Synthesis,characterization, and cytotoxic and antimicrobial activities of ruthenium(II) arene complexes with N,N-bidentate ligands

Three new complexes, [(η⁶-C₆H₆)RuCl(C₅H₄N-2-CH=N-Ar)]PF₆ (Ar = phenylmethylene (1), (4-methoxyphenyl)methylene (2), and phenylhydrazone (3)), were prepared by reacting [(η⁶-C₆H₆)Ru(μ-Cl)Cl]₂ with N,N′-bidentate ligands in a 1 : 2 ratio. Full characterization of the complexes was accomplished using ¹H and ¹³C NMR, elemental and thermal analyses, UV–vis and IR spectroscopy and single crystal X-ray structures. Single crystal structures confirmed a pseudo-octahedral three-legged, piano-stool geometry around Ru(II), with the ligand coordinated to the ruthenium(II) through two N atoms. The cytotoxicity of the mononuclear complexes was established against three human cancer cell lines and selectivity was also tested against non-cancerous human epithelial kidney (HEK 293) cells. The compounds were selective toward the tumor cells in contrast to the known anti-cancer drug 5-fluoro uracil which was not selective between the tumor cells and non-tumor cells. All the compounds showed moderate activity against MCF7 (human breast adenocarcinoma), but showed low antiproliferative activity against Caco-2 and HepG2. Also, antimicrobial activities of the complexes were tested against a panel of antimicrobial-susceptible and -resistant Gram-negative and Gram-positive bacteria. Of special interest is the anti-mycobacterial activity of all three synthesized complexes against Mycobacterium smegmatis, and bactericidal activity against resistant Enterococcus faecalis and methicillin-resistant Staphylococcus aureus ATCC 43300.     

Four new dammarane-type triterpenes derivatives from hydrolyzate of total Gynostemma pentaphyllum saponins and their bioactivities

Phytochemical investigation of hydrolysate of total G. pentaphyllum saponins led to the isolation of four novel triterpenes, Gypensapogenin U (1), Gypensapogenin V (2), Gypensapogenin W (3) and Gypensapogenin X (4). The structures of these compounds were identified by 1D, 2D-NMR and HR-ESI-MS evidences. Additionally, the protective activity of these new compounds against cardiomyocytes injury induced by H₂O₂ and their cytotoxic activity against t-HSC/Cl-6 cells were evaluated.     

A new β-tetralonyl glucoside from the Santalum album derived endophytic fungus Colletotrichum sp. GDMU-1

A new β-tetralonyl glucoside, methylberchemiaside (1), along with five known compounds (2–6) were isolated from a fungus Colletotrichum sp. GDMU-1 derived from the leaves of Santalum album. Their structures were determined by detailed analysis of spectroscopic data. All compounds were tested for the inhibitory effects on the nitric oxide (NO) production in lipopolysaccharide (LPS)-treated RAW264.7 cells. Among them, compounds 4 and 5 showed moderate anti-inflammatory activity with IC₅₀ value of 30.4 and 8.9 μM, respectively.     

两个苯甲羟肟酸有机锡配合物的合成、结构及抗癌活性

合成了2个苯甲羟肟酸有机锡配合物：[(o-Cl-C₆H₄CH₂)₂Sn (C₆H₅CONO)₂](1)和[(o-CH₃-C₆H₄CH₂)₂Sn (C₆H₅CONO)(C₆H₅COO)](2)。通过元素分析、红外光谱、核磁共振氢谱、热重分析、单晶X射线衍射等方法对配合物进行了结构表征,对其结构进行量子化学从头计算和体外抗癌活性研究。结果显示：配合物均为单锡核结构,配合物1为六配位的畸变八面体构型,配合物2为五配位的畸变三角双锥构型;配合物1对人宫颈癌细胞(HeLa)、肝癌细胞(HuH-7)和肺腺癌细胞(H1975)显示出比临床使用的顺铂强的抑制活性,而配合物2的抑制活性要弱得多。     

