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Nano-Diamond Hybrid Materials for Structural Biomedical Application

The ripening of new diamond based bio-mechanically active hybrid nano-structured scaffolds for cartilage cells tissue engineering are proposed in this study. Innovative tissue engineering biomimetic materials based on hydrogel keep shown appealing physical, biological and technical properties in several biomedical applications A highly biocompatible novel hybrid allied based on nanodiamonds and hydrophilic poly-(hydroxyl-ethyl-methacrylate) (pHEMA) is proposed

Nano-Diamond Hybrid Materials for Structural Biomedical Application

Introduction

Biomaterials are today playing a important role in tissue engineering and regenerative medicine applications The alliance between engineers, chemists, physicists, biologists and physicians speeded up research in this field, allowing a faster development of new biomaterials and technologies to overcome the challenges and to sway the assorted needs of each specific tissue-engineering field. Although many biomaterials applications are far from clinical translation, regenerative medicine has greatly advanced during the last years and it bodes well for future translation of research discoveries from bench-to-the-bedside, in directive to advantage in life expectancy and life sort (Montheard et al, 1992; Filmon et al., 2002; Davis et al, 1991; Kabra et al, 1991; Apicella et al., 1993; Peluso et al, 1997; Petrescu et al, 2016 a-e).

Among the different allotropic forms of Carbon, graphite is the other thermodynamically stable at ambient temperatures and pressures, while diamond, in these conditions, may exist only in its metastable field In fact, due to the high-energy hindrance that separated the graphitic sp2 and diamond sp3 configurations (Fig 1A and B), gigantic temperatures and pressures in presence of catalysts are imperative to remodel graphite in diamond.

Nevertheless, a third parameter (surface area) becomes crucial at the nanoscale merit and it become material in the definition of the method equilibrium energy levels: At this nano-dimensions, the Gibbs liberate zest becomes dependent on the contribution of the surface energy, prime to changes in the thermodynamic equilibrium phase diagram (Barnard et al., 2003; 2007; Viecelli et al, 2001) Tetrahedral hydrocarbons in the hole of nano-diamonds of 3 nm hold been demonstrated by atomistic models to be fresh stable than poly-aromatics graphite (Fig 1C)

In addition, a additional perplexing morphological stand is generated at the nanodiamond interface; Barnard and Sternberg (2007) reported that cuboctahedral clusters presented a transition from Sp3 to Sp2 carbons at the surfaces of aggregations of 1.0-3.0 nm (Aversa et al., 2016 a-o, 2017 a-e; Mirsayar et al, 2017)

On this morphological transition at the interface, it has been recently demonstrated by Xiao et al. (2014) that reversible nanodiamond-graphitic carbon onion like phase transformation can transpire even at room temperature and require cardinal to the formation of diamond cores with graphitic shells (bucky-diamond) (Fig 1C) (Barnard and Sternberg, 2007)

These findings allowed us to believe that the nanodiamond surfaces can be then soft modified through the chemistry of graphitic carbon in many different chemical methods, such are the DielsAlder cycloaddition reactions between conjugated diene and dienophile, to haunt functionalised cyclohexene systems (Jarre et al, 2011).

This new status of materials based on Carbon Sp2 and Sp3 nanocrystalline structures is extremely beguiling for future nanotechnological development in biomedical structural applications Nanocrystalline particles, which are often named detonation nanodiamond and characterized by sizes of 3-6 nm, are produced by detonation of carbon explosive materials (Danilenko, 2004; Greiner et al., 1988; Ozawa et al, 2007; Chang et al, 2008)

Detonation nanodiamond have been initially utilized in applications such as galvanic coatings, polishing systems, polymer nano-composities, lubricants New calling applications, however, are recently developing; magnetic recording, adsorbents, diamond ceramics production, coatings in state emission devices, catalyzes of heterogeneous catalysts and in fuel cells as proton-conducting nanocomposite membranes Preliminary evaluation demonstrated that detonation nanodiamonds are non-toxic and biocompatible, forging them remarkably captivating for bio-medical applications considering its doable controllable fecund surface chemistry.

However, it has been reported that detonation nanodiamonds may be characterized by different levels of purity and by the presence of several undesired functional groups/elements at the diamond particles surface, while tall surface chemical purity and uniformity surfaces are obligatory for biomedical applications (Lai and Barnard, 2011a; 2011b) A naive cleansing method utilizes oxidation procedures Depending on the kimd of procedure, the detonation powder of different levels of purities and specific surface characteristics can be obtained. The fraction of the Carbon that is not present as diamond can be clear up to 95% by burden by oxidation at lofty temperatures in air/Ozone atmosphere (Osswald et al., 2006; Shenderova et al, 2011)

Oxidation, while removing undesired processing functional compunds at nanodiamond surfaces, forms oxygen-containing groups, such are anhydrides and carboxylic acids (Shenderova et al, 2011).

