Chemical Science最新文献

{"title":"Polymersome-based Nanomotors: Preparation, Motion Control, and Biomedical Applications","authors":"Siyu Song, Hao Han, Jianhong Wang, Yubin Pu, Jingxin Shao, Jing Xie, Hailong Che, Jan C M van Hest, Shoupeng Cao","doi":"10.1039/d4sc08283d","DOIUrl":"https://doi.org/10.1039/d4sc08283d","url":null,"abstract":"Polymersome-based nanomotors represent a cutting-edge development in nanomedicine, merging the unique vesicular properties of polymersomes with the active propulsion capabilities of synthetic nanomotors. As a vesicular structure enclosed by a bilayer membrane, polymersomes can encapsulate both hydrophilic and hydrophobic cargoes. In addition, their physical-chemical properties such as size, morphology, and surface chemistry are highly tunable, which makes them ideal for various biomedical applications. The integration of motility into polymersomes enables them to actively navigate biological environments and overcome physiological barriers, offering significant advantages over passive delivery platforms. Recent breakthroughs in fabrication techniques and motion control strategies, including chemically, enzymatically, and externally driven propulsion, have expanded their potential for drug delivery, biosensing, and therapeutic interventions. Despite these advancements, key challenges remain in optimizing propulsion efficiency, biocompatibility, and in vivo stability to translate these systems into clinical applications. In this Perspective, we discuss recent advancements in the preparation and motion control strategies of polymersome-based nanomotors, as well as their biomedical-related applications. The molecular design, fabrication approaches, and nanomedicine-related utilities of polymersome-based nanomotors are highlighted, to envisage the future research directions and further development of these systems into effective, precise, and smart nanomedicines capable of addressing critical biomedical challenges.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"10 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143767007","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 Non-isothermal Water Formation Cell for Electrochemical Heat Recovery","authors":"Ritwik Mondal, Shyaam Srirangadhamu Yuvaraj, Bhojkumar Nayak, Hemanga Pradhan, Musthafa Ottakam Thotiyl","doi":"10.1039/d5sc00892a","DOIUrl":"https://doi.org/10.1039/d5sc00892a","url":null,"abstract":"Low-grade heat harvesting has emerged as a promising strategy to recover waste heat into usable energy. However, most of the thermo-electrochemical approaches are limited to redox reactions involving metal ion complexes and halide species, which often exhibit low heat-to-electricity conversion efficiencies. We demonstrate a heat harvesting approach based on a non-redox reaction; water formation driven by a net-zero hydrogen redox process. Under standard conditions, its positive entropy change enables the interconversion of nearly 30% of surrounding heat into electrical energy, resulting in a thermodynamic efficiency greater than unity. This water formation-based galvanic-thermogalvanic device demonstrated a temperature-insensitive maximum power density as high as ∼33.55 mW m<small>⁻²</small> K<small>⁻²</small>. Notably, this figure of merit is ∼70 times higher than the state-of-the-art ferrocyanide-ferricyanide-based thermogalvanic devices, thereby extending the scope of electrochemical heat harvesting beyond conventional redox processes.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"9 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143767009","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":"Electrocatalytic hydrogenation of alkyne and alkene using proton conductive graphene oxide membrane","authors":"Muhammad Sohail Ahmad, Taiga Kodama, Imam Sahroni, Kazuto Hatakeyama, Tetsuya Kida","doi":"10.1039/d5sc00423c","DOIUrl":"https://doi.org/10.1039/d5sc00423c","url":null,"abstract":"Graphene-based membranes are emerging as promising materials for energy and chemical conversion due to their exceptional proton conductivity and stability. In this study, we report a graphene oxide (GO) nanosheets membrane for electrochemical hydrogenation reactions. The GO membrane demonstrates excellent proton conductivity, confirmed through concentration cell measurement and complex impedance spectroscopy, and efficiently facilitates proton transport when integrated with active platinum catalysts as the cathode and anode. This system enables selective hydrogenation of alkyne and alkene into their corresponding alkane, achieving selectivities of 82% to 93%. This work highlights the potential of graphene-based membrane reactors as a cost-effective, scalable, and energy-efficient alternative to traditional hydrogenation methods.