RESUMO
Four new prenylated acetophenone derivatives, including one acetophenone dimer [acronyrone D (1)] and three acetophenone monomers [acronyrones E-G (2-4)], along with seven known analogues (5-11) were obtained from the leaves of Acronychia pedunculata. Their structures and absolute configurations were established by analysis of HRMS and NMR data, single crystal X-ray diffraction studies and quantum chemical calculations. In addition, the isolates were tested for their anti-proliferative acivity against HCT-116, RKO and SW480 cancer cell lines. Remarkably, compound 5 exhibited significant anti-proliferative effects on the three cell lines, with IC50 values ranging from 0.24 to 5.3 µM.
RESUMO
Four pairs of cinnamoyl-ß-triketone derivative enantiomers, (+)- and (-)-xanthostones A-D ((+)- and (-)-1-4), were isolated from Xanthostemon chrysanthus. Compounds 1 and 2 feature a new rearranged cinnamoyl-phloroglucinol scaffold fused with a cinnamyl-ß-triketone framework. Compounds 1, 3, and 4 are the first examples of natural products with a peculiar phenethyl-pyranone acid unit. Their structures with absolute configurations were determined by spectroscopic data, X-ray diffraction analysis and electronic circular dichroism (ECD) calculation. Interestingly, these novel compounds showed a tautomeric behavior in solution, which was revealed by NMR spectroscopy and density functional theory calculation. A plausible biosynthetic pathway toward xanthostones A-D was proposed. Additionally, the anti-inflammatory and antibacterial activities of xanthostones A-D were evaluated.
Assuntos
Myrtaceae , Anti-Inflamatórios , Dicroísmo Circular , Estrutura Molecular , Myrtaceae/química , Floroglucinol/química , EstereoisomerismoRESUMO
Two novel monoterpenoid indole alkaloids (MIAs), gelsechizines A-B (1-2), along with four known ones (3-6) were isolated from the fruits of Gelsemium elegans. Compound 1 features a new carbon skeleton with two additional carbon atoms forming a 4-methylpyridine unit. Their structures with absolute configurations were elucidated by NMR, MS, X-ray diffraction and electronic circular dichroism (ECD) calculations. Compounds 1-3 showed significant anti-inflammatory effects in vivo and in vitro, which may be related to the inhibition of the trecruitment of neutrophils and macrophages as well as the secretion of TNF-α and IL-6. Preliminary structure-activity relationship analysis revealed that the ß-N-acrylate moiety plays an important role in the anti-inflammatory effect.
Assuntos
Anti-Inflamatórios/farmacologia , Gelsemium/química , Macrófagos/efeitos dos fármacos , Alcaloides de Triptamina e Secologanina/química , Animais , Animais Geneticamente Modificados/crescimento & desenvolvimento , Animais Geneticamente Modificados/metabolismo , Anti-Inflamatórios/química , Anti-Inflamatórios/isolamento & purificação , Frutas/química , Frutas/metabolismo , Gelsemium/metabolismo , Interleucina-6/metabolismo , Larva/efeitos dos fármacos , Larva/crescimento & desenvolvimento , Larva/metabolismo , Lipopolissacarídeos/farmacologia , Macrófagos/citologia , Macrófagos/metabolismo , Espectroscopia de Ressonância Magnética , Camundongos , Conformação Molecular , Neutrófilos/citologia , Neutrófilos/patologia , Células RAW 264.7 , Alcaloides de Triptamina e Secologanina/isolamento & purificação , Alcaloides de Triptamina e Secologanina/farmacologia , Relação Estrutura-Atividade , Fator de Necrose Tumoral alfa/metabolismo , Peixe-Zebra/crescimento & desenvolvimento , Peixe-Zebra/metabolismoRESUMO
Leptosparones A-F (1-6), six new dimeric acylphloroglucinol derivatives with unprecedented skeletons, were isolated from Leptospermum scoparium. Compounds 1-3 and 5-6 are phenylpropanoyl-phloroglucinol dimers, while 4 is a phenylpropanoylphloroglucinol-isovalerylphloroglucinol hybrid. Structurally, these compounds represent the first examples of dimeric phloroglucinols with unprecedented C(7')-C(8) linkage between the phloroglucinol core and the acyl side chain. Their structures were elucidated by comprehensive analyses of spectroscopic data, single crystal X-ray diffraction and chemical calculations. In addition, all compounds showed inhibitory effects against α-glucosidase with IC50 values ranging from 39.5 to 186.8â µM.
