Bulletin of the Chemical Society of Japan最新文献

Acid-induced Conformational Switching of Helical Foldamers Containing Imidazole Amide 酸诱导含咪唑酰胺的螺旋折叠体的构象转换

IF 4 3区化学

Bulletin of the Chemical Society of Japan Pub Date : 2024-09-11 DOI: 10.1093/bulcsj/uoae094

Sakiko Kimura, Fumi Takeda, Ayano Ikeda, Asuka Tanimoto, Kosuke Katagiri, Masatoshi Kawahata, Yusuke Okada, Nagao Kobayashi, Hiroyuki Kagechika, Aya Tanatani

{"title":"Acid-induced Conformational Switching of Helical Foldamers Containing Imidazole Amide","authors":"Sakiko Kimura, Fumi Takeda, Ayano Ikeda, Asuka Tanimoto, Kosuke Katagiri, Masatoshi Kawahata, Yusuke Okada, Nagao Kobayashi, Hiroyuki Kagechika, Aya Tanatani","doi":"10.1093/bulcsj/uoae094","DOIUrl":"https://doi.org/10.1093/bulcsj/uoae094","url":null,"abstract":"N-Alkylated oligo- and poly(p-benzamide)s exist as dynamic helical structures with all-cis amide conformation. Imidazole N-alkylated amides also show cis conformational preference, but their major conformer is changed from cis to trans by addition of acid. Here, based on those findings, we designed and synthesized aromatic triamides 3 and hexaamides 4 containing an imidazole ring as candidate foldamers anticipated to exhibit acid-induced conformational change. X-Ray structure analysis of oligomer 3c showed that it takes all-cis conformation in the crystal. In solution, all the oligoamides examined existed as an equilibrium mixture of four conformers, among which the major conformer was the folded all-cis structure as judged from the low-temperature 1H NMR spectra. When trifluoroacetic acid-d was added to a solution of the oligoamides in methylene chloride-d2, only two conformers were observed in the low-temperature 1H NMR spectra, and the major conformer was the (trans, cis) form with respect to the amide bonds of the imidazole at the 4 and 2 positions. Experimental and theoretical analysis of the CD spectra indicated that the conformation of hexaamides 4 changes upon addition of acid. Our results suggest that N-alkylated imidazoleamide can serve as a key structural motif for the construction of foldamers with acid-switchable conformation.","PeriodicalId":9511,"journal":{"name":"Bulletin of the Chemical Society of Japan","volume":"32 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2024-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142186103","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Design of Cyborg Proteins by Loop Region Replacement with Oligo(ethylene glycol): Exploring Suitable Mutations for Cyborg Protein Construction Using Machine Learning 用寡聚（乙二醇）取代环区设计半机械蛋白质：利用机器学习探索构建半机械蛋白质的合适突变

IF 4 3区化学

Bulletin of the Chemical Society of Japan Pub Date : 2024-09-02 DOI: 10.1093/bulcsj/uoae090

Wijak Yospanya, Akari Matsumura, Yukihiro Imasato, Tomoyuki Itou, Yusuke Aoki, Hikaru Nakazawa, Takashi Matsui, Takeshi Yokoyama, Mihoko Ui, Mitsuo Umetsu, Satoru Nagatoishi, Kouhei Tsumoto, Yoshikazu Tanaka, Kazushi Kinbara

