Two new 5-deoxyflavones from Albizia odoratissima

Two new 5-deoxyflavones, 7,8-dimethoxy-3',4'-methylenedioxyflavone (1) and 7,2',4'-trimethoxyflavone (2) together with a known flavone, 7,4'-dimethoxy-3'-hydroxyflavone (3) were isolated from the rootbark of Albizia odoratissima. The structures of these new compounds were elucidated by electrospray ionization mass spectrometry (ESI-MS) and 1D and 2D-NMR spectral studies including (1)H-(1)H correlation spectroscopy (COSY), heteronuclear single quantum coherence (HSQC), heteronuclear multiple bond connectivity (HMBC) and nuclear Overhauser enhancement spectroscopy (NOESY).     

Two new 5-deoxyflavonoids from Calliandra inermis

Two new 5-deoxyflavonoids, 7,2',3',4'-tetramethoxyflavone (1) and 7,2',3',4'-tetramethoxyflavanone (2) together with a known flavone 7,4'-dimethoxy-3'-hydroxyflavone (3) were isolated from the whole plant of Calliandra inermis. The structures of these new compounds were elucidated by high resolution electron impact mass spectrometry (HR-EI-MS) and 1D and 2D-NMR spectral studies including 1H-1H correlation spectroscopy (COSY), heteronuclear single quantum coherence (HSQC), heteronuclear multiple bond connectivity (HMBC) and nuclear Overhauser enhancement spectroscopy (NOESY).     

The Biosynthetic Gene Cluster of Mushroom-Derived Antrocin Encodes Two Dual-Functional Haloacid Dehalogenase-like Terpene Cyclases

(−)-Antrocin ( 1 ), produced by the medicinal mushroom Antrodia cinnamomea, is a potent antiproliferative compound. The biosynthetic gene cluster of 1 was identified, and the pathway was characterized by heterologous expression. We characterized a haloacid dehalogenase-like terpene cyclase AncC that biosynthesizes the drimane-type sesquiterpene (+)-albicanol ( 2 ) from farnesyl pyrophosphate (FPP). Biochemical characterization of AncC, including kinetic studies and mutagenesis, demonstrated the functions of two domains: a terpene cyclase (TC) and a pyrophosphatase (PPase). The TC domain first cyclizes FPP to albicanyl pyrophosphate, and the PPase domain then removes the pyrophosphate to form 2 . Intriguingly, AncA (94 % sequence identity to AncC), in the same gene cluster, converts FPP into (R)-trans-γ-monocyclofarnesol instead of 2 . Notably, Y283/F375 in the TC domain of AncA serve as a gatekeeper in controlling the formation of a cyclofarnesoid rather than a drimane-type scaffold.     

A novel stability-indicating HPLC method for the determination of enantiomeric purity of eluxadoline drug: Amylose tris(3,5-dichlorophenyl carbamate) stationary phase

A simple and sensitive stability-indicating chiral HPLC method has been developed and validated per International Conference on Harmonization guidelines for the determination of enantiomeric purity of eluxadoline (Exdl). The impact of different mobile phase compositions and chiral stationary phases on the separation of Exdl enantiomer along with process- and degradation-related impurities has been studied. Homogeneity of Exdl and stable results of Exdl enantiomer in all degraded samples reveal the fact that the proposed method was specific (stability indicating). Amylose tris(3,5-dichlorophenyl carbamate) stationary phase column Chiralpak IE-3 (150 × 4.6 mm, 3 μm) provided better resolution with polar organic solvents than cellulose derivative, crown ether, and zwitterion stationary phases and nonpolar solvents. The mobile phase consisted of acetonitrile, tetrahydrofuran, methanol, butylamine, and acetic acid in the ratio of 500:500:20:2:1.5 (v/v/v/v/v). Isocratic elution was performed at a flow rate of 1.0 mL/min, column temperature of 35°C, injection volume of 10 μL, and UV detection of 240 nm. The United States Pharmacopeia (USP) resolution of the Exdl enantiomer was found to be more than 4.0 within a 65-min run time. Exdl enantiomer detector response linearity over the concentration range of 0.859–4.524 μg/mL was found to be R² = 0.9985. The limit of detection, limit of quantification, and average percentage recovery values were established as 0.283 μg/mL, 0.859 μg/mL, and 96.0, respectively.     

The Facet method: A hierarchical multilevel modelling scheme for anisotropic convex plastic potentials

An entirely new analytical expression describing plastic anisotropy is presented. It is designed to be used in combination with multilevel models. It makes use of the theory of dual plastic potentials, which is shortly revisited. An analysis of convexity is presented. Note that the new method is not optimal when not used in combination with a multilevel model; other methods are better suited for identification on the basis of mechanical test data. Compared with already existing methods which work with multilevel models, the new method has the following advantages: (i) it is automatically convex anywhere in the six-dimensional stress or strain rate space; (ii) it can be used for materials with a stress differential effect, such as hcp metals or pre-strained cubic materials; (iii) its identification procedure is such that not only the Taylor theory, but also more advanced theories, such as the Alamel-model or self-consistent models, can be used to identify the parameters; (iv) an analytical expression of the plastic potential can be obtained in both strain rate and stress space, which is an important advantage when implementing the model in finite element codes for metal forming. Equipotential surfaces in strain rate space and corresponding yield loci obtained by the new method for four materials (one ferrite single crystal, one aluminium alloy and two types of steel) are presented and discussed.     

