The pyrolysis of a hyperbranched
polyethylenimine (PEI) and glycerol
mixture under microwaves generated the carbon dot (CD) functionalized
with PEI (CD-PEI). Isobutyric amide (IBAm) groups were attached to
CD-PEI through the amidation reaction of isobutyric anhydride and
the PEI moiety, which resulted in the thermoresponsive CD-PEI-IBAm’s.
CD-PEI-IBAm’s were not only thermoresponsive but also responded
to other stimuli, including inorganic salt, pH, and loaded organic
guests. The cloud point temperature (T
cp) of the aqueous solutions of CD-PEI-IBAm’s could be modulated
in a broad range through changing the number of IBAm units of CD-PEI-IBAm
or varying the type and concentration of the inorganic salts, pH,
and loaded organic guests. All the obtained CD-PEI-IBAm’s were
photoluminescent, which could be influenced a little or negligibly
by the added salts, pH, and the organic guests encapsulated.
The salt effects on the water solubility of thermoresponsive hyperbranched polyethylenimine and polyamidoamine possessing large amounts of isobutyramide terminal groups (HPEI-IBAm and HPAMAM-IBAm) were studied systematically. Eight anions with sodium as the counterion and ten cations with chloride as the counterion were used to measure the anion and cation effects on the cloud point temperature (T(cp)) of these dendritic polymers in water. It was found that the T(cp) of these dendritic polymers was much more sensitive to the addition of salts than that of the traditional thermoresponsive linear polymers. At low anion concentration, the electrostatic interaction between anions and the positively charged groups of these polymers was dominant, resulting in the unusual anion effect on the T(cp) of these polymers in water, including (1) T(cp) of these dendritic polymers decreasing nonlinearly with the increase of kosmotropic anion concentration; (2) the chaotropic anions showing abnormal salting-out property at low salt concentration and the stronger chaotropes having much pronounced salting-out ability; (3) anti-Hofmeister ordering at low salt concentration. At moderate to high salt concentration, the specific ranking of these anions in reducing the T(cp) of HPEI-IBAm and HPAMAM-IBAm polymers was PO(4)(3-) > CO(3)(2-) > SO(4)(2-) > S(2)O(3)(2-) > F(-) > Cl(-) > Br(-) > I(-), in accordance with the well-known Hofmeister series. At moderate to high salt concentration, the specific ranking order of inorganic cations in reducing the T(cp) of HPEI-IBAm polymer was Sr(2+) ≈ Ba(2+) > Na(+) ≈ K(+) ≈ Rb(+) > Cs(+) > NH(4)(+) ≈ Ca(2+) > Li(+) ≈ Mg(2+). This sequence was only partially similar to the typical Hofmeister cation series, whereas at low salt concentration the cation effect on T(cp) of the dendritic polymer was insignificant and no obvious specific ranking order could be found.
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