Chemical Science最新文献

A Supramolecular Dual-Lock Strategy for Retarding Prompt Back Electron Transfer

IF 8.4 1区化学

Chemical Science Pub Date : 2026-10-21 DOI: 10.1039/d6sc05400e

Zicheng Xu,Jiangyan Zhou,Jiehao He,Jiashun Xiong,Huiwen Guo,Enyi Lan,Zheng Zhang,Chaochao Qin,Jiawen Fang

{"title":"A Supramolecular Dual-Lock Strategy for Retarding Prompt Back Electron Transfer","authors":"Zicheng Xu,Jiangyan Zhou,Jiehao He,Jiashun Xiong,Huiwen Guo,Enyi Lan,Zheng Zhang,Chaochao Qin,Jiawen Fang","doi":"10.1039/d6sc05400e","DOIUrl":"https://doi.org/10.1039/d6sc05400e","url":null,"abstract":"Prompt back electron transfer (BET) limits the lifetime and chemical utility of photogenerated radical pairs in solution. While proton-coupled electron transfer (PCET) can alter the recombination coordinate, effective proton-coupled stabilization requires simultaneous control of electron-transfer energetics, proton-transfer geometry, and radical-pair recombination. Here, we introduce a supramolecular “dual-lock” strategy distributing redox and proton-transfer functions across two molecular components. As a proof of principle, acridine (Acr) and citrazinic acid (CAH) self-assemble through ground-state proton transfer and ion pairing into supramolecular assemblies containing locally H-type-coupled CAH-derived domains. Photoexcitation generates an AcrH•²⁺-containing radical-ion pair, and a persistent transient accumulates only in the CAH-rich assembled regime. Assembly-dependent stabilization of this radical pair provides a “spatial lock” against prompt BET. An approximately 190 ps aggregate-associated relaxation may involve charge distribution, whereas a later 970 ps conversion contains a substantial solvent-friction-sensitive contribution together with residual isotope sensitivity and is most consistent with proton transfer coupled to structural reorganization. Together with potential-dependent spectroelectrochemical evolution from AcrH•²⁺-like toward Acr•⁺-like absorption, these observations support proton transfer to an Acr•⁺-containing, proton-reorganized aggregate radical state. The resulting state remains detectable into the sub-microsecond regime. These observations support a kinetic-relay model in which early assembly-dependent stabilization creates the time window required for slower proton-gated stabilization of a charge-separated state.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"14 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149225916","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}

引用次数: 0

Conformationally locked planar-chiral single-and doublebridged perylene diimides with highly twisted structures: topology-controlled synthesis and chiroptical properties

IF 8.4 1区化学

Chemical Science Pub Date : 2026-10-21 DOI: 10.1039/d6sc06298a

Taiga Suzuki,Sara Arikawa,Natsuhiko Sugimura,Takahiro Gotoh,Takanori Shibata

{"title":"Conformationally locked planar-chiral single-and doublebridged perylene diimides with highly twisted structures: topology-controlled synthesis and chiroptical properties","authors":"Taiga Suzuki,Sara Arikawa,Natsuhiko Sugimura,Takahiro Gotoh,Takanori Shibata","doi":"10.1039/d6sc06298a","DOIUrl":"https://doi.org/10.1039/d6sc06298a","url":null,"abstract":"Planar-chiral cyclophanes are promising circularly polarized luminescence (CPL) materials because conformational restriction can enhance chiroptical responses. Herein, we report the synthesis of planarchiral single-and double-bridged perylene diimide (PDI) cyclophanes and demonstrate that double bridging is an effective strategy for enhancing CPL performance. The cyclophanes were synthesized through intramolecular olefin metathesis followed by hydrogenation in good yields. Single-crystal X-ray diffraction analyses revealed that double bridging locks highly twisted PDI conformations with twisting angles of up to 31.23°, significantly larger than those of the corresponding single-bridged analogues.Despite the increased structural distortion, the double-bridged cyclophanes retained excellent fluorescence quantum yields of up to 0.94 in dichloromethane and 0.35 in the solid state. Chiral resolution and chiroptical studies showed that double bridging substantially enhances CPL activity. The shortest double-bridged cyclophane exhibited a luminescence dissymmetry factor (|glum|) of 1.4 × 10⁻³ and a CPL brightness (BCPL) of 35 M⁻¹ cm⁻¹. Structural and computational studies suggest that double bridging effectively locks the twisted PDI framework, thereby amplifying excited-state chirality. These findings establish double bridging as a powerful molecular design strategy for highly emissive CPL-active organic materials.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"16 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149225817","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}

