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Dual Antifreeze and Sustained Release Cellulose Nanocrystal-Humic Acid Nanocomposite Hydrogel for Soilless Cultivation. 双重防冻缓释纤维素纳米晶-腐植酸纳米复合水凝胶无土栽培。
IF 5.4 2区 化学 Q1 BIOCHEMISTRY & MOLECULAR BIOLOGY Pub Date : 2026-02-09 Epub Date: 2026-01-25 DOI: 10.1021/acs.biomac.5c02444
Pengxiao Liu, Kai Wei, Yong Liu, Liangjiu Bai, Hou Chen, Wenxiang Wang, Lixia Yang, Huawei Yang, Donglei Wei

Soilless cultivation relies on hydrogel matrices for water and nutrient management, but conventional hydrogels lose performance at low temperature and show unstable sustained release. Here this study develops an antifreeze sustained-release hydrogel (P-GTCH) that integrates l-proline (L-P) with a humic-acid-modified cellulose nanocrystal nanocomposite (CNCs-HA) for nanoenabled controlled release. L-P suppresses ice nucleation via hydrogen bonding, while CNCs-HA boosts HA loading and enables controlled transport within the cross-linked network. HA shows slow, continuous release governed by Fickian diffusion, achieving 96.7% cumulative release over 12 days at 0 °C and mitigating poor fertilizer release in cold environments. P-GTCH provides mechanical support for plant roots, and the synergistic effects of L-P and HA maintain lettuce germination above 86% at 0 °C while promoting root growth. This biobased, biodegradable platform is scalable for low-temperature soilless cultivation.

无土栽培依靠水凝胶基质进行水分和养分管理,但传统的水凝胶在低温下失去性能,并且表现出不稳定的持续释放。本研究开发了一种抗冻缓释水凝胶(P-GTCH),它将l-脯氨酸(L-P)与腐植酸修饰的纤维素纳米晶体纳米复合材料(CNCs-HA)结合在一起,实现纳米控释。L-P通过氢键抑制冰核,而cnc -HA增加HA负载,并在交联网络中控制运输。HA表现出受菲克扩散控制的缓慢连续释放,在0℃条件下12 d内累计释放量达到96.7%,缓解了低温环境下肥料释放不良的情况。P-GTCH为植物根系提供机械支持,L-P和HA的协同作用在促进根系生长的同时,在0℃条件下保持生菜萌发率在86%以上。这种生物基,可生物降解的平台是可扩展的低温无土栽培。
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引用次数: 0
Tyrosinase Cross-Linked PEG Hydrogels with DAT and DATT as Artificial Substrates: Design, Structure, and Functions. 酪氨酸酶交联聚乙二醇水凝胶与DAT和DATT作为人工底物:设计,结构和功能。
IF 5.4 2区 化学 Q1 BIOCHEMISTRY & MOLECULAR BIOLOGY Pub Date : 2026-02-09 Epub Date: 2026-01-26 DOI: 10.1021/acs.biomac.5c01929
Miroslava Racheva, Javier Basalo Lourido, Enise Ece Gurdal, Martin Herbst, Seyhmus Bayar, Daniela Radzik, Elen Bähr, Constanze Zwies, Axel T Neffe, Markus Pietzsch, Andreas Lendlein, Christian Wischke

Enzymes such as oxidases are sustainable tools for hydrogel synthesis, but complex competing reactions have limited the mechanistic understanding and biomedical applications of these materials. Guided by molecular docking and MM-GBSA calculations, we identified two artificial substrates, desaminotyrosine (DAT) and desaminotyrosyltyrosine (DATT), that were experimentally more efficiently converted by mushroom tyrosinase (mTyr) than the natural substrate tyrosine. These substrates were used to synthesize hydrogels from DAT/DATT-functionalized star-shaped oligoethylene glycol (sOEG). Model reactions elucidated the chemical nature and functionality of the hydrogel netpoints. Material properties were systematically investigated depending on sOEG molecular weight (5, 10, 20 kDa), substrate type, and mTyr concentration. Functional mesh sizes and controlled release functions were investigated with fluorescent dextrans (4-500 kDa) and heparin. Cell culture studies with L929 fibroblasts and THP-1 monocytes suggested inertness of the material. These findings provide fundamental insight into mTyr-catalyzed hydrogel formation and support further exploration for in situ hydrogel synthesis.

