Aurophilically cross-linked “dynamic” hydrogels mimicking healthy synovial fluid properties

Casuso, Pablo; Vicente, Adrián Pérez-San; Iribar, Haizea; Gutiérrez-Rivera, Araika; Izeta, Ander; Loinaz, Iraida; Cabañero, Germán; Grande, Hans‐Jürgen; Odriozola, Ibon; Dupin, Damien

doi:10.1039/c4cc05735j

Cited by 39 publications

(46 citation statements)

References 23 publications

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“…The selection of (PEGSH) 4 with an existing cross-linking point to strengthen the final hydrogel was justified, as linear PEG(SH) 2 only led to chain extension after aerial oxidation, as previously reported. 32 Unlike Au20, free-standing PEGSS hydrogel was observed at all pHs. Clearly, the presence of Au−S species is responsible for the dynamic character observed for Au20 at alkaline pH.…”

Section: ■ Experimental Sectionmentioning

confidence: 94%

Injectable and Self-Healing Dynamic Hydrogels Based on Metal(I)-Thiolate/Disulfide Exchange as Biomaterials with Tunable Mechanical Properties

et al. 2015

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Despite numerous strategies involving dynamic covalent bonds to produce self-healing hydrogels with similar frequency-dependent stiffness to native tissues, it remains challenging to use biologically relevant thiol/disulfide exchange to confer such properties to polymeric networks. Herein, we report a new method based on Metal(I) [Au(I) or Ag(I)] capping to protect thiolates from aerial oxidation without preventing thiolate/disulfide exchange. Dynamic hydrogels were readily prepared by injecting simultaneously aqueous solutions of commercially available HAuCl4 and 4-arm thiol-terminated polyethylene glycol [(PEGSH)4], resulting in a network containing a mixture of Au(I)-thiolate (Au-S) and disulfide bonds (SS). While the dynamic properties of the hydrogel were closely dependent on the pH, the mechanical properties could be easily tuned by adjusting (PEGSH)4 concentration and amount of Au-S, as judged by dynamic rheology studies. Permanent Au-S/SS exchange at physiological pH conferred self-healing behavior and frequency-dependent stiffness to the hydrogel. In addition, in vitro studies confirmed that Au-based dynamic material was not cytotoxic to human dermal fibroblasts, demonstrating its potential use as a medical device. Dynamic hydrogels obtained using Ag(I) ions demonstrated that the exchange reaction was not affected by the nature of the Metal(I) capping. Finally, this efficient thiolate capping strategy offers a simple way to produce injectable and self-healing dynamic hydrogels from virtually any thiol-containing polymers.

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Section: ■ Experimental Sectionmentioning

confidence: 94%

Injectable and Self-Healing Dynamic Hydrogels Based on Metal(I)-Thiolate/Disulfide Exchange as Biomaterials with Tunable Mechanical Properties

et al. 2015

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“…11 Among the resulting supramolecular structures obtained with low molecular weight gold(I) complexes, recent reports on hydrogelators should be highlighted. [12][13][14] The formation of these gels has been driven through non-covalent interactions, which are commonly van der Waals forces, hydrogen bonding, electrostatic attractions and  stacking interactions, together with aurophilic interactions. 12 Our recent results on the formation of hydrogels from small organometallic complexes containing Au(I)-alkynyl moieties, [15][16][17] prompted us to go one step further in the design and synthesis of novel supramolecular nanostructures constituted by selfassembly of small molecules.…”

Section: Introductionmentioning

confidence: 99%

Tuning supramolecular aurophilic structures: the effect of counterion, positive charge and solvent

et al. 2016

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The synthesis of the cationic gold(I) complexes [Au (C≡CC 5 These results reveal the importance of the introduction of a positive charge on the global supramolecular assemblies and how the counterion can modify also the resulting package. Interestingly, we have also proved that the aggregation of complexes 2, 3, 5and 6 is also affected by the solvent with direct influence on their absorption and emission properties and the global morphology of the aggregates.

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“…Similar differences can also be found among novel systems proposed as candidates for viscosupplementation. 40,[42][43][44][45] Tests performed on blends with different gel fractions have shown that an acceptable structural recovery after continuous shear application (more than 80-90 %) is attained when the gel fraction is lower than 50 %. Thus, the 6/4 CMCAp/CMCAg blend has been provisionally selected for the final investigation addressed to individuate the most suitable total polymer concentration, apt to compensate the loss in mechanical properties occurring during processing and sterilization.…”

Section: F I G 4 -Viscoelastic Responses Of 25 % Cmcap and 25 % Cmentioning

confidence: 99%

Rheological Studies Dedicated to the Development of a Novel Injectable Polymeric Blend for Viscosupplementation Treatment

Lapasin

Segatti

Mercuri

et al. 2016

Chem. Biochem. Eng. Q.

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Viscosupplementation is an intra-articular symptomatic treatment of mild osteoarthritis. The treatment involves the injection of high-molecular-weight hyaluronan (HA), and especially of cross-linked HA to restore the lubricating and cushioning properties of the synovial fluid.This work involves the development of a novel viscosupplementation fluid based on amidated carboxymethylcellulose and obtained by blending the soluble polymer with its crosslinked derivative. Rheological analyses carried out under both oscillatory and continuous shear provided a rationale to assess the viscosupplement formulation and the production process. The hydrogel fraction content and the total polymer concentration can be properly selected in order to ensure an optimal combination of flowability and viscoelastic properties.

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Aurophilically cross-linked “dynamic” hydrogels mimicking healthy synovial fluid properties

Abstract: We report a new supramolecular dynamic hydrogel, based on a new concept of reversible aurophilic cross-linkers, mimicking the rheological behaviour of healthy synovial fluid under physiological conditions with good cell viability.

Cited by 39 publications

References 23 publications

Injectable and Self-Healing Dynamic Hydrogels Based on Metal(I)-Thiolate/Disulfide Exchange as Biomaterials with Tunable Mechanical Properties

Injectable and Self-Healing Dynamic Hydrogels Based on Metal(I)-Thiolate/Disulfide Exchange as Biomaterials with Tunable Mechanical Properties

Tuning supramolecular aurophilic structures: the effect of counterion, positive charge and solvent

Rheological Studies Dedicated to the Development of a Novel Injectable Polymeric Blend for Viscosupplementation Treatment

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