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PubMedDate not supplied

[The effect of reversed micelles of cetyltrimethylammonium bromide on equilibrium constants and kinetics of oxidation-reduction reactions with the participation of cytochrome c].

To model the effect of membrane environment on the electron transfer reactions we studied the thermodynamics and kinetics of the reactions of cytochrome c and 2,6-dichlorophenolindophenol with ferri- and ferrocyanide in the reversed micelles cetyltrimethylammonium bromide in chloroform/octan mixture. Incorporation of the protein in micelles leads to increasing the equilibrium constant (K1) up to 300 times. This effect is mainly due to a decrease in the ferrocytochrome c oxidation rate constant in the reaction with ferricyanide. Micellar solubilization of the dye also leads to a marked increase in the equilibrium constant K2. The estimations of the values K1 and K2 in water-alcohol mixtures and in aqueous micellar solutions of surfactant together with kinetical and spectral data show that the increase of K1 and K2 in reversed micelles is caused generally by redox potential changes of low-molecular reagents. The latter change their environment after adsorption on the micellar surface.

2,6-Dichloroindophenol↗
PubMed2001

Estimation of radiance reflectance and the concentrations of optically active substances in Lake Mälaren, Sweden, based on direct and inverse solutions of a simple model.

A semi-analytical model which predicts radiance reflectance just below the water surface (Lu/Ed 0-) has been developed and used to predict the spectral variability of radiance reflectance in Lake Mälaren, Sweden. Radiance reflectance is predicted as a function of the optically active substances in the water, which include the concentrations of chlorophyll-a + phaeophytin-a, suspended particular inorganic material (SPIM), suspended particulate organic material (SPOM), and dissolved yellow substances. These substances are linked to the absorption and backscattering coefficients through a series of empirical relationships, and ultimately radiance reflectance is estimated as a function of the ratio of backscattering to absorption. Parameterization of the model, i.e. the development of the empirical relationships linking the optically active substances to the inherent optical properties (IOPs), is based on both in situ measurements and laboratory analyses. We have collected data that allowed us to examine the potential variability in radiance reflectance, as predicted by our model, due to both variations in the optically active substances, and in the model parameterization. Simulations based on a data set collected during the fall of 1997 from 12 sites, which span a large range in water quality (secchi depth 0.8-5.0 m), suggest that, with the proper parameterization, the model can accurately predict the spectra of radiance reflectance as a function of the concentration of optically active substances. Variations in the concentrations of optically active substances accounted for a large portion of the total simulated variability in radiance reflectance (i.e. that resulting from variations in parameterization and in the concentrations of optically active substances). However, the measured variability in parameterization could account for up to 50% of the total variability in simulated radiance reflectance. This suggests that variability in the model parameterization, arising from both real variability and experimental error, will limit the use of this model for interpreting remote sensing data. Nevertheless, inverse solutions of the model are able to estimate the concentrations of chlorophyll, suspended inorganic material (SPIM) and the absorption of yellow substances from measured radiance reflectance spectra The average error for the 12 sites was a -0.07 for chlorophyll, -0.15 for dissolved yellow substances (measured as the absorption at 400 nm) and 0.07 for SPIM, even though individual errors could be as great as 50%.

Chlorophyll↗
PubMed1999

Hybrid finite elements and spectral method for computation of the electric potential generated by a nerve cuff electrode.

An original numerical method is developed to compute the 3D electric potential generated by a dot-contact cuff electrode implanted around an axisymmetrical, inhomogeneous, anisotropic nerve. The technique is based on a 2D finite-element approach coupled with a semi-analytical Fourier spectral decomposition to approximate the solution behaviour in the azymuthal direction. The method only requires a 2D FEM mesh and allows an accurate electrode description, with any number of contacts at different angular positions. Results show that the convergence of the Fourier series is very fast: typically, the relative error due to series truncation (estimated by the norm of the difference between the solution computed with M modes and the one computed with M-1 modes, normalised by the norm of the solution computed with M modes) reaches the order of 10(-3) with six spectral modes (M = 6). As a consequence, the whole algorithm has the complexity of a 2D approach.

Computer Simulation↗
PubMed1996

ESR Studies of A(1u) and A(2u) Oxoiron(IV) Porphyrin pi-Cation Radical Complexes. Spin Coupling between Ferryl Iron and A(1u)/A(2u) Orbitals.

