The Effect of Multidentate Biopolymer Based on Polyacrylamide Grafted onto Kappa-Carrageenan on the Spectrofluorometric Properties of Water-Soluble CdS Quantum Dots
A new fluorescent composite based on CdS quantum dots immobilized on the multidentate biopolymer matrix is prepared through the graft copolymerization of the acrylamide onto kappa-Carrageenan. A variety of techniques like thermogravimetric analysis (TGA), transmission electron microscopy (TEM), and Fourier transform infrared spectroscopy (FT-IR) was used to confirm the structure of the obtained samples. To investigate the spectrofluorometric properties, fluorescence spectroscopy of the obtained quantum dots was studied. 1. Introduction Semiconductor quantum dots (QDs), also called nanocrystals (NCs), have gained increasing attention in the past decade [1–3]. They have been widely investigated because of their potential use in sensors [4], laser materials [5], thin-film light-emitting devices (LEDs) [6–8], and biological labels. Among numerous possible applications of QDs, biological labeling will be pointed out [9, 10]. QDs exhibit larger photostability than organic dyes used routinely, since narrow excitation spectra of conventional dye molecules make difficult simultaneous excitation in most cases. However, QDs display size-dependent tunable florescence (FL) with broad excitation spectra and narrow emission band widths, which span the visible spectrum. This property of QDs allows simultaneous excitation of several particle sizes at a single wavelength, and therefore they facilitate multicolor experiments [11–14]. In addition, QDs have high photochemical stability, excellent resistance to chemical degradation and photodegradation, and good florescence quantum yields. For most biological applications of QDs, their water solubility is indispensable. Three different approaches can be used to prepare water-soluble semiconductor QDs: ligand exchange [15, 16], encapsulation into a water-soluble shell (i.e., the silica or phospholipids) [17, 18], and surface coating with polymers [19, 20]. In comparison, silica encapsulation produces good stability but with larger sizes which are about tens of nanometers to several micrometers [21]. In ligand exchange, the stability of the nanocrystals is limited by the stability of ligands on the QD surfaces. The proper choice of ligand is therefore crucial in order to achieve functionality and retain the optical properties of the QDs, and it usually limits the final application range of the QDs [22]. In this context, polymers may be used as suitable substitutes for the small organic ligand molecules due to their good stability on the surface of QDs [23]. A number of strategies were developed to obtain polymer-coated QDs:
References
[1]
A. Fu, W. Gu, C. Larabell, and A. P. Alivisatos, “Semiconductor nanocrystals for biological imaging,” Current Opinion in Neurobiology, vol. 15, no. 5, pp. 568–575, 2005.
[2]
S. Zhong, L. Zhang, Z. Huang, and S. Wang, “Mixed-solvothermal synthesis of CdS micro/nanostructures and their optical properties,” Applied Surface Science, vol. 257, no. 7, pp. 2599–2603, 2011.
[3]
Y. F. Liu and J. S. Yu, “Selective synthesis of CdTe and high luminescence CdTe/CdS quantum dots: the effect of ligands,” Journal of Colloid and Interface Science, vol. 333, no. 2, pp. 690–698, 2009.
[4]
O. L. Stroyuk, O. Y. Rayevska, A. V. Kozytskiy, and S. Y. Kuchmiy, “Electron energy factors in photocatalytic methylviologen reduction in the presence of semiconductor nanocrystals,” Journal of Photochemistry and Photobiology A, vol. 210, no. 2-3, pp. 209–214, 2010.
[5]
R. Karimzadeh, H. Aleali, and N. Mansour, “Thermal nonlinear refraction properties of Ag2 S semiconductor nanocrystals with its application as a low power optical limiter,” Optics Communications, vol. 284, no. 9, pp. 2370–2375, 2011.
[6]
T. Roques-Carmes Thibault, F. Aldeek, L. Balan, S. Corbel, and R. Schneider, “Aqueous dispersions of core/shell CdSe/CdS quantum dots as nanofluids for electrowetting,” Colloids and Surfaces A, vol. 377, no. 1–3, pp. 278–283, 2011.
[7]
H. Lee, S. Kim, W. S. Chung, K. Kim, and D. Kim, “Hybrid solar cells based on tetrapod nanocrystals: the effects of compositions and type II heterojunction on hybrid solar cell performance,” Solar Energy Materials and Solar Cells, vol. 95, no. 2, pp. 446–452, 2011.
