Article pubs.acs.org/Langmuir
Visible and Near-Infrared Plasmon-Mediated Molecular Release from Cucurbit[6]uril Mesoporous Gated Systems Daniela T. Marquez and Juan C. Scaiano* Department of Chemistry and Biomolecular Sciences and Centre for Catalysis Research and Innovation, University of Ottawa, 10, Marie Curie, Ottawa, Ontario K1N6N5, Canada S Supporting Information *
ABSTRACT: Several hybrid mesoporous materials were synthesized in order to obtain a drug/cargo delivery system in which it is possible to control both the start and rate of the cargo release via surface plasmon (SPR) excitation. The successful incorporation of a thermoresponsive gate based on a cucurbit[6]urilhexamethylene diamine (CB6-Hex) host−guest complex conferred the system with the desired “zero” premature release. This feature combined with the incorporation of gold nanorods (AuNR) and gold nanoparticles (AuNP) capable of acting as a heat source upon SPR excitation enabled a controlled cargo release system active to green and NIR irradiation. The results obtained prove that it is possible to disassemble the CB6-Hex gate complex in a few minutes using either green or NIR irradiation in order to activate the system and start the release process (that can take hours), as well as to further control the diffusion of Naproxen as a model drug.
■
INTRODUCTION The use of mesoporous materials in numerous applications has increased considerably in the last few decades due to their high thermal stability, large surface area, narrow pore diameter and volume distribution, which make these materials unique because of their distinctive physical, chemical, and mechanical properties.1−3 Silicon-based mesoporous materials, such as MCM-41, have proven to be highly tunable due to the ease with which their surface can be functionalized with desirable tethers.2,4−6 All these properties combined have contributed to the numerous applications in which mesoporous materials have been used.7−9 In an earlier publication from our group, hybrid mesoporous silica materials containing gold nanoparticles (AuNP) were investigated as potential drug delivery systems.10 It was shown that upon visible light activation, it is possible to use the surface plasmon heating effect of AuNP to control the release of cargo molecules from these supramolecular structures. Upon excitation of the surface plasmon resonance (SPR) band the surface of the nanoparticles can reach elevated temperatures of up to 500 °C.11 When the SPR of AuNP incorporated in MCM-41 is excited, the surface heating of the nanoparticles induces local changes in viscosity affecting the diffusion of the cargo and concomitantly the release rates of the model drug, in our case Naproxen. The main advantage and novelty of these types of systems is the possibility to use the surface plasmon resonance (SPR) band to achieve control of the drug release rate avoiding the use of UV light, since most of the hosts used in photochemical-based delivery applications are unstable toward UV light, giving place to secondary reactions and decomposition products. Furthermore, UV light can also © XXXX American Chemical Society
damage biological tissues, thus limiting its applications in biological systems. Other very interesting examples using a similar approach have been previously developed.12−14 Nevertheless, the feature of wavelength-controlled rate of release accompanied by the use of a simpler and cheaper irradiation source -LED vs laser- and much lower irradiation powers differentiate the systems proposed in this paper from previous ones. The different “modes” given by the above-mentioned wavelength-controlled release rate of the cargo confer these systems with enough versatility to be used in various circumstances in which continuous irradiation is suitable. Controlled drug delivery offers a series of advantages. By being able to control and modify rates of release, it is possible to minimize drug degradation and loss, prevent side effects, reduce the toxicity, as well as to improve the efficacy of the release. Nevertheless, beyond controlling the delivery process itself, it is just as important to be able to control the start of the release process in order to maximize the advantages noted above. Considerable efforts have been put into regulating the beginning of the delivery process in order to efficiently achieve “zero” premature release (73%.
■
AuNP and AuNR. The additional rate of release obtained compared to previously designed hybrid mesoporous materials contributes to the versatility of the system by having an extra activation component as well as expanding its applicability due to the fact that the longitudinal plasmon band of AuNR is located at the optimum wavelength range for biological tissue penetration.35 We note that decomposition of Naproxen by the elevated local temperatures reached via plasmon excitation was ruled out by H1-NMR studies in a previous publication.10
■
CONCLUSIONS When metal nanoparticles are embedded in supramolecular structures such as MCM-41 the heat released to the medium influences the guests and solvents contained within the channels of the mesoporous material.10 In this work, several hybrid mesoporous systems were designed. The successful incorporation of a thermoresponsive gate based on the CB6− Hex host−guest complex conferred the system with the desirable “zero” premature release. This feature combined with the incorporation of gold nanorods and gold nanoparticles capable of acting as local heaters when their SPR bands are photoexcited, allowed for a cargo release system active to green and NIR light. These findings show it is feasible to use the surface plasmon heating effect to control both the starting point of the cargo release as well as the rates of delivery. The results obtained prove it is possible to open the system using 5 min of either green or near IR irradiation via the disassembly of the Cucurbit[6]uril-hexanediamine gate complex. By means of gold nanorods the NIR light activation component was incorporated into the systems generating an enhanced rate of release beyond those promoted by dark and green light irradiation. These findings expand the versatility of these systems by achieving three different rates of release as well as increasing their applicability by allowing the use of the drug delivery system in biological samples that would require deeper light penetration.
