Configurational entropy of glueball states
Bernardini, Alex E.; Braga, Nelson R. F.; da Rocha, Roldão
2017-02-01
The configurational entropy of glueball states is calculated using a holographic description. Glueball states are represented by a supergravity dual picture, consisting of a 5-dimensional graviton-dilaton action of a dynamical holographic AdS/QCD model. The configurational entropy is studied as a function of the glueball spin and of the mass, providing information about the stability of the glueball states.
Configuration entropy of fractal landscapes
Rodríguez‐Iturbe, Ignacio; D'Odorico, Paolo; Rinaldo, Andrea
1998-01-01
.... The spatial arrangement of two‐dimensional images is found to be an effective way to characterize fractal landscapes and the configurational entropy of these arrangements imposes demanding conditions for models attempting to represent these fields.
Absolute configuration of isovouacapenol C
Hoong-Kun Fun
2010-08-01
Full Text Available The title compound, C27H34O5 {systematic name: (4aR,5R,6R,6aS,7R,11aS,11bR-4a,6-dihydroxy-4,4,7,11b-tetramethyl-1,2,3,4,4a,5,6,6a,7,11,11a,11b-dodecahydrophenanthro[3,2-b]furan-5-yl benzoate}, is a cassane furanoditerpene, which was isolated from the roots of Caesalpinia pulcherrima. The three cyclohexane rings are trans fused: two of these are in chair conformations with the third in a twisted half-chair conformation, whereas the furan ring is almost planar (r.m.s. deviation = 0.003 Å. An intramolecular C—H...O interaction generates an S(6 ring. The absolute configurations of the stereogenic centres at positions 4a, 5, 6, 6a, 7, 11a and 11b are R, R, R, S, R, S and R, respectively. In the crystal, molecules are linked into infinite chains along [010] by O—H...O hydrogen bonds. C...O [3.306 (2–3.347 (2 Å] short contacts and C—H...π interactions also occur.
Configurational entropy in brane-world models
Correa, R. A. C., E-mail: fis04132@gmail.com [CCNH, Universidade Federal do ABC, 09210-580, Santo André, SP (Brazil); Rocha, Roldão da, E-mail: roldao.rocha@ufabc.edu.br [CMCC, Universidade Federal do ABC, 09210-580, Santo André, SP (Brazil); International School for Advanced Studies (SISSA), Via Bonomea 265, 34136, Trieste (Italy)
2015-11-02
In this work we investigate the entropic information on thick brane-world scenarios and its consequences. The brane-world entropic information is studied for the sine-Gordon model and hence the brane-world entropic information measure is shown to be an accurate way for providing the most suitable range for the bulk AdS curvature, in particular from the informational content of physical solutions. Besides, the brane-world configurational entropy is employed to demonstrate a high organisational degree in the structure of the configuration of the system, for large values of a parameter of the sine-Gordon model but the one related to the AdS curvature. The Gleiser and Stamatopoulos procedure is finally applied in order to achieve a precise correlation between the energy of the system and the brane-world configurational entropy.
Configurational entropy in brane-world models
Correa, R.A.C. [CCNH, Universidade Federal do ABC, Santo Andre, SP (Brazil); Rocha, Roldao da [CMCC, Universidade Federal do ABC, Santo Andre, SP (Brazil); International School for Advanced Studies (SISSA), Trieste (Italy)
2015-11-15
In this work we investigate the entropic information on thick brane-world scenarios and its consequences. The brane-world entropic information is studied for the sine-Gordon model and hence the brane-world entropic information measure is shown to be an accurate way for providing the most suitable range for the bulk AdS curvature, in particular from the informational content of physical solutions. Besides, the brane-world configurational entropy is employed to demonstrate a high organisational degree in the structure of the configuration of the system, for large values of a parameter of the sine-Gordon model but the one related to the AdS curvature. The Gleiser and Stamatopoulos procedure is finally applied in order to achieve a precise correlation between the energy of the system and the brane-world configurational entropy. (orig.)
Configurational entropy in brane-world models
Correa, R. A. C.; da Rocha, Roldão
2015-11-01
In this work we investigate the entropic information on thick brane-world scenarios and its consequences. The brane-world entropic information is studied for the sine-Gordon model and hence the brane-world entropic information measure is shown to be an accurate way for providing the most suitable range for the bulk AdS curvature, in particular from the informational content of physical solutions. Besides, the brane-world configurational entropy is employed to demonstrate a high organisational degree in the structure of the configuration of the system, for large values of a parameter of the sine-Gordon model but the one related to the AdS curvature. The Gleiser and Stamatopoulos procedure is finally applied in order to achieve a precise correlation between the energy of the system and the brane-world configurational entropy.
Total Synthesis and Absolute Configuration of the Marine Norditerpenoid Xestenone
Hiroaki Miyaoka
2009-11-01
Full Text Available Xestenone is a marine norditerpenoid found in the northeastern Pacific sponge Xestospongia vanilla. The relative configuration of C-3 and C-7 in xestenone was determined by NOESY spectral analysis. However the relative configuration of C-12 and the absolute configuration of this compound were not determined. The authors have now achieved the total synthesis of xestenone using their developed one-pot synthesis of cyclopentane derivatives employing allyl phenyl sulfone and an epoxy iodide as a key step. The relative and absolute configurations of xestenone were thus successfully determined by this synthesis.
Configurational entropy of anti-de Sitter black holes
Braga, Nelson R. F.; da Rocha, Roldão
2017-04-01
Recent studies indicate that the configurational entropy is an useful tool to investigate the stability and (or) the relative dominance of states for diverse physical systems. Recent examples comprise the connection between the variation of this quantity and the relative fraction of light mesons and glueballs observed in hadronic processes. Here we develop a technique for defining a configurational entropy for an AdS-Schwarzschild black hole. The achieved result corroborates consistency with the Hawking-Page phase transition. Namely, the dominance of the black hole configurational entropy will be shown to increase with the temperature. In order to verify the consistency of the new procedure developed here, we also consider the case of black holes in flat space-time. For such a black hole, it is known that evaporation leads to instability. The configurational entropy obtained for the flat space case is thoroughly consistent with the physical expectation. In fact, we show that the smaller the black holes, the more unstable they are. So, the configurational entropy furnishes a reliable measure for stability of black holes.
Does the configurational entropy of polydisperse particles exist?
Ozawa, Misaki; Berthier, Ludovic
2017-01-07
Classical particle systems characterized by continuous size polydispersity, such as colloidal materials, are not straightforwardly described using statistical mechanics, since fundamental issues may arise from particle distinguishability. Because the mixing entropy in such systems is divergent in the thermodynamic limit, we show that the configurational entropy estimated from standard computational approaches to characterize glassy states also diverges. This reasoning would suggest that polydisperse materials cannot undergo a glass transition, in contradiction to experiments. We explain that this argument stems from the confusion between configurations in phase space and states defined by free energy minima, and propose a simple method to compute a finite and physically meaningful configurational entropy in continuously polydisperse systems. Physically, the proposed approach relies on an effective description of the system as an M(*)-component system with a finite M(*), for which finite mixing and configurational entropies are obtained. We show how to directly determine M(*) from computer simulations in a range of glass-forming models with different size polydispersities, characterized by hard and soft interparticle interactions, and by additive and non-additive interactions. Our approach provides consistent results in all cases and demonstrates that the configurational entropy of polydisperse system exists, is finite, and can be quantitatively estimated.
Confirmation of the absolute configuration of (−)-aurantioclavine
Behenna, Douglas C.
2011-04-01
We confirm our previous assignment of the absolute configuration of (-)-aurantioclavine as 7R by crystallographically characterizing an advanced 3-bromoindole intermediate reported in our previous synthesis. This analysis also provides additional support for our model of enantioinduction in the palladium(II)-catalyzed oxidative kinetic resolution of secondary alcohols. © 2010 Elsevier Ltd. All rights reserved.
Absolute configuration and antiprotozoal activity of minquartynoic acid
Rasmussen, H B; Christensen, Søren Brøgger; Kvist, L P;
2000-01-01
Minquartynoic acid (1) was isolated as an antimalarial and antileishmanial constituent of the Peruvian tree Minquartia guianensis and its absolute configuration at C-17 established to be (+)-S through conversion to the known (+)-(S)-17-hydroxystearic acid (2) and confirmed using Mosher's method....
Absolute configurations of zingiberenols isolated from ginger (Zingiber officinale) rhizomes
The sesquiterpene alcohol zingiberenol, or 1,10-bisaboladien-3-ol, was isolated some time ago from ginger, Zingiber officinale, rhizomes, but its absolute configuration had not been determined. With three chiral centers present in the molecule, zingiberenol can exist in eight stereoisomeric forms. ...
Absolute configuration assignment of (+)-fluralaner using vibrational circular dichroism.
Kong, John; Joyce, Leo A; Liu, Jinchu; Jarrell, Tiffany M; Culberson, J Chris; Sherer, Edward C
2017-10-05
The absolute configurations of the separated enantiomers of fluralaner, a racemic animal health product used to prevent fleas and ticks, have been assigned using vibrational circular dichroism (VCD). The crystallographic structure of the active enantiomer (+)-fluralaner has previously been shown to have the (S) configuration using small molecule crystallography. We sought a faster analytical method to determine the absolute configuration of the separated enantiomers. When comparing the measured IR (infrared) and VCD spectra, it is apparent that the amide carbonyl groups appear in the IR but are nearly absent in the VCD. Computational work to calculate the VCD and IR using in vacuo models, implicit solvation, and explicitly solvated complexes has implicated conformational averaging of the carbonyl VCD intensities. © 2017 Wiley Periodicals, Inc.
Configurational entropy of charged AdS black holes
Lee, Chong Oh
2017-09-01
When we consider charged AdS black holes in higher dimensional spacetime and a molecule number density along coexistence curves is numerically extended to higher dimensional cases. It is found that a number density difference of a small and large black holes decrease as a total dimension grows up. In particular, we find that a configurational entropy is a concave function of a reduced temperature and reaches a maximum value at a critical (second-order phase transition) point. Furthermore, the bigger a total dimension becomes, the more concave function in a configurational entropy while the more convex function in a reduced pressure.
The Role of Configurational Entropy in Amorphous Systems
Kirsten A. Graeser
2010-05-01
Full Text Available Configurational entropy is an important parameter in amorphous systems. It is involved in the thermodynamic considerations, plays an important role in the molecular mobility calculations through its appearance in the Adam-Gibbs equation and provides information on the solubility increase of an amorphous form compared to its crystalline counterpart. This paper presents a calorimetric method which enables the scientist to quickly determine the values for the configurational entropy at any temperature and obtain the maximum of information from these measurements.
On determining absolute entropy without quantum theory or the third law of thermodynamics
Steane, Andrew M.
2016-04-01
We employ classical thermodynamics to gain information about absolute entropy, without recourse to statistical methods, quantum mechanics or the third law of thermodynamics. The Gibbs-Duhem equation yields various simple methods to determine the absolute entropy of a fluid. We also study the entropy of an ideal gas and the ionization of a plasma in thermal equilibrium. A single measurement of the degree of ionization can be used to determine an unknown constant in the entropy equation, and thus determine the absolute entropy of a gas. It follows from all these examples that the value of entropy at absolute zero temperature does not need to be assigned by postulate, but can be deduced empirically.
A Probabilistic Description of the Configurational Entropy of Mixing
Jorge Garcés
2014-05-01
Full Text Available This work presents a formalism to calculate the configurational entropy of mixing based on the identification of non-interacting atomic complexes in the mixture and the calculation of their respective probabilities, instead of computing the number of atomic configurations in a lattice. The methodology is applied in order to develop a general analytical expression for the configurational entropy of mixing of interstitial solutions. The expression is valid for any interstitial concentration, is suitable for the treatment of interstitial short-range order (SRO and can be applied to tetrahedral or octahedral interstitial solutions in any crystal lattice. The effect of the SRO of H on the structural properties of the Nb-H and bcc Zr-H solid solutions is studied using an accurate description of the configurational entropy. The methodology can also be applied to systems with no translational symmetry, such as liquids and amorphous materials. An expression for the configurational entropy of a granular system composed by equal sized hard spheres is deduced.
Configurational entropy of hydrogen-disordered ice polymorphs
Herrero, Carlos P
2014-01-01
The configurational entropy of several H-disordered ice polymorphs is calculated by means of a thermodynamic integration along a path between a totally H-disordered state and one fulfilling the Bernal-Fowler ice rules. A Monte Carlo procedure based on a simple energy model is used, so that the employed thermodynamic path drives the system from high temperatures to the low-temperature limit. This method turns out to be precise enough to give reliable values for the configurational entropy of different ice phases in the thermodynamic limit (number of molecules N --> infinity). The precision of the method is checked for the ice model on a two-dimensional square lattice. Results for the configurational entropy are given for H-disordered arrangements on several polymorphs, including ices Ih, Ic, II, III, IV, V, VI, and XII. The highest and lowest entropy values correspond to ices VI and XII, respectively, with a difference of 3.3\\% between them. The dependence of the entropy on the ice structures has been rational...
Absolute configuration of labdane diterpenoids from Physalis nicandroides.
Maldonado, Emma; Pérez-Castorena, Ana L; Romero, Yunuen; Martínez, Mahinda
2015-02-27
A mixture of the new epimeric labdenetriols 1 and 2 was isolated from the aerial parts of Physalis nicandroides. The structures of 1 and 2, including their absolute configurations, were established by analyses of their spectroscopic data, together with the X-ray diffraction analysis of acetonide 3 and chemical correlation with (-)-(13E)-labd-13-ene-8α,15-diol (6), whose absolute configuration was also confirmed by X-ray analysis of its dibromo derivative 7. The epimeric labdenediols 8 and 9, the known labdanes 6 and 11, and the acylsucroses 12 and 13 were also isolated. Labdanes 6 and 11 showed moderate anti-inflammatory activities in the induced ear edema model.
Enantiomers of a nonylphenol isomer: absolute configurations and estrogenic potencies.
Zhang, Haifeng; Oppel, Iris M; Spiteller, Michael; Guenther, Klaus; Boehmler, Gabriele; Zuehlke, Sebastian
2009-02-01
Enantiomers of 4-(1,1,2-trimethylhexyl)phenol, a chiral isomer of the endocrine disrupting chemical nonylphenol, have been resolved and isolated by preparative chiral HPLC. The absolute configurations of the enantiomers were then determined by an X-ray crystallographic study of the (-)-camphanoyl derivative of the first eluted enantiomer NP(35)E1. The first enantiomer (NP(35)E1) and the second enantiomer (NP(35)E2) eluted were found to have the S and R absolute configurations, respectively. The estrogenic potencies of the S and R enantiomers were tested by the E-screen assay. A slight difference was observed in the relative proliferative effect between the S enantiomer and R enantiomer in the E-screen assay.
Absolute configuration of novel bioactive flavonoids from Tephrosia purpurea.
Chang, L C; Chávez, D; Song, L L; Farnsworth, N R; Pezzuto, J M; Kinghorn, A D
2000-02-24
[structure: see text] Three novel flavonoids, (+)-tephrorins A (1) and B (2) and (+)-tephrosone (3), were isolated from Tephrosia purpurea. Their structures were elucidated by NMR spectral analysis, and their absolute configurations were determined by Mosher ester methodology. Compounds 1 and 2 are flavanones containing an unusual tetrahydrofuran moiety. Compounds 1-3 were evaluated for their potential cancer chemopreventive properties using a cell-based quinone reductase induction assay.
Absolute configuration determination using enantiomeric pairs of molecularly imprinted polymers.
Meador, Danielle S; Spivak, David A
2014-03-07
A new method for determination of absolute configuration (AC) is demonstrated using an enantiomeric pair of molecularly imprinted polymers, referred to as "DuoMIPs". The ratio of HPLC capacity factors (k') for the analyte on each of the DuoMIPs is defined as the γ factor and can be used to determine AC when above 1.2. A mnemonic based on the complementary binding geometry of the DuoMIPs was used to aid in understanding and prediction of AC.
Configurational entropy in f(R,T) brane models
Correa, R.A.C. [Universidade Federal do ABC, CCNH, Santo Andre, Sao Paulo (Brazil); Moraes, P.H.R.S. [ITA, Instituto Tecnologico de Aeronautica, Sao Jose dos Campos, Sao Paulo (Brazil)
2016-02-15
In this work we investigate generalized theories of gravity in the so-called configurational entropy (CE) context. We show, by means of this information-theoretical measure, that a stricter bound on the parameter of f(R, T) brane models arises from the CE. We find that these bounds are characterized by a valley region in the CE profile, where the entropy is minimal. We argue that the CE measure can play a new role and might be an important additional approach to selecting parameters in modified theories of gravitation. (orig.)
Toni Eger
2015-12-01
Full Text Available The present paper analyzes numerically the entropy generation induced by forced convection in a canonical configuration. The configuration itself includes two well known fluid dynamic problems: (1 an external flow (flow around a cylinder, Kármán flow; and (2 an internal flow (flow between two concentric rotating cylinders, Couette flow. In many daily engineering issues (e.g., cooling of electric machines, a combination of these problems occurs and has to be investigated. Using the canonical configuration, the fields of entropy generation are analyzed in this work for a constant wall heat flux but varying two key parameters (Reynolds numbers Re∞ and Re0. The entropy generation due to conduction shows an absolute minimum around Re0 = 10,000. The same minima can be found by a detailed analysis of the temperature profile. Thus, entropy generation seems to be a suitable indicator for optimizing heat exchange processes and delivers a large amount of information concerning fluid and heat transport.
Configurational Information as Potentially Negative Entropy: The Triple Helix Model
Loet Leydesdorff
2008-10-01
Full Text Available Configurational information is generated when three or more sources of variance interact. The variations not only disturb each other relationally, but by selecting upon each other, they are also positioned in a configuration. A configuration can be stabilized and/or globalized. Different stabilizations can be considered as second-order variation, and globalization as a second-order selection. The positive manifestations and the negative selections operate upon one another by adding and reducing uncertainty, respectively. Reduction of uncertainty in a configuration can be measured in bits of information. The variables can also be considered as dimensions of the probabilistic entropy in the system(s under study. The configurational information then provides us with a measure of synergy within a complex system. For example, the knowledge base of an economy can be considered as such a synergy in the otherwise virtual (that is, fourth dimension of a regime
Configurational Information as Potentially Negative Entropy: The Triple Helix Model
Leydesdorff, Loet
2008-12-01
Configurational information is generated when three or more sources of variance interact. The variations not only disturb each other relationally, but by selecting upon each other, they are also positioned in a configuration. A configuration can be stabilized and/or globalized. Different stabilizations can be considered as second-order variation, and globalization as a second-order selection. The positive manifestations and the negative selections operate upon one another by adding and reducing uncertainty, respectively. Reduction of uncertainty in a configuration can be measured in bits of information. The variables can also be considered as dimensions of the probabilistic entropy in the system(s) under study. The configurational information then provides us with a measure of synergy within a complex system. For example, the knowledge base of an economy can be considered as such a synergy in the otherwise virtual (that is, fourth) dimension of a regime
Lassen, Peter Rygaard
2005-01-01
The absolute configuration of the norlignan (+)-nyasol was determined to be S by comparison of the experimental vibrational circular dichroism data with first-principle calculations taking into account the eight lowest energy conformations. The established absolute configuration of (+)-nyasol...
Lassen, Peter Rygaard
2005-01-01
The absolute configuration of the norlignan (+)-nyasol was determined to be S by comparison of the experimental vibrational circular dichroism data with first-principle calculations taking into account the eight lowest energy conformations. The established absolute configuration of (+)-nyasol...
The viscosity of planetary tholeiitic melts: A configurational entropy model
Sehlke, Alexander; Whittington, Alan G.
2016-10-01
The viscosity (η) of silicate melts is a fundamental physical property controlling mass transfer in magmatic systems. Viscosity can span many orders of magnitude, strongly depending on temperature and composition. Several models are available that describe this dependency for terrestrial melts quite well. Planetary basaltic lavas however are distinctly different in composition, being dominantly alkali-poor, iron-rich and/or highly magnesian. We measured the viscosity of 20 anhydrous tholeiitic melts, of which 15 represent known or estimated surface compositions of Mars, Mercury, the Moon, Io and Vesta, by concentric cylinder and parallel plate viscometry. The planetary basalts span a viscosity range of 2 orders of magnitude at liquidus temperatures and 4 orders of magnitude near the glass transition, and can be more or less viscous than terrestrial lavas. We find that current models under- and overestimate superliquidus viscosities by up to 2 orders of magnitude for these compositions, and deviate even more strongly from measured viscosities toward the glass transition. We used the Adam-Gibbs theory (A-G) to relate viscosity (η) to absolute temperature (T) and the configurational entropy of the system at that temperature (Sconf), which is in the form of log η =Ae +Be /TSconf . Heat capacities (CP) for glasses and liquids of our investigated compositions were calculated via available literature models. We show that the A-G theory is applicable to model the viscosity of individual complex tholeiitic melts containing 10 or more major oxides as well or better than the commonly used empirical equations. We successfully modeled the global viscosity data set using a constant Ae of -3.34 ± 0.22 log units and 12 adjustable sub-parameters, which capture the compositional and temperature dependence on melt viscosity. Seven sub-parameters account for the compositional dependence of Be and 5 for Sconf. Our model reproduces the 496 measured viscosity data points with a 1
Redetermination and absolute configuration of pruniflorone M monohydrate
Hoong-Kun Fun
2011-08-01
Full Text Available The title xanthone known as pruniflorone M (systematic name: (2R-5,10-dihydroxy-2-hydroxymethyl-1,1-dimethyl-1H-furo[2,3-c]xanthen-6-one, crystallized in a monohydrate form, C18H16O6·H2O. It was isolated from the green fruits of Cratoxylum formosum ssp. pruniflorum. The structure of the title compound has been reported previously [Boonnak et al. (2010. Aust. J. Chem. 63, 1550–1556], but we report here the absolute configuration determined using Cu Kα radiation. There are two crystallograpically independent molecules in the asymmetric unit, which differ slightly in the bond angles. The hydroxymethyl substituents at position 2 of the furan rings of both pruniflorone M molecules adopt R configurations. In both molecules, the three rings of the xanthone skeleton are approximately coplanar, with an r.m.s. deviation of 0.0124 (2 Å for one molecule and 0.0289 (2 Å for the other, and the furan ring adopts an envelope conformation. In the crystal, molecules of pruniflorone M and water are linked into a two-dimensional network by O—H...O hydrogen bonds and weak C—H...O interactions. The crystal structure is further consolidated by π–π interactions with centroid–centroid distances in the range 3.5987 (13–3.7498 (14 Å. Short C...C [3.378 (3 Å] and O...O [2.918 (3 Å] contacts are also observed.
Redetermined structure, intermolecular interactions and absolute configuration of royleanone
Hoong-Kun Fun
2011-05-01
Full Text Available The structure of the title diterpenoid, C20H28O3, {systematic name: (4bS,8aS-3-hydroxy-2-isopropyl-4b,8,8-trimethyl-4b,5,6,7,8,8a,9,10-octahydrophenanthrene-1,4-dione} is confirmed [Eugster et al. (1993. Private communication (refcode HACGUN. CCDC, Union Road, Cambridge] and its packing is now described. Its absolute structure was established by refinement against data collected with Cu radiation: the two stereogenic centres both have S configurations. One cyclohexane ring adopts a chair conformation whereas the other cyclohexane ring is in a half-chair conformation and the benzoquinone ring is slightly twisted. An intramolecular O—H...O hydrogen bond generates an S(5 ring motif. In the crystal, molecules are linked into chains along [010] by O—H...O hydrogen bonds and weak C—H...O interactions. The packing also features C...O [3.131 (3 Å] short contacts.
Absolute configuration of vouacapen-5α-ol
Hoong-Kun Fun
2010-08-01
Full Text Available The title compound, C20H30O2, {systematic name: (4aR,6aS,7R,11aS,11bR-4,4,7,11b-tetramethyl-1,2,3,4,4a,5,6,6a,7,11,11a,11b-dodecahydrophenanthro[3,2-b]furan-4a-ol}, is a cassane furanoditerpene which was isolated from the roots of Caesalpinia pulcherrima. The absolute configurations at positions 4a, 6a, 7, 11a and 11b are R, S, R, S and R, respectively. The molecule has four-fused rings consisting of two cyclohexane rings, one cyclohexene ring and one furan ring. The cyclohexane and cyclohexene rings are trans-fused. Two cyclohexane rings are in chair conformations, while the cyclohexene ring is in an envelope conformation. In the crystal structure, the molecules are linked by intermolecular O—H...O hydrogen bonds into a zigzag chain along the a axis. A short O...O contact [3.0398 (14 Å] is also present.
A Proposed Absolute Entropy of Near Extremal Kerr-Newman Black Hole
Lin, H
2001-01-01
Some problems have been found as to the definition of entropy of black hole being applied to the extremal Kerr-Newman case, which has conflicts with the third law of thermodynamics. We have proposed a new modification for the near extremal one, which not only obeys the third law, but also does not conflict with other results in black hole thermodynamics. Then we proved that the inner horizon has temperature and proposed that the inner horizon contributes to the entropy of the near extremal one so that the entropy of it has a modified form and vanishes at absolute zero temperature.
The use of X-ray crystallography to determine absolute configuration.
Flack, H D; Bernardinelli, G
2008-05-15
Essential background on the determination of absolute configuration by way of single-crystal X-ray diffraction (XRD) is presented. The use and limitations of an internal chiral reference are described. The physical model underlying the Flack parameter is explained. Absolute structure and absolute configuration are defined and their similarities and differences are highlighted. The necessary conditions on the Flack parameter for satisfactory absolute-structure determination are detailed. The symmetry and purity conditions for absolute-configuration determination are discussed. The physical basis of resonant scattering is briefly presented and the insights obtained from a complete derivation of a Bijvoet intensity ratio by way of the mean-square Friedel difference are exposed. The requirements on least-squares refinement are emphasized. The topics of right-handed axes, XRD intensity measurement, software, crystal-structure evaluation, errors in crystal structures, and compatibility of data in their relation to absolute-configuration determination are described. Characterization of the compounds and crystals by the physicochemical measurement of optical rotation, CD spectra, and enantioselective chromatography are presented. Some simple and some complex examples of absolute-configuration determination using combined XRD and CD measurements, using XRD and enantioselective chromatography, and in multiply-twinned crystals clarify the technique. The review concludes with comments on absolute-configuration determination from light-atom structures.
Correlation as a determinant of configurational entropy in supramolecular and protein systems.
Fenley, Andrew T; Killian, Benjamin J; Hnizdo, Vladimir; Fedorowicz, Adam; Sharp, Dan S; Gilson, Michael K
2014-06-19
For biomolecules in solution, changes in configurational entropy are thought to contribute substantially to the free energies of processes like binding and conformational change. In principle, the configurational entropy can be strongly affected by pairwise and higher-order correlations among conformational degrees of freedom. However, the literature offers mixed perspectives regarding the contributions that changes in correlations make to changes in configurational entropy for such processes. Here we take advantage of powerful techniques for simulation and entropy analysis to carry out rigorous in silico studies of correlation in binding and conformational changes. In particular, we apply information-theoretic expansions of the configurational entropy to well-sampled molecular dynamics simulations of a model host-guest system and the protein bovine pancreatic trypsin inhibitor. The results bear on the interpretation of NMR data, as they indicate that changes in correlation are important determinants of entropy changes for biologically relevant processes and that changes in correlation may either balance or reinforce changes in first-order entropy. The results also highlight the importance of main-chain torsions as contributors to changes in protein configurational entropy. As simulation techniques grow in power, the mathematical techniques used here will offer new opportunities to answer challenging questions about complex molecular systems.
Configurational Entropy,Diffusivity and Potential Energy Landscape in Liquid Argon
DUAN Yong-Ping; MA Cong-Xiao; LI Jia-Yun; LI Cong; WANG Dan; LI Mei-Li; SUN Min-Hua
2009-01-01
The configurational entropy, diffusion coefficient, dynamics and thermodynamics fragility indices of liquid argon are calculated using molecular dynamics simulations at two densities. The relationship between dynamics and thermodynamics properties is studied. The diffusion coefficient depends linearly on configurational entropy, which is consistent with the hypothesis of Adam-Gibbs. The consistence of dynamics and thermodynamics fragility indices demonstrates that dynamical behaviour is governed by thermodynamics behaviour in glass transition of liquid argon.
Topological Research on Standard Absolute Entropies,S(○)298, for Binary Inorganic Compounds
2008-01-01
For predicting the standard entropy of a binary inorganic compound, two novel connectivity indexes mQ,mG and their converse indexes mQ',mG' based on adjacency matrix of molecular graphs and ionic parameters gi, qi were pro-posed. The qi and gi are defined as qi=(1.1+Zi1.1)/(1.7+ni), gi:(1.4d-Zi)/(0.9+ri+ri-1), where Zi, ni, ri are the charge numbers, the outer electronic shell primary quantum numbers, and the radii of ionic I respectively. The good Quantitative Structure-Property Relationship (QSPR) models for the standard entropies of binary inorganic com-pound can be constructed from 0Q,0Q',1G, and 1G', by using a multivariate linear regression (MLR) method and an artificial neural network (NN) method. The correlation coefficient r, the standard error s, and the average absolute deviation of the MLR model and the NN model are 0.9905, 8.29 J·K-1,mol-1 and 6.48 J·K-1·mol-1, and 0.9960,5.37 J·K-1·mol-1 and 3.90 J·K-1·mol-1, respectively, for 371 binary inorganic compounds (training set). The cross-validation by using the leave-one-out method demonstrates that the MLR model is highly reliable from the point of view of statistics. The correlation coefficients, standard deviations and average absolute deviations of pre-dicted values of the standard entropies of other 185 binary inorganic compounds (test set) are 0.9897, 8.64 J·K-1·mol-1 and 6.84 J·K-1·mol-1, and 0.9957, 5.63 J·K-1·mol-1 and 4.18 J·K-1·mol-1 for the MLR model and the Nnmodel, respectively. The results show that the current method is more effective than literature methods for estimat-ing the standard entropy of a binary inorganic compound. Both MLR and NN methods can provide acceptable mod-els for the prediction of the standard entropies of binary inorganic compounds. The NN model for the standard en-tropies appears to be more reliable than the MLR model.
Configurational information as potentially negative entropy: the triple helix model
Leydesdorff, L.
2008-01-01
Configurational information is generated when three or more sources of variance interact. The variations not only disturb each other relationally, but by selecting upon each other, they are also positioned in a configuration. A configuration can be stabilized and/or globalized. Different
Configurational information as potentially negative entropy: the triple helix model
Leydesdorff, L.
2008-01-01
Configurational information is generated when three or more sources of variance interact. The variations not only disturb each other relationally, but by selecting upon each other, they are also positioned in a configuration. A configuration can be stabilized and/or globalized. Different stabilizati
A "configurational-entropy-loss" law for the non-Arrhenius relaxation in disordered systems
Wang, Yi-zhen; Zhang, Jin-xiu
2012-01-01
Based on Nowick's self-induced ordering theory, we develop a new configurational-entropy relation to describe the non-Arrhenius temperature(T)-dependent relaxation in disordered systems. Both the configurational-entropy loss and the coupling interaction among relaxing units (RUs) are explicitly introduced in this relation; thus, it offers a novel connection between kinetics and thermodynamics that is different from the Adam-Gibbs (A-G) entropy relation, and it generalizes several well-known currently used relations. The present relation can provide direct and more accurate estimates of (i) the intrinsic activation enthalpy, (ii) the T-evolvement of the systematic configurational entropy loss and (iii) the self-induced ordering temperature Tc, which characterizes the coupling interaction among RUs. Application of the theory to experimental relaxation-time data for typical organic liquids demonstrates its validity.
Antiausterity activity of arctigenin enantiomers: importance of (2R,3R)-absolute configuration.
Awale, Suresh; Kato, Mamoru; Dibwe, Dya Fita; Li, Feng; Miyoshi, Chika; Esumi, Hiroyasu; Kadota, Shigetoshi; Tezuka, Yasuhiro
2014-01-01
From a MeOH extract of powdered roots of Wikstroemia indica, six dibenzyl-gamma-butyrolactone-type lignans with (2S,3S)-absolute configuration [(+)-arctigenin (1), (+)-matairesinol (2), (+)-trachelogenin (3), (+)-nortrachelogenin (4), (+)-hinokinin (5), and (+)-kusunokinin (6)] were isolated, whereas three dibenzyl-gamma-butyrolactone-type lignans with (2R,3R)-absolute configuration [(-)-arctigenin (1*), (-)-matairesinol (2*), (-)-trachelogenin (3*)] were isolated from Trachelospermum asiaticum. The in vitro preferential cytotoxic activity of the nine compounds was evaluated against human pancreatic PANC-1 cancer cells in nutrient-deprived medium (NDM), but none of the six lignans (1-6) with (2S,3S)-absolute configuration showed preferential cytotoxicity. On the other hand, three lignans (1*-3*) with (2R,3R)-absolute configuration exhibited preferential cytotoxicity in a concentration-dependent manner with PC50 values of 0.54, 6.82, and 5.85 microM, respectively. Furthermore, the effect of (-)- and (+)-arctigenin was evaluated against the activation of Akt, which is a key process in the tolerance to nutrition starvation. Interestingly, only (-)-arctigenin (1*) strongly suppressed the activation of Akt. These results indicate that the (2R,3R)-absolute configuration of (-)-enantiomers should be required for the preferential cytotoxicity through the inhibition of Akt activation.
Jennings, Robert C; Zucchelli, Giuseppe
2014-01-01
We examine ergodicity and configurational entropy for a dilute pigment solution and for a suspension of plant photosystem particles in which both ground and excited state pigments are present. It is concluded that the pigment solution, due to the extreme brevity of the excited state lifetime, is non-ergodic and the configurational entropy approaches zero. Conversely, due to the rapid energy transfer among pigments, each photosystem is ergodic and the configurational entropy is positive. This decreases the free energy of the single photosystem pigment array by a small amount. On the other hand, the suspension of photosystems is non-ergodic and the configurational entropy approaches zero. The overall configurational entropy which, in principle, includes contributions from both the single excited photosystems and the suspension which contains excited photosystems, also approaches zero. Thus the configurational entropy upon photon absorption by either a pigment solution or a suspension of photosystem particles is approximately zero.
Distance-Based Configurational Entropy of Proteins from Molecular Dynamics Simulations.
Fogolari, Federico; Corazza, Alessandra; Fortuna, Sara; Soler, Miguel Angel; VanSchouwen, Bryan; Brancolini, Giorgia; Corni, Stefano; Melacini, Giuseppe; Esposito, Gennaro
2015-01-01
Estimation of configurational entropy from molecular dynamics trajectories is a difficult task which is often performed using quasi-harmonic or histogram analysis. An entirely different approach, proposed recently, estimates local density distribution around each conformational sample by measuring the distance from its nearest neighbors. In this work we show this theoretically well grounded the method can be easily applied to estimate the entropy from conformational sampling. We consider a set of systems that are representative of important biomolecular processes. In particular: reference entropies for amino acids in unfolded proteins are obtained from a database of residues not participating in secondary structure elements;the conformational entropy of folding of β2-microglobulin is computed from molecular dynamics simulations using reference entropies for the unfolded state;backbone conformational entropy is computed from molecular dynamics simulations of four different states of the EPAC protein and compared with order parameters (often used as a measure of entropy);the conformational and rototranslational entropy of binding is computed from simulations of 20 tripeptides bound to the peptide binding protein OppA and of β2-microglobulin bound to a citrate coated gold surface. This work shows the potential of the method in the most representative biological processes involving proteins, and provides a valuable alternative, principally in the shown cases, where other approaches are problematic.
Meirovitch, Hagai
2010-01-01
The commonly used simulation techniques, Metropolis Monte Carlo (MC) and molecular dynamics (MD) are of a dynamical type which enables one to sample system configurations i correctly with the Boltzmann probability, P(i)(B), while the value of P(i)(B) is not provided directly; therefore, it is difficult to obtain the absolute entropy, S approximately -ln P(i)(B), and the Helmholtz free energy, F. With a different simulation approach developed in polymer physics, a chain is grown step-by-step with transition probabilities (TPs), and thus their product is the value of the construction probability; therefore, the entropy is known. Because all exact simulation methods are equivalent, i.e. they lead to the same averages and fluctuations of physical properties, one can treat an MC or MD sample as if its members have rather been generated step-by-step. Thus, each configuration i of the sample can be reconstructed (from nothing) by calculating the TPs with which it could have been constructed. This idea applies also to bulk systems such as fluids or magnets. This approach has led earlier to the "local states" (LS) and the "hypothetical scanning" (HS) methods, which are approximate in nature. A recent development is the hypothetical scanning Monte Carlo (HSMC) (or molecular dynamics, HSMD) method which is based on stochastic TPs where all interactions are taken into account. In this respect, HSMC(D) can be viewed as exact and the only approximation involved is due to insufficient MC(MD) sampling for calculating the TPs. The validity of HSMC has been established by applying it first to liquid argon, TIP3P water, self-avoiding walks (SAW), and polyglycine models, where the results for F were found to agree with those obtained by other methods. Subsequently, HSMD was applied to mobile loops of the enzymes porcine pancreatic alpha-amylase and acetylcholinesterase in explicit water, where the difference in F between the bound and free states of the loop was calculated. Currently
Uchida, Miho; Takamatsu, Satoshi; Arima, Shiho; Miyamoto, Kiyoko T; Kitani, Shigeru; Nihira, Takuya; Ikeda, Haruo; Nagamitsu, Tohru
2011-12-01
The first total synthesis of extracellular factor, "Avenolide", in Streptomyces avermitilis has been achieved using a convergent approach. The stereogenic centers in two key segments were installed using Sharpless epoxidation and dihydroxylation. This synthetic study allowed the determination of the absolute configuration of avenolide as 4S,10R, and yielded important information on its structure-activity relationship.
Structure and absolute configuration of helosides A and B, new saponins from Chamaelirium luteum
Challinor, Victoria L; Stuthe, Julia M U; Bernhardt, Paul V
2011-01-01
Investigation of Chamaelirium luteum roots led to the isolation of two new steroidal saponins, helosides A and B, that contain a previously unreported aglycone, helogenin. Their structures and absolute configuration were elucidated through MS-MS, NMR, chemical degradation, and X-ray crystallography....
Determination of absolute configuration (AC) is one of the most challenging features in the structure elucidation of chiral natural products, especially those with complex structures. With revolutionary advancements in the area of quantum chemical calculations of chiroptical spectroscopy over the pa...
He, Jiangbo; Zhu, Hua Jie; Luo, Gui Fen; Li, Yan; Cheng, Yong Xian [Chinese Academy of Sciences, Kunming (China); Chen, Hao; Chen, Shaopeng; Lu, Xin; Zhou, Guochun [Chinese Academy of Sciences, Guangzhou (China); Liu, Guang Ming [Dali University, Dali (China)
2010-08-15
The whole plant of Euphorbia helioscopia is an important traditional Chinese medicine. Fom its BuOH soluble extract, one new lactam, three new terpenoids including a new naturally occurring compound, and three known compounds were isolated. Their structures were identified by spectroscopic evidences. In particular, the absolute configurations of side chain of compounds 1 and 2 were determined using computational methods.
杨强; 杨卫
2001-01-01
The authors proposed a plausible explanation for the deviation of experimental data for sub-micron polycrystals from the Hall-Petch relation by in troducing the configuration entropy. The present paper extends the previous two dimensional analysis to the three-dimensional case. The statistical distribution of dislocation lengths within a spherical grain and the bow-out of dislocations are con sidered. According to Ashby's model, analyses are pursued for the statistically stored dislocations and geometrically necessary dislocations, respectively. It is confirmed that the configuration entropy model can predict the abnormal Hall-Petch depen dence for grain sizes in the sub-micron range.
The iso-structural viscosity, configurational entropy and fragility of oxide liquids
Yue, Yuanzheng
2009-01-01
the variation of the configurational entropy (Sc) with temperature (T) are obtained from the Avramov-Milchev (AM) and the Vogel-Fulcher- Tammann (VFT) viscosity equations, respectively. The two Sc(T) functions exhibit different relations to the liquid fragility. The AM Sc(T) function is a power function...
Communication: Probing the absolute configuration of chiral molecules at aqueous interfaces
Lotze, Stephan, E-mail: lotze@amolf.nl; Versluis, Jan [FOM Institute for Atomic and Molecular Physics, Science Park 104, 1098 XG Amsterdam (Netherlands); Olijve, Luuk L. C.; Schijndel, Luuk van; Milroy, Lech G.; Voets, Ilja K. [Laboratory of Macromolecular and Organic Chemistry, Department of Chemical Engineering and Chemistry, and Institute for Complex Molecular Systems, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven (Netherlands); Bakker, Huib J., E-mail: bakker@amolf.nl [FOM Institute AMOLF, Science Park 104, 1098 XG Amsterdam (Netherlands)
2015-11-28
We demonstrate that the enantiomers of chiral macromolecules at an aqueous interface can be distinguished with monolayer sensitivity using heterodyne-detected vibrational sum-frequency generation (VSFG). We perform VSFG spectroscopy with a polarization combination that selectively probes chiral molecular structures. By using frequencies far detuned from electronic resonances, we probe the chiral macromolecular structures with high surface specificity. The phase of the sum-frequency light generated by the chiral molecules is determined using heterodyne detection. With this approach, we can distinguish right-handed and left-handed helical peptides at a water-air interface. We thus show that heterodyne-detected VSFG is sensitive to the absolute configuration of complex, interfacial macromolecules and has the potential to determine the absolute configuration of enantiomers at interfaces.
Krief, Alain; Dunkle, Melissa; Bahar, Masoud; Bultinck, Patrick; Herrebout, Wouter; Sandra, Pat
2015-07-01
The absolute configuration of rhizopine, an opine-like natural product present in nitrogen-fixing nodules of alfalfa infected by rhizobia, is elucidated using a combination of state-of-the-art analytical and semi-preparative supercritical fluid chromatography and vibrational circular dichroism spectroscopy. A synthetic peracetylated racemate was fractionated into its enantiomers and subjected to absolute configuration analysis revealing that natural rhizopine exists as a single enantiomer. The stereochemistry of non-derivatized natural rhizopine corresponds to (1R,2S,3R,4R,5S,6R)-4-amino-6-methoxycyclohexane-1,2,3,5-tetraol. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Muñoz, Marcelo A; San-Martín, Aurelio; Joseph-Nathan, Pedro
2015-08-01
The absolute configuration of the diterpenoid 9,12-cyclomulin-13-ol (1), a constituent of Azorella and Laretia species, has been established by vibrational circular dichroism spectroscopy in combination with density functional theory calculations. The obtained normal diterpene absolute configuration confirms that of azorellanol (2), which was determined by single crystal X-ray diffraction.
Configurational Entropy in Brane-world Models: A New Approach to Stability
Correa, R A C
2015-01-01
In this work we investigate the entropic information on thick brane-worlds scenarios and its consequences. The brane-world entropic information is studied for the sine-Gordon model is and hence the brane-world entropic information measure is shown an accurate way for providing the most suitable values for the bulk AdS curvature. Besides, the brane-world configurational entropy is employed to demonstrate a high organisational degree in the structure of the system configuration, for large values of a parameter of the sine-Gordon model but the one related to the AdS curvature. The Gleiser and Stamatopoulos procedure is finally applied in order to achieve a precise correlation between the energy of the system and the brane-world configurational entropy.
Wang, Jian-Rong; Fan, Xiaowu; Ding, Qiaoce; Mei, Xuefeng
2016-09-01
Heavy atom (chloride, bromide, and iodide) based co-crystals for determination of absolute configuration (AC) for chiral molecules were synthesized and evaluated. Co-crystals of cholestanol and L-ascorbic acid were analysed and the effects and potential benefits of varying the heavy atom are discussed. Changing the halogen atoms (chloride, bromide, or iodide) affects the co-crystal formation, X-ray absorption, and anomalous dispersion, and hence the ability to determine AC.
Ortega, Alfredo R; Sánchez-Castellanos, Mariano; Pérez-Hernández, Nury; Robles-Zepeda, Ramón E; Joseph-Nathan, Pedro; Quijano, Leovigildo
2016-05-01
The naturally occurring eudesmanolide farinosin () is now fully characterized for the first time despite its original isolation almost half a century ago. The early assumed relative stereochemistry and absolute configuration were confirmed by vibrational circular dichroism together with evaluation of the Hooft X-ray parameters. The molecular conformation is very similar in the gas stage and in the solid state. Chirality 28:415-419, 2016. © 2016 Wiley Periodicals, Inc.
Wittine, Karlo; Gazivoda, Tatjana; Markuš, Marko; Mrvoš-Sermek, Draginja; Hergold-Brundić, Antonija; Cetina, Mario; Žiher, Dinko; Gabelica, Vesna; Mintas, Mladen; Raić-Malić, Silvana
2004-01-01
Chiral 2,3-O,O-dibenzyl ethers of L-ascorbic acid with 4-(5,6-epoxy)- (4) and 6-O-tosyl- (8) functional groups were studied by X-ray crystallography and circular dichroism (CD) spectroscopy. The stereostructure of 2,3-O,O-dibenzyl-5,6-isopropylidene-L-ascorbic acid (6) and 8 was determined by X-ray crystal structure analysis. Comparison of the CD-spectra of 4 and 8 with the CD-spectra of their synthetic precursors (2-3, 5-7) and L-ascorbic acid (1) itself, as well as crystal structures of 6 and 8 permitted to deduce the absolute configuration of 4. Thus, the chiral atoms C-4 and C-5 in 4 have R and S configurations, which is consistent with the configuration of 1.
Fleck, Markus; Polyansky, Anton A; Zagrovic, Bojan
2016-04-12
Accurate estimation of configurational entropy from the in silico-generated biomolecular ensembles, e.g., from molecular dynamics (MD) trajectories, is dependent strongly on exhaustive sampling for physical reasons. This, however, creates a major computational problem for the subsequent estimation of configurational entropy using the Maximum Information Spanning Tree (MIST) or Mutual Information Expansion (MIE) approaches for internal molecular coordinates. In particular, the available software for such estimation exhibits serious limitations when it comes to molecules with hundreds or thousands of atoms, because of its reliance on a serial program architecture. To overcome this problem, we have developed a parallel, hybrid MPI/openMP C++ implementation of MIST and MIE, called PARENT, which is particularly optimized for high-performance computing and provides efficient estimation of configurational entropy in different biological processes (e.g., protein-protein interactions). In addition, PARENT also allows for a detailed mapping of intramolecular allosteric networks. Here, we benchmark the program on a set of 1-μs-long MD trajectories of 10 different protein complexes and their components, demonstrating robustness and good scalability. A direct comparison between MIST and MIE on the same dataset demonstrates a superior convergence behavior for the former approach, when it comes to total simulation length and configurational-space binning.
Bello, Jan E; McElfresh, J Steven; Millar, Jocelyn G
2015-01-27
Although the effects of stereochemistry have been studied extensively for volatile insect pheromones, little is known about the effects of chirality in the nonvolatile methyl-branched hydrocarbons (MBCHs) used by many insects as contact pheromones. MBCHs generally contain one or more chiral centers and so two or more stereoisomeric forms are possible for each structure. However, it is not known whether insects biosynthesize these molecules in high stereoisomeric purity, nor is it known whether insects can distinguish the different stereoisomeric forms of MBCHs. This knowledge gap is due in part to the lack of methods for isolating individual MBCHs from the complex cuticular hydrocarbon (CHC) blends of insects, as well as the difficulty in determining the absolute configurations of the isolated MBCHs. To address these deficiencies, we report a straightforward method for the isolation of individual cuticular hydrocarbons from the complex CHC blend. The method was used to isolate 36 pure MBCHs from 20 species in nine insect orders. The absolute stereochemistries of the purified MBCHs then were determined by digital polarimetry. The absolute configurations of all of the isolated MBCHs were determined to be (R) by comparison with a library of synthesized, enantiomerically pure standards, suggesting that the biosynthetic pathways used to construct MBCHs are highly conserved within the Insecta. The development of a straightforward method for isolation of specific CHCs will enable determination of their functional roles by providing pure compounds for bioassays.
Configurational entropy as a bounding of Gauss-Bonnet braneworld models
Correa, R A C; Dutra, A de Souza; de Paula, W; Frederico, T
2016-01-01
Configurational entropy has been revealed as a reliable method for constraining some parameters of a given model [Phys. Rev. D \\textbf{92} (2015) 126005, Eur. Phys. J. C \\textbf{76} (2016) 100]. In this letter we calculate the configurational entropy in Gauss-Bonnet braneworld models. Our results restrict the range of acceptability of the Gauss-Bonnet scalar values. In this way, the information theoretical measure in Gauss-Bonnet scenarios opens a new window to probe situations where the additional parameters, responsible for the Gauss-Bonnet sector, are arbitrary. We also show that such an approach is very important in applications that include p and Dp-branes and various superstring-motivated theories.
