Kinetically and thermodynamically stable isomers of thorium chelates of polyaza polycarboxylic macrocycles

NASA Astrophysics Data System (ADS)

Jacques, Vincent; Desreux, Jean F.

1994-10-01

The solution conformation of the thorium(IV) complexes of two polyaza polycarboxylic macrocycles, DOTA and HEHA (1,4,7,10-tetraazacyclododecane-N, N', N(double prime), N(triple prime)-tetraacetic acid and 1,4,7,10,13,16-hexaazacyclooctadecane-N, N', N(double prime), N(triple prime), N(double prime)(double prime), N(double prime)(triple prime)-hexaacetic acid), was investigated by one- and two-dimensional nuclear magnetic resonance spectroscopy. ThHEHA(2+) forms a kinetically stable topomer of C2 symmetry and a thermodynamically stable topomer of S6 symmetry. Both complexes are assigned an icosahedral geometry. The activation energy for the intermolecular exchange is very high (214 kJ/mol). The behavior of ThHEHA(2+) contrasts with the properties of the other Th(IV) chelates that are known to be fluxional.

Thermodynamic, electronic, and magnetic properties of intrinsic vacancy defects in antiperovskite Ca3SnO

NASA Astrophysics Data System (ADS)

Batool, Javaria; Alay-e-Abbas, Syed Muhammad; Amin, Nasir

2018-04-01

The density functional theory based total energy calculations are performed to examine the effect of charge neutral and fully charged intrinsic vacancy defects on the thermodynamic, electronic, and magnetic properties of Ca3SnO antiperovskite. The chemical stability of Ca3SnO is evaluated with respect to binary compounds CaO, CaSn, and Ca2Sn, and the limits of atomic chemical potentials of Ca, Sn, and O atoms for stable synthesis of Ca3SnO are determined within the generalized gradient approximation parametrization scheme. The electronic properties of the pristine and the non-stoichiometric forms of this compound have been explored and the influence of isolated intrinsic vacancy defects (Ca, Sn, and O) on the structural, bonding, and electronic properties of non-stoichiometric Ca3SnO are analyzed. We also predict the possibility of achieving stable ferromagnetism in non-stoichiometric Ca3SnO by means of charge neutral tin vacancies. From the calculated total energies and the valid ranges of atomic chemical potentials, the formation energetics of intrinsic vacancy defects in Ca3SnO are evaluated for various growth conditions. Our results indicate that the fully charged calcium vacancies are thermodynamically stable under the permissible Sn-rich condition of stable synthesis of Ca3SnO, while tin and oxygen vacancies are found to be stable under the extreme Ca-rich condition.

Method of producing highly oxidized superconductors containing barium, copper, and a third metal

DOEpatents

Morris, D.E.

1996-02-20

Novel superconducting materials in the form of compounds, structures or phases are formed by performing otherwise known syntheses in a highly oxidizing atmosphere rather than that created by molecular oxygen at atmospheric pressure or below. This leads to the successful synthesis of novel superconducting compounds which are thermodynamically stable at the conditions under which they are formed. 16 figs.

Thermodynamics and kinetics of vesicles formation processes.

PubMed

Guida, Vincenzo

2010-12-15

Vesicles are hollow aggregates, composed of bilayers of amphiphilic molecules, dispersed into and filled with a liquid solvent. These aggregates can be formed either as equilibrium or as out of equilibrium meta-stable structures and they exhibit a rich variety of different morphologies. The surprising richness of structures, the vast range of industrial applications and the presence of vesicles in a number of biological systems have attracted the interest of numerous researchers and scientists. In this article, we review both the thermodynamics and the kinetics aspects of the phenomena of formation of vesicles. We start presenting the thermodynamics of bilayer membranes formation and deformation, with the aim of deriving the conditions for the existence of equilibrium vesicles. Specifically, we use the results from continuum thermodynamics to discuss the possibility of formation of stable equilibrium vesicles, from both mixed amphiphiles and single component systems. We also link the bilayer membrane properties to the molecular structure of the starting amphiphiles. In the second part of this article, we focus on the dynamics and kinetics of vesiculation. We review the process of vesicles formation both from planar lamellar phase under shear and from isotropic micelles. In order to clarify the physical mechanisms of vesicles formation, we continuously draw a parallel between emulsification and vesiculation processes. Specifically, we compare the experimental results, the driving forces and the relative scaling laws identified for the two processes. Describing the dynamics of vesicles formation, we also discuss why non equilibrium vesicles can be formed by kinetics control and why they are meta-stable. Understanding how to control the properties, the stability and the formation process of vesicles is of fundamental importance for a vast number of industrial applications. Copyright © 2009. Published by Elsevier B.V.

Exploring ultrastability in nanostructured glassy polymer films by fast-scanning calorimetry.

NASA Astrophysics Data System (ADS)

Chowdhury, Mithun; Wang, Yucheng; Jeong, Hyuncheol; Cangialosi, Daniele; Priestley, Rodney

A decade ago ultra-stable small molecule glass formers were discovered. Since then a significant amount of research has been devoted to traverse down the energy landscape of such glass formers via physical vapor deposition (PVD). Matrix assisted pulsed laser evaporation (MAPLE) has the known ability to produce vapour deposited nanostructured polymer glass with exceptional kinetic stability. We explored the role of deposition temperature/ growth rate on thermodynamic and kinetic stabilities of poly (methyl methacrylate) (PMMA) films, deposited over a fast-scanning calorimetry sensor. We found in general any MAPLE deposited glass is kinetically more stable than bulk polymer and its spin-coated film. Moreover slow growth rate and optimum temperature during MAPLE deposition can additionally lead to thermodynamically stable (low-energy) glass. The role of interfaces formed through dramatic nanostructuring and packing of nanoglobules (removal of void space) may have additional role on such ultrastability. NSF-MRSEC through PCCM (Grant: DMR-1420541).

Interfacial engineering of solution-processed Ni nanochain-SiO{sub x} (x < 2) cermets towards thermodynamically stable, anti-oxidation solar selective absorbers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yu, Xiaobai; Wang, Xiaoxin; Liu, Jifeng, E-mail: Jifeng.Liu@dartmouth.edu

Cermet solar thermal selective absorber coatings are an important component of high-efficiency concentrated solar power (CSP) receivers. The oxidation of the metal nanoparticles in cermet solar absorbers is a great challenge for vacuum-free operation. Recently, we have demonstrated that oxidation is kinetically retarded in solution processed, high-optical-performance Ni nanochain-SiO{sub x} cermet system compared to conventional Ni-Al{sub 2}O{sub 3} system when annealed in air at 450–600 °C for several hours. However, for long-term, high-temperature applications in CSP systems, thermodynamically stable antioxidation behavior is highly desirable, which requires new mechanisms beyond kinetically reducing the oxidation rate. Towards this goal, in this paper, wemore » demonstrate that pre-operation annealing of Ni nanochain-SiO{sub x} cermets at 900 °C in N{sub 2} forms the thermodynamically stable orthorhombic phase of NiSi at the Ni/SiO{sub x} interfaces, leading to self-terminated oxidation at 550 °C in air due to this interfacial engineering. In contrast, pre-operation annealing at a lower temperature of 750 °C in N{sub 2} (as conducted in our previous work) cannot achieve interfacial NiSi formation directly, and further annealing in air at 450–600 °C for >4 h only leads to the formation of the less stable (metastable) hexagonal phase of NiSi. Therefore, the high-temperature pre-operation annealing is critical to form the desirable orthorhombic phase of NiSi at Ni/SiO{sub x} interfaces towards thermodynamically stable antioxidation behavior. Remarkably, with this improved interfacial engineering, the oxidation of 80-nm-diameter Ni nanochain-SiO{sub x} saturates after annealing at 550 °C in air for 12 h. Additional annealing at 550 °C in air for as long as 20 h (i.e., 32 h air annealing at >550 °C in total) has almost no further impact on the structural or optical properties of the coatings, the latter being very sensitive to any interfacial changes due to the localized surface plasmon resonances of the metal nanostructures. This phenomenon holds true for Ni nanoparticle diameter down to 40 nm in Ni-SiO{sub x} system, where the optical response remains stable for 53 h at 550 °C in air. The oxidation vs. time curve also shows saturation behavior deviating from the kinetic Deal-Grove oxidation model. These results strongly suggest a promising approach to thermodynamically stable, anti-oxidation Ni/SiO{sub x} cermet absorbers via interfacial engineering.« less

Alloy nanoparticle synthesis using ionizing radiation

DOEpatents

Nenoff, Tina M [Sandia Park, NM; Powers, Dana A [Albuquerque, NM; Zhang, Zhenyuan [Durham, NC

2011-08-16

A method of forming stable nanoparticles comprising substantially uniform alloys of metals. A high dose of ionizing radiation is used to generate high concentrations of solvated electrons and optionally radical reducing species that rapidly reduce a mixture of metal ion source species to form alloy nanoparticles. The method can make uniform alloy nanoparticles from normally immiscible metals by overcoming the thermodynamic limitations that would preferentially produce core-shell nanoparticles.

Encapsulation of testosterone by chitosan nanoparticles.

PubMed

Chanphai, P; Tajmir-Riahi, H A

2017-05-01

The loading of testosterone by chitosan nanoparticles was investigated, using multiple spectroscopic methods, thermodynamic analysis, TEM images and modeling. Thermodynamic parameters showed testosterone-chitosan bindings occur mainly via H-bonding and van der Waals contacts. As polymer size increased more stable steroid-chitosan conjugates formed and hydrophobic contact was also observed. The loading efficacy of testosterone-nanocarrier was 40-55% and increased as chitosan size increased. Testosterone encapsulation markedly alters chitosan morphology. Chitosan nanoparticles are capable of transporting testosterone in vitro. Copyright © 2017 Elsevier B.V. All rights reserved.

Synthesis of Xenon and Iron-Nickel Intermetallic Compounds at Earth's Core Thermodynamic Conditions

NASA Astrophysics Data System (ADS)

Stavrou, Elissaios; Yao, Yansun; Goncharov, Alexander F.; Lobanov, Sergey S.; Zaug, Joseph M.; Liu, Hanyu; Greenberg, Eran; Prakapenka, Vitali B.

2018-03-01

Using in situ synchrotron x-ray diffraction and Raman spectroscopy in concert with first principles calculations we demonstrate the synthesis of stable Xe (Fe ,Fe /Ni )3 and XeNi3 compounds at thermodynamic conditions representative of Earth's core. Surprisingly, in the case of both the Xe-Fe and Xe-Ni systems Fe and Ni become highly electronegative and can act as oxidants. The results indicate the changing chemical properties of elements under extreme conditions by documenting that electropositive at ambient pressure elements could gain electrons and form anions.

Pattern formation, logistics, and maximum path probability

NASA Astrophysics Data System (ADS)

Kirkaldy, J. S.

1985-05-01

The concept of pattern formation, which to current researchers is a synonym for self-organization, carries the connotation of deductive logic together with the process of spontaneous inference. Defining a pattern as an equivalence relation on a set of thermodynamic objects, we establish that a large class of irreversible pattern-forming systems, evolving along idealized quasisteady paths, approaches the stable steady state as a mapping upon the formal deductive imperatives of a propositional function calculus. In the preamble the classical reversible thermodynamics of composite systems is analyzed as an externally manipulated system of space partitioning and classification based on ideal enclosures and diaphragms. The diaphragms have discrete classification capabilities which are designated in relation to conserved quantities by descriptors such as impervious, diathermal, and adiabatic. Differentiability in the continuum thermodynamic calculus is invoked as equivalent to analyticity and consistency in the underlying class or sentential calculus. The seat of inference, however, rests with the thermodynamicist. In the transition to an irreversible pattern-forming system the defined nature of the composite reservoirs remains, but a given diaphragm is replaced by a pattern-forming system which by its nature is a spontaneously evolving volume partitioner and classifier of invariants. The seat of volition or inference for the classification system is thus transferred from the experimenter or theoretician to the diaphragm, and with it the full deductive facility. The equivalence relations or partitions associated with the emerging patterns may thus be associated with theorems of the natural pattern-forming calculus. The entropy function, together with its derivatives, is the vehicle which relates the logistics of reservoirs and diaphragms to the analog logistics of the continuum. Maximum path probability or second-order differentiability of the entropy in isolation are sufficiently strong interpretations of the second law of thermodynamics to define the approach to and the nature of patterned stable steady states. For many pattern-forming systems these principles define quantifiable stable states as maxima or minima (or both) in the dissipation. An elementary statistical-mechanical proof is offered. To turn the argument full circle, the transformations of the partitions and classes which are predicated upon such minimax entropic paths can through digital modeling be directly identified with the syntactic and inferential elements of deductive logic. It follows therefore that all self-organizing or pattern-forming systems which possess stable steady states approach these states according to the imperatives of formal logic, the optimum pattern with its rich endowment of equivalence relations representing the central theorem of the associated calculus. Logic is thus ``the stuff of the universe,'' and biological evolution with its culmination in the human brain is the most significant example of all the irreversible pattern-forming processes. We thus conclude with a few remarks on the relevance of the contribution to the theory of evolution and to research on artificial intelligence.

Solution-Phase Dynamic Assembly of Permanently Interlocked Aryleneethynylene Cages through Alkyne Metathesis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Qi; Yu, Chao; Long, Hai

2015-05-08

Highly stable permanently interlocked aryleneethynylene molecular cages were synthesized from simple triyne monomers using dynamic alkyne metathesis. The interlocked complexes are predominantly formed in the reaction solution in the absence of any recognition motif and were isolated in a pure form using column chromatography. This study is the first example of the thermodynamically controlled solution-phase synthesis of interlocked organic cages with high stability.

Methods of studying aging and stabilization of spray-congealed solid dispersions with carnauba wax. 1. Microcalorimetric investigation.

PubMed

Emås, M; Nyqvist, H

2000-03-20

Rapidly cooled materials are often unstable as a result of changes in their physical properties due to imperfect crystallization. In the process of spray-congealing, melted material is atomized into droplets which very quickly solidify. This increases the possibility of the material crystallizing in different metastable forms. In this study it is shown that isothermal microcalorimetry can be used to observe the change in the thermodynamic state of spray-congealed carnauba wax during storage. In order to accelerate the thermodynamic change in the spray-congealed wax, three annealing procedures have been developed and compared using isothermal microcalorimetry. By means of annealing, a spray-congealed product closer to a thermodynamically stable state has been achieved.

Interactions of hydrogen with amorphous hafnium oxide

NASA Astrophysics Data System (ADS)

Kaviani, Moloud; Afanas'ev, Valeri V.; Shluger, Alexander L.

2017-02-01

We used density functional theory (DFT) calculations to study the interaction of hydrogen with amorphous hafnia (a -HfO2 ) using a hybrid exchange-correlation functional. Injection of atomic hydrogen, its diffusion towards electrodes, and ionization can be seen as key processes underlying charge instability of high-permittivity amorphous hafnia layers in many applications. Hydrogen in many wide band gap crystalline oxides exhibits negative-U behavior (+1 and -1 charged states are thermodynamically more stable than the neutral state) . Our results show that in a -HfO2 hydrogen is also negative-U, with charged states being the most thermodynamically stable at all Fermi level positions. However, metastable atomic hydrogen can share an electron with intrinsic electron trapping precursor sites [Phys. Rev. B 94, 020103 (2016)., 10.1103/PhysRevB.94.020103] forming a [etr -+O -H ] center, which is lower in energy on average by about 0.2 eV. These electron trapping sites can affect both the dynamics and thermodynamics of the interaction of hydrogen with a -HfO2 and the electrical behavior of amorphous hafnia films in CMOS devices.

Molecular dynamics simulation of nanobubble nucleation on rough surfaces

NASA Astrophysics Data System (ADS)

Liu, Yawei; Zhang, Xianren

2017-04-01

Here, we study how nanobubbles nucleate on rough hydrophobic surfaces, using long-time standard simulations to directly observe the kinetic pathways and using constrained simulations combined with the thermodynamic integration approach to quantitatively evaluate the corresponding free energy changes. Both methods demonstrate that a two-step nucleation route involving the formation of an intermediate state is thermodynamically favorable: at first, the system transforms from the Wenzel state (liquid being in full contact with the solid surface) to the Cassie state (liquid being in contact with the peaks of the rough surface) after gas cavities occur in the grooves (i.e., the Wenzel-to-Cassie transition); then, the gas cavities coalesce and form a stable surface nanobubble with pinned contact lines (i.e., the Cassie-to-nanobubble transition). Additionally, the free energy barriers for the two transitions show opposing dependencies on the degree of surface roughness, indicating that the surfaces with moderate roughness are favorable for forming stable surface nanobubbles. Moreover, the simulation results also reveal the coexistence and transition between the Wenzel, Cassie, and nanobubble states on rough surfaces.

Thermodynamic Investigation of Carbamazepine-Saccharin Co-Crystal Polymorphs.

PubMed

Pagire, Sudhir K; Jadav, Niten; Vangala, Venu R; Whiteside, Benjamin; Paradkar, Anant

2017-08-01

Polymorphism in active pharmaceutical ingredients can be regarded as critical for the potential that crystal form can have on the quality, efficacy, and safety of the final drug product. The current contribution aims to characterize thermodynamic interrelationship of a dimorphic co-crystal, FI and FII, involving carbamazepine (CBZ) and saccharin (SAC) molecules. Supramolecular synthesis of CBZ-SAC FI and FII has been performed using thermokinetic methods and systematically characterized by differential scanning calorimetry, powder X-ray diffraction, solubility, and slurry measurements. According to the heat of fusion rule by Burger and Ramberger, FI (ΔH fus  = 121.1 J/g; melting point, 172.5°C) and FII (ΔH fus  = 110.3 J/g; melting point, 164.7°C) are monotropically related. The solubility and van't Hoff plot results suggest FI stable and FII metastable forms. This study reveals that CBZ-SAC co-crystal phases, FI or FII, could be stable to heat-induced stresses; however, FII converts to FI during solution-mediated transformation. Copyright © 2017 The Authors. Published by Elsevier Inc. All rights reserved.

Synthesis of Xenon and Iron-Nickel Intermetallic Compounds at Earth’s Core Thermodynamic Conditions

DOE PAGES

Stavrou, Elissaios; Yao, Yansun; Goncharov, Alexander F.; ...

2018-02-28

In this study, using in situ synchrotron x-ray diffraction and Raman spectroscopy in concert with first principles calculations we demonstrate the synthesis of stable Xe(Fe ,Fe/Ni) 3 and XeNi 3 compounds at thermodynamic conditions representative of Earth’s core. Surprisingly, in the case of both the Xe-Fe and Xe-Ni systems Fe and Ni become highly electronegative and can act as oxidants. In conclusion, the results indicate the changing chemical properties of elements under extreme conditions by documenting that electropositive at ambient pressure elements could gain electrons and form anions.

Variational energy principle for compressible, baroclinic flow. 2: Free-energy form of Hamilton's principle

NASA Technical Reports Server (NTRS)

Schmid, L. A.

1977-01-01

The first and second variations are calculated for the irreducible form of Hamilton's Principle that involves the minimum number of dependent variables necessary to describe the kinetmatics and thermodynamics of inviscid, compressible, baroclinic flow in a specified gravitational field. The form of the second variation shows that, in the neighborhood of a stationary point that corresponds to physically stable flow, the action integral is a complex saddle surface in parameter space. There exists a form of Hamilton's Principle for which a direct solution of a flow problem is possible. This second form is related to the first by a Friedrichs transformation of the thermodynamic variables. This introduces an extra dependent variable, but the first and second variations are shown to have direct physical significance, namely they are equal to the free energy of fluctuations about the equilibrium flow that satisfies the equations of motion. If this equilibrium flow is physically stable, and if a very weak second order integral constraint on the correlation between the fluctuations of otherwise independent variables is satisfied, then the second variation of the action integral for this free energy form of Hamilton's Principle is positive-definite, so the action integral is a minimum, and can serve as the basis for a direct trail and error solution. The second order integral constraint states that the unavailable energy must be maximum at equilibrium, i.e. the fluctuations must be so correlated as to produce a second order decrease in the total unavailable energy.

Biophysics of Artificially Expanded Genetic Information Systems. Thermodynamics of DNA Duplexes Containing Matches and Mismatches Involving 2-Amino-3-nitropyridin-6-one (Z) and Imidazo[1,2-a]-1,3,5-triazin-4(8H)one (P).

PubMed

Wang, Xiaoyu; Hoshika, Shuichi; Peterson, Raymond J; Kim, Myong-Jung; Benner, Steven A; Kahn, Jason D

2017-05-19

Synthetic nucleobases presenting non-Watson-Crick arrangements of hydrogen bond donor and acceptor groups can form additional nucleotide pairs that stabilize duplex DNA independent of the standard A:T and G:C pairs. The pair between 2-amino-3-nitropyridin-6-one 2'-deoxyriboside (presenting a {donor-donor-acceptor} hydrogen bonding pattern on the Watson-Crick face of the small component, trivially designated Z) and imidazo[1,2-a]-1,3,5-triazin-4(8H)one 2'-deoxyriboside (presenting an {acceptor-acceptor-donor} hydrogen bonding pattern on the large component, trivially designated P) is one of these extra pairs for which a substantial amount of molecular biology has been developed. Here, we report the results of UV absorbance melting measurements and determine the energetics of binding of DNA strands containing Z and P to give short duplexes containing Z:P pairs as well as various mismatches comprising Z and P. All measurements were done at 1 M NaCl in buffer (10 mM Na cacodylate, 0.5 mM EDTA, pH 7.0). Thermodynamic parameters (ΔH°, ΔS°, and ΔG° 37 ) for oligonucleotide hybridization were extracted. Consistent with the Watson-Crick model that considers both geometric and hydrogen bonding complementarity, the Z:P pair was found to contribute more to duplex stability than any mismatches involving either nonstandard nucleotide. Further, the Z:P pair is more stable than a C:G pair. The Z:G pair was found to be the most stable mismatch, forming either a deprotonated mismatched pair or a wobble base pair analogous to the stable T:G mismatch. The C:P pair is less stable, perhaps analogous to the wobble pair observed for C:O 6 -methyl-G, in which the pyrimidine is displaced into the minor groove. The Z:A and T:P mismatches are much less stable. Parameters for predicting the thermodynamics of oligonucleotides containing Z and P bases are provided. This represents the first case where this has been done for a synthetic genetic system.

Solid state consolidation nanocrystalline copper-tungsten using cold spray

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hall, Aaron Christopher; Sarobol, Pylin; Argibay, Nicolas

It is well known that nanostructured metals can exhibit significantly improved properties compared to metals with conventional grain size. Unfortunately, nanocrystalline metals typically are not thermodynamically stable and exhibit rapid grain growth at moderate temperatures. This severely limits their processing and use, making them impractical for most engineering applications. Recent work has shown that a number of thermodynamically stable nanocrystalline metal alloys exist. These alloys have been prepared as powders using severe plastic deformation (e.g. ball milling) processes. Consolidation of these powders without compromise of their nanocrystalline microstructure is a critical step to enabling their use as engineering materials. Wemore » demonstrate solid-state consolidation of ball milled copper-tantalum nanocrystalline metal powder using cold spray. Unfortunately, the nanocrystalline copper-tantalum powder that was consolidated did not contain the thermodynamically stable copper-tantalum nanostructure. Nevertheless, this does this demonstrates a pathway to preparation of bulk thermodynamically stable nanocrystalline copper-tantalum. Furthermore, it demonstrates a pathway to additive manufacturing (3D printing) of nanocrystalline copper-tantalum. Additive manufacturing of thermodynamically stable nanocrystalline metals is attractive because it enables maximum flexibility and efficiency in the use of these unique materials.« less

High Entropy Alloys: Criteria for Stable Structure

NASA Astrophysics Data System (ADS)

Tripathy, Snehashish; Gupta, Gaurav; Chowdhury, Sandip Ghosh

2018-01-01

An effort has been made to reassess the phase predicting capability of various thermodynamic and topological parameters across a wide range of HEA systems. These parameters are valence electron concentration, atomic mismatch ( δ), electronegativity difference (Δ χ), mixing entropy (Δ S mix), entropy of fusion (Δ S f), and mismatch entropy ( S σ ). In continuation of that, two new parameters (a) Modified Darken-Gurry parameter ( A = Sσ * χ) and (b) Modified Mismatch Entropy parameter ( B = δ* Sσ) have been designed to predict the stable crystal structure that would form in the HEA systems considered for assessment.

Thermodynamic assessment of the rhodium-ruthenium-oxygen (Rh-Ru-O) system

NASA Astrophysics Data System (ADS)

Gossé, S.; Bordier, S.; Guéneau, C.; Brackx, E.; Domenger, R.; Rogez, J.

2018-03-01

Ruthenium (Ru) and rhodium (Rh) are abundant platinum-group metals formed during burn-up of nuclear fuels. Under normal operating conditions, Rh and Ru accumulate and predominantly form metallic precipitates with other fission products like Mo, Pd and Tc. In the framework of vitrification of high-level nuclear waste, these fission products are poorly soluble in molten glasses. They precipitate as metallic particles and oxide phases. Moreover, these Ru and Rh rich phases strongly depend on temperature and the oxygen fugacity of the glass melt. In case of severe accidental conditions with air ingress, oxidation of the Ru and Rh is possible. At low temperatures (T < 1422 K for rhodium sesquioxide and T < 1815 K for ruthenium dioxide), the formed oxides are relatively stable. On the other hand, at high temperatures (T > 1422 K for rhodium sesquioxide and T > 1815 K for ruthenium dioxide), they may decompose into (Rh)-FCC or (Ru)-HCP metallic phases and radiotoxic volatile gaseous species. A thermodynamic assessment of the Rh-Ru-O system will enable the prediction of: (1) the metallic and oxide phases that form during the vitrification of high-level nuclear wastes and (2) the release of volatile gaseous species during a severe accident. The Calphad method developed herein employs a thermodynamic approach in the investigation of the thermochemistry of rhodium and ruthenium at high temperatures. Current literature on the thermodynamic properties and phase diagram data enables preliminary thermodynamic assessments of the Rh-O and Ru-O systems. Additionally, select compositions in the ternary Rh-Ru-O system underwent experimental tests to complement data found in literature and to establish the phase equilibria in the ternary system.

The loss of a hydrogen bond: Thermodynamic contributions of a non-standard nucleotide

PubMed Central

Jolley, Elizabeth A.

2017-01-01

Abstract Non-standard nucleotides are ubiquitous in RNA. Thermodynamic studies with RNA duplexes containing non-standard nucleotides, whether incorporated naturally or chemically, can provide insight into the stability of Watson–Crick pairs and the role of specific functional groups in stabilizing a Watson–Crick pair. For example, an A-U, inosine•U and pseudouridine•A pair each form two hydrogen bonds. However, an RNA duplex containing a central I•U pair or central Ψ•A pair is 2.4 kcal/mol less stable or 1.7 kcal/mol more stable, respectively, than the corresponding duplex containing an A-U pair. In the non-standard nucleotide purine, hydrogen replaces the exocyclic amino group of A. This replacement results in a P•U pair containing only one hydrogen bond. Optical melting studies were performed with RNA duplexes containing P•U pairs adjacent to different nearest neighbors. The resulting thermodynamic parameters were compared to RNA duplexes containing A-U pairs in order to determine the contribution of the hydrogen bond involving the exocyclic amino group. Results indicate a loss of 1.78 kcal/mol, on average, when an internal P•U replaces A-U in an RNA duplex. This value is compared to the thermodynamics of a hydrogen bond determined by similar methods. Nearest neighbor parameters were derived for use in free energy and secondary structure prediction software. PMID:28180321

Membrane extraction with thermodynamically unstable diphosphonic acid derivatives

DOEpatents

Horwitz, Earl Philip; Gatrone, Ralph Carl; Nash, Kenneth LaVerne

1997-01-01

Thermodynamically-unstable complexing agents which are diphosphonic acids and diphosphonic acid derivatives (or sulphur containing analogs), like carboxyhydroxymethanediphosphonic acid and vinylidene-1,1-diphosphonic acid, are capable of complexing with metal ions, and especially metal ions in the II, III, IV, V and VI oxidation states, to form stable, water-soluble metal ion complexes in moderately alkaline to highly-acidic media. However, the complexing agents can be decomposed, under mild conditions, into non-organic compounds which, for many purposes are environmentally-nondamaging compounds thereby degrading the complex and releasing the metal ion for disposal or recovery. Uses for such complexing agents as well as methods for their manufacture are also described.

Thermodynamics reveal that helix four in the NLS of NF-kappaB p65 anchors IkappaBalpha, forming a very stable complex.

PubMed

Bergqvist, Simon; Croy, Carrie H; Kjaergaard, Magnus; Huxford, Tom; Ghosh, Gourisankar; Komives, Elizabeth A

2006-07-07

IkappaBalpha is an ankyrin repeat protein that inhibits NF-kappaB transcriptional activity by sequestering NF-kappaB outside of the nucleus in resting cells. We have characterized the binding thermodynamics and kinetics of the IkappaBalpha ankyrin repeat domain to NF-kappaB(p50/p65) using surface plasmon resonance (SPR) and isothermal titration calorimetry (ITC). SPR data showed that the IkappaBalpha and NF-kappaB associate rapidly but dissociate very slowly, leading to an extremely stable complex with a K(D,obs) of approximately 40 pM at 37 degrees C. As reported previously, the amino-terminal DNA-binding domain of p65 contributes little to the overall binding affinity. Conversely, helix four of p65, which forms part of the nuclear localization sequence, was essential for high-affinity binding. This was surprising, given the small size of the binding interface formed by this part of p65. The NF-kappaB(p50/p65) heterodimer and p65 homodimer bound IkappaBalpha with almost indistinguishable thermodynamics, except that the NF-kappaB p65 homodimer was characterized by a more favorable DeltaH(obs) relative to the NF-kappaB(p50/p65) heterodimer. Both interactions were characterized by a large negative heat capacity change (DeltaC(P,obs)), approximately half of which was contributed by the p65 helix four that was necessary for tight binding. This could not be accounted for readily by the small loss of buried non-polar surface area and we hypothesize that the observed effect is due to additional folding of some regions of the complex.

Mechanistic aspects of the tyrosinase oxidation of hydroquinone.

PubMed

Ramsden, Christopher A; Riley, Patrick A

2014-06-01

Contradictory reports on the behaviour of hydroquinone as a tyrosinase substrate are reconciled in terms of the ability of the initially formed ortho-quinone to tautomerise to the thermodynamically more stable para-quinone isomer. Oxidation of phenols by native tyrosinase requires activation by in situ formation of a catechol formed via an enzyme generated ortho-quinone. In the special case of hydroquinone, catechol formation is precluded by rapid tautomerisation of the ortho-quinone precursor to catechol formation. Copyright © 2014 Elsevier Ltd. All rights reserved.

On the upper bound of the thermodynamic stability of fullerenes from small to giant

NASA Astrophysics Data System (ADS)

Pankratyev, Evgeniy Yu; Khatymov, Rustem V.; Sabirov, Denis Sh; Yuldashev, Arthur V.

2018-07-01

From the large variety of C20sbnd C720 fullerenes, the energetically most stable isomers were chosen and studied within the PBE/3ζ quantum-chemical approximation. A phenomenological model of the dependence of the standard enthalpy of formation and entropy of the selected isomers on the number of the carbon atoms is developed. From the analysis of the constants of the phenomenological model, it follows that the C60, C70, C180, and C1500 molecules hold a prominent position among the hypothetical and/or experimentally discovered fullerenes. For the selected energy-stable isomers, the values of the singlet-triplet splitting were calculated. The ground state of the C260sbnd C3, C320sbnd D3d and C500sbnd D3d molecules were found to be of triplet multiplicity that may indicate their low kinetic stability and/or possibility of existence in the derivatized forms. In view of the lack of relevant experimental thermodynamic data on fullerenes, the obtained in this work approximation dependences, expressed in a simple analytical form, may provide useful tool for fast assessing the energetic characteristics of fullerenes, as well as for prediction of those undiscovered yet.

Sulfamerazine: Understanding the Influence of Slip Planes in the Polymorphic Phase Transformation through X-Ray Crystallographic Studies and ab Initio Lattice Dynamics.

PubMed

Pallipurath, Anuradha R; Skelton, Jonathan M; Warren, Mark R; Kamali, Naghmeh; McArdle, Patrick; Erxleben, Andrea

2015-10-05

Understanding the polymorphism exhibited by organic active-pharmaceutical ingredients (APIs), in particular the relationships between crystal structure and the thermodynamics of polymorph stability, is vital for the production of more stable drugs and better therapeutics, and for the economics of the pharmaceutical industry in general. In this article, we report a detailed study of the structure-property relationships among the polymorphs of the model API, Sulfamerazine. Detailed experimental characterization using synchrotron radiation is complemented by computational modeling of the lattice dynamics and mechanical properties, in order to study the origin of differences in millability and to investigate the thermodynamics of the phase equilibria. Good agreement is observed between the simulated phonon spectra and mid-infrared and Raman spectra. The presence of slip planes, which are found to give rise to low-frequency lattice vibrations, explains the higher millability of Form I compared to Form II. Energy/volume curves for the three polymorphs, together with the temperature dependence of the thermodynamic free energy computed from the phonon frequencies, explains why Form II converts to Form I at high temperature, whereas Form III is a rare polymorph that is difficult to isolate. The combined experimental and theoretical approach employed here should be generally applicable to the study of other systems that exhibit polymorphism.

Thermodynamic study of dihydrogen phosphate dimerisation and complexation with novel urea- and thiourea-based receptors.

PubMed

Bregović, Nikola; Cindro, Nikola; Frkanec, Leo; Užarević, Krunoslav; Tomišić, Vladislav

2014-11-24

Complexation of dihydrogen phosphate by novel thiourea and urea receptors in acetonitrile and dimethyl sulfoxide was studied in detail by an integrated approach by using several methods (isothermal titration calorimetry, ESI-MS, and (1)H NMR and UV spectroscopy). Thermodynamic investigations into H2PO4(-) dimerisation, which is a process that has been frequently recognised, but rarely quantitatively described, were carried out as well. The corresponding equilibrium was taken into account in the anion-binding studies, which enabled reliable determination of the complexation thermodynamic quantities. In both solvents the thiourea derivatives exhibited considerably higher binding affinities with respect to those containing the urea moiety. In acetonitrile, 1:1 and 2:1 (anion/receptor) complexes formed, whereas in dimethyl sulfoxide only the significantly less stable complexes of 1:1 stoichiometry were detected. The solvent effects on the thermodynamic parameters of dihydrogen phosphate dimerisation and complexation reactions are discussed. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nanoparticle-Seeding Approach to Buried (Semi) Metal Film Growth

DTIC Science & Technology

2014-05-20

semimetals that can be grown epitaxially on zinc-blende III-V substrates, with thermodynamically stable interfaces. However, the rotational symmetry...epitaxially on zinc-blende III-V substrates, with thermodynamically stable interfaces. However, the rotational symmetry mismatch between the III-V and ErAs

Polymorphic drugs examined with neutron spectroscopy: Is making more stable forms really that simple?

NASA Astrophysics Data System (ADS)

Tsapatsaris, Nikolaos; Landsgesell, Sven; Koza, Michael M.; Frick, Bernhard; Boldyreva, Elena V.; Bordallo, Heloisa N.

2013-12-01

Understanding polymorphism in pharmaceutical ingredients is a long-standing challenge in formulation science. A well-known example is paracetamol, C8H9NO2. The marketed stable form I crystallizes with corrugated molecular layers. In contrast, form II, which is thermodynamically favorable at high pressures, has relatively planar layers that can slip over each other without difficulty, but is metastable at ambient conditions. By means of inelastic neutron scattering we demonstrated that the lattice modes of form II exhibit a sudden 1 meV energy shift at 300 K under a pressure of ca 0.4 GPa. Moreover, evidence of an increase of the vibrational energy in both polymorphs was found, which was accompanied, in form I, by an unexpectedly weak increase of the tunnel splitting. These results indicate an anisotropy of the potential surface probed by the methyl rotor, and are discussed in relation to the differences of the strength of the hydrogen bond environment for each polymorph.

Experimental pressure-temperature phase diagram of boron: resolving the long-standing enigma

PubMed Central

Parakhonskiy, Gleb; Dubrovinskaia, Natalia; Bykova, Elena; Wirth, Richard; Dubrovinsky, Leonid

2011-01-01

Boron, discovered as an element in 1808 and produced in pure form in 1909, has still remained the last elemental material, having stable natural isotopes, with the ground state crystal phase to be unknown. It has been a subject of long-standing controversy, if α-B or β-B is the thermodynamically stable phase at ambient pressure and temperature. In the present work this enigma has been resolved based on the α-B-to- β-B phase boundary line which we experimentally established in the pressure interval of ∼4 GPa to 8 GPa and linearly extrapolated down to ambient pressure. In a series of high pressure high temperature experiments we synthesised single crystals of the three boron phases (α-B, β-B, and γ-B) and provided evidence of higher thermodynamic stability of α-B. Our work opens a way for reproducible synthesis of α-boron, an optically transparent direct band gap semiconductor with very high hardness, thermal and chemical stability. PMID:22355614

Thermodynamic and structural characterization of 2′-nitrogen-modified RNA duplexes

PubMed Central

Pham, John W.; Radhakrishnan, Ishwar; Sontheimer, Erik J.

2004-01-01

2′-aminonucleosides are commonly used as sites of post-synthetic chemical modification within nucleic acids. As part of a larger cross-linking strategy, we appended alkyl groups onto the N2′ position of 2′-amino-modified RNAs via 2′-ureido and 2′-amido linkages. We have characterized the thermodynamics of 2′-amino, 2′-alkylamido and 2′-alkylureido-modified RNA duplexes and show that 2′-ureido-modified RNAs are significantly more stable than analogous 2′-amido-modified RNAs. Using NMR spectroscopy and NMR-based molecular modeling of 2′-modified RNA duplexes, we examined the effects that 2′-nitrogen modifications have on RNA helices. Our data suggest that the 2′-ureido group forms a specific intra-nucleoside interaction that cannot occur within 2′-amido-modified helices. These results indicate that 2′-ureido modifications are superior to analogous 2′-amido ones for applications that require stable base pairing. PMID:15247335

Dihydropteridine/Pteridine as a 2H+/2e- Redox Mediator for the Reduction of CO2 to Methanol: A Computational Study.

PubMed

Lim, Chern-Hooi; Holder, Aaron M; Hynes, James T; Musgrave, Charles B

2017-04-27

Conflicting experimental results for the electrocatalytic reduction of CO 2 to CH 3 OH on a glassy carbon electrode by the 6,7-dimethyl-4-hydroxy-2-mercaptopteridine have been recently reported [ J. Am. Chem. Soc. 2014 , 136 , 14007 - 14010 , J. Am. Chem. Soc. 2016 , 138 , 1017 - 1021 ]. In this connection, we have used computational chemistry to examine the issue of this molecule's ability to act as a hydride donor to reduce CO 2 . We first determined that the most thermodynamically stable tautomer of this aqueous compound is its oxothione form, termed here PTE. It is argued that this species electrochemically undergoes concerted 2H + /2e - transfers to first form the kinetic product 5,8-dihydropteridine, followed by acid-catalyzed tautomerization to the thermodynamically more stable 7,8-dihydropteridine PTEH 2 . While the overall conversion of CO 2 to CH 3 OH by three successive hydride and proton transfers from this most stable tautomer is computed to be exergonic by 5.1 kcal/mol, we predict high activation free energies (ΔG ‡ HT ) of 29.0 and 29.7 kcal/mol for the homogeneous reductions of CO 2 and its intermediary formic acid product by PTE/PTEH 2 , respectively. These high barriers imply that PTE/PTEH 2 is unable, by this mechanism, to homogeneously reduce CO 2 on a time scale of hours at room temperature.

Membrane extraction with thermodynamically unstable diphosphonic acid derivatives

DOEpatents

Horwitz, E.P.; Gatrone, R.C.; Nash, K.L.

1997-10-14

Thermodynamically-unstable complexing agents which are diphosphonic acids and diphosphonic acid derivatives (or sulphur containing analogs), like carboxyhydroxymethanediphosphonic acid and vinylidene-1,1-diphosphonic acid, are capable of complexing with metal ions, and especially metal ions in the II, III, IV, V and VI oxidation states, to form stable, water-soluble metal ion complexes in moderately alkaline to highly-acidic media. However, the complexing agents can be decomposed, under mild conditions, into non-organic compounds which, for many purposes are environmentally-nondamaging compounds thereby degrading the complex and releasing the metal ion for disposal or recovery. Uses for such complexing agents as well as methods for their manufacture are also described. 1 fig.

Non-equilibrium freezing behaviour of aqueous systems.

PubMed

MacKenzie, A P

1977-03-29

The tendencies to non-equilibrium freezing behaviour commonly noted in representative aqueous systems derive from bulk and surface properties according to the circumstances. Supercooling and supersaturation are limited by heterogeneous nucleation in the presence of solid impurities. Homogeneous nucleation has been observed in aqueous systems freed from interfering solids. Once initiated, crystal growth is ofter slowed and, very frequently, terminated with increasing viscosity. Nor does ice first formed always succeed in assuming its most stable crystalline form. Many of the more significant measurements on a given systeatter permitting the simultaneous representation of thermodynamic and non-equilibrium properties. The diagram incorporated equilibrium melting points, heterogeneous nucleation temperatures, homogeneous nucleation temperatures, glass transition and devitrification temperatures, recrystallization temperatures, and, where appropriate, solute solubilities and eutectic temperatures. Taken together, the findings on modle systems aid the identification of the kinetic and thermodynamic factors responsible for the freezing-thawing survival of living cells.

Thermodynamic Equilibrium Calculations on Cd Transformation during Sewage Sludge Incineration.

PubMed

Liu, Jing-yong; Huang, Limao; Sun, Shuiyu; Ning, Xun'an; Kuo, Jiahong; Sun, Jian; Wang, Yujie; Xie, Wuming

2016-06-01

Thermodynamic equilibrium calculations were performed to reveal the distribution of cadmium during the sewage sludge incineration process. During sludge incineration in the presence of major minerals, such as SiO2, Al2O3 and CaO, the strongest effect was exerted by SiO2 on the Cd transformation compared with the effect of others. The stable solid product of CdSiO3 was formed easily with the reaction between Cd and SiO2, which can restrain the emissions of gaseous Cd pollutants. CdCl2 was formed more easily in the presence of chloride during incineration, thus, the volatilization of Cd was advanced by increasing chlorine content. At low temperatures, the volatilization of Cd was restrained due to the formation of the refractory solid metal sulfate. At high temperatures, the speciation of Cd was not affected by the presence of sulfur, but sulfur could affect the formation temperature of gaseous metals.

The role of Minkowski functionals in the thermodynamics of two-phase systems

NASA Astrophysics Data System (ADS)

Eder, Gerhard

2018-01-01

Within this work quite old concepts from integral geometry are applied to classical equilibrium thermodynamics of two-phase systems. In addition to the area as basic interfacial quantity the full geometric characterization of the interface is used, which includes the two remaining Minkowski functionals, the mean curvature integral and the Euler Poincaré characteristic. The basic energetic characteristic of the interface (i.e. the interfacial tension) is extended by two additional properties: edge force as (up to a factor 4/π) the work necessary to form a right-angled edge of unit length, and item energy as the work to form an additional item in the phase morphology. Both quantities are of increasing importance, when going to micro- and nano-scales. They are subsequently used for interfaces of arbitrary shape to derive a relationship extending the classical Young-Laplace equation. The supplementary contribution is proportional to the Gaussian curvature, with the edge force as proportionality constant. Furthermore, both edge force and item energy are shown to be applicable to the description of crystal nucleation in liquids (extending the classical Becker Döring theory). It turns out, that even above the thermodynamic melting temperature stable nuclei can be present in the liquid phase. They immediately are able to grow when quenched to a temperature below a characteristic temperature. This temperature of spontaneous homogeneous nucleation is simply connected to the edge force, whereas the number of stable clusters per unit volume is dominated by the item energy. Finally, the additional energetic interfacial properties are used in a similar way to characterize the stability of emulsions.

Punctuated equilibrium as an emergent process and its modified thermodynamic characterization.

PubMed

Wosniack, M E; da Luz, M G E; Schulman, L S

2017-01-07

We address evolutionary dynamics and consider under which conditions the ecosystem interaction network allows punctuated equilibrium (i.e., alternation between hectic and quasi-stable phases). We focus on the links connecting various species and on the strength and sign of those links. For this study we consider the Tangled Nature model, which allows considerable flexibility and plasticity in the analysis of interspecies interactions. We find that it is necessary to have a proper balance of connectivity and interaction intensities so as to establish the kind of mutual cooperation and competition found in nature. It suggests evolutionary punctuated equilibrium as an emergent process, thus displaying features of complex systems. To explicitly demonstrate this fact we consider an extended form of thermodynamics, defining (for the present context) relevant out-of-equilibrium "collective" functions. We then show how to characterize the punctuated equilibrium through entropy-like and free energy-like quantities. Finally, from a close analogy to thermodynamic systems, we propose a protocol similar to simulated annealing. It is based on controlling the species' rate of mutation during the hectic periods, in this way enhancing the exploration of the genome space (similar to the known behavior of bacteria in stressful environments). This allows the system to more rapidly converge to long-duration quasi-stable phases. Copyright © 2016 Elsevier Ltd. All rights reserved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alred, Erik J.; Scheele, Emily G.; Berhanu, Workalemahu M.

Recent experiments indicate a connection between the structure of amyloid aggregates and their cytotoxicity as related to neurodegenerative diseases. Of particular interest is the Iowa Mutant, which causes early-onset of Alzheimer's disease. While wild-type Amyloid β-peptides form only parallel beta-sheet aggregates, the mutant also forms meta-stable antiparallel beta sheets. Since these structural variations may cause the difference in the pathological effects of the two Aβ-peptides, we have studied in silico the relative stability of the wild type and Iowa mutant in both parallel and antiparallel forms. We compare regular molecular dynamics simulations with such where the viscosity of the samplesmore » is reduced, which, we show, leads to higher sampling efficiency. By analyzing and comparing these four sets of all-atom molecular dynamics simulations, we probe the role of the various factors that could lead to the structural differences. Our analysis indicates that the parallel forms of both wild type and Iowa mutant aggregates are stable, while the antiparallel aggregates are meta-stable for the Iowa mutant and not stable for the wild type. The differences result from the direct alignment of hydrophobic interactions in the in-register parallel oligomers, making them more stable than the antiparallel aggregates. The slightly higher thermodynamic stability of the Iowa mutant fibril-like oligomers in its parallel organization over that in antiparallel form is supported by previous experimental measurements showing slow inter-conversion of antiparallel aggregates into parallel ones. Knowledge of the mechanism that selects between parallel and antiparallel conformations and determines their relative stability may open new avenues for the development of therapies targeting familial forms of early-onset Alzheimer's disease.« less

Computing the melting point and thermodynamic stability of the orthorhombic and monoclinic crystalline polymorphs of the ionic liquid 1-n-butyl-3-methylimidazolium chloride

NASA Astrophysics Data System (ADS)

Jayaraman, Saivenkataraman; Maginn, Edward J.

2007-12-01

The melting point, enthalpy of fusion, and thermodynamic stability of two crystal polymorphs of the ionic liquid 1-n-butyl-3-methylimidazolium chloride are calculated using a thermodynamic integration-based atomistic simulation method. The computed melting point of the orthorhombic phase ranges from 365 to 369 K, depending on the classical force field used. This compares reasonably well with the experimental values, which range from 337 to 339 K. The computed enthalpy of fusion ranges from 19 to 29 kJ/mol, compared to the experimental values of 18.5-21.5 kJ/mol. Only one of the two force fields evaluated in this work yielded a stable monoclinic phase, despite the fact that both give accurate liquid state densities. The computed melting point of the monoclinic polymorph was found to be 373 K, which is somewhat higher than the experimental range of 318-340 K. The computed enthalpy of fusion was 23 kJ/mol, which is also higher than the experimental value of 9.3-14.5 kJ/mol. The simulations predict that the monoclinic form is more stable than the orthorhombic form at low temperature, in agreement with one set of experiments but in conflict with another. The difference in free energy between the two polymorphs is very small, due to the fact that a single trans-gauche conformational difference in an alkyl sidechain distinguishes the two structures. As a result, it is very difficult to construct simple classical force fields that are accurate enough to definitively predict which polymorph is most stable. A liquid phase analysis of the probability distribution of the dihedral angles in the alkyl chain indicates that less than half of the dihedral angles are in the gauche-trans configuration that is adopted in the orthorhombic crystal. The low melting point and glass forming tendency of this ionic liquid is likely due to the energy barrier for conversion of the remaining dihedral angles into the gauche-trans state. The simulation procedure used to perform the melting point calculations is an extension of the so-called pseudosupercritical path sampling procedure. This study demonstrates that the method can be effectively applied to quite complex systems such as ionic liquids and that the appropriate choice of tethering potentials for a key step in the thermodynamic path can enable first order phase transitions to be avoided.

Computational Thermodynamics Characterization of 7075, 7039, and 7020 Aluminum Alloys Using JMatPro

DTIC Science & Technology

2011-09-01

parameters of temperature and time may be selected to simulate effects on microstructure during annealing , solution treating, quenching, and tempering...nucleation may be taken into account by use of a wetting angle function. Activation energy may be taken into account for rapidly quenched alloys...the stable forms of precipitates that result from solutionizing, annealing or intermediate heat treatment, and phase formation during nonequilibrium

Refining a complex nickel alloy to remove a sulfur impurity during vacuum induction melting: Part II

NASA Astrophysics Data System (ADS)

Sidorov, V. V.; Min, P. G.

2014-12-01

The results of studying the refining of complexly alloyed nickel melts from sulfur during melting in a vacuum induction furnace or with the use of an oxide calcium crucible, metallic calcium added to a melt, or rare-earth metals additions (which form thermodynamically stable refractory compounds with sulfur and, thus, eliminate the harmful effect of sulfur in the alloys) are reported.

Thermodynamic interpretation of reactive processes in Ni-Al nanolayers from atomistic simulations

NASA Astrophysics Data System (ADS)

Sandoval, Luis; Campbell, Geoffrey H.; Marian, Jaime

2014-03-01

Metals that can form intermetallic compounds by exothermic reactions constitute a class of reactive materials with multiple applications. Ni-Al laminates of thin alternating layers are being considered as model nanometric metallic multilayers for studying various reaction processes. However, the reaction kinetics at short timescales after mixing are not entirely understood. In this work, we calculate the free energies of Ni-Al alloys as a function of composition and temperature for different solid phases using thermodynamic integration based on state-of-the-art interatomic potentials. We use this information to interpret molecular dynamics (MD) simulations of bilayer systems at 800 K and zero pressure, both in isothermal and isenthalpic conditions. We find that a disordered phase always forms upon mixing as a precursor to a more stable nano crystalline B2 phase. We construe the reactions observed in terms of thermodynamic trajectories governed by the state variables computed. Simulated times of up to 30 ns were achieved, which provides a window to phenomena not previously observed in MD simulations. Our results provide insight into the early experimental reaction timescales and suggest that the path (segregated reactants) → (disordered phase) → (B2 structure) is always realized irrespective of the imposed boundary conditions.

DNA-guided nanoparticle assemblies

DOEpatents

Gang, Oleg; Nykypanchuk, Dmytro; Maye, Mathew; van der Lelie, Daniel

2013-07-16

In some embodiments, DNA-capped nanoparticles are used to define a degree of crystalline order in assemblies thereof. In some embodiments, thermodynamically reversible and stable body-centered cubic (bcc) structures, with particles occupying <.about.10% of the unit cell, are formed. Designs and pathways amenable to the crystallization of particle assemblies are identified. In some embodiments, a plasmonic crystal is provided. In some aspects, a method for controlling the properties of particle assemblages is provided. In some embodiments a catalyst is formed from nanoparticles linked by nucleic acid sequences and forming an open crystal structure with catalytically active agents attached to the crystal on its surface or in interstices.

Properties of small Ar sub N-1 K/+/ ionic clusters

NASA Technical Reports Server (NTRS)

Etters, R. D.; Danilowicz, R.; Dugan, J.

1977-01-01

A self-consistent formalism is developed that, based upon a many-body potential, dynamically determines the thermodynamic properties of ionic clusters without an a priori designation of the equilibrium structures. Aggregates consisting of a single closed shell K(+) ion and N-1 isoelectronic argon atoms were studied. The clusters form crystallites at low temperatures, and melting transitions and spontaneous dissociations are indicated. The results confirm experimental evidence that shows that ionic clusters become less stable with increasing N. The crystallite structures formed by four different clusters are isosceles triangle, skewed form, octahedron with ion in the middle, and icosahedron with the ion in the middle.

Thermally Stable Ni-rich Austenite Formed Utilizing Multistep Intercritical Heat Treatment in a Low-Carbon 10 Wt Pct Ni Martensitic Steel

NASA Astrophysics Data System (ADS)

Jain, Divya; Isheim, Dieter; Zhang, Xian J.; Ghosh, Gautam; Seidman, David N.

2017-08-01

Austenite reversion and its thermal stability attained during the transformation is key to enhanced toughness and blast resistance in transformation-induced-plasticity martensitic steels. We demonstrate that the thermal stability of Ni-stabilized austenite and kinetics of the transformation can be controlled by forming Ni-rich regions in proximity of pre-existing (retained) austenite. Atom probe tomography (APT) in conjunction with thermodynamic and kinetic modeling elucidates the role of Ni-rich regions in enhancing growth kinetics of thermally stable austenite, formed utilizing a multistep intercritical ( Quench- Lamellarization- Tempering (QLT)-type) heat treatment for a low-carbon 10 wt pct Ni steel. Direct evidence of austenite formation is provided by dilatometry, and the volume fraction is quantified by synchrotron X-ray diffraction. The results indicate the growth of nm-thick austenite layers during the second intercritical tempering treatment (T-step) at 863 K (590 °C), with austenite retained from first intercritical treatment (L-step) at 923 K (650 °C) acting as a nucleation template. For the first time, the thermal stability of austenite is quantified with respect to its compositional evolution during the multistep intercritical treatment of these steels. Austenite compositions measured by APT are used in combination with the thermodynamic and kinetic approach formulated by Ghosh and Olson to assess thermal stability and predict the martensite-start temperature. This approach is particularly useful as empirical relations cannot be extrapolated for the highly Ni-enriched austenite investigated in the present study.

Stable monolayer honeycomb-like structures of RuX2 (X =S,Se)

NASA Astrophysics Data System (ADS)

Ersan, Fatih; Cahangirov, Seymur; Gökoǧlu, Gökhan; Rubio, Angel; Aktürk, Ethem

2016-10-01

Recent studies show that several metal oxides and dichalcogenides (M X2) , which exist in nature, can be stable in two-dimensional (2D) form and each year several new M X2 structures are explored. The unstable structures in H (hexagonal) or T (octahedral) forms can be stabilized through Peierls distortion. In this paper, we propose new 2D forms of RuS2 and RuSe2 materials. We investigate in detail the stability, electronic, magnetic, optical, and thermodynamic properties of 2D Ru X2 (X =S,Se) structures from first principles. While their H and T structures are unstable, the distorted T structures (T'-Ru X2) are stable and have a nonmagnetic semiconducting ground state. The molecular dynamic simulations also confirm that T'-Ru X2 systems are stable even at 500 K without any structural deformation. T'-RuS2 and T'-RuSe2 have indirect band gaps with 0.745 eV (1.694 eV with HSE) and 0.798 eV (1.675 eV with HSE) gap values, respectively. We also examine their bilayer and trilayer forms and find direct and smaller band gaps. We find that AA stacking is more favorable than the AB configuration. The new 2D materials obtained can be good candidates with striking properties for applications in semiconductor electronic, optoelectronic devices, and sensor technology.

Microfluidic control of droplet formation from stable emulsions formed by aqueous two-phase systems

NASA Astrophysics Data System (ADS)

Teixeira, Alyne G.; Tsai, Meng-Chiao; Frampton, John P.

2018-02-01

Aqueous two-phase systems (ATPSs) form from the thermodynamic separation of two dissolved incompatible solutes, such as two polymers, a polymer and a salt, and a polymer and a surfactant. At most supercritical concentrations, ATPS emulsions can be formed by vigorous mixing. These emulsions typically settle into distinct layers in minutes to hours. However, it is also possible to choose ATPS compositions with extremely long settling times that resemble stable emulsions. Here, we generated stable emulsions from a polyethylene glycol (PEG)-dextran ATPS by selecting ATPS compositions at the extreme ends of the tie lines connecting the binodal curve delineating phase-separating compositions. Droplets of PEG in a continuous dextran phase did not coalesce appreciably over the course of several days when stored in a conical tube or syringe. However, upon exposure to laminar flow conditions in a microfluidic channel, droplets were observed to coalesce. Through microscopic characterization of droplet volume, an increase in droplet size and decrease in overall droplet number was observed as a function of channel distance, suggesting a progressive droplet merging phenomenon. This novel approach to control droplet size by encouraging coalescence of stable emulsions under laminar flow in a microfluidic channel enables the production of droplets ranging from fL to several pL, which may enable various future biotechnology applications.

Thermodynamics and Kinetics of Sulfide Oxidation by Oxygen: A Look at Inorganically Controlled Reactions and Biologically Mediated Processes in the Environment

PubMed Central

Luther, George W.; Findlay, Alyssa J.; MacDonald, Daniel J.; Owings, Shannon M.; Hanson, Thomas E.; Beinart, Roxanne A.; Girguis, Peter R.

2011-01-01

The thermodynamics for the first electron transfer step for sulfide and oxygen indicates that the reaction is unfavorable as unstable superoxide and bisulfide radical ions would need to be produced. However, a two-electron transfer is favorable as stable S(0) and peroxide would be formed, but the partially filled orbitals in oxygen that accept electrons prevent rapid kinetics. Abiotic sulfide oxidation kinetics improve when reduced iron and/or manganese are oxidized by oxygen to form oxidized metals which in turn oxidize sulfide. Biological sulfur oxidation relies on enzymes that have evolved to overcome these kinetic constraints to affect rapid sulfide oxidation. Here we review the available thermodynamic and kinetic data for H2S and HS• as well as O2, reactive oxygen species, nitrate, nitrite, and NOx species. We also present new kinetic data for abiotic sulfide oxidation with oxygen in trace metal clean solutions that constrain abiotic rates of sulfide oxidation in metal free solution and agree with the kinetic and thermodynamic calculations. Moreover, we present experimental data that give insight on rates of chemolithotrophic and photolithotrophic sulfide oxidation in the environment. We demonstrate that both anaerobic photolithotrophic and aerobic chemolithotrophic sulfide oxidation rates are three or more orders of magnitude higher than abiotic rates suggesting that in most environments biotic sulfide oxidation rates will far exceed abiotic rates due to the thermodynamic and kinetic constraints discussed in the first section of the paper. Such data reshape our thinking about the biotic and abiotic contributions to sulfide oxidation in the environment. PMID:21833317

Stability of Iowa mutant and wild type Aβ-peptide aggregates

NASA Astrophysics Data System (ADS)

Alred, Erik J.; Scheele, Emily G.; Berhanu, Workalemahu M.; Hansmann, Ulrich H. E.

2014-11-01

Recent experiments indicate a connection between the structure of amyloid aggregates and their cytotoxicity as related to neurodegenerative diseases. Of particular interest is the Iowa Mutant, which causes early-onset of Alzheimer's disease. While wild-type Amyloid β-peptides form only parallel beta-sheet aggregates, the mutant also forms meta-stable antiparallel beta sheets. Since these structural variations may cause the difference in the pathological effects of the two Aβ-peptides, we have studied in silico the relative stability of the wild type and Iowa mutant in both parallel and antiparallel forms. We compare regular molecular dynamics simulations with such where the viscosity of the samples is reduced, which, we show, leads to higher sampling efficiency. By analyzing and comparing these four sets of all-atom molecular dynamics simulations, we probe the role of the various factors that could lead to the structural differences. Our analysis indicates that the parallel forms of both wild type and Iowa mutant aggregates are stable, while the antiparallel aggregates are meta-stable for the Iowa mutant and not stable for the wild type. The differences result from the direct alignment of hydrophobic interactions in the in-register parallel oligomers, making them more stable than the antiparallel aggregates. The slightly higher thermodynamic stability of the Iowa mutant fibril-like oligomers in its parallel organization over that in antiparallel form is supported by previous experimental measurements showing slow inter-conversion of antiparallel aggregates into parallel ones. Knowledge of the mechanism that selects between parallel and antiparallel conformations and determines their relative stability may open new avenues for the development of therapies targeting familial forms of early-onset Alzheimer's disease.

