The electrochemical oxidation of lignocellulose and plastic waste has been considered a clean and reliable strategy to produce feedstocks for various chemicals and fuels. In this study, we tackle the challenging selective oxidation of various lignocellulose and mixed biodegradable and bio-nondegradable plastics by targeting the oxidative cleavage of the specific C(OH)-C moiety. A monometallic Ni(O)O-H electrocatalyst was used for cellulose-based biomass, a series of lignin-based model complexes, lignin-derived secondary alcohols (KA oil), and mixed plastic waste valorization based on the catalyst’s O-H bond dissociation free energy. The catalyst performs remarkably well to selectively oxidize cellulose and lignin-based model complexes like HMF and PED with excellent yield at a higher current density of 100 mA cm-2. Mechanical insights into this reaction were obtained by in situ transmitted light spectroscopy and Raman measurements. The catalyst was also able to oxidize KA oil to adipic acid with 54% yield at a constant current electrolysis of 20 mA cm-2. Furthermore, Plastic waste precursors having a C(OH)-C bond were selectively oxidized using this catalyst, which was further expanded to mixed plastic waste upgradation resulting the generation of formate and acetate with Faradaic efficiencies of 66% and 74%, respectively, and 100% yield in terephthalic acid accompanied by the co-production of hydrogen.
木质纤维素和塑料废物的电化学氧化被认为是一种清洁可靠的生产各种化学品和燃料原料的策略。在这项研究中，我们通过针对特定的C(OH)-C片段的氧化裂解，解决了各种木质纤维素和混合生物可降解和生物不可降解塑料的具有挑战性的选择性氧化。采用单金属Ni(O)O- h电催化剂对纤维素基生物质、一系列木质素基模型配合物、木质素衍生仲醇（KA油）以及基于催化剂O- h键解离自由能的混合塑料垃圾进行催化。该催化剂在100ma cm-2的电流密度下，对纤维素和木质素为基础的模型配合物（如HMF和PED）具有良好的选择性氧化性能。通过原位透射光谱学和拉曼测量获得了对该反应的机械见解。在20 mA cm-2的恒流电解条件下，该催化剂还能将KA油氧化为己二酸，产率为54%。此外，利用该催化剂对具有C(OH)-C键的塑料废物前驱体进行选择性氧化，进一步扩展到混合塑料废物的升级，生成甲酸酯和乙酸酯，法拉第效率分别为66%和74%，对苯二甲酸收率为100%，并伴有氢气的协同生产。
{"title":"Selective Electrochemical Oxidation of Biomass and Waste Plastic at Higher Current Densities for Simultaneous Hydrogen Generation through Hybrid Water Electrolysis","authors":"Snehanjali Behera, Akanksha Negi, Gayatri Joshi, Chetansinh Chauhan, Dipak Suresh Kanthali, Saumyakanti Khatua, Biswajit Mondal","doi":"10.1039/d5sc04651c","DOIUrl":"https://doi.org/10.1039/d5sc04651c","url":null,"abstract":"The electrochemical oxidation of lignocellulose and plastic waste has been considered a clean and reliable strategy to produce feedstocks for various chemicals and fuels. In this study, we tackle the challenging selective oxidation of various lignocellulose and mixed biodegradable and bio-nondegradable plastics by targeting the oxidative cleavage of the specific C(OH)-C moiety. A monometallic Ni(O)O-H electrocatalyst was used for cellulose-based biomass, a series of lignin-based model complexes, lignin-derived secondary alcohols (KA oil), and mixed plastic waste valorization based on the catalyst’s O-H bond dissociation free energy. The catalyst performs remarkably well to selectively oxidize cellulose and lignin-based model complexes like HMF and PED with excellent yield at a higher current density of 100 mA cm-2. Mechanical insights into this reaction were obtained by in situ transmitted light spectroscopy and Raman measurements. The catalyst was also able to oxidize KA oil to adipic acid with 54% yield at a constant current electrolysis of 20 mA cm-2. Furthermore, Plastic waste precursors having a C(OH)-C bond were selectively oxidized using this catalyst, which was further expanded to mixed plastic waste upgradation resulting the generation of formate and acetate with Faradaic efficiencies of 66% and 74%, respectively, and 100% yield in terephthalic acid accompanied by the co-production of hydrogen.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"26 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145689094","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}
Jordi C. J. Hintzen, Kamiel D. Beckley, Emily L. Goldberg, George M. Burslem
