{"title":"Interfacial engineering of Ru-RuSb<sub>2</sub> for enhanced activity and stability towards alkaline hydrogen oxidation reaction.","authors":"Chaoyi Yang, Zihao Dai, Jianchao Yue, Wei Luo","doi":"10.1039/d5sc03850b","DOIUrl":"10.1039/d5sc03850b","url":null,"abstract":"<p><p>Although Ru has been regarded as the key candidate to replace Pt in alkaline hydrogen oxidation reaction (HOR), the substandard stability owing to its easy oxidation seriously impacts its practical application. In this work, we report the construction of a Ru-RuSb<sub>2</sub> heterostructure, showing excellent performance and stability towards alkaline HOR. Owing to the difference in the work functions of Ru and RuSb<sub>2</sub>, the charge transfer induced by the build-in electric field modifies the electron distribution on the surface, enhancing the OH adsorption on the heterostructure. Moreover, the connectivity of the hydrogen bonding network is promoted with the inducing of OH species, which thereby leads to elevated proton transfer and accelerated HOR process, presenting a mass activity (<i>j</i> <sup>k,m</sup>) of 2.098 mA μg<sup>-1</sup> at 50 mV, which is 6-fold and 20-fold higher than those of Pt/C<sub>com</sub> and Ru/NC, respectively. Owing to the change of the OH adsorption sites on Sb and the rapid HOR process on the surface, the pace of the oxidation on Ru of the heterostructure during the reaction largely slows down, contributing to the outstanding stability with only 2.59% decline in the activity.</p>","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":7.6,"publicationDate":"2025-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12264760/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144658572","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}
Huishan Li, Lok Wan Ng, Dominic J. Black, Wei Han, Robert Pal, David Parker
{"title":"Europium probe binding to serum albumin and α-1-AGP, key importance of configuration, charge and size complementarity","authors":"Huishan Li, Lok Wan Ng, Dominic J. Black, Wei Han, Robert Pal, David Parker","doi":"10.1039/d5sc03017j","DOIUrl":"https://doi.org/10.1039/d5sc03017j","url":null,"abstract":"Combined luminescence studies and stochastic molecular dynamics simulations have revealed for the first time how cooperative hydrophobic binding and reversible metal ion coordination to protein glutamate residues occurs. The approach has been used to explain the very different free energies of binding observed between three structurally analogous chiral europium (III) complexes and the common variants of serum albumin. In particular, reversible binding of a carboxylate from a glutamate residue was observed; this residue is found in human serum albumin but not the other variants. The binding free energy is exquisitely sensitive to the europium probe structure and charge, and favours complexation of a right handed stereoisomer in the chiral binding pocket. Each process has been visualised by short movies, revealing probe conformational exchange dynamics and the pathway to the protein binding site, on a sub-microsecond timescale.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"109 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144577822","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}
Kepeng Chen, Xiaoting Zhang, Jike Wang, Dan Li, Tingjun Hou, Wenbo Yang, Yu Kang
{"title":"Effective Generation of Heavy-Atom-Free Triplet Photosensitizers Containing Multiple Intersystem Crossing Mechanisms Based on Deep Learning","authors":"Kepeng Chen, Xiaoting Zhang, Jike Wang, Dan Li, Tingjun Hou, Wenbo Yang, Yu Kang","doi":"10.1039/d5sc03192c","DOIUrl":"https://doi.org/10.1039/d5sc03192c","url":null,"abstract":"Photodynamic therapy (PDT) is a clinically approved therapeutic modality that has demonstrated significant potential for cancer treatment, and triplet photosensitizers (PSs) play a key role in its efficacy. Despite deep learning has emerged as a next-generation tool for material discovery, existing methods mainly target a limited subset of triplet PSs, such as thermally activated delayed fluorescence (TADF) materials, neglecting the critical intersystem crossing (ISC) between high-lying singlet and triplet states (ΔESnTn). To overcome this limitation, we compiled a comprehensive dataset (~1.90 × 109) of triplet PSs encompassing various ISC mechanisms. Then, we proposed a novel strategy that incorporates two models: a fragment-based model (Frag-MD) and a character-based model (MD), both integrating a conditional transformer, recurrent neural networks, and reinforcement learning. In silico experiments reveal that the Frag-MD model outperforms the MD model in generating larger conjugated motifs with higher average ring numbers and atom counts; while the MD model generates twice as many unique motifs and excels in novelty and diversity, as evaluated by conditional and MOSES metrics. Therefore, our approach is highly effective for modifying conjugated motifs and designing novel triplet PSs. Notably, recently reported high-efficiency triplet PSs have been re-identified through ablation experiments using our proposed models, which target ΔESnTn and significantly outperform traditional baselines, achieving a prediction accuracy of 73% versus 4%. Our approach holds the potential to establish a new paradigm for discovering novel PSs applicable in PDT.