Abstract
Indocyanine green (ICG) was incorporated into poly(ethylenimine)/(phenylthio) acetic acid (PEI/PTA) ion pair self-assembly (IPSAM) as a photosensitizer. PEI/PTA/ICG IPSAM was more stable against a thermal dissolution as the PTA and ICG content were higher. The zeta potential of the IPSAM without ICG (the amino group(A)/carboxyl group(C) molar ratio was 5.3:4.7) was a strong positive charge. Upon the addition of a small amount of ICG (A/C/ICG molar ratio was 5.3:4.7:0.01), it changed to a strong negative charge. The IPSAM on TEM micrographs was found as almost sphere-like nanoparticles and its diameter was around 50 nm. The doxorubicin-loaded IPSAM on CLSM micrographs was found as nano-sized circular red domains, indicating that the anti-cancer drug was successfully loaded in the IPSAM without disrupting the shape. When A to C molar ratio was 4:6, the ICG-incorporated IPSAM released its cargo appreciably under NIR irradiation even though the temperature of the IPSAM suspension could hardly reach the upper critical solution temperature (UCST) under NIR irradiation, suggesting that the release took place mainly by the radical oxygen species (ROS)-induced oxidation of PTA. When A to C molar ratio was 5.3:4.7, the temperature of the IPSAM suspension could reach the UCST under NIR irradiation and the release degree increased in proportion to the temperature increase, indicating the release took place mainly by the temperature change. According to the FT-IR spectroscopy, the NIR irradiation-triggered release could be attributed to the heat and ROS generated by ICG under NIR irradiation.
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References
Schneider ED, Kay JJ (1994) Life as a manifestation of the second law of thermodynamics. Math Comput Model 19:25–48. https://doi.org/10.1016/0895-7177(94)90188-0
Liu Y, Li Y, He J et al (2014) Entropy-driven pattern formation of hybrid vesicular assemblies made from molecular and nanoparticle amphiphiles. J Am Chem Soc 136:2602–2610. https://doi.org/10.1021/ja412172f
Huo Q, Margolese DI, Stucky GD (1996) Surfactant control of phases in the synthesis of mesoporous silica-based materials. Chem Mater 8:1147–1160. https://doi.org/10.1021/cm960137h
Wei H, Cheng S-X, Zhang X-Z, Zhuo R-X (2009) Thermo-sensitive polymeric micelles based on poly(N-isopropylacrylamide) as drug carriers. Prog Polym Sci 34:893–910. https://doi.org/10.1016/j.progpolymsci.2009.05.002
Kita-Tokarczyk K, Grumelard J, Haefele T, Meier W (2005) Block copolymer vesicles—using concepts from polymer chemistry to mimic biomembranes. Polymer (Guildf) 46:3540–3563. https://doi.org/10.1016/j.polymer.2005.02.083
Zhang D, Gökce B, Barcikowski S (2017) Laser synthesis and processing of colloids: fundamentals and applications. Chem Rev 117:3990–4103. https://doi.org/10.1021/acs.chemrev.6b00468
Zahir MH, Irshad K, Aziz MA et al (2019) Shape-stabilized phase change material for solar thermal energy storage: CaO containing MgCO3 mixed with polyethylene glycol. Energy Fuels 33:12041–12051. https://doi.org/10.1021/acs.energyfuels.9b02885
Vladkova TG (2010) Surface engineered polymeric biomaterials with improved biocontact properties. Int J Polym Sci 2010:296094. https://doi.org/10.1155/2010/296094
Szczepanowicz K, Bazylińska U, Pietkiewicz J et al (2015) Biocompatible long-sustained release oil-core polyelectrolyte nanocarriers: from controlling physical state and stability to biological impact. Adv Colloid Interface Sci 222:678–691. https://doi.org/10.1016/j.cis.2014.10.005
Wu W, Wu Z, Yu T et al (2015) Recent progress on magnetic iron oxide nanoparticles: synthesis, surface functional strategies and biomedical applications. Sci Technol Adv Mater 16:23501. https://doi.org/10.1088/1468-6996/16/2/023501
Xu M-M, Liu R-J, Yan Q (2018) Biological stimuli-responsive polymer systems: design, construction and controlled self-assembly. Chinese J Polym Sci 36:347–365. https://doi.org/10.1007/s10118-018-2080-4
Khakzad F, Mahdavian AR, Salehi-Mobarakeh H, Sharifian MH (2018) A step-wise self-assembly approach in preparation of multi-responsive poly(styrene-co-methyl methacrylate) nanoparticles containing spiropyran. J Colloid Interface Sci 515:58–69. https://doi.org/10.1016/j.jcis.2018.01.012