Internally quenched fluorescent (IQF) peptides offer a powerful, modular platform for studying the enzymatic dynamics of post-translational modifications (PTMs) on lysine and arginine. Here we report a versatile IQF system that enables monitoring of PTM installation and removal via proteolytic cleavage by trypsin. This platform is compatible with both native PTMs and PTM mimetics, including acetylation, various other acylations, mono-/di-/trimethylation and citrullination across both histone and non-histone derived peptide substrates. Using synthetically accessible thialysine and thiaarginine analogs, we developed cysteine conjugation chemistries to access a wide array of PTM mimics, including novel reagents for lysine lactylation, β-hydroxybutyrylation and methyl-acetylation. Application of the system revealed distinct substrate preferences and site-specific activities for enzymes such as SIRT3, HDAC2, HDAC6, KDM3A, KDM4A and PAD4. Notably, the system uncovered enzymatic selectivity for acyl chain type and methylation state and demonstrated resistance of the emerging PTM methyl-acetyllysine to erasers. The system was also used to study the recently reported reversibility of acylation modifications by HDAC2 and 6 and is capable of evaluating enzymatic crosstalk between neighboring post-translational modifications. Our platform's adaptability and readout simplicity offer a generalizable chemical biology toolkit for PTM profiling, enzyme characterization, and inhibitor discovery.
{"title":"Internally quenched fluorescent peptides provide insights into underexplored and reversible post-translational modifications","authors":"Jordi C. J. Hintzen, Kamiel D. Beckley, Emily L. Goldberg, George M. Burslem","doi":"10.1039/d5sc08759g","DOIUrl":"https://doi.org/10.1039/d5sc08759g","url":null,"abstract":"Internally quenched fluorescent (IQF) peptides offer a powerful, modular platform for studying the enzymatic dynamics of post-translational modifications (PTMs) on lysine and arginine. Here we report a versatile IQF system that enables monitoring of PTM installation and removal <em>via</em> proteolytic cleavage by trypsin. This platform is compatible with both native PTMs and PTM mimetics, including acetylation, various other acylations, mono-/di-/trimethylation and citrullination across both histone and non-histone derived peptide substrates. Using synthetically accessible thialysine and thiaarginine analogs, we developed cysteine conjugation chemistries to access a wide array of PTM mimics, including novel reagents for lysine lactylation, β-hydroxybutyrylation and methyl-acetylation. Application of the system revealed distinct substrate preferences and site-specific activities for enzymes such as SIRT3, HDAC2, HDAC6, KDM3A, KDM4A and PAD4. Notably, the system uncovered enzymatic selectivity for acyl chain type and methylation state and demonstrated resistance of the emerging PTM methyl-acetyllysine to erasers. The system was also used to study the recently reported reversibility of acylation modifications by HDAC2 and 6 and is capable of evaluating enzymatic crosstalk between neighboring post-translational modifications. Our platform's adaptability and readout simplicity offer a generalizable chemical biology toolkit for PTM profiling, enzyme characterization, and inhibitor discovery.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"22 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145690117","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}
Simin Jiang, Yanmei He, Guo-Xi Yang, Tönu Pullerits, Shi-Jian Su
Organic luminescent narrowband emitters have emerged as promising candidates for wide-color-gamut displays. However, the comprehensive photo-induced structural and vibrational dynamics responsible for the spectral broadening remain poorly understood. In this study, ultrafast spectroscopy is employed to elucidate the excited state dynamics of a sulfone-embedded narrowband emitter, 2tCPD. An intrinsic dual emission, which originates from a reversible conformational transition between boat and chair structures on a timescale of ~ 100 ps, is revealed. In aromatic toluene solution, the metastable chair conformation is stabilized by forming a sandwichlike toluene-2tCPD-toluene complex through the weak π-π interaction, thereby switching the dominant emission to the chair form. Further, the direct observation of coherent oscillations enables the visualization of vibronic coupling in 2tCPD, where the key vibrational mode at 180 cm -1 oscillates along the excited-state potential energy surface of boat conformation. This mode, which involves bending vibration of sulfone and out-of-plane bending of carbonyl and peripheral phenyl groups, mainly drives the structural reorganization during the electronic transition. These findings provide mechanistic insights into conformation-dependent emission in narrowband emitters and underscore the crucial vibrational information in guiding the molecular design toward high color-purity organic fluorophores.