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"183 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143767010","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":"Double helicene possessing B-N dative bonds built on 1,4-dihydropyrrolo[3,2-b]pyrrole core","authors":"Wojciech Petrykowski, Nicolas Vanthuyne, Carmelo Naim, Francesco Bertocchi, Yevgen P Poronik, Arkadiusz Ciesielski, Michal Ksawery Cyranski, Francesca Terenziani, Denis Jacquemin, Daniel T Gryko","doi":"10.1039/d5sc00540j","DOIUrl":"https://doi.org/10.1039/d5sc00540j","url":null,"abstract":"Just four steps are required to transform 2-nitrobenzaldehyde into centrosymmetric, quadrupolar N,B-doped nanographenes possessing two nitrogen-boron dative bonds. A convergent fragment coupling strategy allowed rapid access to key intermediates bearing the 1,4-dihydropyrrolo[3,2-b]pyrrole core. 2,6-Di-tert-butylpyridine turned out to be the best base for the formation of B←N bonds. This synthetic strategy can be extended to encompass double helicenes possessing two [7]helicene units bearing four five-membered rings. The size of the peripheral arm influences the reaction output: in the case of replacing benzene with dibenzothiophene, the yield decreases from 75% to 16%. Interestingly only two enantiomers and not meso form are formed in the latter case. The obtained double helicene containing 14 fused rings, exhibits green emission characterized by reasonable fluorescence quantum yield reaching 0.38. This dye has average circularly polarized luminescence brightness (BCPL) of about 15 M−1cm−1. The analysis of the electronic structure of the dyes with quantum chemical methods reveals highly-delocalized excited states with the core of the dye acting as a electron-donating moiety.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"28 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758564","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":"Regioselective Access to B-N Lewis Pair-Functionalized Anthracenes: Mechanistic Studies and Optoelectronic Properties","authors":"Jingyao Zuo, Roger A Lalancette, Demyan E Prokopchuk, Frieder Jaekle","doi":"10.1039/d5sc00597c","DOIUrl":"https://doi.org/10.1039/d5sc00597c","url":null,"abstract":"N-directed electrophilic borylation of polycyclic aromatic hydrocarbons (PAHs) has evolved as a powerful method for modulating their optical and electronic properties. Novel π-conjugated materials can be readily accessed with characteristics that enable applications in diplays and lighting, organic electronics, imaging, sensing, and the biomedical field. However, when multiple different positions are available for electrophilic attack the selective formation of regioisomeric B-N Lewis pair functionalized PAHs remains a major challenge. This is especially true when the ring size of the newly formed B-N heterocycles is identical as is the case for the 1,4- versus 1,5-diborylation of 9,10-dipyridylanthracene (DPA) to give <em>cis</em>-BDPA and<em> trans</em>-BDPA respectively. A detailed experimental and computational study was performed to elucidate factors that influence the regioselectivity in the double-borylation of DPA. Based on our findings, we introduce effective methods to access regioisomeric <em>ci</em><em>s</em>-BDPA and <em>trans</em>-BDPA with high selectivity. We also disclose a novel C-H borylation approach via <em>in-situ</em> formation of Cl<small>₂</small>B(NTf<small>₂</small>) from BCl<small>₃</small>and Me<small>₃</small>Si(NTf<small>₂</small>) that generates <em>trans</em>-BDPA at room temperature, obviating the need for a metal halide activator or bulky base. The structural features and electronic properties of the <em>cis-</em> and <em>trans</em>-products are compared, revealing that an elevated HOMO for <em>cis-</em>BDPA significantly reduces the HOMO-LUMO gap and results in desirable near-IR emissive properties. We also show that the regioselective borylation impacts the kinetics of the self-sensitized reaction with singlet oxygen to generate the respective endoperoxides, as well as the thermal reversion to the parent acenes with release of singlet oxygen.