Short steps synthesis of unsymmetrical acetylenes from tetrachloroethylene and arylboronic acids, and the use of the metal Mg as the mild reagent for dechlorinations has been developed. Unsymmetrical acetylenes including the donor and acceptor diarylacetylenes were produced in good yields. The reaction optimization, scope and limitations, the scale-up reaction, and the evaluation of the step were studied for this paper.
{"title":"Short steps synthesis of unsymmetrical acetylenes from tetrachloroethylene and arylboronic acids using Suzuki coupling reaction and improvement of mild dechlorinations","authors":"Hiyono Suzuki, Akane Togo, Junya Kikuzawa, Kazuki Miyamoto, Shinsuke Marumoto, Akiko Kuwabara, Masafumi Kobayashi, Kouichi Matsumoto","doi":"10.1093/chemle/upae079","DOIUrl":"https://doi.org/10.1093/chemle/upae079","url":null,"abstract":"Short steps synthesis of unsymmetrical acetylenes from tetrachloroethylene and arylboronic acids, and the use of the metal Mg as the mild reagent for dechlorinations has been developed. Unsymmetrical acetylenes including the donor and acceptor diarylacetylenes were produced in good yields. The reaction optimization, scope and limitations, the scale-up reaction, and the evaluation of the step were studied for this paper.","PeriodicalId":9862,"journal":{"name":"Chemistry Letters","volume":null,"pages":null},"PeriodicalIF":1.6,"publicationDate":"2024-08-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142226440","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Azahelicenes are intriguing luminescent materials with a planar chirality. The properties of aza[9]helicene can be perturbed by attaching substituent at the termini. The impact of the terminal-decoration has been investigated in view of structural and electronic aspects, leading to the control of interlayer interaction.
{"title":"Synthesis of Terminus-Decorated Aza[9]helicenes: Control of Interlayer Interaction","authors":"Yusuke Matsuo, Shu Seki, Takayuki Tanaka","doi":"10.1093/chemle/upae159","DOIUrl":"https://doi.org/10.1093/chemle/upae159","url":null,"abstract":"Azahelicenes are intriguing luminescent materials with a planar chirality. The properties of aza[9]helicene can be perturbed by attaching substituent at the termini. The impact of the terminal-decoration has been investigated in view of structural and electronic aspects, leading to the control of interlayer interaction.","PeriodicalId":9862,"journal":{"name":"Chemistry Letters","volume":null,"pages":null},"PeriodicalIF":1.6,"publicationDate":"2024-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142208335","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Organic-inorganic halide perovskite solar cells using textured transparent conductive films exhibit high efficiencies with improved short-circuit current density. However, uniform electron transport layer (ETL) deposition on textures by solution process is challenging. In this study, uniform ETL were formed by sequentially spin-coating polyelectrolyte with positively and negatively charged segments and negative SnO2 colloids solution and electrostatically enhancing the SnO2 coverage. The stabilized power output (SPO) was improved from 12.9% to 18.6% by incorporating this polyelectrolyte/SnO2 bilayer.
{"title":"Polyelectrolyte-assisted uniform electron transporting layer on texture substrate for perovskite solar cells","authors":"Ryo Ishikawa","doi":"10.1093/chemle/upae158","DOIUrl":"https://doi.org/10.1093/chemle/upae158","url":null,"abstract":"\u0000 Organic-inorganic halide perovskite solar cells using textured transparent conductive films exhibit high efficiencies with improved short-circuit current density. However, uniform electron transport layer (ETL) deposition on textures by solution process is challenging. In this study, uniform ETL were formed by sequentially spin-coating polyelectrolyte with positively and negatively charged segments and negative SnO2 colloids solution and electrostatically enhancing the SnO2 coverage. The stabilized power output (SPO) was improved from 12.9% to 18.6% by incorporating this polyelectrolyte/SnO2 bilayer.","PeriodicalId":9862,"journal":{"name":"Chemistry Letters","volume":null,"pages":null},"PeriodicalIF":1.4,"publicationDate":"2024-08-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141924481","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
We have developed a diazirine–alkyne tag for target protein–ligand interaction analysis. A sulfonamide photoaffinity probe was readily prepared using copper-catalyzed azide–alkyne cycloaddition (CuAAC), which site-specifically formed a covalent bond with human carbonic anhydrase 1 (∼30% labeling yield). The photolabeled position (E58–H64 region) was determined based on the results of a tandem mass spectrometry (MS/MS) analysis of tryptic peptides and was supported by molecular modeling studies. Our method may be useful for determining unknown ligand-binding sites of various target biomolecules.