有机发光窄带发射器已成为宽色域显示的有希望的候选者。然而，全面的光致结构和振动动力学负责光谱展宽仍然知之甚少。在这项研究中，采用超快光谱来阐明嵌入砜的窄带发射极2tCPD的激发态动力学。揭示了在~ 100 ps的时间尺度上，船形和椅形结构之间的可逆构象转变产生的本征双发射。在芳香甲苯溶液中，通过弱π-π相互作用形成三明治状的甲苯- 2tcpd -甲苯配合物，从而将主导发射转换为椅形构象，从而稳定了亚稳态椅子构象。此外，相干振荡的直接观测使2tCPD中的振动耦合可视化，其中180 cm -1处的关键振动模式沿着船形构象的激发态势能面振荡。这种模式涉及到砜的弯曲振动以及羰基和外围苯基的面外弯曲，主要驱动电子跃迁过程中的结构重组。这些发现为窄带发射器的构象依赖性发射提供了机制见解，并强调了指导高颜色纯度有机荧光团分子设计的关键振动信息。
{"title":"Dual Conformational Emission and Vibrational Coherence in Sulfone-Embedded Narrowband Emitter","authors":"Simin Jiang, Yanmei He, Guo-Xi Yang, Tönu Pullerits, Shi-Jian Su","doi":"10.1039/d5sc07981k","DOIUrl":"https://doi.org/10.1039/d5sc07981k","url":null,"abstract":"Organic luminescent narrowband emitters have emerged as promising candidates for wide-color-gamut displays. However, the comprehensive photo-induced structural and vibrational dynamics responsible for the spectral broadening remain poorly understood. In this study, ultrafast spectroscopy is employed to elucidate the excited state dynamics of a sulfone-embedded narrowband emitter, 2tCPD. An intrinsic dual emission, which originates from a reversible conformational transition between boat and chair structures on a timescale of ~ 100 ps, is revealed. In aromatic toluene solution, the metastable chair conformation is stabilized by forming a sandwichlike toluene-2tCPD-toluene complex through the weak π-π interaction, thereby switching the dominant emission to the chair form. Further, the direct observation of coherent oscillations enables the visualization of vibronic coupling in 2tCPD, where the key vibrational mode at 180 cm -1 oscillates along the excited-state potential energy surface of boat conformation. This mode, which involves bending vibration of sulfone and out-of-plane bending of carbonyl and peripheral phenyl groups, mainly drives the structural reorganization during the electronic transition. These findings provide mechanistic insights into conformation-dependent emission in narrowband emitters and underscore the crucial vibrational information in guiding the molecular design toward high color-purity organic fluorophores.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"20 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145690092","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}
We predict that Al4C3 adopts a cubic, anti‑spinel–type structure (Al4C3-II) between 7 and 33 GPa, peaking in stability relative to other Al4C3 structures at 26 GPa. At ambient pressure, Al4C3-II is mechanically robust, with a bulk modulus of 176 GPa and a Vickers hardness of around 30 GPa. Beyond Al4C3-II, we identify three additional post-spinel phases appearing in the Al4C3 phase diagram, including an anti-Th3P4-type at 140 GPa. The clear enthalpy differences under pressure leave little doubt that the known trigonal R‑3m ground state of Al4C3 will undergo multiple phase transitions. The accessible pressure window for spinel-type Al4C3-II is easily accessible in both laser-heated diamond anvil cell and large-volume multi-anvil cell experiments. We therefore encourage experimental exploration of the Al-C system at high pressure.