Assuntos
Inibidores de Glicosídeo Hidrolases/farmacologia , Leptospermum/química , Floroglucinol/farmacologia , alfa-Glucosidases/metabolismo , Cristalografia por Raios X , Relação Dose-Resposta a Droga , Inibidores de Glicosídeo Hidrolases/síntese química , Inibidores de Glicosídeo Hidrolases/química , Humanos , Modelos Moleculares , Estrutura Molecular , Floroglucinol/síntese química , Floroglucinol/químicaRESUMO
Three rearranged triketone-terpene adducts, myrcaulones A-C (1-3), were isolated from the leaves of Myrciaria cauliflora. Myrcaulones A (1) and B (2) feature a new carbon skeleton with an unprecedented spiro[bicyclo[3.1.1]heptane-2,2'-cyclopenta[b]pyran] core. Myrcaulone C (3) possesses an unusual cyclobuta[6,7]cyclonona[1,2-b]cyclopenta[e]pyran backbone. Their structures with absolute configurations were elucidated by NMR spectroscopy, X-ray diffraction, and electronic circular dichroism calculations. A plausible biogenetic pathway for myrcaulones A-C involving the rearrangement of a triketone unit is also proposed. In addition, myrcaulones A (1) and B (2) exhibited inhibitory effects against tumor necrosis factor-α and nitric oxide generation induced by lipopolysaccharide in RAW 264.7 macrophages.
Assuntos
Cetonas/química , Myrtaceae/química , Terpenos/química , Folhas de Planta/química , Análise Espectral/métodosRESUMO
(+)- and (-)-Xanchryones F and G ((+)- and (-)-1 and 2) were isolated from the plant Xanthostemon chrysanthus by chiral separation. Compounds 1 and 2 featured a new carbon skeleton with cinnamoyltriketone-flavone adducts. Their structures with absolute configurations were elucidated by detailed spectroscopic analyses and chemical calculations. The antibacterial and anti-inflammatory activities of (+)- and (-)-1 and 2 were evaluated.
Assuntos
Antibacterianos/farmacologia , Anti-Inflamatórios/farmacologia , Cinamatos/farmacologia , Bactérias Gram-Negativas/efeitos dos fármacos , Bactérias Gram-Positivas/efeitos dos fármacos , Compostos Heterocíclicos com 2 Anéis/farmacologia , Inflamação/tratamento farmacológico , Myrtaceae/química , Animais , Antibacterianos/química , Antibacterianos/isolamento & purificação , Anti-Inflamatórios/química , Anti-Inflamatórios/isolamento & purificação , Cinamatos/química , Cinamatos/isolamento & purificação , Compostos Heterocíclicos com 2 Anéis/química , Compostos Heterocíclicos com 2 Anéis/isolamento & purificação , Lipopolissacarídeos/antagonistas & inibidores , Lipopolissacarídeos/farmacologia , Macrófagos/efeitos dos fármacos , Macrófagos/metabolismo , Camundongos , Testes de Sensibilidade Microbiana , Conformação Molecular , Óxido Nítrico/antagonistas & inibidores , Óxido Nítrico/biossíntese , Células RAW 264.7 , EstereoisomerismoRESUMO
Myrtucomvalones D-F, three new triketone-phloroglucinol-triketone adducts, and three known ones (myrtucommulone E, myrtucommulone D and callistenone D) were obtained from Myrtus communis 'Variegata'. Myrtucomvalone D is a pair of enantiomers which was further resolved into (+)-myrtucomvalone D and (-)-myrtucomvalone D by chiral HPLC. Their structures and complete stereochemistry were established from interpretation of NMR and crystallographic data and chemical calculations. Myrtucomvalone F, myrtucommulone D and callistenone D showed significant antibacterial activities.
