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.
从手性到非手性有机分子的手性转录是超分子化学、有机化学和纳米科学的一个基础研究领域。在这项研究中，我们证明了通过将非手性偶氮苯衍生物（Azo）嵌入螺旋控制的纳米纤维中，可以实现该衍生物的手性转录。螺旋纳米纤维是由不溶于水的 D-12- 羟基硬脂酸（D-HSA）作为手性源与水溶性长链氨基胺衍生物（C18AA）在水中超分子组装而成。加入偶氮的螺旋纳米纤维在 350 纳米波长处出现圆二色性（CD）峰，该峰被归属于反式偶氮苯发色团的 π-π* 过渡带，表明纳米纤维中偶氮分子呈手性排列。由于纳米纤维分散在水中，而偶氮不溶于水，因此选择溶解偶氮的有机溶剂对于偶氮分子的掺入非常重要。当使用不溶于水的甲苯作为溶剂时，由于纳米纤维与偶氮之间的接触受到抑制，偶氮没有被掺入；但当使用不溶于水的甲醇时，偶氮被掺入。偶氮逐渐掺入到预组装的 C18AA + D-HSA 纳米纤维中，但在形成 C18AA + D-HSA 纳米纤维的过程中没有发生共组装。我们还发现，含偶氮的纳米纤维可以在凝胶态到溶胶态之间发生可逆的热相变，从而开关偶氮的 CD 信号。此外，纳米纤维中嵌入的偶氮的反式-顺式-光异构化消除了反式异构体的 CD 峰，没有出现与顺式异构体相对应的新的 CD 峰。
{"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}
Toluene is one of the volatile organic compounds which are harmful to the environment and human health. One promising approach to eliminate toluene is catalytic combustion. Although precious metal based catalysts are known to show high activity for toluene combustion, the high price of the precious metals has restricted their widespread applications. In this study, precious-metal-free catalysts of Co3O4/ZrSn1−xFexO4−δ were synthesized for toluene combustion. Here, scrutinyite-type ZrSnO4 was focused as a promoter which can supply active oxygen species from inside the lattice toward the Co3O4 activator. In addition, Fe2+/3+ ions were introduced into the ZrSnO4 lattice to enhance the oxygen supply ability owing to the improvement of redox properties and the formation of oxygen vacancies for smooth oxide ion migration. The oxygen supply from the ZrSn1−xFexO4−δ lattice facilitated toluene oxidation on Co3O4, and the highest catalytic activity was obtained for the 19 wt% Co3O4/ZrSn0.93Fe0.07O4−δ (Co3O4/ZSF0.07) catalyst, where the complete combustion was realized at the temperature as low as 250 °C. The toluene combustion reaction over Co3O4/ZSF0.07 is considered to proceed along a typical route of the rapid transformation of toluene into the intermediates (benzyl alcohol, benzaldehyde, benzoate, and maleic anhydride) and finally the formation of carbon dioxide and water.
