Nancollas G H, LoRe M, Perez L, Richardson C, Zawacki S J
Department of Chemistry, State University of New York, Buffalo 14214.
Anat Rec. 1989 Jun;224(2):234-41. doi: 10.1002/ar.1092240213.
Many studies of calcium phosphate precipitation have been made using relaxation techniques in which the concentrations of the lattice ions are allowed to decrease as equilibrium is approached. Since the nature of the phases that form depend markedly on the solution composition, this decrease can lead to concomitant phase transformations during the crystallization experiments. The results of the present constant composition (CC) studies show that defect apatites may be formed under conditions of sustained supersaturation with a non-stoichiometric coefficient dependent on the pH of the growth medium. An important factor in analyzing these experiments is the initial surface modification and ion-exchange processes involving H+ and Ca2+ ions after inoculation of the supersaturated solutions. Thereafter, active growth sites may be eliminated as the crystals undergo lattice perfection. Transformation of dicalcium phosphate dihydrate to octacalcium phosphate, involving dissolution and subsequent nucleation and growth of the new phase, is also influenced by surface roughening of the initial phase. Typical inhibitors that reduce the rate of growth of seed crystals in supersaturated solutions may actually induce the nucleation of calcium phosphate phases when immobilized on inert surfaces. This may be a factor in the modulation of crystal growth in many biological systems.
许多关于磷酸钙沉淀的研究采用了弛豫技术,在这种技术中,随着接近平衡,晶格离子的浓度会降低。由于形成的相的性质明显取决于溶液组成,这种降低可能会在结晶实验过程中导致伴随的相变。目前的恒组成(CC)研究结果表明,在持续过饱和条件下可能会形成缺陷磷灰石,其非化学计量系数取决于生长介质的pH值。分析这些实验的一个重要因素是在接种过饱和溶液后涉及H⁺和Ca²⁺离子的初始表面改性和离子交换过程。此后,随着晶体经历晶格完善,活性生长位点可能会被消除。二水磷酸二钙向八钙磷酸钙的转变,涉及初始相的溶解以及新相的随后成核和生长,也受到初始相表面粗糙度的影响。在过饱和溶液中降低籽晶生长速率的典型抑制剂,当固定在惰性表面上时,实际上可能会诱导磷酸钙相的成核。这可能是许多生物系统中晶体生长调节的一个因素。