This study shows the ESR spectra of oxoiron(IV) porphyrin pi-cation radicals of 1-8 in dichloromethane-methanol (5:1) mixture. We reported in a previous paper that oxoiron(IV) porphyrin pi-cation radicals of 1-4 are in an a(1u) radical state while those of 5-8 are in an a(2u) radical. The ESR spectra (g( perpendicular)(eff) approximately 3.1 and g( parallel)(eff) approximately 2.0) for the a(1u) radical complexes, 1-4, appear quite different from those reported previously for the oxoiron(IV) porphyrin pi-cation radical of 5 (g(y) = 4.5, g(x) = 3.6, and g(z) = 1.99). The unique ESR spectra of the a(1u) radical complexes rather resemble those of compound I from Micrococcus lysodeikticus catalase (CAT) and ascorbate peroxidase (ASP). This is the first examples to mimic the ESR spectra of compound I in the enzymes. From spectral analysis based on a spin Hamiltonian containing an exchange interaction, the ESR spectra of 1-4 can be explained as a moderate ferromagnetic state (J/D approximately 0.3) between ferryl S = 1 and the porphyrin pi-cation radical S' = (1)/(2). The magnitudes of zero-field splitting (D) for ferryl iron and isotropic J value, estimated from the temperature-dependence of the half-saturation power of the ESR signals, are approximately 28 and approximately +8 cm(-1), respectively. A change in the electronegativity of the beta-pyrrole substituent hardly changes the ESR spectral feature while that of the meso-substituent slightly does owing to the change in the E/D value. On the basis of the present ESR results, we propose the a(1u) radical state for compound I of CAT and ASP.

Journal Article↗
PubMed1979

Properties of allophycocyanin II and its alpha- and beta-subunits from the thermophilic blue--green alga Mastigocladus laminosus.

Purified allophycocyanin II and its subunits have been examined with respect to spectroscopic properties, sedimentation, reconstitution and isoelectric behaviour. In 0.02m-potassium phosphate buffer, pH8.0, and at a concentration of 0.25mg/ml, allophycocyanin II and its alpha- and beta-subunits show visible absorption maxima at 650, 615 and 615nm respectively, whereas the fluorescence emission maxima were determined to be at 662, 640 and 630nm respectively. The absorption difference spectrum (dilution difference) of allophycocyanin II displays maxima at 650 and 590nm with a minimum at 610nm. The c.d. spectrum of allophycocyanin II showed only one positive-ellipticity band at 635nm, and a major negative-ellipticity band at 340nm. Oxidation of allophycocyanin II, low- and high-pH solutions (pH3.0 and 11.0), various ethanol concentrations as well as dialysis against distilled water induce a spectral change leading to phycocyanin-like characteristics. In most cases these shifts are reversible. Allophycocyanin II is thermostable over a period of 60min at temperatures up to 60 degrees C. The isoelectric points of allophycocyanin II and its alpha- and beta-subunits are 4.65, 4.64 and 4.82 respectively. Estimated molecular weights from sedimentation-equilibrium analyses were 102500 for allophycocycanin II, 16000 for the alpha- and 31500 for the beta-subunit. Recombination of alpha- and beta-subunits leads to allophycocyanin II, which is indistinguishable from native allophycocyanin with respect to its spectral form, to its gel-filtration and to its electrophoretic behaviour.

Cyanobacteria↗
PubMed2000

The effects of frequency region and level on the temporal modulation transfer function.

Temporal modulation transfer functions (TMTFs) were measured using narrow-band AM and QFM noises with upper spectral edges from 0.6 to 4.8 kHz, and spectrum levels of 10 and 40 dB SPL. The cutoff frequency of the TMTF increases as the upper spectral edge is increased up to 4.8 kHz at low levels, and is constant at higher levels. Sensitivity increases with bandwidth if frequency region is constant. In a second experiment, these results were compared to predictions of a model incorporating peripheral and central limitations to modulation detection. To obtain an estimate of peripheral filtering, frequency selectivity was measured using the notched-noise method, with probe frequencies and levels chosen to parallel those in the first experiment. The TMTF data were then predicted using the model. Predicted cutoff frequencies as a function of the upper spectral edge of the test stimulus were lower than but parallel to those of the subjects at the lower stimulus level. The model predicted only a slight increase in cutoff frequency with level, and thus predicted an increase in cutoff frequency with frequency region at the higher level as well, in contrast to the measured data. These results suggest that there are peripheral and central limitations to temporal resolution, but the psychoacoustically derived auditory filter may be only an indirect measure of peripheral filtering, and/or a more complex model may be needed.

