs) remains unknown.In this study,we isolated thr...Quorum quenching (QQ)-based strategies are efficient for biofouling control.However,the feasibility of using QQ bacteria in antibiotic-stressed membrane bioreactors (MBRs) remains unknown.In this study,we isolated three novel QQ strains (Bacillus sp.QX01 and QX03,Delftia sp.QX14) from the activated sludge of an actual MBR.They can degrade 11 N-acylhomoserine lactones (AHLs) with high efficiencies and rates through intracellular QQ pathways involving putative acylases and lactonases.Running two lab-scale MBRs,we found that introducing antibiotics (sulfamethoxazole,azithromycin,and ciprofloxacin,each at100μg/L) shortened the fouling cycle by 71.4%.However,the immobilized inoculation of QX01 into one MBR extended the fouling cycle by 1.5-2.0 times.Quantitative detection revealed that QX01 significantly reduced the concentrations of two AHLs (C4-HSL and C8-HSL),which were positively correlated with the contents of extracellular polymeric substances(EPS)(Pearson’s r=0.62-0.83,P<0.01).This suggests that QX01 could perform its QQ activity robustly under antibiotic stress,thereby inhibiting EPS production (proteins especially) and biofilm formation.Moreover,QX01 notably altered the succession patterns of both sludge and fouling communities,with more pronounced effects on abundant taxa.Genera associated with AHL synthesis and EPS production,such as Terrimonas and Rhodobacter,were significantly depleted,contributing to the mitigated biofouling.Additionally,QX01 increased the bacterial community diversity (evenness especially),which was inhibited by antibiotics.Overall,we demonstrate that the novel QQ bacteria could be effective for biofouling control in antibiotic-stressed MBRs,though future work is needed to develop practical approaches for prolonging QQ activity.展开更多
Chiral aryl cyclohex-3-en ether scaffold is widely present in bioactive natural products and drugs.The exploitation of efficient and enantioselective methods for the construction of aryl cyclohex-3-en ether scaffold i...Chiral aryl cyclohex-3-en ether scaffold is widely present in bioactive natural products and drugs.The exploitation of efficient and enantioselective methods for the construction of aryl cyclohex-3-en ether scaffold is significant.Herein we disclose a chiral N,N’-dioxide/Lewis acid complex-catalyzed asymmetric inverse-electron-demand Diels-Alder(IEDDA)reaction using electron-deficient 3-carboalkoxyl-2-pyrones and less electron-enriched aryl enol ethers as reactants.A wide range of non-and 1,2-disubstituted acyclic aryl enol ethers are applicable to deliver diverse chiral bridged bicyclic lactones in high yields and stereoselectivities(up to 96%yield,>20:1 dr,97:3 er).The bridged bicyclic lactone core can be easily converted into chiral aryl cyclohex-3-en ether scaffold.Notably,DFT calculations revealed a stepwise and endo mechanism to explain the high enantioselectivity controlled by the cooperative effect of the steric factors and the dispersion interactions between ligands and enol ethers.展开更多
Due to its unique electronic properties,the difluoromethylene group(CF2)has served as a valuable unity in the design of biologically active molecules.Sinceγ-lactones display a broad range of biological properties,α,...Due to its unique electronic properties,the difluoromethylene group(CF2)has served as a valuable unity in the design of biologically active molecules.Sinceγ-lactones display a broad range of biological properties,α,α-difluoro-γ-lactones may exhibit unexpected biological activities,and thus their synthesis has received increasing attention.Traditional synthetic methods suffer from tedious multi-step processes,and very few effective methods have been reported recently.Herein,we describe the difunctionalization of alkenes with BrCF_(2)CO_(2)K under photoredox catalysis with the use of a boron-Lewis acid for the access toα,α-difluoro-γ-lactones.In this transformation,the alkene substrates and the used reagents,including BrCF_(2)CO_(2)K and the boron-Lewis acid,PhB(OH)2 or BF3·THF,are cheap and widely available.High efficiency and atom economy may make this protocol attractive.展开更多
