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Estimation of unconjugated, conjugated, and "delta" bilirubin fractions in serum by use of two coated thin films.

We used two coated thin films to measure the concentrations of unconjugated, conjugated, and total bilirubin as well as bilirubin covalently bound to albumin ("delta" bilirubin) in more than 400 serum samples. We measured the unconjugated and conjugated species by determining their reflection densities at two wavelengths (400 and 460 nm) on a coating designed for the enhanced spectral measurement of bilirubin but which does not register the delta form. Total bilirubin was measured by use of a diazo-based thin film (Clin Chem 29: 37-41, 1983). We estimated the concentration of delta bilirubin by subtracting the sum of unconjugated and conjugated bilirubin from the concentration of total bilirubin. All measurements agree well with those by comparative methods, as shown by linear regression. Slopes ranged from 0.92 to 1.02, correlation coefficients from 0.935 and 0.998. Linear combinations of these values can also be used to compute other results; e.g., the sum of conjugated and delta bilirubin can be considered to be an estimate of "direct"-reacting bilirubin.

Autoanalysis↗

Time-frequency representation of the electrogastrogram--application of the exponential distribution.

The aim of this paper was to examine the applicability of the exponential distribution for the time-frequency representation of the electrogastrogram (EGG). The EGG is a noninvasive measurement of the electrical activity of the stomach by placing electrodes on the abdominal skin. Quantitative analysis of the EGG has relied on spectral methods. The normal frequency of the EGG in humans is 3 cycles/min. Electrical dysrhythmia observed in the EGG is associated with motor disorders of the stomach. The exponential distribution was applied in this work for the estimation of EGG frequency and the detection of dysrhythmia in the EGG. A series of computer simulations was conducted, demonstrating the reliability of the exponential distribution in the analysis of nonstationary electrical signals of the stomach. Applications of the exponential distribution in the spectral analysis of typical EGG's were presented. The results showed that there is a great potential for the use of the exponential distribution in EGG analysis.

Computer Simulation↗

Correlation between computed tomography and voltage and current source density spectral EEG parameters in patients with brain lesions.

In a group of patients with space-occupying brain lesions, CT measurements were correlated with absolute power (AP) and relative power (RP) of the delta, theta, alpha and beta EEG bands, calculated from the raw EEG potentials (EEGp) and from the Laplacian estimates also called "current source densities" (CSD). Rank correlations were calculated between the number of abnormal values in each band and the following CT measures: volume of the lesion and of the edema, density of the edema, percentage of ventricular collapse and midline shift. Abnormal spectral values are those which are significantly higher than the norm for the same age, in the delta and theta bands, and significantly lower in the alpha and beta bands. Spectral parameters obtained from the CSD showed higher correlations with CT measures than those calculated from the EEGp. In the Laplacian, all CT measures had a significant correlation with delta AP. Theta AP was significantly correlated with the volume and density of the edema, as well as with midline shift. Significant correlations were also observed with delta and alpha RP. However, changes in RP were considered to be a consequence of the increase in delta AP. Canonical correlation analyses between AP and RP calculated from EEGp or CSD and the first 3 CT measures showed that the volume of the lesion was only correlated with delta AP and RP. The volume and density of the edema showed a significant correlation with delta, theta and alpha AP calculated from EEGp and only with theta and alpha AP in the Laplacian. Since the EEGp tends to produce a more extensive and diffuse picture of abnormality, whereas the Laplacian acts as a spatial filter emphasizing local sources over distant sources, we concluded that edema is related not to delta activity, but to the theta and alpha power.

Adolescent↗

Comparison between color Doppler cineloop- and conventional spectral Doppler-derived maximum velocity and flow in the umbilical vein.