Evangelisti, Luca; Caminati, Walther; Patterson, David; Thomas, Javix; Xu, Yunjie; West, Channing; Pate, Brooks
2017-06-01
The introduction of three wave mixing rotational spectroscopy by Patterson, Schnell, and Doyle [1,2] has expanded applications of molecular rotational spectroscopy into the field of chiral analysis. Chiral analysis of a molecule is the quantitative measurement of the relative abundances of all stereoisomers of the molecule and these include both diastereomers (with distinct molecular rotational spectra) and enantiomers (with equivalent molecular rotational spectra). This work adapts a common strategy in chiral analysis of enantiomers to molecular rotational spectroscopy. A "chiral tag" is attached to the molecule of interest by making a weakly bound complex in a pulsed jet expansion. When this tag molecule is enantiopure, it will create diastereomeric complexes with the two enantiomers of the molecule being analyzed and these can be differentiated by molecule rotational spectroscopy. Identifying the structure of this complex, with knowledge of the absolute configuration of the tag, establishes the absolute configuration of the molecule of interest. Furthermore, the diastereomer complex spectra can be used to determine the enantiomeric excess of the sample. The ability to perform chiral analysis will be illustrated by a study of solketal using propylene oxide as the tag. The possibility of using current methods of quantum chemistry to assign a specific structure to the chiral tag complex will be discussed. Finally, chiral tag rotational spectroscopy offers a "gold standard" method for determining the absolute configuration of the molecule through determination of the substitution structure of the complex. When this measurement is possible, rotational spectroscopy can deliver a quantitative three dimensional structure of the molecule with correct stereochemistry as the analysis output. [1] David Patterson, Melanie Schnell, John M. Doyle, Nature 497, 475 (2013). [2] David Patterson, John M. Doyle, Phys. Rev. Lett. 111, 023008 (2013).
He, Yanan; Wang, Bo; Dukor, Rina K; Nafie, Laurence A
2011-07-01
Determination of the absolute handedness, known as absolute configuration (AC), of chiral molecules is an important step in any field related to chirality, especially in the pharmaceutical industry. Vibrational optical activity (VOA) has become a powerful tool for the determination of the AC of chiral molecules in the solution state after nearly forty years of evolution. VOA offers a novel alternative, or supplement, to X-ray crystallography, permitting AC determinations on neat liquid, oil, and solution samples without the need to grow single crystals of the pure chiral sample molecules as required for X-ray analysis. By comparing the sign and intensity of the measured VOA spectrum with the corresponding ab initio density functional theory (DFT) calculated VOA spectrum of a chosen configuration, one can unambiguously assign the AC of a chiral molecule. Comparing measured VOA spectra with calculated VOA spectra of all the conformers can also provide solution-state conformational populations. VOA consists of infrared vibrational circular dichroism (VCD) and vibrational Raman optical activity (ROA). Currently, VCD is used routinely by researchers in a variety of backgrounds, including molecular chirality, asymmetric synthesis, chiral catalysis, drug screening, pharmacology, and natural products. Although the application of ROA in AC determination lags behind that of VCD, with the recent implementation of ROA subroutines in commercial quantum chemistry software, ROA will in the future complement VCD for AC determination. In this review, the basic principles of the application of VCD to the determination of absolute configuration in chiral molecules are described. The steps required for VCD spectral measurement and calculation are outlined, followed by brief descriptions of recently published papers reporting the determination of AC in small organic, pharmaceutical, and natural product molecules.
Fristrup, Peter; Lassen, Peter Rygaard; Johannessen, Christian;
2006-01-01
obtained from quantum mechanical calculations (density functional theory with the B3LYP hybrid exchange correlation functional with 6-31++G**, aug-cc-pVDZ, or aug-cc-pVTZ basis set) and related to the physical structure of the compounds. The absolute configuration could be established directly in each case...... by comparing experimental and theoretical spectra. In addition, we have been able to document the changes that occur both in structures and in the VA and VCD spectra due to substituent effects on the oxirane ring....
Mondal, Shovan; Naubron, Jean-Valère; Campolo, Damien; Giorgi, Michel; Bertrand, Michéle P; Nechab, Malek
2013-12-01
The absolute configurations (AC) of azaheterocylic compounds resulting from the cascade rearrangement of enediynes involving only light atoms were unambiguously assigned by the joint use of vibrational circular dichroism (VCD) and copper radiation single crystal X-ray diffraction (XRD). These AC determinations proved that the rearrangements of enediynes proceeded with memory of chirality and retention of configuration.
Meninno, Sara; Rizzo, Paola; Abbate, Sergio; Longhi, Giovanna; Mazzeo, Giuseppe; Monaco, Guglielmo; Lattanzi, Alessandra; Zanasi, Riccardo
2016-02-01
Density functional theory calculation of the vibrational circular dichroism spectrum was used to assign the absolute configuration of an all-carbon quaternary β-stereocenter of a γ-butyrolactone recently synthesized through an asymmetric organocatalytic tandem aldol/lactonization sequence. Comparison with the experimental spectrum is satisfactory, on account of the fact that spectroscopic features are weak due to the presence of multiple conformers. As a result, the (R) absolute configuration was assigned to the (+) optical isomer.
Configurational entropy of a set of dipoles placed on a two-dimensional lattice
Dammig Quiña, P. L.; Irurzun, I. M.; Mola, E. E.
2017-01-01
In the present work we calculate the configurational entropy of an arbitrary number of dipoles placed on a square lattice. We use a quasi-two-dimensional (Q2D) space to capture the main features determining the occupation statistics of this system. We show that our result is in agreement with both, lattice-gas predictions at low coverages and the exact value derived in the close-packed limit as well. Therefore our equation provides a substantial improvement to the most recent calculations based on semiempirical models and Monte Carlo simulations.
Structure and Absolute Configuration of Ginkgolide B Characterized by IR- and VCD Spectroscopy
Andersen, Niels Højmark; Christensen, N.J.; Lassen, Peter Rygaard
2010-01-01
Experimental and calculated (B3LYP/6-31G(d)) vibrational Circular dichroism (VCD) and IR spectra are compared, illustrating that the structure and absolute configuration of ginkgolide B (GB) may be characterized directly in solution. A conformational search for GB using MacroModel and subsequent......, displaying different intramolecular hydrogen bonding. Differences between measured and calculated IR and VCD spectra for GB at certain wavenumbers are rationalized in terms of interactions with solvent, intermolecular GB-GB interactions, and the potential presence of more than one conformer....... This is the first detailed investigation of the spectroscopic fingerprint region (850-1300 cm(-1)) of the natural product GB employing infrared absorption and VCD spectroscopy. Chirality 22:217-223, 2010....
Synthesis, Crystal Structure and Absolute Configuration of(+)-O-Phenyl Cyclophosphorodiamidate
何可; 周正洪; 李康应; 赵国锋; 唐除痴; 王宏根
2003-01-01
The title compound, (+)-O-phenyl cyclophosphorodiamidate (C28H33N2O2P, Mr = 460.53), has been synthesized and characterized by 31P NMR, 1H NMR and elemental analysis. X-ray diffraction analysis at 273(2) K indicates that it belongs to orthorhombic system, space group P212121 with a = 11.518(4), b = 13.449(4), c = 16.539(5)(A°), V = 2562(1)(A°)3, Z = 4, Dc = 1.194 g/cm3, F(000) = 984 and μ(MoKα) = 0.134 mm-1. The structure parameters were refined by full-matrix least-squares on F2 to R = 0.0459 and wR = 0.0640. The flack x parameter is 0.03(10), and the absolute configuration of the phosphorus atom in the title compound is S.
Farimani, Mahdi Moridi; Bahadori, Mir Babak; Koulaei, Sheyda Ahmadi; Salehi, Peyman; Ebrahimi, Samad Nejad; Khavasi, Hamid Reza; Hamburger, Matthias
2015-10-01
Two new triterpenoids, urmiensolide B (1) and urmiensic acid (2), with rare carbon skeletons together with three known compounds were isolated from the aerial parts of Salvia urmiensis Bunge, an endemic species of Iran. The structures were established by a combination of 1D and 2D NMR, and HRESIMS, and in the case of 2 and 3, their structures were confirmed by single-crystal X-ray analysis. The absolute configuration of 2 was established by electronic circular dichroism (ECD) spectra. The new compounds were evaluated for their anti-proliferative activities against A549 and MCF-7 human cancer cell lines. Compounds 1 and 2 showed IC50 values of 2.8 and 1.6 μM against MCF-7 cells, respectively.
Bentley, Keith W.; Zhang, Peng; Wolf, Christian
2016-01-01
High-throughput experimentation (HTE) has emerged as a widely used technology that accelerates discovery and optimization processes with parallel small-scale reaction setups. A high-throughput screening (HTS) method capable of comprehensive analysis of crude asymmetric reaction mixtures (eliminating product derivatization or isolation) would provide transformative impact by matching the pace of HTE. We report how spontaneous in situ construction of stereodynamic metal probes from readily available, inexpensive starting materials can be applied to chiroptical chemosensing of the total amount, enantiomeric excess (ee), and absolute configuration of a wide variety of amines, diamines, amino alcohols, amino acids, carboxylic acids, α-hydroxy acids, and diols. This advance and HTS potential are highlighted with the analysis of 1 mg of crude reaction mixtures of a catalytic asymmetric reaction. This operationally simple assay uses a robust mix-and-measure protocol, is amenable to microscale platforms and automation, and provides critical time efficiency and sustainability advantages over traditional serial methods. PMID:26933684
ABSOLUTE CONFIGURATION AND BIOLOGICAL PROPERTIES OF ENANTIOMERS OF CFTR INHIBITOR BPO-27.
Snyder, David S; Tradtrantip, Lukmanee; Battula, Sailaja; Yao, Chenjuan; Phuan, Puay-Wah; Fettinger, James C; Kurth, Mark J; Verkman, A S
2013-05-01
We previously reported benzopyrimido-pyrrolo-oxazinedione (BPO) inhibitors of the cystic fibrosis transmembrane conductance regulator (CFTR) chloride channel and showed their efficacy in a model of polycystic kidney disease. Here, we separated the enantiomers of lead compound BPO-27, (1), which contains a single chiral center, and determined their absolute configuration, activity and metabolic stability. Following separation by chiral supercritical fluid chromatography, the R enantiomer, as determined by x-ray crystallography, inhibited CFTR chloride conductance with IC50 ~ 4 nM, while S enantiomer was inactive. In vitro metabolic stability in hepatic microsomes showed both enantiomers as stable, with <5 % metabolism in 4 h. Following bolus interperitoneal administration in mice, serum (R)-1 decayed with t1/2 ~ 1.6 h and gave sustained therapeutic concentrations in kidney.
Meng, Chun-Wang; He, Yu-Lin; Peng, Cheng; Ding, Xing-Jie; Guo, Li; Xiong, Liang
2017-09-01
Five picrotoxane sesquiterpenoids belonging to the unusual dendrobine-type (1 and 4) and the picrotoxinin-type (2, 3, and 5) were isolated from the stems of Dendrobium nobile Lindl. Their structures were established by spectroscopic analyses and physical properties. Compound 1 was a new dendrobine analogue. Although the planar structure of 2 and 3 had been reported, their absolute configurations were first determined by single-crystal X-ray diffraction and circular dichroism. Compound 2 exhibited angiogenesis effect against sunitinib-induced damage on intersegmental blood vessels in Tg (flk1: EGFP) and Tg (fli1: nEGFP) transgenic zebrafish at concentrations of 3.13, 6.25, 12.50, and 25.00μM. Copyright © 2017. Published by Elsevier B.V.
Dastan, Dara; Salehi, Peyman; Reza Gohari, Ahmad; Zimmermann, Stefanie; Kaiser, Marcel; Hamburger, Matthias; Reza Khavasi, Hamid; Ebrahimi, Samad Nejad
2012-06-01
The first disesquiterpene coumarin, sanandajin, five sesquiterpene coumarins, kamolonol acetate, fekrynol acetate, ethyl galbanate, methyl galbanate, farnesiferol B, and a sesquiterpene, aristolone, were isolated from a n-hexane extract of Ferula pseudalliacea roots. The structures were elucidated by 1D and 2D NMR, HR-ESIMS data, and kamolonol acetate was confirmed by single-crystal X-ray analysis. The absolute configuration of compounds was established by comparison of experimental and simulated ECD spectra using time dependence density function theory (TDDFT). In vitro antiplasmodial activity against Plasmodium falciparum K1 strain was determined. sanandajin, kamolonol acetate and methyl galbanate showed moderate antiplasmodial activity, with IC(50) values of 2.6, 16.1 and 7.1 μM, respectively.
Gao, Rui-Qi; Fan, Jun; Tan, Qi; Guo, Dong; Chen, Tao; He, Ru-Jian; Li, Dan; Zhang, Hui; Zhang, Wei-Guang
2017-09-01
Resolution of chiral compounds has played an important role in the pharmaceutical field, involving detailed studies of pharmacokinetics, physiological, toxicological, and metabolic activities of enantiomers. Herein, a reliable method by high-performance liquid chromatography (HPLC) coupled with an optical rotation detector was developed to separate isoborneol enantiomers. A cellulose tris(3, 5-dimethylphenylcarbamate)-coated chiral stationary phase showed the best separation performance for isoborneol enantiomers in the normal phase among four polysaccharide chiral packings. The effects of alcoholic modifiers and column temperature were studied in detail. Resolution of the isoborneol racemate displayed a downward trend along with an increase in the content of ethanol and column temperature, indicating that less ethanol in the mobile phase and lower temperature were favorable to this process. Moreover, two isoborneol enantiomers were obtained via a semipreparative chiral HPLC technique under optimum conditions, and further characterized by analytical HPLC, and experimental and calculated vibrational circular dichroism (VCD) spectroscopy, respectively. The solution VCD spectrum of the first-eluted component was consistent with the Density Functional Theory (DFT) calculated pattern based on the SSS configuration, indicating that this enantiomer should be (1S, 2S, 4S)-(+)-isoborneol. Briefly, these results have provided reliable information to establish a method for analysis, preparative separation, and absolute configuration of chiral compounds without typical chromophoric groups. © 2017 Wiley Periodicals, Inc.
The Stumbling Block of the Gibbs Entropy: the Reality of the Negative Absolute Temperatures
Anghel Dragoş-Victor
2016-01-01
Full Text Available The second Tisza-Callen postulate of equilibrium thermodynamics states that for any system there exists a function of the system extensive parameters, called entropy, defined for all equilibrium states and having the property that the values assumed by the extensive parameters in the absence of a constraint are those that maximize the entropy over the manifold of constrained equilibrium states. Based on the thermodynamic evolution of systems which (in the Boltzmann description have positive and negative temperatures, we show that this postulate is satisfied by the Boltzmann formula for the entropy and may be violated by the Gibbs formula, therefore invalidating the later. Vice versa, if we assume, by reductio ad absurdum, that for some thermodynamic systems the equilibrium state is determined by the Gibbs’ prescription and not by Boltzmann’s, this implies that such systems have macroscopic fluctuations and therefore do not reach the thermodynamic equilibrium.
Towards the Development of a Universal Expression for the Configurational Entropy of Mixing
Jorge Garcés
2015-12-01
Full Text Available This work discusses the development of analytical expressions for the configurational entropy of different states of matter using a method based on the identification of the energy-independent complexes (clustering of atoms in the system and the calculation of their corresponding probabilities. The example of short-range order (SRO in Nb-H interstitial solid solution is used to illustrate the choice of the atomic complexes and their structural changes with H concentration, providing an alternative methodology to describe critical properties. The calculated critical composition of the miscibility gap is xc = 0.307, in remarkable agreement with the experimental value of xc ~ 0.31. The same methodology is applied to deduce the equation of state (EOS of a hard sphere system. The EOS is suitable to describe the percolation thresholds and fulfills both the low and random close packing limits. The model, based on the partition of the space into Voronoi cells, can be applied to any off-lattice system, thus introducing the possibility of computing the configurational entropy of gases, liquids and glasses with the same level of accuracy.
A Proposed Absolute Entropy of Near Extremal Kerr-Newman Black Hole
Lin, Hai
2001-01-01
Some problems have been found as to the definition of entropy of black hole being applied to the extremal Kerr-Newman case, which has conflicts with the third law of thermodynamics. We have proposed a new modification for the near extremal one, which not only obeys the third law, but also does not conflict with other results in black hole thermodynamics. Then we proved that the inner horizon has temperature and proposed that the inner horizon contributes to the entropy of the near extremal on...
Absolute Configurations and NO Inhibitory Activities of Terpenoids from Curcuma longa.
Xu, Jing; Ji, Feifei; Kang, Jing; Wang, Hao; Li, Shen; Jin, Da-Qing; Zhang, Qiang; Sun, Hongwei; Guo, Yuanqiang
2015-06-24
Curcuma longa L., belonging to the Zingiberaceae family, is a perennial herb and has been used as a spice and a pigment in the food industry. In the ongoing search for inhibitory reagents of NO production and survey of the chemical composition of natural vegetable foods, the chemical constituents of C. longa used as spice were investigated. This investigation resulted in the isolation of 2 new terpenoids and 14 known analogues. Their structures were established on the basis of the extensive analyses of 1D and 2D NMR spectroscopic data, and the absolute configurations of 1-4 were elucidated by comparison of the calculated and experimental ECD spectra. Among them, compound 1 is a rare norditerpene with an ent-labdane skeleton, and 2 is a skeletally novel sesquiterpene having an eight-membered ring. All of the compounds were found to possess NO inhibitory activities in murine microglial BV-2 cells. The discovery of two new compounds in this chemical investigation further disclosed the chemical composition of C. longa used a food spice, and the bioassay implied that the natural food spice C. longa, containing terpenoids with NO inhibitory activities, may be potentially promotive to human health.
Redetermined structure, inter-molecular inter-actions and absolute configuration of royleanone.
Fun, Hoong-Kun; Chantrapromma, Suchada; Salae, Abdul Wahab; Razak, Ibrahim Abdul; Karalai, Chatchanok
2011-05-01
The structure of the title diterpenoid, C(20)H(28)O(3), {systematic name: (4bS,8aS)-3-hy-droxy-2-isopropyl-4b,8,8-trimethyl-4b,5,6,7,8,8a,9,10-octa-hydro-phenanthrene-1,4-dione} is confirmed [Eugster et al. (1993 ▶). Private communication (refcode HACGUN). CCDC, Union Road, Cambridge] and its packing is now described. Its absolute structure was established by refinement against data collected with Cu radiation: the two stereogenic centres both have S configurations. One cyclo-hexane ring adopts a chair conformation whereas the other cyclo-hexane ring is in a half-chair conformation and the benzoquinone ring is slightly twisted. An intra-molecular O-H⋯O hydrogen bond generates an S(5) ring motif. In the crystal, mol-ecules are linked into chains along [010] by O-H⋯O hydrogen bonds and weak C-H⋯O inter-actions. The packing also features C⋯O [3.131 (3) Å] short contacts.
Total Synthesis, Structure Revision, and Absolute Configuration of (−)-Brevenal
Fuwa, Haruhiko; Ebine, Makoto; Bourdelais, Andrea J.; Baden, Daniel G.; Sasaki, Makoto
2008-01-01
Total synthesis of structure 1 originally proposed for brevenal, a nontoxic polycyclic ether natural product isolated from the Florida red tide dinoflagellate, Karenia brevis, was accomplished. The key features of the synthesis involved (i) convergent assembly of the pentacyclic polyether skeleton based on our developed Suzuki–Miyaura coupling chemistry and (ii) stereoselective construction of the multi-substituted (E,E)-dienal side chain by using copper(I) thiophen-2-carboxylate (CuTC)-promoted modified Stille coupling. The disparity of NMR spectra between the synthetic material and the natural product required a revision of the proposed structure. Detailed spectroscopic comparison of synthetic 1 with natural brevenal, coupled with the postulated biosynthetic pathway for marine polyether natural products, suggested that the natural product was most likely represented by 2, the C26 epimer of the proposed structure 1. The revised structure was finally validated by completing the first total synthesis of (−)-2, which also unambiguously established the absolute configuration of the natural product. PMID:17177450
Polavarapu, Prasad L; Jeirath, Neha; Kurtán, Tibor; Pescitelli, Gennaro; Krohn, Karsten
2009-01-01
Cephalochromin, a homodimeric naphthpyranone natural product, contains both axial chirality due to the hindered rotation along the biaryl axis and central chirality due to the C-2, C-2' stereogenic centers of the fused pyranone ring. For determining the absolute configurations (ACs) of central chirality elements, different chiroptical spectroscopic methods, namely vibrational circular dichroism (VCD), electronic circular dichroism (ECD), and optical rotation (OR), have been used. From these experimental data, in conjunction with corresponding quantum chemical predictions at B3LYP/6-311G* level, it is found that the ECD spectra of cephalochromin are dominated by its axial chirality and are not suitable to distinguish the (aS,2S,2'S) and (aS,2R,2'R) diastereomers and hence to determine the ACs of the central chirality elements. OR signs also did not distinguish the (aS,2S,2'S) and (aS,2R,2'R) diastereomers. On other hand, VCD spectrum of cephalochromin exhibited separate spectral features attributable to axial chirality and stereogenic centers, thereby allowing the determination of both types of chirality elements. This is the first investigation demonstrating that, because of vibrations specific to the studied stereogenic centers, VCD spectroscopy can be used to simultaneously determine the ACs of axial and central chirality elements whenever other chiroptical methods (ECD and OR) fail to report on them.
蔡觉晓; 周正洪; 唐除痴; 王宏根
2002-01-01
The title compound (+)-((-hydroxybenzyl)phenylphosphinic acid (C13H13O3P, Mr = 248.20) has been synthesized and characterized by 31P NMR, 1H NMR and elemental analysis. X-ray diffraction analysis at 293(2) K indicates that the compound belongs to monoclinic system, space group C2 with cell parameters: a = 23.560(8), b = 6.947(2), c = 7.854(3) (A。）, β = 91.273(6)°, V = 1285.2(7) (A。）3, Z = 4, Dc = 1.283 g/cm3, F(000) = 520 and ((MoK() = 0.207 mm-1. The number of independent reflections amounts to 1991, of which 1507 are observed reflections. The crystal structure has been determined by direct methods (SHELXL-97). The structure parameters are refined by full-matrix least-squares on F2 to R = 0.0437 and wR = 0.0893. The flack x parameter is - 0.0001. The absolute configuration of the (-carbon in the title compound is S.
Wang, Xiaojuan; Liu, Jiabao; Pandey, Pankaj; Chen, Jiabao; Fronczek, Frank R; Parnham, Stuart; Qi, Xinzhu; Doerksen, Robert J; Ferreira, Daneel; Sun, Hua; Li, Shuai; Hamann, Mark T
2017-09-14
The plants of the genus Kadsura are widely distributed in China, South Korea, and Japan. Their roots and stems are traditionally used to treat blood diseases and pain. The main bioactive constituents of Kadsura longipedunculata comprise highly oxygenated triterpenoids. Schiartane-type nortriterpenoids showed anti-HIV, anti-HBV, and cytotoxic bioactivities. For such compounds, the absolute configuration influences the bioactivities, and hence its unambiguous determination is essential. In this work, the absolute configurations of three highly oxygenated schiartane-type nortriterpenoids were unequivocally assigned using X-ray, ECD, and J-based configuration analysis and HSQC overlay data. The ethanol extract of Kadsura longipedunculata Finet et Gagnep was purified by column chromatography using silica, Sephadex LH-20, and ODS as substrates. To help assign the absolute configuration of schiartane-type nortriterpenoids, X-ray diffraction analysis, ECD experiment compared to ab initio computed data, DP4+ analysis, HSQC overlay, NOESY, and J-based configuration analysis were carried out. Hetero- and homo-nuclear coupling constants were extracted from HETLOC experiments. Three new highly oxygenated triterpenoids, micrandilactone I (1), micrandilactone J (2), and 22, 23-di-epi-micrandilactone J (3) were isolated. Their 2D structures were solved using NMR and HRESIMS data and their absolute configurations were elucidated using X-ray diffraction analysis, ECD experimental results compared to ab initio computed spectra, HSQC overlay, DP4 plus, NOESY, and J-based configuration analysis. Micrandilactone I (1) and 22, 23-di-epi-micrandilactone J (3) showed moderate hepatoprotective activity against APAP-induced toxicity in HepG2 cells with cell survival rates of 53.0 and 50.2%, respectively, at 10μM (bicyclol, 49.0%), while micrandilactone J (2) was inactive. This is the first comprehensive stereochemical assignment of a non-crystalline schiartane-type nortriterpenoid like 3
Muñoz, Marcelo A; González, Natalia; Joseph-Nathan, Pedro
2016-07-01
The absolute configuration of the naturally occurring isomers of 6β-benzoyloxy-3α-tropanol (1) has been established by the combined use of chiral high-performance liquid chromatography with electronic circular dichroism detection and optical rotation detection. For this purpose (±)-1, prepared in two steps from racemic 6-hydroxytropinone (4), was subjected to chiral high-performance liquid chromatography with electronic circular dichroism and optical rotation detection allowing the online measurement of both chiroptical properties for each enantiomer, which in turn were compared with the corresponding values obtained from density functional theory calculations. In an independent approach, preparative high-performance liquid chromatography separation using an automatic fraction collector, yielded an enantiopure sample of OR (+)-1 whose vibrational circular dichroism spectrum allowed its absolute configuration assignment when the bands in the 1100-950 cm(-1) region were compared with those of the enantiomers of esters derived from 3α,6β-tropanediol. In addition, an enantiomerically enriched sample of 4, instead of OR (±)-4, was used for the same transformation sequence, whose high-performance liquid chromatography follow-up allowed their spectroscopic correlation. All evidences lead to the OR (+)-(1S,3R,5S,6R) and OR (-)-(1R,3S,5R,6S) absolute configurations, from where it follows that samples of 1 isolated from Knightia strobilina and Erythroxylum zambesiacum have the OR (+)-(1S,3R,5S,6R) absolute configuration, while the sample obtained from E. rotundifolium has the OR (-)-(1R,3S,5R,6S) absolute configuration.
Santoro, Ernesto; Mazzeo, Giuseppe; Petrovic, Ana G; Cimmino, Alessio; Koshoubu, Jun; Evidente, Antonio; Berova, Nina; Superchi, Stefano
2015-08-01
The absolute configuration (AC) of the plant phytotoxin inuloxin A, produced by Inula viscosa, and of the fungal phytotoxin seiricardine A, obtained from Seiridium fungi, pathogen for cypress, has been determined by experimental measurements and theoretical simulations of chiroptical properties of three related methods, namely, Optical Rotatory Dispersion (ORD), Electronic Circular Dichroism (ECD), and Vibrational Circular Dichroism (VCD). Computational prediction by Density Functional Theory (DFT) of VCD spectra and by Time-dependent DFT (TDDFT) of ORD and ECD spectra allowed to assign (7R,8R,10S) AC to naturally occurring (+)-inuloxin A. In the case of compound (-)-seiricardine A, which lacks useful for the analysis UV-Vis absorption, and thus provides a hardly detectable ECD spectrum and quite low ORD values, an introduction of a suitable chromophore by chemical derivatization was performed. The corresponding derivative, 2-O-p-bromobenzoate ester, gave rise to an intense ECD spectrum and higher ORD and VCD values. The comparison of computed spectra with the experimental ones allowed to assign (1S,2R,3aS,4S,5R,7aS) AC to (-)-2-O-p-bromobenzoate ester of seiricardine A and then to (-)-seiricardine A. This study further supports a recent trend of concerted application of more than a single chiroptical technique toward an unambiguous assignment of AC of flexible and complex natural products. Moreover, the use of chemical derivatization, with insertion of suitable chromophoric moieties has allowed to treat also UV-Vis transparent molecules by ECD and ORD spectroscopies.
Network Entropy Based on Topology Configuration and Its Computation to Random Networks
LI Ji; WANG Bing-Hong; WANG Wen-Xu; ZHOU Tao
2008-01-01
A definition of network entropy is presented, and as an example, the relationship between the value of network entropy of ER network model and the connect probability p as well as the total nodes N is discussed. The theoretical result and the simulation result based on the network entropy of the ER network are in agreement well with each other. The result indicated that different from the other network entropy reported before, the network entropy defined here has an obvious difference from different type of random networks or networks having different total nodes. Thus, this network entropy may portray the characters of complex networks better. It is also pointed out that, with the aid of network entropy defined, the concept of equilibrium networks and the concept of non-equilibrium networks may be introduced, and a quantitative measurement to describe the deviation to equilibrium state of a complex network is carried out.
Evidente, Marco; Santoro, Ernesto; Petrovic, Ana G; Cimmino, Alessio; Koshoubu, Jun; Evidente, Antonio; Berova, Nina; Superchi, Stefano
2016-10-01
The absolute configuration of phytotoxins inuloxins B and C, produced by Inula viscosa, and with potential herbicidal activity for the management of parasitic plants, has been determined by Time-dependent density functional theory computational prediction of electronic circular dichroism and optical rotatory dispersion spectra. The inuloxin B has been converted to its 5-O-acetyl derivative, which due to its more constrained conformational features facilitated the computational analysis of its chiroptical properties. The analysis based on experimental and computed data led to assignment of absolute configuration to naturally occurring (+)-inuloxin B and (-)-inuloxin C as (7R,8R,10S,11S) and (5S,7S,8S,10S), respectively.
Li, Xiaoyong; Tanasova, Marina; Vasileiou, Chrysoula; Borhan, Babak
2008-02-13
A general and sensitive nonempirical protocol to determine the absolute configurations of erythro and threo diols, amino alcohols, and diamines is reported. Binding of diols to the porphyrin tweezer system is greatly enhanced by increasing the Lewis acidity of the metalloporphyrin. Supramolecular complexes formed between the porphyrin tweezer host and chiral substrates exhibited exciton-coupled bisignate CD spectra with predictable signs based on the substituents on the chiral center. The working model suggests that the observed helicity of the porphyrin tweezer is dictated via steric differentiation experienced by the porphyrin ring bound to each chiral center. A variety of erythro and threo substrates were investigated to verify this chiroptical method. Their absolute configurations were unequivocally determined, and thus a general mnemonic is provided for the assignment of chirality.
Lauridsen, A.; Cornett, Claus; Christensen, S. B.
1991-01-01
alpha-beta-Unsaturated esters of allylic alcohols have been shown to exhibit exciton coupling by circular dichroic spectroscopy. This coupling permits the establishment of the absolute configuration. The method was used to prove the absolute configuration at C-2 of archangelolide. Detailed NMR sp...
Bredikhin, Alexander A.; Gubaidullin, Aidar T.; Bredikhina, Zemfira A.; Krivolapov, Dmitry B.; Pashagin, Alexander V.; Litvinov, Igor A.
2009-02-01
Popular chiral drugs, guaifenesin, methocarbamol, and mephenesin were investigated by single-crystal X-ray analysis both for enantiopure and racemic samples. The absolute configurations for all substances were established through Flack parameter method. The conglomerate-forming nature for the compounds was confirmed by equivalence of crystal characteristics of enantiopure and racemic samples. The molecular structures and crystal packing details were evaluated and compared with one another for all three investigated substances.
Wang, Yun-Chao; Zhang, Yu-Wei; Zheng, Li-Hua; Bao, Yong-Li; Wu, Yin; Yu, Chun-Lei; Sun, Lu-Guo; Zhang, Yu; Huang, Yan-Xin; Sun, Ying; Li, Yu-Xin
2013-01-01
A new 2,5-diketopiperazine, (R)-2-(2-(furan-2-yl)-oxoethyl)-octahydropyrrolo[1,2-a]pyrazine-1,4-dione, and seven known compounds were isolated from the ethyl acetate extract of liquid fermentation broth of Armillaria mellea. The structures of the isolated compounds were established from NMR and HR-MS data. The absolute configuration of the new compound was established by comparing the experimental electronic circular dichroism (ECD) spectrum with the calculated ECD data.
Santodonato, Louis J.; Zhang, Yang; Feygenson, Mikhail; Parish, Chad M.; Gao, Michael C.; Weber, Richard J. K.; Neuefeind, Joerg C.; Tang, Zhi; Liaw, Peter K.
2015-01-01
The alloy-design strategy of combining multiple elements in near-equimolar ratios has shown great potential for producing exceptional engineering materials, often known as ‘high-entropy alloys’. Understanding the elemental distribution, and, thus, the evolution of the configurational entropy during solidification, is undertaken in the present study using the Al1.3CoCrCuFeNi model alloy. Here we show that, even when the material undergoes elemental segregation, precipitation, chemical ordering and spinodal decomposition, a significant amount of disorder remains, due to the distributions of multiple elements in the major phases. The results suggest that the high-entropy alloy-design strategy may be applied to a wide range of complex materials, and should not be limited to the goal of creating single-phase solid solutions.
Santodonato, Louis J; Zhang, Yang; Feygenson, Mikhail; Parish, Chad M; Gao, Michael C; Weber, Richard J K; Neuefeind, Joerg C; Tang, Zhi; Liaw, Peter K
2015-01-20
The alloy-design strategy of combining multiple elements in near-equimolar ratios has shown great potential for producing exceptional engineering materials, often known as 'high-entropy alloys'. Understanding the elemental distribution, and, thus, the evolution of the configurational entropy during solidification, is undertaken in the present study using the Al₁.₃CoCrCuFeNi model alloy. Here we show that, even when the material undergoes elemental segregation, precipitation, chemical ordering and spinodal decomposition, a significant amount of disorder remains, due to the distributions of multiple elements in the major phases. The results suggest that the high-entropy alloy-design strategy may be applied to a wide range of complex materials, and should not be limited to the goal of creating single-phase solid solutions.
Revision of the absolute configurations of bethosides B and C and their aglycone
Challinor, Victoria L; Hayes, Patricia Y; Bernhardt, Paul V
2011-01-01
The absolute stereochemistry of the steroidal saponins bethosides B and C was previously assigned as (22R,25R) on the basis of work that employed Horeau's method. Our studies of helosides A and B created doubt about both the original assignment and consequently our conclusion that relied upon it...
Yuan, H.S.H.; Stevens, R.C.; Bau, R. (Univ. of Southern California, Los Angeles, CA (United States)); Mosher, H.S. (Stanford Univ., CA (United States)); Koetzle, T.F. (Brookhaven National Lab., Upton, NY (United States))
1994-12-20
The absolute configuration of (+)-neopentyl-1-d alcohol, prepared by the reduction of 2,2-dimethylpropanol-1-d by actively fermenting yeast, has been determined to be S by neutron diffraction. The neutron study was carried out on the phthalate half ester of neopentyl-1-d alcohol, crystallized as its strychnine salt. The absolute configuration of the (-)-strychninium cation was first determined by an x-ray anomalous dispersion study of its iodide salt. The chiral skeleton of strychnine then served as a reference from which the absolute configuration of the -O-CHD-C(CH[sub 3])[sub 3] group of neopentyl phthalate was determined. Difference Fourier maps calculated from the neutron data showed unambiguously that the -O-CHD-C(CH[sub 3])[sub 3] groups of both independent molecules in the unit cell had the S configuration. This work proves conclusively that the yeast system reduces aldehydes by delivering hydrogen to the re face of the carbonyl group. Crystallographic details: (-)-strychninium (+)-neopentyl-1-d phthalate, space group P2[sub 1] (monoclinic), a = 18.564(6) [angstrom], b = 7.713(2) [angstrom], c = 23.361(8) [angstrom], [beta] = 94.18(4)[degrees], V = 3336.0(5) [angstrom][sup 3], Z = 2 (T = 100 K). Final agreement factors are R(F) = 0.073 for 2768 reflections collected at room temperature (x-ray analysis) and R(F) = 0.144 for 960 reflections collected at 100 K (neutron analysis). 49 refs., 7 figs., 2 tabs.
Chong, Song-Ho; Ham, Sihyun
2011-03-01
We report the recent development of a theoretical method to calculate the protein configurational entropy in explicit solvent from statistical properties of the solvent-averaged protein potential energy surface. This method can be implemented by combining molecular simulation and integral-equation theory of liquids. Our method does not assume Gaussian distribution of protein configurations, and can be applied to unfolded or misfolded states of protein in which an average protein structure is not well defined. An illustrative application is made to misfolded state of 42-residue amyloid beta protein in water.
Ricotta, Carlo
2003-01-01
Traditional diversity measures such as the Shannon entropy are generally computed from the species' relative abundance vector of a given community to the exclusion of species' absolute abundances. In this paper, I first mention some examples where the total information content associated with a given community may be more adequate than Shannon's average information content for a better understanding of ecosystem functioning. Next, I propose a parametric measure of statistical information that contains both Shannon's entropy and total information content as special cases of this more general function.
Kuwada, Takeshi; Fukui, Miyako; Hata, Toshiyuki; Choshi, Tominari; Nobuhiro, Junko; Ono, Yukio; Hibino, Satoshi
2003-01-01
The specific optical rotations of (R)-oxopropaline D calculated by two ab initio MO methods were +52+/-31 degrees and +61+/-29 degrees, respectively, and (+)-oxopropaline D (3) was presumed to have an R-configuration. On the basis of this theoretical result, the reaction of 1-litio-beta-carboline with (R)-glyceraldehyde acetonide followed by oxidation with MnO(2) gave (R)-oxopropaline D acetonide (4a), which was consistent with the previously synthesized (+)-oxopropaline D acetonide (4) in all respects. From the results of theoretical calculations and the experimental synthesis, we determined that natural (+)-oxopropaline D (3) has an R-configuration.
NMR assignment of the absolute configuration of C-25 in furostanol steroidal saponins
Challinor, Victoria L; Piacente, Sonia; De Voss, James J
2012-01-01
solvents led to conflicting assignments of stereochemistry. An experimental survey revealed that, while the chemical shifts of H(2)-26 exhibit a dependence on C-25 configuration, it is less pronounced in methanol-d4 than pyridine-d5 solvent, and thus the general rule derived for pyridine-d5 fails when NMR...
Bredikhina, Zemfira A.; Zakharychev, Dmitry V.; Gubaidullin, Aidar T.; Bredikhin, Alexander A.
2009-11-01
Spontaneous resolution of cardioselective β1-adrenergic blocker bevantolol hydrochloride1·HCl was established by IR spectroscopy, differential scanning calorimetry, and by single crystal X-ray analysis both for enantiopure and racemic samples. The absolute configuration of 1·HCl was evaluated through Flack parameter method. The molecular structure and crystal packing details were evaluated; the symmetry independent fragment of the P1 unit cell consists of two molecules which have almost identical spatial arrangement, but differ sufficiently in the nature of nitrogen atoms: quaternary form in one case and free amine form in the other.
Kowalska, Joanna; Lewdorowicz, Magdalena; Zuberek, Joanna; Bojarska, Elzbieta; Stepinski, Janusz; Stolarski, Ryszard; Darzynkiewicz, Edward; Jemielity, Jacek
2007-01-01
Enzymatic cleavage of the P-chiral diastereoisomers of the 5' mRNA cap analogue bearing phosphorothioate moiety in alfa position of 5',5'-triphosphate bridge (m(7)Gppp(S)G D1 and D2) was performed by human Decapping Scavenger (DcpS) enzyme. Analysis of the degradation products allowed to estimate the absolute configuration at the asymmetric phosphorus atoms in examined compounds via correlation with the R(P) and S(P) diastereoisomers of guanosine 5'-O-(1-thiodiphosphate) (GDPalphaS).
Nakahashi, Atsufumi; Yaguchi, Yoshihiro; Miura, Nobuaki; Emura, Makoto; Monde, Kenji
2011-04-25
Sotolon (1) and maple furanone (2) are naturally occurring chiral furanones. These 5-substituted-2(5H)-furanones are industrially significant aroma compounds due to their characteristic organoleptic properties and extraordinarily low odor thresholds. Each enantiomer of 1 and 2 was successfully obtained by preparative enantioselective supercritical fluid chromatography. The absolute configuration of 1 was confirmed as (R)-(-)-1 and (S)-(+)-1 by adopting the vibrational circular dichroism (VCD) approach. The absolute configuration of 2, which has remained ambiguous since its discovery in 1957, was determined as (R)-(+)-2 and (S)-(-)-2 for the first time by the VCD technique. Surprisingly, the signs of the optical rotation of 2 are opposite of those of 1 regardless of their identical absolute configurations. This observation emphasizes the risk in absolute configurational assignments based on comparison of optical rotation signs of similar structures. Odor evaluation of the enantiomers of 2 revealed different odor intensities.
Absolute configuration of falcarinol (9Z-heptadeca-1,9-diene-4,6-diyn-3-ol) from Pastinaca sativa.
Corell, Mireia; Sheehy, Emile; Evans, Paul; Brunton, Nigel; Valverde, Juan
2013-08-01
Falcarinol (9Z-heptadeca-1,9-diene-4,6-diyn-3-ol; (1) is a polyacetylene commonly found in several plant families. The absolute configuration of naturally occurring 1 is not clear and contradictory results have been reported in the literature. Determination of the absolute configuration of 1 from Pastinaca sativa L. was carried out. Isolation of 95% pure 1 was performed via successive fractionation and preparative-HPLC. A racemic mixture comprised of 3R-1 and 3S-1 was synthesized in order to confirm the absolute configuration of the isolated natural product using chiral HPLC. Based on a combination of chiral HPLC and specific rotation, 1 present in P. saliva was found to have a 3R absolute configuration (i.e. (3R, 9Z)-heptadeca-1,9-diene-4,6-diyn-3-ol).
Schmidt, Manuel; Sun, Han; Rogne, Per; Scriba, Gerhard K E; Griesinger, Christian; Kuhn, Lars T; Reinscheid, Uwe M
2012-02-15
Even though the important antimalaria drug rac-erythro-mefloquine HCl has been on the market as Lariam for decades, the absolute configurations of its enantiomers have not been determined conclusively. This is needed, since the (-) enantiomer is believed to cause adverse side effects in malaria treatment resulting from binding to the adenosine receptor in the human brain. Since there are conflicting assignments based on enantioselective synthesis and anomalous X-ray diffraction, we determined the absolute configuration using a combination of NMR, optical rotatory dispersion (ORD), and circular dichroism (CD) spectroscopy together with density functional theory calculations. First, structural models of erythro-mefloquine HCl compatible with NMR-derived (3)J(HH) scalar couplings, (15)N chemical shifts, rotational Overhauser effects, and residual dipolar couplings were constructed. Second, we calculated ORD and CD spectra of the structural models and compared the calculated data with the experimental values. The experimental results for (-)-erythro-mefloquine HCl matched our calculated chiroptical data for the 11R,12S model. Accordingly, we conclude that the assignment of 11R,12S to (-)-erythro-mefloquine HCl is correct.
Mazzeo, Giuseppe; Santoro, Ernesto; Andolfi, Anna; Cimmino, Alessio; Troselj, Pavle; Petrovic, Ana G; Superchi, Stefano; Evidente, Antonio; Berova, Nina
2013-04-26
The absolute configuration (AC) of the bioactive metabolites phyllostin (1) and scytolide (2), two hexahydro-1,4-benzodioxines produced by Phyllosticta cirsii, and oxysporone (3), a dihydrofuropyranone recently isolated from a strain of Diplodia africana, has been assigned by computational analysis of their optical rotatory dispersion (ORD), electronic circular dichroism (ECD), and vibrational circular dichroism (VCD) spectra. Computational prediction of ORD, ECD, and VCD allowed us to assign (3S,4aR,8S,8aR) AC to naturally occurring (-)-1, while (4aR,8S,8aR) AC was assigned to (-)-2 employing only ECD and VCD, because in this case ORD analysis turned out to be unsuitable for AC assignment. Theoretical prediction of both ORD and ECD spectra of 3 led to assignment of (4S,5R,6R) AC to (+)-3. In this case a satisfactory agreement between experimental and calculated VCD spectra was obtained only after taking into account solvent effects. This study shows that in the case of flexible and complex natural products only a concerted application of more than a single chiroptical technique permits unambiguous assignment of absolute configuration.
Chang, Chih-Wei; Chein, Rong-Jie
2011-05-20
The first enantioselective total synthesis of (+)-(R)-concentricolide, the enantiomer of an anti-HIV-1 agent isolated from Daldinia concentrica, from 2-iodophenol in 7 steps reveals the (S)-configuration for the natural form of the furanophthalide. The key features include an anionic ortho-Fries rearrangement to furnish 3-iodosalicylamide, facile construction of the benzofuran system employing the tandem Sonogashira coupling annulation reaction, directed ortho metalation to introduce a propanoyl group, as well as CBS reduction, establishing the stereocenter enantioselectively.
Rode, Joanna E; Frelek, Jadwiga
2017-11-01
The primary purpose of this work was to demonstrate the suitability of circular dichroism (CD) spectroscopy in stereochemical studies of α,β-unsaturated oximes, with particular emphasis on determination of E and Z geometry of the oxime double bond. As models for this study, O-phenyl and O-triphenylmethyl (trityl) oximes of 4-hydroxy-2-methylcyclopent-2-en-1-one were selected. These model compounds differ in both absolute configuration at C4 carbon atom and E-Z configuration of the oxime double bond. The basic dichroic technique applied was electronic circular dichroism (ECD) assisted by quantum-chemical calculations and vibrational circular dichroism (VCD) for selected cases. Such an approach enabled effective implementation of both goals. Thus, we were able to associate the signs of Cotton effects in the range of 190-240 nm with the absolute configuration at C4 and within 240-300 nm with the E- or Z-geometry of the oxime double bond. Within this work, optical activity of the protecting trityl group was also studied towards formation of the propeller-shaped conformations by using the same combined CD/DFT methodology. As shown, the helical structure of the trityl group has a considerable influence on the ECD spectra. However, the MPM and PMP conformers of the trityl group are in fact almost equally populated in the conformational equilibrium, making it impossible to distinguish them. On the other hand, rotamers of the hydroxyl group at C4 show a decisive impact on the VCD spectra in both phenoxy and trityl oximes. © 2017 Wiley Periodicals, Inc.
Absolute Free Energy of Binding and Entropy of the FKBP12-FK506 Complex: Effects of the Force Field.
General, Ignacio J; Meirovitch, Hagai
2013-10-08
The hypothetical scanning molecular dynamics (HSMD) method combined with thermodynamic integration (HSMD-TI) has been extended recently for calculating ΔA(0)-the absolute free energy of binding of a ligand to a protein. With HSMD-TI, ΔA(0) is obtained in a new way as a sum of several components, among them is ΔSligand-the change in the conformational entropy as the ligand is transferred from the bulk solvent to the active site-this entropy is obtained by a specific reconstruction procedure. This unique aspect of HSMD (which is useful in rational drug design) is in particular important for treating large ligands, where ΔSligand might be significant. Technically, one should verify that the results for ΔSligand converge-a property that might become more difficult for large ligands; therefore, studying ligands of increasing size would define the range of applicability of HSMD-TI for binding. In this paper, we check the performance of HSMD-TI by applying it to the relatively large ligand FK506 (126 atoms) complexed with the protein FKBP12, where ΔA(0) = -12.8 kcal/mol is known experimentally as well as the crystal structure of the complex. This structure was initially equilibrated by carrying out a 100 ns molecular dynamics trajectory, where the system is modeled by the AMBER force field, TIP3P water, and Particle Mesh Ewald. HSMD-TI calculations were carried out in three conformational regions defined by the intervals [0.2,2], [2,5], and [5,100] ns along the trajectory, where local equilibration of the total energy has been observed; we obtained ΔA(0) = -13.6 ± 1.1, -16.6 ± 1.4, and -16.7 ± 1.4 kcal/mol, respectively indicating the following: (1) The second and third regions belong to the same conformational subspace of the complex, which is different from the [0.2,2] ns subspace. (2) The unsatisfactory result for ΔA(0) obtained in the well equilibrated (hence theoretically preferred) latter regions reflects the nonperfect modeling used, which however (3
Banerjee, Atreyee; Nandi, Manoj Kumar; Sastry, Srikanth; Bhattacharyya, Sarika Maitra
2016-07-01
In this paper, we present a study of supercooled liquids interacting with the Lennard Jones potential and the corresponding purely repulsive (Weeks-Chandler-Andersen) potential, over a range of densities and temperatures, in order to understand the origin of their different dynamics in spite of their structures being similar. Using the configurational entropy as the thermodynamic marker via the Adam Gibbs relation, we show that the difference in the dynamics of these two systems at low temperatures can be explained from thermodynamics. At higher densities both the thermodynamical and dynamical difference between these model systems decrease, which is quantitatively demonstrated in this paper by calculating different parameters. The study also reveals the origin of the difference in pair entropy despite the similarity in the structure. Although the maximum difference in structure is obtained in the partial radial distribution function of the B type of particles, the rdf of AA pairs and AB pairs gives rise to the differences in the entropy and dynamics. This work supports the observation made in an earlier study [A. Banerjee et al., Phys. Rev. Lett. 113, 225701 (2014)] and shows that they are generic in nature, independent of density.