Four new sesquiterpene lactones(SLs)(1–4),along with a biosynthetically related SL(5),have been isolated from the leaves of Magnolia grandiflora.Magrandate A(1)is notable as the first C18 homogemarane type SL,featuri...Four new sesquiterpene lactones(SLs)(1–4),along with a biosynthetically related SL(5),have been isolated from the leaves of Magnolia grandiflora.Magrandate A(1)is notable as the first C18 homogemarane type SL,featuring a unique 1,7-dioxaspiro[4.4]nonan-6-one core.Compounds 2 and 3,representing the first instances of chlorine-substituted gemarane-type SL analogs in natural products,were also identified.The structures of these isolates were elucidated through a combination of spectroscopic data analysis,electronic circular dichroism calculations,and X-ray single-crystal diffraction analysis.All isolates demonstrated anti-inflammatory activity in lipopolysaccharide-stimulated RAW264.7 cells.Notably,3–5 showed a significant inhibitory effect on nitric oxide production,with IC50 values ranging from 0.79 to 4.73μmol·L^(−1).Additionally,4 and 5 exhibited moderate cytotoxic activities against three cancer cell lines,with IC50 values between 3.09 and 11.23μmol·L^(−1).展开更多
Nine new germacranolides,sylvaticalides A−H(1-9),and three known analogues(10-12)were isolated from the aeri-al part of Vernonia sylvatica.Their structures were established using comprehensive spectroscopic analysis,i...Nine new germacranolides,sylvaticalides A−H(1-9),and three known analogues(10-12)were isolated from the aeri-al part of Vernonia sylvatica.Their structures were established using comprehensive spectroscopic analysis,including high-resolution electrospray ionization mass spectroscopy(HR-ESI-MS)and 1D and 2D nuclear magnetic resonance(NMR)spectra.Their absolute configurations were determined by X-ray diffraction experiments.The anti-inflammatory activities of all isolated compounds were as-sessed by evaluating their inhibitory effects on the nuclear factor kappa B(NF-κB)pathway,which was activated by lipopolysacchar-ide(LPS)-stimulated human THP1-Dual cells,and the interferon-stimulated gene(ISG)pathway,activated by STING agonist MSA-2 in the same cell model.Compounds 1,2 and 6 showed inhibitory effects on the NF-κB and ISG signaling pathways,with IC_(50)values ranging from 4.12 to 10.57μmol·L^(−1).展开更多
Britanin is a bioactive sesquiterpene lactone known for its potent anti-inflammatory and anti-oxidant properties.It also exhibits significant anti-tumor activity,suppressing tumor growth in vitro and in vivo.The curre...Britanin is a bioactive sesquiterpene lactone known for its potent anti-inflammatory and anti-oxidant properties.It also exhibits significant anti-tumor activity,suppressing tumor growth in vitro and in vivo.The current body of research on Britanin includes thirty papers predominantly related to neoplasms,the majority of which are gastrointestinal tumors that have not been summarized before.To drive academic debate,the present paper reviews the available research on Britanin in gastrointestinal tumors.It also outlines novel research directions using data not directly concerned with the digestive system,but which could be adopted in future gastrointestinal research.Britanin was found to counteract liver,colorectal,pancreatic,and gastric tumors,by regulating proliferation,apoptosis,autophagy,immune response,migration,and angiogenesis.As confirmed in pancreatic,gastric,and liver cancer,its most commonly noted molecular effects include nuclear factor kappa B and B-cell lymphoma 2 downregulation,as well as Bcl-2-associated X protein upregulation.Moreover,it has been found to induce the Akt kinase and Forkhead box O1 axis,activate the AMP-activated protein kinase pathway,elevate interleukin-2 and peroxisome proliferator-activated receptor-γlevels,reduce interleukin-10,as well as downregulate matrix metalloproteinase-9,Twist family bHLH transcription factor 1,and cyclooxygenase-2.It also inhibits Myc–HIF1αinteraction and programmed death ligand 1 transcription by interrupting the Ras/RAF/MEK/ERK pathway and mTOR/P70S6K/4EBP1 signaling.Future research should aim to unravel the link between Britanin and acetylcholinesterase,mast cells,osteolysis,and ischemia,as compelling data have been provided by studies outside the gastrointestinal context.Since the cytotoxicity of Britanin on noncancerous cells is significantly lower than that on tumor cells,while still being effective against the latter,further in-depth studies with the use of animal models are merited.The compound exhibits pleiotropic biological activity and offers considerable promise as an anti-cancer agent,which may address the current paucity of treatment options and high mortality rate among patients with gastrointestinal tumors.展开更多
