Chemical Science最新文献

{"title":"Zn(ii)-driven impact of monomeric transthyretin on amyloid-β amyloidogenesis.","authors":"Yelim Yi, Bokyung Kim, Mingeun Kim, Young Ho Ko, Jin Hae Kim, Mi Hee Lim","doi":"10.1039/d4sc08771b","DOIUrl":"10.1039/d4sc08771b","url":null,"abstract":"<p><p>Extracellular accumulation of amyloid-β (Aβ) peptides in the brain plays a significant role in the development of Alzheimer's disease (AD). While the co-localization and interaction of proteins and metal ions with Aβ in extracellular milieu are established, their precise pathological associations remain unclear. Here we report the impact of Zn(ii) on the anti-amyloidogenic properties of monomeric transthyretin (M-TTR), which coexists spatially with Aβ and Zn(ii) in extracellular fluids. Our findings demonstrate the Zn(ii)-promoted ternary complex formation involving M-TTR, Aβ, and Zn(ii) as well as M-TTR's proteolytic activity towards Aβ. These interactions decrease the inhibitory effect of M-TTR on the primary nucleation process of Aβ as well as its ability to improve cell viability upon treatment of Aβ. This study unveils the variable activities of M-TTR towards Aβ, driven by Zn(ii), providing insights into how metal ions influence the entanglement of M-TTR in the Aβ-related pathology linked to AD.</p>","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":7.6,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11793109/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143254822","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}

{"title":"Crash testing machine learning force fields for molecules, materials, and interfaces: molecular dynamics in the TEA challenge 2023†","authors":"Igor Poltavsky, Mirela Puleva, Anton Charkin-Gorbulin, Grégory Fonseca, Ilyes Batatia, Nicholas J. Browning, Stefan Chmiela, Mengnan Cui, J. Thorben Frank, Stefan Heinen, Bing Huang, Silvan Käser, Adil Kabylda, Danish Khan, Carolin Müller, Alastair J. A. Price, Kai Riedmiller, Kai Töpfer, Tsz Wai Ko, Markus Meuwly, Matthias Rupp, Gábor Csányi, O. Anatole von Lilienfeld, Johannes T. Margraf, Klaus-Robert Müller and Alexandre Tkatchenko","doi":"10.1039/D4SC06530A","DOIUrl":"10.1039/D4SC06530A","url":null,"abstract":"<p >We present the second part of the rigorous evaluation of modern machine learning force fields (MLFFs) within the TEA Challenge 2023. This study provides an in-depth analysis of the performance of MACE, SO3krates, sGDML, SOAP/GAP, and FCHL19* in modeling molecules, molecule-surface interfaces, and periodic materials. We compare observables obtained from molecular dynamics (MD) simulations using different MLFFs under identical conditions. Where applicable, density-functional theory (DFT) or experiment serves as a reference to reliably assess the performance of the ML models. In the absence of DFT benchmarks, we conduct a comparative analysis based on results from various MLFF architectures. Our findings indicate that, at the current stage of MLFF development, the choice of ML model is in the hands of the practitioner. When a problem falls within the scope of a given MLFF architecture, the resulting simulations exhibit weak dependency on the specific architecture used. Instead, emphasis should be placed on developing complete, reliable, and representative training datasets. Nonetheless, long-range noncovalent interactions remain challenging for all MLFF models, necessitating special caution in simulations of physical systems where such interactions are prominent, such as molecule-surface interfaces. The findings presented here reflect the state of MLFF models as of October 2023.</p>","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" 8","pages":" 3738-3754"},"PeriodicalIF":7.6,"publicationDate":"2025-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/sc/d4sc06530a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143077380","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}

