Molecular Systems Design & Engineering最新文献

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Re-engineering luminol: new frontiers in chemiluminescence chemistry 重组发光氨:化学发光化学的新前沿
IF 3.2 3区 工程技术
Molecular Systems Design & Engineering Pub Date : 2025-06-20 DOI: 10.1039/D5ME00065C
Amir M. Alsharabasy
{"title":"Re-engineering luminol: new frontiers in chemiluminescence chemistry","authors":"Amir M. Alsharabasy","doi":"10.1039/D5ME00065C","DOIUrl":"https://doi.org/10.1039/D5ME00065C","url":null,"abstract":"<p >Luminol and its derivatives have emerged as powerful chemiluminescent agents with broad applications in biomedical diagnostics, forensic science, and environmental monitoring. Despite their widespread use, luminol's limitations, including poor solubility, short luminescence duration, and sensitivity to environmental conditions, have driven extensive research into the synthesis of more efficient derivatives. This concise review presents recent advances in the molecular engineering of luminol derivatives, focusing on design strategies that employ electronic modulation (<em>e.g.</em>, introduction of electron-donating or withdrawing substituents) and steric tuning (<em>e.g.</em>, alkylation and ring substitutions) to optimize its chemiluminescence efficiency, kinetics, emission wavelength, solubility, stability, and applicability for specific environments (<em>e.g.</em>, biological systems). The review also discusses how these structural modifications impact luminol's performance within integrated systems, including forensics, bioimaging platforms, immunoassay technologies and microfluidic sensors, thereby linking molecular-level design with macroscopic function. Emerging macromolecular and polymer-based luminol systems, such as those incorporating hydrophilic carriers, nanoparticles, enzyme-responsive linkers, surface-immobilized polymer brushes, and multi-functional hybrid platforms, are also highlighted for their potential to overcome solubility and biocompatibility barriers while enabling targeted delivery or signal amplification. Finally, key challenges and future perspectives are outlined, including the development of near-infrared-emitting derivatives, improved storage stability, and interdisciplinary strategies for translating luminol chemistry into next-generation diagnostics and environmental sensing platforms. By summarizing these advancements, this review underscores the evolving role of luminol chemistry in modern analytical science and its potential to revolutionize next-generation detection technologies.</p>","PeriodicalId":91,"journal":{"name":"Molecular Systems Design & Engineering","volume":" 8","pages":" 606-619"},"PeriodicalIF":3.2,"publicationDate":"2025-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/me/d5me00065c?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144716381","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Fitting a square peg in a round hole: parameterisation of quasi-spherical molecules employing the Mie potential† 在圆孔中安装方钉:准球形分子的参数化,利用米氏势†
IF 3.2 3区 工程技术
Molecular Systems Design & Engineering Pub Date : 2025-06-19 DOI: 10.1039/D5ME00048C
Gustavo Chaparro and Erich A. Müller
{"title":"Fitting a square peg in a round hole: parameterisation of quasi-spherical molecules employing the Mie potential†","authors":"Gustavo Chaparro and Erich A. Müller","doi":"10.1039/D5ME00048C","DOIUrl":"https://doi.org/10.1039/D5ME00048C","url":null,"abstract":"<p >The parameterisation of the force field of a molecular system is essential for accurately describing and predicting macroscopic thermophysical properties. Here, we discuss three approaches to obtain the molecular parameters (<em>σ</em>, <em>ε</em>, and <em>λ</em><small><sub>r</sub></small>) of the Mie force field from experimental data for quasi-spherical molecules. The first approach is based on a classical strategy that considers fitting only to vapour–liquid equilibria data. The second approach entails a simultaneous fit to equilibrium properties and liquid shear viscosity. Finally, a third approach incorporates solid–fluid equilibrium data. The fitting procedure is facilitated by the use of recently published machine-learned equations of state for the Mie particle, which allows the prediction of thermophysical properties given a set of molecular