Design,synthesis,characterization,cytotoxic and structure activity relationships of novel Ru(Ⅱ) complexes

Platinum containing compounds have shown antineoplastic potential, but their clinical applications have been limited by high toxicity. Ruthenium containing complexes have long been known to be well suited for biological applications, and have long been utilized as replacements to popular platinum based-drugs. Here, we report a novel series of ruthenium(II) arene compounds bearing thiosemicarbazone and isonicotinylhydrazone ligands with potent anticancer activity their structure activity relationships and apoptosis was studied. The cytotoxic activity of the new ruthenium(II) arene compounds has been evaluated in several cell lines (Molt 4/C8, L1210, CEM, HL60 and BEL7402). Among them, ten complexes were found to be excellent in vitro growth inhibitory activity against various cell lines with IC50 in the sub-micromolar range.     

Antimicrobial and Antimalarial Activity of Novel Synthetic Mononuclear Ruthenium(II) Compounds

The present work was aimed that the two Ruthenium compounds namely, [Ru(A)₂(B)]Cl₂, where A = 1,10‐phenanthroline; B = 2‐NO₂‐phenyl thiosemicarbazone (Compound R₁)/2‐OH‐phenyl thiosemicarbazone (Compound R₂) have been tested for antibacterial activity at the concentrations of 1 mg/mL against various Gram‐Positive organisms (Lactobacillus, Staphylococcus pyrogenes, Bacillus subtilis, Staphylococcus aureus & Bacillus megatarium) and Gram‐Negative organisms (Pseudomonas aeruginosa, Escherichia coli, Proteus vulgaris, Enterobacter aerogenes, Salmonella paratyphi, Klebsiella pneumonia & Proteus mirabilis). The compounds were also tested for antifungal activity against Aspergillus clavatus, Aspergillus niger, Colletotrichum & Penicillium notatum by using agar diffusion assay and antimalarial activity against Plasmodium falciparum (Strain 3D7) using MTT assay. The results concluded that the compound R₁ exhibited significant antibacterial activity than R₂ against Gram‐Negative bacteria with zones of inhibition ranging from 15‐20 mm. and mild antibacterial activity against Gram‐Positive bacteria in comparison to tetracycline, streptomycin and rifampicin. These complexes were found to have moderate antifungal activity with no activity was however observed against Aspergillus niger. The compound, R₁ exhibited antimalarial activity at 10 μg/mL, whereas R₂ did not show antimalarial activity upto 50 μg/mL. Sensitivity to the compounds was greatest in the gram‐negative bacteria, followed by the gram‐positive bacteria and fungi.     

Biflavonoids from Cycas beddomei

Chemical investigation on the constituents of the cones of Cycas beddomei has resulted in the isolation of a new biflavonoid, 2,3-dihydro-4'-O-methyl amentoflavone, along with 2,3,2',3'-tetrahydro hinokiflavone, 2,3,2',3'-tetrahydro amentoflavone, 2,3-dihydro amentoflavone. The last two compounds were not reported earlier from this plant. The structure of the new compound was established by detailed analysis of its spectral (mainly 1D and 2D NMR) data.     

A simple and efficient one-pot synthesis of 1,4-dihydropyridines using heterogeneous catalyst under solvent-free conditions

One-pot condensation of β-dicarbonyl compounds with aldehydes and ammonium acetate in the presence of HClO₄–SiO₂ at 80 °C under solvent-free conditions with good to excellent yields. The catalyst is easily prepared, stable, reusable and efficiently used under reaction conditions.     

Void growth and coalescence in single crystals

Void growth and coalescence in single crystals are investigated using crystal plasticity based 3D finite element calculations. A unit cell involving a single spherical void and fully periodic boundary conditions is deformed under constant macroscopic stress triaxiality. Simulations are performed for different values of the stress triaxiality, for different crystal orientations, and for low and high work-hardening capacity. Under low stress triaxiality, the void shape evolution, void growth, and strain at the onset of coalescence are strongly dependent on the crystal orientation, while under high stress triaxiality, only the void growth rate is affected by the crystal orientation. These effects lead to significant variations in the ductility defined as the strain at the onset of coalescence. An attempt is made to predict the onset of coalescence using two different versions of the Thomason void coalescence criterion, initially developed in the framework of isotropic perfect plasticity. The first version is based on a mean effective yield stress of the matrix and involves a fitting parameter to properly take into account material strain hardening. The second version of the Thomason criterion is based on a local value of the effective yield stress in the ligament between the voids, with no fitting parameter. The first version is accurate to within 20% relative error for most cases, and often more accurate. The second version provides the same level of accuracy except for one crystal orientation. Such a predictive coalescence criterion constitutes an important ingredient towards the development of a full constitutive model for porous single crystals.