日本化学会公报（BCSJ）致力于发表理论与物理化学、分析与无机化学、有机与生物化学、应用与材料化学等领域的科研论文。 BCSJ 以月刊形式在线出现，并提前发布三种描述原创研究的论文（ACCOUNTS、ARTICLES 和 SHORT ARTICLES）。 BCSJ 的目的是选择和发表对整个化学界具有最广泛意义的最重要的论文。日本化学会希望所有访客都能注意到我们期刊的实用性和丰富的主题，并欢迎来自世界各地的科学家的更多投稿。

The Bulletin of the Chemical Society of Japan (BCSJ) is dedicated to publishing research papers in the fields of theoretical and physical chemistry, analytical and inorganic chemistry, organic and biochemistry, as well as applied and materials chemistry. BCSJ is published online on a monthly basis and features early releases of three types of original research papers (ACCOUNTS, ARTICLES, and SHORT ARTICLES). The aim of BCSJ is to select and publish the most significant papers that hold broad relevance for the entire chemistry community. The Chemical Society of Japan encourages all visitors to recognize the practicality and diverse topics of our journal and welcomes submissions from scientists around the world.

《Bulletin of the Chemical Society of Japan》（BCSJ）致力于发表理论与物理化学、分析与无机化学、有机与生物化学、应用与材料化学等领域的科研论文。BCSJ 以月刊形式在线发布，并提前发布三种类型的原创研究论文（ACCOUNTS、ARTICLES 和 SHORT ARTICLES）。BCSJ 的目标是选择和发表对整个化学界具有广泛意义的重要论文。日本化学会希望所有访客都能注意到我们期刊的实用性和丰富的主题，并欢迎来自世界各地的科学家投稿。

Bulletin of the Chemical Society of Japan

Abstract Electron spin resonance (ESR) spin trapping using 5,5-dimethyl-1-pyrroline N-oxide (DMPO) is commonly applied for quantitative analysis of hydroxyl radical. For better understanding of the analysis, we investigated kinetics related to formation and decay of hydroxyl radical spin adduct of DMPO compared with that of 3,3,5,5-tetramethyl-1-pyrroline N-oxide (M4PO) and 5-(diphenylphosphinoyl)-5-methyl-1-pyrroline N-oxide (DPPMPO). In our study where hydroxyl radical was generated by sonolysis of water, we found that (1) DMPO-OH formation was saturated even though hydroxyl radical was generated continuously and (2) the concentration of DMPO-OH decreased in inverse proportion to time after cessation of ultrasound irradiation, suggesting that the decay is a second-order reaction. Similar results were obtained in an experiment of DMPO-OH generated by photolysis of H2O2. Other than DMPO, M4PO, and DPPMPO also trapped hydroxyl radical but the spin trap efficiency was less than that of DMPO. Furthermore, M4PO-OH and DPPMPO-OH decayed more quickly than DMPO-OH. From this, we conclude that DMPO is more suitable for quantification of hydroxyl radical than M4PO and DPPMPO but results from the quantitative analysis must be interpreted with consideration of the kinetics related to formation and decay of DMPO-OH, especially in quantification of large amount of hydroxyl radical generation.

Keisuke Nakamura

Taro Kanno

Hiroyo Ikai

Emiko Sato

Takayuki Mokudai

Yoshimi Niwano

Toshihiko Ozawa

Masahiro Kohno

Reevaluation of Quantitative ESR Spin Trapping Analysis of Hydroxyl Radical by Applying Sonolysis of Water as a Model System

Abstract A kinetic study was performed for the free-radical scavenging actions of curcumin and half-curcumin, which has a half-structure of curcumin, in order to clarify the mechanism of free-radical-scavenging in curcumin. The second-order rate constants for radical-scavenging reactions of curcumin and half-curcumin were measured by a stopped-flow spectrophotometer in several organic solvents (methanol, ethanol, acetonitrile, chloroform, and benzene) and in aqueous Triton X-100 (5.0 wt %) micelle solutions at various pH. The difference in the rate constant and solvent dependence between curcumin and half-curcumin suggests that the enol structure with the intramolecular hydrogen-bond of curcumin strongly enhances the radical-scavenging activity. Furthermore, notable pH dependences were observed for the rate constants of curcumin and half-curcumin in micelle solutions, suggesting that the acid–base dissociation equilibrium of phenol-protons in curcumin and half-curcumin affects their radical-scavenging activities.

