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PubMed2006

Multifrequency simulations of the EPR spectra of lipid spin labels in membranes.

Simulations are performed of 34- and 9-GHz EPR spectra, together with 94-GHz EPR spectra, from phospholipid probes spin-labelled at the C4-C14 positions of the sn-2 chain, in liquid-ordered and gel-phase membranes of dimyristoyl phosphatidylcholine with high and low cholesterol contents. The multifrequency simulation strategy involves: (i) obtaining partially averaged spin-Hamiltonian tensors from fast-motional simulations of the 94-GHz spectra; (ii) performing slow-motional simulations of the 34- and 9-GHz spectra by using these pre-averaged tensors with the stochastic Liouville formalism; (iii) constructing, by simulation, slow-motional calibrations for the differences, DeltaA(zz)(qx) and Deltag(zz)(qx), in effective A(zz)-hyperfine splittings and g(zz)-values between 34- (or 94-GHz) and 9-GHz spectra; (iv) using such calibrations for DeltaA(zz)(qx) and Deltag(zz)(qx) and dynamic parameters from stage (ii) as a guide to adjust the extent of pre-averaging of the spin-Hamiltonian tensors; and (v) repeating the 34- and 9-GHz simulations of stage (ii). By using this scheme it is possible to obtain consistent values of the rotational diffusion coefficients, D(R perpendicular) and D(R//), and the long-axis order parameter, S(zz), that characterize the slow axial motion of the lipid chains, from spectra at both 34 and 9GHz. Inclusion of spectra at 34GHz greatly improves precision in determining the D(R//) element of the slow diffusion tensor in these systems.

Computer Simulation↗
PubMed2006

Slice profile optimization in arterial spin labeling using presaturation and optimized RF pulses.

OBJECTIVE: An important source of error in arterial spin labeling (ASL) is incomplete static tissue subtraction due to imperfect slice profiles. This effect can be reduced by saturating the spins in the imaging area prior to labeling. In this study, the use of optimized presaturation is compared with the use of optimized RF pulses for minimizing this error. MATERIALS AND METHODS: Different methods for optimizing presaturation were simulated by numerical solution of the Bloch equation. Presaturation was optimized by changing the number of presaturation pulses, their position in the pulse sequence and the area of the crusher gradients following each saturation pulse. It was also investigated whether the use of optimized presaturation could reduce the tag gap needed to ensure complete static tissue subtraction. Simulation results were verified using phantom and in vivo studies at 3T. RESULTS: In proximal inversion with control for off-resonance effects, optimized presaturation could reduce the necessary tag gap to 15% of the imaging slab for experiments using standard RF pulses, while c-FOCI RF pulses could reduce it to 11%. In flow-sensitive alternating inversion recovery, a single presaturation pulse could reduce the inversion width to 122% of the imaging slab and neither multiple presaturation pulses nor optimized RF pulses could reduce it further. CONCLUSION: Optimized presaturation can reduce the necessary inversion width to the same level as if using optimized RF pulses and can, therefore, be used to optimize ASL sensitivity. Furthermore, optimized presaturation can reduce the B(1)-dependent sensitivity in static tissue subtraction.

Adult↗
PubMed2003

Velocity-driven adiabatic fast passage for arterial spin labeling: results from a computer model.

Velocity-driven adiabatic fast passage (AFP) is commonly employed for perfusion imaging by continuous arterial spin labeling (CASL). The degree of inversion of protons in blood determines the sensitivity of CASL to perfusion. For this study, a computer model of the modified Bloch equations was developed to establish the optimum conditions for velocity-driven AFP. Natural variations in blood velocity over the course of the cardiac cycle were found to result in significant variations in the degree of inversion. However, the mean degree of inversion was similar to that for blood moving at a constant velocity, equal to the time-averaged mean, at peak velocities and heart rates within normal ranges. A train of RF pulses instead of a continuous RF pulse for labeling was found to result in a highly nonlinear dependence of the degree of inversion on RF duty cycle. This may have serious implications for the quantification of perfusion.

Animals↗
PubMedDate not supplied

[Interaction of spin-labeled saturated and unsaturated fatty acid derivatives with biological membrane lipid and protein components].