The childlike air/ozone purification, then, produces carboxylated nano-diamond with highly reactive and hydrophilic surface OH terminations rob in biomedical applications (Krueger et al, 2008; Kruger et al, 2006)

Diamond and limpid carbon has been published in literature, however, the toxicity of nano-diamonds remains a real concern (Schrand et al., 2009) In vitro and in vivo studies are inactive needful to evaluate characteristics such as in vivo technical and physiological behaviours (Zhang et al, 2011; Schrand et al., 2009a; 2009b; Yuan et al, 2010; Mohan et al, 2010) as well as cell viability or undesired gene alteration activity

Previous investigations of our squad have shown that tall excellence of biocompatibility and bioactivity has been practical for nano-composite materials made combining amorphous silica nanoparticles of about 7 nm

Bioengineering and nanotechnology applied to micro and nano-materials are being progressively adopted as emerging solutions in 2D (coatings) and 3D applicatons (scaffolds) (Sorrentino et al., 2007; Aversa et al., 2016a) Conclusively, such micro and nano-technologies retain shown a gangling potential for usage in advanced making models finalized to the growth of well-organized tissue engineered structures (Petrescu and Calautit, 2016 a-b)

Bone scaffolds own been always a pertinent debate for research since they should provide sufficiently taut but resilient trellis to be an nonpareil scaffold that momentarily improvised the damaged bone. Nevertheless, they should be able at the alike time to readily biodegrade after the formation of the new tissue in behest to wholly integrate with it (Kabra et al, 1991; Montheard et al, 1992; Peluso et al, 1997; Schiraldi et al., 2004; Buzea et al, 2015; Aversa et al, 2016 a-o)

Our research bunch own investigated hydrogel hybrid composites, based on the fellowship of pHEMA with Amorphous Pyrogenic Silica that were tested for the intake of water, the bill of swelling in bedew and in brackish key and for the cell sensation with assays of adhesion, morphology, distribution, using fibroblasts and osteoblasts as cell-models The presence of the silica makes this biomaterials excellent, with obedience to the pHEMA alone Good properties of osteoinduction own been moreover experimental for differentiation of dental glue originate cells (Abdul-Razzak et al, 2012; Ajith et al, 2009; Ahmed et al., 2011; Apicella and Hopfenberg, 1982; Atasayar et al, 2009; Babaev et al, 2010; Chow et al., 2010; Comerun, 1986; Covic et al, 2007; Frost, 1964, 1990, 1994, 2003; Gramanzini et al, 2016; Holley et al., 1970; Krueger and Boedeker, 2008; Nicolais et al, 1984; Petrescu et al, 2015; Prashantha et al, 2001; Raffaella and Antonio, 2016; Raffaella et al, 2016; Sorrentino et al, 2009; Tyrsa et al., 2001; Wolff, 1892)

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Silica nano-composites synthesized in our laboratory, which contained highly-bioactive unformed fumed, have been found to represent a new position of hybrid polymeric-ceramic scaffolding materials able to follower the specialized behavior of the bone Micro-foamed self assembled nanostructured composite keep been tested as scaffold that showed osteoblast establish facility and emanate cells differentiation (Marrelli et al, 2015)

Materials and Methods

Materials

The monomer 2-hydroxyethylmethacrylate (HEMA), obtained from Sigma-Aldrich Chemicals Co, St Louis, MO, USA, has been used for the polymerization of a hydrophilic composite matrix Raw detonation nanodiamonds (Aldrich, 97%), which mean calibre ranged between 3-5 nm and which specific surface sector was of 400 m2g1, were utilized as bioactive packing HEMA monomers (Fig. 2) own been thermally polymerized in presence of an initiator for forceful polymerization, namely, the – azoisobutyrronitrile (AIBN), obtained from Fluka Milan, Italy In a preliminary inspection of nanocomposite preparation, the nanodiamond were varied in the percentage of 5% by volume with the HEMA monomers and degassed The mixture was then poured into 2.0 mm thick planar moulds before polymerization in the oven that was embrace at the controlled temperature of 60C for 24 h. The nano-composite plates were subjected to a modern post-cure at 90C for 1 h

Results and Discussion

Nano-diamonds dispersion in the HEMA monomer resulted in a clear and clear, illuminate grey colour, clue This behaviour testified the interest dispersion and deprivation of nanofiller clusters. The welfare dispersion flair of the Oxidized Detonation nano-diamonds in the reacting assortment could be attributed to the strong interactions between the oxygen containing functional groups on the filling and the HEMA hydroxyl that led to the preferential self-assembly orientation of the monomers toward the nano-filler surface (Fig. 3 reality upper left) The later polymerization of the HEMA resulted in a passive pronounced and glassy clear hard The good dispersion of the nano-diamond was rather preserved after the polymerization (Abdul-Razzak et al, 2012; Ajith et al., 2009; Ahmed et al, 2011; Apicella and Hopfenberg, 1982; Atasayar et al, 2009; Babaev et al, 2010; Chow et al., 2010; Comerun, 1986; Covic et al, 2007; Frost, 1964, 1990, 1994, 2003; Gramanzini et al, 2016; Holley et al., 1970; Krueger and Boedeker, 2008; Nicolais et al, 1984; Petrescu et al, 2015; Prashantha et al, 2001; Raffaella and Antonio, 2016; Raffaella et al, 2016; Sorrentino et al, 2009; Tyrsa et al., 2001; Wolff, 1892)