The communication system known as quorum sensing (QS) in gram-negative bacteria regulates biofilm formation and many other functions. The particularity of Pseudoalteromonas ulvae TC14 seems to be the absence of a LuxI...The communication system known as quorum sensing (QS) in gram-negative bacteria regulates biofilm formation and many other functions. The particularity of Pseudoalteromonas ulvae TC14 seems to be the absence of a LuxI inducer, and therefore the lack of production of small molecules of Acyl homoserine lactone (AHL). Previous studies had shown that it does not harbor the inducer of the regulatory molecule (AHL). Nevertheless, it is able to regulate these same functions (biofilm, violacein) via AHLs. This could mean the presence of specific receptors for these induction molecules, belonging to the LuxR family. The aim of this study was to test these hypotheses using molecular analysis. Genome sequencing of the P. ulvae TC14 strain was carried out by Molecular Research LP (MR DNA), using the Illumina Hiseq 2500 method. The results revealed the presence of 2,293,242 base pairs, i.e. 100% of the genomic volume. The number of coding gene sequences was 1983, and the Guanine + Cytosine (G+C) percentage of the base number was 41.55%, revealing stability in the sequenced genome. In order to verify the identity of the sequenced genome, a phylogenetic analysis based on RNA16S was carried out. This analysis resulted in 93% homology with the previously sequenced and characterized species Pseudoalteromonas tunicata, showing that it belongs to the genus Pseudoalteromonas. To these comparative results should be added those derived from genome analysis based on nucleotide percentage using the tools available at https://img.jgi.doe.gov/. The results showed that Pseudoalteromonas tunicata D2 has the highest percentage nucleotide identity (ANI) (75.7913%), followed by Pseudoalteromonas flavipulchra NCIMB2033 (72.2736%) and Pseudoalteromonas phenolica KCTC 12086 (71.6685%). Next, the search for the various genes involved in QS was carried out using sequence comparisons via the BLAST method. For LuxI, sequence templates from the genomes of Vibrio, Chromobacterium, Shewanella or even other Pseudoalteromonas species were screened against the TC14 genome. This yielded no conclusive results synonymous with the non-presence of LuxI in TC14 as assumed by previous research. The search for LuxR, on the other hand, gave rise to the presence of eight presumptive sequences. Molecular characterization of the presumptive LuxR sequences was carried out to assess their gene expression. This characterization showed expression of these LuxR homologous sequences in a range from o.11 to 5.33 picograms (pg). Even if these sequences were not analyzed in depth, the retro-transcription technique nevertheless showed a minimum of activity, which could enable us to distinguish them from inactive sequences. The next step was to compare the LuxRs found in TC14 with the so-called Solo LuxRs, which act autonomously. This study shows that P. ulvae TC14 is a bacterium with a particular LuxR-based communication system.展开更多
A chemical investigation of the aerial parts ofArtemisia vestita Wall. led to the isolation of 12 known sesquiterpenes, including 2 furan-containing sesquiterpenoids and 10 eudesmane sesquiterpene lactones. Their stru...A chemical investigation of the aerial parts ofArtemisia vestita Wall. led to the isolation of 12 known sesquiterpenes, including 2 furan-containing sesquiterpenoids and 10 eudesmane sesquiterpene lactones. Their structures were identified as negunfurol （1）, schensianol A （2）, artemine （3）, erivanin （4）, 1,5-diepi-artemin （5）, acetylartemin （6）, naphtho[1,2-b]furan-2（3H）-one, 6-（acetyloxy） decahydro-9a-hydroxy-3,Sa-dimethyl-9-methylene-（3S,3aS,5aS,6S,9aS, ghS） （7）, naphtho[1,2-b]furan-2（3H）-one, 6-（acetyloxy）- 3a,4,5,5a,6,7,8,9b-octahydro-8-hydroxy-3,Sa,9-trimethyl- （3S,3aS, SaR,6S, SS,9bS） （8）, isoerivanin （9）, harrelierin （10）, （11S）-1- oxoeudesm-4（14）-eno-13,6a-lactone （11）, 1-epi-dehydroisoeranin （12）, respectively. All of these compounds were isolated from Artemisia vestita for the first time, and compounds 1 and 2 were isolated from the genus Artemisia for the first time.展开更多
