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Minimalist Second-Sphere Engineering with Polyvinyl Alcohol Drives Cooperative Hydrolysis in Zn(II) System

Zhang, Tong LU and Ye, Lei LU orcid (2026) In Dalton Transactions 55. p.6270-6275
Abstract
First sphere engineering has enabled potent artificial phosphatases, but
strategies that generate enzyme-like second-sphere effects with simple
disordered materials remain limited. Here we demonstrate that partially
hydrolyzed polyvinyl alcohol (PVA80, 80% hydrolyzed) acts as a
minimalist soft matter scaffold that amplifies the hydrolytic activity
of hydrated Zn(II). Rather than functioning as a static
host, the amphiphilic polymer undergoes substrate induced reorganization
to form hydrophobic microdomains. These microdomains enrich the
substrate and organize labile Zn(II) into cooperative
catalytic networks that exhibit cooperative kinetics with a Hill
coefficient of 4.2, and selectivity... (More)
First sphere engineering has enabled potent artificial phosphatases, but
strategies that generate enzyme-like second-sphere effects with simple
disordered materials remain limited. Here we demonstrate that partially
hydrolyzed polyvinyl alcohol (PVA80, 80% hydrolyzed) acts as a
minimalist soft matter scaffold that amplifies the hydrolytic activity
of hydrated Zn(II). Rather than functioning as a static
host, the amphiphilic polymer undergoes substrate induced reorganization
to form hydrophobic microdomains. These microdomains enrich the
substrate and organize labile Zn(II) into cooperative
catalytic networks that exhibit cooperative kinetics with a Hill
coefficient of 4.2, and selectivity for hydrophobic substrates. The
catalyst has an apparent Michaelis–Menten constant (KM) of 0.52 mM and a catalytic efficiency (kcat/KM) of 1.86 × 10−2 M−1 s−1, approaching the performance of synthetic Zn(II) phosphoesterases based on Zn(II)
complexes. Solvatochromic and solvent isotope analyses indicate that
rate enhancement arises from coupled hydrophobic partitioning and
polymer assisted proton transfer. In contrast, Ce(IV)
retains Michaelis–Menten behavior upon polymer addition, with PVA80
primarily enhancing substrate availability without inducing cooperative
activation. These findings show that enzyme like behavior can emerge
from disordered polymer interfaces, and simple polymer chains can
provide an accessible strategy to modulate metal reactivity without
complicated synthesis. (Less)
Please use this url to cite or link to this publication:
author
and
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Dalton Transactions
volume
55
pages
6 pages
publisher
Royal Society of Chemistry
external identifiers
  • pmid:41989432
  • scopus:105035739177
ISSN
1477-9234
DOI
10.1039/d6dt00435k
language
English
LU publication?
yes
id
311ac2c8-8d27-444f-9ee5-5a0e10b0fc3f
date added to LUP
2026-04-29 11:41:06
date last changed
2026-04-30 04:00:51
@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}},
}