哒嗪酮类α1-肾上腺素受体拮抗剂的合成和生物活性研究

将苯(氧)乙胺和苯氧烷胺类α₁-肾上腺素受体拮抗剂中的苯(氧)乙胺、苯氧烷胺片段引入哒嗪酮类化合物中, 设计、合成了30个新的含哒嗪酮环的α₁-肾上腺素受体拮抗剂. 所有新化合物的结构均经¹H NMR, IR, HRMS确证. 生物活性测试表明28个目标物对α₁-肾上腺素受体有较好的拮抗作用(pA₂＞6.00), 化合物6o, 6p, 6q, 6v, 6x, 6y, 10c, 10d的pA₂值＞7.00.     

A new azaphilone from the entomopathogenic fungus Hypocrella sp.

This report describes the isolation of a new azaphilone, designated hypocrellone A (2), together with five known compounds (1, 3–6) from a submerged culture of the entomopathogenic fungus Hypocrella sp. (isolate WYTY-21). The absolute stereostructures of the two compounds (1 and 2) were elucidated based on 1D and 2D NMR spectroscopic and mass spectrometric data combined with the data from various chemical transformations. Hypocrellone A (2) and three (3–6) of the five known compounds were cytotoxic to hepatoma cells (cell line BEL-7404); IC₅₀ values ranged from 6.2 to 17.4 μM. At 200 μM, none of the six compounds was toxic to normal human liver cells (cell line HL-7702) or to normal human kidney epithelial cells (cell line HEK-293T).     

Anti-breast cancer triterpenoid saponins from the thorns of Gleditsia sinensis

One new triterpenoid saponin (1), as well as six known ones (2–7), were isolated from the ethanol extract of the thorns of Gleditsia sinensis. Their structures were elucidated by extensive spectroscopic analysis in conjunction with chemical evidence. Cytotoxic activity of compounds 1–6 was evaluated against human breast cancer MCF 7 cells in vitro by the MTT method. Our results revealed moderate activities for compounds 1–6 with IC₅₀ values of 18.43, 30.47, 18.46, 10.02, 30.76, and 17.32 μM, respectively. Furthermore, compounds 1, 3, 4, and 6 induced apoptosis in MCF 7 cell, with 1 and 6 causing late apoptosis of MCF 7 cells, while 3 and 4 acting oppositely.     

Facile synthesis of highly functionalized novel pyrazolopyridones using oxoketene dithioacetal and their anti-HIV activity

A series of novel 3-amino-4,5-dihydro-6-methyl-4-oxo-N-aryl-1H-pyrazolo[4,3-c]pyridine-7-carboxamide have been synthesized starting from various oxoketene dithioacetals. The cyclocondensation reaction of 2-(bis(methylthio)methylene)-3-oxo-N-arylbutanamide 2a–w with cyanoacetamide using NaOiPr as base under reflux condition afforded novel highly functionalized pyridone 3a–w derivatives. Further, [3?+?2] cyclocondensation reaction of pyridones with hydrazine in the presence of alcohol was yielded pyrazolopyridones (23 nos) 4a–w with excellent yields. All newly synthesized compounds were evaluated for in vitro anti-HIV activity using MTT method. Most of these compounds have showed moderate to potent activity against HIV-1 (III_B) and HIV-2 (ROD) strains with an IC₅₀ ranging from >18 IC₅₀[µg/ml] to <100 IC₅₀[µg/ml]. Among them, compounds 4j and 4v were identified as the most promising compound for both types of HIV strains. (IC₅₀?=?18?µg/ml). Three compounds 4l, 4m, and 4p have been found potent anti-HIV 1 and 2 activity against MT-4 cells.     

