TY - JOUR

T1 - Local electronic structure and nanolevel hierarchical organization of bone tissue

T2 - Theory and NEXAFS study

AU - Pavlychev, A. A.

AU - Avrunin, A. S.

AU - Vinogradov, A. S.

AU - Filatova, E. O.

AU - Doctorov, A. A.

AU - Krivosenko, Yu S.

AU - Samoilenko, D. O.

AU - Svirskiy, G. I.

AU - Konashuk, A. S.

AU - Rostov, D. A.

N1 - Funding Information: The authors acknowledge the RFBR grant 15-02-06369 and St. Petersburg State University grant 11.38.261.2014. Publisher Copyright: © 2016 IOP Publishing Ltd. Copyright: Copyright 2018 Elsevier B.V., All rights reserved.

PY - 2016/11/22

Y1 - 2016/11/22

N2 - Theoretical and experimental investigations of native bone are carried out to understand relationships between its hierarchical organization and local electronic and atomic structure of the mineralized phase. The 3D superlattice model of a coplanar assembly of the hydroxyapatite (HAP) nanocrystallites separated by the hydrated nanolayers is introduced to account the interplay of short-, long- and super-range order parameters in bone tissue. The model is applied to (i) predict and rationalize the HAP-to-bone spectral changes in the electronic structure and (ii) describe the mechanisms ensuring the link of the hierarchical organization with the electronic structure of the mineralized phase in bone. To check the predictions the near-edge x-ray absorption fine structure (NEXAFS) at the Ca 2p, P 2p and O 1s thresholds is measured for native bone and compared with NEXAFS for reference compounds. The NEXAFS analysis has demonstrated the essential hierarchy induced HAP-to-bone red shifts of the Ca and P 2p-to-valence transitions. The lowest O 1s excitation line at 532.2 eV in bone is assigned with superposition of core transitions in the hydroxide OH-(H2O) m anions, Ca2+(H2O) n cations, the carboxyl groups inside the collagen and [PO4]2- and [PO4]- anions with unsaturated P-O bonds.

AB - Theoretical and experimental investigations of native bone are carried out to understand relationships between its hierarchical organization and local electronic and atomic structure of the mineralized phase. The 3D superlattice model of a coplanar assembly of the hydroxyapatite (HAP) nanocrystallites separated by the hydrated nanolayers is introduced to account the interplay of short-, long- and super-range order parameters in bone tissue. The model is applied to (i) predict and rationalize the HAP-to-bone spectral changes in the electronic structure and (ii) describe the mechanisms ensuring the link of the hierarchical organization with the electronic structure of the mineralized phase in bone. To check the predictions the near-edge x-ray absorption fine structure (NEXAFS) at the Ca 2p, P 2p and O 1s thresholds is measured for native bone and compared with NEXAFS for reference compounds. The NEXAFS analysis has demonstrated the essential hierarchy induced HAP-to-bone red shifts of the Ca and P 2p-to-valence transitions. The lowest O 1s excitation line at 532.2 eV in bone is assigned with superposition of core transitions in the hydroxide OH-(H2O) m anions, Ca2+(H2O) n cations, the carboxyl groups inside the collagen and [PO4]2- and [PO4]- anions with unsaturated P-O bonds.

KW - bone

KW - hierarchical matter

KW - hydroxyapatite

KW - mineral matrix

KW - NEXAFS

KW - superlattice

UR - http://www.scopus.com/inward/record.url?scp=85000420327&partnerID=8YFLogxK

U2 - 10.1088/0957-4484/27/50/504002

DO - 10.1088/0957-4484/27/50/504002

M3 - Article

C2 - 27875332

VL - 27

JO - Nanotechnology

JF - Nanotechnology

SN - 0957-4484

IS - 50

M1 - 504002

ER -