Four New Terpenoids from Xylaria sp. 101

One new diterpenoid, xylarenolide ( 1 ), and three new sesquiterpenoids, xylaranol A ( 2 ), xylaranol B ( 3 ), and xylaranic acid ( 4 ), were obtained from the fungal strain Xylaria sp. 101, which was isolated from the fruiting body of Xylaria sp. collected in Gaoligong Mountain, Yunnan Province. Their structures were elucidated by spectroscopic analyses, including 1D‐ and 2D‐NMR experiments, and by HR‐Q‐TOF mass spectrometry. Their antimicrobial activities were evaluated.     

Phytoquinoids and Secoprezizaane‐Type Sesquiterpenes from Illicium arborescens

A phytochemical investigation of the MeOH extract of Illicium arborescens yielded the two new phytoquinoid epimers, 2,3‐didehydro‐5‐O‐methyl‐11‐epiillifunone E ( 1 ) and 2,3‐didehydro‐5‐O‐methylillifunone E ( 2 ), as well as five new sesquiterpene lactones (8,9‐secoprezizaane‐type sesquiterpenes). Two of them, i.e., 3 and 4 , were minwanensin‐type sesquiterpenes, the other two, i.e., 5 and 6 , had the anisatin‐type (or floridanolide type) skeleton, and the fifth, i.e., 7 , was a dunnianin‐type sesquiterpene. Their structures were established by analyses of 1D‐ and 2D‐NMR, HR‐MS, and chemical evidence. The in vitro cytotoxic activity of compounds 1 – 7 was tested against four human tumor cell lines, including HeLa (cervical epitheloid), WiDr (colon), Daoy (medulloblastoma), and Hep2 (liver carcinoma) human‐tumor cells.     

Isopiestic Determination of Water Activity on the System LiNO<Subscript>3</Subscript>+KNO<Subscript>3</Subscript>+H<Subscript>2</Subscript>O at 273.1 and 298.1 K

Water activities in the ternary LiNO₃+KNO₃+H₂O system and its sub-binary systems have been measured by the isopiestic method at 273.1 and 298.1 K. The measured results were treated by a Pitzer-Simonson-Clegg thermodynamic model, from which the predicted solubility isotherms were compared with the experimental results. Based on this comparison, the reliability of the measured results was discussed. The measured results help in predicting the phase diagram of the ternary system, as well as other multi-component systems based on the ternary system.     

Bi3In4S10 and Bi14.7In11.3S38: Two new bismuth sulfides with interesting Bi-Bi bonding

Two new ternary bismuth chalcogenides, Bi₃In₄S₁₀ and Bi_14.7In_11.3S₃₈, were synthesized from the reactions of binary sulfides via a two-step flux technique. Single-crystal X-ray diffraction analyses indicate that Bi₃In₄S₁₀ crystallizes in the non-centrosymmetric space group Pm and Bi_14.7In_11.3S₃₈ crystallizes in the centrosymmetric space group P2₁/m. Both compounds adopt three-dimensional frameworks. A distinct structural feature in the two structures is the presence of chains of Bi atoms with alternating short Bi-Bi bonds of around 3.1 Å and longer distances of around 4.6 Å. The optical band gaps of 1.42(2) eV for Bi₃In₄S₁₀ and 1.45(2) eV for Bi_14.7In_11.3S₃₈ were deduced from the diffuse reflectance spectra.     

KBiMS4 (M=Si, Ge): Synthesis, structure, and electronic structure

Two new bismuth sulfides KBiSiS₄ and KBiGeS₄ have been synthesized by means of the reactive flux method. They adopt the RbBiSiS₄ structure type and crystallize in space group P2₁/c of the monoclinic system. The structure consists of (M=Si, Ge) layers separated by bicapped trigonal-prismatically coordinated K atoms. The M atom is tetrahedrally coordinated to four S atoms and the Bi atom is coordinated to a distorted monocapped trigonal prism of seven S atoms. The optical band gap of 2.25(2) eV for KBiSiS₄ was deduced from the diffuse reflectance spectrum. From a band structure calculation, the optical absorption for KBiSiS₄ originates from the layer. The Si 3p orbitals, Bi 6p orbitals, and S 3p orbitals are highly hybridized near the Fermi level. The orbitals of K have no contributions on both the upper of valence band and the bottom of conduction band.     