Adolescent↗
PubMed2000

Physiological time series: distinguishing fractal noises from motions.

Many physiological signals appear fractal, in having self-similarity over a large range of their power spectral densities. They are analogous to one of two classes of discretely sampled pure fractal time signals, fractional Gaussian noise (fGn) or fractional Brownian motion (fBm). The fGn series are the successive differences between elements of a fBm series; they are stationary and are completely characterized by two parameters, sigma2, the variance, and H, the Hurst coefficient. Such efficient characterization of physiological signals is valuable since H defines the autocorrelation and the fractal dimension of the time series. Estimation of H from Fourier analysis is inaccurate, so more robust methods are needed. Dispersional analysis (Disp) is good for noise signals while bridge detrended scaled windowed variance analysis (bdSWV) is good for motion signals. Signals whose slopes of their power spectral densities lie near the border between fGn and fBm are difficult to classify. A new method using signal summation conversion (SSC), wherein an fGn is converted to an fBm or an fBm to a summed fBm and bdSWV then applied, greatly improves the classification and the reliability of H, the estimates of H, for the times series. Applying these methods to laser-Doppler blood cell perfusion signals obtained from the brain cortex of anesthetized rats gave H of 0.24+/-0.02 (SD, n=8) and defined the signal as a fractional Brownian motion. The implication is that the flow signal is the summation (motion) of a set of local velocities from neighboring vessels that are negatively correlated, as if induced by local resistance fluctuations.

Animals↗
PubMed1983

Cycle detection: a technique for estimating the frequency and amplitude of episodic fluctuations in blood hormone and substrate concentrations.

Investigation of episodic endocrine secretion has been hampered by inadequate analytical techniques for describing patterns of blood concentrations over time. Although standard time series methods, such as autocorrelation and power spectral analysis, are available, their use is limited to special cases in which rhythms are regular. To facilitate the analysis of our own episodic LH data, we have developed a process for determining the frequency and amplitude of both regular and irregular endocrine rhythms (signals) in the presence of high levels of random measurement errors (noise). This process, called cycle detection, engages an iterative, computerized procedure which scans data identifying sequential increases and decreases greater than an initial, preset threshold value. One complete cycle is defined as two increases greater than threshold separated by a decrease which is also greater than threshold. For an initial first pass estimate of frequency and amplitude, the threshold is set at 2.7 times the noise standard deviation. On the next pass, the threshold is readjusted, based on an empirically derived formula, and the data are scanned again. This process is repeated until the threshold reaches a stable value. We have tested the reliability of the cycle detection process by simulating irregular rhythm fluctuations of different frequencies, corrupted by various levels of noise and evaluating the signal characteristics with cycle detection analysis. These tests indicate that cycle detection provides excellent estimates of cycle frequency and amplitude, even with signal to noise ratios as low as 1.5. The ability of this process to analyze cyclic signals of almost any shape, with either regular or irregular rhythms, should make it a valuable tool in the hands of endocrine researchers.

Animals↗
PubMed1997

Clinical relevance of heart rate variability.

Heart rate variability (HRV) has recently become a popular noninvasive research tool in cardiology. Clinical assessment of HRV is frequently based on standard long-term ambulatory electrocardiograms, whereas physiologic studies employ spectral analysis of short-term recordings under controlled conditions. From a general point of view, HRV can be used in clinical practice to estimate (1) the integrity of cardiac autonomic innervation, (2) the physiologic status of cardiac autonomic activity, and (3) the vulnerability to various cardiac arrhythmias resulting from autonomic imbalance. Clinical relevance of HRV has been clearly demonstrated in only two clinical conditions: (1) impaired HRV can be used alone or in a combination with other factors to predict risk of arrhythmic events after acute myocardial infarction, and (2) decrease in HRV is a useful clinical marker for evolving diabetic neuropathy. Substantial advances of our knowledge are required to establish and promote clinical applications in other areas of clinical medicine. To accomplish this task, proper hypotheses should be studied and appropriate techniques selected.