parameters. The goodness-of-fit is assessed based on the deviations between calculated and experimental data. We also assess the behaviour of the thermal conductivity and speed of sound of the saturated liquid phase to evaluate the transferability of the molecular parameters to properties not used in the parametrisation. Apart from the singular case of monoatomic molecules, no single set of parameters can simultaneously describe the fluid phase equilibria, transport, and solid transition properties of quasi-spherical molecules. This result highlights the limitations of the Mie potential for modelling the thermophysical properties of small molecules. Therefore, a compromise must be made, either to achieve a good description of a specific set of properties or to attain modest accuracy across all phase space.</p>","PeriodicalId":91,"journal":{"name":"Molecular Systems Design & Engineering","volume":" 8","pages":" 620-634"},"PeriodicalIF":3.2,"publicationDate":"2025-06-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/me/d5me00048c?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144716382","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Enhanced thermal response of 3D-printed bilayer hydrogels via nanoclay incorporation. 纳米粘土掺入增强3d打印双层水凝胶的热响应。
IF 3.2 3区 工程技术
Molecular Systems Design & Engineering Pub Date : 2025-06-11 DOI: 10.1039/d5me00018a
Francis Klincewicz, Subhash Kalidindi, Siyuan Liu, Kritee Sangroula, LaShanda T J Korley
{"title":"Enhanced thermal response of 3D-printed bilayer hydrogels <i>via</i> nanoclay incorporation.","authors":"Francis Klincewicz, Subhash Kalidindi, Siyuan Liu, Kritee Sangroula, LaShanda T J Korley","doi":"10.1039/d5me00018a","DOIUrl":"10.1039/d5me00018a","url":null,"abstract":"<p><p>There exist numerous opportunities to design stimuli-responsive bilayer hydrogels for enhanced actuation using simple and robust techniques. Specifically, digital light processing (DLP) 3D printing offers a robust technique for multi-layered hydrogel fabrication. However, nanocomposite hydrogels utilizing this technique have not yet been widely realized. Nanoclay incorporation has been shown to improve the actuation of poly(<i>N</i>-isopropyl acrylamide) (pNIPAAm) hydrogels; however, opportunities remain to study the relationship between clay morphology and thermal response, particularly in a 3D-printed bilayer system. In this work, we utilized an ethanol-water cosolvent, hydrogel precursor solution to incorporate montmorillonite (MMT) clay into 3D-printed pNIPAAm hydrogels. By varying the MMT loading, we demonstrated that a low loading of MMT (0.5 wt% relative to the mass of NIPAAm monomer) induced the greatest enhancement of the initial rate and final magnitude of actuation in the studied hydrogels. We utilized poly(2-hydroxyethyl acrylate) (pHEA) as a passive layer to form bilayers by sequentially printing pHEA before the pNIPAAm/MMT hydrogels, and used those hydrogels to demonstrate the accelerated actuation of 3D-printed pNIPAAm/MMT-pHEA bilayers compared to clay-free, pNIPAAm-pHEA bilayers. Through comparison to a mathematical framework and fabrication of an all-pNIPAAm bilayer, we suggested that the model has limitations for the prediction of bilayer curvature in these systems due to the inability of certain hydrogels to overcome the inertia of the passive layer. Overall, this work showcases the utility of MMT as a handle for tunability in 3D-printed pNIPAAm bilayer hydrogels.</p>","PeriodicalId":91,"journal":{"name":"Molecular Systems Design & Engineering","volume":" ","pages":""},"PeriodicalIF":3.2,"publicationDate":"2025-06-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12153420/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144300747","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Origins of curvature in meso-tetra(4-sulfonatophenyl) porphine aggregation: molecular dynamics and electronic spectroscopy† 中四(4-磺酰基)卟啉聚集中曲率的起源:分子动力学和电子能谱
IF 3.2 3区 工程技术
Molecular Systems Design & Engineering Pub Date : 2025-06-09 DOI: 10.1039/D5ME00010F
Laura Baliulyte, Eimantas Urniezius, Vytautas Bubilaitis, Mindaugas Macernis, Lorenzo Cupellini and Darius Abramavicius