氧化酶等酶是水凝胶合成的可持续工具,但复杂的竞争反应限制了这些材料的机理理解和生物医学应用。在分子对接和MM-GBSA计算的指导下,我们确定了两种人工底物,去氨基酪氨酸(DAT)和去氨基酪氨酸基化酪氨酸(DATT),它们在蘑菇酪氨酸酶(mTyr)中的转化效率高于天然底物酪氨酸。这些底物被用于从DAT/DAT功能化的星形低聚乙二醇(sOEG)合成水凝胶。模型反应阐明了水凝胶网点的化学性质和功能。根据sOEG分子量(5,10,20 kDa),底物类型和mTyr浓度系统地研究了材料的性能。用荧光右旋糖酐(4-500 kDa)和肝素研究功能网孔大小和控释功能。L929成纤维细胞和THP-1单核细胞的细胞培养研究表明材料是惰性的。这些发现为mtyr催化水凝胶的形成提供了基本的见解,并为进一步探索原位水凝胶合成提供了支持。
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引用次数: 0
High-Performance Gelatin Eutectogel Dressing for Infection Prevention and Electrical Stimulation-Assisted Wound Therapy. 用于预防感染和电刺激辅助伤口治疗的高性能明胶共聚敷料。
IF 5.4 2区 化学 Q1 BIOCHEMISTRY & MOLECULAR BIOLOGY Pub Date : 2026-02-09 Epub Date: 2026-01-27 DOI: 10.1021/acs.biomac.5c02202
Pingping Liu, Qinghao Zhen, Jiawei Yang, Feng-Lai Yuan, Ruisheng Xu, Xi Chen, Dongjian Shi

Conventional gelatin-based hydrogel wound dressings suffer from weak mechanical properties, poor temperature stability, and slow wound healing, limiting their practical application. Herein, a novel multifunctional gelatin-based eutectogel dressing (PGEWD) was developed via a multicross-linked network constructed from porcine skin gelatin (PG), ε-polylysine (EPL), waterborne polyurethane (WPU), and deep eutectic solvent (DES, choline chloride-glycerol). DES induced PG molecular chain rearrangement to form a dense triple-helix structure. With the optimal formulation of 10% EPL, 0.3% WPU, and 10 min DES immersion, the PGE0.1W0.3D10 composite exhibited high tensile strength (290 kPa), intrinsic conductivity (0.798 mS/cm), wide thermal tolerance (-20 to 60 °C), and ∼100% antibacterial activity. Combined with electrical stimulation (ES), it accelerated wound healing with ∼94.47% closure rate in 14 days. This study provides a versatile strategy for designing multifunctional gelatin-based wound dressings with significant potential in wound regeneration.

传统明胶基水凝胶伤口敷料存在力学性能弱、温度稳定性差、伤口愈合缓慢等问题,限制了其实际应用。以猪皮明胶(PG)、聚赖氨酸(EPL)、水性聚氨酯(WPU)和深层共晶溶剂(DES、氯化胆碱-甘油)为原料,构建了一种新型多功能明胶基共晶敷料(PGEWD)。DES诱导PG分子链重排,形成致密的三螺旋结构。在最佳配方为10% EPL、0.3% WPU和10 min DES浸泡的情况下,pge0.1 w0.3 3d10复合材料具有高拉伸强度(290 kPa)、固有电导率(0.798 mS/cm)、宽耐热性(-20 ~ 60°C)和~ 100%的抗菌活性。结合电刺激(ES), 14天内伤口愈合率达到94.47%。该研究为设计多功能明胶基伤口敷料提供了一种多用途的策略,在伤口再生方面具有重要的潜力。
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引用次数: 0
Crowding-Induced Liquid-Liquid Phase Separation in the ATP-Binding ACC1-13K8 Peptide Leads to a Distinct Amyloid Variant. 拥挤诱导的液-液相分离在atp结合的ACC1-13K8肽中导致不同的淀粉样蛋白变异。
IF 5.4 2区 化学 Q1 BIOCHEMISTRY & MOLECULAR BIOLOGY Pub Date : 2026-02-09 Epub Date: 2026-01-27 DOI: 10.1021/acs.biomac.5c02213
Robert Dec, Wojciech Dzwolak, Roland Winter

Liquid-liquid phase separation (LLPS) is involved in both the self-assembly of vital cellular organelles and the disease-associated protein misfolding, where LLPS precedes a liquid-solid phase transition (LSPT) leading to amyloid aggregates. Chimeric ACC1-13Kn peptides are insightful models to study coupled LLPS/LSPT processes triggered by ATP-binding. Here, we investigated the impact of macromolecular crowding on the selection of the aggregation pathway in the ACC1-13K8-ATP system. While it has been previously shown that peptides with relatively short oligolysine segments (K16 and shorter) skip the LLPS stage on their pathway to amyloid fibrils, we show here that concentrated polyethylene glycol (PEG), mimicking intracellular crowding conditions, induces prior formation of liquid droplets that subsequently facilitate fibril formation. The influence of PEG contrasts with the behavior of other types of macromolecular crowding agents, Dextran and Ficoll, which accelerate aggregation without a detectable LLPS phase, and that of serum albumin, which prolongs the nucleation phase. In the presence of PEG-induced macromolecular crowding, the fibrillization in the ACC1-13K8-ATP system appears to reach a maximal rate limited by diffusion coupled to the conformational dynamics of the polypeptide chains within the droplets. Importantly, the ACC1-13K8-ATP fibrils formed in the presence of PEG are distinct from those of the ACC1-13K8-ATP amyloid formed in the absence of crowding in terms of their infrared characteristics, morphological features, and overall stability. Our findings suggest that macromolecular crowding can switch between kinetically and thermodynamically favored amyloid polymorphs and that the chemical properties of the crowding agents are key factors in their impact on protein aggregation processes. The results are discussed in the context of the mechanisms of LLPS-dependent protein misfolding and amyloid formation.