{"title":"Catalytic Combustion of Toluene over Co3O4 loaded on ZrSn1−xFexO4−δ","authors":"Naoyoshi Nunotani, Takumi Tanaka, Nobuhito Imanaka","doi":"10.1093/bulcsj/uoae084","DOIUrl":"https://doi.org/10.1093/bulcsj/uoae084","url":null,"abstract":"Toluene is one of the volatile organic compounds which are harmful to the environment and human health. One promising approach to eliminate toluene is catalytic combustion. Although precious metal based catalysts are known to show high activity for toluene combustion, the high price of the precious metals has restricted their widespread applications. In this study, precious-metal-free catalysts of Co3O4/ZrSn1−xFexO4−δ were synthesized for toluene combustion. Here, scrutinyite-type ZrSnO4 was focused as a promoter which can supply active oxygen species from inside the lattice toward the Co3O4 activator. In addition, Fe2+/3+ ions were introduced into the ZrSnO4 lattice to enhance the oxygen supply ability owing to the improvement of redox properties and the formation of oxygen vacancies for smooth oxide ion migration. The oxygen supply from the ZrSn1−xFexO4−δ lattice facilitated toluene oxidation on Co3O4, and the highest catalytic activity was obtained for the 19 wt% Co3O4/ZrSn0.93Fe0.07O4−δ (Co3O4/ZSF0.07) catalyst, where the complete combustion was realized at the temperature as low as 250 °C. The toluene combustion reaction over Co3O4/ZSF0.07 is considered to proceed along a typical route of the rapid transformation of toluene into the intermediates (benzyl alcohol, benzaldehyde, benzoate, and maleic anhydride) and finally the formation of carbon dioxide and water.","PeriodicalId":9511,"journal":{"name":"Bulletin of the Chemical Society of Japan","volume":"165 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2024-07-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141773358","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}
Zannatul Mumtarin Moushumy, Hiroshi Yoshida, Kaori Tokusada, Ai Kuraoka, Sota Sakamoto, Masayuki Tsushida, Masato Machida
The surface grafting of NiO onto CeO2 nanocrystallites generates heterointerface structures, providing efficient active sites for CO–NO reactions toward forming N2 and CO2. In this study, we investigated the effects of high-temperature thermal aging on the activity and nanostructure of the NiO/CeO2 catalyst. After thermal aging at 900 °C, the catalyst retained a high catalytic activity, whereas the reference catalysts lost theirs owing to considerable solid-state reactions and sintering. The as-prepared fresh NiO/CeO2 catalyst (calcined at 600 °C) contained high dispersions of NiO species in CeO2 crystallites. Conversely, the thermally aged catalyst comprised grown NiO and CeO2 crystallites were allowed to contact intimately to form thermostable interfaces, where the perimeter in the vicinity provided the Ni2+-incorporated CeO2 surface for removing and filling the oxygen species in the catalytic cycle toward facilitating CO–NO reactions. Based on in situ Fourier transform infrared and parallel isotopic reaction analyses, we confirmed the following as possible pathways: (i) the removal of the surface oxygen by the adsorbed CO to form an oxygen vacancy (VO), (ii) the interaction between the adsorbed NO with VO, and (iii) the N–O bond cleavage and the reaction with CO to form isocyanate, followed by the reaction with NO to produce N2.
NiO 表面接枝到 CeO2 纳米晶上会产生异质界面结构，为 CO-NO 反应生成 N2 和 CO2 提供有效的活性位点。在本研究中，我们研究了高温热老化对 NiO/CeO2 催化剂活性和纳米结构的影响。在 900 °C 高温老化后，催化剂保持了较高的催化活性，而参考催化剂则由于大量固态反应和烧结而丧失了催化活性。新制备的 NiO/CeO2 催化剂（600 ℃ 煅烧）在 CeO2 晶粒中含有大量分散的 NiO 物种。相反，经过热老化的催化剂由生长的 NiO 和 CeO2 结晶体组成，它们紧密接触形成热稳定性界面，附近的周边提供了 Ni2+ 并入的 CeO2 表面，用于去除和填充催化循环中的氧物种，从而促进 CO-NO 反应。根据原位傅立叶变换红外分析和平行同位素反应分析，我们确认了以下可能的途径：(i) 吸附的 CO 清除表面氧，形成氧空位 (VO)；(ii) 吸附的 NO 与 VO 相互作用；(iii) N-O 键裂解，与 CO 反应生成异氰酸酯，然后与 NO 反应生成 N2。
{"title":"The activity of thermostable NiO/CeO2 heterointerface structure toward low-temperature catalytic CO–NO reaction","authors":"Zannatul Mumtarin Moushumy, Hiroshi Yoshida, Kaori Tokusada, Ai Kuraoka, Sota Sakamoto, Masayuki Tsushida, Masato Machida","doi":"10.1093/bulcsj/uoae081","DOIUrl":"https://doi.org/10.1093/bulcsj/uoae081","url":null,"abstract":"The surface grafting of NiO onto CeO2 nanocrystallites generates heterointerface structures, providing efficient active sites for CO–NO reactions toward forming N2 and CO2. In this study, we investigated the effects of high-temperature thermal aging on the activity and nanostructure of the NiO/CeO2 catalyst. After thermal aging at 900 °C, the catalyst retained a high catalytic activity, whereas the reference catalysts lost theirs owing to considerable solid-state reactions and sintering. The as-prepared fresh NiO/CeO2 catalyst (calcined at 600 °C) contained high dispersions of NiO species in CeO2 crystallites. Conversely, the thermally aged catalyst comprised grown NiO and CeO2 crystallites were allowed to contact intimately to form thermostable interfaces, where the perimeter in the vicinity provided the Ni2+-incorporated CeO2 surface for removing and filling the oxygen species in the catalytic cycle toward facilitating CO–NO reactions. Based on in situ Fourier transform infrared and parallel isotopic reaction analyses, we confirmed the following as possible pathways: (i) the removal of the surface oxygen by the adsorbed CO to form an oxygen vacancy (VO), (ii) the interaction between the adsorbed NO with VO, and (iii) the N–O bond cleavage and the reaction with CO to form isocyanate, followed by the reaction with NO to produce N2.","PeriodicalId":9511,"journal":{"name":"Bulletin of the Chemical Society of Japan","volume":"25 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2024-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141773355","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}
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%.