{"title":"Origins of curvature in meso-tetra(4-sulfonatophenyl) porphine aggregation: molecular dynamics and electronic spectroscopy†","authors":"Laura Baliulyte, Eimantas Urniezius, Vytautas Bubilaitis, Mindaugas Macernis, Lorenzo Cupellini and Darius Abramavicius","doi":"10.1039/D5ME00010F","DOIUrl":"https://doi.org/10.1039/D5ME00010F","url":null,"abstract":"<p > <em>meso</em>-Tetra(4-sulfonatophenyl) porphine (TPPS<small><sub>4</sub></small>) is a significant theranostic agent for photodynamic therapy (PDT) and a model system of molecular nanowires. The zwitterionic forms of TPPS<small><sub>4</sub></small> tend to form large chiral nanotubes in acidic conditions at pH ≈1. However, it is still not clear how these aggregates are structured at the molecular level. We describe a computational strategy to model the TPPS<small><sub>4</sub></small> aggregation of small clusters using a molecular dynamics (MD) approach. Two possible forms of zwitterionic TPPS<small><sub>4</sub></small> tetramers were considered, and their absorption and circular dichroism (CD) spectra were calculated using the Frenkel exciton model. Possible molecular packing is suggested as a candidate for the formation of large aggregates.</p>","PeriodicalId":91,"journal":{"name":"Molecular Systems Design & Engineering","volume":" 8","pages":" 635-648"},"PeriodicalIF":3.2,"publicationDate":"2025-06-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/me/d5me00010f?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144716383","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Harnessing peptide–cellulose interactions to tailor the performance of self-assembled, injectable hydrogels† 利用肽-纤维素相互作用来定制自组装的可注射水凝胶的性能。
IF 3.2 3区 工程技术
Molecular Systems Design & Engineering Pub Date : 2025-06-02 DOI: 10.1039/D5ME00009B
Jessica A. Thomas, Alex H. Balzer, Subhash Kalidindi and LaShanda T. J. Korley
{"title":"Harnessing peptide–cellulose interactions to tailor the performance of self-assembled, injectable hydrogels†","authors":"Jessica A. Thomas, Alex H. Balzer, Subhash Kalidindi and LaShanda T. J. Korley","doi":"10.1039/D5ME00009B","DOIUrl":"10.1039/D5ME00009B","url":null,"abstract":"<p >Taking inspiration from natural systems, such as spider silk and mollusk nacre, that employ hierarchical assembly to attain robust material performance, we leveraged matrix–filler interactions within reinforced polymer–peptide hybrids to create self-assembled hydrogels with enhanced properties. Specifically, cellulose nanocrystals (CNCs) were incorporated into peptide–polyurea (PPU) hybrid matrices to tailor key hydrogel features through matrix–filler interactions. Herein, we examined the impact of peptide repeat length and CNC loading on hydrogelation, morphology, mechanics, and thermal behavior of PPU/CNC composite hydrogels. The addition of CNCs into PPU hydrogels resulted in increased gel stiffness; however, the extent of reinforcement of the nanocomposite gels upon nanofiller inclusion also was driven by PPU architecture. Temperature-promoted stiffening transitions observed in nanocomposite PPU hydrogels were dictated by peptide segment length. Analysis of the peptide secondary structure confirmed shifts in the conformation of peptidic domains (α-helices or β-sheets) upon CNC loading. Finally, PPU/CNC hydrogels were probed for their injectability characteristics, demonstrating that nanofiller–matrix interactions were shown to aid rapid network reformation (∼10 s) upon cessation of high shear forces. Overall, this research showcases the potential of modulating matrix–filler interactions within PPU/CNC hydrogels through strategic system design, enabling the tuning of functional hydrogel characteristics for diverse applications.</p>","PeriodicalId":91,"journal":{"name":"Molecular Systems Design & Engineering","volume":" 8","pages":" 662-674"},"PeriodicalIF":3.2,"publicationDate":"2025-06-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12128039/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144223777","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Biodegradable glucosamine-amino acid-based ionic liquids as efficient water-based lubricant additives for green tribological chemistry† 可生物降解的氨基葡萄糖-氨基酸基离子液体作为绿色摩擦化学的高效水性润滑剂添加剂
IF 3.2 3区 工程技术
Molecular Systems Design & Engineering Pub Date : 2025-05-23 DOI: 10.1039/D5ME00036J
Jing Yang, Xiao Liu, Chongyun Sun, Qiang Chen, Pingxia Guo, Kai Feng, Meirong Cai and Feng Zhou