{"title":"Spinel-type Al4C3 Attainable Above 7 GPaand More High-Pressure Phases of Al4C3","authors":"Mitchell Falgoust, Peter Kroll","doi":"10.1039/d5sc06382e","DOIUrl":"https://doi.org/10.1039/d5sc06382e","url":null,"abstract":"We predict that Al<small><sub>4</sub></small>C<small><sub>3</sub></small> adopts a cubic, anti‑spinel–type structure (Al<small><sub>4</sub></small>C<small><sub>3</sub></small>-II) between 7 and 33 GPa, peaking in stability relative to other Al<small><sub>4</sub></small>C<small><sub>3</sub></small> structures at 26 GPa. At ambient pressure, Al<small><sub>4</sub></small>C<small><sub>3</sub></small>-II is mechanically robust, with a bulk modulus of 176 GPa and a Vickers hardness of around 30 GPa. Beyond Al<small><sub>4</sub></small>C<small><sub>3</sub></small>-II, we identify three additional post-spinel phases appearing in the Al<small><sub>4</sub></small>C<small><sub>3</sub></small> phase diagram, including an anti-Th<small><sub>3</sub></small>P<small><sub>4</sub></small>-type at 140 GPa. The clear enthalpy differences under pressure leave little doubt that the known trigonal R‑3m ground state of Al<small><sub>4</sub></small>C<small><sub>3</sub></small> will undergo multiple phase transitions. The accessible pressure window for spinel-type Al<small><sub>4</sub></small>C<small><sub>3</sub></small>-II is easily accessible in both laser-heated diamond anvil cell and large-volume multi-anvil cell experiments. We therefore encourage experimental exploration of the Al-C system at high pressure.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"3 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145690093","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}
E. Ghimire, I. S. Appen, C. A. Lindberg, L. Blagitz de Abreu e Silva, S. J. Rowan
Soft materials can be considered trainable when their functional/mechanical properties can be systematcially improved upon exposure to repeated external environmental stresses, such as mechanical loads. One class of material that has the potential to be trainable is dynamic liquid crystal elastomers (dLCEs), which are lightly crosslinked polymer networks that contain both anisotropic liquid crystalline molecules (mesogens) and dynamic bonds. In this work, the trainability of dLCEs is studied by utilizing the mechanical adaptability of mesogenic units in combination with reprogrammability and reconfigurability enabled by the dynamic bonds. The effects of dynamic bond strength on the thermomechanical and liquid crystalline properties of LCEs were studied by synthesizing a series of aza-Michael based dynamic LCEs by incorporating diamine crosslinkers containing either no dynamic bonds, disulfide bonds, or diselenide bonds. Compared to the two other systems, the LCE containing diselenide bonds exhibited significantly higher toughness at room temperature. The effects of mechanical strain on the trainability of the films was studied under slightly elevated temperatures, where diselenide-containing dLCEs exhibited enhanced actuation and stiffer mechanical properties with higher strain levels. Moreover, using the combined thermal and mechanical training protocols, spiral actuators fabricated from the dLCEs demonstrated self-sustained motion upon heating them above their nematic to isotropic transition temperatures. In addition, retrainability was demonstrated in diselenide LCEs by generating two distinct actuator shapes from a single sample, where blue light was used to spatially control the effective regions of training. Overall, this study examines how the strength of dynamic bonds influences the properties and trainability of LCEs and how functional responses can be tailored by applying different training protocols.