[Objective]The relationship between signal molecule N-acety-homoserine lactones（AHLs） and Microcystis aeruginosa cell apoptosis was studied.[Method]With M.aeruginosa as the test materials treated by 5 μmol/L N-acet...[Objective]The relationship between signal molecule N-acety-homoserine lactones（AHLs） and Microcystis aeruginosa cell apoptosis was studied.[Method]With M.aeruginosa as the test materials treated by 5 μmol/L N-acety-homoserine lactones（AHLs）,the morphology of cell apoptosis was observed through staining with DAPI.[Result]Microcystis aeruginosa cell apoptosis was induced by signal molecule N-acetyhomoserine lactones（AHLs） with the concentration of 1 μmol/L to inhibit the growth and proliferation of Microcystis aeruginosa.[Conclusion] The results provided the important scientific basis and new management ideas for the treatment of water bloom of Microcystis aeruginosa.展开更多
The ginkgo terpenoids including bilobalide and ginkgolides are the main pharmaceutical components in the leaves or extracts of Ginkgo biloba L. In this paper, the analysis of bilobalide and ginkgolides in leaves of Gi...The ginkgo terpenoids including bilobalide and ginkgolides are the main pharmaceutical components in the leaves or extracts of Ginkgo biloba L. In this paper, the analysis of bilobalide and ginkgolides in leaves of Ginkgo biloba L. by high performance liquid chromatography (HPLC)-electrospray ionization (ESI)-mass spectrometry (MS) was carried out. The separation was performed on Inertsil ODS3 column with methanol-water (36:64) as mobile phase, with 1 mL·min -1 of flow rate at 35℃. Then the mass spectrum analysis was conducted by ZMD micromass electrospray ionization (ESI)-mass spectrometer (MS). The HPLC total ion chromatogram and selected ion chromatogram (with 325, 407, 423, 439 of m/z) of the sample and ESI-/MS mass spectra of the peaks in the chromatograms were obtained. So bilobalide, ginkgolide A, B, C and J in Ginkgo biloba L. leaves were identified. The method is easy and rapid, with a good accuracy.展开更多
文摘（-）-Tetrahydrolipstatin 1 was synthesized in three steps and 33.8% overall yield from aldehyde 6 by tandem Mukaiyama-aldol lactonization, which offered a concise, efficient and highly diastereoselective route to this antiobesity drug. We also presented a resolution method for preparation of the crucial intermediate, β- （t-butyldimethylsilyloxy）tetradecanal.
基金supported by the National Fund of Science,Technology and Innovation (FONACIT) (Grant N°201300288)within the framework of the project PCP France-Venezuelaby the CDCHTA-ULA (Grant N°C-1935-15-08-ED).
文摘From aerial parts of Austroeupatorium inulifolium was isolated the ent-nor-furano triol labdane austroeupatol 1.The compound 1 was treated with IBX showing an unexpected selectivity at the potentially oxidizable sites of the sub-strate yielding the 2-oxoaustroeupatol(2)and 2,19-dioxoaustroeupatol(3).The treatment of 2 with sodium periodate yields a heterocyclic derivative(ε-caprolactone derivate 4)formed by oxidative cleavage and unexpected intramo-lecular attack of the hydroxymethylene(C-19)oxygen to the ketonic carbon(C-2).A plausible mechanistic pathway for the obtention of compound 4 is proposed.
文摘?-Phenyl－4－aroylfuran－3－carboxylic acids were reduced in aqueous alkaline solutions ofNaBH4 to afford hydroxy acids in excellent yields． Under the catalysis of boron trifluoride etherate，the hydroxy acids were converted to lactones smoothly．
文摘Herein, we report a novel synthesis of 1,3-oxazin-6-ones from enamides with CO2 through C--H carboxylation and one-pot cyclization. This transition-metal-free and redox-neutral process features broad substrate scope, good functional group tolerance and facile product derivatization. The nucleophilic attack to CO2 from the electron-rich alkene is demonstrated for this reaction.
基金supported by the National Natural Science Foundation of China(21502086)the Natural Science Foundation of Fujian Province(2019J01744)+1 种基金the Key Project of Foundation of Fujian Province(2020J02044)the Natural Science Foundation of Zhangzhou City(ZZ2021J13)。
文摘Direct functionalization of inert C(sp^(3))–H bonds in pharmaceutically significant compounds is very important in modern synthetic organic chemistry.In this article,we disclose a practical and efficient method for the oxidative lactonization of benzylic C(sp^(3))–H bonds enabled by the synergistic interactions of organic dye-type rose bengal,n-Bu_(4)N∙Br,O_(2) and Na_(2)HPO_(4) under visible light irradiation.This reaction does not require transition metal catalysts or strong oxidants.A range of structurally diverse phthalides has been synthesized with excellent selectivity and high functional group compatibility.The late-stage application of this reaction to the preparation of structurally complex phthalides demonstrates its synthetic utility.
基金supported by the National Natural Science Foundation of China(No.52270119).
