Given the importance of organosilicons and atropisomerism, there is a fundamental need to develop new methods to synthesize axially chiral biaryl silanes. By use of an easily accessible chiral picolinamide as a ligand and inexpensive nickel as a catalyst, we realize a desymmetric silylation of prochiral biaryl bis(triflates) with silyl chlorides under net reductive conditions. This cross-electrophile reaction offers a new approach to prepare highly enantioenriched C1-symmetric axially chiral platform molecules, which incorporate both a silane and a triflate moiety as two distinct docking sites for various downstream derivatizations.
{"title":"Reductive Desymmetric Silylation of Biaryl Bis(triflates) Enabled by a Chiral Nickel/Picolinamide Complex","authors":"Zhe Chen, Junjie Zhang, Chuan Wang","doi":"10.1039/d5sc09250g","DOIUrl":"https://doi.org/10.1039/d5sc09250g","url":null,"abstract":"Given the importance of organosilicons and atropisomerism, there is a fundamental need to develop new methods to synthesize axially chiral biaryl silanes. By use of an easily accessible chiral picolinamide as a ligand and inexpensive nickel as a catalyst, we realize a desymmetric silylation of prochiral biaryl bis(triflates) with silyl chlorides under net reductive conditions. This cross-electrophile reaction offers a new approach to prepare highly enantioenriched C1-symmetric axially chiral platform molecules, which incorporate both a silane and a triflate moiety as two distinct docking sites for various downstream derivatizations.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"19 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116088","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}
Frustrated Lewis pairs (FLPs), composed of reactive combinations of Lewis acids (LAs) and bases (LBs) offer a metal-free platform for catalyzing a wide range of chemical transformations. Designing the optimal FLP active site for a particular chemical reaction is a challenging task due to the lack of rigorous principles and countless chemical possibilities. We recently designed principles, which outline the relative disposition (i.e., distance and angle) and chemical composition of the LA and LB centers that maximize activity in B- and N-based FLPs. These criteria were already used to screen 25,000 FLP active sites built on N-containing linkers extracted from the CoRE MOF dataset, but in such an enormous multifunctional catalyst space, inverse design approaches provide a more efficient mean to explore all possible combinations. Here, we use the NaviCatGA genetic algorithm to simultaneously optimize the chemical and geometrical characteristics of intramolecular FLPs while considering synthetic complexity and catalyst quenching constraints. By integrating activity maps and non-linear regression models, our workflow explores a vast chemical space of 1.7 billion FLP candidates built from organic fragments curated from the literature --- released as the open-source FragFLP25 dataset--- to identify optimal compositions suitable for catalytic CO2 hydrogenation. Analyzing the top candidates extracted from various Pareto fronts in the catalyst space, we not only uncover active FLP motifs for hydrogenation that have not been previously reported but also refine and extend the design principles previously established from our high-throughput screening study.
{"title":"Inverse Design of Frustrated Lewis Pairs for Direct Catalytic CO2 Hydrogenation: Refining and Expanding Design Rules","authors":"Ruben Laplaza, Shubhajit Das, Thanapat Worakul, Clemence Corminboeuf","doi":"10.1039/d5sc09530a","DOIUrl":"https://doi.org/10.1039/d5sc09530a","url":null,"abstract":"Frustrated Lewis pairs (FLPs), composed of reactive combinations of Lewis acids (LAs) and bases (LBs) offer a metal-free platform for catalyzing a wide range of chemical transformations. Designing the optimal FLP active site for a particular chemical reaction is a challenging task due to the lack of rigorous principles and countless chemical possibilities. We recently designed principles, which outline the relative disposition (<em>i.e.