■
REFERENCES
(1) Kovalchuk, T. V.; Sfihi, H.; Korchev, A. S.; Kovalenko, A. S.; Il’in, V. G.; Zaitsev, V. N.; Fraissard, J. Synthesis, Structure, and Acidic Properties of MCM-41 Functionalized with Phosphate and Titanium Phosphate Groups. J. Phys. Chem. B 2005, 109 (29), 13948−13956. (2) Mal, N. K.; Fujiwara, M.; Tanaka, Y.; Taguchi, T.; Matsukata, M. Photo-Switched Storage and Release of Guest Molecules in the Pore Void of Coumarin-Modified MCM-41. Chem. Mater. 2003, 15 (17), 3385−3394. (3) Zhao, X. S.; Lu, G. Q.; Hu, X. Characterization of the structural and surface properties of chemically modified MCM-41 material. Microporous Mesoporous Mater. 2000, 41, 37−47. (4) Mal, N. K.; Fujiwara, M.; Tanaka, Y. Photocontrolled reversible release of guest molecules from coumarin-modified mesoporous silica. Nature 2003, 421, 350−353. (5) Song, L.; Bu, T.; Zhu, L.; Zhou, Y.; Xiang, W.; Xia, D. Synthesis of Organically−Inorganically Functionalized MCM-41 for Adsorptive Desulfurization of C4 Hydrocarbons. J. Phys. Chem. C 2014, 118 (18), 9468−9476. (6) Zhang, L.; Qiao, S.; Jin, Y.; Cheng, L.; Yan, Z.; Lu, G. Q. Hydrophobic Functional Group Initiated Helical Mesostructured Silica for Controlled Drug Release. Adv. Funct. Mater. 2008, 18 (23), 3834− 3842. (7) Corma, A. From Microporous to Mesoporous Molecular Sieve Materials and Their Use in Catalysis. Chem. Rev. 1997, 97 (6), 2373− 2420. (8) Shu, X.; He, Y.; Oba, F.; Zhang, Q.; Canlas, C.; Somorjai, G. A.; Alivisatos, P.; Toste, F. D. Silica-Supported Cationic Gold(I) Complexes as Heterogeneous Catalysts for Regio- and Enantioselective Lactonization Reactions. J. Am. Chem. Soc. 2015, 137, 7083− 7086. (9) Wan, Y.; Zhao, D. On the Controllable Soft-Templating Approach to Mesoporous Silicates. Chem. Rev. 2007, 107 (7), 2821−2860. (10) Marquez, D. T.; Carrillo, A. I.; Scaiano, J. C. Plasmon Excitation of Supported Gold Nanoparticles Can Control Molecular Release from Supramolecular Systems. Langmuir 2013, 29, 10521−10528. (11) Fasciani, C.; Bueno Alejo, C. J.; Grenier, M.; Netto-Ferreira, J. C.; Scaiano, J. C. High-Temperature Organic Reactions at Room Temperature Using Plasmon Excitation: Decomposition of Dicumyl Peroxide. Org. Lett. 2011, 13 (2), 204−207. (12) Chang, Y.-T.; Liao, P.-Y.; Sheu, H.-S.; Tseng, Y.-J.; Cheng, F.-Y.; Yeh, C.-S. Near-Infrared Light-Responsive Intracellular Drug and siRNA Release Using Au Nanoensembles with OligonucleotideCapped Silica Shell. Adv. Mater. 2012, 24 (25), 3309−3314. (13) Croissant, J.; Zink, J. I. Nanovalve-Controlled Cargo Release Activated by Plasmonic Heating. J. Am. Chem. Soc. 2012, 134 (18), 7628−7631. (14) Li, H.; Tan, L.-L.; Jia, P.; Li, Q.-L.; Sun, Y.-L.; Zhang, J.; Ning, Y.-Q.; Yu, J.; Yang, Y.-W. Near-infrared light-responsive supra-
ASSOCIATED CONTENT
* Supporting Information S
The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.langmuir.6b03679. Experimental methods and suppementary figures (PDF) F
DOI: 10.1021/acs.langmuir.6b03679 Langmuir XXXX, XXX, XXX−XXX
Article
Langmuir molecular nanovalve based on mesoporous silica-coated gold nanorods. Chemical Science 2014, 5 (7), 2804−2808. (15) Fitzpatrick, S. D.; Fitzpatrick, L. E.; Thakur, A.; Mazumder, M. A. J.; Sheardown, H. Temperature-sensitive polymers for drug delivery. Expert Rev. Med. Devices 2012, 9, 339−351. (16) Huang, X.; Wu, S.; Du, X. Gated mesoporous carbon nanoparticles as drug delivery system for stimuli-responsive controlled release. Carbon 2016, 101, 135−142. (17) Needham, D.; Dewhirst, M. W. The development and testing of a new temperature-sensitive drug delivery system for the treatment of solid tumors. Adv. Drug Delivery Rev. 2001, 53, 285−305. (18) Zhou, J.; Hao, N.; Yan, M.; Ramstrom, O. Lectin-gated, mesoporous, photofunctionalized glyconanoparticles for glutathioneresponsive drug delivery. Chem. Commun. 