Steroids from herbs of Reineckia carnea and their anticomplement activities

A new polyhydroxylated pregnane, named lβ,2β,3β,4β,5β,6β-hexolhydroxy-pregn-16-en-20-one (1), along with nine known (2–10) steroidal saponins were isolated from the whole plant of Reineckia carnea. Structure elucidations of all compounds were established by interpretation of their NMR spectral data, HR-ESI-MS and comparing with literatures. In addition, these compounds were evaluated with anticomplement activity. The result showed that compound 1 exhibited anticomplement effects with the CH₅₀ values of 0.043 mg/mL, but saponins (2–10) showed no inhibition. Interestingly, hydrolysis of steroidal saponins (2–10) resulted in its aglycones (2a–10a) correspondingly which showed anticomplement activity with the CH₅₀ values of 0.049–0.156 mg/mL.     

Two new glycosides isolated from Sapindus mukorossi fruits: effects on cell apoptosis and caspase-3 activation in human lung carcinoma cells

Two new glycosides (1, 2) and two saponins (3, 4) were isolated from the fruits of Sapindus mukorossi Gaertn. The two glycosides were designated as sapindoside G (1) and 4′′,4′′′′′-O-diacetylmukurozioside IIa (2). All four compounds exhibited inhibitory effects against A549 human lung adenocarcinoma cells with inhibition rates up to 69.2–83.3% at a concentration of 100 μg/mL. Flow cytometric analysis revealed that compounds 1–4 could suppress A549 cell growth by promoting cell apoptosis, which was related to the activation of caspase-3.     

Two cobalt coordination polymers based on an asymmetric dicarboxylate: structural diversity tuned by auxiliary ligands

Two 1-D cobalt coordination polymers, [Co(mbtx)(hpht)(H₂O)] _n (1) and [Co(mbix)(hpht)] _n (2) (mbtx?=?1,3-bis(1,2,4-triazol-1-ylmethyl)benzene, mbix?=?1,3-bis(imidazol-1-ylmethyl)benzene, H₂hpht?=?homophthalic acid), were synthesized by hydrothermal reactions and characterized by elemental analyzes, IR spectroscopy, thermogravimetry, and single-crystal X-ray diffraction. Complex 1 is a 1-D heterostranded double-helical chain as a result of bridging hpht and mbtx, and the 1-D chains are further self-assembled into a 2-D layer structure through hydrogen bonds. Complex 2 shows a 1-D molecular ladder structure, linked through C–H···π interactions to give a 2-D layer structure, which is further linked through C–H?O hydrogen bonds to form a 3-D framework. The mbtx adopts cis-conformation in 1, while for 2, mbix has trans-conformation. Factors causing the differences between 1 and 2 are discussed.     

Highly Efficient and Regio-selective Glucosylation of 25(S) Ruscogenin by Gliocladium deliquescens NRRL1086

A new steroidal glycoside, 25(S) ruscogenin 1‐O‐β‐D‐glucopyranoside ( 2 ) was obtained through the microbial transformation of 25(S) ruscogenin ( 1 ) by G. deliquescens NRRL1086 in 54% isolated yield. The structure of the product was elucidated by IR, MS and NMR spectra. This is the first report on the preparation of steroidal saponins by microbial transformation.     

Albidosides H and I,two new triterpene saponins from the barks of Acacia albida Del. (Mimosaceae)

Two new triterpene saponins, albidosides H (1) and I (2), along with the three known saponins were isolated from the barks of Acacia albida. Their structures were elucidated on the basis of extensive 1D- and 2D-NMR studies and mass spectrometry. Albidosides H (1) and I (2) were assayed for their cytotoxicity against HeLa and HL60 cells using MTT method.     

地奥心血康中的两个新甾体皂苷

通过正相和反相硅胶柱层析, 从地奥心血康药粉的正丁醇萃取物中分离纯化出2个微量的新甾体皂苷, 通过MS和NMR(包括HMQC, HMBC和NOESY)等波谱解析, 结合化学降解分析将其结构鉴定为3β,26-二醇-25(R)-Δ^5,20(22)-二烯-呋甾-26-O-β-D-吡喃葡萄糖苷(1)和26-O-β-D-吡喃葡萄糖基-3β,20α,26-三醇-25(R)-Δ^5,22-二烯-呋甾-3-O-α-L-吡喃鼠李糖基(1→2)-[α-L-吡喃鼠李糖基(1→4)]-β-D-吡喃葡萄糖苷(2).     