{"title":"Impact of dynamic bond strength on the training of liquid crystal elastomers","authors":"E. Ghimire, I. S. Appen, C. A. Lindberg, L. Blagitz de Abreu e Silva, S. J. Rowan","doi":"10.1039/d5sc07491f","DOIUrl":"https://doi.org/10.1039/d5sc07491f","url":null,"abstract":"Soft materials can be considered trainable when their functional/mechanical properties can be systematcially improved upon exposure to repeated external environmental stresses, such as mechanical loads. One class of material that has the potential to be trainable is dynamic liquid crystal elastomers (dLCEs), which are lightly crosslinked polymer networks that contain both anisotropic liquid crystalline molecules (mesogens) and dynamic bonds. In this work, the trainability of dLCEs is studied by utilizing the mechanical adaptability of mesogenic units in combination with reprogrammability and reconfigurability enabled by the dynamic bonds. The effects of dynamic bond strength on the thermomechanical and liquid crystalline properties of LCEs were studied by synthesizing a series of aza-Michael based dynamic LCEs by incorporating diamine crosslinkers containing either no dynamic bonds, disulfide bonds, or diselenide bonds. Compared to the two other systems, the LCE containing diselenide bonds exhibited significantly higher toughness at room temperature. The effects of mechanical strain on the trainability of the films was studied under slightly elevated temperatures, where diselenide-containing dLCEs exhibited enhanced actuation and stiffer mechanical properties with higher strain levels. Moreover, using the combined thermal and mechanical training protocols, spiral actuators fabricated from the dLCEs demonstrated self-sustained motion upon heating them above their nematic to isotropic transition temperatures. In addition, retrainability was demonstrated in diselenide LCEs by generating two distinct actuator shapes from a single sample, where blue light was used to spatially control the effective regions of training. Overall, this study examines how the strength of dynamic bonds influences the properties and trainability of LCEs and how functional responses can be tailored by applying different training protocols.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"30 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145690114","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}
Lanthanide luminescence surrounds us in everyday life and is essential for cutting-edge technological and healthcare applications. In 2013, we published a minireview in Chemical Science (Chem. Sci., 2013, 4, 1939–1949, https://doi.org/10.1039/C3SC22126A) that was focused on the latest innovations and less-known aspects of lanthanide luminescence in applications such as biological imaging, sensing and therapy, security inks and anti-counterfeiting tags, luminescent probes and sensors, and solar energy conversion. Herein, a discussion of the progress of this field is provided with support of the most recent examples in the areas of circularly polarized luminescence, nanothermometry and multiplexed biological imaging in the extended second near-infrared window (NIR-II, 1000–3000 nm).
{"title":"A reflection on “Intriguing aspects of lanthanide luminescence”","authors":"Svetlana V. Eliseeva","doi":"10.1039/d5sc90251g","DOIUrl":"https://doi.org/10.1039/d5sc90251g","url":null,"abstract":"Lanthanide luminescence surrounds us in everyday life and is essential for cutting-edge technological and healthcare applications. In 2013, we published a minireview in <em>Chemical Science</em> (<em>Chem. Sci.</em>, 2013, <strong>4</strong>, 1939–1949, https://doi.org/10.1039/C3SC22126A) that was focused on the latest innovations and less-known aspects of lanthanide luminescence in applications such as biological imaging, sensing and therapy, security inks and anti-counterfeiting tags, luminescent probes and sensors, and solar energy conversion. Herein, a discussion of the progress of this field is provided with support of the most recent examples in the areas of circularly polarized luminescence, nanothermometry and multiplexed biological imaging in the extended second near-infrared window (NIR-II, 1000–3000 nm).","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"19 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145674542","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}
Leonardo Tacconi, Shubham Bisht, Alberto Cini, Mauro Perfetti, Tomas Orlando, Maria Fittipaldi, Michael Shatruk, Roberta Sessoli
Molecular antiferromagnetic triangles are a convenient platform to study the effect of an electric field on the magnetic exchange interactions. However, such effects are typically hard to detect, especially in systems with weak spin–orbit coupling. In this work, an asymmetric μ₃-oxo-centered Cr₃ triangle was synthesized and structurally characterized as a non-centrosymmetric molecular crystal suitable for probing Spin Electric Coupling (SEC). A combination of single-crystal magnetometry, cantilever torque magnetometry, and continuous-wave electron paramagnetic resonance (EPR) allowed precise determination of the spin Hamiltonian, including the small Dzyaloshinskii–Moriya interaction. Electric-field-modulated EPR (EFM-EPR) experiments provided the first direct observation of SEC in a CrIII-based complex, revealing measurable electric-field effects on the single-ion g tensor and setting an upper bound for the SEC influence on magnetic exchange interactions. These findings demonstrate the exceptional sensitivity of EFM-EPR spectroscopy for quantifying SEC and highlight the crucial role of molecular symmetry and ligand environment in enabling electric control of spin states, thus advancing the rational design of molecular systems for quantum technologies.