Assuntos
Antibacterianos/farmacologia , Myrtus/química , Floroglucinol/farmacologia , Bactérias/efeitos dos fármacos , Cromatografia Líquida de Alta Pressão , Testes de Sensibilidade Microbiana , Floroglucinol/química , Folhas de Planta/química , Análise Espectral/métodosRESUMO
Myrtucyclitones A-C ((+)- and (-)-1-3), three pairs of new triketone-phloroglucinol-triketone hybrids were isolated from the plant Myrtus communis. Their structures with absolute configurations were established by NMR analysis and chemical calculations. Myrtucyclitones B and C exhibited remarkable antibacterial effect.
Assuntos
Antibacterianos/química , Cetonas/química , Myrtus/química , Floroglucinol/química , Antibacterianos/isolamento & purificação , Antibacterianos/farmacologia , Dicroísmo Circular , Bactérias Gram-Negativas/efeitos dos fármacos , Bactérias Gram-Positivas/efeitos dos fármacos , Espectroscopia de Ressonância Magnética , Testes de Sensibilidade Microbiana , Conformação Molecular , Myrtus/metabolismo , Folhas de Planta/química , Folhas de Planta/metabolismo , Caules de Planta/química , Caules de Planta/metabolismoRESUMO
Three pairs of dimeric phenylpropanoyl-phloroglucinol enantiomers, (+)- and (-)-xanthchrysones A-C [(+)- and (-)-1-3], as well as their postulated biosynthetic precursors, were isolated and identified from the leaves of Xanthostemon chrysanthus. Compound 1 featured an unprecedented bis-phenylpropanoyl-benzo[b]cyclopent[e] oxepine tricyclic backbone. Compounds 2 and 3 represent the first examples of 1-(cyclopentylmethyl)-3-(3-phenylpropanoyl)benzene scaffold. The structures and absolute configurations of 1-3 were determined by spectroscopic and X-ray diffraction analysis as well as electronic circular dichroism (ECD) calculation. Both (+)-2 and (-)-2 showed moderate antibacterial activities including several multidrug-resistant strains.
Assuntos
Myrtaceae/química , Fenilpropionatos/química , Floroglucinol/química , Dimerização , Modelos Moleculares , Estrutura Molecular , EstereoisomerismoRESUMO
Five monoterpenoid bisindole alkaloids with new carbon skeletons, gelsecorydines A-E (1-5), together with their biogenetic precursors were isolated from the fruits of Gelsemium elegans. Compounds 1-5 represent the first examples of heterodimeric frameworks composed of a gelsedine-type alkaloid and a modified corynanthe-type one. Notably, compound 2 featured an unprecedented caged skeleton with a 6/5/7/6/5/6 heterohexacyclic ring system, which possessed a pyridine ring that linked the two monomers. Their structures and absolute configurations were elucidated by spectroscopic analysis, X-ray diffraction, and electronic circular dichroism (ECD) calculation. A plausible biosynthetic pathway for compounds 1-5 is proposed. Compounds 1, 3, 4, and 5 exhibited a significant inhibitory effect against nitric oxide (NO) production in macrophages.
Assuntos
Alcaloides/química , Frutas/química , Gelsemium/química , Indóis/química , Alcaloides/isolamento & purificação , Alcaloides/farmacologia , Animais , Dicroísmo Circular , Cristalografia por Raios X , Relação Dose-Resposta a Droga , Indóis/isolamento & purificação , Indóis/farmacologia , Macrófagos/efeitos dos fármacos , Macrófagos/metabolismo , Camundongos , Modelos Moleculares , Conformação Molecular , Óxido Nítrico/antagonistas & inibidores , Óxido Nítrico/biossíntese , Teoria Quântica , Células RAW 264.7 , Relação Estrutura-AtividadeRESUMO
Callistrilones F - K (1 - 6), six new triketone-phloroglucinol-monoterpene hybrids were isolated from the twigs and leaves of Callistemon rigidus. Their structures with absolute configurations were established by a combination analysis of NMR spectra, X-ray diffraction, and electronic circular dichroism (ECD) calculations. Compounds 3 and 4 exhibited moderate inhibitory activities against herpes simplex virus (HSV-1) with IC50 values of 10.00 ± 2.50 and 12.50 ± 1.30 µm, respectively.