{"title":"Development of diazirine–alkyne tag for protein–ligand interaction analysis with photoaffinity labeling","authors":"Masatoshi Nakatani, Shohei Ebihara, Masaki Kita","doi":"10.1093/chemle/upae142","DOIUrl":"https://doi.org/10.1093/chemle/upae142","url":null,"abstract":"We have developed a diazirine–alkyne tag for target protein–ligand interaction analysis. A sulfonamide photoaffinity probe was readily prepared using copper-catalyzed azide–alkyne cycloaddition (CuAAC), which site-specifically formed a covalent bond with human carbonic anhydrase 1 (∼30% labeling yield). The photolabeled position (E58–H64 region) was determined based on the results of a tandem mass spectrometry (MS/MS) analysis of tryptic peptides and was supported by molecular modeling studies. Our method may be useful for determining unknown ligand-binding sites of various target biomolecules.","PeriodicalId":9862,"journal":{"name":"Chemistry Letters","volume":null,"pages":null},"PeriodicalIF":1.6,"publicationDate":"2024-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141949054","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
δ-NbN powder with particles of approximately 1 µm in size was obtained by heating a mixture of NaNbO3 and BN powders at 1373 K for 1 h, while agglomerates composed of ε-NbN platelet grains up to 50 µm in size were obtained by heating the mixture at the same temperature for 10 h. Metathesis reaction in which sodium borate was formed with replacement of the oxygen and nitrogen from NaNbO3 and BN occurred with the NbN formation. Wavelength-dispersive X-ray analysis showed that the molar ratios of Nb to N in the synthesized δ-NbN and ε-NbN were approximately 1:1. Magnetic susceptibility measurements showed that the δ-NbN powder was a superconductor with a transition temperature of approximately 16 K. In comparison, the ε-NbN agglomerates did not exhibit superconductivity above 2 K.
在 1373 K 下加热 NaNbO3 和 BN 粉末的混合物 1 小时，可获得颗粒大小约为 1 µm 的 δ-NbN 粉末；在相同温度下加热混合物 10 小时，可获得由大小达 50 µm 的 ε-NbN 小板粒组成的团聚体。波长色散 X 射线分析表明，合成的 δ-NbN 和 ε-NbN 中 Nb 与 N 的摩尔比约为 1:1。磁感应强度测量结果表明，δ-NbN 粉末是一种超导体，其转变温度约为 16 K。
{"title":"Synthesis of ε-NbN and δ-NbN by metathesis reaction of NaNbO3 and BN","authors":"Tenshin Osaka, Toshiya Ikenobe, Zenji Hiroi, Hisanori Yamane, Takahiro Yamada","doi":"10.1093/chemle/upae154","DOIUrl":"https://doi.org/10.1093/chemle/upae154","url":null,"abstract":"δ-NbN powder with particles of approximately 1 µm in size was obtained by heating a mixture of NaNbO3 and BN powders at 1373 K for 1 h, while agglomerates composed of ε-NbN platelet grains up to 50 µm in size were obtained by heating the mixture at the same temperature for 10 h. Metathesis reaction in which sodium borate was formed with replacement of the oxygen and nitrogen from NaNbO3 and BN occurred with the NbN formation. Wavelength-dispersive X-ray analysis showed that the molar ratios of Nb to N in the synthesized δ-NbN and ε-NbN were approximately 1:1. Magnetic susceptibility measurements showed that the δ-NbN powder was a superconductor with a transition temperature of approximately 16 K. In comparison, the ε-NbN agglomerates did not exhibit superconductivity above 2 K.","PeriodicalId":9862,"journal":{"name":"Chemistry Letters","volume":null,"pages":null},"PeriodicalIF":1.6,"publicationDate":"2024-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141949053","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ligand-protected metal nanoclusters (NCs) represent a significant advancement in the field of catalysis due to their unique size-specific electronic and geometric structures. These properties are highly dependent on the metal species, number of constituent atoms, and geometric structure of the metal NC. We discuss on the synthesis, stability, structural characterization, and electrocatalytic/photocatalytic applications of these fascinating materials, emphasizing their superior performance over conventional catalysts. In this study, we have obtained a deeper understanding of the interaction between the metal core and the organic ligands protecting the metal NCs, as well as the desorption behavior of the ligands under calcination, which is crucial for the application of metal NCs as heterogeneous catalysts. Based on this understanding, we have demonstrated that metal NCs-supported catalysts with appropriate pretreatment exhibit higher activity as photocatalysts compared to conventional catalysts. Moreover, by suppressing oxygen poisoning through the use of sulfur species in the ligands, Pt NCs showed high activity as cocatalysts for photocatalytic hydrogen evolution in water splitting. Additionally, atomically precised phosphine-protected Pt NCs exhibited high activity as cathode electrocatalysts for fuel cells. These findings are expected to significantly contribute to the development of more diverse catalysts based on metal NCs, including those with varying metal species, numbers of constituent atoms, and geometric structures.
