Isothermal titration calorimetry (ITC) is an apt tool for a total thermodynamic description of self-assembly of atypical amphiphiles such as anionic boron cluster compounds (COSAN) in water. Global fitting of ITC enthalpograms reveals remarkable features that differentiate COSAN from classical amphiphiles: (i) strong enthalpy and weak entropy contribution to the free energy of aggregation, (ii) low degree of counterion binding, and (iii) very low aggregation number, leading to deviations from the ideal closed association model. The counterion condensation obtained from the thermodynamic model was compared with the results of 7Li DOSY NMR of Li[COSAN] micelles, which allows direct tracking of Li cations. The basic thermodynamic study of COSAN alkaline salt aggregation was complemented by NMR and ITC experiments in dilute Li/NaCl and acetonitrile aqueous solutions of COSAN. The strong affinity of acetonitrile molecules to COSAN clusters was microscopically investigated by all-atomic molecular dynamics simulations. The impact of ionic strength on COSAN self-assembling was comparable to the behavior of classical amphiphiles, whereas even a small amount of acetonitrile cosolvent has a pronounced nonclassical character of COSAN aggregation. It demonstrates that large self-assembling changes are triggered by traces of organic solvents.
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http://dx.doi.org/10.1021/acs.langmuir.8b03462 | DOI Listing |
Angew Chem Int Ed Engl
December 2024
Tongji University, School of Material Science and Engineering, CHINA.
A classical crystallization usually grows epitaxially from a crystal nucleus. Presented in this study is an unusual endotaxy growth manner of a crystalline homopolymer to form hexagonal nanosheets. The amphiphilic homopolymer, poly(3-(4-(phenyldiazenyl)phenoxy)propyl methacrylate) (PAzoPMA), is first annealed in isopropanol to afford a hexagonal nut-like structure.
View Article and Find Full Text PDFInt J Nanomedicine
November 2024
School of Pharmacy, Shandong Engineering Research Center of New-Type Drug Loading & Releasing Technology and Preparation, Binzhou Medical University, Yantai, Shandong, People's Republic of China.
Introduction: -induced pneumonia is marked by considerable infiltration of inflammatory cells and biofilm formation, which causes acute and transient lung inflammation and infection. Nevertheless, the discovery of alternative preventative and therapeutic methods is essential due to the high mortality rates in clinical settings and the resistance of infection to multiple medications.
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Colloids Surf B Biointerfaces
January 2025
Shanxi Province Key Laboratory of Oral Diseases Prevention and New Materials, School and Hospital of Stomatology, Shanxi Medical University, Taiyuan, Shanxi 030001, China. Electronic address:
Healing wounds presents a significant challenge due to bacterial biofilm infections and the inherent drug resistance of these biofilms. This report introduces a multifunctional nanoplatform (NPs) designed to combat wound biofilm infections using NIR-II photothermal therapy. The NPs are self-assembled from amphiphilic polymers (AP) to encapsulate photothermal polymers (PT) through classic electrostatic interactions.
View Article and Find Full Text PDFSoft Matter
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A.N. Nesmeyanov Institute of Organoelement Compounds Russian Academy of Sciences, Vavilova ul. 28, bld. 1, Moscow, 119334, Russia.
By means of computer modelling, the self-assembly of amphiphilic A--B macromolecules, grafted onto a spherical nanoparticle, is studied. In a solvent, that is poor for side pendants, the macromolecules self-assemble into thin membrane-like ABBA bilayers deviated from spherical nanoparticles. The bilayers form morphological structures that depend on the grafting density and macromolecular polymerization degree and can be referred to as the classical family of complete embedded minimal surfaces.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
October 2024
Department of Polymer Materials, School of Materials Science and Engineering, Shanghai University, Nanchen Street 333, Shanghai, 200444, China.
The widespread presence of hierarchical asymmetric structures in nature has sparked considerable interest because of their unique functionalities. These ingenious structures across multiple scales often emerge from the transfer and amplification of asymmetry from chiral molecules under various synergistic effects. However, constructing artificial chiral asymmetric structures, particularly in developing hierarchical multicomponent structures analogous to those formed in nature through synergistic non-covalent interactions, still presents tremendous challenges.
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