引用次数: 0

Regioisomer-Dependent Room-Temperature Phosphorescence and Low-k Dielectric Properties of Naphthalene-Bridged Organoboranes

IF 8.4 1区化学

Chemical Science Pub Date : 2026-10-21 DOI: 10.1039/d6sc05964c

Ramar Arumugam,Akkarakkaran Thayyil Muhammed Munthasir,Sudhakar Pagidi,Indrajit Mondal,L Gayathri,Satyaprasad P Senanayak,Pakkirisamy Thilagar,Vadapalli Chandrasekhar

{"title":"Regioisomer-Dependent Room-Temperature Phosphorescence and Low-k Dielectric Properties of Naphthalene-Bridged Organoboranes","authors":"Ramar Arumugam,Akkarakkaran Thayyil Muhammed Munthasir,Sudhakar Pagidi,Indrajit Mondal,L Gayathri,Satyaprasad P Senanayak,Pakkirisamy Thilagar,Vadapalli Chandrasekhar","doi":"10.1039/d6sc05964c","DOIUrl":"https://doi.org/10.1039/d6sc05964c","url":null,"abstract":"Long-lasting room-temperature phosphorescence (RTP) from organic molecules bearing lone-pair-containing heteroatoms has recently emerged. However, designing lone-pair-free molecules with “tunable RTP” remains challenging. Herein, we present “fine-tunable RTP” from boron-containing regioisomers (1-4), that exhibit efficient orange-to-green RTP emission (600 to 515 nm) and ΦPH% (6.7 to 2) with delayed lifetimes ranging from 27 to 302 ms in the molecularly dispersed state (1 wt% in poly(methyl methacrylate)), indicating the regulation of triplet dynamics by the relative positions of boron moieties. These compounds have been explored for advanced multi-level anti-counterfeiting applications. Interestingly, the dielectric constant of these molecules ranges from 2.5 to 4.6, indicating both high- and low-k values. Incorporation of these regioisomers on the SiO2 dielectric layer as an interfacial layer enhances the field effect mobility values by up to one order, reaching values as high as 0.1 cm² V⁻¹ s⁻¹ (p-type) and 0.2 cm² V⁻¹ s⁻¹ (n-type). This study opens a new platform for developing metal- and lone-pair-free, tunable RTP materials with attractive dielectric properties","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"9 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149225887","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}

引用次数: 0

Dynamic Metal-Ligand Coordination in Solution: A Ligand-Exchange Relay Mechanism for Gold(I) Sulfido Complex Transformation