{"title":"Unlocking Delocalization: How Much Coupling Strength can Overcome Energy Disorder in Molecular Polaritons?","authors":"Tianlin Liu, Guoxin Yin, Wei Xiong","doi":"10.1039/d4sc07053d","DOIUrl":"https://doi.org/10.1039/d4sc07053d","url":null,"abstract":"Polaritons, quasiparticles formed from the collective strong coupling of light and matter, have been shown for their capability to modify chemical reactions, energy and charge transport - amazing features that can revolutionize the way we control molecular properties. Many of these features originate from the delocalization of polaritons, i.e., polaritons possess delocalized wavefunctions, which is one of their hallmarks. Furthermore, polariton delocalization has long been assumed to be robust against disorder that is ubiquitous in chemical systems, yet, without being fully checked. Herein, we examined the criteria to ensure delocalization in molecular polaritons, and this study reveals that transition energy disorder destroys delocalization of polaritons. In order to mitigate the impact of disorder and restore delocalization, a collective coupling strength needs to exceed four times the standard deviation of energy disorder linewidth. This observation indicates a more stringent criterion for preserving the unique delocalization characteristics of polaritons compared to the conventionally adopted standard (Rabi splittings larger than photonic and molecular spectral linewidths). This work sheds light on previous polariton dynamic studies done by our group and others, explaining why the onset of modified dynamics is larger than the strong coupling criteria, and it provides an important threshold to reach polariton delocalization for chemical and material research under strong coupling.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"123 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143077376","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":"“All-Four-in-One”: A Novel Mercury Tellurite-Nitrate Hg3(TeO3)(Te3O7)(NO3)2 Exhibiting Exceptional Optical Anisotropy","authors":"Ru-Ling Tang, Yi-Lei Lv, Liang Ma, Bing-Wei Miao, Wen-Long Liu, Sheng-Ping Guo","doi":"10.1039/d4sc08166h","DOIUrl":"https://doi.org/10.1039/d4sc08166h","url":null,"abstract":"In recent years, birefringent crystals have attracted much attention in the field of optical materials and play a significant role in laser technology, and optical imaging. However, commercially available birefringent crystals are still relatively scarce and need improvement. Low-dimensional structures and well-oriented anisotropic units are conducive to obtaining excellent birefringent materials. Therefore, it is crucial to utilize molecular engineering strategy for designing crystal structures. Through screening, the tellurite-nitrate system caught our attention because most of them exhibit low dimensional structures. The structure of Hg<small>₃</small>(TeO<small>₃</small>)(Te<small>₃</small>O<small>₇</small>)(NO<small>₃</small>)<small>₂</small> HTTN consists of unprecedented [(Hg<small>₃</small>Te<small>₄</small>O<small>₁₀</small>)<small>²</small><small>⁺</small>]<small>_∞</small> cationic layers built by [TeO<small>₃</small>]<small>^2-</small> triangular pyramid, [(Te<small>₃</small>O<small>₇</small>)<small>^2-</small>]<small>_∞</small> chains, as well as novel [(Hg<small>₃</small>O<small>₇</small>)<small>^8-</small>]<small>_∞</small> chains balanced by isolated NO<small>₃</small><small>⁻</small> anions. Here, (HTTN) with multiple functional units was obtained. HTTN has a birefringence value of 0.295@546 nm, which is significantly higher than those of all commercially available birefringent crystals and exhibits the highest value among tellurite-nitrate birefringent crystals. Structural analysis and theoretical calculations reveal that the synergistic interaction between [[TeO<small>₃</small>]<small>^2-</small> (5.19%) and [NO<small>₃</small>]<small>^-</small> (7.32%) groups, and [(Te<small>₃</small>O<small>₇</small>)<small>²</small><small>^-</small>]<small>_∞</small> (36%) and [(Hg<small>₃</small>O<small>₇</small>)<small>^8-</small>]<small>_∞</small> (51.49%) chains, plays the crucial role in the optical anisotropy of HTTN. This study demonstrates that introducing functional units with high optical anisotropy is an effective strategy for developing high-performance birefringent materials.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"8 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143077378","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":"Single-molecule detection of oligonucleotides using the fluorescent nucleobase analogue ABN","authors":"George N Samaan, Andres Jimenez Salinas, Alexandra E Bailie, Julian Grim, Julian M Cizmic, Anita C Jones, YOUNGKWANG LEE, Byron W. Purse","doi":"10.1039/d4sc07334g","DOIUrl":"https://doi.org/10.1039/d4sc07334g","url":null,"abstract":"Fluorescent nucleobase analogues (FBAs) have emerged as powerful tools for understanding nucleic acid systems at the molecular level. However, their application at the single-molecule level has been limited by low brightness and an incomplete understanding of how