A new sample preparation method for determination of acidic drugs in sewage sludge applying microwave assisted solvent extraction followed by gas chromatography-mass spectrometry

This paper presents a new sample preparation procedure for determination of selected acidic pharmaceuticals (ibuprofen, naproxen, ketoprofen, and diclofenac) in sewage sludge using microwave assisted solvent extraction, dispersive matrix extraction (DME) followed by the conventionally applied solid phase extraction (SPE), derivatization, and gas chromatography-mass spectrometry. The recoveries calculated from analytical data of spiked sludge samples changed in the range of 80-105% ± 15% for the four pharmaceuticals in mixed and activated sludge depending on the efficiency of the clean-up procedure. The measured concentration values of ibuprofen and naproxen were identical in the mixed and the activated sludge samples. However, ketoprofen and diclofenac showed about twice as high concentration in activated sludge than in the mixed one independently of the applied extraction method. The typical concentration ranges of ibuprofen, naproxen, ketoprofen and diclofenac in sewage sludge were 10-30 ng/g, 30-50 ng/g, 50-130 ng/g, and 50-140 ng/g respectively.     

Gene Cloning,Expression, and Characterization of a Family 51 α-<Emphasis Type="SmallCaps">l</Emphasis>-Arabinofuranosidase from <Emphasis Type="Italic">Streptomyces</Emphasis> sp. S9

An α-l-arabinofuranosidase gene, abf51S9, was cloned from Streptomyces sp. S9 and successfully expressed in Escherichia coli BL21 (DE3). The full-length gene consisted of 1,506 bp and encoded 501 amino acids with a calculated mass of 55.2 kDa. The deduced amino acid sequence was highly homologous with the α-l-arabinofuranosidases belonging to family 51 of the glycoside hydrolases. The recombinant protein was purified to electrophoretic homogeneity by Ni-NTA affinity chromatography and subsequently characterized. The optimal pH and temperature for the recombinant enzyme were 6.0 and 60∼65 °C, respectively. The enzyme showed a broad pH range of stability, retaining over 75% of the maximum activity at pH 5.0 to 11.0. The specific activity, K _m, and V _max with p-nitrophenyl-α-l-arabinofuranoside as substrate were 60.0 U mg⁻¹, 1.45 mM, and 221 μmol min⁻¹ mg⁻¹, respectively. Abf51S9 showed a mild but significant synergistic effect in combination with xylanase on the degradation of oat-spelt xylan and soluble wheat arabinoxylan substrates with a 1.19- and 1.21-fold increase in the amount of reducing sugar released, respectively. These favorable properties make Abf51S9 a good candidate in various industrial applications.     

Interfacial Molecular Assemblies of Metalloporphyrins with Two Trans or One Axial Ligands

Molecular assemblies of metalloporphyrins trans‐dichloro(5,10,15,20‐tetra‐p‐tolylporphyrinato)tin(IV) (SnCl2TPPMe) and trans‐dihydroxo(5,10,15,20‐tetra‐p‐tolylporphyrinato)tin(IV) (Sn(OH)2TPPMe), which have two trans axial ligands, as well 5,10,15,20‐tetrakis(4‐methoxyphenyl)‐21H,23H‐porphine iron(III) chloride (FeClTPPOMe) and 5,10,15,20‐tetraphenyl‐21H,23H‐porphine manganese(III) chloride (MnClTPP), which have one axial ligand, are interfacially organized by Langmuir and Langmuir–Blodgett (LB) techniques. SnCl2TPPMe and Sn(OH)2TPPMe form nanofibrous structures which can display distinct supramolecular chirality, although the molecular units themselves are achiral, while FeClTPPOMe and MnClTPP form irregular nanoparticles that display negligible supramolecular chirality. An interpretation in terms of the effects of the axial ligands is proposed for this interesting phenomenon. Moreover, compared with assemblies of the diprotonated free‐base porphyrins, which are fabricated by interfacial (air/2.4 M HCl) organization of free‐base porphyrin, those of SnCl2TPPMe and Sn(OH)2TPPMe display higher stability in terms of supramolecular chirality. These results indicate that the assembly properties of metalloporphyrins can essentially be affected by the axial ligands that are attached to their chromophores, and that stable chiral porphyrin supramolecular associations can be easily produced by using achiral metalloporphyrins bearing two trans axial ligands.