</em>, distance and angle) and chemical composition of the LA and LB centers that maximize activity in B- and N-based FLPs. These criteria were already used to screen 25,000 FLP active sites built on N-containing linkers extracted from the CoRE MOF dataset, but in such an enormous multifunctional catalyst space, inverse design approaches provide a more efficient mean to explore all possible combinations. Here, we use the NaviCatGA genetic algorithm to simultaneously optimize the chemical and geometrical characteristics of intramolecular FLPs while considering synthetic complexity and catalyst quenching constraints. By integrating activity maps and non-linear regression models, our workflow explores a vast chemical space of 1.7 billion FLP candidates built from organic fragments curated from the literature --- released as the open-source FragFLP25 dataset--- to identify optimal compositions suitable for catalytic CO<small><sub>2</sub></small> hydrogenation. Analyzing the top candidates extracted from various Pareto fronts in the catalyst space, we not only uncover active FLP motifs for hydrogenation that have not been previously reported but also refine and extend the design principles previously established from our high-throughput screening study.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"89 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116090","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}
Samuel Gary, Pei-Hsuan Chen, Nin Mai, Steven Bloom
Amino acids with β,β-carbocyclic sidechains are valuable replacements for endogenous Val, Leu, and Ile, with therapeutic benefits. When placed into ordinary peptides, these annulated variants improve metabolic stability, cell permeability, and receptor affinity and selectivity. Yet, their appearance in modern peptide drugs is often limited to β,β-cyclopentyl- and β,β-cyclohexyl-rings, one reason being the limited availability of resin- and solution-compatible β,β-carbocyclic amino acids for direct coupling. More ‘exotic’ rings, i.e., those with different sizes, chemical compositions, and geometric preferences, could be superior, but finding and assessing their benefits calls for more general ways to incorporate and test them. Herein, we pioneer a modular route to convert a single unsaturated residue, known as β-sulfonyldehydroamino acid (ΔSulf), in a peptide into many unique β,β-carbocycles—cyclic, polycyclic, and heteroatom-containing—in two telescoped steps. First, an unprecedented photocatalyst, Pyronin Y, in an original combination with an organodiiodide, cobalt porphyrin catalyst, sacrificial amine, and green LEDs converts ΔSulf into a Δ-amino acid with a pendant iodide. Adding Zn/Cu couple then triggers an intramolecular and stereoselective Giese cyclization. We detail the mechanism of our procedure, highlighting the interplay between aqueous metallaphotoredox catalysis, halogen-atom abstraction, and ligand-controlled cyclization using spectroscopy, cyclic voltammetry, intermediate-trapping, and radical-clock experiments.
{"title":"A General Route to β,β-carbocyclic Sidechains in Peptides: An Aqueous Metallaphotoredox Approach Driven by Green Light","authors":"Samuel Gary, Pei-Hsuan Chen, Nin Mai, Steven Bloom","doi":"10.1039/d5sc08845c","DOIUrl":"https://doi.org/10.1039/d5sc08845c","url":null,"abstract":"Amino acids with β,β-carbocyclic sidechains are valuable replacements for endogenous Val, Leu, and Ile, with therapeutic benefits. When placed into ordinary peptides, these annulated variants improve metabolic stability, cell permeability, and receptor affinity and selectivity. Yet, their appearance in modern peptide drugs is often limited to β,β-cyclopentyl- and β,β-cyclohexyl-rings, one reason being the limited availability of resin- and solution-compatible β,β-carbocyclic amino acids for direct coupling. More ‘exotic’ rings, i.e., those with different sizes, chemical compositions, and geometric preferences, could be superior, but finding and assessing their benefits calls for more general ways to incorporate and test them. Herein, we pioneer a modular route to convert a single unsaturated residue, known as β-sulfonyldehydroamino acid (ΔSulf), in a peptide into many unique β,β-carbocycles—cyclic, polycyclic, and heteroatom-containing—in two telescoped steps. First, an unprecedented photocatalyst, Pyronin Y, in an original combination with an organodiiodide, cobalt porphyrin catalyst, sacrificial amine, and green LEDs converts ΔSulf into a Δ-amino acid with a pendant iodide. Adding Zn/Cu couple then triggers an intramolecular and stereoselective Giese cyclization. We detail the mechanism of our procedure, highlighting the interplay between aqueous metallaphotoredox catalysis, halogen-atom abstraction, and ligand-controlled cyclization using spectroscopy, cyclic voltammetry, intermediate-trapping, and radical-clock experiments.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"28 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116109","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}
Andjela Brnovic, Gaurav Kumar, Martin Axelsson, Bin Cai, Mariia V. Pavliuk, Lars Kloo, Leif Hammarström, Haining Tian