文摘The inhibitory effects of zinc oxide nanoparticles(ZnO NPs)and impacts of N-acylhomoserine lactone(AHL)-based quorum sensing(QS)on biological nitrogen removal(BNR)performance have beenwell-investigated.However,the effects of ammonia nitrogen(NH_(4)^(+)-N)concentrations on NP toxicity and AHL regulation have seldom been addressed yet.This study consulted on the impacts of ZnO NPs on BNR systems when high NH_(4)^(+)-N concentrationwas available.The synergistic toxic effects of high-strength NH_(4)^(+)-N(200 mg/L)and ZnO NPs resulted in decreased ammonia oxidation rates and dropped the nitrogen removal efficiencies by 17.5%±0.2%.The increased extracellular polymeric substances(EPS)production was observed in response to the high NH_(4)^(+)-N and ZnO NP stress,which indicated the defensemechanism against the toxic effects in the BNR systemswas stimulated.Furthermore,the regulatory effects of exogenous N-decanoyl-homoserine lactone(C_(10)-HSL)-mediated QS system on NP-stressed BNR systems were revealed to improve the BNR performance under different NH_(4)^(+)-N concentrations.The C_(10)-HSL regulated the intracellular reactive oxygen species levels,denitrification functional enzyme activities,and antioxidant enzyme activities,respectively.This probably synergistically enhanced the defense mechanism against NP toxicity.However,compared to the low NH_(4)^(+)-N concentration of 60 mg/L,the efficacy of C_(10)-HSL was inhibited at high NH_(4)^(+)-N levels of 200 mg/L.The findings provided the significant application potential of QS system for BNR when facing toxic compound shock threats.
文摘Direct converting carbon dioxide(CO_(2))and propane(C_(3)H_(8))into aromatics with high carbon utilization offers a desirable opportunity to simultaneously mitigate CO_(2)emission and adequately utilize C_(3)H_(8) in shale gas.Owing to their thermodynamic resistance,converting CO_(2)and C_(3)H_(8) respectively remains difficult.Here,we achieve 60.2%aromatics selectivity and 48.8%propane conversion over H-ZSM-5-25 via a zeolite-catalyzing the coupling of CO_(2)and C_(3)H_(8).Operando dual-beam FTIR spectroscopy combined with ^(13)C-labeled CO_(2)tracing experiments revealed that CO_(2)is directly involved in the generation of aromatics,with its carbon atoms selectively embedded into the aromatic ring,bypassing the reverse water-gas shift pathway.Accordingly,a cooperative aromatization mechanism is proposed.Thereinto,lactones,produced from CO_(2)and olefins,are proven to be the key intermediate.This work not only provides an opportunity for simultaneous conversion of CO_(2)and C_(3)H_(8),but also expends coupling strategy designing of CO_(2)and alkanes over acidic zeolites.
基金financially supported by the Open Project of Sanya Science and Education Innovation Park of Wuhan University of Technology(No.2022KF0005)Researchers Supporting Project(No.RSP-2024-R20)King Saud University,Riyadh,Saudi Arabia.
文摘As a recently emerging wastewater treatment technology,Algal-bacterial granular sludge(ABGS)process shows significant advantages.However,current research on the ABGS system is a lack of a clear and complete understanding of the potential mechanism of signal molecules on the growth of ABGS.This study comprehensively explores the variations in the ABGS under different N-acyl-homoserine lactone(AHL)conditions by constructing three sequencing batch reactor(SBR)systems.The results indicate that N-hexanoyl-l-homoserine lactone(C6-HSL)accelerates the granulation process in the early stages by promoting the loosely bound extracellular polymeric substances(LB-EPS)secretion and filamentous bacteria growth,thereby shortening required time for initial granule formation.On the other hand,N-(3-oxodecanoyl)-l-homoserine lactone(3-oxo-C12-HSL)expedites the granulation process by promoting the tightly bound extracellular polymeric substances(TB-EPS)and aromatic protein secretion,benefiting structural stability and nitrogen and phosphorus removal efficiency of mature ABGS.
文摘Traumatic axonal lesions of peripheral nerves disrupt neuronal connections with their targets,resulting in the loss of motor and sensory functions.Despite the peripheral nervous system’s capacity for axonal regrowth,this may lead to permanent impairements resulting in a loss of quality of life and a high socioeconomic burden.
基金supported by the National Natural Science Foundation of China (Nos.51938001 and 52300073)。
文摘Quorum quenching (QQ)-based strategies are efficient for biofouling control.However,the feasibility of using QQ bacteria in antibiotic-stressed membrane bioreactors (MBRs) remains unknown.In this study,we isolated three novel QQ strains (Bacillus sp.QX01 and QX03,Delftia sp.QX14) from the activated sludge of an actual MBR.They can degrade 11 N-acylhomoserine lactones (AHLs) with high efficiencies and rates through intracellular QQ pathways involving putative acylases and lactonases.Running two lab-scale MBRs,we found that introducing antibiotics (sulfamethoxazole,azithromycin,and ciprofloxacin,each at100μg/L) shortened the fouling cycle by 71.4%.However,the immobilized inoculation of QX01 into one MBR extended the fouling cycle by 1.5-2.0 times.Quantitative detection revealed that QX01 significantly reduced the concentrations of two AHLs (C4-HSL and C8-HSL),which were positively correlated with the contents of extracellular polymeric substances(EPS)(Pearson’s r=0.62-0.83,P<0.01).This suggests that QX01 could perform its QQ activity robustly under antibiotic stress,thereby inhibiting EPS production (proteins especially) and biofilm formation.Moreover,QX01 notably altered the succession patterns of both sludge and fouling communities,with more pronounced effects on abundant taxa.Genera associated with AHL synthesis and EPS production,such as Terrimonas and Rhodobacter,were significantly depleted,contributing to the mitigated biofouling.Additionally,QX01 increased the bacterial community diversity (evenness especially),which was inhibited by antibiotics.Overall,we demonstrate that the novel QQ bacteria could be effective for biofouling control in antibiotic-stressed MBRs,though future work is needed to develop practical approaches for prolonging QQ activity.
