The Biosynthesis of 1-octene-3-ol by a Multifunctional Fatty Acid Dioxygenase and Hydroperoxide Lyase in Agaricus bisporus.

The biosynthetic pathway from linoleic acid to 1-octen-3-ol in Agaricus bisporus has long been established, in which linoleic acid is converted to 10-hydroperoxide (10-HPOD) by deoxygenation, and 10-HPOD is subsequently cleaved to yield 1-octene-3-ol and 10-oxodecanoic acid. However, the corresponding enzymes have not been identified and cloned. In the present study, four putative genes involved in oxylipid biosynthesis, including one lipoxygenase gene named AbLOX, two linoleate diol synthase genes named AbLDS1 and AbLDS2, and one hydroperoxide lyase gene named AbHPL were retrieved from the A. bisporus genome by a homology search and cloned and expressed prokaryotically. AbLOX, AbLDS1, and AbLDS2 all exhibited fatty acid dioxygenase activity, catalyzing the conversion of linoleic acid to generate hydroperoxide, and AbHPL showed a cleaving hydroperoxide activity, as was determined by the KI-starch method. AbLOX and AbHPL catalyzed linoleic acid to 1-octen-3-ol with an optimum temperature of 35 °C and an optimum pH of 7.2, whereas AbLDS1, AbLDS2, and AbHPL catalyzed linoleic acid without 1-octen-3-ol. Reduced AbLOX expression in antisense AbLOX transformants was correlated with a decrease in the yield of 1-octen-3-ol. AbLOX and AbHPL were highly homologous to the sesquiterpene synthase Cop4 of Coprinus cinerea and the yeast sterol C-22 desaturase, respectively. These results reveal that the enzymes for the oxidative cleavage of linoleic acid to synthesize 1-octen-3-ol in A. bisporus are the multifunctional fatty acid dioxygenase AbLOX and hydroperoxide lyase AbHPL.

Copper(I)-Catalyzed Enyne Oxidation/Cyclopropanation: Divergent and Enantioselective Synthesis of Cyclopropanes.

An efficient copper(I)-catalyzed enyne oxidation/cyclopropanation for the modular synthesis of cyclopropane derivatives is described, which represents the first non-noble metal-catalyzed enynes oxidation/cyclopropanation by the in situ generated α-oxo copper carbenes. This protocol allows the assembly of valuable cyclopropane-γ-lactams in generally good to excellent yields with excellent diastereoselectivity. More significantly, the enantioselective version of enyne oxidation/cyclopropanation has been disclosed with chiral copper catalysts.

Taisui TS-2007S, a Large Microbial Mat Discovered in Soil in China.

In this study, Taisui TS-2007S, a previously unidentified biological object discovered in soil in China, was identified. TS-2007S was shown to contain abundant carbohydrates but a scarcity of protein, fat, and minerals. The exopolymers of TS-2007S showed FT-IR spectra that were similar to those of xanthan gum (XG) but that were dissimilar to those of polyvinyl alcohol (PVA). The NMR spectra of TS-2007S exopolymers in D2O were similar to those of PVA but differed from those of xanthan gum. Unlike PVA, TS-2007S exopolymers and xanthan gum were not soluble in dimethyl sulfoxide (DMSO). Furthermore, the exopolymers contained many monosaccharide components, including fucose, rhamnose, mannose, and glucuronic acid in a molar ratio of 87.90:7.49:4.45:0.15. The exopolymers also included traces of glucuronic acid, galactose, and xylose. Taken together, these results suggest that the exopolymers are microbial extracellular polymeric substances (EPSs). The microbial community structure in TS-2007S showed that the predominant bacterial, archaeal, and fungal phyla were Proteobacteria, Euryarchaeota, and Ascomycota at high relative abundances of 90.77, 97.15, and 87.43%, respectively, different from those observed in water and soil environments. Based on these results, we strongly propose that TS-2007S should be defined as a microbial mat formed in soil.

Cu(I)-Catalyzed Oxidative Cyclization of Enynamides: Regioselective Access to Cyclopentadiene Frameworks and 2-Aminofurans.

