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At least 811 records · Page 45Linked to original sources
PubMed1989

Spectroscopic characterization of the iron-sulfur cluster in Bacillus subtilis glutamine phosphoribosylpyrophosphate amidotransferase.

The properties of the [4Fe-4S] cluster in glutamine phosphoribosylpyrophosphate amidotransferase from Bacillus subtilis have been investigated using low temperature magnetic circular dichroism, electron paramagnetic resonance (EPR), and resonance Raman spectroscopies. The Raman spectra of the native enzyme in the Fe-S stretching region show a [4Fe-4S]2+ cluster that is structurally very similar to those in simple redox proteins. Photochemical reduction mediated by 5-deazaflavin with oxalate as the electron donor resulted in [4Fe-4S]+ clusters with a mixture of ground state spin multiplicities. Magnetic circular dichroism and EPR studies of samples ranging in concentration from 0.15 to 0.4 mM concur in finding S = 3/2 [4Fe-4S]+ clusters with predominantly axial and positive zero field splitting as the dominant species. The EPR studies also revealed minor contributions from S = 1/2 [4Fe-4S]+ centers and an S = 5/2 species. The latter becomes the dominant component in more concentrated samples (approximately 2 mM), and arguments are presented in favor of assignment to S = 5/2 [4Fe-4S]+ clusters rather than adventitiously bound high spin Fe(III) ions. The concentration-dependent spin state heterogeneity of the [4Fe-4S]+ cluster in glutamine phosphoribosylpyrophosphate amidotransferase is discussed in light of the magnetic and electronic properties of the [4Fe-4S]+ centers in other enzymes and proteins.

Amidophosphoribosyltransferase↗
PubMed1989

The magnetic and electronic properties of Methanobacterium thermoautotrophicum (strain delta H) methyl coenzyme M reductase and its nickel tetrapyrrole cofactor F430. A low temperature magnetic circular dichroism study.

Variable temperature magnetic circular dichroism (MCD) spectroscopy has been used to characterize the magnetic and electronic properties of the Ni(II) tetrapyrrole, F430, which is the cofactor of the S-methyl coenzyme M methylreductase enzyme from Methanobacterium thermoautotrophicum (strain delta H). 4-Coordinate forms are found to be diamagnetic (S = 0 ground state), whereas 6-coordinate forms are paramagnetic (S = 1 ground state). MCD studies, together with parallel low temperature UV-visible absorption and resonance Raman investigations, show that the equilibrium distribution of 4-coordinate square-planar and 6-coordinate bis-aquo forms of the native isomer of F430 in aqueous solution is affected by both temperature and the presence of glycerol. In the presence of 50% glycerol, the 12,13-diepimer of F430 is shown to be partially 6-coordinate in frozen solution at low temperature. Low temperature MCD magnetization data allow the determination of the axial zero-field splitting (D) of the S = 1 ground state of bis-ligand complexes of F430. The value of D is sensitive to the nature of the Ni(II) axial ligands: bis-aquo F430, D = +9 +/- 1 cm-1; bis-imidazole F430, D = -8 +/- 2 cm-1. Measurement of D = +10 +/- 1 cm-1 for F430 in the methylreductase holoenzyme argues strongly against histidine imidazole coordination to Ni(II) in the enzyme. The possible existence of alcoholic or phenolic oxygen-containing ligands (serine, threonine, tyrosine, water) to Ni(II) in the enzyme-bound cofactor is discussed.

Circular Dichroism↗
PubMedDate not supplied

Molecular interactions between nucleic acids and antitumor substances by Raman and NMR spectroscopy.

1-Methyladenosine (1-MeAdo) and protonated 1-Methyladenosine (1-MeAdo.H+) were chosen as a model to study the molecular interactions between the carcinogen dimethylsulphate (DMS) and the base adenine, and the interactions between the antitumoral electrophilic cis-diamminedichlorophatinum (II) (cis-Pt) and the methylation product of the base, respectively. Raman and multinuclear NMR studies show the molecular perturbations caused by the carcinogen on the base and those of the antitumoral substance on the reaction product base-carcinogen.

Adenosine↗
PubMed1994

Heme-heme oxygenase complex. Structure of the catalytic site and its implication for oxygen activation.

