Biosynthesis of Indole Diterpene Lolitrems: Radical-Induced Cyclization of an Epoxyalcohol Affording a Characteristic Lolitremane Skeleton

Lolitrems are tremorgenic indole diterpenes that exhibit a unique 5/6 bicyclic system of the indole moiety. Although genetic analysis has indicated that the prenyltransferase LtmE and the cytochrome P450 LtmJ are involved in the construction of this unique structure, the detailed mechanism remains to be elucidated. Herein, we report the reconstitution of the biosynthetic pathway for lolitrems employing a recently established genome-editing technique for the expression host Aspergillus oryzae. Heterologous expression and bioconversion of the various intermediates revealed that LtmJ catalyzes multistep oxidation to furnish the lolitrem core. We also isolated the key reaction intermediate with an epoxyalcohol moiety. This observation allowed us to establish the mechanism of radical-induced cyclization, which was firmly supported by density functional theory calculations and a model experiment with a synthetic analogue.     

Spontaneous Formation of Microgroove Arrays on the Surface of p‐Type Porous Silicon Induced by a Turing Instability in Electrochemical Dissolution

Self‐organization plays an imperative role in recent materials science. Highly tunable, periodic structures based on dynamic self‐organization at micrometer scales have proven difficult to design, but are desired for the further development of micropatterning. In the present study, we report a microgroove array that spontaneously forms on a p‐type silicon surface during its electrodissolution. Our detailed experimental results suggest that the instability can be classified as Turing instability. The characteristic scale of the Turing‐type pattern is small compared to self‐organized patterns caused by the Turing instabilities reported so far. The mechanism for the miniaturization of self‐organized patterns is strongly related to the semiconducting property of silicon electrodes as well as the dynamics of their surface chemistry.     

A heuristic approach for dividing graphs into bi-connected components with a size constraint

In this paper we propose a new problem of finding the maximal bi-connected partitioning of a graph with a size constraint (MBCPG-SC). With the goal of finding approximate solutions for the MBCPG-SC, a heuristic method is developed based on the open ear decomposition of graphs. Its essential part is an adaptation of the breadth first search which makes it possible to grow bi-connected subgraphs. The proposed randomized algorithm consists of growing several subgraphs in parallel. The quality of solutions generated in this way is further improved using a local search which exploits neighboring relations between the subgraphs. In order to evaluate the performance of the method, an algorithm for generating pseudo-random unit disc graphs with known optimal solutions is created. Computational experiments have also been conducted on graphs representing electrical distribution systems for the real-world problem of dividing them into a system of fault tolerant interconnected microgrids. The experiments show that the proposed method frequently manages to find optimal solutions and has an average error of only a few percent to known optimal solutions. Further, it manages to find high quality approximate solutions for graphs having up to 10,000 nodes in reasonable time.     

Electrochemical Fluorination of Dithiocarbonates Using a Triarylamine Mediator

Electrochemical oxidation of O-(4-chlorobenzyl) S-methyl dithiocarbonate using tris(2,4-dibromophenyl)amine as a redox mediator was studied by cyclic voltammetric measurements. The triarylamine mediated anodic fluorodesulfurization of O-(4-chlorobenzyl) and O-(4-bromobenzyl) S-methyl dithiocarbonates provided 4-chloro- and 4-bromobenzyl fluorides, respectively in moderate yields. On the other hand, similar anodic fluorination of O-(2-phenethyl) S-octyl dithiocarbonate and O-(4-bromophenyl) S-methyl dithiocarbonate afforded 2-phenethyl trifluoromethyl ether and difluoro(methylthio)methyl 4-bromophenyl ether, respectively. Mechanistic aspects are also discussed.     

Experimental study of heat and mass transfer from a horizontal cylinder in downward air-water mist flow with blockage effect

An experimental study was made on convective heat and mass transfer from a horizontal heated cylinder in a downward flow of air-water mist at a blockage ratio of 0.4. The measured local heat transfer coefficients agree fairly well with the authors' numerical solutions obtained previously for the front surface of a cylinder over the ranges mass flow ratio 0–4.5×10⁻², a temperature difference between the cylinder and air 10–43 K, gas Reynolds number (7.9–23)×10³, Rosin-Rammler size parameter 105–168 μm, and dispersion parameter 3.4–3.7. Heat transfer augmentation, two-pahse to single-phase of greater than 19 was attained at the forward stagnation point. For heat transfer in the rear part of the cylinder, an empirical formula is derived by taking into account the dimensionless governing variables, that is, coolant-feed and evaporation parameters.     

连铸结晶器内部流场及熔渣卷入的数值模拟

针对连铸结晶器内部流场及熔渣卷入过程 ,提出了两方程k -ε湍流模型和充填法数值计算模型 ,并采用硅油 /水模拟体系代替熔渣 /钢液体系 ,进行了模拟试验和数值计算。对充气造成的浸入式水口水流脉动的影响进行分析。计算结果与试验结果符合良好 ,表明本文所采用的数值模拟方法是适用的     

Evaluation of Successive Fractions for Optimum Quantification of Bergenin and Gallic Acid in Three Industrially Important Bergenia species by High-Performance Thin-Layer Chromatography

JPC – Journal of Planar Chromatography – Modern TLC -