OBJECTIVE: To compare the umbilical venous flow velocity derived from color Doppler cineloop recordings with that derived from conventional spectral Doppler in normal pregnancies. METHOD: In 18 uncomplicated pregnancies between 19 and 39 weeks' gestation, color Doppler was used to find the maximum velocity in the cross-sectional vessel area of a free-floating loop of the umbilical vein. The maximum velocity was determined using the software tool HDI_Lab (Philips Medical Systems) after tracing the vessel area of interest. Conventional spectral Doppler was then used to determine the maximum velocity with the High-Q machine option. The cross-sectional area of the umbilical vein was determined using B-mode imaging and was subsequently used to determine the umbilical volume flow from both Doppler methods. Assuming a parabolic flow profile in the umbilical vein, the mean velocity is equal to half the maximum velocity. The fetal weight was estimated from fetal biometry using the four-parameter Hadlock formula. RESULTS: Maximum velocity was significantly (P = 0.003) higher with color Doppler cineloop (14.3 +/- 2.5 cm/s) compared with spectral Doppler (12.7 +/- 3.2 cm/s). Therefore, using the same cross-sectional area for both methods, the umbilical blood flow was significantly higher (P = 0.001) with color Doppler cineloop (127.9 +/- 59.0 mL/min) than it was with spectral Doppler (112.8 +/- 54.1 mL/min). The umbilical blood flow expressed as volume flow per kg fetal weight was significantly (P = 0.01) higher with color Doppler cineloop (126.0 +/- 57.0 mL/min/kg) than it was with spectral Doppler (115.0 +/- 53.0 mL/min/kg). CONCLUSIONS: Umbilical venous flow velocity derived from color Doppler cineloops is approximately 10% higher than that derived from spectral Doppler-derived velocity. The reduced angle dependence of the color Doppler cineloop technique and the large sampling area of the cross-sectional vessel should allow better determination of the correct maximum velocity in the umbilical vein.

Blood Flow Velocity↗

Chemical investigation of Titan and Triton tholins.

We report chromatographic and spectroscopic analyses of both Titan and Triton tholins, organic solids made from the plasma irradiation of 0.9:0.1 and 0.999:0.001 N2/CH4 gas mixtures, respectively. The lower CH4 mixing ratio leads to a nitrogen-richer tholin (N/C > 1), probably including nitrogen heterocyclic compounds. Unlike Titan tholin, bulk Triton tholin is poor in nitriles. From high-pressure liquid chromatography, ultraviolet and infrared spectroscopy, and molecular weight estimation by gel filtration chromatography, we conclude that (1) several H2O-soluble fractions, each with distinct UV and IR spectral signatures, are present, (2) these fractions are not identical in the two tholins, (3) the H2O-soluble fractions of Titan tholins do not contain significant amounts of nitriles, despite the major role of nitriles in bulk Titan tholin, and (4) the H2O-soluble fractions of both tholins are mainly molecules containing about 10 to 50 (C + N) atoms. We report yields of amino acids upon hydrolysis of Titan and Triton tholins. Titan tholin is largely insoluble in the putative hydrocarbon lakes or oceans on Titan, but can yield the H2O-soluble species investigated here upon contact with transient (e.g., impact-generated) liquid water.

Amino Acids↗

Fitting of one ARMA model to multiple trials increases the time resolution of instantaneous coherence.

This study presents a least mean squares (LMS) algorithm for the ensemble modeling of a multivariate ARMA process. Generally, an LMS algorithm makes possible the tracking of parameters for nonstationary time series. Our estimation incorporates multiple process observations that improve the accuracy of the parameter estimation. As a consequence, the estimation sequences come close to the true model parameters with a fast adaptation speed. This advantage also holds true of spectral quantities (e.g., the momentary coherence), which are derived from the model parameters. Thus the extension of the ARMA fitting from one to multiple trajectories allows the investigation of nonstationary biological signals with an increased time resolution. The applicability of the algorithm is demonstrated for event-related EEG coherence analysis of the Sternberg task. The changing interaction between posterior association cortex and anterior brain area was shown for verbal and nonverbal stimuli by means of the time-variant theta coherence.