We have developed two new star-shaped donor-acceptor oligomers, named TxBT and TxNT, with a truxene donor core and either 2,1,3-benzothiadiazole (BT) or a naphtho [1,2-c:5,6-c′]bis[1,2,5]thiadiazole (NT) unit, respectively. Femtosecond transient absorption spectroscopy suggested that both oligomer nanoparticles (NPs) generate long-lived triplet charge-transfer (CT) states following photoexcitation, which undergo reductive quenching by ascorbate. TxNT NPs generate a larger population of reduced species that accumulate and escape recombination compared to TxBT NPs, indicating more efficient charge separation. TxNT NPs show significantly higher hydrogen evolution rate (54 mmol•h⁻¹•g⁻¹) compared to TxBT NPs, which is comparable to the performance of the most efficient heterojunction polymer NP systems. Additionally, morphological analysis revealed that Pt deposition was significantly lower on TxBT than on TxNT NPs. These findings highlight the critical role of triplet CT states, tuning molecular energy levels, optimizing excited-state dynamics, and engineering NP architecture to increase photocatalytic hydrogen evolution of organic photocatalysts. To our knowledge, this is the first report where triplet CT states can mediate photocatalytic hydrogen evolution in donor-acceptor oligomer NPs.
{"title":"Triplet States Enable Efficient Photocatalytic Hydrogen Evolution in Star-Shaped Truxene-Based Nanoparticles","authors":"Andjela Brnovic, Gaurav Kumar, Martin Axelsson, Bin Cai, Mariia V. Pavliuk, Lars Kloo, Leif Hammarström, Haining Tian","doi":"10.1039/d5sc09380e","DOIUrl":"https://doi.org/10.1039/d5sc09380e","url":null,"abstract":"We have developed two new star-shaped donor-acceptor oligomers, named TxBT and TxNT, with a truxene donor core and either 2,1,3-benzothiadiazole (BT) or a naphtho [1,2-c:5,6-c′]bis[1,2,5]thiadiazole (NT) unit, respectively. Femtosecond transient absorption spectroscopy suggested that both oligomer nanoparticles (NPs) generate long-lived triplet charge-transfer (CT) states following photoexcitation, which undergo reductive quenching by ascorbate. TxNT NPs generate a larger population of reduced species that accumulate and escape recombination compared to TxBT NPs, indicating more efficient charge separation. TxNT NPs show significantly higher hydrogen evolution rate (54 mmol•h⁻¹•g⁻¹) compared to TxBT NPs, which is comparable to the performance of the most efficient heterojunction polymer NP systems. Additionally, morphological analysis revealed that Pt deposition was significantly lower on TxBT than on TxNT NPs. These findings highlight the critical role of triplet CT states, tuning molecular energy levels, optimizing excited-state dynamics, and engineering NP architecture to increase photocatalytic hydrogen evolution of organic photocatalysts. To our knowledge, this is the first report where triplet CT states can mediate photocatalytic hydrogen evolution in donor-acceptor oligomer NPs.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"23 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116110","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}
Vignesh Sathyaseelan, John Morgan, Brett M. Savoie
The reverse/reductive tricarboxylic acid (rTCA) cycle is a metabolic pathway that facilitates CO2 fixation in certain anaerobic bacteria and archaea. Its presence in phylogenetically ancient organisms has led to hypotheses about its role in the early evolution of CO2 fixation pathways. While the thermodynamics of the pathway is well studied, the kinetic feasibility of uncatalyzed rTCA cycle reactions remains uncertain. In this study, we report a systematic, mechanistic, and kinetic characterization of the uncatalyzed rTCA cycle and its side reactions. A primitive, uncatalyzed rTCA reaction network is elucidated for carbon dioxide fixation that includes all transition states and water-catalyzed reaction channels. The thermodynamics and kinetics of competing off-cycle reactions and potential cycles that are parallel to the uncatalyzed rTCA cycle are also investigated using a newly developed chemical reaction network exploration method. While previous work examined overall thermodynamics and possible pathways, our work focuses on kinetic bottlenecks, which guide where in nature to search for primordial catalysts (clays, minerals, etc.) that could lower the major transition state barriers. This exploration reveals that the uncatalyzed rTCA pathway lies in a reaction neighborhood that is thermodynamically favored, but several key steps are kinetically challenging in the absence of catalysis owing to competitive intramolecular side-reactions and the absence of favorable parallel cycles. The kinetic modeling also provides intermediates that would accumulate in an uncatalyzed environment, serving as prebiotic signposts.
