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At least 253 records · Page 14Linked to original sources

PubMed2006

Ab initio study of the role of entropy in the kinetics of acetylene production in filament-assisted diamond growth environments.

We present a new theoretical strategy, ab initio rate constants plus integration of rate equations, that is used to characterize the role of entropy in driving high-temperature/low-pressure hydrocarbon chemical kinetics typical of filament-assisted diamond growth environments. Twelve elementary processes were analyzed that produce a viable pathway for converting methane in a feed gas to acetylene. These calculations clearly relate the kinetics of this conversion to the properties of individual species, demonstrating that (1) loss of translational entropy restricts addition of hydrogen (and other radical species) to unsaturated carbon-carbon bonds, (2) rotational entropy determines the direction of the rate-limiting abstraction reactions, and (3) the overall pathway is enhanced by high beta-scission reaction rates driven by translational entropy. These results suggest that the proposed strategy is likely applicable to understand gas-phase chemistry occurring in the systems of combustion and other chemical vapor depositions.

Alkynes↗

PubMed1998

A molar entropy model of age differences in spatial memory.

Two very-short-term-memory, spatial scanning aging experiments were conducted involving a graphics character as a target stimulus. On the probe portion of a trial, the stimulus was presented in the same position as it was on the target portion of the trial (i.e., a same trial) 50% of the time. However, on the remaining 50% of the trials, the probe stimulus was shifted (or transposed) 1, 2, or 3 positions to the right or left of the original presentation (target) position. In Experiment 1, exposure duration was manipulated. In Experiment 2, the number of potential target display positions was manipulated. For both experiments, older adults showed larger transposition distance effects than younger adults for errors. In the past (e.g., P.A. Allen, 1990, 1991), this effect has been attributed to higher levels of internal noise (entropy) in older than younger adults. This research provides converging operations to this contention by using statistical physics methods to rigorously compute the entropy in a molar neural network across age groups. After successfully fitting the statistical mechanics model to the data, the model is proved to have external validity by fitting a simplified version of it to an earlier spatial memory aging experiment reported by P. R. Bruce and J. F. Herman (1986). The results of both traditional reaction time and error rate analyses, as well as the entropy modeling analyses, indicated that older adults exhibited higher levels of entropy than did the younger adults and that this effect appeared to be generalized across processing stage.

Adolescent↗

PubMed2004

Environmental swap energy and role of configurational entropy in transfer of small molecules from water into alkanes.

We studied the effect of segmented solvent molecules on the free energy of transfer of small molecules from water into alkanes (hexane, heptane, octane, decane, dodecane, tetradecane, and hexadecane). For these alkanes we measured partition coefficients of benzene, 3-methylindole (3MI), 2,3,4,6-tetrachlorophenol (TeCP), and 2,4,6-tribromophenol (TriBP) at 3, 11, 20, 33 [corrected], and 47 degrees C. For 3MI, TeCP, and TriBP the dependence of free energy of transfer on length of alkane chains was found to be very different from that for benzene. In contrast to benzene, the energy of transfer for 3MI, TeCP, and TriBP was independent of the number of carbons in alkanes. To interpret data, we used the classic Flory-Huggins (FH) theory of concentrated polymer solutions for the alkane phase. For benzene, the measured dependence of energy of transfer on the number of carbons in alkanes agreed well with predictions based on FH model in which the size of alkane segments was obtained from the ratio of molar volumes of alkanes and the solute. We show that for benzene, the energy of transfer can be divided into two components, one called environmental swap energy (ESE), and one representing the contribution of configurational entropy of alkane chains. For 3MI, TeCP, and TriBP the contribution of configurational entropy was not measurable even though the magnitude of the effect predicted from the FH model for short chain alkanes was as much as 20 times greater than experimental uncertainties. From the temperature dependence of ESE we obtained enthalpy and entropy of transfer for benzene, 3MI, TeCP, and TriBP. Experimental results are discussed in terms of a thermodynamic cycle considering creation of cavity, insertion of solute, and activation of solute-medium attractive interactions. Our results suggest that correcting experimental free energy of transfer by Flory-Huggins configurational entropy term is not generally appropriate and cannot be applied indiscriminately.

Alkanes↗

PubMed2004

Entropy production and thermodynamics of nonequilibrium stationary states: a point of view.