Einhorn, Jacques; Guerrero, Angel; Ducrot, Paul-Henri; Boyer, François-Didier; Gieselmann, Mary; Roelofs, Wendell
1998-01-01
The sex pheromone emitted by the female oleander scale, Aspidiotus nerii (Homoptera, Diaspididae), has been isolated and characterized as (1R,2S)-cis-2-isopropenyl-1-(4′-methyl-4′-penten-1′-yl)cyclobutaneethanol acetate by using advanced MS and NMR spectroscopic methods, as well as a variety of microderivatization sequences. The structure has been confirmed by stereo- and enantioselective synthesis of the four possible stereoisomers. The absolute configuration has been determined by comparison of the activity of the cis (1S,2R) and (1R,2S) enantiomers with that exhibited by the natural material in greenhouse bioassays and field tests. The structure of this sesquiterpenoid pheromone is new in the coccids and in the pheromone field in general. PMID:9707567
Megati, S; Goren, Z; Silverton, J V; Orlina, J; Nishimura, H; Shirasaki, T; Mitsuya, H; Zemlicka, J
1992-10-30
Synthesis of optically pure (-)- and (+)-adenallene 2 and 3 is described. Racemic adenallene (1a) was subjected to deamination with adenosine deaminase monitored by HPLC using a Chiralcel CA-1 column to give (-)-adenallene (2) and (+)-hypoxallene (4). The latter compound was converted to acetate 5. The reaction of 5 with trifluoromethanesulfonic anhydride and pyridine followed by ammonolysis furnished acetate 6 or (+)-adenallene (3) depending on the solvent used in the last step. Acetate 5 was smoothly transformed to the 6-chloro derivative 7, but an attempted ammonolysis led only to racemization and decomposition. Single crystal X-ray diffraction established the R-configuration of (-)-enantiomer 2. The latter forms a pseudosymmetric dimer in the lattice with the adenine moiety in an anti-like conformation. The torsional angles of the allenic bonds show departures from 90 degrees (91 and 97 degrees, respectively) and rotameric preference of the hydroxymethyl groups is different in both molecules of the dimer. The R-enantiomer 2 inhibited the replication and cytopathic effect of human immunodeficiency virus (HIV-1) in ATH8 cell culture with an IC50 of 5.8 microM, whereas the S-enantiomer 3 was less active (IC50 > 200 microM). The enantioselectivity of the anti-HIV effect is significantly lower than that of 2',3'-dideoxyadenosine. Kinetics of deamination of R- and S-enantiomers 2 and 3 catalyzed by adenosine deaminase gave the following parameters: Km values of S-form 3 and R-form 2 were 0.41 and 0.52 mM with Vmax being 530 and 18.5 mumol/min, respectively [corrected]. Again,, a much lower level of enantioselectivity of deamination was observed than that of D- and L-adenosine. These results indicate (i) different enantioselectivity of enantiomers 2 and 3 as HIV inhibitors and adenosine deaminase substrates and (ii) both R- and S-enantiomers 2 and 3 can function as nucleoside analogues with varied enantioselectivity for different enzymes or receptors.
Andras Dezso
2017-05-01
Full Text Available The configurational entropy of nanoscale solutions is discussed in this paper. As follows from the comparison of the exact equation of Boltzmann and its Stirling approximation (widely used for both macroscale and nanoscale solutions today, the latter significantly over-estimates the former for nano-phases and surface regions. On the other hand, the exact Boltzmann equation cannot be used for practical calculations, as it requires the calculation of the factorial of the number of atoms in a phase, and those factorials are such large numbers that they cannot be handled by commonly used computer codes. Herewith, a correction term is introduced in this paper to replace the Stirling approximation by the so-called “de Moivre approximation”. This new approximation is a continuous function of the number of atoms/molecules and the composition of the nano-solution. This correction becomes negligible for phases larger than 15 nm in diameter. However, the correction term does not cause mathematical difficulties, even if it is used for macro-phases. Using this correction, future nano-thermodynamic calculations will become more precise. Equations are worked out for both integral and partial configurational entropies of multi-component nano-solutions. The equations are correct only for nano-solutions, which contain at least a single atom of each component (below this concentration, there is no sense to make any calculations.
Sánchez-Castellanos, Mariano; Bucio, María A; Hernández-Barragán, Angelina; Joseph-Nathan, Pedro; Cuevas, Gabriel; Quijano, Leovigildo
2015-03-01
The absolute configuration of was deduced by vibrational circular dichroism together with the evaluation of the Flack and Hooft X-ray parameters. Vibrational circular dichroism exciton coupling, using the carbonyl group signals, confirmed the absolute configuration of . In addition, sodium borohydride reduction of the 11,13-double bond of 6-epi-desacetyllaurenobiolide () yields an almost equimolecular mixture of C11 epimers, while reduction of the same double bond of 6-epi-laurenobiolide () provided almost exclusively the (11S) diastereoisomer . © 2015 Wiley Periodicals, Inc.
Celia Bustos-Brito
2016-09-01
Full Text Available Chemical investigation of the leaves from Ageratina glabrata yielded four new thymol derivatives, namely: 10-benzoyloxy-8,9-dehydro-6-hydroxythymol isobutyrate (4, 10-benzoyloxy-8,9-dehydrothymol (5, 10-benzoyloxythymol (6 and 10-benzoyloxy-6,8-dihydroxy-9-isobutyryl-oxythymol (7. In addition, (8S-10-benzoyloxy-8,9-epoxy-6-hydroxythymol isobutyrate (1, together with other two already known thymol derivatives identified as 10-benzoyloxy-8,9-epoxy-6-methoxythymol isobutyrate (2 and 10-benzoyloxy-8,9-epoxythymol isobutyrate (3 were also obtained. In this paper, we report the structures and complete assignments of the 1H and 13C-NMR data of compounds 1–7, and the absolute configuration for compound 1, unambiguously established by single crystal X-ray diffraction, and evaluation of the Flack parameter. The in vitro antiprotozoal assay showed that compound 1 and its derivative 1a were the most potent antiamoebic and antigiardial compounds. Both compounds showed selectivity and good antiamoebic activity comparable to emetine and metronidazole, respectively, two antiprotozoal drugs used as positive controls. In relation to anti-propulsive effect, compound 1 and 1a showed inhibitory activity, with activities comparable to quercetin and compound 9, two natural antipropulsive compounds used as positive controls. These data suggest that compound 1 may play an important role in antidiarrheal properties of Ageratina glabrata.
Seo, Jiyoung; Kang, Su-Il; Won, Dongho; Kim, Mihyang; Ryu, Ji-Young; Kang, Suk-Woo; Um, Byung-Hun; Pan, Cheol-Ho; Ahn, Joong-Hoon; Chong, Youhoon; Kanaly, Robert A; Han, Jaehong; Hur, Hor-Gil
2011-03-01
Biphenyl dioxygenase from Pseudomonas pseudoalcaligenes strain KF707 expressed in Escherichia coli was found to exhibit monooxygenase activity toward four stereoisomers of isoflavan-4-ol. LC-MS and LC-NMR analyses of the metabolites revealed that the corresponding epoxides formed between C2' and C3' on the B-ring of each isoflavan-4-ol substrate were the sole products. The relative reactivity of the stereoisomers was found to be in the order: (3S,4S)-cis-isoflavan-4-ol > (3R,4S)-trans-isoflavan-4-ol > (3S,4R)-trans-isoflavan-4-ol > (3R,4R)-cis-isoflavan-4-ol and this likely depended upon the absolute configuration of the 4-OH group on the isoflavanols, as explained by an enzyme-substrate docking study. The epoxides produced from isoflavan-4-ols by P. pseudoalcaligenes strain KF707 were further abiotically transformed into pterocarpan, the molecular structure of which is commonly found as part of plant-protective phytoalexins, such as maackiain from Cicer arietinum and medicarpin from Medicago sativa.
G. E. Aguilar-Pineda
2014-01-01
Full Text Available Temperature and chemically induced denaturation comprise two of the most characteristic mechanisms to achieve the passage from the native state N to any of the unstructured states Dj in the denatured ensemble in proteins and peptides. In this work we present a full analytical solution for the configurational partition function qs of a homopolymer chain poly-X in the extended Zwanzig model (EZM for a quasisigmoidal denaturation profile. This solution is built up from an EZM exact solution in the case where the fraction α of native contacts follows exact linear dependence on denaturant’s concentration ζ; thus an analytical solution for L in the case of an exact linear denaturation profile is also provided. A recently established connection between the number ν of potential nonnative conformations per residue and temperature-independent helical propensity ω complements the model in order to identify specific proteinogenic poly-X chains, where X represents any of the twenty naturally occurring aminoacid residues. From qs, equilibrium thermodynamic potentials like entropy and average internal energy 〈E〉 and thermodynamic susceptibilities like specific heat C are calculated for poly-valine (poly-V and poly-alanine (poly-A chains. The influence of the rate at which native contacts denature as function of ζ on thermodynamic stability is also discussed.
Izumi, Hiroshi; Ogata, Atsushi; Nafie, Laurence A; Dukor, Rina K
2009-01-01
The absolute configuration and solution conformation of (R)-(+)-malathion were determined by using vibrational circular dichroism spectroscopy and a fragment-conformational search with a recently published conformational code. The determination of molecular stereochemistry was carried out without a conformational search using molecular mechanics calculations. Density functional theory calculations of the fragments of (R)-malathion, ethyl propionate, (R)-ethyl 2-(methylthio)propanoate, (R)-diethyl 2-(methylthio)succinate, and O,O,S-trimethyl phosphorodithioate were carried out, and the principal conformational features of the fragments were profiled. This fragment-conformational search reduces the time needed for the selection of the predominant conformations for (R)-malathion and significantly improves the accuracy of the determination of absolute configuration.
Podlech, Joachim; Fleck, Stefanie C; Metzler, Manfred; Bürck, Jochen; Ulrich, Anne S
2014-09-01
Altertoxins I-III, alterlosins I and II, alteichin (alterperylenol), stemphyltoxins I-IV, stemphyperylenol, stemphytriol, 7-epi-8-hydroxyaltertoxin I, and 6-epi-stemphytriol are mycotoxins derived from perylene quinone, for which the absolute configuration was not known. Electronic circular dichroism (ECD) spectra were calculated for these compounds and compared with measured spectra of altertoxins I-III, alteichin, and stemphyltoxin III and with reported Cotton effects. Specific rotations were calculated and compared with reported specific rotations. The absolute configuration of all the toxins, except for stemphyltoxin IV, could thus be determined. The validity of the assignment was high whenever reported ECD data were available for comparison, and the validity was lower when the assignment was based only on the comparison of calculated and reported specific rotations. ECD spectra are intrinsically different for toxins with a biphenyl substructure and for toxins derived from dihydroanthracene.
Omata, Kenji; Fujioka, Mika; Kabuto, Kuninobu; Sasaki, Yoichi
2008-10-28
(1)H NMR analyses of individual alpha-amino acids in their mixture were simultaneously conducted in the presence of Sm-(pdta-d(8)) in water: high regularity, promising for direct simultaneous determination of absolute configurations of each alpha-amino acids in peptide hydrolysate mixtures, was observed between absolute configuration and the induced shifts.
Rúnarsson, Ögmundur Vidar; Benkhäuser, Christian; Christensen, Niels Johan;
2015-01-01
/6-31G(d,p) level of theory. The absolute configuration of (+)-2 was also determined to (R,R)-2 by anomalous X-ray diffraction (AXRD) in a chiral space group P2(1)2(1)2(1) using Cu-irradiation resulting in a very low Flack parameter of -0.06(3), despite the heaviest element being an oxygen atom, thus...
Wang, Zhi-Qiang; Wu, Cheng-Jun; Wang, Zhen-Hui; Huang, Chao; Huang, Jian; Wang, Jin-Hui; Sun, Tie-Min
2017-10-01
In this study, the stereochemistry of a new isopimarane-type diterpenoid isolated from the Callicarpa macrophylla Vahl, Callicapene M3, was studied by experimental electronic circular dichroism and vibrational circular dichroism with the aid of TDDFT theoretical calculations. The good consistence between the experimental and simulated circular dichroism has clearly confirmed the absolute configuration of the title compound as (4S, 5S, 9S, 10S, 13S, 14S)-14α-hydroxy-7,15-isopimaradien-18-oic acid.
Welch, Christopher J; Zawatzky, Kerstin; Makarov, Alexey A; Fujiwara, Satoshi; Matsumoto, Arimasa; Soai, Kenso
2016-12-20
An investigation is reported on the use of the autocatalytic enantioselective Soai reaction, known to be influenced by the presence of a wide variety of chiral materials, as a generic tool for measuring the enantiopurity and absolute configuration of any substance. Good generality for the reaction across a small group of test analytes was observed, consistent with literature reports suggesting a diversity of compound types that can influence the stereochemical outcome of this reaction. Some trends in the absolute sense of stereochemical enrichment were noted, suggesting the possible utility of the approach for assigning absolute configuration to unknown compounds, by analogy to closely related species with known outcomes. Considerable variation was observed in the triggering strength of different enantiopure materials, an undesirable characteristic when dealing with mixtures containing minor impurities with strong triggering strength in the presence of major components with weak triggering strength. A strong tendency of the reaction toward an 'all or none' type of behavior makes the reaction most sensitive for detecting enantioenrichment close to zero. Consequently, the ability to discern modest from excellent enantioselectivity was relatively poor. While these properties limit the ability to obtain precise enantiopurity measurements in a simple single addition experiment, prospects may exist for more complex experimental setups that may potentially offer improved performance.
Majewska, Paulina
2015-08-01
2-Hydroxy-2-(ethoxyphenylphosphinyl)acetic acid, a new type of organophosphorus compound possessing two stereogenic centers, was investigated. Racemic 2-butyryloxy-2-(ethoxyphenylphosphinyl)acetic acid was synthesized and hydrolyzed using four bacterial species as biocatalysts. In all cases the reaction was more or less stereoselective and isomers bearing a phosphorus atom with an (SP)-configuration were hydrolyzed preferentially. The observed (1)H and (31)P NMR chemical shifts of Mosher esters of 2-hydroxy-2-(ethoxyphenylphosphinyl)acetic acid were correlated with the configurations of both stereogenic centers of all four stereoisomers.
CHEN; Fanrong(陈繁荣); Rodney; C.Ewing
2003-01-01
Spent UO2 fuel will rapidly be altered to U6+ phases in nuclear waste repositories. Because most uranyl phases are based on sheet or chain structures and usually contain several molecular water groups, site-mixing, vacancies, as well as disorder in the orientation of hydrogen bonds may occur. A systematic survey of the published crystallographic data for uranates, uranyl oxide hydrates, phosphates, silicates, carbonates, and sulfates demonstrates that site-mixing apparently occurs in the structures of at least 31 uranyl phases. Calculations of the ideal site-mixing entropy indicate that the residual contribution that arises from substitution and vacancies to the third-law entropies of some uranyl phases is large. A brief examination of the crystal chemistry of water molecules in uranyl phases suggests that considerable residual entropy may be caused by the disorder of hydrogen bonds associated with interstitial H2O groups. In the geochemical environment that expected to occur in the near-field of nuclear waste repositories, the existence of structure-configurational entropy may reduce the uranium concentration of several log units in solutions equilibrated with some uranyl phases. Therefore, compositional analysis and structural determinations must be made on the samples used in calorimetric measurements, and the calorimetric data must be combined with solubility data to evaluate the thermodynamic stability of the interested phases.
Covington, Cody L; Raghavan, Vijay; Smuts, Jonathan P; Armstrong, Daniel W; Polavarapu, Prasad L
2017-11-01
The absolute configuration (AC) of an axially chiral sulfonate (aCSO), 3,5-dimethyl-2-(naphthalen-1-yl)-6-(naphthalen-1-yl)benzenesulfonate (labeled as aCSO5), was investigated using optical rotatory dispersion (ORD), electronic circular dichroism (ECD), and vibrational circular dichroism (VCD) spectroscopies. All three methods led to the same conclusion and the AC of aCSO5 is reliably determined to be (-)-(aR, aR), or conversely (+)-(aS, aS). © 2017 Wiley Periodicals, Inc.
I. Wayan Mudianta
2013-12-01
Full Text Available A small sample of (−-(5R,6Z-dendrolasin-5-acetate, which was fully characterized by 2D NMR studies, was isolated from the nudibranch Hypselodoris jacksoni, along with the sesquiterpenes (+-agassizin, (−-furodysinin, (−-euryfuran, (−-dehydroherbadysidolide and (+-pallescensone. A synthetic sample ([α]D −8.7 of the new metabolite was prepared by [1,2]-Wittig rearrangement of a geranylfuryl ether followed by acetylation of purified alcohol isomers. The absolute configuration at C-5 was established as R by the analysis of MPA ester derivatives of (Z-5-hydroxydendrolasin obtained by preparative enantioselective HPLC.
Andrade, Francisco A. da C.; Mendes, Maricleide P. de L.; Fonseca, Neuracy C. da, E-mail: fandrade@ufba.br [Universidade Federal da Bahia (UFBA), Salvador, BA (Brazil). Instituto de Quimica. Departamento de Quimica Organica
2013-06-15
The mandelic, atrolactic and lactic acid esters of the (S)-2-methyl-1-butanol were examined as diastereomeric derivatives for the stereochemical analysis of the mentioned acids by {sup 1}H nuclear magnetic resonance (NMR) at 300 MHz. The diastereomeric esters showed distinctive signals in the methylenic absorption range (O-CH{sub 2}-CH) of the alcoholic moieties. By spectral analysis at this region, absolute configurations were attributed, chemical shifts of the correspondent pro-(R) and pro-(S) hydrogens from the methylene group of the alcohol moiety were assigned and enantiomeric compositions were determined for the original partially resolved acids. (author)
Claudio Bruno
2013-01-01
Full Text Available An efficient microwave-assisted synthesis of (±-mandelic acid-d5 was developed. The racemic mixture was resolved by diastereomeric salt formation using 1-phenylethylamine enantiomers as resolving agents. At each step, the resolution process was checked by determining mandelic acid-d5 enantiomer ee values directly on fractional crystallized diastereomeric salts by chiral capillary electrophoresis analysis. Highly enriched (−- and (+-mandelic acid-d5 (95% and 90% ee, resp. were obtained and their absolute configurations—R and S, respectively—were determined by correlation of the (−-mandelic acid-d5 circular dichroism spectrum to the (R-mandelic acid one.
Goto, M; Hirose, J; Noji, M; Lee, K I; Saito, R; Kidani, Y
1992-04-01
The absolute configuration of the anti-tumor complex trans(OH)-Pt(OH)2(malonato)(1R,2R-cyclohexanediamine) was determined by X-ray anomalous scattering technique. The final unit cell was monoclinic, space group P2(1) with a = 9.142 A, b = 7.788 A, c = 11.946 A, beta = 96.48 degrees, Z = 2. The crystal structure was determined by direct method and difference Fourier synthesis, and refined to R = 0.025 and Rw = 0.033 based on 2768 independent reflections. The platinum atom has roughly octahedral coordination. The cyclohexane ring has the expected chair configuration, with two amino groups in equatorial positions while the malonato ligand, in contrast, shows a boat conformation for six membered Pt O-C-C-C-O ring.
Suzuki, Masaki; Deschamps, Jeffrey R; Jacobson, Arthur E; Rice, Kenner C
2015-04-01
Illicit rac-MDPV (3,4-methylenedioxypyrovalerone), manufactured in clandestine labs, has become widely abused for its cocaine-like stimulant properties. It has recently been found as one of the toxic materials in the so-called "bath salts," producing, among other effects, psychosis and tachycardia in humans when introduced by any of the several routes of administration (e.g., intravenous, oral, etc.). The considerable toxicity of this "designer drug" probably resides in one of the enantiomers of the racemate. In order to obtain a sufficient amount of the enantiomers of rac-MDPV to determine their activity, we improved the known synthesis of rac-MDPV and found chemical resolving agents, (+)- and (-)-2'-bromotetranilic acid, that gave the MDPV enantiomers in >96% enantiomeric excess as determined by (1) H nuclear magnetic resonance and chiral high-performance liquid chromatography. The absolute stereochemistry of these enantiomers was determined by single-crystal X-ray diffraction studies.
Zhou, Zhao-Hui; Yan, Wen-Bin; Wan, Hui-Lin; Tsai, Khi-Rui
2002-06-07
Reaction of sodium or potassium molybdate and excess malic acid in a wide range of pH values (pH 4.0-7.0) resulted in the isolation of two cis-dioxo-bis(malato)-Mo(VI) complexes, viz. Na(3)[MoO(2)H(S-mal)(2)] and K(3)[MoO(2)H(S-mal)(2)].H(2)O (H(3)mal=malic acid). The sodium complex is also characterized by an X-ray structure analysis, showing that the mononuclear Mo units are linked together via very strong symmetric CO(2)...H... O(2)C-hydrogen bond [2.432(5) A], forming a polymeric chain. The molybdenum atoms are quasi-octahedrally coordinated by two cis-oxo groups and two bidentate malate ligands via its alkoxy and alpha-carboxyl groups, while the beta-carboxylic and carboxylate groups remain uncomplexed, as the coordination of vicinal carboxylate and alkoxide of homocitrate in FeMo cofactor of nitrogenase. The absolute configuration of the metal center in this S-malato complex is assigned as Lambda and the homochirality within the chain is established as a homochiral form ...Lambda(S)-Lambda(S)-Lambda(S)-Lambda(S)... . It is proposed that the chiral configuration of the metal center in wild-type FeMo-co biosynthesis might be induced by the early coordination of the chiral R-homocitric acid, while a mixture of raceme might be obtained in the biosynthesis of NifV(-) FeMo-cofactor. The absolute configuration of wild-type FeMo-cofactor is assigned as Delta(R).
Alwera, Shiv; Bhushan, Ravi
2016-08-01
Diastereomers of (RS)-propranolol were synthesized using (S)-levofloxacin-based new chiral derivatizing reagents (CDRs). Levofloxacin was chosen as the pure (S)-enantiomer for its high molar absorptivity (εo ∼ 24000) and availability at a low price. Its -COOH group had N-hydroxysuccinimide and N-hydroxybenzotriazole, which acted as good leaving groups during nucleophilic substitution by the amino group of the racemic (RS)-propranolol; the CDRs were characterized by UV, IR, (1) H-NMR, high resolution mass spectrometry (HRMS) and carbon, hydrogen, nitrogen, and sulphur fundamental elemental components analyser (CHNS). Diastereomers were separated quantitatively using open column chromatography; absolute configuration of the diastereomers was established and the reagent moiety was detagged under microwave-assisted acidic conditions. (S)- and (R)-propranolol as pure enantiomers and (S)-levofloxacin were separated, isolated and characterized. Optimized lowest-energy structures of the diastereomers were developed using Gaussian 09 Rev. A.02 program and hybrid density functional B3LYP with 6-31G* basis set (based on density functional theory) for explanation of elution order and configuration. In addition, RP HPLC conditions for separation of diastereomers were optimized with respect to pH, concentration of buffer, flow rate of mobile phase and nature of organic modifier. HPLC separation method was validated as per International Conference on Harmonization guidelines. With the systematic application of various analytical techniques, absolute configuration of the diastereomers (and the native enantiomers) of (RS)-propranolol was established. Copyright © 2016 John Wiley & Sons, Ltd.
Shuang Zheng
2014-06-01
Full Text Available For all microhelices on aromatic rings of inherently chiral calix[4]arene, an expression was derived from one approximation and one hypothesis on the basis of the electron-on-a-helix model of Tinoco and Woody as follows: 1/E = μ (H − K Δα2 , where μ = 1 for the right-handed microhelix and μ = −1 for the left-handed microhelix; and H and K are constant and greater than zero. The expression correlates microhelical electronic energy (E with the atom polarizability difference (Δα on both microhelix ends, which intuitively and clearly shows the impact of helical substituent polarizability on helical electronic energy. The case analysis almost entirely proves that the qualitative analysis of the helical electronic energy of inherently chiral calix[4]arenes with the expression is scientific and can be used to effectively assign their absolute configuration
Xiao Jiang
2015-06-01
Full Text Available Pyrrolizidine alkaloid-containing plants are widespread in the world and probably the most common poisonous plants affecting livestock, wildlife, and humans. Pyrrolizidine alkaloids require metabolic activation to form dehydropyrrolizidine alkaloids that bind to cellular proteins and DNA leading to hepatotoxicity, genotoxicity, and tumorigenicity. At present, it is not clear how dehydropyrrolizidine alkaloids bind to cellular amino acids and proteins to induced toxicity. We previously reported that reaction of dehydromonocrotaline with valine generated four highly unstable 6,7-dihydro-7-hydroxy-1-hydroxymethyl-5H-pyrrolizine (DHP-derived valine (DHP-valine adducts that upon reaction with phenyl isothiocyanate (PITC formed four DHP-valine-PITC adduct isomers. In this study, we report the absolute configuration and stability of DHP-valine and DHP-valine-PITC adducts, and the mechanism of interconversion between DHP-valine-PITC adducts.
Sadia Sultan
2014-09-01
Full Text Available The anti-inflammatory drug predinisolone (1 was reduced to 20β-hydroxyprednisolone (2 by the marine endophytic fungus Penicilium lapidosum isolated from an alga. The structural elucidation of 2 was achieved by 1D- and 2D-NMR, MS, IR data. Although, 2 is a known compound previously obtained through microbial transformation, the data provided failed to prove the C20 stereochemistry. To solve this issue, DFT and TD-DFT calculations have been carried out at the B3LYP/6–31+G (d,p level of theory in gas and solvent phase. The absolute configuration of C20 was eventually assigned by combining experimental and calculated electronic circular dichroism spectra and 3JHH chemical coupling constants.
Pinedo-Rivilla, Cristina; Aleu, Josefina; Grande Benito, Manuel; Collado, Isidro G
2010-08-21
Enantiomerically pure 2-benzylindane derivatives were prepared using biocatalytic methods and their absolute configuration determined. (1R,2S)-2-Benzylindan-1-ol ((1R,2S)-2) and (S)-2-benzylindan-1-one ((S)-3) were produced by fermenting baker's yeast. Lipase-mediated esterifications and hydrolysis of the corresponding racemic substrates gave rise to the enantiopure compounds (1S,2R)-2-benzylindan-1-ol ((1S,2R)-2) and (1R,2S)-2-benzylindan-1-ol ((1R,2S)-2), respectively. The antifungal activity of these products against two strains of the plant pathogen Botrytis cinerea was tested. The metabolism of anti-(+/-)-2-benzylindan-1-ol (anti-(+/-)-2) by B. cinerea as part of the fungal detoxification mechanism is also described and revealed interesting differences in the genome of both strains.
Voloshina, E.N.; Raabe, G.; Fleischhauer, J.; Kramp, G.J.; Gais, H.J. [Rheinisch-Westfaelische Technische Hochschule Aachen (Germany). Inst. fuer Organische Chemie
2004-07-01
The chiroptical properties of the diastereomeric alcohols (E)-(3S,4S)-4-methyl-1-tributylstannyl-oct-1-en-6-yn-3-ol ((S,S)-3) and (E)-(3R,4S)-4-methyl-1-tributylstannyl-oct-1-en-6-yn-3-ols ((R,S)-3) have been studied experimentally as well as by quantum-chemical calculations. The structures of 20 conformers of each isomer, which were found to represent local minima at the MNDO level, have been optimized with density functional theory (DFT). Based on these geometries the excitation energies and oscillator as well as rotational strengths have been calculated using a time-dependent DFT (TDDFT) method. The CD spectra of the compounds were then obtained as superposition of Boltzmann-weighted spectra for each of the structures. By comparison of the calculated and the experimental CD spectra the absolute configurations have been assigned to the investigated compounds. (orig.)
Voloshina, E. N.; Raabe, G.; Fleischhauer, J.; Kramp, G. J.; Gais, H.-J.
2004-03-01
The chiroptical properties of the diastereomeric alcohols (E)-(3S,4S)-4-methyl-1-tributylstannyloct- 1-en-6-yn-3-ol ((S,S)-) and (E)-(3R,4S)-4-methyl-1-tributylstannyl-oct-1-en-6-yn-3-ols ((R,S)- 3) have been studied experimentally as well as by quantum-chemical calculations. The structures of 20 conformers of each isomer, which were found to represent local minima at the MNDO level, have been optimized with density functional theory (DFT). Based on these geometries the excitation energies and oscillator as well as rotational strengths have been calculated using a time-dependent DFT (TDDFT) method. The CD spectra of the compounds were then obtained as superposition of Boltzmann-weighted spectra for each of the structures. By comparison of the calculated and the experimental CD spectra the absolute configurations have been assigned to the investigated compounds.
Wilk, Andrzej; Grajkowski, Andrzej; Bull, Thomas E; Dixon, Ann M; Freedberg, Darón I; Beaucage, Serge L
2002-02-20
The determination of the absolute configuration of deoxyribonucleoside cyclic N-acylphosphoramidites at phosphorus toward the synthesis of P-stereodifined phosphorothioated oligodeoxyribonucleotides is easily accomplished with computer-assisted molecular modeling and M-GOESY NMR spectroscopy. Specifically, computer-modeling diasteromeric phosphoramidite 3 has identifed a proximal (2.55 A) through-space interaction between benzylic H-5 and sugar H-2' ', which can predictably be detected by M-GOESY NMR in SP-3 but not in RP-3 because of being too distant (5.85 A). Consistent with computer-assisted modeling predictions, M-GOESY NMR spectra of SP-3 and RP-3 revealed NOE signals generated from nuclei near the selectively excited H-2' ' that are common to both SP-3 and RP-3, namely those of H-2', H-4', H-3', and H-1'. In addition, a diagnostic NOE signal at 5.5 ppm (benzylic H-5) is, as predicted, only detected in SP-3 and thus provides an unequivocal assessment of the configuration of the diastereomer at phosphorus. M-GOESY NMR data also confirm that the condensation of deoxyribonucleoside cyclic N-acylphosphoramidites with base-activated nucleosidic or nucleotidic 5'-hydroxyls proceeds via a single nucleophilic event.
Titze, T.; Chmelik, C.; Kärger, J.; van Baten, J.M.; Krishna, R.
2014-01-01
While n-hexane (nC6) can adsorb at any location within the MFI zeolite pore network, configurational considerations cause the branched isomer 2-methylpentane (2MP) to locate preferentially at the channel intersections. For adsorption of nC6/2MP mixtures, infrared microscopy (IRM) measurements show t
Jensen, Christina Mernøe; Chow, Hsiao-Qing; Chen, Ming; Zhai, Lin; Frydenvang, Karla; Liu, Huizhen; Franzyk, Henrik; Christensen, Søren Brøgger
2016-05-23
A library of iminolactones was prepared by esterification of several 2-hydroxyketones with a number of N-protected d- and l-α-amino acids. Some of the hydroxyketones were of terpenoid origin while others were obtained via synthesis. After N-deprotection of the intermediate esters, the free amines spontaneously underwent condensation with the ketone to form iminolactones. Esters of (1S,2S,5S)-2-hydroxypinan-3-one with both d- and l-α-amino acids were partially epimerized at the α-carbon atom to give a diastereomeric ester mixture. Only iminolactones of l-amino acids were formed after cyclization of (1S,2S,5S)-2-hydroxypinan-3-one, and correspondingly only d-amino acid iminolactones were formed after reaction with (1R,2R,5R)-2-hydroxypinan-3-one. The protocol thus enables inversion of the absolute configuration of amino acids. Some members of the prepared library of iminolactones displayed significant anti-proliferative effects toward three cancer cell lines (EL4, MCF7, PC3) with insignificant effect on non-malign cell lines (McCoy, MCF10A, NIH3T3). Thus, iminolactones appear to be potential lead structures for preparation of drugs selectively affecting proliferation of malign cell lines.
Zhixu Zhou
2015-11-01
Full Text Available Pyridinesulfonamide is an important fragment which has a wide range of applications in novel drugs. R- and S-isomers of 5-bromo-2-chloro-N-(1-phenylethylpyridine-3-sulfonamide have been synthesized, and the stereostructures have been researched. Single crystals of both compounds were obtained for X-ray analysis, and the absolute configurations (ACs have been further confirmed by electronic circular dichroism (ECD, optical rotation (OR and quantum chemical calculations. The crystal structures and calculated geometries were extremely similar, which permitted a comparison of the relative reliabilities of ACs obtained by ECD analyses and theoretical simulation. In addition, the effect of stereochemistry on the PI3Kα kinase and anticancer activity were investigated. Compounds 10a and 10b inhibit the activity of PI3Kα kinase with IC50 values of 1.08 and 2.69 μM, respectively. Furthermore, molecular docking was performed to analyze the binding modes of R- and S-isomers.
Kitajima, Mariko; Yokoya, Masashi; Takayama, Hiromitsu; Aimi, Norio
2002-10-01
The structure including the absolute configuration of a new glucoalkaloid, 3,4-dehydro-5(S)-5-carboxystrictosidine, isolated from Peruvian Uña de Gato (Cat's Claw, original plant: Uncaria tomentosa), was confirmed by synthesis starting from secologanin and L-tryptophan.
Lange, B. de; Bolhuis, F. van; Feringa, Bernard
1989-01-01
The synthesis of enantiomerically pure β-amino-γ-butyrolactones via asymmetric conjugate addition of various amines to 5-menthyloxy-2(5H)-furanone is described. This route provides access to new multifunctional homochiral building blocks. The absolute configuration of the β-amino-γ-butyrolactones is
Silva, Alexandre Fonseca Povoa da, E-mail: alexandre.povoa@mar.mil.br [Centro Tecnologico da Marinha em Sao Paulo (CTMSP), Sao Paulo, SP (Brazil); Bitelli, Ulysses d' Utra; Mura, Luiz Ernesto Credidio; Lima, Ana Cecilia de Souza; Betti, Flavio; Santos, Diogo Feliciano dos, E-mail: ubitelli@ipen.br [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil)
2015-07-01
The use of neutron activation foils is a widely spread technique applied to obtain nuclear parameters then comparing the results with those calculated using specific methodologies and available nuclear data. By irradiation of activation foils and subsequent measurement of its induced activity, it is possible to determine the neutron flux at the position of irradiation. The power level during operation of the reactor is a parameter which is directly proportional to the average neutron flux throughout the core. The objective of this work is to gather data from irradiation of gold foils symmetrically placed along a cylindrically configured core which presents only a small excess reactivity in order to derive the power generated throughout the spatial thermal and epithermal neutron flux distribution over the core of the IPEN/MB-01 Nuclear Reactor, eventually lending to a proper calibration of its nuclear channels. The foils are fixed in a Lucite plate then irradiated with and without cadmium sheaths so as to obtain the absolute thermal and epithermal neutron flux. The correlation between the average power neutron flux resulting from the gold foils irradiation, and the average power digitally indicated by the nuclear channel number 6, allows for the calibration of the nuclear channels of the reactor. The reactor power level obtained by thermal neutron flux mapping was (74.65 ± 2.45) watts to a mean counting per seconds of 37881 cps to nuclear channel number 10 a pulse detector, and 0.719.10{sup -5} ampere to nuclear linear channel number 6 (a non-compensated ionization chamber). (author)
Easy Absolute Values? Absolutely
Taylor, Sharon E.; Mittag, Kathleen Cage
2015-01-01
The authors teach a problem-solving course for preservice middle-grades education majors that includes concepts dealing with absolute-value computations, equations, and inequalities. Many of these students like mathematics and plan to teach it, so they are adept at symbolic manipulations. Getting them to think differently about a concept that they…
2015-09-29
understanding of high entropy alloys from phase diagram calculations. Calphad 45, 1–10 (2014). 29. Santodonato, L. et al. Deviation from high-entropy...exist, which exhibit them. Inspired by research activities in the metal alloy communities and fundamental principles of thermodynamics we extend the...yields a single- phase material. The second experiment uses five individual phase diagrams to explore the configurational entropy versus composition trend
Chirikjian, Gregory S
2011-01-01
Proteins fold from a highly disordered state into a highly ordered one. Traditionally, the folding problem has been stated as one of predicting "the" tertiary structure from sequential information. However, new evidence suggests that the ensemble of unfolded forms may not be as disordered as once believed, and that the native form of many proteins may not be described by a single conformation, but rather an ensemble of its own. Quantifying the relative disorder in the folded and unfolded ensembles as an entropy difference may therefore shed light on the folding process. One issue that clouds discussions of "entropy" is that many different kinds of entropy can be defined: entropy associated with overall translational and rotational Brownian motion, configurational entropy, vibrational entropy, conformational entropy computed in internal or Cartesian coordinates (which can even be different from each other), conformational entropy computed on a lattice, each of the above with different solvation and solvent models, thermodynamic entropy measured experimentally, etc. The focus of this work is the conformational entropy of coil/loop regions in proteins. New mathematical modeling tools for the approximation of changes in conformational entropy during transition from unfolded to folded ensembles are introduced. In particular, models for computing lower and upper bounds on entropy for polymer models of polypeptide coils both with and without end constraints are presented. The methods reviewed here include kinematics (the mathematics of rigid-body motions), classical statistical mechanics, and information theory.
Frelek, Jadwiga; Karchier, Michał; Madej, Daria; Michalak, Karol; Różański, Paweł; Wicha, Jerzy
2014-06-01
A series of representative optically active derivatives of 4-hydroxy-5-alkylcyclopent-2-en-1-one were prepared from the respective 2-furyl methyl carbinols via the Piancatelli rearrangement followed by the enzymatic kinetic resolution of racemates. Applicability of chiroptical methods (experimental and calculated electronic circular dichroism [ECD] and vibrational circular dichroism [VCD] spectra) to determine the absolute configuration of both stereogenic centers in 4-hydroxy-5-methylcyclopent-2-en-1-one was demonstrated. It was also demonstrated that the concurrent application of ECD and VCD spectroscopy can be used for the determination of the configuration of two stereogenic centers. © 2014 Wiley Periodicals, Inc.
Ferrarini, Alberta; Ferroni, Fiammetta; Pieraccini, Silvia; Rosini, Carlo; Superchi, Stefano; Spada, Gian Piero
2011-10-01
The conversion into 6,7-dihydro-5H-dibenz[c,e]azepine (DAZ) N-protected amides is a viable route for the determination of the absolute configuration of chiral 2-substituted carboxylic acids. The biphenyl moiety of DAZ, besides being a probe of chirality for the electronic circular dichroism (ECD) spectroscopy, makes these systems suitable for configuration assignment by exploiting the chirality amplification which occurs in nematic liquid crystals. To assess the reliability of the liquid crystal method in detecting the absolute stereochemistry of chiral amides bound to a biphenyl group, we measured the helical twisting power of a series of DAZ-N-protected amides and compared these data with the results obtained from ECD measurements. We will show that the liquid crystal method, corroborated by HTP predictions, is trustworthy with our biphenyl derivatives, even when ECD spectra are ambiguous for the presence of aryl moieties displaying strong UV absorptions in the same range of the biphenyl chromophore.
Mang, Chao-Yong; Liu, Cai-Ping; Liu, Guang-Ming; Jiang, Bei; Lan, Hai; Wu, Ke-Chen; Yan, Ya; Li, Hai-Fei; Yang, Ming-Hui; Zhao, Yu
2015-02-01
A cyclic dipeptide often has the multiple configurations and the abundant conformations. The density functional theory (DFT) method is used to search the preferred conformation of the most probable configuration for cordycedipeptide A isolated from the culture liquid of Cordyceps sinensis. The time-dependent DFT approach is exploited to describe the profile of electronic circular dichroism (CD). The calculated results show that the most probable configuration is 3S6R7S, whose preferred conformation has a negative optical rotation and a positive lowest energy electronic CD band.
Lee, Bum Han; Lee, Sung Keun
2013-07-01
Despite the importance of understanding and quantifying the microstructure of porous networks in diverse geologic settings, the effects of the specific surface area and porosity on the key structural parameters of the networks have not been fully understood. We performed cube-counting fractal dimension (Dcc) and lacunarity analyses of 3D porous networks of model sands and configurational entropy analysis of 2D cross sections of model sands using random packing simulations and nuclear magnetic resonance (NMR) micro-imaging. We established relationships among porosity, specific surface area, structural parameters (Dcc and lacunarity), and the corresponding macroscopic properties (configurational entropy and permeability). The Dcc of the 3D porous networks increases with increasing specific surface area at a constant porosity and with increasing porosity at a constant specific surface area. Predictive relationships correlating Dcc, specific surface area, and porosity were also obtained. The lacunarity at the minimum box size decreases with increasing porosity, and that at the intermediate box size (∼0.469 mm in the current model sands) was reproduced well with specific surface area. The maximum configurational entropy increases with increasing porosity, and the entropy length of the pores decreases with increasing specific surface area and was used to calculate the average connectivity among the pores. The correlation among porosity, specific surface area, and permeability is consistent with the prediction from the Kozeny-Carman equation. From the relationship between the permeability and the Dcc of pores, the permeability can be expressed as a function of the Dcc of pores and porosity. The current methods and these newly identified correlations among structural parameters and properties provide improved insights into the nature of porous media and have useful geophysical and hydrological implications for elasticity and shear viscosity of complex composites of rock
Yamano, Yumiko; Chary, Mahankhali Venu; Wada, Akimori
2010-10-01
The synthesis of 3'-deoxycapsanthin (1) and 3,4-didehydroxy-3'-deoxycapsanthin (2), carotenoids of paprika, has been achieved by employing Lewis acid-promoted regio- and stereoselective rearrangement of the C(15)-epoxy dienal 5a. The absolute stereochemistry of the newly formed C-5 chiral center of rearrangement product 6a was determined to be (R) from its alternative synthesis derived from (+)-(R)-camphonanic acid (11).
Shunsaku Ohta
2005-01-01
@@ 1Introduction Linderol A (1), a monoterpene-polyketide, was isolated in 1995 from the fresh bark of Lindera umbellata (Lauraceae), and its absolute structure was not determined[1]. It was also reported potent inhibitory activity of 1 on the melanin biosynthesis of the cultured B-16 melanoma cells[1]. See Fig. 1. On the other hand,we reported in 1995 an interesting multi-tandem reaction of coumarin derivatives (2; W = electron withdrawing group) by treatment with CH2 = S(O)Me2 to yield stereoselectively a tricyclic 2-substituted cyclopenta [ b ] benzofuran-3-ol derivative (4) via a cyclopropane intermediate (3) (Scheme 1)[2].
Matsunami, Katsuyoshi; Otsuka, Hideaki; Kondo, Kazunari; Shinzato, Takakazu; Kawahata, Masatoshi; Yamaguchi, Kentaro; Takeda, Yoshio
2009-07-01
A lignan glucoside, (+)-pinoresinol 4-O-[6''-O-galloyl]-beta-D-glucopyranoside (1), and two megastigmane glucosides, named macarangiosides E and F (2,3), together with 15 known compounds (4-18) were isolated from leaves of Macaranga tanarius (L.) Müll.-Arg. (Euphorbiaceae). Their structures were elucidated by spectroscopic and chemical analyses. In addition, the absolute stereochemistry of macarangiosides B and C isolated previously from the same plant was also determined for the first time. Compounds 1 and 2 were galloylated on glucose and possessed potent DPPH radical-scavenging activity.
Marizeth L. Barreiros
2005-12-01
Full Text Available This review reports the determination of absolute configuration of primary and secondary alcohols by ¹H NMR spectroscopy, using the Mosher method. This method consists in the derivatization of an alcohol possessig unknown absolute configuration with one or both enantiomers of an auxiliary reagent. The resulting diastereoisomer spectra are registered and compared, and the chemical shift differences (DdR,S = deltaR - deltaS are measured. The determination of the absolute configuration of the alcohol molecule is based on the correlation between its chiral center and the auxiliary reagent's chiral center. Therefore, the determination of the absolute configuration depends on aromatic ring shielding effects on the substituents of the alcohol as evidenced by the ¹H NMR spectrum.
Fujiwara, Toshio; Taniguchi, Yuka; Katsumoto, Yukiteru; Tanaka, Takeyuki; Ozeki, Minoru; Iwasaki, Hiroki; Node, Manabu; Yamashita, Masayuki; Hosoi, Shinzo
2012-10-01
Circular dichroism (CD) spectra of the 2,2'-binaphthyl ester derived from Δ(5)-sterols showed not bisignate CD but diagnostic CD bands at around 210 and 240 nm. These bands might be attributable to an interaction between an olefinic chromophore and a binaphthyl one. Various types of unsaturated sterols were thus derivatized followed by complete hydrogenation, to give saturated sterols. As a result, CD spectra of the binaphthyl derivatives of the saturated sterols showed bisignate curves centered at 240 nm (3S(β): positive chirality; 3R(α): negative one). This suggested a straightforward and practical method for discriminating the absolute stereogenic center at the C-3 positions of sterols based on an induced CD. This finding should contribute significantly to the analysis of metabolites of various types of sterols. Copyright © 2012 Elsevier Inc. All rights reserved.
张鹏; 张卫国; 曾玉婷
2016-01-01
文章运用可能性绝对偏差和比例熵分别度量风险和分散化程度，提出了具有风险控制和线性交易成本的终期财富最大化的多阶段模糊投资组合模型。运用可能理论，将该模型转化为显示的非线性动态优化问题。由于投资过程存在交易成本，上述模型为具有路径依赖性的动态优化问题。文章提出了前向动态规划方法求解。最后，通过实证研究比较了不同熵的取值投资组合最优投资比例和最终财富的变化。%This paper considers a multi-period fuzzy portfolio selection problem maximizing the terminal wealth imposed by risk control, in which risk of assets and the divergence measure of portfolio are, respectively, meas-ured by fuzzy absolute deviation and proportion entropy.Based on the theories of possibility theory, the proposed model is transformed into a crisp nonlinear programming problem.Because of the transaction costs, the multi-period portfolio selection is a dynamic optimization problem with path dependence.Furthermore, a forward dynamic programming method is designed to obtain the optimal portfolio strategy.Finally, an example is given to illustrate the behavior of the proposed model and the designed algorithm.
Physics of negative absolute temperatures
Abraham, Eitan; Penrose, Oliver
2017-01-01
Negative absolute temperatures were introduced into experimental physics by Purcell and Pound, who successfully applied this concept to nuclear spins; nevertheless, the concept has proved controversial: a recent article aroused considerable interest by its claim, based on a classical entropy formula (the "volume entropy") due to Gibbs, that negative temperatures violated basic principles of statistical thermodynamics. Here we give a thermodynamic analysis that confirms the negative-temperature interpretation of the Purcell-Pound experiments. We also examine the principal arguments that have been advanced against the negative temperature concept; we find that these arguments are not logically compelling, and moreover that the underlying "volume" entropy formula leads to predictions inconsistent with existing experimental results on nuclear spins. We conclude that, despite the counterarguments, negative absolute temperatures make good theoretical sense and did occur in the experiments designed to produce them.
J.G.M. van Marrewijk (Charles)
2008-01-01
textabstractA country is said to have an absolute advantage over another country in the production of a good or service if it can produce that good or service using fewer real resources. Equivalently, using the same inputs, the country can produce more output. The concept of absolute advantage can a
Bekenstein Entropy is String Entropy
Halyo, Edi
2009-01-01
We argue that Bekenstein entropy can be interpreted as the entropy of an effective string with a rescaled tension. Using the AdS/CFT correspondence we show that the Bekenstein entropy on the boundary CFT is given by the entropy of a string at the stretched horizon of the AdS black hole in the bulk. The gravitationally redshifted tension and energy of the string match those required to reproduce Bekenstein entropy.
Mario A. Macías
2015-09-01
Full Text Available The absolute configuration of the title compound, C10H16O4, determined as 3aS,4S,5R,7aR on the basis of the synthetic pathway, was confirmed by X-ray diffraction. The molecule contains a five- and a six-membered ring that adopt twisted and envelope conformations, respectively. The dihedral angle between the mean planes of the rings is 76.80 (11° as a result of their cis-fusion. In the crystal, molecules are linked by two pairs of O—H...O hydrogen bonds, forming chains along [010]. These chains are further connected by weaker C—H...O interactions along [100], creating (001 sheets that interact only by weak van der Waals forces.
Giorgio, Egidio; Maddau, Lucia; Spanu, Emanuela; Evidente, Antonio; Rosini, Carlo
2005-01-07
The nonempirical assignment of the absolute configuration of (+)-diplopyrone, the main phytotoxin of Diplodia mutila, i.e., an endophytic fungus, widespread in Sardinian oak forests, and considered one of the main causes of cork oak decline, has been approached by two different methods: (a) the exciton analysis of the circular dichroism (CD) spectrum and (b) the ab initio calculation of the optical rotatory power. Both methods indicate that (+)-diplopyrone is 6-[(1S)-1-hydroxyethyl]-2,4a(S),6(R),8a(S)-tetrahydropyrano[3,2-b]pyran-2-one, so the stereostructure of this important biomolecule is safely determined for the first time. A comparison of advantages and limitations of the two methods of analysis is also presented.
Phillips, Alfred, Jr.
Summ means the entirety of the multiverse. It seems clear, from the inflation theories of A. Guth and others, that the creation of many universes is plausible. We argue that Absolute cosmological ideas, not unlike those of I. Newton, may be consistent with dynamic multiverse creations. As suggested in W. Heisenberg's uncertainty principle, and with the Anthropic Principle defended by S. Hawking, et al., human consciousness, buttressed by findings of neuroscience, may have to be considered in our models. Predictability, as A. Einstein realized with Invariants and General Relativity, may be required for new ideas to be part of physics. We present here a two postulate model geared to an Absolute Summ. The seedbed of this work is part of Akhnaton's philosophy (see S. Freud, Moses and Monotheism). Most important, however, is that the structure of human consciousness, manifest in Kenya's Rift Valley 200,000 years ago as Homo sapiens, who were the culmination of the six million year co-creation process of Hominins and Nature in Africa, allows us to do the physics that we do. .
Tsallis Entropy Composition and the Heisenberg Group
Kalogeropoulos, Nikos
2013-03-01
We present an embedding of the Tsallis entropy into the three-dimensional Heisenberg group, in order to understand the meaning of generalized independence as encoded in the Tsallis entropy composition property. We infer that the Tsallis entropy composition induces fractal properties on the underlying Euclidean space. Using a theorem of Milnor/Wolf/Tits/Gromov, we justify why the underlying configuration/phase space of systems described by the Tsallis entropy has polynomial growth for both discrete and Riemannian cases. We provide a geometric framework that elucidates Abe's formula for the Tsallis entropy, in terms the Pansu derivative of a map between sub-Riemannian spaces.