{"title":"Kinetics overcome thermodynamics in primitive analogs of the reverse tricarboxylic acid cycle","authors":"Vignesh Sathyaseelan, John Morgan, Brett M. Savoie","doi":"10.1039/d5sc05872d","DOIUrl":"https://doi.org/10.1039/d5sc05872d","url":null,"abstract":"The reverse/reductive tricarboxylic acid (rTCA) cycle is a metabolic pathway that facilitates CO<small><sub>2</sub></small> fixation in certain anaerobic bacteria and archaea. Its presence in phylogenetically ancient organisms has led to hypotheses about its role in the early evolution of CO<small><sub>2</sub></small> fixation pathways. While the thermodynamics of the pathway is well studied, the kinetic feasibility of uncatalyzed rTCA cycle reactions remains uncertain. In this study, we report a systematic, mechanistic, and kinetic characterization of the uncatalyzed rTCA cycle and its side reactions. A primitive, uncatalyzed rTCA reaction network is elucidated for carbon dioxide fixation that includes all transition states and water-catalyzed reaction channels. The thermodynamics and kinetics of competing off-cycle reactions and potential cycles that are parallel to the uncatalyzed rTCA cycle are also investigated using a newly developed chemical reaction network exploration method. While previous work examined overall thermodynamics and possible pathways, our work focuses on kinetic bottlenecks, which guide where in nature to search for primordial catalysts (clays, minerals, <em>etc.</em>) that could lower the major transition state barriers. This exploration reveals that the uncatalyzed rTCA pathway lies in a reaction neighborhood that is thermodynamically favored, but several key steps are kinetically challenging in the absence of catalysis owing to competitive intramolecular side-reactions and the absence of favorable parallel cycles. The kinetic modeling also provides intermediates that would accumulate in an uncatalyzed environment, serving as prebiotic signposts.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"89 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116111","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}
Marcello Mercogliano, Valentina Mazziotti, Alba Silipo, Antonio Molinaro, Flaviana Di Lorenzo
Lipopolysaccharides (LPSs) from Gram-negative bacteria are traditionally viewed as potent “endotoxins” recognized by the immune system and capable of triggering robust inflammation. However, increasing evidence from gut commensals is dismantling this one-dimensional view. The gastrointestinal tract is indeed the major reservoir of LPSs, owing to the dense Gram-negative community inhabiting the small and large intestine, with total weight in healthy individuals estimated to exceed one gram. This necessarily means that the mere presence of LPSs cannot be directly linked to inflammation. Moreover, chronic exposure to low-potency or atypical LPSs can recalibrate innate immunity, fostering tolerance or, conversely, failing to provide adequate tonic stimulation and thereby predisposing the system to aberrant activation. Understanding this delicate balance and the structural and cellular mechanisms that sustain it, is essential to interpret the immunological impact of the gut LPSs in health and disease. In this Perspective, we highlight recent advances revealing the remarkable chemical diversity of commensal-derived LPSs and illustrate how subtle variations in LPS lipid A acylation and phosphorylation, core oligosaccharide architecture, O-antigen composition, and overall supramolecular organization profoundly rewire receptor usage and downstream immune outcomes. These insights underscore the enormous, still largely untapped potential of gut LPS chemistry to reveal unifying structural hallmarks that distinguish inflammatory, tolerogenic, and immunologically “tuned” features. Although fragments of this logic are beginning to emerge, a comprehensive framework remains urgently needed. Decoding the chemical language adopted by LPSs in the gut will be essential to reclassify LPSs not merely as dangerous molecules, but as a potential source of immunomodulators and as a blueprint for next-generation tools enabling precision control of host-microbe interactions.
