Chemistry - An Asian Journal最新文献

{"title":"Organocatalyzed Asymmetric Conjugate Addition of Cyclic β-Keto Esters to (E)-β-Nitroacrylate Derivatives.","authors":"Yasuyuki Matsushima, Yoshiyuki Iijima, Chinatsu Tanabe, Kosuke Nakashima, Shin-Ichi Hirashima, Tsuyoshi Miura","doi":"10.1002/asia.202401029","DOIUrl":"10.1002/asia.202401029","url":null,"abstract":"<p><p>A diaminomethylenemalononitrile organocatalyst efficiently promoted the asymmetric conjugate addition of cyclic β-keto esters to (E)-β-nitroacrylate derivatives, yielding the corresponding β-nitro esters derivatives with excellent enantioselectivities (up to >99 % ee). This is the first successful example of highly stereoselective conjugate addition of cyclic β-keto esters to (E)-β-nitroacrylate derivatives to obtain anti-isomers.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e202401029"},"PeriodicalIF":3.5,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142454098","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}

{"title":"Highly Efficient and Selective Hydrodeoxygenation of Guaiacol Using Ni-Supported Honeycomb-Structured Biochar and Phosphomolybdic Acid.","authors":"Tao Yin, Yang Luo, Ripsa Rani Nayak, Riyang Shu, Zhipeng Tian, Chao Wang, Ying Chen, Navneet Kumar Gupta","doi":"10.1002/asia.202400999","DOIUrl":"10.1002/asia.202400999","url":null,"abstract":"<p><p>The sustainable development of energy has always been a concern. Upgrading biomass catalysis into hydrocarbon liquid fuels is one of the effective methods. In order to upgrade biomass derivative guaiacol by Hydrodeoxygenation (HDO) catalysis, this article report a three-dimensional honeycomb structure biochar loaded with Ni nanoparticles and phosphomolybdic acid demonstrating excellent catalytic performance in a short period of time. This is due to the porous structure of biochar, which allows Ni metal nanoparticles to be highly uniformly dispersed on the support, which enhances the catalytic hydrogenation of guaiacol in terms of both rate and efficiency. Furthermore, it was observed that the added phosphomolybdic acid dissolved within the temperature range of 78-90 °C, functioning as a homogeneous catalyst in the process. This proves advantageous, as the phosphomolybdic acid becomes accessible at any location within the porous Ni/C catalyst. The detailed characterization data revealed that the carbon support prepared in this study has a high specific surface area of up to 1375.61 m²/g. Additionally, the phosphomolybdic acid exhibited rich acidity, with Brønsted and Lewis acid contents of 2.55 μmol/g and 21.45 μmol/g, respectively. Reaction data demonstrated that at 240 °C for 180 min, 100 % conversion and 97.9 % cyclohexane selectivity were achieved. This study introduces a bifunctional catalyst with an unique catalyst's structure, facilitating a heterogeneous-homogeneous catalytic reaction and delivering an efficient catalytic effect.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e202400999"},"PeriodicalIF":3.5,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142386672","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}

{"title":"Alkaline Synthesis of Pure Silica ITH Zeolite for Vapor Phase Beckmann Rearrangement of Cyclohexanone Oxime.","authors":"Huimin Luan, Tianming Zai, Qinming Wu, Xiangju Meng, Jianping Wu, Weiliao Liu, Na Sheng, Han Wang, Feng-Shou Xiao","doi":"10.1002/asia.202401057","DOIUrl":"10.1002/asia.202401057","url":null,"abstract":"<p><p>Pure silica ITH zeolite is normally synthesized under neutral or acidic conditions in the presence of HF, but it is challenging for synthesis of this zeolite under alkaline conditions. In this work, it is successful for alkaline synthesis of pure silica ITH in the absence of HF using a designed organic template containing F species, showing that the sample obtained has high crystallinity associated with ITH structure, nanosheet morphology, and rich silanol nests. Very importantly, this ITH zeolite exhibited better performance in vapor phase Beckmann rearrangement of cyclohexanone oxime than that of Silicalite-1 zeolite, one of the best catalysts for this reaction. This work might offer a new opportunity for preparation of pure silica zeolites as efficient catalysts in the Beckmann rearrangement in the future.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e202401057"},"PeriodicalIF":3.5,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142454090","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}