Heme oxygenase, a central monooxygenase enzyme of the heme catabolism and the associated generation of carbon monoxide, forms a 1:1 stoichiometric complex with iron protoporphyrin IX, which is a prosthetic active center and at the same time the substrate of the enzyme. By using EPR, resonance Raman, and optical absorption spectroscopic techniques, we have determined the axial ligand coordination of the enzyme-heme complex. The ferric heme iron in the heme-enzyme complex at neutral pH is six-coordinate high spin, while at alkaline pH (pKa 7.6), the complex becomes low spin. Spectra of ferrous forms of the complex indicate that histidine serves as the iron proximal axial ligand and that the residue is in its neutral imidazole rather than its imidazolate protonation state. Thus, the active site of the heme-heme oxygenase complex has a myoglobin-like structure rather than an active site similar to the large cytochrome P-450 class of monooxygenases. As a consequence, the activated form of the heme-heme oxygenase complex, a peroxo intermediate, is different from that of the cytochrome P-450 monooxygenases, in which the activated form is an oxo intermediate. The overall catalytic mechanism is probably more closely related to that of other monooxygenases with myoglobin-like active sites, such as secondary amine monooxygenase.

Animals↗
PubMed2002

Speech synthesis using damped sinusoids.

A speech synthesizer was developed that operates by summing exponentially damped sinusoids at frequencies and amplitudes corresponding to peaks derived from the spectrum envelope of the speech signal. The spectrum analysis begins with the calculation of a smoothed Fourier spectrum. A masking threshold is then computed for each frame as the running average of spectral amplitudes over an 800-Hz window. In a rough simulation of lateral suppression, the running average is then subtracted from the smoothed spectrum (with negative spectral values set to zero), producing a masked spectrum. The signal is resynthesized by summing exponentially damped sinusoids at frequencies corresponding to peaks in the masked spectra. If a periodicity measure indicates that a given analysis frame is voiced, the damped sinusoids are pulsed at a rate corresponding to the measured fundamental period. For unvoiced speech, the damped sinusoids are pulsed on and off at random intervals. A perceptual evaluation of speech produced by the damped sinewave synthesizer showed excellent sentence intelligibility, excellent intelligibility for vowels in /hVd/ syllables, and fair intelligibility for consonants in CV nonsense syllables.

Communication Devices for People with Disabilities↗
PubMed2002

[Landscape pattern analysis based on boundary characteristics].

Through boundary number to the length distribution spectrum analysis, the relationships between boundary number-length and fragmentation of landscape and element were discussed. Landscape pattern indices such as diversity, evenness, heterogeneity, and spatial complicity were calculated based on boundary number and cumulative length, and these indices were compared with those based on element area proportion. The results indicated that the fast urbanization process caused complication of boundary element distribution pattern and simplification of layer structure. The distribution function parameter alpha could reflect landscape fragmentation properly, and the landscape pattern indices based on boundary characteristics was an useful supplement for traditional pattern analysis.

Agriculture↗
PubMed1994

Detection and volume estimation of embolic air in the middle cerebral artery using transcranial Doppler sonography.

BACKGROUND AND PURPOSE: Cerebral embolism has been implicated in the development of cognitive and neurological deficits following bypass surgery. This study proposes methodology for estimating cerebral air embolus volume using transcranial Doppler sonography. METHODS: Transcranial Doppler audio signals of air bubbles in the middle cerebral artery obtained from in vivo experiments were subjected to a fast-Fourier transform analysis. Audio segments when no air was present as well as artifact resulting from electrocautery and sensor movement were also subjected to fast-Fourier transform analysis. Spectra were compared, and frequency and power differences were noted and used for development of audio band-pass filters for isolation of frequencies associated with air emboli. In a bench model of the middle cerebral artery circulation, repetitive injections of various air volumes between 0.5 and 500 microL were made. Transcranial Doppler audio output was band-pass filtered, acquired digitally, then subjected to a fast-Fourier transform power spectrum analysis and power spectrum integration. A linear least-squares correlation was performed on the data. RESULTS: Fast-Fourier transform analysis of audio segments indicated that frequencies between 250 and 500 Hz are consistently dominant in the spectrum when air emboli are present. Background frequencies appear to be below 240 Hz, and artifact resulting from sensor movement and electrocautery appears to be below 300 Hz. Data from the middle cerebral artery model filtered through a 307- to 450-Hz band-pass filter yielded a linear relation between emboli volume and the integrated value of the power spectrum near 40 microL. Detection of emboli less than 0.5 microL was inconsistent, and embolus volumes greater than 40 microL were indistinguishable from one another. CONCLUSIONS: The preliminary technique described in this study may represent a starting point from which automated detection and volume estimation of cerebral emboli might be approached.

Animals↗
PubMed1997

[Spectral analysis of R-R intervals in adolesent persons during mental stress].

