The pH sensitive properties of carboxymethyl chitosan nanoparticles cross-linked with calcium ions

•Nanoparticle size controlled by varying pH and CaCl2 concentration during synthesis.•In acidic pH the nanoparticles form without added CaCl2.•The interaction between NH3+ and COO− groups is crucial.•pH sensitivity due to protonation/deprotonation of NH3+ and COO− groups.•In pH ≥ 7 the divalent Ca2+ ions are crucial to the formation of the nanoparticles.

In environmental applications the applied materials are required to be non-toxic and biodegradable. Carboxymethyl chitosan nanoparticles cross-linked with Ca2+ ions (CMC-Ca) fulfill these requirements, and they are also renewable. These nanoparticles were applied to oil-spill treatment in our previous study and here we focused on enhancing their properties. It was found that while the divalent Ca2+ ions are crucial for the formation of the CMC-Ca, the attractive interaction between NH3+ and COO− groups contributed significantly to the formation and stability of the CMC-Ca. The stability decreased as a function of pH due to the deprotonation of the amino groups. Therefore, the nanoparticles were found to be fundamentally pH sensitive in solution, if the pH deviated from the pH (7-9) that was used in the synthesis of the nanoparticles. The pH sensitive CMC-Ca synthesized in pH 7 and 8 were most stable in the studied conditions and could find applications in oil-spill treatment or controlled-release of substances.

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