{"title":"Site-Selective Direct γ-Difunctionalization of Diazoenals: Application to the Synthesis of Enal-Functionalized Allenes and Furans.","authors":"Jagadeesh Kalepu, Bapurao Sudam Lad, Pratap Kumar Mandal, Vinaykumar Kanchupalli, Durjay Roy, Sreenivas Katukojvala","doi":"10.1002/asia.202401081","DOIUrl":"10.1002/asia.202401081","url":null,"abstract":"<p><p>A new approach for the synthetically important γ-functionalized enals has been developed. The strategy involves rhodium-catalyzed direct C-C & C-S bond forming site-selective γ-difunctionalization of diazoenals with aryl propargyl sulfides via sulfur ylide [2,3] sigmatropic rearrangement, resulting in the highly functionalized γ-allenyl(sulfanyl)enals in excellent yield at ambient temperature. This highly versatile approach constitutes a viable alternative to the remote carbonyl-directed γ-functionalization of unmodified enals which suffer from competitive side reactions. The synthetic utility of the γ-allenyl(sulfanyl)enals was demonstrated by the InCl₃-catalyzed cycloisomerization to the trisubstituted furanyl-enals via an unusual 1,4-sulfanyl migration. In addition, an operationally simple and efficient one-pot [3+2] annulation of diazoenals and propargyl sulfides, involving combined γ-difunctionalization and cycloisomerization was successfully developed for the diverse enal-functionalized furans.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e202401081"},"PeriodicalIF":3.5,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142491514","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}

{"title":"Strong Non-Reciprocal Chiroptical Properties in Thin Films of Chiral Alkylthio-Decorated 1,4-Phenylene/Thiophene Dyes.","authors":"Marco Bertuolo, Francesco Zinna, Laura Antonella Aronica, Gennaro Pescitelli, Lorenzo Di Bari, Gianluigi Albano","doi":"10.1002/asia.202401160","DOIUrl":"10.1002/asia.202401160","url":null,"abstract":"<p><p>In the context of chiral π-conjugated materials, the use of enantiopure alkylthio appendages represents a valid alternative to conventional alkoxy groups: sulphur atom is bigger and more electron-rich than oxygen, thus allowing for higher polarizability, greater flexibility, larger bulkiness and lower structural anisotropy. In light of these considerations, here we report two new chiral alkylthio-decorated 1,4-phenylene/thiophene dyes, obtained by simple synthetic strategies involving Pd-catalyzed cross-coupling protocols, looking for strong non-reciprocal chiroptical features in thin films. In particular, for the chiral alkylthio-decorated 1,4-phenylene-bis(thiophenylpropynone) (Thio-PTPO) dye, which proved to be the most promising for our purpose, a detailed investigation in thin films was carried out, involving optical and chiroptical spectroscopies in absorption and emission, as well as optical microscopy techniques.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e202401160"},"PeriodicalIF":3.5,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142491515","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}

{"title":"ZnO with Different Morphologies Sensitized by Metalloporphyrins as Catalysts for H₂ Production by Water Splitting Under Sunlight.","authors":"João F Stival, Camila N Cechin, Bernardo A Iglesias, Ernesto S Lang, Júlio S Rebouças, Shirley Nakagaki","doi":"10.1002/asia.202401011","DOIUrl":"10.1002/asia.202401011","url":null,"abstract":"<p><p>In this work, zinc oxide with different morphologies and textural properties were prepared and sensitized with metalloporphyrins (MPs) aiming to improve its solar energy harvesting capability for H₂ production by water splitting under sunlight (a 300 W Xe/Hg lamp). An anionic iron(III)porphyrin and a cationic manganese(III)porphyrin were immobilized on different ZnO solids predominantly by electrostatic interactions. In general, the prepared MP-free ZnO solid yielded modest catalytic results which had apparently no direct correlation with their textural properties or morphology. On the other hand, when these ZnO solids had iron or manganese porphyrin sensitizing them, their catalytic performances changed and a superior yield towards H₂ production was observed in comparison to the pure ZnO solids, making evident the synergy achieved between these two components (ZnO and metalloporphyrins) for the prepared solids. It was also observed that the metalloporphyrins and the respective free-base ligand suffered redox reactions when used as homogenous catalyst in this reaction, which could influence their performances as catalysts. The same was not observed in the solids containing immobilized MP, suggesting some protective effect of the ZnO solids on the MP complexes upon immobilization probably due to interaction of the complexes with the ZnO matrix.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e202401011"},"PeriodicalIF":3.5,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142370373","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}