A similar self collection condition has been described by Aversa et al (2016; 2009) to materialize between nebulous nanosilica particles, which are characterized by a disordered framework containing many not normal rings and not bridging Oxygen atoms (red in Fig. 4) and the corresponding HEMA monomer

The polymerization of HEMA/amorphous nanosilica mixtures leads to the formation of a hybrid nanostructured akin with particularly odd and improved specialist properties and biocompatibility (Aversa, 2016)

In the case of nono-diamond filled pHEMA, the alike improvement of the specialized properties and biocompatibility could be then expected. However, the expected specialized properties enhancements could be much further akin due to diamond much higher rigidity and power (Azo tech spech).

The shear Modulus of synthetic diamond, which ranges from 440 to 470 GPa (Azo tech information), is partly 15 times higher than that of Silica, which ranges from 27.9 to 32.3 (Azo tech spec) According to this message and considering the specialized shear behaviour of the analogous hybrid materials based on silica nanoparticles (Aversa et al, 2016), the behaviour of the variation of the shear modulus as a function of the diamond nanoparticles volume fraction in the hybrid allied could be evaluated Fig. 5.

According to Aversa et al (2016), strong plasticization is induced by the physiological solutions sorption in the hybrid pHEMA-nanosilica composite

It has been described by Aversa et al (2016; 2009) that the measured shear modulus of the Nanosilica hybrid composites at different filler subject was not described by the classical Halpin and Kardos (1976) equation that is commonly utilized for the particulate composites. The hybrid nano-composites showed a linear spacecraft at increasing goods of nanosilica packing This circumstance confirmed the hybrid character of the nanosilica filled pHEMA

At nano-diamond volumetric fractions ranging from 2 to and 5%, the shear moduli were comparable to those of the cortical bone (10-20 GPa, reported as grey field in Fig 5) Similar impact hold been described by Aversa et al (2016; 2009) to eventuate for nanosilica hybrids at higher loading ranging from 15 to 30% by volume.

Conclusion

New bioactive nanodiamond-polymeric hybrid materials to be used as biomechanical active scaffold materials showing passive improved bone scaffold mineralization and ossification properties retain been developed by next a biomimetic approach

The new nanocomposites based on poly-Hydroxyl-Ethyl-Methacrylate (pHEMA) filled with detonation nanodiamonds could be identified as a biomimetic biomaterial at filling concentration up to 5% by volume. Moreover, this glassy hybrid material swells to rubber in presence of aqueous physiological solution picking-up other than 40% of water. At very low levels of nano-diamond loading, the practical behaviour of the proposed hybrid materials could be comparable with that of bone when in the pellucid state, or to that of cartilage and ligaments when in the rubbery field successive wet sorption

The use as scaffolds of these mechanically compatible hybrid hydrogels is expected to rewrite the adaptation mechanisms of the bone by introducing an active interface that could renovate biomimetics by correctly reproducing cartilage and ligaments biomechanical functions (Schwartz-Dabney and Dechow, 2003; Perillo et al, 2010; Apicella et al., 2010; 2011; 2015; Aversa et al, 2016; 2009)

Adaptive properties of bone could behalf of use of biomechanically compatible and bioactive scaffold biomaterials associated to new design odontostomatological prostheses.

Acknowledgement

We acknowledge and thank Mr Taher M. Abu-Lebdeh, Associate Prof at North Carolina A and T State Univesity, United States and Mr Muftah H El-Naas PhD MCIC FICCE QAFCO Chair Professor in Chemical Process Engineering Gas Processing Center College of Engineering Qatar University and Ms Shweta Agarwala, Senior Research Scientist at Singapore Center for 3D Printing Nanyang Technological University Singapore for their suggestions and comments The Authors acknowledge Liquid Metals Technologies Inc, Ca USAthat genial supply the samples for the characterization and Dr Francesco Tatti (FEI Company Application Specialist SEM-SDB) for its contribut in the preparation of this paper experiments and analyses The authors would like to appreciate the facilities and backing provided by the Advanced Technology Dental Research Laboratory, Faculty of dentistry, King Abdul Aziz University The authors would also appreciate the research technicians,Basim Al Turkiand Fahad Al Othaibi for their cooperation

Funding Information

This research was partially funded by Italian Ministry of University and Research with the suppose FIRB Future in Research 2008, # RBFR08T83J

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See the phenomenon with Figures at: http://thescipubcom/abstract/10.3844/ajbbsp2017.34.41