Interaction of saturated and unsaturated derivatives of spin-labelled fatty acids (2,2,6,6-tetramethyl-4-palmitoylpiperidil-l-oxyl (I) and synthetized by us 2,2,6,6-tetramethyl-4-oleoylpiperidil-1-oxyl (II) with sarcoplasmic reticulum membranes, retina rod outer segments and erythorocyte ghosts was studied. ESR spectra of the probe I are practically unresolved singlets, whereas ESR spectra of the probe II appear as more of less resolved triplet signals. The difference in ESR spectra of the probes I and II is the result of distribution of the probe I in pure lipid regions of membranes, the probe II being located both in lipid bilayer and hydrophobic areas of proteins.

Animals↗
PubMed1987

Spin label study of the perturbation effect of the local anaesthetics tetracaine and dibucaine on synaptosomes at pharmacological concentrations.

The method of electron spin resonance spectroscopy of spin probes was used to determine the lowest concentrations of the local anaesthetics dibucaine and tetracaine exerting perturbations on synaptosome membranes. The perturbation depends on the temperature and the membrane depth, as well as on the concentration and the structure of the anaesthetics. Using spin labelled stearic acid at the 5th carbon position a negligible effect of the anaesthetics on the order parameter was found in the membrane both at 1 degree and 22 degrees, within the buffer concentration 0.01-10 mmol/l, but at 37 degrees and concentrations higher than 0.1 mmol/l the disordering effect was significant and of comparable efficiency for dibucaine and tetracaine. Employing stearic acid labelled at the 16th carbon position, disordering of the hydrocarbon core of the membrane caused by tetracaine or dibucaine was detected at 1 degree and 22 degrees, as well as at 37 degrees. The disordering effect occurred at buffer concentrations higher than 0.01 mmol/l for dibucaine, and higher than 0.1 mmol/l for tetracaine. At equal anaesthetic membrane concentrations and at the 16th carbon membrane depth, dibucaine was approximately twice as effective as tetracaine in perturbing synaptosomes. Tetracaine induced nonlamellar phases in the rat brain lipid membrane as detected by 31P NMR spectroscopy. The dynamic and structural perturbation effects of the local anaesthetics was found in that concentration range at which the anaesthetics influence various activities of biological membranes.

Anesthetics, Local↗
PubMedDate not supplied

Procaine incorporation into human erythrocyte membrane--a spin label study.

The positioning of procaine among the components of human erythrocyte membranes was investigated by electron paramagnetic resonance (EPR) using several spin labelled molecules: fatty acids 5-, 12- and 16-doxyl-stearic acids (5DSA, 12DSA, 16DSA), procaine (SLP) and a quaternary ammonium salt (CAT4). It was proved that while procaine significantly modified EPR parameters of both CAT4 and 5DSA, it had no effect at the level of the twelfth or sixteenth carbon atom of the membrane lipid chains. Simultaneous incorporation of 5DSA and SLP and SLP in erythrocyte membranes revealed a shorter than 10 A distance between paramagnetic centers of 5DSA and SLP. It is inferred that procaine interacts with the membrane not only at lipid water interface, but also (at least) up to the fifth carbon atom of the hydrophobic tail of phopolipids. Procaine inclusion does not change the transition point (40 degrees C) at which a break appears in the temperature dependence of the erythrocyte volume, hence no strong interaction between the procaine and the cytoskeleton or the integral proteins responsible for this phase transition occurs. In the temperature domain of 25-42 degrees C, procaine seems to be freely diffusible within the membrane (Debye model can be applied).

Electron Spin Resonance Spectroscopy↗
PubMed2002

Ventilation-perfusion ratio of signal intensity in human lung using oxygen-enhanced and arterial spin labeling techniques.

This study investigates the distribution of ventilation-perfusion (V/Q) signal intensity (SI) ratios using oxygen-enhanced and arterial spin labeling (ASL) techniques in the lungs of 10 healthy volunteers. Ventilation and perfusion images were simultaneously acquired using the flow-sensitive alternating inversion recovery (FAIR) method as volunteers alternately inhaled room air and 100% oxygen. Images of the T(1) distribution were calculated for five volunteers for both selective (T(1f)) and nonselective (T(1)) inversion. The average T(1) was 1360 ms +/- 116 ms, and the average T(1f) was 1012 ms +/- 112 ms, yielding a difference that is statistically significant (P < 0.002). Excluding large pulmonary vessels, the average V/Q SI ratios were 0.355 +/- 0.073 for the left lung and 0.371 +/- 0.093 for the right lung, which are in agreement with the theoretical V/Q SI ratio. Plots of the V/Q SI ratio are similar to the logarithmic normal distribution obtained by multiple inert gas elimination techniques, with a range of ratios matching ventilation and perfusion. This MRI V/Q technique is completely noninvasive and does not involve ionized radiation. A limitation of this method is the nonsimultaneous acquisition of perfusion and ventilation data, with oxygen administered only for the ventilation data.

