Ionic interation with bone mineral. II. The control of Ca2+ and PO4 3-exchange by univalent cation-Ca2+ substitution at the hydroxyapatite crystal surface

Charles Y C Pak, Frederic C. Bartter

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Abstract

Evidence is presented for one-to-one substitution of Ca2+ by Li+, Na+, K+, and Cs+ at the surface of synthetic hydroxyapatite crystals. Such cation substitution alters the surface charge asymmetry, which is then compensated by an altered balance in the opposite sign of ions (Ca2+ and PO4 3-) in the hydration shell of the crystals. Exchangeable PO4 3- and Ca2+ in the hydration shell were calculated from the 45Ca2+ and 32PO4 3- studies. Li+, Na+, K+ and Cs+ increased the exchangeable Ca2+ without altering exchangeable phosphate. This suggests that Ca2+ accumulate in the hydration shell to compensate for the reduction in the net positive charge at the crystal surface which is brought about the substitution of divalent Ca2+ by univalent cations. Conversely, Ca2+ in the solution reduced Ca2+ exchange, probably by producing a net increase in the positive charge at the crystal surface. By these criteria, it could be shown that tetramethylammonium (TMA+) and tris(hydroxymethyl)-aminomethane (Tris+) do not participate in cation substitution. Additional proof for cation substituttion was obtained from 22Na+ and 42K+ wash-out studies indicating that Na+ and K+ exchange with the crystal surface, and from the estimation of net Ca2+ loss from the crystal, demonstrating depletion of surface Ca2+ with cation substitution.

Original languageEnglish (US)
Pages (from-to)410-420
Number of pages11
JournalBBA - General Subjects
Volume141
Issue number2
StatePublished - Jul 25 1967

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Durapatite
Minerals
Cations
Ion exchange
Bone
Substitution reactions
Bone and Bones
Crystals
Hydration
Tromethamine
Surface charge
Phosphates
Ions

ASJC Scopus subject areas

  • Molecular Biology
  • Biophysics
  • Biochemistry
  • Medicine(all)

Cite this

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title = "Ionic interation with bone mineral. II. The control of Ca2+ and PO4 3-exchange by univalent cation-Ca2+ substitution at the hydroxyapatite crystal surface",
abstract = "Evidence is presented for one-to-one substitution of Ca2+ by Li+, Na+, K+, and Cs+ at the surface of synthetic hydroxyapatite crystals. Such cation substitution alters the surface charge asymmetry, which is then compensated by an altered balance in the opposite sign of ions (Ca2+ and PO4 3-) in the hydration shell of the crystals. Exchangeable PO4 3- and Ca2+ in the hydration shell were calculated from the 45Ca2+ and 32PO4 3- studies. Li+, Na+, K+ and Cs+ increased the exchangeable Ca2+ without altering exchangeable phosphate. This suggests that Ca2+ accumulate in the hydration shell to compensate for the reduction in the net positive charge at the crystal surface which is brought about the substitution of divalent Ca2+ by univalent cations. Conversely, Ca2+ in the solution reduced Ca2+ exchange, probably by producing a net increase in the positive charge at the crystal surface. By these criteria, it could be shown that tetramethylammonium (TMA+) and tris(hydroxymethyl)-aminomethane (Tris+) do not participate in cation substitution. Additional proof for cation substituttion was obtained from 22Na+ and 42K+ wash-out studies indicating that Na+ and K+ exchange with the crystal surface, and from the estimation of net Ca2+ loss from the crystal, demonstrating depletion of surface Ca2+ with cation substitution.",
author = "Pak, {Charles Y C} and Bartter, {Frederic C.}",
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N2 - Evidence is presented for one-to-one substitution of Ca2+ by Li+, Na+, K+, and Cs+ at the surface of synthetic hydroxyapatite crystals. Such cation substitution alters the surface charge asymmetry, which is then compensated by an altered balance in the opposite sign of ions (Ca2+ and PO4 3-) in the hydration shell of the crystals. Exchangeable PO4 3- and Ca2+ in the hydration shell were calculated from the 45Ca2+ and 32PO4 3- studies. Li+, Na+, K+ and Cs+ increased the exchangeable Ca2+ without altering exchangeable phosphate. This suggests that Ca2+ accumulate in the hydration shell to compensate for the reduction in the net positive charge at the crystal surface which is brought about the substitution of divalent Ca2+ by univalent cations. Conversely, Ca2+ in the solution reduced Ca2+ exchange, probably by producing a net increase in the positive charge at the crystal surface. By these criteria, it could be shown that tetramethylammonium (TMA+) and tris(hydroxymethyl)-aminomethane (Tris+) do not participate in cation substitution. Additional proof for cation substituttion was obtained from 22Na+ and 42K+ wash-out studies indicating that Na+ and K+ exchange with the crystal surface, and from the estimation of net Ca2+ loss from the crystal, demonstrating depletion of surface Ca2+ with cation substitution.

AB - Evidence is presented for one-to-one substitution of Ca2+ by Li+, Na+, K+, and Cs+ at the surface of synthetic hydroxyapatite crystals. Such cation substitution alters the surface charge asymmetry, which is then compensated by an altered balance in the opposite sign of ions (Ca2+ and PO4 3-) in the hydration shell of the crystals. Exchangeable PO4 3- and Ca2+ in the hydration shell were calculated from the 45Ca2+ and 32PO4 3- studies. Li+, Na+, K+ and Cs+ increased the exchangeable Ca2+ without altering exchangeable phosphate. This suggests that Ca2+ accumulate in the hydration shell to compensate for the reduction in the net positive charge at the crystal surface which is brought about the substitution of divalent Ca2+ by univalent cations. Conversely, Ca2+ in the solution reduced Ca2+ exchange, probably by producing a net increase in the positive charge at the crystal surface. By these criteria, it could be shown that tetramethylammonium (TMA+) and tris(hydroxymethyl)-aminomethane (Tris+) do not participate in cation substitution. Additional proof for cation substituttion was obtained from 22Na+ and 42K+ wash-out studies indicating that Na+ and K+ exchange with the crystal surface, and from the estimation of net Ca2+ loss from the crystal, demonstrating depletion of surface Ca2+ with cation substitution.

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