High Efficiency Microwave Flow Chemistry Towards Synthesis of Functional Materials and Pharmaceutical Cores

[EN] Microwave (MW) heating benefits organic synthesis by affording higher product yields in shorter time periods than conventional heating, yet it suffers from poor scalability and is limited to polar solvents in typical batch mode reactors. Herein, we report a microwave flow reactor using a solid-state semiconductor MW generator. The tunable, single-mode MW heating allows high efficiency, scalable organic synthesis, rapid reaction optimization and is applicable to non-polar solvents (o-Xylene and CPME can be rapidly heated to ca. 260 oC). Auto-frequency tuning compensates for changes in the microwave absorption properties (permittivity, epsilon) with increasing temperature, affording excellent temperature and process control. This technology unlocked unprecedented g/h productivity of C60/fullerene-indene monoadduct (IC60MA) and facilitated a novel, transition metal-free amide-styrene coupling reaction for synthesis of amide-containing pharmaceutical cores in up to 65 g/h (Figure 1). An ortho-Claisen rearrangement reaction was rapidly optimised.The authors gratefully acknowledge the technical support from the National Institute of Advanced Industrial Science and Technology and the University of Shizuoka, as well as financial support from NEDO, Shizuoka Prefectural Government. Joshua P. Barham is grateful for financial support from JSPS (KAKENHI Grant Number JP18F19030). The authors are grateful for Shizuoka University (Prof. Noboyuki Mase’s group) and Gifu Pharmaceutical University (Prof. Hironao Sajiki’s group) for their research in this area.Barham, J.; Koyama, E.; Sugiyama, J.; Norikane, Y.; Egami, H.; Hamashima, Y. (2019). High Efficiency Microwave Flow Chemistry Towards Synthesis of Functional Materials and Pharmaceutical Cores. En AMPERE 2019. 17th International Conference on Microwave and High Frequency Heating. Editorial Universitat Politècnica de València. 409-417. https://doi.org/10.4995/AMPERE2019.2019.9860OCS40941

Host-feeding patterns of Culex tritaeniorhynchus and Anopheles sinensis (Diptera: Culicidae) in a ricefield agroecosystem.

金沢大学理工研究域　自然システム学系水田発生性蚊類成虫の吸血選択を調べるために, 佐賀県西有田町で1996及び1997年の5月から9月に成虫採集を行った。ドライアイス付加ライトトラップと吸虫管により合計31,804頭のコガタアカイエカとシナハマダラカ雌成虫を採集した。調査したすべての牛舎と豚舎ではライトトラップ採集により多数の成虫が捕獲されたが(牛舎7,933,豚6,441,鶏舎5,267), 鶏舎では吸血蚊がほとんど採集されなかった。コガタアカイエカとシナハマダラカの吸血率は, 牛舎と豚舎ではそれぞれ62%(N=7,113), 74%(N=7,261)であったが, 鶏舎では5%以下(N=5,267)であった。ELISAによる吸血源同定の結果, 両種とも鶏よりも牛と豚を選択していることが示された。また, 牛舎と隣接した鶏舎から採集された吸血蚊も90%以上(N=143)が牛を吸血していた。鶏よりも豚と牛から吸血する傾向は採集場所(棚田周辺か平野部), 採集方法(ライトトラップか吸虫管)を問わず観察された。 Adults of rice-field mosquitoes were collected between May and September of 1996 and 1997 in Nishi Arita, Saga Prefecture, Japan, to determine their feeding pattern in an area where animals were available in large numbers. In total, 31,804 female Culex tritaeniorhynchus and Anopheles sinensis were collected from animal sheds using dry ice-baited light traps and mouth aspiration. Light traps in all the animal sheds captured large numbers of mosquitoes (cowsheds 7,933,pigsties 6,441 and chicken sheds 5,267 mosquitoes), although few fed upon the chickens. Overall, 62% (N=7,113) of fed Cx. triaeniorhynchus and 74% (N=7,261) of An. sinensis were caught by light traps at the cowsheds and pigsties compared to less than 5% (N=5,267) at the chickens sheds. The type of animal in the shed was the most important factor determining the feeding rates. Blood-meal identification by direct ELISA indicated that both Cx. tritaeniorhynchus and An. sinensis preferred cows and pigs to chickens. Over 90% (N=143) of the fed mosquitoes collected from one chicken shed had fed upon cows in an adjoining cowshed. The tendency to feed upon cows and pigs more than on chickens was observed both in the hillside (terraced) and lowland ricefields. This trend is shown in the results obtained by both the aspirator and light trap collection methods

