Molecular Systems Design & Engineering最新文献

{"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}

{"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>_r</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}

{"title":"Grain boundaries in periodic vs. in aperiodic crystals composed of colloids with preferred binding angles","authors":"Robert F. B. Weigel and Michael Schmiedeberg","doi":"10.1039/D5ME00076A","DOIUrl":"https://doi.org/10.1039/D5ME00076A","url":null,"abstract":"<p >Using a modified phase field crystal model that we have recently introduced [Weigel <em>et al.</em>, <em>Modelling and Simulation in Materials Science and Engineering</em>, 2022, <strong>30</strong>, 074003], we study grain boundaries that occur in two-dimensional structures composed of particles with preferred binding angles like patchy colloids. In the case of structures with a triangular order, we show how particles with a 5-fold rotational symmetry that differs from the usual 6-fold coordination of a particle in bulk affect the energy of the dislocations in the grain boundaries. Furthermore, for quasicrystals we find that the dislocation pairs recombine easily and the grain boundaries disappear. However, the resulting structure usually possesses a lot of phasonic strain. Our results demonstrate that the preferred symmetry of a particle is important for grain boundaries, and that periodic and aperiodic structures may differ in how stable their domain boundaries are.</p>","PeriodicalId":91,"journal":{"name":"Molecular Systems Design & Engineering","volume":" 10","pages":" 848-854"},"PeriodicalIF":3.2,"publicationDate":"2025-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/me/d5me00076a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145190306","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}

{"title":"Computational screening analysis of iron zeolites for selectively capturing NOx and CO over H2O and CO2†","authors":"Ioannis Karamanis, David Dell'Angelo, Hubert Monnier and Michael Badawi","doi":"10.1039/D5ME00003C","DOIUrl":"https://doi.org/10.1039/D5ME00003C","url":null,"abstract":"<p >This work aims at shedding light on the capture mechanisms of toxic atmospheric pollutants by zeolites. A comprehensive computational investigation has been conducted to evaluate the interaction energies of NO, NO<small>₂</small>, CO, CO<small>₂</small>, and H<small>₂</small>O with Fe<small>²⁺</small> supporting both chabazite and mordenite zeolites using periodic density functional theory calculations. Si/Al ratio sets of {11, 5, 3} and {23, 11, 5} have been respectively chosen for chabazite and mordenite. Our findings show that both systems exhibit a thermodynamic preference for bonding NO and NO<small>₂</small> over H<small>₂</small>O and CO<small>₂</small>. Moreover, <em>ab initio</em> molecular dynamics simulations at 300 K for the Fe-chabazite system with Si/Al = 3 confirm the adsorption of NO, NO<small>₂</small> and CO even in the presence of H<small>₂</small>O molecules, and the radial distribution function was employed to understand how steam affects NO, NO<small>₂</small> and CO bonding. CO<small>₂</small> co-adsorption was eventually neglected in our study due to its low interaction energy. Finally, Bader charges and charge density differences were calculated to analyze bond elongation after adsorption and account for the regeneration of the substrate. Results show that low Si/Al ratios enhance the affinity for NO and NO<small>₂</small> and favour the regenerability of the adsorbent. This study demonstrates that the utilization of zeolites containing iron as the compensating cation presents promising potential as effective adsorbents for capturing NO<small>_<em>x</em></small> and CO in the presence of H<small>₂</small>O and CO<small>₂</small> originating from diesel engine emissions within confined work environments.</p>","PeriodicalId":91,"journal":{"name":"Molecular Systems Design & Engineering","volume":" 10","pages":" 855-867"},"PeriodicalIF":3.2,"publicationDate":"2025-06-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/me/d5me00003c?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145190307","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}

{"title":"Enhanced thermal response of 3D-printed bilayer hydrogels via nanoclay incorporation†","authors":"Francis Klincewicz, Subhash Kalidindi, Siyuan Liu, Kritee Sangroula and LaShanda T. J. Korley","doi":"10.1039/D5ME00018A","DOIUrl":"10.1039/D5ME00018A","url":null,"abstract":"<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(<em>N</em>-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":" 9","pages":" 755-764"},"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}

{"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>₄</small>) is a significant theranostic agent for photodynamic therapy (PDT) and a model system of molecular nanowires. The zwitterionic forms of TPPS<small>₄</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>₄</small> aggregation of small clusters using a molecular dynamics (MD) approach. Two possible forms of zwitterionic TPPS<small>₄</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}

