Draft genome of Omphalotus olearius provides a predictive framework for sesquiterpenoid natural product biosynthesis in Basidiomycota

The secondary metabolome of Basidiomycota represents a largely uncharacterized source of pharmaceutically relevant natural products. Terpenoids are the primary class of bioactive compounds isolated from mushrooms. The Jack O'Lantern mushroom Omphalotus olearius was identified 50 years ago as a prolific producer of anticancer illudin sesquiterpenoids; however, to date there have been exceptionally few studies into the biosynthesis of these important compounds. Here, we report the draft genome sequence of O. olearius, which reveals a diverse network of sesquiterpene synthases and two metabolic gene clusters associated with illudin biosynthesis. Characterization of the sesquiterpene synthases enabled a comprehensive survey of all currently available Basidiomycota genomes, thereby creating a predictive resource for terpenoid natural product biosynthesis in these organisms. Our results will facilitate discovery and biosynthetic production of unique pharmaceutically relevant bioactive compounds from Basidiomycota.     

Diketones from ozonolysis of fused 3-phospholene oxides: Cyclizations to 3-phosphorinone and to 1,4-dihydro-1,4-azaphosphinine derivatives

1-R-3-Methyl-2,4,5,6,7,7a-hexahydro-1(H)-phosphindole 1-oxide and 1-R-3-methyl-6-methoxy-2,8,9,9a-tetrahydro-1(H)-benzo[e]phosphindole 1-oxide (R = Me or Ph) were prepared and ozonized at −78°C to give diketones in good yield. The intramolecular aldol condensation was performed on certain of these ketones to give multicyclic 3-phosphorinone derivatives. In some cases, double-bond rearrangement into the ring-fusion position was encountered. The 1-phenyl derivative in the benzophosphindole series could not be cyclized due to ready displacement of the P fragment from the tetralone system. The diketones reacted with ammonium acetate to give multicyclic derivatives of the 1,4-dihydro-1,4-azaphosphinine ring system. 1,2,3,4,5,6,7,8-Octahydro-3-oxo-1-phenylphosphinoline 1-oxide was used to demonstrate the value of the bicyclic 3-phosphorinones as precursors of 1-phosphadecalone derivatives. The carbonyl group was protected as the ethylene ketal and the double bond (as well as the benzene ring) was hydrogenated with ease. Hydrolysis gave the 1-phospha-3-decalone derivative. Reduction of the same 3-phosphorinone with NaBH₄ gave a mixture of diastereomeric alcohols.     

Diels-Alder adducts of 4-chloro-1,6-dihydrophosphinine derivatives: A new precursor of 2-phosphapropene

The 4-chloro-1,6-dihydrophosphinine derivatives, prepared as a mixture of 3- and 5-methyl isomers from the thermolysis of dichlorocarbene adducts with 1-R-3-methylphospholene oxide (R  Me, MeO, EtO, n-PrO, i-PrO), participate in Diels-Alder reactions with dimethyl acetylenedicarboxylate and N-phenylmaleimide. The former reactant is of special value since the 2-phosphabicyclo[2.2.2]octa-5,7-diene framework is thermally labile and undergoes retrocycloaddition by a different path, eliminating the C P bridging unit as a low-coordinate species. Thus, in the case of R  Me, the initial phosphine oxides (a mixture of isomers) have been reduced to the phosphines and these undergo straightforward fragmentations on heating at 50°C to produce 2-phosphapropene. The reactions of this transient species with water and alcohols have been investigated. Unlike the case of stabilized phosphaalkenes, hydration occurs smoothly without catalysis to produce Me₂P(O)H; addition of alcohols gives phosphinites, Me₂POR. The structure of the Diels-Alder adducts was confirmed by ³¹P, ¹H, and ¹³C NMR spectroscopy. Each of the isomeric 1,6-dihydrophosphinine oxides gives two diastereomeric adducts; partial separation of some of the resulting four-component mixtures was achieved with silica gel chromatography.     

CO Oxidation Activity and Characterization of Ag-Mn、Ag-Ce and Ag-Cu Mixed Oxide Catalysts

Catalytic oxidation is an efficient way to convert CO to CO₂ at low temperature. Precious metal catalysts such as Ft and Pd have been demonstrated to be very effective^[1]. However, attention has also been given to base metals due to the limited availability of precious metals. As a single component base metal catalyst cannot rival a precious metal catalyst, improvement in its activity has been attempted by combining several elements^[2,3]. In the present work, we studied redox and structure of Ag-M(M=Mn、Ce and Cu) catalysts to gain some evidence of the synergism between Ag and base metals, and investigated their catalytic activities.     

GaN光电阴极表面势垒对电子逸出几率的影响

针对GaN光电阴极表面势垒对电子逸出几率的影响问题,应用玻尓兹曼分布和基于Airy函数的传递矩阵法计算了GaN光电阴极的电子逸出几率,发现电子逸出几率主要由I势垒决定,II势垒对电子逸出几率的影响有限.利用自行研制的GaN光电阴极激活评估实验系统,测试了透射式GaN光电阴极样品的激活光电流.实验发现,Cs单独激活引起电子逸出几率的显著增加,而Cs单独充分激活后的Cs/O交替激活对电子逸出几率的影响有限.理论计算结果与激活光电流测试结果一致,其原因是Cs单独激活对降低真空能级的贡献远大于Cs/O共同激活.     

The reaction to the J = 2, 4.46 MeV level in Ne

We have used measurements of the reaction to deduce spectroscopic factors for the three j_n values which contribute to the transition to the 4.46 MeV level in ²²Ne. The results agree with the shell-model calculation of Preedom and Wildenthal.     

Syn to anti isomerization and degradation of phosphines of the 7-phosphanorbornene system by action of methanol

$\text{Syn}$-Substituted phosphines of the 7-phosphanorbornene system form unstable phosphorane adducts with methanol that either fragment by retro-McCormack cycloaddition or undergo polytopal rearrangement and loss of methanol to give the first examples of $\text{anti}$ phosphines.     

The 21N(→d,p)22Ne reaction to the Jπ = 2+, 4.46 MeV level in 22Ne

We have used measurements of the ${}^{21}\text{Ne(}\text{→d}\text{,p)}{}^{22}\text{Ne}$ reaction to deduce spectroscopic factors for the three j_n values which contribute to the transition to the 4.46 MeV level in ²²Ne. The results agree with the shell-model calculation of Preedom and Wildenthal.