Keishi Ohara

Wataru Mizukami

Aiko Tokunaga

Shin-ichi Nagaoka

Hidemitsu Uno

Kazuo Mukai

Kinetic Study of the Mechanism of Free-Radical Scavenging Action in Curcumin: Effects of Solvent and pH

姜黄素自由基清除作用机制的动力学研究：溶剂和pH的影响

The title polycyclic aromatic hydrocarbons were synthesized by Pd-catalyzed Heck-type cyclotrimerization of 2-bromoaceanthrylene derivatives. X-ray analysis of the 2,4,6-trimethylphenyl substituted derivative revealed that molecules took a propeller-shaped aromatic framework. The barrier to propeller inversion of this derivative was determined to be 81 kJ mol−1 by a dynamic NMR method. Decacyclene derivatives with three fused benzene rings were synthesized by Heck-type cyclotrimerization of 2-bromoaceanthrylene derivatives. These compounds have propeller-shaped aromatic frameworks to avoid steric interactions between the anthracene blades. The barrier to propeller inversion of this derivative was determined to be 81 kJ mol−1 by the dynamic NMR method.

Shun Fukamizo

Hiroshi Ikeda

Eiji Tsurumaki

Shinji Toyota

An Alternative Synthesis of Tribenzodecacyclenes and Experimental Barrier to Propeller Inversion

三苯基十环烯的替代合成及螺旋反转实验障碍

Abstract Prussian blue (PB) and its analogues (PBAs) are promising coordination polymers (CPs) with an adjustable composition and open framework. Nonetheless, their intrinsic electrochemical activity and electrical conductivity are poor, which hinder their applications in energy conversion and storage. In catalytic applications, metal compounds derived from PB/PBAs have a lot of advantages, such as outstanding stability, selectivity, and electrical conductivity. Furthermore, they can be used as electrode materials for electrochemical energy storage and conversion, while having preferable electronic conductivity, sufficient catalytic active sites, as well as a larger specific surface area and tunable size to achieve an optimized performance. This review summarizes the current achievements of PB/PBA-derived metallic nanomaterials, as well as the existing limitations, urgent challenges and future development.

Yang Shan

Guangxun Zhang

Wei Yin

Huan Pang

Qiang Xu

BCSJ

Recent Progress in Prussian Blue/Prussian Blue Analogue-Derived Metallic Compounds

普鲁士蓝/普鲁士蓝类似物衍生金属化合物的最新进展

Abstract Micrometer-sized water-in-oil droplets (microdroplets) are attracting attention as carriers for the high-throughput parallel analysis of trace samples. By confining trace amounts of water-soluble samples or reagents within a microdroplet, reactions and detection can be performed while suppressing diffusion dilution. Although many manipulation methods for droplets, such as mixing, merging, and splitting using microfluidic channels have been reported, concentration enrichment and purification techniques for microdroplet inclusions have been limited. Our recently developed method for selective concentration enrichment of microdroplet contents focuses on molecular transport between microdroplets and reverse micelles.

Mao Fukuyama

Understanding Molecular Transfer between Aqueous Phase and Reverse Micelles and Its Application to Bioassays in Microfluidics

理解水相与反胶束之间的分子传递及其在微流控生物检测中的应用

Abstract Zinc glutarate (ZnGA) is used as a solid-state heterogeneous catalyst for the synthesis of aliphatic polycarbonate from the alternating copolymerization of CO2 and epoxide. However, the conventional synthesis of ZnGA involves the use of a large amount of toluene, which is a toxic substance. In present, we developed a solvent-free, environmentally friendly synthesis for ZnGA using a mechanochemical process. This accelerated the formation of flake-like ZnGA microcrystals in a shorter reaction time than that of the conventional method. X-ray diffraction, X-ray photoelectron spectroscopy, X-ray absorption fine structure analyses, and Fourier-transform infrared spectroscopy revealed that ZnO is the most effective source of Zn. This catalyst selectively produced poly(propylene carbonate) from CO2 and propylene oxide, with a molecular weight (Mn) of 25,000 and a molecular weight distribution (Mw/Mn) of 5.27. We believe that this mechanochemical synthesis is a sustainable alternative to conventional approaches.

Norio Saito

Mayayoshi Honda

Hiroshi Sugimoto

Takahiro Takei

Nobuhiro Kumada

Solvent-Free Mechanochemical Synthesis of Zinc Glutarate for the Heterogeneous Catalysis of Propylene Oxide and CO2 Copolymerization

无溶剂机械化学合成戊二酸锌用于丙烯氧化物与二氧化碳共聚的非均相催化

Abstract Life can properly respond to external stimuli. This is because life is constructed by individual components (molecules and macromolecules) and responds to the external environment autonomously as a system, through interactions between components, converting energy, and information. This response contrasts with matter, which responds directly to external fields (heat, electric or magnetic fields, light, etc.). Life self-reproduces by converting ingested essential nutrients for self-reproduction and moves to safe and nourished areas. Life also possesses information molecules and propagates the information to its offspring. In this repeatable process, individuals possessing traits adaptable to their environment become the dominant species through natural selection, leading to evolution. We believe that even such a sophisticated life can be constructed as a dynamic supramolecular system by assembling characteristic molecules and macromolecules. This review shows how giant vesicles, self-assemblies of amphiphilic molecules, self-reproduce as primitive model protocells, expressing life-like features by incorporating new components, and eventually evolve into the ultimate artificial cell model.