An efficient Cu(I)-catalyzed oxidative cyclization of alkynyl-tethered enynamides for the construction of fused bicyclic cyclopentadiene derivatives is disclosed. The cascade proceeds through alkyne oxidation, carbene/alkyne metathesis, and formal (3 + 2) cycloaddition. Employing aryl-tethered enynamides as starting materials, substituted 2-aminofurans can be exclusively formed.

[Study on terahertz spectra of multi-walled carbon nanotubes].

In the present paper, the authors report the characterization of multiwalled carbon nanotube at terahertz (THz) frequency range using terahertz time-domain spectroscopy. The surface appearances and microanalysis of multiwalled carbon nanotubes were measured by scanning electron microscope in order to fully understand the unique features and applications of multiwalled carbon nanotube. The results show that the refractive indexes of the sample decrease with increasing frequency in the frequency range of 0.2 to 2 THz, while the absorption coefficients of the sample increase with increasing frequency. In addition, the curve of terahertz absorption coefficients can be fitted by a straight line with a slope of 1.92. From the results of scanning electron microscope, the ranges of inner diameter and outer diameters of the sample were from 5 to 15 nm and from 15 to 25 nm, respectively, and its length was in the order of micrometer. The results of microanalysis of its elemental composition showed that the content of element C was about 94% and the rest were O and Cl elements, which were impurity elements. Mathematical modes of terahertz absorption and refractive indexes in the frequency range of 0.2 to 2.0 THz were established after taking into account Taylor expansion and Maxwell's equations, and the calculation was in relatively good agreement with the observed values of the sample in general. The terahertz refractive indexes and absorption properties of multiwalled carbon nanotube were mainly attributed to the chemical compositions and molecular weight, and carbon nanotubes with different content of carbon could show different terahertz absorption spectra and disclose different unique functions.

Development of nucleic acid isolation by non-silica-based nanoparticles and real-time PCR kit for edible vegetable oil traceability.

For efficient extraction of amplifiable DNA from edible vegetable oils, we developed a novel DNA extraction approach based on the non-silica-based dipolar nanocomposites. The nanoparticle comprises a hydrophilic polymethyl methacrylate core with abundant capillaries, hydrophilic vesicles decorated with molecules having DNA affinity and a coating hydrophobic polystyrene layer. The nanoparticles are soluble in oil, adsorb the DNA from the aqueous phase and gave a high DNA recovery ratio. All DNA extracts from fully refined vegetable oil soybean, peanut, rapeseed, and cottonseed oils, including their blends, were sufficiently pure to be amplified by real-time PCR targeting the chloroplast ribulose-1,5-bisphosphate gene (rbcL), therefore, the species of origin and their ratios in mixed vegetable oils blended from two or three oil-species could be determined. These results indicate that the novel DNA isolation and real-time PCR kit is a simple, sensitive and efficient tool for the species identification and traceability in refined vegetable oils.

Vibrational spectra of guaiacylglycerol-ß-guaiacyl ether: experiment and theory.

As an important inter-unit of lignin, guaiacylglycerol-ß-guaiacyl (GG) ether has been synthesized, and characterized using terahertz time-domain spectroscopy in the frequency range of 5-85 cm(-1). Seven absorption peaks have been observed. Among these peaks, the 49.8 cm(-1) and 57.6 cm(-1) vibrations are propose to be characteristic absorption peaks of GG ether. Raman spectra were also measured in the range of 50-3500 cm(-1). The vibrations of the two lowest energy forms, i.e., erythro 1r4s and threo 1s4s, were calculated using density functional theory at the B3LYP/6-311G∗∗ level and assigned according to potential energy distribution. In addition, the contents of erythro and threo forms in GG sample could be estimated by comparing the waveform similarities between theoretical and observed curves in the 33.0-80.0 cm(-1) range. Results showed that the observed curve of GG sample is a combination of erythro 1s4r and threo 1s4s. The four absorption vibrations below 33.0 cm(-1) could be assigned to phonon, inter-molecular modes and/or hydrogen bond vibrations. Terahertz spectra and Raman spectra, together with theoretical calculations, could be powerful methods for predicting contents of different isomers in sample.