Chemical Science最新文献

{"title":"CPL Photoscopy: Circularly polarized Luminescence Detected by Chromaticity Differences","authors":"Matteo Cei, Francesco Zinna","doi":"10.1039/d5sc03949e","DOIUrl":"https://doi.org/10.1039/d5sc03949e","url":null,"abstract":"Circularly polarized luminescence (CPL) is attracting growing interest for a wide range of applications, spanning from materials with advanced optical properties to innovative imaging techniques. The traditional approach to CPL consists in measuring the emission intensity difference between the left and right polarizations of light and usually requires spectral separation through color filters or a monochromator. In this work, we show that, under certain circumstances, it is possible to extract CPL information simply from the chromaticity values of a pair of photographs taken under different polarizations. This novel technique requires cheap instrumentation, offers complementary features with respect to the traditional method and could potentially be applied to CPL imaging.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"15 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144622635","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":"Organic probes for NO-activatable biomedical imaging: NIR fluorescence, self-luminescence, and photoacoustic","authors":"Weihao An, Zhongkun Wang, Qingqing Miao, Qing Li","doi":"10.1039/d5sc03611a","DOIUrl":"https://doi.org/10.1039/d5sc03611a","url":null,"abstract":"Nitric oxide (NO) is a crucial signaling molecule involved in diverse physiological and pathological processes, making its precise detection essential for exploring its biological roles. Optical imaging is particularly attractive for NO detection due to its non-invasive nature, high sensitivity, and excellent spatial resolution. However, it suffers from limited tissue penetration and low signal-to-background ratios resulting from strong light scattering and autofluorescence. To overcome these challenges, several advanced imaging strategies have been developed, including near-infrared (NIR) fluorescence imaging that leverages optical regions with less light–tissue interactions, self-luminescence imaging that avoids the need for real-time light excitation, and photoacoustic imaging that detects acoustic signals with minimal attenuation. This review systematically summarizes recent advances in organic molecular probes for NO detection using these imaging modalities, focusing on their design strategies, recognition mechanisms, and biological applications. Finally, current challenges and future directions are discussed to guide the development of next-generation NO probes for both fundamental research and clinical translation.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"202 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144630302","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":"Selectivity for TP53 signalling drives the mode of action of a highly potent N,O,O-tridentate naphthoquinone-based organo-ruthenium anticancer drug candidate","authors":"Alexander Rosner, Lukas Skos, Theresa Mendrina, Dina Baier, Michaela Hejl, Yasmin Borutzki, Mathias Gradl, Heiko Geisler, Thomas Mohr, Anton Legin, Michael Jakupec, Andrea Bileck, Christopher Gerner, Gunda Koellensperger, Petra Heffeter, Walter Berger, Bernhard K Keppler, Wolfgang Kandioller, Samuel M. Meier-Menches","doi":"10.1039/d5sc00735f","DOIUrl":"https://doi.org/10.1039/d5sc00735f","url":null,"abstract":"The metallodrug candidate [(3-ethyl-4-oxo-(pyrazolyl)-dihydronaphthalene)(cymene)ruthenium(II)] (1a) was recently shown to exhibit exceptional antiproliferative activity in the chemo-resistant SW480 cancer cell line with nanomolar potency. This study was conducted to elucidate the determining parameters of the mode of action of this N,O,O-tridentate organoruthenium compound in vitro and in vivo. Four metal(arenes) based on 3-ethyl naphthoquinone (3Et-NQ, a) and 3-morpholine naphthoquinone (3Morph-NQ, b) with ruthenium (1) and osmium (2) were synthesized and characterized. The 3Morph-NQ ligand increased the solubility of the complexes, but showed a 30-fold reduction in antiproliferative activity compared to the 3-Et-NQ ligand and served as biological inactive analogues. The solution reactivity of the four compounds was ligand- and metal-dependent, but they all showed selectivity for amino acids over nucleotides at biologically relevant concentrations. Drug effects were elucidated by proteome profiling at subcellular resolution and showed a pronounced ligand-dependent impact. The 3Et-NQ containing ruthenium- and