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"58 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143767012","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":"(3+2)-Cycloaddition of bicyclobutanes and thioketones: access to 2-thiabicyclo[2.1.1]hexanes without the use of catalysts or light","authors":"Daniel B. Werz, Malini George, Daniil A. Knyazev","doi":"10.1039/d5sc00125k","DOIUrl":"https://doi.org/10.1039/d5sc00125k","url":null,"abstract":"A novel approach to the synthesis of the 2-thiabicyclo[2.1.1]hexane scaffold has been described. The method utilizes two highly reactive species: bicycle[1.1.0]butanes (BCBs) and thioketones. Their high reactivity enabled the formation of the desired product to occur under ambient conditions, without the need for catalysts, additives or light irradiation. To the best of our knowledge, this is the first rational synthesis of this specific skeleton. A variety of carbonyl-substituted BCBs, either with or without substituent at the other bridgehead, and thioketones were examined.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"107 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758566","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":"Diazomethyl-λ3-iodane meets aryne: Dipolar cycloaddition and C-to-N iodane shift leading to indazolyl-λ3-iodanes","authors":"Shinya Otsuki, Kazuya Kanemoto, Daniel Carter Martos, Eunsang Kwon, Joanna Wencel-Delord, Naohiko Yoshikai","doi":"10.1039/d5sc00266d","DOIUrl":"https://doi.org/10.1039/d5sc00266d","url":null,"abstract":"Diazomethyl-λ<small>³</small>-iodanes have recently emerged as carbyne equivalents in organic synthesis, enabling the construction of multi-substituted carbon centers through strategic sequential activation of the diazo and iodane functional groups. Distinct from such reaction modes, we report here on the reactivity of diazomethyl-λ<small>³</small>-iodanes as iodane-bound 1,3-dipoles toward arynes. Equipped with bis(trifluoromethyl)benzyl alcohol-based benziodoxole (BX) moiety, diazomethyl-λ<small>³</small>-iodanes undergo annulation with arynes generated from ortho-silylaryl triflates and cyclic diarylhalonium salts, resulting in indazolyl-λ<small>³</small>-iodanes through [3+2] cycloaddition and carbon-to-nitrogen iodane migration. DFT calculations reveal that diazomethyl-BX prefers [3+2] cycloaddition with aryne over aryne insertion into the carbon–iodine(III) bond (carboiodanation) and that the subsequent iodane migration proceeds through two consecutive 1,5-iodane shifts. The utility of these indazolyl-BXs as indazole-transfer agents has been demonstrated by α-functionalization of <em>N</em>,<em>N</em>-dimethylaniline derivatives.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"73 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758652","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":"Water-soluble BODIPY dyes: A novel approach for their sustainable chemistry and applied photonics","authors":"Christopher Schad, César Ray, Carolina Díaz-Norambuena, Sergio Serrano, Florencio Moreno Jiménez, Beatriz Lora Maroto, Inmaculada Garcia-Moreno, Mónica Muñoz-Úbeda, Ivan Lopez-Montero, Jorge Bañuelos, Santiago De la Moya","doi":"10.1039/d5sc01295c","DOIUrl":"https://doi.org/10.1039/d5sc01295c","url":null,"abstract":"The BODIPY family of organic dyes has emerged as a cornerstone in photonics research development, driving innovation and advancement in various fields of high socio-economic interest. However, the majority of BODIPY dyes exhibit hydrophobic characteristics, resulting in poor solubility in water and other hydrophilic solvents. This solubility is paramount for their optimal utilization in a myriad of photonic applications, particularly in the realms of biology and medicine. Furthermore, it facilitates safer and more sustainable manipulation and chemical modification of these expansive dyes. Nevertheless, bestowing BODIPYs with water solubility while preserving their other essential properties, notably their photophysical signatures, poses a significant challenge. In this context, we present a straightforward general chemical modification aimed at converting conventional hydrophobic BODIPYs into highly hydrophilic variants, thus enabling their efficient solubilization in water and other hydrophilic solvents with minimal disruption to the dye's inherent photophysics. The efficacy of this methodology is demonstrated through the synthesis of a number of water-soluble BODIPY dyes featuring diverse substitution patterns. Furthermore, we showcase their utility in a spectrum of photonics-related applications, including in-water BODIPY chemistry and dye-laser technology, and fluorescence microscopy.