Two new alkaloids from Asparagus stipularis Forssk. roots

Two new alkaloids, aspastipuline (1) and 5-hydroxyaspastipuline (2) were isolated from Asparagus stipularis Forssk. roots. Their structures were elucidated by spectroscopic techniques (1D and 2D NMR, HREIMS). The absolute structure of 2 was established by single-crystal X-ray diffraction analysis. Aspastipuline exhibited a moderate antiproliferative activity against the human mammary gland adenocarcinoma cell line MCF-7.     

In situ synthesis of (5-phenyl-1H-pyrazole-3-carboxylic acid) metal complexes and their stable supramolecular microporous frameworks

By in situ generation of ppc ligand in the presence MCl₂ and 3-phenyl-1H-pyrazole-5-carbohydrazide at room temperature, the complexes, [M(ppc)₂(DMF)₂]·2H₂O (M = Co (1) and Ni (2); ppc = 5-phenyl-1H-pyrazole-3-carboxylic acid), were synthesized and characterized by single-crystal X-ray diffraction, IR spectrum, UV spectra and elemental analysis. X-ray structural analysis revealed that the complexes were formed into 3D supramolecular polymers via C-H?O and π?π interactions. The 3D supramolecular networks of two complexes were constructed from 1D nanochannels along the c-direction with the disorder DMF and water solvent molecules shuttling easily. TG and powder X-ray diffraction analysis showed two complexes had high stability when DMF and H₂O molecules were removed. Upon DMF molecules liberated, two complexes become stable microporous solid with coordination-unsaturated [M(ppc)₂] as center. The electrochemical properties were also investigated.     

X-ray diffraction analysis of the 3D organization of collagen fibrils in the wall of the dogfish egg case

The wall of the egg case of the dogfish,Scyliorhinus canicula, contains a network-forming collagen assembled into a regular three-dimensional (3D) structure. It accomplishes supportive, protective and filtering functions for the embryo contained within it. The collagen molecules in the egg case are organized into a body-centred unit cell of dimensions (mean ± s.d.) (11.6 ± 1.0) nm X (11.6 ± 1.0) nm X (81.6 ± 3.2) nm, which belongs to the I422 space group. At a higher hierarchical level, the collagen molecules assemble into parallel arrays of fibrils, ca. 100 nm in diameter, which aggregate to form laminae ca. 0.5 μm thick. These laminae are organized into a plywood-like structure and account for 98% of the thickness of the wall of the egg case. X-ray diffraction patterns of the wall of the egg case were taken along mutually perpendicular directions, one being perpendicular to the surface of the egg case. Three different kinds of diffraction pattern were observed. One of the patterns was characteristic of an X-ray direction perpendicular to the laminae in the egg case (along the x-direction). The two other patterns were obtained with the X-rays directed parallel to the plane of the laminae, either along the capsule long axis (z) or perpendicular to this (y). These two patterns were observed interchangeably in either of the x- or y-directions depending on the specimen. The diffraction patterns were analysed and interpreted taking into consideration the 3D electron microscope data of the egg case. The results confirm and extend previous findings from transmission electron microscopy and low-angle X-ray diffraction and they suggest that there is only one major type of ordered collagen arrangement in the wall of the egg case.     

Koninginins L and M,two polyketides from Trichoderma koningii 8662

Two new fungal metabolites, named koninginins L (1) and M (2), together with three known koninginins A (3), E (4), and trichodermaketone C (5), were isolated from solid fermentation products of Trichoderma koningii 8662. Koninginins L (1) and M (2) were elucidated by extensive spectroscopic methods, including 1D and 2D NMR, HR-EI-MS experiments, and the absolute configuration of compound 1 was confirmed by single-crystal X-ray diffraction analysis using the anomalous scattering of Cu Kα radiation.     

Acrocalysterols A and B,two new steroids from endophytic fungus Acrocalymma sp

Two new steroids, named acrocalysterols A (1) and B (2), together with five known compounds were isolated and characterized from an endophytic fungus Acrocalymma sp., isolated from the tender stems of Sinomenium acutum. The structures of the isolated metabolites were identified based on UV, IR NMR (1D and 2D), HR-ESI-TOF-MS, single-crystal X-ray diffraction experiment using Cu Kα radiation and CD spectra associated with TD-DFT calculation. The bioassay showed that compound 2 displayed potent cytotoxicity against three cancer cell lines HeLa, HCC-1806, and RKO with IC₅₀ values ranging from 18.37 to 19.64 μM.     

New aspidosperma-type alkaloids from Tabernaemontana bovina

Two new aspidosperma-type alkaloids, taberibogines C and D (1 and 2), along with three known ones (3–5), were isolated from the leaves of Tabernaemontana bovina. Their structures including absolute configurations were elucidated by extensive spectroscopic analysis and X-ray crystal diffraction. Alkaloids 1-2 exhibited moderate inhibitory effects on LPS-induced nitric oxide (NO) production in RAW 264.7 macrophages.     