Lignans from the seeds of Chinese hawthorn (Crataegus pinnatifida var. major N.E.Br.) against β-amyloid aggregation

Phytochemical investigation on the seeds of hawthorn (Crataegus spp.) led to the isolation of a new compound, (7′R, 8′R, 8S)-isolariciresinol (1), along with six known compounds (2–7). The structures of all compounds were determined based on spectroscopic data interpretation. The Aβ_1–42 inhibition activity of all isolated compounds was evaluated in vitro. As a result, compounds 5 and 6 showed stronger inhibition of Aβ_1–42 aggregation than curcumin, with inhibition rates of 70.59 and 68.14% at 20 μM. The possible mechanism of interaction between Aβ_1–42 and the active compounds 5 and 6 was also investigated by molecular docking.     

Synthesis,characterization, antiproliferative,and antimicrobial activity of osmium(II) half-sandwich complexes

New osmium(II)-arene complexes [(η⁶-C₆H₆)OsCl(C₅H₄N-2-CH=N-C₆H₅X)](PF₆) (X = p-flouro (1), p-chloro (2), p-methyl (3)) were synthesized by reaction of the corresponding bidentate N,N′-ligands with the osmium-arene precursor [(η⁶-C₆H₆)Os(μ-Cl)Cl]₂ in a 2:1 ratio. These complexes were characterized by UV–Vis, IR, ¹H, ¹³C NMR spectroscopy, and elemental analysis and, for compound 1, a single crystal X-ray structure was also obtained. The complexes were investigated for antiproliferative activity in vitro against MCF-7 (human breast adenocarcinoma), Caco-2 (human epithelial colorectal adenocarcinoma), and HepG2 (human hepatocellular carcinoma) tumor cell lines. To test their selectivity, the non-tumor HEK293 (human embryonic kidney) cell line was used. The compounds were selective toward the tumor cell lines when compared to the known anticancer drug 5-fluorouracil which displayed low selectivity. The compounds were substantially more active against Caco-2 than 5-fluorouracil. They also showed moderate activity against the other two tumor cell lines. In addition, the antimicrobial activity of complex 2 was explored against a panel of antimicrobial-susceptible and -resistant Gram-negative and Gram-positive bacteria. Complex 2 showed anti-mycobacterial activity against Mycobacterium smegmatis and bactericidal activity against drug-resistant Enterococcus faecalis and methicillin-resistant Staphylococcus aureus ATCC 43300.     

Congmujingnosides B-G,triterpene saponins from the stem of Aralia chinensis and their protective effects against H2O2-induced myocardial cell injury

Phytochemical investigation of the stem of Aralia chinensis yielded six new oleanane-type triterpene saponins named as congmujingnosides B-G (1–6). The new ones were elucidated on the basis of the chemical and spectroscopic analysis. Protective effects of compounds 1?6 were tested against H₂O₂-induced H9c2 cardiomyocyte injury, and the data showed that compounds 1 and 5 had significant cell-protective effects. No significant DPPH radical scavenging activity was observed for compounds 1?6.     

Antifungal,anti-inflamatory and neuritogenic activity of newly-isolated compounds from Disporopsis aspersa

Abstract

A new ester (1) and a terpenoid (2) were isolated from the dried whole plant of Disporopsis aspersa (H_UA) E_NGL. ex D_IELS for the first time and their structures were elucidated, as well as their biological activities are described. The two compounds all showed good antifungal activities, especially furanone (2) exhibited better antifungal activity against Pseudoperonospora cubensis and Phytophthora infestans with EC₅₀ value of 22.82, 18.90?μg/mL, respectively. Compound 1 exhibited a significant promotion on the neurite outgrowth in NGF-induced PC-12 cells, and moderate inhibition on the NO production induced by lipopolysaccharide (LPS) in BV-2 microglial cells.     