Entropy might be a not well defined concept if the system can undergo transformations involving stationary nonequilibria. It might be analogous to the heat content (once called "caloric") in transformations that are not isochoric (i.e., which involve mechanical work): it could be just a quantity that can be transferred or created, like heat in equilibrium. The text first reviews the philosophy behind a recently proposed definition of entropy production in nonequilibrium stationary systems. A detailed technical attempt at defining the entropy of a stationary states via their variational properties follows: the unsatisfactory aspects of the results add arguments in favor of the nonexistence of a function of state to be identified with entropy; at the same time new aspects and properties of the phase space contraction emerge.

Entropy↗

PubMed2002

Entropy, visual diversity, and preference.

The author reports relationships between subjective impressions of visual diversity or pleasure with statistical entropies of stimuli. The stimuli were 34 rows of houses that varied in color, scale, and shape, or in shape and articulation. Entropies ranged from 0.0 to 5.6 bits. Fifty-seven participants rated the stimuli on scales of pleasant/unpleasant and uniform/diverse. The relationship between rated diversity and entropy was strong and linear. The relationship between rated pleasure and entropy was either linear or asymptotic, but no evidence was found for an inverted U relationship.

Adult↗

PubMedDate not supplied

Age differences in entropy: primary versus secondary memory.

We report a spatial-memory scanning experiment that was used to measure age differences in entropy. A target grid consisting of four adjacent letters followed by the presentation of a single probe letter was presented on each trial. Half of the trials presented the probe stimulus in the same spatial position was the target letter (i.e., the probe letter was always a member of the positive set), and half of the trials transposed the target letter one, two, or three spaces of the right or left of the original target display position (i.e., different trials). The experiment involved blocks of primary-memory and secondary-memory tasks. Reaction-time and error-rate data, as well as entropy analyses and the fitting of an entropy model (based on Allen, Kaufman, Smith, and Propper, in press) to the empirical data indicated that older adults showed higher entropy levels than young adults. These results are interpreted in a "computational temperature" framework in which older adults' higher computational temperatures result in less efficient spatial, episodic memory functioning.

Adolescent↗

PubMed2006

A method for finding optimal rna secondary structures using a new entropy model (vsfold).

We are developing a program to calculate optimal RNA secondary structures. The model uses di-nucleotide pairing energies as with most traditional approaches. However, for long-range entropy interactions, the approach uses an entropy-loss model based on the accumulated sum of the entropy of bonding between each base-pair weighted inversely by the correlation of the RNA sequence (the Kuhn length). Stiff RNA forms very different structures from flexible RNA. The results demonstrate that the long-range folding is largely governed by this entropy and the Kuhn length.

Entropy↗

PubMed1996

Minimum cross-entropy reconstruction of PET images using prior anatomical information.

An algorithm is presented for the reconstruction of PET images using prior anatomical information derived from MR images of the same subject. The cross-entropy or Kullback-Leiber distance is a measure of dissimilarity between two images. We propose to reconstruct PET images by minimizing a weighted sum of two cross-entropy terms. The first is the cross-entropy between the measured emission data and the forward projection of the current estimate of the PET image. Minimizing this term alone is equivalent to the ML-EM reconstruction. The second term is the cross-entropy between the current estimate of the PET image and a prior image model which incorporates anatomical information derived from registered MR images. A weighting parameter determines the relative emphasis given to the emission data and the prior model in the reconstruction. Details of this algorithm are presented as well as test reconstructions for real and simulated data. The performance of the algorithm was evaluated with respect to errors in prior anatomical information. The algorithm provided significant improvement in the quality of reconstructed images as compared with the ML-EM reconstruction technique. The reconstructed images had higher resolution as compared with the images obtained from MAP-like reconstructions which do not utilize anatomical information. The algorithm displayed robustness with respect to errors in prior anatomical information.

Algorithms↗

PubMed2003

Correlation of approximate entropy, bispectral index, and spectral edge frequency 95 (SEF95) with clinical signs of "anesthetic depth" during coadministration of propofol and remifentanil.