Abdollahi A, Sahandi-Zangabad K, Roghani-Mamaqani H (2018) Rewritable anticounterfeiting polymer inks based on functionalized stimuli-responsive latex particles containing spiropyran photoswitches: reversible photopatterning and security marking. ACS Appl Mater Interfaces 10:39279–39292. https://doi.org/10.1021/acsami.8b14865
Zhang J, Ma PX (2013) Cyclodextrin-based supramolecular systems for drug delivery: Recent progress and future perspective. Adv Drug Deliv Rev 65:1215–1233. https://doi.org/10.1016/j.addr.2013.05.001
Kim TH, Alle M, Park SC et al (2021) Self-assembly prepared using an ion pair of poly(ethylene imine) and (phenylthio) acetic acid as a drug carrier for oxidation, temperature, and NIR-responsive release. Chem Eng J 415:128954. https://doi.org/10.1016/j.cej.2021.128954
Yu Y, Zhang Z, Wang Y et al (2017) A new NIR-triggered doxorubicin and photosensitizer indocyanine green co-delivery system for enhanced multidrug resistant cancer treatment through simultaneous chemo/photothermal/photodynamic therapy. Acta Biomater 59:170–180. https://doi.org/10.1016/j.actbio.2017.06.026
Sharker SM, Lee JE, Kim SH et al (2015) pH triggered in vivo photothermal therapy and fluorescence nanoplatform of cancer based on responsive polymer-indocyanine green integrated reduced graphene oxide. Biomaterials 61:229–238. https://doi.org/10.1016/j.biomaterials.2015.05.040
Wang X-H, Peng H-S, Yang W et al (2017) Indocyanine green-platinum porphyrins integrated conjugated polymer hybrid nanoparticles for near-infrared-triggered photothermal and two-photon photodynamic therapy. J Mater Chem B 5:1856–1862. https://doi.org/10.1039/C6TB03215J
Li L, Liu Y, Hao P et al (2015) PEDOT nanocomposites mediated dual-modal photodynamic and photothermal targeted sterilization in both NIR I and II window. Biomaterials 41:132–140. https://doi.org/10.1016/j.biomaterials.2014.10.075
Raza A, Hayat U, Rasheed T et al (2019) Smart materials-based near-infrared light-responsive drug delivery systems for cancer treatment: A review. J Mater Res Technol 8:1497–1509. https://doi.org/10.1016/j.jmrt.2018.03.007
Li W, Zhang H, Guo X et al (2017) Gold nanospheres-stabilized indocyanine green as a synchronous photodynamic-photothermal therapy platform that inhibits tumor growth and metastasis. ACS Appl Mater Interfaces 9:3354–3367. https://doi.org/10.1021/acsami.6b13351
Lu Y, Fan L, Yang L-Y et al (2020) PEI-modified core-shell/bead-like amino silica enhanced poly (vinyl alcohol)/chitosan for diclofenac sodium efficient adsorption. Carbohydr Polym 229:115459. https://doi.org/10.1016/j.carbpol.2019.115459
Deng S, Ting Y-P (2005) Characterization of PEI-modified biomass and biosorption of Cu(II), Pb(II) and Ni(II). Water Res 39:2167–2177. https://doi.org/10.1016/j.watres.2005.03.033
Lin C, Zhong Z, Lok MC et al (2006) Linear poly(amido amine)s with secondary and tertiary amino groups and variable amounts of disulfide linkages: Synthesis and in vitro gene transfer properties. J Control Release 116:130–137. https://doi.org/10.1016/j.jconrel.2006.09.009
Zhang N, Zang G-L, Shi C et al (2016) A novel adsorbent TEMPO-mediated oxidized cellulose nanofibrils modified with PEI: Preparation, characterization, and application for Cu(II) removal. J Hazard Mater 316:11–18. https://doi.org/10.1016/j.jhazmat.2016.05.018
Nam YS, Kang HS, Park JY et al (2003) New micelle-like polymer aggregates made from PEI–PLGA diblock copolymers: micellar characteristics and cellular uptake. Biomaterials 24:2053–2059. https://doi.org/10.1016/S0142-9612(02)00641-5
Kanta Sharker K, Ohara Y, Shigeta Y et al (2019) Upper critical solution temperature (UCST) behavior of polystyrene-based polyampholytes in aqueous solution. Polym. 11
Zydziak N, Iqbal MH, Chaumont A et al (2020) Unexpected aqueous UCST behavior of a cationic comb polymer with pentaarginine side chains. Eur Polym J 125:109528. https://doi.org/10.1016/j.eurpolymj.2020.109528