Autonomic Nervous System↗
PubMedDate not supplied

Line scan imaging of brain metabolites with CPMG sequences at 1.5 tesla.

A line scan Carr-Purcell-Meiboom-Gill (CPMG) spectroscopic imaging sequence has been implemented on a standard 1.5 T clinical scanner to map metabolite signals at multiple echo times from voxels along selected tissue columns through the brain. The CPMG multiecho spectroscopic image data sets are used to estimate brain metabolite T2 decay parameters in a group of healthy volunteers and in one tumor patient. Inherent trade-offs between T2 decay, spectral resolution, and echo spacing prove to be important limiting factors. In particular, separate quantitation of choline and creatine resonances at 1.5 T was not achieved in the present implementation. However, the ability to collect data sets suitable for T2 decay analyses of combined choline and creatine resonances and N-acetyl aspartate resonances in under 10 minutes may prove of clinical utility in the study of brain pathology.

Adolescent↗
PubMed1989

Automatic detection of sounds and murmurs in patients with Ionescu-Shiley aortic bioprostheses.

The problems encountered in the automatic detection of cardiac sounds and murmurs are numerous. The phonocardiogram (PCG) is a complex signal produced by deterministic events such as the opening and closing of the heart valves, and by random phenomena such as blood-flow turbulence. In addition, background noise and the dependence of the PCG on the recording sites render automatic detection a difficult task. In the paper we present an iterative automatic detection algorithm based on the a priori knowledge of spectral and temporal characteristics of the first and second heart sounds, the valve opening clicks, and the systolic and diastolic murmurs. The algorithm uses estimates of the PCG envelope and noise level to identify iteratively the position and duration of the significant acoustic events contained in the PCG. The results indicate that it is particularly effective in detecting the second heart sound and the aortic component of the second heart sound in patients with Ionescu-Shiley aortic valve bioprostheses. It has also some potential for the detection of the first heart sound, the systolic murmur and the diastolic murmur.

Algorithms↗
PubMed1986

Biochemical and biophysical properties of cytochrome o of Azotobacter vinelandii.

Cytochrome o, solubilized from the membrane of Azotobacter vinelandii, has been purified to homogeneity as judged by ultracentrifugation and polyacrylamide gel electrophoresis. The detergent-containing cytochrome o is composed of one polypeptide chain with a molecular weight of 28 000-29 000, associated by polyacrylamide gel electrophoresis in the presence of sodium dodecyl sulfate. The enzyme exists as a dimer by gel filtration analysis. The amino analysis which reveals the majority of residues are of hydrophobic nature. The cytochrome o oxidase contains protoheme as its prosthetic group and about 20-40% of phospholipids. The phospholipids are identified as phosphatidylethanolamine and phosphatidylglycerol by radioautographic analysis using 2-dimensional thin-layer chromatography. No copper or nonheme iron can be detected in the purified oxidase preparation by atomic absorption and chemical analyses. Oxidation-reduction titration shows this membrane-bound cytochrome o to be a low-potential component, and Em was determined to be -18 mV in the purified form and -30 mV in the membrane-bound form. Both forms bind CO with a reduced absorption peak at 559 and 557-558 nm in the native and solubilized forms, respectively. A high-spin (g = 6.0) form is assigned to the oxidized cytochrome o by electron paramagnetic resonance analysis, and KCN abolishes this high-spin signal. CO titration of purified cytochrome o in the anaerobic conditions shows the enzyme binds one CO per four protohemes and a dissociation constant is estimated to be 3.2 microM for CO. Cyanide reacts with purified cytochrome o in both oxidized and CO-bound forms, identified by specific spectral compounds absorbed at the Soret region. Cytochrome c, often co-purified with cytochrome c from the membrane, cannot serve as a reductant for cytochrome o in vitro, due to the apparent potential difference of about 300 mV. Upon separation, both cytochrome o and cytochrome c4 show a great tendency of aggregation. Furthermore, the oxidase activity (measured by tetramethyl-p-phenylenediamine oxidation rate) decreases as the cytochrome c concentration is decreased by ammonium sulfate fractionation. All these suggest the structural and functional complex nature of cytochrome c4 and cytochrome o in the membrane of A. vinelandii.

