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Biomedical subjects

Mark W Meisel

Publications and source records attributed to Mark W Meisel.

10 recordsLinked to original sources

High magnetic field induced changes of gene expression in arabidopsis.

BACKGROUND: High magnetic fields are becoming increasingly prevalent components of non-invasive, biomedical imaging tools (such as MRI), thus, an understanding of the molecular impacts associated with these field strengths in biological systems is of central importance. The biological impact of magnetic field strengths up to 30 Tesla were investigated in this study through the use of transgenic Arabidopsis plants engineered with a stress response gene consisting of the alcohol dehydrogenase (Adh) gene promoter driving the beta-glucuronidase (GUS) gene reporter. METHODS: Magnetic field induced Adh/GUS activity was evaluated with histochemical staining to assess tissue specific expression and distribution, and with quantitative, spectrofluometric assays to measure degree of activation. The evaluation of global changes in the Arabidopsis genome in response to exposure to high magnetic fields was facilitated with Affymetrix Gene Chip microarrays. Quantitative analyses of gene expression were performed with quantitative real-time polymerase-chain-reaction (qRT-PCR). RESULTS: Field strengths in excess of about 15 Tesla induce expression of the Adh/GUS transgene in the roots and leaves. From the microarray analyses that surveyed 8000 genes, 114 genes were differentially expressed to a degree greater than 2.5 fold over the control. These results were quantitatively corroborated by qRT-PCR examination of 4 of the 114 genes. CONCLUSION: The data suggest that magnetic fields in excess of 15 Tesla have far-reaching effect on the genome. The wide-spread induction of stress-related genes and transcription factors, and a depression of genes associated with cell wall metabolism, are prominent examples. The roles of magnetic field orientation of macromolecules and magnetophoretic effects are discussed as possible factors that contribute to the mounting of this response.

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Dimethylammonium trichlorocuprate(II): structural transition, low-temperature crystal structure, and unusual two-magnetic chain structure dictated by nonbonding chloride-chloride contacts.

Catena(dimethylammonium-bis(mu2-chloro)-chlorocuprate), (CH3)2NH2CuCl3, forms chains of Cu2Cl6(2-) bifold dimers linked along the structural chain axis by terminal chlorides forming long semicoordinate bonds to adjacent dimers. The structural chains are separated by dimethylammonium ions that hydrogen bond to chloride ions of the dimers. A structural phase transition below room temperature removes disorder in the hydrogen bonding, leaving adjacent dimers along the chain structurally and magnetically inequivalent, with alternating ferromagnetic and antiferromagnetic pairs. The coupled dimers are magnetically isolated from each other along the structural chain axis by the long semicoordinate Cu-Cl bond. However, the dimers couple to like counterparts on adjacent chains via nonbonding Cl...Cl contacts. The result is two independent magnetic chains, one an alternating antiferromagnetic chain and the other an antiferromagnetic chain of ferromagnetically coupled copper dimers, which run perpendicular to the structural chains. This magnetostructural analysis is used to fit unusual low-temperature (1.6 K) magnetization vs field data that display a two-step saturation. The structural phase transition is identified with neutron scattering and capacitance measurements, and the X-ray crystal structures are determined at room temperature and 84 K. The results appear to resolve long-standing confusion about the origins of the magnetic behavior of this compound and provide a compelling example of the importance of two-halide magnetic exchange.

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Magneto-structural correlations in Cu(tn)Cl2 (tn = 1,3-diaminopropane): two-dimensional spatially anisotropic triangular magnet formed by hydrogen bonds.

A novel polymeric one-dimensional compound Cu(tn)Cl2 (tn = 1,3-diaminopropane) was prepared and structurally characterized, and its spectral, magnetic, thermodynamic, and thermal properties were studied. The unique structure shows ladderlike chains composed of Cu(II) atoms and chloro bridging ligands [Cu(-mu(3)-Cl-)Cu2] running along the crystallographic c axis. The coordination geometry about copper (4 + 2) approximates that of a strongly elongated octahedron. The equatorial plane of the coordination octahedron is formed by a chelate N-bonded tn ligand and two chloro ligands. One of the chloro ligands is terminal, and the other one, mu3-Cl-, forms two additional longer bonds to the neighboring copper atoms and thus occupies the axial octahedral positions. The electronic ground state of the Cu(II) ion is of d(z)2 symmetry and suggests the activation of intraladder and interladder Cl...H-N hydrogen bonds as exchange paths that form a two-dimensional pattern of a triangular symmetry. The interaction due to the hydrogen bonds seems to play an important role in molecular packing and magnetic coupling. The studies of magneto-structural correlations including electron paramagnetic resonance measurements and thermodynamic and magnetic properties revealed a two-dimensional character of magnetic correlations with the effective intralayer exchange coupling J/k(B) approximately -3 K. No phase transition to the ordered state has been observed down to 60 mK. Cu(tn)Cl2 with the interlayer coupling J' approximately 10(-3)J and moderate intralayer interaction represents an excellent example of a two-dimensional magnetic system.