BACKGROUND: Several studies relating electroencephalogram parameter values to clinical endpoints using a single (mostly hypnotic) drug at relatively low levels of central nervous system depression (sedation) have been published. However, the usefulness of a parameter derived from the electroencephalogram for clinical anesthesia largely depends on its ability to predict the response to stimuli of different intensity or painfulness under a combination of a hypnotic and an (opioid) analgesic. This study was designed to evaluate the predictive performance of spectral edge frequency 95 (SEF95), BIS, and approximate entropy for the response to increasingly intense stimuli under different concentrations of both propofol and remifentanil in the therapeutic range. METHODS: Ten healthy male and ten healthy female volunteers were studied during coadministration of propofol and remifentanil. After having maintained a specific target concentration for 10 min, the depth of sedation-anesthesia was assessed using the responsiveness component of the Observer's Assessment of Alertness/Sedation (OAA/S) rating scale, which was modified by adding insertion of a laryngeal mask and laryngoscopy. The electroencephalogram derived parameters approximate entropy, bispectral index, and SEF95 were recorded just before sedation level was assessed. RESULTS: The prediction probability values for approximate entropy were slightly, but not significantly, better than those for bispectral index, SEF95, and the combination of drug concentrations. A much lower prediction ability was observed for tolerance of airway manipulation than for hypnotic endpoints. CONCLUSION: Approximate entropy revealed informations on hypnotic and analgesic endpoints using coadministration of propofol and remifentanil comparable to bispectral index, SEF95, and the combination of drug concentrations.

Adult↗

PubMed2004

Spectral entropy as an electroencephalographic measure of anesthetic drug effect: a comparison with bispectral index and processed midlatency auditory evoked response.

BACKGROUND: The authors compared the behavior of two calculations of electroencephalographic spectral entropy, state entropy (SE) and response entropy (RE), with the A-Line ARX Index (AAI) and the Bispectral Index (BIS) and as measures of anesthetic drug effect. They compared the measures for baseline variability, burst suppression, and prediction probability. They also developed pharmacodynamic models relating SE, RE, AAI, and BIS to the calculated propofol effect-site concentration (Ceprop). METHODS: With institutional review board approval, the authors studied 10 patients. All patients received 50 mg/min propofol until either burst suppression greater than 80% or mean arterial pressure less than 50 mmHg was observed. SE, RE, AAI, and BIS were continuously recorded. Ceprop was calculated from the propofol infusion profile. Baseline variability, prediction of burst suppression, prediction probability, and Spearman rank correlation were calculated for SE, RE, AAI, and BIS. The relations between Ceprop and the electroencephalographic measures of drug effect were estimated using nonlinear mixed effect modeling. RESULTS: Baseline variability was lowest when using SE and RE. Burst suppression was most accurately detected by spectral entropy. Prediction probability and individualized Spearman rank correlation were highest for BIS and lowest for SE. Nonlinear mixed effect modeling generated reasonable models relating all four measures to Ceprop. CONCLUSIONS: Compared with BIS and AAI, both SE and RE seem to be useful electroencephalographic measures of anesthetic drug effect, with low baseline variability and accurate burst suppression prediction. The ability of the measures to predict Ceprop was best for BIS.

Adolescent↗

PubMed2004

Comparative evaluation of the Datex-Ohmeda S/5 Entropy Module and the Bispectral Index monitor during propofol-remifentanil anesthesia.

BACKGROUND: Different analytical concepts were introduced to quantify the changes of the electroencephalogram. The Datex-Ohmeda S/5 Entropy Module (Datex-Ohmeda Division, Instrumentarium Corp., Helsinki, Finland) was the first commercial monitor based on the entropy generating two indices, the state entropy (SE) and the response entropy (RE). The aim of the current study was to compare the accuracy of SE and RE with the Bispectral Index(R) monitor (BIS(R); Aspect Medical Systems, Newton, MA) during propofol-remifentanil anesthesia. METHODS: The authors investigated 20 female patients during minor gynecologic surgery. SE, RE, BIS, mean arterial blood pressure, heart rate, and sedation level were recorded every 20 s during stepwise increase (target-controlled infusion, 0.5 microg/ml) of propofol until the patients lost response. Five minutes after loss of response, remifentanil infusion (0.4 microg . kg(-1) . min(-1)) was started. Spearman correlation coefficient and prediction probability were calculated for sedation levels with SE, RE, BIS, mean arterial blood pressure, and heart rate. The ability of the investigated parameters to distinguish between the anesthesia steps awake versus loss of response, awake versus anesthesia, anesthesia versus first reaction, and anesthesia versus extubation was analyzed with the prediction probability. RESULTS: SE correlates best with sedation levels, but no significant differences of the prediction probability values among SE, RE, and BIS were found. The prediction probability for all investigated steps of anesthesia did not show significant differences among SE, RE, and BIS. SE, RE, and BIS were superior to mean arterial blood pressure and heart rate. CONCLUSION: SE, RE, and BIS revealed similar information about the level of sedation and allowed the authors to distinguish between different steps of anesthesia. Both monitors provided useful additional information for the anesthesiologist.