Gravitational entropy of cosmic expansion
Sussman, Roberto A
2014-01-01
We apply a recent proposal to define "gravitational entropy" to the expansion of cosmic voids within the framework of non-perturbative General Relativity. By considering CDM void configurations compatible with basic observational constraints, we show that this entropy grows from post-inflationary conditions towards a final asymptotic value in a late time fully non-linear regime described by the Lemaitre-Tolman-Bondi (LTB) dust models. A qualitatively analogous behavior occurs if we assume a positive cosmological constant consistent with a $\\Lambda$-CDM background model. However, the $\\Lambda$ term introduces a significant suppression of entropy growth with the terminal equilibrium value reached at a much faster rate.
Astuti, Valerio; Rovelli, Carlo
2016-01-01
Building on a technical result by Brunnemann and Rideout on the spectrum of the Volume operator in Loop Quantum Gravity, we show that the dimension of the space of the quadrivalent states --with finite-volume individual nodes-- describing a region with total volume smaller than $V$, has \\emph{finite} dimension, bounded by $V \\log V$. This allows us to introduce the notion of "volume entropy": the von Neumann entropy associated to the measurement of volume.
Progress in High-Entropy Alloys
Gao, Michael C
2013-12-01
Strictly speaking, high-entropy alloys (HEAs) refer to single-phase, solid-solution alloys with multiprincipal elements in an equal or a near-equal molar ratio whose configurational entropy is tremendously high. This special topic was organized to reflect the focus and diversity of HEA research topics in the community.
K B Athreya
2009-09-01
It is shown that (i) every probability density is the unique maximizer of relative entropy in an appropriate class and (ii) in the class of all pdf that satisfy $\\int fh_id_=_i$ for $i=1,2,\\ldots,\\ldots k$ the maximizer of entropy is an $f_0$ that is proportional to $\\exp(\\sum c_i h_i)$ for some choice of $c_i$. An extension of this to a continuum of constraints and many examples are presented.
Black hole entropy, curved space and monsters
Hsu, Stephen D.H. [Institute of Theoretical Science, University of Oregon, Eugene, OR 97403 (United States)], E-mail: hsu@uoregon.edu; Reeb, David [Institute of Theoretical Science, University of Oregon, Eugene, OR 97403 (United States)], E-mail: dreeb@uoregon.edu
2008-01-10
We investigate the microscopic origin of black hole entropy, in particular the gap between the maximum entropy of ordinary matter and that of black holes. Using curved space, we construct configurations with entropy greater than the area A of a black hole of equal mass. These configurations have pathological properties and we refer to them as monsters. When monsters are excluded we recover the entropy bound on ordinary matter Sentropy of black holes is the logarithm of the number of distinct ways in which one can form the black hole from ordinary matter and smaller black holes, but only after the exclusion of monster states.
Paracrystalline property of high-entropy alloys
Shaoqing Wang
2013-10-01
Full Text Available Atomic structure models of six-component high-entropy alloys with body-centered cubic structure are successfully built according to the principle of maximum entropy for the first time. The lattice distortion parameters g of seven typical high-entropy alloys are calculated. From the optimized lattice configuration of high-entropy alloys, we show that these alloys are ideal three-dimensional paracrystals. The formation mechanism, structural feature, mechanical property, and application prospect of high-entropy alloys are discussed in comparison with the traditional alloys. The novel properties of body-centered cubic high-entropy alloys are attributed to the failure of dislocation deformation mechanism and the difficulty of directed particle diffusion.
Entropy Bounds for Constrained Two-Dimensional Fields
Forchhammer, Søren Otto; Justesen, Jørn
1999-01-01
The maximum entropy and thereby the capacity of 2-D fields given by certain constraints on configurations are considered. Upper and lower bounds are derived.......The maximum entropy and thereby the capacity of 2-D fields given by certain constraints on configurations are considered. Upper and lower bounds are derived....
ENTROPY AND NEGENTROPY SIGNS IN LANGUAGE SYSTEM
Ирина Михайловна Некипелова
2013-12-01
Full Text Available The article is devoted to research of entropy in language. Complexity of the description of entropy is connected with that it is not a material factor of development of language, because language is not real, but the imaginable category, existing only in humans thinking. For this reason the modern researches devoted to studying and calculating of entropy are concentrated on the speech and text material. For understanding of the idea of entropy of language (not of its speech expression it is necessary to investigate the entropy of structure of objective language, not sets of subjective languages, i.e. language as model. The research has showed that in system of a natural language signs of entropy are such language phenomena as synonimy, polysemanticism, language redundancy, variability of forms, loyalty and flexibility of rules, existence of styles. These signs are detected in comparison with signs of absolutely systematized language system, acting as a hypothesis. Entropy of such system is reduced to zero. The negentropy as negative entropy is opposed to entropy. Negentropy markers are homonymy, absence of a synonimy, invariancy, strict rules of language, monostyle. DOI: http://dx.doi.org/10.12731/2218-7405-2013-9-58
Universal entropy relations: entropy formulae and entropy bound
Liu, Hang; Xu, Wei; Zhu, Bin
2016-01-01
We survey the applications of universal entropy relations in black holes with multi-horizons. In sharp distinction to conventional entropy product, the entropy relationship here not only improve our understanding of black hole entropy but was introduced as an elegant technique trick for handling various entropy bounds and sum. Despite the primarily technique role, entropy relations have provided considerable insight into several different types of gravity, including massive gravity, Einstein-Dilaton gravity and Horava-Lifshitz gravity. We present and discuss the results for each one.
Thermodynamics, entropy and waterwheels
Bagnoli, Franco
2016-01-01
In textbooks, it is often repeated that Carnot arrived to the formulation of the second law of thermodynamics without knowing the first, using the caloric theory. In fact, in his book, R\\'eflexions sur la puissance motrice du feu, he often repeats that the "fall" of the caloric through a heat engine is equivalent to the fall of the water through a water wheel. Actually, one can play the analogy between thermal and hydraulic machines all the way down, and discover, with the help of the first principle and introducing the concept of the absolute height, what really "falls" through a waterwheel, i.e., the entropy. Adding a bit of relativity it is possible to extend the analogy to real machines and also to introduce the analogous of third law of thermodynamics.
Structural information in two-dimensional patterns: entropy convergence and excess entropy.
Feldman, David P; Crutchfield, James P
2003-05-01
We develop information-theoretic measures of spatial structure and pattern in more than one dimension. As is well known, the entropy density of a two-dimensional configuration can be efficiently and accurately estimated via a converging sequence of conditional entropies. We show that the manner in which these conditional entropies converge to their asymptotic value serves as a measure of global correlation and structure for spatial systems in any dimension. We compare and contrast entropy convergence with mutual-information and structure-factor techniques for quantifying and detecting spatial structure.
Teaching Absolute Value Meaningfully
Wade, Angela
2012-01-01
What is the meaning of absolute value? And why do teachers teach students how to solve absolute value equations? Absolute value is a concept introduced in first-year algebra and then reinforced in later courses. Various authors have suggested instructional methods for teaching absolute value to high school students (Wei 2005; Stallings-Roberts…
Kruglikov, Boris; Rypdal, Martin
2005-01-01
The topological entropy of piecewise affine maps is studied. It is shown that singularities may contribute to the entropy only if there is angular expansion and we bound the entropy via the expansion rates of the map. As a corollary we deduce that non-expanding conformal piecewise affine maps have zero topological entropy. We estimate the entropy of piecewise affine skew-products. Examples of abnormal entropy growth are provided.
Kevin H. Knuth
2014-04-01
Full Text Available The editors were recently made aware that a paper published in Entropy in 2003 [1] exhibited characteristics of duplication and self-plagiarism. After investigating the matter, and discussing the situation with the authors, they have offered to retract this paper (http://www.mdpi.com/1099-4300/5/5/519 .
Carnot to Clausius: Caloric to Entropy
Newburgh, Ronald
2009-01-01
This paper discusses how the Carnot engine led to the formulation of the second law of thermodynamics and entropy. The operation of the engine is analysed both in terms of heat as the caloric fluid and heat as a form of energy. A keystone of Carnot's thinking was the absolute conservation of caloric. Although the Carnot analysis was partly…
Entropy estimates for simple random fields
Forchhammer, Søren; Justesen, Jørn
1995-01-01
We consider the problem of determining the maximum entropy of a discrete random field on a lattice subject to certain local constraints on symbol configurations. The results are expected to be of interest in the analysis of digitized images and two dimensional codes. We shall present some examples...... of binary and ternary fields with simple constraints. Exact results on the entropies are known only in a few cases, but we shall present close bounds and estimates that are computationally efficient...
Lauro Cesar Araujo; Mamede Lima-Marques
2016-01-01
Introduction: The term "configuration information" has emerged in the works of Information Architecture; however, there isn’t a conceptualization of “configuration” within Information Architecture. Objective: The objective is propose a definition for "configuration" and "information configuration" within the Information Architecture discipline, and indicate a teleological corpus from configuration management that can be used as paxis in Information Architecture. Methodolo...
Multidimensional entropy landscape of quantum criticality
Grube, K.; Zaum, S.; Stockert, O.; Si, Q.; Löhneysen, H. V.
2017-08-01
The third law of thermodynamics states that the entropy of any system in equilibrium has to vanish at absolute zero temperature. At nonzero temperatures, on the other hand, matter is expected to accumulate entropy near a quantum critical point, where it undergoes a continuous transition from one ground state to another. Here, we determine, based on general thermodynamic principles, the spatial-dimensional profile of the entropy S near a quantum critical point and its steepest descent in the corresponding multidimensional stress space. We demonstrate this approach for the canonical quantum critical compound CeCu 6-xAux near its onset of antiferromagnetic order. We are able to link the directional stress dependence of S to the previously determined geometry of quantum critical fluctuations. Our demonstration of the multidimensional entropy landscape provides the foundation to understand how quantum criticality nucleates novel phases such as high-temperature superconductivity.
Fogassy, Elemér; Ács, Mária; Tóth, Gábor; Simon, Kálmán; Láng, Tibor; Ladányi, L.; Párkányi, L.
1986-09-01
An optically active hydrogen bromide salt of 1-(3,4-dimethoxyphenyl)-4-methyl-5-ethyl-7,8-dimethoxy-5 H-2,3-benzodiazepine has been prepared and the R5 configuration studied by single-crystal X-ray analysis. The crystals are triclinic with space group P1, with two molecules in a unit cell of dimensions a = 10.798(1), b = 12.669(1) and c = 8.681(1) Å, and α = 97.15(1), β = 99.36(1) and γ = 68.74(1)°. The anomalous chiroptical behaviour is explained on the basis of the chiral interactions between the optically active conformers.
Topological entropy of autonomous flows
Badii, R. [Paul Scherrer Inst. (PSI), Villigen (Switzerland)
1997-06-01
When studying fluid dynamics, especially in a turbulent regime, it is crucial to estimate the number of active degrees of freedom or of localized structures in the system. The topological entropy quantifies the exponential growth of the number of `distinct` orbits in a dynamical system as a function of their length, in the infinite spatial resolution limit. Here, I illustrate a novel method for its evaluation, which extends beyond maps and is applicable to any system, including autonomous flows: these are characterized by lack of a definite absolute time scale for the orbit lengths. (author) 8 refs.
Holographic Entanglement Entropy in Insulator/Superconductor Transition
Cai, Rong-Gen; Li, Li; Zhang, Yun-Long
2012-01-01
We investigate the behaviors of entanglement entropy in the holographical insulator/superconductor phase transition. We calculate the holographic entanglement entropy for two kinds of geometry configurations in a completely back-reacted gravitational background describing the insulator/superconductor phase transition. The non-monotonic behavior of the entanglement entropy is found in this system. In the belt geometry case, there exist four phases characterized by the chemical potential and belt width.
Holographic Entanglement Entropy in Insulator/Superconductor Transition
Cai, Rong-Gen; He, Song; Li, Li; Zhang, Yun-Long
2012-01-01
We investigate the behaviors of entanglement entropy in the holographical insulator/superconductor phase transition. We calculate the holographic entanglement entropy for two kinds of geometry configurations in a completely back-reacted gravitational background describing the insulator/superconductor phase transition. The non-monotonic behavior of the entanglement entropy is found in this system. In the belt geometry case, there exist four phases characterized by the chemical potential and be...
Bekenstein-Hawking Entropy as Entanglement Entropy
Feng, Yu-Lei
2015-01-01
We show that the Bekenstein-Hawking entropy $S_{BH}$ should be treated as an entanglement entropy, provided that the formation and evaporation of a black hole can be described by quantum unitary evolutions. To confirm this statement, we derive statistical mechanics from quantum mechanics effectively by means of open quantum systems. Then a new definition of Boltzmann entropy for a quantum closed system is given to count microstates in a way consistent with the superposition principle. In particular, this new Boltzmann entropy is a constant that depends only on the dimension of the system's relevant Hilbert subspace. Based on this new definition, some kind of "detailed balance" condition is obtained to stabilize the thermal equilibrium between two macroscopic subsystems within a larger closed system. However, the required "detailed balance" condition between black hole and matter would be broken, if the Bekenstein-Hawking entropy was treated as Boltzmann entropy together with the Hawking temperature as thermal...
Coherent states measurement entropy
Kwapien, J; Zyczkowski, K; Kwapien, Jaroslaw; Slomczynski, Wojciech; Zyczkowski, Karol
1996-01-01
Coherent states (CS) quantum entropy can be split into two components. The dynamical entropy is linked with the dynamical properties of a quantum system. The measurement entropy, which tends to zero in the semiclassical limit, describes the unpredictability induced by the process of a quantum approximate measurement. We study the CS--measurement entropy for spin coherent states defined on the sphere discussing different methods dealing with the time limit n \\to \\infty. In particular we propose an effective technique of computing the entropy by iterated function systems. The dependence of CS--measurement entropy on the character of the partition of the phase space is analysed.
Absolute nuclear material assay
Prasad, Manoj K [Pleasanton, CA; Snyderman, Neal J [Berkeley, CA; Rowland, Mark S [Alamo, CA
2012-05-15
A method of absolute nuclear material assay of an unknown source comprising counting neutrons from the unknown source and providing an absolute nuclear material assay utilizing a model to optimally compare to the measured count distributions. In one embodiment, the step of providing an absolute nuclear material assay comprises utilizing a random sampling of analytically computed fission chain distributions to generate a continuous time-evolving sequence of event-counts by spreading the fission chain distribution in time.
Lee, Jeongseog; Safdi, Benjamin R
2014-01-01
Entanglement entropy in even dimensional conformal field theories (CFTs) contains well-known universal terms arising from the conformal anomaly. Renyi entropies are natural generalizations of the entanglement entropy that are much less understood. Above two spacetime dimensions, the universal terms in the Renyi entropies are unknown for general entangling geometries. We conjecture a new structure in the dependence of the four-dimensional Renyi entropies on the intrinsic and extrinsic geometry of the entangling surface. We provide evidence for this conjecture by direct numerical computations in the free scalar and fermion field theories. The computation involves relating the four-dimensional free massless Renyi entropies across cylindrical entangling surfaces to corresponding three-dimensional massive Renyi entropies across circular entangling surfaces. Our numerical technique also allows us to directly probe other interesting aspects of three-dimensional Renyi entropy, including the massless renormalized Reny...
Gagie, Travis
2007-01-01
We trace the history of empirical entropy, touching briefly on its relation to Markov processes, normal numbers, Shannon entropy, the Chomsky hierarchy, Kolmogorov complexity, Ziv-Lempel compression, de Bruijn sequences and stochastic complexity.
Päs, H; P\\"as, Heinrich; Weiler, Thomas J.
2002-01-01
The determination of absolute neutrino masses is crucial for the understanding of theories underlying the standard model, such as SUSY. We review the experimental prospects to determine absolute neutrino masses and the correlations among approaches, using the Delta m^2's inferred from neutrino oscillation experiments and assuming a three neutrino Universe.
Schechter, J.; Shahid, M. N.
2012-01-01
We discuss the possibility of using experiments timing the propagation of neutrino beams over large distances to help determine the absolute masses of the three neutrinos.......We discuss the possibility of using experiments timing the propagation of neutrino beams over large distances to help determine the absolute masses of the three neutrinos....
2016-01-01
We propose an entropy function for simplicial complices. Its value gives the expected cost of the optimal encoding of sequences of vertices of the complex, when any two vertices belonging to the same simplex are indistinguishable. We show that the proposed entropy function can be computed efficiently. By computing the entropy of several complices consisting of hundreds of simplices, we show that the proposed entropy function can be used in the analysis of the large sequences of simplicial com...
Entropy of Baker's Transformation
栾长福
2003-01-01
Four theorems about four different kinds of entropies for Baker's transformation are presented. The Kolmogorov entropy of Baker's transformation is sensitive to the initial flips by the time. The topological entropy of Baker's transformation is found to be log k. The conditions for the state of Baker's transformation to be forbidden are also derived. The relations among the Shanonn, Kolmogorov, topological and Boltzmann entropies are discussed in details.
Relative effects of enthalpy and entropy on the phase stability of equiatomic high-entropy alloys
Otto, Frederik [ORNL; Yang, Ying [ORNL; Bei, Hongbin [ORNL; George, Easo P [ORNL
2013-01-01
High configurational entropies have been hypothesized to stabilize solid solutions in equiatomic, multi-element alloys which have attracted much attention recently as high-entropy alloys with potentially interesting properties. To evaluate the usefulness of configurational entropy as a predictor of single-phase (solid solution) stability, we prepared five new equiatomic, quinary alloys by replacing individual elements one at a time in a CoCrFeMnNi alloy that was previously shown to be single-phase [1]. An implicit assumption here is that, if any one element is replaced by another, while keeping the total number of elements constant, the configurational entropy of the alloy is unchanged; therefore, the new alloys should also be single-phase. Additionally, the substitute elements that we chose, Ti for Co, Mo or V for Cr, V for Fe, and Cu for Ni, had the same room-temperature crystal structure and comparable size/electronegativity as the elements being replaced to maximize solid solubility consistent with the Hume-Rothery rules. For comparison, the base CoCrFeMnNi alloy was also prepared. After three-day anneals at elevated temperatures, multiple phases were observed in all but the base CoCrFeMnNi alloy suggesting that, by itself, configurational entropy is generally not able to override competing driving forces that also govern phase stability. Thermodynamic analyses were carried out for each of the constituent binaries in the investigated alloys (Co-Cr, Fe-Ni, Mo-Mn, etc,). Experimental results combined with the thermodynamic analyses suggest that, in general, enthalpy and non-configurational entropy have bigger influences on phase stability in equiatomic, multi-component alloys. Only when the alloy microstructure is a single-phase, approximately ideal solid solution does the contribution of configurational entropy to the total Gibbs free energy become dominant. Thus, high configurational entropy provides a way to rationalize, after the fact, why a solid solution
Physical entropy, information entropy and their evolution equations
无
2001-01-01
Inspired by the evolution equation of nonequilibrium statistical physics entropy and the concise statistical formula of the entropy production rate, we develop a theory of the dynamic information entropy and build a nonlinear evolution equation of the information entropy density changing in time and state variable space. Its mathematical form and physical meaning are similar to the evolution equation of the physical entropy: The time rate of change of information entropy density originates together from drift, diffusion and production. The concise statistical formula of information entropy production rate is similar to that of physical entropy also. Furthermore, we study the similarity and difference between physical entropy and information entropy and the possible unification of the two statistical entropies, and discuss the relationship among the principle of entropy increase, the principle of equilibrium maximum entropy and the principle of maximum information entropy as well as the connection between them and the entropy evolution equation.
Balian, Roger
We review at a tutorial level the many aspects of the concept of entropy and their interrelations, in thermodynamics, information theory, probability theory and statistical physics. The consideration of relevant entropies and the identification of entropy with missing information enlighten the paradoxes of irreversibility and of Maxwell's demon.
Entropy Is Simple, Qualitatively.
Lambert, Frank L.
2002-01-01
Suggests that qualitatively, entropy is simple. Entropy increase from a macro viewpoint is a measure of the dispersal of energy from localized to spread out at a temperature T. Fundamentally based on statistical and quantum mechanics, this approach is superior to the non-fundamental "disorder" as a descriptor of entropy change. (MM)
Ben-Naim, Arieh
2011-01-01
Changes in entropy can "sometimes" be interpreted in terms of changes in disorder. On the other hand, changes in entropy can "always" be interpreted in terms of changes in Shannon's measure of information. Mixing and demixing processes are used to highlight the pitfalls in the association of entropy with disorder. (Contains 3 figures.)
Entropy in the Tangled Nature Model of evolution
Roach, Ty N.F.; Nulton, James; Sibani, Paolo
2017-01-01
interpretation is supported by mathematical arguments using simulation data generated by the Tangled Nature Model (TNM), a stochastic model of evolving ecologies. We define two types of configurational entropy and study their empirical time dependence obtained from the data. Both entropy measures increase...... in characterizing the number of taxonomic configurations compatible with different niche partitioning and functionality. The TNM serves as an illustrative example of how to calculate and interpret these entropies, which are, however, also relevant to real ecosystems, where they can be used to calculate the number...
Structural entropy of glassy systems from graph isomorphism.
Zhou, Yuxing; Milner, Scott T
2016-09-21
Configurational entropy plays a central role in thermodynamic scenarios of the glass transition. As a measure of the number of basins in the potential energy landscape, configurational entropy for a glass-forming liquid can be evaluated by explicitly counting distinct inherent structures. In this work, we propose a graph-theory based method to examine local structure and obtain the corresponding entropy of hard-particle systems. Voronoi diagrams of associated clusters are classified using a graph isomorphism algorithm. The statistics of these clusters reveal structural motifs such as icosahedron-like order, and also allow us to calculate the structural entropy SG. We find the structural entropy of an n-particle subsystem grows linearly with n. Thus the structural entropy per particle can be obtained from the slope dSG/dn. Our results are consistent with previous values for configurational entropy obtained via thermodynamic integration. Structural entropies per particle are measured for hard-disk and hard-sphere polydisperse systems, and extrapolated for monodisperse hard disks, all of which are nonzero at the dynamic glass transition.
Brissaud, Jean-Bernard
2005-03-01
Entropy is a basic physical quantity that led to various, and sometimes apparently conflicting interpretations. It has been successively assimilated to different concepts such as disorder and information. In this paper we're going to revisit these conceptions, and establish the three following results: Entropy measures lack of information; it also measures information. These two conceptions are complementary. Entropy measures freedom, and this allows a coherent interpretation of entropy formulas and of experimental facts. To associate entropy and disorder implies defining order as absence of freedom. Disorder or agitation is shown to be more appropriately linked with temperature.
Jean-Bernard Brissaud
2005-02-01
Full Text Available Abstract: Entropy is a basic physical quantity that led to various, and sometimes apparently conflicting interpretations. It has been successively assimilated to different concepts such as disorder and information. In this paper we're going to revisit these conceptions, and establish the three following results: Entropy measures lack of information; it also measures information. These two conceptions are complementary. Entropy measures freedom, and this allows a coherent interpretation of entropy formulas and of experimental facts. To associate entropy and disorder implies defining order as absence of freedom. Disorder or agitation is shown to be more appropriately linked with temperature.
Volkenstein, Mikhail V
2009-01-01
The book "Entropy and Information" deals with the thermodynamical concept of entropy and its relationship to information theory. It is successful in explaining the universality of the term "Entropy" not only as a physical phenomenon, but reveals its existence also in other domains. E.g., Volkenstein discusses the "meaning" of entropy in a biological context and shows how entropy is related to artistic activities. Written by the renowned Russian bio-physicist Mikhail V. Volkenstein, this book on "Entropy and Information" surely serves as a timely introduction to understand entropy from a thermodynamic perspective and is definitely an inspiring and thought-provoking book that should be read by every physicist, information-theorist, biologist, and even artist.
RNA Thermodynamic Structural Entropy.
Garcia-Martin, Juan Antonio; Clote, Peter
2015-01-01
Conformational entropy for atomic-level, three dimensional biomolecules is known experimentally to play an important role in protein-ligand discrimination, yet reliable computation of entropy remains a difficult problem. Here we describe the first two accurate and efficient algorithms to compute the conformational entropy for RNA secondary structures, with respect to the Turner energy model, where free energy parameters are determined from UV absorption experiments. An algorithm to compute the derivational entropy for RNA secondary structures had previously been introduced, using stochastic context free grammars (SCFGs). However, the numerical value of derivational entropy depends heavily on the chosen context free grammar and on the training set used to estimate rule probabilities. Using data from the Rfam database, we determine that both of our thermodynamic methods, which agree in numerical value, are substantially faster than the SCFG method. Thermodynamic structural entropy is much smaller than derivational entropy, and the correlation between length-normalized thermodynamic entropy and derivational entropy is moderately weak to poor. In applications, we plot the structural entropy as a function of temperature for known thermoswitches, such as the repression of heat shock gene expression (ROSE) element, we determine that the correlation between hammerhead ribozyme cleavage activity and total free energy is improved by including an additional free energy term arising from conformational entropy, and we plot the structural entropy of windows of the HIV-1 genome. Our software RNAentropy can compute structural entropy for any user-specified temperature, and supports both the Turner'99 and Turner'04 energy parameters. It follows that RNAentropy is state-of-the-art software to compute RNA secondary structure conformational entropy. Source code is available at https://github.com/clotelab/RNAentropy/; a full web server is available at http
RNA Thermodynamic Structural Entropy.
Juan Antonio Garcia-Martin
Full Text Available Conformational entropy for atomic-level, three dimensional biomolecules is known experimentally to play an important role in protein-ligand discrimination, yet reliable computation of entropy remains a difficult problem. Here we describe the first two accurate and efficient algorithms to compute the conformational entropy for RNA secondary structures, with respect to the Turner energy model, where free energy parameters are determined from UV absorption experiments. An algorithm to compute the derivational entropy for RNA secondary structures had previously been introduced, using stochastic context free grammars (SCFGs. However, the numerical value of derivational entropy depends heavily on the chosen context free grammar and on the training set used to estimate rule probabilities. Using data from the Rfam database, we determine that both of our thermodynamic methods, which agree in numerical value, are substantially faster than the SCFG method. Thermodynamic structural entropy is much smaller than derivational entropy, and the correlation between length-normalized thermodynamic entropy and derivational entropy is moderately weak to poor. In applications, we plot the structural entropy as a function of temperature for known thermoswitches, such as the repression of heat shock gene expression (ROSE element, we determine that the correlation between hammerhead ribozyme cleavage activity and total free energy is improved by including an additional free energy term arising from conformational entropy, and we plot the structural entropy of windows of the HIV-1 genome. Our software RNAentropy can compute structural entropy for any user-specified temperature, and supports both the Turner'99 and Turner'04 energy parameters. It follows that RNAentropy is state-of-the-art software to compute RNA secondary structure conformational entropy. Source code is available at https://github.com/clotelab/RNAentropy/; a full web server is available at http
National Oceanic and Atmospheric Administration, Department of Commerce — The NGS Absolute Gravity data (78 stations) was received in July 1993. Principal gravity parameters include Gravity Value, Uncertainty, and Vertical Gradient. The...
Sinha, Supurna
2005-01-01
We present an analytical study of the loss of quantum coherence at absolute zero. Our model consists of a harmonic oscillator coupled to an environment of harmonic oscillators at absolute zero. We find that for an Ohmic bath, the offdiagonal elements of the density matrix in the position representation decay as a power law in time at late times. This slow loss of coherence in the quantum domain is qualitatively different from the exponential decay observed in studies of high temperature envir...
McLeod, Stephen
2014-07-01
Absolute needs (as against instrumental needs) are independent of the ends, goals and purposes of personal agents. Against the view that the only needs are instrumental needs, David Wiggins and Garrett Thomson have defended absolute needs on the grounds that the verb 'need' has instrumental and absolute senses. While remaining neutral about it, this article does not adopt that approach. Instead, it suggests that there are absolute biological needs. The absolute nature of these needs is defended by appeal to: their objectivity (as against mind-dependence); the universality of the phenomenon of needing across the plant and animal kingdoms; the impossibility that biological needs depend wholly upon the exercise of the abilities characteristic of personal agency; the contention that the possession of biological needs is prior to the possession of the abilities characteristic of personal agency. Finally, three philosophical usages of 'normative' are distinguished. On two of these, to describe a phenomenon or claim as 'normative' is to describe it as value-dependent. A description of a phenomenon or claim as 'normative' in the third sense does not entail such value-dependency, though it leaves open the possibility that value depends upon the phenomenon or upon the truth of the claim. It is argued that while survival needs (or claims about them) may well be normative in this third sense, they are normative in neither of the first two. Thus, the idea of absolute need is not inherently normative in either of the first two senses.
Relative entropy equals bulk relative entropy
Jafferis, Daniel L; Maldacena, Juan; Suh, S Josephine
2015-01-01
We consider the gravity dual of the modular Hamiltonian associated to a general subregion of a boundary theory. We use it to argue that the relative entropy of nearby states is given by the relative entropy in the bulk, to leading order in the bulk gravitational coupling. We also argue that the boundary modular flow is dual to the bulk modular flow in the entanglement wedge, with implications for entanglement wedge reconstruction.
Black hole entropy and entropy of entanglement
Kabat, D
1995-01-01
We compute the one-loop correction to the entropy of a very massive black hole, by evaluating the partition function in the presence of a conical singularity for quantum fields of spin zero, one-half, and one. We compare the results to the entropy of entanglement, defined by the density matrix which describes the ground state of the field as seen from one side of a boundary in Minkowski space. Fields of spin zero and one-half contribute an entropy to the black hole which is identical to their entropy of entanglement. For spin one a contact interaction with the horizon appears in the black hole entropy but is absent from the entropy of entanglement. Expressed as a particle path integral the contact term is an integral over paths which begin and end on the horizon; it is the field theory limit of the interaction proposed by Susskind and Uglum which couples a closed string to an open string stranded on the horizon.
Thermodynamic efficiency and entropy production in the climate system.
Lucarini, Valerio
2009-08-01
We present an outlook on the climate system thermodynamics. First, we construct an equivalent Carnot engine with efficiency eta and frame the Lorenz energy cycle in a macroscale thermodynamic context. Then, by exploiting the second law, we prove that the lower bound to the entropy production is eta times the integrated absolute value of the internal entropy fluctuations. An exergetic interpretation is also proposed. Finally, the controversial maximum entropy production principle is reinterpreted as requiring the joint optimization of heat transport and mechanical work production. These results provide tools for climate change analysis and for climate models' validation.
Maximum-entropy probability distributions under Lp-norm constraints
Dolinar, S.
1991-01-01
Continuous probability density functions and discrete probability mass functions are tabulated which maximize the differential entropy or absolute entropy, respectively, among all probability distributions with a given L sub p norm (i.e., a given pth absolute moment when p is a finite integer) and unconstrained or constrained value set. Expressions for the maximum entropy are evaluated as functions of the L sub p norm. The most interesting results are obtained and plotted for unconstrained (real valued) continuous random variables and for integer valued discrete random variables. The maximum entropy expressions are obtained in closed form for unconstrained continuous random variables, and in this case there is a simple straight line relationship between the maximum differential entropy and the logarithm of the L sub p norm. Corresponding expressions for arbitrary discrete and constrained continuous random variables are given parametrically; closed form expressions are available only for special cases. However, simpler alternative bounds on the maximum entropy of integer valued discrete random variables are obtained by applying the differential entropy results to continuous random variables which approximate the integer valued random variables in a natural manner. All the results are presented in an integrated framework that includes continuous and discrete random variables, constraints on the permissible value set, and all possible values of p. Understanding such as this is useful in evaluating the performance of data compression schemes.
Black hole entropy quantization
Corichi, A; Fernandez-Borja, E; Corichi, Alejandro; Diaz-Polo, Jacobo; Fernandez-Borja, Enrique
2006-01-01
Ever since the pioneer works of Bekenstein and Hawking, black hole entropy has been known to have a quantum origin. Furthermore, it has long been argued by Bekenstein that entropy should be quantized in discrete (equidistant) steps given its identification with horizon area in (semi-)classical general relativity and the properties of area as an adiabatic invariant. This lead to the suggestion that black hole area should also be quantized in equidistant steps to account for the discrete black hole entropy. Here we shall show that loop quantum gravity, in which area is not quantized in equidistant steps can nevertheless be consistent with Bekenstein's equidistant entropy proposal in a subtle way. For that we perform a detailed analysis of the number of microstates compatible with a given area and show that an observed oscillatory behavior in the entropy-area relation, when properly interpreted yields an entropy that has discrete, equidistant values that are consistent with the Bekenstein framework.
Hubeny, Veronika E
2014-01-01
A recently explored interesting quantity in AdS/CFT, dubbed 'residual entropy', characterizes the amount of collective ignorance associated with either boundary observers restricted to finite time duration, or bulk observers who lack access to a certain spacetime region. However, the previously-proposed expression for this quantity involving variation of boundary entanglement entropy (subsequently renamed to 'differential entropy') works only in a severely restrictive context. We explain the key limitations, arguing that in general, differential entropy does not correspond to residual entropy. Given that the concept of residual entropy as collective ignorance transcends these limitations, we identify two correspondingly robust, covariantly-defined constructs: a 'strip wedge' associated with boundary observers and a 'rim wedge' associated with bulk observers. These causal sets are well-defined in arbitrary time-dependent asymptotically AdS spacetimes in any number of dimensions. We discuss their relation, spec...
Rosser, J. Barkley
2016-12-01
Entropy is a central concept of statistical mechanics, which is the main branch of physics that underlies econophysics, the application of physics concepts to understand economic phenomena. It enters into econophysics both in an ontological way through the Second Law of Thermodynamics as this drives the world economy from its ecological foundations as solar energy passes through food chains in dissipative process of entropy rising and production fundamentally involving the replacement of lower entropy energy states with higher entropy ones. In contrast the mathematics of entropy as appearing in information theory becomes the basis for modeling financial market dynamics as well as income and wealth distribution dynamics. It also provides the basis for an alternative view of stochastic price equilibria in economics, as well providing a crucial link between econophysics and sociophysics, keeping in mind the essential unity of the various concepts of entropy.
Information Entropy of Fullerenes.
Sabirov, Denis Sh; Ōsawa, Eiji
2015-08-24
The reasons for the formation of the highly symmetric C60 molecule under nonequilibrium conditions are widely discussed as it dominates over numerous similar fullerene structures. In such conditions, evolution of structure rather than energy defines the processes. We have first studied the diversity of fullerenes in terms of information entropy. Sorting 2079 structures from An Atlas of Fullerenes [ Fowler , P. W. ; Manolopoulos , D. E. An Atlas of Fullerenes ; Oxford : Clarendon , 1995 . ], we have found that the information entropies of only 14 fullerenes (entropy, i.e., an exclusive compound among the other members of the fullerene family. Such an efficient sorting demonstrates possible relevance of information entropy to chemical processes. For this reason, we have introduced an algorithm for calculating changes in information entropy at chemical transformations. The preliminary calculations of changes in information entropy at the selected fullerene reactions show good agreement with thermochemical data.
Special Issue: Tsallis Entropy
Anastasios Anastasiadis
2012-01-01
One of the crucial properties of the Boltzmann-Gibbs entropy in the context of classical thermodynamics is extensivity, namely proportionality with the number of elements of the system. The Boltzmann-Gibbs entropy satisfies this prescription if the subsystems are statistically (quasi-) independent, or typically if the correlations within the system are essentially local. In such cases the energy of the system is typically extensive and the entropy is additive. In general, however, the situati...
P. Mitra
1994-01-01
In the talk different definitions of the black hole entropy are discussed and compared. It is shown that the Bekenstein-Hawking entropy $S^{BH}$ (defined by the response of the free energy of a system containing a black hole on the change of the temperature) differs from the statistical- mechanical entropy $S^{SM}=-\\mbox{Tr}(\\hat{\\rho}\\ln \\hat{\\rho})$ (defined by counting internal degrees of freedom of a black hole). A simple explanation of the universality of the Bekenstein-Hawking entropy (...
Frolov, V
1994-01-01
In the talk different definitions of the black hole entropy are discussed and compared. It is shown that the Bekenstein-Hawking entropy S^{BH} (defined by the response of the free energy of a system containing a black hole on the change of the temperature) differs from the statistical- mechanical entropy S^{SM}=-\\mbox{Tr}(\\hat{\\rho}\\ln \\hat{\\rho}) (defined by counting internal degrees of freedom of a black hole). A simple explanation of the universality of the Bekenstein-Hawking entropy (i.e. its independence of the number and properties of the fields which might contribute to S^{SM}) is given.
ENTROPY FUNCTIONAL FOR CONTINUOUS SYSTEMS OF FINITE ENTROPY
M. Rahimi A. Riazi
2012-01-01
In this article,we introduce the concept of entropy functional for continuous systems on compact metric spaces,and prove some of its properties.We also extract the Kolmogorov entropy from the entropy functional.
Projective Power Entropy and Maximum Tsallis Entropy Distributions
Shinto Eguchi; Shogo Kato; Osamu Komori
2011-01-01
We discuss a one-parameter family of generalized cross entropy between two distributions with the power index, called the projective power entropy. The cross entropy is essentially reduced to the Tsallis entropy if two distributions are taken to be equal. Statistical and probabilistic properties associated with the projective power entropy are extensively investigated including a characterization problem of which conditions uniquely determine the projective power entropy up to the power index...
Entropy bounds for uncollapsed rotating bodies
Abreu, Gabriel
2010-01-01
Entropy bounds in black hole physics, based on a wide variety of different approaches, have had a long and distinguished history. Recently the current authors have turned attention to uncollapsed systems and obtained a robust entropy bound for uncollapsed static spherically symmetric configurations. In the current article we extend this bound to rotating systems. This extension is less simple than one might at first suppose. Purely classically, (using only classical general relativity and basic thermodynamics), it is possible to show that the entropy of uncollapsed matter inside a region enclosed by a surface of area A is bounded from above by S = max kappa(FIDOs) / (2 pi). Thus, using only classical general relativity, basic thermodynamics, and the Unruh effect, we are able to argue that for uncollapsed matter S <= {1/2} A.
Huynh, Tri H V; Shim, Irene; Bohr, Henrik; Abrahamsen, Bjarke; Nielsen, Birgitte; Jensen, Anders A; Bunch, Lennart
2012-06-14
The excitatory amino acid transporters (EAATs) play essential roles in regulating the synaptic concentration of the neurotransmitter glutamate in the mammalian central nervous system. To date, five subtypes have been identified, named EAAT1-5 in humans, and GLAST, GLT-1, EAAC1, EAAT4, and EAAT5 in rodents, respectively. In this paper, we present the design, synthesis, and pharmacological evaluation of seven 7-N-substituted analogues of UCPH-101/102. Analogue 9 inhibited EAAT1 in the micromolar range (IC(50) value 20 μM), whereas analogues 8 and 10 were inactive (IC(50) values >100 μM). The diastereomeric pairs 11a/11b and 12a/12b were separated by HPLC and the absolute configuration assigned by VCD technique in combination with ab initio Hartree-Fock calculations. Analogues 11a (RS-isomer) and 12b (RR-isomer) inhibited EAAT1 (IC(50) values 5.5 and 3.8 μM, respectively), whereas analogues 11b (SS-isomer) and 12a (SR-isomer) failed to inhibit EAAT1 uptake (IC(50) values >300 μM).
Absolute Gravimetry in Fennoscandia
Pettersen, B. R; TImmen, L.; Gitlein, O.
motions) has its major axis in the direction of southwest to northeast and covers a distance of about 2000 km. Absolute gravimetry was made in Finland and Norway in 1976 with a rise-and fall instrument. A decade later the number of gravity stations was expanded by JILAg-5, in Finland from 1988, in Norway...
Renyi extrapolation of Shannon entropy
Zyczkowski, K
2003-01-01
Relations between Shannon entropy and Renyi entropies of integer order are discussed. For any N-point discrete probability distribution for which the Renyi entropies of order two and three are known, we provide an lower and an upper bound for the Shannon entropy. The average of both bounds provide an explicit extrapolation for this quantity. These results imply relations between the von Neumann entropy of a mixed quantum state, its linear entropy and traces.
Marder, Daniel
The Second Law of Thermodynamics demonstrates the idea of entropy, the tendency of ordered energy to free itself and thus break apart the system that contains it and dissipate that system into chaos. When applied to communications theory, entropy increases not only with noise but with the density of information--particles of possible meaning…
Finnemann, Niels Ole
2016-01-01
, links, interactive processes, and time scalings, and that the hypertext configuration is a major but not sole source of the messiness of big data. The notion of hypertext will be revalidated, placed at the center of the interpretation of networked digital media, and used in the analysis of the fast...
Entropy and Digital Installation
Susan Ballard
2005-01-01
Full Text Available This paper examines entropy as a process which introduces ideas of distributed materiality to digital installation. Beginning from an analysis of entropy as both force and probability measure within information theory and it’s extension in Ruldof Arnheim’s text ‘Entropy and Art” it develops an argument for the positive rather thannegative forces of entropy. The paper centres on a discussion of two recent works by New Zealand artists Ronnie van Hout (“On the Run”, Wellington City Gallery, NZ, 2004 and Alex Monteith (“Invisible Cities”, Physics Room Contemporary Art Space, Christchurch, NZ, 2004. Ballard suggests that entropy, rather than being a hindrance to understanding or a random chaotic force, discloses a necessary and material politics of noise present in digital installation.
Entropy, Perception, and Relativity
Jaeger, Stefan
2008-01-01
In this paper, I expand Shannon's definition of entropy into a new form of entropy that allows integration of information from different random events. Shannon's notion of entropy is a special case of my more general definition of entropy. I define probability using a so-called performance function, which is de facto an exponential distribution. Assuming that my general notion of entropy reflects the true uncertainty about a probabilistic event, I understand that our perceived uncertainty differs. I claim that our perception is the result of two opposing forces similar to the two famous antagonists in Chinese philosophy: Yin and Yang. Based on this idea, I show that our perceived uncertainty matches the true uncertainty in points determined by the golden ratio. I demonstrate that the well-known sigmoid function, which we typically employ in artificial neural networks as a non-linear threshold function, describes the actual performance. Furthermore, I provide a motivation for the time dilation in Einstein's Sp...
Phonon broadening in high entropy alloys
Körmann, Fritz; Ikeda, Yuji; Grabowski, Blazej; Sluiter, Marcel H. F.
2017-09-01
Refractory high entropy alloys feature outstanding properties making them a promising materials class for next-generation high-temperature applications. At high temperatures, materials properties are strongly affected by lattice vibrations (phonons). Phonons critically influence thermal stability, thermodynamic and elastic properties, as well as thermal conductivity. In contrast to perfect crystals and ordered alloys, the inherently present mass and force constant fluctuations in multi-component random alloys (high entropy alloys) can induce significant phonon scattering and broadening. Despite their importance, phonon scattering and broadening have so far only scarcely been investigated for high entropy alloys. We tackle this challenge from a theoretical perspective and employ ab initio calculations to systematically study the impact of force constant and mass fluctuations on the phonon spectral functions of 12 body-centered cubic random alloys, from binaries up to 5-component high entropy alloys, addressing the key question of how chemical complexity impacts phonons. We find that it is crucial to include both mass and force constant fluctuations. If one or the other is neglected, qualitatively wrong results can be obtained such as artificial phonon band gaps. We analyze how the results obtained for the phonons translate into thermodynamically integrated quantities, specifically the vibrational entropy. Changes in the vibrational entropy with increasing the number of elements can be as large as changes in the configurational entropy and are thus important for phase stability considerations. The set of studied alloys includes MoTa, MoTaNb, MoTaNbW, MoTaNbWV, VW, VWNb, VWTa, VWNbTa, VTaNbTi, VWNbTaTi, HfZrNb, HfMoTaTiZr.
Entanglement Entropy of AdS Black Holes
Maurizio Melis
2010-11-01
Full Text Available We review recent progress in understanding the entanglement entropy of gravitational configurations for anti-de Sitter gravity in two and three spacetime dimensions using the AdS/CFT correspondence. We derive simple expressions for the entanglement entropy of two- and three-dimensional black holes. In both cases, the leading term of the entanglement entropy in the large black hole mass expansion reproduces exactly the Bekenstein-Hawking entropy, whereas the subleading term behaves logarithmically. In particular, for the BTZ black hole the leading term of the entanglement entropy can be obtained from the large temperature expansion of the partition function of a broad class of 2D CFTs on the torus.
Absolute Neutrino Mass Determination
Päs, H
2001-01-01
We discuss four approaches to the determination of absolute neutrino mass. These are the measurement of the zero-neutrino double beta decay rate, of the tritium decay end-point spectrum, of the cosmic ray spectrum above the GZK cutoff, and the cosmological measurement of the power spectrum governing the CMB and large scale structure. The first two approaches are sensitive to the mass eigenstates coupling to the electron neutrino, whereas the latter two are sensitive to the heavy component of the cosmic neutrino background. All mass eigenstates are related by the $\\Delta m^2$'s inferred from neutrino oscillation data. Consequently, the potential for absolute mass determination of each of the four approaches is correlated with the other three, in ways that we point out.
Nonsymmetric entropy I: basic concepts and results
Liu, Chengshi
2006-01-01
A new concept named nonsymmetric entropy which generalizes the concepts of Boltzman's entropy and shannon's entropy, was introduced. Maximal nonsymmetric entropy principle was proven. Some important distribution laws were derived naturally from maximal nonsymmetric entropy principle.
Finnemann, Niels Ole
2016-01-01
, links, interactive processes, and time scalings, and that the hypertext configuration is a major but not sole source of the messiness of big data. The notion of hypertext will be revalidated, placed at the center of the interpretation of networked digital media, and used in the analysis of the fast......The article presents a conceptual framework for distinguishing different sorts of heterogeneous digital materials. The hypothesis is that a wide range of heterogeneous data resources can be characterized and classified due to their particular configurations of hypertext features such as scripts......-growing amounts of heterogeneous digital collections, assemblages, and corpora. The introduction summarizes the wider background of a fast-changing data landscape....
Entropy Coherent and Entropy Convex Measures of Risk
Laeven, R.J.A.; Stadje, M.A.
2011-01-01
We introduce two subclasses of convex measures of risk, referred to as entropy coherent and entropy convex measures of risk. We prove that convex, entropy convex and entropy coherent measures of risk emerge as certainty equivalents under variational, homothetic and multiple priors preferences, respe
Entropy coherent and entropy convex measures of risk
Laeven, R.J.A.; Stadje, M.
2013-01-01
We introduce two subclasses of convex measures of risk, referred to as entropy coherent and entropy convex measures of risk. Entropy coherent and entropy convex measures of risk are special cases of φ-coherent and φ-convex measures of risk. Contrary to the classical use of coherent and convex measur
Entropy of the Mixture of Sources and Entropy Dimension
Smieja, Marek; Tabor, Jacek
2011-01-01
We investigate the problem of the entropy of the mixture of sources. There is given an estimation of the entropy and entropy dimension of convex combination of measures. The proof is based on our alternative definition of the entropy based on measures instead of partitions.
Volcano shapes, entropies, and eruption probabilities
Gudmundsson, Agust; Mohajeri, Nahid
2014-05-01
We propose that the shapes of polygenetic volcanic edifices reflect the shapes of the associated probability distributions of eruptions. In this view, the peak of a given volcanic edifice coincides roughly with the peak of the probability (or frequency) distribution of its eruptions. The broadness and slopes of the edifices vary widely, however. The shapes of volcanic edifices can be approximated by various distributions, either discrete (binning or histogram approximation) or continuous. For a volcano shape (profile) approximated by a normal curve, for example, the broadness would be reflected in its standard deviation (spread). Entropy (S) of a discrete probability distribution is a measure of the absolute uncertainty as to the next outcome/message: in this case, the uncertainty as to time and place of the next eruption. A uniform discrete distribution (all bins of equal height), representing a flat volcanic field or zone, has the largest entropy or uncertainty. For continuous distributions, we use differential entropy, which is a measure of relative uncertainty, or uncertainty change, rather than absolute uncertainty. Volcano shapes can be approximated by various distributions, from which the entropies and thus the uncertainties as regards future eruptions can be calculated. We use the Gibbs-Shannon formula for the discrete entropies and the analogues general formula for the differential entropies and compare their usefulness for assessing the probabilities of eruptions in volcanoes. We relate the entropies to the work done by the volcano during an eruption using the Helmholtz free energy. Many factors other than the frequency of eruptions determine the shape of a volcano. These include erosion, landslides, and the properties of the erupted materials (including their angle of repose). The exact functional relation between the volcano shape and the eruption probability distribution must be explored for individual volcanoes but, once established, can be used to
Leonid M. Martyushev
2015-06-01
Full Text Available The entropy production (inside the volume bounded by a photosphere of main-sequence stars, subgiants, giants, and supergiants is calculated based on B–V photometry data. A non-linear inverse relationship of thermodynamic fluxes and forces as well as an almost constant specific (per volume entropy production of main-sequence stars (for 95% of stars, this quantity lies within 0.5 to 2.2 of the corresponding solar magnitude is found. The obtained results are discussed from the perspective of known extreme principles related to entropy production.
Alkyl chains acting as entropy reservoir in liquid crystalline materials.