{"title":"Design of Cyborg Proteins by Loop Region Replacement with Oligo(ethylene glycol): Exploring Suitable Mutations for Cyborg Protein Construction Using Machine Learning","authors":"Wijak Yospanya, Akari Matsumura, Yukihiro Imasato, Tomoyuki Itou, Yusuke Aoki, Hikaru Nakazawa, Takashi Matsui, Takeshi Yokoyama, Mihoko Ui, Mitsuo Umetsu, Satoru Nagatoishi, Kouhei Tsumoto, Yoshikazu Tanaka, Kazushi Kinbara","doi":"10.1093/bulcsj/uoae090","DOIUrl":"https://doi.org/10.1093/bulcsj/uoae090","url":null,"abstract":"We synthesized a “cyborg protein,” wherein a synthetic molecule partially substitutes the main peptide chain by linking two protein domains with a synthetic oligomer. Green fluorescent protein (GFP) served as the model for constructing the cyborg proteins. We prepared circularly permuted GFP (cpGFP) with new termini between β10 and β11, where the original N- and C-termini were linked by a cleavable peptide loop. The cyborg GFP was constructed from cpGFP by linking the β10 and β11 with oligo(ethylene glycol) using maleimide-cysteine couplings, followed by the enzymatic cleavage of the N- and C-termini linking loop by thrombin. With the help of machine learning, we were able to obtain the cpGFP mutants that significantly alter the fluorescence activity (53% increase) by thrombin treatment, which splits cpGFP into two fragments (fragmented-GFP), and by heat shock. When the cyborg GFP was constructed using this mutant, the fluorescence intensity increased by 13% after heat treatment, similar to cpGFP (33% increase), and the behavior was significantly different from that of the fragmented-GFP. This result suggests the possibility that the oligo(ethylene glycol) chain in the cyborg protein plays a similar role to the peptide in the main chain of the protein.","PeriodicalId":9511,"journal":{"name":"Bulletin of the Chemical Society of Japan","volume":"37 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2024-09-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142186104","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Heterogenous Dynamics of Diffusive Motion in Organic Ionic Plastic Crystal Studied Using Spin-Spin Relaxation Time: N, N-Diethylpyrrolidinium Bis(fluorosulfonyl)amide 利用自旋-自旋弛豫时间研究有机离子塑料晶体中扩散运动的异质动力学：N, N-二乙基吡咯烷双（氟磺酰）酰胺

IF 4 3区化学

Bulletin of the Chemical Society of Japan Pub Date : 2024-08-19 DOI: 10.1093/bulcsj/uoae088

Keiko Nishikawa, Kozo Fujii, Kazuhiko Matsumoto, Hiroshi Abe, Masahiro Yoshizawa-Fujita

{"title":"Heterogenous Dynamics of Diffusive Motion in Organic Ionic Plastic Crystal Studied Using Spin-Spin Relaxation Time: N, N-Diethylpyrrolidinium Bis(fluorosulfonyl)amide","authors":"Keiko Nishikawa, Kozo Fujii, Kazuhiko Matsumoto, Hiroshi Abe, Masahiro Yoshizawa-Fujita","doi":"10.1093/bulcsj/uoae088","DOIUrl":"https://doi.org/10.1093/bulcsj/uoae088","url":null,"abstract":"The temperature dependences of the spin–spin relaxation times (T2) of 1H and 19F nuclei were measured for N, N-diethylpyrrolidinium bis(fluorosulfonyl)amide with a plastic crystal (PC) phase. In the PC phase, two types of T2 were observed in both 1H and 19F experiments, which was considered to be the appearance of heterogeneous dynamics of diffusive motion. By examining temperature dependences of the T2 values and the existence ratios, the following conclusions were reached. (1) The prepared PC sample was in a polycrystalline state, and each crystallite comprised two phases: the core phase (PC phase) and the surface phase formed to relieve surface stress. (2) The 1H-T2 (19F-T2) values of the two phases differed, and ions in the surface phase were more mobile. The 1H-T2 (19F-T2) values for the two phases increased with temperature rise. In particular, the 1H-T2 (19F-T2) values of the surface phase were smoothly connected to the liquid T2 values. (3) The cations and anions exhibited a cooperative diffusive motion. (4) When the temperature was considerably lower than the melting point, the ratio of the surface phase did not significantly differ from when it first formed. However, it rapidly increased near the melting point and became liquid.","PeriodicalId":9511,"journal":{"name":"Bulletin of the Chemical Society of Japan","volume":"46 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2024-08-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142186108","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Structural Generation by Inverse Transformation Using Principal Component Analysis Enhances Conformational Sampling of 利用主成分分析法通过反变换生成结构增强了对

IF 4 3区化学

Bulletin of the Chemical Society of Japan Pub Date : 2024-08-16 DOI: 10.1093/bulcsj/uoae087