Early diagenesis and recrystallization of bone

NASA Astrophysics Data System (ADS)

Keenan, Sarah W.; Engel, Annette Summers

2017-01-01

One of the most challenging problems in paleobiology is determining how bone transforms from a living tissue into a fossil. The geologic record is replete with vertebrate fossils preserved from a range of depositional environments, including wetland systems. However, thermodynamic models suggest that bone (modeled as hydroxylapatite) is generally unstable in a range of varying geochemical conditions and should readily dissolve if it does not alter to a more thermodynamically stable phase, such as a fluorine-enriched apatite. Here, we assess diagenesis of alligator bone from fleshed, articulated skeletons buried in wetland soils and from de-fleshed bones in experimental mesocosms with and without microbial colonization. When microbial colonization of bone was inhibited, bioapatite recrystallization to a more stable apatite phase occurred after one month of burial. Ca-Fe-phosphate phases in bone developed after several months to years due to ion substitutions from the protonation of the hydroxyl ion. These rapid changes demonstrate a continuum of structural and bonding transformations to bone that have not been observed previously. When bones were directly in contact with sediment and microbial cells, rapid bioerosion and compositional alteration occurred after one week, but slowed after one month because biofilms reduced exposed surfaces and subsequent bioapatite lattice substitutions. Microbial contributions are likely essential in forming stable apatite phases during early diagenesis and for enabling bone preservation and fossilization.

Model for capping of membrane receptors based on boundary surface effects

PubMed Central

Gershon, N. D.

1978-01-01

Crosslinking of membrane surface receptors may lead to their segregation into patches and then into a single large aggregate at one pole of the cell. This process is called capping. Here, a novel explanation of such a process is presented in which the membrane is viewed as a supersaturated solution of receptors in the lipid bilayer and the adjacent two aqueous layers. Without a crosslinking agent, a patch of receptors that is less than a certain size cannot stay in equilibrium with the solution and thus should dissolve. Patches greater than a certain size are stable and can, in principle, grow by the precipitation of the remaining dissolved receptors from the supersaturated solution. The task of the crosslinking molecules is to form such stable patches. These considerations are based on a qualitative thermodynamic calculation that takes into account the existence of a boundary tension in a patch (in analogy to the surface tension of a droplet). Thermodynamically, these systems should cap spontaneously after the patches have reached a certain size. But, in practice, such a process can be very slow. A suspension of patches may stay practically stable. The ways in which a cell may abolish this metastable equilibrium and thus achieve capping are considered and possible effects of capping inhibitors are discussed. PMID:274724

Interaction of Gas Phase Oxalic Acid with Ammonia and its Atmospheric Implications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Peng, Xiu-Qiu; Liu, Yi-Rong; Huang, Teng

Oxalic acid is believed to play an important role in the formation and growth of atmospheric organic aerosols. However, as a common organic acid, the understanding of the larger clusters formed by gas phase oxalic acid with multiple ammonia molecules is incomplete. In this work, the structural characteristics and thermodynamics of oxalic acid clusters with up to six ammonia molecules have been investigated at the PW91PW91/6-311++G(3df,3pd) level of theory. We found that oxalic acid forms relatively stable clusters with ammonia molecules, and that ionization events play a key role. The analyses of the thermodynamics and atmospheric relevance indicate that themore » heterodimer (H2C2O4)(NH3) shows an obvious relative concentration in the atmosphere, and thus likely participates in new particle formation. However, with increasing number of ammonia molecules, the concentration of clusters decreases gradually. Additionally, clusters of oxalic acid with ammonia molecules are predicted to form favorably in low temperature conditions and show high Rayleigh scattering intensities.« less

C-H bond activation of hydrocarbons by an imidozirconocene complex.

PubMed

Hoyt, Helen M; Michael, Forrest E; Bergman, Robert G

2004-02-04

Monomeric imidozirconocene complexes of the type Cp2(L)Zr=NCMe3 (Cp = cyclopentadienyl, L = Lewis base) have been shown to activate the carbon-hydrogen bonds of benzene, but not the C-H bonds of saturated hydrocarbons. To our knowledge, this singularly important class of C-H activation reactions has heretofore not been observed in imidometallocene systems. The M=NR bond formed on heating the racemic ethylenebis(tetrahydro)indenyl methyl tert-butyl amide complex, however, cleanly and quantitatively activates a wide range of n-alkane, alkene, and arene C-H bonds. Mechanistic experiments support the proposal of intramolecular elimination of methane followed by a concerted addition of the hydrocarbon C-H bond. Products formed by activation of sp2 C-H bonds are generally more thermodynamically stable than those formed by activation of sp3 C-H bonds, and those resulting from reaction at primary C-H bonds are preferred over secondary sp3 C-H activation products. There is also evidence that thermodynamic selectivity among C-H bonds is sterically rather than electronically controlled.

Formation of co-crystals: Kinetic and thermodynamic aspects

NASA Astrophysics Data System (ADS)

Gagnière, E.; Mangin, D.; Puel, F.; Rivoire, A.; Monnier, O.; Garcia, E.; Klein, J. P.

2009-04-01

Co-crystallisation is a recent method of great interest for the pharmaceutical industry, since pharmaceutical co-crystals represent useful materials for drug products. In this study, an active pharmaceutical ingredient (carbamazepine (CBZ)) co-crystallized with a vitamin (nicotinamide (NCT)) was chosen as a model substance. This work was focused on the construction of a phase diagram for the system CBZ/NCT, split in six domains for kinetic reasons (the different solid phases which might appear during the crystallisation) and in four domains according to thermodynamic aspects (the stable final phase obtained). Although co-crystals are not ionic compounds, the supersaturation of co-crystals can be evaluated by considering the solubility product. Batch crystallisation operations were carried out in a stirred vessel equipped with an in situ video probe. This latter device was a powerful analysis tool to monitor the CBZ/NCT co-crystals and single CBZ crystals since these two crystalline phases grown in ethanol exhibited needle and platelet habits. As concerns kinetics, the different solid phases which might appear during the experiments were observed and competed against each others. In accordance with thermodynamics, the stable solid form was obtained at the end of the operation. Finally some preliminary results indicate that the nucleation of co-crystals may be favoured by the presence of CBZ crystals. Epitaxial relationships between CBZ/NCT co-crystals and CBZ crystals were suspected.

Structural, luminescence, thermodynamic and theoretical studies on mononuclear complexes of Eu(III) with pyridine monocarboxylate-N-oxides in aqueous solution

NASA Astrophysics Data System (ADS)

Dumpala, Rama Mohana Rao; Rawat, Neetika; Boda, Anil; Ali, Sk. Musharaf; Tomar, B. S.

2018-02-01

The mononuclear complexes formed by Eu(III) with three isomeric pyridine monocarboxylate-N-oxides namely picolinic acid-N-oxide (PANO), nicotinic acid-N-oxide (NANO) and isonicotinic acid-N-oxide (IANO) in aqueous solutions were studied by potentiometry, luminescence spectroscopy and isothermal titration calorimetry (ITC) to determine the speciation, coordination, luminescence properties and thermodynamic parameters of the complexes formed during the course of the reaction. More stable six membered chelate complexes with stoichiometry (MLi, i = 1-4) are formed by Eu(III) with PANO while non chelating ML and ML2 complexes are formed by NANO and IANO. The stability of Eu(III) complexes follow the order PANO > IANO > NANO. The ITC studies inferred an endothermic and innersphere complex formation of Eu(III)-PANO and Eu(III)-IANO whereas an exothermic and outer-sphere complex formation for Eu(III)-NANO. The luminescence life time data further supported the ITC results. Density functional theoretical calculations were carried out to optimize geometries of the complexes and to estimate the energies, structural parameters (bond distances, bond angles) and charges on individual atoms of the same. Theoretical approximations are found to be in good agreement with the experimental observations.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Marolf, Donald; Palmer, Belkis Cabrera; Physics Department, Syracuse University, Syracuse, New York 13244

A thermodynamic argument is presented suggesting that near-extremal spinning D1-D5-P black strings become unstable when their angular momentum exceeds J{sub crit}=3Q{sub 1}Q{sub 5}/2{radical}(2). In contrast, the dimensionally reduced black holes are thermodynamically stable. The proposed instability involves a phase in which the spin angular momentum above J{sub crit} is transferred to gyration of the string in space, i.e., to orbital angular momentum of parts of the string about the mean location in space. Thus the string becomes a rotating helical coil. We note that an instability of this form would yield a counter-example to the Gubser-Mitra conjecture, which proposes amore » particular link between dynamic black string instabilities and the thermodynamics of black strings. There may also be other instabilities associated with radiation modes of various fields. Our arguments also apply to the D-brane bound states associated with these black strings in weakly coupled string theory.« less

Spatiotemporal control over the co-conformational switching in pH-responsive flavylium-based multistate pseudorotaxanes.

PubMed

Diniz, Ana Marta; Basílio, Nuno; Cruz, Hugo; Pina, Fernando; Parola, A Jorge

2015-01-01

A multistate molecular dyad containing flavylium and viologen units was synthesized and the pH dependent thermodynamics of the network completely characterized by a variety of spectroscopic techniques such as NMR, UV-vis and stopped-flow. The flavylium cation is only stable at acidic pH values. Above pH ≈ 5 the hydration of the flavylium leads to the formation of the hemiketal followed by ring-opening tautomerization to give the cis-chalcone. Finally, this last species isomerizes to give the trans-chalcone. For the present system only the flavylium cation and the trans-chalcone species could be detected as being thermodynamically stable. The hemiketal and the cis-chalcone are kinetic intermediates with negligible concentrations at the equilibrium. All stable species of the network were found to form 1 : 1 and 2 : 1 host : guest complexes with cucurbit[7]uril (CB7) with association constants in the ranges 10(5)-10(8) M(-1) and 10(3)-10(4) M(-1), respectively. The 1 : 1 complexes were particularly interesting to devise pH responsive bistable pseudorotaxanes: at basic pH values (≈12) the flavylium cation interconverts into the deprotonated trans-chalcone in a few minutes and under these conditions the CB7 wheel was found to be located around the viologen unit. A decrease in pH to values around 1 regenerates the flavylium cation in seconds and the macrocycle is translocated to the middle of the axle. On the other hand, if the pH is decreased to 6, the deprotonated trans-chalcone is neutralized to give a metastable species that evolves to the thermodynamically stable flavylium cation in ca. 20 hours. By taking advantage of the pH-dependent kinetics of the trans-chalcone/flavylium interconversion, spatiotemporal control of the molecular organization in pseudorotaxane systems can be achieved.

Rhodium-catalyzed chemo-, regio-, and enantioselective addition of 2-pyridones to terminal allenes.

PubMed

Li, Changkun; Kähny, Matthias; Breit, Bernhard

2014-12-08

A rhodium-catalyzed chemo-, regio-, and enantioselective addition of 2-pyridones to terminal allenes to give branched N-allyl 2-pyridones is reported. Preliminary mechanistic studies support the hypothesis that the reaction was initiated from the more acidic 2-hydroxypyridine form, and the initial kinetic O-allylation product was finally converted into the thermodynamically more stable N-allyl 2-pyridones. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The influence of sequence context and length on the kinetics of DNA duplex formation from complementary hairpins possessing (CNG) repeats.

PubMed

Paiva, Anthony M; Sheardy, Richard D

2005-04-20

The formation of unusual structures during DNA replication has been invoked for gene expansion in genomes possessing triplet repeat sequences, CNG, where N = A, C, G, or T. In particular, it has been suggested that the daughter strand of the leading strand partially dissociates from the parent strand and forms a hairpin. The equilibrium between the fully duplexed parent:daugter species and the parent:hairpin species is dependent upon their relative stabilities and the rates of reannealing of the daughter strand back to the parent. These stabilities and rates are ultimately influenced by the sequence context of the DNA and its length. Previous work has demonstrated that longer strands are more stable than shorter strands and that the identity of N also influences the thermal stability [Paiva, A. M.; Sheardy, R. D. Biochemistry 2004, 43, 14218-14227]. Here, we show that the rate of duplex formation from complementary hairpins is also sequence context and length dependent. In particular, longer duplexes have higher activation energies than shorter duplexes of the same sequence context. Further, [(CCG):(GGC)] duplexes have lower activation energies than corresponding [(CAG):(GTC)] duplexes of the same length. Hence, hairpins formed from long CNG sequences are more thermodynamically stable and have slower kinetics for reannealing to their complement than shorter analogues. Gene expansion can now be explained in terms of thermodynamics and kinetics.

Solubility and crystal nucleation in organic solvents of two polymorphs of curcumin.

PubMed

Liu, Jin; Svärd, Michael; Hippen, Perschia; Rasmuson, Åke C

2015-07-01

Two crystal polymorphs of 1,7-bis-(4-hydroxy-3-methoxyphenyl)-1,6-heptadiene-3,5-dione (curcumin) have been obtained by crystallization from ethanol (EtOH) solution. The polymorphs have been characterized by differential scanning calorimetry, infrared spectroscopy, and X-ray powder diffraction and shown to be the previously described forms I and III. The solubility of both polymorphs in EtOH and of one polymorph in ethyl acetate (EA) has been measured between 10°C and 50°C with a gravimetric method. Primary nucleation of curcumin from EtOH solution has been investigated in 520 constant temperature crystallization experiments in sealed, magnetically stirred vials under different conditions of supersaturation, temperature, and agitation rate. By a thermodynamic analysis of the melting data and solubility of form I, the solid-state activity is estimated from 10°C up to the melting point. The solubility is lower in EtOH than in EA, and in both solvents, a positive deviation from Raoult's law is observed. Form I has lower solubility than form III and is accordingly thermodynamically more stable over the investigated temperature interval. Extrapolation of solubility regression models indicates that there should be a low-temperature enantiotropic transition point, below which form I will be metastable. By slurry conversion experiments, it is established that this temperature is below -30°C. All nucleation experiments resulted in the stable form I. The induction time is observed to decrease with increasing agitation rate up to a certain point, and then increase with further increasing agitation rate; a trend previously observed for other compounds. By correlating the induction time data obtained at different supersaturation and temperature, the interfacial energy of form I in EtOH is estimated to be 3.0 mJ/m(2) . © 2015 Wiley Periodicals, Inc. and the American Pharmacists Association.

Computational methods in preformulation study for pharmaceutical solid dosage forms of therapeutic proteins

NASA Astrophysics Data System (ADS)

Majee, Sutapa Biswas; Biswas, Gopa Roy

2017-06-01

Design and delivery of protein-based biopharmaceuticals needs detailed planning and strict monitoring of intermediate processing steps, storage conditions and container-closure system to ensure a stable, elegant and biopharmaceutically acceptable dosage form. Selection of manufacturing process variables and conditions along with packaging specifications can be achieved through properly designed preformulation study protocol for the formulation. Thermodynamic stability and biological activity of therapeutic proteins depend on folding-unfolding and three-dimensional packing dynamics of amino acid network in the protein molecule. Lack of favourable environment may cause protein aggregation with loss in activity and even fatal immunological reaction. Although lyophilization can enhance the stability of protein-based formulations in the solid state, it can induce protein unfolding leading to thermodynamic instability. Formulation stabilizers such as preservatives can also result in aggregation of therapeutic proteins. Modern instrumental techniques in conjunction with computational tools enable rapid and accurate prediction of amino acid sequence, thermodynamic parameters associated with protein folding and detection of aggregation "hot-spots." Globular proteins pose a challenge during investigations on their aggregation propensity. Biobetter therapeutic monoclonal antibodies with enhanced stability, solubility and reduced immunogenic potential can be designed through mutation of aggregation-prone zones. The objective of the present review article is to focus on the various analytical methods and computational approaches used in the study of thermodynamic stability and aggregation tendency of therapeutic proteins, with an aim to develop optimal and marketable formulation. Knowledge of protein dynamics through application of computational tools will provide the essential inputs and relevant information for successful and meaningful completion of preformulation studies on solid dosage forms of therapeutic proteins.

Understanding the glass-forming ability of active pharmaceutical ingredients for designing supersaturating dosage forms.

PubMed

Kawakami, Kohsaku; Usui, Toshinori; Hattori, Mitsunari

2012-09-01

Amorphous solid dispersions have great potential for enhancing oral absorption of poorly soluble drugs. Crystallization behavior during storage and after exposure to aqueous media must be examined in detail for designing stable and effective amorphous formulations, and it is significantly affected by the intrinsic properties of an amorphous drug. Many attempts have been made to correlate various thermodynamic parameters of pharmaceutical glasses with their crystallization behavior; however, variations in model drugs that could be used for such investigation has been limited because the amorphous characteristics of drugs possessing a high crystallization tendency are difficult to evaluate. In this study, high-speed differential scanning calorimetry, which could inhibit their crystallization using high cooling rates up to 2000°C/s, was employed for assessing such drugs. The thermodynamic parameters of the glasses, including glass transition temperature (T(g)) and fragility, were obtained to show that their crystallization tendency cannot be explained simply by the parameters, although there have been general thought that fragility may be correlated with crystallization tendency. Also investigated was correlation between the thermodynamic parameters and crystallization tendency upon contact with water, which influences in vivo efficacy of amorphous formulations. T(g) was correlated well with the crystallization tendency upon contact with water. Copyright © 2012 Wiley Periodicals, Inc.

Thermodynamics, Solubility, and Diffusivity of Oxygen in Titanium and Ti-Al Alloys

NASA Technical Reports Server (NTRS)

Mehrotra, Gopal M.

1992-01-01

Titanium aluminides and titanium aluminide-based composites are attractive candidate materials for high-temperature structural applications. As these materials may be exposed to oxidizing environments durine their use at elevated temperatures, it is essential that they possess a good oxidation resistance. Previous studies have shown that the oxidation resistance of Al-rich alloys in the Ti-Al system is superior to that of the Ti-rich alloys. The scales formed on the surface of the Al-rich and Ti-rich alloys have been reported to be predominantly Al2O3 and TiO2, respectively. Since the relative stabilities of the oxides of Al and Ti at various temperatures and oxygen pressures can be assessed from their thermodynamic data, it is possible, With the help of thermodynamic calculations, to determine the compositions of the alloys which would form scales of Al2O3, TiO(x) or a ternary oxide such as TiAl2O5 during oxidation at a given temperature. The thermodynamic calculations require reliable activity data for the Ti-Al system. These data have not been determined for the entire composition and temperature range of interest. Using the data available in the literature, recently performed thermodynamic calculations and concluded that the stable oxide changed from TiO to Al2O3 in the existence region of the tial phase. In the case of titanium aluminide-based composites, another major concern is the mutual chemical compatibility of the matrix material with the reinforcement phase. Fibers of SiC, TiB2 and Al2O3 are currently being investigated for reinforcement of titanium aluminide matrices.

DNA-lipid complexes: stability of honeycomb-like and spaghetti-like structures.

PubMed Central

May, S; Ben-Shaul, A

1997-01-01

A molecular level theory is presented for the thermodynamic stability of two (similar) types of structural complexes formed by (either single strand or supercoiled) DNA and cationic liposomes, both involving a monolayer-coated DNA as the central structural unit. In the "spaghetti" complex the central unit is surrounded by another, oppositely curved, monolayer, thus forming a bilayer mantle. The "honeycomb" complex is a bundle of hexagonally packed DNA-monolayer units. The formation free energy of these complexes, starting from a planar cationic/neutral lipid bilayer and bare DNA, is expressed as a sum of electrostatic, bending, mixing, and (for the honeycomb) chain frustration contributions. The electrostatic free energy is calculated using the Poisson-Boltzmann equation. The bending energy of the mixed lipid layers is treated in the quadratic curvature approximation with composition-dependent bending rigidity and spontaneous curvature. Ideal lipid mixing is assumed within each lipid monolayer. We found that the most stable monolayer-coated DNA units are formed when the charged/neutral lipid composition corresponds (nearly) to charge neutralization; the optimal monolayer radius corresponds to close DNA-monolayer contact. These conclusions are also valid for the honeycomb complex, as the chain frustration energy is found to be negligible. Typically, the stabilization energies for these structures are on the order of 1 k(B)T/A of DNA length, reflecting mainly the balance between the electrostatic and bending energies. The spaghetti complexes are less stable due to the additional bending energy of the external monolayer. A thermodynamic analysis is presented for calculating the equilibrium lipid compositions when the complexes coexist with excess bilayer. PMID:9370436

Hidden in Plain Sight: Subtle Effects of the 8-Oxoguanine Lesion on the Structure, Dynamics, and Thermodynamics of a 15-Base-Pair Oligodeoxynucleotide Duplex†

PubMed Central

Crenshaw, Charisse M.; Wade, Jacqueline E.; Arthanari, Haribabu; Frueh, Dominique; Lane, Benjamin F.; Núñez, Megan E.

2011-01-01

The base lesion 8-oxoguanine is formed readily by oxidation of DNA, potentially leading to G→T transversion mutations. Despite the apparent similarity of 8-oxoguanine-cytosine base pairs to normal guanine-cytosine base pairs, cellular base excision repair systems effectively recognize the lesion base. Here we apply several techniques to examine a single 8-oxoguanine lesion at the center of a nonpalindromic 15-mer duplex oligonucleotide in an effort to determine what, if anything, distinguishes an 8-oxoguanine-cytosine base pair from a normal base pair. The lesion duplex is globally almost indistinguishable from the unmodified parent duplex using CD spectroscopy and UV melting thermodynamics. The DNA mismatch-detecting photocleavage agent Rh(bpy)2chrysi3+ cleaves only weakly and nonspecifically, revealing that the 8oxoG-C pair is locally stable at the level of the individual base pairs. NMR spectra are also consistent with a well-conserved B-form duplex structure. In the 2D NOESY spectra, base-sugar and imino-imino crosspeaks are strikingly similar between parent and lesion duplexes. Changes in chemical shift due to the 8oxoG lesion are localized to its complementary cytosine and to the 2–3 base pairs immediately flanking the lesion on the lesion strand. Residues further removed from the lesion are shown to be unperturbed by its presence. Notably, imino exchange experiments indicate that the 8-oxoguanine-cytosine pair is strong and stable, with an apparent equilibrium constant for opening equal to that of other internal guanine-cytosine base pairs, on the order of 10−6. This collection of experiments shows that the 8-oxoguanine-cytosine base pair is incredibly stable and similar to the native pair. PMID:21902242

Assessing the mineralogy and hydration of rocky cores of satellites: insights from experiments and thermodynamics

NASA Astrophysics Data System (ADS)

Reynard, B.; Neri, A.; Sotin, C.

2016-12-01

Icy satellites and similar objects likely form from a mixture of hydrated rocky material, such as the CI chondrites, and various amounts of ices. Mass-balance estimates show that hydrous silicates such as serpentine, and brucite, the simple Mg-Fe hydroxide, dominate fully hydrated mineralogy. The inferred iron content of these minerals is, however, very dependent on assumptions of iron redox state, and whether it forms sulfides or segregates into a metal core. From the determination of the moment of inertia inferred from gravity measurements at Jupiter and Saturn by the Galileo and Cassini spacecraft, Ganymede and Europa would have a differentiated iron-rich core whereas Titan and Enceladus would not. Whatever the case, iron content is generally significantly higher than that of the terrestrial ultrabasic rocks used as analogs in modeling of hydrated satellite cores. Thus, we investigated the phase relations of iron-rich ultrabasic systems based on chondritic composition by combining thermodynamic modeling and preliminary high-pressure experiments. Our starting composition model is that of CI carbonaceous chondrites. Stable mineral assemblages are calculated with the PerpleX package (Connolly, 1990), assuming excess water, and various amounts of iron in the silicate phase through varying the amount of iron sulfide (troilite) or iron oxide (magnetite). Results show stable hydrated minerals are serpentine, chlorite, brucite, Na-phlogopite and in extreme cases, talc in the 1.5-5 GPa range relevant to bodies larger than about 1000 km in radius. Dehydration temperatures are extremely sensitive to the iron content, hence on the chosen amount of iron bearing phase (troilite or magnetite), and to a lower extent on average CI composition. An experimental approach was developed to simulate hydrous alteration of CI-like material. A mixture of synthetic silicates, troilite, and organic compounds, to which excess water is added, is used. Mineralogy and composition is checked using scanning electron microscopy and Raman spectroscopy. Preliminary results at 1.5 GPa are consistent with thermodynamic calculations. Implications for rocky cores are discussed. Connolly, J. A. D. (1990). Multivariable phase diagrams : an algorithm based on generalized thermodynamics, American Journal of Science, 290, 666-718.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stavrou, Elissaios; Yao, Yansun; Goncharov, Alexander F.

In this study, using in situ synchrotron x-ray diffraction and Raman spectroscopy in concert with first principles calculations we demonstrate the synthesis of stable Xe(Fe ,Fe/Ni) 3 and XeNi 3 compounds at thermodynamic conditions representative of Earth’s core. Surprisingly, in the case of both the Xe-Fe and Xe-Ni systems Fe and Ni become highly electronegative and can act as oxidants. In conclusion, the results indicate the changing chemical properties of elements under extreme conditions by documenting that electropositive at ambient pressure elements could gain electrons and form anions.

Solubility of oxygen in CdS single crystals and their physicochemical properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Morozova, N. K., E-mail: MorozovaNK@mail.ru; Kanakhin, A. A.; Shnitnikov, A. S.

2016-07-15

The specific features of oxygen dissolution in CdS using the example of single crystals grown by the gas-transport method with deviations from stoichiometry at 1100°C are considered. The effect of various types of intrinsic point defects in crystals of different composition on the form in the presence of oxygen is analyzed. It is shown that the most stable composition thermodynamically is that corresponding to nonstoichiometric “self-activated cadmium sulphide” stabilized with oxygen.

Solid state characterization of E2101, a novel antispastic drug.

PubMed

Kushida, Ikuo; Ashizawa, Kazuhide

2002-10-01

E2101, a novel antispastic drug, was found to exist in at least two polymorphs that were confirmed by X-ray powder diffraction (XRD). These two species are designated forms I and II. The physicochemical and thermodynamic properties of these polymorphs were characterized by variable temperature XRD, thermal analysis, hygroscopicity measurements, and dissolution studies. The transition temperature was also estimated from the solubilities determined at various temperatures. The E2101 polymorphs were anhydrous and adsorbed little moisture under high humidity conditions. The melting onsets and heats of fusion for form I were 148.1 +/- 0.2 degrees C and 38.2 +/- 1.0 kJ/mol, respectively, and for form II were 139.8 +/- 0.4 degrees C and 35.2 +/- 0.5 kJ/mol, respectively. The intrinsic dissolution rate of form II in JP 2 medium was 1.5-fold faster than that of form I, corresponding to the rank order of the aqueous solubility and the enthalpy of fusion. Accordingly, form I was thought to be thermodynamically more stable than form II and thus suitable for further development. According to the thermal analysis and variable temperature XRD results, the recrystallization of form I occurred at approximately 145 degrees C after form II melted, however, no crystal transition behavior was observed below the lower melting point. The DSC thermograms at various heating rates and van't Hoff plots from the solubility studies indicated that the polymorphic pair would be monotropic. Copyright 2002 Wiley-Liss Inc. and the American Pharmaceutical Association

Stable carbon and sulfur isotopes as records of the early biosphere

NASA Technical Reports Server (NTRS)

Desmarais, David J.

1989-01-01

The abundance ratios of the stable isotopes of light elements such as carbon and sulfur can differ between various naturally-occurring chemical compounds. If coexisting compounds have achieved mutual chemical and isotopic equilibrium, then the relative isotopic composition can record the conditions at which equilibrium was last maintained. If coexisting chemical compounds indeed formed simultaneously but had not achieved mutual equilibrium, then their relative isotopic compositions often reflect the conditions and mechanisms associated with the kinetically controlled reactions responsible for their production. In the context of Mars, the stable isotopic compositions of various minerals might record not only the earlier environmental conditions of the planet, but also whether or not the chemistry of life ever occurred there. Two major geochemical reservoirs occur in Earth's crust, both for carbon and sulfur. In rocks formed in low temperature sedimentary environments, the oxidized forms of these elements tend to be enriched in the isotope having the larger mass, relative to the reduced forms. In sediments where the organics and sulfides were formed by biological processes, these isotopic contrasts were caused by the processes of biological CO2 fixation and dissimilatory sulfate reduction. Such isotopic contrasts between oxidized and reduced forms of carbon and sulfur are permitted by thermodynamics at ambient temperatures. However, nonbiological chemical reactions associated with the production of organic matter and the reduction of organics and sulfides are extremely slow at ambient temperatures. Thus the synthesis of organics and sulfides under ambient conditions illustrates life's profound role as a chemical catalyst that has altered the chemistry of Earth's crust. Because the stable isotopes of carbon and sulfur can reflect their chemistry, they are useful probes of the Martian surface.

First-Principles Prediction of Thermodynamically Stable Two-Dimensional Electrides

DOE PAGES

Ming, Wenmei; Yoon, Mina; Univ. of Tennessee, Knoxville, TN; ...

2016-10-21

Two-dimensional (2D) electrides, emerging as a new type of layered material whose electrons are confined in interlayer spaces instead of at atomic proximities, are receiving interest for their high performance in various (opto)electronics and catalytic applications. Experimentally, however, 2D electrides have been only found in a couple of layered nitrides and carbides. We report new thermodynamically stable alkaline-earth based 2D electrides by using a first-principles global structure optimization method, phonon spectrum analysis, and molecular dynamics simulation. The method was applied to binary compounds consisting of alkaline-earth elements as cations and group VA, VIA, or VIIA nonmetal elements as anions. Wemore » also revealed that the stability of a layered 2D electride structure is closely related to the cation/anion size ratio; stable 2D electrides possess a sufficiently large cation/anion size ratio to minimize electrostatic energy among cations, anions, and anionic electrons. This work demonstrates a new avenue to the discovery of thermodynamically stable 2D electrides beyond experimental material databases and provides new insight into the principles of electride design.« less

Magnetic properties and stability of Cu3V2O8 compound in the different phases

NASA Astrophysics Data System (ADS)

Jezierski, Andrzej

2016-11-01

The magnetic and thermodynamic properties of Cu3V2O8 compound in four structures (P-1, P21/c, P21/m and Cmca) are reported. The calculations are performed by using the Full-Potential Local Orbital Minimum Basis (FPLO) and Vienna ab initio Simulation Package (VASP) methods. We have applied the local density approximation (LDA) with the generalized gradient corrections (GGA). The effect of electron correlations was also included in GGA+U approximation. The thermodynamic properties were obtained in the quasi-harmonic Debye-Grüneisen model using the equation of states (EOS) in the form of Poirier-Tarantola. Our ab-intio results indicate that α (P-1) phase is stable below 1.87 GPa, β (P21/c) exists in the region 1.87

High-throughput density functional calculations to optimize properties and interfacial chemistry of piezoelectric materials

NASA Astrophysics Data System (ADS)

Barr, Jordan A.; Lin, Fang-Yin; Ashton, Michael; Hennig, Richard G.; Sinnott, Susan B.

2018-02-01

High-throughput density functional theory calculations are conducted to search through 1572 A B O3 compounds to find a potential replacement material for lead zirconate titanate (PZT) that exhibits the same excellent piezoelectric properties as PZT and lacks both its use of the toxic element lead (Pb) and the formation of secondary alloy phases with platinum (Pt) electrodes. The first screening criterion employed a search through the Materials Project database to find A -B combinations that do not form ternary compounds with Pt. The second screening criterion aimed to eliminate potential candidates through first-principles calculations of their electronic structure, in which compounds with a band gap of 0.25 eV or higher were retained. Third, thermodynamic stability calculations were used to compare the candidates in a Pt environment to compounds already calculated to be stable within the Materials Project. Formation energies below or equal to 100 meV/atom were considered to be thermodynamically stable. The fourth screening criterion employed lattice misfit to identify those candidate perovskites that have low misfit with the Pt electrode and high misfit of potential secondary phases that can be formed when Pt alloys with the different A and B components. To aid in the final analysis, dynamic stability calculations were used to determine those perovskites that have dynamic instabilities that favor the ferroelectric distortion. Analysis of the data finds three perovskites warranting further investigation: CsNb O3 , RbNb O3 , and CsTa O3 .

The effect of particle size on the morphology and thermodynamics of diblock copolymer/tethered-particle membranes.

PubMed

Zhang, Bo; Edwards, Brian J

2015-06-07

A combination of self-consistent field theory and density functional theory was used to examine the effect of particle size on the stable, 3-dimensional equilibrium morphologies formed by diblock copolymers with a tethered nanoparticle attached either between the two blocks or at the end of one of the blocks. Particle size was varied between one and four tenths of the radius of gyration of the diblock polymer chain for neutral particles as well as those either favoring or disfavoring segments of the copolymer blocks. Phase diagrams were constructed and analyzed in terms of thermodynamic diagrams to understand the physics associated with the molecular-level self-assembly processes. Typical morphologies were observed, such as lamellar, spheroidal, cylindrical, gyroidal, and perforated lamellar, with the primary concentration region of the tethered particles being influenced heavily by particle size and tethering location, strength of the particle-segment energetic interactions, chain length, and copolymer radius of gyration. The effect of the simulation box size on the observed morphology and system thermodynamics was also investigated, indicating possible effects of confinement upon the system self-assembly processes.

Thermodynamically stable vesicle formation from glycolipid biosurfactant sponge phase.

PubMed

Imura, Tomohiro; Yanagishita, Hiroshi; Ohira, Junko; Sakai, Hideki; Abe, Masahiko; Kitamoto, Dai

2005-06-25

Thermodynamically stable vesicle (L(alpha1)) formation from glycolipid biosurfactant sponge phase (L(3)) and its mechanism were investigated using a "natural" biocompatible mannosyl-erythritol lipid-A (MEL-A)/L-alpha-dilauroylphosphatidylcholine (DLPC) mixture by varying the composition. The trapping efficiency for calcein and turbidity measurements clearly indicated the existence of three regions: while the trapping efficiencies of the mixed MEL-A/DLPC assemblies at the compositions with X(DLPC)< or =0.1 or X(DLPC)> or =0.8 were almost zero, the mixed assemblies at the compositions with 0.1 or =0.8 were multilamellar vesicles (L(alpha)) with diameter from 2 to 10 microm. Meanwhile, dynamic light scattering (DLS) measurement revealed that the average size of the vesicles at the composition of X(DLPC)=0.3 was 633.2 nm, which is remarkably small compared to other compositions. Moreover, the mixed vesicle solution at the composition of X(DLPC)=0.3 was slightly bluish and turbid and kept its dispersion stability at 25 degrees C for more than 3 months, indicating the formation of a thermodynamically stable vesicle (L(alpha1)). These results exhibited the formation of a thermodynamically stable vesicle (L(alpha1)) with a high dispersibility from the MEL-A/DLPC mixture. The asymmetric distribution of MEL-A and DLPC in the two vesicle monolayers caused by the difference in geometrical structures is very likely to have changed their self-assembled structure from a sponge phase (L(3)) to a thermodynamically stable vesicle (L(alpha1)).

Absorbing a Little Water: The Structural, Thermodynamic, and Kinetic Relationship between Pyrogallol and Its Tetarto-Hydrate

PubMed Central

2013-01-01

The anhydrate and the stoichiometric tetarto-hydrate of pyrogallol (0.25 mol water per mol pyrogallol) are both storage stable at ambient conditions, provided that they are phase pure, with the system being at equilibrium at aw (water activity) = 0.15 at 25 °C. Structures have been derived from single crystal and powder X-ray diffraction data for the anhydrate and hydrate, respectively. It is notable that the tetarto-hydrate forms a tetragonal structure with water in channels, a framework that although stabilized by water, is found as a higher energy structure on a computationally generated crystal energy landscape, which has the anhydrate crystal structure as the most stable form. Thus, a combination of slurry experiments, X-ray diffraction, spectroscopy, moisture (de)sorption, and thermo-analytical methods with the computationally generated crystal energy landscape and lattice energy calculations provides a consistent picture of the finely balanced hydration behavior of pyrogallol. In addition, two monotropically related dimethyl sulfoxide monosolvates were found in the accompanying solid form screen. PMID:24027438

Absorbing a Little Water: The Structural, Thermodynamic, and Kinetic Relationship between Pyrogallol and Its Tetarto-Hydrate.

PubMed

Braun, Doris E; Bhardwaj, Rajni M; Arlin, Jean-Baptiste; Florence, Alastair J; Kahlenberg, Volker; Griesser, Ulrich J; Tocher, Derek A; Price, Sarah L

2013-09-04

The anhydrate and the stoichiometric tetarto-hydrate of pyrogallol (0.25 mol water per mol pyrogallol) are both storage stable at ambient conditions, provided that they are phase pure, with the system being at equilibrium at a w (water activity) = 0.15 at 25 °C. Structures have been derived from single crystal and powder X-ray diffraction data for the anhydrate and hydrate, respectively. It is notable that the tetarto-hydrate forms a tetragonal structure with water in channels, a framework that although stabilized by water, is found as a higher energy structure on a computationally generated crystal energy landscape, which has the anhydrate crystal structure as the most stable form. Thus, a combination of slurry experiments, X-ray diffraction, spectroscopy, moisture (de)sorption, and thermo-analytical methods with the computationally generated crystal energy landscape and lattice energy calculations provides a consistent picture of the finely balanced hydration behavior of pyrogallol. In addition, two monotropically related dimethyl sulfoxide monosolvates were found in the accompanying solid form screen.

Relationships between molecular structure and kinetic and thermodynamic controls in lipid systems. Part II: Phase behavior and transformation paths of SSS, PSS and PPS saturated triacylglycerols--effect of chain length mismatch.

PubMed

Bouzidi, Laziz; Narine, Suresh S

2012-01-01

The kinetic phase behavior and phase transformation paths of purified tristearoylglycerol (SSS), 3-palmitoyl-1,2-distearoyl-sn-glycerol (PSS) and 1,2-dipalmitoyl-3-stearoyl-sn-glycerol (PPS) were investigated in terms of polymorphism, crystallization and melting. The details of the phase transformation paths were obtained using the heating cycles of two sets of experiments: (a) cooling rate was varied and heating rate fixed and (b) cooling rate was fixed and heating rate varied. Kinetic effects were manifest in all measured properties, underscoring the complexity of the phase transformation paths for each TAG, and the intricate thermodynamics-molecular relationships. For the first time, XRD data obtained for SSS, PSS and PPS TAGs, cooled at rates higher than 0.5°C/min, suggested the formation of a transient structure similar to the so-called α(2)-phase which has been observed in mixed saturated-unsaturated TAGs quenched from the melt. The more stable phases (β' in PSS and PPS, and β in SSS) were only observed for cooling rates lower than 1.0°C/min. The kinetic and thermodynamic differences observed in the crystallization, structure and melting of SSS, PSS and PPS are proposed to be mainly due to the disturbances introduced at the "terrace" level via methyl-end group interactions, i.e., the missing of two or four CH(2) groups compared to SSS. The symmetrical SSS with a relatively flat "terrace" crystallizes preferably in the most stable β-form. Two missing CH(2) groups at the sn-1 position (PSS) introduces enough structural disturbances to promote the relative prevalence and persistence of the β'-phase, and four missing CH(2) groups at the sn-1 and sn-2 positions (PPS) is relatively too large of a disturbance and therefore favors the α-form. Copyright © 2011 Elsevier Ireland Ltd. All rights reserved.

Thermodynamic Stability of Ice II and Its Hydrogen-Disordered Counterpart: Role of Zero-Point Energy.

PubMed

Nakamura, Tatsuya; Matsumoto, Masakazu; Yagasaki, Takuma; Tanaka, Hideki

2016-03-03

We investigate why no hydrogen-disordered form of ice II has been found in nature despite the fact that most of hydrogen-ordered ices have hydrogen-disordered counterparts. The thermodynamic stability of a set of hydrogen-ordered ice II variants relative to ice II is evaluated theoretically. It is found that ice II is more stable than the disordered variants so generated as to satisfy the simple ice rule due to the lower zero-point energy as well as the pair interaction energy. The residual entropy of the disordered ice II phase gradually compensates the unfavorable free energy with increasing temperature. The crossover, however, occurs at a high temperature well above the melting point of ice III. Consequently, the hydrogen-disordered phase does not exist in nature. The thermodynamic stability of partially hydrogen-disordered ices is also scrutinized by examining the free-energy components of several variants obtained by systematic inversion of OH directions in ice II. The potential energy of one variant is lower than that of the ice II structure, but its Gibbs free energy is slightly higher than that of ice II due to the zero-point energy. The slight difference in the thermodynamic stability leaves the possibility of the partial hydrogen-disorder in real ice II.

Phase transition and thermodynamic stability of topological black holes in Hořava-Lifshitz gravity

NASA Astrophysics Data System (ADS)

Ma, Meng-Sen; Zhao, Ren; Liu, Yan-Song

2017-08-01

On the basis of horizon thermodynamics, we study the thermodynamic stability and P-V criticality of topological black holes constructed in Hořava-Lifshitz (HL) gravity without the detailed-balance condition (with general ɛ). In the framework of horizon thermodynamics, we do not need the concrete black hole solution (the metric function) and the concrete matter fields. It is shown that the HL black hole for k=0 is always thermodynamically stable. For k=1 , the thermodynamic behaviors and P-V criticality of the HL black hole are similar to those of RN-AdS black hole for some \

Divalent cations and molecular crowding buffers stabilize G-triplex at physiologically relevant temperatures

PubMed Central

Jiang, Hong-Xin; Cui, Yunxi; Zhao, Ting; Fu, Hai-Wei; Koirala, Deepak; Punnoose, Jibin Abraham; Kong, De-Ming; Mao, Hanbin

2015-01-01

G-triplexes are non-canonical DNA structures formed by G-rich sequences with three G-tracts. Putative G-triplex-forming sequences are expected to be more prevalent than putative G-quadruplex-forming sequences. However, the research on G-triplexes is rare. In this work, the effects of molecular crowding and several physiologically important metal ions on the formation and stability of G-triplexes were examined using a combination of circular dichroism, thermodynamics, optical tweezers and calorimetry techniques. We determined that molecular crowding conditions and cations, such as Na+, K+, Mg2+ and Ca2+, promote the formation of G-triplexes and stabilize these structures. Of these four metal cations, Ca2+ has the strongest stabilizing effect, followed by K+, Mg2+, and Na+ in a decreasing order. The binding of K+ to G-triplexes is accompanied by exothermic heats, and the binding of Ca2+ with G-triplexes is characterized by endothermic heats. G-triplexes formed from two G-triad layers are not stable at physiological temperatures; however, G-triplexes formed from three G-triads exhibit melting temperatures higher than 37°C, especially under the molecular crowding conditions and in the presence of K+ or Ca2+. These observations imply that stable G-triplexes may be formed under physiological conditions. PMID:25787838

DNA triplex structure, thermodynamics, and destabilisation: insight from molecular simulations.

PubMed

Boehm, Belinda J; Whidborne, Charles; Button, Alexander L; Pukala, Tara L; Huang, David M

2018-05-23

Molecular dynamics simulations are used to elucidate the structure and thermodynamics of DNA triplexes associated with the neurodegenerative disease Friedreich's ataxia (FRDA), as well as complexes of these triplexes with the small molecule netropsin, which is known to destabilise triplexes. The ability of molecular simulations in explicit solvent to accurately capture triplex thermodynamics is verified for the first time, with the free energy to dissociate a 15-base antiparallel purine triplex-forming oligomer (TFO) from the duplex found to be slightly higher than reported experimentally. The presence of netropsin in the minor groove destabilises the triplex as expected, reducing the dissociation free energy by approximately 50%. Netropsin binding is associated with localised narrowing of the minor groove near netropsin, an effect that has previously been under contention. This leads to localised widening of the major groove, weakening hydrogen bonds between the TFO and duplex. Consequently, destabilisation is found to be highly localised, occurring only when netropsin is bound directly opposite the TFO. The simulations also suggest that near saturation of the minor groove with ligand is required for complete triplex dissociation. A structural analysis of the DNA triplexes that can form with the FRDA-related duplex sequence indicates that the triplex with a parallel homopyrimidine TFO is likely to be more stable than the antiparallel homopurine-TFO triplex, which may have implications for disease onset and treatment.

Beating the thermodynamic limit with photo-activation of n-doping in organic semiconductors

NASA Astrophysics Data System (ADS)

Lin, Xin; Wegner, Berthold; Lee, Kyung Min; Fusella, Michael A.; Zhang, Fengyu; Moudgil, Karttikay; Rand, Barry P.; Barlow, Stephen; Marder, Seth R.; Koch, Norbert; Kahn, Antoine

2017-12-01

Chemical doping of organic semiconductors using molecular dopants plays a key role in the fabrication of efficient organic electronic devices. Although a variety of stable molecular p-dopants have been developed and successfully deployed in devices in the past decade, air-stable molecular n-dopants suitable for materials with low electron affinity are still elusive. Here we demonstrate that photo-activation of a cleavable air-stable dimeric dopant can result in kinetically stable and efficient n-doping of host semiconductors, whose reduction potentials are beyond the thermodynamic reach of the dimer’s effective reducing strength. Electron-transport layers doped in this manner are used to fabricate high-efficiency organic light-emitting diodes. Our strategy thus enables a new paradigm for using air-stable molecular dopants to improve conductivity in, and provide ohmic contacts to, organic semiconductors with very low electron affinity.

Simulation of free energies of bicontinuous morphologies formed through block copolymer/homopolymer self-assembly

NASA Astrophysics Data System (ADS)

Padmanabhan, Poornima; Martinez-Veracoechea, Francisco; Escobedo, Fernando

Different types of bicontinuous phases can be formed from A-B diblock copolymers by the addition of A-type homopolymers over a range of compositions and relative chain lengths. Particle-based molecular simulations were used to study three bicontinuous phases - double gyroid (G), double diamond (D) and plumber's nightmare (P) - near their triple point of coexistence. For 3-D ordered phases, the stability of the morphology formed in simulation is highly sensitive to box size whose exact size is unknown a-priori. Accurate free energy estimates are required to ascertain the stable phase, particularly when multiple competing phases spontaneously form at the conditions of interest. A variant of thermodynamic integration was implemented to obtain free energies and hence identify the stable phases and their optimal box sizes by tracing a reversible path that connects the ordered and disordered phases. Clear evidence was found of D-G and D-P phase coexistence, consistent with previous predictions for the same blend using Self-consistent field theory. Our simulations also allowed us to examine the microscopic details of these coexisting bicontinuous phases and detect key differences between the microstructure of their nodes and struts.

Energy storage systems for terrestrial solar generators

NASA Astrophysics Data System (ADS)

Jung, M.

1981-05-01

Mercury can react with Raney nickel to form the alloy NiHg4. This intermetallic compound is the basis of an excellently rechargeable positive electrode material. In combination with cadmium it forms a rechargeable cadmium/mercury oxide cell which can be operated under hermetically sealed conditions. Since both electrodes are thermodynamically stable in aqueous alkaline electrolytes, the self discharge rate of the cell is very low and hence the Coulomb efficiency even at very low charge rates in the order of 1000 - 2000 hrs. is higher than 95%. The cadmium/mercury oxide cells can be cycled more than a hundred times. These cells are particularly qualified to serve as an energy storage in combination with photovoltaic cells.

Interactions of Water Vapor with Oxides at Elevated Temperatures

NASA Technical Reports Server (NTRS)

Jacobson, Nathan; Opila, Elizabeth; Copland, Evan; Myers, Dwight

2003-01-01

Many volatile metal hydroxides form by reaction of the corresponding metal oxide with water vapor. These reactions are important in a number of high temperature corrosion processes. Experimental methods for studying the thermodynamics of metal hydroxides include: gas leak Knudsen cell mass spectrometry, free jet sampling mass spectrometry, transpiration and hydrogen-oxygen flame studies. The available experimental information is reviewed and the most stable metal hydroxide species are correlated with position in the periodic table. Current studies in our laboratory on the Si-O-H system are discussed.

Configuration-specific synthesis of the facial and meridional isomers of tris(8-hydroxyquinolinate)aluminum (Alq3).

PubMed

Katakura, Ryo; Koide, Yoshihiro

2006-07-24

Treatment of AlO(OH) with 3 equiv of 8-hydroxyquinolinol in refluxing deionized water provided the meridional and facial isomers of tris(8-hydroxyquinolinate)aluminum (Alq3) with good yields as solid deposits after 1 and 90 h, respectively. X-ray diffraction and solid-state 13C NMR studies revealed that mer-Alq3 is formed in the early stage of the reaction and then gradually converts to fac-Alq3, which is thermodynamically less stable, although no existence of a catalyst substance is implied.

Thermodynamic Stability of Low- and High-Index Spinel LiMn 2 O 4 Surface Terminations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Warburton, Robert E.; Iddir, Hakim; Curtiss, Larry A.

2016-05-04

Density functional theory calculations are performed within the generalized gradient approximation (GGA+U) to determine stable terminations of both low- and high-index spinel LiMn2O4 (LMO) surfaces. A grand canonical thermodynamic approach is employed, permitting a direct comparison of offstoichiometric surfaces with previously reported stoichiometric surface terminations at various environmental conditions. Within this formalism, we have identified trends in the structure of the low-index surfaces as a function of the Li and O chemical potentials. The results suggest that, under a range of chemical potentials for which bulk LMO is stable, Li/O and Li-rich (111) surface terminations are favored, neither of whichmore » adopts an inverse spinel structure in the subsurface region. This thermodynamic analysis is extended to identify stable structures for certain high-index surfaces, including (311), (331), (511), and (531), which constitute simple models for steps or defects that may be present on real LMO particles. The low- and high-index results are combined to determine the relative stability of each surface facet under a range of environmental conditions. The relative surface energies are further employed to predict LMO particle shapes through a Wulff construction approach, which suggests that LMO particles will adopt either an octahedron or a truncated octahedron shape at conditions in which LMO is thermodynamically stable. These results are in agreement with the experimental observations of LMO particle shapes.« less

Thermodynamic characteristics of a novel wind-solar-liquid air energy storage system

NASA Astrophysics Data System (ADS)

Ji, W.; Zhou, Y.; Sun, Y.; Zhang, W.; Pan, C. Z.; Wang, J. J.

2017-12-01

Due to the nature of fluctuation and intermittency, the utilization of wind and solar power will bring a huge impact to the power grid management. Therefore a novel hybrid wind-solar-liquid air energy storage (WS-LAES) system was proposed. In this system, wind and solar power are stored in the form of liquid air by cryogenic liquefaction technology and thermal energy by solar thermal collector, respectively. Owing to the high density of liquid air, the system has a large storage capacity and no geographic constraints. The WS-LAES system can store unstable wind and solar power for a stable output of electric energy and hot water. Moreover, a thermodynamic analysis was carried out to investigate the best system performance. The result shows that the increases of compressor adiabatic efficiency, turbine inlet pressure and inlet temperature all have a beneficial effect.

Immobilization of actinides in stable mineral type and ceramic materials (high temperature synthesis)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Starkov, O.; Konovalov, E.

1996-05-01

Alternative vitrification technologies are being developed in the world for the immobilization of high radioactive waste in materials with improved thermodynamic stability, as well as improved chemical and thermal stability and stability to radiation. Oxides, synthesized in the form of analogs to rock-forming minerals and ceramics, are among those materials that have highly stable properties and are compatible with the environment. In choosing the appropriate material, we need to be guided by its geometric stability, the minimal number of cations in the structure of the material and the presence of structural elements in the mineral that are isomorphs of uraniummore » and thorium, actinoids found in nature. Rare earth elements, yttrium, zirconium and calcium are therefore suitable. The minerals listed in the table (with the exception of the zircon) are pegatites by origin, i.e. they are formed towards the end of the magma crystallization of silicates form the residual melt, enriched with Ta, Nb, Ti, Zr, Ce, Y, U and Th. Uranium and thorium in the form of isomorphic admixtures form part of the lattice of the mineral. These minerals, which are rather simple in composition and structure and are formed under high temperatures, may be viewed as natural physio-chemical systems that are stable and long-lived in natural environments. The similarity of the properties of actinoids and lanthanoids plays an important role in the geochemistry of uranium and thorium; however, uranium (IV) is closer to the {open_quotes}heavy{close_quotes} group of lanthanoids (the yttrium group) while thorium (IV) is closer to the {open_quotes}light{close_quotes} group (the cerium group). That is why rare earth minerals contain uranium and thorium in the form of isomorphic admixtures.« less

A new polymorph of 4'-hydroxyvalerophenone revealed by thermoanalytical and X-ray diffraction studies

NASA Astrophysics Data System (ADS)

Lopes, Cátia S. D.; Bernardes, Carlos E. S.; Piedade, M. Fátima M.; Diogo, Hermínio P.; da Piedade, Manuel E. Minas

2017-04-01

A new polymorph of 1-(4-hydroxyphenyl)pentan-1-one (4'-hydroxyvalerophenone, HVP) was identified by using differential scanning calorimetry, hot stage microscopy, and X-ray powder diffraction. This novel crystal form (form II) was obtained by crystallization from melt. It has a fusion temperature of T fus = 324.3 ± 0.2 K and an enthalpy of fusion Δfus H m o = 18.14±0.18 kJ·mol-1. These values are significantly lower than those observed for the previously known phase (form I, monoclinic, space group P21/ c, T fus = 335.6 ± 0.7 K; Δfus H m o = 26.67±0.04 kJ·mol-1), which can be prepared by crystallization from ethanol. The results here obtained, therefore, suggest that form I is thermodynamically more stable than the newly identified form II and, furthermore, that the two polymorphs are monotropically related.

The topological pressure-temperature phase diagram of ritonavir, an extraordinary case of crystalline dimorphism.

PubMed

Céolin, R; Rietveld, I B

2015-01-01

A topological pressure-temperature phase diagram involving the phase relationships of ritonavir forms I and II has been constructed using experimental calorimetric and volumetric data available from the literature. The triple point I-II-liquid is located at a temperature of about 407 K and a pressure as extraordinarily small as 17.5 MPa (175 bar). Thus, the less soluble solid phase (form II) will become metastable on increasing pressure. At room temperature, form I becomes stable around 100 MPa indicating that form II may turn into form I at a relatively low pressure of 1000 bar, which may occur under processing conditions such as mixing or grinding. This case is a good example for which a proper thermodynamic evaluation trumps "rules of thumb" such as the density rule. Copyright © 2014 Elsevier Masson SAS. All rights reserved.

Reversible interconversion of carbon dioxide and formate by an electroactive enzyme

PubMed Central

Reda, Torsten; Plugge, Caroline M.; Abram, Nerilie J.; Hirst, Judy

2008-01-01

Carbon dioxide (CO2) is a kinetically and thermodynamically stable molecule. It is easily formed by the oxidation of organic molecules, during combustion or respiration, but is difficult to reduce. The production of reduced carbon compounds from CO2 is an attractive proposition, because carbon-neutral energy sources could be used to generate fuel resources and sequester CO2 from the atmosphere. However, available methods for the electrochemical reduction of CO2 require excessive overpotentials (are energetically wasteful) and produce mixtures of products. Here, we show that a tungsten-containing formate dehydrogenase enzyme (FDH1) adsorbed to an electrode surface catalyzes the efficient electrochemical reduction of CO2 to formate. Electrocatalysis by FDH1 is thermodynamically reversible—only small overpotentials are required, and the point of zero net catalytic current defines the reduction potential. It occurs under thoroughly mild conditions, and formate is the only product. Both as a homogeneous catalyst and on the electrode, FDH1 catalyzes CO2 reduction with a rate more than two orders of magnitude faster than that of any known catalyst for the same reaction. Formate oxidation is more than five times faster than CO2 reduction. Thermodynamically, formate and hydrogen are oxidized at similar potentials, so formate is a viable energy source in its own right as well as an industrially important feedstock and a stable intermediate in the conversion of CO2 to methanol and methane. FDH1 demonstrates the feasibility of interconverting CO2 and formate electrochemically, and it is a template for the development of robust synthetic catalysts suitable for practical applications. PMID:18667702

The stability of a crystal with diamond structure for patchy particles with tetrahedral symmetry.

PubMed

Noya, Eva G; Vega, Carlos; Doye, Jonathan P K; Louis, Ard A

2010-06-21

The phase diagram of model anisotropic particles with four attractive patches in a tetrahedral arrangement has been computed at two different values of the range of the potential, with the aim of investigating the conditions under which a diamond crystal can be formed. We find that the diamond phase is never stable for our longer-ranged potential. At low temperatures and pressures, the fluid freezes into a body-centered-cubic solid that can be viewed as two interpenetrating diamond lattices with a weak interaction between the two sublattices. Upon compression, an orientationally ordered face-centered-cubic crystal becomes more stable than the body-centered-cubic crystal, and at higher temperatures, a plastic face-centered-cubic phase is stabilized by the increased entropy due to orientational disorder. A similar phase diagram is found for the shorter-ranged potential, but at low temperatures and pressures, we also find a region over which the diamond phase is thermodynamically favored over the body-centered-cubic phase. The higher vibrational entropy of the diamond structure with respect to the body-centered-cubic solid explains why it is stable even though the enthalpy of the latter phase is lower. Some preliminary studies on the growth of the diamond structure starting from a crystal seed were performed. Even though the diamond phase is never thermodynamically stable for the longer-ranged model, direct coexistence simulations of the interface between the fluid and the body-centered-cubic crystal and between the fluid and the diamond crystal show that at sufficiently low pressures, it is quite probable that in both cases the solid grows into a diamond crystal, albeit involving some defects. These results highlight the importance of kinetic effects in the formation of diamond crystals in systems of patchy particles.

Distance-dependent duplex DNA destabilization proximal to G-quadruplex/i-motif sequences

PubMed Central

König, Sebastian L. B.; Huppert, Julian L.; Sigel, Roland K. O.; Evans, Amanda C.

2013-01-01

G-quadruplexes and i-motifs are complementary examples of non-canonical nucleic acid substructure conformations. G-quadruplex thermodynamic stability has been extensively studied for a variety of base sequences, but the degree of duplex destabilization that adjacent quadruplex structure formation can cause has yet to be fully addressed. Stable in vivo formation of these alternative nucleic acid structures is likely to be highly dependent on whether sufficient spacing exists between neighbouring duplex- and quadruplex-/i-motif-forming regions to accommodate quadruplexes or i-motifs without disrupting duplex stability. Prediction of putative G-quadruplex-forming regions is likely to be assisted by further understanding of what distance (number of base pairs) is required for duplexes to remain stable as quadruplexes or i-motifs form. Using oligonucleotide constructs derived from precedented G-quadruplexes and i-motif-forming bcl-2 P1 promoter region, initial biophysical stability studies indicate that the formation of G-quadruplex and i-motif conformations do destabilize proximal duplex regions. The undermining effect that quadruplex formation can have on duplex stability is mitigated with increased distance from the duplex region: a spacing of five base pairs or more is sufficient to maintain duplex stability proximal to predicted quadruplex/i-motif-forming regions. PMID:23771141

Simulation studies of glassy nanoclusters

NASA Astrophysics Data System (ADS)

Bowles, Richard

2015-03-01

Glassy materials are amorphous solids usually formed by rapidly cooling a liquid below its equilibrium freezing temperature, trapping the particles in a liquid-like structure at the glass transition temperature. While appearing throughout nature and industry, these systems continue to challenge the way we think about the dynamics and thermodynamics of condensed matter and a fundamental understanding of the glass state remains elusive. This talk describes molecular simulation studies of glassy behaviour in binary Lennard-Jones nanoclusters. We show that the relaxation dynamics of the clusters is nonuniform and the core of the cluster goes through a glass transition at higher temperatures than at the surface. As the nanoclusters are cooled, they also exhibit a fragile-strong crossover in their dynamics and we explore how this phenomena is linked to the potential energy landscape of the clusters. Finally, we compare the properties of nanoclusters formed through vapour condensation, directly to the glassy state, with those of glassy clusters formed through traditional supercooling. The condensation clusters are shown to form ultra-stable glassy states analogous to the ultra-stable glasses formed by thin film vapour deposition onto a cold substrate. In all, our work suggests that nanoscale clusters exhibit some unique glassy features, while also offering potential insights into the fundamental nature of the glass transition.

Rotigotine: Unexpected Polymorphism with Predictable Overall Monotropic Behavior.

PubMed

Rietveld, Ivo B; Céolin, René

2015-12-01

Crystallization of polymorphs still has a touch of art, as even prior observations of polymorphs do not guarantee their crystallization. However, once crystals of various polymorphs have been obtained, their relative stabilities can be established with a straightforward thermodynamic approach even if the conclusion will depend on the quality of the experimental data. Rotigotine is an active pharmaceutical ingredient, which has suffered the same setback as Ritonavir: a sudden appearance of a more stable crystalline polymorph than the one used for the formulation. Although the cause of the defect in the formulation was quickly established, the interpretation of the phase behavior of rotigotine has been lacking in clarity. In the present paper, data published in the patents resulting from the discovery of the new polymorph have been used to establish the pressure-temperature phase diagram of the two known solid forms of rotigotine. The analysis clearly demonstrates that form II is the stable solid phase and form I is metastable in the entire pressure-temperature domain: form I is overall monotropic in relation to form II. Thus, it was a sensible decision of European Medicines Agency to ask for a reformulation, as the first formulation was metastable even if crystallization appeared to be very slow. © 2015 Wiley Periodicals, Inc. and the American Pharmacists Association.