{"title":"Biodegradable glucosamine-amino acid-based ionic liquids as efficient water-based lubricant additives for green tribological chemistry†","authors":"Jing Yang, Xiao Liu, Chongyun Sun, Qiang Chen, Pingxia Guo, Kai Feng, Meirong Cai and Feng Zhou","doi":"10.1039/D5ME00036J","DOIUrl":"https://doi.org/10.1039/D5ME00036J","url":null,"abstract":"<p >Water-based lubricants demonstrate significant development potential in machining and automotive manufacturing industries owing to their environmental friendliness, safety profile, and ease of cleaning. In this study, two eco-friendly amino acid-based ionic liquids (AAILs), <em>N</em>-ethyl-<small>D</small>-glucamine-2-(<em>N</em>-methyldodecanamido) acetate acid (EDG-LS) and <em>N</em>-octyl-<small>D</small>-glucamine-2-(<em>N</em>-methyldodecanamido) acetate (ODG-LS), were synthesized using 2-(<em>N</em>-methyldodecanamido) acetic acid and glucosamine as raw materials. When AAILs were employed as water-based lubrication additives, the physicochemical characteristics, tribological performances, and lubrication mechanisms of the lubricants were systematically evaluated. The results of the cast iron tests demonstrate that adding just 1 wt% of AAIL additives can significantly reduce the corrosion of water. Moreover, EDG-LS exhibits superior friction reduction (69.9% decrease) and anti-wear properties (91.4% reduction) compared to water. The combined influence of physically adsorbed films and tribochemical reaction layers endows AAILs with outstanding tribological performance. Additionally, two kinds of AAILs exhibit favorable biodegradability, with a biodegradation rate approaching 60%. This research provides theoretical insights for creating eco-friendly, biodegradable, and multifunctional water-based lubricant additives.</p>","PeriodicalId":91,"journal":{"name":"Molecular Systems Design & Engineering","volume":" 8","pages":" 649-661"},"PeriodicalIF":3.2,"publicationDate":"2025-05-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144716384","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
DynaMate: leveraging AI-agents for customized research workflows DynaMate:利用ai代理来定制研究工作流程
IF 3.2 3区 工程技术
Molecular Systems Design & Engineering Pub Date : 2025-05-22 DOI: 10.1039/D5ME00062A
Orlando A. Mendible-Barreto, Misael Díaz-Maldonado, Fernando J. Carmona Esteva, J. Emmanuel Torres, Ubaldo M. Córdova-Figueroa and Yamil J. Colón
{"title":"DynaMate: leveraging AI-agents for customized research workflows","authors":"Orlando A. Mendible-Barreto, Misael Díaz-Maldonado, Fernando J. Carmona Esteva, J. Emmanuel Torres, Ubaldo M. Córdova-Figueroa and Yamil J. Colón","doi":"10.1039/D5ME00062A","DOIUrl":"https://doi.org/10.1039/D5ME00062A","url":null,"abstract":"<p >Developments related to large language models (LLMs) have deeply impacted everyday activities and are even more significant in scientific applications. They range from simple chatbots that respond to a prompt to very complex agents that plan, conduct, and analyze experiments. As more models and algorithms continue to be developed at a rapid pace, the complexity involved in building this framework increases. Additionally, editing these algorithms for personalized applications has become increasingly challenging. To this end, we present a modular code template that allows easy implementation of custom Python code functions to enable a multi-agent framework capable of using these functions to perform complex tasks. We used the template to build DynaMate, a complex framework for generating, running, and analyzing molecular simulations. We performed various tests that included the simulation of solvents and metal–organic frameworks, calculation of radial distribution functions, and determination of free energy landscapes. The modularity of these templates allows for easy editing and the addition of custom tools, which enables rapid access to the many tools that can be involved in scientific workflows.</p>","PeriodicalId":91,"journal":{"name":"Molecular Systems Design & Engineering","volume":" 7","pages":" 585-598"},"PeriodicalIF":3.2,"publicationDate":"2025-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/me/d5me00062a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144519600","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Bioinspired design rules for flipping across the lipid bilayer from systematic simulations of membrane protein segments† 从系统模拟膜蛋白片段†的脂质双分子层翻转的生物启发设计规则