Rikuri Morita, Yasuteru Shigeta, Ryuhei Harada

{"title":"Structural Generation by Inverse Transformation Using Principal Component Analysis Enhances Conformational Sampling of","authors":"Rikuri Morita, Yasuteru Shigeta, Ryuhei Harada","doi":"10.1093/bulcsj/uoae087","DOIUrl":"https://doi.org/10.1093/bulcsj/uoae087","url":null,"abstract":"Molecular dynamics (MD) simulations are frequently used to elucidate the molecular mechanisms underlying protein behaviour. Based on a conformational search with MD simulations, protein structures rich in high-dimensional data can be quantitatively evaluated in free-energy landscapes (FELs). Generally, FELs are defined in low-dimensional subspaces spanned by reaction coordinates (RCs) to characterize biological functions. When calculating FELs of proteins, principal component analysis (PCA) is particularly useful for capturing large-amplitude motions via dimensionality reduction into low-dimensional subspaces. In this study, to efficiently calculate FELs, a simple and convenient method is proposed by accelerating conformational search in a PCA subspace, which is achieved by quick generation of protein configurations. Specifically, inverse transformation driven by PCA facilitates the quick generation of diverse protein configurations from arbitrary grids in a defined PCA subspace. In our conformational search, a set of newly generated configurations serves as initial structures for multiple MD simulations, enabling one to calculate FELs of proteins by building Markov state models from their multiple trajectories. In conclusion, the conformational search from protein configurations broadly distributed in a PCA subspace accelerates FEL calculations, which supports a comprehensive approach to understanding collective protein dynamics.","PeriodicalId":9511,"journal":{"name":"Bulletin of the Chemical Society of Japan","volume":"12 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2024-08-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142186151","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Development of organic photoreactions utilizing the characteristics of elements with low electronegativity 利用低电负性元素的特性发展有机光反应

IF 4 3区化学

Bulletin of the Chemical Society of Japan Pub Date : 2024-08-07 DOI: 10.1093/bulcsj/uoae080

Yuki Nagashima

引用次数: 0

Imparting chiroptical property to achiral azobenzene derivative via incorporation into chiral-controlled helical nanofibers 通过将非手性偶氮苯衍生物纳入手性控制螺旋纳米纤维，赋予其气光特性

IF 4 3区化学

Bulletin of the Chemical Society of Japan Pub Date : 2024-07-29 DOI: 10.1093/bulcsj/uoae075

Tomoki Ito, Makoto Nakagawa, Takeshi Kawai

{"title":"Imparting chiroptical property to achiral azobenzene derivative via incorporation into chiral-controlled helical nanofibers","authors":"Tomoki Ito, Makoto Nakagawa, Takeshi Kawai","doi":"10.1093/bulcsj/uoae075","DOIUrl":"https://doi.org/10.1093/bulcsj/uoae075","url":null,"abstract":"Chiral transcription from chiral to achiral organic molecules is a fundamental research area in supramolecular chemistry, organic chemistry, and nanoscience. In this study, we demonstrated that chiral transcription of an achiral azobenzene derivative (Azo) can be achieved by embedding it within helically controlled nanofibers. Helical nanofibers were produced via supramolecular assembly of water-insoluble D-12-hydroxystearic acid (D-HSA) as a chiral source and a water-soluble long-chain amidoamine derivative (C18AA) in water. Azo-incorporated helical nanofibers exhibited a circular dichroism (CD) peak at 350 nm, which was assigned to the π−π* transition band of trans-azobenzene chromophore, suggesting a chiral arrangement of Azo molecules in the nanofibers. Because the nanofibers are dispersed in water and Azo is not soluble in water, the selection of an organic solvent to dissolve Azo is important for the incorporation of Azo molecules. When water-immiscible toluene was used as the solvent, Azo incorporation did not occur, because contact between the nanofibers and Azo was inhibited; however, when water-miscible methanol was used, incorporation was achieved. The incorporation of Azo gradually occurred in the pre-assembled C18AA + D-HSA nanofibers, but co-assembly did not occur during the formation of the C18AA + D-HSA nanofibers. We also showed that Azo-containing nanofibers can undergo a reversible thermal phase transition between gel-to-sol states, switching the CD signal of Azo on and off. Furthermore, trans–cis-photoisomerization of Azo embedded in the nanofibers eliminated the CD peak of the trans-isomer, and no new CD peak corresponding to the cis-isomer appeared.","PeriodicalId":9511,"journal":{"name":"Bulletin of the Chemical Society of Japan","volume":"20 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2024-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141869240","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Black Phosphorus Quantum Dots Functionalized with Photochromic Poly(vinylspiropyran)-Grafted Polydopamine for Transient Digital-Type Memristors 用于瞬态数字式 Memristors 的光致变色聚（乙烯基硅吡喃）接枝多多巴胺功能化黑磷量子点

IF 4 3区化学

Bulletin of the Chemical Society of Japan Pub Date : 2024-07-19 DOI: 10.1093/bulcsj/uoae083