Insights into Hydrate Formation and Stability of Morphinanes from a Combination of Experimental and Computational Approaches

PubMed Central

2014-01-01

Morphine, codeine, and ethylmorphine are important drug compounds whose free bases and hydrochloride salts form stable hydrates. These compounds were used to systematically investigate the influence of the type of functional groups, the role of water molecules, and the Cl– counterion on molecular aggregation and solid state properties. Five new crystal structures have been determined. Additionally, structure models for anhydrous ethylmorphine and morphine hydrochloride dihydrate, two phases existing only in a very limited humidity range, are proposed on the basis of computational dehydration modeling. These match the experimental powder X-ray diffraction patterns and the structural information derived from infrared spectroscopy. All 12 structurally characterized morphinane forms (including structures from the Cambridge Structural Database) crystallize in the orthorhombic space group P212121. Hydrate formation results in higher dimensional hydrogen bond networks. The salt structures of the different compounds exhibit only little structural variation. Anhydrous polymorphs were detected for all compounds except ethylmorphine (one anhydrate) and its hydrochloride salt (no anhydrate). Morphine HCl forms a trihydrate and dihydrate. Differential scanning and isothermal calorimetry were employed to estimate the heat of the hydrate ↔ anhydrate phase transformations, indicating an enthalpic stabilization of the respective hydrate of 5.7 to 25.6 kJ mol–1 relative to the most stable anhydrate. These results are in qualitative agreement with static 0 K lattice energy calculations for all systems except morphine hydrochloride, showing the need for further improvements in quantitative thermodynamic prediction of hydrates having water···water interactions. Thus, the combination of a variety of experimental techniques, covering temperature- and moisture-dependent stability, and computational modeling allowed us to generate sufficient kinetic, thermodynamic and structural information to understand the principles of hydrate formation of the model compounds. This approach also led to the detection of several new crystal forms of the investigated morphinanes. PMID:25036525

Thermodynamics, stability and Hawking-Page transition of Kerr black holes from Rényi statistics

NASA Astrophysics Data System (ADS)

Czinner, Viktor G.; Iguchi, Hideo

2017-12-01

Thermodynamics of rotating black holes described by the Rényi formula as equilibrium and zeroth law compatible entropy function is investigated. We show that similarly to the standard Boltzmann approach, isolated Kerr black holes are stable with respect to axisymmetric perturbations in the Rényi model. On the other hand, when the black holes are surrounded by a bath of thermal radiation, slowly rotating black holes can also be in stable equilibrium with the heat bath at a fixed temperature, in contrast to the Boltzmann description. For the question of possible phase transitions in the system, we show that a Hawking-Page transition and a first order small black hole/large black hole transition occur, analogous to the picture of rotating black holes in AdS space. These results confirm the similarity between the Rényi-asymptotically flat and Boltzmann-AdS approaches to black hole thermodynamics in the rotating case as well. We derive the relations between the thermodynamic parameters based on this correspondence.

Crystallization kinetics and molecular mobility of an amorphous active pharmaceutical ingredient: A case study with Biclotymol.

PubMed

Schammé, Benjamin; Couvrat, Nicolas; Malpeli, Pascal; Delbreilh, Laurent; Dupray, Valérie; Dargent, Éric; Coquerel, Gérard

2015-07-25

The present case study focuses on the crystallization kinetics and molecular mobility of an amorphous mouth and throat drug namely Biclotymol, through differential scanning calorimetry (DSC), temperature resolved X-ray powder diffraction (TR-XRPD) and hot stage microscopy (HSM). Kinetics of crystallization above the glass transition through isothermal and non-isothermal cold crystallization were considered. Avrami model was used for isothermal crystallization process. Non-isothermal cold crystallization was investigated through Augis and Bennett model. Differences between crystallization processes have been ascribed to a site-saturated nucleation mechanism of the metastable form, confirmed by optical microscopy images. Regarding molecular mobility, a feature of molecular dynamics in glass-forming liquids as thermodynamic fragility index m was determined through calorimetric measurements. It turned out to be around m=100, describing Biclotymol as a fragile glass-former for Angell's classification. Relatively long-term stability of amorphous Biclotymol above Tg was analyzed indirectly by calorimetric monitoring to evaluate thermodynamic parameters and crystallization behavior of glassy Biclotymol. Within eight months of storage above Tg (T=Tg+2°C), amorphous Biclotymol does not show a strong inclination to crystallize and forms a relatively stable glass. This case study, involving a multidisciplinary approach, points out the importance of continuing looking for stability predictors. Copyright © 2015 Elsevier B.V. All rights reserved.

Packing Polymorphism of Dapivirine and Its Impact on the Performance of a Dapivirine-Releasing Silicone Elastomer Vaginal Ring.

PubMed

McCoy, Clare F; Murphy, Diarmaid J; Boyd, Peter; Derrick, Tiffany; Spence, Patrick; Devlin, Brid; Malcolm, R Karl

2017-08-01

A silicone elastomer vaginal ring providing sustained release over 28 days of the anti-retroviral microbicide dapivirine has recently completed phase III clinical testing and showed moderate protection against HIV acquisition. In support of the product licensure program, we report the impact of dapivirine packing polymorphism on the thermal and solubility characteristics of dapivirine and on the in vitro performance of the 25 mg dapivirine ring product. This is the first time that polymorphism has been reported for a drug-releasing vaginal ring product. Thermal, particle size, powder X-ray diffraction, and thermodynamic solubility analyses of dapivirine polymorphic forms I and IV, both of which are persistent at room temperature and with form I being the thermodynamically stable form, were conducted for both micronized and non-micronized materials. No significant differences in solubility between DPV forms I and IV were observed in media commonly used for in vitro release testing. Matrix-type silicone elastomer vaginal rings were manufactured and the impact of dapivirine polymorphism on key in vitro parameters (compression and tensile behavior; content assay; in vitro release; residual content assay) was investigated. The data demonstrate that dapivirine packing polymorphism has no significant impact on in vitro performance of the 25 mg dapivirine vaginal ring. Copyright © 2017 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

Thermodynamics and NMR studies on Duck, Heron and Human HBV encapsidation signals

PubMed Central

Girard, Frederic C.; Ottink, Otmar M.; Ampt, Kirsten A.M.; Tessari, Marco; Wijmenga, Sybren S.

2007-01-01

Hepatitis B virus (HBV) replication is initiated by binding of its reverse transcriptase (P) to the apical stem-loop (AL) and primer loop (PL) of epsilon, a highly conserved RNA element at the 5′-end of the RNA pregenome. Mutation studies on duck/heron and human in vitro systems have shown similarities but also differences between their P–epsilon interaction. Here, NMR and UV thermodynamic data on AL (and PL) from these three species are presented. The stabilities of the duck and heron ALs were found to be similar, and much lower than that of human. NMR data show that this low stability stems from an 11-nt internal bulge destabilizing the stem of heron AL. In duck, although structured at low temperature, this region also forms a weak point as its imino resonances broaden to disappearance between 30 and 35°C well below the overall AL melting temperature. Surprisingly, the duck- and heron ALs were both found to be capped by a stable well-structured UGUU tetraloop. All avian ALs are expected to adhere to this because of their conserved sequence. Duck PL is stable and structured and, in view of sequence similarities, the same is expected for heron - and human PL. PMID:17430968

Comparison of atmospheric reactions of NH3 and NH2 with hydroxyl radical on the singlet, doublet and triplet potential energy surfaces, kinetic and mechanistic study

NASA Astrophysics Data System (ADS)

Vahedpour, Morteza; Douroudgari, Hamed; Afshar, Sheida; Asgharzade, Somaie

2018-05-01

The NH2 + OH and NH3 + OH reactions on the singlet, doublet and triplet potential energy surfaces carry out using MP2, QCISD, G3MP2, M06-2X, B3LYP, and CCSD(T)//MP2 levels. Three pre-reactive complexes, 1C1, 3C1 and 3C2 were formed among amidogen and hydroxyl radicals. From variety of the 1C1, four types of products are obtained that 1HNO + H2 is thermodynamically stable and three others are being stable after relaxation to triplet state. On the triplet state, five types of adducts are obtained that four of them have enough thermodynamic stability. Two intersystem crossing are presented among triplet and singlet states of the NH2 + OH reaction. 3NH + H2O adduct is spontaneous and exothermic in standard condition. Results lead to different adducts which are playing significant role in the atmospheric and combustion chemistry. The rate constants of selected pathways are calculated at the 300-2500 K temperature range at M06-2X/aug-ccpvqz and CCSD(T)/6-311++G(3df, 3pd) levels of theory.

The third law of thermodynamics and the fractional entropies

NASA Astrophysics Data System (ADS)

Baris Bagci, G.

2016-08-01

We consider the fractal calculus based Ubriaco and Machado entropies and investigate whether they conform to the third law of thermodynamics. The Ubriaco entropy satisfies the third law of thermodynamics in the interval 0 < q ≤ 1 exactly where it is also thermodynamically stable. The Machado entropy, on the other hand, yields diverging inverse temperature in the region 0 < q ≤ 1, albeit with non-vanishing negative entropy values. Therefore, despite the divergent inverse temperature behavior, the Machado entropy fails the third law of thermodynamics. We also show that the aforementioned results are also supported by the one-dimensional Ising model with no external field.

Comparison of the relative stability of pharmaceutical cocrystals consisting of paracetamol and dicarboxylic acids.

PubMed

Suzuki, Naoto; Kawahata, Masatoshi; Yamaguchi, Kentaro; Suzuki, Toyofumi; Tomono, Kazuo; Fukami, Toshiro

2018-04-01

The aim of this study is to evaluate the relative stability of pharmaceutical cocrystals consisting of paracetamol (APAP) and oxalic acid (OXA) or maleic acid (MLA). These observations of cocrystal stability under various conditions are useful coformer criteria when cocrystals are selected as the active pharmaceutical ingredient in drug development. The relative stability was determined from the preferentially formed cocrystals under various conditions. Cocrystal of APAP-OXA was more stable than that of APAP-MLA in a ternary cogrinding system and possessed thermodynamical stability. On the other hand, when grinding with moisture or maintaining at high temperatures and relative humidity conditions, APAP-MLA was more stable, and OXA converted to OXA dihydrate. In the slurry method, APAP-OXA was more stable in aprotic solvents because the APAP-OXA with low-solubility product precipitated. The relative stability order was affected by preparing conditions of presence of moisture. This order might attribute to the small difference of crystal structure in the extension of the hydrogen bond network.

Thermodynamic and redox properties of graphene oxides for lithium-ion battery applications: a first principles density functional theory modeling approach.

PubMed

Kim, Sunghee; Kim, Ki Chul; Lee, Seung Woo; Jang, Seung Soon

2016-07-27

Understanding the thermodynamic stability and redox properties of oxygen functional groups on graphene is critical to systematically design stable graphene-based positive electrode materials with high potential for lithium-ion battery applications. In this work, we study the thermodynamic and redox properties of graphene functionalized with carbonyl and hydroxyl groups, and the evolution of these properties with the number, types and distribution of functional groups by employing the density functional theory method. It is found that the redox potential of the functionalized graphene is sensitive to the types, number, and distribution of oxygen functional groups. First, the carbonyl group induces higher redox potential than the hydroxyl group. Second, more carbonyl groups would result in higher redox potential. Lastly, the locally concentrated distribution of the carbonyl group is more beneficial to have higher redox potential compared to the uniformly dispersed distribution. In contrast, the distribution of the hydroxyl group does not affect the redox potential significantly. Thermodynamic investigation demonstrates that the incorporation of carbonyl groups at the edge of graphene is a promising strategy for designing thermodynamically stable positive electrode materials with high redox potentials.

Solubility behavior of lamivudine crystal forms in recrystallization solvents.

PubMed

Jozwiakowski, M J; Nguyen, N A; Sisco, J M; Spancake, C W

1996-02-01

Lamivudine can be obtained as acicular crystals (form I, 0.2 hydrate) from water or methanol and as bipyramidal crystals (form II, nonsolvated) from many nonaqueous solvents. Form II is thermodynamically favored in the solid state (higher melting point and greater density than form I) at ambient relative humidities. Solubility measurements on both forms versus solvent and temperature was used to determine whether entropy or enthalpy was the driving force for solubility. Solution calorimetry data indicated that form I is favored (less soluble) in all solvents studied on the basis of enthalpy alone. In higher alcohols and other organic solvents, form I has a larger entropy of solution than form II, which compensates for the enthalpic factors and results in physical stability for form II in these systems. The metastable crystal form solubility at 25 degrees C was estimated to be 1.2-2.3 times as high as the equilibrium solubility of the stable form, depending on the temperature, solvent, and crystal form. Binary solvent studies showed that > 18-20% water must be present in ethanol to convert the excess solid to form I at equilibrium.

The effect of particle size on the morphology and thermodynamics of diblock copolymer/tethered-particle membranes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Bo; Edwards, Brian J., E-mail: bje@utk.edu

A combination of self-consistent field theory and density functional theory was used to examine the effect of particle size on the stable, 3-dimensional equilibrium morphologies formed by diblock copolymers with a tethered nanoparticle attached either between the two blocks or at the end of one of the blocks. Particle size was varied between one and four tenths of the radius of gyration of the diblock polymer chain for neutral particles as well as those either favoring or disfavoring segments of the copolymer blocks. Phase diagrams were constructed and analyzed in terms of thermodynamic diagrams to understand the physics associated withmore » the molecular-level self-assembly processes. Typical morphologies were observed, such as lamellar, spheroidal, cylindrical, gyroidal, and perforated lamellar, with the primary concentration region of the tethered particles being influenced heavily by particle size and tethering location, strength of the particle-segment energetic interactions, chain length, and copolymer radius of gyration. The effect of the simulation box size on the observed morphology and system thermodynamics was also investigated, indicating possible effects of confinement upon the system self-assembly processes.« less

Noncommutative geometry inspired Einstein–Gauss–Bonnet black holes

NASA Astrophysics Data System (ADS)

Ghosh, Sushant G.

2018-04-01

Low energy limits of a string theory suggests that the gravity action should include quadratic and higher-order curvature terms, in the form of dimensionally continued Gauss–Bonnet densities. Einstein–Gauss–Bonnet is a natural extension of the general relativity to higher dimensions in which the first and second-order terms correspond, respectively, to general relativity and Einstein–Gauss–Bonnet gravity. We obtain five-dimensional (5D) black hole solutions, inspired by a noncommutative geometry, with a static spherically symmetric, Gaussian mass distribution as a source both in the general relativity and Einstein–Gauss–Bonnet gravity cases, and we also analyzes their thermodynamical properties. Owing the noncommutative corrected black hole, the thermodynamic quantities have also been modified, and phase transition is shown to be achievable. The phase transitions for the thermodynamic stability, in both the theories, are characterized by a discontinuity in the specific heat at r_+=rC , with the stable (unstable) branch for r < (>) rC . The metric of the noncommutative inspired black holes smoothly goes over to the Boulware–Deser solution at large distance. The paper has been appended with a calculation of black hole mass using holographic renormalization.

Physicochemical Characterization and Thermodynamic Studies of Nanoemulsion-Based Transdermal Delivery System for Fullerene

PubMed Central

Basri, Mahiran; Tripathy, Minaketan; Abdul-Malek, Emilia

2014-01-01

Fullerene nanoemulsions were formulated in palm kernel oil esters stabilized by low amount of mixed nonionic surfactants. Pseudoternary phase diagrams were established in the colloidal system of PKOEs/Tween 80 : Span 80/water incorporated with fullerene as antioxidant. Preformulation was subjected to combination of high and low energy emulsification methods and the physicochemical characteristics of fullerene nanoemulsions were analyzed using electroacoustic spectrometer. Oil-in-water (O/W) nanoemulsions with particle sizes in the range of 70–160 nm were formed. The rheological characteristics of colloidal systems exhibited shear thinning behavior which fitted well into the power law model. The effect of xanthan gum (0.2–1.0%, w/w) and beeswax (1–3%, w/w) in the estimation of thermodynamics was further studied. From the energetic parameters calculated for the viscous flow, a moderate energy barrier for transport process was observed. Thermodynamic study showed that the enthalpy was positive in all xanthan gum and beeswax concentrations indicating that the formation of nanoemulsions could be endothermic in nature. Fullerene nanoemulsions with 0.6% or higher xanthan gum content were found to be stable against creaming and flocculation when exposed to extreme environmental conditions. PMID:25165736

Group additivity-Pourbaix diagrams advocate thermodynamically stable nanoscale clusters in aqueous environments

PubMed Central

Wills, Lindsay A.; Qu, Xiaohui; Chang, I-Ya; Mustard, Thomas J. L.; Keszler, Douglas A.; Persson, Kristin A.; Cheong, Paul Ha-Yeon

2017-01-01

The characterization of water-based corrosion, geochemical, environmental and catalytic processes rely on the accurate depiction of stable phases in a water environment. The process is aided by Pourbaix diagrams, which map the equilibrium solid and solution phases under varying conditions of pH and electrochemical potential. Recently, metastable or possibly stable nanometric aqueous clusters have been proposed as intermediate species in non-classical nucleation processes. Herein, we describe a Group Additivity approach to obtain Pourbaix diagrams with full consideration of multimeric cluster speciation from computations. Comparisons with existing titration results from experiments yield excellent agreement. Applying this Group Additivity-Pourbaix approach to Group 13 elements, we arrive at a quantitative evaluation of cluster stability, as a function of pH and concentration, and present compelling support for not only metastable but also thermodynamically stable multimeric clusters in aqueous solutions. PMID:28643782

Group additivity-Pourbaix diagrams advocate thermodynamically stable nanoscale clusters in aqueous environments

NASA Astrophysics Data System (ADS)

Wills, Lindsay A.; Qu, Xiaohui; Chang, I.-Ya; Mustard, Thomas J. L.; Keszler, Douglas A.; Persson, Kristin A.; Cheong, Paul Ha-Yeon

2017-06-01

The characterization of water-based corrosion, geochemical, environmental and catalytic processes rely on the accurate depiction of stable phases in a water environment. The process is aided by Pourbaix diagrams, which map the equilibrium solid and solution phases under varying conditions of pH and electrochemical potential. Recently, metastable or possibly stable nanometric aqueous clusters have been proposed as intermediate species in non-classical nucleation processes. Herein, we describe a Group Additivity approach to obtain Pourbaix diagrams with full consideration of multimeric cluster speciation from computations. Comparisons with existing titration results from experiments yield excellent agreement. Applying this Group Additivity-Pourbaix approach to Group 13 elements, we arrive at a quantitative evaluation of cluster stability, as a function of pH and concentration, and present compelling support for not only metastable but also thermodynamically stable multimeric clusters in aqueous solutions.

RRKM and master equation kinetic analysis of parallel addition reactions of isomeric radical intermediates in hydrocarbon flames

NASA Astrophysics Data System (ADS)

Winter, Pierre M.; Rheaume, Michael; Cooksy, Andrew L.

2017-08-01

We have calculated the temperature-dependent rate coefficients of the addition reactions of butadien-2-yl (C4H5) and acroylyl (C3H3O) radicals with ethene (C2H4), carbon monoxide (CO), formaldehyde (H2CO), hydrogen cyanide (HCN), and ketene (H2CCO), in order to explore the balance between kinetic and thermodynamic control in these combustion-related reactions. For the C4H5 radical, the 1,3-diene form of the addition products is more stable than the 1,2-diene, but the 1,2-diene form of the radical intermediate is stabilized by an allylic delocalization, which may influence the relative activation energies. For the reactions combining C3H3O with C2H4, CO, and HCN, the opposite is true: the 1,2-enone form of the addition products is more stable than the 1,3-enone, whereas the 1,3-enone is the slightly more stable radical species. Optimized geometries and vibrational modes were computed with the QCISD/aug-cc-pVDZ level and basis, followed by single-point CCSD(T)-F12a/cc-pVDZ-F12 energy calculations. Our findings indicate that the kinetics in all cases favor reaction along the 1,3 pathway for both the C4H5 and C3H3O systems. The Rice-Ramsperger-Kassel-Marcus (RRKM) microcanonical rate coefficients and subsequent solution of the chemical master equation were used to predict the time-evolution of our system under conditions from 500 K to 2000 K and from 10-5 bar to 10 bars. Despite the 1,3 reaction pathway being more favorable for the C4H5 system, our results predict branching ratios of the 1,2 to 1,3 product as high as 0.48 at 1 bar. Similar results hold for the acroylyl system under these combustion conditions, suggesting that under kinetic control the branching of these reactions may be much more significant than the thermodynamics would suggest. This effect may be partly attributed to the low energy difference between 1,2 and 1,3 forms of the radical intermediate. No substantial pressure-dependence is found for the overall forward reaction rates until pressures decrease below 0.1 bar.

An equilibrium ab initio atomistic thermodynamics study of chlorine adsorption on the Cu(001) surface.

PubMed

Suleiman, Ibrahim A; Radny, Marian W; Gladys, Michael J; Smith, Phillip V; Mackie, John C; Kennedy, Eric M; Dlugogorski, Bogdan Z

2011-06-07

The effect of chlorine (Cl) chemisorption on the energetics and atomic structure of the Cu(001) surface over a wide range of chlorine pressures and temperatures has been studied using equilibrium ab initio atomistic thermodynamics to elucidate the formation of cuprous chloride (CuCl) as part of the Deacon reaction on copper metal. The calculated surface free energies show that the 1/2 monolayer (ML) c(2 × 2)-Cl phase with chlorine atoms adsorbed at the hollow sites is the most stable structure for a wide range of Cl chemical potential, in agreement with experimental observations. It is also found that at very low pressure and exposure, but elevated temperature, the 1/9 ML and 1/4 ML phases become the most stable. By contrast, a high coverage of Cl does not lead to thermodynamically stable geometries. The subsurface adsorption of Cl atoms, however, dramatically increases the stability of the 1 ML and 2 ML adsorption configurations providing a possible pathway for the formation of the bulk-chloride surface phases in the kinetic regime.

Ionic solutions of two-dimensional materials

NASA Astrophysics Data System (ADS)

Cullen, Patrick L.; Cox, Kathleen M.; Bin Subhan, Mohammed K.; Picco, Loren; Payton, Oliver D.; Buckley, David J.; Miller, Thomas S.; Hodge, Stephen A.; Skipper, Neal T.; Tileli, Vasiliki; Howard, Christopher A.

2017-03-01

Strategies for forming liquid dispersions of nanomaterials typically focus on retarding reaggregation, for example via surface modification, as opposed to promoting the thermodynamically driven dissolution common for molecule-sized species. Here we demonstrate the true dissolution of a wide range of important 2D nanomaterials by forming layered material salts that spontaneously dissolve in polar solvents yielding ionic solutions. The benign dissolution advantageously maintains the morphology of the starting material, is stable against reaggregation and can achieve solutions containing exclusively individualized monolayers. Importantly, the charge on the anionic nanosheet solutes is reversible, enables targeted deposition over large areas via electroplating and can initiate novel self-assembly upon drying. Our findings thus reveal a unique solution-like behaviour for 2D materials that enables their scalable production and controlled manipulation.

Observation of Two-Dimensional Localized Jones-Roberts Solitons in Bose-Einstein Condensates

NASA Astrophysics Data System (ADS)

Meyer, Nadine; Proud, Harry; Perea-Ortiz, Marisa; O'Neale, Charlotte; Baumert, Mathis; Holynski, Michael; Kronjäger, Jochen; Barontini, Giovanni; Bongs, Kai

2017-10-01

Jones-Roberts solitons are the only known class of stable dark solitonic solutions of the nonlinear Schrödinger equation in two and three dimensions. They feature a distinctive elongated elliptical shape that allows them to travel without change of form. By imprinting a triangular phase pattern, we experimentally generate two-dimensional Jones-Roberts solitons in a three-dimensional atomic Bose-Einstein condensate. We monitor their dynamics, observing that this kind of soliton is indeed not affected by dynamic (snaking) or thermodynamic instabilities, that instead make other classes of dark solitons unstable in dimensions higher than one. Our results confirm the prediction that Jones-Roberts solitons are stable solutions of the nonlinear Schrödinger equation and promote them for applications beyond matter wave physics, like energy and information transport in noisy and inhomogeneous environments.

The OpenCalphad thermodynamic software interface.

PubMed

Sundman, Bo; Kattner, Ursula R; Sigli, Christophe; Stratmann, Matthias; Le Tellier, Romain; Palumbo, Mauro; Fries, Suzana G

2016-12-01

Thermodynamic data are needed for all kinds of simulations of materials processes. Thermodynamics determines the set of stable phases and also provides chemical potentials, compositions and driving forces for nucleation of new phases and phase transformations. Software to simulate materials properties needs accurate and consistent thermodynamic data to predict metastable states that occur during phase transformations. Due to long calculation times thermodynamic data are frequently pre-calculated into "lookup tables" to speed up calculations. This creates additional uncertainties as data must be interpolated or extrapolated and conditions may differ from those assumed for creating the lookup table. Speed and accuracy requires that thermodynamic software is fully parallelized and the Open-Calphad (OC) software is the first thermodynamic software supporting this feature. This paper gives a brief introduction to computational thermodynamics and introduces the basic features of the OC software and presents four different application examples to demonstrate its versatility.

The OpenCalphad thermodynamic software interface

PubMed Central

Sundman, Bo; Kattner, Ursula R; Sigli, Christophe; Stratmann, Matthias; Le Tellier, Romain; Palumbo, Mauro; Fries, Suzana G

2017-01-01

Thermodynamic data are needed for all kinds of simulations of materials processes. Thermodynamics determines the set of stable phases and also provides chemical potentials, compositions and driving forces for nucleation of new phases and phase transformations. Software to simulate materials properties needs accurate and consistent thermodynamic data to predict metastable states that occur during phase transformations. Due to long calculation times thermodynamic data are frequently pre-calculated into “lookup tables” to speed up calculations. This creates additional uncertainties as data must be interpolated or extrapolated and conditions may differ from those assumed for creating the lookup table. Speed and accuracy requires that thermodynamic software is fully parallelized and the Open-Calphad (OC) software is the first thermodynamic software supporting this feature. This paper gives a brief introduction to computational thermodynamics and introduces the basic features of the OC software and presents four different application examples to demonstrate its versatility. PMID:28260838

Origins of hydration differences in homochiral and racemic crystals of aspartic acid.

PubMed

Juliano, Thomas R; Korter, Timothy M

2015-02-26

The propensity for crystalline hydrates of organic molecules to form is related to the strength of the interactions between molecules, including the chiral composition of the molecular solids. Specifically, homochiral versus racemic crystalline samples can exhibit distinct differences in their ability to form energetically stable hydrates. The focus of the current study is a comparison of the crystal structures and intermolecular forces found in solid-state L-aspartic acid, DL-aspartic acid, and L-aspartic acid monohydrate. The absence of experimental evidence for the DL-aspartic acid monohydrate is considered here in terms of the enhanced thermodynamic stability of the DL-aspartic acid anhydrate crystal as compared to the L-aspartic acid anhydrate as revealed through solid-state density functional theory calculations and terahertz spectroscopic measurements. The results indicate that anhydrous DL-aspartic acid is the more stable solid, not due to intermolecular forces alone but also due to the improved conformations of the molecules within the racemic solid. Hemihydrated and monohydrated forms of DL-aspartic acid have been computationally evaluated, and in each case, the hydrates produce destabilized aspartic acid conformations that prevent DL-aspartic acid hydrate formation from occurring.

Formation and Characterization of Anisotropic Block Copolymer Gels

NASA Astrophysics Data System (ADS)

Liaw, Chya Yan; Joester, Derk; Burghardt, Wesley; Shull, Kenneth

2012-02-01

Cylindrical micelles formed from block copolymer solutions closely mimic biological fibers that are presumed to guide mineral formation during biosynthesis of hard tissues like bone. The goal of our work is to use acrylic block copolymers as oriented templates for studying mineral formation reactions in model systems where the structure of the underlying template is well characterized and reproducible. Self-consistent mean field theory is first applied to investigate the thermodynamically stable micellar morphologies as a function of temperature and block copolymer composition. Small-angle x-ray scattering, optical birefringence and shear rheometry are used to study the morphology development during thermal processing. Initial experiments are based on a thermally-reversible alcohol-soluble system that can be converted to an aqueous gel by hydrolysis of a poly(t-butyl methacrylate) block to a poly(methacrylic acid) block. Aligned cylindrical domains are formed in the alcohol-based system when shear is applied in an appropriate temperature regime, which is below the critical micelle temperature but above the temperature at which the relaxation time of the gels becomes too large. Processing strategies for producing the desired cylindrical morphologies are being developed that account for both thermodynamic and kinetic effects.

Theoretical investigation on thermodynamic properties of ZnO1-x Te x alloys

NASA Astrophysics Data System (ADS)

Long, Debing; Li, Mingkai; Luo, Minghai; Zhu, Jiakun; Yang, Hui; Huang, Zhongbing; Ahuja, Rajeev; He, Yunbin

2017-05-01

In this study, the formation energy, phase diagram (with/without phonon contribution) and the relationship between bond stiffness and bond length for wurtzite (WZ) and zincblende (ZB) structures of ZnO1-x Te x (0  ⩽  x  ⩽  1) alloys have been investigated by combining first-principles calculations and cluster expansion method. The formation energy of ZnO1-x Te x alloys is very high in both structures, which means that it is difficult for ZnO and ZnTe to form stable ternary alloys ZnO1-x Te x . In the phase diagrams, both structures do not have stable phase of ternary alloys and ZnO1-x Te x ternary alloys can only exist in the form of metastable phase. These results indicate that ZnO and ZnTe easily form solid solubility gap when they form alloys. After considering vibrational free energy, we found the solubility of Te in ZnO and O in ZnTe was increased and the vibrational entropy improved the solubility furthermore. The phonon contribution is not ignorable to improve solid solubility. The phonon density of states was analyzed for ZnO1-x Te x alloys and the contribution from vibrational entropy was discussed.

Uranyl peroxide enhanced nuclear fuel corrosion in seawater.

PubMed

Armstrong, Christopher R; Nyman, May; Shvareva, Tatiana; Sigmon, Ginger E; Burns, Peter C; Navrotsky, Alexandra

2012-02-07

The Fukushima-Daiichi nuclear accident brought together compromised irradiated fuel and large amounts of seawater in a high radiation field. Based on newly acquired thermochemical data for a series of uranyl peroxide compounds containing charge-balancing alkali cations, here we show that nanoscale cage clusters containing as many as 60 uranyl ions, bonded through peroxide and hydroxide bridges, are likely to form in solution or as precipitates under such conditions. These species will enhance the corrosion of the damaged fuel and, being thermodynamically stable and kinetically persistent in the absence of peroxide, they can potentially transport uranium over long distances.

Uranyl peroxide enhanced nuclear fuel corrosion in seawater

PubMed Central

Armstrong, Christopher R.; Nyman, May; Shvareva, Tatiana; Sigmon, Ginger E.; Burns, Peter C.; Navrotsky, Alexandra

2012-01-01

The Fukushima-Daiichi nuclear accident brought together compromised irradiated fuel and large amounts of seawater in a high radiation field. Based on newly acquired thermochemical data for a series of uranyl peroxide compounds containing charge-balancing alkali cations, here we show that nanoscale cage clusters containing as many as 60 uranyl ions, bonded through peroxide and hydroxide bridges, are likely to form in solution or as precipitates under such conditions. These species will enhance the corrosion of the damaged fuel and, being thermodynamically stable and kinetically persistent in the absence of peroxide, they can potentially transport uranium over long distances. PMID:22308442

Study of base pair mutations in proline-rich homeodomain (PRH)-DNA complexes using molecular dynamics.

PubMed

Jalili, Seifollah; Karami, Leila; Schofield, Jeremy

2013-06-01

Proline-rich homeodomain (PRH) is a regulatory protein controlling transcription and gene expression processes by binding to the specific sequence of DNA, especially to the sequence 5'-TAATNN-3'. The impact of base pair mutations on the binding between the PRH protein and DNA is investigated using molecular dynamics and free energy simulations to identify DNA sequences that form stable complexes with PRH. Three 20-ns molecular dynamics simulations (PRH-TAATTG, PRH-TAATTA and PRH-TAATGG complexes) in explicit solvent water were performed to investigate three complexes structurally. Structural analysis shows that the native TAATTG sequence forms a complex that is more stable than complexes with base pair mutations. It is also observed that upon mutation, the number and occupancy of the direct and water-mediated hydrogen bonds decrease. Free energy calculations performed with the thermodynamic integration method predict relative binding free energies of 0.64 and 2 kcal/mol for GC to AT and TA to GC mutations, respectively, suggesting that among the three DNA sequences, the PRH-TAATTG complex is more stable than the two mutated complexes. In addition, it is demonstrated that the stability of the PRH-TAATTA complex is greater than that of the PRH-TAATGG complex.

Thermodynamic properties of asymptotically Reissner–Nordström black holes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hendi, S.H., E-mail: hendi@shirazu.ac.ir

2014-07-15

Motivated by possible relation between Born–Infeld type nonlinear electrodynamics and an effective low-energy action of open string theory, asymptotically Reissner–Nordström black holes whose electric field is described by a nonlinear electrodynamics (NLED) are studied. We take into account a four dimensional topological static black hole ansatz and solve the field equations, exactly, in terms of the NLED as a matter field. The main goal of this paper is investigation of thermodynamic properties of the obtained black holes. Moreover, we calculate the heat capacity and find that the nonlinearity affects the minimum size of stable black holes. We also use Legendre-invariantmore » metric proposed by Quevedo to obtain scalar curvature divergences. We find that the singularities of the Ricci scalar in Geometrothermodynamics (GTD) method take place at the Davies points. -- Highlights: •We examine the thermodynamical properties of black holes in Einstein gravity with nonlinear electrodynamics. •We investigate thermodynamic stability and discuss about the size of stable black holes. •We obtain analytical solutions of higher dimensional theory.« less

An entropy stable nodal discontinuous Galerkin method for the two dimensional shallow water equations on unstructured curvilinear meshes with discontinuous bathymetry

NASA Astrophysics Data System (ADS)

Wintermeyer, Niklas; Winters, Andrew R.; Gassner, Gregor J.; Kopriva, David A.

2017-07-01

We design an arbitrary high-order accurate nodal discontinuous Galerkin spectral element approximation for the non-linear two dimensional shallow water equations with non-constant, possibly discontinuous, bathymetry on unstructured, possibly curved, quadrilateral meshes. The scheme is derived from an equivalent flux differencing formulation of the split form of the equations. We prove that this discretization exactly preserves the local mass and momentum. Furthermore, combined with a special numerical interface flux function, the method exactly preserves the mathematical entropy, which is the total energy for the shallow water equations. By adding a specific form of interface dissipation to the baseline entropy conserving scheme we create a provably entropy stable scheme. That is, the numerical scheme discretely satisfies the second law of thermodynamics. Finally, with a particular discretization of the bathymetry source term we prove that the numerical approximation is well-balanced. We provide numerical examples that verify the theoretical findings and furthermore provide an application of the scheme for a partial break of a curved dam test problem.

A second look at the second law

NASA Astrophysics Data System (ADS)

Bejan, Adrian

1988-05-01

An account is given of Bejan's (1988) reformulation of the axioms of engineering thermodynamics in terms of heat transfer, rather than mechanics. Attention is given to graphic constructions that can be used to illustrate the properties in question, such as the 'stability star' diagram summarizing various extrema reached by certain thermodynamic properties when a closed system settles into stable (unconstrained) equilibrium. Also noted are the exergy analysis and refrigeration applications to which the present reformulation of the second law of thermodynamics can be put.

Thermodynamics of Surface Nanobubbles.

PubMed

Zargarzadeh, Leila; Elliott, Janet A W

2016-11-01

In this paper, we examine the thermodynamic stability of surface nanobubbles. The appropriate free energy is defined for the system of nanobubbles on a solid surface submerged in a supersaturated liquid solution at constant pressure and temperature, under conditions where an individual nanobubble is not in diffusive contact with a gas phase outside of the system or with other nanobubbles on the time scale of the experiment. The conditions under which plots of free energy versus the radius of curvature of the nanobubbles show a global minimum, which denotes the stable equilibrium state, are explored. Our investigation shows that supersaturation and an anomalously high contact angle (measured through the liquid) are required to have stable surface nanobubbles. In addition, the anomalously high contact angle of surface nanobubbles is discussed from the standpoint of a framework recently proposed by Koch, Amirfazli, and Elliott that relates advancing and receding contact angles to thermodynamic equilibrium contact angles, combined with the existence of a gas enrichment layer.

Using the laws of thermodynamics to understand how matrix metalloproteinases coordinate the myocardial response to injury.

PubMed

Iyer, Rugmani Padmanabhan; Jung, Mira; Lindsey, Merry L

Following myocardial infarction (MI), the left ventricle (LV) undergoes a series of molecular, cellular, and functional alterations that are both part of the wound healing response to form a scar in the infarct region and the consequence of that response. Using the laws of thermodynamics as an analogy, we present here three laws for categorizing the post-MI LV remodeling process. The first law is that the LV will attempt to maintain equilibrium and compensate as a way to maximize function, the second law is that remodeling is progressive and unidirectional, and the third law is that the final goal is (ideally, but not always achievable) a stable, equilibrated scar. This comparison helps to define the boundaries of the system, whether it be the infarct zone, the LV, the heart, or the entire body. This review provides an overview for those not directly in the field and establishes a framework to help prioritize future research directions.

Using the laws of thermodynamics to understand how matrix metalloproteinases coordinate the myocardial response to injury

PubMed Central

Iyer, Rugmani Padmanabhan; Jung, Mira; Lindsey, Merry L

2016-01-01

Following myocardial infarction (MI), the left ventricle (LV) undergoes a series of molecular, cellular, and functional alterations that are both part of the wound healing response to form a scar in the infarct region and the consequence of that response. Using the laws of thermodynamics as an analogy, we present here three laws for categorizing the post-MI LV remodeling process. The first law is that the LV will attempt to maintain equilibrium and compensate as a way to maximize function, the second law is that remodeling is progressive and unidirectional, and the third law is that the final goal is (ideally, but not always achievable) a stable, equilibrated scar. This comparison helps to define the boundaries of the system, whether it be the infarct zone, the LV, the heart, or the entire body. This review provides an overview for those not directly in the field and establishes a framework to help prioritize future research directions. PMID:27376092

Phlogopite Decomposition, Water, and Venus

NASA Technical Reports Server (NTRS)

Johnson, N. M.; Fegley, B., Jr.

2005-01-01

Venus is a hot and dry planet with a surface temperature of 660 to 740 K and 30 parts per million by volume (ppmv) water vapor in its lower atmosphere. In contrast Earth has an average surface temperature of 288 K and 1-4% water vapor in its troposphere. The hot and dry conditions on Venus led many to speculate that hydrous minerals on the surface of Venus would not be there today even though they might have formed in a potentially wetter past. Thermodynamic calculations predict that many hydrous minerals are unstable under current Venusian conditions. Thermodynamics predicts whether a particular mineral is stable or not, but we need experimental data on the decomposition rate of hydrous minerals to determine if they survive on Venus today. Previously, we determined the decomposition rate of the amphibole tremolite, and found that it could exist for billions of years at current surface conditions. Here, we present our initial results on the decomposition of phlogopite mica, another common hydrous mineral on Earth.

Structure, dynamics, and thermodynamics of a family of potentials with tunable softness

NASA Astrophysics Data System (ADS)

Shi, Zane; Debenedetti, Pablo G.; Stillinger, Frank H.; Ginart, Paul

2011-08-01

We investigate numerically the structure, thermodynamics, and relaxation behavior of a family of (n, 6) Lennard-Jones-like glass-forming binary mixtures interacting via pair potentials with variable softness, fixed well depth, and fixed well depth location. These constraints give rise to progressively more negative attractive tails upon softening, for separations greater than the potential energy minimum. Over the range of conditions examined, we find only modest dependence of structure on softness. In contrast, decreasing the repulsive exponent from n = 12 to n = 7 causes the diffusivity to increase by as much as two orders of magnitude at fixed temperature and density, and produces mechanically stable packings (inherent structures) with cohesive energies that are, on average, ˜1.7 well depths per particle larger than for the corresponding Lennard-Jones (n = 12) case. The softer liquids have markedly higher entropies and lower Kauzmann temperatures than their Lennard-Jones (n = 12) counterparts, and they remain diffusive down to appreciably lower temperatures. We find that softening leads to a modest increase in fragility.

Thermodynamics of Terrestrial Evolution

PubMed Central

Kirkaldy, J. S.

1965-01-01

The causal element of biological evolution and development can be understood in terms of a potential function which is generalized from the variational principles of irreversible thermodynamics. This potential function is approximated by the rate of entropy production in a configuration space which admits of macroscopic excursions by fluctuation and regression as well as microscopic ones. Analogously to Onsager's dissipation function, the potential takes the form of a saddle surface in this configuration space. The path of evolution following from an initial high dissipation state within the fixed constraint provided by the invariant energy flux from the sun tends toward the stable saddle point by a series of spontaneous regressions which lower the entropy production rate and by an alternating series of spontaneous fluctuations which introduce new internal constraints and lead to a higher entropy production rate. The potential thus rationalizes the system's observed tendency toward “chemical imperialism” (high dissipation) while simultaneously accommodating the development of “dynamic efficiency” and complication (low dissipation). PMID:5884019

Influence of thermodynamically unfavorable secondary structures on DNA hybridization kinetics

PubMed Central

Hata, Hiroaki; Kitajima, Tetsuro

2018-01-01

Abstract Nucleic acid secondary structure plays an important role in nucleic acid–nucleic acid recognition/hybridization processes, and is also a vital consideration in DNA nanotechnology. Although the influence of stable secondary structures on hybridization kinetics has been characterized, unstable secondary structures, which show positive ΔG° with self-folding, can also form, and their effects have not been systematically investigated. Such thermodynamically unfavorable secondary structures should not be ignored in DNA hybridization kinetics, especially under isothermal conditions. Here, we report that positive ΔG° secondary structures can change the hybridization rate by two-orders of magnitude, despite the fact that their hybridization obeyed second-order reaction kinetics. The temperature dependence of hybridization rates showed non-Arrhenius behavior; thus, their hybridization is considered to be nucleation limited. We derived a model describing how ΔG° positive secondary structures affect hybridization kinetics in stopped-flow experiments with 47 pairs of oligonucleotides. The calculated hybridization rates, which were based on the model, quantitatively agreed with the experimental rate constant. PMID:29220504

Morphological Transformation between Nanocoils and Nanoribbons via Defragmentation Structural Rearrangement or Fragmentation-recombination Mechanism

NASA Astrophysics Data System (ADS)

Zhang, Yibin; Zheng, Yingxuan; Xiong, Wei; Peng, Cheng; Zhang, Yifan; Duan, Ran; Che, Yanke; Zhao, Jincai

2016-06-01

Kinetic control over the assembly pathways towards novel metastable functional materials or far-from-equilibrium systems has been much less studied compared to the thermodynamic equilibrium self-assembly. Herein, we report the distinct morphological transformation between nanocoils and nanoribbons in the self-assembly of unsymmetric perylene diimide (PDI) molecules. We demonstrate that the morphological transformation of the kinetically trapped assemblies into the thermodynamically stable forms proceeds via two distinct mechanisms, i.e., a direct structural rearrangement (molecule 1 or 2) and a fragmentation-recombination mechanism (molecule 4), respectively. The subtle interplay of the steric hindrance of the bulky substituents and the flexibility of the linker structure between the bulky moiety and the perylene core was demonstrated to enable the effective modulation of the energetic landscape of the assemblies and thus modulation of the assembly pathways. Herein, our work presents a new approach to control the self-assembly pathways and thereby can be used to achieve novel far-from-equilibrium systems.

Thermodynamic Paradigm for Solution Demixing Inspired by Nuclear Transport in Living Cells

NASA Astrophysics Data System (ADS)

Wang, Ching-Hao; Mehta, Pankaj; Elbaum, Michael

2017-04-01

Living cells display a remarkable capacity to compartmentalize their functional biochemistry. A particularly fascinating example is the cell nucleus. Exchange of macromolecules between the nucleus and the surrounding cytoplasm does not involve traversing a lipid bilayer membrane. Instead, large protein channels known as nuclear pores cross the nuclear envelope and regulate the passage of other proteins and RNA molecules. Beyond simply gating diffusion, the system of nuclear pores and associated transport receptors is able to generate substantial concentration gradients, at the energetic expense of guanosine triphosphate hydrolysis. In contrast to conventional approaches to demixing such as reverse osmosis and dialysis, the biological system operates continuously, without application of cyclic changes in pressure or solvent exchange. Abstracting the biological paradigm, we examine this transport system as a thermodynamic machine of solution demixing. Building on the construct of free energy transduction and biochemical kinetics, we find conditions for the stable operation and optimization of the concentration gradients as a function of dissipation in the form of entropy production.

Thermodynamics of a class of regular black holes with a generalized uncertainty principle

NASA Astrophysics Data System (ADS)

Maluf, R. V.; Neves, Juliano C. S.

2018-05-01

In this article, we present a study on thermodynamics of a class of regular black holes. Such a class includes Bardeen and Hayward regular black holes. We obtained thermodynamic quantities like the Hawking temperature, entropy, and heat capacity for the entire class. As part of an effort to indicate some physical observable to distinguish regular black holes from singular black holes, we suggest that regular black holes are colder than singular black holes. Besides, contrary to the Schwarzschild black hole, that class of regular black holes may be thermodynamically stable. From a generalized uncertainty principle, we also obtained the quantum-corrected thermodynamics for the studied class. Such quantum corrections provide a logarithmic term for the quantum-corrected entropy.

Atomistic modeling of dropwise condensation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sikarwar, B. S., E-mail: bssikarwar@amity.edu; Singh, P. L.; Muralidhar, K.

The basic aim of the atomistic modeling of condensation of water is to determine the size of the stable cluster and connect phenomena occurring at atomic scale to the macroscale. In this paper, a population balance model is described in terms of the rate equations to obtain the number density distribution of the resulting clusters. The residence time is taken to be large enough so that sufficient time is available for all the adatoms existing in vapor-phase to loose their latent heat and get condensed. The simulation assumes clusters of a given size to be formed from clusters of smallermore » sizes, but not by the disintegration of the larger clusters. The largest stable cluster size in the number density distribution is taken to be representative of the minimum drop radius formed in a dropwise condensation process. A numerical confirmation of this result against predictions based on a thermodynamic model has been obtained. Results show that the number density distribution is sensitive to the surface diffusion coefficient and the rate of vapor flux impinging on the substrate. The minimum drop radius increases with the diffusion coefficient and the impinging vapor flux; however, the dependence is weak. The minimum drop radius predicted from thermodynamic considerations matches the prediction of the cluster model, though the former does not take into account the effect of the surface properties on the nucleation phenomena. For a chemically passive surface, the diffusion coefficient and the residence time are dependent on the surface texture via the coefficient of friction. Thus, physical texturing provides a means of changing, within limits, the minimum drop radius. The study reveals that surface texturing at the scale of the minimum drop radius does not provide controllability of the macro-scale dropwise condensation at large timescales when a dynamic steady-state is reached.« less

Metallic impurities-silicon carbide interaction in HTGR fuel particles

NASA Astrophysics Data System (ADS)

Minato, Kazuo; Ogawa, Toru; Kashimura, Satoru; Fukuda, Kousaku; Shimizu, Michio; Tayama, Yoshinobu; Takahashi, Ishio

1990-12-01

Corrosion of the coating layers of silicon carbide (SiC) by metallic impurities was observed in irradiated Triso-coated uranium dioxide particles for high temperature gas-cooled reactors with an optical microscope and an electron probe micro-analyzer. The SiC layers were attacked from the outside of the particles. The main element observed in the corroded areas was iron, but sometimes iron and nickel were found. These elements must have been contained as impurities in the graphite matrix in which the coated particles were dispersed. Since these elements are more stable thermodynamically in the presence of SiC than in the presence of graphite at irradiation temperatures, they were transferred to the SiC layer to form more stable silicides. During fuel manufacturing processes, intensive care should be taken to prevent the fuel from being contaminated with those elements which react with SiC.

Thermodynamic properties and atomic structure of Ca-based liquid alloys

NASA Astrophysics Data System (ADS)

Poizeau, Sophie

To identify the most promising positive electrodes for Ca-based liquid metal batteries, the thermodynamic properties of diverse Ca-based liquid alloys were investigated. The thermodynamic properties of Ca-Sb alloys were determined by emf measurements. It was found that Sb as positive electrode would provide the highest voltage for Ca-based liquid metal batteries (1 V). The price of such a battery would be competitive for the grid-scale energy storage market. The impact of Pb, a natural impurity of Sb, was predicted successfully and confirmed via electrochemical measurements. It was shown that the impact on the open circuit voltage would be minor. Indeed, the interaction between Ca and Sb was demonstrated to be much stronger than between Ca and Pb using thermodynamic modeling, which explains why the partial thermodynamic properties of Ca would not vary much with the addition of Pb to Sb. However, the usage of the positive electrode would be reduced, which would limit the interest of a Pb-Sb positive electrode. Throughout this work, the molecular interaction volume model (MIVM) was used for the first time for alloys with thermodynamic properties showing strong negative deviation from ideality. This model showed that systems such as Ca-Sb have strong short-range order: Ca is most stable when its first nearest neighbors are Sb. This is consistent with what the more traditional thermodynamic model, the regular association model, would predict. The advantages of the MIVM are the absence of assumption regarding the composition of an associate, and the reduced number of fitting parameters (2 instead of 5). Based on the parameters derived from the thermodynamic modeling using the MIVM, a new potential of mixing for liquid alloys was defined to compare the strength of interaction in different Ca-based alloys. Comparing this trend with the strength of interaction in the solid state of these systems (assessed by the energy of formation of the intermetallics), the systems with the most stable intermetallics were found to have the strongest interaction in the liquid state. Eventually, a new criteria was formulated to select electrode materials for liquid metal batteries. Systems with the most stable intermetallics, which can be evaluated by the enthalpy of formation of these systems, will yield the highest voltage when assembled as positive and negative electrodes in a liquid metal battery. (Copies available exclusively from MIT Libraries, libraries.mit.edu/docs - docs@mit.edu)

Symmetric and antisymmetric forms of the Pauli master equation.

PubMed

Klimenko, A Y

2016-07-21

When applied to matter and antimatter states, the Pauli master equation (PME) may have two forms: time-symmetric, which is conventional, and time-antisymmetric, which is suggested in the present work. The symmetric and antisymmetric forms correspond to symmetric and antisymmetric extensions of thermodynamics from matter to antimatter - this is demonstrated by proving the corresponding H-theorem. The two forms are based on the thermodynamic similarity of matter and antimatter and differ only in the directions of thermodynamic time for matter and antimatter (the same in the time-symmetric case and the opposite in the time-antisymmetric case). We demonstrate that, while the symmetric form of PME predicts an equibalance between matter and antimatter, the antisymmetric form of PME favours full conversion of antimatter into matter. At this stage, it is impossible to make an experimentally justified choice in favour of the symmetric or antisymmetric versions of thermodynamics since we have no experience of thermodynamic properties of macroscopic objects made of antimatter, but experiments of this kind may become possible in the future.

Raman studies of methane-ethane hydrate metastability.

PubMed

Ohno, Hiroshi; Strobel, Timothy A; Dec, Steven F; Sloan, E Dendy; Koh, Carolyn A

2009-03-05

The interconversion of methane-ethane hydrate from metastable to stable structures was studied using Raman spectroscopy. sI and sII hydrates were synthesized from methane-ethane gas mixtures of 65% or 93% methane in ethane and water, both with and without the kinetic hydrate inhibitor, poly(N-vinylcaprolactam). The observed faster structural conversion rate in the higher methane concentration atmosphere can be explained in terms of the differences in driving force (difference in chemical potential of water in sI and sII hydrates) and kinetics (mass transfer of gas and water rearrangement). The kinetic hydrate inhibitor increased the conversion rate at 65% methane in ethane (sI is thermodynamically stable) but retards the rate at 93% methane in ethane (sII is thermodynamically stable), implying there is a complex interaction between the polymer, water, and hydrate guests at crystal surfaces.

Charge ordering in two-dimensional ionic liquids

NASA Astrophysics Data System (ADS)

Perera, Aurélien; Urbic, Tomaz

2018-04-01

The structural properties of model two-dimensional (2D) ionic liquids are examined, with a particular focus on the charge ordering process, with the use of computer simulation and integral equation theories. The influence of the logarithmic form of the Coulomb interaction, versus that of a 3D screened interaction form, is analysed. Charge order is found to hold and to be analogous for both interaction models, despite their very different form. The influence of charge ordering in the low density regime is discussed in relation to well known properties of 2D Coulomb fluids, such as the Kosterlitz-Thouless transition and criticality. The present study suggests the existence of a stable thermodynamic labile cluster phase, implying the existence of a liquid-liquid "transition" above the liquid-gas binodal. The liquid-gas and Kosterlitz-Thouless transitions would then take place inside the predicted cluster phase.

A route to possible civil engineering materials: the case of high-pressure phases of lime

NASA Astrophysics Data System (ADS)

Bouibes, A.; Zaoui, A.

2015-07-01

Lime system has a chemical composition CaO, which is known as thermodynamically stable. The purpose here is to explore further possible phases under pressure, by means of variable-composition ab initio evolutionary algorithm. The present investigation shows surprisingly new stable compounds of lime. At ambient pressure we predict, in addition to CaO, CaO2 as new thermodynamically stable compound. The latter goes through two phases transition from C2/c space group structure to Pna21 at 1.5 GPa, and Pna21 space group structure to I4/mcm at 23.4 GPa. Under increasing pressure, further compounds such as CaO3 become the most stable and stabilize in P-421m space group structure above 65 GPa. For the necessary knowledge of the new predicted compounds, we have computed their mechanical and electronic properties in order to show and to explain the main reasons leading to the structural changes.

A route to possible civil engineering materials: the case of high-pressure phases of lime.

PubMed

Bouibes, A; Zaoui, A

2015-07-23

Lime system has a chemical composition CaO, which is known as thermodynamically stable. The purpose here is to explore further possible phases under pressure, by means of variable-composition ab initio evolutionary algorithm. The present investigation shows surprisingly new stable compounds of lime. At ambient pressure we predict, in addition to CaO, CaO2 as new thermodynamically stable compound. The latter goes through two phases transition from C2/c space group structure to Pna21 at 1.5 GPa, and Pna21 space group structure to I4/mcm at 23.4 GPa. Under increasing pressure, further compounds such as CaO3 become the most stable and stabilize in P-421m space group structure above 65 GPa. For the necessary knowledge of the new predicted compounds, we have computed their mechanical and electronic properties in order to show and to explain the main reasons leading to the structural changes.

Selectivity in Ligand Binding to Uranyl Compounds: A Synthetic, Structural, Thermodynamic and Computational Study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Arnold, John

The uranyl cation (UO 2 2+) is the most abundant form of uranium on the planet. It is estimated that 4.5 billion tons of uranium in this form exist in sea water. The ability to bind and extract the uranyl cation from aqueous solution while separating it from other elements would provide a limitless source of nuclear fuel. A large body of research concerns the selective recognition and extraction of uranyl. A stable molecule, the cation has a linear O=U=O geometry. The short U-O bonds (1.78 Å) arise from the combination of uranium 5f/6d and oxygen 2p orbitals. Due tomore » the oxygen moieties being multiply bonded, these sites were not thought to be basic enough for Lewis acidic coordination to be a viable approach to sequestration. We believe that the goal of developing a practical system for uranium separation from seawater will not be attained without new insights into our existing fundamental knowledge of actinide chemistry. We posit that detailed studies of the kinetic and thermodynamic factors that influence interactions between f-elements and ligands with a range of donor atoms is essential to any major advance in this important area. The goal of this research is thus to broaden the coordination chemistry of the uranyl ion by studying new ligand systems via synthetic, structural, thermodynamic and computational methods. We anticipate that this fundamental science will find use beyond actinide separation technologies in areas such as nuclear waste remediation and nuclear materials.« less

Structure and thermodynamics of uranium-containing iron garnets

NASA Astrophysics Data System (ADS)

Guo, Xiaofeng; Navrotsky, Alexandra; Kukkadapu, Ravi K.; Engelhard, Mark H.; Lanzirotti, Antonio; Newville, Matthew; Ilton, Eugene S.; Sutton, Stephen R.; Xu, Hongwu

2016-09-01

Use of crystalline garnet as a waste form phase appears to be advantageous for accommodating actinides from nuclear waste. Previous studies show that large amounts of uranium (U) and its analogues such as cerium (Ce) and thorium (Th) can be incorporated into the garnet structure. In this study, we synthesized U loaded garnet phases, Ca3UxZr2-xFe3O12 (x = 0.5-0.7), along with the endmember phase, Ca3(Zr2)SiFe3+2O12, for comparison. The oxidation states of U were determined by X-ray photoelectron and absorption spectroscopies, revealing the presence of mixed pentavalent and hexavalent uranium in the phases with x = 0.6 and 0.7. The oxidation states and coordination environments of Fe were measured using transmission 57Fe-Mössbauer spectroscopy, which shows that all iron is tetrahedrally coordinated Fe3+. U substitution had a significant effect on local environments, the extent of U substitution within this range had a minimal effect on the structure, and unlike in the x = 0 sample, Fe exists in two different environments in the substituted garnets. The enthalpies of formation of garnet phases from constituent oxides and elements were first time determined by high temperature oxide melt solution calorimetry. The results indicate that these substituted garnets are thermodynamically stable under reducing conditions. Our structural and thermodynamic analysis further provides explanation for the formation of natural uranium garnet, elbrusite-(Zr), and supports the potential use of Ca3UxZr2-xFe3O12 as viable waste form phases for U and other actinides.

Thermodynamic properties of charged three-dimensional black holes in the scalar-tensor gravity theory

NASA Astrophysics Data System (ADS)

Dehghani, M.

2018-02-01

Making use of the suitable transformation relations, the action of three-dimensional Einstein-Maxwell-dilaton gravity theory has been obtained from that of scalar-tensor modified gravity theory coupled to the Maxwell's electrodynamics as the matter field. Two new classes of the static three-dimensional charged dilatonic black holes, as the exact solutions to the coupled scalar, electromagnetic and gravitational field equations, have been obtained in the Einstein frame. Also, it has been found that the scalar potential can be written in the form of a generalized Liouville-type potential. The conserved black hole charge and masses as well as the black entropy, temperature, and electric potential have been calculated from the geometrical and thermodynamical approaches, separately. Through comparison of the results arisen from these two alternative approaches, the validity of the thermodynamical first law has been proved for both of the new black hole solutions in the Einstein frame. Making use of the canonical ensemble method, a black hole stability or phase transition analysis has been performed. Regarding the black hole heat capacity, with the black hole charge as a constant, the points of type-1 and type-2 phase transitions have been determined. Also, the ranges of the black hole horizon radius at which the Einstein black holes are thermally stable have been obtained for both of the new black hole solutions. Then making use of the inverse transformation relations, two new classes of the string black hole solutions have been obtained from their Einstein counterpart. The thermodynamics and thermal stability of the new string black hole solutions have been investigated. It has been found that thermodynamic properties of the new charged black holes are identical in the Einstein and Jordan frames.

Methylammonium Bismuth Iodide as a Lead-Free, Stable Hybrid Organic-Inorganic Solar Absorber.