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Dramatic variation of magnetic exchange through double end-on azide bridges in a series of ladder-like copper(II) coordination polymers.

Three ladder-like coordination polymers, [Cu2(phprpy)2-mu-(N3)2(N3)2], 1; [Cu2(terpy)2-mu-(N3)4Cu2-mu-(N3)2(N3)2], 2; and[Cu2(terpy)2-mu-(N3)2(N3)2Cu3-mu-(N3)4(N3)2], 3, consisting of Cu2+ ions with double end-on azide bridges were synthesized, their crystal structures and magnetic properties were determined, and spin dimer analysis was performed to explain the signs and strengths of their strong spin exchange interactions [phprpy is 4-(3-phenylpropyl)pyridine and terpy is 2,2':6,2''-terpyridine]. Although these compounds have ladder-like arrangements of Cu2+ ions, their magnetic structures are described as isolated dimers for 1 and 2 and as isolated trimers for 3. The predominant spin exchange paths in 1-3 have double end-on azide bridges linking adjacent Cu2+ ions, and the geometrical parameters of these bridging structures are similar. However, the spin dimer of 1 exhibits a strong ferromagnetic coupling; that of 2, a strong antiferromagnetic coupling; and that of 3, a weak ferromagnetic coupling. These findings are well explained by the present spin dimer analysis and show that the nature and geometry of the nonbridging ligands can have a strong influence on the sign and strength of the spin exchange interaction between Cu2+ ions connected by double end-on azide bridges.

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High-frequency and -field EPR spectroscopy of tris(2,4-pentanedionato)manganese(III): investigation of solid-state versus solution Jahn-Teller effects.

High-frequency and -field electron paramagnetic resonance (HFEPR) spectroscopy of a classical coordination complex, Mn(acac)(3) (Hacac = 2,4-pentanedione), has been performed on both solid powder and frozen solution (in CH(2)Cl(2)/toluene, 3:2 v/v) samples. Parallel mode detection X-band EPR spectra exhibiting resolved (55)Mn hyperfine coupling were additionally obtained for frozen solutions. Magnetic susceptibility and field-dependent magnetization measurements were also made on powder samples. Analysis of the entire EPR data set for the frozen solution allowed extraction of the relevant spin Hamiltonian parameters: D = -4.52(2); |E| = 0.25(2) cm(-1); g(iso) = 1.99(1). The somewhat lower quality solid-state HFEPR data and the magnetic measurements confirmed these parameters. These parameters are compared to those for other complexes of Mn(III) and to previous studies on Mn(acac)(3) using X-ray crystallography, solution electronic absorption spectroscopy, and powder magnetic susceptibility. Crystal structures have been reported for Mn(acac)(3) and show tetragonal distortion, as expected for this Jahn-Teller ion (Mn(3+), 3d(4)). However, in one case, the molecule exhibits axial compression and, in another, axial elongation. The current HFEPR studies clearly show the negative sign of D, which corresponds to an axial (tetragonal) elongation in frozen solution. The correspondence among solution and solid-state HFEPR data, solid-state magnetic measurements, and an HFEPR study by others on a related complex indicates that the form of Mn(acac)(3) studied here exhibits axial elongation in all cases. Such tetragonal elongation has been found for Mn(3+) and Cr(2+) complexes with homoleptic pseudooctahedral geometry as well as for Mn(3+) in square pyramidal geometry. This taken together with the results obtained here for Mn(acac)(3) in frozen solution indicates that axial elongation could be considered the "natural" form of Jahn-Teller distortion for octahedral high-spin 3d(4) ions. The previous electronic absorption data together with current HFEPR and magnetic data allow estimation of ligand-field parameters for Mn(acac)(3).

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Monolayer, bilayer, multilayers: evolving magnetic behavior in Langmuir-Blodgett films containing a two-dimensional iron-nickel cyanide square grid network.

