Chemical Science最新文献

{"title":"An explainable “family bucket” model for simultaneous prediction of K-edge XANES for multiple light transition metals","authors":"Chenyu Huang, Yunjiang Zhang, Shuyuan Li, Huimin Wang, Yaxin Wang, Shihao Wei, Shaorui Sun","doi":"10.1039/d5sc00494b","DOIUrl":"https://doi.org/10.1039/d5sc00494b","url":null,"abstract":"X-ray near-edge structure (XANES) is a crucial bridge between the local structures and chemical properties of materials. Although there have been a number of studies devoted to the development of predictive K-edge XANES spectral models, existing methods are usually still limited to separate modeling for a specific absorbing element. Currently, there is a lack of a K-edge XANES spectra prediction model that can be broadly applied to a wide range of elements, which would enable data dispersed in terms of absorbing elements to be integrated and well utilized. In this work, we develop an innovative “family bucket” model based on a multi-head graph attention convolutional neural network by combining a multi-element mixed dataset with a crystal topology approach for the localized environment. The model is able to predict the K-edge XANES spectra for a wide range of light transition metals (periods 3 and 4) simultaneously. Moreover, it is demonstrated that the training scheme not only improves the accuracy of the model but also the efficiency of its training. In terms of interpretability, several fascinating insights were gained, uncovering the underlying mechanisms of the model for spectral prediction. We investigate the collective behavior of neurons by employing a range of responses to different samples as descriptive features. Notably, the analysis revealed that neurons in the neural network exhibit functional differentiation characteristics analogous to Brodmann areas in the cerebral cortex. The homology of data analysis indicates that the mutual learning of samples from different absorbing elements is occurring between close elements of the same period. Additionally, the attention scores of the samples are determined by both the absorbing element and its surrounding atomic environment. In conclusion, this research advances the understanding of the relationship between XANES spectra and material structures while providing valuable insights into neural networks, enhancing the comprehension of neuronal behavior.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"11 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144756498","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":"Dual-Emissive Self-Reporting Photosensitizers Characterized with Kasha/Anti-Kasha Behaviors Engineered via Gradient Donor-Acceptor Strategy","authors":"Xixin Gu, xinyi Zhang, Yujie Han, Ju Mei, Qi-Wei Zhang, Jianli Hua","doi":"10.1039/d5sc03880d","DOIUrl":"https://doi.org/10.1039/d5sc03880d","url":null,"abstract":"Real-time monitoring of photodynamic therapy (PDT) is essential for precision medicine, yet remains hindered by microenvironmental interference and photobleaching of conventional mono-emissive photosensitizers (PSs). Herein, inspired by the energy level gradients depicted in Jablonski diagram, we report a gradient donor-acceptor molecular design strategy to overcome Kasha’s rule, achieving intrinsic dual-emissive PSs. Combining femtosecond transient absorption spectroscopy with theoretical calculations, we have verified the Kasha/anti-Kasha properties of the compounds: near-infrared (NIR) emission peaking at 710 nm exhibiting viscosity dependence stems from the S1-to-S0 excited-state decay of the primary acceptor-donor framework, whereas visible emission at 530–590 nm significantly enhanced upon DNA binding originates from the S2-to-S0 excited-state decay of the additional acceptor-donor segment. Systematic comparison of the effects of additional acceptors on anti-Kasha behaviors and photogenerated reactive oxygen species (ROS) performance has been conducted by constructing two diketopyrrolopyrrole (DPP)-based isomers, namely DPP-F32 and DPP-F34. Both PSs target Golgi apparatus to activate NIR signals, but only DPP-F32 exhibits visible emission in the nucleus of apoptotic cells, enabling ratiometric tracking of PDT process at two-/three-dimensional cellular models via dual-channel imaging. This study provides a new paradigm for self-reporting PSs with Kasha/anti-Kasha behaviors that combine precise targeting, efficient ROS generation, and real-time dynamic monitoring.