Spatiotemporal Control Over Base‐Catalyzed Hydrogelation Using a Bilayer System

Ravarino, Paolo; Panja, Santanu; Adams, Dave J.

doi:10.1002/marc.202200606

Cited by 6 publications

(6 citation statements)

References 41 publications

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“…It should be noted that the self-assembly is usually driven by multiple noncovalent interactions. Control over supramolecular self-assembly using chemical reactions has received great interest in the past two decades, and this allows for: (1) triggering self-assembly in an aqueous environment immediately without the necessity of heating-cooling or solvent exchange; [14][15][16] (2) interfering with the selfassembly kinetics, thus leading to kinetically favoured assemblies with spatiotemporally resolved structures and functions; [17][18][19][20][21] (3) giving rise to highly dynamic assemblies at out-of-equilibrium states by taking the energy released by the chemical reaction. 11,[22][23][24][25] Amongst these developed examples of chemical reaction mediated supramolecular self-assembly, molecular hydrogels have been of particular interest because of their potent applications in biomedicine, and these are the focus of this feature article.…”

Section: Hucheng Wangmentioning

confidence: 99%

Dynamic supramolecular hydrogels mediated by chemical reactions

Chen,

Wang,

Long

et al. 2023

Chem. Commun.

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Section: Hucheng Wangmentioning

confidence: 99%

Dynamic supramolecular hydrogels mediated by chemical reactions

Chen,

Wang,

Long

et al. 2023

Chem. Commun.

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“…We have also reported a multicomponent system in which diffusion of individual components across a gel–gel interface led to interpenetrated gel networks . Others have made use of diffusion across oil–water interfaces to achieve spatially controlled gel assembly . Alternatively, the diffusion of LMWG precursors into a polymer gel loaded with an activating enzyme can generate an LMWG:PG network, and researchers have begun to explore spatial resolution …”

Section: Introductionmentioning

confidence: 96%

“… 6 Others have made use of diffusion across oil–water interfaces to achieve spatially controlled gel assembly. 7 Alternatively, the diffusion of LMWG precursors into a polymer gel loaded with an activating enzyme can generate an LMWG:PG network, and researchers have begun to explore spatial resolution. 8 …”

Section: Introductionmentioning

confidence: 99%

Fabricating Shaped and Patterned Supramolecular Multigelator Objects via Diffusion-Adhesion Gel Assembly

Tangsombun,

Smith

2023

J. Am. Chem. Soc.

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We report the use of acid-diffusion to assemble core–shell supramolecular gel beads with different low-molecular-weight gelators (LMWGs) in the core and shell. These gel beads grow a shell of dibenzylidenesorbitol-based DBS-COOH onto a core comprising DBS-CONHNH2 and agarose that has been loaded with acetic acid. Diffusion of the acid from the core triggers shell assembly. The presence of DBS-CONHNH2 enables the gel core to be loaded with metal nanoparticles (NPs) as acyl hydrazide reduces metal salts in situ. The pH-responsiveness of DBS-COOH allows responsive assembly of the shell with both temporal and spatial control. By fixing multiple gel beads in a Petri dish, the cores become linked to one another by the assembled DBS-COOH gel shella process we describe as diffusion-adhesion assembly. By controlling the geometry of the beads with respect to one another, it is possible to pattern the structures, and using a layer-by-layer approach, 3D objects can be fabricated. If some of the beads are loaded with basic DBS-carboxylate instead of CH3COOH, they act as a “sink” for diffusing protons, preventing DBS-COOH shell assembly in the close proximity. Those beads do not adhere to the remainder of the growing gel object and can be simply removed once diffusion-assembly is complete, acting as templates, and enabling the fabrication of 3D “imprinted” multigel architectures. Preloading the gel beads with AuNPs or AgNPs suspends these functional units within the cores at precisely defined locations within a wider gel object. In summary, this approach enables the dynamic fabrication of shaped and patterned gels with embedded metal NPssuch objects have potential next-generation applications in areas including soft nanoelectronics and regenerative medicine.

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“…The use of triggers has been widely studied by several researchers, 26–31 as a careful choice of the trigger strongly impacts the gel's final properties. For instance, the replacement of HCl with a hydrolysing reagent such as glucono‐δ‐lactone (GdL) 32,33 or 1,3‐propanesultone 34,35 induces gelation by a slow pH change allowing the formation of strong homogeneous hydrogels.…”

Section: Introductionmentioning

confidence: 99%

“…23,24 It should also be noticed that in this field, it is of extreme importance to work in a reproducible way, carefully controlling all the parameters and steps involved in the gelation process (solvent, concentration, time, temperature, etc.). 25 The use of triggers has been widely studied by several researchers, [26][27][28][29][30][31] as a careful choice of the trigger strongly impacts the gel's final properties. For instance, the replacement of HCl with a hydrolysing reagent such as glucono-δ-lactone (GdL) 32,33 or 1,3-propanesultone 34,35 induces gelation by a slow pH change allowing the formation of strong homogeneous hydrogels.…”

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confidence: 99%

A short oxazolidine‐2‐one containing peptide forms supramolecular hydrogels under controlled conditions

Ravarino

Giuri

Tomasini

2023

Journal of Peptide Science

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Low‐molecular‐weight hydrogels are made of a small percentage of small organic molecules dispersed in an aqueous medium, which may aggregate in several manners using different methods. However, often the organic gelator in water has poor solubility, so the addition of a solubilising agent is required. In the case of acidic gelators, this mainly consists of the addition of a strong base, that is sodium hydroxide, that deprotonates the acidic moiety, so the gelator molecules become more soluble and tend to assemble into micelles, forming a dispersion. Some gelators, however, are sensitive to the harsh pH and get hydrolysed. This is the case of some molecules presenting carbamates in their features, like Fmoc‐protected or oxazolidinone‐containing peptides. In this paper, we present a valid alternative to sodium hydroxide, by dissolving a tripeptide containing an oxazolidinone moiety in a phosphate buffer (PB) medium at pH 7.4. The results obtained with the NaOH dissolution are compared with the ones with PB, as both methods present advantages and drawbacks. The use of NaOH produces transparent but weak hydrogels, as it exposes the gelator to harsh conditions that end up in its partial hydrolysis, which is more pronounced at high concentrations (≥10 mM). Using PB to dissolve the gelator, this problem is completely avoided as no hydrolysis product has been detected in the hydrogels, which are very stiff although more opaque. By tuning the preparation conditions, we can obtain a wide variety of hydrogels, with the properties required by the final application.

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Spatiotemporal Control Over Base‐Catalyzed Hydrogelation Using a Bilayer System

Cited by 6 publications

References 41 publications

Dynamic supramolecular hydrogels mediated by chemical reactions

Dynamic supramolecular hydrogels mediated by chemical reactions

Fabricating Shaped and Patterned Supramolecular Multigelator Objects via Diffusion-Adhesion Gel Assembly

A short oxazolidine‐2‐one containing peptide forms supramolecular hydrogels under controlled conditions

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