Zemiao Zhao, Qiang Che, Qian Chen, Kexin Wang, Kejia Zhao, Chenjian Zhang, Haidong He, Xinzhu Wang, Yu Chen

{"title":"Black Phosphorus Quantum Dots Functionalized with Photochromic Poly(vinylspiropyran)-Grafted Polydopamine for Transient Digital-Type Memristors","authors":"Zemiao Zhao, Qiang Che, Qian Chen, Kexin Wang, Kejia Zhao, Chenjian Zhang, Haidong He, Xinzhu Wang, Yu Chen","doi":"10.1093/bulcsj/uoae083","DOIUrl":"https://doi.org/10.1093/bulcsj/uoae083","url":null,"abstract":"The covalent functionalization of black phosphorus quantum dots (BPQDs) with organic species or polymers will inevitably change or damage their electronic structure and intrinsic structure. To address this problem and explore application of BPQDs in transient digital-type memristors, a polydopamine (PDA) thin film is first synthesized in situ on the surface of BPQDs to produce a donor–acceptor type BPQDs@PDA composite which is directly used to react with 2-bromoisobutyryl bromide to give BPQDs@PDA-Br. By using BPQDs@PDA-Br as atom transfer radical polymerization agent, a large number of polyvinylspiropyran chains (PSP) are in situ grown from the PDA surface to yield BPQDs@PDA-PSP. Upon UV/visible light illumination, the spiropyran’s two isomers (ring-closed spiropyran form and ring-opened merocyanine) in the PSP moieties will interconvert into each other rapidly. As expected, the as-fabricated ITO/BPQDs@PDA-PSP/ITO device exhibits typical nonvolatile digital-type memristive performance under visible irradiation, with a small turn-on voltage of -1.52 V, a turn-off voltage of +1.16 V, and an ON/OFF ratio of with an ON/OFF current ratio of 1.02 ×104. Upon UV illumination, the information stored in the device is quickly and completely erased within six seconds. By utilizing a simple memristor-based convolutional neural network, one can easily realize handwritten digit recognition. After 10 epochs of training, numeral recognition accuracy can reach up to 96.21%.","PeriodicalId":9511,"journal":{"name":"Bulletin of the Chemical Society of Japan","volume":"25 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2024-07-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141744752","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

A Layered Titanate Nanowire Helps Pt/TiO2 Photocatalyst for Solar Hydrogen Evolution from Water with High Quantum Efficiency 层状钛酸盐纳米线帮助 Pt/TiO2 光催化剂实现高量子效率的太阳能水氢转化

IF 4 3区化学

Bulletin of the Chemical Society of Japan Pub Date : 2024-07-16 DOI: 10.1093/bulcsj/uoae079

Rafat Tahawy, Mohamed Esmat, Hamza El-Hosainy, Fatma E Farghaly, El-Sayed A Abdel-Aal, F I El-Hosiny, Yusuke Ide

{"title":"A Layered Titanate Nanowire Helps Pt/TiO2 Photocatalyst for Solar Hydrogen Evolution from Water with High Quantum Efficiency","authors":"Rafat Tahawy, Mohamed Esmat, Hamza El-Hosainy, Fatma E Farghaly, El-Sayed A Abdel-Aal, F I El-Hosiny, Yusuke Ide","doi":"10.1093/bulcsj/uoae079","DOIUrl":"https://doi.org/10.1093/bulcsj/uoae079","url":null,"abstract":"Research into TiO2 photocatalysts for solar H2 evolution from water is still growing for environmentally benign and economically valid H2 production. Herein, in contrast to many researches on the modification of TiO2 toward higher photocatalytic activities, we develop a photocatalytically inactive TiO2-based nanostructure and use it, like graphene, as a booster of a benchmark TiO2. A layered potassium titanate with two-dimensional plate-like particle morphology was converted to the corresponding one-dimensional nanowire form via a hydrothermal reaction, after which the layered potassium titanate nanowire was acid-treated to obtain a layered titanate nanowire. This nanowire was completely inactive toward H2 evolution from water containing methanol under solar simulator irradiation. However, when Pt nanoparticle-loaded P25 TiO2 (Pt/P25) was mixed with a considerably smaller amount of the layered titanate nanowire in water, a durable composite was obtained and the composite showed a good photocatalytic activity three times higher than Pt/P25. The apparent quantum efficiency of the reaction at wavelength of 350 nm was 56%, which was higher than or comparable to those of the state-of-the-art TiO2-based photocatalysts. The possible reason for the enhanced photocatalytic activity of the Pt/P25 and layered titanate nanowire composite involved the transfer of photogenerated holes from Pt/P25 to the nanowire to suppress charge recombination and/or disaggregation (improved dispersion) of Pt/P25 particles on the nanowire.","PeriodicalId":9511,"journal":{"name":"Bulletin of the Chemical Society of Japan","volume":"26 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2024-07-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141721366","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Assembly/Disassembly Control of Gold Nanorods with Uniform Orientation on Anionic Polymer Brush Substrates 在阴离子聚合物刷基底上组装/拆卸方向一致的金纳米棒的控制方法

