Pore Structure Tuning of Poly-EGDMA Biomedical Material by Varying the O-Quinone Photoinitiator

Porous polymer monoliths with thicknesses of 2 and 4 mm were obtained via polymerization of ethylene glycol dimethacrylate (EGDMA) under the influence visible-light irradiation in the presence of a 70 wt% 1-butanol porogenic agent and o-quinone photoinitiators. The o-quinones used were: 3,5-di-tret-butyl-benzoquinone-1,2 (35Q), 3,6-di-tret-butyl-benzoquinone-1,2 (36Q), camphorquinone (CQ), and 9,10-phenanthrenequinone (PQ). Porous monoliths were also synthesized from the same mixture but using 2,2′-azo-bis(iso-butyronitrile) (AIBN) at 100 °C instead o-quinones. According to the results of scanning electron microscopy, all the resulting samples were conglomerates of spherical, polymeric particles with pores between them. Use of mercury porometry showed that the interconnected pore systems of all the polymers were open. The average pore size, Dmod, in such polymers strongly depended on both the nature of the initiator and the method of initiation of polymerization. For polymers obtained in the presence of AIBN, the Dmod value was as low as 0.8 μm. For polymers obtained via photoinitiation in the presence of 36Q, 35Q, CQ, and PQ, the Dmod values were significantly greater, i.e., 9.9, 6.4, 3.6, and 3.7 μm, respectively. The compressive strength and Young’s modulus of the porous monoliths increased symbatically in the series PQ < CQ < 36Q < 35Q < AIBN with decreasing proportions of large pores (over 12 μm) in their polymer structures. The photopolymerization rate of the EGDMA and 1-butanol, 30:70 wt% mixture was maximal for PQ and minimal for 35Q. All polymers tested were non-cytotoxic. Based on the data from MTT testing, it can be noted that the polymers obtained via photoinitiation were characterized by their positive effect on the proliferative activity of human dermal fibroblasts. This makes them promising osteoplastic materials for clinical trials.

[1]  V. B. Fedoseev,et al.  Porogen Concentration Effect on the Pore Structure and Properties Evolution of Polymer Monolith Based on Oligocarbonate Dimethacrylate OCM-2 , 2023, Materials.

[2]  S. Han,et al.  Hyaluronic acid-quercetin pendant drug conjugate for wound healing applications. , 2023, International journal of biological macromolecules.

[3]  C. Laurencin,et al.  Oxygen-Generating Biomaterials for Translational Bone Regenerative Engineering. , 2023, ACS applied materials & interfaces.

[4]  C. Laurencin,et al.  Ultra-low binder content 3D printed calcium phosphate graphene scaffolds as resorbable, osteoinductive matrices that support bone formation in vivo , 2022, Scientific Reports.

[5]  M. Shurygina,et al.  Photoreduction Reaction of Carbonyl-Containing Compounds in the Synthesis and Modification of Polymers , 2021, Polymer Science, Series B.

[6]  Mahaveer D. Kurkuri,et al.  Functionalized Porous Hydroxyapatite Scaffolds for Tissue Engineering Applications: A Focused Review. , 2021, ACS biomaterials science & engineering.

[7]  Maheswaran W Archunan,et al.  Bone Grafts in Trauma and Orthopaedics , 2021, Cureus.

[8]  M. Shurygina,et al.  Synthesis and photoinitiating ability of substituted 4,5-di-tert-alkyl-o-benzoquinones in radical polymerization , 2021, Russian Chemical Bulletin.

[9]  M. I. Zaslavskaya,et al.  Porous Polymer Scaffolds based on Cross-Linked Poly-EGDMA and PLA: Manufacture, Antibiotics Encapsulation, and In Vitro Study. , 2021, Macromolecular bioscience.

[10]  Guangjin Chen,et al.  Insight into the roles of melatonin in bone tissue and bone-related diseases (Review) , 2021, International journal of molecular medicine.

[11]  J. Sokołowski,et al.  The Photoinitiators Used in Resin Based Dental Composite—A Review and Future Perspectives , 2021, Polymers.

[12]  R. Kovylin,et al.  Modern Porous Polymer Implants: Synthesis, Properties, and Application , 2021, Polymer Science, Series C.

[13]  A. G. Morozov,et al.  Biological Response to a Novel Hybrid Polyoligomer: in vitro and in vivo Models , 2020, Sovremennye tekhnologii v meditsine.

[14]  S. Chesnokov,et al.  Photopolymerization of OCDMA Dimetacrylate Initiated by 3,5-Di-tert-Butyl-o- Quinone and its Bis-O-Benzoquinone , 2020 .