osmium(arenes) down-regulated TP53 as a central hub in the perturbation network, connected to down-regulated proliferative MAPK3 signalling. Complex 1a strongly down-regulated TP53 and potently inhibited cell cycle progression at the G2/M phase. Furthermore, 1a was found to disrupt the TP53-DDX3-p21 signalling axis by direct interaction with DDX3X and loss of p21 expression. The 3Et-NQ complexes, particularly 1a, showed tumour inhibitory effects in vivo in a CT26 colon carcinoma mouse model, while the 3Morph-NQ complexes were inactive. Tissue proteome analysis of livers of 1a-treated mice displayed similar stress responses as observed in vitro. Finally, tumour tissue of 1a-treated mice revealed down-regulated EGFR, consistent with the impact on the TP53 signalling axis in vitro.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"11 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144630305","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":"Breaking the Heavy-Atom Paradigm: Weak-Donor-Engineered Triplet Harvesting in BODIPY Photosensitizers for Immunogenic Pyroptosis Therapy","authors":"Hyeong Seok Kim, Hyeonji Rha, Mohammad Izadyar, Supphachok Chanmungkalakul, Haiqiao Huang, Yi Young Kang, Jae-Won Ka, Yunjie Xu, Mingle Li, Xiaogang Liu, Jong Seung Kim","doi":"10.1039/d5sc03466c","DOIUrl":"https://doi.org/10.1039/d5sc03466c","url":null,"abstract":"Boron-dipyrromethene (BODIPY)-based dyes emerge as promising agents for phototherapy; however, traditional methods to enhance spin-orbit coupling (SOC) through halogenation introduce dark toxicity and limit therapeutic applications. Here, we present a thiophene-bridged BODIPY functionalized scaffold with carbazole-benzothiophene (Cbz-Bth) substituents at the 2,6-positions. This design employs a weak yet semi-rigid donor to destabilize charge-transfer (CT) states, enabling T₂-mediated spin-orbit charge-transfer intersystem crossing (SOCT-ISC). The resulting photosensitizer, Cbz-Bth-BDP, demonstrates effective reactive oxygen species generation and the photocatlytic transformation of biomolecules such as nicotinamide adenine dinucleotide (NADH) and cytochrome c (Cyt c). Notably, Cbz-Bth-BDP induces pyroptosis by activating gasdermin E (GSDME), leading to cell swelling and the release of intracellular content. In a 3D tumor spheroid model, Cbz-Bth-BDP significantly inhibits tumor growth by reducing adenosine triphosphate (ATP) levels. This study highlights the advantages of accessing higher excited triplet states and positions Cbz-Bth-BDP as a promising, heavy-atom-free photosensitizer for cancer treatment through pyroptosis activation.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"47 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144622639","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":"Direct Sequencing of DNA 5-Methylcytosine by Engineered Dioxygenase NTET-assisted eNAPS","authors":"Shan Zhang, Neng-Bin Xie, Li Zeng, Fang-Yin Gang, Yao-Hua Gu, Min Wang, Xia Guo, Tong-Tong Ji, Jun Xiong, Bi-Feng Yuan","doi":"10.1039/d5sc03634h","DOIUrl":"https://doi.org/10.1039/d5sc03634h","url":null,"abstract":"DNA methylation (5-methylcytosine, 5mC) represents the most prevalent modification in mammals, which is closely linked to disease pathogenesis and cancer development. Single-base resolution sequencing and quantitative analysis of 5mC are essential for elucidating its biological functions. However, current methods are still limited by resolution, sequencing bias, and false positives. In this study, we engineered a Naegleria TET-like protein (NTET) , yielding a recombinant engineered NTET (eNTET), to improve both its oxidation activity and sequence compatibility for 5mC. Combined with pyridine borane reduction, we developed engineered NTET-assisted pyridine borane sequencing (eNAPS) to quantitatively detect 5mC in DNA at single-base resolution. In eNAPS, 5mC is oxidized by eNTET to 5‑formylcytosine (5fC) and 5-carboxylcytosine (5caC), which are further reduced to dihydrouracil (DHU) by pyridine borane and read as thymine (T) in the subsequent sequencing. The direct conversion of 5mC-to-T allows for precise mapping of 5mC in DNA at single-base resolution. Compared with conventional bisulfite sequencing (BS-seq), eNAPS exhibits advantages such as non-destruction, enhanced sensitivity, improved accuracy, and greater efficiency. Using the eNAPS method, we achieved quantitative analysis of 5mC at single-base resolution in genomic DNA of lung tumor and tumor-adjacent normal tissues. Overall, eNAPS is a mild and bisulfite-free method with high accuracy, making it a valuable tool for investigating the dynamic interplay of 5mC in epigenetic regulation and disease pathogenesis.