Sorai, Michio; Saito, Kazuya
2003-01-01
The roles played by the conformational disordering of alkyl chains in determining the aggregation states of matter are reviewed for liquid crystalline materials from a thermodynamic perspective. Entropy, which is one of the most macroscopic concepts but which has a clear microscopic meaning, provides crucial microscopic information for complex systems for which a microscopic description is hard to establish. Starting from structural implication by absolute (third-law) entropy for crystalline solids, the existence of successive phase transitions caused by the successive conformational melting of alkyl chains in discotic mesogens is explained. An experimental basis is given for the "quasi-binary picture" of thermotropic liquid crystals, i.e., the highly disordered alkyl chains behave like a second component (solvent). A novel entropy transfer between the "components" of a molecule and the resulting "alkyl chains as entropy reservoir" mechanism are explained for cubic mesogens.
Entropy of Fuzzy Partitions and Entropy of Fuzzy Dynamical Systems
Dagmar Markechová
2016-01-01
Full Text Available In the paper we define three kinds of entropy of a fuzzy dynamical system using different entropies of fuzzy partitions. It is shown that different definitions of the entropy of fuzzy partitions lead to different notions of entropies of fuzzy dynamical systems. The relationships between these entropies are studied and connections with the classical case are mentioned as well. Finally, an analogy of the Kolmogorov–Sinai Theorem on generators is proved for fuzzy dynamical systems.
Kevin H. Knuth
2014-01-01
Full Text Available In 2013, Entropy instituted the “Best Paper” award to recognize outstanding papers in the area of entropy and information studies published in Entropy [1]. We are pleased to announce the “Entropy Best Paper Award” for 2014. Nominations were selected by the Editor-in-Chief and designated Editorial Board Members from all the papers published in 2010.
Entropy of international trades
Oh, Chang-Young; Lee, D.-S.
2017-05-01
The organization of international trades is highly complex under the collective efforts towards economic profits of participating countries given inhomogeneous resources for production. Considering the trade flux as the probability of exporting a product from a country to another, we evaluate the entropy of the world trades in the period 1950-2000. The trade entropy has increased with time, and we show that it is mainly due to the extension of trade partnership. For a given number of trade partners, the mean trade entropy is about 60% of the maximum possible entropy, independent of time, which can be regarded as a characteristic of the trade fluxes' heterogeneity and is shown to be derived from the scaling and functional behaviors of the universal trade-flux distribution. The correlation and time evolution of the individual countries' gross-domestic products and the number of trade partners show that most countries achieved their economic growth partly by extending their trade relationship.
Kyle, Benjamin G.
1988-01-01
Illustrates qualitative and metaphoric applications of entropy in the areas of cosmology, the birth and death of the universe and time; life and evolution; literature and art; and social science. (RT)
Baumann, Henri
This work consists of a feasibility study of a first stage prototype airborne absolute gravimeter system. In contrast to relative systems, which are using spring gravimeters, the measurements acquired by absolute systems are uncorrelated and the instrument is not suffering from problems like instrumental drift, frequency response of the spring and possible variation of the calibration factor. The major problem we had to resolve were to reduce the influence of the non-gravitational accelerations included in the measurements. We studied two different approaches to resolve it: direct mechanical filtering, and post-processing digital compensation. The first part of the work describes in detail the different mechanical passive filters of vibrations, which were studied and tested in the laboratory and later in a small truck in movement. For these tests as well as for the airborne measurements an absolute gravimeter FG5-L from Micro-G Ltd was used together with an Inertial navigation system Litton-200, a vertical accelerometer EpiSensor, and GPS receivers for positioning. These tests showed that only the use of an optical table gives acceptable results. However, it is unable to compensate for the effects of the accelerations of the drag free chamber. The second part describes the strategy of the data processing. It is based on modeling the perturbing accelerations by means of GPS, EpiSensor and INS data. In the third part the airborne experiment is described in detail, from the mounting in the aircraft and data processing to the different problems encountered during the evaluation of the quality and accuracy of the results. In the part of data processing the different steps conducted from the raw apparent gravity data and the trajectories to the estimation of the true gravity are explained. A comparison between the estimated airborne data and those obtained by ground upward continuation at flight altitude allows to state that airborne absolute gravimetry is feasible and
Multifractals and Entropy Computing
Slomczynski, W; Zyczkowski, K; Slomczynski, Wojciech; Kwapien, Jaroslaw; Zyczkowski, Karol
1998-01-01
We discuss the properties of invariant measures corresponding to iterated function systems (IFSs) with place-dependent probabilities and compute their shown that with certain dynamical systems one can associate the corresponding IFSs in such a way that their generalized entropies are equal. We use this method to compute entropy of some classical and quantum dynamical systems. Numerical techniques are based on integration over fractal measures.
Entropy and environmental mystery.
Stamps, Arthur E
2007-06-01
Two studies are reported regarding the effects of entropy, lighting, and occlusion on impressions of mystery in physical environments. The theoretical context of this study was the "informational theory" of environmental preference, which, among other claims, holds that mystery can be measured by the extent to which people perceive a promise of more information if they move deeper into an environment. Entropy, in the context of this article, is visual diversity as measured using information theory. Mystery was measured by a semantic differential scale. The definition of mystery was left up to each individual participant. Entropy of occluded objects was used to obtain an objective, experimentally manipulatable and operational definition of "promise of more information." Exp. 1 had 12 stimuli and 15 participants. Exp. 2 had 12 stimuli and 16 participants. Entropy of occluded objects ranged from 0 to 6 bits. Entropy of occluded objects was used to measure the promise that there would be more information if one moved deeper into an environment. Overall, amount of light had the strongest effect on responses of mystery (r = -.63, darker was more mysterious), followed by occlusion (r = .26, occluding objects made a scene seem more mysterious), and by the promise of more information if one moved about in the scene (r = .13), the more entropy in occluded objects, the greater the impression of mystery). The theoretical contribution of this work is that a relationship between subjective impressions of mystery and an objective measure of "promise of more information" was found.
Special Issue: Tsallis Entropy
Anastasios Anastasiadis
2012-02-01
Full Text Available One of the crucial properties of the Boltzmann-Gibbs entropy in the context of classical thermodynamics is extensivity, namely proportionality with the number of elements of the system. The Boltzmann-Gibbs entropy satisfies this prescription if the subsystems are statistically (quasi- independent, or typically if the correlations within the system are essentially local. In such cases the energy of the system is typically extensive and the entropy is additive. In general, however, the situation is not of this type and correlations may be far from negligible at all scales. Tsallis in 1988 introduced an entropic expression characterized by an index q which leads to a non-extensive statistics. Tsallis entropy, Sq, is the basis of the so called non-extensive statistical mechanics, which generalizes the Boltzmann-Gibbs theory. Tsallis statistics have found applications in a wide range of phenomena in diverse disciplines such as physics, chemistry, biology, medicine, economics, geophysics, etc. The focus of this special issue of Entropy was to solicit contributions that apply Tsallis entropy in various scientific fields. [...
Entropy of universe as entanglement entropy
Bak, Dongsu
2012-01-01
We note that the observable part of universe at a certain time t_P is necessarily limited, when there is a beginning of universe. We argue that an appropriate spacetime region associated with an observer from t_I to t_P is the causal diamond which is the overlap of the past/future of the observer at t_P/t_I respectively. We also note that the overlap surface \\partial D of the future and the past lightcones bisects the spatial section including \\partial D into two regions D and \\bar D where D is the region inside the causal diamond and \\bar D the remaining part of the spatial section. We propose here that the entropy of universe associated with a causal diamond is given by an entanglement entropy where one is tracing over the Hilbert space associated with the region \\bar D which is not accessible by the observer. We test our proposal for various examples of cosmological spacetimes, including flat, open or closed FRW universes, by showing that the entropy as the area of \\partial D divided by 4G is a non-decreas...
Absolutely Indecomposable Modules
Göbel, Rüdiger
2007-01-01
A module is called absolutely indecomposable if it is directly indecomposable in every generic extension of the universe. We want to show the existence of large abelian groups that are absolutely indecomposable. This will follow from a more general result about R-modules over a large class of commutative rings R with endomorphism ring R which remains the same when passing to a generic extension of the universe. It turns out that `large' in this context has the precise meaning, namely being smaller then the first omega-Erdos cardinal defined below. We will first apply result on large rigid trees with a similar property established by Shelah in 1982, and will prove the existence of related ` R_omega-modules' (R-modules with countably many distinguished submodules) and finally pass to R-modules. The passage through R_omega-modules has the great advantage that the proofs become very transparent essentially using a few `linear algebra' arguments accessible also for graduate students. The result gives a new constru...
Okada, H; Bravar, A; Bunce, G; Dhawan, S; Eyser, K O; Gill, R; Haeberli, W; Huang, H; Jinnouchi, O; Makdisi, Y; Nakagawa, I; Nass, A; Saitô, N; Stephenson, E; Sviridia, D; Wise, T; Wood, J; Zelenski, A
2007-01-01
Precise and absolute beam polarization measurements are critical for the RHIC spin physics program. Because all experimental spin-dependent results are normalized by beam polarization, the normalization uncertainty contributes directly to final physics uncertainties. We aimed to perform the beam polarization measurement to an accuracy of $\\Delta P_{beam}/P_{beam} < 5%$. The absolute polarimeter consists of Polarized Atomic Hydrogen Gas Jet Target and left-right pairs of silicon strip detectors and was installed in the RHIC-ring in 2004. This system features \\textit{proton-proton} elastic scattering in the Coulomb nuclear interference (CNI) region. Precise measurements of the analyzing power $A_N$ of this process has allowed us to achieve $\\Delta P_{beam}/P_{beam} =4.2%$ in 2005 for the first long spin-physics run. In this report, we describe the entire set up and performance of the system. The procedure of beam polarization measurement and analysis results from 2004-2005 are described. Physics topics of $A...
On the Conditional Rényi Entropy
S. Fehr (Serge); S. Berens (Stefan)
2014-01-01
htmlabstractThe Rényi entropy of general order unifies the well-known Shannon entropy with several other entropy notions, like the min-entropy or the collision entropy. In contrast to the Shannon entropy, there seems to be no commonly accepted definition for the conditional Rényi entropy: several ve
On the Conditional Rényi Entropy
Fehr, S.; Berens, S.
2014-01-01
The Rényi entropy of general order unifies the well-known Shannon entropy with several other entropy notions, like the min-entropy or the collision entropy. In contrast to the Shannon entropy, there seems to be no commonly accepted definition for the conditional Rényi entropy: several versions have
EEG entropy measures in anesthesia
Zhenhu eLiang
2015-02-01
Full Text Available Objective: Entropy algorithms have been widely used in analyzing EEG signals during anesthesia. However, a systematic comparison of these entropy algorithms in assessing anesthesia drugs’ effect is lacking. In this study, we compare the capability of twelve entropy indices for monitoring depth of anesthesia (DoA and detecting the burst suppression pattern (BSP, in anesthesia induced by GA-BAergic agents.Methods: Twelve indices were investigated, namely Response Entropy (RE and State entropy (SE, three wavelet entropy (WE measures (Shannon WE (SWE, Tsallis WE (TWE and Renyi WE (RWE, Hilbert-Huang spectral entropy (HHSE, approximate entropy (ApEn, sample entropy (SampEn, Fuzzy entropy, and three permutation entropy (PE measures (Shannon PE (SPE, Tsallis PE (TPE and Renyi PE (RPE. Two EEG data sets from sevoflurane-induced and isoflu-rane-induced anesthesia respectively were selected to assess the capability of each entropy index in DoA monitoring and BSP detection. To validate the effectiveness of these entropy algorithms, phar-macokinetic / pharmacodynamic (PK/PD modeling and prediction probability analysis were applied. The multifractal detrended fluctuation analysis (MDFA as a non-entropy measure was compared.Results: All the entropy and MDFA indices could track the changes in EEG pattern during different anesthesia states. Three PE measures outperformed the other entropy indices, with less baseline vari-ability, higher coefficient of determination and prediction probability, and RPE performed best; ApEn and SampEn discriminated BSP best. Additionally, these entropy measures showed an ad-vantage in computation efficiency compared with MDFA.Conclusion: Each entropy index has its advantages and disadvantages in estimating DoA. Overall, it is suggested that the RPE index was a superior measure.Significance: Investigating the advantages and disadvantages of these entropy indices could help improve current clinical indices for monitoring DoA.
孔祥波; 王鸿斌; 张真
2012-01-01
The Chinese scholar tree looper,Semiothisa cinerearia Bremer et Grey (Lepidoptera:Geometridae),is the major defoliator of the Chinese scholar tree Sophora japonica L.in China.The elucidation of the absolute chemical structure of the sex pheromone component of S.cinerearia may provide a potential chemical for the pest control against the S.cinerearia infestations in the urban area.In this study,two sex pheromone gland compounds,i.e.,(6Z,9Z)-6,9-cis-3,4-epoxy-heptadecadiene (6Z,9Z-cis-3,4-epoxy-17:H) and (3Z,6Z,9Z)-3,6,9-heptadecatriene (3Z,6Z,9Z-17:H),were detected in a 100:4.8 ± 1.3 ratio (N =12) during analyses of solvent extracts from virgin female S.cinerearia (2 - 3 d old) by comparison of their gas chromatography (GC) retention time and mass spectra (MS) with those of synthetic standards.Furthermore,the absolute configuration of 6Z,9Z-cis-3,4-epoxy-17:H in the sex pheromone gland of S.cinerearia was determined as (6Z,9Z)-3R,4S-epoxy-heptadecadiene by using a chiral capillary column ( CycloSil-B,30 m × 0.25 mm × 0.25 μm film) GC under the optimized oven temperature program.The mixture of the two synthetic enantiomers of 6Z,9Z-3R,4S-epoxy-17:H and 6Z,9Z-3S,4R-epoxy-17:H in a ratio of 1.28∶1 was injected into the female extracts,and thus the ratio was changed to 1.55∶ 1.Based on this analysis,the absolute configuration of the gland component 6Z,9Z-cis-3,4-epoxy-17:H was further confirmed as 3R,4S.It is anticipated that control of S.cinerearia infestation with enantiomerically pure materials will be much more effective.%槐庶尺蛾Semiothisa cinerearia Bremer et Grey(鳞翅目:尺蛾科)是我国北方国槐Sophora japonicaL.上的重要食叶害虫.本研究的主要目的是阐明槐庶尺蛾性信息素成分化学结构的绝对构型,为在城市地区环境友好地防控槐庶尺蛾的为害提供一种新方法.经与标准品比较气相色谱保留时间和质谱特征离子,从槐庶尺蛾处女雌蛾(2-3日龄)性信息素腺体溶
Absolute Gravimetry in Fennoscandia
Pettersen, B. R; TImmen, L.; Gitlein, O.
The Fennoscandian postglacial uplift has been mapped geometrically using precise levelling, tide gauges, and networks of permanent GPS stations. The results identify major uplift rates at sites located around the northern part of the Gulf of Bothnia. The vertical motions decay in all directions...... motions) has its major axis in the direction of southwest to northeast and covers a distance of about 2000 km. Absolute gravimetry was made in Finland and Norway in 1976 with a rise-and fall instrument. A decade later the number of gravity stations was expanded by JILAg-5, in Finland from 1988, in Norway...... from 1991, and in Sweden from 1992. FG5 was introduced in these three countries in 1993 (7 stations) and continued with an extended campaign in 1995 (12 stations). In 2003 a project was initiated by IfE, Hannover to collect observations simultaneously with GRACE on an annual cycle. New instruments were...
Optical tweezers absolute calibration
Dutra, R S; Neto, P A Maia; Nussenzveig, H M
2014-01-01
Optical tweezers are highly versatile laser traps for neutral microparticles, with fundamental applications in physics and in single molecule cell biology. Force measurements are performed by converting the stiffness response to displacement of trapped transparent microspheres, employed as force transducers. Usually, calibration is indirect, by comparison with fluid drag forces. This can lead to discrepancies by sizable factors. Progress achieved in a program aiming at absolute calibration, conducted over the past fifteen years, is briefly reviewed. Here we overcome its last major obstacle, a theoretical overestimation of the peak stiffness, within the most employed range for applications, and we perform experimental validation. The discrepancy is traced to the effect of primary aberrations of the optical system, which are now included in the theory. All required experimental parameters are readily accessible. Astigmatism, the dominant effect, is measured by analyzing reflected images of the focused laser spo...
Maximum entropy production and the fluctuation theorem
Dewar, R C [Unite EPHYSE, INRA Centre de Bordeaux-Aquitaine, BP 81, 33883 Villenave d' Ornon Cedex (France)
2005-05-27
Recently the author used an information theoretical formulation of non-equilibrium statistical mechanics (MaxEnt) to derive the fluctuation theorem (FT) concerning the probability of second law violating phase-space paths. A less rigorous argument leading to the variational principle of maximum entropy production (MEP) was also given. Here a more rigorous and general mathematical derivation of MEP from MaxEnt is presented, and the relationship between MEP and the FT is thereby clarified. Specifically, it is shown that the FT allows a general orthogonality property of maximum information entropy to be extended to entropy production itself, from which MEP then follows. The new derivation highlights MEP and the FT as generic properties of MaxEnt probability distributions involving anti-symmetric constraints, independently of any physical interpretation. Physically, MEP applies to the entropy production of those macroscopic fluxes that are free to vary under the imposed constraints, and corresponds to selection of the most probable macroscopic flux configuration. In special cases MaxEnt also leads to various upper bound transport principles. The relationship between MaxEnt and previous theories of irreversible processes due to Onsager, Prigogine and Ziegler is also clarified in the light of these results. (letter to the editor)
Absolute multilateration between spheres
Muelaner, Jody; Wadsworth, William; Azini, Maria; Mullineux, Glen; Hughes, Ben; Reichold, Armin
2017-04-01
Environmental effects typically limit the accuracy of large scale coordinate measurements in applications such as aircraft production and particle accelerator alignment. This paper presents an initial design for a novel measurement technique with analysis and simulation showing that that it could overcome the environmental limitations to provide a step change in large scale coordinate measurement accuracy. Referred to as absolute multilateration between spheres (AMS), it involves using absolute distance interferometry to directly measure the distances between pairs of plain steel spheres. A large portion of each sphere remains accessible as a reference datum, while the laser path can be shielded from environmental disturbances. As a single scale bar this can provide accurate scale information to be used for instrument verification or network measurement scaling. Since spheres can be simultaneously measured from multiple directions, it also allows highly accurate multilateration-based coordinate measurements to act as a large scale datum structure for localized measurements, or to be integrated within assembly tooling, coordinate measurement machines or robotic machinery. Analysis and simulation show that AMS can be self-aligned to achieve a theoretical combined standard uncertainty for the independent uncertainties of an individual 1 m scale bar of approximately 0.49 µm. It is also shown that combined with a 1 µm m‑1 standard uncertainty in the central reference system this could result in coordinate standard uncertainty magnitudes of 42 µm over a slender 1 m by 20 m network. This would be a sufficient step change in accuracy to enable next generation aerospace structures with natural laminar flow and part-to-part interchangeability.
王传会; 方志耕; 公维凤
2013-01-01
采用极大熵方法配置参数,构建了考虑体外循环的GERT网络模型,研究投资决策参量的相关参数的函数关系、运算法则及确定方法,提出了考虑体外循环的GERT网络模型求解算法.将该GERT网络模型应用于房地产市场领域,研究房地产市场中各参与主体之间的投资决策流动系统.结果显示,利用该GERT网络模型能充分反映房地产市场中各部门之间、房地产市场部门与体外环境部门之间的交互影响关系,可得到科学合理的量化结论.%This paper constructs a GERT network model with extracorporeal feedback loop through using the method of maximum entropy to make the parametric configuration, and analyzes the function relation and the operating regulation of parameters about investment decision. Then it provides an analytic algorithm of this GERT network model. And it applies this GERT network model to study the investment decision flowing system of participants in real estate market. The result shows the mutual influence relationship among sections in real estate market,and the mutual influence relationship between sections in real estate market and sections in extracorporeal feedback loop could be reflected by this GERT network model.
Comparisons of Black Hole Entropy
Kupferman, Judy
2016-01-01
In this thesis I examine several different concepts of black hole entropy in order to understand whether they describe the same quantity. I look at statistical and entanglement entropies, Wald entropy and Carlip's entropy from conformal field theory, and compare their behavior in a few specific aspects: divergence at the BH horizon, dependence on space time curvature and behavior under a geometric variation. I find that statistical and entanglement entropy may be similar but they seem to differ from the entropy of Wald and Carlip. Chapters 2 and 3 overlap with 1010.4157 and 1310.3938. Chapter 4 does not appear elsewhere.
Entropy, color, and color rendering.
Price, Luke L A
2012-12-01
The Shannon entropy [Bell Syst. Tech J.27, 379 (1948)] of spectral distributions is applied to the problem of color rendering. With this novel approach, calculations for visual white entropy, spectral entropy, and color rendering are proposed, indices that are unreliant on the subjectivity inherent in reference spectra and color samples. The indices are tested against real lamp spectra, showing a simple and robust system for color rendering assessment. The discussion considers potential roles for white entropy in several areas of color theory and psychophysics and nonextensive entropy generalizations of the entropy indices in mathematical color spaces.
Speeding up Derivative Configuration from Product Platforms
Ruben Heradio
2014-06-01
Full Text Available To compete in the global marketplace, manufacturers try to differentiate their products by focusing on individual customer needs. Fulfilling this goal requires that companies shift from mass production to mass customization. Under this approach, a generic architecture, named product platform, is designed to support the derivation of customized products through a configuration process that determines which components the product comprises. When a customer configures a derivative, typically not every combination of available components is valid. To guarantee that all dependencies and incompatibilities among the derivative constituent components are satisfied, automated configurators are used. Flexible product platforms provide a big number of interrelated components, and so, the configuration of all, but trivial, derivatives involves considerable effort to select which components the derivative should include. Our approach alleviates that effort by speeding up the derivative configuration using a heuristic based on the information theory concept of entropy.
Cardinal, Jean; Joret, Gwenaël
2008-01-01
We study graph orientations that minimize the entropy of the in-degree sequence. The problem of finding such an orientation is an interesting special case of the minimum entropy set cover problem previously studied by Halperin and Karp [Theoret. Comput. Sci., 2005] and by the current authors [Algorithmica, to appear]. We prove that the minimum entropy orientation problem is NP-hard even if the graph is planar, and that there exists a simple linear-time algorithm that returns an approximate solution with an additive error guarantee of 1 bit. This improves on the only previously known algorithm which has an additive error guarantee of log_2 e bits (approx. 1.4427 bits).
Holographic entropy production
Tian, Yu; Wu, Xiao-Ning; Zhang, Hongbao
2014-10-01
The suspicion that gravity is holographic has been supported mainly by a variety of specific examples from string theory. In this paper, we propose that such a holography can actually be observed in the context of Einstein's gravity and at least a class of generalized gravitational theories, based on a definite holographic principle where neither is the bulk space-time required to be asymptotically AdS nor the boundary to be located at conformal infinity, echoing Wilson's formulation of quantum field theory. After showing the general equilibrium thermodynamics from the corresponding holographic dictionary, in particular, we provide a rather general proof of the equality between the entropy production on the boundary and the increase of black hole entropy in the bulk, which can be regarded as strong support to this holographic principle. The entropy production in the familiar holographic superconductors/superfluids is investigated as an important example, where the role played by the holographic renormalization is explained.
Holographic Entropy Production
Tian, Yu; Zhang, Hong-Bao
2014-01-01
The suspicion that gravity is holographic has been supported mainly by a variety of specific examples from string theory. In this paper, we propose that such a holography can actually be observed in the context of Einstein's gravity and at least a class of generalized gravitational theories, based on a definite holographic principle where neither is the bulk space-time required to be asymptotically AdS nor the boundary to be located at conformal infinity, echoing Wilson's formulation of quantum field theory. After showing the general equilibrium thermodynamics from the corresponding holographic dictionary, in particular, we provide a rather general proof of the equality between the entropy production on the boundary and the increase of black hole entropy in the bulk, which can be regarded as strong support to this holographic principle. The entropy production in the familiar holographic superconductors/superfluids is investigated as an important example, where the role played by the holographic renormalizatio...
Entropy Message Passing Algorithm
Ilic, Velimir M; Branimir, Todorovic T
2009-01-01
Message passing over factor graph can be considered as generalization of many well known algorithms for efficient marginalization of multivariate function. A specific instance of the algorithm is obtained by choosing an appropriate commutative semiring for the range of the function to be marginalized. Some examples are Viterbi algorithm, obtained on max-product semiring and forward-backward algorithm obtained on sum-product semiring. In this paper, Entropy Message Passing algorithm (EMP) is developed. It operates over entropy semiring, previously introduced in automata theory. It is shown how EMP extends the use of message passing over factor graphs to probabilistic model algorithms such as Expectation Maximization algorithm, gradient methods and computation of model entropy, unifying the work of different authors.
Kay, Bernard S
2015-01-01
We give an account of the matter-gravity entanglement hypothesis which, unlike the standard approach to entropy based on coarse-graining, offers a definition for the entropy of a closed system as a real and objective quantity. We explain how this new approach offers an explanation for the Second Law of Thermodynamics in general and a non-paradoxical understanding of information loss during black hole formation and evaporation in particular. We also very briefly review some recent related work on the nature of equilibrium states involving quantum black holes and point out how it promises to resolve some puzzling issues in the current version of the string theory approach to black hole entropy.
Hongwei Yao
2016-05-01
Full Text Available Guided by CALPHAD (Calculation of Phase Diagrams modeling, the refractory medium-entropy alloy MoNbTaV was synthesized by vacuum arc melting under a high-purity argon atmosphere. A body-centered cubic solid solution phase was experimentally confirmed in the as-cast ingot using X-ray diffraction and scanning electron microscopy. The measured lattice parameter of the alloy (3.208 Å obeys the rule of mixtures (ROM, but the Vickers microhardness (4.95 GPa and the yield strength (1.5 GPa are about 4.5 and 4.6 times those estimated from the ROM, respectively. Using a simple model on solid solution strengthening predicts a yield strength of approximately 1.5 GPa. Thermodynamic analysis shows that the total entropy of the alloy is more than three times the configurational entropy at room temperature, and the entropy of mixing exhibits a small negative departure from ideal mixing.
Sharp continuity bounds for entropy and conditional entropy
Chen, ZhiHua; Ma, ZhiHao; Nikoufar, Ismail; Fei, Shao-Ming
2017-02-01
The Renyi entropy plays an essential role in quantum information theory. We study the continuity estimation of the Renyi entropy. An inequality relating the Renyi entropy difference of two quantum states to their trace norm distance is derived. This inequality is shown to be tight in the sense that equality can be attained for every prescribed value of the trace norm distance. It includes the sharp Fannes inequality for von Neumann entropy as a special case.
The entropy balance for boiling flow
Collado, Francisco-Javier E-mail: fjk@posta.unizar.es
2001-10-01
Subcooled forced convection boiling of water is recognized as one of the best means of accommodating the very high heat fluxes that plasma facing components of fusion reactors have to withstand. The boiling curve, giving the wall temperature in function of the applied flux and flow conditions, is essential for the design of such cooling configurations. In this paper, a new entropy balance for subcooled boiling flow, which allows the wall temperature to be obtained, is presented and successfully compared with experimental data from the Joint US-EURATOM R and D Program. The derivation of this entropy balance is based on a new strict application of the Reynolds theorem to multiphase flows recently proposed by the author.
The Elusive Nature of Entropy and Its Physical Meaning
Milivoje M. Kostic
2014-02-01
Full Text Available Entropy is the most used and often abused concept in science, but also in philosophy and society. Further confusions are produced by some attempts to generalize entropy with similar but not the same concepts in other disciplines. The physical meaning of phenomenological, thermodynamic entropy is reasoned and elaborated by generalizing Clausius definition with inclusion of generated heat, since it is irrelevant if entropy is changed due to reversible heat transfer or irreversible heat generation. Irreversible, caloric heat transfer is introduced as complementing reversible heat transfer. It is also reasoned and thus proven why entropy cannot be destroyed but is always generated (and thus over-all increased locally and globally, at every space and time scales, without any exception. It is concluded that entropy is a thermal displacement (dynamic thermal-volume of thermal energy due to absolute temperature as a thermal potential (dQ = TdS, and thus associated with thermal heat and absolute temperature, i.e., distribution of thermal energy within thermal micro-particles in space. Entropy is an integral measure of (random thermal energy redistribution (due to heat transfer and/or irreversible heat generation within a material system structure in space, per absolute temperature level: dS = dQSys/T = mCSysdT/T, thus logarithmic integral function, with J/K unit. It may be also expressed as a measure of “thermal disorder”, being related to logarithm of number of all thermal, dynamic microstates W (their position and momenta, S = kBlnW, or to the sum of their logarithmic probabilities S = −kB∑pilnpi, that correspond to, or are consistent with the given thermodynamic macro-state. The number of thermal microstates W, is correlated with macro-properties temperature T and volume V for ideal gases. A system form and/or functional order or disorder are not (thermal energy order/disorder and the former is not related to Thermodynamic entropy. Expanding
Åqvist, Johan; Kazemi, Masoud; Isaksen, Geir Villy; Brandsdal, Bjørn Olav
2017-02-21
The role played by entropy for the enormous rate enhancement achieved by enzymes has been debated for many decades. There are, for example, several confirmed cases where the activation free energy is reduced by around 10 kcal/mol due to entropic effects, corresponding to a rate enhancement of ∼10(7) compared to the uncatalyzed reaction. However, despite substantial efforts from both the experimental and theoretical side, no real consensus has been reached regarding the origin of such large entropic contributions to enzyme catalysis. Another remarkable instance of entropic effects is found in enzymes that are adapted by evolution to work at low temperatures, near the freezing point of water. These cold-adapted enzymes invariably show a more negative entropy and a lower enthalpy of activation than their mesophilic orthologs, which counteracts the exponential damping of reaction rates at lower temperature. The structural origin of this universal phenomenon has, however, remained elusive. The basic problem with connecting macroscopic thermodynamic quantities, such as activation entropy and enthalpy derived from Arrhenius plots, to the 3D protein structure is that the underlying detailed (microscopic) energetics is essentially inaccessible to experiment. Moreover, attempts to calculate entropy contributions by computer simulations have mostly focused only on substrate entropies, which do not provide the full picture. We have recently devised a new approach for accessing thermodynamic activation parameters of both enzyme and solution reactions from computer simulations, which turns out to be very successful. This method is analogous to the experimental Arrhenius plots and directly evaluates the temperature dependence of calculated reaction free energy profiles. Hence, by extensive molecular dynamics simulations and calculations of up to thousands of independent free energy profiles, we are able to extract activation parameters with sufficient precision for making
Dimensional Equations of Entropy
Sparavigna, Amelia Carolina
2015-01-01
Entropy is a quantity which is of great importance in physics and chemistry. The concept comes out of thermodynamics, proposed by Rudolf Clausius in his analysis of Carnot cycle and linked by Ludwig Boltzmann to the number of specific ways in which a physical system may be arranged. Any physics classroom, in its task of learning physics, has therefore to face this crucial concept. As we will show in this paper, the lectures can be enriched by discussing dimensional equations linked to the entropy of some physical systems.
F. TopsÃƒÂ¸e
2001-09-01
Full Text Available Abstract: In its modern formulation, the Maximum Entropy Principle was promoted by E.T. Jaynes, starting in the mid-fifties. The principle dictates that one should look for a distribution, consistent with available information, which maximizes the entropy. However, this principle focuses only on distributions and it appears advantageous to bring information theoretical thinking more prominently into play by also focusing on the "observer" and on coding. This view was brought forward by the second named author in the late seventies and is the view we will follow-up on here. It leads to the consideration of a certain game, the Code Length Game and, via standard game theoretical thinking, to a principle of Game Theoretical Equilibrium. This principle is more basic than the Maximum Entropy Principle in the sense that the search for one type of optimal strategies in the Code Length Game translates directly into the search for distributions with maximum entropy. In the present paper we offer a self-contained and comprehensive treatment of fundamentals of both principles mentioned, based on a study of the Code Length Game. Though new concepts and results are presented, the reading should be instructional and accessible to a rather wide audience, at least if certain mathematical details are left aside at a rst reading. The most frequently studied instance of entropy maximization pertains to the Mean Energy Model which involves a moment constraint related to a given function, here taken to represent "energy". This type of application is very well known from the literature with hundreds of applications pertaining to several different elds and will also here serve as important illustration of the theory. But our approach reaches further, especially regarding the study of continuity properties of the entropy function, and this leads to new results which allow a discussion of models with so-called entropy loss. These results have tempted us to speculate over
Entropy, materials, and posterity
Cloud, P.
1977-01-01
Materials and energy are the interdependent feedstocks of economic systems, and thermodynamics is their moderator. It costs energy to transform the dispersed minerals of Earth's crust into ordered materials and structures. And it costs materials to collect and focus the energy to perform work - be it from solar, fossil fuel, nuclear, or other sources. The greater the dispersal of minerals sought, the more energy is required to collect them into ordered states. But available energy can be used once only. And the ordered materials of industrial economies become disordered with time. They may be partially reordered and recycled, but only at further costs in energy. Available energy everywhere degrades to bound states and order to disorder - for though entropy may be juggled it always increases. Yet industry is utterly dependent on low entropy states of matter and energy, while decreasing grades of ore require ever higher inputs of energy to convert them to metals, with ever increasing growth both of entropy and environmental hazard. Except as we may prize a thing for its intrinsic qualities - beauty, leisure, love, or gold - low-entropy is the only thing of real value. It is worth whatever the market will bear, and it becomes more valuable as entropy increases. It would be foolish of suppliers to sell it more cheaply or in larger amounts than their own enjoyment of life requires, whatever form it may take. For this reason, and because of physical constraints on the availability of all low-entropy states, the recent energy crises is only the first of a sequence of crises to be expected in energy and materials as long as current trends continue. The apportioning of low-entropy states in a modern industrial society is achieved more or less according to the theory of competitive markets. But the rational powers of this theory suffer as the world grows increasingly polarized into rich, over-industrialized nations with diminishing resource bases and poor, supplier nations
Yuri, Shtarkov; Justesen, Jørn
1997-01-01
The concept of entropy for an image on a discrete two dimensional grid is introduced. This concept is used as an information theoretic bound on the coding rate for the image. It is proved that this quantity exists as a limit for arbitrary sets satisfying certain conditions.......The concept of entropy for an image on a discrete two dimensional grid is introduced. This concept is used as an information theoretic bound on the coding rate for the image. It is proved that this quantity exists as a limit for arbitrary sets satisfying certain conditions....
An Entropy-Weighted Sum over Non-Perturbative Vacua
Gregori, Andrea
2007-01-01
We discuss how, in a Universe restricted to the causal region connected to the observer, General Relativity implies the quantum nature of physical phenomena and directly leads to a string theory scenario, whose dynamics is ruled by a functional that weights all configurations according to their entropy. The most favoured configurations are those of minimal entropy. Along this class of vacua a four-dimensional space-time is automatically selected; when, at large volume, a description of space-time in terms of classical geometry can be recovered, the entropy-weighted sum reduces to the ordinary Feynman's path integral. What arises is a highly predictive scenario, phenomenologically compatible with the experimental observations and measurements, in which everything is determined in terms of the fundamental constants and the age of the Universe, with no room for freely-adjustable parameters. We discuss how this leads to the known spectrum of particles and interactions. Besides the computation of masses and coupli...
On Joint and Conditional Entropies
D. V. Gokhale
1999-05-01
Full Text Available Abstract: It is shown that if the conditional densities of a bivariate random variable have maximum entropies, subject to certain constraints, then the bivariate density also maximizes entropy, subject to appropriate constraints. Some examples are discussed.
Neuronal spike train entropy estimation by history clustering.
Watters, Nicholas; Reeke, George N
2014-09-01
Neurons send signals to each other by means of sequences of action potentials (spikes). Ignoring variations in spike amplitude and shape that are probably not meaningful to a receiving cell, the information content, or entropy of the signal depends on only the timing of action potentials, and because there is no external clock, only the interspike intervals, and not the absolute spike times, are significant. Estimating spike train entropy is a difficult task, particularly with small data sets, and many methods of entropy estimation have been proposed. Here we present two related model-based methods for estimating the entropy of neural signals and compare them to existing methods. One of the methods is fast and reasonably accurate, and it converges well with short spike time records; the other is impractically time-consuming but apparently very accurate, relying on generating artificial data that are a statistical match to the experimental data. Using the slow, accurate method to generate a best-estimate entropy value, we find that the faster estimator converges to this value more closely and with smaller data sets than many existing entropy estimators.
Connecting diffusion and entropy of bulk water at the single particle level
DEBASIS SAHA; ARNAB MUKHERJEE
2017-07-01
The relation between the dynamic (e.g., diffusion) and thermodynamic (e.g., entropy) properties of water and water-like liquids has been an active area of research for a long time. Although several studies have investigated the diffusivity and entropy for different systems, these studies have probed either the configurational entropy or the excess entropy of the overall system. In this study, we focus on the entropy of water at a single molecule level at different temperatures. We have used a method developed in our group to calculate thetranslational and rotational entropy of individual water molecules at various temperatures. We find that the single water translational and rotational entropy exhibit a transition at around 240 K. The translational entropyof individual water molecules shows a consistent variation with change in temperature whereas the variation in the case of rotational entropy is much smaller at different temperatures. We have also calculated diffusioncoefficients of water molecules at these temperatures. We find that diffusion also shows the well-known fragile to strong crossover transition at around the same temperature where transition in entropy values has been seen. We have calculated both kinetic and thermodynamic fragilities and crossover points using diffusion and single water translational entropy values. Finally, we correlate the diffusion and translational entropy of individual water molecules using an analog of the Adam-Gibbs relation.
Third law of thermodynamics as a key test of generalized entropies.
Bento, E P; Viswanathan, G M; da Luz, M G E; Silva, R
2015-02-01
The laws of thermodynamics constrain the formulation of statistical mechanics at the microscopic level. The third law of thermodynamics states that the entropy must vanish at absolute zero temperature for systems with nondegenerate ground states in equilibrium. Conversely, the entropy can vanish only at absolute zero temperature. Here we ask whether or not generalized entropies satisfy this fundamental property. We propose a direct analytical procedure to test if a generalized entropy satisfies the third law, assuming only very general assumptions for the entropy S and energy U of an arbitrary N-level classical system. Mathematically, the method relies on exact calculation of β=dS/dU in terms of the microstate probabilities p(i). To illustrate this approach, we present exact results for the two best known generalizations of statistical mechanics. Specifically, we study the Kaniadakis entropy S(κ), which is additive, and the Tsallis entropy S(q), which is nonadditive. We show that the Kaniadakis entropy correctly satisfies the third law only for -1law for q<1. Finally, we give a concrete example of the power of our proposed method by applying it to a paradigmatic system: the one-dimensional ferromagnetic Ising model with nearest-neighbor interactions.
Nernst Theorem and Statistical Entropy of 5-Dimensional Rotating Black Hole
ZHAO Ren; WU Yue-Qin; ZHANG Li-Chun
2003-01-01
In this paper, by using quantum statistical method, we obtain the partition function of Bose field and Fermi field on the background of the 5-dimensional rotating black hole. Then via the improved brick-wall method and membrane model, we calculate the entropy of Bose field and Fermi field of the black hole. And it is obtained that the entropy of the black hole is not only related to the area of the outer horizon but also is the function of inner horizon's area. In our results, there are not the left out term and the divergent logarithmic term in the original brick-wall method.The doubt that why the entropy of the scalar or Dirac field outside the event horizon is the entropy of the black hole in the original brick-wall method does not exist. The influence of spinning degeneracy of particles on entropy of the black hole is also given. It is shown that the entropy determined by the areas of the inner and outer horizons will approach zero,when the radiation temperature of the black hole approaches absolute zero. It satisfies Nernst theorem. The entropy can be taken as the Planck absolute entropy. We provide a way to study higher dimensional black hole.
Estimating Absolute Site Effects
Malagnini, L; Mayeda, K M; Akinci, A; Bragato, P L
2004-07-15
The authors use previously determined direct-wave attenuation functions as well as stable, coda-derived source excitation spectra to isolate the absolute S-wave site effect for the horizontal and vertical components of weak ground motion. They used selected stations in the seismic network of the eastern Alps, and find the following: (1) all ''hard rock'' sites exhibited deamplification phenomena due to absorption at frequencies ranging between 0.5 and 12 Hz (the available bandwidth), on both the horizontal and vertical components; (2) ''hard rock'' site transfer functions showed large variability at high-frequency; (3) vertical-motion site transfer functions show strong frequency-dependence, and (4) H/V spectral ratios do not reproduce the characteristics of the true horizontal site transfer functions; (5) traditional, relative site terms obtained by using reference ''rock sites'' can be misleading in inferring the behaviors of true site transfer functions, since most rock sites have non-flat responses due to shallow heterogeneities resulting from varying degrees of weathering. They also use their stable source spectra to estimate total radiated seismic energy and compare against previous results. they find that the earthquakes in this region exhibit non-constant dynamic stress drop scaling which gives further support for a fundamental difference in rupture dynamics between small and large earthquakes. To correct the vertical and horizontal S-wave spectra for attenuation, they used detailed regional attenuation functions derived by Malagnini et al. (2002) who determined frequency-dependent geometrical spreading and Q for the region. These corrections account for the gross path effects (i.e., all distance-dependent effects), although the source and site effects are still present in the distance-corrected spectra. The main goal of this study is to isolate the absolute site effect (as a function of frequency
Entropy is a Mathematical Formula
Garai, Jozsef
2003-01-01
The microscopic explanation of entropy has been challenged from both experimental and theoretical point of view. The expression of entropy is derived from the first law of thermodynamics indicating that entropy or the second law of thermodynamics is not an independent law.
Relations Among Some Fuzzy Entropy Formulae
卿铭
2004-01-01
Fuzzy entropy has been widely used to analyze and design fuzzy systems, and many fuzzy entropy formulae have been proposed. For further in-deepth analysis of fuzzy entropy, the axioms and some important formulae of fuzzy entropy are introduced. Some equivalence results among these fuzzy entropy formulae are proved, and it is shown that fuzzy entropy is a special distance measurement.
Rescaling Temperature and Entropy
Olmsted, John, III
2010-01-01
Temperature and entropy traditionally are expressed in units of kelvin and joule/kelvin. These units obscure some important aspects of the natures of these thermodynamic quantities. Defining a rescaled temperature using the Boltzmann constant, T' = k[subscript B]T, expresses temperature in energy units, thereby emphasizing the close relationship…
Optimized Kernel Entropy Components.
Izquierdo-Verdiguier, Emma; Laparra, Valero; Jenssen, Robert; Gomez-Chova, Luis; Camps-Valls, Gustau
2016-02-25
This brief addresses two main issues of the standard kernel entropy component analysis (KECA) algorithm: the optimization of the kernel decomposition and the optimization of the Gaussian kernel parameter. KECA roughly reduces to a sorting of the importance of kernel eigenvectors by entropy instead of variance, as in the kernel principal components analysis. In this brief, we propose an extension of the KECA method, named optimized KECA (OKECA), that directly extracts the optimal features retaining most of the data entropy by means of compacting the information in very few features (often in just one or two). The proposed method produces features which have higher expressive power. In particular, it is based on the independent component analysis framework, and introduces an extra rotation to the eigen decomposition, which is optimized via gradient-ascent search. This maximum entropy preservation suggests that OKECA features are more efficient than KECA features for density estimation. In addition, a critical issue in both the methods is the selection of the kernel parameter, since it critically affects the resulting performance. Here, we analyze the most common kernel length-scale selection criteria. The results of both the methods are illustrated in different synthetic and real problems. Results show that OKECA returns projections with more expressive power than KECA, the most successful rule for estimating the kernel parameter is based on maximum likelihood, and OKECA is more robust to the selection of the length-scale parameter in kernel density estimation.
Rescaling Temperature and Entropy
Olmsted, John, III
2010-01-01
Temperature and entropy traditionally are expressed in units of kelvin and joule/kelvin. These units obscure some important aspects of the natures of these thermodynamic quantities. Defining a rescaled temperature using the Boltzmann constant, T' = k[subscript B]T, expresses temperature in energy units, thereby emphasizing the close relationship…
Zucker, M. H.
This paper is a critical analysis and reassessment of entropic functioning as it applies to the question of whether the ultimate fate of the universe will be determined in the future to be "open" (expanding forever to expire in a big chill), "closed" (collapsing to a big crunch), or "flat" (balanced forever between the two). The second law of thermodynamics declares that entropy can only increase and that this principle extends, inevitably, to the universe as a whole. This paper takes the position that this extension is an unwarranted projection based neither on experience nonfact - an extrapolation that ignores the powerful effect of a gravitational force acting within a closed system. Since it was originally presented by Clausius, the thermodynamic concept of entropy has been redefined in terms of "order" and "disorder" - order being equated with a low degree of entropy and disorder with a high degree. This revised terminology more subjective than precise, has generated considerable confusion in cosmology in several critical instances. For example - the chaotic fireball of the big bang, interpreted by Stephen Hawking as a state of disorder (high entropy), is infinitely hot and, thermally, represents zero entropy (order). Hawking, apparently focusing on the disorderly "chaotic" aspect, equated it with a high degree of entropy - overlooking the fact that the universe is a thermodynamic system and that the key factor in evaluating the big-bang phenomenon is the infinitely high temperature at the early universe, which can only be equated with zero entropy. This analysis resolves this confusion and reestablishes entropy as a cosmological function integrally linked to temperature. The paper goes on to show that, while all subsystems contained within the universe require external sources of energization to have their temperatures raised, this requirement does not apply to the universe as a whole. The universe is the only system that, by itself can raise its own
Entropy equilibrium equation and dynamic entropy production in environment liquid
无
2002-01-01
The entropy equilibrium equation is the basis of the nonequilibrium state thermodynamics. But the internal energy implies the kinetic energy of the fluid micelle relative to mass center in the classical entropy equilibrium equation at present. This internal energy is not the mean kinetic energy of molecular movement in thermodynamics. Here a modified entropy equilibrium equation is deduced, based on the concept that the internal energy is just the mean kinetic energy of the molecular movement. A dynamic entropy production is introduced into the entropy equilibrium equation to describe the dynamic process distinctly. This modified entropy equilibrium equation can describe not only the entropy variation of the irreversible processes but also the reversible processes in a thermodynamic system. It is more reasonable and suitable for wider applications.
Kevin H. Knuth
2013-02-01
Full Text Available The journal Entropy is initiating a “Best Paper” award to recognize outstanding papers in the area of entropy and information studies published in Entropy. We are pleased to announce the first “Entropy Best Paper Award” for 2013. Nominations were selected by the Editor-in-Chief and selected Editorial Board Members from all the papers published in 2009 and evaluated by the Entropy Best Paper Award Committee. Reviews and articles were evaluated separately. A first prize is awarded to the selected review paper, and a first and second prize is awarded to the top two selected research articles.
Maximizing Entropy over Markov Processes
Biondi, Fabrizio; Legay, Axel; Nielsen, Bo Friis
2013-01-01
computation reduces to finding a model of a specification with highest entropy. Entropy maximization for probabilistic process specifications has not been studied before, even though it is well known in Bayesian inference for discrete distributions. We give a characterization of global entropy of a process...... as a reward function, a polynomial algorithm to verify the existence of an system maximizing entropy among those respecting a specification, a procedure for the maximization of reward functions over Interval Markov Chains and its application to synthesize an implementation maximizing entropy. We show how...
Maximizing entropy over Markov processes
Biondi, Fabrizio; Legay, Axel; Nielsen, Bo Friis
2014-01-01
computation reduces to finding a model of a specification with highest entropy. Entropy maximization for probabilistic process specifications has not been studied before, even though it is well known in Bayesian inference for discrete distributions. We give a characterization of global entropy of a process...... as a reward function, a polynomial algorithm to verify the existence of a system maximizing entropy among those respecting a specification, a procedure for the maximization of reward functions over Interval Markov Chains and its application to synthesize an implementation maximizing entropy. We show how...
Notes on absolute Hodge classes
Charles, François
2011-01-01
We survey the theory of absolute Hodge classes. The notes include a full proof of Deligne's theorem on absolute Hodge classes on abelian varieties as well as a discussion of other topics, such as the field of definition of Hodge loci and the Kuga-Satake construction.
Entropies in Alloy Design for High-Entropy and Bulk Glassy Alloys
Akihiro Makino
2013-09-01
Full Text Available High-entropy (H-E alloys, bulk metallic glasses (BMGs and high-entropy BMGs (HE-BMGs were statistically analyzed with the help of a database of ternary amorphous alloys. Thermodynamic quantities corresponding to heat of mixing and atomic size differences were calculated as a function of composition of the multicomponent alloys. Actual calculations were performed for configurational entropy (Sconfig. in defining the H-E alloys and mismatch entropy (Ss normalized with Boltzmann constant (kB, together with mixing enthalpy (DHmix based on Miedema’s empirical model and Delta parameter (d as a corresponding parameter to Ss/kB. The comparison between DHmix–d and DHmix– diagrams for the ternary amorphous alloys revealed Ss/kB ~ (d /222. The zones S, S′ and B’s where H-E alloys with disordered solid solutions, ordered alloys and BMGs are plotted in the DHmix–d diagram are correlated with the areas in the DHmix – Ss /kB diagram. The results provide mutual understandings among H-E alloys, BMGs and HE-BMGs.
Thermal expansion anomaly regulated by entropy.
