Using surface-tension measurements, we study the brush-limited adsorption dynamics of a range of amphiphilic polymers, PAAH-[Formula: see text]-[Formula: see text] composed of a poly(acrylic acid) backbone, PAAH, grafted with a fraction [Formula: see text] of alkyl moieties, containing either n = 8 or n = 12 carbon atoms, at pH conditions where the PAAH backbone is not charged. At short times, the surface tension decreases more sharply as the degree of grafting increases, while, at long times, the adsorption dynamics becomes logarithmic in time and is slower as the degree of grafting increases. This logarithmic behavior at long times indicates the building of a free-energy barrier which grows over time. To account for the observed surface tension evolution with the degree of grafting we propose a scenario, where the free-energy barrier results from both the deformation of the incoming polymer coils and the deformation of the adsorbed brush. Our model involves only two fitting parameters, the monomer size and the area needed for one molecule during adsorption and is in agreement with the experimental data. We obtain a reasonable value for the monomer size and find an area per adsorbed polymer chain of the order of 1 nm, showing that the polymer chains are strongly stretched as they adsorb.
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http://dx.doi.org/10.1140/epje/i2018-11711-y | DOI Listing |
Adv Mater
January 2025
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun, 130012, China.
The design and synthesis of metal-organic frameworks (MOFs) with outstanding light-harvesting and photoexcitation for artificial photocatalytic CO reduction is an attractive but challenging task. In this work, a novel aggregation-induced emission (AIE)-active ligand, tetraphenylpyrazine (PTTBPC) is proposed and utilized for the first time to construct a Zr-MOF photocatalyst via coordination with stable Zr-oxo clusters. Zr-MOF is featured by a scu topology with a two-fold interpenetrated framework, wherein the PTTBPC ligands enable strong light-harvesting and photoexcitation, while the Zr-oxo clusters facilitate CO adsorption and activation, as well as offer potential sites for further metal modification.
View Article and Find Full Text PDFLangmuir
January 2025
Department of Mechanical Engineering, Imperial College London, South Kensington Campus, London SW7 2BX, United Kingdom.
Engine deposits can reduce performance and increase emissions, particularly for modern direct-injection fuel delivery systems. Surfactants known as deposit control additives (DCAs) adsorb and self-assemble on the surface of deposit precursors to keep them suspended in the fuel. Here, we show how molecular simulations can be used to virtually screen the ability of surfactants to bind to polyaromatic hydrocarbons, comprising a major class of carbonaceous deposits.
View Article and Find Full Text PDFLangmuir
January 2025
School of Physics, East China University of Science and Technology, Shanghai 200237, China.
Black phosphorus (BP), a promising two-dimensional material, faces significant challenges for its applications due to its instability in air and water. Herein, molecular dynamics simulations reveal that a self-assembled ferrocene (FeCp) molecular layer can form on BP surfaces and remain stable in aqueous environments, predicting its effectiveness for passivation. This theoretical finding is corroborated by X-ray photoelectron spectroscopy, Fourier-transform infrared spectroscopy, Raman spectroscopy, and optical microscopy observations.
View Article and Find Full Text PDFAcc Chem Res
January 2025
Key Lab of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, China.
ConspectusFor chemical reactions with complex pathways, it is extremely difficult to adjust the catalytic performance. The previous strategies on this issue mainly focused on modifying the fine structures of the catalysts, including optimization of the geometric/electronic structure of the metal nanoparticles (NPs), regulation of the chemical composition/morphology of the supports, and/or adjustment of the metal-support interactions to modulate the reaction kinetics on the catalyst surface. Although significant advances have been achieved, the catalytic performance is still unsatisfactory.
View Article and Find Full Text PDFNat Commun
January 2025
Key Laboratory of Special Functional and Smart Polymer Materials of Ministry of Industry and Information Technology, Xi'an Key Laboratory of Functional Organic Porous Materials, School of Chemistry and Chemical Engineering, Northwestern Polytechnical University, Xi'an, Shaanxi, China.
Separation of multi-component mixtures in an energy-efficient manner has important practical impact in chemical industry but is highly challenging. Especially, targeted simultaneous removal of multiple impurities to purify the desired product in one-step separation process is an extremely difficult task. We introduced a pore integration strategy of modularizing ordered pore structures with specific functions for on-demand assembly to deal with complex multi-component separation systems, which are unattainable by each individual pore.
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