Assuntos
Antivirais/farmacologia , Cetonas/farmacologia , Monoterpenos/farmacologia , Myrtaceae/química , Floroglucinol/farmacologia , Simplexvirus/efeitos dos fármacos , Antivirais/química , Antivirais/isolamento & purificação , Relação Dose-Resposta a Droga , Cetonas/química , Cetonas/isolamento & purificação , Testes de Sensibilidade Microbiana , Conformação Molecular , Monoterpenos/química , Monoterpenos/isolamento & purificação , Floroglucinol/química , Floroglucinol/isolamento & purificação , Estereoisomerismo , Relação Estrutura-AtividadeRESUMO
Kopsileuconines A-D (1-4), four monoterpenoid bisindole alkaloids with unprecedented skeletons, along with their biosynthetically related precursors (5-8) were isolated from the roots of Kopsia hainanensis. Compound 1 possessed an undescribed C-6-C-5' dimerization pattern of aspidofractinine-type alkaloids. Compounds 2-4 were rhazinilam-kopsine (2) and rhazinilam-aspidofractinine type (3 and 4) bisindole alkaloids with undescribed skeletons, respectively. Their structures with absolute configurations were fully accomplished by extensive spectroscopic analysis, quantum-chemical calculations, and X-ray crystallography. A plausible biosynthetic pathway for 1-4 was proposed. Compound 2 exhibited a significant inhibitory effect against human lung cancer cell lines PC9 (EGFR mutant), with an IC50 value of 15.07 ± 1.19 µM.
Assuntos
Antineoplásicos Fitogênicos , Apocynaceae , Ensaios de Seleção de Medicamentos Antitumorais , Alcaloides Indólicos , Humanos , Antineoplásicos Fitogênicos/farmacologia , Antineoplásicos Fitogênicos/química , Antineoplásicos Fitogênicos/isolamento & purificação , Alcaloides Indólicos/química , Alcaloides Indólicos/farmacologia , Alcaloides Indólicos/isolamento & purificação , Apocynaceae/química , Estrutura Molecular , Linhagem Celular Tumoral , Relação Estrutura-Atividade , Proliferação de Células/efeitos dos fármacos , Raízes de Plantas/química , Relação Dose-Resposta a Droga , Cristalografia por Raios XRESUMO
We reported the discovery of six novel coumarins, toddasirins A-F (1-6), each endowed with modified isoprenyl or geranyl side chains, derived from the roots of Toddalia asiatica. Comprehensive structural elucidation was achieved through multispectroscopic analyses, single-crystal X-ray diffraction experiments, and advanced quantum mechanical electronic circular dichroism (ECD) calculations. Furthermore, the anti-inflammatory activity of these compounds was assessed. Notably, compounds 1-3 and 6 demonstrated notable inhibitory effects on nitric oxide (NO) production in lipopolysaccharide (LPS)-induced RAW 264.7 cells, with 50% inhibitory concentration (IC50) values of 3.22, 4.78, 8.90, and 4.31 µmol·L-1, respectively.
Assuntos
Cumarínicos , Rutaceae , Camundongos , Animais , Cumarínicos/farmacologia , Cumarínicos/química , Rutaceae/química , Anti-Inflamatórios/farmacologia , Extratos Vegetais/química , Células RAW 264.7 , Óxido Nítrico , Estrutura MolecularRESUMO
Inorganic ions are ubiquitous in all kinds of cells with highly dynamic spatial and temporal distribution. Taking advantage of different types of fluorescent probes, fluorescence microscopic imaging and quantitative analysis of ion concentrations in cells have rapidly advanced. A family of fluorescent nanoprobes based on ionophores has emerged in recent years with the potential to establish a unique platform for the analysis of common biological ions including Na+, K+, Ca2+, Cl-, and so on. This article aims at providing a retrospect and outlook of ionophore-based ion-selective nanoprobes and the applications in cell imaging.
RESUMO
Two novel prenylated acetophenones with new carbon skeletons, acronyrones A and B (1 and 2), and a new analogue, acronyrone C (3), together with two known compounds (4 and 5) were isolated from the leaves of Acronychia pedunculata. Their structures with absolute configurations were identified by interpretation of spectroscopic data, single crystal X-ray diffraction, and electronic circular dichroism (ECD) calculations. Compounds 1 and 2 represent the first example of prenylated acetophenones possessed a C7 (1) and a C6 (2) side chain, forming a 4-isobutylchroman-2-one unit and a 3-(2-methylpropylidene)benzofuran-2(3H)-one moiety with the acetophenone core, respectively. In addition, compound 4 exhibited significant dose-dependent transcriptional activation effect against retinoid X receptor-α (RXRα), and could be regarded as a new type of non-classical RXR ligand.