液-液相分离(LLPS)涉及重要细胞器的自组装和疾病相关蛋白的错误折叠,其中LLPS先于液-固相转变(LSPT)导致淀粉样蛋白聚集。嵌合ACC1-13Kn肽是研究atp结合引发的LLPS/LSPT偶联过程的有效模型。在这里,我们研究了大分子拥挤对ACC1-13K8-ATP系统中聚集途径选择的影响。虽然之前已经证明具有相对较短的低聚赖氨酸片段(K16或更短)的肽在其通往淀粉样蛋白原纤维的途径中跳过LLPS阶段,但我们在这里展示了浓缩聚乙二醇(PEG),模拟细胞内拥挤条件,诱导液滴的预先形成,随后促进原纤维的形成。聚乙二醇的影响与其他类型的大分子拥挤剂,葡聚糖和Ficoll的行为形成对比,它们加速聚集,但没有检测到LLPS期,血清白蛋白的影响则延长成核期。在聚乙二醇诱导的大分子拥挤中,ACC1-13K8-ATP体系的纤溶化似乎达到了最大速率,这受到液滴内多肽链的构象动力学和扩散耦合的限制。重要的是,在PEG存在下形成的ACC1-13K8-ATP原纤维与在没有拥挤的情况下形成的ACC1-13K8-ATP淀粉样蛋白在红外特征、形态特征和整体稳定性方面是不同的。我们的研究结果表明,大分子拥挤可以在动力学和热力学上有利于淀粉样蛋白多态性之间切换,拥挤剂的化学性质是影响蛋白质聚集过程的关键因素。这些结果在llps依赖性蛋白错误折叠和淀粉样蛋白形成机制的背景下进行了讨论。
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引用次数: 0
Fragment-Guided New Therapeutic Molecule Discovery and Mapping of Clinically Relevant Interactomes. 片段导向的新治疗分子发现和临床相关相互作用组的定位。
IF 5.3 2区 化学 Q1 CHEMISTRY, MEDICINAL Pub Date : 2026-02-09 Epub Date: 2026-01-27 DOI: 10.1021/acs.jcim.5c02503
Austė Kanapeckaitė, Sarper Okuyan, David James Wagg, Jan Koster, Ligita Jančorienė, Indrė Sakalauskaitė, Birutė Brasiu̅nienė, Andrea Townsend-Nicholson

Therapeutic interventions for complex diseases depend on the targeted modulation of key pathological pathways. While growing clinical needs continue to drive advancements in the drug discovery space, current strategies primarily rely on searching large volumes of chemical data without addressing the specific contributions of molecular features. Moreover, both clinicians and researchers recognize the need for improved drug discovery methods and characterization that could aid in clinical strategy selection. To address these challenges, we propose a new perspective on targeted therapy development as well as interactome mapping, utilizing molecular fragments. The present study focuses on therapeutic areas that represent emerging targets, namely JAK2 and GLP-1R, both of which have broad clinical potential. We developed a new self-adjusting neural network that enabled us to discover novel therapeutic candidates with improved in silico binding profiles, gain additional insights into drug-target binding that were not previously reported, and identify new metabolic trajectories. Importantly, our work revealed that even a small compound library can effectively generate lead candidates, expediting the search and exploration process. In addition, the fragment-guided bridging of chemical and biological spaces has revealed new opportunities for drug repurposing efforts and a means of improving the prediction of side effects. We concluded our study with insights into the recent high-profile clinical trial failure of danuglipron and how this could have been prevented with our methodology. Thus, building a robust in silico pipeline with integrated screening data can significantly reduce costs and guide therapy adoption. Furthermore, our proposed strategy highlights promising avenues for the discovery of new therapeutics and the development of clinical interventions.