基金National Natural Science Foundation of China(Nos.22001177,22203023)Guangdong Pearl River Talent Program(no.2021QN020268)+3 种基金the Natural Science Foundation of Guangdong Province(Nos.2024A1515012381,2022A1515011859)Shenzhen Bay Laboratory Startup Fund(No.S201100003)Major Program of Shenzhen Bay Laboratory(No.S211101001-4)Shenzhen Bay Qihang Fellow Program(No.QH23001)for generous financial support.
文摘Chiral aryl cyclohex-3-en ether scaffold is widely present in bioactive natural products and drugs.The exploitation of efficient and enantioselective methods for the construction of aryl cyclohex-3-en ether scaffold is significant.Herein we disclose a chiral N,N’-dioxide/Lewis acid complex-catalyzed asymmetric inverse-electron-demand Diels-Alder(IEDDA)reaction using electron-deficient 3-carboalkoxyl-2-pyrones and less electron-enriched aryl enol ethers as reactants.A wide range of non-and 1,2-disubstituted acyclic aryl enol ethers are applicable to deliver diverse chiral bridged bicyclic lactones in high yields and stereoselectivities(up to 96%yield,>20:1 dr,97:3 er).The bridged bicyclic lactone core can be easily converted into chiral aryl cyclohex-3-en ether scaffold.Notably,DFT calculations revealed a stepwise and endo mechanism to explain the high enantioselectivity controlled by the cooperative effect of the steric factors and the dispersion interactions between ligands and enol ethers.
基金We thank the National Key Research and Development Program of China(2021YFF0701700)the National Natural Science Foundation of China(21971252,21991122,22271181)the Science and Technology Commission of Shanghai Municipality(22ZR1423600)for financial support.
文摘Due to its unique electronic properties,the difluoromethylene group(CF2)has served as a valuable unity in the design of biologically active molecules.Sinceγ-lactones display a broad range of biological properties,α,α-difluoro-γ-lactones may exhibit unexpected biological activities,and thus their synthesis has received increasing attention.Traditional synthetic methods suffer from tedious multi-step processes,and very few effective methods have been reported recently.Herein,we describe the difunctionalization of alkenes with BrCF_(2)CO_(2)K under photoredox catalysis with the use of a boron-Lewis acid for the access toα,α-difluoro-γ-lactones.In this transformation,the alkene substrates and the used reagents,including BrCF_(2)CO_(2)K and the boron-Lewis acid,PhB(OH)2 or BF3·THF,are cheap and widely available.High efficiency and atom economy may make this protocol attractive.
基金supported by the National Natural Science Foundation of China(Nos.82060631 and 32270413)the Science and Technology Department of Guizhou Province[Nos.QKH JC(2020)1Z076 and QKH JC(2020)1Y400],the Cultivation Project of National Natural Science Foundation of Guizhou Medical University(No.2023-106)+2 种基金the Outstanding Young Scientific and Technological Talents in Guizhou Province[No.QKH PTRC(2021)5633],High-level Innovative Talents in Guizhou Province(Thousand Levels of Talent for YUAN Chunmao in 2018)“Light of the West”Talent Cultivation Program of Chinese Academy of Sciences for YUAN Chunmao[RZ(2020)82],Guizhou Science and Technology Innovation Talent Team(No.QKHPTRCCXTD[2022]007)the Natural Science Foundation of Guizhou Province[No.QKHZYD(2022)4015].