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"21 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144577807","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":"Harnessing emergent multiple scattering resonances in a photonic glass structure for photoelectrochemical energy conversion","authors":"Ashlyn G. DesCarpentrie, Robert H. Coridan","doi":"10.1039/d5sc02916c","DOIUrl":"https://doi.org/10.1039/d5sc02916c","url":null,"abstract":"Light trapping nanostructures are often necessary to improve carrier collection yields in semiconductor photoelectrodes with intrinsically poor electron transport. Photonic crystal templates can generate tailorable light trapping <em>via</em> periodic and precise nanostructure, though this is not a scalable strategy for photoelectrochemical (PEC) applications. It is therefore critical to identify alternative mechanisms for light trapping that tolerate disorder. Light trapping in disordered media is generated by the diffusive transport caused by multiple scattering. In some cases, multiple scattering can generate resonances that resemble those observed in photonic crystals. While resonant multiple scattering is a disorder tolerant light trapping mechanism, it is unclear if the effect is sufficiently adaptable, or even useful, for PEC applications. Here, we describe a photonic omission glass, a nanostructure that can controllably induce resonances in multiple scattering transport. We characterized the emergence of these resonances after coating a disordered SiO<small><sub>2</sub></small> colloidal structure with a layer of TiO<small><sub>2</sub></small>, which functions both as dielectric contrast and as a light absorbing semiconductor. We show in finite element simulations and spectroscopic characterization that the resonant multiple scattering effect improves light trapping near the interface between the structure and the bulk electrolyte. This effect, coupled with the increased electrochemically active surface area, results in a hierarchically structured TiO<small><sub>2</sub></small> photoanode with orders of magnitude higher photocurrents compared to an equivalent planar photoanode for PEC reactions such as alkaline water oxidation. We show that controlling this resonant multiple scattering effect can be advantageous for improving PEC energy conversion in disordered photoelectrodes.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"31 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144577808","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":"Identification, occurrence and prevention of aspartimide-related byproducts in chemical protein synthesis","authors":"Vincent Aucagne, El hadji Cisse","doi":"10.1039/d5sc03824c","DOIUrl":"https://doi.org/10.1039/d5sc03824c","url":null,"abstract":"Formation of a five-membered ring aspartimide through the attack of a backbone amide to the side chain of aspartate and asparagine residues is a long-known side-reaction in solid phase peptide synthesis, and is also associated with in vivo protein ageing and instability of purified proteins. Conversely, its possible occurrence during chemical ligation-based protein synthesis, in particular when using the gold-standard reaction NCL (native chemical ligation), is dubious. We herein report a systematic study which demonstrates that the prevalence of this side-reaction may have been overlooked, due to the difficulty to identify it through standard HPLC analytical methods, but also the in situ conversion of aspartimide into other byproducts, having the same molecular mass as the parent aspartate residue. We show that the formation of aspartimide and derived byproducts can be limited by adopting \"good NCL practices\", which involve restricting the ligation temperature and reaction times, as well as replacing the commonly used phosphate buffer with HEPES. However, the efficiency of such precautions is expected to vary considerably depending on the sequence of the target protein, and the amount of byproducts is expected to grow with the length of the target protein, as a result of the number of NCL reactions and potential aspartimide hotspots. To overcome such limitations, we developed a novel straightforward and potentially generally applicable methodology based on the temporary protection of the backbone nitrogen by a 2-(4-aminobutanoyloxy)-4-methoxybenzyl (GABA-Hmb) group. This strategy was validated by the byproduct-free synthesis of SUMO-2 and a SUMOylated peptide mimic.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"93 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144577809","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":"Regulating the donor number of solvents for long-cycle anode-free lithium metal batteries","authors":"Yining Zhao, Shaopeng Li, Yahui Li, Shu Xu, Lingtong Zhu, Hui Dou, Xiaogang Zhang","doi":"10.1039/d5sc02399h","DOIUrl":"https://doi.org/10.1039/d5sc02399h","url":null,"abstract":"Anode-free lithium-metal batteries (AFLMBs) are one of the up-and-coming high-energy-density battery systems because they eliminate the need for conventional graphite electrodes or excess lithium metal anodes (LMAs). However, AFLMBs have serious problems of low coulombic efficiencies (CEs) and poor cycle stability. Herein, this study proposes a local high-concentration electrolyte (LHCE) based on donor number (DN) modulation, which achieves stable dissolution of LiNO3 and an anion-enhanced solvation structure through the synergistic action of a high DN solvent (Tetraglyme, G4) and an ultra-low DN diluent (1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether, TTE). The design addresses the core challenges of low CEs and poor cycling stability in AFLMBs due to the lack of lithium source. Computational and experimental results show that regulating the DN value of the solvent significantly reduces the Li+ desolvation energy and forms an inorganic-rich solid electrolyte interphase (SEI), which guides the uniform deposition of Li. The electrolyte achieves