{"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}
Capacitive deionization (CDI) is an efficient and cost-effective technology for ion removal from brackish water. Here, we demonstrate a sulfonate-functionalized covalent organic framework (COF) as a novel faradaic cathode material for CDI applications. Due to its orderly arranged adsorption units in the COF, the resulting COF demonstrate a superior sodium cations removal capacity of 19.56 mg g−1 and a maximum desalination rate of 3.15 mg g-1 s−1 in a 500 ppm NaCl solution.
{"title":"Sulfonate-Functionalized Covalent Organic Frameworks for Capacitive Deionization","authors":"Dong Jiang, Xingtao Xu, Yoshio Bando, Saad M Alshehri, Miharu Eguchi, Toru Asahi, Yusuke Yamauchi","doi":"10.1093/bulcsj/uoae074","DOIUrl":"https://doi.org/10.1093/bulcsj/uoae074","url":null,"abstract":"Capacitive deionization (CDI) is an efficient and cost-effective technology for ion removal from brackish water. Here, we demonstrate a sulfonate-functionalized covalent organic framework (COF) as a novel faradaic cathode material for CDI applications. Due to its orderly arranged adsorption units in the COF, the resulting COF demonstrate a superior sodium cations removal capacity of 19.56 mg g−1 and a maximum desalination rate of 3.15 mg g-1 s−1 in a 500 ppm NaCl solution.","PeriodicalId":9511,"journal":{"name":"Bulletin of the Chemical Society of Japan","volume":"64 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2024-07-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141744757","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}
Moriaki Sakihara, Shuhei Shimoyama, Miki B Kurosawa, Junichiro Yamaguchi
In this study, we developed a method to synthesize deoxygenative functionalized products by reacting aromatic dicarbonyls with DBU, TMSOTf, diphenylphosphine oxide, and a range of nucleophiles. Moreover, we demonstrated that sequential application of phospha-Brook rearrangement and benzylic substitution conditions to aromatic aldehydes affords the deoxygenative functionalized products effectively. With highly nucleophilic reagents, it was possible to proceed with the deoxygenative functionalization without TMSOTf.