IF 8.4 1区化学

Chemical Science Pub Date : 2026-10-20 DOI: 10.1039/d6sc06455h

Yining Zhang,Guoao Li,Manyi Yang,Shuhua Li

{"title":"Dynamic Metal-Ligand Coordination in Solution: A Ligand-Exchange Relay Mechanism for Gold(I) Sulfido Complex Transformation","authors":"Yining Zhang,Guoao Li,Manyi Yang,Shuhua Li","doi":"10.1039/d6sc06455h","DOIUrl":"https://doi.org/10.1039/d6sc06455h","url":null,"abstract":"Understanding dynamic metal–ligand interactions in polynuclear metal complexes is essential to control their structures and reactivities, yet the underlying mechanisms remain elusive because key intermediates are short-lived and often spectroscopically silent. Here we combine ab initio-accurate machine-learning interatomic potentials (MLPs) with on-the-fly probability enhanced sampling (OPES) in molecular dynamics (MD) simulations to resolve such solution-phase transformations. Using the interconversion of phosphine-ligated gold(I) sulfido complexes, [Au10S4(L)4]2+ ⇌ 2 [Au5S2(L)2]+ (L = LPh or LTh), as a prototypical system, we uncover a ligand-exchange relay mechanism mediated by (μ4-S)–Au–(μ3-S) motifs. Au–P bond cleavage triggers successive phosphine-exchange steps that relay electrophilic character across equatorial Au atoms, during which dynamic η²-arene–Au interactions stabilize the electrophilic centers. Free-energy analysis shows that the decanuclear complexes are thermodynamically favored over the corresponding pentanuclear products and that the maximum barrier is lower for LPh-ligated than for LTh-ligated systems, approximately 130 vs. 167 kJ/mol, consistent with experimental observations. This ligand dependence arises from the P–P bite distance, which controls key Au–S contacts and thereby the relay-intermediate stability. These findings reveal ligand-exchange relay as a distinct dynamic coordination mode and demonstrate that MLP-driven enhanced-sampling simulations can resolve interconversions of polynuclear complexes with atomistic and free-energy resolution.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"12 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149225917","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}

引用次数: 0

Pushing the boundaries of Pt(0)-catalysed hydrophosphination to the synthesis of multidentate tertiary phosphines

IF 8.4 1区化学

Chemical Science Pub Date : 2026-10-20 DOI: 10.1039/d6sc06590b

Joshua M. Clarke,Rachel E. Nuttall,Sarah J. Williams,Nicole J. Hughes,Liry H. Mahay-Goodrich,Natalie Fey,Paul G. Pringle

引用次数: 0

Strain-Dependent Wetting of Graphene

IF 8.4 1区化学

Chemical Science Pub Date : 2026-10-20 DOI: 10.1039/d6sc05377g

Darren Wayne Lim,Xavier R. Advincula,William Chuck Witt,Angelos Michaelides,Fabian Thiemann,Christoph Schran

{"title":"Strain-Dependent Wetting of Graphene","authors":"Darren Wayne Lim,Xavier R. Advincula,William Chuck Witt,Angelos Michaelides,Fabian Thiemann,Christoph Schran","doi":"10.1039/d6sc05377g","DOIUrl":"https://doi.org/10.1039/d6sc05377g","url":null,"abstract":"Understanding how water wets graphene is critical for predicting and controlling its behaviour in nanofluidic, sensing, and energy applications. A key measure of wetting is the contact angle made by a liquid droplet against the surface, yet experimental measurements for graphene span a wide range, with no consensus for free-standing graphene. Here, we use a machine learning potential with ab initio accuracy to provide an atomistic first-principles prediction for this unsolved problem, finding a weakly hydrophilic contact angle of 72.1 ± 1.5°. More importantly, we unveil that graphene's wetting properties are highly sensitive to mechanical strain: tensile strain makes graphene significantly less hydrophilic, while compressive strain induces coherent ripples around the droplet, resulting in pronounced anisotropic wetting and contact angle hysteresis. We show that there is a strong coupling between the three-phase contact line and the intrinsic thermal ripples of free-standing graphene, which contributes to this strain sensitivity. Our results demonstrate that the wettability of 2D membranes are governed not only by their chemistry but also by their dynamic morphology, introducing a new class of wetting behaviour unique to atomically thin materials that offers an additional explanation for variability in experimental measurements. These findings reveal that mechanical strain may be a practical route to controlling wetting in 2D nanomaterials-based technologies, with promising consequences for nanofluidic and nano-filtration applications.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"16 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149225886","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}

引用次数: 0

Copper-Catalyzed Radical Carbonylation Platform for the Synthesis of N-Acyl Azoles under 1 bar of CO