{"title":"On the Role of a Polymer Matrix in Enhancing Energy Transfer Efficiency Using Coumarin 6 and Rhodamine B as Donor and Acceptor Pairs.","authors":"Igor Osorio-Román, Cristian Bachmann, Caroline S Danna, Airton Germano Bispo-Jr, Fernando Aparecido Sigoli, Marcelo A Muñoz, Rodrigo Ormazabal-Toledo, Benedetta M Squeo, Camilo Segura","doi":"10.1002/asia.202401525","DOIUrl":"https://doi.org/10.1002/asia.202401525","url":null,"abstract":"<p><p>This study investigates the critical role of polymer matrices in optimizing luminescence and energy transfer, utilizing the commercial dyes Coumarin 6 (C6) and Rhodamine B (RhB) as a donor-acceptor pair. Solution-phase experiments revealed a dependence of energy transfer efficiency on solvent dielectric constant. Furthermore, embedding the dyes within Poly(methyl methacrylate) (PMMA) or Poly(vinyl butyral) (PVB) matrices significantly enhance energy transfer due to increased molecular proximity. A modified approach for calculating the overlap integral J(λ) was employed to analyze energy transfer in the solid state, providing insights beyond traditional Förster-type calculations. Photostability studies demonstrated superior performance of PVB films compared to PMMA films under exposure to monochromatic (405 nm, 515 nm) and white light irradiation. Finally, a proof-of-concept device was developed to harness this enhanced energy transfer for light-to-electricity conversion, achieving a maximum efficiency of 7.28%.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e202401525"},"PeriodicalIF":3.5,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142913333","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}