a high CE (about 99.0%) and long cycle life (1400 h). Based on this, AFLMB maintains 86.3% capacity after 50 cycles, far exceeding the 25-cycle life of conventional carbonate electrolytes (CCE).","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"21 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144577818","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":"Unlocking Inverted Singlet-Triplet Gap in Alternant Hydrocarbons with Heteroatoms","authors":"Atreyee Majumdar, Surajit Das, Raghunathan Ramakrishnan","doi":"10.1039/d5sc02309b","DOIUrl":"https://doi.org/10.1039/d5sc02309b","url":null,"abstract":"Fifth-generation organic light-emitting diodes exhibit delayed fluorescence enabled by exothermic reverse intersystem crossing due to a negative singlet–triplet gap, where the first excited singlet lies below the triplet. This phenomenon, termed delayed fluorescence from inverted singlet and triplet states (DFIST), has been experimentally confirmed only in two triangular molecules with a 12-annulene periphery and a central nitrogen atom. Here, we report a high-throughput virtual screening of 30,797 BN-substituted polycyclic aromatic hydrocarbons (BNPAH) derived from 77 parent scaffolds with 2–6 rings. Using a multi-level workflow that combines structural stability criteria with accurate excited-state calculations, we identify the top 46 DFIST-BNPAH candidates with singlet-triplet gaps less than -0.015 eV. Notably, this set includes BN-helicenes, where inversion arises from through-space charge-transfer states. Our findings reveal new design motifs for DFIST that extend beyond known frameworks, thereby expanding the chemical space for next-generation emitters based on heteroatom-embedded aromatic systems.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"697 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144577810","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}
Simon B. H. Karnbrock, Jan F. Köster, Isabelle Becker, Christopher Golz, Franc Meyer, Martí Gimferrer, Manuel Alcarazo
{"title":"Bis(amidophenolate)-supported pnictoranides: Lewis acid-induced electromerism in a bismuth complex","authors":"Simon B. H. Karnbrock, Jan F. Köster, Isabelle Becker, Christopher Golz, Franc Meyer, Martí Gimferrer, Manuel Alcarazo","doi":"10.1039/d5sc03374h","DOIUrl":"https://doi.org/10.1039/d5sc03374h","url":null,"abstract":"The synthesis of the complete series of 10-Pn-4 bis(amidophenolate)-supported pnictoranide anions is reported. Coordination of these anions to the cyclopentadienyliron(<small>II</small>) dicarbonyl fragment, [CpFe(CO)<small><sub>2</sub></small>]<small><sup>+</sup></small>, delivers the corresponding 10-Pn-5 complexes for P, As and Sb, while in the case of Bi an electron redistribution takes place, and the corresponding 12-Bi-5 compound is isolated. This case of Lewis acid-induced electromerism has been experimentally confirmed through X-ray diffraction analyses as well as IR, UV-Vis and Mössbauer spectroscopy. Effective Oxidation State analysis of the Fe-complexes assigns an oxidation state +3 to all Pn, while it predicts the Fe-atom to be reduced to Fe(0) in the Bi-derivative. The mixture of the Bi(6p) orbital with the π-system of the bis(amidophenolate) ligand and the efficient electronic donation from this orbital to the Fe-center explain this situation.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"16 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144577811","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}
Debasis Saha, Rahul Aich, Arnab Mukherjee and Biman Jana
{"title":"Correction: Water entropy at the threonine-rich surface of antifreeze and ice-nucleating proteins: small changes make a big difference","authors":"Debasis Saha, Rahul Aich, Arnab Mukherjee and Biman Jana","doi":"10.1039/D5SC90146D","DOIUrl":"10.1039/D5SC90146D","url":null,"abstract":"<p >Correction for ‘Water entropy at the threonine-rich surface of antifreeze and ice-nucleating proteins: small changes make a big difference’ by Debasis Saha <em>et al.</em>, <em>Chem. Sci.</em>, 2025, <strong>16</strong>, 10771–10784, https://doi.org/10.1039/D4SC08383K.</p>","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" 29","pages":" 13547-13547"},"PeriodicalIF":7.6,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/sc/d5sc90146d?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144577645","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}
Natasha Videcrantz Faurschou, Christian Marcus Pedersen
{"title":"Discovery of Novel Glycosylation Methods using Bayesian Optimization: Lithium Salt Directed Stereoselective Glycosylations","authors":"Natasha Videcrantz Faurschou, Christian Marcus Pedersen","doi":"10.1039/d5sc03244j","DOIUrl":"https://doi.org/10.1039/d5sc03244j","url":null,"abstract":"In recent years, Bayesian optimization hasgained increasing interest as a tool for reaction optimization.Here we use Bayesian optimization in a reaction discoveryfashion by treating the glycosylation reaction classas a black box function. This provides access to new areasof the glycosylation reaction space and leads to the discoveryof novel stereoselective glycosylation methodologies,where stereoselectivity can be directed by the addition oflithium salts in interplay with other reaction conditions.Black box functions are inherently difficult to interpret,but we show how partial dependence plots can be used toinfer trends from the obtained data in a similar fashion tothe commonly used one-variable-at-time approach.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"13 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144577819","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}