The syntheses of polylactides (PLAs) with branched peptide end groups containing reactive (ionic) moieties such as amino or carboxyl groups are described and were used to prepare PLA‐based microspheres (MSs) with positively or negatively charged surfaces. Branched peptides with hydroxyl end groups and four protected amino or carboxyl groups, Boc4‐K3‐OH or Bn4‐E3‐OH, were synthesized, and the hydroxyl group converted to an alkoxide and was used as the initiation site for the ring‐opening polymerization of L ‐lactide. Subsequent deprotection gave PLAs end‐capped with branched peptides having four amino or carboxyl groups, respectively (K3‐PLA and E3‐PLA). K3‐PLA and E3‐PLA were converted to K34+‐PLA and E34?‐PLA by acid or base treatment, respectively. MSs with charged surfaces were then prepared using K34+‐PLA or E34?‐PLA as a surfactant [MS(K34+‐PLA) or MS(E34?‐PLA)]. The ionic surface state of the MSs was confirmed by colloidal titration and zeta potential analysis.
Double‐shelled zirconia/titania (ZrO2/TiO2) hollow microspheres were prepared by the selective removal of the polymer components via the calcination of the corresponding tetra‐layer poly(N,N′‐methylenebisacryl amide‐co‐methacrylic acid) (P(MBA‐co‐MAA))/Zr(OH)4/poly(ethyleneglycol dimethacrylate‐co‐methacrylic acid) (P(EGDMA‐co‐MAA))/TiO2 hybrid microspheres. These tetra‐layer microspheres were synthesized by the combination of the distillation copolymerization of N,N(‐methylenebisacryl amide‐co‐methacrylic acid (MBA) or ethyleneglycol dimethacrylate (EGDMA) crosslinker and methacrylic acid (MAA) for the preparation of polymer core and third‐layer as well as the controlled sol‐gel hydrolysis of inorganic precursors for the construction of zirconium hydroxide (Zr(OH)4) and titania (TiO2) layers. The thicknesses of zirconia and titania shell‐layers were conveniently controlled via varying the feed of zirconium n‐butoxide (Zr(OBu)4) and titanium tetrabutoxide (TBOT) during the sol‐gel hydrolysis, while the sizes of polymer layers were tuned through a multi‐stage distillation precipitation copolymerization. The structure and morphology of the resultant microspheres were characterized by transmission electron microscopy (TEM), X‐ray diffractometer (XRD), X‐ray photoelectronic spectroscopy (XPS), and thermogrametric analysis (TGA). 相似文献