复杂疾病的治疗干预依赖于关键病理通路的靶向调节。虽然不断增长的临床需求继续推动药物发现领域的进步,但目前的策略主要依赖于搜索大量的化学数据,而没有解决分子特征的具体贡献。此外,临床医生和研究人员都认识到需要改进药物发现方法和特征,以帮助临床策略选择。为了解决这些挑战,我们提出了靶向治疗发展的新视角以及利用分子片段进行相互作用组定位的新视角。目前的研究重点是代表新兴靶点的治疗领域,即JAK2和GLP-1R,两者都具有广泛的临床潜力。我们开发了一种新的自我调节神经网络,使我们能够发现具有改进的硅结合谱的新型治疗候选者,获得以前未报道的药物靶标结合的额外见解,并确定新的代谢轨迹。重要的是,我们的工作表明,即使是一个小的化合物库也可以有效地产生先导候选物,加快搜索和探索过程。此外,片段引导的化学和生物空间的桥接为药物再利用工作提供了新的机会,并为改进副作用预测提供了一种手段。我们总结了我们的研究,深入了解了最近备受瞩目的丹格列酮临床试验的失败,以及如何用我们的方法预防这种失败。因此,建立一个强大的集成筛选数据的硅管道可以显着降低成本并指导治疗的采用。此外,我们提出的策略强调了发现新疗法和临床干预发展的有希望的途径。
{"title":"Fragment-Guided New Therapeutic Molecule Discovery and Mapping of Clinically Relevant Interactomes.","authors":"Austė Kanapeckaitė, Sarper Okuyan, David James Wagg, Jan Koster, Ligita Jančorienė, Indrė Sakalauskaitė, Birutė Brasiu̅nienė, Andrea Townsend-Nicholson","doi":"10.1021/acs.jcim.5c02503","DOIUrl":"10.1021/acs.jcim.5c02503","url":null,"abstract":"<p><p>Therapeutic interventions for complex diseases depend on the targeted modulation of key pathological pathways. While growing clinical needs continue to drive advancements in the drug discovery space, current strategies primarily rely on searching large volumes of chemical data without addressing the specific contributions of molecular features. Moreover, both clinicians and researchers recognize the need for improved drug discovery methods and characterization that could aid in clinical strategy selection. To address these challenges, we propose a new perspective on targeted therapy development as well as interactome mapping, utilizing molecular fragments. The present study focuses on therapeutic areas that represent emerging targets, namely JAK2 and GLP-1R, both of which have broad clinical potential. We developed a new self-adjusting neural network that enabled us to discover novel therapeutic candidates with improved in silico binding profiles, gain additional insights into drug-target binding that were not previously reported, and identify new metabolic trajectories. Importantly, our work revealed that even a small compound library can effectively generate lead candidates, expediting the search and exploration process. In addition, the fragment-guided bridging of chemical and biological spaces has revealed new opportunities for drug repurposing efforts and a means of improving the prediction of side effects. We concluded our study with insights into the recent high-profile clinical trial failure of danuglipron and how this could have been prevented with our methodology. Thus, building a robust in silico pipeline with integrated screening data can significantly reduce costs and guide therapy adoption. Furthermore, our proposed strategy highlights promising avenues for the discovery of new therapeutics and the development of clinical interventions.</p>","PeriodicalId":44,"journal":{"name":"Journal of Chemical Information and Modeling ","volume":" ","pages":"1482-1497"},"PeriodicalIF":5.3,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146058410","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Tuning the Half-Wave Potential and Binding Constant of PAQ Molecules for the Enhanced O2-Tolerant Electrochemical CO2 Capture Process 调整PAQ分子的半波电位和结合常数以增强耐o2电化学CO2捕获过程
IF 8.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-09 DOI: 10.1021/acssuschemeng.5c11680
Xingqian Wang,Di Zhang,Zehong Chen,Qiaolin Ren,Jiaxin Wang,Wenjun Yan,Jiaqi Qin,Zhongde Wang
The O2 sensitivity of electroactive organic quinone molecules in the field of electrochemical-mediated carbon capture (EMCC) restricts their electrochemical CO2 capture/release process. In this work, 9,10-Phenanthrenequinone (PAQ) was chosen as a capture carrier to precisely regulate the half-wave potential E1/2(Q–1/Q–2) and the CO2 binding constant KCO2 through intermolecular hydrogen-bonding networks between alcohols and reducing quinones. The electrochemical behavior of PAQ was systematically evaluated when different alcohol hydrogen-bond donors were introduced. A Hammett equation was constructed for alcohol hydrogen-bonding systems to quantify the theoretical relationship between electronic structure parameters and macroscopic electrochemical properties of alcohol alkyl groups. The experimental results indicated that proton donors with smaller pKa values and steric hindrance were more likely to form stable intermolecular hydrogen-bonding networks with reduced quinones. Density functional theory confirmed that hydrogen-bond networks obviously reduce the free energy of the inherent reaction system of PAQ, which is the main reason for achieving a better balance of the two key parameters. When the ethanol (EtOH) concentration was 0.66 M, the E1/2(Q–1/Q–2) of PAQ anodically shifted to −0.85 V vs Ag/AgCl; simultaneously, an appropriate Log(KCO2) (8.55) was still maintained at this time, and the estimated minimum energy consumption of the electrochemical system was 50.94 kJ/mol, which was significantly lower than that of the original electrolyte (73.43 kJ/mol). This suggested that constructing intermolecular hydrogen-bonding networks is beneficial for alleviating the O2 stability problem of quinone molecules with strong CO2 complexation.