PubMed

Hoye, Robert L Z; Brandt, Riley E; Osherov, Anna; Stevanović, Vladan; Stranks, Samuel D; Wilson, Mark W B; Kim, Hyunho; Akey, Austin J; Perkins, John D; Kurchin, Rachel C; Poindexter, Jeremy R; Wang, Evelyn N; Bawendi, Moungi G; Bulović, Vladimir; Buonassisi, Tonio

2016-02-18

Methylammonium lead halide (MAPbX3 ) perovskites exhibit exceptional carrier transport properties. But their commercial deployment as solar absorbers is currently limited by their intrinsic instability in the presence of humidity and their lead content. Guided by our theoretical predictions, we explored the potential of methylammonium bismuth iodide (MBI) as a solar absorber through detailed materials characterization. We synthesized phase-pure MBI by solution and vapor processing. In contrast to MAPbX3, MBI is air stable, forming a surface layer that does not increase the recombination rate. We found that MBI luminesces at room temperature, with the vapor-processed films exhibiting superior photoluminescence (PL) decay times that are promising for photovoltaic applications. The thermodynamic, electronic, and structural features of MBI that are amenable to these properties are also present in other hybrid ternary bismuth halide compounds. Through MBI, we demonstrate a lead-free and stable alternative to MAPbX3 that has a similar electronic structure and nanosecond lifetimes. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A superhard sp3 microporous carbon with direct bandgap

NASA Astrophysics Data System (ADS)

Pan, Yilong; Xie, Chenlong; Xiong, Mei; Ma, Mengdong; Liu, Lingyu; Li, Zihe; Zhang, Shuangshuang; Gao, Guoying; Zhao, Zhisheng; Tian, Yongjun; Xu, Bo; He, Julong

2017-12-01

Carbon allotropes with distinct sp, sp2, and sp3 hybridization possess various different properties. Here, a novel all-sp3 hybridized tetragonal carbon, namely the P carbon, was predicted by the evolutionary particle swarm structural search. It demonstrated a low density among all-sp3 carbons, due to the corresponding distinctive microporous structure. P carbon is thermodynamically stable than the known C60 and could be formed through the single-walled carbon nanotubes (SWCNTs) compression. P carbon is a direct bandgap semiconductor displaying a strong and superhard nature. The unique combination of electrical and mechanical properties constitutes P carbon a potential superhard material for semiconductor industrial fields.

Thermodynamic Tuning of Mg-Based Hydrogen Storage Alloys: A Review

PubMed Central

Zhu, Min; Lu, Yanshan; Ouyang, Liuzhang; Wang, Hui

2013-01-01

Mg-based hydrides are one of the most promising hydrogen storage materials because of their relatively high storage capacity, abundance, and low cost. However, slow kinetics and stable thermodynamics hinder their practical application. In contrast to the substantial progress in the enhancement of the hydrogenation/dehydrogenation kinetics, thermodynamic tuning is still a great challenge for Mg-based alloys. At present, the main strategies to alter the thermodynamics of Mg/MgH2 are alloying, nanostructuring, and changing the reaction pathway. Using these approaches, thermodynamic tuning has been achieved to some extent, but it is still far from that required for practical application. In this article, we summarize the advantages and disadvantages of these strategies. Based on the current progress, finding reversible systems with high hydrogen capacity and effectively tailored reaction enthalpy offers a promising route for tuning the thermodynamics of Mg-based hydrogen storage alloys. PMID:28788353

Calculating phase diagrams using PANDAT and panengine

NASA Astrophysics Data System (ADS)

Chen, S.-L.; Zhang, F.; Xie, F.-Y.; Daniel, S.; Yan, X.-Y.; Chang, Y. A.; Schmid-Fetzer, R.; Oates, W. A.

2003-12-01

Knowledge of phase equilibria or phase diagrams and thermodynamic properties is important in alloy design and materials-processing simulation. In principle, stable phase equilibrium is uniquely determined by the thermodynamic properties of the system, such as the Gibbs energy functions of the phases. PANDAT, a new computer software package for multicomponent phase-diagram calculation, was developed under the guidance of this principle.

Domain-Swapped Dimers of Intracellular Lipid-Binding Proteins: Evidence for Ordered Folding Intermediates.

PubMed

Assar, Zahra; Nossoni, Zahra; Wang, Wenjing; Santos, Elizabeth M; Kramer, Kevin; McCornack, Colin; Vasileiou, Chrysoula; Borhan, Babak; Geiger, James H

2016-09-06

Human Cellular Retinol Binding Protein II (hCRBPII), a member of the intracellular lipid-binding protein family, is a monomeric protein responsible for the intracellular transport of retinol and retinal. Herein we report that hCRBPII forms an extensive domain-swapped dimer during bacterial expression. The domain-swapped region encompasses almost half of the protein. The dimer represents a novel structural architecture with the mouths of the two binding cavities facing each other, producing a new binding cavity that spans the length of the protein complex. Although wild-type hCRBPII forms the dimer, the propensity for dimerization can be substantially increased via mutation at Tyr60. The monomeric form of the wild-type protein represents the thermodynamically more stable species, making the domain-swapped dimer a kinetically trapped entity. Hypothetically, the wild-type protein has evolved to minimize dimerization of the folding intermediate through a critical hydrogen bond (Tyr60-Glu72) that disfavors the dimeric form. Copyright © 2016 Elsevier Ltd. All rights reserved.

Polymorphism of paracetamol: relative stabilities of the monoclinic and orthorhombic phases inferred from topological pressure-temperature and temperature-volume phase diagrams.

PubMed

Espeau, Philippe; Céolin, René; Tamarit, Josep-Lluis; Perrin, Marc-Antoine; Gauchi, Jean-Pierre; Leveiller, Franck

2005-03-01

The thermodynamic relationships between the two known polymorphs of paracetamol have been investigated, and the subsequent pressure-temperature and temperature-volume phase diagrams were constructed using data from crystallographic and calorimetric measurements as a function of the temperature. Irrespective of temperature, monoclinic Form I and orthorhombic Form II are stable phases at ordinary and high pressures, respectively. The I and II phase regions in the pressure-temperature diagram are bordered by the I-II equilibrium curve, for which a negative slope (dp/dT approximately -0.3 MPa x K(-1)) was determined although it was not observed experimentally. This curve goes through the I-II-liquid triple point whose coordinates (p approximately 234 MPa, T approximately 505 K) correspond to the crossing point of the melting curves, for which dp/dT values of +3.75 MPa x K(-1) (I) and +3.14 MPa x K(-1) (II) were calculated from enthalpy and volume changes upon fusion. More generally, this case exemplifies how the stability hierarchy of polymorphs may be inferred from the difference in their sublimation curves, as topologically positioned with respect to each other, using the phase rule and simple inferences resorting to Gibbs equilibrium thermodynamics. Copyright 2004 Wiley-Liss, Inc. and the American Pharmacists Association.

Thermodynamic studies of a series of homologous HIV-1 TAR RNA ligands reveal that loose binders are stronger Tat competitors than tight ones

PubMed Central

Pascale, Lise; Azoulay, Stéphane; Di Giorgio, Audrey; Zenacker, Laura; Gaysinski, Marc; Clayette, Pascal; Patino, Nadia

2013-01-01

RNA is a major drug target, but the design of small molecules that modulate RNA function remains a great challenge. In this context, a series of structurally homologous ‘polyamide amino acids’ (PAA) was studied as HIV-1 trans-activating response (TAR) RNA ligands. An extensive thermodynamic study revealed the occurence of an enthalpy–entropy compensation phenomenon resulting in very close TAR affinities for all PAA. However, their binding modes and their ability to compete with the Tat fragment strongly differ according to their structure. Surprisingly, PAA that form loose complexes with TAR were shown to be stronger Tat competitors than those forming tight ones, and thermal denaturation studies demonstrated that loose complexes are more stable than tight ones. This could be correlated to the fact that loose and tight ligands induce distinct RNA conformational changes as revealed by circular dichroism experiments, although nuclear magnetic resonance (NMR) experiments showed that the TAR binding site is the same in all cases. Finally, some loose PAA also display promising inhibitory activities on HIV-infected cells. Altogether, these results lead to a better understanding of RNA interaction modes that could be very useful for devising new ligands of relevant RNA targets. PMID:23605042

Thermodynamic studies of a series of homologous HIV-1 TAR RNA ligands reveal that loose binders are stronger Tat competitors than tight ones.

PubMed

Pascale, Lise; Azoulay, Stéphane; Di Giorgio, Audrey; Zenacker, Laura; Gaysinski, Marc; Clayette, Pascal; Patino, Nadia

2013-06-01

RNA is a major drug target, but the design of small molecules that modulate RNA function remains a great challenge. In this context, a series of structurally homologous 'polyamide amino acids' (PAA) was studied as HIV-1 trans-activating response (TAR) RNA ligands. An extensive thermodynamic study revealed the occurence of an enthalpy-entropy compensation phenomenon resulting in very close TAR affinities for all PAA. However, their binding modes and their ability to compete with the Tat fragment strongly differ according to their structure. Surprisingly, PAA that form loose complexes with TAR were shown to be stronger Tat competitors than those forming tight ones, and thermal denaturation studies demonstrated that loose complexes are more stable than tight ones. This could be correlated to the fact that loose and tight ligands induce distinct RNA conformational changes as revealed by circular dichroism experiments, although nuclear magnetic resonance (NMR) experiments showed that the TAR binding site is the same in all cases. Finally, some loose PAA also display promising inhibitory activities on HIV-infected cells. Altogether, these results lead to a better understanding of RNA interaction modes that could be very useful for devising new ligands of relevant RNA targets.

Uniqueness of thermodynamic projector and kinetic basis of molecular individualism

NASA Astrophysics Data System (ADS)

Gorban, Alexander N.; Karlin, Iliya V.

2004-05-01

Three results are presented: First, we solve the problem of persistence of dissipation for reduction of kinetic models. Kinetic equations with thermodynamic Lyapunov functions are studied. Uniqueness of the thermodynamic projector is proven: There exists only one projector which transforms any vector field equipped with the given Lyapunov function into a vector field with the same Lyapunov function for a given anzatz manifold which is not tangent to the Lyapunov function levels. Second, we use the thermodynamic projector for developing the short memory approximation and coarse-graining for general nonlinear dynamic systems. We prove that in this approximation the entropy production increases. ( The theorem about entropy overproduction.) In example, we apply the thermodynamic projector to derive the equations of reduced kinetics for the Fokker-Planck equation. A new class of closures is developed, the kinetic multipeak polyhedra. Distributions of this type are expected in kinetic models with multidimensional instability as universally as the Gaussian distribution appears for stable systems. The number of possible relatively stable states of a nonequilibrium system grows as 2 m, and the number of macroscopic parameters is in order mn, where n is the dimension of configuration space, and m is the number of independent unstable directions in this space. The elaborated class of closures and equations pretends to describe the effects of “molecular individualism”. This is the third result.

Study on the intrinsic defects in tin oxide with first-principles method

NASA Astrophysics Data System (ADS)

Sun, Yu; Liu, Tingyu; Chang, Qiuxiang; Ma, Changmin

2018-04-01

First-principles and thermodynamic methods are used to study the contribution of vibrational entropy to defect formation energy and the stability of the intrinsic point defects in SnO2 crystal. According to thermodynamic calculation results, the contribution of vibrational entropy to defect formation energy is significant and should not be neglected, especially at high temperatures. The calculated results indicate that the oxygen vacancy is the major point defect in undoped SnO2 crystal, which has a higher concentration than that of the other point defect. The property of negative-U is put forward in SnO2 crystal. In order to determine the most stable defects much clearer under different conditions, the most stable intrinsic defect as a function of Fermi level, oxygen partial pressure and temperature are described in the three-dimensional defect formation enthalpy diagrams. The diagram visually provides the most stable point defects under different conditions.

Symmetric and antisymmetric forms of the Pauli master equation

PubMed Central

Klimenko, A. Y.

2016-01-01

When applied to matter and antimatter states, the Pauli master equation (PME) may have two forms: time-symmetric, which is conventional, and time-antisymmetric, which is suggested in the present work. The symmetric and antisymmetric forms correspond to symmetric and antisymmetric extensions of thermodynamics from matter to antimatter — this is demonstrated by proving the corresponding H-theorem. The two forms are based on the thermodynamic similarity of matter and antimatter and differ only in the directions of thermodynamic time for matter and antimatter (the same in the time-symmetric case and the opposite in the time-antisymmetric case). We demonstrate that, while the symmetric form of PME predicts an equibalance between matter and antimatter, the antisymmetric form of PME favours full conversion of antimatter into matter. At this stage, it is impossible to make an experimentally justified choice in favour of the symmetric or antisymmetric versions of thermodynamics since we have no experience of thermodynamic properties of macroscopic objects made of antimatter, but experiments of this kind may become possible in the future. PMID:27440454

Density functional theory study of defects in unalloyed δ-Pu

DOE PAGES

Hernandez, S. C.; Freibert, F. J.; Wills, J. M.

2017-03-19

Using density functional theory, we explore in this paper various classical point and complex defects within the face-centered cubic unalloyed δ-plutonium matrix that are potentially induced from self-irradiation. For plutonium only defects, the most energetically stable defect is a distorted split-interstitial. Gallium, the δ-phase stabilizer, is thermodynamically stable as a substitutional defect, but becomes unstable when participating in a complex defect configuration. Finally, complex uranium defects may thermodynamically exist as uranium substitutional with neighboring plutonium interstitial and stabilization of uranium within the lattice is shown via partial density of states and charge density difference plots to be 5f hybridization betweenmore » uranium and plutonium.« less

Density functional theory study of defects in unalloyed δ-Pu

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hernandez, S. C.; Freibert, F. J.; Wills, J. M.

Using density functional theory, we explore in this paper various classical point and complex defects within the face-centered cubic unalloyed δ-plutonium matrix that are potentially induced from self-irradiation. For plutonium only defects, the most energetically stable defect is a distorted split-interstitial. Gallium, the δ-phase stabilizer, is thermodynamically stable as a substitutional defect, but becomes unstable when participating in a complex defect configuration. Finally, complex uranium defects may thermodynamically exist as uranium substitutional with neighboring plutonium interstitial and stabilization of uranium within the lattice is shown via partial density of states and charge density difference plots to be 5f hybridization betweenmore » uranium and plutonium.« less

Thermodynamic phase transition in the rainbow Schwarzschild black hole

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gim, Yongwan; Kim, Wontae, E-mail: yongwan89@sogang.ac.kr, E-mail: wtkim@sogang.ac.kr

2014-10-01

We study the thermodynamic phase transition in the rainbow Schwarzschild black hole where the metric depends on the energy of the test particle. Identifying the black hole temperature with the energy from the modified dispersion relation, we obtain the modified entropy and thermodynamic energy along with the modified local temperature in the cavity to provide well defined black hole states. It is found that apart from the conventional critical temperature related to Hawking-Page phase transition there appears an additional critical temperature which is of relevance to the existence of a locally stable tiny black hole; however, the off-shell free energymore » tells us that this black hole should eventually tunnel into the stable large black hole. Finally, we discuss the reason why the temperature near the horizon is finite in the rainbow black hole by employing the running gravitational coupling constant, whereas it is divergent near the horizon in the ordinary Schwarzschild black hole.« less

Crystallization of calcium carbonate with the filtration of aqueous solutions through a microporous membrane

NASA Astrophysics Data System (ADS)

Ananeva, E. A.; Mesyats, E. A.; Sergievskii, V. V.

2017-11-01

It is established that the filtration of water through a microporous membrane does not change the hardness of the water; it does, however, reduce the amount of scale deposit, due to the crystallization of salts in water in the form of aragonite. The effect is consistently observed in water with a hardness of more than 7.0 H, a content of hydrocarbonate ions of more than 500 mg/L, and a pH ≥ 7.3. It is shown that introducing the seeds of calcite crystals into a filtrate results in the precipitation of calcite rather than aragonite. It is concluded that quasi-softening in the case of hard water microfiltration is caused by the removal of calcite micronuclei, and thus by conditions being created for the crystallization of aragonite as a thermodynamically less stable form.

Astronomical observations of solid phase carbon

NASA Technical Reports Server (NTRS)

Jura, M.

1990-01-01

In the outer envelopes of red giants, when the gas cools sufficiently, molecules and solids form. Thermodynamically, the most stable molecule is CO, and it is usually assumed that all the available carbon and oxygen are consumed in the formation of this molecule (Salpeter 1977). If the carbon abundance is greater than the oxygen abundance, then the carbon left over after the formation of CO is available for solid grains. Because carbon is by far the most abundant species available for making solids in these environments, researchers anticipate that the grains are composed of nearly pure carbon in some form. The observations which can be used to infer the nature of this solid phase carbon are discussed. The observations of the dust around carbon-rich red giants are discussed. These results are then placed into their broader astrophysical context.

Characterization and Thermodynamic Relationship of Three Polymorphs of a Xanthine Oxidase Inhibitor, Febuxostat.

PubMed

Patel, Jinish; Jagia, Moksh; Bansal, Arvind Kumar; Patel, Sarsvatkumar

2015-11-01

Febuxostat (FXT), a xanthine oxidase inhibitor, is an interesting and unique molecule, which exhibits extensive polymorphism, with over 15 polymorphic forms reported to date. The primary purpose of the study was to characterize the three polymorphic forms with respect to their thermodynamic quantities and establish thermodynamic relationship between them. The polymorphs were characterized by thermal and powder X-ray diffraction methods. Three different methods were used to calculate the transition temperatures (Ttr) and thereby their thermodynamic relationships. Although the first and second method used calorimetric data (melting point and heat of fusion), the third method employed the use of configurational free energy phase diagram. The onset melting points of three polymorphic forms were found to be 482.89 ± 0.37 K for form I, 476.30 ± 1.21 K for form II, and 474.19 ± 0.11 K for form III. Moreover, the powder X-ray diffraction patterns for each form were also unique. The polymorphic pair of form I and II and of form I and III was found to be enantiotropic, whereas pair of form II and III was monotropic. Besides the relative thermodynamic aspects (free energy differences, enthalpy, entropy contributions) using different methods, the pharmaceutical implications and phase transformation aspects have also been covered. © 2015 Wiley Periodicals, Inc. and the American Pharmacists Association.

First principles investigations of small bimetallic PdGa clusters as catalysts for hydrogen dissociation

NASA Astrophysics Data System (ADS)

Kaul, Indu; Ghosh, Prasenjit

2017-04-01

Using first principles density functional theory based calculations, we have studied hydrogen dissociation on sub nanometer bimetallic clusters formed from d-block (Pd) and p-block (Ga) elements in gas phase to explore the feasibility of using them as cheap catalysts for hydrogen dissociation. Our calculations show that the dimers, trimers and tetramers of these clusters are thermodynamically more stable than the pure ones for all Ga concentrations. For a given cluster size, we find that the clusters containing equal amount of Pd and Ga are the most stable ones. In contrast to bulk PdGa, the contribution of Pd-d states to the highest occupied molecular orbitals of the bimetallic clusters are either very small or absent. Study of adsorption of hydrogen molecule on these clusters show that hydrogen binds in an activated form only on the Pd rich clusters. From the calculations of hydrogen dissociation barriers on tetramers of pure Pd, 25% Ga (Pd3Ga) and 50% Ga (Pd2Ga2) we find that Pd3Ga is the most efficient catalyst for hydrogen dissociation with barriers even lower than that on the PdGa surfaces.

Selective self-assembly of adenine-silver nanoparticles forms rings resembling the size of cells

NASA Astrophysics Data System (ADS)

Choi, Sungmoon; Park, Soonyoung; Yang, Seon-Ah; Jeong, Yujin; Yu, Junhua

2015-12-01

Self-assembly has played critical roles in the construction of functional nanomaterials. However, the structure of the macroscale multicomponent materials built by the self-assembly of nanoscale building blocks is hard to predict due to multiple intermolecular interactions of great complexity. Evaporation of solvents is usually an important approach to induce kinetically stable assemblies of building blocks with a large-scale specific arrangement. During such a deweting process, we tried to monitor the possible interactions between silver nanoparticles and nucleobases at a larger scale by epifluorescence microscopy, thanks to the doping of silver nanoparticles with luminescent silver nanodots. ssDNA oligomer-stabilized silver nanoparticles and adenine self-assemble to form ring-like compartments similar to the size of modern cells. However, the silver ions only dismantle the self-assembly of adenine. The rings are thermodynamically stable as the drying process only enrich the nanoparticles-nucleobase mixture to a concentration that activates the self-assembly. The permeable membrane-like edge of the ring is composed of adenine filaments glued together by silver nanoparticles. Interestingly, chemicals are partially confined and accumulated inside the ring, suggesting that this might be used as a microreactor to speed up chemical reactions during a dewetting process.

Local Characteristics of the Nocturnal Boundary Layer in Response to External Pressure Forcing

NASA Astrophysics Data System (ADS)

van der Linden, Steven; Baas, Peter; van Hooft, Antoon; van Hooijdonk, Ivo; Bosveld, Fred; van de Wiel, Bas

2017-04-01

Geostrophic wind speed data, derived from pressure observations, are used in combination with tower measurements to investigate the nocturnal stable boundary layer at Cabauw, The Netherlands. Since the geostrophic wind speed is not directly influenced by local nocturnal stability, it may be regarded as an external forcing parameter of the nocturnal stable boundary layer. This is in contrast to local parameters such as in situ wind speed, the Monin-Obukhov stability parameter (z/L) or the local Richardson number. To characterize the stable boundary layer, ensemble averages of clear-sky nights with similar geostrophic wind speed are formed. In this manner, the mean dynamical behavior of near-surface turbulent characteristics, and composite profiles of wind and temperature is systematically investigated. We find that the classification results in a gradual ordering of the diagnosed variables in terms of the geostrophic wind speed. In an ensemble sense the transition from the weakly stable to very stable boundary layer is more gradual than expected. Interestingly, for very weak geostrophic winds turbulent activity is found to be negligibly small while the resulting boundary cooling stays finite. Realistic numerical simulations for those cases should therefore have a a solid description of other thermodynamic processes such as soil heat conduction and radiative transfer. This prerequisite poses a challenge for Large-Eddy Simulations of weak wind nocturnal boundary layers.

Do nonbonded H--H interactions in phenanthrene stabilize it relative to anthracene? A possible resolution to this question and its implications for ligands such as 2,2'-bipyridyl.

PubMed

Hancock, Robert D; Nikolayenko, Igor V

2012-08-23

The problem of whether interactions between the hydrogen atoms at the 1,10-positions in the "cleft" of the "bent" phenanthrene stabilize the latter molecule thermodynamically relative to "linear" anthracene, or whether the higher stability of phenanthrene is due to a more energetically favorable π-system, is considered. DFT calculations at the X3LYP/cc-pVTZ(-f)++ level of the ground state energies (E) of anthracene, phenanthrene, and the set of five benzoquinolines are reported. In the gas phase, "bent" phenanthrene was computed to be thermodynamically more stable than "linear" anthracene by -28.5 kJ mol(-1). This fact was attributed predominantly to the phenomenon of higher aromatic stabilization of the π-system of phenanthrene relative to anthracene, and not to the stabilizing influence of the nonbonding H--H interactions in its cleft. In fact, these interactions in phenanthrene were shown to be destabilizing. Similar calculations for five benzoquinolines (bzq) indicate that ΔE values vary as: 6,7-bzq (linear) ≤ 2,3-bzq (linear) < 5,6-bzq (bent) ≤ 3,4-bzq (bent) < 7,8-bzq (bent, no H--H nonbonding interactions in cleft), supporting the idea that it is a more stable π-system that favors 7,8-bzq over 2,3-bzq and 6,7-bzq, and that the H--H interactions in the clefts of 3,4-bzq and 5,6-bzq are destabilizing. Intramolecular hydrogen bonding in the cleft of 7,8-bzq plays a secondary role in its stabilization relative 6,7-bzq. The question of whether H--H nonbonded interactions between H atoms at the 3 and 3' positions of 2,2'-bipyridyl (bpy) coordinated to metal ions are stabilizing or destabilizing is then considered. The energy of bpy is scanned as a function of N-C-C-N torsion angle (χ) in the gas-phase, and it is found that the trans form is 32.8 kJ mol(-1) more stable than the cis conformer. A relaxed coordinate scan of energy of bpy in aqueous solution as a function of χ is modeled using the PBF approach, and it is found that the trans conformer is still more stable than the cis, but now only by 5.34 kJ mol(-1). The effect that the latter energy has on the thermodynamic stability of complexes of metal ions with bpy in aqueous solution is discussed.

Mechanical Properties of Stable Glasses Using Nanoindentation

NASA Astrophysics Data System (ADS)

Wolf, Sarah; Liu, Tianyi; Jiang, Yijie; Ablajan, Keyume; Zhang, Yue; Walsh, Patrick; Turner, Kevin; Fakhraai, Zahra

Glasses with enhanced stability over ordinary, liquid quenched glasses have been formed via the process of Physical Vapor Deposition (PVD) by using a sufficiently slow deposition rate and a substrate temperature slightly below the glass transition temperature. These stable glasses have been shown to exhibit higher density, lower enthalpy, and better kinetic stability over ordinary glass, and are typically optically birefringent, due to packing and orientational anisotropy. Given these exceptional properties, it is of interest to further investigate how the properties of stable glasses compare to those of ordinary glass. In particular, the mechanical properties of stable glasses remain relatively under-investigated. While the speed of sound and elastic moduli have been shown to increase with increased stability, little is known about their hardness and fracture toughness compared to ordinary glasses. In this study, glasses of 9-(3,5-di(naphthalen-1-yl)phenyl)anthracene were deposited at varying temperatures relative to their glass transition temperature, and their mechanical properties measured by nanoindentation. Hardness and elastic modulus of the glasses were compared across substrate temperatures. After indentation, the topography of these films were studied using Atomic Force Microscopy (AFM) in order to further compare the relationship between thermodynamic and kinetic stability and mechanical failure. Z.F. and P.W. acknowledge funding from NSF(DMREF-1628407).

Four new polymorphic forms of suplatast tosilate.

PubMed

Nagai, Keiko; Ushio, Takanori; Miura, Hidenori; Nakamura, Takashi; Moribe, Kunikazu; Yamamoto, Keiji

2014-01-02

We found four new polymorphic forms (γ-, ε-, ζ-, and η-forms) of suplatast tosilate (ST) by recrystallization and seeding with ST-analogous compounds; three polymorphic forms (α-, β-, and δ-forms) of ST have been previously reported. The physicochemical properties of these new forms were investigated using infrared (IR) spectroscopy, solid-state nuclear magnetic resonance (NMR) spectroscopy, differential scanning calorimetry, and powder X-ray diffractometry. The presence of hydrogen bonds in the new forms was assessed from the IR and solid-state NMR spectra. The crystal structures of the ε- and η-forms were determined from their powder X-ray diffraction data using the direct space approach and the Monte Carlo method, followed by Rietveld refinement. The structures determined for the ε- and η-forms supported the presence of hydrogen bonds between the ST molecules, as the IR and solid-state NMR spectra indicated. The thermodynamic characteristics of the seven polymorphic forms were evaluated by determining the solubility of each form. The α-form was the most insoluble in 2-propanol at 35°C, and was thus concluded to be the most stable form. The ε-form was the most soluble, and a polymorphic transition from the ε- to the α-form was observed during solubility testing. Copyright © 2013 Elsevier B.V. All rights reserved.

Structure and thermodynamics of uranium-containing iron garnets

DOE PAGES

Guo, Xiaofeng; Navrotsky, Alexandra; Kukkadapu, Ravi K.; ...

2016-09-15

Use of crystalline garnet as a waste form phase appears to be advantageous for accommodating actinides from nuclear waste. Previous studies show that large amounts of uranium (U) and its analogues such as cerium (Ce) and thorium (Th) can be incorporated into the garnet structure. In this study, we synthesized U loaded garnet phases, Ca 3U xZr 2–xFe 3O 12 (x = 0.5–0.7), along with the endmember phase, Ca 3(Zr 2)SiFe 3+ 2O 12, for comparison. The oxidation states of U were determined by X-ray photoelectron and absorption spectroscopies, revealing the presence of mixed pentavalent and hexavalent uranium in themore » phases with x = 0.6 and 0.7. The oxidation states and coordination environments of Fe were measured using transmission 57Fe-Mössbauer spectroscopy, which shows that all iron is tetrahedrally coordinated Fe 3+. U substitution had a significant effect on local environments, the extent of U substitution within this range had a minimal effect on the structure, and unlike in the x = 0 sample, Fe exists in two different environments in the substituted garnets. The enthalpies of formation of garnet phases from constituent oxides and elements were first time determined by high temperature oxide melt solution calorimetry. The results indicate that these substituted garnets are thermodynamically stable under reducing conditions. Furthermore, our structural and thermodynamic analysis further provides explanation for the formation of natural uranium garnet, elbrusite-(Zr), and supports the potential use of Ca 3U xZr 2–xFe 3O 12 as viable waste form phases for U and other actinides.« less

Thermodynamic and spectroscopic study of Al3+ interaction with glycine, l-cysteine and tranexamic acid in aqueous solution.

PubMed

Cardiano, Paola; Giacobello, Fausta; Giuffrè, Ottavia; Sammartano, Silvio

2017-11-01

In this paper a thermodynamic and spectroscopic study on the interaction between Al 3+ and glycine (Gly), l-cysteine (Cys), tranexamic acid (Tranex) is reported. Speciation models have been obtained by processing potentiometric titration data to determine stability constants of the species formed in aqueous solution at T=298.15K, 0.15≤I/molL -1 ≤1 in NaCl. Thermodynamic formation parameters have been obtained from calorimetric titration data, at T=298.15K, I=0.15molL -1 using NaCl as ionic medium. Al 3+ -Cys system was also investigated by spectrophotometric and 1 H NMR measurements. 1 H NMR experiments were performed on Al 3+ -Tranex system as well. Different speciation models have been observed for the three systems. The results showed the formation of MLH, ML and M 2 L 2 (OH) 2 species for Gly, ML, M 2 L and MLOH for Cys, MLH and MLOH for Tranex. The formed species are quite stable, i.e. for ML, logβ=7.18, 11.91 for Gly and Cys, respectively, at I=0.15molL -1 and T=298.15K. For all the systems the dependence of formation constants on ionic strength over the range 0.1-1molL -1 is reported. The sequestering ability of the ligands under study was also evaluated by pL 0.5 empiric parameter. For Gly, Cys and Tranex, pL 0.5 =2.51, 3.74, 3.91 respectively, at pH=5, I=0.15molL -1 and T=298.15K. Copyright © 2017 Elsevier B.V. All rights reserved.

Thermodynamic and Kinetic Aspects Involved in the Development of Nanocarriers and Drug Delivery Systems Based on Cationic Biopolymers.

PubMed

Bianco, Ismael D; Alasino, Roxana V; Leonhard, Victoria; Beltramo, Dante M

2016-01-01

During the last years we have seen an increasing number of reports describing new properties and potential applications of cationic polymers and derived nanostructures. This review gives a summary of their applications in drug delivery, the preparation methods for nano and microstructures and will attempt to give a glimpse on how their structure, chemical composition and properties may be affected or modulated as to make them suitable for an intended application as drug delivery nanocarriers. The compositional complexity with the existence of several reacting groups makes cationic nanostructures critically sensitive to the contribution of thermodynamic and kinetic parameters in the determination of the type and stability of a particular structure and its ability to respond to changes in environmental conditions in the right time frame. Curiously, and contrarily to what could be expected, despite the fact that cationic polymers can form strong electrostatic interactions the contribution of the entropic component has been often found to be very important for their association with negatively charged supramolecular structures. Some general considerations indicate that when considering a complex multimolecular system like a nanocarrier containing an active ingredient it is frequently possible to find conditions under which enthalpic and entropic contributions are compensated leading to stable structures with a marginal thermodynamic stability (free energy change close to zero) which make them able to respond relatively fast to changes in the environmental conditions and therefore suitable for the design of smart drug delivery systems. Like with other nanocarriers, it should always be kept in mind that the properties of cationic nanocarriers will depend not only on their chemical composition but also on the properties of the structures formed by them.

Real-space evidence of the equilibrium ordered bicontinuous double diamond structure of a diblock copolymer.

PubMed

Chu, C Y; Jiang, X; Jinnai, H; Pei, R Y; Lin, W F; Tsai, J C; Chen, H L

2015-03-14

The ordered bicontinuous double diamond (OBDD) structure has long been believed to be an unstable ordered network nanostructure, which is relative to the ordered bicontinuous double gyroid (OBDG) structure for diblock copolymers. Using electron tomography, we present the first real-space observation of the thermodynamically stable OBDD structure in a diblock copolymer composed of a stereoregular block, syndiotactic polypropylene-block-polystyrene (sPP-b-PS), in which the sPP tetrapods are interconnected via a bicontinuous network with Pn3̄m symmetry. The OBDD structure underwent a thermally reversible order-order transition (OOT) to OBDG upon heating, and the transition was accompanied with a slight reduction of domain spacing, as demonstrated both experimentally and theoretically. The thermodynamic stability of the OBDD structure was attributed to the ability of the configurationally regular sPP block to form helical segments, even above its melting point, as the reduction of internal energy associated with the helix formation may effectively compensate the greater packing frustration in OBDD relative to that in the tripods of OBDG.

A cuboctahedral platinum (Pt79) nanocluster enclosed by well defined facets favours di-sigma adsorption and improves the reaction kinetics for methanol fuel cells.

PubMed

Mahata, Arup; Choudhuri, Indrani; Pathak, Biswarup

2015-08-28

The methanol dehydrogenation steps are studied very systematically on the (111) facet of a cuboctahedral platinum (Pt79) nanocluster enclosed by well-defined facets. The various intermediates formed during the methanol decompositions are adsorbed at the edge and bridge site of the facet either vertically (through C- and O-centres) or in parallel. The di-sigma adsorption (in parallel) on the (111) facet of the nanocluster is the most stable structure for most of the intermediates and such binding improves the interaction between the substrate and the nanocluster and thus the catalytic activity. The reaction thermodynamics, activation barrier, and temperature dependent reaction rates are calculated for all the successive methanol dehydrogenation steps to understand the methanol decomposition mechanism, and these values are compared with previous studies to understand the catalytic activity of the nanocluster. We find the catalytic activity of the nanocluster is excellent while comparing with any previous reports and the methanol dehydrogenation thermodynamics and kinetics are best when the intermediates are adsorbed in a di-sigma manner.

Fabrication of hydroxyapatite block from gypsum block based on (NH4)2HPO4 treatment.

PubMed

Suzuki, Yumiko; Matsuya, Shigeki; Udoh, Koh-ichi; Nakagawa, Masaharu; Tsukiyama, Yoshihiro; Koyano, Kiyoshi; Ishikawa, Kunio

2005-12-01

The aim of this study was to evaluate the feasibility of fabricating low-crystalline, porous apatite block using set gypsum as a precursor based on the fact that apatite is thermodynamically more stable than gypsum. When the set gypsum was immersed in 1 mol/L diammonium hydrogen phosphate aqueous solution at 100 degrees C, it transformed to low-crystalline porous apatite retaining its original shape. The transformation reaction caused a release of sulfate ions due to an ion exchange with phosphate ions, thus leading to a decrease in the pH of the solution. Then, due to decreased pH, dicalcium phosphate anhydrous--which has similar thermodynamic stability at lower pH--was also produced as a by-product. Apatite formed in the present method was low-crystalline, porous B-type carbonate apatite that contained approximately 0.5 wt% CO3, even though no carbonate sources--except carbon dioxide from air--were added to the reaction system. We concluded therefore that this is a useful bone filler fabrication method since B-type carbonate apatite is the biological apatite contained in bone.

Chromatic patchy particles: Effects of specific interactions on liquid structure

DOE PAGES

Vasilyev, Oleg A.; Tkachenko, Alexei V.; Klumov, Boris A.

2015-07-13

We study the structural and thermodynamic properties of patchy particle liquids, with a special focus on the role of “color,” i.e., specific interactions between individual patches. A possible experimental realization of such “chromatic” interactions is by decorating the particle patches with single-stranded DNA linkers. The complementarity of the linkers can promote selective bond formation between predetermined pairs of patches. By using MD simulations, we compare the local connectivity, the bond orientation order, and other structural properties of the aggregates formed by the “colored” and “colorless” systems. The analysis is done for spherical particles with two different patch arrangements (tetrahedral andmore » cubic). It is found that the aggregated (liquid) phase of the “colorless” patchy particles is better connected, denser and typically has stronger local order than the corresponding “colored” one. This, in turn, makes the colored liquid less stable thermodynamically. Specifically, we predict that in a typical case the chromatic interactions should increase the relative stability of the crystalline phase with respect to the disordered liquid, thus expanding its region in the phase diagram.« less

Spermine moiety attached to the C-5 position of deoxyuridine enhances the duplex stability of the phosphorothioate DNA/complementary DNA and shows the susceptibility of the substrate to RNase H.

PubMed

Moriguchi, Tomohisa; Sakai, Hideaki; Suzuki, Hideo; Shinozuka, Kazuo

2008-09-01

Novel phosphorothioate-modified oligodeoxynucleotides (S-ODNs) containing a deoxyuridine derivative bearing a spermine moiety at the C-5 position were synthesized. The study of the thermal stability and the thermodynamic stability showed that the modified S-ODNs have been able to form the stable duplexes with the complementary DNA. It was also found that the duplex composed of the modified S-ODN and its complementary RNA strand is the substrate for Escherichia coli RNase H, and the cleavage of the RNA strand by the enzyme was almost similar as in the case of the unmodified one.

Extracting metal ions with diphosphonic acid, or derivative thereof

DOEpatents

Horwitz, Earl P.; Gatrone, Ralph C.; Nash, Kenneth L.

1994-01-01

Thermodynamically-unstable complexing agents which are diphosphonic acids and diphosphonic acid derivatives (or sulphur containing analogs), like carboxyhydroxymethanediphosphonic acid and vinylidene-1,1-diphosphonic acid, are capable of complexing with metal ions, and especially metal ions in the II, III, IV, V and VI oxidation states, to form stable, water-soluble metal ion complexes in moderately alkaline to highly-acidic media. However, the complexing agents can be decomposed, under mild conditions, into non-organic compounds which, for many purposes are environmentally-nondamaging compounds thereby degrading the complex and releasing the metal ion for disposal or recovery. Uses for such complexing agents as well as methods for their manufacture are also described.

Pressure-tuning micro-Raman spectra of artists' pigments: α- and β-copper phthalocyanine polymorphs.

PubMed

Beaulieu-Houle, Guillaume; Gilson, Denis F R; Butler, Ian S

2014-01-03

The two polymorphs of copper phthalocyanine, α- and β-CuPc, have been examined by micro-Raman spectroscopy at pressures approaching 5.0 GPa. The metastable α-polymorph does not exhibit any structural changes, while the more thermodynamically stable β-polymorph does exhibit a reversible phase transition at 2.0 GPa. The pressure dependences (dν/dP) for a selected number of vibrational modes are reported. Two regions of the Raman spectra, 800-900 cm(-1) and 1100-1200 cm(-1), are sensitive to pressure such that they can be used as indicators of the polymorphic form. Copyright © 2013 Elsevier B.V. All rights reserved.

Chemical evolution of the Earth: Equilibrium or disequilibrium process?

NASA Technical Reports Server (NTRS)

Sato, M.

1985-01-01

To explain the apparent chemical incompatibility of the Earth's core and mantle or the disequilibrium process, various core forming mechanisms have been proposed, i.e., rapid disequilibrium sinking of molten iron, an oxidized core or protocore materials, and meteorite contamination of the upper mantle after separation from the core. Adopting concepts used in steady state thermodynamics, a method is devised for evaluating how elements should distribute stable in the Earth's interior for the present gradients of temperature, pressure, and gravitational acceleration. Thermochemical modeling gives useful insights into the nature of chemical evolution of the Earth without overly speculative assumptions. Further work must be done to reconcile siderophile elements, rare gases, and possible light elements in the outer core.

Extracting metal ions with diphosphonic acid, or derivative thereof

DOEpatents

Horwitz, E.P.; Gatrone, R.C.; Nash, K.L.

1994-07-26

Thermodynamically-unstable complexing agents which are diphosphonic acids and diphosphonic acid derivatives (or sulfur containing analogs), like carboxyhydroxymethanediphosphonic acid and vinylidene-1,1-diphosphonic acid, are capable of complexing with metal ions, and especially metal ions in the II, III, IV, V and VI oxidation states, to form stable, water-soluble metal ion complexes in moderately alkaline to highly-acidic media. However, the complexing agents can be decomposed, under mild conditions, into non-organic compounds which, for many purposes are environmentally-nondamaging compounds thereby degrading the complex and releasing the metal ion for disposal or recovery. Uses for such complexing agents as well as methods for their manufacture are also described. 1 fig.

Polyelectrolyte bundles

NASA Astrophysics Data System (ADS)

Limbach, H. J.; Sayar, M.; Holm, C.

2004-06-01

Using extensive Molecular Dynamics simulations we study the behavior of polyelectrolytes with hydrophobic side chains, which are known to form cylindrical micelles in aqueous solution. We investigate the stability of such bundles with respect to hydrophobicity, the strength of the electrostatic interaction, and the bundle size. We show that for the parameter range relevant for sulfonated poly-para-phenylenes (PPP) one finds a stable finite bundle size. In a more generic model we also show the influence of the length of the precursor oligomer on the stability of the bundles. We also point out that our model has close similarities to DNA solutions with added condensing agents, hinting to the possibility that the size of DNA aggregates is under certain circumstances thermodynamically limited.

Irreversible thermodynamic analysis and application for molecular heat engines

NASA Astrophysics Data System (ADS)

Lucia, Umberto; Açıkkalp, Emin

2017-09-01

Is there a link between the macroscopic approach to irreversibility and microscopic behaviour of the systems? Consumption of free energy keeps the system away from a stable equilibrium. Entropy generation results from the redistribution of energy, momentum, mass and charge. This concept represents the essence of the thermodynamic approach to irreversibility. Irreversibility is the result of the interaction between systems and their environment. The aim of this paper is to determine lost works in a molecular engine and compare results with macro (classical) heat engines. Firstly, irreversible thermodynamics are reviewed for macro and molecular cycles. Secondly, irreversible thermodynamics approaches are applied for a quantum heat engine with -1/2 spin system. Finally, lost works are determined for considered system and results show that macro and molecular heat engines obey same limitations. Moreover, a quantum thermodynamic approach is suggested in order to explain the results previously obtained from an atomic viewpoint.

Impact of Alkyl Spacer Length on Aggregation Pathways in Kinetically Controlled Supramolecular Polymerization.

PubMed

Ogi, Soichiro; Stepanenko, Vladimir; Thein, Johannes; Würthner, Frank

2016-01-20

We have investigated the kinetic and thermodynamic supramolecular polymerizations of a series of amide-functionalized perylene bisimide (PBI) organogelator molecules bearing alkyl spacers of varied lengths (ethylene to pentylene chains, PBI-1-C2 to PBI-1-C5) between the amide and PBI imide groups. These amide-functionalized PBIs form one-dimensional fibrous nanostructures as the thermodynamically favored states in solvents of low polarity. Our in-depth studies revealed, however, that the kinetic behavior of their supramolecular polymerization is dependent on the spacer length. Propylene- and pentylene-tethered PBIs follow a similar polymerization process as previously observed for the ethylene-tethered PBI. Thus, the monomers of these PBIs are kinetically trapped in conformationally restricted states through intramolecular hydrogen bonding between the amide and imide groups. In contrast, the intramolecularly hydrogen-bonded monomers of butylene-tethered PBI spontaneously self-assemble into nanoparticles, which constitute an off-pathway aggregate state with regard to the thermodynamically stable fibrous supramolecular polymers obtained. Thus, for this class of π-conjugated system, an unprecedented off-pathway aggregate with high kinetic stability could be realized for the first time by introducing an alkyl linker of optimum length (C4 chain) between the amide and imide groups. Our current system with an energy landscape of two competing nucleated aggregation pathways is applicable to the kinetic control over the supramolecular polymerization by the seeding approach.

Thermodynamic analyses of hydrogen production from sub-quality natural gas. Part I: Pyrolysis and autothermal pyrolysis

NASA Astrophysics Data System (ADS)

Huang, Cunping; T-Raissi, Ali

Sub-quality natural gas (SQNG) is defined as natural gas whose composition exceeds pipeline specifications of nitrogen, carbon dioxide (CO 2) and/or hydrogen sulfide (H 2S). Approximately one-third of the U.S. natural gas resource is sub-quality gas [1]. Due to the high cost of removing H 2S from hydrocarbons using current processing technologies, SQNG wells are often capped and the gas remains in the ground. We propose and analyze a two-step hydrogen production scheme using SQNG as feedstock. The first step of the process involves hydrocarbon processing (via steam-methane reformation, autothermal steam-methane reformation, pyrolysis and autothermal pyrolysis) in the presence of H 2S. Our analyses reveal that H 2S existing in SQNG is stable and can be considered as an inert gas. No sulfur dioxide (SO 2) and/or sulfur trioxide (SO 3) is formed from the introduction of oxygen to SQNG. In the second step, after the separation of hydrogen from the main stream, un-reacted H 2S is used to reform the remaining methane, generating more hydrogen and carbon disulfide (CS 2). Thermodynamic analyses on SQNG feedstock containing up to 10% (v/v) H 2S have shown that no H 2S separation is required in this process. The Part I of this paper includes only thermodynamic analyses for SQNG pyrolysis and autothermal pyrolysis.

Applications of Protein Thermodynamic Database for Understanding Protein Mutant Stability and Designing Stable Mutants.

PubMed

Gromiha, M Michael; Anoosha, P; Huang, Liang-Tsung

2016-01-01

Protein stability is the free energy difference between unfolded and folded states of a protein, which lies in the range of 5-25 kcal/mol. Experimentally, protein stability is measured with circular dichroism, differential scanning calorimetry, and fluorescence spectroscopy using thermal and denaturant denaturation methods. These experimental data have been accumulated in the form of a database, ProTherm, thermodynamic database for proteins and mutants. It also contains sequence and structure information of a protein, experimental methods and conditions, and literature information. Different features such as search, display, and sorting options and visualization tools have been incorporated in the database. ProTherm is a valuable resource for understanding/predicting the stability of proteins and it can be accessed at http://www.abren.net/protherm/ . ProTherm has been effectively used to examine the relationship among thermodynamics, structure, and function of proteins. We describe the recent progress on the development of methods for understanding/predicting protein stability, such as (1) general trends on mutational effects on stability, (2) relationship between the stability of protein mutants and amino acid properties, (3) applications of protein three-dimensional structures for predicting their stability upon point mutations, (4) prediction of protein stability upon single mutations from amino acid sequence, and (5) prediction methods for addressing double mutants. A list of online resources for predicting has also been provided.

Charge transfer complex studies between some non-steroidal anti-inflammatory drugs and π-electron acceptors

NASA Astrophysics Data System (ADS)

Duymus, Hulya; Arslan, Mustafa; Kucukislamoglu, Mustafa; Zengin, Mustafa

2006-12-01

Charge transfer (CT) complexes of some non-steroidal anti-inflammatory drugs, naproxen and etodolac which are electron donors with some π-acceptors, such as tetracyanoethylene (TCNE), 2,3-dichloro-5,6-dicyano- p-benzoquinone (DDQ), p-chloranil ( p-CHL), have been investigated spectrophotometrically in chloroform at 21 °C. The coloured products are measured spectrophotometrically at different wavelength depending on the electronic transition between donors and acceptors. Beer's law is obeyed and colours were produced in non-aqueous media. All complexes were stable at least 2 h except for etodolac with DDQ stable for 5 min. The equilibrium constants of the CT complexes were determined by the Benesi-Hildebrand equation. The thermodynamic parameters Δ H, Δ S, Δ G° were calculated by Van't Hoff equation. Stochiometries of the complexes formed between donors and acceptors were defined by the Job's method of the continuous variation and found in 1:1 complexation with donor and acceptor at the maximum absorption bands in all cases.

Combined crystal structure prediction and high-pressure crystallization in rational pharmaceutical polymorph screening

PubMed Central

Neumann, M. A.; van de Streek, J.; Fabbiani, F. P. A.; Hidber, P.; Grassmann, O.

2015-01-01

Organic molecules, such as pharmaceuticals, agro-chemicals and pigments, frequently form several crystal polymorphs with different physicochemical properties. Finding polymorphs has long been a purely experimental game of trial-and-error. Here we utilize in silico polymorph screening in combination with rationally planned crystallization experiments to study the polymorphism of the pharmaceutical compound Dalcetrapib, with 10 torsional degrees of freedom one of the most flexible molecules ever studied computationally. The experimental crystal polymorphs are found at the bottom of the calculated lattice energy landscape, and two predicted structures are identified as candidates for a missing, thermodynamically more stable polymorph. Pressure-dependent stability calculations suggested high pressure as a means to bring these polymorphs into existence. Subsequently, one of them could indeed be crystallized in the 0.02 to 0.50 GPa pressure range and was found to be metastable at ambient pressure, effectively derisking the appearance of a more stable polymorph during late-stage development of Dalcetrapib. PMID:26198974

Violation of the isolated square rule for group 13-15 oligomers: theoretical prediction of a new class of inorganic polymers.

PubMed

Timoshkin, Alexey Y; Schaefer, Henry F

2005-02-21

It is widely thought that the oligomer compounds [RMYR]n (M-group 13, Y-group 15 element) should obey the isolated square rule found for the boron-nitrogen cages. In contrast to these expectations, the needle-shaped oligomers, which violate this rule, are more stable compared to the cage (fullerene-like) oligomers for all MY pairs (M = B, Al, Ga, In; Y = N, P, As). The stability of the needle-shaped clusters improves with increasing oligomerization degree. Thus, the isolated square rule, which is analogous to the isolated pentagon rule widely applied for fullerenes, should not serve as the basis for searches for the most stable structures of the inorganic oligomers. Generation of the needle-shaped oligomers from the group 13 and 15 hydrides is thermodynamically favorable. A synthesis of novel inorganic polymers, formed by fusion of trimeric M3Y3 rings, is expected to be viable.

Long-term stable water vapor permeation barrier properties of SiN/SiCN/SiN nanolaminated multilayers grown by plasma-enhanced chemical vapor deposition at extremely low pressures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Choi, Bum Ho, E-mail: bhchoi@kitech.re.kr; Lee, Jong Ho

2014-08-04

We investigated the water vapor permeation barrier properties of 30-nm-thick SiN/SiCN/SiN nanolaminated multilayer structures grown by plasma enhanced chemical vapor deposition at 7 mTorr. The derived water vapor transmission rate was 1.12 × 10{sup −6} g/(m{sup 2} day) at 85 °C and 85% relative humidity, and this value was maintained up to 15 000 h of aging time. The X-ray diffraction patterns revealed that the nanolaminated film was composed of an amorphous phase. A mixed phase was observed upon performing high resolution transmission electron microscope analysis, which indicated that a thermodynamically stable structure was formed. It was revealed amorphous SiN/SiCN/SiN multilayer structures that are freemore » from intermixed interface defects effectively block water vapor permeation into active layer.« less

The Thermodynamic Properties of Cubanite

NASA Technical Reports Server (NTRS)

Berger, E. L.; Lauretta, D. S.; Keller, L. P.

2012-01-01

CuFe2S3 exists in two polymorphs, a low-temperature orthorhombic form (cubanite) and a high-temperature cubic form (isocubanite). Cubanite has been identified in the CI-chondrite and Stardust collections. However, the thermodynamic properties of cubanite have neither been measured nor estimated. Our derivation of a thermodynamic model for cubanite allows constraints to be placed on the formation conditions. This data, along with the temperature constraint afforded by the crystal structure, can be used to assess the environments in which cubanite formation is (or is not) thermodynamically favored.

A new strategy of transforming pharmaceutical crystal forms.

PubMed

Tian, Jian; Dalgarno, Scott J; Atwood, Jerry L

2011-02-09

The robust nature of network materials allows them to (for example) respond to external stimuli such as pressure, temperature, light, or gas/solvent adsorption and desorption. There is difficulty in retaining long-range order in purely molecular organic solids, due to weak intermolecular interactions such as van der Waals forces. Here, we show gas-induced transformations of the well-known pharmaceuticals clarithromycin and lansoprazole. For clarithromycin, the stimulus is capable of converting the kinetic solvate and guest-free crystal forms to the commercial thermodynamically stable polymorph with a huge saving in energy cost relative to industrially employed methods. The synthesis of the marketing form of lansoprazole involves a solvate that readily decomposes and that is stirred in water, filtered, and dried intensively. Our method readily circumvents such synthetic problems and transforms the sensitive solvate to the marketed drug substance with ease. Such expedient transformations hold great implications for the pharmaceutical industry in general when considering the ease of transformation and mild conditions employed.

Two-electron Reduction versus One-electron Oxidation of the Type 3 Pair in the Multicopper Oxidases

PubMed Central

Kjaergaard, Christian H.; Jones, Stephen M.; Gounel, Sébastien; Mano, Nicolas; Solomon, Edward I.

2015-01-01

Multicopper Oxidases (MCOs) utilize an electron shuttling Type 1 Cu (T1) site in conjunction with a mononuclear Type 2 (T2) and a binuclear Type 3 (T3) site, arranged in a trinuclear copper cluster (TNC), to reduce O2 to H2O. Reduction of O2 occurs with limited overpotential indicating that all the coppers in the active site can be reduced via high-potential electron donors. Two forms of the resting enzyme have been observed in MCOs: the Alternative Resting form (AR), where only one of the three TNC Cu’s is oxidized, and the Resting Oxidized form (RO), where all three TNC Cu’s are oxidized. In contrast to the AR form, we show that in the RO form of a high-potential MCO, the binuclear T3 Cu(II) site can be reduced via the 700 mV T1 Cu. Systematic spectroscopic evaluation reveals that this proceeds by a two-electron process, where delivery of the first electron, forming a high energy, meta-stable half reduced T3 state, is followed by the rapid delivery of a second energetically favorable electron to fully reduce the T3 site. Alternatively, when this fully reduced binuclear T3 site is oxidized via the T1 Cu, a different thermodynamically favored half oxidized T3 form, i.e. the AR site, is generated. This behavior is evaluated by DFT calculations, which reveal that the protein backbone plays a significant role in controlling the environment of the active site coppers. This allows for the formation of the meta-stable, half reduced state and thus the complete reductive activation of the enzyme for catalysis. PMID:26075678

Spectroscopic and first-principles calculation studies of the chemical forms of palladium ion in nitric acid solution for development of disposal of high-level radioactive nuclear wastes

NASA Astrophysics Data System (ADS)

Watanabe, Shinta; Sato, Toshikazu; Yoshida, Tomoko; Nakaya, Masato; Yoshino, Masahito; Nagasaki, Takanori; Inaba, Yusuke; Takeshita, Kenji; Onoe, Jun

2018-04-01

We have investigated the chemical forms of palladium (Pd) ion in nitric acid solution, using XAFS/UV-vis spectroscopic and first-principles methods in order to develop the disposal of high-level radioactive nuclear liquid wastes (HLLW: radioactive metal ions in 2 M nitric acid solution). The results of theoretical calculations and XAFS/UV-vis spectroscopy indicate that Pd is a divalent ion and forms a square-planar complex structure coordinated with four nitrate ions, [Pd(NO3)4]2-, in nitric acid solution. This complex structure is also thermodynamically predicted to be most stable among complexes [Pd(H2O)x(NO3)4-x]x-2 (x = 0-4). Since the overall feature of UV-vis spectra of the Pd complex was independent of nitric acid concentration in the range 1-6 M, the structure of the Pd complex remains unchanged in this range. Furthermore, we examined the influence of γ-ray radiation on the [Pd(NO3)4]2- complex, using UV-vis spectroscopy, and found that UV-vis spectra seemed not to be changed even after 1.0 MGy irradiation. This implies that the Pd complex structure will be still stable in actual HLLW. These findings obtained above are useful information to develop the vitrification processes for disposal of HLLW.

Thermodynamic and Kinetic Effects in the Crystallization of Metal-Organic Frameworks.

PubMed

Cheetham, Anthony K; Kieslich, G; Yeung, H H-M

2018-03-20

The evolution of metal-organic frameworks (MOFs) has been one of the most exciting aspects of materials chemistry over the last 20 years. In this Account, we discuss the development during this period in our understanding of the factors that control the crystallization of MOFs from solution. Both classical porous MOFs and dense MOF phases are considered. This is an opportune time at which to examine this complex area because the experimental tools now available to interrogate crystallization processes have matured significantly in the last 5 years, particularly with the use of in situ synchrotron X-ray diffraction. There have also been impressive developments in the use of density functional theory (DFT) to treat not only the energies of very complex structures but also their entropies. This is particularly important in MOF frameworks because of their much greater flexibility compared with inorganic structures such as zeolites. The first section of the Account describes how early empirical observations on the crystallization of dense MOFs pointed to a strong degree of thermodynamic control, with both enthalpic and entropic factors playing important roles. For example, reactions at higher temperatures tend to lead to denser structures with higher degrees of framework connectivity and lower levels of solvation, and polymorphs tend to form according to their thermodynamic stabilities. In the case of metal tartrates, these trends have been validated by calorimetric studies. It has been clear for more than a decade, however, that certain phases crystallize under kinetic control, especially when a change in conformation of the ligand or coordination around a metal center might be necessary to form the thermodynamically preferred product. We describe how this can lead to time-dependent crystallization processes that evolve according to the Ostwald rule of stages and can be observed by in situ methods. We then consider the crystallization of porous MOFs, which presents additional challenges because of solvation effects. In spite of these problems, much has been learned about the energetics of the underlying frameworks, where the relationship between porosity and stability initially seemed to mirror the behavior of zeolites, with more porous structures being less stable. Recently, however, this simple relationship has had to be reconsidered with the emergence of some very flexible structures wherein the open structures are more stable than their denser analogues at finite temperatures because of their large vibrational entropies. In the final section we describe how the concepts developed in the MOF work have been extended into the closely related area of hybrid organic-inorganic perovskites. We describe recent studies on polymorphism in hybrid perovskites, which is amenable to total free energy calculations using a combination of DFT and lattice dynamics methods.

Quantification of the Thermodynamically Linked Quaternary and Tertiary Structural Stabilities of Transthyretin and its Disease-Associated Variants–the Relationship between Stability and Amyloidosis†

PubMed Central

Hurshman Babbes, Amy R.; Powers, Evan T.; Kelly, Jeffery W.

2009-01-01

Urea denaturation studies were carried out as a function of transthyretin (TTR) concentration to quantify the thermodynamically linked quaternary and tertiary structural stability and to better understand the relationship between mutant folding energetics and amyloid disease phenotype. Urea denaturation of TTR involves at least two equilibria—dissociation of tetramers into folded monomers, and monomer unfolding. To deal with the thermodynamic linkage of these equilibria, we analyzed concentration-dependent denaturation data by global fitting to an equation that simultaneously accounts for the two-step denaturation process. Using this method, the quaternary and tertiary structural stabilities of well-behaved TTR sequences, wild type (WT) TTR and the disease-associated variant V122I, were scrutinized. The V122I variant is linked to late onset familial amyloid cardiomyopathy, the most common familial TTR amyloid disease. V122I TTR exhibits a destabilized quaternary structure and a stable tertiary structure relative to WT TTR. Three other variants of TTR were also examined, L55P, V30M, and A25T TTR. The L55P mutation is associated with the most aggressive familial TTR amyloid disease. L55P TTR has a complicated denaturation pathway that includes dimers and trimers, and so globally fitting its concentration-dependent urea denaturation data yielded error-laden estimates of stability parameters. Nevertheless, it is clear that L55P TTR is substantially less stable than WT TTR, primarily because its tertiary structure is unstable, although its quaternary structure is destabilized as well. V30M is the most common mutation associated with neuropathic forms of TTR amyloid disease. V30M TTR is certainly destabilized relative to WT TTR, but like L55P TTR it has a complex denaturation pathway that cannot be fit to the aforementioned two-step denaturation model. Literature data suggest that V30M TTR has stable quaternary structure but unstable tertiary structure. The A25T mutant, associated with central nervous system amyloidosis, is highly aggregation-prone and exhibits drastically reduced quaternary and tertiary structural stability. The observed differences in stability amongst the disease-associated TTR variants highlight the complexity and the heterogeneity of TTR amyloid disease, an observation having important implications for the treatment of these diseases. PMID:18537267

Thermodynamics of higher dimensional black holes with higher order thermal fluctuations

NASA Astrophysics Data System (ADS)

Pourhassan, B.; Kokabi, K.; Rangyan, S.

2017-12-01

In this paper, we consider higher order corrections of the entropy, which coming from thermal fluctuations, and find their effect on the thermodynamics of higher dimensional charged black holes. Leading order thermal fluctuation is logarithmic term in the entropy while higher order correction is proportional to the inverse of original entropy. We calculate some thermodynamics quantities and obtain the effect of logarithmic and higher order corrections of entropy on them. Validity of the first law of thermodynamics investigated and Van der Waals equation of state of dual picture studied. We find that five-dimensional black hole behaves as Van der Waals, but higher dimensional case have not such behavior. We find that thermal fluctuations are important in stability of black hole hence affect unstable/stable black hole phase transition.

