Chemical Science最新文献

{"title":"On the nature of the triplet electronic states of naphthalene dimers.","authors":"Lara Martinez-Fernandez, Peicong Wu, Lin-Tao Bao, Xueli Wang, Rui-Hua Zhang, Wei Wang, Hai-Bo Yang, Jinquan Chen, Roberto Improta","doi":"10.1039/d4sc07982e","DOIUrl":"https://doi.org/10.1039/d4sc07982e","url":null,"abstract":"Elucidating the photophysical mechanisms within multi-chromophore assembly (MCA) is essential for many key technological and biological processes. Although it has been established that one of the most important photoactivated application of MCA is intimately linked to efficient intersystem crossing (ISC) to triplet states and the interplay between delocalized/localized triplet excited states, the underlying mechanism between such equilibrium and the observed optical properties remain elusive. Herein, four suitably-designed dinaphthyl compounds, covalently bonded in a face-to-face configuration and encompassing the primary possible stacking geometries, were prepared and their triplet states properties investigated by combining transient absorption spectroscopy experiments with quantum chemistry calculations. Our results offer direct evidence of both localized and delocalized triplet states, with the most stable and long-lived triplet state consistently localized on a single naphthalene unit, irrespective of the stacking configuration. Moreover, depending on the stacking geometry, even if localized, the triplet transient absorption spectrum was demonstrated to be significantly different from that of an isolated naphthalene.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"15 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143050773","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"An encodable amino acid for targeted photocatalysis.","authors":"Man Sing Wong, Utsa Karmakar, Marco Bertolini, Abigail E Reese, Lorena Mendive-Tapia, Marc Vendrell","doi":"10.1039/d4sc08594a","DOIUrl":"10.1039/d4sc08594a","url":null,"abstract":"<p><p>Photocatalysts are excellent scaffolds for the light-mediated control of bioactive molecules. Current photocatalytic structures are not compatible with genetic encoding and therefore cannot be directly incorporated into the sequences of native proteins. Herein, we developed new amino acids incorporating Si-rosamine photocatalytic units, and introduced them <i>via</i> aminoacylation of tRNAs into specific positions of different proteins to enable targeted photocatalytic reactions in defined populations of immune cells.</p>","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":7.6,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11793017/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143254818","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Discovery of Intermolecular Cascade Annulation for Dihydrobenzo[b][1,8]naphthyridine-Ylidene-Pyrrolidinetriones","authors":"Wenjun Luo, Xinghua Zheng, Hehua Lin, Li Fu, Lipeng Long, Daohong Yu, Zhengwang Chen, Min Yang, Zhong-Xia Wang","doi":"10.1039/d4sc07999j","DOIUrl":"https://doi.org/10.1039/d4sc07999j","url":null,"abstract":"Developing efficient procedures for the synthesis of combinations of pharmacophores continues to be a vital objective in synthetic science. Herein, we report an unprecedented family of dihydrobenzo[b][1,8]naphthyridine-ylidene-pyrrolidinetriones achieved by reacting ortho-halogenated quinolinchalcones with aminomaleimides under metal-free conditions. Among these compounds, several exhibit the potential to serve as fluorescent dyes for biological applications. Mechanistic investigations indicate that the reaction proceeds via a 1,4-Michael addition followed by an intermolecular cascade annulation, which involves aniline fragment transfer and SNAr processes. As far as we know, studies regarding the synthesis of dihydrobenzo[b][1,8]naphthyridine-ylidene-pyrrolidinetriones are rare. This discovery offers great inspiration for a feasible approach toward the creation of more complex and useful molecules.