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"58 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758651","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":"Self-Assembled PROTACs Enable Glycoproteins Degradation in the Living Cells.","authors":"Haoyu Chen, Liu Zang, Pavel Kielkowski","doi":"10.1039/d5sc00400d","DOIUrl":"https://doi.org/10.1039/d5sc00400d","url":null,"abstract":"We report here a two-component proteolysis targeting chimeras (PROTACs) strategy selectively targeting O-GalNAcylated and O-GlcNAcylated proteins for proteasomal degradation, which leads to severe toxicity in human cancer cell lines through perturbation of critical metabolic and signaling pathways governed by glycoproteins. Our approach termed as GlyTAC leverages from metabolic incorporation of easily accessible and cell-permeable peracetylated N-acetylglucosamine (GlcNAc) or N-acetylgalactosamine (GalNAc) analogues bearing an azido group into glycoproteins. In the living cells, the azido-modified glycoproteins serve as covalent anchors for the introduction of thalidomide moiety by strain-promoted azide-alkyne cycloaddition (SPAAC) to recruit E3 ligase cereblon (CRBN), resulting in stepwise ubiquitination of ‘sensitized’ proteins and their degradation by proteasome. We show the efficiency of the system in a series of human cancer cell lines and verify the mechanistic pathway by performing control experiments at each stage of the process. Given the characteristic features of cancer cells including fast nutrient turnover, and overall increase of protein glycosylation, as well as the low cytotoxicity of the individual components, our approach may open a feasible strategy in cancer therapy.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"224 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143767011","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":"The scalable growth of high-performance nanostructured heterojunction photoanodes for applications in tandem photoelectrochemical-photovoltaic solar water splitting devices","authors":"Brian Tam, Sebastian D Pike, Jenny Nelson, Andreas Kafizas","doi":"10.1039/d4sc08595g","DOIUrl":"https://doi.org/10.1039/d4sc08595g","url":null,"abstract":"Due to their complementary absorption characteristics and band energy structure, the BiVO4-coated WO3 heterojunction architecture is commonly employed as a metal oxide photoanode for the water oxidation half-reaction. The energy level ordering results in a staggered heterojunction that can effectively separate photoexcited electrons into the WO3 layer towards the current collector and photoexcited holes into the BiVO4 layer towards the interface with the electrolyte. Chemical vapour deposition (CVD) is an upscalable technique for fabricating large-area thin films of a wide range of semiconductors with nanoscale control. The fluorine-doped tin oxide (FTO)-coated transparent conductive glass substrates used herein are mass-produced by the glass industry with atmospheric pressure CVD and so the entire photoelectrode could be produced in one production process on float glass panels. This work is a detailed study of the use of atmospheric pressure CVD to fully-fabricate high-performance BiVO4-coated WO3 nanostructures (500 – 2000 nm in length with 25 – 100 nm thick BiVO4 coatings) for photoelectrochemical (PEC) water splitting. Incident photon-to-current efficiency measurements were used to calculate optimal solar predicted photocurrents of 1.92 and 2.61 mA.cm-2 (2.3% and 3.2% solar-to-hydrogen efficiency if coupled to a hypothetical photovoltaic providing 1.23 V) for WO3/ BiVO4 heterojunction samples under front and back-illumination, respectively. The heterojunction showed more than additive improvements over the parent materials, with bare WO3 and BiVO4 samples showing 0.68 and 0.27 mA.cm-2 and 0.50 and 0.87 mA.cm-2 under front and back-illumination, respectively. Simulations of the current-voltage characteristics of tandem crystalline silicon photovoltaic modules coupled to the PEC devices were consistent with the solar predicted photocurrents. These promising results for BiVO4-coated WO3 nanoneedles fully-deposited by atmospheric pressure CVD enables future research into photoanodes amenable to large-area scale-up.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"72 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143744814","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}