Preparation of Photoresponsive Functionalized Acrylic Nanoparticles Containing Carbazole Groups for Smart Cellulosic Papers

Document Type : Research Paper

Authors

Polymer Science Department, Faculty of Science, Iran Polymer and Petrochemical Institute, P.O. Box 14965/115, Tehran, Iran

Abstract

Photoresponsive functionalized polymer nanoparticles were prepared as useful materials for preparation of smart papers. Such polymer nanoparticles have wide applications in several fields including papers, sensors, bioimaging and biomedicine. First, carbazole as a photosensitive compound was modified with 2-bromoethanol through substitution nucleation reaction to its hydroxyl derivative (N-(2-hydroxyethyl) carbazole, CzEtOH). The synthesis of 2-N-carbazolylethyl acrylate (CzEtA) monomer was carried out by modification reaction of CzEtOH with acryloyl chloride and the chemical structures of the products were characterized. Next, CzEtA, methyl methacrylate (MMA) and butyl acrylate were copolymerized to prepare photoresponsive functionalized polymer nanoparticles through mini-emulsion polymerization in order to form a hydrophobic core. This was followed by copolymerization of MMA and glycidyl methacrylate by seeded emulsion polymerization to give a functionalized outer layer on the latex particles. Absorption characteristics, size, size distribution (narrow size distribution) and morphology of the nanoparticles were studied by ultraviolet-visible (UV-Vis) spectroscopy, dynamic laser light scattering (DLS) analysis and scanning electron microscopy (SEM) micrographs, respectively. Finally, due to the importance of photoresponsive smart papers and their wide applications, cellulosic fibers were reacted with the prepared functionalized latex particles for preparation of smart papers. Morphology of the fibers was investigated with respect to the surface-immobilized polymers on the cellulosic paper and their smart behavior was evaluated by UV irradiation at 254 nm. The results revealed fast color changes and the obtained cellulosic papers became violet upon irradiation. This work shows some promising feature of these materials for preparation of anti-counterfeiting papers, where the safety becomes a major concern.

