Ring‐Opening Metathesis Polymerization‐Based Synthesis of CaCO₃ Nanoparticle‐Reinforced Polymeric Monoliths for Tissue Engineering

Abstract

Porous monolithic materials have been prepared via ring-opening metathesis polymerization from norborn-2-ene and a 7-oxanorborn-2-ene-based cross-linker in the presence of porogenic solvents (i.e., 2-propanol and toluene) and norborn-2-enephosphonate surface-modified CaCO(3) nanoparticles, using the 3(rd) -generation Grubbs-initiator RuCl(2) (Py)(2) (IMesH(2) )(CHPh). The experimental setup and the conditions chosen allowed for the manufacturing of polymeric monoliths characterized by a homogeneous distribution of the inorganic nanoparticles throughout the polymeric monolith. Depending on the nanoparticle content, the macropore diameters could be varied in the 30-120 µm regime. Noteworthy, the addition of nanoparticles did not affect the phase separation-triggered formation of the monolithic matrix nor the meso- and microporosity as evidenced by N(2) -adsorption experiments.

Catalysts Immobilized on Organic Polymeric Monolithic Supports: From Molecular Heterogeneous Catalysis to Biocatalysis

“…[88] There is an increasing demand for the use of porous monolithic media in biocatalysis and as biosupports due to the simplicity of their preparation, their high throughput, and their ability to withstand higher flow rates or pressures. Their large pores also facilitate the in-growth of cells into their structure and even support cell differentiation.…”

“…Inclusion of the CaCO 3 nanoparticles was homogeneous and reinforced the polymer matrix, which provides monoliths with greater mechanical integrity. [88] Additional monoliths were prepared by using the polar monomer cis-5-cyclooctene-trans-1,2-diol and a biocompatible 7-oxanorborne-2-ene-based cross-linking reagent with 12 wt % or less of either CaCO 3 or calcium hydroxyapatite (HAp) nanoparticles. [134] These nanoparticles were of size 50-100 nm obtained by SEM and less than 20 nm platelets obtained by X-ray diffraction.…”

“…[21] We also reported on the successful synthesis of monolithic materials through Schrock-based catalysts and their protein and amino acid separation properties, [89] and we have also explored reinforcing monolithic materials with CaCO 3 nanoparticles for applications in biocatalysis and tissue engineering. [63,88] Furthermore, weak cation-exchange monoliths were synthesized from NBE-based monomers, [34] and Pd-functionalized ROMP-based monoliths were prepared for Heck-and Suzuki-type reactions. [11,41] Continued efforts also exist toward the development of continuous organometallic catalysis on monolithic supports.…”

Less common applications of monoliths: V. Monolithic scaffolds modified with nanostructures for chromatographic separations and tissue engineering

“…Calcium hydroxyapatite and calcium carbonate nanoparticles are currently receiving great attention because of their extensive applications in biomedical research and regenerative medicine including bone and tooth implants, bone fillings, and adsorbents. Recently, monolithic scaffolds incorporating these nanoparticles were applied in cell cultivation and tissue engineering []. Porous monolithic inorganic/polymeric hybrid materials in a disk format were prepared using ring‐opening metathesis polymerization (ROMP).…”

Particles without a Box: Brush-first Synthesis of Photodegradable PEG Star Polymers under Ambient Conditions

“…Schrock and co-workers reported the first arm-first ROMP synthesis of star polymers via crosslinking of norbornene, dicarbomethoxynorbornadiene, and trimethylsilyl protected dicarboxynorbornene linear polymers with a bifunctional norbornene crosslinker. 11,12 Buchmeiser has extended this methodology for the synthesis of materials with a range of applications that include supported catalysis, tissue-engineering, and chromatography [13][14][15][16][17] . Otani and coworkers have made star polymer nanoparticles with functional surfaces via a related "in-out" polymerization strategy 18,19 .…”