Tadashi Sugawara

Muneyuki Matsuo

Taro Toyota

“Life” as a Dynamic Supramolecular System Created Through Constructive Approach

“生命”作为通过构建性方法创造的动态超分子系统

Abstract Corminboeuf et al. theoretically predicted that closely π-stacked dimers of antiaromatic molecules tend to exhibit aromatic characters in the sense of magnetic and structural criteria due to the strong intermolecular orbital interactions. This phenomenon is usually called stacked-ring aromaticity. Several experimental and theoretical studies have been conducted to elucidate the aromaticity switching mechanism in the π-stacked dimers and proposed molecular systems realizing this type of phenomenon. So far, most of these studies focused on the aromatic characters of dimers. This paper aims to examine aromatic characters of π-stacked multimers of antiaromatic molecules where the number of monomers, N, is more than two. We constructed theoretical and calculation models of π-stacked N-mers consisting of cyclobutadienes (CBDs) with different stacking distances d. Applying the theoretical analyses based on the Hückel theory, we clarified the mechanisms of N-, d- and monomer position dependences of aromatic characters that are evaluated from the density functional theory (DFT) calculations of these models. It is found that the terminal monomers in the π-stacked N-mer (N &amp;gt; 2) exhibit the most significant antiaromatic character, whereas the second terminal monomers show the most reduced antiaromatic characters at small d. These results demonstrate that, in addition to the stacking distance and configuration, the number and the positions of monomers can be useful factors in controlling the aromaticity switching in π-stacked assemblies of antiaromatic molecules.

Ryota Sugimori

Masato Ikeuchi

Ryohei Kishi

Yasutaka Kitagawa

Theoretical study on aromatic characters in π-stacked multimers composed of antiaromatic molecules

反芳香性分子组成的π堆积多聚体的芳香性特征的理论研究

Abstract A relationship between the single-molecule electron conductivity, spin states, and substituents is investigated on the paddlewheel-type dichromium(II,II) tetracarboxylate complexes as the simplest model of the extended metal atom chains. The electronic structures and single-molecule electron conductivity of some model complexes with different substituents are calculated by the broken-symmetry density functional theory and elastic scattering Green's functions methods, respectively. The calculated results indicate that the electron conductivity of the complexes is changed by the electron-donating/withdrawing groups introduced into the bridging ligands. In addition, it is also found that a ratio of the electron conductivities between the antiferromagnetic and ferromagnetic coupling states in the Cr(II)2 unit can be changed by these substituents. These results suggest that the electron conductivity of these complexes can be controlled by changing the spin state.

Naoka Amamizu

Keisuke Sasaki

Mitsuhiro Nishida

Koki Masuda

Ren Inoue

Kaito Taka

Kohei Tada

Theoretical study on single-molecule electron conductivity of paddlewheel-type dichromium(II,II) tetracarboxylate complexes

双铬(II,II)四羧酸轮式配合物的单分子电子导电性理论研究

Abstract We developed an on-site system for the rapid simultaneous determination of multiple elements that integrates microdroplet technology with a handheld X-ray fluorescence spectrometer. This system combines the concentration of heavy metals in microdroplets through homogeneous liquid–liquid extraction with the widespread application of handheld X-ray fluorescence spectrometry. The focus of our research was the analysis of heavy metals, specifically lead. Under optimal conditions, we achieved a high extraction percentage of 93.3%, and a high volume ratio of 120 times was achieved (from 23.9 to 0.200 mL). Building on these optimal conditions, we explored a mixed solution of copper and lead to facilitate the simultaneous rapid determination of multiple elements. By exposing a 200-μL microdroplet to a focused X-ray beam (9.0 mm in diameter), we confirmed a good proportional relationship for copper and lead concentrations ranging from 0.0837 to 0.126 mg/L. The determination limit (10 σ) was 0.040 mg/L for copper and 0.030 mg/L for lead. This system enables the stable evaluation of heavy metals at low concentrations (ppb level) with a straightforward operation.

Takeshi Kato

Ryo Ando

Yoshitaka Takagai

Development and application of on-site multielement simultaneous rapid determination system using microdroplets and a handheld X-ray fluorescence spectrometer

基于微滴和手持式X射线荧光光谱仪的现场多元素同时快速测定系统的开发与应用

Abbreviation	Bull. Chem. Soc. Jpn.
Journal Impact	3.46
Quartiles(Global)	CHEMISTRY, MULTIDISCIPLINARY(Q2)

ISSN	0009-2673, 1348-0634
h-index	106

Publication Information	Publisher: Chemical Society of Japan，Publishing cycle: Monthly，Journal Type: journal，Open Access Journals: No
Basic data	Year of publication: 1965，Proportion of original research papers: 89.57%，Self Citation Rate:3.00%， Gold OA Rate: 1.03%
Average review cycle	网友分享经验：一般,3-8周
Average recruitment ratio	网友分享经验：容易

Bulletin of the Chemical Society of Japan

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