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"50 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144756499","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":"Tuning the Surface Chemistry of NHC–Protected Au13 Nanoclusters Via a Robust Amide Coupling Procedure","authors":"Andrew LDM Laluk, Dennis Alexander Buschmann, Shinjiro Takano, Angus I. Sullivan, Parimah Aminfar, Kevin Stamplecoskie, Tatsuya Tsukuda, Cathleen Crudden","doi":"10.1039/d5sc02951a","DOIUrl":"https://doi.org/10.1039/d5sc02951a","url":null,"abstract":"There is significant potential use for gold nanoclusters in biomedicine owing to their favorable biological and optical properties. To access this potential, there is a need for methods to alter the ligand scaffold of gold nanoclusters to tune their biological properties. Surface modifications to the ligands must occur with molecular precision to generate monodisperse products for the accurate determination of structure activity relationships and eventual translation to clinical practice. Herein, we describe methods for molecularly precise surface modifications to Au<small>₁₃</small> nanoclusters via amide couplings to -COOH functionalities and their stability to conditions necessary for the removal of protecting groups used in amide coupling chemistry. These clusters were found to be highly stable to basic conditions for the removal of base-labile -Fmoc and -OMe groups but less stable to acidic conditions for the removal of acid-labile -Boc and -O<em><small>^t</small></em>Bu groups. The ligand shell and Au<small>₁₃</small> core of such clusters were found to be preserved following modifications to the ligand shell allowing the solubility and biological properties of the cluster to be altered independently of their optical properties. The nature of the protecting ligand was found be instrumental for cluster stability to enable the use of the harsh conditions necessary to yield monodisperse products.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"19 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144747663","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":"Bacteria-driven bio-electroactive sterilization","authors":"Mingming Qin, Qiuping Qian, Xiaoqing Gao, Tianxi Shen, Feng Jia, Min Wu, Kelong Fan, Yunlong Zhou","doi":"10.1039/d5sc04234h","DOIUrl":"https://doi.org/10.1039/d5sc04234h","url":null,"abstract":"Developing responsive antibacterial materials is crucial in addressing antibiotic overuse. While many materials respond to indirect external stimuli like pH, light, and enzymes, bacterial self-metabolism remains an underutilized activation mechanism for precision sterilization. Here, we present a self-sustaining bioreactor consisting of bacteria–reduced graphene oxide-copper biohybrids (BrGO–Cu), wherein living bacteria activate graphene oxide–copper ions (GO–Cu) for self-termination through metabolic redirection. Bacterial extracellular electron transfer (BEET) cascade reduced graphene oxide, promotes Cu2+ to Cu+ conversion, and ultimately kills bacteria through •OH generation. Meanwhile, BrGO–Cu bioreactor effectively prevents biofilm formation with negligible cytotoxicity. Notably, the bacteria-responsive bioreactor exhibits lasting bactericidal activity upon recapture of live bacteria for up to 129 passages without bacterial resistance. Our work pioneers a BEET-redirecting strategy that enables pathogen-specific, long-lasting antimicrobial protection through precisely controlled feedback loops.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"12 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144747664","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":"Distinct Structural Interactions of polyAdenine and polyThymine on Gold Nanoparticles: From Single Strands to Duplexes","authors":"Jinyi Dong, Isabel García, Bjorn De Busschere, Nathalie Claes, Sara Bals, Luis M. Liz-Marzan, Manuel Núñez-Martínez","doi":"10.1039/d5sc04459f","DOIUrl":"https://doi.org/10.1039/d5sc04459f","url":null,"abstract":"Motivated by potential applications in fields such as medicine or materials science, various methodologies have been developed for the preparation of so-called spherical nucleic acids, based on oligonucleotides and metal nanoparticles. Despite optimization through various parameters such as loading efficiency or nanoconjugate stability, much remains to be known regarding the actual conformations of oligonucleotides and their interactions with the nanoparticle surface. We employed a combination of spectroscopic techniques and liquid transmission electron microscopy to analyze the interactions and conformations adopted by polyAdenine (polyA) and polyThymine (polyT) chains in contact with gold nanoparticles (AuNPs). These studies revealed the presence of AuNP@polyA dimers, with polyA strands forming duplexes, whereas polyT forms isolated strands on the AuNP. The presence or absence of polyA duplexes on AuNPs can be modulated by external stimuli such as temperature or NaCl. This study contributes to understanding the interactions and secondary structure of oligonucleotides on AuNPs.