The design of films using a one-pot process has recently attracted increasing interest in the field of polymer thin film formation. Herein we describe the preparation of one-pot supramolecular polyrotaxane (PRX) films using the morphogen-driven self-construction process. This one-pot buildup strategy where the film growth is triggered by the electrochemical formation and diffusion of a catalyst in close vicinity of the substrate has recently been introduced by our group. A one-pot mixture was used that contained (i) poly(acrylic acid) (PAA) functionalized by azide groups grafted on the polymer chain through oligo(ethylene glycol) (EG) arms, leading to PAA-EG13-N3, (ii) cyclodextrins (α and β CD), as macrocycles that can be threaded along EG arms, (iii) alkyne-functionalized stoppers (ferrocene or adamantane), to cap the PRX assembly by click chemistry, and (iv) copper sulfate. The one-pot mixture solution was brought into contact with a gold electrode. Cu(I), the morphogen, was generated electrochemically from Cu(II) at the electrode/one-pot solution interface. This electrotriggered click reaction leads to the capping of polypseudorotaxane yielding to PRXs. The PRXs can self-assemble through lateral supramolecular interactions to form aggregates and ensure the cohesion of the film. The film buildup was investigated using different types of CD and alkyne functionalized stoppers. Supramolecular PRX aggregates were characterized by X-ray diffraction measurements. The film topographies were imaged by atomic force microscopy. The influence of the concentration in CD and the presence of a competitor were studied as well. The stability of the resulting film was tested in contact with 8 M urea and during the electrochemical oxidation of ferrocene.
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http://dx.doi.org/10.1021/la402454e | DOI Listing |
J Nanobiotechnology
November 2024
Guangdong Provincial Key Laboratory of Spine and Spinal Cord Reconstruction, The Fifth Affiliated Hospital (Heyuan Shenhe People's Hospital), Jinan University, Heyuan, 517000, China.
Bacterial biofilms are one of the major contributors to the refractoriness of septic arthritis. Although nitric oxide (NO)-enhanced photodynamic (PDT) therapy has been involved in biofilm eradication, the anti-biofilm efficacy is usually hindered by the short half-life and limited diffusion distance of active molecules. Herein, we report a three-arm structure using the photosensitive core chlorin e6 to integrate three α-cyclodextrin (α-CD) polyrotaxane chains as the supramolecular nanocarrier of NO-enhanced PDT therapy, in which NO was loaded on the cationic rings (α-CDs).
View Article and Find Full Text PDFChem Sci
December 2024
Department of Chemistry, Faculty of Technology, Tomas Bata University in Zlín Vavrečkova 5669 760 01 Zlín Czech Republic
Rotaxanes can be regarded as storage systems for their wheel components, which broadens their application potential as a complement to the supramolecular systems that retain a mechanically interlocked structure. However, utilising rotaxanes in this way requires a method to release the wheel while preserving the integrity of all molecular constituents. Herein, we present simple rotaxanes based on cucurbit[6]uril (CB6), with an axis equipped with an additional binding motif that enables the binding of another macrocycle, cucurbit[7]uril (CB7).
View Article and Find Full Text PDFJ Colloid Interface Sci
February 2025
The Key Laboratory of Biomedical Material, School of Life Science and Technology, Xinxiang Medical University, Xinxiang, PR China.
A new type of pH-sensitive hydrogel containing supramolecular structures was fabricated from maleimide-functionalized polyrotaxane, ɛ-polylysine and furan-functionalized hyaluronic acid by Diels-Alder reaction and amino-maleimide reaction. Firstly, pseudo polyrotaxane was obtained through self-assembly of polyethylene glycol and α-cyclodextrin, and then capped with 1-adamantanecarboxylic acid to convert it into polyrotaxane. Secondly, a maleimide-functionalized slidable crosslinker was obtained by modifying the polyrotaxane with 3-maleimide propionic acid, and furan-functionalized hyaluronic acid was prepared by modifying it with 2-furanmethylamine.
View Article and Find Full Text PDFChemistry
November 2024
State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing, 100029, P. R. China.
A series of unprecedented supramolecular complexes of covalently modified Anderson-type polyoxometalates (POMs) and α-cyclodextrins (α-CDs) have been obtained and characterized in solid state by single-crystal X-ray diffraction, and in aqueous solution using various techniques including H DOSY NMR, 2D NOESY H NMR, isothermal titration calorimetry (ITC), and electrospray ionization time-of-flight mass spectroscopy (ESI-TOF-MS). It has been demonstrated that the supramolecular assembly process could be modulated by different covalent modification modes of the Anderson POMs, giving rise to a new type of POM/α-CD complexes featuring organic-inorganic pseudo-rotaxane structures, which are in good contrast to those of POM/γ-CD complexes of poly-rotaxane structures. Moreover, it is delighted to find that these pseudo-rotaxanes of POM/α-CD complexes exhibit stable chirality in aqueous solution, which has not been accomplished in previously reported POM/CD assemblies.
View Article and Find Full Text PDFSoft Matter
November 2024
Department of Chemistry, Dartmouth College, Hanover, New Hampshire 03755, USA.
Controlling the distribution of rings on polymer axles, such as α-cyclodextrin (αCD) on polyethylene glycol (PEG), is paramount in imparting robust mechanical properties to slide-ring gels and polyrotaxane-based networks. Previous experiments demonstrated that the functionalization of polymer ends could modulate the coverage of αCDs on PEG. To explore the design rule, we propose a multi-scale framework for predicting αCD assembly on bare and functionalized PEG.
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