Liu, Zi-Kui; Wang, Yi; Shang, ShunLi
2014-11-13
Thermal expansion, defined as the temperature dependence of volume under constant pressure, is a common phenomenon in nature and originates from anharmonic lattice dynamics. However, it has been poorly understood how thermal expansion can show anomalies such as colossal positive, zero, or negative thermal expansion (CPTE, ZTE, or NTE), especially in quantitative terms. Here we show that changes in configurational entropy due to metastable micro(scopic)states can lead to quantitative prediction of these anomalies. We integrate the Maxwell relation, statistic mechanics, and first-principles calculations to demonstrate that when the entropy is increased by pressure, NTE occurs such as in Invar alloy (Fe3Pt, for example), silicon, ice, and water, and when the entropy is decreased dramatically by pressure, CPTE is expected such as in anti-Invar cerium, ice and water. Our findings provide a theoretic framework to understand and predict a broad range of anomalies in nature in addition to thermal expansion, which may include gigantic electrocaloric and electromechanical responses, anomalously reduced thermal conductivity, and spin distributions.
Holographic Entanglement Entropy
Rangamani, Mukund
2016-01-01
We review the developments in the past decade on holographic entanglement entropy, a subject that has garnered much attention owing to its potential to teach us about the emergence of spacetime in holography. We provide an introduction to the concept of entanglement entropy in quantum field theories, review the holographic proposals for computing the same, providing some justification for where these proposals arise from in the first two parts. The final part addresses recent developments linking entanglement and geometry. We provide an overview of the various arguments and technical developments that teach us how to use field theory entanglement to detect geometry. Our discussion is by design eclectic; we have chosen to focus on developments that appear to us most promising for further insights into the holographic map. This is a preliminary draft of a few chapters of a book which will appear sometime in the near future, to be published by Springer. The book in addition contains a discussion of application o...
Preimage entropy dimension of topological dynamical systems
Lei LIU; Zhou, Xiaomin; Zhou, Xiaoyao
2014-01-01
We propose a new definition of preimage entropy dimension for continuous maps on compact metric spaces, investigate fundamental properties of the preimage entropy dimension, and compare the preimage entropy dimension with the topological entropy dimension. The defined preimage entropy dimension holds various basic properties of topological entropy dimension, for example, the preimage entropy dimension of a subsystem is bounded by that of the original system and topologically conjugated system...
Bernard S. Kay
2015-12-01
Full Text Available We give a review, in the style of an essay, of the author’s 1998 matter-gravity entanglement hypothesis which, unlike the standard approach to entropy based on coarse-graining, offers a definition for the entropy of a closed system as a real and objective quantity. We explain how this approach offers an explanation for the Second Law of Thermodynamics in general and a non-paradoxical understanding of information loss during black hole formation and evaporation in particular. It also involves a radically different from usual description of black hole equilibrium states in which the total state of a black hole in a box together with its atmosphere is a pure state—entangled in just such a way that the reduced state of the black hole and of its atmosphere are each separately approximately thermal. We also briefly recall some recent work of the author which involves a reworking of the string-theory understanding of black hole entropy consistent with this alternative description of black hole equilibrium states and point out that this is free from some unsatisfactory features of the usual string theory understanding. We also recall the author’s recent arguments based on this alternative description which suggest that the Anti de Sitter space (AdS/conformal field theory (CFT correspondence is a bijection between the boundary CFT and just the matter degrees of freedom of the bulk theory.
Quantum and Ecosystem Entropies
A. D. Kirwan
2008-06-01
Full Text Available Ecosystems and quantum gases share a number of superficial similarities including enormous numbers of interacting elements and the fundamental role of energy in such interactions. A theory for the synthesis of data and prediction of new phenomena is well established in quantum statistical mechanics. The premise of this paper is that the reason a comparable unifying theory has not emerged in ecology is that a proper role for entropy has yet to be assigned. To this end, a phase space entropy model of ecosystems is developed. Specification of an ecosystem phase space cell size based on microbial mass, length, and time scales gives an ecosystem uncertainty parameter only about three orders of magnitude larger than PlanckÃ¢Â€Â™s constant. Ecosystem equilibria is specified by conservation of biomass and total metabolic energy, along with the principle of maximum entropy at equilibria. Both Bose - Einstein and Fermi - Dirac equilibrium conditions arise in ecosystems applications. The paper concludes with a discussion of some broader aspects of an ecosystem phase space.
Holographic entanglement entropy
Rangamani, Mukund
2017-01-01
This book provides a comprehensive overview of developments in the field of holographic entanglement entropy. Within the context of the AdS/CFT correspondence, it is shown how quantum entanglement is computed by the area of certain extremal surfaces. The general lessons one can learn from this connection are drawn out for quantum field theories, many-body physics, and quantum gravity. An overview of the necessary background material is provided together with a flavor of the exciting open questions that are currently being discussed. The book is divided into four main parts. In the first part, the concept of entanglement, and methods for computing it, in quantum field theories is reviewed. In the second part, an overview of the AdS/CFT correspondence is given and the holographic entanglement entropy prescription is explained. In the third part, the time-dependence of entanglement entropy in out-of-equilibrium systems, and applications to many body physics are explored using holographic methods. The last part f...
Quantum Dynamical Entropies and Gács Algorithmic Entropy
Fabio Benatti
2012-07-01
Full Text Available Several quantum dynamical entropies have been proposed that extend the classical Kolmogorov–Sinai (dynamical entropy. The same scenario appears in relation to the extension of algorithmic complexity theory to the quantum realm. A theorem of Brudno establishes that the complexity per unit time step along typical trajectories of a classical ergodic system equals the KS-entropy. In the following, we establish a similar relation between the Connes–Narnhofer–Thirring quantum dynamical entropy for the shift on quantum spin chains and the Gács algorithmic entropy. We further provide, for the same system, a weaker linkage between the latter algorithmic complexity and a different quantum dynamical entropy proposed by Alicki and Fannes.
Generalized entanglement entropy and holography
Bizet, Nana Cabo
2015-01-01
In this work, we first introduce a generalized von Neumann entropy that depends only on the density matrix. This is based on a previous proposal by one of us modifying the Shannon entropy by considering non-equilibrium systems on stationary states, and an entropy functional depending only on the probability. We propose a generalization of the replica trick and find that the resulting modified von Neumann entropy is precisely the previous mentioned entropy that was obtained by other assumptions. Then, we address the question whether alternative entanglement entropies can play a role in the gauge/gravity duality. Our focus are 2d CFT and their gravity duals. Our results show corrections to the von Neumann entropy $S_0$ that are larger than the usual $UV$ ones and also than the corrections to the length dependent $AdS_3$ entropy which result comparable to the $UV$ ones. The correction terms due to the new entropy would modify the Ryu-Takayanagi identification between the CFT and the gravitational $AdS_3$ entropi...
An exploration for the macroscopic physical meaning of entropy
无
2010-01-01
The macroscopic physical meaning of entropy is analyzed based on the exergy (availability) of a combined system (a closed system and its environment), which is the maximum amount of useful work obtainable from the system and the environment as the system is brought into equilibrium with the environment. The process the system experiences can be divided in two sequent sub-processes, the process at constant volume, which represents the heat interaction of the system with the environment, and the adiabatic process, which represents the work interaction of the system with the environment. It is shown that the macroscopic physical meaning of entropy is a measure of the unavailable energy of a closed system for doing useful work through heat interaction. This statement is more precise than those reported in prior literature. The unavailability function of a closed system can be defined as T0S and p0V in volume constant process and adiabatic process, respectively. Their changes, that is, AiTgS) and A (p0V) represent the unusable parts of the internal energy of a closed system for doing useful work in corresponding processes. Finally, the relation between Clausius entropy and Boltzmann entropy is discussed based on the comparison of their expressions for absolute entropy.
Graus, Sara; Tejedor, Rosa M; Uriel, Santiago; Serrano, José Luis; Alkorta, Ibon; Elguero, José
2010-06-16
The achiral 4-methoxy-4-(p-methoxyphenyl)-cyclohexanone ethylene ketal (1) resolves spontaneously. The crystal structure is solved in chiral spatial group P2(1). Because compound 1 is composed of only light atoms (C, H, O) it is not possible to determine its absolute structure configuration. An efficient procedure for the absolute structure configuration determination of flexible molecules containing only light atoms is proposed, based on the combination of X-ray diffraction, solid-state VCD, and DFT calculations.
Gyrokinetic Statistical Absolute Equilibrium and Turbulence
Jian-Zhou Zhu and Gregory W. Hammett
2011-01-10
A paradigm based on the absolute equilibrium of Galerkin-truncated inviscid systems to aid in understanding turbulence [T.-D. Lee, "On some statistical properties of hydrodynamical and magnetohydrodynamical fields," Q. Appl. Math. 10, 69 (1952)] is taken to study gyrokinetic plasma turbulence: A finite set of Fourier modes of the collisionless gyrokinetic equations are kept and the statistical equilibria are calculated; possible implications for plasma turbulence in various situations are discussed. For the case of two spatial and one velocity dimension, in the calculation with discretization also of velocity v with N grid points (where N + 1 quantities are conserved, corresponding to an energy invariant and N entropy-related invariants), the negative temperature states, corresponding to the condensation of the generalized energy into the lowest modes, are found. This indicates a generic feature of inverse energy cascade. Comparisons are made with some classical results, such as those of Charney-Hasegawa-Mima in the cold-ion limit. There is a universal shape for statistical equilibrium of gyrokinetics in three spatial and two velocity dimensions with just one conserved quantity. Possible physical relevance to turbulence, such as ITG zonal flows, and to a critical balance hypothesis are also discussed.
Ansari, Mohammad H
2016-01-01
A common approach to evaluate entropy in quantum systems is to solve a master-Bloch equation to determine density matrix and substitute it in entropy definition. However, this method has been recently understood to lack many energy correlators. The new correlators make entropy evaluation to be different from the substitution method described above. The reason for such complexity lies in the nonlinearity of entropy. In this paper we present a pedagogical approach to evaluate the new correlators and explain their contribution in the analysis. We show that the inherent nonlinearity in entropy makes the second law of thermodynamics to carry new terms associated to the new correlators. Our results show important new remarks on quantum black holes. Our formalism reveals that the notion of degeneracy of states at the event horizon makes an indispensable deviation from black hole entropy in the leading order.
Entropy: From Thermodynamics to Hydrology
Demetris Koutsoyiannis
2014-02-01
Full Text Available Some known results from statistical thermophysics as well as from hydrology are revisited from a different perspective trying: (a to unify the notion of entropy in thermodynamic and statistical/stochastic approaches of complex hydrological systems and (b to show the power of entropy and the principle of maximum entropy in inference, both deductive and inductive. The capability for deductive reasoning is illustrated by deriving the law of phase change transition of water (Clausius-Clapeyron from scratch by maximizing entropy in a formal probabilistic frame. However, such deductive reasoning cannot work in more complex hydrological systems with diverse elements, yet the entropy maximization framework can help in inductive inference, necessarily based on data. Several examples of this type are provided in an attempt to link statistical thermophysics with hydrology with a unifying view of entropy.
Generalized Entropy Concentration for Counts
Oikonomou, Kostas N
2016-01-01
We consider the phenomenon of entropy concentration under linear constraints in a discrete setting, using the "balls and bins" paradigm, but without the assumption that the number of balls allocated to the bins is known. Therefore instead of \\ frequency vectors and ordinary entropy, we have count vectors with unknown sum, and a certain generalized entropy. We show that if the constraints bound the allowable sums, this suffices for concentration to occur even in this setting. The concentration can be either in terms of deviation from the maximum generalized entropy value, or in terms of the norm of the difference from the maximum generalized entropy vector. Without any asymptotic considerations, we quantify the concentration in terms of various parameters, notably a tolerance on the constraints which ensures that they are always satisfied by an integral vector. Generalized entropy maximization is not only compatible with ordinary MaxEnt, but can also be considered an extension of it, as it allows us to address...
Müller-Lennert, Martin; Dupont-Dupuis, Fréderic; Szehr, Oleg
2013-01-01
in information theory and beyond. Various generalizations of Rényi entropies to the quantum setting have been proposed, most prominently Petz's quasi-entropies and Renner's conditional min-, max-, and collision entropy. However, these quantum extensions are incompatible and thus unsatisfactory. We propose a new...... quantum generalization of the family of Rényi entropies that contains the von Neumann entropy, min-entropy, collision entropy, and the max-entropy as special cases, thus encompassing most quantum entropies in use today. We show several natural properties for this definition, including data...
Zimak, Petr; Strazewski, Peter
2009-01-01
When the difference between changes in energy and entropy at a given temperature is correlated with the ratio between the same changes in energy and entropy at zero average free energy of an ensemble of similar but distinct molecule-sized objects, a highly significant linear dependence results from which a relationship between energy and entropy is derived and the degree of similarity between the distinctly different members within the group of objects can be quantified. This fundamental energy-entropy relationship is likely to be of general interest in physics, most notably in particle physics and cosmology. We predict a consistent and testable way of classifying mini black holes, to be generated in future Large Hadron Collider experiments, by their gravitational energy and area entropy. For any isolated universe we propose absolute temperature and absolute time to be equivalent, much in the same way as energy and entropy are for an isolated ensemble of similar objects. According to this principle, the cosmo...
Residual entropy and simulated annealing
Ettelaie, R.; Moore, M. A.
1985-01-01
Determining the residual entropy in the simulated annealing approach to optimization is shown to provide useful information on the true ground state energy. The one-dimensional Ising spin glass is studied to exemplify the procedure and in this case the residual entropy is related to the number of one-spin flip stable metastable states. The residual entropy decreases to zero only logarithmically slowly with the inverse cooling rate.
Entropy and its relationship to allometry
Shour, Robert
2008-01-01
The entropy of an organism's capacity to supply energy through its circulatory system is 4/3 the entropy of the organism's energy requirements. Organisms appear to maximize entropy. The concept of entropy enables shorter derivations of some allometric equations, further evidence of the concept's utility. Entropy helps explain emergence in social, lexical, and biological networks.
Entanglement Entropy of Black Holes
Solodukhin, Sergey N.
2011-10-01
The entanglement entropy is a fundamental quantity, which characterizes the correlations between sub-systems in a larger quantum-mechanical system. For two sub-systems separated by a surface the entanglement entropy is proportional to the area of the surface and depends on the UV cutoff, which regulates the short-distance correlations. The geometrical nature of entanglement-entropy calculation is particularly intriguing when applied to black holes when the entangling surface is the black-hole horizon. I review a variety of aspects of this calculation: the useful mathematical tools such as the geometry of spaces with conical singularities and the heat kernel method, the UV divergences in the entropy and their renormalization, the logarithmic terms in the entanglement entropy in four and six dimensions and their relation to the conformal anomalies. The focus in the review is on the systematic use of the conical singularity method. The relations to other known approaches such as 't Hooft's brick-wall model and the Euclidean path integral in the optical metric are discussed in detail. The puzzling behavior of the entanglement entropy due to fields, which non-minimally couple to gravity, is emphasized. The holographic description of the entanglement entropy of the blackhole horizon is illustrated on the two- and four-dimensional examples. Finally, I examine the possibility to interpret the Bekenstein-Hawking entropy entirely as the entanglement entropy.
Entanglement Entropy of Black Holes
Sergey N. Solodukhin
2011-10-01
Full Text Available The entanglement entropy is a fundamental quantity, which characterizes the correlations between sub-systems in a larger quantum-mechanical system. For two sub-systems separated by a surface the entanglement entropy is proportional to the area of the surface and depends on the UV cutoff, which regulates the short-distance correlations. The geometrical nature of entanglement-entropy calculation is particularly intriguing when applied to black holes when the entangling surface is the black-hole horizon. I review a variety of aspects of this calculation: the useful mathematical tools such as the geometry of spaces with conical singularities and the heat kernel method, the UV divergences in the entropy and their renormalization, the logarithmic terms in the entanglement entropy in four and six dimensions and their relation to the conformal anomalies. The focus in the review is on the systematic use of the conical singularity method. The relations to other known approaches such as ’t Hooft’s brick-wall model and the Euclidean path integral in the optical metric are discussed in detail. The puzzling behavior of the entanglement entropy due to fields, which non-minimally couple to gravity, is emphasized. The holographic description of the entanglement entropy of the black-hole horizon is illustrated on the two- and four-dimensional examples. Finally, I examine the possibility to interpret the Bekenstein-Hawking entropy entirely as the entanglement entropy.
Entropy Generation in Regenerative Systems
Kittel, Peter
1995-01-01
Heat exchange to the oscillating flows in regenerative coolers generates entropy. These flows are characterized by oscillating mass flows and oscillating temperatures. Heat is transferred between the flow and heat exchangers and regenerators. In the former case, there is a steady temperature difference between the flow and the heat exchangers. In the latter case, there is no mean temperature difference. In this paper a mathematical model of the entropy generated is developed for both cases. Estimates of the entropy generated by this process are given for oscillating flows in heat exchangers and in regenerators. The practical significance of this entropy is also discussed.
The different paths to entropy
Benguigui, L
2012-01-01
In order to undestand how the complex concept of entropy emerged,we propose a trip towards the past reviewing the works of Clausius, Boltzmann, Gibbs and Planck. In particular, since the Gibbs's work is not very well known, we present a detailed analysis, recalling the three definitions of the entropy that Gibbs gives. May be one of the most important aspect of the entropy is to see it as a thermodynamic potential like the other thermodynamic potentials as proposed by Callen. We close with some remarks on entropy and irreversibility.
Howard, Eric M
2016-01-01
We analyze spacetimes with horizons and study the thermodynamic aspects of causal horizons, suggesting that the resemblance between gravitational and thermodynamic systems has a deeper quantum mechanical origin. We find that the observer dependence of such horizons is a direct consequence of associating a temperature and entropy to a spacetime. The geometrical picture of a horizon acting as a one-way membrane for information flow can be accepted as a natural interpretation of assigning a quantum field theory to a spacetime with boundary, ultimately leading to a close connection with thermodynamics.
Minimum Error Entropy Classification
Marques de Sá, Joaquim P; Santos, Jorge M F; Alexandre, Luís A
2013-01-01
This book explains the minimum error entropy (MEE) concept applied to data classification machines. Theoretical results on the inner workings of the MEE concept, in its application to solving a variety of classification problems, are presented in the wider realm of risk functionals. Researchers and practitioners also find in the book a detailed presentation of practical data classifiers using MEE. These include multi‐layer perceptrons, recurrent neural networks, complexvalued neural networks, modular neural networks, and decision trees. A clustering algorithm using a MEE‐like concept is also presented. Examples, tests, evaluation experiments and comparison with similar machines using classic approaches, complement the descriptions.
Hansen, Britt Rosendahl; Kuhn, Luise Theil; Bahl, Christian Robert Haffenden
2010-01-01
in the temperature of a magnetic material when a magnetic eld is applied or removed. For many years, experimentalists have made use of dilute paramagnetic materials to achieve milliKelvin temperatures by use of the magnetocaloric eect. Also, research is done on materials, which might be used for hydrogen, helium...... the eect: the isothermal magnetic entropy change and the adiabatic temperature change. Some of the manifestations and utilizations of the MCE will be touched upon in a general way and nally I will talk about the results I have obtained on a sample of Gadolinium Iron Garnet (GdIG, Gd3Fe5O12), which...
Nonextensive entropy interdisciplinary applications
Tsallis, Constantino
2004-01-01
A great variety of complex phenomena in many scientific fields exhibit power-law behavior, reflecting a hierarchical or fractal structure. Many of these phenomena seem to be susceptible to description using approaches drawn from thermodynamics or statistical mechanics, particularly approaches involving the maximization of entropy and of Boltzmann-Gibbs statistical mechanics and standard laws in a natural way. The book addresses the interdisciplinary applications of these ideas, and also on various phenomena that could possibly be quantitatively describable in terms of these ideas.
Definition of Turbulent Boundary-Layer with Entropy Concept
Zhao Rui
2016-01-01
Full Text Available The relationship between the entropy increment and the viscosity dissipation in turbulent boundary-layer is systematically investigated. Through theoretical analysis and direct numerical simulation (DNS, an entropy function fs is proposed to distinguish the turbulent boundary-layer from the external flow. This approach is proved to be reliable after comparing its performance in the following complex flows, namely, low-speed airfoil flows with different wall temperature, supersonic cavity-ramp flow dominated by the combination of free-shear layer, larger recirculation and shocks, and the hypersonic flow past an aeroplane configuration. Moreover, fs is deduced from the point of energy, independent of any particular turbulent quantities. That is, this entropy concept could be utilized by other engineering applications related with turbulent boundary-layer, such as turbulence modelling transition prediction and engineering thermal protection.
Absolute stereochemistry of altersolanol A and alterporriols.
Kanamaru, Saki; Honma, Miho; Murakami, Takanori; Tsushima, Taro; Kudo, Shinji; Tanaka, Kazuaki; Nihei, Ken-Ichi; Nehira, Tatsuo; Hashimoto, Masaru
2012-02-01
The absolute stereochemistry of altersolanol A (1) was established by observing a positive exciton couplet in the circular dichroism (CD) spectrum of the C3,C4-O-bis(2-naphthoyl) derivative 10 and by chemical correlations with known compound 8. Before the discussion, the relative stereochemistry of 1 was confirmed by X-ray crystallographic analysis. The shielding effect at C7'-OMe group by C1-O-benzoylation established the relative stereochemical relationship between the C8-C8' axial bonding and the C1-C4/C1'-C4' polyol moieties of alterporriols E (3), an atropisomer of the C8-C8' dimer of 1. As 3 could be obtained by dimerization of 1 in vitro, the absolute configuration of its central chirality elements (C1-C4) must be identical to those of 1. Spectral comparison between the experimental and theoretical CD spectra supported the above conclusion. Axial stereochemistry of novel C4-O-deoxy dimeric derivatives, alterporriols F (4) and G (5), were also revealed by comparison of their CD spectra to those of 2 and 3.
Information Entropy Measures for Stand Structural Diversity:Joint Entropy
Lei Xiangdong; Lu Yuanchang
2004-01-01
Structural diversity is the key attribute of a stand. A set of biodiversity measures in ecology was introduced in forest management for describing stand structure, of which Shannon information entropy (Shannon index) has been the most widely used measure of species diversity. It is generally thought that tree size diversity could serve as a good proxy for height diversity. However, tree size diversity and height diversity for stand structure is not completely consistent. Stand diameter cannot reflect height information completely. Either tree size diversity or height diversity is one-dimensional information entropy measure. This paper discussed the method of multiple-dimensional information entropy measure with the concept of joint entropy. It is suggested that joint entropy is a good measure for describing overall stand structural diversity.
RG flow of entanglement entropy to thermal entropy
Kim, Ki-Seok
2016-01-01
Utilizing the holographic technique, we investigate how the entanglement entropy evolves along the RG flow. After defining a new generalized entanglement temperature which satisfies the thermodynamics-like law even in the IR regime, we show that the renormalized entanglement entropy and temperature in the IR limit approach to the thermal entropy and temperature of a real thermal system. Intriguingly, the thermalization of the IR entanglement entropy generally happens regardless of the detail of a dual field theory. We check such a universality for a two-dimensional CFT, a Lifshitz field theory, and a non-conformal field theory. In addition, we also show that for a two-dimensional scale invariant theory the first quantum correction to the IR entanglement entropy leads to a logarithmic term caused by the remnant of the short distance quantum correlation near the entangling surface.
Absoluteness or relativity of morality
I. A. Kadievskaya
2014-02-01
Full Text Available Article is dedicated to the case study of absoluteness or relativity of morals. The questions are in a new way comprehended: Can exist absolute morals? Is how its content? Is necessary it for humanity? Is moral personality absolute value? Does justify the purpose of means? It is substantiated, that reflecting about the problem of absoluteness or relativity of morals, one ought not to be abstracted from the religion billions of people find in it the basis of their morals. Accumulated ethical experience is infinitely rich and diverse in humanity: it includes and the proclaimed prophets godly revelations, and the brilliant enlightenment of secular philosophers. Are analyzed such concepts, as morals, absolute morals, relativity, moral rigorizm, moral personality, formal ethics. The specific character of the moral relativity, which proclaims historicity and changeability of standards and standards of human behavior, is established. Moral rigorizm is understood as the principle, according to which the man must act only from the considerations of moral debt, whereas all other external motivations (interest, happiness, friendship, etc have no moral value. Is shown the priority significance of the nerigoristskoy formal ethics, in which strong idealizations and abstractions of the ethics of moral rigorizma are substituted by the weaker more realistic and more humane. In the nerigoristskoy formal ethics, as in the life, moral estimations completely can be and in the overwhelming majority of the cases are relative.
Weak entropy inequalities and entropic convergence
GAO FuQing; LI LiNa
2008-01-01
A criterion for algebraic convergence of the entropy is presented and an algebraic convergence result for the entropy of an exclusion process is improved.A weak entropy inequality is considered and its relationship to entropic convergence is discussed.
Weak entropy inequalities and entropic convergence
2008-01-01
A criterion for algebraic convergence of the entropy is presented and an algebraic convergence result for the entropy of an exclusion process is improved. A weak entropy inequality is considered and its relationship to entropic convergence is discussed.
John Scales Avery
2012-04-01
Full Text Available In this essay, human society is regarded as a “superorganism”, analogous to colonies of social insects. The digestive system of the human superorganism is the global economy, which ingests both free energy and resources, and later excretes them in a degraded form. This process involves an increase in entropy. Early in the 20th century, both Frederick Soddy and Nicholas Georgescu-Roegen discussed the relationship between entropy and economics. Soddy called for an index system to regulate the money supply and a reform of the fractional reserve banking system, while Georgescu-Roegen pointed to the need for Ecological Economics, a steady-state economy, and population stabilization. As we reach the end of the fossil fuel era and as industrial growth falters, massive unemployment can only be avoided by responsible governmental action. The necessary steps include shifting labor to projects needed for a sustainable economy, dividing the available work fairly among those seeking employment, and reforming the practices of the financial sector.
Singh, Priti; Chakraborty, Abhishek; Manoj, B. S.
2017-01-01
In this paper we propose a new metric, Link Influence Entropy (LInE), which describes importance of each node based on the influence of each link present in a network. Influence of a link can neither be effectively estimated using betweenness centrality nor using degree based probability measures. The proposed LInE metric which provides an effective way to estimate the influence of a link in the network and incorporates this influence to identify nodal characteristics, performs better compared to degree based entropy. We found that LInE can differentiate various network types which degree-based or betweenness centrality based node influence metrics cannot. Our findings show that spatial wireless networks and regular grid networks, respectively, have lowest and highest LInE values. Finally, performance analysis of LInE is carried out on a real-world network as well as on a wireless mesh network testbed to study the influence of our metric as well as influence stability of nodes in dynamic networks.
Connectivity in the human brain dissociates entropy and complexity of auditory inputs.
Nastase, Samuel A; Iacovella, Vittorio; Davis, Ben; Hasson, Uri
2015-03-01
Complex systems are described according to two central dimensions: (a) the randomness of their output, quantified via entropy; and (b) their complexity, which reflects the organization of a system's generators. Whereas some approaches hold that complexity can be reduced to uncertainty or entropy, an axiom of complexity science is that signals with very high or very low entropy are generated by relatively non-complex systems, while complex systems typically generate outputs with entropy peaking between these two extremes. In understanding their environment, individuals would benefit from coding for both input entropy and complexity; entropy indexes uncertainty and can inform probabilistic coding strategies, whereas complexity reflects a concise and abstract representation of the underlying environmental configuration, which can serve independent purposes, e.g., as a template for generalization and rapid comparisons between environments. Using functional neuroimaging, we demonstrate that, in response to passively processed auditory inputs, functional integration patterns in the human brain track both the entropy and complexity of the auditory signal. Connectivity between several brain regions scaled monotonically with input entropy, suggesting sensitivity to uncertainty, whereas connectivity between other regions tracked entropy in a convex manner consistent with sensitivity to input complexity. These findings suggest that the human brain simultaneously tracks the uncertainty of sensory data and effectively models their environmental generators.
Database applicaton for absolute spectrophotometry
Bochkov, Valery V.; Shumko, Sergiy
2002-12-01
32-bit database application with multidocument interface for Windows has been developed to calculate absolute energy distributions of observed spectra. The original database contains wavelength calibrated observed spectra which had been already passed through apparatus reductions such as flatfielding, background and apparatus noise subtracting. Absolute energy distributions of observed spectra are defined in unique scale by means of registering them simultaneously with artificial intensity standard. Observations of sequence of spectrophotometric standards are used to define absolute energy of the artificial standard. Observations of spectrophotometric standards are used to define optical extinction in selected moments. FFT algorithm implemented in the application allows performing convolution (deconvolution) spectra with user-defined PSF. The object-oriented interface has been created using facilities of C++ libraries. Client/server model with Windows Socket functionality based on TCP/IP protocol is used to develop the application. It supports Dynamic Data Exchange conversation in server mode and uses Microsoft Exchange communication facilities.
Colossal dielectric constant in high entropy oxides
Berardan, David; Franger, Sylvain; Dragoe, Diana; Meena, Arun Kumar; Dragoe, Nita [ICMMO (UMR 8182 CNRS), Universite Paris-Sud, Universite Paris-Saclay, 91405, Orsay (France)
2016-04-15
Entropic contributions to the stability of solids are very well understood and the mixing entropy has been used for forming various solids, for instance such as inverse spinels, see Nawrotsky et al., J. Inorg. Nucl. Chem. 29, 2701 (1967) [1]. A particular development was related to high entropy alloys by Yeh et al., Adv. Eng. Mater. 6, 299 (2004) [2] and Cantor et al., Mater. Sci. Eng. A 375-377, 213 (2004) [3] (for recent reviews see Zhang et al., Prog. Mater. Sci. 61, 1 (2014) [4] and Tsai et al., Mater. Res. Lett. 2, 107 (2014) [5]) in which the configurational disorder is responsible for forming simple solid solutions and which are thoroughly studied for various applications especially due to their mechanical properties, e.g. Gludovatz et al., Science 345, 1153 (2014) [6] and Lu et al., Sci. Rep. 4, 6200 (2014) [7], but also electrical properties, Kozelj et al., Phys. Rev. Lett. 113, 107001 (2014) [8], hydrogen storage, Kao et al., Int. J. Hydrogen Energy 35, 9046 (2010) [9], magnetic properties, Zhang et al., Sci. Rep. 3, 1455 (2013) [10]. Many unexplored compositions and properties still remain for this class of materials due to their large phase space. In a recent report it has been shown that the configurational disorder can be used for stabilizing simple solid solutions of oxides, which should normally not form solid solutions, see Rost et al., Nature Commun. 6, 8485 (2015) [11] these new materials were called ''entropy-stabilized oxides''. In this pioneering report, it was shown that mixing five equimolar binary oxides yielded, after heating at high temperature and quenching, an unexpected rock salt structure compound with statistical distribution of the cations in a face centered cubic lattice. Following this seminal study, we show here that these high entropy oxides (named HEOx hereafter) can be substituted by aliovalent elements with a charge compensation mechanism. This possibility largely increases the potential development of new
Entropy production by resonance decays
Ochs, S; Ochs, Stefan; Heinz, Ulrich
1996-01-01
We investigate entropy production for an expanding system of particles and resonances with isospin symmetry -- in our case pions and \\rho mesons -- within the framework of relativistic kinetic theory. A cascade code to simulate the kinetic equations is developed and results for entropy production and particle spectra are presented.
Kevin H. Knuth
2015-02-01
Full Text Available We are pleased to announce the “Entropy Best Paper Award” for 2015. Nominations were selected by the Editor-in-Chief and designated Editorial Board Members from all the papers published in 2011. Reviews and research papers were evaluated separately. We gladly announce that the following three papers have won the Entropy Best Paper Award in 2015:[...
Ignaccolo, M; Jernajczyk, W; Grigolini, P; West, B J
2009-01-01
EEG time series are analyzed using the diffusion entropy method. The resulting EEG entropy manifests short-time scaling, asymptotic saturation and an attenuated alpha-rhythm modulation. These properties are faithfully modeled by a phenomenological Langevin equation interpreted within a neural network context.
Conditional entropy of glueball states
Bernardini, Alex E; da Rocha, Roldao
2016-01-01
The conditional entropy of glueball states is calculated using a holographic description. Glueball states are represented by a supergravity dual picture, consisting of a 5-dimensional graviton-dilaton action of a dynamical holographic AdS/QCD model. The conditional entropy is studied as a function of the glueball spin and of the mass, providing information about the stability of the glueball states.
Conceptualizing Embedded Configuration
Oddsson, Gudmundur Valur; Hvam, Lars; Lysgaard, Ole
2006-01-01
and services. The general idea can be named embedded configuration. In this article we intend to conceptualize embedded configuration, what it is and is not. The difference between embedded configuration, sales configuration and embedded software is explained. We will look at what is needed to make embedded...... configuration systems. That will include requirements to product modelling techniques. An example with consumer electronics will illuminate the elements of embedded configuration in settings that most can relate to. The question of where embedded configuration would be relevant is discussed, and the current...
Entropy, Its Language, and Interpretation
Leff, Harvey S.
2007-12-01
The language of entropy is examined for consistency with its mathematics and physics, and for its efficacy as a guide to what entropy means. Do common descriptors such as disorder, missing information, and multiplicity help or hinder understanding? Can the language of entropy be helpful in cases where entropy is not well defined? We argue in favor of the descriptor spreading, which entails space, time, and energy in a fundamental way. This includes spreading of energy spatially during processes and temporal spreading over accessible microstates states in thermodynamic equilibrium. Various examples illustrate the value of the spreading metaphor. To provide further support for this metaphor’s utility, it is shown how a set of reasonable spreading properties can be used to derive the entropy function. A main conclusion is that it is appropriate to view entropy’s symbol S as shorthand for spreading.
Good Use of a `Bad' Metaphor. Entropy as Disorder
Haglund, Jesper
2017-05-01
Entropy is often introduced to students through the use of the disorder metaphor. However, many weaknesses and limitations of this metaphor have been identified, and it has therefore been argued that it is more harmful than useful in teaching. For instance, under the influence of the disorder metaphor, students tend to focus on spatial configuration with regard to entropy but disregard the role of energy, which may lead their intuition astray in problem solving. Albeit so, a review of research of students' ideas about entropy in relation to the disorder metaphor shows that students can use the metaphor in developing a more nuanced, complex view of the concept, by connecting entropy as disorder to other concepts such as microstates and spreading. The disorder metaphor—in combination with other explanatory approaches—can be used as a resource for learning, in giving students an early flavour of what entropy means, so long as we acknowledge its limitations; we can put this "bad" metaphor to good use in teaching.
Winter, Andreas
2016-10-01
We present a bouquet of continuity bounds for quantum entropies, falling broadly into two classes: first, a tight analysis of the Alicki-Fannes continuity bounds for the conditional von Neumann entropy, reaching almost the best possible form that depends only on the system dimension and the trace distance of the states. Almost the same proof can be used to derive similar continuity bounds for the relative entropy distance from a convex set of states or positive operators. As applications, we give new proofs, with tighter bounds, of the asymptotic continuity of the relative entropy of entanglement, E R , and its regularization {E_R^{∞}}, as well as of the entanglement of formation, E F . Using a novel "quantum coupling" of density operators, which may be of independent interest, we extend the latter to an asymptotic continuity bound for the regularized entanglement of formation, aka entanglement cost, {E_C=E_F^{∞}}. Second, we derive analogous continuity bounds for the von Neumann entropy and conditional entropy in infinite dimensional systems under an energy constraint, most importantly systems of multiple quantum harmonic oscillators. While without an energy bound the entropy is discontinuous, it is well-known to be continuous on states of bounded energy. However, a quantitative statement to that effect seems not to have been known. Here, under some regularity assumptions on the Hamiltonian, we find that, quite intuitively, the Gibbs entropy at the given energy roughly takes the role of the Hilbert space dimension in the finite-dimensional Fannes inequality.
Absolute luminosity measurements at LHCb
Hopchev, Plamen
2011-01-01
Absolute luminosity measurements are of general interest for colliding-beam experiments at storage rings. These measurements are necessary to determine the absolute cross-sections of reaction processes and are valuable to quantify the performance of the accelerator. LHCb has applied two methods to determine the absolute scale of its luminosity measurements for proton-proton collisions at the LHC running at a centre-of-mass energy of 7 TeV. In addition to the classic ``van der Meer'' scan method a novel technique has been developed which makes use of direct imaging of the individual beams using both proton-gas and proton-proton interactions. The beam imaging method is made possible by the high resolution of the LHCb vertex detector and the close proximity of the detector to the beams, and allows beam parameters such as positions, angles and widths to be determined. We describe both methods and compare the two results. In addition, we present the techniques used to transport the absolute luminosity measurement ...
Relativistic Absolutism in Moral Education.
Vogt, W. Paul
1982-01-01
Discusses Emile Durkheim's "Moral Education: A Study in the Theory and Application of the Sociology of Education," which holds that morally healthy societies may vary in culture and organization but must possess absolute rules of moral behavior. Compares this moral theory with current theory and practice of American educators. (MJL)
Absolute Standards for Climate Measurements
Leckey, J.
2016-10-01
In a world of changing climate, political uncertainty, and ever-changing budgets, the benefit of measurements traceable to SI standards increases by the day. To truly resolve climate change trends on a decadal time scale, on-orbit measurements need to be referenced to something that is both absolute and unchanging. One such mission is the Climate Absolute Radiance and Refractivity Observatory (CLARREO) that will measure a variety of climate variables with an unprecedented accuracy to definitively quantify climate change. In the CLARREO mission, we will utilize phase change cells in which a material is melted to calibrate the temperature of a blackbody that can then be observed by a spectrometer. A material's melting point is an unchanging physical constant that, through a series of transfers, can ultimately calibrate a spectrometer on an absolute scale. CLARREO consists of two primary instruments: an infrared (IR) spectrometer and a reflected solar (RS) spectrometer. The mission will contain orbiting radiometers with sufficient accuracy to calibrate other space-based instrumentation and thus transferring the absolute traceability. The status of various mission options will be presented.
Population entropies estimates of proteins
Low, Wai Yee
2017-05-01
The Shannon entropy equation provides a way to estimate variability of amino acids sequences in a multiple sequence alignment of proteins. Knowledge of protein variability is useful in many areas such as vaccine design, identification of antibody binding sites, and exploration of protein 3D structural properties. In cases where the population entropies of a protein are of interest but only a small sample size can be obtained, a method based on linear regression and random subsampling can be used to estimate the population entropy. This method is useful for comparisons of entropies where the actual sequence counts differ and thus, correction for alignment size bias is needed. In the current work, an R based package named EntropyCorrect that enables estimation of population entropy is presented and an empirical study on how well this new algorithm performs on simulated dataset of various combinations of population and sample sizes is discussed. The package is available at https://github.com/lloydlow/EntropyCorrect. This article, which was originally published online on 12 May 2017, contained an error in Eq. (1), where the summation sign was missing. The corrected equation appears in the Corrigendum attached to the pdf.
Evolutionary algorithm based configuration interaction approach
Chakraborty, Rahul
2016-01-01
A stochastic configuration interaction method based on evolutionary algorithm is designed as an affordable approximation to full configuration interaction (FCI). The algorithm comprises of initiation, propagation and termination steps, where the propagation step is performed with cloning, mutation and cross-over, taking inspiration from genetic algorithm. We have tested its accuracy in 1D Hubbard problem and a molecular system (symmetric bond breaking of water molecule). We have tested two different fitness functions based on energy of the determinants and the CI coefficients of determinants. We find that the absolute value of CI coefficients is a more suitable fitness function when combined with a fixed selection scheme.
Electrochemical systems configured to harvest heat energy
Lee, Seok Woo; Yang, Yuan; Ghasemi, Hadi; Chen, Gang; Cui, Yi
2017-01-31
Electrochemical systems for harvesting heat energy, and associated electrochemical cells and methods, are generally described. The electrochemical cells can be configured, in certain cases, such that at least a portion of the regeneration of the first electrochemically active material is driven by a change in temperature of the electrochemical cell. The electrochemical cells can be configured to include a first electrochemically active material and a second electrochemically active material, and, in some cases, the absolute value of the difference between the first thermogalvanic coefficient of the first electrochemically active material and the second thermogalvanic coefficient of the second electrochemically active material is at least about 0.5 millivolts/Kelvin.
Entanglement entropy converges to classical entropy around periodic orbits
Asplund, Curtis T., E-mail: ca2621@columbia.edu [Department of Physics, Columbia University, 538 West 120th Street, New York, NY 10027 (United States); Berenstein, David, E-mail: dberens@physics.ucsb.edu [Department of Applied Mathematics and Theoretical Physics, University of Cambridge, Wilberforce Road, Cambridge CB3 0WA (United Kingdom)
2016-03-15
We consider oscillators evolving subject to a periodic driving force that dynamically entangles them, and argue that this gives the linearized evolution around periodic orbits in a general chaotic Hamiltonian dynamical system. We show that the entanglement entropy, after tracing over half of the oscillators, generically asymptotes to linear growth at a rate given by the sum of the positive Lyapunov exponents of the system. These exponents give a classical entropy growth rate, in the sense of Kolmogorov, Sinai and Pesin. We also calculate the dependence of this entropy on linear mixtures of the oscillator Hilbert-space factors, to investigate the dependence of the entanglement entropy on the choice of coarse graining. We find that for almost all choices the asymptotic growth rate is the same.
The concept of entropy. Relation between action and entropy
J.-P.Badiali
2005-01-01
Full Text Available The Boltzmann expression for entropy represents the traditional link between thermodynamics and statistical mechanics. New theoretical developments like the Unruh effect or the black hole theory suggest a new definition of entropy. In this paper we consider the thermodynamics of black holes as seriously founded and we try to see what we can learn from it in the case of ordinary systems for which a pre-relativistic description is sufficient. We introduce a space-time model and a new definition of entropy considering the thermal equilibrium from a dynamic point of view. Then we show that for black hole and ordinary systems we have the same relation relating a change of entropy to a change of action.
Ingo Klein
2016-07-01
Full Text Available A new kind of entropy will be introduced which generalizes both the differential entropy and the cumulative (residual entropy. The generalization is twofold. First, we simultaneously define the entropy for cumulative distribution functions (cdfs and survivor functions (sfs, instead of defining it separately for densities, cdfs, or sfs. Secondly, we consider a general “entropy generating function” φ, the same way Burbea et al. (IEEE Trans. Inf. Theory 1982, 28, 489–495 and Liese et al. (Convex Statistical Distances; Teubner-Verlag, 1987 did in the context of φ-divergences. Combining the ideas of φ-entropy and cumulative entropy leads to the new “cumulative paired φ-entropy” ( C P E φ . This new entropy has already been discussed in at least four scientific disciplines, be it with certain modifications or simplifications. In the fuzzy set theory, for example, cumulative paired φ-entropies were defined for membership functions, whereas in uncertainty and reliability theories some variations of C P E φ were recently considered as measures of information. With a single exception, the discussions in the scientific disciplines appear to be held independently of each other. We consider C P E φ for continuous cdfs and show that C P E φ is rather a measure of dispersion than a measure of information. In the first place, this will be demonstrated by deriving an upper bound which is determined by the standard deviation and by solving the maximum entropy problem under the restriction of a fixed variance. Next, this paper specifically shows that C P E φ satisfies the axioms of a dispersion measure. The corresponding dispersion functional can easily be estimated by an L-estimator, containing all its known asymptotic properties. C P E φ is the basis for several related concepts like mutual φ-information, φ-correlation, and φ-regression, which generalize Gini correlation and Gini regression. In addition, linear rank tests for scale that
Zero Modes and Entanglement Entropy
Yazdi, Yasaman K
2016-01-01
Ultraviolet divergences are widely discussed in studies of entanglement entropy. Also present, but much less understood, are infrared divergences due to zero modes in the field theory. In this note, we discuss the importance of carefully handling zero modes in entanglement entropy. We give an explicit example for a chain of harmonic oscillators in 1D, where a mass regulator is necessary to avoid an infrared divergence due to a zero mode. We also comment on a surprising contribution of the zero mode to the UV-scaling of the entanglement entropy.
Rindler Energy is Wald Entropy
Halyo, Edi
2014-01-01
We show that, in any theory of gravity, the entropy of any nonextreme black hole is given by $2 \\pi E_R$ where $E_R$ is the dimensionless Rindler energy. Separately, we show that $E_R$ is exactly Wald's Noether charge and therefore this entropy is identical to Wald entropy. However, it is off--shell and derived solely from the time evolution of the black hole. We examine Gauss--Bonnet black holes as an example and speculate on the degrees of freedom that $E_R$ counts.
Nonequilibrium stationary states and entropy.
Gallavotti, G; Cohen, E G D
2004-03-01
In transformations between nonequilibrium stationary states, entropy might not be a well defined concept. It might be analogous to the "heat content" in transformations in equilibrium which is not well defined either, if they are not isochoric (i.e., do involve mechanical work). Hence we conjecture that in a nonequilibrium stationary state the entropy is just a quantity that can be transferred or created, such as heat in equilibrium, but has no physical meaning as "entropy content" as a property of the system.
Relative Entropy and Torsion Coupling
Lin, Feng-Li
2016-01-01
We evaluate the relative entropy on a ball region near the UV fixed point of a holographic conformal field theory deformed by a fermionic operator of nonzero vacuum expectation value. The positivity of the relative entropy considered here is implied by the expected monotonicity of decrease of quantum entanglement under RG flow. The calculations are done in the perturbative framework of Einstein-Cartan gravity in four-dimensional asymptotically anti-de Sitter space with a postulated standard bilinear coupling between axial fermion current and torsion. Our results however imply that the positivity of the relative entropy disfavors such a coupling.
Optomechanics for absolute rotation detection
Davuluri, Sankar
2016-07-01
In this article, we present an application of optomechanical cavity for the absolute rotation detection. The optomechanical cavity is arranged in a Michelson interferometer in such a way that the classical centrifugal force due to rotation changes the length of the optomechanical cavity. The change in the cavity length induces a shift in the frequency of the cavity mode. The phase shift corresponding to the frequency shift in the cavity mode is measured at the interferometer output to estimate the angular velocity of absolute rotation. We derived an analytic expression to estimate the minimum detectable rotation rate in our scheme for a given optomechanical cavity. Temperature dependence of the rotation detection sensitivity is studied.
Entropy exchange for infinite-dimensional systems
Duan, Zhoubo; Hou, Jinchuan
2017-01-01
In this paper the entropy exchange for channels and states in infinite-dimensional systems are defined and studied. It is shown that, this entropy exchange depends only on the given channel and the state. An explicit expression of the entropy exchange in terms of the state and the channel is proposed. The generalized Klein’s inequality, the subadditivity and the triangle inequality about the entropy including infinite entropy for the infinite-dimensional systems are established, and then, applied to compare the entropy exchange with the entropy change. PMID:28164995
Effects of the temperature dependence of the bulk modulus on magnetic exchange-entropy
Silva, J.A. da [Departamento de Física, Universidade Federal de Sergipe, 49100-000 São Cristóvão, SE (Brazil); Plaza, E.J.R., E-mail: ejrplaza@gmail.com [Departamento de Física, Universidade Federal de Sergipe, 49100-000 São Cristóvão, SE (Brazil); Campoy, J.C.P. [Departamento de Ciências Naturais, Universidade Federal de São João del Rei, 36301-160 São João del Rei, MG (Brazil)
2015-05-25
Highlights: • A thermodynamic route for the field-induced additional exchange-entropy was studied. • The temperature dependence of bulk modulus leads to the additional exchange-entropy. • The total entropy change matches with the sum of conventional and additional terms. • We obtained analytical expressions for deformation and additional exchange-entropy. - Abstract: We have studied the field-induced additional exchange-entropy on an elastic ferromagnet as a response effect of the dependence of its bulk modulus with temperature. We consider that the temperature dependence of the bulk modulus follows a linear behavior or a Wachtman-type equation. Our analysis is based on a free energy model containing exchange, Zeeman and elastic terms. From the deduced expressions for the exchange parameter, the additional exchange-entropy was obtained. This quantity must be the difference between the conventional and the total entropy change which were calculated from well-established thermodynamic expressions, i.e., configurational spin disorder and Maxwell’s equation, respectively. In addition, we established an analytical relation between the field-induced additional exchange-entropy and the temperature dependence of the bulk modulus.
Mechanical Properties of Refractory High Entropy Alloys Fabricated by Powder Processing
Kuk, Seoung Woo; Kim, Ki Hwan [Korea Atomic Energy Research Institute, Yuseong, Daejeon (Korea, Republic of); Lim, Woo Jin; Kang, Byung Chul; Hong, Soon Hyung; Ryu, Ho Jin [KAIST, Daejeon (Korea, Republic of)
2015-10-15
The effects of high configurational entropy, lattice distortion and sluggish diffusion are attributed to the distinguishable behavior of high entropy alloys. The structural applications of high entropy alloys are also promising in advanced nuclear energy systems for nuclear fission and fusion applications. Because of the randomly occupied lattice points by atoms with different atomic radius, lattice distortions and local atomic level strain were developed. The local lattice distortions influence the mechanical properties of high entropy alloys. The strengthening of high entropy alloys is attributed to the lattice distortions and local atomic level strain that increase the resistance to the dislocation motion. Some high entropy alloys exhibit remarkable irradiation resistance. Nagase et al. reported that the Conference alloy was irradiation resistant up to 40 dpa. Ega mi proposed that the irradiation defects can be self-healed because the recrystallization happens more easily in high entropy alloys. The mechanically alloyed and sintered samples have a much smaller grain size than that in cast high entropy alloys.