Extraction and identification of steroidal saponins from Polygonatum cyrtonema Hua using natural deep eutectic solvent-synergistic quartz sand-assisted extraction method

In this study, quartz sand with particularly sharp nanoscale edges acted like a nanoscale knife physically cut cells of Polygonatum cyrtonema Hua into nanosized particles and was synergized with natural deep eutectic solvent to extract steroidal saponins of Polygonatum cyrtonema Hua. The natural deep eutectic solvent (choline chloride-lactic acid)-synergistic quartz sand-assisted extraction was optimized using response surface methodology. The steroidal saponins purified with AB-8 macroporous resin were identified using ultra-high-performance liquid chromatography-triple time of flight mass spectrometry. The results showed that the experimental total saponins content value (36.97 ± 0.12 mg dioscin equivalent/g dry weight) at optimal extraction conditions with a temperature of 68°C, a rotational speed of 20 400 rpm, shear time of 4.3 min, the liquid-solid ratio of 38 ml/g, was close to the maximum possible theoretical value (36.64 mg dioscin equivalent/g dry weight). A total of 20 steroidal saponins were identified, among which the content of (25R)-Kingianoside E was the highest (102.66 ± 3.47 mg/g). Furthermore, a new steroid saponin (3β,25S)-26-(β-D-glucopyranosyloxy)-22-hydroxyfurost-5-en-3-yl 4-O-β-D-glucopyranosyl-β-D-galactopyranoside+Glc was found for the first time. These results revealed that natural deep eutectic solvent-synergistic quartz sand-assisted extraction was an efficient and green method to extract a variety of steroidal saponins.     

Syntheses,crystal structures,and luminescence of coordination polymers [Cu(μ-Br)(μ-phpzm)] n , [{Cu(μ-SCN)}2(μ-phpzm)] n,and [(phpzm)Cu(μ-CN)] n (phpzm = bis(4-phenylpyrazol-1-yl)methane)

Solvothermal reactions of CuX (X?=?Br, SCN, CN) with bis(4-phenyl-pyrazol-1-yl)methane (phpzm) gave two 2-D coordination polymers, [Cu(μ-Br)(μ-phpzm)] _n (1) and [{Cu(μ-SCN)}₂(μ-phpzm)] _n (2), and a 1-D coordination polymer, [(phpzm)Cu(μ-CN)] _n (3). Compounds 1–3 were characterized by elemental analysis, IR spectra, and X-ray crystallography. Compounds 1 and 2 have 2-D networks in which split-stair [Cu(μ-Br)] _n chains (1) or staircase-like [Cu(μ-SCN)] _n double chains (2) are linked by μ-phpzm bridges. Compound 3 consists of a zigzag chain formed by linking [Cu(phpzm)] fragments via cyanide bridges. Luminescence properties of 1–3 along with phpzm in the solid state at ambient temperature were also investigated.     

Six New Steroidal Saponins from Helleborus thibetanus

Six steroidal saponins, including five spirostanol glycosides, 1 – 5 , and one furostanol glycoside 1‐sulfonate, 6 , previously unknown in nature, together with three known compounds, 7 – 9 , were isolated from dried roots and rhizomes of Helleborus thibetanus. Their structures were elucidated by extensive 1D‐ and 2D‐NMR experiments, along with IR and HR‐ESI‐MS data, as well as the results of acid hydrolysis. Compounds 1 – 5 possessed a C(25)?C(27) bond and were glycosylated at HO? C(1), which was unusual in steroidal saponins.     

Synthesis,structures, and properties of lead(II) and cobalt(II) metal-organic frameworks based on a flexible benzophenone-2,4′-dicarboxylic acid (H2bpdc)

Two new coordination polymers, [Pb(bpdc)] _n (1) and [Co(bpdc)(phen)] _n (2) [H₂bpdc?=?benzophenone-2,4′-dicarboxylic acid, phen?=?1,10-phenanthroline], have been synthesized and structurally characterized. Hydrogen bonding and π?···?π stacking extend 1 and 2 into 3-D supramolecular architectures, where 1 exhibits a 3-D framework with 1-D hairpin-like helicates based on Pb–O covalent bonds and 2 displays a 3-D network with 1-D zipper-like chains based on Co–O and Co–N covalent bonds. The FT-IR spectra, PXRD and TG analyses are discussed for 1 and 2. Fluorescence spectra and luminescent lifetime are studied for 1.     