Keywords


Crano J.C. and Guglielmetti R.J., Organic Photochromic and Thermochromic Compounds: Main Photochromic Families, 1st ed. Kluwer Academic, Boston, 1, 1-9, 2002.
Zhou X., Du Y., and Wang X., Azo Polymer Janus Particles and Their Photoinduced, Symmetry-Breaking Deformation, ACS Macro Lett., 5, 234-237, 2016.
Florea L., McKeon A., Diamond D., and Benito-Lopez F., Spiropyran Polymeric Microcapillary Coatings for Photodetection of Solvent Polarity, Langmuir, 29, 2790-2797, 2013.
Tian Z. and Li A.D.Q., Photoswitching-enabled Novel Optical Imaging: Innovative Solutions for Real-World Challenges in Fluorescence Detections, Acc. Chem. Res., 46, 269-279, 2013.
da Luz L.L., Milani R., Felix J.F., Ribeiro I.R.B., Talhavini M., Neto B.A.D., Chojnacki J., Rodrigues M.O., and Junior S.A., Inkjet Printing of Lanthanide–Organic Frameworks for Anti-counterfeiting Applications, ACS Appl. Mater. Interfaces, 7, 27115-27123, 2015.
Krasia T.C. and Patrickios C.S., Synthesis and Aqueous Solution Characterization of Amphiphilic Diblock Copolymers Containing Carbazole, Polymer, 43, 2917-2920, 2002.
Chen J., Zeng F., Wu S., Su J., and Tong Z., Photoreversible Fluorescent Modulation of Nanoparticles via One-step Miniemulsion Polymerization, Small, 5, 970-978, 2009.
Keyvan Rad J., Mahdavian A.R., Khoei S., and Janati-Esfahani A., FRET-based Acrylic Nanoparticles with Dual-color Photoswitchable Properties in DU145 Human Prostate Cancer Cell Line Labeling, Polymer, 98, 263-269, 2016.
Palayangoda S.S., Cai X., Adhikari R.M., and Neckers D.C., Carbazole-based Donor-Acceptor Compounds: Highly Fluorescent Organic Nanoparticles, Org. lett., 10, 281-284, 2008.
Grazulevicius J.V, Strohriegl P., Pielichowski J., and Pielichowski K., Carbazole-Containing Polymers: Synthesis, Properties and Applications, Prog. Polym. Sci., 28, 1297-1353, 2003.
Keyvan Rad J., Mahdavian A.R., Salehi-Mobarakeh H., and Abdollahi A., FRET Phenomenon in Photoreversible Dual-Color Fluorescent Polymeric Nanoparticles Based on Azocarbazole/Spiropyran Derivatives, Macromolecules, 49, 141-152, 2016.
Shah R.Y., Prajapati P.N., and Agrawal Y.K., Anticounterfeit Packaging Technologies, J. Adv. Pharm. Technol. Res., 1, 368-373, 2010.
d’Halluin M., Rull-Barrull J., Le Grognec E., Jacquemin D., and Felpin F.X., Writing and Erasing Hidden Optical Information on Covalently Modified Cellulose Paper, Chem. Commun., 52, 7672-7675, 2016.
Deisingh A.K., Pharmaceutical Counterfeiting, Analyst, 130, 271-279, 2005.
You M., Zhong J., Hong Y., Duan Z., Lin M., Xu F., Inkjet Printing of Upconversion Nanoparticles for Anti-counterfeit Applications, Nanoscale, 7, 4423-4431, 2015.
Finnell J., Invisible Markings and Conservation Treatment: An Exploratory Study, Library and Archival Security, 24, 19-24, 2011.
Pishvaei M., Rouhani S., and Madadi S., Synthesis of a Fluorescent Nanocomposite of Methacrylate Polymer via Miniemulsion Polymerization, Polym. Bull., 7, 1843-1855, 2014.
Sun B., He Z., Hou Q., Liu Z., Cha R., and Ni Y., Interaction of a Spirooxazine Dye with Latex and Its Photochromic Efficiency on Cellulosic Paper, Carbohydr. Polym., 95, 598-605, 2013.
Tian W. and Tian J., Synergy of Different Fluorescent Enhancement Effects on Spiropyran Appended onto Cellulose, Langmuir, 30, 3223-3227, 2014.
Keyvan Rad J. and Mahdavian A.R., Preparation of Fast Photoresponsive Cellulose and Kinetic Study of Photoisomerization, J. Phys. Chem. C, 120, 9985-9991, 2016.
Abdollahi A., Keyvan Rad J., and Mahdavian A.R., Stimuli-Responsive Cellulose Modified by Epoxy-Functionalized Polymer Nanoparticles with Photochromic and Solvatochromic Properties, Carbohydr. Polym., 150, 131-138, 2016.
Ho M.S., Barrett C., Paterson J., Esteghamatian M., Natansohn A., and Rochon P., Synthesis and Optical Properties of Poly {(4-nitrophenyl)-[3-[N-[2-(methacryloyloxy) ethyl]-carbazo-lyl]] diazene}, Macromolecules, 29, 4613-4618, 1996.
Uryu T., Ohkawa H., and Oshima R., Synthesis and High Hole Mobility of Isotactic Poly (2-N-carbazolylethyl acrylate), Macromolecules, 20, 712–716, 1987.
Pavia D.L., Lampman G.M., Kriz G.S., and Vyvyan J.A., Introduction to Spectroscopy, Cengage Learining, Western Washington, USA, 2008.
Yeh K., Lee C., and Chen Y., Host Copolymers Containing Pendant Carbazole and Oxadiazole Groups: Synthesis, Characterization and Optoelectronic Applications for Efficient Green Phosphorescent OLEDs, J. Polym. Sci., Part A: Polym. Chem., 46, 5180-5193, 2008.
Jang J., Nam Y., and Yoon H., Fabrication of Polypyrrole–Poly (N‐vinylcarbazole) Core–Shell Nanoparticles with Excellent Electrical and Optical Properties, Adv. Mater., 17, 1382-1386, 2005.
Keyvan Rad J. and Mahdavian A.R., Photoswitchable Dual-Color Fluorescent Particles from Seeded Emulsion Polymerization and Role of Some Affecting Parameters on FRET Process, Eur. Polym. J., 88, 56-66, 2017.
Abdollahi A., Mahdavian A.R., and Salehi-Mobarakeh H., Preparation of Stimuli-Responsive Functionalized Latex Nanoparticles: The Effect of Spiropyran Concentration on Size and Photochromic Properties, Langmuir, 31, 10672-10682, 2015.