电活性有机醌分子在电化学碳捕集(EMCC)领域的O2敏感性限制了其电化学CO2捕集/释放过程。本研究选择9,10-菲醌(PAQ)作为捕获载体,通过醇类与还原醌分子间的氢键网络,精确调节半波电位E1/2(Q-1 / Q-2)和CO2结合常数KCO2。在不同醇类氢键给体的条件下,系统地评价了PAQ的电化学行为。建立了醇类氢键体系的Hammett方程,量化了醇类烷基的电子结构参数与宏观电化学性能之间的理论关系。实验结果表明,具有较小pKa值和位阻的质子供体更容易与还原醌形成稳定的分子间氢键网络。密度泛函理论证实,氢键网络明显降低了PAQ固有反应体系的自由能,这是实现两个关键参数较好平衡的主要原因。当乙醇(EtOH)浓度为0.66 M时,PAQ的E1/2(Q-1 / Q-2)阳极位移为- 0.85 V /Ag /AgCl;同时,此时仍保持一个合适的Log(KCO2)(8.55),并且电化学系统的估计最小能量消耗为50.94 kJ/mol,明显低于原始电解质(73.43 kJ/mol)。这说明构建分子间氢键网络有利于缓解CO2络合强的醌分子的O2稳定性问题。
{"title":"Tuning the Half-Wave Potential and Binding Constant of PAQ Molecules for the Enhanced O2-Tolerant Electrochemical CO2 Capture Process","authors":"Xingqian Wang,Di Zhang,Zehong Chen,Qiaolin Ren,Jiaxin Wang,Wenjun Yan,Jiaqi Qin,Zhongde Wang","doi":"10.1021/acssuschemeng.5c11680","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c11680","url":null,"abstract":"The O2 sensitivity of electroactive organic quinone molecules in the field of electrochemical-mediated carbon capture (EMCC) restricts their electrochemical CO2 capture/release process. In this work, 9,10-Phenanthrenequinone (PAQ) was chosen as a capture carrier to precisely regulate the half-wave potential E1/2(Q–1/Q–2) and the CO2 binding constant KCO2 through intermolecular hydrogen-bonding networks between alcohols and reducing quinones. The electrochemical behavior of PAQ was systematically evaluated when different alcohol hydrogen-bond donors were introduced. A Hammett equation was constructed for alcohol hydrogen-bonding systems to quantify the theoretical relationship between electronic structure parameters and macroscopic electrochemical properties of alcohol alkyl groups. The experimental results indicated that proton donors with smaller pKa values and steric hindrance were more likely to form stable intermolecular hydrogen-bonding networks with reduced quinones. Density functional theory confirmed that hydrogen-bond networks obviously reduce the free energy of the inherent reaction system of PAQ, which is the main reason for achieving a better balance of the two key parameters. When the ethanol (EtOH) concentration was 0.66 M, the E1/2(Q–1/Q–2) of PAQ anodically shifted to −0.85 V vs Ag/AgCl; simultaneously, an appropriate Log(KCO2) (8.55) was still maintained at this time, and the estimated minimum energy consumption of the electrochemical system was 50.94 kJ/mol, which was significantly lower than that of the original electrolyte (73.43 kJ/mol). This suggested that constructing intermolecular hydrogen-bonding networks is beneficial for alleviating the O2 stability problem of quinone molecules with strong CO2 complexation.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"23 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138387","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}
引用次数: 0
Dynamic Evolution of Cuδ+ Quantification in Mutually Reinforced Copper–Ceria Catalysts for Electrochemical CO2 Reduction Cuδ+在铜-铈互增强催化剂中电化学还原CO2的动态演化
IF 12.9 1区 化学 Q1 CHEMISTRY, PHYSICAL Pub Date : 2026-02-09 DOI: 10.1021/acscatal.5c08410
Jianing Mao,Guanghui Feng,Bingbao Mei,Ziran Xu,Yiheng Wei,Xiaohu Liu,Jingyuan Ma,Fanfei Sun,Guihua Li,Yanfang Song,Xiao Dong,Wei Chen,Fei Song,Zheng Jiang