Adult↗
PubMed1990

Incorporation of spin-labeled fatty acids into bovine brain clathrin coated vesicles.

Stearic acids with a nitroxide radical at selected positions have been incorporated in the phospholipid bilayers of clathrin coated vesicles, uncoated vesicles and sonicated liposomes made from the lipids extracted from the uncoated vesicles. The extent of incorporation was found minimum for stearic acids labeled on C-12 and for bilayers of uncoated vesicles. The ESR spectra of the spin-labeled fatty acids incorporated in the bilayers showed a pronounced temperature dependence (without discontinuity) and a decrease in the hyperfine splitting as the nitroxide group was inserted deeper in the hydrophobic core of the membranes. An abrupt phospholipid phase transition or a phase separation could be excluded. The presence of the external proteins (the clathrin coat) on the membranes was not found to noticeably influence the gradient of flexibility of the fatty acid chains of the phospholipids. The influence of the internal proteins embedded in the bilayers was evidenced by a detailed analysis of the ESR spectra of (7,8)SA in terms of two components: one component arising from the labels surrounded exclusively by phospholipids, the other component arising from labels of reduced mobility perturbed by the vicinity of the proteins. These results support the persistence of lipidic domains in the endocytic vesicles despite the accumulation of receptors which follows their formation.

Animals↗
PubMed1980

Spin label and biochemical studies of erythrocyte membranes in Alzheimer's disease.

Electron spin resonance, enzymatic, and SDS-polyacrylamide gel electrophoretic investigations of erythrocyte membranes from patients with Alzheimer's disease were performed. Alterations in the physical state of membrane proteins in Alzheimer's disease erythrocytes were found by spin labeling studies. However, no alterations in membrane lipid fluidity or in the activities of membrane-bound sodium plus potassium-stimulated, magnesium-dependent adenosine triphosphatase or acetylcholinesterase could be demonstrated. Also, no changes in staining profiles of AD erythrocyte membrane proteins subjected to electrophoresis were observed. The altered conformation and/or organization of extraneural membrane proteins in Alzheimer's disease suggests the possibility that this disorder may have more widespread membrane involvement than was originally thought.

Acetylcholinesterase↗
PubMedDate not supplied

[Structural changes in erythrocyte membranes in diabetes mellitus using spin labelled fatty acids].

Microviscosity and polarity of erythrocyte membranes of the blood of patients suffering from diabetes were studied by ESR using spin-labeled fatty acids. Structural changes were discovered 0.6-0.8 nm from the membrane surface in the lipid bilayer of erythrocytes obtained from patients' blood. No essential immobilization of the acyl chains of phospholipids was found in deeper layers as compared with the control. The bilayer polarity at different depth was not essentially changed either.

Adolescent↗
PubMed1983

Collisions between nitrogen-14 and nitrogen-15 spin-labels. 1. Lipid-lipid interactions in model membranes.

A new method is described to evaluate collision frequencies between spin-labeled molecules in membranes. This method utilizes a mixture of 14N and 15N nitroxides. The extent of spin-spin interaction between the two different isotopes can be determined by comparing experimental ESR spectra with simulated spectra. The latter are calculated by using modified Bloch equations and by assuming that the spin exchange process is the dominant broadening mechanism. A more approximate analysis is also described; it is based on the evaluation of the line broadening from the measurement of peak heights. Both analyses show that relatively low concentrations of label can be utilized: 1-5% labeled lipids in a membrane give a broadening sufficient to allow quantitation. Collision frequencies equal to or larger than 0.1 MHz can be evaluated by this method. Because of the limited overlap between 15N and 14N spectra, this method allows the investigation of the collisions between unlike molecules of very different concentration. From the collision frequencies, the topological domain explored by a probe can be inferred as well as its lateral diffusion constant. In this paper, it is shown that in spite of the low order of the chain residues near their methyl terminal, a probe linked at the omega - 2 position of an ionized stearic acid does not interact with a probe positioned near the polar region. Nevertheless the former probe, deeply embedded in the membrane, explores a larger volume. It is also shown that if the nitroxide is attached to a fatty ester, the probe "sees" evenly the whole hydrophobic region of the membrane.