Shih Y-J, Chang Y, Deratani A, Quemener D (2012) Schizophrenic hemocompatible copolymers via switchable thermoresponsive transition of nonionic/zwitterionic block self-assembly in human blood. Biomacromolecules 13:2849–2858. https://doi.org/10.1021/bm3008764
Basheer A, Shahid S, Kang MJ et al (2021) Switchable self-assembly of elastin- and resilin-based block copolypeptides with converse phase transition behaviors. ACS Appl Mater Interfaces 13:24385–24400. https://doi.org/10.1021/acsami.1c00676
Zheng M, Yue C, Ma Y et al (2013) Single-step assembly of DOX/ICG loaded lipid-polymer nanoparticles for highly effective chemo-photothermal combination therapy. ACS Nano 7:2056–2067. https://doi.org/10.1021/nn400334y
Zheng M, Zhao P, Luo Z et al (2014) Robust ICG theranostic nanoparticles for folate targeted cancer imaging and highly effective photothermal therapy. ACS Appl Mater Interfaces 6:6709–6716. https://doi.org/10.1021/am5004393
Jia K, Bai Y, Wang L et al (2021) Emulsion confinement self-assembly regulated lanthanide coordinating polymeric microparticles for multicolor fluorescent nanofibers. Polymer (Guildf) 230:124043. https://doi.org/10.1016/j.polymer.2021.124043
Xie J, Jia K, Liu C et al (2021) Aromatic block copolymer ligand sensitized lanthanide nanostructures as ratiometric fluorescence probe for determination of residual K2CO3 in super engineering thermoplastics. Sens Actuators B Chem 334:129611. https://doi.org/10.1016/j.snb.2021.129611
He X, Jia K, Bai Y et al (2021) Quantum dots encoded white-emitting polymeric superparticles for simultaneous detection of multiple heavy metal ions. J Hazard Mater 405:124263. https://doi.org/10.1016/j.jhazmat.2020.124263
He X, Jia K, Marks R et al (2021) 3D confined self-assembling of QD within super-engineering block copolymers as biocompatible superparticles enabling stimulus responsive solid state fluorescence. Nano Res 14:285–294. https://doi.org/10.1007/s12274-020-3086-0
Huang L, Han G (2018) Near infrared boron dipyrromethene nanoparticles for optotheranostics. Small Methods 2:1700370. https://doi.org/10.1002/smtd.201700370
Han L, Zhang Y, Chen X-W et al (2016) Protein-modified hollow copper sulfide nanoparticles carrying indocyanine green for photothermal and photodynamic therapy. J Mater Chem B 4:105–112. https://doi.org/10.1039/C5TB02002F
Schmidt-Erfurth U, Hasan T (2000) Mechanisms of action of photodynamic therapy with verteporfin for the treatment of age-related macular degeneration. Surv Ophthalmol 45:195–214. https://doi.org/10.1016/S0039-6257(00)00158-2
Syu W-J, Huang C-C, Hsiao J-K et al (2019) Co-precipitation synthesis of near-infrared iron oxide nanocrystals on magnetically targeted imaging and photothermal cancer therapy via photoablative protein denature. Nanotheranostics 3:236–254. https://doi.org/10.7150/ntno.24124
Luo T (2014) In vitro studies of improvement in treatment efficiency of photodynamic therapy of cancers through near-infrared/bioluminescent activation
Wang X, Yu Y, Cheng K et al (2019) Polylysine modified conjugated polymer nanoparticles loaded with the singlet oxygen probe 1,3-diphenylisobenzofuran and the photosensitizer indocyanine green for use in fluorometric sensing and in photodynamic therapy. Microchim Acta 186:842. https://doi.org/10.1007/s00604-019-3924-5
Cardillo JA, Jorge R, Costa RA et al (2008) Experimental selective choriocapillaris photothrombosis using a modified indocyanine green formulation. Br J Ophthalmol 92:276–280. https://doi.org/10.1136/bjo.2007.129395
Acknowledgements
This research was supported by Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education(No. 2018R1A6A1A03025582). This work was supported by the Technology Innovation Program (20009663) funded By the Ministry of Trade, Industry & Energy(MOTIE, Korea).
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Long, W., Kim, JC. Poly (ethylenimine)/(phenylthio) acetic acid ion pair self-assembly incorporating indocyanine green and its NIR–responsive release property. J Polym Res 28, 442 (2021). https://doi.org/10.1007/s10965-021-02800-x
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DOI: https://doi.org/10.1007/s10965-021-02800-x