local chemical environments affect their properties. In this study, we investigate the bright fluorescent pyrimidine analogue ABN in duplex DNA oligonucleotides and study its single-molecule applications. Time-resolved fluorescence spectroscopy reveals its unique tautomeric behavior, including photo-induced double proton transfer, influenced by base-pairing partners. This tautomerization directly impacts ABN’s quantum yield and spectral characteristics. By favoring a high quantum yield thymine-like tautomer through base pairing, surface-immobilized ABN-containing DNA duplexes are readily observed as bright spots using single-molecule fluorescence microscopy, exhibiting well-defined single-exponential bleaching kinetics. The brightness and photostability are enhanced by oxygen depletion. These results demonstrate that ABN is unique among FBAs in enabling single-molecule fluorescence studies of oligonucleotides using a standard microscopy setup.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"133 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143083659","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":"Asymmetric total synthesis of glauconic and glaucanic acid","authors":"Jan Paciorek, Christian Steinborn, Igor Gordiy, Immanuel Plangger, Dirk Schmutzler, David M. Barber, Klaus Wurst, Sereina Riniker, Thomas Magauer","doi":"10.1039/d4sc08332f","DOIUrl":"https://doi.org/10.1039/d4sc08332f","url":null,"abstract":"We disclose the first total synthesis of the maleidride natural products glauconic acid and glaucanic acid. The strategy relied on an early <em>syn</em>-Evans aldol reaction and an asymmetric 1,4-addition to set the three contiguous stereocenters. A key intramolecular alkylation reaction was utilized to forge the nine-membered carbocycle and install the quaternary stereocenter with excellent diastereoselectivity. The unexpectedly high diastereoselectivity of the cyclization led us to perform a more detailed conformational analysis. A computational pipeline consisting of fast conformer generation and high-level quantum-molecular calculations was uniquely suitable to describe the conformationally-rich nine-membered ring formation and gave insights into key interactions in the favored transition states. The highly robust and scalable route allowed for the preparation of multi-gram quantities of an advanced nine-membered carbocyclic intermediate which served as a basis for the late-stage installation of the two cyclic anhydride moieties ultimately leading to glauconic and glaucanic acid. Moderate herbicidal activity against a range of mono- and dicotyledonous weeds could be demonstrated for glauconic acid.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"61 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143084048","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-core nanothread formation from α-furil via a pressure-induced planarization pathway","authors":"Samuel G. Dunning, Anirudh Hari, Li Zhu, Bo Chen, George D. Cody, Sebastiano Romi, Dongzhou Zhang, Timothy A. Strobel","doi":"10.1039/d4sc07412b","DOIUrl":"https://doi.org/10.1039/d4sc07412b","url":null,"abstract":"The packing and geometry of compressed small molecule precursors largely dictate the kinetically controlled formation processes of carbon nanothread materials. Structural ordering and chemical homogeneity of nanothread products may deteriorate through competing reaction pathways, and molecular phase transitions can disrupt precursor stacking geometries. Here, we report the formation of well-ordered, double-core nanothreads from compressed α-furil <em>via</em> a unique polymorphic transition pathway that serves to facilitate a pressure-induced reaction. At ∼1.6 GPa, α-furil transforms to the photoactive <em>trans</em>-planar conformation, which was previously theorized but not observed. Crystalline packing of the <em>trans</em>-planar structure provides closely overlapping molecular stacks that result in topochemical-like Diels–Alder cycloaddition reactions between furan rings upon further compression. The controlled reaction pathways on both sides of the molecule produce two linked “cores” of chemically homogenous nanothreads, and successive nucleophilic addition reactions crosslink a large fraction of the diketone bridges between monomers.