IF 4 3区化学

Bulletin of the Chemical Society of Japan Pub Date : 2024-07-12 DOI: 10.1093/bulcsj/uoae073

Jingyan Yang, Yu Sekizawa, Xu Shi, Kuniharu Ijiro, Hideyuki Mitomo

{"title":"Assembly/Disassembly Control of Gold Nanorods with Uniform Orientation on Anionic Polymer Brush Substrates","authors":"Jingyan Yang, Yu Sekizawa, Xu Shi, Kuniharu Ijiro, Hideyuki Mitomo","doi":"10.1093/bulcsj/uoae073","DOIUrl":"https://doi.org/10.1093/bulcsj/uoae073","url":null,"abstract":"Sophisticated control of the spatial arrangement of gold nanorods provides significant advantages in the design of plasmonic systems. However, dynamic modulation of the gold nanorod spatial arrangements remains challenging. Here, we present a novel strategy for dynamic control of thermo-responsive gold nanorods with uniform alignment on a solid substrate using polymer brushes. In this system, cationic-thermo-responsive gold nanorods were immobilized into anionic polymer brushes via moderate electrostatic interactions, providing vertically aligned gold nanorod arrays. Upon heating, the gold nanorods were assembled while maintaining their vertical orientation within the polymer brushes. They returned to the original state upon cooling, indicating reversible assembly/disassembly. It is noticeable that this system exhibits rapid changes in nanostructure arrangement even when immobilized in the polymer brush substrate on a solid substrate rather than those dispersed in solution. Importantly, the gold nanorods showed good adhesion stability in polymer brushes without any significant detachment during washing and thermal cycling processes, but performed assembly formation even at largely separated conditions, indicating the traveling of considerable distances similar to the lateral diffusion of membrane proteins in cell membranes. In addition to providing unprecedented control over gold nanorod spatial configurations, our approach introduces a versatile platform for developing advanced plasmonic devices.","PeriodicalId":9511,"journal":{"name":"Bulletin of the Chemical Society of Japan","volume":"29 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2024-07-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141613951","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Discrete Polyketones: Synthesis, Derivatization, and Potential Applications 离散多酮类化合物：合成、衍生和潜在应用

IF 4 3区化学

Bulletin of the Chemical Society of Japan Pub Date : 2024-07-04 DOI: 10.1093/bulcsj/uoae072

Yasuhide Inokuma

{"title":"Discrete Polyketones: Synthesis, Derivatization, and Potential Applications","authors":"Yasuhide Inokuma","doi":"10.1093/bulcsj/uoae072","DOIUrl":"https://doi.org/10.1093/bulcsj/uoae072","url":null,"abstract":"The present account reviews recent progress in the synthesis, functionalization, and application of discrete polyketones. Whereas most polyketones are synthesized as polydisperse polymers with various molecular chain lengths and sizes, discrete polyketones are obtained in chemically pure forms. This allows precise structural analysis using NMR and X-ray diffraction. Discrete polyketones have been used to determine the critical chain length that distinguishes the crystallization behaviors of small molecules from those of macromolecules. Calix[3]pyrrole, which is a ring-contracted analogue of porphyrinogen, was first obtained from a cyclic hexaketone. The discovery of the strain-induced ring expansion reaction of calix[3]pyrroles has provided an important insight into solving a long-standing enigma in porphyrin synthesis. Chemical derivatization of discrete polyketones using ketone-derived transformations has resulted in the generation of various functional molecules for potential applications. These molecules have been used to develop several materials, including luminescent chromophores, ion adsorbents, drug–drug conjugates, and microfluidic devices for cancer diagnosis.","PeriodicalId":9511,"journal":{"name":"Bulletin of the Chemical Society of Japan","volume":"14 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2024-07-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141548439","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0