Abstract:The folding of synthetic polymers into single chain nanoparticles draws inspiration from the folding of polypeptides into the functional macromolecular architectures of proteins. The building blocks of their natural inspiration,...
“…For instance, SCNPs folded through hydrogen bonding (HB) interactions were found to unfold upon acidification, by addition of a competitive HB compound, − anion, solvent, or by increasing temperature. , Additionally, reversible SCNPs have been unfolded triggered by addition of a base, under interrupted illumination (i.e., dark conditions), by losing CO 2 molecules , or upon external voltage stimuli . Complementary, SCNPs folded through dynamic covalent bonds like disulfide , or enamine bonds went back to their linear precursor chains in the presence of reducing agents or by lowering the pH, respectively. The decrease in activity of some catalytic SCNPs in vivo was attributed to the spontaneous unfolding of these reversible SCNPs in these complex media …”
Herein, we disclose a unique and selective reagent for the cleavage of stable azaylides prepared by the nonhydrolysis Staudinger reaction, enabling the on-demand unfolding of robust single-chain nanoparticles (SCNPs). SCNPs with promising use in catalysis, nanomedicine, and sensing are obtained through intrachain folding of discrete synthetic polymer chains. The unfolding of SCNPs involving reversible interactions triggered by a variety of external stimuli (e.g., pH, temperature, light, and redox potential) or substances (e.g., competitive reagents, solvents, and anions) is well known. Conversely, methods for the unfolding (i.e., intrachain disassembly) of SCNPs with stronger covalent interactions are scarce. We show that trimethylsilanol (Me 3 SiOH) triggers the efficient unfolding of robust "Staudinger" SCNPs with stable azaylide (−N�P−) moieties as intrachain cross-linking units showing exceptional stability toward water, air, and CS 2 , a standard reagent for azaylides. As a consequence, Me 3 SiOH arises as a rare, exceptional, and valuable reagent for the cleavage of stable azaylides prepared by the nonhydrolysis Staudinger reaction.
“…For instance, SCNPs folded through hydrogen bonding (HB) interactions were found to unfold upon acidification, by addition of a competitive HB compound, − anion, solvent, or by increasing temperature. , Additionally, reversible SCNPs have been unfolded triggered by addition of a base, under interrupted illumination (i.e., dark conditions), by losing CO 2 molecules , or upon external voltage stimuli . Complementary, SCNPs folded through dynamic covalent bonds like disulfide , or enamine bonds went back to their linear precursor chains in the presence of reducing agents or by lowering the pH, respectively. The decrease in activity of some catalytic SCNPs in vivo was attributed to the spontaneous unfolding of these reversible SCNPs in these complex media …”
Herein, we disclose a unique and selective reagent for the cleavage of stable azaylides prepared by the nonhydrolysis Staudinger reaction, enabling the on-demand unfolding of robust single-chain nanoparticles (SCNPs). SCNPs with promising use in catalysis, nanomedicine, and sensing are obtained through intrachain folding of discrete synthetic polymer chains. The unfolding of SCNPs involving reversible interactions triggered by a variety of external stimuli (e.g., pH, temperature, light, and redox potential) or substances (e.g., competitive reagents, solvents, and anions) is well known. Conversely, methods for the unfolding (i.e., intrachain disassembly) of SCNPs with stronger covalent interactions are scarce. We show that trimethylsilanol (Me 3 SiOH) triggers the efficient unfolding of robust "Staudinger" SCNPs with stable azaylide (−N�P−) moieties as intrachain cross-linking units showing exceptional stability toward water, air, and CS 2 , a standard reagent for azaylides. As a consequence, Me 3 SiOH arises as a rare, exceptional, and valuable reagent for the cleavage of stable azaylides prepared by the nonhydrolysis Staudinger reaction.
“…Indeed several SCNPs bearing the serine-aspartate-histidine catalytic triad have been incorporated into SCNPs to mimic the hydrolytic activity of esterase. 14,15 Perhaps the simplest way to fold an SCNP is via the collapse of a hydrophobic segment of a polymer in water. Tuning the structure of the polymer can give sufficient control over the collapsed structure for many applications.…”
Section: Introductionmentioning
confidence: 99%
“…Indeed several SCNPs bearing the serine–aspartate–histidine catalytic triad have been incorporated into SCNPs to mimic the hydrolytic activity of esterase. 14,15…”
Folding polymers into a well defined structures in solution is a critical step towards fully synthetic protein mimics. Peptides motifs such as diphenylalanine (FF) provide a versatile and thermally reversible...
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