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. 2015 Dec 7;21(50):18047-51.
doi: 10.1002/chem.201504087. Epub 2015 Oct 29.

Enzymatic Dissolution of Biocomposite Solids Consisting of Phosphopeptides to Form Supramolecular Hydrogels

Junfeng Shi  1 , Dan Yuan  1 , Richard Haburcak  1 , Qiang Zhang  2 , Chao Zhao  2 , Xixiang Zhang  2 , Bing Xu  3
Affiliations

Enzymatic Dissolution of Biocomposite Solids Consisting of Phosphopeptides to Form Supramolecular Hydrogels

Junfeng Shi et al. Chemistry. .

Abstract

Enzyme-catalyzed dephosphorylation is essential for biomineralization and bone metabolism. Here we report the exploration of using enzymatic reaction to transform biocomposites of phosphopeptides and calcium (or strontium) ions to supramolecular hydrogels as a mimic of enzymatic dissolution of biominerals. (31) P NMR shows that strong affinity between the phosphopeptides and alkaline metal ions (e.g., Ca(2+) or Sr(2+) ) induces the formation of biocomposites as precipitates. Electron microscopy reveals that the enzymatic reaction regulates the morphological transition from particles to nanofibers. Rheology confirms the formation of a rigid hydrogel. As the first example of enzyme-instructed dissolution of a solid to form supramolecular nanofibers/hydrogels, this work provides an approach to generate soft materials with desired properties, expands the application of supramolecular hydrogelators, and offers insights to control the demineralization of calcified soft tissues.

Keywords: bone mineralization; enzyme; phosphopeptide; self-assembly; solid-gel transition.

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Figures

Figure 1
Figure 1
a) Enzymatic dephosphorylation of 1P to 1. b) A typical procedure for preparation of the hydrogels via the enzymatic solid-gel transition: 1P dissolves in 7.4 tris-HCl buffer at initial concentration of 0.6 wt% (8.29 mM), the concentration of saturated Ca3(PO4)2 is around 3.87 μM, and [1P]0:[M]0 is 1:2.
Figure 2
Figure 2
31P NMR spectra show the formation of precipitates made of 1P and M2+ (M = Ca or Sr) after the addition of various amounts of CaCl2 (left panel) and SrCl2 (right panel) into the solution of 1P (0.6 wt%) for 12h. 1P is dissolved in pH 7.4 Tris-HCl buffer, all NMR experiment are performed at same condition (nt = 350, bs = 2).
Figure 3
Figure 3
TEM images showing the time course of nanostructure formation in the suspension of a) Cax[1P]y and b) Srx[1P]y with different amounts of ALP. [1P]0 = 0.6 wt%, [1P]0:[ Ca2+]0 = 1:2.
Figure 4
Figure 4
a) Dynamic oscillatory rheology demonstrates the formation of a hydrogel after treating the suspension of Cax[1P]y or Srx[1P]y with ALP (0.05U/mL). b) Expansion of dashed box shows gelation process during the initial stage. [1P]0 = 0.6 wt%, [1P]0:[M]0 = 1:2.
Scheme 1
Scheme 1
Conceptual illustration of enzyme-instructed solid-gel transition of the biocomposite made of small phosphopeptides and alkaline earth metal ions.
See this image and copyright information in PMC

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