Electroencephalography↗

Multivariate time series discrimination in the spectral domain.

Multivariate time series discrimination for evoked potentials from two cognitively different populations is discussed. A method for constructing linear and quadratic discriminant functions in the spectral domain using a stepwise frequency selection procedure is described and applied. Further, the effects of rank transformations on the estimated nonerror rates are examined. Finally, the validity of the signal plus stationary noise model (SSN) is examined. The performance of the SSN model is compared with the performance of a model (SNN) which consists of a signal plus nonstationary noise and a model (Mix) which consists of mixtures of subpopulations.

Evoked Potentials, Visual↗

Detection and evolution of rhythmic components in ictal EEG using short segment spectra and discriminant analysis.

An automated method for analysis of ictal EEG is described which aims to reliably detect one or several rhythmic components in short EEG segments (2 sec) and to display their presence, frequency, amplitude, location, and temporal evolution. Spectra were estimated and compared using fast Fourier transform (FFT) and autoregressive modelling (AR). A subsequent linear discriminant analysis decided whether a spectral peak is likely to be caused by rhythmic activity or by the inherent statistical variability. FFT was found to perform better than AR in the detection of rhythmic components, yielding a false-positive rate of 0.825%, a false-negative rate of 2% (signal to noise ratio -4.6 dB), a frequency resolution of 2 Hz, and a temporal resolution of 0.5 sec. Seizure analysis revealed that the ictal scalp EEG of even short seizures can show a complex evolution of rhythmic patterns which are impossible or difficult to recognize by visual inspection or conventional spectral analysis. The following phenomena are demonstrated: superposition of two rhythmic components suggesting two cerebral regions discharging simultaneously and independently with their own pacemakers, sudden and gradual change of frequencies, and gradual development of harmonic frequencies. It is suggested that a more precise correlation between rhythmic generators and seizure symptomatology might allow more predictable pharmacological responses in antiepileptic therapy.

Adult↗

Doppler developments in the last quinquennium.

The major advances which have taken place during the last five years in the development of ultrasonic Doppler devices and methods of Doppler signal analysis are reviewed. The following aspects of instrumentation are considered: crossed beam Doppler systems, range measuring Doppler systems, duplex systems, flow mapping systems, transducers and measurements of system performance. Analytical methods are discussed in the following categories: waveform analysis, including the extraction of single-value waveforms and their applications to the diagnosis of vascular disease; spectral analysis, including the derivation of frequency spectra and their application in the study of blood flow; and volume flow estimation. It is concluded that it is likely to be in the study of the information in Doppler frequency spectra, two-dimensional real-time Doppler images and in the measurement of blood flow volume that most progress will be made.

Blood Volume Determination↗

Spectral deconvolution and operational use of stripping ratios in airborne radiometrics.

Spectral deconvolution using stripping ratios for a set of pre-defined energy windows is the simplest means of reducing the most important part of gamma-ray spectral information. In this way, the effective interferences between the measured peaks are removed, leading, through a calibration, to clear estimates of radionuclide inventory. While laboratory measurements of stripping ratios are relatively easy to acquire, with detectors placed above small-scale calibration pads of known radionuclide concentrations, the extrapolation to measurements at altitudes where airborne survey detectors are used bring difficulties such as air-path attenuation and greater uncertainties in knowing ground level inventories. Stripping ratios are altitude dependent, and laboratory measurements using various absorbers to simulate the air-path have been used with some success. Full-scale measurements from an aircraft require a suitable location where radionuclide concentrations vary little over the field of view of the detector (which may be hundreds of metres). Monte Carlo simulations offer the potential of full-scale reproduction of gamma-ray transport and detection mechanisms. Investigations have been made to evaluate stripping ratios using experimental and Monte Carlo methods.

Air Pollution, Radioactive↗

An NMR shielding model for protons above the plane of a carbonyl group.

