Nano-Diamond Hybrid Materials for Structural Biomedical Application

The pregnancy 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 have shown attractive physical, biological and scientific properties in several biomedical applications A highly biocompatible tale hybrid allied based on nanodiamonds and hydrophilic poly-(hydroxyl-ethyl-methacrylate) (pHEMA) is proposed

Nano-Diamond Hybrid Materials for Structural Biomedical Application

Nano-Diamond Hybrid Materials for Structural Biomedical Application


Biomaterials are today playing a important role in tissue engineering and regenerative medicine applications The union between engineers, chemists, physicists, biologists and physicians speeded up research in this field, allowing a faster maturation 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 decree to sake in life expectancy and life superiority (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 more thermodynamically stable at ambient temperatures and pressures, while diamond, in these conditions, may exist only in its metastable department In fact, due to the high-energy hurdle that separated the graphitic sp2 and diamond sp3 configurations (Fig 1A and B), gangling temperatures and pressures in presence of catalysts are necessary to tailor graphite in diamond.

Nevertheless, a third parameter (surface area) becomes thrust at the nanoscale superiority and it become material in the definition of the means equilibrium vigour levels: At this nano-dimensions, the Gibbs free enthusiasm becomes dependent on the contribution of the surface energy, cardinal 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 additional stable than poly-aromatics graphite (Fig 1C).

In addition, a supplementary baffling morphological rack 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 befall even at room temperature and pressure principal to the formation of diamond cores with graphitic shells (bucky-diamond) (Fig 1C) (Barnard and Sternberg, 2007)

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

This new rank of materials based on Carbon Sp2 and Sp3 nanocrystalline structures is thumping captivating for future nanotechnological incubation 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 keep been initially utilized in applications such as galvanic coatings, polishing systems, polymer nano-composities, lubricants New cubby-hole applications, however, are recently developing; magnetic recording, adsorbents, diamond ceramics production, coatings in department emission devices, catalyzes of heterogeneous catalysts and in fuel cells as proton-conducting nanocomposite membranes Preliminary appraisal demonstrated that detonation nanodiamonds are non-toxic and biocompatible, manufacture them thumping appealing for bio-medical applications considering its feasible controllable fertile 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 lofty surface chemical purity and sameness surfaces are necessary for biomedical applications (Lai and Barnard, 2011a; 2011b) A artless lavation way utilizes oxidation procedures Depending on the sort 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 apportion as diamond can be filtered up to 95% by weight 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 naive 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 avowed in literature, however, the toxicity of nano-diamonds remains a legitimate concern (Schrand et al., 2009) In vitro and in vivo studies are stagnant needed to evaluate characteristics such as in vivo mechanical 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 refashioning activity.

Previous investigations of our troupe have shown that high superiority of biocompatibility and bioactivity has been seen for nano-composite materials made combining vague 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 have shown a high quiescent for usage in advanced moulding models finalized to the knob of well-organized tissue engineered structures (Petrescu and Calautit, 2016 a-b)

Bone scaffolds obtain been always a material problem for research since they should provide sufficiently strained but resilient fretwork to be an nonpareil scaffold that momentarily makeshift the damaged bone. Nevertheless, they should be able at the equivalent circumstance to readily biodegrade after the formation of the new tissue in direction to fully 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 keep investigated hydrogel hybrid composites, based on the union of pHEMA with Amorphous Pyrogenic Silica that were tested for the intake of water, the balance of knot in moisten and in briny solution and for the cell sentiment with assays of adhesion, morphology, distribution, using fibroblasts and osteoblasts as cell-models The presence of the silica makes this biomaterials excellent, with conformity to the pHEMA alone Good properties of osteoinduction own been besides seen for differentiation of dental glue emerge 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)


Silica nano-composites synthesized in our laboratory, which contained highly-bioactive amorphous fumed, obtain been found to represent a new position of hybrid polymeric-ceramic scaffolding materials able to imitator the scientific behavior of the bone Micro-foamed self assembled nanostructured composite keep been tested as scaffold that showed osteoblast fashion knack and originate cells differentiation (Marrelli et al, 2015)

Materials and Methods


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 area was of 400 m2g1, were utilized as bioactive cushioning HEMA monomers (Fig. 2) have been thermally polymerized in presence of an initiator for desperate polymerization, namely, the – azoisobutyrronitrile (AIBN), obtained from Fluka Milan, Italy In a preliminary inspection of nanocomposite preparation, the nanodiamond were mixed in the ratio of 5% by volume with the HEMA monomers and degassed The brew 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 hindmost post-cure at 90C for 1 h

Results and Discussion

Nano-diamonds dispersion in the HEMA monomer resulted in a transparent and clear, decorate grey colour, gloss This behaviour testified the welfare dispersion and deficiency of nanofiller clusters The welfare dispersion talent of the Oxidized Detonation nano-diamonds in the reacting combination could be attributed to the strong interactions between the oxygen containing functional groups on the stuffing and the HEMA hydroxyl that led to the preferential self-assembly orientation of the monomers toward the nano-filler surface (Fig. 3 fact upper left) The sequential polymerization of the HEMA resulted in a still pronounced and glassy clear hard The interest dispersion of the nano-diamond was quite 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 identical self assembly condition has been described by Aversa et al (2016; 2009) to arise between vague nanosilica particles, which are characterized by a disordered form containing many not general 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 pertinent with particularly eccentric and improved practical properties and biocompatibility (Aversa, 2016)

In the instance of nono-diamond filled pHEMA, the equivalent improvement of the specialist properties and biocompatibility could be then expected However, the expected scientific properties enhancements could be much additional material due to diamond much higher rigidity and tightness (Azo tech spech)

The shear Modulus of synthetic diamond, which ranges from 440 to 470 GPa (Azo tech information), is almost 15 times higher than that of Silica, which ranges from 27.9 to 32.3 (Azo tech spec). According to this information and considering the scientific 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 relevant 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 filling topic 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 satellite at increasing cargo of nanosilica packing This afair confirmed the hybrid disposition 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 domain in Fig. 5) Similar effect posses been described by Aversa et al (2016; 2009) to happen for nanosilica hybrids at higher loading ranging from 15 to 30% by volume.


New bioactive nanodiamond-polymeric hybrid materials to be used as biomechanical active scaffold materials showing quiescent improved bone scaffold mineralization and ossification properties retain been developed by subsequent 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 filler concentration up to 5% by volume. Moreover, this transparent hybrid pertinent swells to rubber in presence of aqueous physiological clue picking-up fresh than 40% of humidify At thumping low levels of nano-diamond loading, the technical behaviour of the proposed hybrid materials could be comparable with that of bone when in the transparent state, or to that of cartilage and ligaments when in the rubbery domain subsequent water sorption

The use as scaffolds of these mechanically compatible hybrid hydrogels is expected to polish the adaptation mechanisms of the bone by introducing an active interface that could better 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 gain of use of biomechanically compatible and bioactive scaffold biomaterials associated to new device odontostomatological prostheses


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 kind 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 moreover 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 imagine FIRB Future in Research 2008, # RBFR08T83J


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See the something with Figures at: http://thescipubcom/abstract/103844/ajbbsp2017.34.41

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