Chemical Phenomena↗
PubMed1991

Spin label detection and free radical nature of DNA damage by hydralazine.

1. Incubation with hydralazine was shown to induce degradative changes of calf thymus DNA spin-labeled with 3-(2-bromoacetamido)-2,2,5,5-tetramethyl-1-pyrrolidono-1-oxyl and 4-(2-bromoacetamido)-2,2,6,6-tetramethylpiperidino-1-oxyl detectable from electron spin resonance specta. 2. Hydralazine, especially in the presence of Fe2+ induced formation of thiobarbituric acid (TBA)-reactive DNA degradation products. 3. The formation of TBA-reactive products was prevented by catalase, EDTA and scavengers of .OH radicals and enhanced by superoxide dismutase which suggests that .OH radicals formed by the Fenton mechanism mediate the DNA damage by hydralazine-Fe2+.

Catalase↗
PubMed1987

Contribution of tryptophan residues to the combining site of a monoclonal anti dinitrophenyl spin-label antibody.

Two Fab fragments of the monoclonal anti dinitrophenyl (DNP) spin-label antibody AN02 were prepared by recombination of specifically deuterated heavy and light chains. In the recombinant H(I)L(II) all the tyrosines and phenylalanines were perdeuterated as were the tryptophan residues of the heavy chain. In the recombinant H(II)L(I) all the tyrosines and phenylalanines were perdeuterated as were the tryptophan residues of the light chain. Saturation of three resonances of H(I)L(II), assigned to tryptophan protons of the light chain, resulted in magnetization transfer to the aromatic proton at position 6 of the DNP ring and to the CH2 protons of the glycines linked to the DNP in a diamagnetic hapten (DNP-DG). Saturation of three resonances of H(II)L(I) assigned to tryptophan protons of the heavy chain resulted in magnetization transfer to the CH2 protons of the glycines in DNP-DG. From the dependence of the magnetization transfer on the irradiation time, the cross relaxation rates between the involved protons were estimated. The inferred distances between these protons of the hapten and certain tryptophan protons are 3-4 A. It is concluded that in the combining site of AN02 there is one tryptophan from the light chain and one tryptophan from the heavy chain that are very near the hapten. When all tyrosines and phenylalanines were perdeuterated and all tryptophan aromatic protons were deuterated except for the protons at positions 2 and 5, titration of the Fab fragments with variable amounts of paramagnetic hapten showed that one proton from the light chain tryptophan is near (less than 7 A) the unpaired electron and that three other protons are significantly closer than 15 A.(ABSTRACT TRUNCATED AT 250 WORDS)

Amino Acid Sequence↗
PubMed1983

The role of membranes in the mechanism of action of the antineoplastic agent adriamycin. Spin-labeling studies with chronically hypoxic and drug-resistant tumor cells.

Electron spin resonance spectroscopy has been employed to analyze the changes in membrane order parameter in Sarcoma 180 cells under conditions in which an alteration in cellular susceptibility to the chemotherapeutic agent adriamycin is demonstrable. Changes in relative membrane fluidity using the paramagnetic probe 5-doxyl stearic acid were found to be associated with two phenomena which result in an altered cellular response to adriamycin: (a) the presence of an oxygen-deficient environment and (b) the expression of drug resistance. Under hypoxic conditions, in which the susceptibility to the cytotoxic action of adriamycin is increased, a decrease in bulk membrane order parameter was observed. Upon reoxygenation, the membrane fluidity and enhanced susceptibility to adriamycin reverted to control conditions with the same time course. In the case of drug-resistant cells, a progressive decrease in membrane fluidity was also observed which correlated with the degree of resistance to adriamycin. These data suggest that the physical alterations in the membrane reported by the spin label may be functionally linked to biological alterations in sensitivity to adriamycin.

Aerobiosis↗
PubMed1976

Model membrane studies of spin-label probes. Part 1. Mixed monolayers of 12-nitroxide stearic acid and myristic acid.