Acoustic Stimulation↗

PubMed1997

The total entropy for evaluating 31P-magnetic resonance spectra of the liver in healthy volunteers and patients with metastases.

RATIONALE AND OBJECTIVES: The authors describe the clinical status of liver tissue with only a single numerical quantity (total entropy) derived from spectroscopic data of 31P-magnetic resonance (MR) spectra. METHODS: Twenty-four patients with liver metastases and 20 volunteers were investigated with image-guided volume selective 31P-MR spectroscopy on a 1.5-T whole body scanner. From each in vivo 31P-MR spectrum, the ratios of phosphomonoester (PME)/beta-adenosine triphosphate (ATP), inorganic phosphate (Pi)/beta-ATP and phosphodiester (PDE)/ beta-ATP and the total entropy (H*) were calculated. Mean values and standard deviations were determined and significance of the differences were tested with Student's t test. RESULTS: For patients, the H* = 4.7 +/- 4.3, PME/beta-ATP 0.72 +/- 0.28, Pi/beta-ATP = 1.00 +/- 0.39, PDE/beta-ATP = 1.68 +/- 0.59. For the volunteers, H* = 7.6 +/- 2.5, PME/beta-ATP = 0.39 +/- 0.15, Pi/beta-ATP = 0.90 +/- 0.19, PDE/beta-ATP = 1.25 +/- 0.28. The total entropy of patients' spectra showed significantly lower values compared with those of volunteers. PME/beta-ATP and PDE/beta-ATP of the patients increased and differed significantly from volunteer data. CONCLUSIONS: It was demonstrated that the results of in vivo 31P-MR spectroscopy may be described with a single criterion by means of the total entropy.

Adenosine Triphosphate↗

PubMed2006

Bispectral index and spectral entropy in neuroanesthesia.

Spectral Entropy (SpEn) is an alternative tool to the bispectral index (BIS) for monitoring depth of hypnosis. SpEn measures response entropy (RE) and state entropy (SE). This open-label prospective study was designed to evaluate SpEn and BIS in 20 patients undergoing elective supratentorial neurosurgery with craniotomy and resection of brain tumors. SpEn and BIS were obtained continuously by Datex Ohmeda M-entropy module S/5 (Helsinki, Finland) and Aspect Medical System BIS (Newton), respectively. Total intravenous anesthesia was performed in all patients by Fresenius Vial infusion system (Brezins, France) to maintain a plasma concentration of propofol of 2.5 to 5 microg mL(-1) and sufentanil of 0.2 to 0.4 etag mL(-1). SpEn, BIS, the estimated propofol effect-site concentrations (Ce), the mean arterial pressure (MAP), and the heart rate (HR) were recorded during 12 specific events: induction of anesthesia, patient stop counting, loss of blinking reflex, intubation, mayfield pinning, craniotomy, termination of propofol infusion, recovery of blinking reflex, coughing, limb movement, order execution, and extubation. Stated that prediction probability or P(K) represents an indicator probability to predict correctly the rank order of an arbitrary pair of distinct observed indices of depth of hypnosis (ie, clinical settings and SpEn indices, or BIS, Ce, MAP, HR), PK of BIS, SE, RE, and Ce provided a better depth of hypnosis than MAP and HR; RE being the best for rapidity, SE for sensitivity, and BIS for specificity. There is good correlation between the 3 hypnosis indices and Ce. This study demonstrates that SpEn provides a reproducible hypnosis index for patients undergoing supratentorial neurosurgical procedures.

Adolescent↗

PubMed2004

Gradient-based manipulation of nonparametric entropy estimates.

This paper derives a family of differential learning rules that optimize the Shannon entropy at the output of an adaptive system via kernel density estimation. In contrast to parametric formulations of entropy, this nonparametric approach assumes no particular functional form of the output density. We address problems associated with quantized data and finite sample size, and implement efficient maximum likelihood techniques for optimizing the regularizer. We also develop a normalized entropy estimate that is invariant with respect to affine transformations, facilitating optimization of the shape, rather than the scale, of the output density. Kernel density estimates are smooth and differentiable; this makes the derived entropy estimates amenable to manipulation by gradient descent. The resulting weight updates are surprisingly simple and efficient learning rules that operate on pairs of input samples. They can be tuned for data-limited or memory-limited situations, or modified to give a fully online implementation.

Algorithms↗

PubMed2007

Comparison of skin conductance with entropy during intubation, tetanic stimulation and emergence from general anaesthesia.