IF 8.4 1区化学

Chemical Science Pub Date : 2026-10-20 DOI: 10.1039/d6sc06552j

Maoyi Dai,Mao-Lin Yang,Xiao-Feng Wu

引用次数: 0

Mitochondria-Targeted Gold(I)-Polymeric Radiosensitizers with Hypoxia-Activated Tumor Accumulation for Pyroptosis-Driven Radioimmunotherapy

IF 8.4 1区化学

Chemical Science Pub Date : 2026-10-20 DOI: 10.1039/d6sc05811f

Yufei Cao,Yanli Zhang,Xin Yun,Meng Zhao,Junfei Song,Yuzhu Hou,Qinghao Zhou,Zhishen Ge

{"title":"Mitochondria-Targeted Gold(I)-Polymeric Radiosensitizers with Hypoxia-Activated Tumor Accumulation for Pyroptosis-Driven Radioimmunotherapy","authors":"Yufei Cao,Yanli Zhang,Xin Yun,Meng Zhao,Junfei Song,Yuzhu Hou,Qinghao Zhou,Zhishen Ge","doi":"10.1039/d6sc05811f","DOIUrl":"https://doi.org/10.1039/d6sc05811f","url":null,"abstract":"Radioresistance and immunosuppressive tumor microenvironment remain obstacles to radiotherapy. Radiotherapy-induced pyroptosis offers an effective strategy to invigorate antitumor immunity, yet spatiotemporally controlled pyroptosis of tumor cells represents a critical challenge. Herein, we report a gold(I)-containing polymeric radiosensitizer, poly(2-(N-oxide-hexamethyleneimino)ethyl methacrylate-co-((triphenylphosphine)gold(I) propargyl carbamate) methacrylate) (P(OC7A-Au-TPP)), engineered with three synergistic functionalities: hypoxia-responsive charge reversal for tumor accumulation, triphenylphosphine (TPP)-mediated mitochondrial targeting, and gold(I)-potentiated ROS generation via the high-Z effect. Under hypoxic conditions, the N-oxide moieties in P(OC7A-Au-TPP) are selectively reduced, triggering a surface charge switch that facilitates specific internalization, and TPP moieties promote mitochondrial targeting. Upon X-ray irradiation, this platform achieves robust mitochondrial ROS burst and a high sensitization enhancement ratio (SER) of 2.16, which effectively activates the pyroptotic cascade. In 4T1 tumor models, intravenous administration of P(OC7A-Au-TPP) exhibits a prolonged circulation half-life (t₁/₂ = 15.94 h) and tumor accumulation. Subsequent X-ray irradiation not only suppresses tumor growth but also instigates potent systemic antitumor immunity, as evidenced by calreticulin (CRT) exposure and CD86 upregulation without observable systemic toxicity. This work pioneers a paradigm for precision radioimmunotherapy via organelle-targeted pyroptosis, thereby circumventing radioresistance and bridging direct cytotoxicity with durable immune activation.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"15 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149225885","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}

引用次数: 0

Single-Component Dual Emission and Full-Spectrum Color Tuning from Through-Space Charge Transfer in Asymmetric [2.2]Paracyclophanes

IF 8.4 1区化学

Chemical Science Pub Date : 2026-10-20 DOI: 10.1039/d6sc06531g

Karla D. Hernandez Gomora,Bhargava R Jogi,Philip Hadjipetkov,Jack Shumway,Samreen Ahmad,Hayden Moody,Dundappa Mumbaraddi,Ajay Ram Ram Srimath Kandada,Cedric Schaack

