Calcium Carbonate/Polymers Microparticles Tuned by Complementary Polyelectrolytes as Complex Macromolecular Templates

Abstract

This study describes the effects of mixed anionic/ cationic polyelectrolytes on the crystallization of calcium carbonate in supersaturated solutions in comparison with polyanion-based CaCO 3 composite structures. Two simple methods of introducing the polycation in the crystallogenesis of calcium carbonate are proposed: preformed nonstoichiometric polyelectrolyte complexes (NPECs) or in situ mixing of complementary polyelectrolytes, with a very large range of ratios between complementary polyions. For this purpose three polyanionspoly(acrylic acid) sodium salt, poly(sodium 4styrenesulfonate) and poly(sodium vinylsulfonate)and poly-(diallyl-dimethylammonium chloride) as polycation were used. The molar ratio between complementary polyelectrolytes used in CaCO 3 composite synthesis varied between 0 (just polyanions) up to 0.95 (close to the equimolar ratio between ionic charges of complementary polyelectrolytes). The polymer presence into the composite particles, as a function of polyanion structure and the preparation mode, was evidenced by energy dispersive X-ray diffraction and particle charge detection in the supernatant fraction. Scanning electron microscopy was used to provide the particles' morphology, and Fourier transform infrared-attenuated total reflection (FTIR-ATR) spectroscopy was used to determine the polymorph content ratio. The enhanced CaCO 3 / polyanion/polycation microparticles stability in ethylenediamine tetraacetic acid has been also shown compared to CaCO 3 / polyanion microparticles as a function of the molar ratio between complementary polyelectrolytes and the method of introducing the polycation in the crystallogenesis system.

Facile preparation of micro and nano-sized CaCO3 particles by a new CO2-storage material

“…In order to obtain uniform CaCO 3 nanoparticles, bio-macromolecules [15], synthetic macromolecules [16], reverse microemulsion or complex micelle [17], self-assembled monomolecular (SAM) films [18], Langmuir monolayers [19], and double hydrophilic block copolymers (DHBCs) [20], as effective tools or templates, have been studied. In previous studies [21][22][23], the arranged carboxyl groups in a fibrous protein had been used as templates to form aragonite nanorods [21]; meanwhile, with a presence of the synthetic macromolecules, such as polyvinyl alcohol and polyethylene glycol [22], the aragonite crystal CaCO 3 was formed.…”

Biofunctionalized Polyelectrolyte Microcapsules Encoded with Fluorescent Semiconductor Nanocrystals for Highly Specific Targeting and Imaging of Cancer Cells

“…This could be explained by a higher molecular weight of the dye comparing to that of EDTA and its calcium complexes, ensuring slower diffusion of trypan blue into the microcapsules, particularly at the initial time points during core removal. The residuals of calcium carbonate microparticles possibly remaining inside the microcapsule shell during short-term template dissolution could have acted as a barrier for the dye penetration [21,22]. However, after longer incubation of the templated microcapsules in the EDTA solution, a moderate decrease in trypan blue entrapment efficiency was observed.…”

Calcium Carbonate and Poly(2-Acrylamido-2-Methylpropanesulfonic Acid-Co-Acrylic Acid). A Review

“…Even if there are numerous studies on polyanions control of CaCO 3 growth, the use of nonstoichiometric polyelectrolyte complexes (NPEC) as templates for controlling CaCO 3 crystals growth has been reported up to now only by our group. 36,76,81 Polyelectrolyte complexes (PECs) are obtained by mixing aqueous solutions of oppositely charged polymers. 82 PECs are of interest due to their facile preparation and responsiveness to environmental stimuli.…”