Pure and mixed monomolecular films of a cell membrane spin label probe, 12-nitroxide stearic acid have been studied where myristic acid was selected as the host lipid. The behavior of 12-nitroxide stearic acid at the air water interface is understood in terms of two molecular configurations: erect (with only the carboxyl group in the interface) and bent (with both the carboxyl group and the oxazolidine ring in the interface). In mixed films both of these conformations play a role at high surface pressures. At low probe concentrations, 12-nitroxide stearic acid is primarily in an erect conformation, while at high probe concentrations the reverse is true. This particular host lipid appears capable of erecting the probe molecule with only small concentrations of myristic acid. In a condensed host lipid, the probe is partially immiscible, and segregates to form a heterogeneous film from which it is readily collapsed. The probe is seen to perturb the molecular packing in this mixed system and the perturbation to be dependent on both the molecular shape and nature of the probe.

Binding Sites↗
PubMed2006

Perfusion MR imaging with FAIR true FISP spin labeling in patients with and without renal artery stenosis: initial experience.

The purpose of this study was to prospectively evaluate an arterial spin-labeling technique, flow-sensitive alternating inversion-recovery (FAIR) true fast imaging with steady-state precession (FISP), for noninvasive quantification of renal perfusion in patients without a history of renal artery stenosis (RAS) and in patients with proved RAS. The study was approved by the local ethics committee, and all participants provided written informed consent. Six patients with hypertension but no history of renal artery disease and 12 patients with RAS underwent FAIR true FISP magnetic resonance (MR) imaging in a whole-body 1.5-T unit. RAS grade and scintigraphic perfusion data served as the reference standards. On the FAIR true FISP perfusion images, severe RAS (>70% luminal narrowing) could be clearly distinguished from no or mild RAS and moderate RAS (< or =70% luminal narrowing) (P < .005). Significant correlations between FAIR perfusion data and stenosis grade (r = -0.76) and between FAIR and single photon emission computed tomographic perfusion values (r = 0.83) were observed. FAIR true FISP was found to be suitable for quantitative perfusion imaging of the kidneys in patients with RAS.

Aged↗
PubMed2005

In vivo assessment of absolute perfusion and intracapillary blood volume in the murine myocardium by spin labeling magnetic resonance imaging.

The absolute perfusion and the intracapillary or regional blood volume (RBV) in murine myocardium were assessed in vivo by spin labeling magnetic resonance imaging. Pixel-based perfusion and RBV maps were calculated at a pixel resolution of 469 x 469 mum and a slice thickness of 2 mm. The T(1) imaging module was a segmented inversion recovery snapshot fast low angle shot sequence with velocity compensation in all three gradient directions. The group average myocardial perfusion at baseline was determined to be 701 +/- 53 mL (100 g . min)(-1) for anesthesia with isoflurane (N = 11) at a mean heart rate (HR) of 455 +/- 10 beats per minute (bpm). This value is in good agreement with perfusion values determined by invasive microspheres examinations. For i.v. administration of the anesthetic Propofol, the baseline perfusion decreased to 383 +/- 40 mL (100 g . min)(-1) (N = 17, P < 0.05 versus. isoflurane) at a mean heart rate of 261 +/- 13 bpm (P < 0.05 versus isoflurane). In addition, six mice with myocardial infarction were studied under isoflurane anesthesia (HR 397 +/- 7 bpm). The perfusion maps showed a clear decrease of the perfusion in the infarcted area. The perfusion in the remote myocardium decreased significantly to 476 +/- 81 mL (100 g . min)(-1) (P < 0.05 versus sham). Regarding the regional blood volume, a mean value of 11.8 +/- 0.8 vol % was determined for healthy murine myocardium under anesthesia with Propofol (N = 4, HR 233 +/- 17 bpm). In total, the presented techniques provide noninvasive in vivo assessment of the perfusion and the regional blood volume in the murine myocardium for the first time and seem to be promising tools for the characterization of mouse models in cardiovascular research.

Analysis of Variance↗
PubMed1996

Dynamic electron spin resonance (ESR) imaging of the distribution of spin labeled dextran in a mouse.

The nitroxide group 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) was covalently bound to a dextran via an N-acetamido linkage to produce a novel spin probe, TEMPO-dextran (TEMPO-DX), which circulates for long time periods in an animal without metabolic degradation. TEMPO-DX was stable in mice, while small TEMPO analogs quickly disappeared after administration. Since dextran was reduced somewhat in size during synthesis, the resultant spin-labeled dextran could be excreted through the kidney. A strong L-band electron spin resonance signal was obtained shortly after intravenous administration of TEMPO-DX into the tail vein of a mouse, from which three-dimensional images of specific organs were calculated. The signal was found to persist for well over 1 h.

Animals↗