The Oxidative Esterification of Propionaldehyde to Methyl Propionate in the Liquid-Phase Using a Heterogeneous Palladium Catalyst

The optimization of the oxidative esterification of propionaldehyde to methyl propionate using a supported palladium catalyst in methanol under heavy-metal-free and pressurized-oxygen conditions, which we recently reported in a previous paper, were carried out together with a study of the reaction route, the nature of the catalytic active sites, and the effect of the support. In our previous paper, we reported significantly improved activity for oxidative esterification using commercially available 5%Pd/Al2O3 at 1.5 MPa of O2 gas and 333 K and emphasized that the doping of 5%Pd/Al2O3 with lead was not needed for the reaction system, but we could not improve the activity that was reported when using 5%Pd/γ-Al2O3 doped with 5% Pb (a 93.2% conversion of propionaldehyde, 76.8% selectivity for methyl propionate and a 71.6% yield of methyl propionate) at 0.3 MPa of O2 gas and 353 K, as reported by another laboratory. In the present study, however, we exceeded those values and obtained a 98.3% conversion of propionaldehyde, 75.3% selectivity for methyl propionate and a 74.0% yield of methyl propionate using 5%Pd/γ-Al2O3 undoped with Pb at 1.5 MPa of O2 gas and 333 K. It should be noted that, in the preparation of the present 5%Pd/γ-Al2O3, Pd was doped onto Al2O3 that had been previously treated with aqueous NaOH. Another active alumina support,η-Al2O3, prepared from boehmite, afforded activity that was substantially lower than that of γ-Al2O3 and depended on the calcination temperature of boehmite to η-Al2O3. When using various concentrations of CH3OH in the aqueous reaction solution, the oxidative esterification proceeded through the formation of propionic acid. To determine why the Al2O3 support afforded better activity than the active carbon support, Pd/Al2O3 and Pd/C catalysts were examined by XAFS (X-ray absorption fine structure). XAFS revealed that Pd on Al2O3 shows a better redox nature than Pd on C, which resulted in activity on Pd/Al2O3 that was better than that on Pd/C

A Culturally Nuanced Test of Gottfredson and Hirschi’s ‘‘General Theory’’: Dimensionality and Generalizability in Japan and the United States

The current research addresses two specific issues that direct attention to the relatively neglected topic of the cross-cultural applicability of Gottfredson and Hirschi’s ‘‘general theory’’ that has been developed in and tested primarily in the United States. With theoretical and empirical guidance from the literature on dimensionality of low self-control, we first predict that the six elements identified in the theory form a multidimensional latent construct in two diverse societies—Japan and the United States. Drawing on the literature concerning cultural variability in individualism, and inconsistent with self-control theory, the authors then expect that although low self-control leads to deviance in both societies, the causal relationship is stronger among Americans than among Japanese. Analysis of identical survey data collected simultaneously from college students in Japan and the United States provides somewhat mixed support for our expectations and the findings appear largely consistent with predictions by self-control theory.Yeshttps://us.sagepub.com/en-us/nam/manuscript-submission-guideline

A Case of Early Gastric Cancer Arising from Gastritis Cystica Profunda Treated by Endoscopic Submucosal Dissection

Gastritis cystica profunda (GCP) consists of hyperplasia and cystic dilatation of the gastric glands extending into the submucosa. It occurs in the residual stomach post surgery and in the unoperated stomach. GCP is considered a benign lesion, but there is controversy about its malignant potential. We report a case of early gastric cancer arising from GCP treated by endoscopic submucosal dissection (ESD) in a 55-year-old unoperated man. Upper gastrointestinal endoscopy revealed a 15-mm diameter submucosal tumor (SMT) in the upper corpus of the stomach. The surface had angiotelectasia and slight depression covered with normal mucosa. Neither ulceration nor erosion was seen. Narrow-band imaging endoscopy showed no abnormalities suggesting gastric cancer. Endoscopic ultrasonography visualized the internally low-echoic SMT, harboring tiny cystic lesions, mainly within the second and third layers of the gastric wall. The SMT was removed by ESD to avoid retention and allow for comprehensive diagnosis. It was diagnosed as GCP with partial well-differentiated adenocarcinoma without involvement of the lateral and deep margins, lymphatic invasion, vascular invasion and perineural invasion. The gastric epithelium comprised normal mucosa without dysplasia. ESD seems to be useful for the diagnosis of SMT, including GCP harboring gastric cancer, and avoids unnecessary surgical procedures