IF 3.2 3区 工程技术
Molecular Systems Design & Engineering Pub Date : 2025-05-09 DOI: 10.1039/D5ME00032G
ByungUk Park and Reid C. Van Lehn
{"title":"Bioinspired design rules for flipping across the lipid bilayer from systematic simulations of membrane protein segments†","authors":"ByungUk Park and Reid C. Van Lehn","doi":"10.1039/D5ME00032G","DOIUrl":"https://doi.org/10.1039/D5ME00032G","url":null,"abstract":"<p >The orientation of integral membrane proteins (IMPs) with respect to the membrane is established during protein synthesis and insertion into the membrane. After synthesis, IMP orientation is thought to be fixed due to the thermodynamic barrier for “flipping” protein loops or helices across the hydrophobic core of the membrane in a process analogous to lipid flip-flop. A notable exception is EmrE, a homodimeric IMP with an N-terminal transmembrane helix that can flip across the membrane until flipping is arrested upon dimerization. Understanding the features of the EmrE sequence that permit this unusual flipping behavior would be valuable for guiding the design of synthetic materials capable of translocating or flipping charged groups across lipid membranes. To elucidate the molecular mechanisms underlying flipping in EmrE and derive bioinspired design rules, we employ atomistic molecular dynamics simulations and enhanced sampling techniques to systematically investigate the flipping of truncated segments of EmrE. Our results demonstrate that a membrane-exposed charged glutamate residue at the center of the N-terminal helix lowers the energetic barrier for flipping (from ∼12.1 kcal mol<small><sup>−1</sup></small> to ∼5.4 kcal mol<small><sup>−1</sup></small>) by stabilizing water defects and minimizing membrane perturbation. Comparative analysis reveals that the marginal hydrophobicity of this helix, rather than the marginal hydrophilicity of its loop, is the key determinant of flipping propensity. Our results further indicate that interhelical hydrogen bonding upon dimerization inhibits flipping. These findings establish several bioinspired design principles to govern flipping in related materials: (1) marginally hydrophobic helices with membrane-exposed charged groups promote flipping, (2) modulating protonation states of membrane-exposed groups tunes flipping efficiency, and (3) interhelical hydrogen bonding can be leveraged to arrest flipping. These insights provide a foundation for engineering synthetic peptides, engineered proteins, and biomimetic nanomaterials with controlled flipping or translocation behavior for applications in intracellular drug delivery and membrane protein design.</p>","PeriodicalId":91,"journal":{"name":"Molecular Systems Design & Engineering","volume":" 7","pages":" 567-584"},"PeriodicalIF":3.2,"publicationDate":"2025-05-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144519604","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Flame growth of nickel-based cocatalyst for efficient solar water splitting of BiVO4 photoanode† BiVO4光阳极高效太阳能水分解镍基助催化剂火焰生长研究
IF 3.2 3区 工程技术
Molecular Systems Design & Engineering Pub Date : 2025-05-06 DOI: 10.1039/D5ME00006H
Haohua Wang, Youyi Su, Xiangui Pang, Ming Zhang, Wufang Wang, Pingping Yang, Xinxin Lu and Jiale Xie
{"title":"Flame growth of nickel-based cocatalyst for efficient solar water splitting of BiVO4 photoanode†","authors":"Haohua Wang, Youyi Su, Xiangui Pang, Ming Zhang, Wufang Wang, Pingping Yang, Xinxin Lu and Jiale Xie","doi":"10.1039/D5ME00006H","DOIUrl":"https://doi.org/10.1039/D5ME00006H","url":null,"abstract":"<p >The low charge separation efficiency and slow water oxidation kinetics of bismuth vanadate (BiVO<small><sub>4</sub></small>, BVO) limit its performance for solar water splitting. Here, a flame growth method has been developed to rapidly grow a nickel-based cocatalyst (NiO<small><sub><em>x</em></sub></small>) on the surface of the worm-like BVO films. After 20 s flame growth, the NiO<small><sub><em>x</em></sub></small> cocatalyst, which is comprised of Ni, NiO, and NiOOH, can be uniformly and rapidly synthesized. The NiO<small><sub><em>x</em></sub></small>/BVO composite photoanode achieves a photocurrent density of 3.80 mA cm<small><sup>−2</sup></small> at 1.23 V <em>vs.