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"1 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144747666","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":"Conjugation effect of amine molecules in non-aqueous Mg redox flow batteries","authors":"Yunan Qin, Vaidyanathan Sethuraman, Seong-Gyu Choi, Richard Gonzalez, Chengxiang Chen, Lei Cheng, Chao Luo, Tao Gao","doi":"10.1039/d5sc04532k","DOIUrl":"https://doi.org/10.1039/d5sc04532k","url":null,"abstract":"Nonaqueous magnesium redox flow batteries (Mg RFBs) are attractive for low-cost, high-energy-density and long-cycle-life stationary energy storage applications. However, state-of-the-art cathode redox-active molecules suffer from low solubility and low redox potential. Herein, we screened a range of cathode redox-active molecules and identified amine molecules as optimal to couple with Mg anode. The properties of amine derivatives and their performances were collected to establish the correlation between molecular structures and electrochemical performances. The results confirm that the redox potential and solubility of these amine molecules are influenced by π-conjugated and non-conjugated structures of amine derivatives. Density functional theory (DFT) simulations and inverse aromatic fluctuation index (FLU<small>^-1</small>) verified that the conjugation plays an important role in stabilizing the molecule and increasing its redox potential. Notably, tris[4-(diethylamino)phenyl]amine (TDPA) achieves the highest theoretical energy density (~120 Wh/L) due to its high solubility (~0.9 M) and voltage (~2.5 V vs. Mg/Mg<small>²⁺</small>). The study also demonstrates that ether solvents are crucial for stable, high-solubility catholytes, while bulk anions do not affect the redox potential of these <em>p</em>-type molecules. In a Mg-amine RFB configuration, the battery delivered 2.50 V, 106.5 mAh/g specific discharge capacity, 90.74% initial Coulombic efficiency, and 93.88% capacity retention after 150 cycles.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"27 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144756502","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":"Near-infrared light-activated Z-to-E isomerization of azobenzene via triplet sensitization from PbS quantum dots","authors":"Yanan Feng, Qingxin Luan, Shuai Zhang, Lin Xi, Shijie Zhang, Kezhou Chen, Tiegen Liu, Lili Hou","doi":"10.1039/d5sc03719k","DOIUrl":"https://doi.org/10.1039/d5sc03719k","url":null,"abstract":"Azobenzene (Azo) photoswitches have attracted significant attention for developing smart photoresponsive materials owing to their reversible light-induced isomerization between E and Z configurations. However, it is challenging to design Azo capable of quantitative and efficient Z→E photoisomerization under low-energy photon irradiation, particularly near-infrared (NIR) light above 800 nm. Here, we demonstrate that Z→E photoswitching of Azo can be achieved under 808 nm light irradiation when comprised PbS quantum dots (QDs) with carboxylate Azo (Azo1). The unique spin-orbit coupling of PbS QDs facilitates efficient triplet energy transfer to Z-Azo1 under NIR light irradiation, thereby facilitating Z→E photoswitching via the excited triplet surface. Importantly, the broad absorption spectrum of PbS QDs enables activation of Z→E photoisomerization using any desired wavelength across the visible and NIR spectra up to 900 nm. The photoswitching of Azo1 when combined with PbS QDs exhibits reversible photoisomerization and good fatigue resistance over alternating irradiation cycles of 365 nm and 808 nm light. Our strategy of combining Azo and QDs holds promise for advancing the development of high-performance NIR light-activated optoelectronic materials and devices.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"12 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144747670","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":"Chiral population analysis: A real space visualization of X-ray circular dichroism","authors":"Victor Manuel Freixas Lemus, Jeremy Rouxel, Sergei Tretiak, Niranjan Govind, S. Mukamel","doi":"10.1039/d5sc04423e","DOIUrl":"https://doi.org/10.1039/d5sc04423e","url":null,"abstract":"The microscopic understanding of probing and controlling molecular chirality is of considerable interest. Numerous spectroscopic techniques are capable of monitoring molecular asymmetry and its consequences, ranging from the infrared to the X-ray regime. Resonant X-rays have long been used to investigate local atomic sites within molecules