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Novel Intrapolymerization Doped Manganese-Eumelanin Coordination Nanocomposites with Ultrahigh Relaxivity and Their Application in Tumor Theranostics.

ABSTRACT: While magnetic resonance imaging contrast agents have potential in noninvasive image-guided tumor treatment, further developments are needed to increase contrast, biodegradability, and safety. Here, novel engineered manganese-eumelanin coordination nanocomposites (MnEMNPs) are developed via a facile one-pot intrapolymerization doping (IPD) approach in aqueous solution, through simple chemical oxidation-polymerization of the 3,4-dihydroxy-DL-phenylalanine precursor with potassium permanganate serving as the Mn source and an oxidant. The resulting MnEMNPs possess ultrahigh longitudinal relaxivity (r₁ value up to 60.8 mM^-1 s^-1 at 1.5 T) attributed to the high manganese doping efficiency (>10%) and geometrically confined conformation. Due to their high manganese chelation stability, excellent biocompatibility, and strong near-infrared absorption, high-performance longitudinal-transverse (T₁-T₂) dual-modal magnetic resonance/photoacoustic imaging and photothermal tumor ablation are achieved. Furthermore, the hydrogen peroxide-triggered decomposition behavior of MnEMNPs circumvents the poor biodegradation issue of many nanomaterials. This facile, convenient, economical, and efficient IPD strategy will open up new avenues for the development of high-performance multifunctional theranostic nanoplatforms in bionanomedicine.

SUBMITTER: Liu H

PROVIDER: S-EPMC6051206 | biostudies-literature | 2018 Jul

REPOSITORIES: biostudies-literature

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Novel Intrapolymerization Doped Manganese-Eumelanin Coordination Nanocomposites with Ultrahigh Relaxivity and Their Application in Tumor Theranostics.

Liu Heng H Chu Chengchao C Liu Yu Y Pang Xin X Wu Yayun Y Zhou Zijian Z Zhang Pengfei P Zhang Weiguo W Liu Gang G Chen Xiaoyuan X

Advanced science (Weinheim, Baden-Wurttemberg, Germany) 20180325 7

While magnetic resonance imaging contrast agents have potential in noninvasive image-guided tumor treatment, further developments are needed to increase contrast, biodegradability, and safety. Here, novel engineered manganese-eumelanin coordination nanocomposites (MnEMNPs) are developed via a facile one-pot intrapolymerization doping (IPD) approach in aqueous solution, through simple chemical oxidation-polymerization of the 3,4-dihydroxy-DL-phenylalanine precursor with potassium permanganate ser ...[more]

PMID: 30027037

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Project description:A library of 10 Mn-containing complexes capable of switching reversibly between the Mn(II) and Mn(III) oxidation states was prepared and evaluated for potential usage as MRI reporters of tissue redox activity. We synthesized N-(2-hydroxybenzyl)-N,N',N'-ethylenediaminetriacetic acid (HBET) and N-(2-hydroxybenzyl-N,N',N'-trans-1,2-cyclohexylenediaminetriacetic acid (CyHBET) ligands functionalized (-H, -OMe, -NO2) at the 5-position of the aromatic ring. The Mn(II) complexes of all ligands and the Mn(III) complexes of the 5-H and 5-NO2 functionalized ligands were synthesized and isolated, but the Mn(III) complexes with the 5-OMe functionalized ligands were unstable. (1)H relaxivity of the 10 isolable complexes was measured at pH 7.4 and 37 °C, 1.4 T. Thermodynamic stability, pH-dependent complex speciation, hydration state, water exchange kinetics of the Mn(II) complexes, and pseudo-first order reduction kinetics of the Mn(III) complexes were studied using a combination of pH-potentiometry, UV-vis spectroscopy, and (1)H and (17)O NMR measurements. The effects of ligand structural and electronic modifications on the Mn(II/III) redox couple were studied by cyclic voltammetry. The Mn(II) complexes are potent relaxation agents as compared to the corresponding Mn(III) species with [Mn(II)(CyHBET)(H2O)](2-) exhibiting a 7.5-fold higher relaxivity (3.3 mM(-1) s(-1)) than the oxidized form (0.4 mM(-1) s(-1)). At pH 7.4, Mn(II) exists as a mixture of fully deprotonated (ML) and monoprotonated (HML) complexes and Mn(II) complex stability decreases as the ligands become more electron-releasing (pMn for 10 μM [Mn(II)(CyHBET-R')(H2O)](2-) decreases from 7.6 to 6.2 as R' goes from -NO2 to -OMe, respectively). HML speciation increases as the electron-releasing nature of the phenolato-O donor increases. The presence of a water coligand is maintained upon conversion from HML to ML, but the water exchange rate of ML is faster by up to 2 orders of magnitude (k(ex)(310) for H[Mn(II)(CyHBET)(H2O)](-) and [Mn(II)(CyHBET)(H2O)](2-) are 1.2 × 10(8) and 1.0 × 10(10) s(-1), respectively). The Mn(II/III) redox potential can be tuned over a range of 0.30 V (E(1/2) = 0.27-0.57 V) through electronic modifications to the 5-substituent of the aromatic ligand component. However, care must be taken in tuning the ligand electronics to avoid Mn(III)-ligand autoredox. Taken together, these results serve to establish criteria for optimizing Mn(III) versus Mn(II) relaxivity differentials, complex stability, and Mn(II/III) redox potential.

Dataset Information

Novel Intrapolymerization Doped Manganese-Eumelanin Coordination Nanocomposites with Ultrahigh Relaxivity and Their Application in Tumor Theranostics.

Publications

Novel Intrapolymerization Doped Manganese-Eumelanin Coordination Nanocomposites with Ultrahigh Relaxivity and Their Application in Tumor Theranostics.

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