[15]  A. Bhaskar,et al.  Hierarchical porosity in additively manufactured bioengineering scaffolds: Fabrication & characterisation. , 2020, Journal of the mechanical behavior of biomedical materials.

[16]  S. Mlyavykh,et al.  Visible-light induced synthesis of biocompatible porous polymers from oligocarbonatedimethacrylate (OСM-2) in the presence of dialkyl phthalates , 2020 .

[17]  M. Shurygina,et al.  A blue to red light sensitive photoinitiating systems based on 3,5-di-tert-butyl-o-benzoquinone derivatives for free radical polymerization , 2020 .

[18]  B. Koes,et al.  Prevalence of lumbar spinal stenosis in general and clinical populations: a systematic review and meta-analysis , 2020, European Spine Journal.

[19]  S. N. Mensov,et al.  Use of photodegradable inhibitors in UV‐curable compositions to form polymeric 2D‐structures by visible light , 2020 .

[20]  J. Lalevée,et al.  Sulfinates and sulfonates as high performance co-initiators in CQ based systems: Towards aromatic amine-free systems for dental restorative materials. , 2019, Dental materials : official publication of the Academy of Dental Materials.

[21]  B. Pratap,et al.  Resin based restorative dental materials: characteristics and future perspectives , 2019, The Japanese dental science review.

[22]  M. Hadis,et al.  Increased rates of photopolymerisation by ternary type II photoinitiator systems in dental resins. , 2019, Journal of the mechanical behavior of biomedical materials.

[23]  R. Kovylin,et al.  One-step photolytic synthesis of hydrophobic porous polymer materials by the copolymerization of the dimethacrylate—alkyl methacrylate system in the presence of methanol , 2019, Russian Chemical Bulletin.

[24]  G. A. Abakumov,et al.  Photopolymerization of Thick Layers of Compositions for Mask-Based Stereolithographic Synthesis , 2019, High Energy Chemistry.

[25]  S. Mlyavykh,et al.  Biocompatible Non‐Toxic Porous Polymeric Materials Based on Carbonate‐ and Phthalate‐Containing Dimethacrylates , 2019, ChemistrySelect.

[26]  C. Cooper,et al.  State of the art in osteoporosis risk assessment and treatment , 2019, Journal of endocrinological investigation.

[27]  M. Shurygina,et al.  Influence of Viscosity of Compositions Based on Dimethacrylate Esters on Kinetics of Their Photopolymerization Initiated by 9,10-Phenanthrenequinone , 2018, Polymer Science, Series B.

[28]  R. Kovylin,et al.  Photoreduction of 9,10-Phenanthrenequinone in the Presence of Dimethacrylate Oligomers and Their Polymers , 2018, High Energy Chemistry.

[29]  M. Fernández-García,et al.  Effect of Camphorquinone Concentration in Physical-Mechanical Properties of Experimental Flowable Resin Composites , 2018, BioMed research international.

[30]  V. B. Fedoseev,et al.  Effect of Viscosity of Dimethacrylate Ester-Based Compositions on the Kinetics of Their Photopolymerization in Presence of o-Quinone Photoinitiators , 2017, Polymer Science, Series B.

[31]  A. Poddel’sky,et al.  Preparation of new dioxygen-active triphenylantimony(V) catecholate-containing porous polymer , 2017 .

[32]  M. Shurygina,et al.  Effect of donor and acceptor properties of solvents on the kinetics of photoreduction of sterically hindered о-benzoquinones , 2016, High Energy Chemistry.

[33]  D. Watts,et al.  Effect of diphenyliodonium hexafluorophosphate on the physical and chemical properties of ethanolic solvated resins containing camphorquinone and 1-phenyl-1,2-propanedione sensitizers as initiators. , 2016, Dental materials : official publication of the Academy of Dental Materials.

[34]  J. Fouassier,et al.  The Camphorquinone/Amine and Camphorquinone/Amine/Phosphine Oxide Derivative Photoinitiating Systems: Overview, Mechanistic Approach, and Role of the Excitation Light Source , 2015 .

[35]  P. P. Albuquerque,et al.  Degree of conversion, depth of cure, and color stability of experimental dental composite formulated with camphorquinone and phenanthrenequinone photoinitiators. , 2015, Journal of esthetic and restorative dentistry : official publication of the American Academy of Esthetic Dentistry ... [et al.].

[36]  Sumathi Shanmugam,et al.  Antimicrobial and cytotoxicity evaluation of aliovalent substituted hydroxyapatite , 2014 .

