Incorporation of photochromic compounds to polymer matrix through chemical bonding results in an enhancement of photoactivity and stabilization of optical properties. Here, spiropyran ethyl acrylate monomer (SPEA) was synthesized, and then photochromic particles bearing epoxy functional groups were prepared through semicontinuous emulsion copolymerization. Dynamic light scattering (DLS) and scanning electron microscopy (SEM) results depicted an increase in particle size and particle size distribution with the increase in SPEA monomer-surfactants ratio. Studies on photochromic properties by UV-vis analysis demonstrated a decrease in the absorption intensity despite the increase in SPEA content due to the enhancement in particle size. The prepared acrylic copolymer particles showed reasonable photostability, photoreversibility, and fast photoresponsivness according to the convenient test methods under UV/vis irradiation. DSC and DMTA analyses indicate an increase in Tg of the obtained copolymers with the increase in SPEA content. Finally, stimuli-responsive cellulosic papers were prepared by impregnation, and their photochromic behavior was investigated in dry and wet forms in various media under UV radiation. Morphology studies, due to stabilization of the photochromic copolymer on cellulose fibers, were conducted by SEM micrographs and showed good adhesion and compatibility between the two phases.

Chemical bonding between photochromic compounds and polymer matrices will induce several consitions such as photostability, photoreversibility, elimination of dye aggregation, and undesirable negative photochromism. In such polymeric systems, the switching rate and photoisomerization are closely dependent on several parameters like chain flexibility, steric restrictions, polarity, and even proticity of the surrounding medium. Here, copolymerization of a synthesized spiropyran-based monomer with butyl acrylate (BA) and methyl methacrylate (MMA) comonomers was carried out with various compositions of MMA and BA through emulsion polymerization, and the corresponding photoisomerization kinetics were studied. Particle sizes and their distributions were analyzed by dynamic light scattering, and morphologies were investigated by scanning and transmission electron microscopic analyses. The results showed the particles are spherical with diameter 62-82 nm. Differential scanning calorimetric thermograms were employed to determine T of the prepared copolymers, which ranged from -23 to 93 °C. The kinetics of photoisomerization was then studied by UV-vis spectroscopy. Finally, a latex containing spiropyran/acrylic copolymer with T of about 0 °C and optimum rate of coloration and decoloration was considered in reversible optical data storage studies due to its fast photochromism and good film-formation properties.

No abstract

Incorporation of chromophores into a polymer chain results in prominent photoreversibility and fatigue resistance, photostability over the long term, and restriction of the internal conversion (IC). Here, we report the copolymerization of two photoactive monomers with methyl methacrylate via emulsion polymerization in order to obtain photoswitchable dual-color fluorescent nanoparticles. For this purpose, azocarbazole ethyl acrylate (AzoCzEA) and spiropyran ethyl acrylate (SPEA) were synthesized and the fluorescence polymeric latex nanoparticles were prepared correspondingly. FT-IR and 1 HNMR spectra were used to confirm the structure of novel fluorescent AzoCzEA. UV−vis studies of the obtained nanoparticles displayed the spectral features of both AzoCzEA and SPEA under stimuli-irradiation and inclusion of these chromophores into the polymer particles. DSC analysis revealed an increase in T g of the prepared copolymer, indicating covalently incorporation of the photoactive monomers into the polymer chains. The optimum ratio of two chromophores to achieve complete quenching and highest energy transfer was determined by UV−vis spectroscopy. DLS and SEM results demonstrated particle size distribution of 40−80 nm with spherical morphology. Fluorescence spectra revealed remarkable fluorescence resonance energy transfer (FRET) from AzoCzEA to SPEA after UV irradiation at 365 nm and dual-color characteristic of the prepared nanoparticles. Besides, an enhancement in the photoreversibility, photostability, prevention of IC, dye leakage, and aggregation were studied elaborately. The obtained results were attributed to the involvement of such chromophores into the polymeric matrix via covalent bonding. Labeling and tracking of living cells and rewriteable patterning are potential applications for such dual-color fluorescent nanoparticles.

No abstract