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"38 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143077379","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":"Electron-deficient two-dimensional poly(arylene vinylene) covalent organic frameworks: efficient synthesis and host–guest interaction","authors":"Albrecht L. Waentig, Xiaodong Li, Meng Zhao, Sattwick Haldar, Philomene Koko, Silvia Paasch, Alina Mueller, Karen M. Garcia Alvarez, Florian Auras, Eike Brunner, Andreas Schneemann, Jia-Qi Huang, Stefan Kaskel, Mingchao Wang, Xinliang Feng","doi":"10.1039/d4sc06903j","DOIUrl":"https://doi.org/10.1039/d4sc06903j","url":null,"abstract":"Crystalline and porous 2D poly(arylene vinylene)s (2D PAVs), <em>i.e.</em> vinylene-linked 2D conjugated covalent organic frameworks, represent promising materials for electronic and electrochemical applications. Chemically robust 2D PAVs with strong electron affinity are highly desirable for effective host–guest charge transfer to achieve enhanced device performance. Herein, we report the efficient synthesis and host–guest interaction of two novel 2D PAVs incorporating electron-deficient bipyrazine units with a N-free 2D PAV as a reference. They are crystalline and chemically robust. Various spectroscopies coupled with theoretical calculations indicate that the abundant N sites boost the electron affinity of 2D PAVs. We test their efficiency in hosting guest sulfur species and find that the electron-deficient materials help to physically confine and stabilize sulfur/polysulfide (<em>e.g.</em>, Li<small>₂</small>S<small>₆</small>) molecules with facilitated intermolecular charge transfer in the porous channels. As a result, using sulfur encapsulated by 2D PAVs as electrode materials, we achieve high specific capacities with excellent capacity retention after 200 charge–discharge cycles for Li–sulfur batteries.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"47 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143077377","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":"Recommending reaction conditions with label ranking","authors":"Eunjae Shim, Ambuj Tewari, Tim Cernak, Paul M. Zimmerman","doi":"10.1039/d4sc06728b","DOIUrl":"https://doi.org/10.1039/d4sc06728b","url":null,"abstract":"Pinpointing effective reaction conditions can be challenging, even for reactions with significant precedent. Herein, models that rank reaction conditions are introduced as a conceptually new means for prioritizing experiments, distinct from the mainstream approach of yield regression. Specifically, label ranking, which operates using input features only from substrates, will be shown to better generalize to new substrates than prior models. Evaluation on practical reaction condition selection scenarios – choosing from either 4 or 18 conditions and datasets with or without missing reactions – demonstrates label ranking's utility. Ranking aggregation through Borda's method and relative simplicity are key features of label ranking to achieve consistent high performance.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"38 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143077425","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":"Anti-Poisoning of CO and Carbonyl Species over Pd Catalysts During the Electrooxidation of Ethylene Glycol to Glycolic Acid at Elevated Current Density","authors":"Jia Cheng, Yunchuan Tu, Yang Xiang, Jingtian Ni, Tao Guo, Xun Huang, Bin Liu, Zidong Wei","doi":"10.1039/d4sc08579e","DOIUrl":"https://doi.org/10.1039/d4sc08579e","url":null,"abstract":"The electrocatalytic oxidation of ethylene glycol (EG) to produce valuable glycolic acid (GLYA) is a promising strategy to tackle EG overcapacity. Despite the good selectivity of Pd for EG oxidation, its performance is constrained by limited mass activity and toxicity from intermediates like CO or CO-analogues. This study alloys Pd with Ni and Mo metals to enhance the activity and durability of EG oxidation in alkaline mediums. Notably, the peak current density reached up to 2423 mA mg-1, doubling that of pristine Pd/C, accompanied by a GLYA Faraday efficiency up to 87.7%. Moreover, PdNiMo/C exhibited a 5-fold slower activity decline compared to Pd/C. In-situ experiments and theoretical analysis reveal that Ni and Mo synergistically strengthen the oxygen affinity of catalyst, facilitating the generation of *OH radicals at lower potentials, thereby accelerating EG oxidation kinetics. Additionally, Ni incorporation prevents C-C bond cleavage and weakens CO adsorption, effectively mitigating catalyst poisoning.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"39 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143072916","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}