Covalently bonded hydrogen nuclei located over the plane of a carbonyl group in a strong magnetic field experience magnetic shielding (or deshielding) that results from the combined effect of the magnetic anisotropy of the carbon-oxygen double bond and various other intramolecular shielding effects. GIAO-HF in Gaussian 98 was employed to calculate isotropic shielding values and to predict the net proton NMR shielding increment for a simple model system: the proximate proton of methane held in various positions over formaldehyde. The net shielding increments of the proximate proton of methane, plotted against its Cartesian coordinates relative to the center of the carbon-oxygen double bond, led to the development of a single empirical equation for predicting the NMR shielding experienced by a covalently bonded proton over the plane of a carbonyl group. The predictive capability of this equation has been validated by calculating the shielding increments of protons over the plane of a carbonyl group in known structures, using this as a correction to the chemical shift estimated by subtituent effects and comparing the result to experimentally observed chemical shifts. Shielding is predicted by this equation for protons located in the region from over the center of the carbon-oxygen double bond to beyond the carbon atom; deshielding is predicted for protons located above and beyond the oxygen atom. This prediction differs from those made by the long-held "shielding cone" model found in nearly every textbook on NMR, but is consistent with experimental observations. The algorithm for predicting the shielding increment for a proton over a carbonyl group can be used in a spreadsheet or incorporated into software that estimates chemical shifts using additive substituent constants or a database of structures. Its use can improve the accuracy of the estimated chemical shift of a proton in the vicinity of a carbon-oxygen double bond, and thus assist in spectral assignments and in correct structure determination.

Anisotropy↗

An algorithm for predicting proton nuclear magnetic resonance deshielding over a carbon-carbon double bond.

Hydrogen nuclei located over a carbon-carbon double bond in a strong magnetic field experience NMR shielding effects that result from the magnetic anisotropy of the nearby double bond and various other intramolecular shielding effects. We have used GIAO, a subroutine in Gaussian 98, to calculate isotropic shielding values and to predict the proton NMR shielding increment for a simple model system: methane held in various orientations, positions, and distances over ethene. The average proton NMR shielding increments of several orientations of methane have been plotted versus the Cartesian coordinates of the methane protons relative to the center of ethene. A single empirical equation for predicting the NMR shielding experienced by protons over a carbon-carbon double bond has been developed from these data. The predictive capability of this equation has been validated by comparing the shielding increments for several alkenes calculated using our equation to the experimentally observed shielding increments. This equation predicts the NMR shielding effects more accurately than previous models that were based on fewer geometries of methane over ethene. In fact, deshielding is predicted by this equation for protons over the center and within about 3 A of a carbon-carbon double bond. This result is in sharp contrast to predictions made by the long-held McConnell "shielding cone" model found in nearly every textbook on NMR, but is consistent with experimental observations. The algorithm for predicting the (de)shielding increment for a proton over an alkene can be used in a spreadsheet on a PC or incorporated into software that estimates chemical shifts using additive substituent constants or a database of structures. In either application its use can substantially improve the accuracy of the estimated chemical shift of a proton in the vicinity of a carbon-carbon double bond, and thus assist in spectral assignments and in correct structure determination.

Algorithms↗

Comparative study on the chromophore binding sites of rod and red-sensitive cone visual pigments by use of synthetic retinal isomers and analogues.

