TY - JOUR
T1 - On the surface effects of citrates on nano-apatites
T2 - Evidence of a decreased hydrophilicity
AU - Ivanchenko, Pavlo
AU - Delgado-López, José Manuel
AU - Iafisco, Michele
AU - Gómez-Morales, Jaime
AU - Tampieri, Anna
AU - Martra, Gianmario
AU - Sakhno, Yuriy
N1 - Funding Information:
The following institutions are kindly acknowledged for financial support: University of Torino, project DAMA_ RILO_16_01, local research funds 2015 (by Y.S., P.I. and G.M.); European Commission, project SMILEY, contract no. FP7 NMP 2012 SMALL-6-310637; (by M.I., A.T.), Spanish Junta de Andalucía (Andalucía Talent Hub call) and EU-FP7 Marie Curie Actions (FP7-PEOPLE-2011-COFUND), project BioBone (by JM.D.L), MINECO and FEDER, project MAT2014-60533-R (by J.G.-M). Mr. Greg Buchan, who was a visiting student at the Department of Chemisty, on leave from the University of Aberdeen, is kindly acknowledged for his support in revising the text.
Publisher Copyright:
© 2017 The Author(s).
PY - 2017/12/1
Y1 - 2017/12/1
N2 - The surface structure and hydrophilicity of synthetic nanocrystalline apatite with strongly bound citrates on their surface are here investigated at the molecular level, by combining advanced IR spectroscopy, microgravimetry and adsorption microcalorimetry. Citrate are found to form unidentate-like and ionic-like complexes with surface Ca2+ ions, with a surface coverage closely resembling that present in bone apatite platelets (i.e., 1 molecule/(n nm)2, with n ranging between 1.4 and 1.6). These surface complexes are part of a hydrated non-apatitic surface layer with a sub-nanometre thickness. Noticeably, it is found that the hydrophilicity of the nanoparticles, measured in terms of adsorption of water molecules in the form of multilayers, decreases in a significant extent in relation to the presence of citrates, most likely because of the exposure toward the exterior of -CH2 groups. Our findings provide new insights on the surface properties of bio-inspired nano-apatites, which can be of great relevance for better understanding the role of citrate in determining important interfacial properties, such as hydrophobicity, of bone apatite platelets. The evaluation and comprehension of surface composition and structure is also of paramount interest to strictly control the functions of synthetic biomaterials, since their surface chemistry strongly affects the hosting tissue response.
AB - The surface structure and hydrophilicity of synthetic nanocrystalline apatite with strongly bound citrates on their surface are here investigated at the molecular level, by combining advanced IR spectroscopy, microgravimetry and adsorption microcalorimetry. Citrate are found to form unidentate-like and ionic-like complexes with surface Ca2+ ions, with a surface coverage closely resembling that present in bone apatite platelets (i.e., 1 molecule/(n nm)2, with n ranging between 1.4 and 1.6). These surface complexes are part of a hydrated non-apatitic surface layer with a sub-nanometre thickness. Noticeably, it is found that the hydrophilicity of the nanoparticles, measured in terms of adsorption of water molecules in the form of multilayers, decreases in a significant extent in relation to the presence of citrates, most likely because of the exposure toward the exterior of -CH2 groups. Our findings provide new insights on the surface properties of bio-inspired nano-apatites, which can be of great relevance for better understanding the role of citrate in determining important interfacial properties, such as hydrophobicity, of bone apatite platelets. The evaluation and comprehension of surface composition and structure is also of paramount interest to strictly control the functions of synthetic biomaterials, since their surface chemistry strongly affects the hosting tissue response.
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U2 - 10.1038/s41598-017-09376-x
DO - 10.1038/s41598-017-09376-x
M3 - Article
C2 - 28827557
AN - SCOPUS:85029451001
VL - 7
JO - Scientific Reports
JF - Scientific Reports
SN - 2045-2322
IS - 1
M1 - 8901
ER -