Low-valence copper species (Cuδ+, 0 < δ < 1) on Cu-based electrocatalysts are crucial for C–C coupling to form C2+ products, yet the stability of Cuδ+ especially at industrial-scale current, remains a significant challenge. Herein, we designed a strongly correlated metal–metal oxide nanosphere catalyst (Cu@CeO2–x) that stabilizes Cuδ+ species and establishes a Cu0–Cu+ interface to better regulate hydrogen adsorption, achieving a maximum faradaic efficiency for C2+ products of 82.5% at 300 mA cm–2 and −0.62 VRHE, while maintaining stable CO2 reduction reaction performance for over 72 h. Operando X-ray absorption fine structure and in-situ Raman spectroscopy indicated that Cu@CeO2–x underwent in-situ surface reconstruction, enabling a CeO2-mediated Cuδ+ redox cycle. This dynamic charge equilibrium forms a Cu0–Cu+ interface through the self-sacrifice of Ce sites to avoid an immoderate reduction of Cu. Furthermore, density functional calculations together with in-situ attenuated total reflection–surface-enhanced infrared absorption spectroscopy indicated that Cu0–Cu+ interface enhances *CO adsorption, and facilitates C–C coupling for C2+ products formation. The findings provide a blueprint for designing Cu-based electrocatalysts to combat rapid deactivation, enhancing performance toward higher-value products.
cu基电催化剂上的低价铜(Cuδ+, 0 < δ < 1)是C-C耦合形成C2+产物的关键,但Cuδ+的稳定性,特别是在工业规模电流下,仍然是一个重大挑战。在此,我们设计了一种强相关的金属-金属氧化物纳米球催化剂(Cu@CeO2 -x),该催化剂稳定了Cuδ+,并建立了Cu0-Cu +界面,以更好地调节氢的吸附,在300 mA cm-2和- 0.62 VRHE下,C2+产物的最大法拉第效率为82.5%。同时保持稳定的CO2还原反应性能超过72 h。Operando x射线吸收精细结构和原位拉曼光谱表明Cu@CeO2 -x进行了原位表面重构,实现了ceo2介导的Cuδ+氧化还原循环。这种动态电荷平衡通过Ce位的自我牺牲形成了Cu - Cu+界面,以避免Cu的过度还原。此外,密度泛函计算和原位衰减全反射-表面增强红外吸收光谱结果表明,cu - cu +界面增强了*CO吸附,促进了C-C耦合形成C2+产物。这一发现为设计铜基电催化剂提供了蓝图,以对抗快速失活,提高产品的性能。
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引用次数: 0
Highly Stable Photoluminescent CeF3 Nanocrystal as a Versatile Probe for Neurotoxic Alkaloid (Anabasine) Sensing via Fluorescence Modulation 高稳定的光致发光CeF3纳米晶体作为荧光调制神经毒性生物碱传感的多功能探针
IF 7.4 1区 化学 Q1 CHEMISTRY, ANALYTICAL Pub Date : 2026-02-09 DOI: 10.1021/acs.analchem.5c05171
Deepak Dabur,Jie Li,Priyanka Rana,Hui-Fen Wu
This study introduces highly stable photoluminescent CeF3 nanocrystals as a first ratiometric fluorescent probe for the selective detection of the neurotoxic alkaloid anabasine in environmental water matrices. The hexagonal-phase CeF3 nanocrystals (40–50 nm) exhibit dual-emission bands at 322 (quenched) and 433 nm (enhanced) upon anabasine binding, enabling sensitive (LOD: 0.17 μM) and matrix-resistant quantification. Structural (XRD, TEM, EDS) and optical (pH and thermal stability: pH 4–10, 30–90 °C) characterizations confirm robustness for real-world applications. Recovery assays (95–103%) in lake, river, and tap water demonstrate minimal matrix interference, outperforming LC-MS/MS and GC-FID methods that require derivatization or complex sample pretreatment. The cost-effectiveness, simplicity, and ratiometric self-calibration of the method highlight its potential for on-site environmental monitoring of tobacco-derived contaminants.