{"title":"Precise Synthesis of Ligand-Protected Metal Nanoclusters for Electrochemical/Photoelectrochemical Applications","authors":"T. Kawawaki, Yuichi Negishi","doi":"10.1093/chemle/upae155","DOIUrl":"https://doi.org/10.1093/chemle/upae155","url":null,"abstract":"\u0000 Ligand-protected metal nanoclusters (NCs) represent a significant advancement in the field of catalysis due to their unique size-specific electronic and geometric structures. These properties are highly dependent on the metal species, number of constituent atoms, and geometric structure of the metal NC. We discuss on the synthesis, stability, structural characterization, and electrocatalytic/photocatalytic applications of these fascinating materials, emphasizing their superior performance over conventional catalysts. In this study, we have obtained a deeper understanding of the interaction between the metal core and the organic ligands protecting the metal NCs, as well as the desorption behavior of the ligands under calcination, which is crucial for the application of metal NCs as heterogeneous catalysts. Based on this understanding, we have demonstrated that metal NCs-supported catalysts with appropriate pretreatment exhibit higher activity as photocatalysts compared to conventional catalysts. Moreover, by suppressing oxygen poisoning through the use of sulfur species in the ligands, Pt NCs showed high activity as cocatalysts for photocatalytic hydrogen evolution in water splitting. Additionally, atomically precised phosphine-protected Pt NCs exhibited high activity as cathode electrocatalysts for fuel cells. These findings are expected to significantly contribute to the development of more diverse catalysts based on metal NCs, including those with varying metal species, numbers of constituent atoms, and geometric structures.","PeriodicalId":9862,"journal":{"name":"Chemistry Letters","volume":null,"pages":null},"PeriodicalIF":1.4,"publicationDate":"2024-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141927183","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The structure and stability of proteins are affected by ions. We have previously reported that cytochrome c can form a 3D domain-swapped dimer. The structure of the cytochrome c domain-swapped dimer becomes more compact in the presence of kosmotropic anions, whereas the thermal stability of the dimer decreased with addition of chaotropic anions based on the Hofmeister series. Dimers were formed by incubating cytochrome c at 50 °C in the presence of citrate ions.
蛋白质的结构和稳定性受到离子的影响。我们以前曾报道过细胞色素 c 可以形成三维结构域互换二聚体。细胞色素 c 结构域互换二聚体的结构在各向同性阴离子的存在下变得更加紧凑，而二聚体的热稳定性则随着基于霍夫迈斯特系列的各向混沌阴离子的加入而降低。将细胞色素 c 在柠檬酸根离子存在下于 50 °C孵育可形成二聚体。
{"title":"Anion effects on the structure and stability of 3D domain-swapped cytochrome c dimer","authors":"Kodai Fujiwara, Michiko Ryuzaki, Masaru Yamanaka, Tsuyoshi Mashima, Tomonori Saotome, Shun-ichi Kidokoro, Shun Hirota","doi":"10.1093/chemle/upae150","DOIUrl":"https://doi.org/10.1093/chemle/upae150","url":null,"abstract":"The structure and stability of proteins are affected by ions. We have previously reported that cytochrome c can form a 3D domain-swapped dimer. The structure of the cytochrome c domain-swapped dimer becomes more compact in the presence of kosmotropic anions, whereas the thermal stability of the dimer decreased with addition of chaotropic anions based on the Hofmeister series. Dimers were formed by incubating cytochrome c at 50 °C in the presence of citrate ions.","PeriodicalId":9862,"journal":{"name":"Chemistry Letters","volume":null,"pages":null},"PeriodicalIF":1.6,"publicationDate":"2024-08-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141881290","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Shengxiang Zhang, Kai Asanuma, Satoshi Inagaki, Yoshihiro Kubota
A novel large-pore titanosilicate with YFI topology, [Ti]-YNU-5, was prepared via post-synthetic isomorphous substitution of Ti for Al in the YFI framework. It exhibited the enhanced catalytic performances in the liquid-phase epoxidation of bulky alkenes and the oxidation of phenol with hydrogen peroxide. Hydrophobicity was found to be an important factor.