[37]  R. Liska,et al.  Strategies to reduce oxygen inhibition in photoinduced polymerization. , 2014, Chemical reviews.

[38]  G. A. Abakumov,et al.  Photoinitiation of methacrylate polymerization with an o-benzoquinone-amine system , 2014, Polymer Science Series B.

[39]  J. Chan,et al.  Advances in Bone Tissue Engineering , 2013 .

[40]  M. Hadis,et al.  Competitive light absorbers in photoactive dental resin-based materials. , 2012, Dental materials : official publication of the Academy of Dental Materials.

[41]  M. Shurygina,et al.  The mechanism of photoinduced hydrogen transfer during photoreduction of carbonyl compounds , 2011 .

[42]  T. Tennikova,et al.  Hydrophilic methacrylate monoliths as platforms for protein microarray , 2011 .

[43]  M. Shurygina,et al.  Products and mechanisms of photochemical transformations of o-quinones , 2010 .

[44]  S. Bertoldi,et al.  Ability of polyurethane foams to support placenta-derived cell adhesion and osteogenic differentiation: preliminary results , 2010, Journal of materials science. Materials in medicine.

[45]  S. Chesnokov,et al.  Inhibition of polymerization of methyl methacrylate by an ortho-benzoquinone-amine system , 2009 .

[46]  W. Cook,et al.  Photobleaching of camphorquinone during polymerization of dimethacrylate-based resins. , 2009, Dental materials : official publication of the Academy of Dental Materials.

[47]  S. Ban,et al.  Effect of various visible light photoinitiators on the polymerization and color of light-activated resins. , 2009, Dental materials journal.

[48]  W. Cook,et al.  Photoinitiation rate profiles during polymerization of a dimethacrylate-based resin photoinitiated with camphorquinone/amine. Influence of initiator photobleaching rate , 2009 .

[49]  P. Kasten,et al.  Porosity and pore size of beta-tricalcium phosphate scaffold can influence protein production and osteogenic differentiation of human mesenchymal stem cells: an in vitro and in vivo study. , 2008, Acta biomaterialia.

[50]  P. Lambrechts,et al.  Systematic review of the chemical composition of contemporary dental adhesives. , 2007, Biomaterials.

[51]  M. Shurygina,et al.  o-benzoquinone photoreduction products in the presence of N,N-dimethylanilines , 2006 .

[52]  D. Nicodem,et al.  Solvent effects on the quenching of the equilibrating n,π* and π,π* triplet states of 9,10-phenanthrenequinone by 2-propanol , 2005 .

[53]  D. Nicodem,et al.  Solvent and temperature effects on the phosphorescence of 9,10-phenanthrenequinone in fluid solution , 2004 .

[54]  J. Fouassier,et al.  Camphorquinone–amines photoinitating systems for the initiation of free radical polymerization , 2003 .

[55]  Jan Feijen,et al.  Porous polymeric structures for tissue engineering prepared by a coagulation, compression moulding and salt leaching technique. , 2003, Biomaterials.

[56]  G. A. Abakumov,et al.  Influence of o-benzoquinone nature on initiation of radical polymerization by the o-benzoquinone—tert-amine system , 2001 .

[57]  V. Cherkasov,et al.  Photoreduction ofortho-benzoquinones in the presence ofpara-substitutedN,N-dimethylanilines , 2000 .

[58]  F. Švec,et al.  Preparation of porous hydrophilic monoliths: Effect of the polymerization conditions on the porous properties of poly (acrylamide‐co‐N,N′‐methylenebisacrylamide) monolithic rods , 1997 .

[59]  T. Mosmann Rapid colorimetric assay for cellular growth and survival: application to proliferation and cytotoxicity assays. , 1983, Journal of immunological methods.

[60]  V. Viswanathan,et al.  Management Of Thoracolumbar Fractures In Adults: Current Algorithm , 2019 .

[61]  Amy J Wagoner Johnson,et al.  A review of the mechanical behavior of CaP and CaP/polymer composites for applications in bone replacement and repair. , 2011, Acta biomaterialia.

[62]  Edward D Harder,et al.  Influence of solvent polarity on the photoreactivity of 2–4-ring aromatic o-quinones , 1999 .

[63]  F. Tüdös,et al.  Kinetics of radical polymerization—XLV. Steric effects in the radical reactivity of quinones , 1985 .

[64]  V. M. Granchak,et al.  Kinetic studies of the photopolymerization of methyl methacrylate in solution by benzophenones in presence of amines , 1985 .

[65]  S. Patai,et al.  The Chemistry of the quinonoid compounds , 1974 .