In this study, power spectrum analysis of the autoregressive model was used to quantitatively estimate the power spectrum of R-R intervals in adolesent during the state of the mental stress. The power spectrum density of the lower frequency (HF: 0.05-0.15 Hz) and the high frequency (HF: 0.15-0.5 Hz) component were acquired. The results showed that during the mental stress the HF component decreased significantly (P < 0.001) while the LF component increased relatively and the center frequency of the HF increased remarkably (P < 0.001). This suggests that the spectral analysis of heart rate variability (R-R interval) offers an efficient non-invasive method to assess the autonomic nerve activity of cardiovascular system during the stress condition.

Adult↗
PubMed2006

The role of different EMG methods in evaluating myopathy.

For the diagnosis of myopathy, EMG may have an important role along with blood tests, muscle biopsies and genetic testing. This review evaluates different EMG methods in the diagnosis of myopathy. These include manual analysis of individual motor unit potentials and multi-motor unit potential analysis sampled at weak effort. At high effort, turns-amplitude analyses such as the cloud analysis and the peak ratio analysis have a high diagnostic yield. The EMG can seldom be used to differentiate between different types of myopathy. In the channelopathies, myotonia, exercise test and cooling of the muscle are helpful. Macro-EMG, single-fibre EMG and muscle fibre conduction velocity analysis have a limited role in myopathy, but provide information about the changes seen. Analysis of the firing rate of motor units, power spectrum analysis, as well as multichannel surface EMG may have diagnostic potential in the future. EMG is of great importance in the diagnosing of patients with myopathy, preferably a needle electrode and quantitative analyses should be used. A combination of a method at weak effort as well as a method at stronger effort seems optimal.

Electromyography↗
PubMed2005

Photoinduced nitric oxide release from nitrobenzene derivatives.

A new type of photoinduced nitric oxide (NO) donors was designed from nitrobenzene derivatives. Visible-light irradiation of 2,6-dimethylnitrobenzenes bearing extended pi-electron systems at the 4-position revealed efficient NO release using ESR analysis and the Griess assay. Computational study and ultraviolet spectrum analysis suggested that the NO-releasing activity was closely related to the conformation of the nitro group, the absorption intensity, and the length of the conjugated pi-electron system. Employing the photodependent cytotoxicity of compound 14 against HCT116 human colon cancer cells, it was demonstrated that 4-substituted-2,6-dimethylnitrobenzene analogues are useful NO donors for the time- and site-controlled NO treatment.

Cell Line, Tumor↗
PubMed2004

Linear and nonlinear approaches to the analysis of R-R interval variability.

Analysis techniques derived from linear and non-linear dynamics systems theory qualify and quantify physiological signal variability. Both clinicians and researchers use physiological signals in their scopes of practice. The clinician monitors patients with signal-analysis technology, and the researcher analyzes physiological data with signal-analysis techniques. Understanding the theoretical basis for analyzing physiological signals within one's scope of practice ensures proper interpretation of the relationship between physiolgical function and signal variability. This article explains the concepts of linear and nonlinear signal analysis and illustrates these concepts with descriptions of power spectrum analysis and recurrence quantification analysis. This article also briefly describes the relevance of these 2 techniques to R-to-R wave interval (i.e., heart rate variability) signal analysis and demonstrates their application to R-to-R wave interval data obtained from an isolated rat heart model.

Animals↗
PubMedDate not supplied

Power spectral analysis of auditory brainstem responses and MRI findings in patients with spinocerebellar degeneration.

Power spectrum analysis of auditory brainstem responses (ABR) and magnetic resonance imaging (MRI) findings were obtained from 14 patients, 9 with olivopontocerebellar atrophy (OPCA; Dejerine-Thomas type) and 5 with Holmes-type cerebello-olivary degeneration, and compared to data from normal controls. The power spectrum was divided into three components according to frequency: up to 400 Hz (slow component); from 400 to 800 Hz (middle component); and 800 to 3,000 Hz (fast component). In patients with OPCA, the slow component appeared significantly less often than in both groups, normal controls (p < 0.0005) and patients with Holmes-type degeneration (p < 0.005), and the middle component appeared significantly more often than in both groups (p < 0.0005). There was a significant positive correlation between the proportion of the slow component and midbrain diameter (p = 0.04) and a significant negative correlation between the proportion of the fast component and midbrain diameter (p = 0.02). We conclude that the power spectrum differs between OPCA and Holmes-type degeneration, and that the proportion of each component of the power spectrum is related to midbrain volume.