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"17 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143050774","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Multifaceted role of H2O2 in the solvothermal synthesis of green-emitting nitrogen-doped graphene quantum dots","authors":"Clara Carrera, Alejandro Galán-González, Wolfgang K. Maser, Ana M. Benito","doi":"10.1039/d4sc07896a","DOIUrl":"https://doi.org/10.1039/d4sc07896a","url":null,"abstract":"Fluorescent nitrogen-doped carbon dots (N-GQDs) with long-wavelength emission properties are of increased interest for technological applications. They are widely synthesized through the solvothermal treatment of graphene oxide (GO) using <em>N</em>,<em>N</em>-dimethylformamide (DMF) as a cleaving and doping agent. However, this process simultaneously generates undesired interfering blue-emissive by-products. In this study, we present a straightforward method for synthesizing N-GQDs exclusively exhibiting green fluorescence. The key innovation lies in the addition of hydrogen peroxide (H<small>₂</small>O<small>₂</small>) to the DMF-driven one-pot solvothermal cleavage process. Systematically controlling the reaction conditions, we elucidate the threefold beneficial role of H<small>₂</small>O<small>₂</small>: first, it acts as a radical source facilitating the degradation of DMF and the generation of nitrogen-containing radicals, essential for N-GQD formation; second, it prevents the thermal reduction of GO, thus ensuring persistent reaction pathways with DMF-derived radicals; and third, it suppresses the self-reaction of DMF-derived radicals, thereby avoiding the formation of undesired blue-fluorescent by-products. Our findings on the reaction mechanism and the advantageous role of H<small>₂</small>O<small>₂</small> open new possibilities for the rational design of N-GQDs genuinely emitting at long wavelengths.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"78 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143050768","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Enzymatic Peptide Macrocyclization via Indole-N-Acylation","authors":"Hiroto Maruyama, Yuito Yamada, Yasuhiro Igarashi, Kenichi Matsuda, Toshiyuki Wakimoto","doi":"10.1039/d4sc07839j","DOIUrl":"https://doi.org/10.1039/d4sc07839j","url":null,"abstract":"Indole <em>N</em>-acylation is chemically challenging, due to the low nucleophilicity of the indole nitrogen. Although a few similar transformations have been proposed in the biosynthesis of indole-containing natural products, their enzymatic basis remains elusive. Here, we show that BulbE TE is an <em>N</em>-acylindole-forming macrocyclase involved in the biosynthesis of the non-ribosomal cyclopeptide bulbiferamide. BulbE catalyzed macrocyclization not only via the indole nitrogen, but also via a primary amine and an alcohol. The uncommon catalytic residue Cys731 in BulbE TE was indispensable for the nucleophilic attack from the indole nitrogen. While the C731S variant failed to utilize the indole nitrogen and primary alcohol as nucleophiles, it retained the ability to employ the amine nucleophile, showing a clear correlation between the catalytic residues and the nucleophile scope. A model of the acyl-enzyme complex revealed how the substrate is recognized, including interactions involving a unique second lid-like structural motif in BulbE TE. This study provides an enzymatic basis for indole <em>N</em>-acylation and offers important insights into the nucleophile specificity in TE-mediated macrocyclization.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"10 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143050681","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Natural biomolecules for cell-interface engineering","authors":"Tong-Kai Zhang, Zi-Qian Yi, Yao-Qi Huang, Wei Geng and Xiao-Yu Yang","doi":"10.1039/D4SC08422E","DOIUrl":"10.1039/D4SC08422E","url":null,"abstract":"<p >Cell-interface engineering is a way to functionalize cells through direct or indirect self-assembly of functional materials around the cells, showing an enhancement to cell functions. Among the materials used in cell-interface engineering, natural biomolecules play pivotal roles in the study of biological interfaces, given that they have good advantages such as biocompatibility and rich functional groups. In this review, we summarize and overview the development of studies of natural biomolecules that have been used in cell-biointerface engineering and then review the five main types of biomolecules used in constructing biointerfaces, namely DNA polymers, amino acids, polyphenols, proteins and polysaccharides, to show their applications in green energy, biocatalysis, cell therapy and environmental protection and remediation. Lastly, the current prospects and challenges in this area are presented with potential solutions to solve these problems, which in turn benefits the design of next-generation cell engineering.