Azotobacter↗
PubMed1994

Lipid-protein interactions and protein dynamics in vesicles containing the nicotinic acetylcholine receptor: a study with ethanol.

Electron paramagnetic resonance (EPR) spectroscopy was used to study the action of ethanol on the protein side chain motions of the nicotinic acetylcholine receptor (nAcChoR) in alkaline extracted membranes from Torpedo nobiliana. EPR spectra of the nAcChoR derivatized with maleimide spin label contain both strongly and weakly immobilized components. The rotational correlation time of the strongly immobilized component decreases by a factor of 2-3-fold with the addition of 1.6 M ethanol, while that of the weakly immobilized component is not significantly altered. EPR spectroscopy was also used to probe the lipid environment immediately surrounding the nAcChoR with stearic acid and phosphatidylcholine spin labeled at the fourteenth acyl carbons (14-SASL and 14-PCSL, respectively), and the steroid spin label androstanol (ASL). EPR spectra of these probes reveal a component corresponding to lipids that are motionally restricted by the receptor (annular lipids) in addition to a more fluid component arising from bulk lipid. Using spectral subtraction, the order of selectivity of these spin labels for the nAcChoR was determined to be ASL > or = 14-SASL > 14-PCSL. The estimated rotational correlation times of the high affinity 14-SASL and ASL probes ranged from approx. 20 to 35 ns. The correlation times of the lower affinity 14-PCSL were generally shorter than those for 14-SASL and ASL and ranged from about 10 to 25 ns. The addition of up to 0.9 M ethanol altered neither the affinity nor the mobility of the motionally restricted EPR component. This suggests that ethanol's actions on the nAcChoR are not mediated via changes at the lipid/protein interface near the center of the bilayer.

Animals↗
PubMed1986

A deuterium NMR study of labelled n-alkanol anesthetics in a model membrane.

The 2H-NMR spectra of 50 wt.% aqueous multilamellar dispersions of dipalmitoylphosphatidylcholine (DPPC) containing either selectively deuterated 1-decanol (25 mol%) or [2H17]-1-octanol (25 mol%) have been measured as a function of temperature. Both alkanols are potent anesthetics. A detailed carbon-deuterium bond order parameter profile of 1-decanol in liquid crystalline phospholipid dispersions at 50 degrees C was determined from the quadrupolar splittings of 1-decanols deuterated at eight different positions. A maximum order parameter SCD = 0.20 was obtained for [5,5-2H2]-1-decanol, with labels at both ends of the 1-decanol exhibiting reduced order parameters. Explanations for the reduced order towards the hydroxyl group of 1-decanol are discussed in terms of either increased amplitudes of motion or geometric effects due to hydrogen bonding. By comparing the order parameter profile of sn-2 chain deuterated phosphatidylcholine dispersions containing 25 mol% 1-decanol (J.L. Thewalt, S.R. Wassall, H. Gorrissen and R.J. Cushley, Biochim. Biophys. Acta, 817 (1985) 355) with the profile of deuterated 1-decanol in DPPC, we estimate that decanol is approximately parallel to the C-3 to C-13 region of the phosphatidylcholine's sn-2 chain. Variation of the spectral moments M1 with temperature indicates that both 1-decanol and 1-octanol are sensitive to the packing of the lipid in which they are dissolved. Below the phase transition temperature, the 2H-NMR spectra of either 1-decanol (selectively deuterated) or 1-octanol (perdeuterated) are broad powder patterns, characteristic of axially symmetric rotation about the alcohol's long axis. This is in contrast to the 2H-NMR spectra obtained from deuterated phosphatidylcholine under similar conditions, which implies that the phospholipid acyl chain conformations are more restricted than those of the alcohol at these temperatures. From the M1 behavior of the various alkanol chain segments with temperature, the gel to liquid crystalline phase transition is seen to initiate in the middle of the DPPC/1-alkanol bilayer.

Anesthetics↗
PubMed1985

Power spectra for ocular drift and tremor.

