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Cholesterol-Tethered Platinum II-Based Supramolecular Nanoparticle Increases Antitumor Efficacy and Reduces Nephrotoxicity

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Cholesterol-Tethered Platinum II-Based Supramolecular Nanoparticle Increases Antitumor Efficacy and Reduces Nephrotoxicity Cholesterol-tethered platinum II-based supramolecular nanoparticle increases antitumor efficacy and reduces nephrotoxicity The MIT Faculty has made this article openly available. Please share how this access benefits you. Your story matters. Citation Sengupta, P. et al. “Cholesterol-tethered Platinum II-based Supramolecular Nanoparticle Increases Antitumor Efficacy and Reduces Nephrotoxicity.” Proceedings of the National Academy of Sciences 109.28 (2012): 11294–11299. Web. As Published http://dx.doi.org/10.1073/pnas.1203129109 Publisher National Academy of Sciences (U.S.) Version Final published version Citable link http://hdl.handle.net/1721.1/76785 Terms of Use Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use. Cholesterol-tethered platinum II-based supramolecular nanoparticle increases antitumor efficacy and reduces nephrotoxicity Poulomi Senguptaa,b,1, Sudipta Basua,b,1,2,3, Shivani Sonia,b,1,4, Ambarish Pandeya,b,5, Bhaskar Roya,b,5, Michael S. Oha,b, Kenneth T. Chinc, Abhimanyu S. Paraskara,b, Sasmit Sarangia,b, Yamicia Connora,b,d, Venkata S. Sabbisettib,e, Jawahar Kopparama,b, Ashish Kulkarnia,b, Katherine Mutoc, Chitra Amarasiriwardenaf,g, Innocent Jayawardenef,g, Nicola Lupolif,g, Daniela M. Dinulescub,c, Joseph V. Bonventreb,e, Raghunath A. Mashelkara,h, and Shiladitya Senguptaa,b,d,i,j,3 aLaboratory for Nanomedicine, Division of Biomedical Engineering, Department of Medicine and Center for Regenerative Therapeutics, eRenal Division and Division of Biomedical Engineering, cDepartment of Pathology, and gChanning Laboratory, Brigham and Women’s Hospital, Cambridge, MA 02139; bHarvard Medical School, Boston, MA 02115; dHarvard–MIT Division of Health Sciences and Technology, Cambridge, MA 02139; fHarvard School of Public Health, Boston, MA 02215; hNational Chemical Laboratories, Pune 411021, India; iIndo–United States Joint Center for Nanobiotechnology, Cambridge, MA 02139; and jDana-Farber Cancer Institute, Brookline, MA 02445 Edited* by Jean-Marie P. Lehn, Universite de Strasbourg, Strasbourg Cedex, France, and approved May 28, 2012 (received for review February 22, 2012) Nanoscale drug delivery vehicles have been harnessed extensively these challenges, we propose a unique paradigm moving beyond as carriers for cancer chemotherapeutics. However, traditional traditional encapsulation strategies to the rational design of mol- pharmaceutical approaches for nanoformulation have been a chal- ecules that facilitate supramolecular assembly in the nanoscale lenge with molecules that exhibit incompatible physicochemical dimension. In this study, we decided to use cisplatin [cis-dichlor- properties, such as platinum-based chemotherapeutics. Here we odiamineplatinum (II)] as an example to test this hypothesis. propose a paradigm based on rational design of active molecules Cisplatin is one of the most widely used chemotherapeutic agents that facilitate supramolecular assembly in the nanoscale dimen- (8) but poses significant challenges for nanoformulations (9, 10). sion. Using cisplatin as a template, we describe the synthesis of For example, SPI-077, a sterically stabilized liposome encapsu- a unique platinum (II) tethered to a cholesterol backbone via lating cisplatin, exhibited poor clinical efficacy resulting from a unique monocarboxylato and O→Pt coordination environment impaired drug release (11, 12). that facilitates nanoparticle assembly with a fixed ratio of phos- To achieve supramolecular nanoassembly, we synthesized phatidylcholine and 1,2-distearoyl-sn-glycero-3-phosphoethanol- a cholesterol-tethered cisplatinum (II) amphiphile. The design of amine-N-[amino (polyethylene glycol)-2000]. The nanoparticles the tether was inspired by the process of “aquation,” wherein the formed exhibit lower IC values compared with carboplatin or chloride leaving groups of cisplatin are rapidly displaced to form 50 cis + cis 2+ cisplatin in vitro, and are active in cisplatin-resistant conditions. -Pt[(NH3)2(OH2)Cl] and -Pt[(NH3)2(OH2)2] (8). Self- Additionally, the nanoparticles exhibit significantly enhanced assembling cholesterol-succinic acid-cisplatinum II-based nano- in vivo antitumor efficacy in murine 4T1 breast cancer and in particles (SACNs) exhibited increased potency and efficacy fl fl K-RasLSL/+/Pten / ovarian cancer models with decreased systemic- in vitro and in vivo, respectively. Additionally, the SACNs exceed and nephro-toxicity. Our results indicate that integrating rational the size cutoff for clearance by the kidney (13), and therefore drug design and supramolecular nanochemistry can emerge as