文摘Four new sesquiterpene lactones(SLs)(1–4),along with a biosynthetically related SL(5),have been isolated from the leaves of Magnolia grandiflora.Magrandate A(1)is notable as the first C18 homogemarane type SL,featuring a unique 1,7-dioxaspiro[4.4]nonan-6-one core.Compounds 2 and 3,representing the first instances of chlorine-substituted gemarane-type SL analogs in natural products,were also identified.The structures of these isolates were elucidated through a combination of spectroscopic data analysis,electronic circular dichroism calculations,and X-ray single-crystal diffraction analysis.All isolates demonstrated anti-inflammatory activity in lipopolysaccharide-stimulated RAW264.7 cells.Notably,3–5 showed a significant inhibitory effect on nitric oxide production,with IC50 values ranging from 0.79 to 4.73μmol·L^(−1).Additionally,4 and 5 exhibited moderate cytotoxic activities against three cancer cell lines,with IC50 values between 3.09 and 11.23μmol·L^(−1).
文摘Nine new germacranolides,sylvaticalides A−H(1-9),and three known analogues(10-12)were isolated from the aeri-al part of Vernonia sylvatica.Their structures were established using comprehensive spectroscopic analysis,including high-resolution electrospray ionization mass spectroscopy(HR-ESI-MS)and 1D and 2D nuclear magnetic resonance(NMR)spectra.Their absolute configurations were determined by X-ray diffraction experiments.The anti-inflammatory activities of all isolated compounds were as-sessed by evaluating their inhibitory effects on the nuclear factor kappa B(NF-κB)pathway,which was activated by lipopolysacchar-ide(LPS)-stimulated human THP1-Dual cells,and the interferon-stimulated gene(ISG)pathway,activated by STING agonist MSA-2 in the same cell model.Compounds 1,2 and 6 showed inhibitory effects on the NF-κB and ISG signaling pathways,with IC_(50)values ranging from 4.12 to 10.57μmol·L^(−1).
文摘Britanin is a bioactive sesquiterpene lactone known for its potent anti-inflammatory and anti-oxidant properties.It also exhibits significant anti-tumor activity,suppressing tumor growth in vitro and in vivo.The current body of research on Britanin includes thirty papers predominantly related to neoplasms,the majority of which are gastrointestinal tumors that have not been summarized before.To drive academic debate,the present paper reviews the available research on Britanin in gastrointestinal tumors.It also outlines novel research directions using data not directly concerned with the digestive system,but which could be adopted in future gastrointestinal research.Britanin was found to counteract liver,colorectal,pancreatic,and gastric tumors,by regulating proliferation,apoptosis,autophagy,immune response,migration,and angiogenesis.As confirmed in pancreatic,gastric,and liver cancer,its most commonly noted molecular effects include nuclear factor kappa B and B-cell lymphoma 2 downregulation,as well as Bcl-2-associated X protein upregulation.Moreover,it has been found to induce the Akt kinase and Forkhead box O1 axis,activate the AMP-activated protein kinase pathway,elevate interleukin-2 and peroxisome proliferator-activated receptor-γlevels,reduce interleukin-10,as well as downregulate matrix metalloproteinase-9,Twist family bHLH transcription factor 1,and cyclooxygenase-2.It also inhibits Myc–HIF1αinteraction and programmed death ligand 1 transcription by interrupting the Ras/RAF/MEK/ERK pathway and mTOR/P70S6K/4EBP1 signaling.Future research should aim to unravel the link between Britanin and acetylcholinesterase,mast cells,osteolysis,and ischemia,as compelling data have been provided by studies outside the gastrointestinal context.Since the cytotoxicity of Britanin on noncancerous cells is significantly lower than that on tumor cells,while still being effective against the latter,further in-depth studies with the use of animal models are merited.The compound exhibits pleiotropic biological activity and offers considerable promise as an anti-cancer agent,which may address the current paucity of treatment options and high mortality rate among patients with gastrointestinal tumors.