</p>","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" 7","pages":" 3019-3044"},"PeriodicalIF":7.6,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11773181/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143063935","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Phase engineering of covalent triazine frameworks to enhance photocatalytic hydrogen evolution performance.","authors":"Peng Wu, Jijun Lu, Fengshuo Xi, Xiufeng Li, Wenhui Ma, Fangyuan Kang, Shaoyuan Li, Zhongqiu Tong, Qichun Zhang","doi":"10.1039/d4sc06496h","DOIUrl":"10.1039/d4sc06496h","url":null,"abstract":"<p><p>Photocatalytic water splitting for hydrogen production has been considered as an effective approach to address the current energy crisis and environmental challenges. Among all materials for such applications, covalent triazine frameworks (CTFs) are regarded as ideal candidates owing to their conjugated structures with rich aromatic nitrogen atoms, which can provide abundant active sites, suitable bandgaps, good structural tunability, and high chemical stability. Although current research studies have shown that the modification of functional groups in CTFs can adjust the band structure and carrier flow characteristics of photocatalysts, leading to improved performance, the impact of the intrinsic structural characteristics of CTFs (<i>e.g.</i>, stacking modes, hydrogen bonding) on their photocatalytic performance remains unclear. In this paper, we demonstrate that the photocatalytic hydrogen evolution performance of CTFs can be enhanced through tuning their stacking arrangement, because the stacking modes affect the bandgaps of materials as well as their carrier separation and transfer efficiency. Under visible light conditions, CTF-AA (AA stacking) exhibited a hydrogen evolution rate of 4691.73 μmol g^-1 h^-1, which is 37.4% higher than that of CTF-AB (AB stacking, 3415.30 μmol g^-1 h^-1). Clearly, the stacking modes significantly influence the cycling stability of CTFs. After eight cycles (over 32 h), CTF-AA maintains its photocatalytic activity and initial performance with a slight decline, while CTF-AB only retains 56.8% of its initial hydrogen evolution rate. Theoretical calculations and physical characterization confirm that the transition of the stacking mode from AB to AA enhances interlayer overlapping, increases the energy level of the lowest unoccupied molecular orbital, and improves the separation and mobility of carriers. These combined factors significantly enhance the photocatalytic performance of CTF-AA. This work offers new insights into the relationship between the photocatalytic performance of CTFs and their stacking patterns, providing new guidelines for designing CTF catalysts with improved activity.</p>","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":7.6,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11788819/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143188398","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"CoII-organic ‘soft’ metallo-supramolecular polymer nanofibers for efficient photoreduction of CO2","authors":"Souvik Mondal, Faruk Ahamed Rahimi, Tarak Nath Das, Sukhendu Nath, Tapas Kumar Maji","doi":"10.1039/d4sc08814j","DOIUrl":"https://doi.org/10.1039/d4sc08814j","url":null,"abstract":"Coordination-driven metallo-supramolecular polymers hold significant potential as highly efficient catalysts for photocatalytic CO<small>₂</small> reduction, owing to the covalent integration of the light harvesting unit, catalytic center and intrinsic hierarchical nanostructures. In this study, we present the synthesis, characterization, and gelation behaviour of a novel low molecular weight gelator (LMWG) integrating a benzo[1,2-<em>b</em>:4,5-<em>b</em>′]dithiophene core with terpyridine (TPY) units <em>via</em> alkyl amide chains (TPY-BDT). The two TPY ends of the TPY-BDT unit efficiently chelate with metal ions, enabling the formation of a metallo-supramolecular polymer that brings together the catalytic center and a photosensitizer in close proximity, maximizing catalytic efficiency for CO<small>₂</small> reduction. The self-assembly of TPY-BDT with Co<small>^II</small> ions yields a Co-TPY-BDT coordination polymer gel (CPG) with a 3D interconnected fibrous