The O‐phospho‐L‐serine [Ser(P)] containing peptides and proteins play an important role in controlling the morphology of biominerals. The poly[Ser(P)] and copoly[Ser(P)xAspy] affect the calcium carbonate (CaCO3) morphology and polymorph. The CaCO3 helical structures were obtained in the presence of copoly[Ser(P)75Asp25]. When the L‐copolymer was used as an additive, a clockwise P twisted spiral morphology was formed. On the other hand, when using D‐copolymer, a counterclockwise M twisted spiral morphology was obtained.
The modification of CaCO(3) crystal growth by synthetic L-Ser(PO(3)H(2)) and L-Thr(PO(3)H(2)) containing polypeptides is described. The amino acids Gly, L-Glu, L-Asp, L-Ser, L-Ala, and L-Lys induced rhombohedral calcite with a rough surface. Dipeptides, Xaa-L-Ser(PO(3)H(2)) (Xaa = Gly, L-Glu, L-Asp, L-Ser, L-Ala and L-Lys) induced vaterite crystals in the lower [Ca(2+)]. On the other hand, L-Ser(PO(3)H(2))-containing polypeptides formed spherical vaterite and fibrous calcite. The characteristic helical calcite was found in the presence of copoly[L-Ser(PO(3)H(2))(75)L-Asp(25)] or poly[L-Ser(PO(3)H(2))(3)-L-Asp]. Fibrous calcite, spherical vaterite, and helical calcite crystals were subjected to XRD and EDX analysis. XRD revealed the specific faces of these crystals. EDX spectra and surface analysis visualized the localization of the polypeptides and CaCO(3) components. Together with TEM and SAED data, we propose hypothetical growth mechanisms for the fibrous and helical calcite crystals.
Recently, a variety of amphiphilic block copolymers for water-based color inks as pigment dispersants have been developed. Although such dispersants require both high adsorption of pigments and dispersion-stability in water, the most crucial issue is the difficulty in controlling the affinity balance of the polymeric dispersants between the pigments and aqueous media. Therefore, it is important to increase the solubility of the hydrophobic polymers with low acid-value for ink design. Amphiphilic block copolymers containing styrene-based blocks as hydrophobic segments and methacrylic acid blocks as hydrophilic segments were prepared. The polymers with low acid-value could not dissolve in the alkaline solution directly. They could dissolve in methyl-ethyl-ketone (MEK) at room temperature and diethylene glycol (DEG), with heating. Polymer aqueous solutions were successfully prepared using polymer solutions in DEG as the pre-solutions. Because they were also unable to dissolve directly even in an alkaline solution containing DEG, the existence of DEG is not important, but the process employing the pre-solution is important. The influence of pre-solution viscosity on solubility in water was evaluated. The result suggests that the high viscosity of the DEG solution would work to slowly disperse the polymers in the alkaline solution, efficiently converting polymers into an aqueous soluble state, owing to there being enough time for the neutralization of the carboxylic acids of the polymers. Note that in the pre-solution of a lower concentration, the aqueous solution did not become clear, and the larger particle sizes were detected. These results showed that the viscosity of the pre-solution is an essential factor in solubilization in water. Using this method, the polymeric dispersants with low hydrophilicity were well dissolved in water, up to a high concentration.
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