{"title":"Evaluating the density of organic compounds at variable temperatures by a norm descriptor-based QSPR model†","authors":"Yueji Wang, Yu Gu, Qiaoyan Shang, Qingzhu Jia, Qiang Wang, Yin-Ning Zhou and Fangyou Yan","doi":"10.1039/D5ME00035A","DOIUrl":"https://doi.org/10.1039/D5ME00035A","url":null,"abstract":"<p >Accurately predicting the density of organic compounds is essential in chemical engineering. This study develops a robust quantitative structure–property relationship (QSPR) model using a multiple linear regression (MLR) methodology, based on a comprehensive dataset of 5478 organic compounds and 23 866 data points to predict density over a broad temperature range (115.0 to 594.1 K). Notably, norm indices (NIs) are applied for QSPR modeling of organic compound density for the first time. The model demonstrates excellent predictive performance, with a squared correlation coefficient (<em>R</em><small>²</small>) of 0.9953 and a mean absolute error (MAE) of 10.11 kg m<small>⁻³</small>. Rigorous internal, external, and extrapolation validations are applied to confirm the model's reliability, accuracy, and generalization. The model achieves an <em>R</em><small>²</small> value of 0.9951 and a MAE of 9.31 kg m<small>⁻³</small> in external validation, while in internal validation using leave-one-out cross-validation, the corresponding values are 0.9951 and 10.51 kg m<small>⁻³</small>, respectively. Extrapolation validation, a novel approach recently introduced, further confirms the model's extrapolation ability, with most descriptors achieving the root mean square error (RMSE) of the test set (EV) values well below the training set's standard deviation (<em>σ</em><small>₉₅</small> = 140.89 kg m<small>⁻³</small>), closely aligning with RMSE<small>_test</small> (model). The RMSE of forward test exhibits a significant increase for NI<small>₈</small> and NI<small>₂₇</small> when the extrapolation degree (ED) exceeds 0.02, which suggests that it is not recommended to apply these two NIs for extrapolation. Overall, the results validate the robustness and broad applicability of the <em>ρ</em>(NI,<em>T</em>)-QSPR model, confirming its reliability for organic compound density prediction in industrial applications.</p>","PeriodicalId":91,"journal":{"name":"Molecular Systems Design & Engineering","volume":" 9","pages":" 776-789"},"PeriodicalIF":3.2,"publicationDate":"2025-06-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144909520","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}

{"title":"The potential of microcrystalline cellulose-g-poly(itaconic acid) as α-tocopherol carrier material†","authors":"Ikhsan Ibrahim, Rachmawati Rachmawati and Mia Ledyastuti","doi":"10.1039/D5ME00023H","DOIUrl":"https://doi.org/10.1039/D5ME00023H","url":null,"abstract":"<p >According to the Food and Drug Administration (FDA), a drug is defined as a substance used for the mitigation, treatment, and therapy of a disease. In increasing the effectiveness of treatment, drugs need a carrier to produce a controlled delivery pattern. This study used microcrystalline cellulose-<em>graft</em>-poly(itaconic acid) copolymer as a drug carrier, while α-tocopherol was used as a drug model. The copolymer main chain is hydrophilic, while the side chains are hydrophobic. The amphiphilic structure can result in the formation of micelles. The success of copolymer synthesis was proven by the presence of a new peak in the infrared absorption band at 1645 cm<small>⁻¹</small>. The peak indicated the presence of a C<img>O group of itaconic acid grafted onto the main chain of microcrystalline cellulose. The molecular process of carrying α-tocopherol can be observed based on the results of molecular dynamics simulations. The carriage of α-tocopherol is characterized by a copolymer radial distribution function (RDF) peak at a range of 0.5–0.9 nm and a decrease in the solvent-accessible surface area (SASA). The drug release data were modeled using the exponential model (first-order kinetic), the Weibull model (fractal-like first-order kinetic), and the diffusion-based Higuchi model.</p>","PeriodicalId":91,"journal":{"name":"Molecular Systems Design & Engineering","volume":" 9","pages":" 765-775"},"PeriodicalIF":3.2,"publicationDate":"2025-06-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144909519","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}

{"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}

{"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}