{"title":"Sensitive Detection of Spin-Electric Coupling in a Cr3 Antiferromagnetic Triangle","authors":"Leonardo Tacconi, Shubham Bisht, Alberto Cini, Mauro Perfetti, Tomas Orlando, Maria Fittipaldi, Michael Shatruk, Roberta Sessoli","doi":"10.1039/d5sc08012f","DOIUrl":"https://doi.org/10.1039/d5sc08012f","url":null,"abstract":"Molecular antiferromagnetic triangles are a convenient platform to study the effect of an electric field on the magnetic exchange interactions. However, such effects are typically hard to detect, especially in systems with weak spin–orbit coupling. In this work, an asymmetric μ₃-oxo-centered Cr₃ triangle was synthesized and structurally characterized as a non-centrosymmetric molecular crystal suitable for probing Spin Electric Coupling (SEC). A combination of single-crystal magnetometry, cantilever torque magnetometry, and continuous-wave electron paramagnetic resonance (EPR) allowed precise determination of the spin Hamiltonian, including the small Dzyaloshinskii–Moriya interaction. Electric-field-modulated EPR (EFM-EPR) experiments provided the first direct observation of SEC in a Cr<small><sup>III</sup></small>-based complex, revealing measurable electric-field effects on the single-ion <em>g</em> tensor and setting an upper bound for the SEC influence on magnetic exchange interactions. These findings demonstrate the exceptional sensitivity of EFM-EPR spectroscopy for quantifying SEC and highlight the crucial role of molecular symmetry and ligand environment in enabling electric control of spin states, thus advancing the rational design of molecular systems for quantum technologies.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"29 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145674544","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}
Wenhao Li, Mengyao Niu, Yi-Yun Zhu, Man Zhang, Haoyu Gao, Xin-Chao Zhang, Bo Yang, Donghui Wei, Xuenian Chen
The precise modulation of photophysical properties and elucidation of fluorescence mechanisms are paramount challenges for organic optoelectronic materials. Herein, we present a strategy for achieving robust fluorescence tuning from blue (462 nm) to near-infrared (677 nm) by accurately positioning electron-withdrawing groups relative to phenothiazine donors in cyanobenzene-phenothiazine derivatives, as well as adjusting molecular conformations, noncovalent interactions, and interplays between aggregation. Crystallographic analysis and theoretical calculations revealed that 4-phenothiazino-isophthaliconitrile (4-PTZIPN) achieves both the highest solid-state fluorescence quantum yield (39.7%) and the longest fluorescence lifetime (1.26 μs) among the series, which is attributed to J-aggregation sustained by multiple intermolecular interactions. The conformation and rigidified non-canonical J-aggregation suppressed non-radiative decay pathways, leading to a significant increase in the quantum yield of 2,4,6-triphenothiazinobenzonitrile (1CN3PTZ) and a substantial extension of its fluorescence lifetime from 761.47 ns in the solid-state to 1.10 μs. Notably, 2,4,6-triphenothiazino-isophthaliconitrile (2CN3PTZ) demonstrates a pronounced bathochromic shift to 677 nm, driven by its helical columnar packing, which is orchestrated by cooperative π-π, dipole-dipole, and C-H···S interactions. This work not only elucidated the structure-photophysical relationships within the cyano-phenothiazine system but also provided a conformation-aggregation dual regulation strategy for the design of innovative organic optoelectronic materials through molecular engineering.