Magnetically charged regular black hole in a model of nonlinear electrodynamics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ma, Meng-Sen, E-mail: mengsenma@gmail.com

2015-11-15

We obtain a magnetically charged regular black hole in general relativity. The source to the Einstein field equations is nonlinear electrodynamic field in a physically reasonable model of nonlinear electrodynamics (NED). “Physically” here means the NED model is constructed on the basis of three conditions: the Maxwell asymptotic in the weak electromagnetic field limit; the presence of vacuum birefringence phenomenon; and satisfying the weak energy condition (WEC). In addition, we analyze the thermodynamic properties of the regular black hole in two ways. According to the usual black hole thermodynamics, we calculate the heat capacity at constant charge, from which wemore » know the smaller black hole is more stable. We also employ the horizon thermodynamics to discuss the thermodynamic quantities, especially the heat capacity at constant pressure.« less

An unusual type of polymorphism in a liquid crystal

DOE PAGES

Li, Lin; Salamonczyk, Miroslaw; Shadpour, Sasan; ...

2018-02-19

Polymorphism is a remarkable concept in chemistry, materials science, computer science, and biology. Whether it is the ability of a material to exist in two or more crystal structures, a single interface connecting to two different entities, or alternative phenotypes of an organism, polymorphism determines function and properties. In materials science, polymorphism can be found in an impressively wide range of materials, including crystalline materials, minerals, metals, alloys, and polymers. Here in this paper we report on polymorphism in a liquid crystal. A bent-core liquid crystal with a single chiral side chain forms two structurally and morphologically significantly different liquidmore » crystal phases solely depending on the cooling rate from the isotropic liquid state. On slow cooling, the thermodynamically more stable oblique columnar phase forms, and on rapid cooling, a not heretofore reported helical microfilament phase. Since structure determines function and properties, the structural color for these phases also differs.« less

Crystal nucleation and metastable bcc phase in charged colloids: A molecular dynamics study

NASA Astrophysics Data System (ADS)

Ji, Xinqiang; Sun, Zhiwei; Ouyang, Wenze; Xu, Shenghua

2018-05-01

The dynamic process of homogenous nucleation in charged colloids is investigated by brute-force molecular dynamics simulation. To check if the liquid-solid transition will pass through metastable bcc, simulations are performed at the state points that definitely lie in the phase region of thermodynamically stable fcc. The simulation results confirm that, in all of these cases, the preordered precursors, acting as the seeds of nucleation, always have predominant bcc symmetry consistent with Ostwald's step rule and the Alexander-McTague mechanism. However, the polymorph selection is not straightforward because the crystal structures formed are not often determined by the symmetry of intermediate precursors but have different characters under different state points. The region of the state point where bcc crystal structures of large enough size are formed during crystallization is narrow, which gives a reasonable explanation as to why the metastable bcc phase in charged colloidal suspensions is rarely detected in macroscopic experiments.

Three-dimensional metal-intercalated covalent organic frameworks for near-ambient energy storage

PubMed Central

Gao, Fei; Ding, Zijing; Meng, Sheng

2013-01-01

A new form of nanoporous material, metal intercalated covalent organic framework (MCOF) is proposed and its energy storage property revealed. Employing density functional and thermodynamical analysis, we find that stable, chemically active, porous materials could form by stacking covalent organic framework (COF) layers with metals as a gluing agent. Metal acts as active sites, while its aggregation is suppressed by a binding energy significantly larger than the corresponding cohesive energy of bulk metals. Two important parameters, metal binding and metal-metal separation, are tuned by selecting suitable building blocks and linkers when constructing COF layers. Systematic searches among a variety of elements and organic molecules identify Ca-intercalated COF with diphenylethyne units as optimal material for H2 storage, reaching a striking gravimetric density ~ 5 wt% at near-ambient conditions (300 K, 20 bar), in comparison to < 0.1 wt% for bare COF-1 under the same condition. PMID:23698018

Molecular dynamics simulation of shock-wave loading of copper and titanium

NASA Astrophysics Data System (ADS)

Bolesta, A. V.; Fomin, V. M.

2017-10-01

At extreme pressures and temperatures common materials form new dense phases with compacted atomic arrangements. By classical molecular dynamics simulation we observe that FCC copper undergo phase transformation to BCC structure. The transition occurs under shock wave loading at the pressures above 80 GPa and corresponding temperatures above 2000 K. We calculate phase diagram, show that at these pressures and low temperature FCC phase of copper is still stable and discuss the thermodynamic reason for phase transformation at high temperature shock wave regime. Titanium forms new hexagonal phase at high pressure as well. We calculate the structure of shock wave in titanium and observe that shock front splits in three parts: elastic, plastic and phase transformation. The possibility of using a phase transition behind a shock wave with further unloading for designing nanocrystalline materials with a reduced grain size is also shown.

Supramolecular block copolymers by kinetically controlled co-self-assembly of planar and core-twisted perylene bisimides

PubMed Central

Görl, Daniel; Zhang, Xin; Stepanenko, Vladimir; Würthner, Frank

2015-01-01

New synthetic methodologies for the formation of block copolymers have revolutionized polymer science within the last two decades. However, the formation of supramolecular block copolymers composed of alternating sequences of larger block segments has not been realized yet. Here we show by transmission electron microscopy (TEM), 2D NMR and optical spectroscopy that two different perylene bisimide dyes bearing either a flat (A) or a twisted (B) core self-assemble in water into supramolecular block copolymers with an alternating sequence of (AmBB)n. The highly defined ultralong nanowire structure of these supramolecular copolymers is entirely different from those formed upon self-assembly of the individual counterparts, that is, stiff nanorods (A) and irregular nanoworms (B), respectively. Our studies further reveal that the as-formed supramolecular block copolymer constitutes a kinetic self-assembly product that transforms into thermodynamically more stable self-sorted homopolymers upon heating. PMID:25959777

Cation specific binding with protein surface charges

PubMed Central

Hess, Berk; van der Vegt, Nico F. A.

2009-01-01

Biological organization depends on a sensitive balance of noncovalent interactions, in particular also those involving interactions between ions. Ion-pairing is qualitatively described by the law of “matching water affinities.” This law predicts that cations and anions (with equal valence) form stable contact ion pairs if their sizes match. We show that this simple physical model fails to describe the interaction of cations with (molecular) anions of weak carboxylic acids, which are present on the surfaces of many intra- and extracellular proteins. We performed molecular simulations with quantitatively accurate models and observed that the order K+ < Na+ < Li+ of increasing binding affinity with carboxylate ions is caused by a stronger preference for forming weak solvent-shared ion pairs. The relative insignificance of contact pair interactions with protein surfaces indicates that thermodynamic stability and interactions between proteins in alkali salt solutions is governed by interactions mediated through hydration water molecules. PMID:19666545

An unusual type of polymorphism in a liquid crystal

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Lin; Salamonczyk, Miroslaw; Shadpour, Sasan

Polymorphism is a remarkable concept in chemistry, materials science, computer science, and biology. Whether it is the ability of a material to exist in two or more crystal structures, a single interface connecting to two different entities, or alternative phenotypes of an organism, polymorphism determines function and properties. In materials science, polymorphism can be found in an impressively wide range of materials, including crystalline materials, minerals, metals, alloys, and polymers. Here in this paper we report on polymorphism in a liquid crystal. A bent-core liquid crystal with a single chiral side chain forms two structurally and morphologically significantly different liquidmore » crystal phases solely depending on the cooling rate from the isotropic liquid state. On slow cooling, the thermodynamically more stable oblique columnar phase forms, and on rapid cooling, a not heretofore reported helical microfilament phase. Since structure determines function and properties, the structural color for these phases also differs.« less

Citrate synthase proteins in extremophilic organisms: Studies within a structure-based model

DOE Office of Scientific and Technical Information (OSTI.GOV)

Różycki, Bartosz, E-mail: rozycki@ifpan.edu.pl; Cieplak, Marek

2014-12-21

We study four citrate synthase homodimeric proteins within a structure-based coarse-grained model. Two of these proteins come from thermophilic bacteria, one from a cryophilic bacterium and one from a mesophilic organism; three are in the closed and two in the open conformations. Even though the proteins belong to the same fold, the model distinguishes the properties of these proteins in a way which is consistent with experiments. For instance, the thermophilic proteins are more stable thermodynamically than their mesophilic and cryophilic homologues, which we observe both in the magnitude of thermal fluctuations near the native state and in the kineticsmore » of thermal unfolding. The level of stability correlates with the average coordination number for amino acid contacts and with the degree of structural compactness. The pattern of positional fluctuations along the sequence in the closed conformation is different than in the open conformation, including within the active site. The modes of correlated and anticorrelated movements of pairs of amino acids forming the active site are very different in the open and closed conformations. Taken together, our results show that the precise location of amino acid contacts in the native structure appears to be a critical element in explaining the similarities and differences in the thermodynamic properties, local flexibility, and collective motions of the different forms of the enzyme.« less

Geochemical transformations and modeling of two deep-well injected hazardous wastes

USGS Publications Warehouse

Roy, W.R.; Seyler, B.; Steele, J.D.; Mravik, S.C.; Moore, D.M.; Krapac, I.G.; Peden, J.M.; Griffin, R.A.

1991-01-01

Two liquid hazardous wastes (an alkaline brine-like solution and a dilute acidic waste) were mixed with finely ground rock samples of three injection-related lithologies (sandstone, dolomite, and siltstone) for 155 to 230 days at 325??K-10.8 MPa. The pH and inorganic chemical composition of the alkaline waste were not significantly altered by any of the rock samples after 230 days of mixing. The acidic waste was neutralized as a consequence of carbonate dissolution, ion exchange, or clay-mineral dissolution, and hence was transformed into a nonhazardous waste. Mixing the alkaline waste with the solid phases yielded several reaction products: brucite, Mg(OH)2; calcite, CaCO3; and possibly a type of sodium metasilicate. Clay-like minerals formed in the sandstone, and hydrotalcite, Mg6Al2-CO3(OH)16??4H2O, may have formed in the siltstone at trace levels. Mixing the alkaline waste with a synthetic brine yielded brucite, calcite, and whewellite (CaC2O4??H2O). The thermodynamic model PHRQPITZ predicted that brucite and calcite would precipitate from solution in the dolomite and siltstone mixtures and in the alkaline waste-brine system. The dilute acidic waste did not significantly alter the mineralogical composition of the three rock types after 155 days of contact. The model PHREEQE indicated that the calcite was thermodynamically stable in the dolomite and siltstone mixtures.

Resolving the Chemically Discrete Structure of Synthetic Borophene Polymorphs.

PubMed

Campbell, Gavin P; Mannix, Andrew J; Emery, Jonathan D; Lee, Tien-Lin; Guisinger, Nathan P; Hersam, Mark C; Bedzyk, Michael J

2018-05-09

Atomically thin two-dimensional (2D) materials exhibit superlative properties dictated by their intralayer atomic structure, which is typically derived from a limited number of thermodynamically stable bulk layered crystals (e.g., graphene from graphite). The growth of entirely synthetic 2D crystals, those with no corresponding bulk allotrope, would circumvent this dependence upon bulk thermodynamics and substantially expand the phase space available for structure-property engineering of 2D materials. However, it remains unclear if synthetic 2D materials can exist as structurally and chemically distinct layers anchored by van der Waals (vdW) forces, as opposed to strongly bound adlayers. Here, we show that atomically thin sheets of boron (i.e., borophene) grown on the Ag(111) surface exhibit a vdW-like structure without a corresponding bulk allotrope. Using X-ray standing wave-excited X-ray photoelectron spectroscopy, the positions of boron in multiple chemical states are resolved with sub-angström spatial resolution, revealing that the borophene forms a single planar layer that is 2.4 Å above the unreconstructed Ag surface. Moreover, our results reveal that multiple borophene phases exhibit these characteristics, denoting a unique form of polymorphism consistent with recent predictions. This observation of synthetic borophene as chemically discrete from the growth substrate suggests that it is possible to engineer a much wider variety of 2D materials than those accessible through bulk layered crystal structures.

Citrate synthase proteins in extremophilic organisms: Studies within a structure-based model

NASA Astrophysics Data System (ADS)

RóŻycki, Bartosz; Cieplak, Marek

2014-12-01

We study four citrate synthase homodimeric proteins within a structure-based coarse-grained model. Two of these proteins come from thermophilic bacteria, one from a cryophilic bacterium and one from a mesophilic organism; three are in the closed and two in the open conformations. Even though the proteins belong to the same fold, the model distinguishes the properties of these proteins in a way which is consistent with experiments. For instance, the thermophilic proteins are more stable thermodynamically than their mesophilic and cryophilic homologues, which we observe both in the magnitude of thermal fluctuations near the native state and in the kinetics of thermal unfolding. The level of stability correlates with the average coordination number for amino acid contacts and with the degree of structural compactness. The pattern of positional fluctuations along the sequence in the closed conformation is different than in the open conformation, including within the active site. The modes of correlated and anticorrelated movements of pairs of amino acids forming the active site are very different in the open and closed conformations. Taken together, our results show that the precise location of amino acid contacts in the native structure appears to be a critical element in explaining the similarities and differences in the thermodynamic properties, local flexibility, and collective motions of the different forms of the enzyme.

Accelerated and decelerated expansion in a causal dissipative cosmology

NASA Astrophysics Data System (ADS)

Cruz, Miguel; Cruz, Norman; Lepe, Samuel

2017-12-01

In this work we explore a new cosmological solution for an universe filled with one dissipative fluid, described by a barotropic equation of state (EoS) p =ω ρ , in the framework of the full Israel-Stewart theory. The form of the bulk viscosity has been assumed of the form ξ =ξ0ρ1 /2. The relaxation time is taken to be a function of the EoS, the bulk viscosity and the speed of bulk viscous perturbations, cb. The solution presents an initial singularity, where the curvature scalar diverges as the scale factor goes to zero. Depending on the values for ω , ξ0, cb accelerated and decelerated cosmic expansion can be obtained. In the case of accelerated expansion, the viscosity drives the effective EoS to be of quintessence type, for the single fluid with positive pressure. Nevertheless, we show that only the solution with decelerated expansion satisfies the thermodynamics conditions d S /d t >0 (growth of the entropy) and d2S /d t2<0 (convexity condition). We show that an exact stiff matter EoS is not allowed in the framework of the full causal thermodynamic approach; and in the case of a EoS very close to the stiff matter regime, we found that dissipative effects becomes negligible so the entropy remains constant. Finally, we show numerically that the solution is stable under small perturbations.

Investigating the Crystallization Propensity of Structurally Similar Organic Molecules From Amorphous State

NASA Astrophysics Data System (ADS)

Kalra, Arjun

Combinatorial chemistry and high-throughput screening approaches utilized during drug discovery have resulted in many potent pharmacologically active molecules with low aqueous solubility and consequently poor bioavailability. Enabling technologies, such as amorphous solid dispersions (ASD's), can obviate these challenges and provide an efficient route to formulate the drug as an oral solid dosage form. However, high-energy amorphous materials have an inherent tendency to crystallize and in doing so can negate the apparent solubility advantage achieved by using such formulations. Crystallization can occur during (1) cooling the drug molecule from the melt state (such as during hot melt extrusion); (2) during storage of an amorphous formulation; (3) during pharmaceutical processing unit operations such as compression, granulation etc. Current knowledge with regards to the relationship between crystallization propensity of an active pharmaceutical ingredient (API) from the amorphous state (supercooled liquid and glass) and its thermodynamic, kinetic and molecular properties is limited. Furthermore, examining the mechanistic steps involved in crystallization of organic molecules under conditions of supercooling provides an opportunity to examine supramolecular aggregation events occurring during early stages of crystallization. Studying crystallization mechanism from amorphous state is important for pharmaceutical formulation development because a molecular-level understanding of the crystallization process would provide clues regarding the intermolecular interactions at the early stages of nucleation and help in rational selection of polymeric excipients to hinder such events. The primary goal of this research is to develop an understanding of phase transition from amorphous pharmaceuticals, specifically focusing on the role of thermodynamic, kinetic and molecular properties of a series of structurally similar compounds. It is hypothesized that the there exists a link between thermodynamics quantities, kinetic properties, molecular interactions and glass forming ability. Furthermore, it is hypothesized that the molecular heterogeneity in supercooled liquids and glassy state, manifested through intermolecular interactions and conformational flexibility impacts the observed crystallization behavior. Understanding the phase transition kinetics and mechanism of crystallization from amorphous pharmaceuticals is critical for development of stable formulations for drug delivery. The specific goals of this research include: (1) Investigating the link between thermodynamic and kinetic factors affecting the crystallization propensity of organic compounds from supercooled liquid state. (2) Evaluating the role of intermolecular interactions and conformational distribution on glass forming ability and stability. (3) Examining the relationship between supramolecular aggregates present in glassy state and polymorphic outcome. It is believed that successful completion of this research will provide a fundamental understanding of amorphous solid-state chemistry as well as provide useful tools for the implementation of ASD's as solid oral dosage forms.

Transformations between Extensive and Intensive Versions of Thermodynamic Relationships

ERIC Educational Resources Information Center

Eberhart, James G.

2010-01-01

Most thermodynamic properties are either extensive (e.g., volume, energy, entropy, amount, etc.) or intensive (e.g., temperature, pressure, chemical potential, mole fraction, etc.). By the same token most of the mathematical relationships in thermodynamics can be written in extensive or intensive form. The basic laws of thermodynamics are usually…

Phase transition, thermodynamics properties and IR spectrum of α- and γ-RDX: First principles and MD studies

NASA Astrophysics Data System (ADS)

Yuan, Jiaonan; Ji, Guangfu; Chen, Xiangrong; Wei, Dongqing; Zhao, Feng; Wu, Qiang

2016-01-01

In present letter, based on density functional theory plus dispersion (DFT-D) and a self-consistent charge density-functional tight-binding (SCC-DFTB) method, the structural and electronic properties are reported, and the phase transition are investigated by analyzing its thermodynamics properties and IR spectrum of RDX. The anisotropy of α- and γ-RDX were discussed at 0⿿10 GPa. By fitting the third-order Birch⿿Murnaghan equation of states, the bulk modulus and its pressure derivative of RDX were determined. The α-RDX phase is found stable at ambient condition, however, under pressures, both the values of lattice constants a, b, c and the οEvdw at around 4 GPa show abrupt changes which indicate a structural transition occurred. By analyzing the linear compressibility of a, b, c axes at 0⿿8 GPa, one clearly see that the molecules in α-RDX phase underwent rotations and translational motion to their position in the γ-RDX phase at about 4 GPa, which validates the α⿿γ phase transition. The IR spectra of α-form and γ-form RDX was calculated by analyzing the trajectory of molecules motion, which also show the phase transition from the spectra changes. Employing the quasi-harmonic Debye model, the enthalpy and specific heat were investigated at various pressures of both phases. The condition of equal enthalpies in both phases also indicates the phase transition of α-form to γ-form at around 4 GPa. The variation of specific heat with temperature approaches to the classical Dulong⿿Petit's law at high temperature, while at low-temperature it obeys the Debye's T3 law.

Thermodynamics of rock forming crystalline solutions

NASA Technical Reports Server (NTRS)

Saxena, S. K.

1971-01-01

Analysis of phase diagrams and cation distributions within crystalline solutions as means of obtaining thermodynamic data on rock forming crystalline solutions is discussed along with some aspects of partitioning of elements in coexisting phases. Crystalline solutions, components in a silicate mineral, and chemical potentials of these components were defined. Examples were given for calculating thermodynamic mixing functions in the CaW04-SrW04, olivine-chloride solution, and orthopyroxene systems.

The structural, electronic, magnetic and optical properties of the half-metallic binary alloys ZCl3 (Z=Be, Mg, Ca, Sr): A first-principles study

NASA Astrophysics Data System (ADS)

Song, Jun-Tao; Zhang, Jian-Min

2018-06-01

The investigations of the electronic and magnetic properties show the binary Heusler alloys ZCl3 (Z = Be, Mg, Ca, Sr) are half-metallic (HM) ferromagnets with an integer magnetic moment (Mt) of 1 μB /f.u.. The alloy BeCl3 is thermodynamic meta-stable, while other alloys are thermodynamic stable according to their cohesive energies and formation energies. Moreover, wide HM regions for alloys ZCl3 (Z = Be, Mg, Ca, Sr) show their HM characters are robust when the lattices are expanded or compressed under uniform and tetragonal strains. Finally, some optical properties are analyzed in detail, such as the dielectric function, the absorption coefficient, the refractive index and the extinction coefficient.

A cyclobutane thymine–N4-methylcytosine dimer is resistant to hydrolysis but strongly blocks DNA synthesis

PubMed Central

Yamamoto, Junpei; Oyama, Tomoko; Kunishi, Tomohiro; Masutani, Chikahide; Hanaoka, Fumio; Iwai, Shigenori

2014-01-01

Exposure of DNA to ultraviolet light produces harmful crosslinks between adjacent pyrimidine bases, to form cyclobutane pyrimidine dimers (CPDs) and pyrimidine(6–4)pyrimidone photoproducts. The CPD is frequently formed, and its repair mechanisms have been exclusively studied by using a CPD formed at a TT site. On the other hand, biochemical analyses using CPDs formed within cytosine-containing sequence contexts are practically difficult, because saturated cytosine easily undergoes hydrolytic deamination. Here, we found that N-alkylation of the exocyclic amino group of 2′-deoxycytidine prevents hydrolysis in CPD formation, and an N-methylated cytosine-containing CPD was stable enough to be derivatized into its phosphoramidite building block and incorporated into oligonucleotides. Kinetic studies of the CPD-containing oligonucleotide indicated that its lifetime under physiological conditions is relatively long (∼7 days). In biochemical analyses using human DNA polymerase η, incorporation of TMP opposite the N-methylcytosine moiety of the CPD was clearly detected, in addition to dGMP incorporation, and the incorrect TMP incorporation blocked DNA synthesis. The thermodynamic parameters confirmed the formation of this unusual base pair. PMID:24185703

Electrically active induced energy levels and metastability of B and N vacancy-complexes in 4H–SiC

NASA Astrophysics Data System (ADS)

Igumbor, E.; Olaniyan, O.; Mapasha, R. E.; Danga, H. T.; Omotoso, E.; Meyer, W. E.

2018-05-01

Electrically active induced energy levels in semiconductor devices could be beneficial to the discovery of an enhanced p or n-type semiconductor. Nitrogen (N) implanted into 4H–SiC is a high energy process that produced high defect concentrations which could be removed during dopant activation annealing. On the other hand, boron (B) substituted for silicon in SiC causes a reduction in the number of defects. This scenario leads to a decrease in the dielectric properties and induced deep donor and shallow acceptor levels. Complexes formed by the N, such as the nitrogen-vacancy centre, have been reported to play a significant role in the application of quantum bits. In this paper, results of charge states thermodynamic transition level of the N and B vacancy-complexes in 4H–SiC are presented. We explore complexes where substitutional N/N or B/B sits near a Si (V) or C (V) vacancy to form vacancy-complexes (NV, NV, NV, NV, BV, BV, BV and BV). The energies of formation of the N related vacancy-complexes showed the NV to be energetically stable close to the valence band maximum in its double positive charge state. The NV is more energetically stable in the double negative charge state close to the conduction band minimum. The NV on the other hand, induced double donor level and the NV induced a double acceptor level. For B related complexes, the BV and BV were energetically stable in their single positive charge state close to the valence band maximum. As the Fermi energy is varied across the band gap, the neutral and single negative charge states of the BV become more stable at different energy levels. B and N related complexes exhibited charge state controlled metastability behaviour.

Role of stacking disorder in ice nucleation

NASA Astrophysics Data System (ADS)

Lupi, Laura; Hudait, Arpa; Peters, Baron; Grünwald, Michael; Gotchy Mullen, Ryan; Nguyen, Andrew H.; Molinero, Valeria

2017-11-01

The freezing of water affects the processes that determine Earth’s climate. Therefore, accurate weather and climate forecasts hinge on good predictions of ice nucleation rates. Such rate predictions are based on extrapolations using classical nucleation theory, which assumes that the structure of nanometre-sized ice crystallites corresponds to that of hexagonal ice, the thermodynamically stable form of bulk ice. However, simulations with various water models find that ice nucleated and grown under atmospheric temperatures is at all sizes stacking-disordered, consisting of random sequences of cubic and hexagonal ice layers. This implies that stacking-disordered ice crystallites either are more stable than hexagonal ice crystallites or form because of non-equilibrium dynamical effects. Both scenarios challenge central tenets of classical nucleation theory. Here we use rare-event sampling and free energy calculations with the mW water model to show that the entropy of mixing cubic and hexagonal layers makes stacking-disordered ice the stable phase for crystallites up to a size of at least 100,000 molecules. We find that stacking-disordered critical crystallites at 230 kelvin are about 14 kilojoules per mole of crystallite more stable than hexagonal crystallites, making their ice nucleation rates more than three orders of magnitude higher than predicted by classical nucleation theory. This effect on nucleation rates is temperature dependent, being the most pronounced at the warmest conditions, and should affect the modelling of cloud formation and ice particle numbers, which are very sensitive to the temperature dependence of ice nucleation rates. We conclude that classical nucleation theory needs to be corrected to include the dependence of the crystallization driving force on the size of the ice crystallite when interpreting and extrapolating ice nucleation rates from experimental laboratory conditions to the temperatures that occur in clouds.

Role of stacking disorder in ice nucleation.

PubMed

Lupi, Laura; Hudait, Arpa; Peters, Baron; Grünwald, Michael; Gotchy Mullen, Ryan; Nguyen, Andrew H; Molinero, Valeria

2017-11-08

The freezing of water affects the processes that determine Earth's climate. Therefore, accurate weather and climate forecasts hinge on good predictions of ice nucleation rates. Such rate predictions are based on extrapolations using classical nucleation theory, which assumes that the structure of nanometre-sized ice crystallites corresponds to that of hexagonal ice, the thermodynamically stable form of bulk ice. However, simulations with various water models find that ice nucleated and grown under atmospheric temperatures is at all sizes stacking-disordered, consisting of random sequences of cubic and hexagonal ice layers. This implies that stacking-disordered ice crystallites either are more stable than hexagonal ice crystallites or form because of non-equilibrium dynamical effects. Both scenarios challenge central tenets of classical nucleation theory. Here we use rare-event sampling and free energy calculations with the mW water model to show that the entropy of mixing cubic and hexagonal layers makes stacking-disordered ice the stable phase for crystallites up to a size of at least 100,000 molecules. We find that stacking-disordered critical crystallites at 230 kelvin are about 14 kilojoules per mole of crystallite more stable than hexagonal crystallites, making their ice nucleation rates more than three orders of magnitude higher than predicted by classical nucleation theory. This effect on nucleation rates is temperature dependent, being the most pronounced at the warmest conditions, and should affect the modelling of cloud formation and ice particle numbers, which are very sensitive to the temperature dependence of ice nucleation rates. We conclude that classical nucleation theory needs to be corrected to include the dependence of the crystallization driving force on the size of the ice crystallite when interpreting and extrapolating ice nucleation rates from experimental laboratory conditions to the temperatures that occur in clouds.

Correlation of the thermodynamic calculation and the experimental observation of Ni-Mo-Cr low alloy steel changing Ni, Mo, and Cr contents

NASA Astrophysics Data System (ADS)

Park, Sang-Gyu; Kim, Min-Chul; Lee, Bong-Sang; Wee, Dang-Moon

2010-12-01

SA508 Gr.4N Ni-Mo-Cr low alloy steel has improved fracture toughness and strength compared to commercial low alloy steels such as SA508 Gr.3 Mn-Mo-Ni low alloy steel, which has less than 1% Ni. Higher strength and fracture toughness of low alloy steels can be achieved by increasing the Ni and Cr contents. In this study, the effects of the alloying elements of Ni and Cr on the microstructural characteristics and mechanical properties of SA508 Gr.4N Ni-Mo-Cr low alloy steel are evaluated. Changes in the stable phases of SA508 Gr.4N low alloy steel with these alloying elements were evaluated using thermodynamic calculation software. These values were then compared with the observed microstructural results. Additionally, tensile tests and Charpy impact test were carried out to evaluate the mechanical properties. The thermodynamic calculations show that Ni mainly affects the change of the matrix phase of γ and α rather than the carbide phase. Contrary to the Ni effect, Cr and Mo primarily affect the precipitation behavior of the carbide phases of Cr 23C 6, Cr 7C 3 and Mo 2C. In the microscopic observations, the lath martensitic structure becomes finer as the Ni content increases without affecting the carbides. When the Cr content decreases, the Cr carbide becomes unstable and carbide coarsening occurs. Carbide Mo 2C in the form of fine needles were observed in the high-Mo alloy. Greater strength was obtained after additions of Ni and Mo and the transition properties were improved as the Ni and Cr contents increased. These results were correlated with the thermodynamic calculation results.

Petrogenetic grids for sapphirine-bearing granulites

NASA Astrophysics Data System (ADS)

Podlesskii, Konstantin K.

2010-05-01

Phase relations involving sapphirine, garnet, spinel, orthopyroxene, olivine, cordierite, alumina silicates, corundum, and quartz have been calculated in the system FeO-MgO-Al2O3-SiO2 based on internally consitent thermodynamic properties of both the end-member minerals and the solid solutions (Gerya et al., 2004; Podlesskii et al., 2008). The derived P-T diagrams imply stable invariant points and stability fields of key assemblages that differ from those proposed by other authors (Kelsey et al., 2004; Harley 2008). The sapphirine + quartz assemblage, which is widely recognized as indicative of ultrahigh-temperature metamorphism, can be stable down to 835° C and ~6 kbar. The sapphirine + kyanite assemblage has been found stable at temperatures below 860° C and 11.3 kbar, whereas the sapphirine + forsterite assemblage may be stable below 800° C only under specific conditions of a very low activity of water. The existing constraints on the thermodynamic properties of sapphirine are considered insufficient to make decisive conclusions about metamorphic conditions. Granulites containing the sapphirine + quartz assemblage have been investigated with the microprobe to apply both the conventional thermobarometry and thermometry based on Ti contents of quartz (TitaniQ, Wark & Watson, 2006). The results demonstrate that, in some cases, this assemblage might have formed at relatively low temperatures during retrograde stages of metamorphism. The research has been supported by the RFBR grant 09-05-00193. References Gerya,T.V., Perchuk,L.L., & Podlesskii,K.K. In: Zharikov,V.A. & Fed'kin,V.V. (eds.) Experimental Mineralogy: Some Results on the Century's Frontier. Moscow: Nauka, Vol. 2, 188-206 (2004). Harley,S.L. Refining the P-T records of UHT crustal metamorphism. Journal of Metamorphic Geology, 26, 125-154 (2008). Kelsey,D.E., White,R.W., Holland,T.J.B., & Powell,R. Journal of Metamorphic Geology, 22, 559-578 (2004). Podlesskii,K.K., Aranovich,L.Y., Gerya,T.V., & Kosyakova,N.A. Sapphirine-bearing assemblages in the system MgO-Al2O3-SiO2: A continuing ambiguity. European Journal of Mineralogy, 20, 721-734 (2008). Wark,D.A. & Watson,E.B. TitaniQ: a titanium-in-quartz geothermometer. Contributions to Mineralogy and Petrology, 152, 743-754 (2006).

Molecular dynamics analysis of stabilities of the telomeric Watson-Crick duplex and the associated i-motif as a function of pH and temperature.

PubMed

Panczyk, Tomasz; Wolski, Pawel

2018-06-01

This work deals with a molecular dynamics analysis of the protonated and deprotonated states of the natural sequence d[(CCCTAA) 3 CCCT] of the telomeric DNA forming the intercalated i-motif or paired with the sequence d[(CCCTAA) 3 CCCT] and forming the Watson-Crick (WC) duplex. By utilizing the amber force field for nucleic acids we built the i-motif and the WC duplex either with native cytosines or using their protonated forms. We studied, by applying molecular dynamics simulations, the role of hydrogen bonds between cytosines or in cytosine-guanine pairs in the stabilization of both structures in the physiological fluid. We found that hydrogen bonds exist in the case of protonated i-motif and in the standard form of the WC duplex. They, however, vanish in the case of the deprotonated i-motif and protonated form of the WC duplex. By determining potentials of mean force in the enforced unwrapping of these structures we found that the protonated i-motif is thermodynamically the most stable. Its deprotonation leads to spontaneous and observed directly in the unbiased calculations unfolding of the i-motif to the hairpin structure at normal temperature. The WC duplex is stable in its standard form and its slight destabilization is observed at the acidic pH. However, the protonated WC duplex unwraps very slowly at 310 K and its decomposition was not observed in the unbiased calculations. At higher temperatures (ca. 400 K or more) the WC duplex unwraps spontaneously. Copyright © 2018. Published by Elsevier B.V.

Extreme thermodynamic conditions: novel stoichiometries, violations of textbook chemistry, and intriguing possibilities for the synthesis of new materials

NASA Astrophysics Data System (ADS)

Stavrou, Elissaios

As evidenced by numerous experimental and theoretical studies, application of high pressure can dramatically modify the atomic arrangement and electronic structures of both elements and compounds. However, the great majority of research has been focused on the effect of pressure on compounds with constant stoichiometries (typically those stable under ambient conditions). Recent theoretical predictions, using advanced search algorithms, suggest that composition is another important variable in the search for stable compounds, i.e. that the more stable stoichiometry at elevated pressures is not a priory the same as that at ambient pressure. Indeed, thermodynamically stable compounds with novel compositions were theoretically predicted and experimentally verified even in relatively simple chemical systems including: Na-Cl, C-N, Li-H, Na-H, Cs-N, H-N, Na-He, Xe-Fe. These materials are stable due to the formation of novel chemical bonds that are absent, or even forbidden, at ambient conditions. Tuning the composition of the system thus represents another important, but poorly explored approach to the synthesis of novel materials. By varying the stoichiometry one can design novel materials with enhanced properties (e.g. high energy density, hardness, superconductivity etc.), that are metastable at ambient conditions and synthesized at thermodynamic conditions less extreme than that those required for known stoichiometries. Moreover, current outstanding questions, ``anomalies'' and ``paradoxes'' in geo- and planetary science (e.g. the Xenon paradox) could be addressed based on the stability of surprising, stoichiometries that challenge our traditional ``textbook'' picture. In this talk, I will briefly present recent results and highlight the need of close synergy between experimental and theoretical efforts to understand the challenging and complex field of variable stoichiometry under pressure. Finally, possible new routes for the synthesis of novel materials will be discussed. This work was performed under the auspices of the U. S. Department of Energy by Lawrence Livermore National Security, LLC under Contract DE-AC52-07NA27344.

Thermodynamic Modeling of Hydrogen Storage Capacity in Mg-Na Alloys

PubMed Central

Abdessameud, S.; Mezbahul-Islam, M.; Medraj, M.

2014-01-01

Thermodynamic modeling of the H-Mg-Na system is performed for the first time in this work in order to understand the phase relationships in this system. A new thermodynamic description of the stable NaMgH3 hydride is performed and the thermodynamic models for the H-Mg, Mg-Na, and H-Na systems are reassessed using the modified quasichemical model for the liquid phase. The thermodynamic properties of the ternary system are estimated from the models of the binary systems and the ternary compound using CALPHAD technique. The constructed database is successfully used to reproduce the pressure-composition isotherms for MgH2 + 10 wt.% NaH mixtures. Also, the pressure-temperature equilibrium diagram and reaction paths for the same composition are predicted at different temperatures and pressures. Even though it is proved that H-Mg-Na does not meet the DOE hydrogen storage requirements for onboard applications, the best working temperatures and pressures to benefit from its full catalytic role are given. Also, the present database can be used for thermodynamic assessments of higher order systems. PMID:25383361

Thermodynamic modeling of hydrogen storage capacity in Mg-Na alloys.

PubMed

Abdessameud, S; Mezbahul-Islam, M; Medraj, M

2014-01-01

Thermodynamic modeling of the H-Mg-Na system is performed for the first time in this work in order to understand the phase relationships in this system. A new thermodynamic description of the stable NaMgH3 hydride is performed and the thermodynamic models for the H-Mg, Mg-Na, and H-Na systems are reassessed using the modified quasichemical model for the liquid phase. The thermodynamic properties of the ternary system are estimated from the models of the binary systems and the ternary compound using CALPHAD technique. The constructed database is successfully used to reproduce the pressure-composition isotherms for MgH2 + 10 wt.% NaH mixtures. Also, the pressure-temperature equilibrium diagram and reaction paths for the same composition are predicted at different temperatures and pressures. Even though it is proved that H-Mg-Na does not meet the DOE hydrogen storage requirements for onboard applications, the best working temperatures and pressures to benefit from its full catalytic role are given. Also, the present database can be used for thermodynamic assessments of higher order systems.

Black hole thermodynamics in Lovelock gravity's rainbow with (A)dS asymptote

NASA Astrophysics Data System (ADS)

Hendi, Seyed Hossein; Dehghani, Ali; Faizal, Mir

2017-01-01

In this paper, we combine Lovelock gravity with gravity's rainbow to construct Lovelock gravity's rainbow. Considering the Lovelock gravity's rainbow coupled to linear and also nonlinear electromagnetic gauge fields, we present two new classes of topological black hole solutions. We compute conserved and thermodynamic quantities of these black holes (such as temperature, entropy, electric potential, charge and mass) and show that these quantities satisfy the first law of thermodynamics. In order to study the thermal stability in canonical ensemble, we calculate the heat capacity and determinant of the Hessian matrix and show in what regions there are thermally stable phases for black holes. Also, we discuss the dependence of thermodynamic behavior and thermal stability of black holes on rainbow functions. Finally, we investigate the critical behavior of black holes in the extended phase space and study their interesting properties.

Synthesis and Thermoelectric Properties of Charge-Compensated SyPdxCo4-xSb12 Skutterudites.

PubMed

Wan, Shun; Qiu, Pengfei; Huang, Xiangyang; Song, Qingfeng; Bai, Shengqiang; Shi, Xun; Chen, Lidong

2018-01-10

Recently, the electronegative elements (e.g., S, Se, Cl, and Br) filled skutterudites have attracted great attention in thermoelectric community. Via doping of some electron donors at the Sb sites, these electronegative elements can be filled into the voids of CoSb 3 forming thermodynamically stable compounds, which greatly extends the scope of filled skutterudites. In this study, we show that doping appropriate elements at the Co sites can also stabilize the electronegative elements in the voids of CoSb 3 . A series of S y Pd x Co 4-x Sb 12 compounds were successfully fabricated by a traditional solid state reaction method combined with a spark plasma sintering technique. The phase composition and electrical and thermal transport properties were systematically characterized, and the related mechanisms were deeply discussed. It is found that the charge compensation between Pd doping and S filling is the main reason for the formation of thermodynamically stable S y Pd x Co 4-x Sb 12 compounds. Filling S element in the voids of CoSb 3 provides additional holes to reduce the carrier concentration while scarcely affecting the carrier mobility. However, doping Pd at the Co sites not only changes the carrier scattering mechanism but also deteriorates the carrier mobility. Low lattice thermal conductivities are observed in these S y Pd x Co 4-x Sb 12 compounds, which are attributed to the low resonant frequency of the S element. Finally, a maximal figure of merit of 0.85 is obtained for S 0.05 Pd 0.25 Co 3.75 Sb 12 at 700 K.

Thermodynamic Stability Analysis of Tolbutamide Polymorphs and Solubility in Organic Solvents.

PubMed

Svärd, Michael; Valavi, Masood; Khamar, Dikshitkumar; Kuhs, Manuel; Rasmuson, Åke C

2016-06-01

Melting temperatures and enthalpies of fusion have been determined by differential scanning calorimetry (DSC) for 2 polymorphs of the drug tolbutamide: FI(H) and FV. Heat capacities have been determined by temperature-modulated DSC for 4 polymorphs: FI(L), FI(H), FII, FV, and for the supercooled melt. The enthalpy of fusion of FII at its melting point has been estimated from the enthalpy of transition of FII into FI(H) through a thermodynamic cycle. Calorimetric data have been used to derive a quantitative polymorphic stability relationship between these 4 polymorphs, showing that FII is the stable polymorph below approximately 333 K, above which temperature FI(H) is the stable form up to its melting point. The relative stability of FV is well below the other polymorphs. The previously reported kinetic reversibility of the transformation between FI(L) and FI(H) has been verified using in situ Raman spectroscopy. The solid-liquid solubility of FII has been gravimetrically determined in 5 pure organic solvents (methanol, 1-propanol, ethyl acetate, acetonitrile, and toluene) over the temperature range 278 to 323 K. The ideal solubility has been estimated from calorimetric data, and solution activity coefficients at saturation in the 5 solvents determined. All solutions show positive deviation from Raoult's law, and all van't Hoff plots of solubility data are nonlinear. The solubility in toluene is well below that observed in the other investigated solvents. Solubility data have been correlated and extrapolated to the melting point using a semiempirical regression model. Copyright © 2016 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

Hydration of copper(II): new insights from density functional theory and the COSMO solvation model.

PubMed

Bryantsev, Vyacheslav S; Diallo, Mamadou S; van Duin, Adri C T; Goddard, William A

2008-09-25

The hydrated structure of the Cu(II) ion has been a subject of ongoing debate in the literature. In this article, we use density functional theory (B3LYP) and the COSMO continuum solvent model to characterize the structure and stability of [Cu(H2O)n](2+) clusters as a function of coordination number (4, 5, and 6) and cluster size (n = 4-18). We find that the most thermodynamically favored Cu(II) complexes in the gas phase have a very open four-coordinate structure. They are formed from a stable square-planar [Cu(H2O)8](2+) core stabilized by an unpaired electron in the Cu(II) ion d(x(2)-y(2)) orbital. This is consistent with cluster geometries suggested by recent mass-spectrometric experiments. In the aqueous phase, we find that the more compact five-coordinate square-pyramidal geometry is more stable than either the four-coordinate or six-coordinate clusters in agreement with recent combined EXAFS and XANES studies of aqueous solutions of Cu(II). However, a small energetic difference (approximately 1.4 kcal/mol) between the five- and six-coordinate models with two full hydration shells around the metal ion suggests that both forms may coexist in solution.

Selective self-assembly of adenine-silver nanoparticles forms rings resembling the size of cells

PubMed Central

Choi, Sungmoon; Park, Soonyoung; Yang, Seon-Ah; Jeong, Yujin; Yu, Junhua

2015-01-01

Self-assembly has played critical roles in the construction of functional nanomaterials. However, the structure of the macroscale multicomponent materials built by the self-assembly of nanoscale building blocks is hard to predict due to multiple intermolecular interactions of great complexity. Evaporation of solvents is usually an important approach to induce kinetically stable assemblies of building blocks with a large-scale specific arrangement. During such a deweting process, we tried to monitor the possible interactions between silver nanoparticles and nucleobases at a larger scale by epifluorescence microscopy, thanks to the doping of silver nanoparticles with luminescent silver nanodots. ssDNA oligomer-stabilized silver nanoparticles and adenine self-assemble to form ring-like compartments similar to the size of modern cells. However, the silver ions only dismantle the self-assembly of adenine. The rings are thermodynamically stable as the drying process only enrich the nanoparticles-nucleobase mixture to a concentration that activates the self-assembly. The permeable membrane-like edge of the ring is composed of adenine filaments glued together by silver nanoparticles. Interestingly, chemicals are partially confined and accumulated inside the ring, suggesting that this might be used as a microreactor to speed up chemical reactions during a dewetting process. PMID:26643504

Reverse micelle-loaded lipid nano-emulsions: new technology for nano-encapsulation of hydrophilic materials.

PubMed

Anton, Nicolas; Mojzisova, Halina; Porcher, Emilien; Benoit, Jean-Pierre; Saulnier, Patrick

2010-10-15

This study presents novel, recently patented technology for encapsulating hydrophilic species in lipid nano-emulsions. The method is based on the phase-inversion temperature method (the so-called PIT method), which follows a low-energy and solvent-free process. The nano-emulsions formed are stable for months, and exhibit droplet sizes ranging from 10 to 200 nm. Hydrophilic model molecules of fluorescein sodium salt are encapsulated in the oily core of these nano-emulsion droplets through their solubilisation in the reverse micellar system. As a result, original, multi-scaled nano-objects are generated with a 'hydrophilic molecule in a reverse-micelles-in-oil-in-water' structure. Once fluorescein has been encapsulated it remains stable, for thermodynamic reasons, and the encapsulation yields can reach 90%. The reason why such complex objects can be formed is due to the soft method used (PIT method) which allows the conservation of the structure of the reverse micelles throughout the formulation process, up to their entrapment in the nano-emulsion droplets. In this study, we focus the investigation on the process itself, revealing its potential and limits. Since the formulation of nanocarriers for the encapsulation of hydrophilic substances still remains a challenge, this study may constitute a significant advance in this field. Copyright 2010 Elsevier B.V. All rights reserved.

Anharmonic and Quantum Fluctuations in Molecular Crystals: A First-Principles Study of the Stability of Paracetamol

NASA Astrophysics Data System (ADS)

Rossi, Mariana; Gasparotto, Piero; Ceriotti, Michele

2016-09-01

Molecular crystals often exist in multiple competing polymorphs, showing significantly different physicochemical properties. Computational crystal structure prediction is key to interpret and guide the search for the most stable or useful form, a real challenge due to the combinatorial search space, and the complex interplay of subtle effects that work together to determine the relative stability of different structures. Here we take a comprehensive approach based on different flavors of thermodynamic integration in order to estimate all contributions to the free energies of these systems with density-functional theory, including the oft-neglected anharmonic contributions and nuclear quantum effects. We take the two main stable forms of paracetamol as a paradigmatic example. We find that anharmonic contributions, different descriptions of van der Waals interactions, and nuclear quantum effects all matter to quantitatively determine the stability of different phases. Our analysis highlights the many challenges inherent in the development of a quantitative and predictive framework to model molecular crystals. However, it also indicates which of the components of the free energy can benefit from a cancellation of errors that can redeem the predictive power of approximate models, and suggests simple steps that could be taken to improve the reliability of ab initio crystal structure prediction.

A serendipitous survey of prediction algorithms for amyloidogenicity

PubMed Central

Roland, Bartholomew P.; Kodali, Ravindra; Mishra, Rakesh; Wetzel, Ronald

2014-01-01

SUMMARY The 17- amino acid N-terminal segment of the Huntingtin protein, httNT, grows into stable α-helix rich oligomeric aggregates when incubated under physiological conditions. We examined 15 scrambled sequence versions of an httNT peptide for their stabilities against aggregation in aqueous solution at low micromolar concentration and physiological conditions. Surprisingly, given their derivation from a sequence that readily assembles into highly stable α-helical aggregates that fail to convert into β-structure, we found that three of these scrambled peptides rapidly grow into amyloid-like fibrils, while two others also develop amyloid somewhat more slowly. The other 10 scrambled peptides do not detectibly form any aggregates after 100 hrs incubation under these conditions. We then analyzed these sequences using four previously described algorithms for predicting the tendencies of peptides to grow into amyloid or other β-aggregates. We found that these algorithms – Zyggregator, Tango, Waltz and Zipper – varied greatly in the number of sequences predicted to be amyloidogenic and in their abilities to correctly identify the amyloid forming members of scrambled peptide collection. The results are discussed in the context of a review of the sequence and structural factors currently thought to be important in determining amyloid formation kinetics and thermodynamics. PMID:23893755

Clock-Work Trade-Off Relation for Coherence in Quantum Thermodynamics

NASA Astrophysics Data System (ADS)

Kwon, Hyukjoon; Jeong, Hyunseok; Jennings, David; Yadin, Benjamin; Kim, M. S.

2018-04-01

In thermodynamics, quantum coherences—superpositions between energy eigenstates—behave in distinctly nonclassical ways. Here we describe how thermodynamic coherence splits into two kinds—"internal" coherence that admits an energetic value in terms of thermodynamic work, and "external" coherence that does not have energetic value, but instead corresponds to the functioning of the system as a quantum clock. For the latter form of coherence, we provide dynamical constraints that relate to quantum metrology and macroscopicity, while for the former, we show that quantum states exist that have finite internal coherence yet with zero deterministic work value. Finally, under minimal thermodynamic assumptions, we establish a clock-work trade-off relation between these two types of coherences. This can be viewed as a form of time-energy conjugate relation within quantum thermodynamics that bounds the total maximum of clock and work resources for a given system.

Thermodynamic and Turbulence Characteristics of the Southern Great Plains Nocturnal Boundary Layer Under Differing Turbulent Regimes

NASA Astrophysics Data System (ADS)

Bonin, Timothy A.; Blumberg, William G.; Klein, Petra M.; Chilson, Phillip B.

2015-12-01

The nocturnal stable boundary layer (SBL) can generally be classified into the weakly stable boundary layer (wSBL) and very stable boundary layer (vSBL). Within the wSBL, turbulence is relatively continuous, whereas in the vSBL, turbulence is intermittent and not well characterized. Differentiating characteristics of each type of SBL are still unknown. Herein, thermodynamic and kinematic data collected by a suite of instruments in north central Oklahoma in autumn 2012 are analyzed to better understand both SBL regimes and their differentiating characteristics. Many low-level jets were observed during the experiment, as it took place near a climatological maximum. A threshold wind speed, above which bulk shear-generated turbulence develops, is found to exist up to 300 m. The threshold wind speed must also be exceeded at lower heights (down to the surface) in order for strong turbulence to develop. Composite profiles, which are normalized using low-level jet scaling, of potential temperature, wind speed, vertical velocity variance, and the third-order moment of vertical velocity (overline{w'^3}) are produced for weak and moderate/strong turbulence regimes, which exhibit features of the vSBL and wSBL, respectively. Within the wSBL, turbulence is generated at the surface and transported upward. In the vSBL, values of vertical velocity variance are small throughout the entire boundary layer, likely due to the fact that a strong surface inversion typically forms after sunset. The temperature profile tends to be approximately isothermal in the lowest portions of the wSBL, and it did not substantially change over the night. Within both types of SBL, stability in the residual layer tends to increase as the night progresses. It is thought that this stability increase is due to differential warm air advection, which frequently occurs in the southern Great Plains when southerly low-level jets and a typical north-south temperature gradient are present. Differential radiative flux divergence also contributes to this increase in stability.

Phase relation of CaSO4 at high pressure and temperature up to 90 GPa and 2300 K

NASA Astrophysics Data System (ADS)

Fujii, Taku; Ohfuji, Hiroaki; Inoue, Toru

2016-05-01

Calcium sulfate (CaSO4), one of the major sulfate minerals in the Earth's crust, is expected to play a major role in sulfur recycling into the deep mantle. Here, we investigated the crystal structure and phase relation of CaSO4 up to ~90 GPa and 2300 K through a series of high-pressure experiments combined with in situ X-ray diffraction. CaSO4 forms three thermodynamically stable polymorphs: anhydrite (stable below 3 GPa), monazite-type phase (stable between 3 and ~13 GPa) and barite-type phase (stable up to at least 93 GPa). Anhydrite to monazite-type phase transition is induced by pressure even at room temperature, while monazite- to barite-type transition requires heating at least to 1500 K at ~20 GPa. The barite-type phase cannot always be quenched from high temperature and is distorted to metastable AgMnO4-type structure or another modified barite structure depending on pressure. We obtained the pressure-volume data and density of anhydrite, monazite- and barite-type phases and found that their densities are lower than those calculated from the PREM model in the studied P-T conditions. This suggests that CaSO4 is gravitationally unstable in the mantle and fluid/melt phase into which sulfur dissolves and/or sulfate-sulfide speciation may play a major role in the sulfur recycling into the deep Earth.

Phenomenology of Polymorphism, III: p, TDiagram and Stability of Piracetam Polymorphs

NASA Astrophysics Data System (ADS)

Céolin, R.; Agafonov, V.; Louër, D.; Dzyabchenko, V. A.; Toscani, S.; Cense, J. M.

1996-02-01

The nootropic drug Piracetam is known to crystallize in three phases. In order to obtain their stability hierarchy from sublimation pressure inequalities, the drawing of a topologicalp,Tdiagram was attempted. For such a purpose and also for quality control, crystallographic and thermodynamic data were required. Powder X-ray diffractometry (XRD) and differential scanning calorimetry (DSC) were used. Molecular energy calculations were performed. Phase I melts at 426 K (ΔfusH(I) = +180 J·g-1). Phase II transforms into Phase I at 399 K (Δ(II→I)H= +24 J·g-1). Phase III transforms into phase I at 392 K (Δ(III→I)H= +28 J·g-1) or melts at 412 K (ΔfusH(III) = +210 J·g-1). Thep,Tdiagram shows that phase I is stable at higher temperature and phase II at lower temperature, like phase III, which is stable under high pressure. At room temperature, phase II is the more stable form, and phase I the less stable one. This agrees with the spontaneous I → II transformation observed at 298 K within a few hours, and with lattice energies, calculated previously. Molecular energy calculations and crystal structure comparison show how intermolecular hydrogen bonds and H-bonded dimers, in phases II and III, may stabilize conformations higher in energy than those of the isolated molecule and of phase I.

Identification and characterization of monomeric, volatile SiCl3NH2 as product of the reaction between SiCl4 and NH3: an important intermediate on the way to silicon nitride?

PubMed

Himmel, Hans-Jörg; Schiefenhövel, Nils; Binnewies, Michael

2003-03-17

We studied the reaction of SiCl(4) with NH(3) by mass spectrometry and IR spectroscopy. By means of mass spectrometry, SiCl(3)NH(2) was for the first time identified as an intermediate generated in significant amounts in the course of the reaction. In additional experiments, SiCl(3)NH(2) was formed as a stable gaseous product of the ammonolysis of SiCl(4), and the product was identified and characterized in detail by IR spectroscopic methods (gas phase and matrix isolation) in combination with quantum-chemical calculations. The calculations also gave access to important thermodynamical data.

Equilibrium p-T Phase Diagram of Boron: Experimental Study and Thermodynamic Analysis

PubMed Central

Solozhenko, Vladimir L.; Kurakevych, Oleksandr O.

2013-01-01

Solid-state phase transformations and melting of high-purity crystalline boron have been in situ and ex situ studied at pressures to 20 GPa in the 1500–2500 K temperature range where diffusion processes become fast and lead to formation of thermodynamically stable phases. The equilibrium phase diagram of boron has been constructed based on thermodynamic analysis of experimental and literature data. The high-temperature part of the diagram contains p-T domains of thermodynamic stability of rhombohedral β-B106, orthorhombic γ-B28, pseudo-cubic (tetragonal) t'-B52, and liquid boron (L). The positions of two triple points have been experimentally estimated, i.e. β–t'–L at ~ 8.0 GPa and ~ 2490 K; and β–γ–t' at ~ 9.6 GPa and ~ 2230 K. Finally, the proposed phase diagram explains all thermodynamic aspects of boron allotropy and significantly improves our understanding of the fifth element. PMID:23912523

Asymptotically flat, stable black hole solutions in Einstein-Yang-Mills-Chern-Simons theory.

PubMed

Brihaye, Yves; Radu, Eugen; Tchrakian, D H

2011-02-18

We construct finite mass, asymptotically flat black hole solutions in d=5 Einstein-Yang-Mills-Chern-Simons theory. Our results indicate the existence of a second order phase transition between Reissner-Nordström solutions and the non-Abelian black holes which generically are thermodynamically preferred. Some of the non-Abelian configurations are also stable under linear, spherically symmetric perturbations.

Experimental and Theoretical Evaluation of the Stability of True MOF Polymorphs Explains Their Mechanochemical Interconversions.

PubMed

Akimbekov, Zamirbek; Katsenis, Athanassios D; Nagabhushana, G P; Ayoub, Ghada; Arhangelskis, Mihails; Morris, Andrew J; Friščić, Tomislav; Navrotsky, Alexandra

2017-06-14

We provide the first combined experimental and theoretical evaluation of how differences in ligand structure and framework topology affect the relative stabilities of isocompositional (i.e., true polymorph) metal-organic frameworks (MOFs). We used solution calorimetry and periodic DFT calculations to analyze the thermodynamics of two families of topologically distinct polymorphs of zinc zeolitic imidazolate frameworks (ZIFs) based on 2-methyl- and 2-ethylimidazolate linkers, demonstrating a correlation between measured thermodynamic stability and density, and a pronounced effect of the ligand substituent on their stability. The results show that mechanochemical syntheses and transformations of ZIFs are consistent with Ostwald's rule of stages and proceed toward thermodynamically increasingly stable, more dense phases.

Discrete Thermodynamics

DOE PAGES

Margolin, L. G.; Hunter, A.

2017-10-18

Here, we consider the dependence of velocity probability distribution functions on the finite size of a thermodynamic system. We are motivated by applications to computational fluid dynamics, hence discrete thermodynamics. We then begin by describing a coarsening process that represents geometric renormalization. Then, based only on the requirements of conservation, we demonstrate that the pervasive assumption of local thermodynamic equilibrium is not form invariant. We develop a perturbative correction that restores form invariance to second-order in a small parameter associated with macroscopic gradients. Finally, we interpret the corrections in terms of unresolved kinetic energy and discuss the implications of ourmore » results both in theory and as applied to numerical simulation.« less

Discrete Thermodynamics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Margolin, L. G.; Hunter, A.

Here, we consider the dependence of velocity probability distribution functions on the finite size of a thermodynamic system. We are motivated by applications to computational fluid dynamics, hence discrete thermodynamics. We then begin by describing a coarsening process that represents geometric renormalization. Then, based only on the requirements of conservation, we demonstrate that the pervasive assumption of local thermodynamic equilibrium is not form invariant. We develop a perturbative correction that restores form invariance to second-order in a small parameter associated with macroscopic gradients. Finally, we interpret the corrections in terms of unresolved kinetic energy and discuss the implications of ourmore » results both in theory and as applied to numerical simulation.« less

Thermodynamics and statistical mechanics. [thermodynamic properties of gases

NASA Technical Reports Server (NTRS)

1976-01-01

The basic thermodynamic properties of gases are reviewed and the relations between them are derived from the first and second laws. The elements of statistical mechanics are then formulated and the partition function is derived. The classical form of the partition function is used to obtain the Maxwell-Boltzmann distribution of kinetic energies in the gas phase and the equipartition of energy theorem is given in its most general form. The thermodynamic properties are all derived as functions of the partition function. Quantum statistics are reviewed briefly and the differences between the Boltzmann distribution function for classical particles and the Fermi-Dirac and Bose-Einstein distributions for quantum particles are discussed.

The fundamental flaw of the HSAB principle is revealed by a complete speciation analysis of the [PtCl(6-n)Br(n)](2-) (n = 0-6) system.

PubMed

Gerber, W J; van Wyk, P-H; van Niekerk, D M E; Koch, K R

2015-02-28

Bjerrum's model of step-wise ligand exchange is extended to compute a complete speciation diagram for the [PtCl6-nBrn](2-) (n = 0-6) system including all 17 equilibrium constants concerning the Pt(IV) chlorido-bromido exchange reaction network (HERN). In contrast to what the hard soft acid base (HSAB) principle "predicts", the thermodynamic driving force for the replacement of chloride by bromide in an aqueous matrix, for each individual ligand exchange reaction present in the Pt(IV) HERN, is due to the difference in halide hydration energy and not bonding interactions present in the acid-base complex. A generalized thermodynamic test calculation was developed to illustrate that the HSAB classified class (b) metal cations Ag(+), Au(+), Au(3+), Rh(3+), Cd(2+), Pt(2+), Pt(4+), Fe(3+), Cd(2+), Sn(2+) and Zn(2+) all form thermodynamically stable halido complexes in the order F(-) ≫ Cl(-) > Br(-) > I(-) irrespective of the sample matrix. The bonding interactions in the acid-base complex, e.g. ionic-covalent σ-bonding, Π-bonding and electron correlation effects, play no actual role in the classification of these metal cations using the HSAB principle. Instead, it turns out that the hydration/solvation energy of halides is the reason why metal cations are categorized into two classes using the HSAB principle which highlights the fundamental flaw of the HSAB principle.

The Formation of Chimeric Nanomorphologies, as a Reflection of Naturally Occurring Thermodynamic Processes

NASA Astrophysics Data System (ADS)

Naziris, N.; Demetzos, C.

2017-11-01

The self-assembly process of different in nature biomaterials leads to the morphogenesis of various nano-structures, where the individual molecule properties (e.g. hydrophilic-to-hydrophobic balance and elasticity), profoundly affect the intermediate surfaces’ interfacial thermodynamics. Herein, the mixing of a phospholipid and an amphiphilic block copolymer, through the thin-film hydration method, gave different morphologies, among which there were vesicles (i.e. liposomes and polymersomes), micelles and worm-like structures. The formation of such variety of structures is attributed to divergent entropic pathways, which are determined by a number of parameters, such as the lipid:polymer molar ratio and the polymer composition. The developed nanosystems are considered as chimeric/mixed, because of the two different in type biomaterials that compose them. The vesicles also exhibited membrane “irregularities”, which are connected with their biophysical behavior. Nature has “chosen” vesicular forms to be the thermodynamically stable “biological apartments”, in which life was enclosed and additionally, vesicles provided compartmentalized systems, where the intracellular environment was built. Phospholipid properties result in membranes/bilayers that harmonically assimilate other molecules, like proteins and retain their integrity and functionality, while gaining additional features. A cause that alters this relationship might induce changes in the membrane composition and morphology, with respect to lipid rafts/domains, what has been linked with the activation and development of certain human disorders/diseases. The self-assembly of two different biomaterials into various structures that present distinct membrane phenomena is believed to simulate these natural processes.

