Search results for "Spin Labels"
showing 10 items of 35 documents
Self-assembled PAA-based nanoparticles as potential gene and protein delivery systems
2012
A series of nanoparticles is prepared via layer-by-layer assembly of oppositely charged, synthetic biocompatible polyamidoamine polymers as potential carriers. Particle size, surface charge and internal chain mobility are quantified as a function of the polymer type and number of layers. The effect of addition of surfactant is examined to simulate the effects of nanoparticle dissolution. The cyctotoxicity of these particles (in epithelia and murine cell lines) are orders of magnitude lower than polyethyleneimine controls. Stable nanoparticles may be prepared from mixtures of strongly, oppositely charged polymers, but less successfully from weakly charged polymers, and, given their acceptabl…
Self-Assembled Monolayer-Functionalized Half-Metallic Manganite for Molecular Spintronics
2012
(La,Sr)MnO(3) manganite (LSMO) has emerged as the standard ferromagnetic electrode in organic spintronic devices due to its highly spin-polarized character and air stability. Whereas organic semiconductors and polymers have been mainly envisaged to propagate spin information, self-assembled monolayers (SAMs) have been overlooked and should be considered as promising materials for molecular engineering of spintronic devices. Surprisingly, up to now the first key step of SAM grafting protocols over LSMO surface thin films is still missing. We report the grafting of dodecyl (C12P) and octadecyl (C18P) phosphonic acids over the LSMO half-metallic oxide. Alkylphosphonic acids form ordered self-a…
Guest Effect on Nanopatterned Spin-Crossover Thin Films
2011
International audience; Nanopatterned thin films of the metal–organic framework {Fe(bpac)[Pt(CN)4]} (bpac=bis(4‐pyridyl)acetylene) are elaborated by the combination of a sequential assembly process and a lithographic method. Raman microspectroscopy is used to probe the temperature dependence of the spin state of the iron(II) ions in the films (40–90 nm in thickness), and reveals an incomplete but cooperative spin transition comparable to that of the bulk material. Adsorption/desorption of pyridine guest molecules is found to have a substantial influence on the spin‐crossover properties of the thin layers. This interplay between host–guest and spin‐crossover properties in thin films and nano…
Heme Binding Constricts the Conformational Dynamics of the Cytochrome b559′ Heme Binding Cavity
2012
Cytochrome b(559)' is a transmembrane protein formed by homodimerization of the 44-residue PsbF polypeptide and noncovalent binding of a heme cofactor. The PsbF polypeptide can dimerize in the absence and presence of heme. To monitor structural alterations associated with binding of heme to the apo-cytochrome, we analyzed the apo- and holo-cytochrome structure by electron paramagnetic resonance spectroscopy. Spin labeling of amino acids located close to the heme binding domain of the cytochrome revealed that the structure of the heme binding domain is unconstrained in the absence of heme. Heme binding restricts the conformational dynamics of the heme binding domain, resulting in the structu…
Fluidity of liposome membranes doped with metalloporphyrins: An ESR study
2008
Changes in membrane fluidity of porphyrin-doped liposomes have been investigated to assess the kinetics of the fluidization process. Metal complexes of tert-butylphenyl mesosubstituted porphyrin, containing ions of Mg, Mn, Fe, Co, Ni and Cu, were used as dopants. Liposomes were obtained by sonication of hen egg yolk lecithin (EYL). Electron paramagnetic resonance (ESR) was applied using two spin probes, TEMPO (2,2,6,6-tetramethylpiperidine- 1-oxyl) and 16-DOXYL-stearic acid [2-ethyl-2-(15-methoxy-15-oxopentadecyl)-4,4- dimethyl-3-oxazolidinyloxyl], localized at different sites within the membrane to determine the spectroscopic parameters: partition (F) and rotation correlation time (τ), rel…
Vibrational spectrum of the spin crossover complex [Fe(phen)(2)(NCS)(2)] studied by IR and Raman spectroscopy, nuclear inelastic scattering and DFT c…
2006
The vibrational modes of the low-spin and high-spin isomers of the spin crossover complex [Fe(phen)(2)(NCS)(2)] (phen = 1,10-phenanthroline) have been measured by IR and Raman spectroscopy and by nuclear inelastic scattering. The vibrational frequencies and normal modes and the IR and Raman intensities have been calculated by density functional methods. The vibrational entropy difference between the two isomers, DeltaS(vib), which is--together with the electronic entropy difference DeltaS(el)--the driving force for the spin-transition, has been determined from the measured and from the calculated frequencies. The calculated difference (DeltaS(vib) = 57-70 J mol(-1) K(-1), depending on the m…
DNP in MRI: an in-bore approach at 1.5 T.
2011
Abstract We have used liquid state (“Overhauser”) Dynamic Nuclear Polarization (DNP) to significantly enhance the signal to noise ratio (SNR) of Magnetic Resonance Imaging (MRI). For the first time this was achieved by hyperpolarizing directly in the MRI-scanner field of 1.5 T in continuous flow mode and immediately delivering the hyperpolarized substance to the imaging site to ensure maximum contrast between hyperpolarized sample and sample at thermal polarization. We achieve a maximum absolute signal enhancement factor of 98; while the hyperpolarized sample is transported at a flow rate of up to 30 ml/h yielding an average flow speed up to 470 mm/s over a distance of approximately 80 mm. …
Photochemical and photobiological studies with acridine and phenanthridine hydroperoxides in cell-free DNA.
1997
The acridine and phenanthridine hydroperoxides 3 and 7 were synthesized as photochemical hydroxyl radical sources for oxidative DNA damage studies. The generation of hydroxyl radicals upon UVA irradiation (lambda = 350 nm) was verified by trapping experiments with 5,5-dimethyl-1-pyrroline N-oxide and benzene. The enzymatic assays of the damage in cell-free DNA from bacteriophage PM2 caused by the acridine and phenanthridine hydroperoxides 3 and 7 under near-UVA irradiation revealed a wide range of DNA modifications. Particularly, extensive single-strand break formation and DNA base modifications sensitive to formamidopyrimidine DNA glycosylase (Fpg protein) were observed. In the photooxidat…
Recombinant water-soluble chlorophyll protein from Brassica oleracea var. Botrys binds various chlorophyll derivatives.
2003
A gene coding for water-soluble chlorophyll-binding protein (WSCP) from Brassica oleracea var. Botrys has been used to express the protein, extended by a hexahistidyl tag, in Escherichia coli. The protein has been refolded in vitro to study its pigment binding behavior. Recombinant WSCP was found to bind two chlorophylls (Chls) per tetrameric protein complex but no carotenoids in accordance with previous observations with the native protein [Satoh, H., Nakayama, K., Okada, M. (1998) J. Biol. Chem. 273, 30568-30575]. WSCP binds Chl a, Chl b, bacteriochlorophyll a, and the Zn derivative of Chl a but not pheophytin a, indicating that the central metal ion in Chl is essential for binding. WSCP …
Magnetized boxes for housing polarized spins in homogeneous fields
2010
Abstract We present novel types of permanently magnetized as well as current powered boxes built from soft-ferromagnetic materials. They provide shielded magnetic fields which are homogeneous within a large fraction of the enclosed volume, thus minimizing size, weight, and costs. For the permanently magnetized solutions, homogenization is achieved either by an optimized distribution of the permanent field sources or by jacketing the field with a soft-ferromagnetic cylindrical shell which is magnetized in parallel to the enclosed field. The latter principle may be applied up to fields of about 0.1 T. With fields of about 1 mT, such boxes are being used for shipping spin-polarized 3 He worldw…