Design,synthesis and biological evaluation of novel N1,N8-bis(((4-((5-aryl-1,3,4-oxadiazol-2-yl)methoxy)phenyl)amino)oxy)-1-naphthamide derivatives

A new series of 1,8-bis(4-((5-phenyl-1,3,4-oxadiazol-2-yl) methoxy)-substituted aryl) naphthalene-1,8-dicarboxamide derivatives (6a–j) were synthesized in the presence of POCl₃ and obtained good yields. All the synthesized novel compounds were characterized by IR, ¹H NMR, ¹³C NMR, HRMS spectroscopic data and elemental analysis. All the synthesized compounds evaluated for their antibacterial and antifungal activities. The antibacterial activity screened against Gram-positive bacteria Staphylococcus aureus and Gram-negative bacteria Escherichia coli and used standard reference drug ciprofloxacin. The antifungal activity screened against two pathogenic fungal strains Aspergillus niger and Candida albicans used a reference standard drug Voriconazole. All these compounds (6a–j) demonstrate good antibacterial and antifungal activity. Among them, compounds 6h and 6c show highest antibacterial and antifungal activity.     

A new aldehyde compound from the fruit of Pandanus tectorius Parkinson ex Du Roi

From the fruit of Pandanus tectorius Parkinson ex Du Roi, one new (1) and six known aldehyde compounds (2–7) were isolated by various chromatography methods. Based on their spectroscopic data, these compounds were identified as (Z)-4-hydroxy-3-(4-hydroxy-3-methylbut-2-en-1-yl) benzaldehyde (1), p-hydroxybenzaldehyde (2), syringaldehyde (3), (E)-ferulaldehyde (4), (E)-sinapinaldehyde (5), vanillin (6) and 5-hydroxymethylfurfual (7). The α-glucosidase inhibitory activity of all compounds was measured. The isolated compounds (1–6) showed better α-glucosidase inhibitory activity (IC₅₀ values ranging from 36.5 to 192.4 μM) than the standard drug acarbose (IC₅₀ = 214.5 μM).     

2,3-Seco-2,3-dioxo-lyngbyatoxin A from a Red Sea strain of the marine cyanobacterium Moorea producens

Chemical investigation of the organic extract of a Red Sea strain of the cyanobacterium Moorea producens has afforded 2,3-seco-2,3-dioxo-lyngbyatoxin A (1). Five known compounds including lyngbyatoxin A (2), majusculamides A and B (3 and 4), aplysiatoxin (5) and debromoaplysiatoxin (6) were also isolated. Their structures were elucidated by using HR-FAB-MS, 1D and 2D NMR analyses. The compounds were evaluated for antiproliferative activity against HeLa cancer cells. Lyngbyatoxin A (2) showed potent activity, with an IC₅₀ of 9.2 nM, while 5 and 6 displayed modest activity with IC₅₀ values of 13.3 and 3.03 μM, respectively. In contrast, compounds 1, 3 and 4 were inactive, with IC₅₀ values greater than 50 μM. The lack of cytotoxicity for 2,3-seco-2,3-dioxo-lyngbyatoxin A (1) demonstrates that the indole moiety in lyngbyatoxin (2) is essential for its cytotoxicity, and suggests that detoxification of 2 may be carried out by biological oxidation of the indole moiety to yield 1.     

Five macrocyclic glycosides from Schoenoplectus tabernaemontani

Macrocyclic glycosides with unique 22-membered dimeric lactone skeleton, are rare occurring natural products. There are only ten compounds reported so far. Herein we reported the isolation and characterisation of five macrocyclic glycosides from Schoenoplectus tabernaemontani, including three new compounds (Schoenopolide A-C, 1–3) and two known ones, Berchemolide (4) and Clemoarmanoside B (5). Their structures were established on the basis of extensive analysis of spectroscopic data. In addition, the anti-oxidative activity of Berchemolide (4) against H₂O₂-induced of renal tubular epithelial (HK-2) cells was also evaluated.     