Richert, Ranko
2017-02-01
On the basis of adiabatic calorimetry data and results obtained from dielectric relaxation studies in the presence of a high static electric field, the effects of temperature and electric field induced changes of the excess entropy are compared for the same sample: supercooled cresolphthalein dimethylether. A field induced reduction of the excess entropy by 45 mJ K-1 mol-1 at constant temperature increases the structural relaxation time by 0.75%, while the same entropy change originating from lowering the temperature at constant field increases the time constant by 3.5%. Therefore, there is no simple link connecting excess entropy and relaxation time that is independent of the control parameter that is used to modify the entropy. A consequence is that the Adam-Gibbs approach does not provide a quantitative prediction for how the dynamics of liquids depend on the electric field, and, more generally, on excess entropy. This work compares the dynamics for temperature versus field induced changes of isobaric excess entropy, thereby eliminating previous uncertainties arising from isochoric versus isobaric conditions and from unknown relations between thermodynamic, excess, and configurational entropies.
Two Aspects of Black hole entropy in Lanczos-Lovelock models of gravity
Kolekar, Sanved; Padmanabhan, T
2011-01-01
We consider two specific approaches to evaluate the black hole entropy which are known to produce correct results in the case of Einstein's theory and generalize them to Lanczos-Lovelock models. In the first approach (which could be called extrinsic) we use a procedure motivated by earlier work by Pretorius, Vollick and Israel, and by Oppenheim, and evaluate the entropy of a configuration of densely packed gravitating shells on the verge of forming a black hole in Lanczos-Lovelock theories of gravity. We find that this matter entropy is not equal to (it is less than) Wald entropy, except in the case of Einstein theory, where they are equal. The matter entropy is proportional to the Wald entropy if we consider a specific m-th order Lanczos-Lovelock model, with the proportionality constant depending on the spacetime dimensions D and the order m of the Lanczos-Lovelock theory as (D-2m)/(D-2). Since the proportionality constant depends on m, the proportionality between matter entropy and Wald entropy breaks down ...
Two aspects of black hole entropy in Lanczos-Lovelock models of gravity
Kolekar, Sanved; Kothawala, Dawood; Padmanabhan, T.
2012-03-01
We consider two specific approaches to evaluate the black hole entropy which are known to produce correct results in the case of Einstein’s theory and generalize them to Lanczos-Lovelock models. In the first approach (which could be called extrinsic), we use a procedure motivated by earlier work by Pretorius, Vollick, and Israel, and by Oppenheim, and evaluate the entropy of a configuration of densely packed gravitating shells on the verge of forming a black hole in Lanczos-Lovelock theories of gravity. We find that this matter entropy is not equal to (it is less than) Wald entropy, except in the case of Einstein theory, where they are equal. The matter entropy is proportional to the Wald entropy if we consider a specific mth-order Lanczos-Lovelock model, with the proportionality constant depending on the spacetime dimensions D and the order m of the Lanczos-Lovelock theory as (D-2m)/(D-2). Since the proportionality constant depends on m, the proportionality between matter entropy and Wald entropy breaks down when we consider a sum of Lanczos-Lovelock actions involving different m. In the second approach (which could be called intrinsic), we generalize a procedure, previously introduced by Padmanabhan in the context of general relativity, to study off-shell entropy of a class of metrics with horizon using a path integral method. We consider the Euclidean action of Lanczos-Lovelock models for a class of metrics off shell and interpret it as a partition function. We show that in the case of spherically symmetric metrics, one can interpret the Euclidean action as the free energy and read off both the entropy and energy of a black hole spacetime. Surprisingly enough, this leads to exactly the Wald entropy and the energy of the spacetime in Lanczos-Lovelock models obtained by other methods. We comment on possible implications of the result.
An adaptable binary entropy coder
Kiely, A.; Klimesh, M.
2001-01-01
We present a novel entropy coding technique which is based on recursive interleaving of variable-to-variable length binary source codes. We discuss code design and performance estimation methods, as well as practical encoding and decoding algorithms.
Entropy of Quantum States: Ambiguities
Balachandran, A P; Vaidya, S
2012-01-01
The von Neumann entropy of a generic quantum state is not unique unless the state can be uniquely decomposed as a sum of extremal or pure states. As pointed out to us by Sorkin, this happens if the GNS representation (of the algebra of observables in some quantum state) is reducible, and some representations in the decomposition occur with non-trivial degeneracy. This non-unique entropy can occur at zero temperature. We will argue elsewhere in detail that the degeneracies in the GNS representation can be interpreted as an emergent broken gauge symmetry, and play an important role in the analysis of emergent entropy due to non-Abelian anomalies. Finally, we establish the analogue of an H-theorem for this entropy by showing that its evolution is Markovian, determined by a stochastic matrix.
Entropy of Open Lattice Systems
Derrida, B.; Lebowitz, J. L.; Speer, E. R.
2007-03-01
We investigate the behavior of the Gibbs-Shannon entropy of the stationary nonequilibrium measure describing a one-dimensional lattice gas, of L sites, with symmetric exclusion dynamics and in contact with particle reservoirs at different densities. In the hydrodynamic scaling limit, L → ∞, the leading order ( O( L)) behavior of this entropy has been shown by Bahadoran to be that of a product measure corresponding to strict local equilibrium; we compute the first correction, which is O(1). The computation uses a formal expansion of the entropy in terms of truncated correlation functions; for this system the k th such correlation is shown to be O( L - k+1). This entropy correction depends only on the scaled truncated pair correlation, which describes the covariance of the density field. It coincides, in the large L limit, with the corresponding correction obtained from a Gaussian measure with the same covariance.
Renyi entropy and conformal defects
Bianchi, Lorenzo [Humboldt-Univ. Berlin (Germany). Inst. fuer Physik; Hamburg Univ. (Germany). II. Inst. fuer Theoretische Physik; Meineri, Marco [Scuola Normale Superiore, Pisa (Italy); Perimeter Institute for Theoretical Physics, Waterloo, ON (Canada); Istituto Nazionale di Fisica Nucleare, Pisa (Italy); Myers, Robert C. [Perimeter Institute for Theoretical Physics, Waterloo, ON (Canada); Smolkin, Michael [California Univ., Berkely, CA (United States). Center for Theoretical Physics and Department of Physics
2016-04-18
We propose a field theoretic framework for calculating the dependence of Renyi entropies on the shape of the entangling surface in a conformal field theory. Our approach rests on regarding the corresponding twist operator as a conformal defect and in particular, we define the displacement operator which implements small local deformations of the entangling surface. We identify a simple constraint between the coefficient defining the two-point function of the displacement operator and the conformal weight of the twist operator, which consolidates a number of distinct conjectures on the shape dependence of the Renyi entropy. As an example, using this approach, we examine a conjecture regarding the universal coefficient associated with a conical singularity in the entangling surface for CFTs in any number of spacetime dimensions. We also provide a general formula for the second order variation of the Renyi entropy arising from small deformations of a spherical entangling surface, extending Mezei's results for the entanglement entropy.
Quantum entropy and special relativity.
Peres, Asher; Scudo, Petra F; Terno, Daniel R
2002-06-10
We consider a single free spin- 1 / 2 particle. The reduced density matrix for its spin is not covariant under Lorentz transformations. The spin entropy is not a relativistic scalar and has no invariant meaning.
Wang, W. H.
2014-10-01
The high-entropy alloys are defined as solid-solution alloys containing five or more than five principal elements in equal or near-equal atomic percent. The concept of high mixing entropy introduces a new way for developing advanced metallic materials with unique physical and mechanical properties that cannot be achieved by the conventional microalloying approach based on only a single base element. The metallic glass (MG) is the metallic alloy rapidly quenched from the liquid state, and at room temperature it still shows an amorphous liquid-like structure. Bulk MGs represent a particular class of amorphous alloys usually with three or more than three components but based on a single principal element such as Zr, Cu, Ce, and Fe. These materials are very attractive for applications because of their excellent mechanical properties such as ultrahigh (near theoretical) strength, wear resistance, and hardness, and physical properties such as soft magnetic properties. In this article, we review the formation and properties of a series of high-mixing-entropy bulk MGs based on multiple major elements. It is found that the strategy and route for development of the high-entropy alloys can be applied to the development of the MGs with excellent glass-forming ability. The high-mixing-entropy bulk MGs are then loosely defined as metallic glassy alloys containing five or more than five elements in equal or near-equal atomic percent, which have relatively high mixing entropy compared with the conventional MGs based on a single principal element. The formation mechanism, especially the role of the mixing entropy in the formation of the high-entropy MGs, is discussed. The unique physical, mechanical, chemical, and biomedical properties of the high-entropy MGs in comparison with the conventional metallic alloys are introduced. We show that the high-mixing-entropy MGs, along the formation idea and strategy of the high-entropy alloys and based on multiple major elements, might provide
Boundary effects in entanglement entropy
Berthiere, Clément; Solodukhin, Sergey N.
2016-09-01
We present a number of explicit calculations of Renyi and entanglement entropies in situations where the entangling surface intersects the boundary of d-dimensional Minkowski spacetime. When the boundary is a single plane we compute the contribution to the entropy due to this intersection, first in the case of the Neumann and Dirichlet boundary conditions, and then in the case of a generic Robin type boundary condition. The flow in the boundary coupling between the Neumann and Dirichlet phases is analyzed in arbitrary dimension d and is shown to be monotonic, the peculiarity of d = 3 case is noted. We argue that the translational symmetry along the entangling surface is broken due the presence of the boundary which reveals that the entanglement is not homogeneous. In order to characterize this quantitatively, we introduce a density of entanglement entropy and compute it explicitly. This quantity clearly indicates that the entanglement is maximal near the boundary. We then consider the situation where the boundary is composed of two parallel planes at a finite separation and compute the entanglement entropy as well as its density in this case. The complete contribution to entanglement entropy due to the boundaries is shown not to depend on the distance between the planes and is simply twice the entropy in the case of single plane boundary. Additionally, we find how the area law, the part in the entropy proportional to the area of entire entangling surface, depends on the size of the separation between the two boundaries. The latter is shown to appear in the UV finite part of the entropy.
Holographic avatars of entanglement entropy
Barbon, J.L.F. [Instituto de Fisica Teorica IFT UAM/CSIC, Ciudad Universitaria de Cantoblanco 28049, Madrid (Spain)
2009-07-15
This is a rendering of the blackboard lectures at the 2008 Cargese summer school, discussing some elementary facts regarding the application of AdS/CFT techniques to the computation of entanglement entropy in strongly coupled systems. We emphasize the situations where extensivity of the entanglement entropy can be used as a crucial criterion to characterize either nontrivial dynamical phenomena at large length scales, or nonlocality in the short-distance realm.
On Entropy Bounds and Holography
Halyo, Edi
2009-01-01
We show that the holographic entropy bound for gravitational systems and the Bekenstein entropy bound for nongravitational systems are holographically related. Using the AdS/CFT correspondence, we find that the Bekenstein bound on the boundary is obtained from the holographic bound in the bulk by minimizing the boundary energy with respect the AdS radius or the cosmological constant. This relation may also ameliorate some problems associated with the Bekenstein bound.
Applications of Entropy in Finance: A Review
Guanqun Tong
2013-11-01
Full Text Available Although the concept of entropy is originated from thermodynamics, its concepts and relevant principles, especially the principles of maximum entropy and minimum cross-entropy, have been extensively applied in finance. In this paper, we review the concepts and principles of entropy, as well as their applications in the field of finance, especially in portfolio selection and asset pricing. Furthermore, we review the effects of the applications of entropy and compare them with other traditional and new methods.
Possible extended forms of thermodynamic entropy
Sasa, Shin-ichi
2013-01-01
Thermodynamic entropy is determined by a heat measurement through the Clausius equality. The entropy then formalizes a fundamental limitation of operations by the second law of thermodynamics. The entropy is also expressed as the Shannon entropy of the microscopic degrees of freedom. Whenever an extension of thermodynamic entropy is attempted, we must pay special attention to how its three different aspects just mentioned are altered. In this paper, we discuss possible extensions of the therm...
Entropy Production in Chemical Reactors
Kingston, Diego; Razzitte, Adrián C.
2017-06-01
We have analyzed entropy production in chemically reacting systems and extended previous results to the two limiting cases of ideal reactors, namely continuous stirred tank reactor (CSTR) and plug flow reactor (PFR). We have found upper and lower bounds for the entropy production in isothermal systems and given expressions for non-isothermal operation and analyzed the influence of pressure and temperature in entropy generation minimization in reactors with a fixed volume and production. We also give a graphical picture of entropy production in chemical reactions subject to constant volume, which allows us to easily assess different options. We show that by dividing a reactor into two smaller ones, operating at different temperatures, the entropy production is lowered, going as near as 48 % less in the case of a CSTR and PFR in series, and reaching 58 % with two CSTR. Finally, we study the optimal pressure and temperature for a single isothermal PFR, taking into account the irreversibility introduced by a compressor and a heat exchanger, decreasing the entropy generation by as much as 30 %.
Cheeseman, Peter; Stutz, John
2005-01-01
A long standing mystery in using Maximum Entropy (MaxEnt) is how to deal with constraints whose values are uncertain. This situation arises when constraint values are estimated from data, because of finite sample sizes. One approach to this problem, advocated by E.T. Jaynes [1], is to ignore this uncertainty, and treat the empirically observed values as exact. We refer to this as the classic MaxEnt approach. Classic MaxEnt gives point probabilities (subject to the given constraints), rather than probability densities. We develop an alternative approach that assumes that the uncertain constraint values are represented by a probability density {e.g: a Gaussian), and this uncertainty yields a MaxEnt posterior probability density. That is, the classic MaxEnt point probabilities are regarded as a multidimensional function of the given constraint values, and uncertainty on these values is transmitted through the MaxEnt function to give uncertainty over the MaXEnt probabilities. We illustrate this approach by explicitly calculating the generalized MaxEnt density for a simple but common case, then show how this can be extended numerically to the general case. This paper expands the generalized MaxEnt concept introduced in a previous paper [3].
HLT configuration management system
Daponte, Vincenzo
2015-01-01
The CMS High Level Trigger (HLT) is implemented running a streamlined version of the CMS offline reconstruction software running on thousands of CPUs. The CMS software is written mostly in C++, using Python as its configuration language through an embedded CPython interpreter. The configuration of each process is made up of hundreds of modules, organized in sequences and paths. As an example, the HLT configurations used for 2011 data taking comprised over 2200 different modules, organized in more than 400 independent trigger paths. The complexity of the HLT configurations and the large number of configuration produced require the design of a suitable data management system. The present work describes the designed solution to manage the considerable number of configurations developed and to assist the editing of new configurations. The system is required to be remotely accessible and OS-independent as well as easly maintainable easy to use. To meet these requirements a three-layers architecture has been choose...
Entropy production rate as a constraint for collisionless fluid closures
Fleurence, E.; Sarazin, Y.; Garbet, X.; Dif-Pradalier, G.; Ghendrih, Ph.; Grandgirard, V.; Ottaviani, M.
2006-11-01
A novel method is proposed to construct collisionless fluid closures accounting for some kinetic properties. The first dropped fluid moment is assumed to be a linear function of the lower order ones. Optimizing the agreement between the fluid and kinetic entropy production rates is used to constrain the coefficients of the linear development. This procedure is applied to a reduced version of the interchange instability. The closure, involving the absolute value of the wave vector, is non-local in real space. In this case, the linear instability thresholds are the same, and the linear growth rates exhibit similar characteristics. Such a method is applicable to other models and classes of instabilities.
Android Apps for Absolute Beginners
Jackson, Wallace
2011-01-01
Anybody can start building simple apps for the Android platform, and this book will show you how! Android Apps for Absolute Beginners takes you through the process of getting your first Android applications up and running using plain English and practical examples. It cuts through the fog of jargon and mystery that surrounds Android application development, and gives you simple, step-by-step instructions to get you started.* Teaches Android application development in language anyone can understand, giving you the best possible start in Android development * Provides simple, step-by-step exampl
Business Model Process Configurations
Taran, Yariv; Nielsen, Christian; Thomsen, Peter
2015-01-01
Purpose – The paper aims: 1) To develop systematically a structural list of various business model process configuration and to group (deductively) these selected configurations in a structured typological categorization list. 2) To facilitate companies in the process of BM innovation......, by developing (inductively) an ontological classification framework, in view of the BM process configurations typology developed. Design/methodology/approach – Given the inconsistencies found in the business model studies (e.g. definitions, configurations, classifications) we adopted the analytical induction...... method of data analysis. Findings - A comprehensive literature review and analysis resulted in a list of business model process configurations systematically organized under five classification groups, namely, revenue model; value proposition; value configuration; target customers, and strategic...
Chiral hydroxy phosphonates: synthesis, configuration and biological properties
Kolodiazhnyi, Oleg I [Institute of Bioorganic Chemistry and Petrochemistry, National Academy of Sciences of Ukraine, Kiev (Ukraine)
2006-03-31
Published data on the synthesis, absolute configurations and biological properties of chiral hydroxy phosphonates are generalised and described systematically. Examples of asymmetric synthesis of hydroxy phosphonates by the phospho-aldol reaction, reduction of keto phosphonates, chemo-enzymatic approach, and so on are discussed. Methods for determination of the optical purity and absolute configuration of hydroxy phosphonates using modification by chiral reagents, NMR, circular dichroism, GLC and HPLC on columns with chiral sorbents are considered. The significance of hydroxy phosphonates as promising compounds for the development of new drugs and bioregulators is demonstrated.
Chiral hydroxy phosphonates: synthesis, configuration and biological properties
Kolodiazhnyi, Oleg I.
2006-03-01
Published data on the synthesis, absolute configurations and biological properties of chiral hydroxy phosphonates are generalised and described systematically. Examples of asymmetric synthesis of hydroxy phosphonates by the phospho-aldol reaction, reduction of keto phosphonates, chemo-enzymatic approach, and so on are discussed. Methods for determination of the optical purity and absolute configuration of hydroxy phosphonates using modification by chiral reagents, NMR, circular dichroism, GLC and HPLC on columns with chiral sorbents are considered. The significance of hydroxy phosphonates as promising compounds for the development of new drugs and bioregulators is demonstrated.
Software configuration management
Keyes, Jessica
2004-01-01
Software Configuration Management discusses the framework from a standards viewpoint, using the original DoD MIL-STD-973 and EIA-649 standards to describe the elements of configuration management within a software engineering perspective. Divided into two parts, the first section is composed of 14 chapters that explain every facet of configuration management related to software engineering. The second section consists of 25 appendices that contain many valuable real world CM templates.
Numerical Stability of Generalized Entropies
Steinbrecher, György
2016-01-01
In many applications, the probability density function is subject to experimental errors. In this work the continuos dependence of a class of generalized entropies on the experimental errors is studied. This class includes the C. Shannon, C. Tsallis, A. R\\'enyi and generalized R\\'enyi entropies. By using the connection between R\\'enyi or Tsallis entropies, and the "distance" in a family of metric functional spaces, family that includes the Lebesgue normed vector spaces, we introduce a further extensive generalizations of the R\\'enyi entropy. In this work we suppose that the experimental error is measured by some $L^{p}$ norm. In line with the methodology normally used for treating the so called "ill-posed problems", auxiliary stabilizing conditions are determined, such that small - in the sense of $L^{p}$ metric - experimental errors provoke small variations of the classical and generalized entropies. These stabilizing conditions are formulated in terms of $L^{p}$ metric in a class of generalized $L^{p}$ spac...
Maximum Entropy in Drug Discovery
Chih-Yuan Tseng
2014-07-01
Full Text Available Drug discovery applies multidisciplinary approaches either experimentally, computationally or both ways to identify lead compounds to treat various diseases. While conventional approaches have yielded many US Food and Drug Administration (FDA-approved drugs, researchers continue investigating and designing better approaches to increase the success rate in the discovery process. In this article, we provide an overview of the current strategies and point out where and how the method of maximum entropy has been introduced in this area. The maximum entropy principle has its root in thermodynamics, yet since Jaynes’ pioneering work in the 1950s, the maximum entropy principle has not only been used as a physics law, but also as a reasoning tool that allows us to process information in hand with the least bias. Its applicability in various disciplines has been abundantly demonstrated. We give several examples of applications of maximum entropy in different stages of drug discovery. Finally, we discuss a promising new direction in drug discovery that is likely to hinge on the ways of utilizing maximum entropy.
Mutual information challenges entropy bounds
Casini, H
2006-01-01
We consider some formulations of the entropy bounds at the semiclassical level. The entropy S(V) localized in a region V is divergent in quantum field theory (QFT). Instead of it we focus on the mutual information I(V,W)=S(V)+S(W)-S(V U W) between two different non-intersecting sets V and W. This is a low energy quantity, independent of the regularization scheme. In addition, the mutual information is bounded above by twice the entropy corresponding to the sets involved. Calculations of I(V,W) in QFT show that the entropy in empty space cannot be renormalized to zero, and must be actually very large. We find that this entropy due to the vacuum fluctuations violates the FMW bound in Minkowski space. The mutual information also gives a precise, cutoff independent meaning to the statement that the number of degrees of freedom increases with the volume in QFT. If the holographic bound holds, this points to the essential non locality of the physical cutoff. Violations of the Bousso bound would require conformal th...
Airport Configuration Prediction Project
National Aeronautics and Space Administration — Airport configuration is a primary factor in various airport characteristics such as arrival and departure capacities and terminal area traffic patterns. These...
A. Alsaed
2004-11-18
''The Disposal Criticality Analysis Methodology Topical Report'' prescribes an approach to the methodology for performing postclosure criticality analyses within the monitored geologic repository at Yucca Mountain, Nevada. An essential component of the methodology is the ''Configuration Generator Model for In-Package Criticality'' that provides a tool to evaluate the probabilities of degraded configurations achieving a critical state. The configuration generator model is a risk-informed, performance-based process for evaluating the criticality potential of degraded configurations in the monitored geologic repository. The method uses event tree methods to define configuration classes derived from criticality scenarios and to identify configuration class characteristics (parameters, ranges, etc.). The probabilities of achieving the various configuration classes are derived in part from probability density functions for degradation parameters. The NRC has issued ''Safety Evaluation Report for Disposal Criticality Analysis Methodology Topical Report, Revision 0''. That report contained 28 open items that required resolution through additional documentation. Of the 28 open items, numbers 5, 6, 9, 10, 18, and 19 were concerned with a previously proposed software approach to the configuration generator methodology and, in particular, the k{sub eff} regression analysis associated with the methodology. However, the use of a k{sub eff} regression analysis is not part of the current configuration generator methodology and, thus, the referenced open items are no longer considered applicable and will not be further addressed.
Ansible configuration management
Hall, Daniel
2013-01-01
Ansible Configuration Management"" is a step-by-step tutorial that teaches the use of Ansible for configuring Linux machines.This book is intended for anyone looking to understand the basics of Ansible. It is expected that you will have some experience of how to set up and configure Linux machines. In parts of the book we cover configuration files of BIND, MySQL, and other Linux daemons, therefore a working knowledge of these would be helpful but are certainly not required.
A Model of Mechanothermodynamic Entropy in Tribology
Leonid A. Sosnovskiy
2017-03-01
Full Text Available A brief analysis of entropy concepts in continuum mechanics and thermodynamics is presented. The methods of accounting for friction, wear and fatigue processes in the calculation of the thermodynamic entropy are described. It is shown that these and other damage processes of solids are more adequately described by tribo-fatigue entropy. It was established that mechanothermodynamic entropy calculated as the sum of interacting thermodynamic and tribo-fatigue entropy components has the most general character. Examples of usage (application of tribo-fatigue and mechanothermodynamic entropies for practical analysis of wear and fatigue processes are given.
Information Entropy Production of Spatio-Temporal Maximum Entropy Distributions
Cofre, Rodrigo
2015-01-01
Spiking activity from populations of neurons display causal interactions and memory effects. Therefore, they are expected to show some degree of irreversibility in time. Motivated by the spike train statistics, in this paper we build a framework to quantify the degree of irreversibility of any maximum entropy distribution. Our approach is based on the transfer matrix technique, which enables us to find an homogeneous irreducible Markov chain that shares the same maximum entropy measure. We provide relevant examples in the context of spike train statistics
Bekenstein-Hawking Entropy as Topological Entanglement Entropy
McGough, Lauren; Verlinde, Herman
2013-01-01
Black holes in 2+1 dimensions enjoy long range topological interactions similar to those of non-abelian anyon excitations in a topologically ordered medium. Using this observation, we compute the topological entanglement entropy of BTZ black holes, via the established formula S_top = log(S^a_0), with S_b^a the modular S-matrix of the Virasoro characters chi_a(tau). We find a precise match with the Bekenstein-Hawking entropy. This result adds a new twist to the relationship between quantum ent...
Entanglement Entropy for Singular Surfaces
Myers, Robert C
2012-01-01
We study entanglement entropy for regions with a singular boundary in higher dimensions using the AdS/CFT correspondence and find that various singularities make new universal contributions. When the boundary CFT has an even spacetime dimension, we find that the entanglement entropy of a conical surface contains a term quadratic in the logarithm of the UV cut-off. In four dimensions, the coefficient of this contribution is proportional to the central charge 'c'. A conical singularity in an odd number of spacetime dimensions contributes a term proportional to the logarithm of the UV cut-off. We also study the entanglement entropy for various boundary surfaces with extended singularities. In these cases, similar universal terms may appear depending on the dimension and curvature of the singular locus.
Boundary effects in entanglement entropy
Berthiere, Clement
2016-01-01
We present a number of explicit calculations of Renyi and entanglement entropies in situations where the entangling surface intersects the boundary in $d$-dimensional Minkowski spacetime. When the boundary is a single plane we compute the contribution to the entropy due to this intersection, first in the case of the Neumann and Dirichlet boundary conditions, and then in the case of a generic Robin type boundary condition. The flow in the boundary coupling between the Neumann and Dirichlet phases is analyzed in arbitrary dimension $d$ and is shown to be monotonic, the peculiarity of $d=3$ case is noted. We argue that the translational symmetry along the entangling surface is broken due the presence of the boundary which reveals that the entanglement is not homogeneous. In order to characterize this quantitatively, we introduce a density of entanglement entropy and compute it explicitly. This quantity clearly indicates that the entanglement is maximal near the boundary. We then consider the situation where the ...
Lemons, Don S
2013-01-01
Striving to explore the subject in as simple a manner as possible, this book helps readers understand the elusive concept of entropy. Innovative aspects of the book include the construction of statistical entropy, the derivation of the entropy of classical systems from purely classical assumptions, and a statistical thermodynamics approach to the ideal Fermi and ideal Bose gases. Derivations are worked through step-by-step and important applications are highlighted in over 20 worked examples. Nearly 50 end-of-chapter exercises test readers' understanding. The book also features a glossary giving definitions for all essential terms, a time line showing important developments, and list of books for further study. It is an ideal supplement to undergraduate courses in physics, engineering, chemistry and mathematics.
Quantum geometry and gravitational entropy
Simon, Joan; Balasubramanian, Vijay; Czech, Bart Iomiej; Larjo, Klaus; Marolf, Donald; Simon, Joan
2007-05-29
Most quantum states have wavefunctions that are widely spread over the accessible Hilbert space and hence do not have a good description in terms of a single classical geometry. In order to understand when geometric descriptions are possible, we exploit the AdS/CFT correspondence in the half-BPS sector of asymptotically AdS_5 x S5 universes. In this sector we devise a"coarse-grained metric operator" whose eigenstates are well described by a single spacetime topology and geometry. We show that such half-BPS universes have a non-vanishing entropy if and only if the metric is singular, and that the entropy arises from coarse-graining the geometry. Finally, we use our entropy formula to find the most entropic spacetimes with fixed asymptotic moments beyond the global charges.
Relative entropy and torsion coupling
Ning, Bo; Lin, Feng-Li
2016-12-01
We evaluate the relative entropy on a ball region near the UV fixed point of a holographic conformal field theory deformed by a fermionic operator of nonzero vacuum expectation value. The positivity of the relative entropy considered here is implied by the expected monotonicity of the decrease of quantum entanglement under the renormalization group flow. The calculations are done in the perturbative framework of Einstein-Cartan gravity in four-dimensional asymptotic anti-de Sitter space with a postulated standard bilinear coupling between the axial fermion current and torsion. By requiring positivity of relative entropy, our result yields a constraint on axial current-torsion coupling, fermion mass, and equation of state.
Unraveling the success and failure of mode coupling theory from consideration of entropy.
Nandi, Manoj Kumar; Banerjee, Atreyee; Sengupta, Shiladitya; Sastry, Srikanth; Bhattacharyya, Sarika Maitra
2015-11-07
We analyze the dynamics of model supercooled liquids in a temperature regime where predictions of mode coupling theory (MCT) are known to be valid qualitatively. In this regime, the Adam-Gibbs (AG) relation, based on an activation picture of dynamics, also describes the dynamics satisfactorily, and we explore the mutual consistency and interrelation of these descriptions. Although entropy and dynamics are related via phenomenological theories, the connection between MCT and entropy has not been argued for. In this work, we explore this connection and provide a microscopic derivation of the phenomenological Rosenfeld theory. At low temperatures, the overlap between the MCT power law regime and AG relation implies that the AG relation predicts an avoided divergence at Tc, the origin of which can be related to the vanishing of pair configurational entropy, which we find occurring at the same temperature. We also show that the residual multiparticle entropy plays an important role in describing the relaxation time.
Unraveling the success and failure of mode coupling theory from consideration of entropy
Nandi, Manoj Kumar; Banerjee, Atreyee; Sengupta, Shiladitya; Sastry, Srikanth; Bhattacharyya, Sarika Maitra
2015-11-01
We analyze the dynamics of model supercooled liquids in a temperature regime where predictions of mode coupling theory (MCT) are known to be valid qualitatively. In this regime, the Adam-Gibbs (AG) relation, based on an activation picture of dynamics, also describes the dynamics satisfactorily, and we explore the mutual consistency and interrelation of these descriptions. Although entropy and dynamics are related via phenomenological theories, the connection between MCT and entropy has not been argued for. In this work, we explore this connection and provide a microscopic derivation of the phenomenological Rosenfeld theory. At low temperatures, the overlap between the MCT power law regime and AG relation implies that the AG relation predicts an avoided divergence at Tc, the origin of which can be related to the vanishing of pair configurational entropy, which we find occurring at the same temperature. We also show that the residual multiparticle entropy plays an important role in describing the relaxation time.
Automated absolute phase retrieval in across-track interferometry
Madsen, Soren N.; Zebker, Howard A.
1992-01-01
Discussed is a key element in the processing of topographic radar maps acquired by the NASA/JPL airborne synthetic aperture radar configured as an across-track interferometer (TOPSAR). TOPSAR utilizes a single transmit and two receive antennas; the three-dimensional target location is determined by triangulation based on a known baseline and two measured slant ranges. The slant range difference is determined very accurately from the phase difference between the signals received by the two antennas. This phase is measured modulo 2pi, whereas it is the absolute phase which relates directly to the difference in slant range. It is shown that splitting the range bandwidth into two subbands in the processor and processing each individually allows for the absolute phase. The underlying principles and system errors which must be considered are discussed, together with the implementation and results from processing data acquired during the summer of 1991.
Construction of microcanonical entropy on thermodynamic pillars.
Campisi, Michele
2015-05-01
A question that is currently highly debated is whether the microcanonical entropy should be expressed as the logarithm of the phase volume (volume entropy, also known as the Gibbs entropy) or as the logarithm of the density of states (surface entropy, also known as the Boltzmann entropy). Rather than postulating them and investigating the consequence of each definition, as is customary, here we adopt a bottom-up approach and construct the entropy expression within the microcanonical formalism upon two fundamental thermodynamic pillars: (i) The second law of thermodynamics as formulated for quasistatic processes: δQ/T is an exact differential, and (ii) the law of ideal gases: PV=k(B)NT. The first pillar implies that entropy must be some function of the phase volume Ω. The second pillar singles out the logarithmic function among all possible functions. Hence the construction leads uniquely to the expression S=k(B)lnΩ, that is, the volume entropy. As a consequence any entropy expression other than that of Gibbs, e.g., the Boltzmann entropy, can lead to inconsistencies with the two thermodynamic pillars. We illustrate this with the prototypical example of a macroscopic collection of noninteracting spins in a magnetic field, and show that the Boltzmann entropy severely fails to predict the magnetization, even in the thermodynamic limit. The uniqueness of the Gibbs entropy, as well as the demonstrated potential harm of the Boltzmann entropy, provide compelling reasons for discarding the latter at once.
Residual entropy of ice III from Monte Carlo simulation.
Kolafa, Jiří
2016-03-28
We calculated the residual entropy of ice III as a function of the occupation probabilities of hydrogen positions α and β assuming equal energies of all configurations. To do this, a discrete ice model with Bjerrum defect energy penalty and harmonic terms to constrain the occupation probabilities was simulated by the Metropolis Monte Carlo method for a range of temperatures and sizes followed by thermodynamic integration and extrapolation to N = ∞. Similarly as for other ices, the residual entropies are slightly higher than the mean-field (no-loop) approximation. However, the corrections caused by fluctuation of energies of ice samples calculated using molecular models of water are too large for accurate determination of the chemical potential and phase equilibria.
Maximum-Entropy Inference with a Programmable Annealer
Chancellor, Nicholas; Vinci, Walter; Aeppli, Gabriel; Warburton, Paul A
2015-01-01
Optimisation problems in science and engineering typically involve finding the ground state (i.e. the minimum energy configuration) of a cost function with respect to many variables. If the variables are corrupted by noise then this approach maximises the likelihood that the solution found is correct. An alternative approach is to make use of prior statistical information about the noise in conjunction with Bayes's theorem. The maximum entropy solution to the problem then takes the form of a Boltzmann distribution over the ground and excited states of the cost function. Here we use a programmable Josephson junction array for the information decoding problem which we simulate as a random Ising model in a field. We show experimentally that maximum entropy decoding at finite temperature can in certain cases give competitive and even slightly better bit-error-rates than the maximum likelihood approach at zero temperature, confirming that useful information can be extracted from the excited states of the annealing...
Cosmology with Negative Absolute Temperatures
Vieira, J P P; Lewis, Antony
2016-01-01
Negative absolute temperatures (NAT) are an exotic thermodynamical consequence of quantum physics which has been known since the 1950's (having been achieved in the lab on a number of occasions). Recently, the work of Braun et al (2013) has rekindled interest in negative temperatures and hinted at a possibility of using NAT systems in the lab as dark energy analogues. This paper goes one step further, looking into the cosmological consequences of the existence of a NAT component in the Universe. NAT-dominated expanding Universes experience a borderline phantom expansion ($w<-1$) with no Big Rip, and their contracting counterparts are forced to bounce after the energy density becomes sufficiently large. Both scenarios might be used to solve horizon and flatness problems analogously to standard inflation and bouncing cosmologies. We discuss the difficulties in obtaining and ending a NAT-dominated epoch, and possible ways of obtaining density perturbations with an acceptable spectrum.
Cosmology with negative absolute temperatures
Vieira, J. P. P.; Byrnes, Christian T.; Lewis, Antony
2016-08-01
Negative absolute temperatures (NAT) are an exotic thermodynamical consequence of quantum physics which has been known since the 1950's (having been achieved in the lab on a number of occasions). Recently, the work of Braun et al. [1] has rekindled interest in negative temperatures and hinted at a possibility of using NAT systems in the lab as dark energy analogues. This paper goes one step further, looking into the cosmological consequences of the existence of a NAT component in the Universe. NAT-dominated expanding Universes experience a borderline phantom expansion (w inflation and bouncing cosmologies. We discuss the difficulties in obtaining and ending a NAT-dominated epoch, and possible ways of obtaining density perturbations with an acceptable spectrum.
PIV Logon Configuration Guidance
Lee, Glen Alan [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
2016-03-04
This document details the configurations and enhancements implemented to support the usage of federal Personal Identity Verification (PIV) Card for logon on unclassified networks. The guidance is a reference implementation of the configurations and enhancements deployed at the Los Alamos National Laboratory (LANL) by Network and Infrastructure Engineering – Core Services (NIE-CS).
Entropy power inequalities for qudits
Audenaert, Koenraad; Datta, Nilanjana; Ozols, Maris
2016-05-01
Shannon's entropy power inequality (EPI) can be viewed as a statement of concavity of an entropic function of a continuous random variable under a scaled addition rule: f ( √{ a } X + √{ 1 - a } Y ) ≥ a f ( X ) + ( 1 - a ) f ( Y ) ∀ a ∈ [ 0 , 1 ] . Here, X and Y are continuous random variables and the function f is either the differential entropy or the entropy power. König and Smith [IEEE Trans. Inf. Theory 60(3), 1536-1548 (2014)] and De Palma, Mari, and Giovannetti [Nat. Photonics 8(12), 958-964 (2014)] obtained quantum analogues of these inequalities for continuous-variable quantum systems, where X and Y are replaced by bosonic fields and the addition rule is the action of a beam splitter with transmissivity a on those fields. In this paper, we similarly establish a class of EPI analogues for d-level quantum systems (i.e., qudits). The underlying addition rule for which these inequalities hold is given by a quantum channel that depends on the parameter a ∈ [0, 1] and acts like a finite-dimensional analogue of a beam splitter with transmissivity a, converting a two-qudit product state into a single qudit state. We refer to this channel as a partial swap channel because of the particular way its output interpolates between the states of the two qudits in the input as a is changed from zero to one. We obtain analogues of Shannon's EPI, not only for the von Neumann entropy and the entropy power for the output of such channels, but also for a much larger class of functions. This class includes the Rényi entropies and the subentropy. We also prove a qudit analogue of the entropy photon number inequality (EPnI). Finally, for the subclass of partial swap channels for which one of the qudit states in the input is fixed, our EPIs and EPnI yield lower bounds on the minimum output entropy and upper bounds on the Holevo capacity.
Grammar Specialization through Entropy Thresholds
Samuelsson, C
1994-01-01
Explanation-based generalization is used to extract a specialized grammar from the original one using a training corpus of parse trees. This allows very much faster parsing and gives a lower error rate, at the price of a small loss in coverage. Previously, it has been necessary to specify the tree-cutting criteria (or operationality criteria) manually; here they are derived automatically from the training set and the desired coverage of the specialized grammar. This is done by assigning an entropy value to each node in the parse trees and cutting in the nodes with sufficiently high entropy values.
Entanglement entropy of round spheres
Solodukhin, Sergey N., E-mail: Sergey.Solodukhin@lmpt.univ-tours.f [Laboratoire de Mathematiques et Physique Theorique, Universite Francois-Rabelais Tours Federation Denis Poisson - CNRS, Parc de Grandmont, 37200 Tours (France)
2010-10-18
We propose that the logarithmic term in the entanglement entropy computed in a conformal field theory for a (d-2)-dimensional round sphere in Minkowski spacetime is identical to the logarithmic term in the entanglement entropy of extreme black hole. The near horizon geometry of the latter is H{sub 2}xS{sub d-2}. For a scalar field this proposal is checked by direct calculation. We comment on relation of this and earlier calculations to the 'brick wall' model of 't Hooft. The case of generic 4d conformal field theory is discussed.
Barrañon, A; Roa, J E
2005-01-01
Distinct entropy definitions have been used to obtain an inverse correlation between the residual size and entropy for Heavy Ion Collisions. This explains the existence of several temperatures for different residual size bins, as reported elsewhere (Natowitz et. al., 2002). HIC collisions were simulated using binary interaction LATINO model where Pandharipande potential replicates internucleonic interaction. System temperature is defined as the temperature obtained when Kinetic Gas Theory is applied to the nucleons in the participant region. Fragments are detected with an Early Cluster Recognition Algorithm that optimizes the partitions in energy space.
Numerical Study of Entropy Generation Within Thermoacoustic Heat Exchangers with Plane Fins
Antonio Piccolo
2015-12-01
Full Text Available In this paper a simplified two-dimensional computational model for studying the entropy generation characteristics of thermoacoustic heat exchangers with plane fins is presented. The model integrates the equations of the standard linear thermoacoustic theory into an energy balance-based numerical calculus scheme. Relevant computation results are the spatial distribution of the time-averaged temperature, heat fluxes and entropy generation rates within a channel of a parallel-plate stack and adjoining heat exchangers. For a thermoacoustic device working in the refrigeration mode, this study evidences as a target refrigeration output level can be achieved selecting simultaneously the heat exchangers fin length and fin interspacing for minimum entropy generation and that the resulting configuration is a point of maximum coefficient of performance. The proposed methodology, when extended to other configurations, could be used as a viable design tool for heat exchangers in thermoacoustic applications.
Antenna entropy in plant photosystems does not reduce the free energy for primary charge separation.
Jennings, Robert C; Zucchelli, Giuseppe
2014-12-01
We have investigated the concept of the so-called "antenna entropy" of higher plant photosystems. Several interesting points emerge: 1. In the case of a photosystemwhich harbours an excited state, the “antenna entropy” is equivalent to the configurational (mixing) entropy of a thermodynamic canonical ensemble. The energy associated with this parameter has been calculated for a hypothetical isoenergetic photosystem, photosystem I and photosystem II, and comes out in the range of 3.5 - 8% of the photon energy considering 680 nm. 2. The “antenna entropy” seems to be a rather unique thermodynamic phenomenon, in as much as it does not modify the free energy available for primary photochemistry, as has been previously suggested. 3. It is underlined that this configurational (mixing) entropy, unlike heat dispersal in a thermal system, does not involve energy dilution. This points out an important difference between thermal and electronic energy dispersal.
Holographic entanglement entropy and the extended phase structure of STU black holes
Caceres, Elena; Pedraza, Juan F
2015-01-01
We study the extended thermodynamics, obtained by considering the cosmological constant as a thermodynamic variable, of STU black holes in 4-dimensions in the fixed charge ensemble. The associated phase structure is conjectured to be dual to an RG-flow on the space of field theories. We find that for some charge configurations the phase structure resembles that of a Van der Waals gas: the system exhibits a family of first order phase transitions ending in a second order phase transition at a critical temperature. We calculate the holographic entanglement entropy for several charge configurations and show that for the cases where the gravity background exhibits Van der Waals behavior, the entanglement entropy presents a transition at the same critical temperature. To further characterize the phase transition we calculate appropiate critical exponents show that they coincide. Thus, the holographic entanglement entropy successfully captures the information of the extended phase structure. Finally, we discuss the...
Vibrational entropy of a protein: large differences between distinct conformations.
Goethe, Martin; Fita, Ignacio; Rubi, J Miguel
2015-01-13
In this article, it is investigated whether vibrational entropy (VE) is an important contribution to the free energy of globular proteins at ambient conditions. VE represents the major configurational-entropy contribution of these proteins. By definition, it is an average of the configurational entropies of the protein within single minima of the energy landscape, weighted by their occupation probabilities. Its large part originates from thermal motion of flexible torsion angles giving rise to the finite peak widths observed in torsion angle distributions. While VE may affect the equilibrium properties of proteins, it is usually neglected in numerical calculations as its consideration is difficult. Moreover, it is sometimes believed that all well-packed conformations of a globular protein have similar VE anyway. Here, we measure explicitly the VE for six different conformations from simulation data of a test protein. Estimates are obtained using the quasi-harmonic approximation for three coordinate sets, Cartesian, bond-angle-torsion (BAT), and a new set termed rotamer-degeneracy lifted BAT coordinates by us. The new set gives improved estimates as it overcomes a known shortcoming of the quasi-harmonic approximation caused by multiply populated rotamer states, and it may serve for VE estimation of macromolecules in a very general context. The obtained VE values depend considerably on the type of coordinates used. However, for all coordinate sets we find large entropy differences between the conformations, of the order of the overall stability of the protein. This result may have important implications on the choice of free energy expressions used in software for protein structure prediction, protein design, and NMR refinement.
Duality of Maximum Entropy and Minimum Divergence
Shinto Eguchi
2014-06-01
Full Text Available We discuss a special class of generalized divergence measures by the use of generator functions. Any divergence measure in the class is separated into the difference between cross and diagonal entropy. The diagonal entropy measure in the class associates with a model of maximum entropy distributions; the divergence measure leads to statistical estimation via minimization, for arbitrarily giving a statistical model. The dualistic relationship between the maximum entropy model and the minimum divergence estimation is explored in the framework of information geometry. The model of maximum entropy distributions is characterized to be totally geodesic with respect to the linear connection associated with the divergence. A natural extension for the classical theory for the maximum likelihood method under the maximum entropy model in terms of the Boltzmann-Gibbs-Shannon entropy is given. We discuss the duality in detail for Tsallis entropy as a typical example.
The entropy principle thermodynamics for the unsatisfied
Thess, André
2011-01-01
Entropy is the most important and the most difficult to understand term of thermodynamics. This book helps make this key concept understandable. It includes seven illustrative examples of applications of entropy, which are presented step by step.
Using entropy measures to characterize human locomotion.
Leverick, Graham; Szturm, Tony; Wu, Christine Q
2014-12-01
Entropy measures have been widely used to quantify the complexity of theoretical and experimental dynamical systems. In this paper, the value of using entropy measures to characterize human locomotion is demonstrated based on their construct validity, predictive validity in a simple model of human walking and convergent validity in an experimental study. Results show that four of the five considered entropy measures increase meaningfully with the increased probability of falling in a simple passive bipedal walker model. The same four entropy measures also experienced statistically significant increases in response to increasing age and gait impairment caused by cognitive interference in an experimental study. Of the considered entropy measures, the proposed quantized dynamical entropy (QDE) and quantization-based approximation of sample entropy (QASE) offered the best combination of sensitivity to changes in gait dynamics and computational efficiency. Based on these results, entropy appears to be a viable candidate for assessing the stability of human locomotion.
On thermodynamic limits of entropy densities
Moriya, H; Van Enter, A
1998-01-01
We give some sufficient conditions which guarantee that the entropy density in the thermodynamic limit is equal to the thermodynamic limit of the entropy densities of finite-volume (local) Gibbs states.
An improved estimate of black hole entropy in the quantum geometry approach
Ghosh, A
2005-01-01
The corrected counting of states for black holes in the quantum geometry approach shows that the dominant configurations are distributions of spins that include spins exceeding one-half at the punctures. This alters the value of the Immirzi parameter and the black hole entropy. The logarithmic correction coefficient is -1/2 as before.
System Design of the ATLAS Absolute Luminosity Monitor
Anghinolfi, Francis; Franz, Sebastien; Iwanski, W; Lundberg, B; PH-EP
2007-01-01
The ATLAS absolute luminosity monitor is composed of 8 roman pots symmetrically located in the LHC tunnel. Each pot contains 23 multi anode photomultiplier tubes, and each one of those is fitted with a front-end assembly called PMF. A PMF provides the high voltage biasing of the tube, the frontend readout chip and the readout logic in a very compact arrangement. The 25 PMFs contained in one roman pot are connected to a motherboard used as an interface to the backend electronics. The system allows to configure the front-end electronics from the ATLAS detector control system and to transmit the luminosity data over Slink.
Absolute Measurement of Quantum-Limited Interferometric Displacements
Thiel, Valérian; Treps, Nicolas; Roslund, Jonathan
2016-01-01
A methodology is introduced that enables an absolute, quantum-limited measurement of sub-wavelength interferometric displacements. The technique utilizes a high-frequency optical path modulation within an interferometer operated in a homodyne configuration. All of the information necessary to fully characterize the resultant path displacement is contained within the relative strengths of the various harmonics of the phase modulation. The method, which is straightforward and readily implementable, allows a direct measurement of the theoretical Cram\\'er-Rao limit of detection without any assumptions on the nature of the light source.
Entropy of local smeared field observables
Satz, Alejandro
2017-01-01
We re-conceptualize the usual entanglement entropy of quantum fields in a spatial region as a limiting case of a more general and well-defined quantity, the entropy of a subalgebra of smeared field observables. We introduce this notion, discuss various examples, and recover from it the area law for the entanglement entropy of a sphere in Minkowski space.
Remainder terms for some quantum entropy inequalities
Carlen, Eric A.; Lieb, Elliott H. [Department of Mathematics, Hill Center, Rutgers University, 110 Frelinghuysen Road, Piscataway, New Jersey 08854-8019 (United States); Departments of Mathematics and Physics, Jadwin Hall, Princeton University, Washington Road, Princeton, New Jersey 08544-0001 (United States)
2014-04-15
We consider three von Neumann entropy inequalities: subadditivity; Pinsker's inequality for relative entropy; and the monotonicity of relative entropy. For these we state conditions for equality, and we prove some new error bounds away from equality, including an improved version of Pinsker's inequality.
Abbe Mowshowitz
2015-03-01
Full Text Available This paper demonstrates properties of Hosoya entropy, a quantitative measure of graph complexity based on a decomposition of the vertices linked to partial Hosoya polynomials. Connections between the information content of a graph and Hosoya entropy are established, and the special case of Hosoya entropy of trees is investigated.
Entropy and temperatures of Nariai black hole
Eune, Myungseok; Kim, Wontae
2013-06-01
The statistical entropy of the Nariai black hole in a thermal equilibrium is calculated by using the brick-wall method. Even if the temperature depends on the choice of the timelike Killing vector, the entropy can be written by the ordinary area law which agrees with the Wald entropy. We discuss some physical consequences of this result and the properties of the temperatures.
Tachyon condensation and black hole entropy.
Dabholkar, Atish
2002-03-04
String propagation on a cone with deficit angle 2pi(1-1 / N) is considered for the purpose of computing the entropy of a large mass black hole. The entropy computed using the recent results on condensation of twisted-sector tachyons in this theory is found to be in precise agreement with the Bekenstein-Hawking entropy.