Steroidal Saponins from the Rhizomes of Smilacina henryi

Five steroidal saponins, namely henryiosides A–E ( 1 – 5 ), were isolated from the EtOH extract of the rhizomes of Smilacina henryi. Their structures were elucidated by the extensive use of 1D‐ and 2D‐NMR experiments, along with HR‐MALDI‐MS analysis and the results of acid hydrolysis. The aglycones of henryiosides A–E possess a C(7)?C(8) or C(9)?C(11) bond and were not previously found in saponins.     

Construction of three 2-D silver(I) coordination architectures with a flexible pyrazine-based ligand

To investigate the impact of weak intermolecular interactions in construction of metal–organic frameworks, three silver(I) coordination complexes with the flexible N-heterocyclic ligand 1-((2-pyrazinyl)-1H-benzoimidazol-1-yl)methyl)-1H-benzotriazole (PBMBT), {Ag(C₁₈H₁₃N₇)NO₃} _n (1), {Ag(C₁₈H₁₃N₇)ClO₄} _n (2), and {Ag(C₁₈H₁₃N₇)SO₃CF₃} _n (3), were prepared under solvothermal conditions and structurally characterized by single-crystal X-ray diffraction, IR spectrum, and elemental analyses. Complexes 1–3 exhibit 2-D reticulate structures, and these 2-D layers are further connected into 3-D supramolecular motifs by π···π interactions and hydrogen bonds. Luminescence indicates that 1–3 show analogous fluorescent emissions compared with the PBMBT in the solid state at room temperature.     

New Triterpene Saponins from Herniaria glabra

Three new saponins 1–3 were isolated from Herniaria glabra by means of prep. HPLC and TLC. The structures were established mainly by a combination of 2D-NMR techniques (COSY, TOCSY, ROESY, HMQC, and HMBC) as O-α-L -rhamnopyranosyl-(1→4)-O-β-D -glucopyranosyl-(1-→6)-O-[β-D -glucopyranosyl-(1→2)]-β-D -glucopyranosyl medicagen-28-ate (herniaria saponin 4; 1 ), O-β-D -glucopyranosyl-(1→3)-O-α-L -rhamnopyranosyl-(1→2)-O-[β-(3R)-D -apiofuranosyl-(1→3)]-β-D -4-O-acetylfucopyranosyl 3-O-(β-D -glucuronopyranosyl)-16α-hydroxymedicagen-28-ate (herniaria saponin 5; 2 ), and O-α-L -rhamnopyranosyl-(1→4)-O-β-D -glucopyranosyl-(1→6)-O-[β-D -6-O-acetylglucopyra nosyl-(1→2)]-β-D -glucopyranosyl medicagen-28-ate (herniaria saponin 6; 3 ).     

Metal–organic supramolecular architectures derived from a new zwitterionic dicarboxylate ligand

A series of new coordination compounds with 1-carboxymethylpyridinium-4-benzoate (L) and transition metal ions have been synthesized. They are formulated as [M(L)₂(H₂O)₄]?·?4H₂O M=Mn (1) and Co (2), {[M(L)₂]?·?xH₂O} _n M=Mn, x?=?1 (3); M=Co, x?=?2 (4), and M=Cu, x?=?3 (5). In 1 and 2, the zwitterionic dicarboxylate ligand is monodentate through only one carboxylate to generate mononuclear molecules. The molecules are assembled through O–H?···?O interactions to give 3-D pillared layer-like architectures, in which interesting 1-D tape-like hydrogen bonding motifs are connected into 2-D layers via carboxylate-mediated hydrogen bonds. In 3–5, the organic ligands serve as bridges with one carboxylate monodentate and the other chelating, and the metal ions are linked by double bridges to give 1-D polymeric chains, which are zigzag (3) or stair-like (4 and 5) due to the cis or trans coordination geometry around metal ions. The chains are further stabilized and associated into 3-D architectures through intra- and interchain hydrogen bonding and/or π–π stacking interactions.     