BACKGROUND: The number of skin conductance fluctuations (NSCF) expresses sympathetic skin nerve activity. The response entropy (RE) measures electromyographic and electroencephalographic activity in the forehead. The state entropy (SE) measures mainly electroencephalographic activity. When the suppression of frontal muscular activity is complete, RE is equal to SE. RE-Delta is defined as SE minus RE. The purposes of this study were to examine whether NSCF and RE-Delta correlate with signs of clinical stress during intubation and tetanic noxious stimulation and to elucidate how rapidly and accurately entropy and NSCF react during emergence from general anaesthesia. METHODS: Twenty women scheduled for gynaecological laparotomy were studied. During intubation in remifentanil and propofol general anaesthesia, NSCF and RE-Delta were correlated with the clinical stress score. After a wash-out period, two series of tetanic stimuli were given, the first with (R+) and the second without (R-) remifentanil infusion. The tetanic pre-stimuli periods were compared with the tetanic post-stimuli periods, and R+ was compared with R-. During emergence, the responses of entropy and skin conductance were related to the time of extubation. RESULTS: NSCF correlated well with the clinical stress score during intubation (r(2)= 0.73, P < 0.0005). RE-Delta showed a weaker correlation (r(2)= 0.33, P= 0.007). During tetanic stimuli, the NSCF pre-stimuli level was lower than the post-stimuli level (P < 0.001), and the NSCF R+ response was lower than the NSCF R- response (P= 0.002). RE-Delta did not show similar differences. During emergence, RE reacted before NSCF and SE (P= 0.003). CONCLUSION: NSCF was better than RE-Delta for the measurement of clinical stress during intubation, and was sensitive to tetanic stimuli at different opioid analgesic levels, by contrast with RE-Delta. Both modalities were able to predict emergence at the end of anaesthesia, but RE was more rapid.

Adult↗

PubMed2004

Conditional entropy as an indicator of pleomorphism in astrocytic tumors.

The entropies of nuclear arrangements as an indicator of pleomorphism are assessed using a morphometric method. Sixty astrocytic tumors (grades I, II, III and IV; 15 cases each) were reviewed and analyzed. All slides were stained with HE and MIB-1 antibody. The MIB-1 labeling index (LI) was assessed by counting nuclei under a microscope. Images of HE-stained slides were digitized and segmented using the watershed algorithm. Then, six nuclear parameters were measured automatically: (i) the number of total nuclei in the image, (ii) percentage of total nuclear area in the image, (iii) the mean area of the nucleus, (iv) the standard deviation of the area of the nucleus, (v) the entropy of nuclear arrangement (Entropysimple), and (vi) conditional entropy of nuclear arrangement (Entropyconditional). Entropysimple was defined according to the area of the nucleus and Entropyconditional was defined according to both the area of the nucleus and the area of its neighboring nuclei. Image processing and image analysis were performed with public domain software developed in the laboratory. Segmentation of the images resulted in inappropriate segmentation in a few percent of the images. The measurements obtained for each parameter were classified using discriminant analysis. The percentage of correct classification with Entropyconditional was 62%, which was the highest value among all the measurements. Classification based on the combination of all measurements resulted in a rate of correct classification of 88%. Thus, conditional entropy of nuclear arrangement is useful for grading of astrocytic tumors and it is proposed as an indicator of pleomorphism.

Astrocytoma↗

PubMed2004

Flow-induced endothelial surface reorganization and minimization of entropy generation rate.

Effects of hydrodynamic shear on the shape of the endothelial surface are examined based on evaluations of the rate of entropy generation at the cell surface. A linear solution of the flow over a sinusoidally varying endothelial surface is used to evaluate the entropy generation rate on the cell surface for which measured cell dimensions are available. Both the local rate of entropy generation (equivalent to the rate of energy dissipation by viscous shear) at the peak of a cell and the total entropy generation rate over the cell surface are minimized under conditions of a constant cell surface area and a constant cell peak height; which yields horizontal cell dimensions that are close to those obtained experimentally.

Animals↗

PubMed2003

Entropy learning and relevance criteria for neural network pruning.

In this paper, entropy is a term used in the learning phase of a neural network. As learning progresses, more hidden nodes get into saturation. The early creation of such hidden nodes may impair generalisation. Hence an entropy approach is proposed to dampen the early creation of such nodes by using a new computation called entropy cycle. Entropy learning also helps to increase the importance of relevant nodes while dampening the less important nodes. At the end of learning, the less important nodes can then be pruned to reduce the memory requirements of the neural network.

Algorithms↗