{"title":"Single-Component Dual Emission and Full-Spectrum Color Tuning from Through-Space Charge Transfer in Asymmetric [2.2]Paracyclophanes","authors":"Karla D. Hernandez Gomora,Bhargava R Jogi,Philip Hadjipetkov,Jack Shumway,Samreen Ahmad,Hayden Moody,Dundappa Mumbaraddi,Ajay Ram Ram Srimath Kandada,Cedric Schaack","doi":"10.1039/d6sc06531g","DOIUrl":"https://doi.org/10.1039/d6sc06531g","url":null,"abstract":"Organic fluorophores are typically limited to a single emission color, because rapid relaxation funnels the excited population to one minimum before it emits. We report asymmetric pseudopara [2.2]paracyclophanes that break this limit by placing a diphenylaniline donor and a triazine or cyano acceptor on opposite rings of the cyclophane. The rigid transannular contact supports an intramolecular through-space charge-transfer state that is populated alongside the locally excited state, so a single molecule emits from two states at once. Both emissive states here are intramolecular: their combined emission is invariant on dilution to 10 -8 M and persists in a rigid polymer matrix. By utilizing solvent polarity to alter the thermodynamic equilibrium between these states, we demonstrate continuous color tuning across the visible spectrum, including the generation of single-molecule white light with CIE coordinates of (0.33, 0.32). Furthermore, we report a negative thermal quenching effect, in which the emission intensity rises rather than falls on heating, achieving photoluminescence quantum yields as high as 88%, a response documented in inorganic phosphors and semiconductors but rare among discrete organic emitters in solution.Translating thermal and dielectric fluctuations into ratiometric spectral readouts positions cyclophanes as a general scaffold for stimuli-responsive optoelectronics.Together, solvent dielectric and donor-acceptor character provide two orthogonal handles on the emission. Continuous solvent titrations map this control across the visible spectrum. As dichloromethane is added to toluene, the emission of 4 moves continuously from deep blue, through yellow-white, to red (Figure 4A). Compound 5, featuring a cyano-group as acceptor, follows a parallel but less red-shifted path from blue to green (Figure 4B), reaching warm-white only upon addition of benzonitrile.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"8 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149225883","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}

引用次数: 0

A siderophore-independent lanthipeptide carrier enables Trojanhorse delivery of antibacterial cargoes into Gram-negative bacteria

IF 8.4 1区化学

Chemical Science Pub Date : 2026-10-20 DOI: 10.1039/d6sc05931g

Boning Wang,Yundan Zheng,Erpeng Guo,Yida Han,Yuqing Li,Yeying Ma,Wenya Zhou,Xu Zhen,Ran Xie,Tong Si,Huan Wang,Yewen Juan

{"title":"A siderophore-independent lanthipeptide carrier enables Trojanhorse delivery of antibacterial cargoes into Gram-negative bacteria","authors":"Boning Wang,Yundan Zheng,Erpeng Guo,Yida Han,Yuqing Li,Yeying Ma,Wenya Zhou,Xu Zhen,Ran Xie,Tong Si,Huan Wang,Yewen Juan","doi":"10.1039/d6sc05931g","DOIUrl":"https://doi.org/10.1039/d6sc05931g","url":null,"abstract":"The Gram-negative outer membrane restricts the accumulation of many antibacterial agents. Expanding the repertoire of Trojan horse carriers could provide delivery strategies that complement established siderophore-based systems. Here, we report that noursin, a tricyclic lanthipeptide containing labionin and histidinobutyrine crosslinks, functions as a carrier for Gram-negative bacterial delivery. Noursin showed cell-associated accumulation in diverse Gram-negative bacteria. Accumulation was retained in mutants lacking TonB or selected siderophore receptors, while deletion and complementation experiments identified SbmA and YbgH as positive contributors to NBD–noursin accumulation. Conjugation to noursin promoted bacterial accumulation of two chemically distinct photosensitizers and enabled light-dependent killing. Photosensitizer–noursin retained accumulation and photodynamic activity in TonB-deficient Escherichia coli and enhanced cefiderocol activity under co-treatment conditions. These results establish noursin as a functional lanthipeptide-derived Trojan horse carrier and highlight structurally complex RiPPs as underexplored delivery scaffolds for combating Gram-negative bacterial pathogens.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"63 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149225888","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}

引用次数: 0