DOI: 10.48436/ps2jm-cy016
title: Research data for "Cleavable silyl ether monomers with elevated thermomechanical properties for bone regeneration"

description: Context

This dataset was created from original work conducted in the framework of a PhD project and compiled in a publication ("Cleavable silyl ether monomers with elevated thermomechanical properties for bone regeneration“, doi: 10.1021/acsabm.5c01174). It provides the raw data of the results presented and discussed therein.

 

Technical details

MS Excel file „Raw Data_ Cleavable silyl ether monomers”

Tab 1 – “Figure 2” Raw Data (triplicates) obtained for real-time NIR photorheology of NSE-TSE, VCH-TCH, VCH-TSE and NSE-TCH 

Tab 2 – “Figure 3” Raw Data obtained for DMTA measurements of NSE-TSE, VCH-TCH, VCH-TSE and NSE-TCH 

Tab 3 – “Figure 4” Raw Data obtained for tensile tests of NSE-TSE, VCH-TCH, VCH-TSE and NSE-TCH 

Tab 4 – “Figure 5” Raw Data obtained for hydrolytic degradation of NSE-TSE, VCH-TCH, VCH-TSE and NSE-TCH at pH 4, 7.4 and 10

Tab 5 – “Figure 6” Raw Data obtained for cytotoxicity of NSE-TSE, VCH-TCH, VCH-TSE and NSE-TCH 

Tab 6 – “Figure S15” Raw Data obtained for UHPLC-MS chromatogram (ELSD detection) of TSE

Tab 7 – “Figure S16” Raw Data obtained for mass spectrum (D-) at retention time 1.78 mins of TSE

Tab 8 – “Figure S17” Raw Data obtained for UHPLC-MS chromatogram (ELSD detection) of NSE

Tab 9 – “Figure S18” Raw Data obtained for mass spectrum (D+) at retention time 1.78 mins of NSE

Tab 10 – “Figure S19” Raw Data obtained for UHPLC-MS chromatogram (ELSD detection) of NM-dimer

Tab 11 – “Figure S20” Raw Data obtained for mass spectrum (D+) at retention time 1.69 mins of NM-dimer

Tab 12 – “Figure S21” Raw Data obtained for mass spectrum (D+) at retention time 1.79 mins of NM-dimer

Tab 13 – “Figure S22” Raw Data obtained for mass spectrum (D+) at retention time 1.94 mins of NM-dimer

Tab 14 – “Figure S30” Raw Data obtained for Jacobs’ working curve

NMR zip file

NMR data obtained during all synthesis steps of the silyl ether monomers NSE and TSE, the non-cleavable monomer TCH and the network degradation product NM-dimer used herein. A software to display NMR-spectra is needed, such as MestreNova or Topspin.

Compound descriptions

Compound descriptions in the files included herein adhere to the naming in the related publication referenced in the Related Works section, where all compounds are described in detail and drawn as structural formulas. In brief:

NMTA: C-methyl (hydroxymethyl)-2-norbornanecarbothioate

NMT: (mercapto-2-norbornanyl)methanol

TSE: 6-((bis((6-mercapto-2-norbornanyl)methoxy)(methyl)siloxy)methyl)-2-norbornanethiol

NSE: methyltris((5-norbornen-2-yl)methoxy)silane

TACH: C-methyl3-(2,4-bis(2-[(methylthio)carbonyl]ethylcyclohexyl)¬propane¬thioate

TCH: 2-[2,4-bis(2-mercaptoethyl)cyclohexyl]ethanethiol

NM-dimer: (6-[6-(hydroxymethyl)-2-norbornanylthio]-2-norbornanyl)methanol

 

Abstract (English):

Over the last years, stereolithography developed to be one of the most promising fabrication techniques in tissue engineering. Posing the possibility to fabricate patient-specific, porous implants, it became especially attractive for scaffold fabrication for the treatment of critical sized bone defects. State-of-the-art photopolymer systems mostly consist of potentially cytotoxic compounds, such as (meth)acrylates, that furthermore show insufficient degradation and lead to acidic degradation products that could induce adverse tissue reactions. Herein, we introduced trifunctional monomers comprising cleavable silyl ether groups for thiol-ene photopolymerization to enlarge the material platform for printed bone grafts. Polymer networks comprising a high number of silyl ether moieties typically tend to be mechanically weak and exhibit low T<sub>g</sub>s, especially when combined with thioether bonds, which are a direct result of polymerization via thiol-ene click reaction. To push thermomechanical properties to a level where they are sufficient for bone grafting (T<sub>g</sub> > 37 °C), we introduced rigid bridged alicyclic structures in the form of norbornane-derived motifs into the silyl ether monomers, resulting in a norbornene-containing double bond monomer and a norbornane-derived thiol monomer. Together with non-cleavable comonomers, we were able to demonstrate a substantial increase in T<sub>g</sub> up to 62 °C, which is well above the values reported until now for similar thiol-ene networks. Furthermore, in this study, we demonstrated high photoreactivity for some of the monomers and also successfully performed proof-of-concept printing using a DLP setup. Besides excellent thermomechanical behavior, the mechanical strength of the silyl ether-based polymer network showed to be outstanding. Cleavability of the silyl ethers was displayed with a quasi-linear degradation rate of 6.5 % per month with moderate swelling. Additionally, the degradation product of the silyl ether-based network was isolated and shown to exhibit no relevant cytotoxicity to mouse fibroblast cells.