{"title":"Deoxygenative Functionalizations of Aromatic Dicarbonyls and Aldehydes","authors":"Moriaki Sakihara, Shuhei Shimoyama, Miki B Kurosawa, Junichiro Yamaguchi","doi":"10.1093/bulcsj/uoae078","DOIUrl":"https://doi.org/10.1093/bulcsj/uoae078","url":null,"abstract":"In this study, we developed a method to synthesize deoxygenative functionalized products by reacting aromatic dicarbonyls with DBU, TMSOTf, diphenylphosphine oxide, and a range of nucleophiles. Moreover, we demonstrated that sequential application of phospha-Brook rearrangement and benzylic substitution conditions to aromatic aldehydes affords the deoxygenative functionalized products effectively. With highly nucleophilic reagents, it was possible to proceed with the deoxygenative functionalization without TMSOTf.","PeriodicalId":9511,"journal":{"name":"Bulletin of the Chemical Society of Japan","volume":"64 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2024-07-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141744750","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}
Recent advances in chain-growth reversible deactivation radical polymerization (CG-RDRP), i.e. the so-called “living radical polymerization”, have synergistically developed step-growth radical polymerizations via controlled formation of radical species from covalent bonds followed by irreversible deactivation of the resulting radical species. The monomers for radical polyaddition are thus designed to possess carbon–halogen or thioester bonds, which can generate radical species in the presence of transition metal catalysts and radical initiators, as well as carbon‒carbon double bonds, which will irreversibly form carbon–halogen or thioester bonds. Radical polycondensations are achievable via radical coupling reactions of carbon-centered radicals generated from carbon–halogen bonds or radical quenching reactions with nitroxides. Furthermore, radical addition-condensation polymerizations are achieved by a sequence of reactions, i.e. the formation of radical species from carbon–halogen bonds, radical addition to nitroso or thiocarbonylthio compounds, and coupling or quenching reactions with the resulting stable radical. These step-growth irreversible deactivation radical polymerizations (SG-IDRP) enable the synthesis of a variety of polymers, such as polyethers, polyesters, polyamides, and polyimides, which have aliphatic, aromatic, polar, and degradable groups in their main chains. Sequence-regulated vinyl polymer structures can also be constructed by designing monomers. Combinations with CG-RDRPs further lead to unique hybrid block, multiblock, graft, hyperbranched, and network polymers.
{"title":"Step-growth irreversible deactivation radical polymerization: synergistic developments with chain-growth reversible deactivation radical polymerization","authors":"Masami Kamigaito","doi":"10.1093/bulcsj/uoae069","DOIUrl":"https://doi.org/10.1093/bulcsj/uoae069","url":null,"abstract":"Recent advances in chain-growth reversible deactivation radical polymerization (CG-RDRP), i.e. the so-called “living radical polymerization”, have synergistically developed step-growth radical polymerizations via controlled formation of radical species from covalent bonds followed by irreversible deactivation of the resulting radical species. The monomers for radical polyaddition are thus designed to possess carbon–halogen or thioester bonds, which can generate radical species in the presence of transition metal catalysts and radical initiators, as well as carbon‒carbon double bonds, which will irreversibly form carbon–halogen or thioester bonds. Radical polycondensations are achievable via radical coupling reactions of carbon-centered radicals generated from carbon–halogen bonds or radical quenching reactions with nitroxides. Furthermore, radical addition-condensation polymerizations are achieved by a sequence of reactions, i.e. the formation of radical species from carbon–halogen bonds, radical addition to nitroso or thiocarbonylthio compounds, and coupling or quenching reactions with the resulting stable radical. These step-growth irreversible deactivation radical polymerizations (SG-IDRP) enable the synthesis of a variety of polymers, such as polyethers, polyesters, polyamides, and polyimides, which have aliphatic, aromatic, polar, and degradable groups in their main chains. Sequence-regulated vinyl polymer structures can also be constructed by designing monomers. Combinations with CG-RDRPs further lead to unique hybrid block, multiblock, graft, hyperbranched, and network polymers.","PeriodicalId":9511,"journal":{"name":"Bulletin of the Chemical Society of Japan","volume":"17 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2024-07-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141744753","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}
Rafat Tahawy, Mohamed Esmat, Hamza El-Hosainy, Fatma E Farghaly, El-Sayed A Abdel-Aal, F I El-Hosiny, Yusuke Ide
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.
{"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}
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.