本研究引入了高度稳定的光致发光CeF3纳米晶体,作为选择检测环境水基质中神经毒性生物碱苦楝碱的第一个比率荧光探针。六方相CeF3纳米晶体(40-50 nm)在anabasine结合后呈现出322(淬灭)和433 nm(增强)的双发射带,实现了灵敏度(LOD: 0.17 μM)和抗基体的定量。结构(XRD, TEM, EDS)和光学(pH和热稳定性:pH 4 - 10,30 - 90°C)表征证实了实际应用的鲁棒性。在湖泊、河流和自来水中的回收率测定(95-103%)显示基质干扰最小,优于需要衍生化或复杂样品预处理的LC-MS/MS和GC-FID方法。该方法的成本效益、简单性和比例自校准突出了其对烟草衍生污染物的现场环境监测的潜力。
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引用次数: 0
Chiral Co-assembled Exciplex Host Achieved Extremely Outstanding Narrowband Circularly Polarized Electroluminescence 手性共组装异构体宿主实现了极其优异的窄带圆极化电致发光
IF 8.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-09 DOI: 10.1039/d5sc09684g
Chao Liu, Jun Zeng, Zhenhao Jiang, Yihan Chen, Junsheng Zhang, Yixiang Cheng
High-performance circularly polarized organic light-emitting diodes (CP-OLEDs) that can simultaneously achieve narrowband emission and high electroluminescence asymmetry factor (gEL) values remain a formidable challenge. In this study, a simple strategy utilizing co-assembled chiral exciplex as host material was employed to fabricate high-performance CP-OLEDs. The exciplex was constructed from chiral acceptor enantiomers (R/S‑TRZ) and an achiral liquid-crystalline donor (CzTPA). Upon thermal annealing, the resulting co-assembled films exhibited circularly polarized luminescence (CPL) with luminescence asymmetry factor (glum) up to 0.58. Introducing the achiral green multiple-resonance thermally activated delayed fluorescence (MR-TADF) emitter to the exciplex host enabled high-performance circularly polarized electroluminescence (CP-EL). The resulting device exhibited a large gEL value of 0.28, a narrow full width at half-maximum (FWHM) of 33 nm, and negligible efficiency roll-off. This work describes the first case of narrowband CP-OLEDs based on chiral co-assembled exciplex host materials, representing one of the highest gEL values of the reported narrowband emission CP-OLEDs to date. It further establishes a general strategy for fabricating high‑performance CP‑OLEDs with readily available achiral emitters, thereby significantly broadening applications in chiral optoelectronics.
同时实现窄带发射和高电致发光不对称系数(gEL)的高性能圆极化有机发光二极管(cp - oled)仍然是一个艰巨的挑战。在本研究中,采用一种简单的策略,利用共组装手性外络合物作为主体材料来制备高性能的cp - oled。该配合物由手性受体对映体(R/S - TRZ)和非手性液晶给体(CzTPA)组成。经热退火后,共组装薄膜呈现圆偏振发光(CPL),发光不对称系数(glum)高达0.58。将非手性绿色多共振热激活延迟荧光(MR-TADF)发射器引入到外加宿主中,使高性能圆极化电致发光(CP-EL)成为可能。所得到的器件具有0.28的大凝胶值,33 nm的半最大全宽(FWHM)和可以忽略不计的效率滚降。这项工作描述了基于手性共组装外络合物主体材料的窄带cp - oled的第一个案例,代表了迄今为止报道的窄带发射cp - oled的最高凝胶值之一。它进一步建立了用现成的非手性发射器制造高性能CP - oled的一般策略,从而显着扩大了手性光电子学的应用。
{"title":"Chiral Co-assembled Exciplex Host Achieved Extremely Outstanding Narrowband Circularly Polarized Electroluminescence","authors":"Chao Liu, Jun Zeng, Zhenhao Jiang, Yihan Chen, Junsheng Zhang, Yixiang Cheng","doi":"10.1039/d5sc09684g","DOIUrl":"https://doi.org/10.1039/d5sc09684g","url":null,"abstract":"High-performance circularly polarized organic light-emitting diodes (CP-OLEDs) that can simultaneously achieve narrowband emission and high electroluminescence asymmetry factor (gEL) values remain a formidable challenge. In this study, a simple strategy utilizing co-assembled chiral exciplex as host material was employed to fabricate high-performance CP-OLEDs. The exciplex was constructed from chiral acceptor enantiomers (R/S‑TRZ) and an achiral liquid-crystalline donor (CzTPA). Upon thermal annealing, the resulting co-assembled films exhibited circularly polarized luminescence (CPL) with luminescence asymmetry factor (glum) up