Exploring N-Rich Phases in Li(x)N(y) Clusters for Hydrogen Storage at Nanoscale.

PubMed

Bhattacharya, Amrita; Bhattacharya, Saswata

2015-09-17

We have performed cascade genetic algorithm and ab initio atomistic thermodynamics under the framework of first-principles-based hybrid density functional theory to study the (meta-)stability of a wide range of Li(x)N(y) clusters. We found that hybrid xc-functional is essential to address this problem as a local/semilocal functional simply fails even to predict a qualitative prediction. Most importantly, we find that though in bulk lithium nitride, the Li-rich phase, that is, Li3N, is the stable stoichiometry; in small Li(x)N(y) clusters, N-rich phases are more stable at thermodynamic equilibrium. We further show that these N-rich clusters are promising hydrogen storage material because of their easy adsorption and desorption ability at respectively low (≤300 K) and moderately high temperature (≥600 K).

Identification of thermodynamically stable ceramic reinforcement materials for iron aluminide matrices

NASA Technical Reports Server (NTRS)

Misra, Ajay K.

1990-01-01

Aluminide-base intermetallic matrix composites are currently being considered as potential high-temperature materials. One of the key factors in the selection of a reinforcement material is its chemical stability in the matrix. In this study, chemical interactions between iron aluminides and several potential reinforcement materials, which include carbides, oxides, borides, and nitrides, are analyzed from thermodynamic considerations. Several chemically compatible reinforcement materials are identified for the iron aluminides with Al concentrations ranging from 40 to 50 at. pct.

Mechanochemically Reduced SiO2 by Ti Incorporation as Lithium Storage Materials.

PubMed

Kim, Kyungbae; Moon, Janghyuk; Lee, Jaewoo; Yu, Ji-Sang; Cho, Maenghyo; Cho, Kyeongjae; Park, Min-Sik; Kim, Jae-Hun; Kim, Young-Jun

2015-09-21

This study presents a simple and effective method of reducing amorphous silica (a-SiO2 ) with Ti metal through high-energy mechanical milling for improving its reactivity when used as an anode material in lithium-ion batteries. Through thermodynamic calculations, it is determined that Ti metal can easily take oxygen atoms from a-SiO2 by forming a thermodynamically stable SiO2-x /TiOx composite, meaning that electrochemically inactive a-SiO2 is partially reduced by the addition of Ti metal powder during milling. This mechanically reduced SiO2-x /TiOx composite anode exhibits a greatly improved electrochemical reactivity, with a reversible capacity of more than 700 mAh g(-1) and excellent cycle performance over 100 cycles. Furthermore, an enhancement in the mechanical and thermal stability of the composite during cycling can be mainly attributed to the in situ formation of the SiO2-x /TiOx phase. These findings provide new insight into the rational design of robust, high-capacity, Si-based anode materials, as well as their reaction mechanism. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Phase Diagram of Kob-Andersen-Type Binary Lennard-Jones Mixtures

NASA Astrophysics Data System (ADS)

Pedersen, Ulf R.; Schrøder, Thomas B.; Dyre, Jeppe C.

2018-04-01

The binary Kob-Andersen (KA) Lennard-Jones mixture is the standard model for computational studies of viscous liquids and the glass transition. For very long simulations, the viscous KA system crystallizes, however, by phase separating into a pure A particle phase forming a fcc crystal. We present the thermodynamic phase diagram for KA-type mixtures consisting of up to 50% small (B ) particles showing, in particular, that the melting temperature of the standard KA system at liquid density 1.2 is 1.028(3) in A particle Lennard-Jones units. At large B particle concentrations, the system crystallizes into the CsCl crystal structure. The eutectic corresponding to the fcc and CsCl structures is cutoff in a narrow interval of B particle concentrations around 26% at which the bipyramidal orthorhombic PuBr3 structure is the thermodynamically stable phase. The melting temperature's variation with B particle concentration at two constant pressures, as well as at the constant density 1.2, is estimated from simulations at pressure 10.19 using isomorph theory. Our data demonstrate approximate identity between the melting temperature and the onset temperature below which viscous dynamics appears. Finally, the nature of the solid-liquid interface is briefly discussed.

Carbon substitution for oxygen in silicates in planetary interiors

PubMed Central

Sen, Sabyasachi; Widgeon, Scarlett J.; Navrotsky, Alexandra; Mera, Gabriela; Tavakoli, Amir; Ionescu, Emanuel; Riedel, Ralf

2013-01-01

Amorphous silicon oxycarbide polymer-derived ceramics (PDCs), synthesized from organometallic precursors, contain carbon- and silica-rich nanodomains, the latter with extensive substitution of carbon for oxygen, linking Si-centered SiOxC4-x tetrahedra. Calorimetric studies demonstrated these PDCs to be thermodynamically more stable than a mixture of SiO2, C, and silicon carbide. Here, we show by multinuclear NMR spectroscopy that substitution of C for O is also attained in PDCs with depolymerized silica-rich domains containing lithium, associated with SiOxC4-x tetrahedra with nonbridging oxygen. We suggest that significant (several percent) substitution of C for O could occur in more complex geological silicate melts/glasses in contact with graphite at moderate pressure and high temperature and may be thermodynamically far more accessible than C for Si substitution. Carbon incorporation will change the local structure and may affect physical properties, such as viscosity. Analogous carbon substitution at grain boundaries, at defect sites, or as equilibrium states in nominally acarbonaceous crystalline silicates, even if present at levels at 10–100 ppm, might form an extensive and hitherto hidden reservoir of carbon in the lower crust and mantle. PMID:24043830

Carbon substitution for oxygen in silicates in planetary interiors.

PubMed

Sen, Sabyasachi; Widgeon, Scarlett J; Navrotsky, Alexandra; Mera, Gabriela; Tavakoli, Amir; Ionescu, Emanuel; Riedel, Ralf

2013-10-01

Amorphous silicon oxycarbide polymer-derived ceramics (PDCs), synthesized from organometallic precursors, contain carbon- and silica-rich nanodomains, the latter with extensive substitution of carbon for oxygen, linking Si-centered SiO(x)C(4-x) tetrahedra. Calorimetric studies demonstrated these PDCs to be thermodynamically more stable than a mixture of SiO2, C, and silicon carbide. Here, we show by multinuclear NMR spectroscopy that substitution of C for O is also attained in PDCs with depolymerized silica-rich domains containing lithium, associated with SiO(x)C(4-x) tetrahedra with nonbridging oxygen. We suggest that significant (several percent) substitution of C for O could occur in more complex geological silicate melts/glasses in contact with graphite at moderate pressure and high temperature and may be thermodynamically far more accessible than C for Si substitution. Carbon incorporation will change the local structure and may affect physical properties, such as viscosity. Analogous carbon substitution at grain boundaries, at defect sites, or as equilibrium states in nominally acarbonaceous crystalline silicates, even if present at levels at 10-100 ppm, might form an extensive and hitherto hidden reservoir of carbon in the lower crust and mantle.

Theoretical Study of Trimethylacetic Acid Adsorption on CeO 2 (111) Surface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Weina; Thevuthasan, S.; Wang, Wenliang

We investigated trimethylacetic acid (TMAA) adsorption on stoichiometric and oxygen-deficient CeO 2(111) surfaces using density functional theory that accounts for the on-site Coulomb interaction via a Hubbard term (DFT+U) and long-range dispersion correction. Both the molecular state and dissociative state (TMAA → TMA– + H +) were identified on stoichiometric and oxygen-deficient CeO 2(111) surfaces. For the stoichiometric surface, two thermodynamically favorable configurations with adsorption energies of the order of -30 kcal/mol are identified; one is a molecule adsorption state, and the other one is a dissociative state. For the oxygen-deficient surface, dissociative states are more favorable than molecular states.more » Moreover, the most favorable configuration is the dissociative adsorption of TMAA with the adsorption energy of the order of -77 kcal/mol. The dissociated TMA moiety takes the position of oxygen vacancy, forming three Ce–O bonds. The signature vibrational frequencies for these thermodynamically stable structures are reported as well as their electronic structures. The effects of long-range dispersion interactions are found to be negligible for geometries but important for adsorption energies.« less

Theoretical Study of Trimethylacetic Acid Adsorption on CeO 2 (111) Surface

DOE PAGES

Wang, Weina; Thevuthasan, S.; Wang, Wenliang; ...

2016-01-11

We investigated trimethylacetic acid (TMAA) adsorption on stoichiometric and oxygen-deficient CeO 2(111) surfaces using density functional theory that accounts for the on-site Coulomb interaction via a Hubbard term (DFT+U) and long-range dispersion correction. Both the molecular state and dissociative state (TMAA → TMA– + H +) were identified on stoichiometric and oxygen-deficient CeO 2(111) surfaces. For the stoichiometric surface, two thermodynamically favorable configurations with adsorption energies of the order of -30 kcal/mol are identified; one is a molecule adsorption state, and the other one is a dissociative state. For the oxygen-deficient surface, dissociative states are more favorable than molecular states.more » Moreover, the most favorable configuration is the dissociative adsorption of TMAA with the adsorption energy of the order of -77 kcal/mol. The dissociated TMA moiety takes the position of oxygen vacancy, forming three Ce–O bonds. The signature vibrational frequencies for these thermodynamically stable structures are reported as well as their electronic structures. The effects of long-range dispersion interactions are found to be negligible for geometries but important for adsorption energies.« less

Microhydration of caesium compounds: Cs, CsOH, CsI and Cs₂I₂ complexes with one to three H₂O molecules of nuclear safety interest.

PubMed

Sudolská, Mária; Cantrel, Laurent; Cernušák, Ivan

2014-04-01

Structure and thermodynamic properties (standard enthalpies of formation and Gibbs free energies) of hydrated caesium species of nuclear safety interest, Cs, CsOH, CsI and its dimer Cs₂I₂, with one up to three water molecules, are calculated to assess their possible existence in severe accident occurring to a pressurized water reactor. The calculations were performed using the coupled cluster theory including single, double and non-iterative triple substitutions (CCSD(T)) in conjunction with the basis sets (ANO-RCC) developed for scalar relativistic calculations. The second-order spin-free Douglas-Kroll-Hess Hamiltonian was used to account for the scalar relativistic effects. Thermodynamic properties obtained by these correlated ab initio calculations (entropies and thermal capacities at constant pressure as a function of temperature) are used in nuclear accident simulations using ASTEC/SOPHAEROS software. Interaction energies, standard enthalpies and Gibbs free energies of successive water molecules addition determine the ordering of the complexes. CsOH forms the most hydrated stable complexes followed by CsI, Cs₂I₂, and Cs. CsOH still exists in steam atmosphere even at quite high temperature, up to around 1100 K.

Le Chatelier's principle in replicator dynamics

NASA Astrophysics Data System (ADS)

Allahverdyan, Armen E.; Galstyan, Aram

2011-10-01

The Le Chatelier principle states that physical equilibria are not only stable, but they also resist external perturbations via short-time negative-feedback mechanisms: a perturbation induces processes tending to diminish its results. The principle has deep roots, e.g., in thermodynamics it is closely related to the second law and the positivity of the entropy production. Here we study the applicability of the Le Chatelier principle to evolutionary game theory, i.e., to perturbations of a Nash equilibrium within the replicator dynamics. We show that the principle can be reformulated as a majorization relation. This defines a stability notion that generalizes the concept of evolutionary stability. We determine criteria for a Nash equilibrium to satisfy the Le Chatelier principle and relate them to mutualistic interactions (game-theoretical anticoordination) showing in which sense mutualistic replicators can be more stable than (say) competing ones. There are globally stable Nash equilibria, where the Le Chatelier principle is violated even locally: in contrast to the thermodynamic equilibrium a Nash equilibrium can amplify small perturbations, though both types of equilibria satisfy the detailed balance condition.

Le Chatelier's principle in replicator dynamics.

PubMed

Allahverdyan, Armen E; Galstyan, Aram

2011-10-01

The Le Chatelier principle states that physical equilibria are not only stable, but they also resist external perturbations via short-time negative-feedback mechanisms: a perturbation induces processes tending to diminish its results. The principle has deep roots, e.g., in thermodynamics it is closely related to the second law and the positivity of the entropy production. Here we study the applicability of the Le Chatelier principle to evolutionary game theory, i.e., to perturbations of a Nash equilibrium within the replicator dynamics. We show that the principle can be reformulated as a majorization relation. This defines a stability notion that generalizes the concept of evolutionary stability. We determine criteria for a Nash equilibrium to satisfy the Le Chatelier principle and relate them to mutualistic interactions (game-theoretical anticoordination) showing in which sense mutualistic replicators can be more stable than (say) competing ones. There are globally stable Nash equilibria, where the Le Chatelier principle is violated even locally: in contrast to the thermodynamic equilibrium a Nash equilibrium can amplify small perturbations, though both types of equilibria satisfy the detailed balance condition.

Cubic and orthorhombic structures of aluminum hydride Al H3 predicted by a first-principles study

NASA Astrophysics Data System (ADS)

Ke, Xuezhi; Kuwabara, Akihide; Tanaka, Isao

2005-05-01

The most stable structure of aluminum hydride AlH3 is believed to be a hexagonal symmetry. However, using the density functional theory, we have identified two more stable structures for the AlH3 with the cubic and orthorhombic symmetries. Based on the quasiharmonic approximation, the cubic and orthorhombic AlH3 are almost degenerate when the zero-point energies are included. The geometric and electronic structures, the phonon, and the thermodynamic properties for the hexagonal, cubic, and orthorhombic AlH3 have been studied by means of density functional theory and direct ab initio force constant approach. The calculated electronic structures, phonon density of states, and thermodynamic functions [including S(T) and H(T)-H(0) ] for the three hydrides are similar. The results show that these three hydrides have negative enthalpies of formation, but positive free energies of formation. This conclusion is the same as that made by Wolverton for the hexagonal AlH3 [Phys. Rev. B 69, 144109 (2004)]. The thermodynamic properties indicate that the orthorhombic and cubic AlH3 should be more difficult to dissociate than the hexagonal AlH3 .

Thermodynamics of HMX Polymorphs and HMX/RDX Mixtures

DOE PAGES

Myint, Philip C.; Nichols, Albert L.

2016-12-09

In this paper, we present thermodynamic models for the five most commonly studied phases of the energetic material octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX): liquid HMX and four solid polymorphs (α-, β-, γ-, and δ-HMX). We show results for the density, heat capacity, bulk modulus, and sound speed, as well as a phase diagram that illustrates the temperature and pressure regions over which the various HMX phases are most thermodynamically stable. The models are based on the same equation of state presented in our recently published paper [Myint et al., Ind. Eng. Chem. Res., 2016, 55, 2252] on another energetic material, hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX). Wemore » combine our HMX and RDX models together so that the equation of state can also be applied to liquid and solid mixtures of HMX/RDX. This allows us to generate an HMX/RDX phase diagram and calculate the enthalpy change associated with a few different kinds of phase transitions that these mixtures may undergo. Our paper is the first to present a single equation of state that is capable of modeling both pure HMX and HMX/RDX mixtures. A distinct feature of HMX is the strongly metastable nature of its polymorphs. This has caused some ambiguity in the literature regarding the thermodynamic stability of α-HMX. Finally, by examining possible arrangements for the relative order of the six different solid-solid transition (α–β, α–γ, α–δ, β–γ, β–δ, and γ–δ) temperatures, we conclude that α-HMX must be thermodynamically stable so that the HMX phase diagram must have an α phase region.« less

Extended forms of the second law for general time-dependent stochastic processes.

PubMed

Ge, Hao

2009-08-01

The second law of thermodynamics represents a universal principle applicable to all natural processes, physical systems, and engineering devices. Hatano and Sasa have recently put forward an extended form of the second law for transitions between nonequilibrium stationary states [Phys. Rev. Lett. 86, 3463 (2001)]. In this paper we further extend this form to an instantaneous interpretation, which is satisfied by quite general time-dependent stochastic processes including master-equation models and Langevin dynamics without the requirements of the stationarity for the initial and final states. The theory is applied to several thermodynamic processes, and its consistence with the classical thermodynamics is shown.

SiC Composite for Fuel Structure Applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yueh, Ken

Extensive evaluation was performed to determine the suitability of using SiC composite as a boiling water reactor (BWR) fuel channel material. A thin walled SiC composite box, 10 cm in dimension by approximately 1.5 mm wall thickness was fabricated using chemical vapor deposition (CVD) for testing. Mechanical test results and performance evaluations indicate the material could meet BWR channel mechanical design requirement. However, large mass loss of up to 21% was measured in in-pile corrosion test under BWR-like conditions in under 3 months of irradiation. A fresh sister sample irradiated in a follow-up cycle under PWR conditions showed no measureablemore » weight loss and thus supports the hypothesis that the oxidizing condition of the BWR-like coolant chemistry was responsible for the high corrosion rate. A thermodynamic evaluation showed SiC is not stable and the material may oxidize to form SiO 2 and CO 2. Silica has demonstrated stability in high temperature steam environment and form a protective oxide layer under severe accident conditions. However, it does not form a protective layer in water under normal BWR operational conditions due to its high solubility. Corrosion product stabilization by modifying the SiC CVD surface is an approach evaluated in this study to mitigate the high corrosion rate. Titanium and zirconium have been selected as stabilizing elements since both TiSiO 4 and ZrSiO 4 are insoluble in water. Corrosion test results in oxygenated water autoclave indicate TiSiO4 does not form a protective layer. However, zirconium doped test samples appear to form a stable continuous layer of ZrSiO 4 during the corrosion process. Additional process development is needed to produce a good ZrSiC coating to verify functionality of the mitigation concept.« less

First-principles calculations of the thermodynamic properties of transuranium elements in a molten salt medium

NASA Astrophysics Data System (ADS)

Noh, Seunghyo; Kwak, Dohyun; Lee, Juseung; Kang, Joonhee; Han, Byungchan

2014-03-01

We utilized first-principles density-functional-theory (DFT) calculations to evaluate the thermodynamic feasibility of a pyroprocessing methodology for reducing the volume of high-level radioactive materials and recycling spent nuclear fuels. The thermodynamic properties of transuranium elements (Pu, Np and Cm) were obtained in electrochemical equilibrium with a LiCl-KCl molten salt as ionic phases and as adsorbates on a W(110) surface. To accomplish the goal, we rigorously calculated the double layer interface structures on an atomic resolution, on the thermodynamically most stable configurations on W(110) surfaces and the chemical activities of the transuranium elements for various coverages of those elements. Our results indicated that the electrodeposition process was very sensitive to the atomic level structures of Cl ions at the double-layer interface. Our studies are easily expandable to general electrochemical applications involving strong redox reactions of transition metals in non-aqueous solutions.

Thermodynamic signature of secondary nano-emulsion formation by isothermal titration calorimetry.

PubMed

Fotticchia, Iolanda; Fotticchia, Teresa; Mattia, Carlo Andrea; Netti, Paolo Antonio; Vecchione, Raffaele; Giancola, Concetta

2014-12-09

The stabilization of oil in water nano-emulsions by means of a polymer coating is extremely important; it prolongs the shelf life of the product and makes it suitable for a variety of applications ranging from nutraceutics to cosmetics and pharmaceutics. To date, an effective methodology to assess the best formulations in terms of thermodynamic stability has yet to be designed. Here, we perform a complete physicochemical characterization based on isothermal titration calorimetry (ITC) compared to conventional dynamic light scattering (DLS) to identify polymer concentration domains that are thermodynamically stable and to define the degree of stability through thermodynamic functions depending upon any relevant parameter affecting the stability itself, such as type of polymer coating, droplet distance, etc. For instance, the method was proven by measuring the energetics in the case of two different biopolymers, chitosan and poly-L-lysine, and for different concentrations of the emulsion coated with poly-L-lysine.

Half-Heusler Alloys as Promising Thermoelectric Materials

NASA Astrophysics Data System (ADS)

Page, Alexander A.

This thesis describes Ph.D. research on the half-Heusler class of thermoelectric materials. Half-Heusler alloys are a versatile class of materials that have been studied for use in photovoltaics, phase change memory, and thermoelectric power generation. With respect to thermoelectric power generation, new approaches were recently developed in order to improve the thermoelectric figure of merit, ZT, of half-Heusler alloys. Two of the strategies discussed in this work are adding excess Ni within MNiSn (M = Ti, Zr, or Hf) compounds to form full-Heusler nanostructures and using isoelectronic substitution of Ti, Zr, and Hf in MNiSn compounds to create microscale grain boundaries. This work uses computational simulations based on density functional theory, combined with the cluster expansion method, to predict the stable phases of pseudo-binary and pseudo-ternary composition systems. Statistical mechanics methods were used to calculate temperature-composition phase diagrams that relate the equilibrium phases. It is shown that full-Heusler nanostructures are predicted to remain stable even at high temperatures, and the microscale grain boundaries observed in (Ti,Zr,Hf)NiSn materials are found to be thermodynamically unstable at equilibrium. A new strategy of combining MNiSn materials with ZrNiPb has also recently emerged, and theoretical and experimental work show that a solid solution of the two materials is stable.

Bismuth-embedded SBA-15 mesoporous silica for radioactive iodine capture and stable storage

NASA Astrophysics Data System (ADS)

Yang, Jae Hwan; Cho, Yong-Jun; Shin, Jin Myeong; Yim, Man-Sung

2015-10-01

Efficient capture and stable storage of the long-lived iodine-129 (129I), released as off-gas from nuclear fuel reprocessing, have been of significant concern in the waste management field. In this study, bismuth-embedded SBA-15 mesoporous silica was firstly applied for iodine capture and storage. SBA-15 was functionalized with thiol (-SH) groups, followed by bismuth adsorption with Bi-S bonding, which was thermally treated to form Bi2S3 within SBA-15. The bismuth-embedded SBA-15s demonstrated high iodine loading capacities (up to 540 mg-I/g-sorbent), which benefitted from high surface area and porosity of SBA-15 as well as the formation of thermodynamically stable BiI3 compound. Iodine physisorption was effectively suppressed due to the large pores present in SBA-15, resulting in chemisorption as a main mechanism for iodine confinement. Furthermore, a chemically durable iodine-bearing material was made with a facile post-sorption process, during which the iodine-incorporated phase was changed from BiI3 to chemically durable Bi5O7I. Thus, our results showed that both efficient capture and stabilization of 129I would be possible with the bismuth-embedded SBA-15, in contrast to other sorbents mainly focused on iodine capture.

Structure and stability of CaH 2 surfaces: on the possibility of electron-rich surfaces in metal hydrides for catalysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ong, Phuong-Vu; Johnson, Lewis E.; Hosono, Hideo

Structure, thermodynamic stability, and electronic properties of CaH 2 surfaces in (001),(110), and (111) crystallographic orientations are investigated using ab initio modeling. We show that stoichiometric surfaces terminated with a hydrogen atomic plane are the most energetically favorable and discuss properties of hydrogen vacancies (VH) at these surfaces. The average calculated work function of the most stable pristine surfaces (~5.2 eV) is in agree-ment with experimental data for powder samples. Neutral hydrogen vacancies host localized electrons and induce defect states in the band gap, thereby shifting the effective work function to much lower values of ~2.7 eV. Surface VH aremore » predicted to aggregate into dimers and form electron-rich centers (e -)Ca 2+(e -) stable to over 800 K. These results suggest that hydrogen-deficient surfaces of CaH 2 can host a large concentration of localized electrons and, thus, give rise to new catalytic functionalities involving electron transfer between the surface, catalysts supported on it, and reacting species.« less

Coarse-grained modeling of crystal growth and polymorphism of a model pharmaceutical molecule.

PubMed

Mandal, Taraknath; Marson, Ryan L; Larson, Ronald G

2016-10-04

We describe a systematic coarse-graining method to study crystallization and predict possible polymorphs of small organic molecules. In this method, a coarse-grained (CG) force field is obtained by inverse-Boltzmann iteration from the radial distribution function of atomistic simulations of the known crystal. With the force field obtained by this method, we show that CG simulations of the drug phenytoin predict growth of a crystalline slab from a melt of phenytoin, allowing determination of the fastest-growing surface, as well as giving the correct lattice parameters and crystal morphology. By applying meta-dynamics to the coarse-grained model, a new crystalline form of phenytoin (monoclinic, space group P2 1 ) was predicted which is different from the experimentally known crystal structure (orthorhombic, space group Pna2 1 ). Atomistic simulations and quantum calculations then showed the polymorph to be meta-stable at ambient temperature and pressure, and thermodynamically more stable than the conventional orthorhombic crystal at high pressure. The results suggest an efficient route to study crystal growth of small organic molecules that could also be useful for identification of possible polymorphs as well.

A highly stable l-alanine-based mono(aquated) Mn(ii) complex as a T1-weighted MRI contrast agent.

PubMed

Khannam, Mahmuda; Weyhermüller, Thomas; Goswami, Upashi; Mukherjee, Chandan

2017-08-08

The synthesized lithium (S)-6,6'-(1-carboxyethylazanediyl)bis(methylene)dipicolinate (Li 3 cbda) is a new chiral, alanine-based ligand bearing two picolinate functionalities. The trianionic form of the ligand [(cbda) 3- ] constitutes a seven-coordinate, water-soluble, pentagonal bipyramidal Mn(ii) complex (1). The structural analysis reveals the presence of a water coordinating site in the complex. The complex is thermodynamically very stable, and the stability is not affected by the presence of physiological anions (HCO 3 - , PO 4 3- , and F - ). The pH of the medium exerts a small effect on the stability of the complex. The r 1 relaxivity of 3.02 mM -1 s -1 is exhibited by the complex at 1.41 T, pH ∼7.4, and 25 °C. Phantom images obtained via a clinical MRI BRIVO MR355 system established concentration-dependent signal enhancement by the complex. The cytotoxicity test confirmed complex 1 as a biocompatible potential T 1 -weighted MRI contrast agent.

Nitrogen doping and CO2 adsorption on graphene: A thermodynamical study

NASA Astrophysics Data System (ADS)

Re Fiorentin, Michele; Gaspari, Roberto; Quaglio, Marzia; Massaglia, Gulia; Saracco, Guido

2018-04-01

Nitrogen-doped graphene has raised considerable interest for its possible applications as carbon dioxide adsorber and catalyst. In this paper, we provide a theoretical study of graphitic, pyridiniclike and pyrroliclike nitrogen defects in a free-standing graphene layer, focusing on their formation and adsorption behavior. Using density functional theory and thermodynamics, we analyze the various defects, highlighting the great stability of graphitic nitrogen in a wide temperature and pressure range. CO2 adsorption proves to be moderately thermodynamically disfavored around standard conditions for the most stable nitrogen defects and slightly favored for the more energetic ones. The combination of the results on defect stability and CO2 adsorption may open interesting possibilities in the design of carbon-based materials with promising adsorption performances.

Quintessence background for 5D Einstein-Gauss-Bonnet black holes

NASA Astrophysics Data System (ADS)

Ghosh, Sushant G.; Amir, Muhammed; Maharaj, Sunil D.

2017-08-01

As we know that the Lovelock theory is an extension of the general relativity to the higher-dimensions, in this theory the first- and the second-order terms correspond to general relativity and the Einstein-Gauss-Bonnet gravity, respectively. We obtain a 5D black hole solution in Einstein-Gauss-Bonnet gravity surrounded by the quintessence matter, and we also analyze their thermodynamical properties. Owing to the quintessence corrected black hole, the thermodynamic quantities have also been corrected except for the black hole entropy, and a phase transition is achievable. The phase transition for the thermodynamic stability is characterized by a discontinuity in the specific heat at r=r_C, with the stable (unstable) branch for r < (>) r_C.

Teaching Thermodynamics of Ideal Solutions: An Entropy-Based Approach to Help Students Better Understand and Appreciate the Subtleties of Solution Models

ERIC Educational Resources Information Center

Tomba, J. Pablo

2015-01-01

The thermodynamic formalism of ideal solutions is developed in most of the textbooks postulating a form for the chemical potential of a generic component, which is adapted from the thermodynamics of ideal gas mixtures. From this basis, the rest of useful thermodynamic properties can be derived straightforwardly without further hypothesis. Although…

Density functional theory studies on the electronic, structural, phonon dynamical and thermo-stability properties of bicarbonates MHCO3, M = Li, Na, K

NASA Astrophysics Data System (ADS)

Duan, Yuhua; Zhang, Bo; Sorescu, Dan C.; Johnson, J. Karl; Majzoub, Eric H.; Luebke, David R.

2012-08-01

The structural, electronic, phonon dispersion and thermodynamic properties of MHCO3 (M = Li, Na, K) solids were investigated using density functional theory. The calculated bulk properties for both their ambient and the high-pressure phases are in good agreement with available experimental measurements. Solid phase LiHCO3 has not yet been observed experimentally. We have predicted several possible crystal structures for LiHCO3 using crystallographic database searching and prototype electrostatic ground state modeling. Our total energy and phonon free energy (FPH) calculations predict that LiHCO3 will be stable under suitable conditions of temperature and partial pressures of CO2 and H2O. Our calculations indicate that the {{HCO}}_{3}^{-} groups in LiHCO3 and NaHCO3 form an infinite chain structure through O⋯H⋯O hydrogen bonds. In contrast, the {{HCO}}_{3}^{-} anions form dimers, ({{HCO}}_{3}^{-})_{2}, connected through double hydrogen bonds in all phases of KHCO3. Based on density functional perturbation theory, the Born effective charge tensor of each atom type was obtained for all phases of the bicarbonates. Their phonon dispersions with the longitudinal optical-transverse optical splitting were also investigated. Based on lattice phonon dynamics study, the infrared spectra and the thermodynamic properties of these bicarbonates were obtained. Over the temperature range 0-900 K, the FPH and the entropies (S) of MHCO3 (M =Li, Na, K) systems vary as FPH(LiHCO3) > FPH(NaHCO3) > FPH(KHCO3) and S(KHCO3) > S(NaHCO3) > S(LiHCO3), respectively, in agreement with the available experimental data. Analysis of the predicted thermodynamics of the CO2 capture reactions indicates that the carbonate/bicarbonate transition reactions for Na and K could be used for CO2 capture technology, in agreement with experiments.

Solution thermodynamic stability of complexes formed with the octadentate hydroxypyridinonate ligand 3,4,3-LI(1,2-HOPO): A critical feature for efficient chelation of lanthanide(IV) and actinide(IV) ions

PubMed Central

Deblonde, Gauthier J-P.; Sturzbecher-Hoehne, Manuel; Abergel, Rebecca J.

2013-01-01

The solution thermodynamics of water soluble complexes formed between Ce(III), Ce(IV), Th(IV) and the octadentate chelating agent 3,4,3-LI(1,2-HOPO) were investigated. Several techniques including spectrofluorimetric and automated spectrophotometric titrations were used to overcome the slow spontaneous oxidation of Ce(III) complexes yielding to stability constants of log β110 = 17.4 ± 0.5, log β11-1 = 8.3 ± 0.4 and log β111 = 21.2 ± 0.4 for [Ce(III)(3,4,3-LI(1,2-HOPO))]−, [Ce(III)(3,4,3-LI(1,2-HOPO)(OH)]2− and [Ce(III)(3,4,3-LI(1,2-HOPO)H], respectively. Using the spectral properties of the hydroxypyridinonate chelator in ligand competition titrations against nitrilotriacetic acid, the stability constant log β110 = 41.5 ± 0.5 was determined for [Ce(IV)(3,4,3-LI(1,2-HOPO))]. Finally, the extraordinarily stable complex [Ce(IV)(3,4,3-LI(1,2-HOPO))] was used in Th(IV) competition titrations, resulting in a stability constant of log β110 = 40.1 ± 0.5 for [Th(IV)3,4,3-LI(1,2-HOPO))]. These experimental values are in excellent agreement with previous estimates, they are discussed with respect to the ionic radius and oxidation state of each cationic metal and allow predictions on the stability of other actinide complexes including [U(IV)(3,4,3-LI(1,2-HOPO))], [Np(IV)(3,4,3-LI(1,2-HOPO))] and [Pu(IV)(3,4,3-LI(1,2-HOPO))]. Comparisons with the standard ligand diethylenetriamine pentaacetic acid (DTPA) provide a thermodynamic basis for the observed significantly higher efficacy of 3,4,3-LI(1,2-HOPO) as an in vivo actinide decorporation agent. PMID:23855806

First-principles prediction of stabilities and instabilities of compounds and alloys in the ternary B-As-P system

NASA Astrophysics Data System (ADS)

Ektarawong, A.; Simak, S. I.; Alling, B.

2017-07-01

We examine the thermodynamic stability of compounds and alloys in the ternary B-As-P system theoretically using first-principles calculations. We demonstrate that the icosahedral B12As2 is the only stable compound in the binary B-As system, while the zinc-blende BAs is thermodynamically unstable with respect to B12As2 and the pure arsenic phase at 0 K, and increasingly so at higher temperature, suggesting that BAs may merely exist as a metastable phase. On the contrary, in the binary B-P system, both zinc-blende BP and icosahedral B12P2 are predicted to be stable. As for the binary As-P system, As1 -xPx disordered alloys are predicted at elevated temperature—for example, a disordered solid solution of up to ˜75 at.% As in black phosphorus as well as a small solubility of ˜1 at.% P in gray arsenic at T =750 K, together with the presence of miscibility gaps. The calculated large solubility of As in black phosphorus explains the experimental syntheses of black-phosphorus-type As1 -xPx alloys with tunable compositions, recently reported in the literature. We investigate the phase stabilities in the ternary B-As-P system and demonstrate a high tendency for a formation of alloys in the icosahedral B12(As1 -xPx )2 structure by intermixing of As and P atoms at the diatomic chain sites. The phase diagram displays noticeable mutual solubility of the icosahedral subpnictides in each other even at room temperature as well as a closure of a pseudobinary miscibility gap around 900 K. As for pseudobinary BAs1 -xPx alloys, only a tiny amount of BAs is predicted to be able to dissolve in BP to form the BAs1 -xPx disordered alloys at elevated temperature. For example, less than 5% of BAs can dissolve in BP at T =1000 K. The small solubility limit of BAs in BP is attributed to the thermodynamic instability of BAs with respect to B12As2 and As.

Studies on the kinetics of killing and the proposed mechanism of action of microemulsions against fungi.

PubMed

Al-Adham, Ibrahim S I; Ashour, Hana; Al-Kaissi, Elham; Khalil, Enam; Kierans, Martin; Collier, Phillip J

2013-09-15

Microemulsions are physically stable oil/water clear dispersions, spontaneously formed and thermodynamically stable. They are composed in most cases of water, oil, surfactant and cosurfactant. Microemulsions are stable, self-preserving antimicrobial agents in their own right. The observed levels of antimicrobial activity associated with microemulsions may be due to the direct effect of the microemulsions themselves on the bacterial cytoplasmic membrane. The aim of this work is to study the growth behaviour of different microbes in presence of certain prepared physically stable microemulsion formulae over extended periods of time. An experiment was designed to study the kinetics of killing of a microemulsion preparation (17.3% Tween-80, 8.5% n-pentanol, 5% isopropyl myristate and 69.2% sterile distilled water) against selected test microorganisms (Candida albicans, Aspergillus niger, Schizosaccharomyces pombe and Rhodotorula spp.). Secondly, an experiment was designed to study the effects of the microemulsion preparation on the cytoplasmic membrane structure and function of selected fungal species by observation of 260 nm component leakage. Finally, the effects of the microemulsion on the fungal membrane structure and function using S. pombe were studied using transmission electron microscopy. The results showed that the prepared microemulsions are stable, effective antimicrobial systems with effective killing rates against C. albicans, A. niger, S. pombe and Rhodotorula spp. The results indicate a proposed mechanism of action of significant anti-membrane activity, resulting in the gross disturbance and dysfunction of the cytoplasmic membrane structure which is followed by cell wall modifications, cytoplasmic coagulation, disruption of intracellular metabolism and cell death. Copyright © 2013 Elsevier B.V. All rights reserved.

Thermodynamic stability and structure of cuprous chloride surfaces: a DFT investigation.

PubMed

Suleiman, Ibrahim A; Radny, Marian W; Gladys, Michael J; Smith, Phillip V; Mackie, John C; Kennedy, Eric M; Dlugogorski, Bogdan Z

2015-03-14

Density functional theory together with ab initio atomistic thermodynamics has been utilized to study the structures and stabilities of the low index CuCl surfaces. It is shown that the Cl-terminated structures are more stable than the Cu-terminated configurations, and that the defective CuCl(110)-Cu structure is more stable than the stoichiometric CuCl(110) surface. The equilibrium shape of a cuprous chloride nanostructure terminated by low-index CuCl surfaces has also been predicted using a Wulff construction. It was found that the (110) facets dominate at low chlorine concentration. As the chlorine concentration is increased, however, the contributions of the (100) and (111) facets to the Wulff construction also increase giving the crystal a semi-prism shape. At high chlorine concentration, and close to the rich limit, the (111) facets were found to be the only contributors to the Wulff construction, resulting in prismatic nanocrystals.

Structural and thermochemical Aspects of (III-V)IV3 Material Assembly from First Principles

NASA Astrophysics Data System (ADS)

Chizmeshya, Andrew; Kouvetakis, John

2014-03-01

Alloys with (III-V)-(IV) compositions, including Si3(AlP), Si5-2y(AlP)y, Si3Al(As1-xNx), Si5-2yAl(P1-xNx)y and Ge5-2y(InP)y and have recently been synthesized as mono-crystalline films on Si substrates, using a synthesis route specifically designed to avoid phase separation between the III-V and IV constituents. Molecular ``building blocks'' containing group-V-centered III-V-IV3 cores, formed via interactions of group-III atoms and reactive silyly/germyl hydride precursors of desired composition (e.g, P(SiH3)3 , P(GeH3)3 , etc), assemble to form stable, covalent, diamond-like materials with the inherent tetrahedral symmetry and composition of the III-V-IV3 units. The resulting systems may provide access to a broad range of new semiconductor systems with extended optoelectronic properties, provided that the required molecular sources are available, the thermodynamic processes are viable, and the resulting alloy composition can be tuned to lattice-match the growth substrate. Molecular/solid-state simulations are used to identify promising synthetic pathways and guide the epitaxial creation of new (III-V)-(IV) materials. The thermodynamics of gas phase synthesis reactions, energetic stability of the alloys, and their epitaxial/chemical compatibility with the substrate are combined to form a global figure of merit. The latter corroborates the synthesis of known systems and predicts that formation of GaPSi3/Si(100), GaAsSi3/SiGe(100), AlPGe3/Ge(100) and InAsSi3/Ge(100) may also be favorable. Supported by NSF-DMR under SusChEM award #1309090.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wintermeyer, Niklas; Winters, Andrew R., E-mail: awinters@math.uni-koeln.de; Gassner, Gregor J.

We design an arbitrary high-order accurate nodal discontinuous Galerkin spectral element approximation for the non-linear two dimensional shallow water equations with non-constant, possibly discontinuous, bathymetry on unstructured, possibly curved, quadrilateral meshes. The scheme is derived from an equivalent flux differencing formulation of the split form of the equations. We prove that this discretization exactly preserves the local mass and momentum. Furthermore, combined with a special numerical interface flux function, the method exactly preserves the mathematical entropy, which is the total energy for the shallow water equations. By adding a specific form of interface dissipation to the baseline entropy conserving schememore » we create a provably entropy stable scheme. That is, the numerical scheme discretely satisfies the second law of thermodynamics. Finally, with a particular discretization of the bathymetry source term we prove that the numerical approximation is well-balanced. We provide numerical examples that verify the theoretical findings and furthermore provide an application of the scheme for a partial break of a curved dam test problem.« less

Nitrosamine formation in amine scrubbing at desorber temperatures.

PubMed

Fine, Nathan A; Goldman, Mark J; Rochelle, Gary T

2014-01-01

Amine scrubbing is a thermodynamically efficient and industrially proven method for carbon capture, but amine solvents can nitrosate in the desorber, forming potentially carcinogenic nitrosamines. The kinetics of reactions involving nitrite and monoethanolamine (MEA), diethanolamine (DEA), methylethanolamine (MMEA), and methyldiethanolamine (MDEA) were determined under desorber conditions. The nitrosations of MEA, DEA, and MMEA are first order in nitrite, carbamate species, and hydronium ion. Nitrosation of MDEA, a tertiary amine, is not catalyzed by the addition of CO2 since it cannot form a stable carbamate. Concentrated and CO2 loaded MEA was blended with low concentrations of N-(2-hydroxyethyl) glycine (HeGly), hydroxyethyl-ethylenediamine (HEEDA), and DEA, secondary amines common in MEA degradation. Nitrosamine yield was proportional to the concentration of secondary amine and was a function of CO2 loading and temperature. Blends of tertiary amines with piperazine (PZ) showed n-nitrosopiperazine (MNPZ) yields close to unity, validating the slow nitrosation rates hypothesized for tertiary amines. These results provide a useful tool for estimating nitrosamine accumulation over a range of amine solvents.

Revealing the properties of defects formed by CH3NH2 molecules in organic-inorganic hybrid perovskite MAPbBr3

NASA Astrophysics Data System (ADS)

Wang, Ji; Zhang, Ao; Yan, Jun; Li, Dan; Chen, Yunlin

2017-03-01

The properties of defects in organic-inorganic hybrid perovskite are widely studied from the first-principles calculation. However, the defects of methylamine (methylamine = CH3NH2), which would be easily formed during the preparation of the organic-inorganic hybrid perovskite, are rarely investigated. Thermodynamic properties as well as defect states of methylamine embedded MAPbX3 (MA = methyl-ammonium = CH3NH3, X = Br, I) are studied based on first-principles calculations of density functional theory. It was found that there is a shallow defect level near the highest occupied molecular orbital, which induced by the interstitial methylamine defect in MAPbBr3, will lead to an increase of photoluminescence. The calculation results showed that interstitial defect states of methylamine may move deeper due to the interaction between methylamine molecules and methyl-ammonium cations. It was also showed that the interstitial methylamine defect is stable at room temperature, and the defect can be removed easily by annealing.

Encapsulation of labetalol, pseudoephedrine in β-cyclodextrin cavity: spectral and molecular modeling studies.

PubMed

Prabhu, A Antony Muthu; Rajendiran, N

2012-11-01

The absorption and fluorescence spectra of labetalol and pseudoephedrine have been studied in different polarities of solvents and β-cyclodextrin (β-CD). The inclusion complexation with β-CD is investigated by UV-visible, steady state and time resolved fluorescence spectra and PM3 method. In protic solvents, the normal emission originates from a locally excited state and the longer wavelength emission is due to intramolecular charge transfer (TICT). Labetalol forms a 1:2 complex and pseudoephedrine forms 1:1 complex with β-CD. Nanosecond time-resolved studies indicated that both molecules show triexponential decay. Thermodynamic parameters (ΔG, ΔH, ΔS) and HOMO, LUMO orbital investigations confirm the stability of the inclusion complex. The geometry of the most stable complex shows that the aromatic ring is deeply self included inside the β-CD cavity and intermolecular hydrogen bonds were established between host and guest molecules. This suggests that hydrophobic effect and hydrogen bond play an important role in the inclusion process.

Formation of a new archetypal Metal-Organic Framework from a simple monatomic liquid

NASA Astrophysics Data System (ADS)

Metere, Alfredo; Oleynikov, Peter; Dzugutov, Mikhail; O'Keeffe, Michael

2014-12-01

We report a molecular-dynamics simulation of a single-component system of particles interacting via a spherically symmetric potential that is found to form, upon cooling from a liquid state, a low-density porous crystalline phase. Its structure analysis demonstrates that the crystal can be described by a net with a topology that belongs to the class of topologies characteristic of the Metal-Organic Frameworks (MOFs). The observed net is new, and it is now included in the Reticular Chemistry Structure Resource database. The observation that a net topology characteristic of MOF crystals, which are known to be formed by a coordination-driven self-assembly process, can be reproduced by a thermodynamically stable configuration of a simple single-component system of particles opens a possibility of using these models in studies of MOF nets. It also indicates that structures with MOF topology, as well as other low-density porous crystalline structures can possibly be produced in colloidal systems of spherical particles, with an appropriate tuning of interparticle interaction.

Simulation of Benchmark Cases with the Terminal Area Simulation System (TASS)

NASA Technical Reports Server (NTRS)

Ahmad, Nash'at; Proctor, Fred

2011-01-01

The hydrodynamic core of the Terminal Area Simulation System (TASS) is evaluated against different benchmark cases. In the absence of closed form solutions for the equations governing atmospheric flows, the models are usually evaluated against idealized test cases. Over the years, various authors have suggested a suite of these idealized cases which have become standards for testing and evaluating the dynamics and thermodynamics of atmospheric flow models. In this paper, simulations of three such cases are described. In addition, the TASS model is evaluated against a test case that uses an exact solution of the Navier-Stokes equations. The TASS results are compared against previously reported simulations of these banchmark cases in the literature. It is demonstrated that the TASS model is highly accurate, stable and robust.

Formation of Gas-Phase Formate in Thermal Reactions of Carbon Dioxide with Diatomic Iron Hydride Anions.

PubMed

Jiang, Li-Xue; Zhao, Chongyang; Li, Xiao-Na; Chen, Hui; He, Sheng-Gui

2017-04-03

The hydrogenation of carbon dioxide involves the activation of the thermodynamically very stable molecule CO 2 and formation of a C-H bond. Herein, we report that HCO 2 - and CO can be formed in the thermal reaction of CO 2 with a diatomic metal hydride species, FeH - . The FeH - anions were produced by laser ablation, and the reaction with CO 2 was analyzed by mass spectrometry and quantum-chemical calculations. Gas-phase HCO 2 - was observed directly as a product, and its formation was predicted to proceed by facile hydride transfer. The mechanism of CO 2 hydrogenation in this gas-phase study parallels similar behavior of a condensed-phase iron catalyst. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Simulation of Benchmark Cases with the Terminal Area Simulation System (TASS)

NASA Technical Reports Server (NTRS)

Ahmad, Nashat N.; Proctor, Fred H.

2011-01-01

The hydrodynamic core of the Terminal Area Simulation System (TASS) is evaluated against different benchmark cases. In the absence of closed form solutions for the equations governing atmospheric flows, the models are usually evaluated against idealized test cases. Over the years, various authors have suggested a suite of these idealized cases which have become standards for testing and evaluating the dynamics and thermodynamics of atmospheric flow models. In this paper, simulations of three such cases are described. In addition, the TASS model is evaluated against a test case that uses an exact solution of the Navier-Stokes equations. The TASS results are compared against previously reported simulations of these benchmark cases in the literature. It is demonstrated that the TASS model is highly accurate, stable and robust.

Thermodynamic and radiative structure of stratocumulus-topped boundary layers*

DOE PAGES

Ghate, Virendra P.; Miller, Mark A.; Albrecht, Bruce A.; ...

2015-01-05

Stratocumulus Topped Boundary Layers (STBL) observed in three different regions with distinctive environments are described in the context of their thermodynamic and radiative properties. Here, the primary data set consisted of 131 soundings from the South East Pacific (SEP), 90 soundings from the island of Graciosa (GRW) in the North Atlantic and 83 soundings from the US Southern Great Plains (SGP). A new technique that preserves the depths of the sub-layers within a STBL is proposed for averaging the profiles of thermodynamic and radiative variables. The STBL was deepest over SEP and had the strongest radiative cooling rates near cloudmore » top among the three locations. Although the radiative cooling rates were comparable over GRW and SGP, the STBL was deeper over GRW compared to that over SGP. On average the STBL inversion was strongest over SEP (11.7 k and -5.43 g kg -1) and weakest over the SGP (6.89 k and -0.41 g kg -1). Significantly larger liquid water path, integrated water vapor, and variability in these two properties was found over GRW and evidence presented suggests that conditions at cloud top may play a lesser role in determining the resident cloud structure over GRW than over SEP. A modal analysis revealed ~26% of the STBL to be well-mixed, ~20% of STBL to be stable and ~30% STBL having a stable layer in-between a surface mixed layer and the cloud layer. Over all the three locations, the STBL was shallowest in well-mixed mode and deepest in the stable mode.« less

Effect of medium acidity on the thermodynamics and kinetics of the reaction of pyridoxal 5'-phosphate with isoniazid in an aqueous solution

NASA Astrophysics Data System (ADS)

Gamov, G. A.; Zavalishin, M. N.; Usacheva, T. R.; Sharnin, V. A.

2017-05-01

Thermodynamic characteristics of the formation of the Schiff base between isoniazid and pyridoxal 5'-phosphate in an aqueous solution at different pH values of a medium are determined by means of spectrophotometry and calorimetric titration. The process kinetics is studied spectrophotometrically, and the reaction rate constants for the formation of the imine at different acidities of a medium are determined. Biochemical aspects of the binding of pyridoxal 5'-phosphate into stable compounds are discussed.

Dynamics and thermodynamics of polymer glasses.

PubMed

Cangialosi, D

2014-04-16

The fate of matter when decreasing the temperature at constant pressure is that of passing from gas to liquid and, subsequently, from liquid to crystal. However, a class of materials can exist in an amorphous phase below the melting temperature. On cooling such materials, a glass is formed; that is, a material with the rigidity of a solid but exhibiting no long-range order. The study of the thermodynamics and dynamics of glass-forming systems is the subject of continuous research. Within the wide variety of glass formers, an important sub-class is represented by glass forming polymers. The presence of chain connectivity and, in some cases, conformational disorder are unfavourable factors from the point of view of crystallization. Furthermore, many of them, such as amorphous thermoplastics, thermosets and rubbers, are widely employed in many applications. In this review, the peculiarities of the thermodynamics and dynamics of glass-forming polymers are discussed, with particular emphasis on those topics currently the subject of debate. In particular, the following aspects will be reviewed in the present work: (i) the connection between the pronounced slowing down of glassy dynamics on cooling towards the glass transition temperature (Tg) and the thermodynamics; and, (ii) the fate of the dynamics and thermodynamics below Tg. Both aspects are reviewed in light of the possible presence of a singularity at a finite temperature with diverging relaxation time and zero configurational entropy. In this context, the specificity of glass-forming polymers is emphasized.

Polymorphism in sulfadimidine/4-aminosalicylic acid cocrystals: solid-state characterization and physicochemical properties.

PubMed

Grossjohann, Christine; Serrano, Dolores R; Paluch, Krzysztof J; O'Connell, Peter; Vella-Zarb, Liana; Manesiotis, Panagiotis; Mccabe, Thomas; Tajber, Lidia; Corrigan, Owen I; Healy, Anne Marie

2015-04-01

Polymorphism of crystalline drugs is a common phenomenon. However, the number of reported polymorphic cocrystals is very limited. In this work, the synthesis and solid-state characterization of a polymorphic cocrystal composed of sulfadimidine (SD) and 4-aminosalicylic acid (4-ASA) is reported for the first time. By liquid-assisted milling, the SD:4-ASA 1:1 form I cocrystal, the structure of which has been previously reported, was formed. By spray drying, a new polymorphic form (form II) of the SD:4-ASA 1:1 cocrystal was discovered which could also be obtained by solvent evaporation from ethanol and acetone. Structure determination of the form II cocrystal was calculated using high-resolution X-ray powder diffraction. The solubility of the SD:4-ASA 1:1 cocrystal was dependent on the pH and predicted by a model established for a two amphoteric component cocrystal. The form I cocrystal was found to be thermodynamically more stable in aqueous solution than form II, which showed transformation to form I. Dissolution studies revealed that the dissolution rate of SD from both cocrystals was enhanced when compared with a physical equimolar mixture and pure SD. © 2015 Wiley Periodicals, Inc. and the American Pharmacists Association J Pharm Sci 104:1385-1398, 2015. © 2015 Wiley Periodicals, Inc. and the American Pharmacists Association.

[Thermodynamics of the origin of life, evolution and aging].

PubMed

Gladyshev, G P

2014-01-01

Briefly discusses the history of the search of thermodynamic approach to explain the origin of life, evolution and aging of living beings. The origin of life is the result of requirement by the quasi-equilibrium hierarchical thermodynamics, in particular, the supramolecular thermodynamics. The evolution and aging of living beings is accompanied with changes of chemical and supramolecular compositions of living bodies, as well as with changes in the composition and structure of all hierarchies of the living world. The thermodynamic principle of substance stability predicts the existence of a single genetic code in our universe. The thermodynamic theory optimizes physiology and medicine and recommends antiaging diets and medicines. Hierarchical thermodynamics forms the design diversity of culture and art. The thermodynamic theory of origin of life, evolution and aging is the development of Clausius-Gibbs thermodynamics. Hierarchical thermodynamics is the mirror of Darwin-Wallace's-theory.

Complexes of oxovanadium(IV), dioxovanadium(V) and dioxouranium(VI) with aminoacids in aqueous solution

NASA Astrophysics Data System (ADS)

Lagrange, P.; Schneider, M.; Lagrange, J.

1998-11-01

The equilibria between three oxocations (VO2+, VO2+ and UO22+) and several ?- aminoacids (glycine, serine, asparagine, lysine, aspartic acid and glutamic acid) are studied in aqueous solution. Stoichiometry and stability of the complexes formed are determined from a combination of potentiometric and spectroscopic measurements. Solution structures of the different complexes are proposed based on the thermodynamic results. The oxovanadium(IV) complexes appear less stable than the corresponding dioxouranium(VI) and dioxovanadium(V) complexes. VO2+ can be bound to only one ligand to form monodentate or chelate complexes. UO22+ and VO2+ cations may be chelated by one or two ligands. Les équilibres entre trois oxocations, VO2+, VO2+ et UO22+ et plusieurs α-aminoacides, glycine, sérine, asparagine, lysine et acides aspartique et glutamique, sont étudiés en solution aqueuse par potentiométrie couplée à la spectrophotométrie. Les complexes de VO2+ sont moins stables que les complexes de VO2+ et UO22+ de même stoechiométrie. VO2+ ne peut se lier qu'à un seul ligand pour former soit des complexes monodentés, soit des chélates. UO22+ et VO2+ peuvent être chélatés par un ou deux ligands. Des structures hypothétiques en solution sont proposées.

Thermodynamics of Quantum Gases for the Entire Range of Temperature

ERIC Educational Resources Information Center

Biswas, Shyamal; Jana, Debnarayan

2012-01-01

We have analytically explored the thermodynamics of free Bose and Fermi gases for the entire range of temperature, and have extended the same for harmonically trapped cases. We have obtained approximate chemical potentials for the quantum gases in closed forms of temperature so that the thermodynamic properties of the quantum gases become…

A Unified Graphical Representation of Chemical Thermodynamics and Equilibrium

ERIC Educational Resources Information Center

Hanson, Robert M.

2012-01-01

During the years 1873-1879, J. Willard Gibbs published his now-famous set of articles that form the basis of the current perspective on chemical thermodynamics. The second article of this series, "A Method of Geometrical Representation of the Thermodynamic Properties of Substances by Means of Surfaces," published in 1873, is particularly notable…

Computational and Experimental Characterization of Five Crystal Forms of Thymine: Packing Polymorphism, Polytypism/Disorder and Stoichiometric 0.8-Hydrate.

PubMed

Braun, Doris E; Gelbrich, Thomas; Wurst, Klaus; Griesser, Ulrich J

2016-06-01

New polymorphs of thymine emerged in an experimental search for solid forms, which was guided by the computationally generated crystal energy landscape. Three of the four anhydrates (AH) are homeoenergetic ( A° - C ) and their packing modes differ only in the location of oxygen and hydrogen atoms. AHs A° and B are ordered phases, whereas AH C shows disorder (X-ray diffuse scattering). Anhydrates AHs A° and B are ordered phases, whereas AH C shows disorder (X-ray diffuse scattering). Analysis of the crystal energy landscape for alternative AH C hydrogen bonded ribbon motifs identified a number of different packing modes, whose 3D structures were calculated to deviate by less than 0.24 kJ mol -1 in lattice energy. These structures provide models for stacking faults. The three anhydrates A ° - C show strong similarity in their powder X-ray diffraction, thermoanalytical and spectroscopic (IR and Raman) characteristics. The already known anhydrate AH A ° was identified as the thermodynamically most stable form at ambient conditions; AH B and AH C are metastable but show high kinetic stability. The hydrate of thymine is stable only at water activities ( a w ) > 0.95 at temperatures ≤ 25 °C. It was found to be a stoichiometric hydrate despite being a channel hydrate with an unusual water:thymine ratio of 0.8:1. Depending on the dehydration conditions, either AH C or AH D is obtained. The hydrate is the only known precursor to AH D . This study highlights the value and complementarity of simultaneous explorations of computationally and experimentally generated solid form landscapes of a small molecule anhydrate ↔ hydrate system.

Experimental Constraints on the Stability of Clinopyroxene (+) Magnesite in Iron Bearing Planetary Mantles: Implications for Nakhlite Formation

NASA Technical Reports Server (NTRS)

Martin, Audrey M.; Righter, Kevin

2010-01-01

Carbon is present in various forms in the Earth s upper mantle (carbonate- or diamond-bearing mantle xenoliths, carbonatite magmas, CO2 emissions from volcanoes...). Moreover, there is enough carbon in chondritic material to stabilize carbonates into the mantles of Mars or Venus as well as in the Earth. However, the interactions with iron have to be constrained, because Fe is commonly thought to buffer oxygen fugacity into planetary mantles. [1] and [2] show evidences of the stability of clinopyroxene Ca(Mg,Fe)Si2O6 + magnesite (Mg,Fe)CO3 in the Earth s mantle around 6GPa (about 180km). The stability of oxidized forms of carbon (like magnesite) depends on the oxygen fugacity of the system. In the Earth s mantle, the maximum carbon content is 10000 ppm [3]. The fO2 parameter varies vertically as a function of pressure, but also laterally because of geodynamic processes like subduction. Thus, carbonates, graphite, diamond, C-rich gases and melts are all stable forms of carbon in the Earth s mantle. [4] show that the fO2 variations observed in SNC meteorites can be explained by polybaric graphite-CO-CO2 equilibria in the Martian mantle. [5] inferred from thermodynamic calculations that the stable form of carbon in the source regions of the Martian basalts should be graphite (and/or diamond). After [6], a metasomatizing agent like a CO2-rich melt may infiltrate the mantle source of nakhlites. However, according to [7] and [8], the FeO wt% value in the Martian bulk mantle is more than twice that of the Earth s mantle (KLB-1 composition by [9]). As iron and carbon are two elements with various oxidation states, Fe/C interaction mechanisms must be considered.

Computational and Experimental Characterization of Five Crystal Forms of Thymine: Packing Polymorphism, Polytypism/Disorder and Stoichiometric 0.8-Hydrate

PubMed Central

Braun, Doris E.; Gelbrich, Thomas; Wurst, Klaus; Griesser, Ulrich J.

2017-01-01

New polymorphs of thymine emerged in an experimental search for solid forms, which was guided by the computationally generated crystal energy landscape. Three of the four anhydrates (AH) are homeoenergetic (A° – C) and their packing modes differ only in the location of oxygen and hydrogen atoms. AHs A° and B are ordered phases, whereas AH C shows disorder (X-ray diffuse scattering). Anhydrates AHs A° and B are ordered phases, whereas AH C shows disorder (X-ray diffuse scattering). Analysis of the crystal energy landscape for alternative AH C hydrogen bonded ribbon motifs identified a number of different packing modes, whose 3D structures were calculated to deviate by less than 0.24 kJ mol–1 in lattice energy. These structures provide models for stacking faults. The three anhydrates A° – C show strong similarity in their powder X-ray diffraction, thermoanalytical and spectroscopic (IR and Raman) characteristics. The already known anhydrate AH A° was identified as the thermodynamically most stable form at ambient conditions; AH B and AH C are metastable but show high kinetic stability. The hydrate of thymine is stable only at water activities (aw) > 0.95 at temperatures ≤ 25 °C. It was found to be a stoichiometric hydrate despite being a channel hydrate with an unusual water:thymine ratio of 0.8:1. Depending on the dehydration conditions, either AH C or AH D is obtained. The hydrate is the only known precursor to AH D. This study highlights the value and complementarity of simultaneous explorations of computationally and experimentally generated solid form landscapes of a small molecule anhydrate ↔ hydrate system. PMID:28663717

Cavitation in liquid cryogens. 2: Hydrofoil

NASA Technical Reports Server (NTRS)

Hord, J.

