@article{311ac2c8-8d27-444f-9ee5-5a0e10b0fc3f,
  abstract     = {{First sphere engineering has enabled potent artificial phosphatases, but<br>
 strategies that generate enzyme-like second-sphere effects with simple <br>
disordered materials remain limited. Here we demonstrate that partially <br>
hydrolyzed polyvinyl alcohol (PVA80, 80% hydrolyzed) acts as a <br>
minimalist soft matter scaffold that amplifies the hydrolytic activity <br>
of hydrated Zn(II). Rather than functioning as a static <br>
host, the amphiphilic polymer undergoes substrate induced reorganization<br>
 to form hydrophobic microdomains. These microdomains enrich the <br>
substrate and organize labile Zn(II) into cooperative <br>
catalytic networks that exhibit cooperative kinetics with a Hill <br>
coefficient of 4.2, and selectivity for hydrophobic substrates. The <br>
catalyst has an apparent Michaelis–Menten constant (<em>K</em><sub>M</sub>) of 0.52 mM and a catalytic efficiency (<em>k</em><sub>cat</sub>/<em>K</em><sub>M</sub>) of 1.86 × 10<sup>−2</sup> M<sup>−1</sup> s<sup>−1</sup>, approaching the performance of synthetic Zn(II) phosphoesterases based on Zn(II)<br>
 complexes. Solvatochromic and solvent isotope analyses indicate that <br>
rate enhancement arises from coupled hydrophobic partitioning and <br>
polymer assisted proton transfer. In contrast, Ce(IV) <br>
retains Michaelis–Menten behavior upon polymer addition, with PVA80 <br>
primarily enhancing substrate availability without inducing cooperative <br>
activation. These findings show that enzyme like behavior can emerge <br>
from disordered polymer interfaces, and simple polymer chains can <br>
provide an accessible strategy to modulate metal reactivity without <br>
complicated synthesis.}},
  author       = {{Zhang, Tong and Ye, Lei}},
  issn         = {{1477-9234}},
  language     = {{eng}},
  pages        = {{6270--6275}},
  publisher    = {{Royal Society of Chemistry}},
  series       = {{Dalton Transactions}},
  title        = {{Minimalist Second-Sphere Engineering with Polyvinyl Alcohol Drives Cooperative Hydrolysis in Zn(II) System}},
  url          = {{http://dx.doi.org/10.1039/d6dt00435k}},
  doi          = {{10.1039/d6dt00435k}},
  volume       = {{55}},
  year         = {{2026}},
}