Uncommon secondary metabolites from Etlingera pavieana rhizomes

From the rhizomes of Etlingera pavieana (Pierre ex Gagnep.) R.M. Sm., four phenylpropens, (E)-3-(4-methoxyphenyl)prop-2-en-1-amine (1), (E)-4-methoxycinamaldehyde (2), (E)-4-methoxycinamic acid (3) and (E)-1-methoxy-4-(3-methoxyprop-1-enyl)benzene (4), together with two other compounds, (E)-((E)-3-(4-methoxyphenyl)allyl)3-(4-hydroxyphenyl)acrylate (5) and 4-methoxybenzoic acid (6) were isolated. This is the first report on the presence of all compounds in Etlingera. Compounds 1 and 5 have been previously synthesised, but this is the first report of their isolation from a natural source. Compound 5 exhibited weak activity against Mycobacterium tuberculosis with MIC 50.00 μg/mL and cytotoxic activity against the KB, MCF7 and NCI-H187 cells with IC₅₀ values of 25.11, 20.16 and 34.83 μg/mL, respectively.     

New phenyl derivatives from endophytic fungus Botryosphaeria sp. SCSIO KcF6 derived of mangrove plant Kandelia candel

Two new phenyl derivatives (1 and 3), along with two new natural products (4 and 5), and three known compounds (2, 6 and 7), were isolated from an endophytic fungus Botryosphaeria sp. SCSIO KcF6. The structures of these compounds 1–7 were elucidated by the extensive 1D and 2D-NMR and HRESIMS Data analysis, and compared with those of reported data. The absolute configuration of the compounds 1 and 3 were assigned by optical rotation and CD data. The isolated compounds were evaluated for their cytotoxic, anti-inflammatory (COX-2) and antimicrobial activities. Compound 3 exhibited a specific COX-2 inhibitory activity with the IC₅₀ value of 1.12 μM.     

含苯并噻唑基乳糖基胍的合成

2,3,6,2',3',4',6'-七-O-乙酰基-β-乳糖基异硫氰酸酯(1)分别与2-氨基-4/6-取代苯并噻唑2a～2e反应, 制得糖基硫脲3a～3e, 将其在HgCl₂作用下与伯胺反应, 制得一系列新化合物N-烷基/芳基-N'-(4/6-取代-苯并噻唑-2-基)-N'-(2,3,6,2',3',4',6'-七-O-乙酰基-β-乳糖基)胍4～6. 然后, 在CH₃ONa/CH₃OH作用下, 脱乙酰基得含苯并噻唑基的乳糖基胍类化合物7～9. 所有新化合物的结构均经IR, ¹H NMR, MS谱和元素分析证实, 所得产物均为b-构型. 对代表性化合物的生物活性测试结果表明, 乳糖基胍类化合物对HIV-1蛋白酶、血管紧张素转化酶(ACE)的抑制活性较差.     

Insecticidal,cytotoxic and anti-phytopathogenic fungal activities of chemical constituents from the aerial parts of Ferula sinkiangensis

Abstract

A new rare monoterpene coumarin (1) and its two known analogues (2–3), together with two sesquiterpenes (6–7) and ferulic acid (8) were isolated from the aerial parts of Ferula sinkiangensis. The structure of new compound was established on the basis of 1D and 2D NMR data and HRESIMS data interpretation. Insecticidal, cytotoxic and anti-phytopathogenic fungal activities of isolated compounds were evaluated against third-instar larvae of Spodoptera exigua and its cell line, and three plant pathogenic fungi respectively. Compounds 1–3 and 6–7 were found to be more effective contact toxicity to S. exigua with the corrected mortality values of 38.89%-58.89% at 10?μg/larva doses for 24?h. Further studies showed that compounds 3 and 6 exhibited cell growth inhibitory activity against S. exigua cell line with the EC₅₀ values of 22.78 and 14.64?µM for 72?h. In addition, compound 6 exhibited potent antifungal activity with MICs?=?16–32?µg/mL.