1973-01-01

Boundary layer principles, along with two-phase concepts, are used to improve existing correlative theory for developed cavity data. Details concerning cavity instrumentation, data analysis, correlative techniques, and experimental and theoretical aspects of a cavitating hydrofoil are given. Both desinent and thermodynamic data, using liquid hydrogen and liquid nitrogen, are reported. The thermodynamic data indicated that stable thermodynamic equilibrium exists throughout the vaporous cryogen cavities. The improved correlative formulas were used to evaluate these data. A new correlating parameter based on consideration of mass limiting two-phase flow flux across the cavity interface, is proposed. This correlating parameter appears attractive for future correlative and predictive applications. Agreement between theory and experiment is discussed, and directions for future analysis are suggested. The front half of the cavities, developed on the hydrofoil, may be considered as parabolically shaped.

Structural stability, elastic and thermodynamic properties of Au-Cu alloys from first-principles calculations

NASA Astrophysics Data System (ADS)

Kong, Ge-Xing; Ma, Xiao-Juan; Liu, Qi-Jun; Li, Yong; Liu, Zheng-Tang

2018-03-01

Using first-principles calculations method based on density functional theory (DFT) with the Perdew-Burke-Ernzerhof (PBE) implementation of the generalized gradient approximation (GGA), we investigate the structural, elastic and thermodynamic properties of gold-copper intermetallic compounds (Au-Cu ICs). The calculated lattice parameters are in excellent agreement with experimental data. The elastic constants show that all the investigated Au-Cu alloys are mechanically stable. Elastic properties, including the shear modulus, Young's modulus, Poisson's ratio and Pugh's indicator, of the intermetallic compounds are evaluated and discussed, with special attention to the remarkable anisotropy displayed by Au-Cu ICs. Thermodynamic and transport properties including the Debye temperature, thermal conductivity and melting point are predicted from the averaged sound velocity and elastic moduli, using semi-empirical formulas.

An anisotropic thermomechanical damage model for concrete at transient elevated temperatures.

PubMed

Baker, Graham; de Borst, René

2005-11-15

The behaviour of concrete at elevated temperatures is important for an assessment of integrity (strength and durability) of structures exposed to a high-temperature environment, in applications such as fire exposure, smelting plants and nuclear installations. In modelling terms, a coupled thermomechanical analysis represents a generalization of the computational mechanics of fracture and damage. Here, we develop a fully coupled anisotropic thermomechanical damage model for concrete under high stress and transient temperature, with emphasis on the adherence of the model to the laws of thermodynamics. Specific analytical results are given, deduced from thermodynamics, of a novel interpretation on specific heat, evolution of entropy and the identification of the complete anisotropic, thermomechanical damage surface. The model is also shown to be stable in a computational sense, and to satisfy the laws of thermodynamics.

Ecosystem functioning and maximum entropy production: a quantitative test of hypotheses.

PubMed

Meysman, Filip J R; Bruers, Stijn

2010-05-12

The idea that entropy production puts a constraint on ecosystem functioning is quite popular in ecological thermodynamics. Yet, until now, such claims have received little quantitative verification. Here, we examine three 'entropy production' hypotheses that have been forwarded in the past. The first states that increased entropy production serves as a fingerprint of living systems. The other two hypotheses invoke stronger constraints. The state selection hypothesis states that when a system can attain multiple steady states, the stable state will show the highest entropy production rate. The gradient response principle requires that when the thermodynamic gradient increases, the system's new stable state should always be accompanied by a higher entropy production rate. We test these three hypotheses by applying them to a set of conventional food web models. Each time, we calculate the entropy production rate associated with the stable state of the ecosystem. This analysis shows that the first hypothesis holds for all the food webs tested: the living state shows always an increased entropy production over the abiotic state. In contrast, the state selection and gradient response hypotheses break down when the food web incorporates more than one trophic level, indicating that they are not generally valid.

Surface thermodynamic analysis of fluid confined in a cone and comparison with the sphere-plate and plate-plate geometries.

PubMed

Zargarzadeh, Leila; Elliott, Janet A W

2013-10-22

The behavior of pure fluid confined in a cone is investigated using thermodynamic stability analysis. Four situations are explained on the basis of the initial confined phase (liquid/vapor) and its pressure (above/below the saturation pressure). Thermodynamic stability analysis (a plot of the free energy of the system versus the size of the new potential phase) reveals whether the phase transition is possible and, if so, the number and type (unstable/metastable/stable) of equilibrium states in each of these situations. Moreover we investigated the effect of the equilibrium contact angle and the cone angle (equivalent to the confinement's surface separation distance) on the free energy (potential equilibrium states). The results are then compared to our previous study of pure fluid confined in the gap between a sphere and a flat plate and the gap between two flat plates.1 Confined fluid behavior of the four possible situations (for these three geometries) can be explained in a unified framework under two categories based on only the meniscus shape (concave/convex). For systems with bulk-phase pressure imposed by a reservoir, the stable coexistence of pure liquid and vapor is possible only when the meniscus is concave.

Electronic and thermodynamic properties of layered Hf2Sfrom first-principles calculations

NASA Astrophysics Data System (ADS)

Nandadasa, Chandani; Yoon, Mina; Kim, Seong-Gon; Erwin, Steve; Kim, Sungho; Kim, Sung Wng; Lee, Kimoon

Theoretically we explored two stable phases of inorganic fullerene-like structure of the layered dihafnium sulfide (Hf2 S) . We investigated structural and electronic properties of the two phases of Hf2 S by using first-principles calculations. Our calculation identifies experimentally observed anti-NbS2 structure of Hf2 S . Our electronic calculation results indicate that the density of states of anti- NbS2 structure of Hf2 S at fermi level is less than that of the other phase of Hf2 S . To study the relative stability of different phases at finite temperature Helmholtz free energies of two phases are obtained using density functional theory and density functional perturbation theory. The free energy of the anti-NbS2 structure of Hf2 S always lies below the free energy of the other phase by confirming the most stable structure of Hf2 S . The phonon dispersion, phonon density of states including partial density of states and total density of states are obtained within density functional perturbation theory. Our calculated zero-pressure phonon dispersion curves confirm that the thermodynamic stability of Hf2 S structures. For further investigation of thermodynamic properties, the temperature dependency of thermal expansion, heat capacities at constant pressure and volume are evaluated within the quasiharmonic approximations (QHA).

Final Report for Department of Energy Grant No. DE-FG02-02ER45997, "Alloy Design of Nanoscale Precipitation Strengthened Alloys: Design of a Heat Treatable Aluminum Alloy Useful to 400C"

DOE Office of Scientific and Technical Information (OSTI.GOV)

Morris E. Fine; Gautam Ghosh; Dieter Isheim

A creep resistant high temperature Al base alloy made by conventional processing procedures is the subject of this research. The Ni-based superalloys have volume fractions of cubic L1{sub 2} phase precipitates near 50%. This is not attainable with Al base alloys and the approach pursued in this research was to add L1{sub 2} structured precipitates to the Al-Ni eutectic alloy, 2.7 at. % Ni-97.3 at. % Al. The eutectic reaction gives platelets of Al{sub 3}Ni (DO{sub 11} structure) in an almost pure Al matrix. The Al{sub 3}Ni platelets give reinforcement strengthening while the L1{sub 2} precipitates strengthen the Al alloymore » matrix. Based on prior research and the extensive research reported here modified cubic L1{sub 2} Al{sub 3}Zr is a candidate. While cubic Al{sub 3}Zr is metastable, the stable phase is tetragonal, only cubic precipitates were observed after 1600 hrs at 425 C and they hardly coarsened at all with time at this temperature. Also addition of Ti retards the cubic to tetragonal transformation; however, a thermodynamically stable precipitate is desired. A very thorough ab initio computational investigation was done on the stability of L1{sub 2} phases of composition, (Al,X){sub 3}(Zr,Ti) and the possible occurrence of tie lines between a stable L1{sub 2} phase and the Al alloy terminal solid solution. Precipitation of cubic (Al{sub (1-x)}Zn{sub x}){sub 3}Zr in Al was predicted by these computations and subsequently observed by experiment (TEM). To test the combined reinforcement-precipitation concept to obtain a creep resistant Al alloy, Zr and Ti were added to the Al-Ni eutectic alloy. Cubic L1{sub 2} precipitates did form. The first and only Al-Ni-Zr-Ti alloy tested for creep gave a steady state creep rate at 375 C of 8 x 10{sup -9} under 20MPa stress. The goal is to optimize this alloy and add Zn to achieve a thermodynamically stable precipitate.« less

A Tractable Disequilbrium Framework for Integrating Computational Thermodynamics and Geodynamics

NASA Astrophysics Data System (ADS)

Spiegelman, M. W.; Tweed, L. E. L.; Evans, O.; Kelemen, P. B.; Wilson, C. R.

2017-12-01

The consistent integration of computational thermodynamics and geodynamics is essential for exploring and understanding a wide range of processes from high-PT magma dynamics in the convecting mantle to low-PT reactive alteration of the brittle crust. Nevertheless, considerable challenges remain for coupling thermodynamics and fluid-solid mechanics within computationally tractable and insightful models. Here we report on a new effort, part of the ENKI project, that provides a roadmap for developing flexible geodynamic models of varying complexity that are thermodynamically consistent with established thermodynamic models. The basic theory is derived from the disequilibrium thermodynamics of De Groot and Mazur (1984), similar to Rudge et. al (2011, GJI), but extends that theory to include more general rheologies, multiple solid (and liquid) phases and explicit chemical reactions to describe interphase exchange. Specifying stoichiometric reactions clearly defines the compositions of reactants and products and allows the affinity of each reaction (A = -Δ/Gr) to be used as a scalar measure of disequilibrium. This approach only requires thermodynamic models to return chemical potentials of all components and phases (as well as thermodynamic quantities for each phase e.g. densities, heat capacity, entropies), but is not constrained to be in thermodynamic equilibrium. Allowing meta-stable phases mitigates some of the computational issues involved with the introduction and exhaustion of phases. Nevertheless, for closed systems, these problems are guaranteed to evolve to the same equilibria predicted by equilibrium thermodynamics. Here we illustrate the behavior of this theory for a range of simple problems (constructed with our open-source model builder TerraFERMA) that model poro-viscous behavior in the well understood Fo-Fa binary phase loop. Other contributions in this session will explore a range of models with more petrologically interesting phase diagrams as well as other rheologies.

Carbide/nitride grain refined rare earth-iron-boron permanent magnet and method of making

DOEpatents

McCallum, R.W.; Branagan, D.J.

1996-01-23

A method of making a permanent magnet is disclosed wherein (1) a melt is formed having a base alloy composition comprising RE, Fe and/or Co, and B (where RE is one or more rare earth elements) and (2) TR (where TR is a transition metal selected from at least one of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, and Al) and at least one of C and N are provided in the base alloy composition melt in substantially stoichiometric amounts to form a thermodynamically stable compound (e.g. TR carbide, nitride or carbonitride). The melt is rapidly solidified in a manner to form particulates having a substantially amorphous (metallic glass) structure and a dispersion of primary TRC, TRN and/or TRC/N precipitates. The amorphous particulates are heated above the crystallization temperature of the base alloy composition to nucleate and grow a hard magnetic phase to an optimum grain size and to form secondary TRC, TRN and/or TRC/N precipitates dispersed at grain boundaries. The crystallized particulates are consolidated at an elevated temperature to form a shape. During elevated temperature consolidation, the primary and secondary precipitates act to pin the grain boundaries and minimize deleterious grain growth that is harmful to magnetic properties. 33 figs.

Methane bursts as a trigger for intermittent lake-forming climates on post-Noachian Mars

NASA Astrophysics Data System (ADS)

Kite, Edwin S.; Gao, Peter; Goldblatt, Colin; Mischna, Michael A.; Mayer, David P.; Yung, Yuk L.

2017-10-01

Lakes existed on Mars later than 3.6 billion years ago, according to sedimentary evidence for deltaic deposition. The observed fluviolacustrine deposits suggest that individual lake-forming climates persisted for at least several thousand years (assuming dilute flow). But the lake watersheds’ little-weathered soils indicate a largely dry climate history, with intermittent runoff events. Here we show that these observational constraints, although inconsistent with many previously proposed triggers for lake-forming climates, are consistent with a methane burst scenario. In this scenario, chaotic transitions in mean obliquity drive latitudinal shifts in temperature and ice loading that destabilize methane clathrate. Using numerical simulations, we find that outgassed methane can build up to atmospheric levels sufficient for lake-forming climates, if methane clathrate initially occupies more than 4% of the total volume in which it is thermodynamically stable. Such occupancy fractions are consistent with methane production by water-rock reactions due to hydrothermal circulation on early Mars. We further estimate that photochemical destruction of atmospheric methane curtails the duration of individual lake-forming climates to less than a million years, consistent with observations. We conclude that methane bursts represent a potential pathway for intermittent excursions to a warm, wet climate state on early Mars.

Carbide/nitride grain refined rare earth-iron-boron permanent magnet and method of making

DOEpatents

McCallum, R. William; Branagan, Daniel J.

1996-01-23

A method of making a permanent magnet wherein 1) a melt is formed having a base alloy composition comprising RE, Fe and/or Co, and B (where RE is one or more rare earth elements) and 2) TR (where TR is a transition metal selected from at least one of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, and Al) and at least one of C and N are provided in the base alloy composition melt in substantially stoichiometric amounts to form a thermodynamically stable compound (e.g. TR carbide, nitride or carbonitride). The melt is rapidly solidified in a manner to form particulates having a substantially amorphous (metallic glass) structure and a dispersion of primary TRC, TRN and/or TRC/N precipitates. The amorphous particulates are heated above the crystallization temperature of the base alloy composition to nucleate and grow a hard magnetic phase to an optimum grain size and to form secondary TRC, TRN and/or TRC/N precipitates dispersed at grain boundaries. The crystallized particulates are consolidated at an elevated temperature to form a shape. During elevated temperature consolidation, the primary and secondary precipitates act to pin the grain boundaries and minimize deleterious grain growth that is harmful to magnetic properties.

Thermodynamic analysis of water molecules at the surface of proteins and applications to binding site prediction and characterization.

PubMed

Beuming, Thijs; Che, Ye; Abel, Robert; Kim, Byungchan; Shanmugasundaram, Veerabahu; Sherman, Woody

2012-03-01

Water plays an essential role in determining the structure and function of all biological systems. Recent methodological advances allow for an accurate and efficient estimation of the thermodynamic properties of water molecules at the surface of proteins. In this work, we characterize these thermodynamic properties and relate them to various structural and functional characteristics of the protein. We find that high-energy hydration sites often exist near protein motifs typically characterized as hydrophilic, such as backbone amide groups. We also find that waters around alpha helices and beta sheets tend to be less stable than waters around loops. Furthermore, we find no significant correlation between the hydration site-free energy and the solvent accessible surface area of the site. In addition, we find that the distribution of high-energy hydration sites on the protein surface can be used to identify the location of binding sites and that binding sites of druggable targets tend to have a greater density of thermodynamically unstable hydration sites. Using this information, we characterize the FKBP12 protein and show good agreement between fragment screening hit rates from NMR spectroscopy and hydration site energetics. Finally, we show that water molecules observed in crystal structures are less stable on average than bulk water as a consequence of the high degree of spatial localization, thereby resulting in a significant loss in entropy. These findings should help to better understand the characteristics of waters at the surface of proteins and are expected to lead to insights that can guide structure-based drug design efforts. Copyright © 2011 Wiley Periodicals, Inc.

Thermodynamic variables of first-order entropy corrected Lovelock-AdS black holes: P{-}V criticality analysis

NASA Astrophysics Data System (ADS)

Haldar, Amritendu; Biswas, Ritabrata

2018-06-01

We investigate the effect of thermal fluctuations on the thermodynamics of a Lovelock-AdS black hole. Taking the first order logarithmic correction term in entropy we analyze the thermodynamic potentials like Helmholtz free energy, enthalpy and Gibbs free energy. We find that all the thermodynamic potentials are decreasing functions of correction coefficient α . We also examined this correction coefficient must be positive by analysing P{-}V diagram. Further we study the P{-}V criticality and stability and find that presence of logarithmic correction in it is necessary to have critical points and stable phases. When P{-}V criticality appears, we calculate the critical volume V_c, critical pressure P_c and critical temperature T_c using different equations and show that there is no critical point for this black hole without thermal fluctuations. We also study the geometrothermodynamics of this kind of black holes. The Ricci scalar of the Ruppeiner metric is graphically analysed.

Studies on Pidotimod Enantiomers With Chiralpak-IA: Crystal Structure, Thermodynamic Parameters and Molecular Docking.

PubMed

Dou, Xiaorui; Su, Xin; Wang, Yue; Chen, Yadong; Shen, Weiyang

2015-11-01

Pidotimod, a synthetic dipeptide, has two chiral centers with biological and immunological activity. Its enantiomers were characterized by x-ray crystallographic analysis. A chiral stationary phase (CSP) Chiralpak-IA based on amylose derivatized with tris-(3, 5-dimethylphenyl carbamate) was used to separate pidotimod enantiomers. The mobile phase was prepared in a ratio of 35:65:0.2 of methyl-tert-butyl-ether and acetonitrile trifluoroaceticacid. In addition, thermodynamics and molecular docking methods were used to explain the enantioseparation mechanism by Chiralpak-IA. Thermodynamic studies were carried out from 10 to 45 °C. In general, both retention and enantioselectivity decreased as the temperature increased. Thermodynamic parameters indicate that the interaction force between the pidotimod enantiomer (4S, 2'R) and IA CSP is stronger and their complex model is more stable. According to GOLD molecular docking simulation, Van der Waals force is the leading cause of pidotimod enantiomers separation by IA CSP. © 2015 Wiley Periodicals, Inc.

Energy-dependent topological anti-de Sitter black holes in Gauss-Bonnet Born-Infeld gravity

NASA Astrophysics Data System (ADS)

Hendi, S. H.; Behnamifard, H.; Bahrami-Asl, B.

2018-03-01

Employing higher-curvature corrections to Einstein-Maxwell gravity has garnered a great deal of attention motivated by the high-energy regime in the quantum nature of black hole physics. In addition, one may employ gravity's rainbow to encode quantum gravity effects into black hole solutions. In this paper, we regard an energy-dependent static spacetime with various topologies and study its black hole solutions in the context of Gauss-Bonnet Born-Infeld (GB-BI) gravity. We study the thermodynamic properties and examine the first law of thermodynamics. Using a suitable local transformation, we endow the Ricci-flat black hole solutions with a global rotation and study the effects of rotation on thermodynamic quantities. We also investigate thermal stability in a canonical ensemble by calculating the heat capacity. We obtain the effects of various parameters on the horizon radius of stable black holes. Finally, we discuss a second-order phase transition in the extended phase space thermodynamics and investigate the critical behavior.

Methane clathrates in the solar system.

PubMed

Mousis, Olivier; Chassefière, Eric; Holm, Nils G; Bouquet, Alexis; Waite, Jack Hunter; Geppert, Wolf Dietrich; Picaud, Sylvain; Aikawa, Yuri; Ali-Dib, Mohamad; Charlou, Jean-Luc; Rousselot, Philippe

2015-04-01

We review the reservoirs of methane clathrates that may exist in the different bodies of the Solar System. Methane was formed in the interstellar medium prior to having been embedded in the protosolar nebula gas phase. This molecule was subsequently trapped in clathrates that formed from crystalline water ice during the cooling of the disk and incorporated in this form into the building blocks of comets, icy bodies, and giant planets. Methane clathrates may play an important role in the evolution of planetary atmospheres. On Earth, the production of methane in clathrates is essentially biological, and these compounds are mostly found in permafrost regions or in the sediments of continental shelves. On Mars, methane would more likely derive from hydrothermal reactions with olivine-rich material. If they do exist, martian methane clathrates would be stable only at depth in the cryosphere and sporadically release some methane into the atmosphere via mechanisms that remain to be determined. In the case of Titan, most of its methane probably originates from the protosolar nebula, where it would have been trapped in the clathrates agglomerated by the satellite's building blocks. Methane clathrates are still believed to play an important role in the present state of Titan. Their presence is invoked in the satellite's subsurface as a means of replenishing its atmosphere with methane via outgassing episodes. The internal oceans of Enceladus and Europa also provide appropriate thermodynamic conditions that allow formation of methane clathrates. In turn, these clathrates might influence the composition of these liquid reservoirs. Finally, comets and Kuiper Belt Objects might have formed from the agglomeration of clathrates and pure ices in the nebula. The methane observed in comets would then result from the destabilization of clathrate layers in the nuclei concurrent with their approach to perihelion. Thermodynamic equilibrium calculations show that methane-rich clathrate layers may exist on Pluto as well. Key Words: Methane clathrate-Protosolar nebula-Terrestrial planets-Outer Solar System. Astrobiology 15, 308-326.

Analysis of Rapidly Developing Low Cloud Ceilings in a Stable Environment

NASA Technical Reports Server (NTRS)

Wheeler, Mark M.; Case, Jonathan L.

2005-01-01

This report describes the work done by the Applied Meteorology Unit (AMU) in developing a database of days that experienced rapid (< 90 minutes) low cloud formation in a stable atmosphere, resulting in ceilings at the Shuttle Landing Facility (TTS) that violated Space Shuttle Flight Rules (FR). The meteorological conditions favoring the rapid formation of low ceilings include the presence of any inversion below 8000 ft, high relative humidity beneath the inversion, and a clockwise turning of the winds from the surface to the middle troposphere (approx. 15000 ft). The AMU compared and contrasted the atmospheric and thermodynamic conditions between days with rapid low ceiling formation and days with low ceiling resulting from other mechanism. The AMU found that the vertical wind profile is the probable discerning factor between the rapidly-forming ceiling days and other low ceiling days at TTS. Most rapidly-developing low ceiling days had a clockwise turning of the winds with height, whereas other low ceiling days typically had a counter-clockwise turning of the winds with height or negligible vertical wind shear. Forecasters at the Space Meteorology Group (SMG) issue 30 to 90 minute forecasts for low cloud ceilings at TTS to support Space Shuttle landings. Mission verification statistics have shown ceilings to be the number one forecast challenge. More specifically, forecasters at SMG are concerned with any rapidly developing clouds ceilings below 8000 ft in a stable, capped thermodynamic environment, Therefore, the AMU was tasked to examine archived events of rapid stable cloud formation resulting in ceilings below 8000 ft, and document the atmospheric regimes favoring this type of cloud development. The AMU examined the cool season months of November to March during the years of 1993-2003 for days that had low-level inversions and rapid, stable low cloud formation that resulted in ceilings violating the Space Shuttle FR. The AMU wrote and modified existing code to identify inversions from the morning Cape Canaveral, FL rawinsonde (XMR) during the cool season and output pertinent sounding information. They parsed all days with cloud ceilings below 8000 ft at TTS, forming a database of possible rapidly-developing low ceiling events. Days with precipitation or noticeable fog bum-off situations were excluded from the database. Only the daytime hours were examined for possible ceiling development events since low clouds are easier to diagnose with visible satellite imagery. Follow-on work would expand the database to include nighttime cases, using a special enhancement of the infrared imagery for identifying areas of low clouds. The report presents two sample cases of rapidly-developing low cloud ceilings. These cases depict the representative meteorological and thermodynamic characteristics of such events. The cases also illustrate how quickly the cloud decks can develop, sometimes forming in 30 minutes or less. The report also summarizes the composite meteorological conditions for 20 event days with rapid low cloud ceiling formation and 48 non-events days consisting of advection or widespread low cloud ceilings. The meteorological conditions were quite similar for both the event and non-event days, since both types of days experienced low cloud ceilings. Both types of days had a relatively moist environment beneath the inversion based below 8000 ft. In the 20 events identified, de onset of low ceilings occurred between 1200-1800 UTC in every instance. The distinguishing factor between the event and non-event days appears to be the vertical wind profile in the XMR sounding. Eighty-five percent of the event days had a clockwise turning of the winds with height in the lower to middle troposphere whereas 83% of the non-events had a counter-clockwise turning of the winds with height or negligible vertical wind shear. A clockwise turning of the winds with height indicates a warm advection regime, which supports large-scale rising motn and possible cloud formation. Meanwhile, a counter-clockwise turning of the winds with height indicates cold advection or sinking motion in a post-cold frontal environment.

Stable Low Cloud Phase II: Nocturnal Event Study

NASA Technical Reports Server (NTRS)

Bauman, William H., III; Barrett, Joe, III

2007-01-01

This report describes the work done by the Applied Meteorology Unit (AMU) in developing a database of nights that experienced rapid (< 90 minutes) low cloud formation in a stable atmosphere, resulting in ceilings at the Shuttle Landing Facility (TTS) that violated Space Shuttle Flight Rules (FR). This work is the second phase of a similar AMU task that examined the same phenomena during the day. In the first phase of this work, the meteorological conditions favoring the rapid formation of low ceilings include the presence of any inversion below 8000 ft, high relative humidity (RH) beneath the inversion and a clockwise turning of the winds from the surface to the middle troposphere (-15000 ft). The AMU compared and contrasted the atmospheric and thermodynamic conditions between nights with rapid low ceiling formation and nights with low ceilings resulting from other mechanisms. The AMU found that there was little to discern between the rapidly-forming ceiling nights and other low ceiling nights at TTS. When a rapid development occurred, the average RH below the inversions was 87% while non-events had an average RH of 79%. One key parameter appeared to be the vertical wind profile in the Cape Canaveral, FL radiosonde (XMR) sounding. Eighty-three percent of the rapid development events had veering winds with height from the surface to the middle troposphere (-15,000 ft) while 61% of the non-events had veering winds with height. Veering winds indicate a warm-advection regime, which supports large-scale rising motion and ultimately cloud formation in a moist environment. However, only six of the nights (out of 86 events examined) with low cloud ceilings had an occurrence of rapidly developing ceilings. Since only 7% rapid development events were observed in this dataset, it is likely that rapid low cloud development is not a common occurrence during the night, or at least not as common as during the day. In the AMU work on the daytime rapid low cloud development (Case and Wheeler 2005), nearly 30% of the low cloud ceiling cases investigated were identified as rapidly developing events. Forecasters at the Space Meteorology Group (SMG) issue 30 to 90 minute forecasts for low cloud ceilings at TTS to support Space Shuttle landings. Mission verification statistics have shown ceilings to be the number one forecast challenge. More specifically, forecasters at SMG are concerned with any rapidly developing clouds/ceilings below 8000 R in a stable, capped thermodynamic environment. Therefore, the AMU was tasked to examine archived events of rapid stable cloud formation resulting in ceilings below 8000 ft, and document the atmospheric regimes favoring this type of cloud development. The AMU examined the cool season months of November to March during the years of 1994-2005 for nights that had low-level inversions and rapid, stable low cloud formation that resulted in ceilings violating the Space Shuttle FR. The AMU wrote and modified existing code to identify inversions from the evening and morning XMR radiosonde during the cool season and output pertinent sounding information. They parsed all days with cloud ceilings below 8000 ft at TTS, forming a database of possible rapidly-developing low ceiling events. Nights with precipitation or noticeable fog burn-off situations were excluded from the database. Only the nighttime hours were examined for possible ceiling development events since the daytime events were examined in the first phase of this work. The report presents one sample case of rapidly-developing low cloud ceilings. The case depicts the representative meteorological and thermodynamic characteristics of such events. The case also illustrates how quickly the cloud decks can develop, sometimes forming in 30 minutes or less. The report also summarizes the composite meteorological conditions for 6 event nights with rapid low cloud ceiling formation and 80 non-events nights consisting of advection or widespread low cloud ceilings. The teorological conditions were quite similar for both the event and non-event nights, since both types of nights experienced low cloud ceilings. Both types of nights had a relatively moist environment beneath an inversion based below 8000 ft.

A thermodynamically consistent model of the post-translational Kai circadian clock

PubMed Central

Lubensky, David K.; ten Wolde, Pieter Rein

2017-01-01

The principal pacemaker of the circadian clock of the cyanobacterium S. elongatus is a protein phosphorylation cycle consisting of three proteins, KaiA, KaiB and KaiC. KaiC forms a homohexamer, with each monomer consisting of two domains, CI and CII. Both domains can bind and hydrolyze ATP, but only the CII domain can be phosphorylated, at two residues, in a well-defined sequence. While this system has been studied extensively, how the clock is driven thermodynamically has remained elusive. Inspired by recent experimental observations and building on ideas from previous mathematical models, we present a new, thermodynamically consistent, statistical-mechanical model of the clock. At its heart are two main ideas: i) ATP hydrolysis in the CI domain provides the thermodynamic driving force for the clock, switching KaiC between an active conformational state in which its phosphorylation level tends to rise and an inactive one in which it tends to fall; ii) phosphorylation of the CII domain provides the timer for the hydrolysis in the CI domain. The model also naturally explains how KaiA, by acting as a nucleotide exchange factor, can stimulate phosphorylation of KaiC, and how the differential affinity of KaiA for the different KaiC phosphoforms generates the characteristic temporal order of KaiC phosphorylation. As the phosphorylation level in the CII domain rises, the release of ADP from CI slows down, making the inactive conformational state of KaiC more stable. In the inactive state, KaiC binds KaiB, which not only stabilizes this state further, but also leads to the sequestration of KaiA, and hence to KaiC dephosphorylation. Using a dedicated kinetic Monte Carlo algorithm, which makes it possible to efficiently simulate this system consisting of more than a billion reactions, we show that the model can describe a wealth of experimental data. PMID:28296888

Structural basis of light chain amyloidogenicity: comparison of the thermodynamic properties, fibrillogenic potential and tertiary structural features of four vλ6 proteins

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wall, J.S.; Gupta, V.; Wilkerson, M.

2004-04-01

Primary (AL) amyloidosis results from the pathologic deposition of monoclonal light chains as amyloid fibrils. Studies of recombinant-derived variable region (V{sub L}) fragments of these proteins have shown an inverse relationship between thermodynamic stability and fibrillogenic potential. Further, ionic interactions within the V{sub L} domain were predicted to influence the kinetics of light chain fibrillogenicity, as evidenced from our analyses of a relatively stable V{sub {lambda}}6 protein (Jto) with a long range electrostatic interaction between Asp and Arg side chains at position 29 and 68, respectively, and an unstable, highly fibrillogenic V{sub {lambda}}6 protein (Wil) that had neutral amino acidsmore » at these locations. To test this hypothesis, we have generated two Jto-related mutants designed to disrupt the interaction between Asp 29 and Arg 68 (JtoD29A and JtoR68S). Although the thermodynamic stabilities of unfolding for these two molecules were identical, they exhibited very different kinetics of fibril formation: the rate of JtoD29A fibrillogenesis was slow and comparable to the parent molecule, whereas that of JtoR68S was significantly faster. High-resolution X-ray diffraction analyses of crystals prepared from the two mutants having the same space group and unit cell dimensions revealed no significant main-chain conformational changes. However, several notable side-chain alterations were observed in JtoR68S, as compared with JtoD29A, that resulted in the solvent exposure of a greater hydrophobic surface and modifications in the electrostatic potential surface. We posit that these differences contributed to the enhanced fibrillogenic potential of the Arg 68 mutant, since both Jto mutants lacked the intrachain ionic interaction and were equivalently unstable. The information gleaned from our studies has provided insight into structural parameters that in addition to overall thermodynamic stability, contribute to the fibril forming propensity of immunoglobulin light chains.« less

Unfolding thermodynamics of intramolecular G-quadruplexes: base sequence contributions of the loops.

PubMed

Olsen, Chris M; Lee, Hui-Ting; Marky, Luis A

2009-03-05

G-quadruplexes are a highly studied DNA motif with a potential role in a variety of cellular processes and more recently are considered novel targets for drug therapy in aging and anticancer research. In this work, we have investigated the thermodynamic contributions of the loops on the stable formation of G-quadruplexes. Specifically, we use a combination of UV, circular dichroism (CD) and fluorescence spectroscopies, and differential scanning calorimetry (DSC) to determine thermodynamic profiles, including the differential binding of ions and water, for the unfolding of the thrombin aptamer: d(GGT2GGTGTGGT2GG) that is referred to as G2. The sequences in italics, TGT and T2, are known to form loops. Other sequences examined contained base substitutions in the TGT loop (TAT, TCT, TTT, TAPT, and UUU), in the T2 loops (T4, U2), or in both loops (UGU and U2, UUU and U2). The CD spectra of all molecules show a positive band centered at 292 nm, which corresponds to the "chair" conformation. The UV and DSC melting curves of each G-quadruplex show monophasic transitions with transition temperatures (T(M)s) that remained constant with increasing strand concentration, confirming their intramolecular formation. These G-quadruplexes unfold with T(M)s in the range from 43.2 to 56.5 degrees C and endothermic enthalpies from 22.9 to 37.2 kcal/mol. Subtracting the contribution of a G-quartet stack from each experimental profile indicated that the presence of the loops stabilize each G-quadruplex by favorable enthalpy contributions, larger differential binding of K+ ions (0.1-0.6 mol K+/ mol), and a variable uptake/release of water molecules (-6 to 8 mol H2O/mol). The thermodynamic contributions for these specific base substitutions are discussed in terms of loop stacking (base-base stacking within the loops) and their hydration effects.

Air-stable magnesium nanocomposites provide rapid and high-capacity hydrogen storage without using heavy-metal catalysts

NASA Astrophysics Data System (ADS)

Jeon, Ki-Joon; Moon, Hoi Ri; Ruminski, Anne M.; Jiang, Bin; Kisielowski, Christian; Bardhan, Rizia; Urban, Jeffrey J.

2011-04-01

Hydrogen is a promising alternative energy carrier that can potentially facilitate the transition from fossil fuels to sources of clean energy because of its prominent advantages such as high energy density (142 MJ kg-1 ref. 1), great variety of potential sources (for example water, biomass, organic matter), light weight, and low environmental impact (water is the sole combustion product). However, there remains a challenge to produce a material capable of simultaneously optimizing two conflicting criteria—absorbing hydrogen strongly enough to form a stable thermodynamic state, but weakly enough to release it on-demand with a small temperature rise. Many materials under development, including metal-organic frameworks, nanoporous polymers, and other carbon-based materials, physisorb only a small amount of hydrogen (typically 1-2 wt%) at room temperature. Metal hydrides were traditionally thought to be unsuitable materials because of their high bond formation enthalpies (for example MgH2 has a ΔHf˜75 kJ mol-1), thus requiring unacceptably high release temperatures resulting in low energy efficiency. However, recent theoretical calculations and metal-catalysed thin-film studies have shown that microstructuring of these materials can enhance the kinetics by decreasing diffusion path lengths for hydrogen and decreasing the required thickness of the poorly permeable hydride layer that forms during absorption. Here, we report the synthesis of an air-stable composite material that consists of metallic Mg nanocrystals (NCs) in a gas-barrier polymer matrix that enables both the storage of a high density of hydrogen (up to 6 wt% of Mg, 4 wt% for the composite) and rapid kinetics (loading in <30 min at 200 °C). Moreover, nanostructuring of the Mg provides rapid storage kinetics without using expensive heavy-metal catalysts.

Analysis of Rapidly Developing Low Cloud Ceilings in a Stable Environment

NASA Technical Reports Server (NTRS)

Bauman, William H., III; Barrett, Joe H., III; Case, Jonathan L.; Wheeler, Mark M.; Baggett, G. Wayne

2006-01-01

Forecasters at the Space Meteorology Group (SMG) issue 30 to 90 minute forecasts for low cloud ceilings at the Space Shuttle Landing Facility (TTS) to support Space Shuttle landings. Mission verification statistics have shown ceilings to be the number one forecast challenge for SMG. More specifically, forecasters at SMG are concerned with any rapidly developing clouds/ceilings below 8000 ft in a stable, capped thermodynamic environment. Therefore, the Applied Meteorology Unit (AMU) was tasked to examine archived events of rapid stable cloud formation resulting in ceilings below 8000 ft, and document the atmospheric regimes favoring this type of cloud development. The AMU examined the cool season months of November to March during the years of 1993-2003 for days that had low-level inversions and rapid, stable low cloud formation that resulted in ceilings violating the Space Shuttle Flight Rules. The AMU wrote and modified existing code to identify inversions from the morning (-10 UTC) Cape Canaveral, FL rawinsonde (XMR) during the cool season and output pertinent sounding information. They parsed all days with cloud ceilings below 8000 ft at TTS, forming a database of possible rapidly-developing low ceiling events. Days with precipitation or noticeable fog burn-off situations were excluded from the database. In the first phase of this work, only the daytime hours were examined for possible ceiling development events since low clouds are easier to diagnose with visible satellite imagery. Phase II of this work includes expanding the database to include nighttime cases which is underway as this abstract is being written. For the nighttime cases, the AMU will analyze both the 00 UTC soundings and the 10 UTC soundings to examine those data for the presence of a low-level inversion. The 00 UTC soundings will probably not have a surface-based inversion, but the presence of inversions or "neutral" layers aloft and below 8,000 ft will most likely help define the stable regime, being a thermodynamically "capped" environment. Occurrences of elevated low-level inversions or stable layers will be highlighted in conjunction with nights that experienced a possible development or onset of cloud ceilings below 8,000 ft. Using these criteria to narrow down the database, the AMU will then use archived IR satellite imagery for these possible events. This presentation summarizes the composite meteorological conditions for 20 daytime event days with rapid low cloud ceiling formation and 48 non-events days consisting of advection or widespread low cloud ceilings and describes two sample cases of daytime rapidly-developing low cloud ceilings. The authors will also summarize the work from the nighttime cases and describe a representative sample case from this data set.

Studies on self-nanoemulsifying drug delivery system of flurbiprofen employing long, medium and short chain triglycerides.

PubMed

Daar, Junaid; Khan, Ahmad; Khan, Jallat; Khan, Amjad; Khan, Gul Majid

2017-03-01

The aim of the study was to successfully design, formulate and evaluate self-nanoemulsifying drug delivery system (SNEDDS) of poorly aqueous soluble drug viz. flurbiprofen using long (LCT), medium (MCT) and short chain triglycerides (SCT). The SNEDDS are thermodynamically stable lipid based drug delivery systems which consist of mixture of oil, surfactant and co-surfactant. Upon aqueous dilution, this mixture produces nano-emulsion spontaneously on slight agitation. The excipients intended to be used were screened for their potential to dissolve the drug and to form clear dispersion upon aqueous dilution. Labrafil M 1944 CS, capryol-90 and triacetin were selected as long, medium and short chain triglycerides, respectively, as lipids while tween-80 and polyethylene glycol-400 (PEG-400)/ethanol (3:1 ratio) were selected as surfactant and co-surfactant, respectively. The excipients were studied at every possible combination ratios using pseudo-ternary diagram. The LCT, MCT and SCT-SNEDDS were optimized using thermodynamic studies, percentage transmittance value, viscosity, refractive index (RI), electrical conductivity, globule size analysis and in-vitro drug release studies. The drug release profiles of optimized SNEDDS were then compared with market product at different pH mediums. The LCT-SNEDDS was considered to be superior for enhancement of the drug bioavailability when compared with other SNEDDS formulations and market product.

Molecular dynamics simulations on interaction between bacterial proteins: Implication on pathogenic activities.

PubMed

Mondal, Manas; Chakrabarti, Jaydeb; Ghosh, Mahua

2018-03-01

We perform molecular dynamics simulation studies on interaction between bacterial proteins: an outer-membrane protein STY3179 and a yfdX protein STY3178 of Salmonella Typhi. STY3179 has been found to be involved in bacterial adhesion and invasion. STY3178 is recently biophysically characterized. It is a soluble protein having antibiotic binding and chaperon activity capabilities. These two proteins co-occur and are from neighboring gene in Salmonella Typhi-occurrence of homologs of both STY3178 and STY3179 are identified in many Gram-negative bacteria. We show using homology modeling, docking followed by molecular dynamics simulation that they can form a stable complex. STY3178 belongs to aqueous phase, while the beta barrel portion of STY3179 remains buried in DPPC bilayer with extra-cellular loops exposed to water. To understand the molecular basis of interaction between STY3178 and STY3179, we compute the conformational thermodynamics which indicate that these two proteins interact through polar and acidic residues belonging to their interfacial region. Conformational thermodynamics results further reveal instability of certain residues in extra-cellular loops of STY3179 upon complexation with STY3178 which is an indication for binding with host cell protein laminin. © 2017 Wiley Periodicals, Inc.

Thermodynamic consideration and ground-state search of icosahedral boron subselenide B12(B1-xSex) 2 from a first-principles cluster expansion

NASA Astrophysics Data System (ADS)

Ektarawong, A.

2018-05-01

The phase stability of icosahedral boron subselenide B12(B1-xSex) 2 , where 0.5 ≤x ≤1 , is explored using a first-principles cluster expansion. The results shows that, instead of a continuous solid solution, B12(B1-xSex) 2 is thermodynamically stable as an individual line compound at the composition of B9.5Se . The ground-state configuration of B9.5Se is represented by a mixture of B12(Se-Se), B12(B-Se), and B12(Se-B) with a ratio of 1:1:1, where they form a periodic A B C A B C ⋯ stacking sequence of B12(Se-Se), B12(B-Se), and B12(Se-B) layers along the c axis of the hexagonal conventional unit cell. The structural and electronic properties of the ground-state B9.5Se are also derived and discussed. By comparing the derived ground-state properties of B9.5Se to the existing experimental data of boron subselenide B˜13Se , I proposed that the as-synthesized boron subselenide B˜13Se , as reported in the literature, has the actual composition of B9.5Se .

Understanding the true shape of Au-catalyzed GaAs nanowires.

PubMed

Jiang, Nian; Wong-Leung, Jennifer; Joyce, Hannah J; Gao, Qiang; Tan, Hark Hoe; Jagadish, Chennupati

2014-10-08

With increasing interest in nanowire-based devices, a thorough understanding of the nanowire shape is required to gain tight control of the quality of nanowire heterostructures and improve the performance of related devices. We present a systematic study of the sidewalls of Au-catalyzed GaAs nanowires by investigating the faceting process from the beginning with vapor-liquid-solid (VLS) nucleation, followed by the simultaneous radial growth on the sidewalls, and to the end with sidewall transformation during annealing. The VLS nucleation interface of our GaAs nanowires is revealed by examining cross sections of the nanowire, where the nanowire exhibits a Reuleaux triangular shape with three curved surfaces along {112}A. These curved surfaces are not thermodynamically stable and adopt {112}A facets during radial growth. We observe clear differences in radial growth rate between the ⟨112⟩A and ⟨112⟩B directions with {112}B facets forming due to the slower radial growth rate along ⟨112⟩B directions. These sidewalls transform to {110} facets after high temperature (>500 °C) annealing. A nucleation model is proposed to explain the origin of the Reuleaux triangular shape of the nanowires, and the sidewall evolution is explained by surface kinetic and thermodynamic limitations.

Leaching of lead by ammonium salts and EDTA from Salvinia minima biomass produced during aquatic phytoremediation.

PubMed

Núñez-López, Roberto Aurelio; Meas, Yunny; Gama, Silvia Citlalli; Borges, Raúl Ortega; Olguín, Eugenia J

2008-06-15

Plant biomass harvested after heavy-metal phytoremediation must be considered as a hazardous waste that should be contained or treated appropriately before disposal or reuse. As a potential method to detoxify the biomass and to convert this material to a suitable fertilizer or mulch, leaching of lead (Pb) from Salvinia minima biomass was studied by testing water, several aqueous ammonium salts, and EDTA solution as lead extractants. The research was carried out in two phases: (i) a leaching study to determine the lead-extraction efficiency of the different leachants, and (ii) a thermodynamic analysis to identify the likely reactions and stable Pb(II) species formed in the leaching systems of the most efficient leachants. Experimentally, lead concentrations measured in leached biomass and in leachates were significantly different among the various leachants. It was determined that the extraction strength of the leachants followed the order: EDTA>ammonium oxalate>water approximately ammonium nitrate>ammonium acetate, achieving Pb extraction efficiencies of 99%, 70%, 7.2%, 6.9% and 1.3%, respectively, in single-stage extractions. The thermodynamic study indicated that the dominant species produced by the leaching process should be the soluble species PbEDTA2- for EDTA system, and the insoluble Pb(COO)2S precipitate for the oxalate system.

Dimerization of the keto tautomer of acetohydroxamic acid—infrared matrix isolation and theoretical study

NASA Astrophysics Data System (ADS)

Sałdyka, Magdalena; Mielke, Zofia

2005-05-01

Dimerization of the keto tautomer of acetohydroxamic acid has been studied using FTIR matrix isolation spectroscopy and DFT(B3LYP)/6-31+G(d,p) calculations. Analysis of CH 3CONHOH/Ar matrix spectra indicates formation of two dimers in which two intramolecular CO···H sbnd ON bonds within two interacting acetohydroxamic acid molecules are retained. A chain dimer I is stabilized by the intermolecular CO···H sbnd N hydrogen bond, whereas the cyclic dimer II is stabilized by two intermolecular N sbnd H···O(H)N bonds. Twelve vibrations were identified for dimer I and six vibrations for dimer II; the observed frequency shifts show a good agreement with the calculated ones for the structures I and II. Both dimers have comparable binding energies ( ΔEZPECPI, II = -7.02, -6.34 kcal mol -1) being less stable than calculated structures III and IV ( ΔEZPECPIII, IV = -9.50, -8.87 kcal mol -1) in which one or two intramolecular hydrogen bonds are disrupted. In the most stable 10-membered cyclic dimer III, two intermolecular CO···H sbnd ON hydrogen bonds are formed at expense of intramolecular hydrogen bonds of the same type. The formation of the less stable (AHA) 2 dimers in the studied matrixes indicates that the formation of (AHA) 2 is kinetically and not thermodynamically controlled.

Sensitivity of predicted scaling and permeability in Enhanced Geothermal Systems to Thermodynamic Data and Activity Models

NASA Astrophysics Data System (ADS)

Hingerl, Ferdinand F.; Wagner, Thomas; Kulik, Dmitrii A.; Kosakowski, Georg; Driesner, Thomas; Thomsen, Kaj

2010-05-01

A consortium of research groups from ETH Zurich, EPF Lausanne, the Paul Scherrer Institut and the University of Bonn collaborates in a comprehensive program of basic research on key aspects of the Enhanced Geothermal Systems (EGSs). As part of this GEOTHERM project (www.geotherm.ethz.ch), we concentrate on the fundamental investigation of thermodynamic models suitable for describing fluid-rock interactions at geothermal conditions. Predictions of the fluid-rock interaction in EGS still face several major challenges. Slight variations in the input thermodynamic and kinetic parameters may result in significant differences in the predicted mineral solubilities and stable assemblage. Realistic modeling of mineral precipitation in turn has implications onto our understanding of the permeability evolution of the geothermal reservoir, as well as the scaling in technical installations. In order to reasonably model an EGS, thermodynamic databases and activity models must be tailored to geothermal conditions. We therefore implemented in GEMS code the Pitzer formalism, which is the standard model used for computing thermodynamic excess properties of brines at elevated temperatures and pressures. This model, however, depends on a vast amount of interaction parameters, which are to a substantial extend unknown. Furthermore, a high order polynomial temperature interpolation makes extrapolation unreliable if not impossible. As an alternative we additionally implemented the EUNIQUAC activity model. EUNIQUAC requires fewer empirical fit parameters (only binary interaction parameters needed) and uses simpler and more stable temperature and pressure extrapolations. This results in an increase in computation speed, which is of crucial importance when performing coupled long term simulations of geothermal reservoirs. To achieve better performance under geothermal conditions, we are currently partly reformulating EUNIQUAC and refitting the existing parameter set. First results of the Pitzer-EUNIQUAC benchmark applied to relevant aqueous solutions at elevated temperature, pressure and ionic strength will be presented.

Disulphide bond exchange inhibited by air - kinetic and thermodynamic products in a library of macrocyclic cysteine derivatives.

PubMed

Cholewiak, Agnieszka; Dobrzycki, Łukasz; Jurczak, Janusz; Ulatowski, Filip

2018-04-04

In this paper we present the synthesis and reactivity of dithiols comprising of two cysteine moieties attached to a dipicolinic acid core. Oxidation of these thiols provides oligomeric macrocycles. Monomers with 13-membered rings are kinetic products which are, however, strained and readily transform into higher oligomers under basic conditions or elevated temperature via a disulphide exchange reaction. Dimers, which are the most stable thermodynamic products, equilibrate only under inert conditions with thiolate as a catalyst. Under aerobic conditions, the thiols are oxidised before the equilibrium is reached.

Mean-field potential approach for thermodynamic properties of lanthanide: Europium as a prototype

NASA Astrophysics Data System (ADS)

Kumar, Priyank; Bhatt, N. K.; Vyas, P. R.; Gohel, V. B.

2018-03-01

In the present paper, a simple conjunction scheme [mean-field potential (MFP) + local pseudopotential] is used to study the thermodynamic properties of divalent lanthanide europium (Eu) at extreme environment. Present study has been carried out due to the fact that divalent nature of Eu arises because of stable half-filled 4f-shell at ambient condition, which has great influence on the thermodynamic properties at extreme environment. Due to such electronic structure, it is different from remaining lanthanides having incomplete 4f-shell. The presently computed results of thermodynamic properties of Eu are in good agreement with the experimental results. Looking to such success, it seems that the concept of MFP approach is successful to account contribution due to nuclear motion to the total Helmholtz free energy at finite temperatures and pressure-induced inter-band transfer of electrons for condensed state of matter. The local pseudopotential is used to evaluate cold energy and hence MFP accounts the s-p-d-f hybridization properly. Looking to the reliability and transferability along with its computational and conceptual simplicity, we would like to extend the present scheme for the study of thermodynamic properties of remaining lanthanides and actinides at extreme environment.

Quantum thermodynamics of nanoscale steady states far from equilibrium

NASA Astrophysics Data System (ADS)

Taniguchi, Nobuhiko

2018-04-01

We develop an exact quantum thermodynamic description for a noninteracting nanoscale steady state that couples strongly with multiple reservoirs. We demonstrate that there exists a steady-state extension of the thermodynamic function that correctly accounts for the multiterminal Landauer-Büttiker formula of quantum transport of charge, energy, or heat via the nonequilibrium thermodynamic relations. Its explicit form is obtained for a single bosonic or fermionic level in the wide-band limit, and corresponding thermodynamic forces (affinities) are identified. Nonlinear generalization of the Onsager reciprocity relations are derived. We suggest that the steady-state thermodynamic function is also capable of characterizing the heat current fluctuations of the critical transport where the thermal fluctuations dominate. Also, the suggested nonequilibrium steady-state thermodynamic relations seemingly persist for a spin-degenerate single level with local interaction.

Gibbs free energy of reactions involving SiC, Si3N4, H2, and H2O as a function of temperature and pressure

NASA Technical Reports Server (NTRS)

Isham, M. A.

1992-01-01

Silicon carbide and silicon nitride are considered for application as structural materials and coating in advanced propulsion systems including nuclear thermal. Three-dimensional Gibbs free energy were constructed for reactions involving these materials in H2 and H2/H2O. Free energy plots are functions of temperature and pressure. Calculations used the definition of Gibbs free energy where the spontaneity of reactions is calculated as a function of temperature and pressure. Silicon carbide decomposes to Si and CH4 in pure H2 and forms a SiO2 scale in a wet atmosphere. Silicon nitride remains stable under all conditions. There was no apparent difference in reaction thermodynamics between ideal and Van der Waals treatment of gaseous species.

Attaching Be or Mg to BH3 results in the formation of BeBH3 and MgBH3 molecules capable of forming stable anions

NASA Astrophysics Data System (ADS)

Anusiewicz, Iwona; Skurski, Piotr

2018-04-01

Stability of BeBH3 and MgBH3 molecules and their (BeBH3)- and (MgBH3)- anions is investigated on the basis of correlated ab initio calculations. The electronic and thermodynamic stability of all species is confirmed by estimating the excess electron binding energies of the anions and by evaluating the Gibbs free energies for various fragmentation paths. The bonding effects in BeBH3 and MgBH3 have been identified as the result of alkaline earth metal ns2 lone-pair donation to the empty 2p boron orbital. Adiabatic and vertical electronic stabilities of the (BeBH3)- and (MgBH3)- anions were found to span 1.114-1.301 and 0.675-0.744 eV range, respectively.

Design for Oxidation Resistance

NASA Technical Reports Server (NTRS)

Smialek, James L.; Schaeffer, Jon C.; Barrett, Charles A.

1997-01-01

Alloys intended for use in high-temperature environment rely on the formation of a continuous, compact, slow-growing oxide layer for oxidation and hot corrosion resistance. To be protective, this oxide layer must be chemically, thermodynamically stable. Successful alloy design for oxidative environment is best achieved by developing alloys that are capable of forming adherent scales of either alumina (Al2O3), chromia (Cr2O3), or silica (SiO2). In this article, emphasis has been placed on the issue related to high-temperature oxidation of superalloys used in gas turbine engine application. Despite the complexity of these alloys, optimal performance has been associated with protective alumina scale formation. As will be described below, both compositional makeup and protective coatings play key role in providing oxidation protection. Other high-temperature materials described include nickel and titanium aluminide intermetallics, refractory metal, and ceramics.

Canonical fluid thermodynamics

NASA Technical Reports Server (NTRS)

Schmid, L. A.

1972-01-01

The space-time integral of the thermodynamic pressure plays the role of the thermodynamic potential for compressible, adiabatic flow in the sense that the pressure integral for stable flow is less than for all slightly different flows. This stability criterion can be converted into a variational minimum principle by requiring the molar free-enthalpy and the temperature, which are the arguments of the pressure function, to be generalized velocities, that is, the proper-time derivatives of scalar spare-time functions which are generalized coordinates in the canonical formalism. In a fluid context, proper-time differentiation must be expressed in terms of three independent quantities that specify the fluid velocity. This can be done in several ways, all of which lead to different variants (canonical transformations) of the same constraint-free action integral whose Euler-Lagrange equations are just the well-known equations of motion for adiabatic compressible flow.

Wafer-scale Thermodynamically Stable GaN Nanorods via Two-Step Self-Limiting Epitaxy for Optoelectronic Applications

NASA Astrophysics Data System (ADS)

Kum, Hyun; Seong, Han-Kyu; Lim, Wantae; Chun, Daemyung; Kim, Young-Il; Park, Youngsoo; Yoo, Geonwook

2017-01-01

We present a method of epitaxially growing thermodynamically stable gallium nitride (GaN) nanorods via metal-organic chemical vapor deposition (MOCVD) by invoking a two-step self-limited growth (TSSLG) mechanism. This allows for growth of nanorods with excellent geometrical uniformity with no visible extended defects over a 100 mm sapphire (Al2O3) wafer. An ex-situ study of the growth morphology as a function of growth time for the two self-limiting steps elucidate the growth dynamics, which show that formation of an Ehrlich-Schwoebel barrier and preferential growth in the c-plane direction governs the growth process. This process allows monolithic formation of dimensionally uniform nanowires on templates with varying filling matrix patterns for a variety of novel electronic and optoelectronic applications. A color tunable phosphor-free white light LED with a coaxial architecture is fabricated as a demonstration of the applicability of these nanorods grown by TSSLG.

Retained austenite thermal stability in a nanostructured bainitic steel

DOE Office of Scientific and Technical Information (OSTI.GOV)

Avishan, Behzad, E-mail: b_avishan@sut.ac.ir; Garcia-Mateo, Carlos, E-mail: cgm@cenim.csic.es; Yazdani, Sasan, E-mail: yazdani@sut.ac.ir

2013-07-15

The unique microstructure of nanostructured bainite consists of very slender bainitic ferrite plates and high carbon retained austenite films. As a consequence, the reported properties are opening a wide range of different commercial uses. However, bainitic transformation follows the T{sub 0} criteria, i.e. the incomplete reaction phenomena, which means that the microstructure is not thermodynamically stable because the bainitic transformation stops well before austenite reaches an equilibrium carbon level. This article aims to study the different microstructural changes taking place when nanostructured bainite is destabilized by austempering for times well in excess of that strictly necessary to end the transformation.more » Results indicate that while bainitic ferrite seems unaware of the extended heat treatment, retained austenite exhibits a more receptive behavior to it. - Highlights: • Nanostructured bainitic steel is not thermodynamically stable. • Extensive austempering in these microstructures has not been reported before. • Precipitation of cementite particles is unavoidable at longer austempering times. • TEM, FEG-SEM and XRD analysis were used for microstructural characterization.« less

Role of Boron Element on the Electronic Properties of α-Nb5Si3: A First-Principle Study

NASA Astrophysics Data System (ADS)

Pan, Yong; Lin, Yuanhua

2018-03-01

Transition metal silicides (TMSis) are attracting increasing interest from the microelectronics and nanoelectronic industries. In this paper, we use the first-principles method to investigate the B-doped mechanism and the influence of B on the electronic properties of α-Nb5Si3. The calculated results show that B-doped Nb5Si3 is thermodynamically stable at the ground state. The calculated electronic structure shows that the thermodynamically stable B-doped Nb5Si3 is attributed to the 3D-network B-Si bonds and B-Nb bond. In particular, B element prefers to occupy B -IT4 site in comparison to other sites. Moreover, the calculated band structure indicates that Nb5Si3 exhibits metallic behavior at the ground state. We find that B-doping can improve charge overlap between conduction band and the valence band, which effectively improves the electronic properties of Nb5Si3.

Full Kinetics from First Principles of the Chlorine Evolution Reaction over a RuO2 (110) Model Electrode.

PubMed

Exner, Kai S; Anton, Josef; Jacob, Timo; Over, Herbert

2016-06-20

Current progress in modern electrocatalysis research is spurred by theory, frequently based on ab initio thermodynamics, where the stable reaction intermediates at the electrode surface are identified, while the actual energy barriers are ignored. This approach is popular in that a simple tool is available for searching for promising electrode materials. However, thermodynamics alone may be misleading to assess the catalytic activity of an electrochemical reaction as we exemplify with the chlorine evolution reaction (CER) over a RuO2 (110) model electrode. The full procedure is introduced, starting from the stable reaction intermediates, computing the energy barriers, and finally performing microkinetic simulations, all performed under the influence of the solvent and the electrode potential. Full kinetics from first-principles allows the rate-determining step in the CER to be identified and the experimentally observed change in the Tafel slope to be explained. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thermodynamic, crystallographic, and dielectric study of the nature of glass transitions in cyclo-octanol

NASA Astrophysics Data System (ADS)

Puertas, Ricardo; Rute, Maria A.; Salud, Josep; López, David O.; Diez, Sergio; van Miltenburg, J. Kees; Pardo, Luis C.; Tamarit, Josep Ll.; Barrio, Maria; Pérez-Jubindo, Miguel A.; de La Fuente, Maria R.

2004-06-01

The stable solid polymorphism of cyclooctanol (C8H16O, for short C8 OH) is revealed to be a complex problem and only two stable solid phases, denoted on cooling from the liquid as phases I and II, are found using static (thermodynamic and x-ray diffraction) as well as dynamic (dielectric spectroscopy) experimental techniques. Both solid phases are known to exhibit glass transitions if they are cooled down fast enough to prevent transition to ordered crystalline states. Although glass transitions corresponding to both phases had been well documented by means of specific heat measurements, x-ray measurements constitute, as far as we know, the first evidence from the structural point of view. In addition, a great amount of dielectric works devoted to phase I and its glass transition, were published in the past but next to nothing relating to the dielectric properties of phase II and its glass transition. The nature of the disorder of phase II will be discussed.

