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Bioinspired Citrate-Apatite Nanocrystals Doped with Divalent Transition Metal Ions

Martinez, Francisco LU ; Iafisco, Michele; Manuel Delgado-Lopez, Jose; Martinez-Benito, Carla; Ruiz-Perez, Catalina; Colangelo, Donato; Oltolina, Francesca; Prat, Maria and Gomez-Morales, Jaime (2016) In Crystal Growth & Design 16(1). p.145-153
Abstract
Bioinspired citrate-carbonate-apatite (cAp) nanocrystals doped with divalent transition metal (M) ions, i.e., Mn2+, Co2+, and Ni2+, were prepared by batch thermal decomplexing of Ca2+/M/citrate/phosphate/carbonate solutions at 80 and 37 degrees C, with initial Ca2+/M molar ratios of 9:1 and 5:5, and at different crystallization times ranging from 1 to 96 h. A thorough chemical, crystallographic, and morphological characterization was carried out on the doped nanocrystals revealing that (i) using similar crystallization conditions the amount of incorporated M normally followed the order Mn2+ > Co2+ > Ni2+; (ii) the growth of nano crystals was clearly enhanced at 80 degrees C and when a lower amount of M was incorporated in the crystal... (More)
Bioinspired citrate-carbonate-apatite (cAp) nanocrystals doped with divalent transition metal (M) ions, i.e., Mn2+, Co2+, and Ni2+, were prepared by batch thermal decomplexing of Ca2+/M/citrate/phosphate/carbonate solutions at 80 and 37 degrees C, with initial Ca2+/M molar ratios of 9:1 and 5:5, and at different crystallization times ranging from 1 to 96 h. A thorough chemical, crystallographic, and morphological characterization was carried out on the doped nanocrystals revealing that (i) using similar crystallization conditions the amount of incorporated M normally followed the order Mn2+ > Co2+ > Ni2+; (ii) the growth of nano crystals was clearly enhanced at 80 degrees C and when a lower amount of M was incorporated in the crystal structure; (iii) the increase of the M content increased the aspect ratio (length/width) of the M-doped cAp nanocrystals compared to undoped ones, (iv) the incorporation of the 6.5 wt % of M is a threshold for the long-range order of the nano crystal; in fact, with a higher M content, amorphous materials were mainly produced. Additionally, we found that citrate controlled the activity of hydrated M ions in solution, the extension of the doping process, and protected the M ions against oxidation in solution as well as in the outermost layer of doped nanocrystals. Preliminary in vitro cytotoxicity studies on the murine MS1 endothelial cell line showed that the produced Mn2+- and Co2+-doped nanocrystals were highly biocompatible at doses comparable to those of undoped ones, with the exception of the nanocrystals substituted with the highest Co2+ content at the higher doses. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Crystal Growth & Design
volume
16
issue
1
pages
145 - 153
publisher
The American Chemical Society
external identifiers
  • wos:000367963400017
  • scopus:84954071738
ISSN
1528-7483
DOI
10.1021/acs.cgd.5b01045
language
English
LU publication?
yes
id
195d1a3b-4034-4ed0-9182-805ff07f3386 (old id 8747915)
date added to LUP
2016-02-23 10:12:25
date last changed
2017-07-02 03:10:40
@article{195d1a3b-4034-4ed0-9182-805ff07f3386,
  abstract     = {Bioinspired citrate-carbonate-apatite (cAp) nanocrystals doped with divalent transition metal (M) ions, i.e., Mn2+, Co2+, and Ni2+, were prepared by batch thermal decomplexing of Ca2+/M/citrate/phosphate/carbonate solutions at 80 and 37 degrees C, with initial Ca2+/M molar ratios of 9:1 and 5:5, and at different crystallization times ranging from 1 to 96 h. A thorough chemical, crystallographic, and morphological characterization was carried out on the doped nanocrystals revealing that (i) using similar crystallization conditions the amount of incorporated M normally followed the order Mn2+ > Co2+ > Ni2+; (ii) the growth of nano crystals was clearly enhanced at 80 degrees C and when a lower amount of M was incorporated in the crystal structure; (iii) the increase of the M content increased the aspect ratio (length/width) of the M-doped cAp nanocrystals compared to undoped ones, (iv) the incorporation of the 6.5 wt % of M is a threshold for the long-range order of the nano crystal; in fact, with a higher M content, amorphous materials were mainly produced. Additionally, we found that citrate controlled the activity of hydrated M ions in solution, the extension of the doping process, and protected the M ions against oxidation in solution as well as in the outermost layer of doped nanocrystals. Preliminary in vitro cytotoxicity studies on the murine MS1 endothelial cell line showed that the produced Mn2+- and Co2+-doped nanocrystals were highly biocompatible at doses comparable to those of undoped ones, with the exception of the nanocrystals substituted with the highest Co2+ content at the higher doses.},
  author       = {Martinez, Francisco and Iafisco, Michele and Manuel Delgado-Lopez, Jose and Martinez-Benito, Carla and Ruiz-Perez, Catalina and Colangelo, Donato and Oltolina, Francesca and Prat, Maria and Gomez-Morales, Jaime},
  issn         = {1528-7483},
  language     = {eng},
  number       = {1},
  pages        = {145--153},
  publisher    = {The American Chemical Society},
  series       = {Crystal Growth & Design},
  title        = {Bioinspired Citrate-Apatite Nanocrystals Doped with Divalent Transition Metal Ions},
  url          = {http://dx.doi.org/10.1021/acs.cgd.5b01045},
  volume       = {16},
  year         = {2016},
}