{"title":"An Improved Gold(I) Catalytic System for the Preparation of Coumarins via Intramolecular Cyclization.","authors":"Francesco Ravera, Federico Floreani, Cristina Tubaro, Marco Roverso, Riccardo Pedrazzani, Marco Bandini, Andrea Biffis","doi":"10.1002/asia.202400725","DOIUrl":"10.1002/asia.202400725","url":null,"abstract":"<p><p>A catalytic system comprising a gold(I) complex with an N-heterocyclic carbene (NHC) ligand in an ionic liquid as solvent exhibits higher catalytic efficiency compared to state of the art systems in the title reaction, which enables using down to 0.01 mol % gold. A commercial gold(I) catalyst such as IPrAuNTf₂ can be employed for this purpose. In the case of less reactive substrates bearing electron-withdrawing substituents at the phenol moiety, a tailor made NHC-gold(I) precatalyst exhibits improved reactivity and can be advantageously employed compared to the commercial one.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e202400725"},"PeriodicalIF":3.5,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11697228/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142454091","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synthesis and Optical Properties of Organic-Inorganic Hybrid [(18-Crown-6)K][MoOCl₄(H₂O)].","authors":"Animesh Ghosh, Sajid Saikia, Maxim S Molokeev, Angshuman Nag","doi":"10.1002/asia.202401052","DOIUrl":"10.1002/asia.202401052","url":null,"abstract":"<p><p>Crown ether anchored organic-inorganic hybrid halides have been recently reported as interesting luminescent materials in the visible region of electromagnetic spectrum. Is it possible to develop such crown ether anchored hybrid materials for near infrared emission? Motivated by this question, we designed a new hybrid material, namely, [(18-Crown-6)K][MoOCl₄(H₂O)]. 18-Crown-6 ether bound with K⁺ form the cationic part [(18-Crown-6)K]⁺. The K⁺ of [(18-Crown-6)K]⁺ electrostatically interacts with Cl^- of the anionic part [MoOCl₄(H₂O)]^-, forming the hybrid crystal [(18-Crown-6)K][MoOCl₄(H₂O)]. It crystallizes in orthorhombic crystal system with Pnma space group. The Mo(V) possesses one d-electron (d¹) in <math> <semantics><msub><mi>C</mi> <mrow><mn>4</mn> <mi>v</mi></mrow> </msub> <annotation>${{C}_{4v}}$</annotation> </semantics> </math> point group symmetry in the [MoOCl₄(H₂O)]^- polyhedra. This electronic configuration leads to multiple spin-allowed <math> <semantics><mrow><mi>d</mi> <mo>-</mo> <mi>d</mi></mrow> <annotation>${d-d}$</annotation> </semantics> </math> transitions along with a ligand to metal charge transfer (LMCT) resulting into multiple optical absorption bands in the near UV-visible-near infrared (NIR) region. The lowest energy <math> <semantics><mrow><mi>d</mi> <mo>-</mo> <mi>d</mi></mrow> <annotation>${d-d}$</annotation> </semantics> </math> transition via ²E ( <math> <semantics><msubsup><mi>d</mi> <mrow><mi>x</mi> <mi>z</mi></mrow> <mn>1</mn></msubsup> <annotation>${{d}_{xz}^{1}}$</annotation> </semantics> </math> , <math> <semantics><msub><mi>d</mi> <mrow><mi>y</mi> <mi>z</mi></mrow> </msub> <annotation>${{d}_{yz}}$</annotation> </semantics> </math> )/²E ( <math> <semantics> <mrow><msub><mi>d</mi> <mrow><mi>x</mi> <mi>z</mi></mrow> </msub> <mo>,</mo> <msubsup><mi>d</mi> <mrow><mi>y</mi> <mi>z</mi></mrow> <mn>1</mn></msubsup> </mrow> <annotation>${{d}_{xz},{d}_{yz}^{1}}$</annotation> </semantics> </math> ) <math><semantics><mo>→</mo> <annotation>${to }$</annotation> </semantics> </math> ²B₂ ( <math> <semantics><msubsup><mi>d</mi> <mrow><mi>x</mi> <mi>y</mi></mrow> <mn>1</mn></msubsup> <annotation>${{d}_{xy}^{1}}$</annotation> </semantics> </math> ) leads to NIR PL with peak at 952 nm, but with a poor intensity at room temperature.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e202401052"},"PeriodicalIF":3.5,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142386678","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}

{"title":"Hydrogen Sulfide (H₂S) Activatable Photodynamic Therapy Against Colon Cancer by Tunable FRET Effect.","authors":"Mengting Zhu, Baoxuan Huang, Guoliang Yang, Weian Zhang, Jia Tian","doi":"10.1002/asia.202400840","DOIUrl":"10.1002/asia.202400840","url":null,"abstract":"<p><p>Developing activatable photodynamic agents is becoming a promising mode for realizing selective photodynamic therapy (PDT) in cancer treatment. However, till now only a few H₂S-activatable photodynamic agents have been involved in this field. Here, we fabricated H₂S-activatable nano-assemblies (P@TPPCY) for the treatment of colon cancer containing high concentration H₂S. The H₂S-activatable photosensitizer (TPPCY) was synthesized by covalent conjugation between tetraphenylporphyrin (TPP) and heptamethine cyanine (Cy7), and then TPPCY was encapsulated by an amphiphilic polymer DSPE-mPEG to form P@TPPCY nano-assemblies. We demonstrated that the photosensitizing effect of TPP was efficiently quenched by Cy7 with strong absorption in the NIR region via fluorescence resonance energy transfer (FRET) effect. Interestingly, the FRET effect between Cy7 and TPP was attenuated by the decrease of absorption of Cy7 in the NIR region after the Cy7 reacted with H₂S, and then the photosensitizing effect of TPP in P@TPPCY was activated. Strikingly, the P@TPPCY showed efficient H₂S-activatable photodynamic therapy (PDT) in vitro against HCT116 cells (human colon carcinoma cell line), thus this work provides a new method for realizing accurate treatment of colon cancer in virtue of high H₂S concentration microenvironment.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e202400840"},"PeriodicalIF":3.5,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142454096","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}