exhibited limited cisplatin-associated nephrotoxicity (14). We a powerful strategy for drug development. Furthermore, given that demonstrate that rational drug design can enable the increase platinum-based chemotherapeutics form the frontline therapy for in the supramolecular dimension from the Angstrom- to the a broad range of cancers, the increased efficacy and toxicity profile nano-scale, thereby conferring unique biological properties. Fur- — indicate the constructed nanostructure could translate into a next- thermore, only three platinates cisplatin, carboplatin, and oxa- — generation platinum-based agent in the clinics. liplatin have been successfully used in the clinics (8). The increased efficacy with improved therapeutic index of the current chemotherapy | nanomedicine molecule compared with the existing platinates indicates the ancer remains one of the main causes of death in the United States and many western countries. In addition, the incidence Author contributions: P.S., S.B., S. Soni, A.P., B.R., A.S.P., V.S.S., A.K., D.M.D., R.A.M., and C S. Sengupta designed research; P.S., S.B., S. Soni, A.P., B.R., M.S.O., K.T.C., A.S.P., S. Sarangi, is also increasing in less developed and economically tran- Y.C., V.S.S., J.K., A.K., K.M., C.A., I.J., N.L., and D.M.D. performed research; P.S., S.B., sitioning countries (1). The World Health Organization projects S. Soni, A.P., B.R., M.S.O., K.T.C., A.S.P., S. Sarangi, Y.C., V.S.S., D.M.D., J.V.B., and over 12 million deaths worldwide in 2030 because of cancer, up S. Sengupta analyzed data; and P.S., S.B., S. Soni, A.P., B.R., V.S.S., D.M.D., R.A.M., from 7.6 million in 2008 (2). To address this growing problem, and S. Sengupta wrote the paper. there is an urgent need to develop treatment strategies that Conflict of interest statement: P.S., S.B., S. Soni, A.S.P., and S. Sengupta are listed as are more efficaceous with lesser adverse effects. An increasingly inventors on a patent filed by Brigham and Women’s Hospital. pursued approach to achieve these goals is the use of nano- *This Direct Submission article had a prearranged editor. technology to preferentially target anticancer agents to solid Freely available online through the PNAS open access option. tumors (3). This approach capitalizes on the unique leaky an- 1P.S., S.B., and S. Soni contributed equally to this work. giogenic tumor vasculature coupled with impaired intratumoral 2Present address: Department of Chemistry, Indian Institute of Science Education and lymphatic drainage, contributing to an enhanced permeation Research (IISER) Pune, Sutarwadi, Pashan, Pune, Maharashtra, 411021, India. and retention (EPR) effect (4). Indeed, nanoparticles carrying 3To whom correspondence may be addressed. E-mail: [email protected], or a doxorubicin payload or an albumin-paclitaxel nanocomplex [email protected]. increase intratumoral drug concentration (5, 6) and are currently 4Present address: Department of Biological Sciences, Alabama State University, Montgomery, in the clinics (7). However, traditional processes for nanofor- AL 36104. mulation are often incompatible with physicochemical properties 5A.P. and B.R. contributed equally to this work. of many chemotherapeutic agents, which limit the entrapment This article contains supporting information online at www.pnas.org/lookup/suppl/doi:10. efficiency or introduce suboptimal release kinetics. To address 1073/pnas.1203129109/-/DCSupplemental. 11294–11299 | PNAS | July 10, 2012 | vol. 109 | no. 28 www.pnas.org/cgi/doi/10.1073/pnas.1203129109 potential for clinical translation as the next-generation platinum- Synthesis and Characterization of SACNs. We engineered the based chemotherapeutic. SACNs from the cholesterol-succinic acid-platinum (II) molecule, phosphatidylcholine (PC) and 1,2-distearoyl-sn-glycero-3-phos- Results phoethanolamine-N-[amino(polyethylene glycol)-2000] (DSPE- Synthesis of Cholesterol-Succinic Acid-Pt(II) Molecule. Aquation of PEG) in 1:2:0.2 weight ratio using a lipid-film hydration self as- cisplatin results in the rapid formation of active species cis-[Pt sembly method (20) (Fig. 1A). The ultrastructure analysis using (NH ) Cl(OH )]+ and cis-[Pt(NH ) (OH ) ]2+ with a rate con- cryo-transmission electron microscopy (cryo-TEM) (Fig. 1B) 3 2 2 − − 3 2 2 2 stant of 8 × 10 5 s 1 (15). In contrast, the rate constant for revealed the formation of predominantly uni- and rare multi- aquation of carboplatin, where the platinum is coordinated with lamellar structures less than 200 nm in diameter, with a membrane a stable bidentate 1,1-cyclobutanedicarboxylato ligand, was found thickness ∼5 nm. Dynamic light scattering further confirmed the − − to be 7.2 × 10 7 s 1. This difference in their rate of aquation was size distribution of SACNs with a mean hydrodynamic diameter of matched by their rates of binding to DNA, indicating that the rate 141.4
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