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"12 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144603838","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":"Extrinsic gating of the rotary direction of a light-driven molecular motor by dynamic boronic acid–diol complexation","authors":"Zi-Jian Chen, Hsiu-Feng Lu, Chun-Wei Chiu, Yi-Hung Liu, Chao-Ping Hsu, Jye-Shane Yang","doi":"10.1039/d5sc03240g","DOIUrl":"https://doi.org/10.1039/d5sc03240g","url":null,"abstract":"Chiral sterically overcrowded alkenes are potential candidates for artificial light-driven rotary molecular motors (LRMMs), which perform a full 360° unidirectional rotation around the C<img alt=\"[double bond, length as m-dash]\" border=\"0\" src=\"https://www.rsc.org/images/entities/char_e001.gif\"/>C bond through a series of photochemical and thermal isomerization processes. However, the majority of the reported LRMMs adopt an intrinsic chirality (<em>i.e.</em>, an integration of the chirality center with the photoresponsive unit), which hampers the effective gating of their rotary direction through chirality switching. Herein, we report a new sterically overcrowded alkene equipped with a boronic acid receptor for dynamic covalent bonding with chiral vicinal diols, enabling it to function as an extrinsic chirality-based LRMM. The dynamic boronic acid-chiral diol B–O bonding not only implements the extrinsic chirality to induce a helical preference in the alkene backbone but also facilitates chirality switching through diol exchange to reverse the rotation direction. This work demonstrates that dynamic covalent bonding for extrinsic chirality implementation is an effective strategy for designing direction-switchable LRMMs, paving the way for more sophisticated molecular motors with applications in complex (bio)environments.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"109 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144603841","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":"Spin Polarization Induced Rapid Reconstruction of Transition Metal Oxide for Efficient Water Electrolysis","authors":"Zi-Qiang Chen, Wei-Jie Cai, Hui Jian Zhang, Kang Xiao, Bolong Huang, Zhao-Qing Liu","doi":"10.1039/d5sc04336k","DOIUrl":"https://doi.org/10.1039/d5sc04336k","url":null,"abstract":"Although high-valent metal hydroxyl oxides formed in situ through electrochemical oxidation of the metal oxide matrix are key active sites for the oxygen evolution reaction (OER) in transition metal oxides, such a sluggish structural reconstruction largely hinders the electrocatalytic performance. Herein, we present a novel spin polarization engineering strategy to accelerate the formation of high-valent CoOOH, thereby significantly enhancing the OER performance. Through strategic substitutional doping of Mn atoms into the CoO lattice and subsequent confinement of the resulting bimetallic oxides within hollow mesoporous carbon spheres (Mn-CoO/HMCS), the as-prepared catalyst demonstrates markedly enhanced electrocatalytic activity, delivering approximately 5.9-fold higher mass activity compared to the undoped CoO/HMCS counterpart. In situ spectroscopy and theoretical calculations elucidate that Mn doping induces lattice distortion and symmetry breaking, which alters the orbital filling of Co with a lower energy barrier for the structural reconstruction from Co²⁺ to Co³⁺. The spin state transition from a high-spin configuration in Co²⁺ to a low-spin state in Co³⁺ further facilitates the formation of CoOOH active intermediates for OER. This work not only paves new avenues for promoting the dynamic reconstruction of active hydroxyl oxides but also highlights the untapped potential of cobalt-based materials through rational electronic structure modulation.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"1 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144603837","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":"Phototoxicity of Hydroxymethyl-BODIPYs: Are Photocages That Innocent?","authors":"Kirill M. Kuznetsov, Pierre Mesdom, Kallol Purkait, Olivier Blacque, Arthur H. Winter, Kevin Cariou, Gilles Gasser","doi":"10.1039/d5sc04032a","DOIUrl":"https://doi.org/10.1039/d5sc04032a","url":null,"abstract":"Photocages are photosensitive molecules that can release specific compounds, usually of biological relevance (e.g., drugs, cellular messengers, etc.), under light irradiation. Along with these compounds, the photocages themselves are putative release byproducts. The (photo-)cytotoxicity