Shreya Mukherjee

Redox-Activated Manganese-Based MR Contrast Agent

Here we report a simple Mn coordination complex with utility as a redox-sensitive MR probe. The HBET ligand stabilizes both the Mn(2+) and Mn(3+) oxidation states. In the presence of glutathione (GSH), low relaxivity Mn(III)-HBET is converted to high relaxivity Mn(II)-HBET with a 3-fold increase in relaxivity, and concomitant increase in MR signal. Alternately, hydrogen peroxide can convert Mn(II)-HBET to Mn(III)-HBET with a reduction in MR signal.

A new family of nonanuclear lanthanide clusters displaying magnetic and optical properties.

The initial employment of 2-(hydroxymethyl)pyridine in 4f metal chemistry has afforded a new family of Ln(III)(9) clusters with a sandglass-like topology and dual physical properties; the Dy(III) member shows single-molecule magnetism behavior, while the Eu(III) analogue exhibits intense red photoluminescence.

Electronic structural changes of Mn in the oxygen-evolving complex of photosystem II during the catalytic cycle.

The oxygen-evolving complex (OEC) in photosystem II (PS II) was studied in the S0 through S3 states using 1s2p resonant inelastic X-ray scattering spectroscopy. The spectral changes of the OEC during the S-state transitions are subtle, indicating that the electrons are strongly delocalized throughout the cluster. The result suggests that, in addition to the Mn ions, ligands are also playing an important role in the redox reactions. A series of Mn(IV) coordination complexes were compared, particularly with the PS II S3 state spectrum to understand its oxidation state. We find strong variations of the electronic structure within the series of Mn(IV) model systems. The spectrum of the S3 state best resembles those of the Mn(IV) complexes Mn3(IV)Ca2 and saplnMn2(IV)(OH)2. The current result emphasizes that the assignment of formal oxidation states alone is not sufficient for understanding the detailed electronic structural changes that govern the catalytic reaction in the OEC.

Towards models of the oxygen-evolving complex (OEC) of photosystem II: a Mn4Ca cluster of relevance to low oxidation states of the OEC

Synthetic access has been achieved into high oxidation state Mn/Ca chemistry with the 4 : 1 Mn : Ca stoichiometry of the oxygen-evolving complex (OEC) of plants and cyanobacteria; the anion of (Et(3)NH)(2)[Mn(III)(4)Ca(O(2)CPh)(4)(shi)(4)] has a square pyramidal metal topology and an S = 0 ground state.

Comproportionation Reactions to Manganese(III/IV) Pivalate Clusters: A New Half-Integer Spin Single-Molecule Magnet

The comproportionation reaction between Mn(II) and Mn(VII) reagents under acidic conditions has been investigated in the presence of pivalic acid as a route to new high oxidation state manganese pivalate clusters containing some Mn(IV). The reaction of Mn(O(2)CBu(t))(2) and NBu(n)(4)MnO(4) with an excess of pivalic acid in the presence of Mn(ClO(4))(2) and NBu(n)(4)Cl in hot MeCN led to the isolation of [Mn(8)O(6)(OH)(O(2)CBu(t))(9)Cl(3)(Bu(t)CO(2)H)(0.5)(MeCN)(0.5)] (1). In contrast, the reaction of Mn(NO(3))(2) and NBu(n)(4)MnO(4) in hot MeCN with an excess of pivalic acid gave a different octanuclear complex, [Mn(8)O(9)(O(2)CBu(t))(12)] (2). The latter reaction but with Mn(O(2)CBu(t))(2) in place of Mn(NO(3))(2), and in a MeCN/THF solvent medium, gave [Mn(9)O(7)(O(2)CBu(t))(13)(THF)(2)] (3). Complexes 1-3 possess rare or unprecedented Mn(x) topologies: 1 possesses a [Mn(III)(7)Mn(IV)(μ(3)-O)(4)(μ(4)-O)(2)(μ(3)-OH)(μ(4)-Cl)(μ(2)-Cl)](8+) core consisting of two body-fused Mn(4) butterfly units attached to the remaining Mn atoms via bridging O(2-), OH(-), and Cl(-) ions. In contrast, 2 possesses a [Mn(6)(IV)Mn(2)(III)(μ(3)-O)(6)(μ-O)(3)](12+) core consisting of two [Mn(3)O(4)] incomplete cubanes linked by their O(2-) ions to two Mn(III) atoms. The cores of 1 and 2 are unprecedented in Mn chemistry. The [Mn(III)(9)(μ(3)-O)(7)](13+) core of 3 also contains two body-fused Mn(4) butterfly units, but they are linked to the remaining Mn atoms in a different manner than in 1. Solid-state direct current (dc) and/or alternating current (ac) magnetic susceptibility data established S = (15)/(2), S = 2, and S = 1 ground states for 1·MeCN, 2·(1)/(4)MeCN, and 3, respectively. The ac susceptibility data also revealed nonzero, frequency-dependent out-of-phase (χ″(M)) signals for 1·MeCN at temperatures below 3 K, suggesting possible single-molecule magnet behavior, which was confirmed by single-crystal magnetization vs dc field scans that exhibited hysteresis loops. The combined work thus demonstrates the continuing potential of comproportionation reactions for isolating high oxidation state Mn(x) clusters, and the sensitivity of the product identity to minor changes in the reaction conditions.

Raising the spin of Fe(III)7 disklike clusters: the power of molecular spin frustration.

Two clusters with a new type of Fe(III)(7) disklike structure have been prepared; in contrast to other Fe(III)(7) disks, they possess high ground-state spins (S = (15)/(2) and (21)/(2)), which have been rationalized by analysis of the spin-frustration patterns.

Whole brain mapping of water pools and molecular dynamics with rotating frame MR relaxation using gradient modulated low-power adiabatic pulses.

Nuclear magnetic resonance (NMR) relaxation in the rotating frame is sensitive to molecular dynamics on the time scale of water molecules interacting with macromolecules or supramolecular complexes, such as proteins, myelin and cell membranes. Hence, longitudinal (T1ρ) and transverse (T2ρ) relaxation in the rotating frame may have a great potential to probe the macromolecular fraction of tissues. This stimulated a large interest in using this MR contrast to image brain under healthy and disease conditions. However, experimental challenges related to the use of intense radiofrequency irradiation have limited the widespread use of T1ρ and T2ρ imaging. Here, we present methodological development to acquire 3D high-resolution or 2D (multi-)slice selective T1ρ and T2ρ maps of the entire human brain within short acquisition times. These improvements are based on a class of gradient modulated adiabatic pulses that reduce the power deposition, provide slice selection, and mitigate artifacts resulting from inhomogeneities of B1 and B0 magnetic fields. Based on an analytical model of the T1ρ and T2ρ relaxation we compute the maps of macromolecular bound water fraction, correlation and exchange time constants as quantitative biomarkers informative of tissue macromolecular content. Results obtained from simulations, phantoms and five healthy subjects are included.

Discrete antiferromagnetic spin-wave excitations in the giant ferric wheel Fe18

The low-temperature elementary spin excitations in the AFM molecular wheel Fe

“Squaring the clusters”: a MnIII4NiII4 molecular square from nickel(II)-induced structural transformation of a MnII/III/IV12 cage

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Experimental Determination of the Weiss Temperature of Mn12-Ac and Mn12-Ac-MeOH

were studied experimentally by inelastic neutron scattering and theoretically by modern numerical methods, such as dynamical density matrix renormalization group or quantum Monte Carlo techniques, and analytical spin-wave theory calculations. Fe