{"title":"Regulation and Mechanisms of Full-Visible-Spectrum Emission in Solid and Liquid States for D-π-A Cyanobenzene-Phenothiazine Fluorescent Molecules","authors":"Wenhao Li, Mengyao Niu, Yi-Yun Zhu, Man Zhang, Haoyu Gao, Xin-Chao Zhang, Bo Yang, Donghui Wei, Xuenian Chen","doi":"10.1039/d5sc06095h","DOIUrl":"https://doi.org/10.1039/d5sc06095h","url":null,"abstract":"The precise modulation of photophysical properties and elucidation of fluorescence mechanisms are paramount challenges for organic optoelectronic materials. Herein, we present a strategy for achieving robust fluorescence tuning from blue (462 nm) to near-infrared (677 nm) by accurately positioning electron-withdrawing groups relative to phenothiazine donors in cyanobenzene-phenothiazine derivatives, as well as adjusting molecular conformations, noncovalent interactions, and interplays between aggregation. Crystallographic analysis and theoretical calculations revealed that 4-phenothiazino-isophthaliconitrile (4-PTZIPN) achieves both the highest solid-state fluorescence quantum yield (39.7%) and the longest fluorescence lifetime (1.26 μs) among the series, which is attributed to J-aggregation sustained by multiple intermolecular interactions. The conformation and rigidified non-canonical J-aggregation suppressed non-radiative decay pathways, leading to a significant increase in the quantum yield of 2,4,6-triphenothiazinobenzonitrile (1CN3PTZ) and a substantial extension of its fluorescence lifetime from 761.47 ns in the solid-state to 1.10 μs. Notably, 2,4,6-triphenothiazino-isophthaliconitrile (2CN3PTZ) demonstrates a pronounced bathochromic shift to 677 nm, driven by its helical columnar packing, which is orchestrated by cooperative π-π, dipole-dipole, and C-H···S interactions. This work not only elucidated the structure-photophysical relationships within the cyano-phenothiazine system but also provided a conformation-aggregation dual regulation strategy for the design of innovative organic optoelectronic materials through molecular engineering.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"115 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145697095","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}
Yang Sun, Fan Yang, Kexin Wei, Siyuan Sun, Li Sun, Junpu An, Chunhui Yu, Qing Guo, Conghan Zhang, Guang Ma, Hongchen Liu, Yongfeng Li
Constructing an asymmetric charge distribution and built-in electric field (BIEF) has proven to be an effective strategy for enhancing the catalytic performance of both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) catalysts. Herein, a Mo-doped Ni/WO3 heterojunction catalyst was immobilized on Ni foam for enhancing the performance of the HER and OER. The constructed Ni/WO3 heterointerface facilitates electron transport, while the incorporation of Mo further amplifies charge asymmetry in the interfacial region. The optimized Mo3–Ni/WO3 catalyst exhibits excellent performance, requiring only 13 mV and 328 mV overpotential to reach current densities of 10 and 100 mA cm−2 for the HER and OER, respectively. Besides, it maintains stable overall water splitting performance at 100 mA cm−2 for 90 h. The asymmetric distribution of Ni/WO3 interfacial charge is promoted and electron transport is enhanced by Mo doping. Theoretical results show that element doping in the heterostructure turns W sites into additional adsorption centers, optimizing the energetics of H* adsorption during the HER. Mo doping reduces the work function (φ) of Mo3–Ni/WO3, promoting efficient electron transfer and lowering the energy barrier for intermediate formation, thereby enhancing OER activity. This strategic modulation of charge asymmetry in heterojunction architectures provides a new approach for the rational design of high-performance bifunctional electrocatalysts.
构建不对称电荷分布和内置电场（BIEF）是提高析氢反应（HER）和析氧反应（OER）催化剂催化性能的有效策略。本文将mo掺杂的Ni/WO3异质结催化剂固定在Ni泡沫上，以提高HER和OER的性能。构建的Ni/WO3异质界面有利于电子的传递，而Mo的加入进一步放大了界面区域的电荷不对称性。优化后的Mo3-Ni /WO3催化剂表现出优异的性能，仅需要13 mV和328 mV过电位，HER和OER的电流密度分别达到10和100 mA cm−2。同时，在100 mA cm−2条件下，在90 h内保持了稳定的整体水分解性能。Mo的掺杂促进了Ni/WO3界面电荷的不对称分布，增强了电子传递。理论结果表明，异质结构中的元素掺杂使W位成为附加的吸附中心，从而优化了氢离子吸附过程中的能量学。Mo掺杂降低了Mo3-Ni /WO3的功函数（φ），促进了有效的电子转移，降低了中间体形成的能垒，从而提高了OER活性。这种对异质结结构中电荷不对称的战略性调制为高性能双功能电催化剂的合理设计提供了新的途径。