{"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}
Copper iodide (CuI) is a wide-bandgap (colorless) p-type semiconductor with a high Seebeck coefficient. Although CuI is promising for fabricating transparent thermoelectric devices and hole-transfer layers of solar cells, the insolubility in common solvents due to 3-dimensional coordination networks has been a drawback to constructing low-temperature solution-processed thin films. Moreover, it is challenging to fabricate void-and-crack-free CuI thin films through a convenient spin-coating process. In limited solvents of acetonitrile and diethyl sulfide, CuI is dissolved by forming soluble CuI complexes; however, void-and-crack-free CuI thin films have never been prepared. In this study, we report that CuI-alkanolamine complexes are soluble in alcohols and the spin-coated complexes undergo thermal decomposition to a CuI thin film at moderately low temperatures until 150 °C. We discover that the CuI-alkanolamines show different properties such as solubility and melting/decomposition temperatures depending on their structures. Specifically, by using 1-amino-2-propanol, we obtain void-and-crack-free and transparent CuI thin films with controlled thicknesses of >50 nm. The conductivity, carrier density, mobility, and Seebeck coefficient of the CuI thin film are 9.35 S·cm-1, 6.38×1019 cm-3, 0.96 cm2·V-1·S-1, and 192 µV･K-1, respectively.
碘化铜（CuI）是一种具有高塞贝克系数的宽带隙（无色）p 型半导体。虽然 CuI 有望用于制造透明热电设备和太阳能电池的空穴传输层，但其三维配位网络导致的在普通溶剂中的不溶性一直是构建低温溶液加工薄膜的一个缺点。此外，通过便捷的旋涂工艺制作无空隙和裂缝的 CuI 薄膜也具有挑战性。在乙腈和硫化二乙烷等有限的溶剂中，CuI 通过形成可溶性 CuI 复合物而溶解；然而，无空隙和裂缝的 CuI 薄膜却从未制备出来。在这项研究中，我们发现 CuI-烷醇胺络合物可溶于醇类，并且旋涂络合物在 150 °C 之前的中等低温下会发生热分解，生成 CuI 薄膜。我们发现，CuI-烷醇胺因其结构不同而显示出不同的特性，如溶解度和熔化/分解温度。具体来说，通过使用 1-氨基-2-丙醇，我们获得了无空隙、无裂纹、透明的 CuI 薄膜，厚度控制在 50 nm。CuI 薄膜的电导率、载流子密度、迁移率和塞贝克系数分别为 9.35 S-cm-1、6.38×1019 cm-3、0.96 cm2-V-1-S-1 和 192 µV・K-1。
{"title":"Three-type Precursors for Low-Temperature Solution-Processed Void-and-Crack-Free CuI Films: Comparison of Electrical Conductivities and Optical Transparency","authors":"Manabu Ishizaki, Naoki Koya, Yoshitomo Gotoh, Kodai Muramatsu, Masato Kurihara","doi":"10.1093/bulcsj/uoae071","DOIUrl":"https://doi.org/10.1093/bulcsj/uoae071","url":null,"abstract":"Copper iodide (CuI) is a wide-bandgap (colorless) p-type semiconductor with a high Seebeck coefficient. Although CuI is promising for fabricating transparent thermoelectric devices and hole-transfer layers of solar cells, the insolubility in common solvents due to 3-dimensional coordination networks has been a drawback to constructing low-temperature solution-processed thin films. Moreover, it is challenging to fabricate void-and-crack-free CuI thin films through a convenient spin-coating process. In limited solvents of acetonitrile and diethyl sulfide, CuI is dissolved by forming soluble CuI complexes; however, void-and-crack-free CuI thin films have never been prepared. In this study, we report that CuI-alkanolamine complexes are soluble in alcohols and the spin-coated complexes undergo thermal decomposition to a CuI thin film at moderately low temperatures until 150 °C. We discover that the CuI-alkanolamines show different properties such as solubility and melting/decomposition temperatures depending on their structures. Specifically, by using 1-amino-2-propanol, we obtain void-and-crack-free and transparent CuI thin films with controlled thicknesses of >50 nm. The conductivity, carrier density, mobility, and Seebeck coefficient of the CuI thin film are 9.35 S·cm-1, 6.38×1019 cm-3, 0.96 cm2·V-1·S-1, and 192 µV･K-1, respectively.","PeriodicalId":9511,"journal":{"name":"Bulletin of the Chemical Society of Japan","volume":"22 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2024-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141613949","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}
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