{"title":"The Hidden Language of Gut-derived Lipopolysaccharides: Fine Chemistry, Huge Immunological Consequences","authors":"Marcello Mercogliano, Valentina Mazziotti, Alba Silipo, Antonio Molinaro, Flaviana Di Lorenzo","doi":"10.1039/d5sc09900e","DOIUrl":"https://doi.org/10.1039/d5sc09900e","url":null,"abstract":"Lipopolysaccharides (LPSs) from Gram-negative bacteria are traditionally viewed as potent “endotoxins” recognized by the immune system and capable of triggering robust inflammation. However, increasing evidence from gut commensals is dismantling this one-dimensional view. The gastrointestinal tract is indeed the major reservoir of LPSs, owing to the dense Gram-negative community inhabiting the small and large intestine, with total weight in healthy individuals estimated to exceed one gram. This necessarily means that the mere presence of LPSs cannot be directly linked to inflammation. Moreover, chronic exposure to low-potency or atypical LPSs can recalibrate innate immunity, fostering tolerance or, conversely, failing to provide adequate tonic stimulation and thereby predisposing the system to aberrant activation. Understanding this delicate balance and the structural and cellular mechanisms that sustain it, is essential to interpret the immunological impact of the gut LPSs in health and disease. In this Perspective, we highlight recent advances revealing the remarkable chemical diversity of commensal-derived LPSs and illustrate how subtle variations in LPS lipid A acylation and phosphorylation, core oligosaccharide architecture, O-antigen composition, and overall supramolecular organization profoundly rewire receptor usage and downstream immune outcomes. These insights underscore the enormous, still largely untapped potential of gut LPS chemistry to reveal unifying structural hallmarks that distinguish inflammatory, tolerogenic, and immunologically “tuned” features. Although fragments of this logic are beginning to emerge, a comprehensive framework remains urgently needed. Decoding the chemical language adopted by LPSs in the gut will be essential to reclassify LPSs not merely as dangerous molecules, but as a potential source of immunomodulators and as a blueprint for next-generation tools enabling precision control of host-microbe interactions.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"3 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116092","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}
Dajeong Kim, Bryan Duoto, Meghana Varanasi, George Goldenfeld, Nicole F. Steinmetz
Nucleic acids have emerged as a robust modality for the treatment of various diseases that are considered undruggable in the context of small-molecule therapeutics. However, their clinical translation is hindered by the lack of safe and effective delivery across extracellular and intracellular barriers. Mammalian viral vectors and synthetic non-viral carriers have long dominated the delivery landscape, but these raise concerns about safety and immunogenicity, driving the search for alternative strategies. Recently, non-mammalian viral vectors (based on plant viruses or bacteriophages) and virus-like particles (VLPs) derived from them have gained attention as bioinspired platforms for nucleic acid drug delivery. Their well-defined architecture, scalable production, and ability to encapsulate or display drug cargoes offer versatility for drug delivery. This review highlights recent progress in the engineering of plant viruses and bacteriophages for nucleic acid delivery, emphasizing their potential as non-infectious viral scaffolds for next-generation therapeutic platforms.
