Amplified Rate Acceleration by Simultaneous Up-Regulation of Multiple Active Sites in an Endo-Functionalized Porous Capsule

Sivil Kopilevich; Achim Müller; Ira A. Weinstock

doi:10.1021/jacs.5b06211

Amplified Rate Acceleration by Simultaneous Up-Regulation of Multiple Active Sites in an Endo-Functionalized Porous Capsule

Sivil Kopilevich, Achim Müller, Ira A. Weinstock

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

21 Scopus citations

Abstract

Using the hydrolysis of epoxides in water as a model reaction, the effect of multiple active sites on Michaelis-Menten compliant rate accelerations in a porous capsule is demonstrated. The capsule is a water-soluble I_h-symmetry Keplerate-type complex of the form, [{Mo^VI₆O₂₁(H₂O)₆}₁₂{Mo^V₂O₄(L)}₃₀]^42-, in which 12 pentagonal "ligands," {(Mo^VI)Mo^VI₅O₂₁(H₂O)₆}^6-, are coordinated to 30 dimolybdenum sites, {Mo^V₂O₄L}¹⁺ (L = an endohedrally coordinated ν²-bound carboxylate anion), resulting in 20 Mo₉O₉ pores. When "up-regulated" by removal of ca. one-third of the blocking ligands, L, an equal number of dimolybdenum sites are activated, and the newly freed-up space allows for encapsulation of nearly twice as many substrate guests, leading to a larger effective molarity (amplification), and an increase in the rate acceleration (k_cat/k_uncat) from 16,000 to an enzyme-like value of 182,800.

Original language	English
Pages (from-to)	12740-12743
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	137
Issue number	40
DOIs	https://doi.org/10.1021/jacs.5b06211
State	Published - 14 Oct 2015

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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title = "Amplified Rate Acceleration by Simultaneous Up-Regulation of Multiple Active Sites in an Endo-Functionalized Porous Capsule",

abstract = "Using the hydrolysis of epoxides in water as a model reaction, the effect of multiple active sites on Michaelis-Menten compliant rate accelerations in a porous capsule is demonstrated. The capsule is a water-soluble Ih-symmetry Keplerate-type complex of the form, [{MoVI6O21(H2O)6}12{MoV2O4(L)}30]42-, in which 12 pentagonal {"}ligands,{"} {(MoVI)MoVI5O21(H2O)6}6-, are coordinated to 30 dimolybdenum sites, {MoV2O4L}1+ (L = an endohedrally coordinated ν2-bound carboxylate anion), resulting in 20 Mo9O9 pores. When {"}up-regulated{"} by removal of ca. one-third of the blocking ligands, L, an equal number of dimolybdenum sites are activated, and the newly freed-up space allows for encapsulation of nearly twice as many substrate guests, leading to a larger effective molarity (amplification), and an increase in the rate acceleration (kcat/kuncat) from 16,000 to an enzyme-like value of 182,800.",

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AU - Müller, Achim

AU - Weinstock, Ira A.

PY - 2015/10/14

Y1 - 2015/10/14

N2 - Using the hydrolysis of epoxides in water as a model reaction, the effect of multiple active sites on Michaelis-Menten compliant rate accelerations in a porous capsule is demonstrated. The capsule is a water-soluble Ih-symmetry Keplerate-type complex of the form, [{MoVI6O21(H2O)6}12{MoV2O4(L)}30]42-, in which 12 pentagonal "ligands," {(MoVI)MoVI5O21(H2O)6}6-, are coordinated to 30 dimolybdenum sites, {MoV2O4L}1+ (L = an endohedrally coordinated ν2-bound carboxylate anion), resulting in 20 Mo9O9 pores. When "up-regulated" by removal of ca. one-third of the blocking ligands, L, an equal number of dimolybdenum sites are activated, and the newly freed-up space allows for encapsulation of nearly twice as many substrate guests, leading to a larger effective molarity (amplification), and an increase in the rate acceleration (kcat/kuncat) from 16,000 to an enzyme-like value of 182,800.

AB - Using the hydrolysis of epoxides in water as a model reaction, the effect of multiple active sites on Michaelis-Menten compliant rate accelerations in a porous capsule is demonstrated. The capsule is a water-soluble Ih-symmetry Keplerate-type complex of the form, [{MoVI6O21(H2O)6}12{MoV2O4(L)}30]42-, in which 12 pentagonal "ligands," {(MoVI)MoVI5O21(H2O)6}6-, are coordinated to 30 dimolybdenum sites, {MoV2O4L}1+ (L = an endohedrally coordinated ν2-bound carboxylate anion), resulting in 20 Mo9O9 pores. When "up-regulated" by removal of ca. one-third of the blocking ligands, L, an equal number of dimolybdenum sites are activated, and the newly freed-up space allows for encapsulation of nearly twice as many substrate guests, leading to a larger effective molarity (amplification), and an increase in the rate acceleration (kcat/kuncat) from 16,000 to an enzyme-like value of 182,800.

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Amplified Rate Acceleration by Simultaneous Up-Regulation of Multiple Active Sites in an Endo-Functionalized Porous Capsule

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