Adult↗
PubMed2001

Fluidity of the myelin sheath in the peripheral nerves of diabetic rats.

In the present study we examined the structural integrity of the myelin sheath in the peripheral nerves from short-term streptozotocin (STZ)-treated diabetic rats, using ESR spectroscopy as a tool in determining the dynamic state and the structure of the myelin lipid phase. Experiments were performed on spin-labeled sciatic and sural nerves from STZ-treated Hannover-Wistar rats and age-matched controls. The spectrum analysis employed a numerical simulation model with the set of fitting parameters that in the same time relate the ESR line shape and structure and dynamics of the probed environment. The simulation considered three spectral components weighted and summed in the composite spectrum. The comparative analysis of results showed the fraction of the spectral component II to be significantly increased in the spectra of diabetic rats, indicating the significant increase in overall fluidity of the myelin structure. The origin of fluidity changes was further investigated using an experimental model for demyelination (local injection of ethidium bromide in vivo), proteolytic action of trypsin in vitro, and osmotic myelin swelling in vitro. Analysis and comparison of the results suggested a conclusion in terms of changed biophysical properties of the myelin lipid phase in peripheral nerves in the pathology of diabetes.

Animals↗
PubMed1981

An assessment of spectral analysis of amphetamine-induced behavior.

Testing of a new radio frequency capacitance field type transducer and power spectrum analysis system for assessment of rat behavior is described. Power spectrum estimates of amphetamine-induced behavior had an orderly relationship with behavior ratings ranging from inactive to intense stereotypy. The effects of thorazine dose-response blocking on amphetamine-induced behavior were linear. Separation between adjacent doses could not be accomplished with a single frequency, but required differential frequency-time period information.

Amphetamine↗
PubMed2002

Determination of Behcet disease with the application of FFT and AR methods.

In this study, Doppler signals recorded from ophthalmic artery of 86 patients were processed by personal computer using fast Fourier transform, Burg autoregressive (AR), and least-squares AR methods. By using these spectrum analysis techniques, the variations in the shape of the Doppler spectrums as a function of time were presented in the form of sonograms in order to obtain medical information. These sonograms were then used to compare the applied methods in terms of their frequency resolution and the effects in determination of Behcet disease.

Adult↗
PubMed1998

Pooled analysis of p53 mutations in hematological malignancies.

A computerized database is described that contains information about 507 mutations in the p53 gene of hematologic tumors and corresponding cell lines. Analysis of these mutations indicated the following findings: First, mutational spectrum analysis in these tumors was found to be similar to the pattern found for other solid tumors. However, when the patterns of base substitutions were examined separately according to the types of hematologic malignancies, followed by subgroup analysis, notable differences (in some cases of statistical significance) emerged. Second, mutational pattern analysis indicates that about 48% of base substitutions in hematologic tumors are suspected to be associated with carcinogen exposure. Third, deletions and insertions are localized mainly to exons 5-8 and repeated DNA sequences. However, the unusual profile of variations in frequency within each type of tumor suggests that, in addition to endogenous damage to template DNA, there is the factor of exposure to environmental physical and chemical carcinogens/mutagens. Fourth, p53 protein alterations analysis indicate that most of the changes in the amino acids are "semiconservative," presumably in order to avoid disrupting the structure of the p53 monomer. Consistent with this notion, structural mutations are more conservative than the binding mutations. Finally, molecular mechanisms that lead to p53 mutations, etiological factors that play a role in their formation, and the pathophysiological significance of consequent p53 protein alterations are discussed.

Amino Acid Substitution↗
PubMed2003

Determination of stenosis and occlusion in arteries with the application of FFT, AR, and ARMA methods.

Doppler ultrasound is a noninvasive technique that allows the examination of the direction, velocity, and volume of blood flow. Therefore, Doppler ultrasonography is known as reliable technique, which demonstrates the flow characteristics and resistance of arteries in various vascular disease. In this study, arterial Doppler signals recorded from 105 subjects were processed by PC-computer using fast Fourier transform, Burg autoregressive, and least squares modified Yule-Walker autoregressive moving average methods. Doppler power spectrums of arterial Doppler signals were obtained by using these spectrum analysis techniques. The variations in the shape of the Doppler power spectrums as a function of time were presented in the form of sonograms in order to obtain medical information. These sonograms were then used to compare the applied methods in terms of their frequency resolution and the effects in determination of stenosis and occlusion in arteries. Reliable information on hemodynamic alterations in arteries can be obtained by evaluation of these sonograms.

Blood Flow Velocity↗