2015, 51, 9833−9836. (19) Wang, H.; Liu, H.; Wang, Y. A pH-responsive drug delivery system with an aggregation-induced emission feature for cell imaging and intracellular drug delivery. Polym. Chem. 2015, 6, 4715−4718. (20) Kumar, S.; Kumar, R.; Ratnam, A.; Mishra, N. C.; Ghosh, K. Novel drug delivery system for photoinduced nitric oxide (NO) delivery. Inorg. Chem. Commun. 2015, 53, 23−25. (21) Mody, V. V.; Cox, A.; Shah, S.; Singh, A.; Bevins, W.; Parihar, H. Magnetic Nanoparticle Drug Delivery Systems for Targeting Tumor. Appl. Nanosci. 2014, 4, 385−392. (22) Mura, S.; Nicolas, J.; Couvreur, P. Stimuli Responsive Nanocarriers for Drug Delivery. Nat. Mater. 2013, 12, 991−1003. (23) Saint-Cricq, P.; Deshayes, S.; Kasko, A. M. Magnetic field activated drug delivery using thermodegradable azo-functionalised pegcoated core-shell mesoporous silica nanoparticles. Nanoscale 2015, 7, 13168−13172. (24) Chen, C.; Geng, J.; Yang, X.; Ren, J.; Qu, X. Polyvalent Nucleic Acid/Mesoporous Silica Nanoparticle Conjugates: Dual StimuliResponsive Vehicles for Intracellular Drug Delivery. Angew. Chem., Int. Ed. 2011, 50, 882−886. (25) Slowing, I. I.; Vivero-Escoto, J. L.; Wu, C. W.; Lin, V. S. Y. Mesoporous Silica Nanoparticles as Controlled Release Drug Delivery and Gene Transfection Carriers. Adv. Drug Delivery Rev. 2008, 60, 1278−1288. (26) Liu, J.; Du, X.; Zhang, X. Enzyme-Inspired Controlled Release of Cucurbit[7]uril Nanovalves by Using Magnetic Mesoporous Silica. Chem. - Eur. J. 2011, 17, 810−815. (27) Thomas, C. R.; Ferris, D. P.; Lee, J.; Choi, E.; Cho, M. H.; Kim, E. S.; Stoddart, J. F.; Shin, J.; Cheon, I. J.; Zink, J. I. Noninvasive Remote-Controlled Release of Drug Molecules in Vitro Using Magnetic Actuation of Mechanized Nanoparticles. J. Am. Chem. Soc. 2010, 132, 10623−10625. (28) Uzunova, V. D.; Cullinane, C.; Brix, K.; Nau, W. M.; Day, A. I. Toxicity of cucurbit[7]uril and cucurbit[8]uril: an exploratory in vitro and in vivo study. Org. Biomol. Chem. 2010, 8 (9), 2037−2042. (29) Hettiarachchi, G.; Nguyen, D.; Wu, J.; Lucas, D.; Ma, D.; Isaacs, L.; Briken, V. Toxicology and Drug Delivery by Cucurbit[n]uril Type Molecular Containers. PLoS One 2010, 5 (5), e10514. (30) French, L. Dysmenorrhea. Am. Fam. Physician 2005, 71 (22), 285−291. (31) Berenguer-Murcia, A.; García-Martínez, J.; Cazorla-Amorós, D.; Martínez-Alonso, A.; Tascón, J. M. D.; Linares-Solano, Á . About the exclusive mesoporous character of MCM-41. In Studies in Surface Science and Catalysis; Elsevier: Amsterdam, 2002; Vol. 144. (32) Zheng, Z.; Tachikawa, T.; Majima, T. Single-Particle Study of Pt-Modified Au Nanorods for Plasmon-Enhanced Hydrogen Generation in Visible to Near Infrared Region. J. Am. Chem. Soc. 2014, 136, 6870−6873. (33) Kelly, K. L.; Coronado, E.; Zhao, L. L.; Schatz, G. C. The optical properties of metal nanoparticles: the influence of size, shape, and dielectric environment. J. Phys. Chem. B 2003, 107, 668−677. (34) Feng, Y.; Xue, S.; Fan, Z.; Zhang, Y.; Zhu, Q.; Tao, Z. Host− guest complexes of some cucurbit[n]urils with the hydrochloride salts of some imidazole derivatives. J. Inclusion Phenom. Mol. Recognit. Chem. 2009, 64, 121−131.
(35) Smith, K. C. The Photobiological Basis of Low Level Laser Irradiation Therapy. Laser Therapy 1991, 3, 19−24.
G
DOI: 10.1021/acs.langmuir.6b03679 Langmuir XXXX, XXX, XXX−XXX