morphology, facilitating rapid electron transfer and efficient substrate diffusion. The Co-TPY-BDT CPG achieves an outstanding CO<small>₂</small> to CO conversion, producing 33.74 mmol g<small>⁻¹</small> of CO in 18 hours with ∼99% selectivity under visible light irradiation, using triethylamine (TEA) as a sacrificial electron donor. Remarkably, the Co-TPY-BDT CPG demonstrates significant catalytic activity even under low-concentration CO<small>₂</small> atmospheres (5% CO<small>₂</small>, 95% Ar), producing 1.9 mmol g<small>⁻¹</small> of CO in 10 hours with a selectivity of 94.6%. Moreover, <em>In situ</em> diffuse reflectance Fourier transform (DRIFT) study, femtosecond transient absorption spectroscopy, and DFT calculations were employed to elucidate the CO<small>₂</small> to CO reaction mechanism.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"38 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143044327","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Mechanistic insights into the regiodivergent insertion of bicyclo[1.1.0]butanes towards carbocycle-tethered N-heteroarenes","authors":"Johannes E. Erchinger, Madina Lenz, Poulami Mukherjee, Yan-Bo Li, Adhya Suresh, Constantin Gabriel Daniliuc, Osvaldo Gutierrez, Frank Glorius","doi":"10.1039/d4sc08637f","DOIUrl":"https://doi.org/10.1039/d4sc08637f","url":null,"abstract":"Ring scaffolds constitute important sub-structures in nature and across the chemical industries. However, their straight-forward introduction into a target molecule or cross-linkage between cyclic motifs of choice comprise major challenges for methodology development. Herein, the interconnection of two prominent representatives of the 2D and 3D cyclic chemical space—namely N-heteroarenes and unsaturated carbocycles—in the form of hybrid cyclobutane-tethered N-heteroarenes is targeted. The diastereoselective introduction of decorated cyclobutanes is promoted by the insertion of strained bicyclo[1.1.0]butanes (BCBs) into the C–S bond of C2–thioether aza-arenes. In-depth density functional theory (DFT) studies provide insights on the key factors governing the unexpected regiodivergent insertion outcomes. A broad scope of mono- and bicyclic aza-arenes along with mono- and disubstituted BCBs are shown to be competent. Detailed mechanistic studies support an oxidative activation of the N-heteroarenes.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"22 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143044395","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A focus on chasing pharmaceutical polyamorphs to design better oral drug formulations","authors":"Ana M. Belenguer","doi":"10.1039/D4SC90250E","DOIUrl":"10.1039/D4SC90250E","url":null,"abstract":"<p >The pharmaceutical industry cares about reducing toxic side effects of drugs in oral formulation. The best solution is to reduce the drug dose. To do so, drugs are required to have high aqueous solubility to ensure good bioavailability. Amorphous drugs are much more water soluble than their crystalline counterparts, but can lack physical stability. Martins and Rades, <em>et al.</em> (I. C. B. Martins and T. Rades <em>et al.</em>, <em>Chem. Sci</em>., 2023, <strong>14</strong>, 11447–11455, DOI: https://doi.org/10.1039/D3SC02802J) demonstrate for the first time that poly<em>a</em>morphs (amorphous polymorphs) of drugs are now a reality. They demonstrated proof-of-concept, reproducible preparation methods for 3 poly<em>a</em>morphs (I, II and III) of hydrochlorothiazide (HCT) that display different glass transitions temperatures (<em>T</em><small>_g</small>) and distinct structural relaxation profiles as excellent analytical indicators for discriminating between the poly<em>a</em>morphs. HCT poly<em>a</em>morph-II displayed improved physical stability with respect to the other HCT poly<em>a</em>morphs. A tangible benefit of poly<em>a</em>morphism research is the opportunity to select a specific poly<em>a</em>morph of a drug with the desired solubility and physical stability to be incorporated in an oral formulation, a strategy that should improve drug effectiveness.</p>","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" 6","pages":" 2480-2482"},"PeriodicalIF":7.6,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/sc/d4sc90250e?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143044394","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}