[8]
Z. Cheng, F. Su, L. Pan, M. Cao, and Z. Sun, “CdS quantum dot-embedded silica film as luminescent down-shifting layer for crystalline Si solar cells,” Journal of Alloys and Compounds, vol. 494, no. 1-2, pp. L7–L10, 2010.
[9]
A. Papagiannaros, T. Levchenko, W. Hartner, D. Mongayt, and V. Torchilin, “Quantum dots encapsulated in phospholipid micelles for imaging and quantification of tumors in the near-infrared region,” Nanomedicine, vol. 5, no. 2, pp. 216–224, 2009.
[10]
W. W. Yu, E. Chang, R. Drezek, and V. L. Colvin, “Water-soluble quantum dots for biomedical applications,” Biochemical and Biophysical Research Communications, vol. 348, no. 3, pp. 781–786, 2006.
[11]
G. R. Bardajee, C. Vancaeyzeele, J. C. Haley, A. Y. Li, and M. A. Winnik, “Synthesis, characterization, and energy transfer studies of dye-labeled poly(butyl methacrylate) latex particles prepared by miniemulsion polymerization,” Polymer, vol. 48, no. 20, pp. 5839–5849, 2007.
[12]
D. Andrews, G. Scholes, and G. Wiederrecht, Comprehensive Nanoscience and Technology, Academic Press, New York, NY, USA, 2010.
[13]
X. C. Shen, X. Y. Liou, L. P. Ye, H. Liang, and Z. Y. Wang, “Spectroscopic studies on the interaction between human hemoglobin and CdS quantum dots,” Journal of Colloid and Interface Science, vol. 311, no. 2, pp. 400–406, 2007.
[14]
Z. Zhelev, R. Jose, T. Nagase et al., “Enhancement of the photoluminescence of CdSe quantum dots during long-term UV-irradiation: privilege or fault in life science research?” Journal of Photochemistry and Photobiology B, vol. 75, no. 1-2, pp. 99–105, 2004.
[15]
S. Moeno, E. Antunes, and T. Nyokong, “The determination of the photosensitizing properties of mercapto substituted phthalocyanine derivatives in the presence of quantum dots capped with mercaptopropionic acid,” Journal of Photochemistry and Photobiology A, vol. 218, no. 1, pp. 101–110, 2011.
[16]
Y.-C. Yeh, D. Patra, B. Yan et al., “Synthesis of cationic quantum dots via a two-step ligand exchange process,” Chemical Communications, vol. 47, no. 11, pp. 3069–3071, 2011.
[17]
S. Pathak, S. K. Choi, N. Arnheim, and M. E. Thompson, “Hydroxylated quantum dots as luminescent probes for in situ hybridization,” Journal of the American Chemical Society, vol. 123, no. 17, pp. 4103–4104, 2001.
[18]
T. Kim, D. Choe, S. W. Joo, S. Y. Lee, and K. Lee, “Mathematical modeling of DNA-mediated selective aggregation of CdS quantum dots,” Journal of Colloid and Interface Science, vol. 347, no. 2, pp. 209–214, 2010.
[19]
N. Joumaa, M. Lansalot, A. Théretz et al., “Synthesis of quantum dot-tagged submicrometer polystyrene particles by miniemulsion polymerization,” Langmuir, vol. 22, no. 4, pp. 1810–1816, 2006.
[20]
V. I. Slaveykova and K. Startchev, “Effect of natural organic matter and green microalga on carboxyl-polyethylene glycol coated CdSe/ZnS quantum dots stability and transformations under freshwater conditions,” Environmental Pollution, vol. 157, no. 12, pp. 3445–3450, 2009.
[21]
A. Wolcott, D. Gerion, M. Visconte et al., “Silica-coated CdTe quantum dots functionalized with thiols for bioconjugation to IgG proteins,” Journal of Physical Chemistry B, vol. 110, no. 11, pp. 5779–5789, 2006.
[22]
I. D. Tomlinson, M. R. Warnerment, J. N. Mason et al., “Synthesis and characterization of a pegylated derivative of 3-(1,2,3,6-tetrahydro-pyridin-4yl)-1H-indole (IDT199): a high affinity SERT ligand for conjugation to quantum dots,” Bioorganic and Medicinal Chemistry Letters, vol. 17, no. 20, pp. 5656–5660, 2007.
[23]
B. Lounis, H. A. Bechtel, D. Gerion, P. Alivisatos, and W. E. Moerner, “Photon antibunching in single CdSe/ZnS quantum dot fluorescence,” Chemical Physics Letters, vol. 329, no. 5-6, pp. 399–404, 2000.