{"title":"Virus-like particles based on plant viruses and bacteriophages: emerging strategies for the delivery of nucleic acid therapeutics","authors":"Dajeong Kim, Bryan Duoto, Meghana Varanasi, George Goldenfeld, Nicole F. Steinmetz","doi":"10.1039/d5sc02211h","DOIUrl":"https://doi.org/10.1039/d5sc02211h","url":null,"abstract":"Nucleic acids have emerged as a robust modality for the treatment of various diseases that are considered undruggable in the context of small-molecule therapeutics. However, their clinical translation is hindered by the lack of safe and effective delivery across extracellular and intracellular barriers. Mammalian viral vectors and synthetic non-viral carriers have long dominated the delivery landscape, but these raise concerns about safety and immunogenicity, driving the search for alternative strategies. Recently, non-mammalian viral vectors (based on plant viruses or bacteriophages) and virus-like particles (VLPs) derived from them have gained attention as bioinspired platforms for nucleic acid drug delivery. Their well-defined architecture, scalable production, and ability to encapsulate or display drug cargoes offer versatility for drug delivery. This review highlights recent progress in the engineering of plant viruses and bacteriophages for nucleic acid delivery, emphasizing their potential as non-infectious viral scaffolds for next-generation therapeutic platforms.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"301 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116106","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}
Nanoemitters play a pivotal role in advancing OLED technologies toward flexible, efficient, and sustainable display platforms. However, current quantum dots and perovskite LEDs suffer from structural instability and environmental sensitivity, limiting their scalability. Here, we introduce a post-synthetic gridization strategy to construct robust, solution-processable organic nanodots. The resulting A-shaped nanogrid (AG) framework provides a rigid and sterically protected donor scaffold that suppresses aggregation-caused quenching, promotes horizontal dipole orientation and ozone resistance, and minimizes reorganization energy. Based on this design, the thermally activated delayed fluorescence (TADF) emitter AG-PXZ-TRZ exhibits a 3.1-fold enhancement in the radiative decay rate and a 5.5-fold acceleration of reverse intersystem crossing relative to the parent emitter PXZ-TRZ, together with an improved horizontal molecular orientation of 83%. Solution-processed OLEDs based on AG-PXZ-TRZ achieve an external quantum efficiency of 28.9%, markedly surpassing the performance of both PXZ-TRZ and the arylmethylated analogue DPFPXZ-TRZ. This work establishes molecular gridization as an effective pathway toward stable and high-performance organic nanoemitters for next-generation optoelectronic displays.
{"title":"Post-synthetic gridization enhances spin-flip dynamics, horizontal alignment, and ozone resistance in solution-processable TADF macrocycles","authors":"Quanyou Feng, Aiyun Zhu, Qiuhu Han, Kewei Guo, Yunfei Zhu, Yue Cao, Jingyao Ma, Hao Li, Hongjian Wang, Yuyu Pan, Xinxin Ban, Mengna Yu, Man Xu, Zilu Wang, Guohua Xie, Linghai Xie, Wei Huang","doi":"10.1039/d5sc08430j","DOIUrl":"https://doi.org/10.1039/d5sc08430j","url":null,"abstract":"Nanoemitters play a pivotal role in advancing OLED technologies toward flexible, efficient, and sustainable display platforms. However, current quantum dots and perovskite LEDs suffer from structural instability and environmental sensitivity, limiting their scalability. Here, we introduce a post-synthetic gridization strategy to construct robust, solution-processable organic nanodots. The resulting A-shaped nanogrid (AG) framework provides a rigid and sterically protected donor scaffold that suppresses aggregation-caused quenching, promotes horizontal dipole orientation and ozone resistance, and minimizes reorganization energy. Based on this design, the thermally activated delayed fluorescence (TADF) emitter AG-PXZ-TRZ exhibits a 3.1-fold enhancement in the radiative decay rate and a 5.5-fold acceleration of reverse intersystem crossing relative to the parent emitter PXZ-TRZ, together with an improved horizontal molecular orientation of 83%. Solution-processed OLEDs based on AG-PXZ-TRZ achieve an external quantum efficiency of 28.9%, markedly surpassing the performance of both PXZ-TRZ and the arylmethylated analogue DPFPXZ-TRZ. This work establishes molecular gridization as an effective pathway toward stable and high-performance organic nanoemitters for next-generation optoelectronic displays.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"89 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116133","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}
Lukáš Tomaník, Florian Trinter, Petr Slavíček, Bernd Winter
We present the first comprehensive, internally consistent analysis of core-level chemical shifts for aqueous-phase solutes using Electron Spectroscopy for Chemical Analysis of Liquids (ESCAL). An absolute binding-energy calibration enables high accuracy and cross-molecule comparability. The C 1s spectra of oxygenated aliphatic compounds display functional-group-specific shifts that increase with carbon oxidation state. Although these trends depart from gas- and solid-phase behavior, highlighting solvent and hydration effects, they correlate closely with calculated core-level orbital energies, providing a useful first-order predictor. We further resolve secondary, through-bond shifts over one and two bonds, the magnitudes of which depend sensitively on specific functional-group interactions (notably carboxylic acid and ketone motifs). Such element- and oxidation-state-specific structural information establishes the principles and reference data needed to build a predictive ESCAL database for liquid-phase structural and chemical analysis. The results will be contrasted with NMR studies.