A comparative study on the chromophore (retinal) binding sites of the opsin (R-photopsin) from chicken red-sensitive cone visual pigment (iodopsin) and that scotopsin) from bovine rod pigment (rhodopsin) was made by the aid of geometric isomers of retinal (all-trans, 13-cis, 11-cis, 9-cis, and 7-cis) and retinal analogues including fluorinated (14-F, 12-F, 10-F, and 8-F) and methylated (12-methyl) 11-cis-retinals. The stereoselectivity of R-photopsin for the retinal isomers and analogues was almost identical with that of scotopsin, indicating that the shapes of the chromophore binding sites of both opsins are similar, although the former appears to be somewhat more restricted than the latter. The rates of pigment formation from R-photopsin were considerably greater than those from scotopsin. In addition, all the iodopsin isomers and analogues were more susceptible to hydroxylamine than were the rhodopsin ones. These observations suggest that the retinal binding site of iodopsin is located near the protein surface. On the basis of the spectral properties of fluorinated analogues, a polar group in the chromophore binding site of iodopsin as well as rhodopsin was estimated to be located near the hydrogen atom at the C10 position of the retinylidene chromophore. A large difference in wavelength between the absorption maxima of iodopsin and rhodopsin was significantly reduced in the 9-cis and 7-cis pigments. On the assumption that the retinylidene chromophore is anchored rigidly at the alpha-carbon of the lysine residue and loosely at the cyclohexenyl ring, each of the two isomers would have the Schiff-base nitrogen at a position altered from that of the 11-cis pigments.(ABSTRACT TRUNCATED AT 250 WORDS)

Animals↗

The Valence-Detrapping Phase Transition in a Crystal of the Mixed-Valence Trinuclear Iron Cyanoacetate Complex [Fe(3)O(O(2)CCH(2)CN)(6)(H(2)O)(3)].

A mixed-valence trinuclear iron cyanoacetate complex, [Fe(3)O(O(2)CCH(2)CN)(6)(H(2)O)(3)] (1), was prepared, and the nature of the electron-detrapping phase transition was studied by a multitemperature single-crystal X-ray structure determination (296, 135, and 100 K) and calorimetry by comparison with an isostructural mixed-metal complex, [CoFe(2)O(O(2)CCH(2)CN)(6)(H(2)O)(3)] (2). The mixed-valence states at various temperatures were also determined by (57)Fe Mössbauer spectroscopy. The Mössbauer spectrum of 1 showed a valence-detrapped state at room temperature. With decreasing temperature the spectrum was abruptly transformed into a valence-trapped state around 129 K, well corresponding to the heat-capacity anomaly due to the phase transition (T(trs) = 128.2 K) observed in the calorimetry. The single-crystal X-ray structure determination revealed that 1 has an equilateral structure at 296 and 135 K, and that the structure changes into an isosceles one at 100 K due to the electron trapping. The crystal system of 1 at 296 K is rhombohedral, space group R&thremacr; with Z = 6 and a = 20.026(1) Å, c = 12.292(2) Å; at 135 K, a = 19.965(3) Å, c = 12.145(4) Å; and at 100 K, the crystal system changes into triclinic system, space group P&onemacr;, with Z = 2 and a = 12.094(2) Å, b = 12.182(3) Å, c = 12.208(3) Å, alpha = 110.04(2) degrees, beta = 108.71(2) degrees, gamma = 109.59(2) degrees. The X-ray structure determination at 100 K suggests that the electronically trapped phase of 1 at low temperature is an antiferroelectrically ordered phase, because the distorted Fe(3)O molecules, which are expected to possess a nonzero electronic dipole moment, oriented alternatively in the opposite direction with respect to the center of symmetry. On the other hand, no heat-capacity anomaly was observed in 2 between 7 and 300 K, and X-ray structure determination indicated that 2 shows no structure change when the temperature is decreased from 296 K down to 102 K. The crystal system of 2 at 296 K is rhombohedral, space group R&thremacr; with Z = 6 and a = 19.999(1) Å, c = 12.259(1) Å; at 102 K, a = 19.915(2) Å, c = 12.061(1) Å. Even at 102 K the CoFe(2)O complex still has a C(3) axis, and the three metal ion sites are crystallographically equivalent because of a static positional disorder of two Fe(III) ions and one Co(II) ion. The activation energy of intramolecular electron transfer of 1 in the high-temperature disordered phase was estimated to be 3.99 kJ mol(-)(1) from the temperature dependence of the Mössbauer spectra with the aid of the spectral simulation including the relaxation effect of intramolecular electron transfer. Finally the phase-transition mechanism of 1 was discussed in connection with the intermolecular dielectric interaction.