The assembly of two-dimensional cyanide-bridged Fe(III)-Ni(II) square grid networks at the air-water interface and subsequent transfer of these networks as isolated monolayer, isolated bilayer, and multiple bilayer (multilayer) films via the Langmuir-Blodgett technique results in novel low-dimensional systems in which the effects of dimensionality on magnetic behavior in molecule-based materials can be observed. The magnetic response of these films between 2 < T < 300 K in dc fields from -50 < H < 50 kG and in 4 G ac fields from 1 Hz to 1 kHz are reported. The results show the presence of ferromagnetic domains with characteristic hysteresis in each of the three systems. The magnetic response for all three samples is anisotropic with a stronger field-cooled magnetization observed when the planes of the films are aligned parallel to the applied field. Additionally, each of the three samples shows frequency dependence in both the real and imaginary components of the ac susceptibility. This behavior is interpreted as being characteristic of spin glass-type ordering of ferromagnetic domains to form a cluster glass. A lower glass temperature (T(g)) is observed in the isolated monolayer film relative to the bilayer and multilayer samples. The bilayer sample shows two glass transitions at T(g1) = 3.8 K and T(g2) = 5.4 K, whereas only one transition at T(g) = 5.4 K is observed in the multilayer sample. The different magnetic responses of the three films are attributed to different in-plane, interplane, and long-range dipolar exchange interactions.

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Supramolecular assembly at interfaces: formation of an extended two-dimensional coordinate covalent square grid network at the air-water interface.

Reaction of a Langmuir monolayer of an amphiphilic pentacyanoferrate(3+) complex with Ni(2+) ions from the subphase results in the formation of a two-dimensional iron-nickel cyanide-bridged network at the air-water interface. The network can be transferred to various supports to form monolayer or multilayer lamellar films by the Langmuir-Blodgett (LB) technique. The same network does not form from homogeneous reaction conditions. Therefore, the results demonstrate the potential utility of an interface as a structure director in the assembly of low dimensional coordinate covalent network solids. Characterization of the LB film extended networks by X-ray photoelectron spectroscopy (XPS), FT-IR spectroscopy, SQUID magnetometry, X-ray absorption fine structure (XAFS), and grazing incidence synchrotron X-ray diffraction (GIXD) revealed a face-centered square grid structure with an average domain size of 3600 A(2). Magnetic measurements indicated that the network undergoes a transition to a ferromagnetic state below a T(c) of 8 K.

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EPR spectra from "EPR-silent" species: high-frequency and high-field EPR spectroscopy of pseudotetrahedral complexes of nickel(II).

High-frequency and high-field electron paramagnetic resonance (HFEPR) spectroscopy (using frequencies of approximately 90-550 GHz and fields up to approximately 15 T) has been used to probe the non-Kramers, S = 1, Ni(2+) ion in a series of pseudotetrahedral complexes of general formula NiL(2)X(2), where L = PPh(3) (Ph = phenyl) and X = Cl, Br, and I. Analysis based on full-matrix solutions to the spin Hamiltonian for an S = 1 system gave zero-field splitting parameters: D = +13.20(5) cm(-1), /E/ = 1.85(5) cm(-1), g(x) = g(y) = g(z) = 2.20(5) for Ni(PPh(3))(2)Cl(2). These values are in good agreement with those obtained by powder magnetic susceptibility and field-dependent magnetization measurements and with earlier, single-crystal magnetic susceptibility measurements. For Ni(PPh(3))(2)Br(2), HFEPR suggested /D/ = 4.5(5) cm(-1), /E/ = 1.5(5) cm(-1), g(x) = g(y) = 2.2(1), and g(z) = 2.0(1), which are in agreement with concurrent magnetic measurements, but do not agree with previous single-crystal work. The previous studies were performed on a minor crystal form, while the present study was performed on the major form, and apparently the electronic parameters differ greatly between the two. HFEPR of Ni(PPh(3))(2)I(2) was unsuccessful; however, magnetic susceptibility measurements indicated /D/ = 27.9(1) cm(-1), /E/ = 4.7(1), g(x) = 1.95(5), g(y) = 2.00(5), and g(z) = 2.11(5). This magnitude of the zero-field splitting ( approximately 840 GHz) is too large for successful detection of resonances, even for current HFEPR spectrometers. The electronic structure of these complexes is discussed in terms of their molecular structure and previous electronic absorption spectroscopic studies. This analysis, which involved fitting of experimental data to ligand-field parameters, shows that the halo ligands act as strong pi-donors, while the triphenylphosphane ligands are pi-acceptors.

Electron Spin Resonance Spectroscopy↗