Dataset Information

EPR and Structural Characterization of Water-Soluble Mn²⁺-Doped Si Nanoparticles.

ABSTRACT: Water-soluble poly(allylamine) Mn²⁺-doped Si (Si_Mn) nanoparticles (NPs) were prepared and show promise for biologically related applications. The nanoparticles show both strong photoluminescence and good magnetic resonance contrast imaging. The morphology and average diameter were obtained through transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM); spherical crystalline Si NPs with an average diameter of 4.2 ± 0.7 nm were observed. The doping maximum obtained through this process was an average concentration of 0.4 ± 0.3% Mn per mole of Si. The water-soluble Si_Mn NPs showed a strong photoluminescence with a quantum yield up to 13%. The Si_Mn NPs had significant T₁ contrast with an r₁ relaxivity of 11.1 ± 1.5 mM^-1 s^-1 and r₂ relaxivity of 32.7 ± 4.7 mM^-1 s^-1 where the concentration is in mM of Mn²⁺. Dextran-coated poly(allylamine) Si_Mn NPs produced NPs with T₁ and T₂ contrast with a r₁ relaxivity of 27.1 ± 2.8 mM^-1 s^-1 and r₂ relaxivity of 1078.5 ± 1.9 mM^-1 s^-1. X-band electron paramagnetic resonance spectra are fit with a two-site model demonstrating that there are two types of Mn²⁺ in these NP's. The fits yield hyperfine splittings (A) of 265 and 238 MHz with significant zero field splitting (D and E terms). This is consistent with Mn in sites of symmetry lower than tetrahedral due to the small size of the NP's.

SUBMITTER: Atkins TM

PROVIDER: S-EPMC5278496 | biostudies-literature | 2017 Jan

REPOSITORIES: biostudies-literature

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Publications

EPR and Structural Characterization of Water-Soluble Mn2+-Doped Si Nanoparticles.

Atkins Tonya M TM Walton Jeffrey H JH Singh Mani P MP Ganguly Shreyashi S Janka Oliver O Louie Angelique Y AY Kauzlarich Susan M SM

The journal of physical chemistry. C, Nanomaterials and interfaces 20161222 3

Water-soluble poly(allylamine) Mn2+-doped Si (SiMn) nanoparticles (NPs) were prepared and show promise for biologically related applications. The nanoparticles show both strong photoluminescence and good magnetic resonance contrast imaging. The morphology and average diameter were obtained through transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM); spherical crystalline Si NPs with an average diameter of 4.2 ± 0.7 nm were obs ...[more]

PMID: 28154618

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Project description:Hydrogen-atom-transfer (HAT) reactions are a class of proton-coupled electron-transfer (PCET) reactions used in biology to promote substrate oxidation. The driving force for such reactions depends on both the oxidation potential of the catalyst and the pKa value of the proton-acceptor site. Both high-valent transition-metal oxo M(IV)?O (M = Fe, Mn) and lower-valent transition-metal hydroxo compounds M(III)OH (M = Fe, Mn) have been shown to promote these reactions. Herein we describe the synthesis, structure, and reactivity properties of a series of Mn(III)OR compounds [R = (p)NO2Ph (5), Ph (6), Me (7), H (8)], some of which abstract H atoms. The Mn(III)OH complex 8 is water-soluble and represents a rare example of a stable mononuclear Mn(III)OH. In water, the redox potential of 8 was found to be pH-dependent and the Pourbaix (E(p,c) vs pH) diagram has a slope (52 mV pH(-1)) that is indicative of the transfer a single proton with each electron (i.e., PCET). The two compounds with the lowest oxidation potential, hydroxide- and methoxide-bound 7 and 8, are found to oxidize 2,2',6,6'-tetramethylpiperidin-1-ol (TEMPOH), whereas the compounds with the highest oxidation potential, phenol-ligated 5 and 6, are shown to be unreactive. Hydroxide-bound 8 reacts with TEMPOH an order of magnitude faster than methoxide-bound 7. Kinetic data [kH/kD = 3.1 (8); kH/kD = 2.1 (7)] are consistent with concerted H-atom abstraction. The reactive species 8 can be aerobically regenerated in H2O, and at least 10 turnovers can be achieved without significant degradation of the "catalyst". The linear correlation between the redox potential and pH, obtained from the Pourbaix diagram, was used to calculate the bond dissociation free energy (BDFE) = 74.0 ± 0.5 kcal mol(-1) for Mn(II)OH2 in water, and in MeCN, its BDFE was estimated to be 70.1 kcal mol(-1). The reduced protonated derivative of 8, [Mn(II)(S(Me2)N4(tren))(H2O)](+) (9), was estimated to have a pKa of 21.2 in MeCN. The ability (7) and inability (5 and 6) of the other members of the series to abstract a H atom from TEMPOH was used to estimate either an upper or lower limit to the Mn(II)O(H)R pKa based on their experimentally determined redox potentials. The trend in pKa [21.2 (R = H) > 16.2 (R = Me) > 13.5 (R = Ph) > 12.2 (R = (p)NO2Ph)] is shown to oppose that of the oxidation potential E(p,c) [-220 (R = (p)NO2Ph) > -300 (R = Ph) > -410 (R = Me) > -600 (R = H) mV vs Fc(+/0)] for this particular series.

Dataset Information

EPR and Structural Characterization of Water-Soluble Mn²⁺-Doped Si Nanoparticles.

Publications

EPR and Structural Characterization of Water-Soluble Mn<sup>2+</sup>-Doped Si Nanoparticles.

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