to 0.58. Introducing the achiral green multiple-resonance thermally activated delayed fluorescence (MR-TADF) emitter to the exciplex host enabled high-performance circularly polarized electroluminescence (CP-EL). The resulting device exhibited a large gEL value of 0.28, a narrow full width at half-maximum (FWHM) of 33 nm, and negligible efficiency roll-off. This work describes the first case of narrowband CP-OLEDs based on chiral co-assembled exciplex host materials, representing one of the highest gEL values of the reported narrowband emission CP-OLEDs to date. It further establishes a general strategy for fabricating high‑performance CP‑OLEDs with readily available achiral emitters, thereby significantly broadening applications in chiral optoelectronics.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"15 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138756","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}
引用次数: 0
Component-Specific Functions of Cu, Zn, and Zr in Inverse ZnZrOx/Cu Catalysts for CO2 Hydrogenation to Methanol Cu、Zn和Zr在ZnZrOx/Cu逆催化剂中对CO2加氢制甲醇的组分特异性作用
IF 15 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-09 DOI: 10.1021/jacs.5c19915
Yu Gao,Erfan Shahroudi,Stefan Bouts,Yonghui Fan,Yin Li,Peeranat Chaipornchalerm,Junbu Wang,Konstantin Klementiev,Nikolay Kosinov,Emiel J. M. Hensen
Cu-based ternary catalysts often outperform their binary counterparts in the hydrogenation of CO2 to methanol. Unraveling the underlying synergistic effects among multiple components remains challenging and requires comprehensive operando characterization. In this study, we present a detailed investigation into the synergistic Cu−Zn−Zr interactions in inverse ZnZrOx/Cu catalysts, which show strong promise for enhancing the synthesis of methanol from CO2. In situ X-ray diffraction revealed that ZrO2 clusters effectively stabilize Cu nanoparticles against sintering during the H2 reduction. Operando X-ray absorption spectroscopy at the Cu, Zn, and Zr K-edges demonstrated that the enhanced reducibility of Zn and Zr species arises from synergistic Cu–Zn–Zr interactions. Upon H2 reduction, partially reduced ZrO2 facilitated CO2 adsorption and activation. Initially dispersed Zn2+ species were partially transformed into the CuZn alloy, which remained stable under reaction conditions. Notably, the CuZn alloy significantly enhanced the hydrogenation of key formate reaction intermediates to methanol. Moreover, Zn incorporation in Cu inhibited methanol decomposition to CO. The combined effects of efficient H2 activation on highly dispersed metallic Cu, enhanced CO2 activation by reduced ZrO2 clusters, and rapid formate hydrogenation facilitated by the CuZn alloy rendered inverse ZnZrOx/Cu catalysts superior in methanol formation rates as compared to inverse ZnOx/Cu, ZrOx/Cu catalysts, a commercial CuZnAl catalyst, and previously reported CuZnZr catalysts.
铜基三元催化剂在二氧化碳加氢制甲醇方面的表现往往优于二元催化剂。揭示多种成分之间潜在的协同效应仍然具有挑战性,需要全面的operando表征。在这项研究中,我们详细研究了逆ZnZrOx/Cu催化剂中Cu - Zn - Zr的协同相互作用,该催化剂在提高二氧化碳合成甲醇方面表现出很强的前景。原位x射线衍射表明,在H2还原过程中,ZrO2簇簇有效地稳定了Cu纳米颗粒,防止了烧结。在Cu, Zn和Zr k边的Operando x射线吸收光谱表明,Zn和Zr的还原性增强是由Cu - Zn - Zr的协同相互作用引起的。H2还原后,部分还原的ZrO2有利于CO2的吸附和活化。初始分散的Zn2+部分转化为CuZn合金,CuZn合金在反应条件下保持稳定。值得注意的是,CuZn合金显著促进了甲酸酯反应关键中间体加氢生成甲醇。此外,锌在Cu中的加入抑制了甲醇分解成CO。高分散金属Cu的高效H2活化、还原ZrO2簇增强CO2活化以及CuZn合金促进甲酸氢的快速加氢的综合作用使得ZnZrOx/Cu逆催化剂的甲醇生成速率优于ZnOx/Cu逆催化剂、ZrOx/Cu逆催化剂、商品CuZnAl催化剂和先前报道的CuZnZr催化剂。
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