Virginols A–C,three new withanolides from Physalis virginiana

Virginols A–C are three new withanolides containing an epoxylactol at the side chain. They were isolated from the aerial parts of Physalis virginiana Miller. Structures of these compounds were determined by analyses of their spectroscopic data, including 1D and 2D NMR. The structure of virginol A was confirmed by X-ray diffraction analysis. The anti-inflammatory activity of virginols was evaluated in the TPA-induced ear mouse edema model.     

Structural and stereochemical studies of five new pregnane steroids from the stem bark of Toona ciliata var. pubescens

Five new pregnane steroids, toonasterones A (1), B (2), (Z)-aglawone (3), (Z)-toonasterone C (4), and (E)-toonasterone C (5), were isolated from the stem bark of Toona ciliata var. pubescens. Their structures were elucidated by means of detailed spectroscopic (IR, MS, and 2D NMR) analysis, and the stereochemistry of 1 was secured by X-ray diffraction analysis. (Z)-aglawone (3) exhibited moderate inhibitory activity of protein tyrosine phosphatase 1B (PTP1B), a potential drug target for treatment of type-II diabetes and obesity, with an IC₅₀ value of 1.12 μg/mL.     

Absolute configurations of tubulin inhibitors taltobulin (HTI-286) and HTI-042 characterized by X-ray diffraction analysis and NMR studies

The stereochemistry of the tubulin inhibitors taltobulin HTI-286 (2) and HTI-042 (3) was determined by utilizing the DPFGSE 1D NOE experiment. Single crystal X-ray diffraction analysis further confirmed the absolute configuration of these two compounds, which carry the (S,S,S)-configuration necessary for biological activity.     

Two new labdane diterpenoids and one new β-lactam from the aerial parts of Roylea cinerea

Two new labdane diterpenoids cinereanoid C (1), cinereanoid D (2), a new β-lactam, cinerealactam E (3) as well as six known flavonoid glycosides (4–9) were isolated from the aerial parts of Roylea cinerea (Lamiaceae). The structures of (1–9) were all determined by MS, IR and NMR spectroscopy. The structure of cinereanoid D (2) was further proven by single crystal X-ray diffraction. Six known flavonoid glycosides (4–9) were also isolated for the first time from this plant. 2, 5, 6 and 7 were found to significantly inhibit the ATP binding of a tumour growth-promoting heat shock protein, Hsp90.     

An exact coordination mode of 6-thiopurine with an organotin(IV): preparation and crystal structure of triphenyl(6-thiopurinyl)tin(IV)

Triphenyl(6-thiopurinyl)tin has been prepared and its structure reinvestigated by X-ray diffraction. In the structure, a new coordination mode was observed that was different from those reported previously from investigations by infrared and Mössbauer spectroscopy. In the molecule, 6-thiopurine coordinated to tin by the S and N(1) atoms. The discrete molecules were connected to form a zigzag 1D network through intermolecular H?N hydrogen bonds. The tin environment is pentacoordinated with cis-trigonal bipyramidal geometry.     

Antineoplastic agents 582. Part 1: Isolation and structure of a cyclobutane-type sesquiterpene cancer cell growth inhibitor from Coprinus cinereus (Coprinaceae)

Bioassay-guided (murine P388 lymphocytic leukemia and human cancer cell lines) separation of an ethyl acetate extract prepared from the inky cap fungus Coprinus cinereus led to the isolation of three new sesquiterpenes, 7,7a-diepicoprinastatin 1 (1), 14-hydroxy-5-desoxy-2S,3S,9R-illudosin (2), and 4,5-dehydro-5-deoxyarmillol (3), together with the known armillol (4). The structure and relative configuration of 1 was determined by single-crystal X-ray diffraction experiments. The structures of compounds 2, 3, and 4 were each deduced by a combination of HRMS and 1D and 2D NMR techniques. Cyclobutane 2 led to modest inhibition of the murine P388 leukemia cell line.     

Drechmerin H,a novel 1(2), 2(18)-diseco indole diterpenoid from the fungus Drechmeria sp. as a natural agonist of human pregnane X receptor

A novel 1(2), 2(18)-diseco indole diterpenoid, drechmerin H (1), was isolated from the fermentation broth of Drechmeria sp. together with a new indole diterpenoid, 2′-epi terpendole A (3), and a known analogue, terpendole A (2). Their structures were determined by HRESIMS, 1D and 2D NMR, ECD, and X-ray single crystal diffraction analyses as well as quantum chemical calculation. The abosulte configuration of terpendole A (2) was determined for the first time. Compound 1 displayed the significant agonistic effect on pregnane X receptor (PXR) with EC₅₀ value of 134.91 ± 2.01 nM, and its interaction with PXR was investigated by molecular docking. Meantime, a plausible biosynthetic pathway for compounds 1–3 is also discussed in the present work.     

Synthesis, crystal structure, magnetic properties and EPR studies of Cu/Hg bimetallic thiocyanato-bridged coordination polymer

The new Cu/Hg bimetallic thiocyanato-bridged coordination polymer, [Cu(2-bzpy)Hg(SCN)₄]_n, has been synthesized and characterized by elemental analysis, magnetic measurements, EPR, and X-ray crystallography. X-ray diffraction analysis reveals that the title complex structure creates 3D network.     