Assuntos
Rutaceae , Thoracica , Animais , Estrutura Molecular , Rutaceae/química , Acetofenonas/química , Folhas de Planta/químicaRESUMO
Hydrogel is a unique family of biocompatible materials with growing applications in chemical and biological sensors. During the past few decades, various hydrogel-based optical ion sensors have been developed aiming at point-of-care testing and environmental monitoring. In this Perspective, we provide an overview of the research field including topics such as photonic crystals, DNAzyme cross-linked hydrogels, ionophore-based ion sensing hydrogels, and fluoroionophore-based optodes. As the different sensing principles are summarized, each strategy offers its advantages and limitations. In a nutshell, developing optical ion sensing hydrogels is still in the early stage with many opportunities lying ahead, especially with challenges in selectivity, assay time, detection limit, and usability.
Assuntos
DNA Catalítico , Hidrogéis , Monitoramento Ambiental , Óptica e Fotônica , Testes ImediatosRESUMO
Myrcauones A-D (1-4), four new phloroglucinol-terpene adducts were isolated from the leaves of Myrciaria cauliflora. Their structures with absolute configurations were elucidated by combination of spectroscopic analysis, single crystal X-ray diffraction, and electronic circular dichroism (ECD) calculations. Compound 1 was a rearranged isobutylphloroglucinol-pinene adduct featuring an unusual 2,3,4,4a,10,11-hexahydro-1H-3,11a-methanodibenzo[b,f]oxepin backbone. Compound 4 showed moderate antibacterial activity against Gram-positive bacteria including multiresistant strains.
RESUMO
Leptosperols A and B (1 and 2), two cinnamoylphloroglucinol-sesquiterpenoid hybrids featuring unprecedented 1-benzyl-2-(2-phenylethyl) cyclodecane and 2-benzyl-3-phenylethyl decahydronaphthalene backbones, along with their biosynthetic precursor (3), were isolated from Leptospermum scoparium. Compounds 1 and 2 represent the first example of phloroglucinol derivatives biogenetically constructed by a De Mayo reaction. The biomimetic synthesis of leptosperol B (2) was achieved using the proposed biosynthetic pathway. In addition, compounds 1 and 2 showed significant anti-inflammatory effects in zebrafish acute inflammatory models.
Assuntos
Leptospermum/química , Floroglucinol/química , Sesquiterpenos/química , Biomimética , Estrutura Molecular , Floroglucinol/análogos & derivados , Sesquiterpenos/síntese químicaRESUMO
Four new cinnamoyl-phloroglucinols (1-4) were isolated from the leaves of Xanthostemon chrysanthus. Compounds 1 and 2 represent the first example of natural phloroglucinols with an oxazole unit. Their structures were elucidated on the basis of NMR spectroscopic data and single crystal X-ray diffraction. Compound 3 showed moderate cytotoxic activity against MDA-MB-231 and SGC-7901 cells with IC50 values of 25.26⯱â¯0.35⯵M and 31.2⯱â¯0.94⯵M, respectively.
Assuntos
Myrtaceae/química , Floroglucinol/isolamento & purificação , Folhas de Planta/química , Antineoplásicos Fitogênicos/isolamento & purificação , Antineoplásicos Fitogênicos/farmacologia , Linhagem Celular Tumoral , Humanos , Estrutura Molecular , Floroglucinol/farmacologiaRESUMO
Two pairs of atropisomeric bisindole alkaloids, gelsekoumidines A (1) and B (2), with a new carbon skeleton, were isolated from the roots of Gelsemium elegans. Compounds 1 and 2 represent the first examples of seco-koumine-gelsedine type alkaloids, which feature an unprecedented 20,21-seco-koumine scaffold fused with a gelsedine framework via a double bond. Their structures including absolute stereochemistry were elucidated by spectroscopic data, single-crystal X-ray diffraction, and electronic circular dichroism (ECD) calculation. A plausible biogenetic pathway for the new compounds is also proposed. Compound 2 exhibited a moderate inhibitory effect against nitric oxide (NO) production.