</em> RHE in a neutral electrolyte, which is 6.67 times higher than that of the pristine BiVO<small><sub>4</sub></small>. Under the assistance of polyacrylamide hydrogel coating, the photocurrent of the NiO<small><sub><em>x</em></sub></small>/BVO photoanode can be well maintained at 62.26% after a 24 h long-term stability test. The performance improvement can be mainly attributed to the fact that the NiO<small><sub><em>x</em></sub></small> layer reduces the resistance of the charge transfer and the energy barrier of the oxygen evolution reactions, and introduces a large number of oxygen vacancies. This research confirms that the flame growth of cocatalysts is an efficient method for preparing the cocatalytic layer on the nanostructure photoelectrode, which can well maintain the nanostructures.</p>","PeriodicalId":91,"journal":{"name":"Molecular Systems Design & Engineering","volume":" 8","pages":" 675-681"},"PeriodicalIF":3.2,"publicationDate":"2025-05-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144716438","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Quantum chemical screening of eutectic solvent components for insights into CO2 complexation mechanisms† 共晶溶剂组分的量子化学筛选,以深入了解二氧化碳络合机制†
IF 3.2 3区 工程技术
Molecular Systems Design & Engineering Pub Date : 2025-05-02 DOI: 10.1039/D5ME00034C
Stephen P. Vicchio, Osasumwen J. Ikponmwosa and Rachel B. Getman
{"title":"Quantum chemical screening of eutectic solvent components for insights into CO2 complexation mechanisms†","authors":"Stephen P. Vicchio, Osasumwen J. Ikponmwosa and Rachel B. Getman","doi":"10.1039/D5ME00034C","DOIUrl":"https://doi.org/10.1039/D5ME00034C","url":null,"abstract":"<p >Developing new negative emission technologies (NETs) to capture atmospheric CO<small><sub>2</sub></small> is necessary to limit global temperature rise below 1.5 °C by 2050. The technologies, such as direct air capture (DAC), rely on sorption materials to harvest trace amounts of CO<small><sub>2</sub></small> from ambient air. Deep eutectic solvents (DESs) and eutectic solvents (ESs), a subset of ionic liquids (ILs), are all promising new CO<small><sub>2</sub></small> sorption materials for DAC. However, the experimental design space for different DESs/ESs/ILs is vast, with the exact CO<small><sub>2</sub></small> complexation pathways difficult to elucidate; this creates significant limitations in rationally designing new materials with targeted CO<small><sub>2</sub></small> sorption energetics. Herein, the CO<small><sub>2</sub></small> complexation pathways for a structural library of different DES/ES components are computed using quantum chemical calculations (<em>i.e.</em>, density functional theory). For the entire structure library, we report the energies of elementary CO<small><sub>2</sub></small> binding and proton transfer reactions as these reactions are fundamental in DAC within DESs and ESs. These elementary reactions are combined to generate CO<small><sub>2</sub></small> complexation pathways and calculate their free energies. The different elementary steps and reaction pathways demonstrate the range of CO<small><sub>2</sub></small> complexation free energies and the significance between CO<small><sub>2</sub></small> binding and proton transfer reactions. We also report the CO<small><sub>2</sub></small> complexation free energies with different functional groups around the CO<small><sub>2</sub></small> sorption site, supporting the concept of functionalization for tuning CO<small><sub>2</sub></small> complexation thermodynamics. Additionally, our findings suggest potential descriptors, such as proton affinity or p<em>K</em><small><sub>a</sub></small>, could be useful when identifying candidate species for ESs and predicting/rationalizing product distributions. Our work has implications for experimental synthesis, characterization, and performance evaluation of new DAC sorption materials.</p>","PeriodicalId":91,"journal":{"name":"Molecular Systems Design & Engineering","volume":" 6","pages":" 447-458"},"PeriodicalIF":3.2,"publicationDate":"2025-05-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/me/d5me00034c?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144206272","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
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