Logical entropy of quantum dynamical systems
Ebrahimzadeh Abolfazl
2016-01-01
Full Text Available This paper introduces the concepts of logical entropy and conditional logical entropy of hnite partitions on a quantum logic. Some of their ergodic properties are presented. Also logical entropy of a quantum dynamical system is dehned and ergodic properties of dynamical systems on a quantum logic are investigated. Finally, the version of Kolmogorov-Sinai theorem is proved.
The Entropy of Morbidity Trauma and Mortality
Neal-Sturgess, Clive
2010-01-01
In this paper it is shown that statistical mechanics in the form of thermodynamic entropy can be used as a measure of the severity of individual injuries (AIS), and that the correct way to account for multiple injuries is to sum the entropies. It is further shown that summing entropies according to the Planck-Boltzmann (P-B) definition of entropy is formally the same as ISS, which is why ISS works. Approximate values of the probabilities of fatality are used to calculate the Gibb's entropy, which is more accurate than the P-B entropy far from equilibrium, and are shown to be again proportional to ISS. For the categorisation of injury using entropies it is necessary to consider the underlying entropy of the individuals morbidity to which is added the entropy of trauma, which then may result in death. Adding in the underlying entropy and summing entropies of all AIS3+ values gives a more extended scale than ISS, and so entropy is considered the preferred measure. A small scale trial is conducted of these concep...
Entropy production by simple electrical circuits
Miranda, E N
2012-01-01
The entropy production by simple electrical circuits (R, RC, RL) is analyzed. It comes out that the entropy production is minimal, in agreement with a well known theorem due to Prigogine. In this way, it is wrong a recent result by Zupanovic, Juretic and Botric (Physica Review E 70, 056198) who claimed that the entropy production in simple electrical circuits is a maximum
A Note on Entropy Relations of Black Hole Horizons
Meng, Xin-He; Xu, Wei; Wang, Jia
2014-01-01
We focus on the entropy relations of black holes in three, four and higher dimensions. These entropy relations include entropy product, "part" entropy product and entropy sum. We also discuss their differences and similarities, in order to make a further study on understanding the origin of black hole entropy at the microscopic level.
Probability representation entropy for spin-state tomogram
Man'ko, O. V.; Man'ko, V. I.
2004-01-01
Probability representation entropy (tomographic entropy) of arbitrary quantum state is introduced. Using the properties of spin tomogram to be standard probability distribution function the tomographic entropy notion is discussed. Relation of the tomographic entropy to Shannon entropy and von Neumann entropy is elucidated.
Alternative Multiview Maximum Entropy Discrimination.
Chao, Guoqing; Sun, Shiliang
2016-07-01
Maximum entropy discrimination (MED) is a general framework for discriminative estimation based on maximum entropy and maximum margin principles, and can produce hard-margin support vector machines under some assumptions. Recently, the multiview version of MED multiview MED (MVMED) was proposed. In this paper, we try to explore a more natural MVMED framework by assuming two separate distributions p1( Θ1) over the first-view classifier parameter Θ1 and p2( Θ2) over the second-view classifier parameter Θ2 . We name the new MVMED framework as alternative MVMED (AMVMED), which enforces the posteriors of two view margins to be equal. The proposed AMVMED is more flexible than the existing MVMED, because compared with MVMED, which optimizes one relative entropy, AMVMED assigns one relative entropy term to each of the two views, thus incorporating a tradeoff between the two views. We give the detailed solving procedure, which can be divided into two steps. The first step is solving our optimization problem without considering the equal margin posteriors from two views, and then, in the second step, we consider the equal posteriors. Experimental results on multiple real-world data sets verify the effectiveness of the AMVMED, and comparisons with MVMED are also reported.
Holographic Entropy and Calabi's Diastasis
D'Hoker, Eric
2014-01-01
The entanglement entropy for interfaces and junctions of two-dimensional CFTs is evaluated on holographically dual half-BPS solutions to six-dimensional Type 4b supergravity with m anti-symmetric tensor supermultiplets. It is shown that the moduli space for an N-junction solution projects to N points in the Kaehler manifold SO(2,m)/( SO(2) x SO(m)). For N=2 the interface entropy is expressed in terms of the central charge and Calabi's diastasis function on SO(2,m)/(SO(2) x SO(m)), thereby lending support from holography to a proposal of Bachas, Brunner, Douglas, and Rastelli. For N=3, the entanglement entropy for a 3-junction decomposes into a sum of diastasis functions between pairs, weighed by combinations of the three central charges, provided the flux charges are all parallel to one another or, more generally, provided the space of flux charges is orthogonal to the space of unattracted scalars. Under similar assumptions for N>3, the entanglement entropy for the N-junction solves a variational problem whos...
Entropy of Quantum Black Holes
Romesh K. Kaul
2012-02-01
Full Text Available In the Loop Quantum Gravity, black holes (or even more general Isolated Horizons are described by a SU(2 Chern-Simons theory. There is an equivalent formulation of the horizon degrees of freedom in terms of a U(1 gauge theory which is just a gauged fixed version of the SU(2 theory. These developments will be surveyed here. Quantum theory based on either formulation can be used to count the horizon micro-states associated with quantum geometry fluctuations and from this the micro-canonical entropy can be obtained. We shall review the computation in SU(2 formulation. Leading term in the entropy is proportional to horizon area with a coefficient depending on the Barbero-Immirzi parameter which is fixed by matching this result with the Bekenstein-Hawking formula. Remarkably there are corrections beyond the area term, the leading one is logarithm of the horizon area with a definite coefficient −3/2, a result which is more than a decade old now. How the same results are obtained in the equivalent U(1 framework will also be indicated. Over years, this entropy formula has also been arrived at from a variety of other perspectives. In particular, entropy of BTZ black holes in three dimensional gravity exhibits the same logarithmic correction. Even in the String Theory, many black hole models are known to possess such properties. This suggests a possible universal nature of this logarithmic correction.
Mushotzky, R.
2008-01-01
I will discuss how one can determine the origin of the 'extra entropy' in groups and clusters and the feedback needed in models of galaxy formation. I will stress the use of x-ray spectroscopy and imaging and the critical value that Con-X has in this regard.
Exponential convergence rate in entropy
Mu-Fa Chen
2007-01-01
The exponential convergence rate in entropy is studied for symmetric forms, with a specia! attention to the Markov chain with a state space having two points only. Some upper and lower bounds of the rate are obtained and five examples with precise or qualitatively exact estimates are presented.
Biosemiotic Entropy: Concluding the Series
John W. Oller
2014-07-01
Full Text Available This article concludes the special issue on Biosemiotic Entropy looking toward the future on the basis of current and prior results. It highlights certain aspects of the series, concerning factors that damage and degenerate biosignaling systems. As in ordinary linguistic discourse, well-formedness (coherence in biological signaling systems depends on valid representations correctly construed: a series of proofs are presented and generalized to all meaningful sign systems. The proofs show why infants must (as empirical evidence shows they do proceed through a strict sequence of formal steps in acquiring any language. Classical and contemporary conceptions of entropy and information are deployed showing why factors that interfere with coherence in biological signaling systems are necessary and sufficient causes of disorders, diseases, and mortality. Known sources of such formal degeneracy in living organisms (here termed, biosemiotic entropy include: (a toxicants, (b pathogens; (c excessive exposures to radiant energy and/or sufficiently powerful electromagnetic fields; (d traumatic injuries; and (e interactions between the foregoing factors. Just as Jaynes proved that irreversible changes invariably increase entropy, the theory of true narrative representations (TNR theory demonstrates that factors disrupting the well-formedness (coherence of valid representations, all else being held equal, must increase biosemiotic entropy—the kind impacting biosignaling systems.
Entropy, semantic relatedness and proximity.
Hahn, Lance W; Sivley, Robert M
2011-09-01
Although word co-occurrences within a document have been demonstrated to be semantically useful, word interactions over a local range have been largely neglected by psychologists due to practical challenges. Shannon's (Bell Systems Technical Journal, 27, 379-423, 623-665, 1948) conceptualization of information theory suggests that these interactions should be useful for understanding communication. Computational advances make an examination of local word-word interactions possible for a large text corpus. We used Brants and Franz's (2006) dataset to generate conditional probabilities for 62,474 word pairs and entropy calculations for 9,917 words in Nelson, McEvoy, and Schreiber's (Behavior Research Methods, Instruments, & Computers, 36, 402-407, 2004) free association norms. Semantic associativity correlated moderately with the probabilities and was stronger when the two words were not adjacent. The number of semantic associates for a word and the entropy of a word were also correlated. Finally, language entropy decreases from 11 bits for single words to 6 bits per word for four-word sequences. The probabilities and entropies discussed here are included in the supplemental materials for the article.
Global Value Chain Configuration
Hernandez, Virginia; Pedersen, Torben
2017-01-01
This paper reviews the literature on global value chain configuration, providing an overview of this topic. Specifically, we review the literature focusing on the concept of the global value chain and its activities, the decisions involved in its configuration, such as location, the governance...... modes chosen and the different ways of coordinating them. We also examine the outcomes of a global value chain configuration in terms of performance and upgrading. Our aim is to review the state of the art of these issues, identify research gaps and suggest new lines for future research that would...
Absolutely separating quantum maps and channels
Filippov, S. N.; Magadov, K. Yu; Jivulescu, M. A.
2017-08-01
Absolutely separable states ϱ remain separable under arbitrary unitary transformations U\\varrho {U}\\dagger . By example of a three qubit system we show that in a multipartite scenario neither full separability implies bipartite absolute separability nor the reverse statement holds. The main goal of the paper is to analyze quantum maps resulting in absolutely separable output states. Such absolutely separating maps affect the states in a way, when no Hamiltonian dynamics can make them entangled afterwards. We study the general properties of absolutely separating maps and channels with respect to bipartitions and multipartitions and show that absolutely separating maps are not necessarily entanglement breaking. We examine the stability of absolutely separating maps under a tensor product and show that {{{Φ }}}\\otimes N is absolutely separating for any N if and only if Φ is the tracing map. Particular results are obtained for families of local unital multiqubit channels, global generalized Pauli channels, and combination of identity, transposition, and tracing maps acting on states of arbitrary dimension. We also study the interplay between local and global noise components in absolutely separating bipartite depolarizing maps and discuss the input states with high resistance to absolute separability.
Relation Entropy and Transferable Entropy Think of Aggregation on Group Decision Making
CHENG Qi-yue; QIU Wan-hua; LIU Xiao-feng
2002-01-01
In this paper, aggregation question based on group decision making and a single decision making is studied. The theory of entropy is applied to the sets pair analysis. The system of relation entropy and the transferable entropy notion are put. The character is studied. An potential by the relation entropy and transferable entropy are defined. It is the consistency measure on the group between a single decision making. We gained a new aggregation effective definition on the group misjudge.
Banerjee, Atreyee; Sengupta, Shiladitya; Sastry, Srikanth; Bhattacharyya, Sarika Maitra
2014-11-01
We present a study of two model liquids with different interaction potentials, exhibiting similar structure but significantly different dynamics at low temperatures. By evaluating the configurational entropy, we show that the differences in the dynamics of these systems can be understood in terms of their thermodynamic differences. Analyzing their structure, we demonstrate that differences in pair correlation functions between the two systems, through their contribution to the entropy, dominate the differences in their dynamics, and indeed overestimate the differences. Including the contribution of higher order structural correlations to the entropy leads to smaller estimates for the relaxation times, as well as smaller differences between the two studied systems.
Airport Configuration Prediction Project
National Aeronautics and Space Administration — There is presently poor knowledge throughout the National Airspace System (NAS) of the airport configurations currently in use at each airport. There is even less...
The LHCb configuration database
Abadie, Lana; Gaspar, Clara; Jacobsson, Richard; Jost, Beat; Neufeld, Niko
2005-01-01
The Experiment Control System (ECS) will handle the monitoring, configuration and operation of all the LHCb experimental equipment. All parameters required to configure electronics equipment under the control of the ECS will reside in a configuration database. The database will contain two kinds of information: 1.\tConfiguration properties about devices such as hardware addresses, geographical location, and operational parameters associated with particular running modes (dynamic properties). 2.\tConnectivity between devices : this consists of describing the output and input connections of a device (static properties). The representation of these data using tables must be complete so that it can provide all the required information to the ECS and must cater for all the subsystems. The design should also guarantee a fast response time, even if a query results in a large volume of data being loaded from the database into the ECS. To fulfil these constraints, we apply the following methodology: Determine from the d...
Firewall Configuration Errors Revisited
Wool, Avishai
2009-01-01
The first quantitative evaluation of the quality of corporate firewall configurations appeared in 2004, based on Check Point FireWall-1 rule-sets. In general that survey indicated that corporate firewalls were often enforcing poorly written rule-sets, containing many mistakes. The goal of this work is to revisit the first survey. The current study is much larger. Moreover, for the first time, the study includes configurations from two major vendors. The study also introduce a novel "Firewall Complexity" (FC) measure, that applies to both types of firewalls. The findings of the current study indeed validate the 2004 study's main observations: firewalls are (still) poorly configured, and a rule-set's complexity is (still) positively correlated with the number of detected risk items. Thus we can conclude that, for well-configured firewalls, ``small is (still) beautiful''. However, unlike the 2004 study, we see no significant indication that later software versions have fewer errors (for both vendors).
Drupal 8 configuration management
Borchert, Stefan
2015-01-01
Drupal 8 Configuration Management is intended for people who use Drupal 8 to build websites, whether you are a hobbyist using Drupal for the first time, a long-time Drupal site builder, or a professional web developer.
ATLAS DAQ Configuration Databases
I.Alexandrov; A.Amorim; 等
2001-01-01
The configuration databases are an important part of the Trigger/DAQ system of the future ATLAS experiment .This paper describes their current status giving details of architecture,implementation,test results and plans for future work.
Configuration Management Automation (CMA) -
Department of Transportation — Configuration Management Automation (CMA) will provide an automated, integrated enterprise solution to support CM of FAA NAS and Non-NAS assets and investments. CMA...
Configuration by Modularisation
Riitahuhta, Asko; Andreasen, Mogens Myrup
1998-01-01
Globally operating companies have realized that locally customized products and services are today the prerequisite for the success. The capability or the paradigm to act locally in global markets is called Mass Customization [Victor 1997]. The prerequisite for Mass Customization is Configuration...... for the creation of a structured product family is presented and examples are given. The concepts of a novel Dynamic Modularisation method, Metrics for Modularisation and Design for Configurability are presented....
Riemannian-geometric entropy for measuring network complexity
Franzosi, Roberto; Felice, Domenico; Mancini, Stefano; Pettini, Marco
2016-06-01
A central issue in the science of complex systems is the quantitative characterization of complexity. In the present work we address this issue by resorting to information geometry. Actually we propose a constructive way to associate with a—in principle, any—network a differentiable object (a Riemannian manifold) whose volume is used to define the entropy. The effectiveness of the latter in measuring network complexity is successfully proved through its capability of detecting a classical phase transition occurring in both random graphs and scale-free networks, as well as of characterizing small exponential random graphs, configuration models, and real networks.
Renormalized entanglement entropy flow in mass-deformed ABJM theory
Kim, Kyung Kiu; Kwon, O.-Kab; Park, Chanyong; Shin, Hyeonjoon
2014-08-01
We investigate a mass deformation effect on the renormalized entanglement entropy (REE) near the UV fixed point in (2+1)-dimensional field theory. In the context of the gauge/gravity duality, we use the Lin-Lunin-Maldacena geometries corresponding to the vacua of the mass-deformed ABJM theory. We analytically compute the small mass effect for various droplet configurations and show in holographic point of view that the REE is monotonically decreasing, positive, and stationary at the UV fixed point. These properties of the REE in (2+1)-dimensions are consistent with the Zamolodchikov c-function proposed in (1+1)-dimensional conformal field theory.
Entropy-based portfolio models: Practical issues
Shirazi, Yasaman Izadparast; Sabiruzzaman, Md.; Hamzah, Nor Aishah
2015-10-01
Entropy is a nonparametric alternative of variance and has been used as a measure of risk in portfolio analysis. In this paper, the computation of entropy risk for a given set of data is discussed with illustration. A comparison between entropy-based portfolio models is made. We propose a natural extension of the mean entropy portfolio to make it more general and diversified. In terms of performance, this new model is similar to the mean-entropy portfolio when applied to real and simulated data, and offers higher return if no constraint is set for the desired return; also it is found to be the most diversified portfolio model.
Towards information inequalities for generalized graph entropies.
Lavanya Sivakumar
Full Text Available In this article, we discuss the problem of establishing relations between information measures for network structures. Two types of entropy based measures namely, the Shannon entropy and its generalization, the Rényi entropy have been considered for this study. Our main results involve establishing formal relationships, by means of inequalities, between these two kinds of measures. Further, we also state and prove inequalities connecting the classical partition-based graph entropies and partition-independent entropy measures. In addition, several explicit inequalities are derived for special classes of graphs.
Receiver function estimated by maximum entropy deconvolution
吴庆举; 田小波; 张乃铃; 李卫平; 曾融生
2003-01-01
Maximum entropy deconvolution is presented to estimate receiver function, with the maximum entropy as the rule to determine auto-correlation and cross-correlation functions. The Toeplitz equation and Levinson algorithm are used to calculate the iterative formula of error-predicting filter, and receiver function is then estimated. During extrapolation, reflective coefficient is always less than 1, which keeps maximum entropy deconvolution stable. The maximum entropy of the data outside window increases the resolution of receiver function. Both synthetic and real seismograms show that maximum entropy deconvolution is an effective method to measure receiver function in time-domain.
Enthalpy-entropy compensation in protein unfolding
无
2000-01-01
Enthalpy-entropy compensation was found to be a universal law in protein unfolding based on over 3 000 experimental data. Water molecular reorganization accompanying the protein unfolding was suggested as the origin of the enthalpy-entropy compensation in protein unfolding. It is indicated that the enthalpy-entropy compensation constitutes the physical foundation that satisfies the biological need of the small free energy changes in protein unfolding, without the sacrifice of the bio-diversity of proteins. The enthalpy-entropy compensation theory proposed herein also provides valuable insights into the Privalov's puzzle of enthalpy and entropy convergence in protein unfolding.
Negative temperatures and the definition of entropy
Swendsen, Robert H.; Wang, Jian-Sheng
2016-07-01
The concept of negative temperature has recently received renewed interest in the context of debates about the correct definition of the thermodynamic entropy in statistical mechanics. Several researchers have identified the thermodynamic entropy exclusively with the "volume entropy" suggested by Gibbs, and have further concluded that by this definition, negative temperatures violate the principles of thermodynamics. We disagree with these conclusions. We demonstrate that volume entropy is inconsistent with the postulates of thermodynamics for systems with non-monotonic energy densities, while a definition of entropy based on the probability distributions of macroscopic variables does satisfy the postulates of thermodynamics. Our results confirm that negative temperature is a valid extension of thermodynamics.
A violation of the covariant entropy bound?
Masoumi, Ali
2014-01-01
Several arguments suggest that the entropy density at high energy density $\\rho$ should be given by the expression $s=K\\sqrt{\\rho/G}$, where $K$ is a constant of order unity. On the other hand the covariant entropy bound requires that the entropy on a light sheet be bounded by $A/4G$, where $A$ is the area of the boundary of the sheet. We find that in a suitably chosen cosmological geometry, the above expression for $s$ violates the covariant entropy bound. We consider different possible explanations for this fact; in particular the possibility that entropy bounds should be defined in terms of volumes of regions rather than areas of surfaces.
Generalized gravitational entropy from total derivative action
Dong, Xi; Miao, Rong-Xin
2015-12-01
We investigate the generalized gravitational entropy from total derivative terms in the gravitational action. Following the method of Lewkowycz and Maldacena, we find that the generalized gravitational entropy from total derivatives vanishes. We compare our results with the work of Astaneh, Patrushev, and Solodukhin. We find that if total derivatives produced nonzero entropy, the holographic and the field-theoretic universal terms of entanglement entropy would not match. Furthermore, the second law of thermodynamics could be violated if the entropy of total derivatives did not vanish.
Generalized Gravitational Entropy from Total Derivative Action
Dong, Xi
2015-01-01
We investigate the generalized gravitational entropy from total derivative terms in the gravitational action. Following the method of Lewkowycz and Maldacena, we find that the generalized gravitational entropy from total derivatives vanishes. We compare our results with the work of Astaneh, Patrushev, and Solodukhin. We find that if total derivatives produced nonzero entropy, the holographic and the field-theoretic universal terms of entanglement entropy would not match. Furthermore, the second law of thermodynamics could be violated if the entropy of total derivatives did not vanish.
Sort entropy-based for the analysis of EEG during anesthesia
Ma, Liang; Huang, Wei-Zhi
2010-08-01
The monitoring of anesthetic depth is an absolutely necessary procedure in the process of surgical operation. To judge and control the depth of anesthesia has become a clinical issue which should be resolved urgently. EEG collected wiil be processed by sort entrop in this paper. Signal response of the surface of the cerebral cortex is determined for different stages of patients in the course of anesthesia. EEG is simulated and analyzed through the fast algorithm of sort entropy. The results show that discipline of phasic changes for EEG is very detected accurately,and it has better noise immunity in detecting the EEG anaesthetized than approximate entropy. In conclusion,the computing of Sort entropy algorithm requires shorter time. It has high efficiency and strong anti-interference.
Beyond Gibbs-Boltzmann-Shannon: General Entropies -- The Gibbs-Lorentzian Example
Rudolf A. Treumann
2014-08-01
Full Text Available We propose a generalisation of Gibbs' statistical mechanics into the domain of non-negligible phase space correlations. Derived are the probability distribution and entropy as a generalised ensemble average, replacing Gibbs-Boltzmann-Shannon's entropy definition enabling construction of new forms of statistical mechanics. The general entropy may also be of importance in information theory and data analysis. Application to generalised Lorentzian phase space elements yields the Gibbs-Lorentzian power law probability distribution and statistical mechanics. The corresponding Boltzmann, Fermi and Bose-Einstein distributions are found. They apply only to finite temperature states including correlations. As a by-product any negative absolute temperatures are categorically excluded, supporting a recent ``no-negative $T$ claim.
Measurement of the absolute speed is possible?
Shevchenko, Sergey V.; Vladimir V. Tokarevsky
2016-01-01
One of popular problems, which are experimentally studied in physics in a long time, is the testing of the special relativity theory, first of all – measurements of isotropy and constancy of light speed; as well as attempts to determine so called “absolute speed”, i.e. the Earth speed in the absolute spacetime (absolute reference frame), if this spacetime (ARF) exists. Corresponding experiments aimed at the measuring of proper speed of some reference frame in oth...
To measure the absolute speed is possible?
Shevchenko, Sergey; Tokarevsky, Vladimir
2013-01-01
One of popular problems, which are experimentally studied in physics in a long time, is the testing of the special relativity theory, first of all – measurements of isotropy and constancy of light speed; as well as attempts to determine so called “absolute speed”, i.e. the Earth speed in the absolute spacetime (absolute reference frame), if this spacetime (ARF) exists. Corresponding experiments aimed at the measuring of proper speed of some reference frame in other one, incl...
Entropy-based financial asset pricing.
Mihály Ormos
Full Text Available We investigate entropy as a financial risk measure. Entropy explains the equity premium of securities and portfolios in a simpler way and, at the same time, with higher explanatory power than the beta parameter of the capital asset pricing model. For asset pricing we define the continuous entropy as an alternative measure of risk. Our results show that entropy decreases in the function of the number of securities involved in a portfolio in a similar way to the standard deviation, and that efficient portfolios are situated on a hyperbola in the expected return-entropy system. For empirical investigation we use daily returns of 150 randomly selected securities for a period of 27 years. Our regression results show that entropy has a higher explanatory power for the expected return than the capital asset pricing model beta. Furthermore we show the time varying behavior of the beta along with entropy.
Entropy-based financial asset pricing.
Ormos, Mihály; Zibriczky, Dávid
2014-01-01
We investigate entropy as a financial risk measure. Entropy explains the equity premium of securities and portfolios in a simpler way and, at the same time, with higher explanatory power than the beta parameter of the capital asset pricing model. For asset pricing we define the continuous entropy as an alternative measure of risk. Our results show that entropy decreases in the function of the number of securities involved in a portfolio in a similar way to the standard deviation, and that efficient portfolios are situated on a hyperbola in the expected return-entropy system. For empirical investigation we use daily returns of 150 randomly selected securities for a period of 27 years. Our regression results show that entropy has a higher explanatory power for the expected return than the capital asset pricing model beta. Furthermore we show the time varying behavior of the beta along with entropy.
Entropy Generation Across Earth's Bow Shock
Parks, George K.; McCarthy, Michael; Fu, Suiyan; Lee E. s; Cao, Jinbin; Goldstein, Melvyn L.; Canu, Patrick; Dandouras, Iannis S.; Reme, Henri; Fazakerley, Andrew; Lin, Naiguo; Wilber, Mark
2011-01-01
Earth's bow shock is a transition layer that causes an irreversible change in the state of plasma that is stationary in time. Theories predict entropy increases across the bow shock but entropy has never been directly measured. Cluster and Double Star plasma experiments measure 3D plasma distributions upstream and downstream of the bow shock that allow calculation of Boltzmann's entropy function H and his famous H-theorem, dH/dt O. We present the first direct measurements of entropy density changes across Earth's bow shock. We will show that this entropy generation may be part of the processes that produce the non-thermal plasma distributions is consistent with a kinetic entropy flux model derived from the collisionless Boltzmann equation, giving strong support that solar wind's total entropy across the bow shock remains unchanged. As far as we know, our results are not explained by any existing shock models and should be of interests to theorists.
Thermodynamic law from the entanglement entropy bound
Park, Chanyong
2015-01-01
From black hole thermodynamics, the Bekenstein bound has been proposed as a universal thermal entropy bound. It has been further generalized to an entanglement entropy bound which is valid even in a quantum system. In a quantumly entangled system, the non-negativity of the relative entropy leads to the entanglement entropy bound. When the entanglement entropy bound is saturated, a quantum system satisfies the thermodynamics-like law with an appropriately defined entanglement temperature. We show that the saturation of the entanglement entropy bound accounts for a universal feature of the entanglement temperature proportional to the inverse of the system size. In addition, we also find that a global quench unlike the excitation does not preserve the entanglement entropy bound.
Thermodynamic law from the entanglement entropy bound
Park, Chanyong
2016-04-01
From black hole thermodynamics, the Bekenstein bound has been proposed as a universal thermal entropy bound. It has been further generalized to an entanglement entropy bound which is valid even in a quantum system. In a quantumly entangled system, the non-negativity of the relative entropy leads to the entanglement entropy bound. When the entanglement entropy bound is saturated, a quantum system satisfies the thermodynamicslike law with an appropriately defined entanglement temperature. We show that the saturation of the entanglement entropy bound accounts for a universal feature of the entanglement temperature proportional to the inverse of the system size. In addition, we show that the deformed modular Hamiltonian under a global quench also satisfies the generalized entanglement entropy boundary after introducing a new quantity called the entanglement chemical potential.
How objective is black hole entropy?
Lau, Y K
1994-01-01
The objectivity of black hole entropy is discussed in the particular case of a Schwarzchild black hole. Using Jaynes' maximum entropy formalism and Euclidean path integral evaluation of partition function, it is argued that in the semiclassical limit when the fluctutation of metric is neglected, the black hole entropy of a Schwarzchild black hole is equal to the maximal information entropy of an observer whose sole knowledge of the black hole is its mass. Black hole entropy becomes a measure of number of its internal mass eigenstates in accordance with the Boltzmann principle only in the limit of negligible relative mass fluctutation. {}From the information theoretic perspective, the example of a Schwarzchild black hole seems to suggest that black hole entropy is no different from ordinary thermodynamic entropy. It is a property of the experimental data of a black hole, rather than being an intrinsic physical property of a black hole itself independent of any observer. However, it is still weakly objective in...
Reference frame for Product Configuration
Ladeby, Klaes Rohde; Oddsson, Gudmundur Valur
2011-01-01
on configuration systems in the shape of anecdotal reporting on the development of information systems that perhaps support the configuration task – perhaps not. Consequently, the definition of configuration has become ambiguous as different research groups defines configuration differently. This paper propose...... a reference frame for configuration that permits 1) a more precise understanding of a configuration system, 2) a understanding of how the configuration system relate to other systems, and 3) a definition of the basic concepts in configuration. The total configuration system, together with the definition...
Mosher Amides: Determining the Absolute Stereochemistry of Optically-Active Amines
Allen, Damian A.; Tomaso, Anthony E., Jr.; Priest, Owen P.; Hindson, David F.; Hurlburt, Jamie L.
2008-01-01
The use of chiral reagents for the derivatization of optically-active amines and alcohols for the purpose of determining their enantiomeric purity or absolute configuration is a tool used by many chemists. Among the techniques used, Mosher's amide and Mosher's ester analyses are among the most reliable and one of the most often used. Despite this,…
Mosher Amides: Determining the Absolute Stereochemistry of Optically-Active Amines
Allen, Damian A.; Tomaso, Anthony E., Jr.; Priest, Owen P.; Hindson, David F.; Hurlburt, Jamie L.
2008-01-01
The use of chiral reagents for the derivatization of optically-active amines and alcohols for the purpose of determining their enantiomeric purity or absolute configuration is a tool used by many chemists. Among the techniques used, Mosher's amide and Mosher's ester analyses are among the most reliable and one of the most often used. Despite this,…
Maximum-Entropy Inference with a Programmable Annealer.
Chancellor, Nicholas; Szoke, Szilard; Vinci, Walter; Aeppli, Gabriel; Warburton, Paul A
2016-03-03
Optimisation problems typically involve finding the ground state (i.e. the minimum energy configuration) of a cost function with respect to many variables. If the variables are corrupted by noise then this maximises the likelihood that the solution is correct. The maximum entropy solution on the other hand takes the form of a Boltzmann distribution over the ground and excited states of the cost function to correct for noise. Here we use a programmable annealer for the information decoding problem which we simulate as a random Ising model in a field. We show experimentally that finite temperature maximum entropy decoding can give slightly better bit-error-rates than the maximum likelihood approach, confirming that useful information can be extracted from the excited states of the annealer. Furthermore we introduce a bit-by-bit analytical method which is agnostic to the specific application and use it to show that the annealer samples from a highly Boltzmann-like distribution. Machines of this kind are therefore candidates for use in a variety of machine learning applications which exploit maximum entropy inference, including language processing and image recognition.
Functional determinants, index theorems, and exact quantum black hole entropy
Murthy, Sameer; Reys, Valentin
2015-12-01
The exact quantum entropy of BPS black holes can be evaluated using localization in supergravity. An important ingredient in this program, that has been lacking so far, is the one-loop effect arising from the quadratic fluctuations of the exact deformation (the QV operator). We compute the fluctuation determinant for vector multiplets and hyper multiplets around Q-invariant off-shell configurations in four-dimensional N=2 supergravity with AdS 2 × S 2 boundary conditions, using the Atiyah-Bott fixed-point index theorem and a subsequent zeta function regularization. Our results extend the large-charge on-shell entropy computations in the literature to a regime of finite charges. Based on our results, we present an exact formula for the quantum entropy of BPS black holes in N=2 supergravity. We explain cancellations concerning 1/8 -BPS black holes in N=8 supergravity that were observed in arXiv:1111.1161. We also make comments about the interpretation of a logarithmic term in the topological string partition function in the low energy supergravity theory.
Functional determinants, index theorems, and exact quantum black hole entropy
Murthy, Sameer
2015-01-01
The exact quantum entropy of BPS black holes can be evaluated using localization in supergravity. An important ingredient in this program, that has been lacking so far, is the one-loop effect arising from the quadratic fluctuations of the exact deformation (the $Q\\mathcal{V}$ operator). We compute the fluctuation determinant for vector multiplets and hyper multiplets around $Q$-invariant off-shell configurations in four-dimensional $\\mathcal{N}=2$ supergravity with $AdS_{2} \\times S^{2}$ boundary conditions, using the Atiyah-Bott fixed-point index theorem and a subsequent zeta function regularization. Our results extend the large-charge on-shell entropy computations in the literature to a regime of finite charges. Based on our results, we present an exact formula for the quantum entropy of BPS black holes in $\\mathcal{N}=2$ supergravity. We explain cancellations concerning $\\frac18$-BPS black holes in $\\mathcal{N}=8$ supergravity that were observed previously. We also make comments about the interpretation of...
Preserved entropy and fragile magnetism.
Canfield, Paul C; Bud'ko, Sergey L
2016-08-01
A large swath of quantum critical and strongly correlated electron systems can be associated with the phenomena of preserved entropy and fragile magnetism. In this overview we present our thoughts and plans for the discovery and development of lanthanide and transition metal based, strongly correlated systems that are revealed by suppressed, fragile magnetism, quantum criticality, or grow out of preserved entropy. We will present and discuss current examples such as YbBiPt, YbAgGe, YbFe2Zn20, PrAg2In, BaFe2As2, CaFe2As2, LaCrSb3 and LaCrGe3 as part of our motivation and to provide illustrative examples.
Entropy of Isolated Horizons revisited
Basu, Rudranil; Majumdar, Parthasarathi
2009-01-01
The decade-old formulation of the isolated horizon classically and within loop quantum gravity, and the extraction of the microcanonical entropy of such a horizon from this formulation, is reviewed, in view of recent renewed interest. There are two main approaches to this problem: one employs an SU(2) Chern-Simons theory describing the isolated horizon degrees of freedom, while the other uses a reduced U(1) Chern-Simons theory obtained from the SU(2) theory, with appropriate constraints imposed on the spectrum of boundary states `living' on the horizon. It is shown that both these ways lead to the same infinite series asymptotic in horizon area for the microcanonical entropy of an isolated horizon. The leading area term is followed by an unambiguous correction term logarithmic in area with a coefficient $-\\frac32$, with subleading corrections dropping off as inverse powers of the area.
Entropy: The Markov Ordering Approach
Alexander N. Gorban
2010-05-01
Full Text Available The focus of this article is on entropy and Markov processes. We study the properties of functionals which are invariant with respect to monotonic transformations and analyze two invariant “additivity” properties: (i existence of a monotonic transformation which makes the functional additive with respect to the joining of independent systems and (ii existence of a monotonic transformation which makes the functional additive with respect to the partitioning of the space of states. All Lyapunov functionals for Markov chains which have properties (i and (ii are derived. We describe the most general ordering of the distribution space, with respect to which all continuous-time Markov processes are monotonic (the Markov order. The solution differs significantly from the ordering given by the inequality of entropy growth. For inference, this approach results in a convex compact set of conditionally “most random” distributions.
Entanglement Entropy in Jammed CFTs
Mefford, Eric
2016-01-01
We construct solutions to the Einstein equations for asymptotically locally Anti-de Sitter spacetimes with four, five, and six dimensional Reissner-Nordstr\\"om boundary metrics. These spacetimes are gravitational duals to "jammed" CFTs on those backgrounds at infinite N and strong coupling. For these spacetimes, we calculate the boundary stress tensor as well as compute entanglement entropies for ball shaped regions as functions of the boundary black hole temperature $T_{BH}$. From this, we see how the CFT prevents heat flow from the black hole to the vacuum at spatial infinity. We also compute entanglement entropies for a three dimensional boundary black hole using the AdS C-metric. We compare our results to previous work done in similar spacetimes.
Entanglement Entropy of Two Spheres
Shiba, Noburo
2012-01-01
We study the entanglement entropy S_{AB} of a massless free scalar field on two spheres A and B whose radii are R_1 and R_2, respectively, and the distance between them is r. The state of the massless free scalar field is the vacuum state. We obtain the result that the mutual information S_{A;B}:=S_A+S_B-S_{AB} is independent of the ultraviolet cutoff and proportional to the product of the areas of the two spheres when r>>R_1,R_2, where S_A and S_B are the entanglement entropy on the inside region of A and B, respectively. We discuss possible connections of this result with the physics of black holes.
Dark energy from entanglement entropy
Capozziello, Salvatore
2013-01-01
We show that quantum decoherence, in the context of observational cosmology, can be connected to the cosmic dark energy. The decoherence signature could be characterized by the existence of quantum entanglement between cosmological eras. As a consequence, the Von Neumann entropy related to the entanglement process, can be compared to the thermodynamical entropy in a homogeneous and isotropic universe. The corresponding cosmological models are compatible with the current observational bounds being able to reproduce viable equations of state without introducing {\\it a priori} any cosmological constant. In doing so, we investigate two cases, corresponding to two suitable cosmic volumes, $V\\propto a^3$ and $V\\propto H^{-3}$, and find two models which fairly well approximate the current cosmic speed up. The existence of dark energy can be therefore reinterpreted as a quantum signature of entanglement, showing that the cosmological constant represents a limiting case of a more complicated model derived from the qua...
Mixing and electronic entropy contributions to thermal energy storage in low melting point alloys
Shamberger, Patrick J.; Mizuno, Yasushi; Talapatra, Anjana A.
2017-07-01
Melting of crystalline solids is associated with an increase in entropy due to an increase in configurational, rotational, and other degrees of freedom of a system. However, the magnitude of chemical mixing and electronic degrees of freedom, two significant contributions to the entropy of fusion, remain poorly constrained, even in simple 2 and 3 component systems. Here, we present experimentally measured entropies of fusion in the Sn-Pb-Bi and In-Sn-Bi ternary systems, and decouple mixing and electronic contributions. We demonstrate that electronic effects remain the dominant contribution to the entropy of fusion in multi-component post-transition metal and metalloid systems, and that excess entropy of mixing terms can be equal in magnitude to ideal mixing terms, causing regular solution approximations to be inadequate in the general case. Finally, we explore binary eutectic systems using mature thermodynamic databases, identifying eutectics containing at least one semiconducting intermetallic phase as promising candidates to exceed the entropy of fusion of monatomic endmembers, while simultaneously maintaining low melting points. These results have significant implications for engineering high-thermal conductivity metallic phase change materials to store thermal energy.
Holistic Entropy Reduction for Collaborative Filtering
Szwabe Andrzej
2014-07-01
Full Text Available We propose a collaborative filtering (CF method that uses behavioral data provided as propositions having the RDF-compliant form of (user X, likes, item Y triples. The method involves the application of a novel self-configuration technique for the generation of vector-space representations optimized from the information-theoretic perspective. The method, referred to as Holistic Probabilistic Modus Ponendo Ponens (HPMPP, enables reasoning about the likelihood of unknown facts. The proposed vector-space graph representation model is based on the probabilistic apparatus of quantum Information Retrieval and on the compatibility of all operators representing subjects, predicates, objects and facts. The dual graph-vector representation of the available propositional data enables the entropy-reducing transformation and supports the compositionality of mutually compatible representations. As shown in the experiments presented in the paper, the compositionality of the vector-space representations allows an HPMPP-based recommendation system to identify which of the unknown facts having the triple form (user X, likes, item Y are the most likely to be true in a way that is both effective and, in contrast to methods proposed so far, fully automatic.
Multicomponent and High Entropy Alloys
Brian Cantor
2014-08-01
Full Text Available This paper describes some underlying principles of multicomponent and high entropy alloys, and gives some examples of these materials. Different types of multicomponent alloy and different methods of accessing multicomponent phase space are discussed. The alloys were manufactured by conventional and high speed solidification techniques, and their macroscopic, microscopic and nanoscale structures were studied by optical, X-ray and electron microscope methods. They exhibit a variety of amorphous, quasicrystalline, dendritic and eutectic structures.
Multivariate Generalized Multiscale Entropy Analysis
Anne Humeau-Heurtier
2016-11-01
Full Text Available Multiscale entropy (MSE was introduced in the 2000s to quantify systems’ complexity. MSE relies on (i a coarse-graining procedure to derive a set of time series representing the system dynamics on different time scales; (ii the computation of the sample entropy for each coarse-grained time series. A refined composite MSE (rcMSE—based on the same steps as MSE—also exists. Compared to MSE, rcMSE increases the accuracy of entropy estimation and reduces the probability of inducing undefined entropy for short time series. The multivariate versions of MSE (MMSE and rcMSE (MrcMSE have also been introduced. In the coarse-graining step used in MSE, rcMSE, MMSE, and MrcMSE, the mean value is used to derive representations of the original data at different resolutions. A generalization of MSE was recently published, using the computation of different moments in the coarse-graining procedure. However, so far, this generalization only exists for univariate signals. We therefore herein propose an extension of this generalized MSE to multivariate data. The multivariate generalized algorithms of MMSE and MrcMSE presented herein (MGMSE and MGrcMSE, respectively are first analyzed through the processing of synthetic signals. We reveal that MGrcMSE shows better performance than MGMSE for short multivariate data. We then study the performance of MGrcMSE on two sets of short multivariate electroencephalograms (EEG available in the public domain. We report that MGrcMSE may show better performance than MrcMSE in distinguishing different types of multivariate EEG data. MGrcMSE could therefore supplement MMSE or MrcMSE in the processing of multivariate datasets.
Entropy estimation and Fibonacci numbers
Timofeev, Evgeniy A.; Kaltchenko, Alexei
2013-05-01
We introduce a new metric on a space of right-sided infinite sequences drawn from a finite alphabet. Emerging from a problem of entropy estimation of a discrete stationary ergodic process, the metric is important on its own part and exhibits some interesting properties. Notably, the number of distinct metric values for a set of sequences of length m is equal to Fm+3 - 1, where Fm is a Fibonacci number.
Entropy-based benchmarking methods
2012-01-01
We argue that benchmarking sign-volatile series should be based on the principle of movement and sign preservation, which states that a bench-marked series should reproduce the movement and signs in the original series. We show that the widely used variants of Denton (1971) method and the growth preservation method of Causey and Trager (1981) may violate this principle, while its requirements are explicitly taken into account in the pro-posed entropy-based benchmarking methods. Our illustrati...
Entropy Bounds in Spherical Space
Brevik, I; Odintsov, S D; Brevik, Iver; Milton, Kimball A.; Odintsov, Sergei D.
2002-01-01
Exact calculations are given for the Casimir energy for various fields in $R\\times S^3$ geometry. The Green's function method naturally gives a result in a form convenient in the high-temperature limit, while the statistical mechanical approach gives a form appropriate for low temperatures. The equivalence of these two representations is demonstrated. Some discrepancies with previous work are noted. In no case, even for ${\\cal N}=4$ SUSY, is the ratio of entropy to energy found to be bounded.
The Homological Nature of Entropy
Pierre Baudot
2015-05-01
Full Text Available We propose that entropy is a universal co-homological class in a theory associated to a family of observable quantities and a family of probability distributions. Three cases are presented: (1 classical probabilities and random variables; (2 quantum probabilities and observable operators; (3 dynamic probabilities and observation trees. This gives rise to a new kind of topology for information processes, that accounts for the main information functions: entropy, mutual-informations at all orders, and Kullback–Leibler divergence and generalizes them in several ways. The article is divided into two parts, that can be read independently. In the first part, the introduction, we provide an overview of the results, some open questions, future results and lines of research, and discuss briefly the application to complex data. In the second part we give the complete definitions and proofs of the theorems A, C and E in the introduction, which show why entropy is the first homological invariant of a structure of information in four contexts: static classical or quantum probability, dynamics of classical or quantum strategies of observation of a finite system.
Economics and Maximum Entropy Production
Lorenz, R. D.
2003-04-01
Price differentials, sales volume and profit can be seen as analogues of temperature difference, heat flow and work or entropy production in the climate system. One aspect in which economic systems exhibit more clarity than the climate is that the empirical and/or statistical mechanical tendency for systems to seek a maximum in production is very evident in economics, in that the profit motive is very clear. Noting the common link between 1/f noise, power laws and Self-Organized Criticality with Maximum Entropy Production, the power law fluctuations in security and commodity prices is not inconsistent with the analogy. There is an additional thermodynamic analogy, in that scarcity is valued. A commodity concentrated among a few traders is valued highly by the many who do not have it. The market therefore encourages via prices the spreading of those goods among a wider group, just as heat tends to diffuse, increasing entropy. I explore some empirical price-volume relationships of metals and meteorites in this context.
Linearity of Holographic Entanglement Entropy
Almheiri, Ahmed; Swingle, Brian
2016-01-01
We consider the question of whether the leading contribution to the entanglement entropy in holographic CFTs is truly given by the expectation value of a linear operator as is suggested by the Ryu-Takayanagi formula. We investigate this property by computing the entanglement entropy, via the replica trick, in states dual to superpositions of macroscopically distinct geometries and find it consistent with evaluating the expectation value of the area operator within such states. However, we find that this fails once the number of semi-classical states in the superposition grows exponentially in the central charge of the CFT. Moreover, in certain such scenarios we find that the choice of surface on which to evaluate the area operator depends on the density matrix of the entire CFT. This nonlinearity is enforced in the bulk via the homology prescription of Ryu-Takayanagi. We thus conclude that the homology constraint is not a linear property in the CFT. We also discuss the existence of entropy operators in genera...
Absolute Income, Relative Income, and Happiness
Ball, Richard; Chernova, Kateryna
2008-01-01
This paper uses data from the World Values Survey to investigate how an individual's self-reported happiness is related to (i) the level of her income in absolute terms, and (ii) the level of her income relative to other people in her country. The main findings are that (i) both absolute and relative income are positively and significantly…
Newton On Absolute Space A Commentary
Adewole, A I A
2001-01-01
Newton seems to have stated a quantitative relationship between the position of a body in relative space and the position of the body in absolute space in the first scholium of his Principia. We show that if this suspected relationship is assumed to hold, it will dispel many errors and misrepresentations that have befallen Newton's ideas on absolute space.
Investigating Absolute Value: A Real World Application
Kidd, Margaret; Pagni, David
2009-01-01
Making connections between various representations is important in mathematics. In this article, the authors discuss the numeric, algebraic, and graphical representations of sums of absolute values of linear functions. The initial explanations are accessible to all students who have experience graphing and who understand that absolute value simply…
Monolithically integrated absolute frequency comb laser system
Wanke, Michael C.
2016-07-12
Rather than down-convert optical frequencies, a QCL laser system directly generates a THz frequency comb in a compact monolithically integrated chip that can be locked to an absolute frequency without the need of a frequency-comb synthesizer. The monolithic, absolute frequency comb can provide a THz frequency reference and tool for high-resolution broad band spectroscopy.
Beltramello, O
In order to enable Technical Coordination to manage the detector configuration and to be aware of all changes in this configuration, a baseline of the envelopes has been created in April 2001. Fifteen system and multi-system envelope drawings have been approved and baselined. An EDMS file is associated with each approved envelope, which provides a list of the current known unsolved conflicts related to the envelope and a list of remaining drawing inconsistencies to be corrected. The envelope status with the associated drawings and EDMS file can be found on the web at this adress: http://atlasinfo.cern.ch/Atlas/TCOORD/Activities/Installation/Configuration/ Any modification in the baseline has to be requested via the Engineering Change Requests. The procedure can be found under: http://atlasinfo.cern.ch/Atlas/TCOORD/Activities/TcOffice/Quality/ECR/ TC will review all the systems envelopes in the near future and manage conflict resolution with the collaboration of the systems.
The LHCb configuration database
Abadie, L; Van Herwijnen, Eric; Jacobsson, R; Jost, B; Neufeld, N
2005-01-01
The aim of the LHCb configuration database is to store information about all the controllable devices of the detector. The experiment's control system (that uses PVSS ) will configure, start up and monitor the detector from the information in the configuration database. The database will contain devices with their properties, connectivity and hierarchy. The ability to store and rapidly retrieve huge amounts of data, and the navigability between devices are important requirements. We have collected use cases to ensure the completeness of the design. Using the entity relationship modelling technique we describe the use cases as classes with attributes and links. We designed the schema for the tables using relational diagrams. This methodology has been applied to the TFC (switches) and DAQ system. Other parts of the detector will follow later. The database has been implemented using Oracle to benefit from central CERN database support. The project also foresees the creation of tools to populate, maintain, and co...
Measurements of entropy-layer instabilities over cone-ogive-cylinders at Mach 6
Greenwood, Roger T.
Predicting the onset of boundary layer transition is critical in hypersonic flight. To improve transition prediction methods, it is necessary to understand the underlying instability mechanisms that cause transition. Entropy-layer instabilities are of particular interest in the design of blunt reentry vehicles and other blunt supersonic and hypersonic vehicles. Entropy-layer instabilities from outside the boundary layer may enter the boundary layer and have a significant effect on transition. There is little experimental data for entropy-layer instabilities. Experimental measurements of what appear to be entropy-layer instabilities have been made in the Boeing/AFOSR Mach-6 Quiet Tunnel (BAM6QT) using surface pressure transducers and hot-wire anemometry. A long cone-ogive-cylinder model with interchangeable cone-ogive noses was used to generate the shock curvature that resulted in an entropy layer conducive to instability growth. The nosetip angles of the cone-ogive range from 25 to 40 degrees, with a majority of the measurements taken with the sharp 30 to 35-degree nosetips. Surface measurements of the entropy-layer instabilities using the 30 to 35-degree configurations show disturbances between 15 and 50 kHz. As the nosetip angle increases, the frequency of the instability decreases slightly. Results also show that the instability magnitude as measured on the model surface increases with downstream distance, then decreases, before starting to increase again. The decrease is likely due to stabilization that occurs during the entropy-layer swallowing process. Off-surface measurements using hot wires have also been made for each of the cone-ogive-cylinder configurations. These measurements show the location, frequency, and relative magnitude of the entropy-layer instability. As the instability progresses downstream, it grows inside the entropy layer, then at a certain distance downstream, the instability approaches the model surface and enters the boundary layer