Rare earth ions (Tm3+, Er3+, and Yb3+)-doped cubic Gd2O3 nanocrystals were prepared by a simple sol−gel method. Raman and FT-IR spectra were measured to evaluate the vibrational feature of the samples. Under 980 nm laser excitation, blue (488 nm), green (564 nm), and red (661 nm) upconversion has been recorded in Gd2O3:Tm+Yb and Gd2O3:Er (Gd2O3:Er+Yb), respectively. A great enhancement of red emission and diminishment of green emission of Er3+ in Gd2O3:Er+Yb have been observed. Laser power and doping concentration dependence of the upconverted emissions were studied to understand the upconversion mechanisms. Excited absorption and energy-transfer processes are discussed as the possible mechanisms for the visible emissions.

A new cysteine-based methacrylic monomer (CysMA) was conveniently synthesized via selective thia-Michael addition of a commercially available methacrylate-acrylate precursor in aqueous solution without recourse to protecting group chemistry. Poly(cysteine methacrylate) (PCysMA) brushes were grown from the surface of silicon wafers by atom-transfer radical polymerization. Brush thicknesses of ca. 27 nm were achieved within 270 min at 20 °C. Each CysMA residue comprises a primary amine and a carboxylic acid. Surface zeta potential and atomic force microscopy (AFM) studies of the pH-responsive PCysMA brushes confirm that they are highly extended either below pH 2 or above pH 9.5, since they possess either cationic or anionic character, respectively. At intermediate pH, PCysMA brushes are zwitterionic. At physiological pH, they exhibit excellent resistance to biofouling and negligible cytotoxicity. PCysMA brushes undergo photodegradation: AFM topographical imaging indicates significant mass loss from the brush layer, while XPS studies confirm that exposure to UV radiation produces surface aldehyde sites that can be subsequently derivatized with amines. UV exposure using a photomask yielded sharp, well-defined micropatterned PCysMA brushes functionalized with aldehyde groups that enable conjugation to green fluorescent protein (GFP). Nanopatterned PCysMA brushes were obtained using interference lithography, and confocal microscopy again confirmed the selective conjugation of GFP. Finally, PCysMA undergoes complex base-catalyzed degradation in alkaline solution, leading to the elimination of several small molecules. However, good long-term chemical stability was observed when PCysMA brushes were immersed in aqueous solution at physiological pH.

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