of them is hardly known and scarcely studied. To explore these compounds, we synthesized the known BODIPY derivatives commonly used as photocages, i.e., WinterGreen and WinterRed. We investigated in depth their photophysical properties in organic solvents and phosphate buffer. The formation of aggregates by the compounds was analyzed by dynamic light scattering (DLS) and spectral methods, which demonstrated their J-aggregate nature. All compounds exhibited significant phototoxicity in biological assays upon light irradiation at two wavelengths (510 and 645 nm), corresponding to their absorption maxima, in both cancerous (A549) and non-cancerous (RPE-1) cell lines. Investigations into the reactive oxygen species (ROS) generation in organic solutions and intracellularly suggested that the observed phototoxicity arises via a Type I photodynamic therapy (PDT) mechanism. These findings highlight the need for greater scrutiny of photocages themselves in biological studies. Far from being inert carriers, they may exert substantial biological effects, and in some cases, their activity could even surpass that of the released therapeutic agent.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"706 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144603840","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":"Intracellular evaluation of protein droplet-forming capability using self-assembling peptide tags","authors":"Takayuki Miki, Masahiro Hashimoto, Masatoshi Shimizu, Hiroki Takahashi, Hisakazu Mihara","doi":"10.1039/d5sc00871a","DOIUrl":"https://doi.org/10.1039/d5sc00871a","url":null,"abstract":"Protein droplet formation is a crucial process involved in transient cellular responses and pathogenic protein aggregations. Conventionally, the droplet-forming capability of target proteins has been evaluated through <em>in vitro</em> reconstitution studies, where purified proteins are dissolved in buffer solutions. However, such droplets are highly sensitive to environmental factors, including temperature, ionic strength, and molecular crowding. Therefore, <em>in situ</em> evaluation within living cells is highly desirable. Additionally, since droplet formation is typically initiated by nucleation involving dynamic protein oligomerization, simply expressing proteins in cells often fails to induce droplet formation, making intracellular evaluation challenging. In this study, we present an intracellular droplet-forming assay based on our peptide tag technique. This system employs short self-assembling YK peptide tags (7–15 residues), genetically fused to target proteins, to artificially induce oligomerization. Using this approach, we discover that the co-chaperone Hsp70/Hsp90 organizing protein possesses droplet-forming capability and identify the essential region required for its droplet formation.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"4 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144603839","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":"Isolation of a phosphinidene sulfide and selenide","authors":"Chenyang Hu, Maren Pink, Jose M. Goicoechea","doi":"10.1039/d5sc04352b","DOIUrl":"https://doi.org/10.1039/d5sc04352b","url":null,"abstract":"We describe the synthesis of an isolable phosphinidene sulfide and phosphinidene selenide (BnArNP<img alt=\"[double bond, length as m-dash]\" border=\"0\" src=\"https://www.rsc.org/images/entities/char_e001.gif\"/>Ch; Ch = S, Se) by reaction of a sterically protected phosphinidene oxide (BnArNP<img alt=\"[double bond, length as m-dash]\" border=\"0\" src=\"https://www.rsc.org/images/entities/char_e001.gif\"/>O) with Lawesson's or Woollins' reagents, respectively. These compounds reveal short P<img alt=\"[double bond, length as m-dash]\" border=\"0\" src=\"https://www.rsc.org/images/entities/char_e001.gif\"/>E bonds consistent with a high degree of p<small>_π</small>–p<small>_π</small> double bond character. The pendant amido group on the phosphorus atom plays an important role in their stabilization through nitrogen lone pair donation into the P–Ch π* orbital, and evidence for isomerism about the N–P bond was observed for both species. Dimeric intermediates featuring mixed phosphorus(<small>III</small>)/phosphorus(<small>V</small>) centers could be isolated and structurally authenticated during the course of these studies providing some insight into the mechanism of formation of the titular compounds.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"109 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144630079","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}