{"title":"Electron spectroscopy for chemical analysis of liquids","authors":"Lukáš Tomaník, Florian Trinter, Petr Slavíček, Bernd Winter","doi":"10.1039/d5sc09061j","DOIUrl":"https://doi.org/10.1039/d5sc09061j","url":null,"abstract":"We present the first comprehensive, internally consistent analysis of core-level chemical shifts for aqueous-phase solutes using Electron Spectroscopy for Chemical Analysis of Liquids (ESCAL). An absolute binding-energy calibration enables high accuracy and cross-molecule comparability. The C 1s spectra of oxygenated aliphatic compounds display functional-group-specific shifts that increase with carbon oxidation state. Although these trends depart from gas- and solid-phase behavior, highlighting solvent and hydration effects, they correlate closely with calculated core-level orbital energies, providing a useful first-order predictor. We further resolve secondary, through-bond shifts over one and two bonds, the magnitudes of which depend sensitively on specific functional-group interactions (notably carboxylic acid and ketone motifs). Such element- and oxidation-state-specific structural information establishes the principles and reference data needed to build a predictive ESCAL database for liquid-phase structural and chemical analysis. The results will be contrasted with NMR studies.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"1 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116020","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}
The dissociative chemisorption of heteronuclear molecules is a cornerstone of heterogeneous catalysis. However, the ability to predict and control how rotational excitation governs reactivity has remained a fundamental challenge, lagging far behind the established understanding of vibrational effects. Here, through six-dimensional quantum dynamics simulations of HCl dissociation on bimetallic surfaces, we report unprecedented rotational enhancement, with efficacies reaching roughly 225 and 56 on Ag/Pt(111) and Cu/Pt(111), respectively. This dramatic effect originates from interfacial charge transfer driven by work function differences between the substrate and the supported metal monolayer (Φsub > Φsup), which generates a non-monotonic orientation-dependent potential energy landscape. We further establish a quantitative, predictive design principle, where rotational efficacy scales primarily with the work function difference and is systematically modulated by surface strain, with the highest efficacy achieved when a large work function difference is combined with compressive strain. This multivariate framework resolves a long standing dichotomy by demonstrating that rotational effects depend decisively on the global topography of the potential energy surface (PES), a mechanism fundamentally distinct from the transition state (TS) localized picture of vibrational promotion. The resulting quantum state control window enables rotation to act as a precise external knob for steering reactivity, advancing a new paradigm for the design of catalysts with targeted, state selective function.
{"title":"Harnessing work-function-driven rotational steering for quantum state control in HCl dissociation on bimetallic alloys","authors":"Tianhui Liu, Kaixin Meng","doi":"10.1039/d6sc00201c","DOIUrl":"https://doi.org/10.1039/d6sc00201c","url":null,"abstract":"The dissociative chemisorption of heteronuclear molecules is a cornerstone of heterogeneous catalysis. However, the ability to predict and control how rotational excitation governs reactivity has remained a fundamental challenge, lagging far behind the established understanding of vibrational effects. Here, through six-dimensional quantum dynamics simulations of HCl dissociation on bimetallic surfaces, we report unprecedented rotational enhancement, with efficacies reaching roughly 225 and 56 on Ag/Pt(111) and Cu/Pt(111), respectively. This dramatic effect originates from interfacial charge transfer driven by work function differences between the substrate and the supported metal monolayer (<em>Φ</em><small><sub>sub</sub></small> > <em>Φ</em><small><sub>sup</sub></small>), which generates a non-monotonic orientation-dependent potential energy landscape. We further establish a quantitative, predictive design principle, where rotational efficacy scales primarily with the work function difference and is systematically modulated by surface strain, with the highest efficacy achieved when a large work function difference is combined with compressive strain. This multivariate framework resolves a long standing dichotomy by demonstrating that rotational effects depend decisively on the global topography of the potential energy surface (PES), a mechanism fundamentally distinct from the transition state (TS) localized picture of vibrational promotion. The resulting quantum state control window enables rotation to act as a precise external knob for steering reactivity, advancing a new paradigm for the design of catalysts with targeted, state selective function.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"398 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116091","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}
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