通过在 YFI 框架中用 Ti 对 Al 进行后合成异构取代，制备了具有 YFI 拓扑结构的新型大孔钛硅酸盐 [Ti]-YNU-5。它在大块烯烃的液相环氧化反应和苯酚与过氧化氢的氧化反应中表现出更强的催化性能。疏水性是一个重要因素。
{"title":"[Ti]-YNU-5: a large-pore titanosilicate as an efficient catalyst for selective oxidations","authors":"Shengxiang Zhang, Kai Asanuma, Satoshi Inagaki, Yoshihiro Kubota","doi":"10.1093/chemle/upae130","DOIUrl":"https://doi.org/10.1093/chemle/upae130","url":null,"abstract":"A novel large-pore titanosilicate with YFI topology, [Ti]-YNU-5, was prepared via post-synthetic isomorphous substitution of Ti for Al in the YFI framework. It exhibited the enhanced catalytic performances in the liquid-phase epoxidation of bulky alkenes and the oxidation of phenol with hydrogen peroxide. Hydrophobicity was found to be an important factor.","PeriodicalId":9862,"journal":{"name":"Chemistry Letters","volume":null,"pages":null},"PeriodicalIF":1.6,"publicationDate":"2024-07-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141770580","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yan Song, Hiroki Hayashi, Saeesh R Mangaonkar, Tsuyoshi Mita
The reactivity of the carbon dioxide radical anion (CO2•−) toward alkenes has garnered remarkable attention owing to its potential to synthesize valuable organic compounds. Herein, we report the reactions between CO2•− and 1,6-dienes, yielding 5-membered lactam derivatives via highly trans-selective 5-exo-trig cyclization. Both carboxylative cyclization and hydrocyclization occur with up to 74% combined yield. Computational studies show that the transition state during cyclization favors the trans-configuration over cis. This work offers new insights into the synthesis of N-heterocycles.
{"title":"Trans-Selective Carboxylative Cyclization of 1,6-Dienes Using the CO2 Radical Anion","authors":"Yan Song, Hiroki Hayashi, Saeesh R Mangaonkar, Tsuyoshi Mita","doi":"10.1093/chemle/upae149","DOIUrl":"https://doi.org/10.1093/chemle/upae149","url":null,"abstract":"The reactivity of the carbon dioxide radical anion (CO2•−) toward alkenes has garnered remarkable attention owing to its potential to synthesize valuable organic compounds. Herein, we report the reactions between CO2•− and 1,6-dienes, yielding 5-membered lactam derivatives via highly trans-selective 5-exo-trig cyclization. Both carboxylative cyclization and hydrocyclization occur with up to 74% combined yield. Computational studies show that the transition state during cyclization favors the trans-configuration over cis. This work offers new insights into the synthesis of N-heterocycles.","PeriodicalId":9862,"journal":{"name":"Chemistry Letters","volume":null,"pages":null},"PeriodicalIF":1.6,"publicationDate":"2024-07-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141770579","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yasuyuki Okumura, Eisuke Sato, Koichi Mitsudo, Seiji Suga
Electrochemical organic synthesis has attracted attention as an environmentally friendly method for constructing heterocyclic compounds via carbon–heteroatom bond formation. Herein, we describe the representative examples of electrochemical reactions to produce heterocycles, and discuss them according to whether they involve direct or indirect electrolysis.
{"title":"Electrochemical Synthesis of Heterocyclic Compounds via Carbon–Heteroatom Bond Formation: Direct and Indirect Electrolysis","authors":"Yasuyuki Okumura, Eisuke Sato, Koichi Mitsudo, Seiji Suga","doi":"10.1093/chemle/upae146","DOIUrl":"https://doi.org/10.1093/chemle/upae146","url":null,"abstract":"Electrochemical organic synthesis has attracted attention as an environmentally friendly method for constructing heterocyclic compounds via carbon–heteroatom bond formation. Herein, we describe the representative examples of electrochemical reactions to produce heterocycles, and discuss them according to whether they involve direct or indirect electrolysis.","PeriodicalId":9862,"journal":{"name":"Chemistry Letters","volume":null,"pages":null},"PeriodicalIF":1.6,"publicationDate":"2024-07-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141770584","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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