Eye position during fixation has been measured without contact and the power spectrum of drift and tremor eye movements has been estimated. In the 0-40 Hz frequency range power declines with frequency roughly as 1/f2. In the 40-100 Hz frequency range the dominant spectral component is a broad spectral peak with a peak amplitude of about 6 arc sec. The shape of the broad spectral peak is dependent on the fixation direction. A model that explains qualitatively the shape of the power spectra function is presented. It is suggested that tremor eye movements are by-products of the clock-like firing of motor neurons.

Eye Movements↗
PubMed1991

Foveal cone detection statistics in color-normals and dichromats.

We measured for six male observers, the psychometric functions for the detection of two simultaneously presented points of light. The test stimuli were two 1 min point sources separated by 17 min arc, and pulsed for 0.5 msec. The stimuli varied in wavelength from 500 to 620 nm. The psychometric functions were fit with a model that assumes ideal detection and the following properties: (1) Poisson-distributed quantal absorptions; (2) binomial sampling of foveal long-wavelength-sensitive (LWS) and middle-wavelength-sensitive (MWS) cones; (3) independent responses of the LWS and MWS cones; and (4) the Smith-Pokorny fundamentals for cone spectral sensitivities. Based on chi 2 fits to the psychometric functions for detecting neither, one or both of the two-point stimuli presented, estimates were derived for the minimum quantal catch by a single cone for detection (C), the number of effective cones illuminated by a point stimulus at threshold (N) and the proportion of central foveal cones of the LWS type (PL). Three observers were color-normal, two were protanopes and one was a deuteranope. A second deuteranope was included in the design but his data were too unreliable for an unambiguous solution. The estimated quantal requirement C was consistently near 5(4-6), and the effective number of illuminated cones always was 1 or 2. The plausible range of PL (98% confidence interval) for the color-normal observers was 0.48-0.68 (observer YY), 0.76-0.90 (observer MW) and 0.77-0.95 (observer DF). The best fitting PL solution for these observers were 0.61, 0.82 and 0.88, respectively. These were comparable to the values obtained from flicker photometric data. The best PL value for each of the protanopes was 0.00 and for the deuteranope the best PL value was 0.98.

Color Perception↗
PubMed1992

Simulation of Doppler ultrasound signals for a laminar, pulsatile, nonuniform flow.

A simulation for Doppler ultrasound quadrature signals from pulsatile, nonuniform flow is presented. It is an extension of an earlier simulation presented by Jones and Giddens (1990a) which was valid for laminar, uniform, steady flow and which included the stochastic characteristics introduced by scattering particles which enter and leave the sample volume at random times. Fourier transform and autoregressive spectral analysis techniques are used to compare the simulated signals to Doppler signals collected from an in vitro flow setup. Power spectra, Doppler frequency estimates and standard deviations of these estimates serve as standards of comparison. Results show that the simulation model generates realistic quadrature signals. The study improves the understanding of the physics of the Doppler process and shows that it can be modeled for complex flow conditions. The input parameters of the simulation are the Doppler instrument parameters and flow characteristics. This allows the simulation to be used for transducer design as well as in the study of the applicability of signal analysis techniques to Doppler ultrasound.

Blood Flow Velocity↗
PubMed1996

31P-magnetic resonance spectroscopy studies of nucleated and non-nucleated erythrocytes; time domain data analysis (VARPRO) incorporating prior knowledge can give information on the binding of ADP.

Human erythrocytes have no nucleus, mitochondria or endoplasmic reticulum, whereas chicken erythrocytes have a nucleus and mitochondria and are closer in internal morphology, to cells such as the hepatocyte. Erythrocytes were used to test the hypothesis that 31P-MRS invisibility of ADP is associated with the presence of intracellular organelles. Simple frequency domain spectral analysis methods showed that all the acid extractable ADP (and ATP) was MR-visible in human erythrocytes. However, such methods gave variable estimates for 31P-NMR spectra of fresh chicken erythrocytes from which no conclusions could be drawn about the MR-visibility of ADP. Only when the data were fitted by a method incorporating prior knowledge of the ATP and ADP peak structure, using the time domain VARPRO method, was it possible to conclude that in fresh chicken erythrocytes, similar to other nucleated cells (liver, muscle), all the acid extractable ADP appeared to be MRS invisible, indicating binding or sequestration by intracellular organelles.

Adenosine Diphosphate↗

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