文摘The communication system known as quorum sensing (QS) in gram-negative bacteria regulates biofilm formation and many other functions. The particularity of Pseudoalteromonas ulvae TC14 seems to be the absence of a LuxI inducer, and therefore the lack of production of small molecules of Acyl homoserine lactone (AHL). Previous studies had shown that it does not harbor the inducer of the regulatory molecule (AHL). Nevertheless, it is able to regulate these same functions (biofilm, violacein) via AHLs. This could mean the presence of specific receptors for these induction molecules, belonging to the LuxR family. The aim of this study was to test these hypotheses using molecular analysis. Genome sequencing of the P. ulvae TC14 strain was carried out by Molecular Research LP (MR DNA), using the Illumina Hiseq 2500 method. The results revealed the presence of 2,293,242 base pairs, i.e. 100% of the genomic volume. The number of coding gene sequences was 1983, and the Guanine + Cytosine (G+C) percentage of the base number was 41.55%, revealing stability in the sequenced genome. In order to verify the identity of the sequenced genome, a phylogenetic analysis based on RNA16S was carried out. This analysis resulted in 93% homology with the previously sequenced and characterized species Pseudoalteromonas tunicata, showing that it belongs to the genus Pseudoalteromonas. To these comparative results should be added those derived from genome analysis based on nucleotide percentage using the tools available at https://img.jgi.doe.gov/. The results showed that Pseudoalteromonas tunicata D2 has the highest percentage nucleotide identity (ANI) (75.7913%), followed by Pseudoalteromonas flavipulchra NCIMB2033 (72.2736%) and Pseudoalteromonas phenolica KCTC 12086 (71.6685%). Next, the search for the various genes involved in QS was carried out using sequence comparisons via the BLAST method. For LuxI, sequence templates from the genomes of Vibrio, Chromobacterium, Shewanella or even other Pseudoalteromonas species were screened against the TC14 genome. This yielded no conclusive results synonymous with the non-presence of LuxI in TC14 as assumed by previous research. The search for LuxR, on the other hand, gave rise to the presence of eight presumptive sequences. Molecular characterization of the presumptive LuxR sequences was carried out to assess their gene expression. This characterization showed expression of these LuxR homologous sequences in a range from o.11 to 5.33 picograms (pg). Even if these sequences were not analyzed in depth, the retro-transcription technique nevertheless showed a minimum of activity, which could enable us to distinguish them from inactive sequences. The next step was to compare the LuxRs found in TC14 with the so-called Solo LuxRs, which act autonomously. This study shows that P. ulvae TC14 is a bacterium with a particular LuxR-based communication system.
基金National Natural Science Foundation of China(Grant No.30973629)National Key Technology R&D Program "New Drug Innovation" of China(Grant No.2012ZX09301002-002-002,2012ZX09304-005)
文摘A chemical investigation of the aerial parts ofArtemisia vestita Wall. led to the isolation of 12 known sesquiterpenes, including 2 furan-containing sesquiterpenoids and 10 eudesmane sesquiterpene lactones. Their structures were identified as negunfurol （1）, schensianol A （2）, artemine （3）, erivanin （4）, 1,5-diepi-artemin （5）, acetylartemin （6）, naphtho[1,2-b]furan-2（3H）-one, 6-（acetyloxy） decahydro-9a-hydroxy-3,Sa-dimethyl-9-methylene-（3S,3aS,5aS,6S,9aS, ghS） （7）, naphtho[1,2-b]furan-2（3H）-one, 6-（acetyloxy）- 3a,4,5,5a,6,7,8,9b-octahydro-8-hydroxy-3,Sa,9-trimethyl- （3S,3aS, SaR,6S, SS,9bS） （8）, isoerivanin （9）, harrelierin （10）, （11S）-1- oxoeudesm-4（14）-eno-13,6a-lactone （11）, 1-epi-dehydroisoeranin （12）, respectively. All of these compounds were isolated from Artemisia vestita for the first time, and compounds 1 and 2 were isolated from the genus Artemisia for the first time.
基金Supported by National Natural Science Fund(30960036)Key Schoollevel Project of Kunming University(20091016)~~
文摘[Objective]The relationship between signal molecule N-acety-homoserine lactones（AHLs） and Microcystis aeruginosa cell apoptosis was studied.[Method]With M.aeruginosa as the test materials treated by 5 μmol/L N-acety-homoserine lactones（AHLs）,the morphology of cell apoptosis was observed through staining with DAPI.[Result]Microcystis aeruginosa cell apoptosis was induced by signal molecule N-acetyhomoserine lactones（AHLs） with the concentration of 1 μmol/L to inhibit the growth and proliferation of Microcystis aeruginosa.[Conclusion] The results provided the important scientific basis and new management ideas for the treatment of water bloom of Microcystis aeruginosa.
文摘The ginkgo terpenoids including bilobalide and ginkgolides are the main pharmaceutical components in the leaves or extracts of Ginkgo biloba L. In this paper, the analysis of bilobalide and ginkgolides in leaves of Ginkgo biloba L. by high performance liquid chromatography (HPLC)-electrospray ionization (ESI)-mass spectrometry (MS) was carried out. The separation was performed on Inertsil ODS3 column with methanol-water (36:64) as mobile phase, with 1 mL·min -1 of flow rate at 35℃. Then the mass spectrum analysis was conducted by ZMD micromass electrospray ionization (ESI)-mass spectrometer (MS). The HPLC total ion chromatogram and selected ion chromatogram (with 325, 407, 423, 439 of m/z) of the sample and ESI-/MS mass spectra of the peaks in the chromatograms were obtained. So bilobalide, ginkgolide A, B, C and J in Ginkgo biloba L. leaves were identified. The method is easy and rapid, with a good accuracy.