{"title":"Construction of a built-in electric field in Mo-doped Ni/WO3 to enhance asymmetric charge distribution for efficient overall water splitting","authors":"Yang Sun, Fan Yang, Kexin Wei, Siyuan Sun, Li Sun, Junpu An, Chunhui Yu, Qing Guo, Conghan Zhang, Guang Ma, Hongchen Liu, Yongfeng Li","doi":"10.1039/d5sc06522d","DOIUrl":"https://doi.org/10.1039/d5sc06522d","url":null,"abstract":"Constructing an asymmetric charge distribution and built-in electric field (BIEF) has proven to be an effective strategy for enhancing the catalytic performance of both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) catalysts. Herein, a Mo-doped Ni/WO<small><sub>3</sub></small> heterojunction catalyst was immobilized on Ni foam for enhancing the performance of the HER and OER. The constructed Ni/WO<small><sub>3</sub></small> heterointerface facilitates electron transport, while the incorporation of Mo further amplifies charge asymmetry in the interfacial region. The optimized Mo<small><sub>3</sub></small>–Ni/WO<small><sub>3</sub></small> catalyst exhibits excellent performance, requiring only 13 mV and 328 mV overpotential to reach current densities of 10 and 100 mA cm<small><sup>−2</sup></small> for the HER and OER, respectively. Besides, it maintains stable overall water splitting performance at 100 mA cm<small><sup>−2</sup></small> for 90 h. The asymmetric distribution of Ni/WO<small><sub>3</sub></small> interfacial charge is promoted and electron transport is enhanced by Mo doping. Theoretical results show that element doping in the heterostructure turns W sites into additional adsorption centers, optimizing the energetics of H* adsorption during the HER. Mo doping reduces the work function (<em>φ</em>) of Mo<small><sub>3</sub></small>–Ni/WO<small><sub>3</sub></small>, promoting efficient electron transfer and lowering the energy barrier for intermediate formation, thereby enhancing OER activity. This strategic modulation of charge asymmetry in heterojunction architectures provides a new approach for the rational design of high-performance bifunctional electrocatalysts.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"8 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145689095","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}
Rising invasive fungal infections necessitate the rapid development of new, highly efficient antifungal platforms with proven biocompatibility. We report a new class of photoactivated antifungal polymers that incorporate cationic, hydrophobic, and hydrophilic functionalities with a highly efficient photosensitizer. Our approach relies on the use of an acrylate-functionalized zinc(II) tetraphenylporphyrin (acryl-ZnTPP) monomer, that performs a dual role: it acts as both the photocatalyst for PET-RAFT polymerization, enabling controlled polymerization, and as an embedded photosensitizer capable of generating reactive oxygen species (ROS) upon light irradiation. Under green or red-light exposure, these polymers show 4–8-fold lower minimum inhibitory concentrations (MICs) and up to 8-fold lower minimum fungicidal concentrations (MFCs) against diverse Candida species compared with control polymers (i.e., without acryl-ZnTPP). Hemolysis assays confirm excellent hemocompatibility of these polymers containing ZnTPP as photosensitizer. This approach offers tunable, light-enhanced antifungal activity, providing a promising strategy to combat fungal infections.
{"title":"Photoactivated Antifungal Polymers Prepared by PET-RAFT Polymerization","authors":"Hatu Gmedhin, Md Aquib, Dr Nathaniel Corrigan, Megan Lenardon, Cyrille Boyer","doi":"10.1039/d5sc08534a","DOIUrl":"https://doi.org/10.1039/d5sc08534a","url":null,"abstract":"Rising invasive fungal infections necessitate the rapid development of new, highly efficient antifungal platforms with proven biocompatibility. We report a new class of photoactivated antifungal polymers that incorporate cationic, hydrophobic, and hydrophilic functionalities with a highly efficient photosensitizer. Our approach relies on the use of an acrylate-functionalized zinc(II) tetraphenylporphyrin (acryl-ZnTPP) monomer, that performs a dual role: it acts as both the photocatalyst for PET-RAFT polymerization, enabling controlled polymerization, and as an embedded photosensitizer capable of generating reactive oxygen species (ROS) upon light irradiation. Under green or red-light exposure, these polymers show 4–8-fold lower minimum inhibitory concentrations (MICs) and up to 8-fold lower minimum fungicidal concentrations (MFCs) against diverse <em>Candida</em> species compared with control polymers (i.e., without acryl-ZnTPP). Hemolysis assays confirm excellent hemocompatibility of these polymers containing ZnTPP as photosensitizer. This approach offers tunable, light-enhanced antifungal activity, providing a promising strategy to combat fungal infections.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"32 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145664875","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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