Journal Article↗

Shoulder posture and localized muscle fatigue and discomfort.

In many industries workers perform manual assembly tasks with hands postured above the shoulders. Awkward shoulder and arm postures are often viewed as acceptable given costs of workplace modification, postural exertions which are in compliance with current design recommendations, ready availability of strong workers, and numbers of electromyographic studies which fail to detect significant signs of localized muscle fatigue (LMF). An experiment was conducted to: (a) study the onset and severity of (LMF) in the shoulder when performing a stylus-to-hole Fitts reciprocal movement task under a range of postures, hand loads, ratios of work-to-rest, and task durations, and (b) to evaluate the efficacy of three techniques (i.e., changes in EMG behaviour, postural tremor, and cross-modal matching estimates) in detecting and monitoring posturally-based LMF and discomfort in the shoulder complex. Experimental findings showed that posturing hands above shoulder level significantly increased the risk of LMF and postural discomfort even in light-weight manual assembly environs where postural exertions are small, and that cross-modal matching estimates and postural tremor were more sensitive metrics of LMF in the shoulder complex than EMG RMS voltage and mean spectral power frequency metrics. The basis for experimental findings, as well as potential application of LMF metrics in future postural stress investigations, are discussed. Recommendations for workplace posture are provided for job designers facing work height decisions in manual assembly environs.

Adult↗

Traceable calibration of ultraviolet meters used with broadband, extended sources.

A calibration system has been developed to provide increased accuracy in the measurement of the irradiance responsivity appropriate for UV meters used with broadband, extended sources of the type employed in phototherapy. The single wavelength responsivity of the test meter is obtained in the wavelength range 250-400 nm by intercomparison with a transfer standard meter in a narrow, monochromatic beam. Traceability to primary standard irradiance scales is provided via the National Measurement System with a best uncertainty of 7% (at 95% confidence). The effective responsivity of the test meter, when used with broadband extended sources, is calculated using the measured spectral and angular response of the meter and tabulated data on the spectral and spatial characteristics of the source radiance. The uncertainty in the effective responsivity, independent of the source variability, is estimated to be 10% (at 95% confidence). The advantages of this calibration system over existing approaches are discussed.

Calibration↗

Dissecting fluctuating selection: A unified population and quantitative genetics framework.

One of the longstanding debates in evolutionary biology is the effect of fluctuating selection on genetic changes in populations. However, the extent to which these periodic forces influence organisms at both genomic and phenotypic levels remains unclear. Despite the compelling evidence of fluctuating selection from recent studies, there is a disconnect between empirical and theoretical findings concerning the underlying mechanisms due to the limited evidence regarding the scale and processes that generate genome-wide oscillations. This study aims to elucidate how both genetic factors (e.g. heritability, number of causative loci) and ecological factors (e.g. season length, the difference in the phenotypic optima between seasons, population size dynamics) drive fluctuating selection and to identify the parameters that produce consistent oscillatory patterns. We developed a modeling framework integrating quantitative and population genetics to simulate a population under various selection regimes. We applied spectral analysis to detect periodicity, indicating cyclical selective environments. Our simulations highlight the conditions sustaining oscillations in allele frequencies over time. Spectral analysis successfully identifies the periodic patterns from allele frequency trajectories, even under highly complex selection regimes. Not only does our study clarify the conditions that yield oscillatory behaviors, but these parameters can also potentially be estimated in natural populations, providing a possibility of empirically testing these models.

Fluctuating selection↗

Representations of the long-term spectra of speech.

Numerous and somewhat different representations of the long-term spectra of speech are available in the literature. Various estimates of speech spectra have been converted to a consistent audiogram format for presentation here. Even so, plots of speech spectral levels across the frequency region of 125 to 8000 Hz vary considerably. Bases for some of these variations and clinical utilization of a speech spectrum are discussed.

Auditory Threshold↗