Native protein hydrogels by dynamic boronic acid chemistry

Dynamic Core–Shell Bioconjugates for Targeted Protein Delivery and Release

“…These binding partners mainly involve 1,2 cis ‐diols like glucose, catechols and also other multivalent interactions involving nitrogen donors such as MIDA and salicyl hydroxamates . Depending on the electronic demand, these binding events can occur with a broad range of binding affinities under physiological conditions, leading to the construction of materials ranging from click‐type peptide ligations, responsive nanosystems to bulk materials like hydrogels . These interactions are reversibly dependent on pH, with cis ‐diols dissociating at acidic medium (≈pH 5) and MIDA boronates at basic conditions (≈pH 9) .…”

“…[12] Depending on the electronic demand, these binding eventsc an occur with ab road range of binding affinities under physiological conditions, leadingt ot he construction of materials ranging from click-type peptidel igations, [13] responsiven anosystems [14] to bulk materials like hydrogels. [15] These interactions are reversibly dependent on pH, with cisdiols dissociating at acidic medium (% pH 5) [12] and MIDA boronates at basic conditions (% pH 9). [16] Moreover,g iven that boronic acids are widely used in Suzukicross coupling reactions, [11] the enormous syntheticl ibrary provides an atural advantage in terms of design strategies over most dynamic covalent systems.…”

“…Separately,t he protein surface of CytC and HSA was statistically primedw ith boronic acid groups (BA) via condensation of phenylboronic acid N-hydroxysuccinimidyl ester onto the solvent accessible lysine residues (FigureS8). [14,15] The functionalized proteins (CytC-BA, HSA-BA, Figure S2) were purified by centrifugal ultrafiltration and the numbers of BA moieties were analysed from MALDIT OF MS spectra, affording1 1B Ag roups for CytC-BA( Figure S9) and 22 for HSA-BA ( Figure S10). The quantification wasc ross-checkedb yafluorescencet itration assay based on Alizarin Red S, af luorogenic sensor that detects BA moieties.…”

Cross‐Linking Building Blocks Using a “Boronate Bridge” to Build Functional Hybrid Materials

“…Seidler et al also developed native protein hydrogels consisting of proteins modified with BAs and a linear or 4-armed poly(ethylene glycol) modified with salicyl-hydroxamate at termini. [25] The obtained hydrogel, upon mixing BA-modified cytochrome c and salicylhydroxamate-modified PEG, could be degraded at slightly acidic pH, leading to the enzyme-induced apoptosis of cancer cells. Montanari et al developed a tyrosinase-mediated bioconjugation system based on hyaluronic acid modified with 3-aminoPBA and various biomacromolecules that had tyrosine residues ( Figure 3).…”

“…Seidler et al. also developed native protein hydrogels consisting of proteins modified with BAs and a linear or 4‐armed poly(ethylene glycol) modified with salicyl‐hydroxamate at termini . The obtained hydrogel, upon mixing BA‐modified cytochrome c and salicyl‐hydroxamate‐modified PEG, could be degraded at slightly acidic pH, leading to the enzyme‐induced apoptosis of cancer cells.…”