[24]
A. L. Rogach, A. Kornowski, M. Gao, A. Eychmüller, and H. Weller, “Synthesis and characterization of a size series of extremely small thiol-stabilized CdSe nanocrystals,” Journal of Physical Chemistry B, vol. 103, no. 16, pp. 3065–3069, 1999.
[25]
K. Sato, Y. Tachibana, S. Hattori, T. Chiba, and S. Kuwabata, “Polyacrylic acid coating of highly luminescent CdS nanocrystals for biological labeling applications,” Journal of Colloid and Interface Science, vol. 324, no. 1-2, pp. 257–260, 2008.
[26]
A. Emanuele, L. Di Stefano, D. Giacomazza, M. Trapanese, M. B. Palma-Vittorelli, and M. U. Palma, “Time-resolved study of network self-organization from a biopolymeric solution,” Biopolymers, vol. 31, no. 7, pp. 859–868, 1991.
[27]
M. R. Mangione, D. Giacomazza, D. Bulone, V. Martorana, and P. L. San Biagio, “Thermoreversible gelation of κ-Carrageenan: relation between conformational transition and aggregation,” Biophysical Chemistry, vol. 104, no. 1, pp. 95–105, 2003.
[28]
E. R. Morris, D. A. Rees, and G. Robinson, “Cation-specific aggregation of carrageenan helices: domain model of polymer gel structure,” Journal of Molecular Biology, vol. 138, no. 2, pp. 349–362, 1980.
[29]
P. L. San Biagio, D. Bulone, A. Emanuele, M. B. Palma-Vittorelli, and M. U. Palma, “Spontaneous symmetry-breaking pathways: time-resolved study of agarose gelation,” Food Hydrocolloids, vol. 10, no. 1, pp. 91–97, 1996.
[30]
A. M. Hermansson, “Rheological and microstructural evidence for transient states during gelation of kappa-carrageenan in the presence of potassium,” Carbohydrate Polymers, vol. 10, no. 3, pp. 163–181, 1989.
[31]
D. Slootmaekers, C. De Jonghe, H. Reynaers, F. A. Varkevisser, and C. J. Bloys van Treslong, “Static light scattering from κ-carrageenan solutions,” International Journal of Biological Macromolecules, vol. 10, no. 3, pp. 160–168, 1988.
[32]
L. Campanella, R. Roversi, M. P. Sammartino, and M. Tomassetti, “Hydrogen peroxide determination in pharmaceutical formulations and cosmetics using a new catalase biosensor,” Journal of Pharmaceutical and Biomedical Analysis, vol. 18, no. 1-2, pp. 105–116, 1998.
[33]
M. F. Perutz, “Glutamine repeats and inherited neurodegenerative diseases: molecular aspects,” Current Opinion in Structural Biology, vol. 6, no. 6, pp. 848–858, 1996.
[34]
K. Makino, R. Idenuma, T. Murakami, and H. Ohshima, “Design of a rate- and time-programming drug release device using a hydrogel: pulsatile drug release from κ-carrageenan hydrogel device by surface erosion of the hydrogel,” Colloids and Surfaces B, vol. 20, no. 4, pp. 355–359, 2001.
[35]
C. Rochas, M. Rinaudo, and S. Landry, “Relation between the molecular structure and mechanical properties of carrageenan gels,” Carbohydrate Polymers, vol. 10, no. 2, pp. 115–127, 1989.
[36]
R. M. Murphy, “Peptide aggregation in neurodegenerative disease,” Annual Review of Biomedical Engineering, vol. 4, pp. 155–174, 2002.
[37]
A. M. Garcia and E. S. Ghaly, “Preliminary spherical agglomerates of water soluble drug using natural polymer and cross-linking technique,” Journal of Controlled Release, vol. 40, no. 3, pp. 179–186, 1996.
[38]
M. Marandi, N. Taghavinia, A. Iraji Zad, and S. M. Mahdavi, “A photochemical method for controlling the size of CdS nanoparticles,” Nanotechnology, vol. 16, no. 2, pp. 334–338, 2005.
[39]
Z. Sedaghat, N. Taghavinia, and M. Marandi, “Thermal control of the size and crystalline phase of CdS nanoparticles,” Nanotechnology, vol. 17, no. 15, article 034, pp. 3812–3816, 2006.