Two M(II)-1,5-NDS-dafo supramolecular architectures (M = Cu,Cd): syntheses,structures, and photoluminescence properties

Under hydrothermal conditions, reaction of Cu(II)/Cd(II) salts with 1,5-naphthalenedisulfonate (1,5-NDS) and 4,5-diazafluoren-9-one (dafo) afforded [Cu(dafo)₂(1,5-NDS)]_n (1) and [Cd(dafo)₂(1,5-NDS)]_n (2), respectively. The compounds were characterized by elemental analysis, IR, PXRD, TG-DSC, and single-crystal X-ray diffraction. Both 1 and 2, which are the first M(II)-1,5-NDS-dafo systems, exhibit 3-D supramolecular structures generated by 1-D chains via C–H?O hydrogen bonds and π–π interactions. Solid-state photoluminescence properties of both 1 and 2 were investigated with emission bands at 426–496?nm (λ _ex?=?280, 270?nm for 1 and 2, respectively).     

Polysciosides J and K,two new oleanane-type triterpenoid saponins from the leaves of Polyscias fruticosa (L.) harms. cultivating in An Giang Province,Viet Nam

Abstract

For the first time, the phytochemical constituents of the leaves of Polyscias fruticosa (L.) Harms. cultivating in An Giang Province, Viet Nam were investigated and led to purify two new oleanane-type triterpenoid saponins, named polyscioside J (1) and polyscioside K (2) together with two known saponins, ladyginoside A (3) and chikusetsusaponin IVa (4) using variously chromatographic methods. Saponin (4) was reported for the first time from this species. Their structures were verified by IR, UV, HR-ESI-MS, NMR 1D and 2D experiments and compared with previous literatures.     

Two novel steroidal derivatives from chloroform-soluble extract of Hoya longifolia

The structures of two novel steroidal derivatives (1 and 4) were elucidated. Steroidal derivatives namely fologenin (1) and hoyagenin (4) have been isolated from chloroform-soluble extract of the whole plant of Hoya longifolia (family: Asclepiadaceae), and their structures were determined by using ¹H NMR, ¹³C NMR, ¹H–¹H COSY and FAB-MS techniques as well as chemical degradation and derivatisation.     

Syntheses,crystal structures,and luminescent properties of two cadmium(II) complexes based on bis(imidazole) and dicarboxylate

Two complexes, [Cd(ip–OH)(H₂biim)(H₂O)][Cd(ip–OH)(H₂biim)(H₂O)₃]·8(H₂O) (1) and [Cd(Himdc)(H₂biim)] _n (2) (H₂ip–OH?=?5-hydroxylisophthalic acid, H₂biim?=?2,2’-biimidazolate, H₃imdc?=?4,5-imidazoledicarboxylic acid), have been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction. 1 is a 3-D supramolecular network constructed by 0-D and 1-D motifs through hydrogen bonds and π?π interactions. Complex 2 is a 1-D zigzag polymeric coordination chain and the chains are connected to form a 3-D supramolecular network by hydrogen bonds. The complexes were characterized by elemental and thermogravimetric analyses. Fluorescence was also investigated.     

Spirostanol Saponins from the Fibrous Roots of Ophiopogon japonicus (Thunb.) Ker‐Gawl

Three new steroidal saponins, (25R)‐ruscogenin‐3‐yl α‐L ‐rhamnopyranosyl‐(1→2)‐[β‐D ‐xylopyranosyl‐(1→4)]‐β‐D ‐glucopyranoside ( 1 ), diosgenin‐3‐yl 2‐O‐acetyl‐α‐L ‐rhamnopyranosyl‐(1→2)‐[β‐D ‐xylopyranosyl‐(1→4)]‐β‐D ‐glucopyranoside ( 2 ), and pennogenin‐3‐yl 2‐O‐acetyl‐α‐L ‐rhamnopyranosyl‐(1→2)‐[β‐D ‐xylopyranosyl‐(1→4)]‐β‐D ‐glucopyranoside ( 3 ) were isolated from the fibrous roots of Ophiopogon japonicus (Thunb .) Ker‐Gawl . Their structures were determined by spectroscopic methods including IR, HR‐ESI‐MS, and 1D‐ and 2D‐NMR. All of these three steroidal saponins exhibited weak cytotoxicities against Hela and Hep2 cell lines.     

New cytotoxic constituents in the water-soluble fraction from Momordicae Semen

Abstract

Two new lignans mubezhisol (1) and mubezhisal (2), together with twenty six known compounds (3–28) were isolated from water-soluble fraction from the semens of Momordica cochinchinensis. In the subsequent action evaluation, four saponins (4, 6, 13, 27), six lignans (1, 2, 16, 17, 22, 23), and one naphthoquinone (24) exhibited the significant cytotoxicity. The results indicated that various saponins and lignans were mainly responsible for the antitumor activities of Momordicae Semen.