thanks to the localized nature of core electronic transitions. These techniques can be used to determine the extent to which chirality is a local versus a delocalized property. However, how to systematically partition dichroic contributions from the point of view of electronic structure simulations remains an open question. Here, we introduce the concept of chiral population analysis that connects chirality to the atomic orbital picture. In analogy with Mulliken population analysis, that assigns charges to atomic orbitals, chiral populations allow the dichroic response to be distributed among the participating atomic orbitals. This decomposition can be further visualized in real space by representing it in terms of isosurface plots, providing an intuitive way to connect the dichroic response to its origins. Thus chiral population analysis can be particularly useful to assess the extent to which a given electronic transition is sensitive to chirality as a local or global feature of the molecular geometry.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"15 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144756501","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":"DNA attachment to polymeric, soft and quantum materials: mechanisms and applications","authors":"Mohamad Zandieh, Jung Heon Lee, Juewen Liu","doi":"10.1039/d5sc03552j","DOIUrl":"https://doi.org/10.1039/d5sc03552j","url":null,"abstract":"Polymeric and soft materials offer excellent biocompatibility, a high capacity for loading of guest molecules, and cost-effectiveness. Additionally, recent studies on nanodiamonds as quantum materials have revealed interesting applications at ambient temperatures. The attachment of DNA oligonucleotides to these materials enables molecular recognition, directed assembly and targeting capabilities, offering unique advantages for biomedical, analytical and environmental applications. In this article, the mechanisms of DNA adsorption to various metal-free materials, including polydopamine (PDA), hydrogels, microplastics, cellulose crystals, nanodiamonds, and carbon quantum dots are reviewed. Key interactions involved in these systems include π-π stacking, hydrogen bonding, hydrophobic interactions, and metal bridging. We highlight how material properties such as surface charge, functional groups, and wettability influence DNA adsorption and release. Stimuli-responsive systems, such as pH-switchable PDA and thermoresponsive hydrogels, allow controlled DNA adsorption and release. Furthermore, sequence-specific aptamers developed for microplastics and cellulose are discussed, demonstrating the potential for selective DNA binding to nanomaterials. Finally, applications including fluorescence-based biosensors, intracellular delivery, high-density DNA storage, and surface probing are presented. Remaining challenges and future directions are also discussed to guide further advancements in this emerging field.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"26 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144747665","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":"Brønsted bases promote interfacial proton transfer for enhanced biomass electrocatalysis","authors":"Jia Wu, Jianlong Zhang, Zhixiang Zhai, Zelong Sun, Zhangyue Zheng, Junxin Chen, Zihui Ning, Huan Wen, Shibin Yin","doi":"10.1039/d5sc04035c","DOIUrl":"https://doi.org/10.1039/d5sc04035c","url":null,"abstract":"Efficient electrooxidation of 5-hydroxymethylfurfural (HMF) is essential for the production of valuable chemicals from biomass. However, the sluggish interfacial proton transfer kinetics during the reaction significantly hinder its progress. This study proposes that the introduction of Bronsted bases on cobalt-based catalysts can enhance HMF oxidation by modulating interfacial proton transfer kinetics. Density functional theory calculations, in situ spectroscopy, and experimental results demonstrate that phosphate (Pi) groups on the cobalt surface shorten the distance between the proton donor and acceptor, effectively promoting interfacial proton transfer during the dehydrogenation of HMF. Consequently, the Pi-functionalized catalyst shows a 6.5-fold increase in current density compared with the unmodified cobalt catalyst and achieves near 100% selectivity for 2,5-furandicarboxylic acid, attaining a current density of 1000 mA cm‒2 at 1.41 VRHE for efficient HMFOR. This work provides insights into designing efficient catalysts for industrial applications through surface site functionalization.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"134 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144747669","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}