Rearranged abietane diterpenoid hydroquinones from aerial parts of Ajuga decumbens Thunb

Four new rearranged abietane diterpenoid hydroquinones, ajudecumins A–D (1–4), together with two known rearranged abietane diterpenoids, three neo-clerodane diterpenoids, four megastigmane derivatives, two flavonoids as well as a bisabolene sesquiterpenoid were isolated from the aerial parts of Ajuga decumbens. Their structures were established on the basis of extensive spectroscopic analysis and the stereochemistry of 1 was confirmed by single-crystal X-ray diffraction analysis. Among the diterpenoids, compounds 1 and 3 exhibited moderate inhibitory activity on the proliferation of human breast cancer MCF-7 cells.     

Syntheses, structures and magnetic properties of two new metal complexes based on a pyridyl-diphosphonate ligand

Two new first-raw transition metal diphosphonate complexes, namely, {[Ni₃([hpyedpH)₂(H₂O)₄]·(H₂O)₂}_n (1) and [Mn[hpyedpH₂](H₂O)]_n (2), based on a multidentate ligand 1-hydroxy-2-(3-pyridyl)-ethylidene-1,1-diphosphonic acid (hpyedpH₄) have been synthesized under hydrothermal reaction and structurally characterized by single-crystal X-ray diffraction, IR spectroscopy and element analyses. The data reveals that complex 1 is a 2D layer structure, whereas the complex 2 possesses a 1D motif. The powder X-ray diffraction (PXRD) patterns for complexes 1 and 2 were collected as well, which match well with the ones calculated from their single-crystal structure data. Magnetic measurements show that complex 1 is a ferrimagnet with T_c = 5.0 K. Magnetic studies of complex 2 indicate antiferromagnetic behavior.     

Synthesis, structures, luminescence/magnetic properties of complexes of the M/1-hydroxybenzotriazole, M = cobalt, nickel, silver, zinc and copper

Five novel complexes, Co(OBt)₂ · 7H₂O (1) (OBt = 1-hydroxybenzotriazole ion), Ni₃(OBt)₆ · 6H₂O (2), [Ag(OBt)(HOBt)]_n (3), [Zn(OBt)₂]_n (4) and [Cu₂(OBt)₄ · 3H₂O]_n (5) were synthesized by hydrothermal method and characterized by elemental analysis, IR spectroscopy, TGA, XRPD, and single-crystal X-ray diffraction. The results from single-crystal X-ray diffraction indicate that 1-5 are zero-dimensional (0D), zero-dimensional, one-dimensional (1D), and three-dimensional (3D) frameworks, respectively. In particular, 3 is twin crystal; 4 possesses of double-stranded chains; 5 crystallizes in orthorhombic space group P2₁2₁2₁ with a helical chain in its structure. The luminescence properties and the magnetic properties of the five complexes were investigated.     

An unusual spinaceamine-bearing pregnane from a soft coral Scleronephthya sp. inhibits the migration of tumor cells

An unprecedented spinaceamine-bearing pregnane namely scleronine (1) was isolated from a Chinese soft coral Scleronephthya sp. Its structure was determined on the basis of 1D and 2D NMR spectroscopic analyses in association with the HRESIMS data, while the absolute configurations were deduced by the single-crystal X-ray diffraction analysis. In addition, a dehydrogenated analogue (3) was synthesized through six steps with pregna-1,20-dien-3-one (2) as a precursor. The significantly inhibitory effects of 1 and 3 against the migration of tumor cells A549 and B16 accompanying the down-regulation of key genes (TGFβ, TNFα, IL-1β, and IL-6) were observed. These findings suggested that both 1 and 3 are potential for therapeutic usage aiming at cancer metastasis inhibition.     

Synthesis, structure and luminescence of a new series of rigid-flexible lanthanide coordination polymers constructed from benzene sulfonic acid and glutaric acid

A new series of rigid-flexible lanthanide coordination polymers, namely, [Eu(BSA)(glu)(H₂O)₂]·H₂O (Ln = Eu(1), Sm(2), Ce(3), Pr(4), Nd(5)); H₂glu = glutaric acid, HBSA = benzene sulfonic acid), have been constructed by a solution synthesis method from the self-assembly of the lanthanide ions (Ln³⁺) with the flexible aliphatic dicarboxylate glutaric and the rigid aromatic benzene sulfonic acid. All of them were characterized by elemental analysis, IR spectroscopy, and single-crystal X-ray diffraction. X-ray single crystal analyses reveal that they crystallize in monoclinic, space group P2₁/n, possessing 2D net-structures. In addition, the phase purities of the bulk samples were identified by X-ray powder diffraction. The thermogravimetric analysis of 1 and photoluminescent properties of 1 and 2 were investigated in detailed.     

Petiolins J–M,prenylated acylphloroglucinols from Hypericum pseudopetiolatum var. kiusianum

Four new prenylated acylphloroglucinols, petiolins J?M (1?4), were isolated from aerial parts of Hypericum pseudopetiolatum var. kiusianum, and the structures were elucidated by spectroscopic data and a single-crystal X-ray diffraction analysis. Petiolin J (1) exhibited antimicrobial activity.