A thermodynamic and experimental study of the conditions of thaumasite formation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schmidt, Thomas; Lothenbach, Barbara; Romer, Michael

2008-03-15

The formation of thaumasite was investigated with the progressive equilibrium approach (PEA). This approach experimentally simulates the conditions of various levels of sulfate addition in hardened cement pastes. The influence of limestone, time, C{sub 3}A content, temperature and leaching on thaumasite formation was investigated. The results show that thaumasite formation is favoured at lower temperatures (8 deg. C) independently of the type of cement clinker (high or low C{sub 3}A content) used. Thaumasite was found to form only in systems where limestone was present and where sufficient sulfate had been added. Thaumasite precipitated only in systems where the Al presentmore » has already been consumed to form ettringite and the molar SO{sub 3}/Al{sub 2}O{sub 3} ratio exceeded 3. In leached samples (reduction of portlandite and alkalis) slightly less thaumasite was formed whereas gypsum and ettringite are favoured under these conditions. The PEA, used to investigate the chemical aspects of sulfate attack was found to be a good tool for simulating external sulfate attack. Generally, thaumasite was detected were it was modelled to be stable in significant amounts. However, in this study equilibrium conditions were not reached after 9 months.« less

A divalent rare earth oxide semiconductor: Yttrium monoxide

NASA Astrophysics Data System (ADS)

Kaminaga, Kenichi; Sei, Ryosuke; Hayashi, Kouichi; Happo, Naohisa; Tajiri, Hiroo; Oka, Daichi; Fukumura, Tomoteru; Hasegawa, Tetsuya

Rare earth sesquioxides like Y2O3 are known as widegap insulators with the highly stable closed shell trivalent rare earth ions. On the other hand, rare earth monoxides such as YO have been recognized as gaseous phase, and only EuO and YbO were thermodynamically stable solid-phase rock salt monoxides. In this study, solid-phase rock salt yttrium monoxide, YO, was synthesized in a form of epitaxial thin film by pulsed laser deposition method. YO possesses unusual valence of Y2+ ([Kr] 4d1) . In contrast with Y2O3, YO was narrow gap semiconductor with dark-brown color. The electrical conductivity was tunable from 10-1 to 103 Ω-1 cm-1 by introducing oxygen vacancies as electron donor. Weak antilocalization behavior was observed indicating significant spin-orbit coupling owing to 4 d electron carrier. The absorption spectral shape implies the Mott-Hubbard insulator character of YO. Rare earth monoixdes will be new platform of functional oxides. This work was supported by JST-CREST, the Japan Society for the Promotion of Science (JSPS) with Grant-in-Aid for Scientific Research on Innovative Areas (Nos. 26105002 and 26105006), and Nanotechnology Platform (Project No.12024046) of MEXT, Japan.

The thermal stability of the nanograin structure in a weak solute segregation system.

PubMed

Tang, Fawei; Song, Xiaoyan; Wang, Haibin; Liu, Xuemei; Nie, Zuoren

2017-02-08

A hybrid model that combines first principles calculations and thermodynamic evaluation was developed to describe the thermal stability of a nanocrystalline solid solution with weak segregation. The dependence of the solute segregation behavior on the electronic structure, solute concentration, grain size and temperature was demonstrated, using the nanocrystalline Cu-Zn system as an example. The modeling results show that the segregation energy changes with the solute concentration in a form of nonmonotonic function. The change in the total Gibbs free energy indicates that at a constant solute concentration and a given temperature, a nanocrystalline structure can remain stable when the initial grain size is controlled in a critical range. In experiments, dense nanocrystalline Cu-Zn alloy bulk was prepared, and a series of annealing experiments were performed to examine the thermal stability of the nanograins. The experimental measurements confirmed the model predictions that with a certain solute concentration, a state of steady nanograin growth can be achieved at high temperatures when the initial grain size is controlled in a critical range. The present work proposes that in weak solute segregation systems, the nanograin structure can be kept thermally stable by adjusting the solute concentration and initial grain size.

Ground state structure of high-energy-density polymeric carbon monoxide

NASA Astrophysics Data System (ADS)

Xia, Kang; Sun, Jian; Pickard, Chris J.; Klug, Dennis D.; Needs, Richard J.

2017-04-01

Crystal structure prediction methods and first-principles calculations have been used to explore low-energy structures of carbon monoxide (CO). Contrary to the standard wisdom, the most stable structure of CO at ambient pressure was found to be a polymeric structure of P n a 21 symmetry rather than a molecular solid. This phase is formed from six-membered (four carbon + two oxygen) rings connected by C=C double bonds with two double-bonded oxygen atoms attached to each ring. Interestingly, the polymeric P n a 21 phase of CO has a much higher energy density than trinitrotoluene (TNT). On compression to about 7 GPa, P n a 21 is found to transform into another chainlike phase of C c symmetry which has similar ring units to P n a 21 . On compression to 12 GPa, it is energetically favorable for CO to polymerize into a purely single bonded C m c a phase, which is stable over a wide pressure range and transforms into the previously known C m c m phase at around 100 GPa. Thermodynamic stability of these structures was verified using calculations with different density functionals, including hybrid and van der Waals corrected functionals.

Predicting new multicomponent materials for hydrogen storage using first-principles calculations

NASA Astrophysics Data System (ADS)

Aidhy, Dilpuneet; Wolverton, Chris

2010-03-01

Wide research has unraveled some very promising hydrogen storage materials such as metal borohydrides, amides and alanates. However, all of these materials are limited either thermodynamically or kinetically. The recent observation of mixing in these systems (e.g., borohydride-amide mixing in Li4(BH4)(NH2)3 [1] and metal mixing in NaZn2(BH4)3) [2] has demonstrated the possibility of forming new multicomponent ordered compounds that may have desirable hydrogen storage properties. However, these multicomponent systems are largely unexplored. Here, we use density functional theory (DFT) along with Monte Carlo-based crystal structure prediction methods to search for new multicomponent hydrides. We find evidence for stable compounds in the Mg(BH4)2/Mg(NH2)2 system, which have not yet been observed. In addition, we also study a wide range of mixed metal borohydride systems, and find evidence of ordered stable structures such as Li2Na(BH4)3. 1. F. E. Pinkerton, M. S. Meyer, G. P. Meisner and M. P. Balogh, J. Phys. Chem. B 110, 7967 (2006). 2. D. Ravnsbeak, Y. Filinchuk, Y. Cerenius, H. J. Jakobsen, F. Besenbacher, J. Skibsted and T. R. Jensen, Angew. Chem. 48, 6659 (2009).

On atomic mechanisms governing the oxidation of Bi2Te3.

PubMed

Music, Denis; Chang, Keke; Schmidt, Paul; Braun, Felix N; Heller, Martin; Hermsen, Steffen; Pöllmann, Peter J; Schulzendorff, Till; Wagner, Cedric

2017-11-09

Oxidation of Bi 2 Te 3 (space group R [Formula: see text] m) has been investigated using experimental and theoretical means. Based on calorimetry, x-ray photoelectron spectroscopy and thermodynamic modelling, Bi 2 Te 3 is at equilibrium with Bi 2 O 3 and TeO 2 , whereby the most stable compound is Bi 2 Te 3 , followed by Bi 2 O 3 . The reactivity of Bi towards oxygen is expected to be higher than that of Te. This notion is supported by density functional theory. The strongest bond is formed between Bi and Te, followed by Bi-O. This gives rise to unanticipated atomic processes. Dissociatively adsorbed oxygen diffuses through Bi and Te basal planes of Bi 2 Te 3 (0 0 0 1) and preferably interacts with Bi. The Te termination considerably retards this process. These findings may clarify conflicting literature data. Any basal plane off-cut or Bi terminations trigger oxidation, but a perfect basal cleavage, where only Te terminations are exposed to air, may be stable for a longer period of time. These results are of relevance for applications in which surfaces are of key importance, such as nanostructured Bi 2 Te 3 thermoelectric devices.

On atomic mechanisms governing the oxidation of Bi2Te3

NASA Astrophysics Data System (ADS)

Music, Denis; Chang, Keke; Schmidt, Paul; Braun, Felix N.; Heller, Martin; Hermsen, Steffen; Pöllmann, Peter J.; Schulzendorff, Till; Wagner, Cedric

2017-12-01

Oxidation of Bi2Te3 (space group R \\overline{3} m) has been investigated using experimental and theoretical means. Based on calorimetry, x-ray photoelectron spectroscopy and thermodynamic modelling, Bi2Te3 is at equilibrium with Bi2O3 and TeO2, whereby the most stable compound is Bi2Te3, followed by Bi2O3. The reactivity of Bi towards oxygen is expected to be higher than that of Te. This notion is supported by density functional theory. The strongest bond is formed between Bi and Te, followed by Bi-O. This gives rise to unanticipated atomic processes. Dissociatively adsorbed oxygen diffuses through Bi and Te basal planes of Bi2Te3(0 0 0 1) and preferably interacts with Bi. The Te termination considerably retards this process. These findings may clarify conflicting literature data. Any basal plane off-cut or Bi terminations trigger oxidation, but a perfect basal cleavage, where only Te terminations are exposed to air, may be stable for a longer period of time. These results are of relevance for applications in which surfaces are of key importance, such as nanostructured Bi2Te3 thermoelectric devices.

Protonation States of Homocitrate and Nearby Residues in Nitrogenase Studied by Computational Methods and Quantum Refinement.

PubMed

Cao, Lili; Caldararu, Octav; Ryde, Ulf

2017-09-07

Nitrogenase is the only enzyme that can break the triple bond in N 2 to form two molecules of ammonia. The enzyme has been thoroughly studied with both experimental and computational methods, but there is still no consensus regarding the atomic details of the reaction mechanism. In the most common form, the active site is a MoFe 7 S 9 C(homocitrate) cluster. The homocitrate ligand contains one alcohol and three carboxylate groups. In water solution, the triply deprotonated form dominates, but because the alcohol (and one of the carboxylate groups) coordinate to the Mo ion, this may change in the enzyme. We have performed a series of computational calculations with molecular dynamics (MD), quantum mechanical (QM) cluster, combined QM and molecular mechanics (QM/MM), QM/MM with Poisson-Boltzmann and surface area solvation, QM/MM thermodynamic cycle perturbations, and quantum refinement methods to settle the most probable protonation state of the homocitrate ligand in nitrogenase. The results quite conclusively point out a triply deprotonated form (net charge -3) with a proton shared between the alcohol and one of the carboxylate groups as the most stable at pH 7. Moreover, we have studied eight ionizable protein residues close to the active site with MD simulations and determined the most likely protonation states.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Khodam-Mohammadi, A.; Monshizadeh, M.

We give a review of the existence of Taub-NUT/bolt solutions in Einstein Gauss-Bonnet gravity with the parameter {alpha} in six dimensions. Although the spacetime with base space S{sup 2}xS{sup 2} has a curvature singularity at r=N, which does not admit NUT solutions, we may proceed with the same computations as in the CP{sup 2} case. The investigation of thermodynamics of NUT/bolt solutions in six dimensions is carried out. We compute the finite action, mass, entropy, and temperature of the black hole. Then the validity of the first law of thermodynamics is demonstrated. It is shown that in NUT solutions allmore » thermodynamic quantities for both base spaces are related to each other by substituting {alpha}{sup CP{sup k}}=[(k+1)/k]{alpha}{sup S{sup 2}}{sup xS{sup 2}}{sup x...S{sub k}{sup 2}}. So, no further information is given by investigating NUT solutions in the S{sup 2}xS{sup 2} case. This relation is not true for bolt solutions. A generalization of the thermodynamics of black holes to arbitrary even dimensions is made using a new method based on the Gibbs-Duhem relation and Gibbs free energy for NUT solutions. According to this method, the finite action in Einstein Gauss-Bonnet is obtained by considering the generalized finite action in Einstein gravity with an additional term as a function of {alpha}. Stability analysis is done by investigating the heat capacity and entropy in the allowed range of {alpha}, {lambda}, and N. For NUT solutions in d dimensions, there exists a stable phase at a narrow range of {alpha}. In six-dimensional bolt solutions, the metric is completely stable for B=S{sup 2}xS{sup 2} and is completely unstable for the B=CP{sup 2} case.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Myint, Philip C.; Nichols, Albert L.

In this paper, we present thermodynamic models for the five most commonly studied phases of the energetic material octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX): liquid HMX and four solid polymorphs (α-, β-, γ-, and δ-HMX). We show results for the density, heat capacity, bulk modulus, and sound speed, as well as a phase diagram that illustrates the temperature and pressure regions over which the various HMX phases are most thermodynamically stable. The models are based on the same equation of state presented in our recently published paper [Myint et al., Ind. Eng. Chem. Res., 2016, 55, 2252] on another energetic material, hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX). Wemore » combine our HMX and RDX models together so that the equation of state can also be applied to liquid and solid mixtures of HMX/RDX. This allows us to generate an HMX/RDX phase diagram and calculate the enthalpy change associated with a few different kinds of phase transitions that these mixtures may undergo. Our paper is the first to present a single equation of state that is capable of modeling both pure HMX and HMX/RDX mixtures. A distinct feature of HMX is the strongly metastable nature of its polymorphs. This has caused some ambiguity in the literature regarding the thermodynamic stability of α-HMX. Finally, by examining possible arrangements for the relative order of the six different solid-solid transition (α–β, α–γ, α–δ, β–γ, β–δ, and γ–δ) temperatures, we conclude that α-HMX must be thermodynamically stable so that the HMX phase diagram must have an α phase region.« less

Theoretical analysis of co-solvent effect on the proton transfer reaction of glycine in a water-acetonitrile mixture

NASA Astrophysics Data System (ADS)

Kasai, Yukako; Yoshida, Norio; Nakano, Haruyuki

2015-05-01

The co-solvent effect on the proton transfer reaction of glycine in a water-acetonitrile mixture was examined using the reference interaction-site model self-consistent field theory. The free energy profiles of the proton transfer reaction of glycine between the carboxyl oxygen and amino nitrogen were computed in a water-acetonitrile mixture solvent at various molar fractions. Two types of reactions, the intramolecular proton transfer and water-mediated proton transfer, were considered. In both types of the reactions, a similar tendency was observed. In the pure water solvent, the zwitterionic form, where the carboxyl oxygen is deprotonated while the amino nitrogen is protonated, is more stable than the neutral form. The reaction free energy is -10.6 kcal mol-1. On the other hand, in the pure acetonitrile solvent, glycine takes only the neutral form. The reaction free energy from the neutral to zwitterionic form gradually increases with increasing acetonitrile concentration, and in an equally mixed solvent, the zwitterionic and neutral forms are almost isoenergetic, with a difference of only 0.3 kcal mol-1. The free energy component analysis based on the thermodynamic cycle of the reaction also revealed that the free energy change of the neutral form is insensitive to the change of solvent environment but the zwitterionic form shows drastic changes. In particular, the excess chemical potential, one of the components of the solvation free energy, is dominant and contributes to the stabilization of the zwitterionic form.

First-principles study of the elastic and thermodynamic properties of thorium hydrides at high pressure

NASA Astrophysics Data System (ADS)

Xiao-Lin, Zhang; Yuan-Yuan, Wu; Xiao-Hong, Shao; Yong, Lu; Ping, Zhang

2016-05-01

The high pressure behaviors of Th4H15 and ThH2 are investigated by using the first-principles calculations based on the density functional theory (DFT). From the energy-volume relations, the bct phase of ThH2 is more stable than the fcc phase at ambient conditions. At high pressure, the bct ThH2 and bcc Th4H15 phases are more brittle than they are at ambient pressure from the calculated elastic constants and the Poisson ratio. The thermodynamic stability of the bct phase ThH2 is determined from the calculated phonon dispersion. In the pressure domain of interest, the phonon dispersions of bcc Th4H15 and bct ThH2 are positive, indicating the dynamical stability of these two phases, while the fcc ThH2 is unstable. The thermodynamic properties including the lattice vibration energy, entropy, and specific heat are predicted for these stable phases. The vibrational free energy decreases with the increase of the temperature, and the entropy and the heat capacity are proportional to the temperature and inversely proportional to the pressure. As the pressure increases, the resistance to the external pressure is strengthened for Th4H15 and ThH2. Project supported by the Long-Term Subsidy Mechanism from the Ministry of Finance and the Ministry of Education of China.

First-Principles Analysis of Defect Thermodynamics and Ion Transport in Inorganic SEI Compounds: LiF and NaF

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yildirim, Handan; Kinaci, Alper; Chan, Maria K. Y.

The formation mechanism and composition of the solid electrolyte interphase (SEI) in lithium ion batteries has been widely explored. However, relatively little is known about the function of the SEI as a transport medium. Such critical information is directly relevant to battery rate performance, power loss, and capacity fading. To partially bridge this gap in the case of inorganic SEI compounds, we report herein the results of first-principles calculations on the defect thermodynamics, the dominant diffusion carriers, and the diffusion pathways associated with crystalline LiF and NaF, which are stable components of the SEI in Li-ion and Na-ion batteries, respectively.more » The thermodynamics of common point defects are computed, and the dominant diffusion carriers are determined over a voltage range of 0-4 V, corresponding to conditions relevant to both anode and cathode SEI's. Our analyses reveal that for both compounds, vacancy defects are energetically more favorable, therefore form more readily than interstitials, due to the close-packed nature of the crystal structures. However, the vacancy concentrations are very small for the diffusion processes facilitated by defects. Ionic conductivities are calculated as a function of voltage, considering the diffusion carrier concentration and the diffusion barriers as determined by nudged elastic band calculations. These conductivities are more than ten orders of magnitude smaller in NaF than in LiF. As compared to the diffusivity of Li in other common inorganic SEI compounds, such as Li2CO3 and Li2O,the cation diffusivity in LiF and NaF is quite low, with at least three orders of magnitude lower ionic conductivities. The results quantify the extent to which fluorides pose rate limitations in Li and Na batteries.« less

Speciation of the major inorganic salts in atmospheric aerosols of Beijing, China: Measurements and comparison with model

NASA Astrophysics Data System (ADS)

Tang, Xiong; Zhang, Xiaoshan; Ci, Zhijia; Guo, Jia; Wang, Jiaqi

2016-05-01

In the winter and summer of 2013-2014, we used a sampling system, which consists of annular denuder, back-up filter and thermal desorption set-up, to measure the speciation of major inorganic salts in aerosols and the associated trace gases in Beijing. This sampling system can separate volatile ammonium salts (NH4NO3 and NH4Cl) from non-volatile ammonium salts ((NH4)2SO4), as well as the non-volatile nitrate and chloride. The measurement data was used as input of a thermodynamic equilibrium model (ISORROPIA II) to investigate the gas-aerosol equilibrium characteristics. Results show that (NH4)2SO4, NH4NO3 and NH4Cl were the major inorganic salts in aerosols and mainly existed in the fine particles. The sulfate, nitrate and chloride associated with crustal ions were also important in Beijing where mineral dust concentrations were high. About 19% of sulfate in winter and 11% of sulfate in summer were associated with crustal ions and originated from heterogeneous reactions or direct emissions. The non-volatile nitrate contributed about 33% and 15% of nitrate in winter and summer, respectively. Theoretical thermodynamic equilibrium calculations for NH4NO3 and NH4Cl suggest that the gaseous precursors were sufficient to form stable volatile ammonium salts in winter, whereas the internal mixing with sulfate and crustal species were important for the formation of volatile ammonium salts in summer. The results of the thermodynamic equilibrium model reasonably agreed with the measurements of aerosols and gases, but large discrepancy existed in predicting the speciation of inorganic ammonium salts. This indicates that the assumption on crustal species in the model was important for obtaining better understanding on gas-aerosol partitioning and improving the model prediction.

Thermodynamics and structural analysis of positive allosteric modulation of the ionotropic glutamate receptor GluA2.

PubMed

Krintel, Christian; Frydenvang, Karla; Olsen, Lars; Kristensen, Maria T; de Barrios, Oriol; Naur, Peter; Francotte, Pierre; Pirotte, Bernard; Gajhede, Michael; Kastrup, Jette S

2012-01-01

Positive allosteric modulators of the ionotropic glutamate receptor-2 (GluA2) are promising compounds for the treatment of cognitive disorders, e.g. Alzheimer's disease. These modulators bind within the dimer interface of the LBD (ligand-binding domain) and stabilize the agonist-bound conformation slowing receptor desensitization and/or deactivation. In the present study, we employ isothermal titration calorimetry to determine binding affinities and thermodynamic details of binding of modulators of GluA2. A mutant of the LBD of GluA2 (LBD-L483Y-N754S) that forms a stable dimer in solution was used. The potent GluA2 modulator BPAM-97 was used as a reference compound. Evidence that BPAM-97 binds in the same pocket as the well-known GluA2 modulator cyclothiazide was obtained from X-ray structures. The LBD-L483Y-N754S:BPAM-97 complex has a Kd of 5.6 μM (ΔH=-4.9 kcal/mol, -TΔS=-2.3 kcal/mol; where 1 kcal≈4.187 kJ). BPAM-97 was used in a displacement assay to determine a Kd of 0.46 mM (ΔH=-1.2 kcal/mol, -TΔS=-3.3 kcal/mol) for the LBD-L483Y-N754S:IDRA-21 complex. The major structural factors increasing the potency of BPAM-97 over IDRA-21 are the increased van der Waals contacts to, primarily, Met496 in GluA2 imposed by the ethyl substituent of BPAM-97. These results add important information on binding affinities and thermodynamic details, and provide a new tool in the development of drugs against cognitive disorders.

Evaluating the Energetic Driving Force for Cocrystal Formation.

PubMed

Taylor, Christopher R; Day, Graeme M

2018-02-07

We present a periodic density functional theory study of the stability of 350 organic cocrystals relative to their pure single-component structures, the largest study of cocrystals yet performed with high-level computational methods. Our calculations demonstrate that cocrystals are on average 8 kJ mol -1 more stable than their constituent single-component structures and are very rarely (<5% of cases) less stable; cocrystallization is almost always a thermodynamically favorable process. We consider the variation in stability between different categories of systems-hydrogen-bonded, halogen-bonded, and weakly bound cocrystals-finding that, contrary to chemical intuition, the presence of hydrogen or halogen bond interactions is not necessarily a good predictor of stability. Finally, we investigate the correlation of the relative stability with simple chemical descriptors: changes in packing efficiency and hydrogen bond strength. We find some broad qualitative agreement with chemical intuition-more densely packed cocrystals with stronger hydrogen bonding tend to be more stable-but the relationship is weak, suggesting that such simple descriptors do not capture the complex balance of interactions driving cocrystallization. Our conclusions suggest that while cocrystallization is often a thermodynamically favorable process, it remains difficult to formulate general rules to guide synthesis, highlighting the continued importance of high-level computation in predicting and rationalizing such systems.

Freezing Transition Studies Through Constrained Cell Model Simulation

NASA Astrophysics Data System (ADS)

Nayhouse, Michael; Kwon, Joseph Sang-Il; Heng, Vincent R.; Amlani, Ankur M.; Orkoulas, G.

2014-10-01

In the present work, a simulation method based on cell models is used to deduce the fluid-solid transition of a system of particles that interact via a pair potential, , which is of the form with . The simulations are implemented under constant-pressure conditions on a generalized version of the constrained cell model. The constrained cell model is constructed by dividing the volume into Wigner-Seitz cells and confining each particle in a single cell. This model is a special case of a more general cell model which is formed by introducing an additional field variable that controls the number of particles per cell and, thus, the relative stability of the solid against the fluid phase. High field values force configurations with one particle per cell and thus favor the solid phase. Fluid-solid coexistence on the isotherm that corresponds to a reduced temperature of 2 is determined from constant-pressure simulations of the generalized cell model using tempering and histogram reweighting techniques. The entire fluid-solid phase boundary is determined through a thermodynamic integration technique based on histogram reweighting, using the previous coexistence point as a reference point. The vapor-liquid phase diagram is obtained from constant-pressure simulations of the unconstrained system using tempering and histogram reweighting. The phase diagram of the system is found to contain a stable critical point and a triple point. The phase diagram of the corresponding constrained cell model is also found to contain both a stable critical point and a triple point.

Phase behavior of binary mixture systems of saturated-unsaturated mixed-acid triacylglycerols: effects of glycerol structures and chain-chain interactions.

PubMed

Bayés-García, Laura; Calvet, Teresa; Cuevas-Diarte, Miquel Àngel; Ueno, Satoru; Sato, Kiyotaka

2015-03-26

We systematically examined the phase behavior of binary mixtures of mixed-acid triacylglycerols (TAGs) containing palmitic and oleic acid moieties 1,3-dioleoyl-2-palmitoyl-glycerol (OPO), 1,2-dipalmitoyl-3-oleoyl-rac-glycerol (PPO), and 1,2-dioleoyl-3-palmitoyl-rac-glycerol (OOP), which are widely present in natural fats and are employed in the food, pharmaceutical, and cosmetic industries. Differential scanning calorimetry and X-ray diffraction methods were applied to observe the mixing behavior of PPO/OPO, OOP/OPO, and PPO/OOP under metastable and stable conditions. The results led to three conclusions: (1) Eutectic behavior was observed in PPO/OPO. (2) Molecular compound (MC) crystals were formed in the mixtures of OOP/OPO and PPO/OOP. (3) However, the MC crystals occurred only under metastable conditions and tended to separate into component TAGs to form eutectic mixture systems after 17 months of incubation. These results were contrary to those of previous studies on 1,3-dipalmitoyl-2-oleoyl glycerol (POP)/OPO and POP/PPO in which the MC crystals were thermodynamically stable. We determined that specific molecular interactions may cause this different phase behavior (stability of POP/OPO and POP/PPO MC crystals and metastability of OOP/OPO and PPO/OOP MC crystals). All results confirm the significant effects of molecular structures of glycerol groups, interactions of fatty acid chains, and polymorphism of the component TAGs on the mixing behavior of mixed-acid TAGs.

Examining the base stacking interaction in a dinucleotide context via reversible cyclobutane dimer analogue formation under UV irradiation.

PubMed

Liu, Degang; Li, Lei

2013-11-14

Substituted tolyl groups are considered as close isosteres of the thymine (T) residue. They can be recognized by DNA polymerases as if they were thymine. Although these toluene derivatives are relatively inert toward radical additions, our recent finding suggests that the dinucleotide analogue TpTo (To = 2'-deoxy-1-(3-tolyl)-β-D-ribofuranose) supports an ortho photocycloaddition reaction upon UV irradiation, producing two cyclobutane pyrimidine dimer (CPD) analogues 2 and 3 . Our report here further shows that formation of these CPD species is reversible under UVC irradiation, resembling the photochemical property of the CPD species formed between two Ts. Analyzing the stability of these CPD analogues suggests that one ( 2 ) is more stable than the other ( 3 ). The TpTo conformer responsible for 2 formation is also more stable than that responsible for 3 formation, as indicated by the Gibbs free energy change calculated from the constructed Bordwell thermodynamic cycle. These different stabilities are not due to the varying photochemical properties, as proved by quantum yields determined from the corresponding photoreactions. Instead, they are ascribed to the different stacking interaction between the T and the To rings both in the TpTo dinucleotide as well as in the formed CPD analogues. Factors contributing to the ring stacking interactions are also discussed. Our proof-of-concept approach suggests that a carefully designed Bordwell cycle coupled with reversible CPD formations under UV irradiation can be very useful in studying DNA base interactions.

Examining the base stacking interaction in a dinucleotide context via reversible cyclobutane dimer analogue formation under UV irradiation

PubMed Central

Liu, Degang; Li, Lei

2013-01-01

Substituted tolyl groups are considered as close isosteres of the thymine (T) residue. They can be recognized by DNA polymerases as if they were thymine. Although these toluene derivatives are relatively inert toward radical additions, our recent finding suggests that the dinucleotide analogue TpTo (To = 2'-deoxy-1-(3-tolyl)-β-D-ribofuranose) supports an ortho photocycloaddition reaction upon UV irradiation, producing two cyclobutane pyrimidine dimer (CPD) analogues 2 and 3. Our report here further shows that formation of these CPD species is reversible under UVC irradiation, resembling the photochemical property of the CPD species formed between two Ts. Analyzing the stability of these CPD analogues suggests that one (2) is more stable than the other (3). The TpTo conformer responsible for 2 formation is also more stable than that responsible for 3 formation, as indicated by the Gibbs free energy change calculated from the constructed Bordwell thermodynamic cycle. These different stabilities are not due to the varying photochemical properties, as proved by quantum yields determined from the corresponding photoreactions. Instead, they are ascribed to the different stacking interaction between the T and the To rings both in the TpTo dinucleotide as well as in the formed CPD analogues. Factors contributing to the ring stacking interactions are also discussed. Our proof-of-concept approach suggests that a carefully designed Bordwell cycle coupled with reversible CPD formations under UV irradiation can be very useful in studying DNA base interactions. PMID:24223299

Soft matter: rubber and networks

NASA Astrophysics Data System (ADS)

McKenna, Gregory B.

2018-06-01

Rubber networks are important and form the basis for materials with properties ranging from rubber tires to super absorbents and contact lenses. The development of the entropy ideas of rubber deformation thermodynamics provides a powerful framework from which to understand and to use these materials. In addition, swelling of the rubber in the presence of small molecule liquids or solvents leads to materials that are very soft and ‘gel’ like in nature. The review covers the thermodynamics of polymer networks and gels from the perspective of the thermodynamics and mechanics of the strain energy density function. Important relationships are presented and experimental results show that the continuum ideas contained in the phenomenological thermodynamics are valid, but that the molecular bases for some of them remain to be fully elucidated. This is particularly so in the case of the entropic gels or swollen networks. The review is concluded with some perspectives on other networks, ranging from entropic polymer networks such as thermoplastic elastomers to physical gels in which cross-link points are formed by glassy or crystalline domains. A discussion is provided for other physical gels in which the network forms a spinodal-like decomposition, both in thermoplastic polymers that form a glassy network upon phase separation and for colloidal gels that seem to have a similar behavior.

Design of a biomimetic self-healing superalloy composite

NASA Astrophysics Data System (ADS)

Files, Bradley Steven

1997-10-01

Use of systems engineering concepts to design technologically advanced materials has allowed ambitious goals of self-healing alloys to be realized. Shape memory alloy reinforcements are embedded in an alloy matrix to demonstrate concepts of stable crack growth and matrix crack closure. Computer methods are used to design thermodynamically compatible iron-based alloys using bio-inspired concepts of crack bridging and self-healing. Feasibility of crack closure and stable crack growth is shown in a prototype system with a Sn-Bi matrix and TiNi fibers. Design of Fe-Ni-Co-Ti-Al alloys using thermodynamic models to determine stabilities and phase equilibria allows for a methodical system designing compatible multicomponent alloys for composite systems. Final alloy computations for this project led to the alloy Fe-27.6Ni-18.2Co-4.1Ti-1.6Al as a compatible shape memory a with a 650sp°C 90 minute heat treatment leading to martensite and austenite start temperatures (Msbs and Asbs) near room temperature. Thin slices of this alloy were able to fully recover at least 5% strain upon unloading heating. Composites made from the designed shape memory alloy and a compatible Fe-based B2 matrix were used to test self-healing concepts in the superalloy system. Diffusion couple experiments verified thermodynamic compatibility between matrix and reinforcement alloys at the solution treatment temperature of 1100sp°C. Concepts of stable crack growth and crack bridging were demonstrated in the composite, leading to enhanced toughness of the brittle matrix. However, healing behavior in this system was limited by intergranular fracture of the reinforcement alloy. It is believed that use of rapidly solidified powders could eliminate intergranular fracture, leading to greatly enhanced properties of toughening and healing. Crack clamping and stable crack growth were achieved in a feasibility study using a Sn-Bi matrix reinforced with TiNi fibers. Tensile specimens with less than 1% fibers showed an ability upon heating to recover over 80% of the plastic deformation induced during a tensile test. Further straining proved that stable crack growth can be realized in this system due to crack bridging of the shape memory fibers. Macroscopic cracks were clamped shut after heating of the material above the TiNi reversion temperature.

First-principles studies of phase stability and crystal structures in Li-Zn mixed-metal borohydrides

NASA Astrophysics Data System (ADS)

Wang, Yongli; Zhang, Yongsheng; Wolverton, C.

2013-07-01

We address the problem of finding mixed-metal borohydrides with favorable thermodynamics and illustrate the approach using the example of LiZn2(BH4)5. Using density functional theory (DFT), along with the grand-canonical linear programming method (GCLP), we examine the experimentally and computationally proposed crystal structures and the finite-temperature thermodynamics of dehydrogenation for the quaternary hydride LiZn2(BH4)5. We find the following: (i) For LiZn2(BH4)5, DFT calculations of the experimental crystal structures reveal that the structure from the neutron diffraction experiments of Ravnsbæk is more stable [by 24 kJ/(mol f.u.)] than that based on a previous x-ray study. (ii) Our DFT calculations show that when using the neutron-diffraction structure of LiZn2(BH4)5, the recently theoretically predicted LiZn(BH4)3 compound is unstable with respect to the decomposition into LiZn2(BH4)5+LiBH4. (iii) GCLP calculations show that even though LiZn2(BH4)5 is a combination of weakly [Zn(BH4)2] and strongly (LiBH4) bound borohydrides, its decomposition is not intermediate between the two individual borohydrides. Rather, we find that the decomposition of LiZn2(BH4)5 is divided into a weakly exothermic step [LiZn2(BH4)5→2Zn+(1)/(5)LiBH4+(2)/(5)Li2B12H12+(36)/(5)H2] and three strong endothermic steps (12LiBH4→10LiH+Li2B12H12+13H2; Zn+LiH→LiZn+(1)/(2)H2; 2Zn+Li2B12H12→2LiZn+12B+6H2). DFT-calculated ΔHZPET=0K values for the first three LiZn2(BH4)5 decomposition steps are -19, +37, +74 kJ/(mol H2), respectively. The behavior of LiZn2(BH4)5 shows that mixed-metal borohydrides formed by mixing borohydrides of high and low thermodynamics stabilities do not necessarily have an intermediate decomposition tendency. Our results suggest the correct strategy to find intermediate decomposition in mixed-metal borohydrides is to search for stable mixed-metal products such as ternary metal borides.

Thermodynamic Analysis of Oxygen-Enriched Direct Smelting of Jamesonite Concentrate

NASA Astrophysics Data System (ADS)

Zhang, Zhong-Tang; Dai, Xi; Zhang, Wen-Hai

2017-12-01

Thermodynamic analysis of oxygen-enriched direct smelting of jamesonite concentrate is reported in this article. First, the occurrence state of lead, antimony and other metallic elements in the smelting process was investigated theoretically. Then, the verification test was carried out. The results indicate that lead and antimony mainly exist in the alloy in the form of metallic lead and metallic antimony. Simultaneously, lead and antimony were also oxidized into the slag in the form of lead-antimony oxide. Iron and copper could be oxidized into the slag in the form of oxides in addition to combining with antimony in the alloy, while zinc was mainly oxidized into the slag in the form of zinc oxide. The verification test indicates that the main phases in the alloy contain metallic lead, metallic antimony and a small amount of Cu2Sb, FeSb2 intermetallic compounds, and the slag is mainly composed of kirschsteinite, fayalite and zinc oxide, in agreement with the thermodynamic analysis.

Modeling the Hydrogen Solubility in Liquid Aluminum Alloys

NASA Astrophysics Data System (ADS)

Harvey, Jean-Philippe; Chartrand, Patrice

2010-08-01

The modeling of hydrogen solubility in multicomponent Al-(Li, Mg, Cu, and Si) liquid phase has been performed with a thermodynamic approach using the modified quasichemical model with the pair approximation (MQMPA). All hydrogen solubility data available in literature was assessed critically to obtain the binary parameters of the MQMPA model for the Al-H, Li-H, Mg-H, Cu-H, Zn-H, and Si-H melts. For the Li-H system, a new thermodynamic description of the stable solid lithium hydride was determined based on the c p found in literature. The thermodynamic model for the Al-Li system also was reassessed in this work to take into account the short-range ordering observed for this system. Built-in interpolation techniques allow the model to estimate the thermodynamic properties of the multicomponent liquid solution from the liquid model parameters of the lower order subsystems. A comparison of the calculated hydrogen solubility performed at various equilibrium conditions of temperature, pressure, and composition with the available experimental data found in the literature is presented in this work, as well as a comparison with some results from previous modeling.

Equilibrium econophysics: A unified formalism for neoclassical economics and equilibrium thermodynamics

NASA Astrophysics Data System (ADS)

Sousa, Tânia; Domingos, Tiago

2006-11-01

We develop a unified conceptual and mathematical structure for equilibrium econophysics, i.e., the use of concepts and tools of equilibrium thermodynamics in neoclassical microeconomics and vice versa. Within this conceptual structure the results obtained in microeconomic theory are: (1) the definition of irreversibility in economic behavior; (2) the clarification that the Engel curve and the offer curve are not descriptions of real processes dictated by the maximization of utility at constant endowment; (3) the derivation of a relation between elasticities proving that economic elasticities are not all independent; (4) the proof that Giffen goods do not exist in a stable equilibrium; (5) the derivation that ‘economic integrability’ is equivalent to the generalized Le Chatelier principle and (6) the definition of a first order phase transition, i.e., a transition between separate points in the utility function. In thermodynamics the results obtained are: (1) a relation between the non-dimensional isothermal and adiabatic compressibilities and the increase or decrease in the thermodynamic potentials; (2) the distinction between mathematical integrability and optimization behavior and (3) the generalization of the Clapeyron equation.

Nonequilibrium thermodynamics of the shear-transformation-zone model

NASA Astrophysics Data System (ADS)

Luo, Alan M.; Ã-ttinger, Hans Christian

2014-02-01

The shear-transformation-zone (STZ) model has been applied numerous times to describe the plastic deformation of different types of amorphous systems. We formulate this model within the general equation for nonequilibrium reversible-irreversible coupling (GENERIC) framework, thereby clarifying the thermodynamic structure of the constitutive equations and guaranteeing thermodynamic consistency. We propose natural, physically motivated forms for the building blocks of the GENERIC, which combine to produce a closed set of time evolution equations for the state variables, valid for any choice of free energy. We demonstrate an application of the new GENERIC-based model by choosing a simple form of the free energy. In addition, we present some numerical results and contrast those with the original STZ equations.

Generalized second law of thermodynamics in f(R,T) theory of gravity

NASA Astrophysics Data System (ADS)

Momeni, D.; Moraes, P. H. R. S.; Myrzakulov, R.

2016-07-01

We present a study of the generalized second law of thermodynamics in the scope of the f(R,T) theory of gravity, with R and T representing the Ricci scalar and trace of the energy-momentum tensor, respectively. From the energy-momentum tensor equation for the f(R,T)=R+f(T) case, we calculate the form of the geometric entropy in such a theory. Then, the generalized second law of thermodynamics is quantified and some relations for its obedience in f(R,T) gravity are presented. Those relations depend on some cosmological quantities, as the Hubble and deceleration parameters, and also on the form of f(T).

Density functional theory study on carbon dioxide absorption into aqueous solutions of 2-amino-2-methyl-1-propanol using a continuum solvation model.

PubMed

Yamada, Hidetaka; Matsuzaki, Yoichi; Higashii, Takayuki; Kazama, Shingo

2011-04-14

We used density functional theory (DFT) calculations with the latest continuum solvation model (SMD/IEF-PCM) to determine the mechanism of CO(2) absorption into aqueous solutions of 2-amino-2-methyl-1-propanol (AMP). Possible absorption process reactions were investigated by transition-state optimization and intrinsic reaction coordinate (IRC) calculations in the aqueous solution at the SMD/IEF-PCM/B3LYP/6-31G(d) and SMD/IEF-PCM/B3LYP/6-311++G(d,p) levels of theory to determine the absorption pathways. We show that the carbamate anion forms by a two-step reaction via a zwitterion intermediate, and this occurs faster than the formation of the bicarbonate anion. However, we also predict that the carbamate readily decomposes by a reverse reaction rather than by hydrolysis. As a result, the final product is dominated by the thermodynamically stable bicarbonate anion that forms from AMP, H(2)O, and CO(2) in a single-step termolecular reaction.

Vacancies and holes in bulk and at 180° domain walls in lead titanate

NASA Astrophysics Data System (ADS)

Paillard, Charles; Geneste, Grégory; Bellaiche, Laurent; Dkhil, Brahim

2017-12-01

Domain walls (DWs) in ferroic materials exhibit a plethora of unexpected properties that are different from the adjacent ferroic domains. Still, the intrinsic/extrinsic origin of these properties remains an open question. Here, density functional theory calculations are used to investigate the interaction between vacancies and 180° DWs in the prototypical ferroelectric PbTiO3, with a special emphasis on cationic vacancies and released holes. All vacancies are more easily formed within the DW than in the domains. This is interpreted, using a phenomenological model, as the partial compensation of an extra-tensile stress when the defect is created inside the DW. Oxygen vacancies are found to be always fully ionized, independently of the thermodynamic conditions, while cationic vacancies can be either neutral or partially ionized (oxygen-rich conditions), or fully ionized (oxygen-poor conditions). Therefore, in oxidizing conditions, holes are induced by neutral and partially ionized Pb vacancies. In the bulk PbTiO3, these holes are more stable as delocalized rather than small polarons, but at DWs, the two forms are found to be possible.

Poly(propyleneimine) glycodendrimers non-covalently bind ATP in a pH- and salt-dependent manner - model studies for adenosine analogue drug delivery.

PubMed

Gorzkiewicz, Michał; Buczkowski, Adam; Appelhans, Dietmar; Voit, Brigitte; Pułaski, Łukasz; Pałecz, Bartłomiej; Klajnert-Maculewicz, Barbara

2018-06-10

Adenosine analogue drugs (such as fludarabine or cladribine) require transporter-mediated uptake into cells and subsequent phosphorylation for anticancer activity. Therefore, application of nanocarrier systems for direct delivery of active triphosphate forms has been proposed. Here, we applied isothermal titration calorimetry and zeta potential titration to determine the stoichiometry and thermodynamic parameters of interactions between 4th generation poly(propyleneimine) dendrimers (unmodified or sugar-modified for increased biocompatibility) and ATP as a model adenosine nucleotide. We showed that glycodendrimers have the ability to efficiently interact with nucleoside triphosphates and to form stable complexes via electrostatic interactions between the ionized phosphate and amino groups on the nucleotide and the dendrimer, respectively. The complexation process is spontaneous, enthalpy-driven and depends on buffer composition (strongest interactions in organic buffer) and pH (more binding sites in acidic pH). These properties allow us to consider maltose-modified dendrimers as especially promising carriers for adenosine analogues. Copyright © 2018 Elsevier B.V. All rights reserved.

Sulfur radical species form gold deposits on Earth

PubMed Central

Pokrovski, Gleb S.; Kokh, Maria A.; Guillaume, Damien; Borisova, Anastassia Y.; Gisquet, Pascal; Hazemann, Jean-Louis; Lahera, Eric; Del Net, William; Proux, Olivier; Testemale, Denis; Haigis, Volker; Jonchière, Romain; Seitsonen, Ari P.; Ferlat, Guillaume; Vuilleumier, Rodolphe; Saitta, Antonino Marco; Boiron, Marie-Christine; Dubessy, Jean

2015-01-01

Current models of the formation and distribution of gold deposits on Earth are based on the long-standing paradigm that hydrogen sulfide and chloride are the ligands responsible for gold mobilization and precipitation by fluids across the lithosphere. Here we challenge this view by demonstrating, using in situ X-ray absorption spectroscopy and solubility measurements, coupled with molecular dynamics and thermodynamic simulations, that sulfur radical species, such as the trisulfur ion S3−, form very stable and soluble complexes with Au+ in aqueous solution at elevated temperatures (>250 °C) and pressures (>100 bar). These species enable extraction, transport, and focused precipitation of gold by sulfur-rich fluids 10–100 times more efficiently than sulfide and chloride only. As a result, S3− exerts an important control on the source, concentration, and distribution of gold in its major economic deposits from magmatic, hydrothermal, and metamorphic settings. The growth and decay of S3− during the fluid generation and evolution is one of the key factors that determine the fate of gold in the lithosphere. PMID:26460040

Characterization of the N-terminal segment used by the barley yellow dwarf virus movement protein to promote interaction with the nuclear membrane of host plant cells.

PubMed

Dennison, Sarah Rachel; Harris, Frederick; Brandenburg, Klaus; Phoenix, David Andrew

2007-11-01

The barley yellow dwarf virus movement protein (BYDV-MP) requires its N-terminal sequence to promote the transport of viral RNA into the nuclear compartment of host plant cells. Here, graphical analysis predicts that this sequence would form a membrane interactive amphiphilic alpha-helix. Confirming this prediction, NT1, a peptide homologue of the BYDV-MP N-terminal sequence, was found to be alpha-helical (65%) in the presence of vesicles mimics of the nuclear membrane. The peptide increased the fluidity of these nuclear membrane mimics (rise in wavenumber of circa 0.5-1.0 cm(-1)) and induced surface pressure changes of 2 mN m(-1) in lipid monolayers with corresponding compositions. Taken with isotherm analysis these results suggest that BYDV-MP forms an N-terminal amphiphilic alpha-helix, which partitions into the nuclear membrane primarily through thermodynamically stable associations with the membrane lipid headgroup region. We speculate that these associations may play a role in targeting of the nuclear membrane by BYDM-MP.

Susceptibility of Iα- and Iβ-Dominated Cellulose to TEMPO-Mediated Oxidation.

PubMed

Carlsson, Daniel O; Lindh, Jonas; Strømme, Maria; Mihranyan, Albert

2015-05-11

The susceptibility of Iα- and Iβ-dominated cellulose to TEMPO-mediated oxidation was studied in this work since the cellulose Iα-allomorph is generally considered to be thermodynamically less stable and therefore more reactive than the cellulose Iβ-allomorph. Highly crystalline Cladophora nanocellulose, which is dominated by the Iα-allomorph, was oxidized to various degrees with TEMPO oxidant via bulk electrolysis in the absence of co-oxidants. Further, the Cladophora nanocellulose was thermally annealed in glycerol to produce its Iβ-dominated form and then oxidized. The produced materials were subsequently studied using FTIR, CP/MAS (13)C NMR, XRD, and SEM. The solid-state analyses confirmed that the annealed Cladophora cellulose was successfully transformed from an Iα- to an Iβ-dominated form. The results of the analyses of pristine and annealed TEMPO-oxidized samples suggest that Iα- and Iβ-dominated cellulose do not differ in susceptibility to TEMPO-oxidation. This work hence suggests that cellulose from different sources are not expected to differ in susceptibility to the oxidation due to differences in allomorph composition.

Formation of a new archetypal Metal-Organic Framework from a simple monatomic liquid

DOE Office of Scientific and Technical Information (OSTI.GOV)

Metere, Alfredo, E-mail: alfredo.metere@mmk.su.se; Oleynikov, Peter; Dzugutov, Mikhail

2014-12-21

We report a molecular-dynamics simulation of a single-component system of particles interacting via a spherically symmetric potential that is found to form, upon cooling from a liquid state, a low-density porous crystalline phase. Its structure analysis demonstrates that the crystal can be described by a net with a topology that belongs to the class of topologies characteristic of the Metal-Organic Frameworks (MOFs). The observed net is new, and it is now included in the Reticular Chemistry Structure Resource database. The observation that a net topology characteristic of MOF crystals, which are known to be formed by a coordination-driven self-assembly process,more » can be reproduced by a thermodynamically stable configuration of a simple single-component system of particles opens a possibility of using these models in studies of MOF nets. It also indicates that structures with MOF topology, as well as other low-density porous crystalline structures can possibly be produced in colloidal systems of spherical particles, with an appropriate tuning of interparticle interaction.« less

Formation, Physicochemical Characterization, and Thermodynamic Stability of the Amorphous State of Drugs and Excipients.

PubMed

Martino, Piera Di; Magnoni, Federico; Peregrina, Dolores Vargas; Gigliobianco, Maria Rosa; Censi, Roberta; Malaj, Ledjan

2016-01-01

Drugs and excipients used for pharmaceutical applications generally exist in the solid (crystalline or amorphous) state, more rarely as liquid materials. In some cases, according to the physicochemical nature of the molecule, or as a consequence of specific technological processes, a compound may exist exclusively in the amorphous state. In other cases, as a consequence of specific treatments (freezing and spray drying, melting and co-melting, grinding and compression), the crystalline form may convert into a completely or partially amorphous form. An amorphous material shows physical and thermodynamic properties different from the corresponding crystalline form, with profound repercussions on its technological performance and biopharmaceutical properties. Several physicochemical techniques such as X-ray powder diffraction, thermal methods of analysis, spectroscopic techniques, gravimetric techniques, and inverse gas chromatography can be applied to characterize the amorphous form of a compound (drug or excipient), and to evaluate its thermodynamic stability. This review offers a survey of the technologies used to convert a crystalline solid into an amorphous form, and describes the most important techniques for characterizing the amorphous state of compounds of pharmaceutical interest.

Perspective: Structural fluctuation of protein and Anfinsen's thermodynamic hypothesis

NASA Astrophysics Data System (ADS)

Hirata, Fumio; Sugita, Masatake; Yoshida, Masasuke; Akasaka, Kazuyuki

2018-01-01

The thermodynamics hypothesis, casually referred to as "Anfinsen's dogma," is described theoretically in terms of a concept of the structural fluctuation of protein or the first moment (average structure) and the second moment (variance and covariance) of the structural distribution. The new theoretical concept views the unfolding and refolding processes of protein as a shift of the structural distribution induced by a thermodynamic perturbation, with the variance-covariance matrix varying. Based on the theoretical concept, a method to characterize the mechanism of folding (or unfolding) is proposed. The transition state, if any, between two stable states is interpreted as a gap in the distribution, which is created due to an extensive reorganization of hydrogen bonds among back-bone atoms of protein and with water molecules in the course of conformational change. Further perspective to applying the theory to the computer-aided drug design, and to the material science, is briefly discussed.

Shape transformation of viral capsids and HIV

NASA Astrophysics Data System (ADS)

Nguyen, Toan

2005-03-01

We present a continuum description of the shape transformation of viral capsids. The cone-like HIV virus is shown to be an thermodynamic stable shape, intermediate between icosahedral and sphero-cylinder capsid shapes. A generalized Caspar-Klug classification is introduced to describe spherical, conical and cylinderical shapes of virus.

Increasing the hydrolysis constant of the reactive site upon introduction of an engineered Cys¹⁴-Cys³⁹ bond into the ovomucoid third domain from silver pheasant.

PubMed

Hemmi, Hikaru; Kumazaki, Takashi; Kojima, Shuichi; Yoshida, Takuya; Ohkubo, Tadayasu; Yokosawa, Hideyoshi; Miura, Kin-Ichiro; Kobayashi, Yuji

2011-08-01

P14C/N39C is the disulfide variant of the ovomucoid third domain from silver pheasant (OMSVP3) introducing an engineered Cys¹⁴-Cys³⁹ bond near the reactive site on the basis of the sequence homology between OMSVP3 and ascidian trypsin inhibitor. This variant exhibits a narrower inhibitory specificity. We have examined the effects of introducing a Cys¹⁴-Cys³⁹ bond into the flexible N-terminal loop of OMSVP3 on the thermodynamics of the reactive site peptide bond hydrolysis, as well as the thermal stability of reactive site intact inhibitors. P14C/N39C can be selectively cleaved by Streptomyces griseus protease B at the reactive site of OMSVP3 to form a reactive site modified inhibitor. The conversion rate of intact to modified P14C/N39C is much faster than that for wild type under any pH condition. The pH-independent hydrolysis constant (K(hyd) °) is estimated to be approximately 5.5 for P14C/N39C, which is higher than the value of 1.6 for natural OMSVP3. The reactive site modified form of P14C/N39C is thermodynamically more stable than the intact one. Thermal denaturation experiments using intact inhibitors show that the temperature at the midpoint of unfolding at pH 2.0 is 59 °C for P14C/N39C and 58 °C for wild type. There have been no examples, except P14C/N39C, where introducing an engineered disulfide causes a significant increase in K(hyd) °, but has no effect on the thermal stability. The site-specific disulfide introduction into the flexible N-terminal loop of natural Kazal-type inhibitors would be useful to further characterize the thermodynamics of the reactive site peptide bond hydrolysis. Copyright © 2011 European Peptide Society and John Wiley & Sons, Ltd.

Antiferromagnetic MnN layer on the MnGa(001) surface

NASA Astrophysics Data System (ADS)

Guerrero-Sánchez, J.; Takeuchi, Noboru

2016-12-01

Spin polarized first principles total energy calculations have been applied to study the stability and magnetic properties of the MnGa(001) surface and the formation of a topmost MnN layer with the deposit of nitrogen. Before nitrogen adsorption, surface formation energies show a stable gallium terminated ferromagnetic surface. After incorporation of nitrogen atoms, the antiferromagnetic manganese terminated surface becomes stable due to the formation of a MnN layer (Mn-N bonding at the surface). Spin density distribution shows a ferromagnetic/antiferromagnetic arrangement in the first surface layers. This thermodynamically stable structure may be exploited to growth MnGa/MnN magnetic heterostructures as well as to look for exchange biased systems.

Solid state characterization of dehydroepiandrosterone.

PubMed

Chang, L C; Caira, M R; Guillory, J K

1995-10-01

Three polymorphs (forms I-III), a monohydrate (form S2), and three new solvates [4:1 hydrate (form S1), monohydrate (form S3), and methanol half-solvate (form S4)] were isolated and characterized by X-ray powder diffractometry (XRPD), IR spectroscopy, differential scanning calorimetry (DSC), hot stage microscopy, solution calorimetry, and their dissolution rates. A new polymorph, designated as form V, melting at 146.5-148 degrees C, was observed by hot stage microscopy. Our results indicate that only forms I and S4 exhibit reproducible DSC thermograms. Five of the isolated modifications undergo phase transformation on heating, and their DSC thermograms are not reproducible. Interpretation of DSC thermograms was facilitated by use of hot stage microscopy. The identification of each modification is based on XRPD patterns (except forms S3 and S4, for which the XRPD patterns are indistinguishable) and IR spectra. In the IR spectra, a significant difference was observed in the OH stretching region of all seven modifications. In a purity determination study, 5% of a contaminant modification in binary mixtures of several modifications could be detected by use of XRPD. To obtain a better understanding of the thermodynamic properties of these modifications, a series of increasing heating rates and different pan types were used in DSC. According to Burger's rule, forms I-III are monotropic polymorphs with decreasing stability in the order form I > form II > form III. The melting onsets and heats of fusion for forms I-III are 149.1 degrees C, 25.5 kJ/mol; 140.8 degrees C, 24.6 kJ/mol; and 137.8 degrees C, 24.0 kJ/mol, respectively. For form III the heat of fusion was calculated from heat of solution and DSC data. In the case of form S1 the melting point, 127.2 degrees C, was obtained by DSC using a hermetically sealed pan. The relative stabilities of the six modifications stored under high humidity conditions were predicted to be, on the basis of the heat of solution and thermal analysis data, from S2 > form S3 > form S1 > form I > form II > form III. However, the results of the dissolution rate determination were inconsistent with the heat of solution data. The stable form I shows a higher initial dissolution rate than the metastable form II and unstable form III. All modifications were converted into the stable monohydrate, form S2, during the dissolution study, suggesting that the moisture level in solid formulations should be carefully controlled.

An automated parallel crystallisation search for predicted crystal structures and packing motifs of carbamazepine.

PubMed

Florence, Alastair J; Johnston, Andrea; Price, Sarah L; Nowell, Harriott; Kennedy, Alan R; Shankland, Norman

2006-09-01

An automated parallel crystallisation search for physical forms of carbamazepine, covering 66 solvents and five crystallisation protocols, identified three anhydrous polymorphs (forms I-III), one hydrate and eight organic solvates, including the single-crystal structures of three previously unreported solvates (N,N-dimethylformamide (1:1); hemi-furfural; hemi-1,4-dioxane). Correlation of physical form outcome with the crystallisation conditions demonstrated that the solvent adopts a relatively nonspecific role in determining which polymorph is obtained, and that the previously reported effect of a polymer template facilitating the formation of form IV could not be reproduced by solvent crystallisation alone. In the accompanying computational search, approximately half of the energetically feasible predicted crystal structures exhibit the C=O...H--N R2(2)(8)dimer motif that is observed in the known polymorphs, with the most stable correctly corresponding to form III. Most of the other energetically feasible structures, including the global minimum, have a C=O...H--N C(4) chain hydrogen bond motif. No such chain structures were observed in this or any other previously published work, suggesting that kinetic, rather than thermodynamic, factors determine which of the energetically feasible crystal structures are observed experimentally, with the kinetics apparently favouring nucleation of crystal structures based on the CBZ-CBZ R2(2)(8) motif. (c) 2006 Wiley-Liss, Inc. and the American Pharmacists Association.

Thermodynamic integration from classical to quantum mechanics.

PubMed

Habershon, Scott; Manolopoulos, David E

2011-12-14

We present a new method for calculating quantum mechanical corrections to classical free energies, based on thermodynamic integration from classical to quantum mechanics. In contrast to previous methods, our method is numerically stable even in the presence of strong quantum delocalization. We first illustrate the method and its relationship to a well-established method with an analysis of a one-dimensional harmonic oscillator. We then show that our method can be used to calculate the quantum mechanical contributions to the free energies of ice and water for a flexible water model, a problem for which the established method is unstable. © 2011 American Institute of Physics

First principles investigation of structural, vibrational and thermal properties of black and blue phosphorene

NASA Astrophysics Data System (ADS)

Arif Khalil, R. M.; Ahmad, Javed; Rana, Anwar Manzoor; Bukhari, Syed Hamad; Tufiq Jamil, M.; Tehreem, Tuba; Nissar, Umair

2018-05-01

In this investigation, structural, dynamical and thermal properties of black and blue phosphorene (P) are presented through the first principles calculations based on the density functional theory (DFT). These DFT calculations depict that due to the approximately same values of ground state energy at zero Kelvin and Helmholtz free energy at room-temperature, it is expected that both structures can coexist at transition temperature. Lattice dynamics of both phases were investigated by using the finite displacement supercell approach. It is noticed on the basis of harmonic approximation thermodynamic calculations that the blue phase is thermodynamically more stable than the black phase above 155 K.

On Thermodynamic Constraints upon Turbulence Modeling

NASA Astrophysics Data System (ADS)

Huang, Yu-Ning; Durst, Franz

2000-11-01

Turbulence is a continuum phenomenon which can be described within the framework of continuum mechanics. Such foundation has the potential for improving turbulence modeling, making it less heuristic and more rational. In the present research, we consider the compatibility of turbulence modeling with the second law of thermodynamics. We show that the Clausius-Planck inequality, as an expression of the principle of entropy growth, places a thermodynamic restriction upon the turbulence modeling of an incompressible Navier-Stokes fluid in an isothermal temperature field. This thermodynamic restriction is given in the form of an inequality, which ensures non-negativeness of the mean internal dissipation. As an illustration, we show the thermodynamic constraints on the modeling of a few typical homogeneous turbulent flows.

[1,5]-Anion relay via intramolecular proton transfer to generate 3,3-bis(silyl) allyloxy lithium: a useful scaffold for syn-addition to aldehydes and ketones.

PubMed

Lin, Xinglong; Ye, Xincui; Sun, Xianwei; Zhang, Yuebao; Gao, Lu; Song, Zhenlei

2014-02-21

A [1,5]-anion relay has been achieved in 3,3-bis(silyl) benzyl enol ether. Deprotonation at the sterically more accessible benzyl position triggers an intramolecular proton transfer to generate the thermodynamically more stable 3,3-bis(silyl) allyloxy lithium. This endo-oriented allyl anion is stable at -78 °C and undergoes diastereoselective syn-addition at the γ-position with aldehydes and ketones to give monobenzyl-substituted 1,2-diols.

Comparison of Optimal Thermodynamic Models of the Tricarboxylic Acid Cycle from Heterotrophs, Cyanobacteria, and Green Sulfur Bacteria.

PubMed

Thomas, Dennis G; Jaramillo-Riveri, Sebastian; Baxter, Douglas J; Cannon, William R

2014-12-26

We have applied a new stochastic simulation approach to predict the metabolite levels, material flux, and thermodynamic profiles of the oxidative TCA cycles found in E. coli and Synechococcus sp. PCC 7002, and in the reductive TCA cycle typical of chemolithoautotrophs and phototrophic green sulfur bacteria such as Chlorobaculum tepidum. The simulation approach is based on modeling states using statistical thermodynamics and employs an assumption similar to that used in transition state theory. The ability to evaluate the thermodynamics of metabolic pathways allows one to understand the relationship between coupling of energy and material gradients in the environment and the self-organization of stable biological systems, and it is shown that each cycle operates in the direction expected due to its environmental niche. The simulations predict changes in metabolite levels and flux in response to changes in cofactor concentrations that would be hard to predict without an elaborate model based on the law of mass action. In fact, we show that a thermodynamically unfavorable reaction can still have flux in the forward direction when it is part of a reaction network. The ability to predict metabolite levels, energy flow, and material flux should be significant for understanding the dynamics of natural systems and for understanding principles for engineering organisms for production of specialty chemicals.

Stabilization of RNA hairpins using non-nucleotide linkers and circularization.

PubMed

Kiliszek, Agnieszka; Blaszczyk, Leszek; Kierzek, Ryszard; Rypniewski, Wojciech

2017-06-02

An RNA hairpin is an essential structural element of RNA. Hairpins play crucial roles in gene expression and intermolecular recognition but are also involved in the pathogenesis of some congenital diseases. Structural studies of the hairpin motifs are impeded by their thermodynamic instability, as they tend to unfold to form duplexes, especially at high concentrations required for crystallography or nuclear magnetic resonance spectroscopy. We have elaborated techniques to stabilize the RNA hairpins by linking the free ends of the RNA strand at the base of the hairpin stem. One method involves stilbene diether or hexaethylene glycol linkers and circularization by T4 RNA ligase. Another method uses click chemistry to stitch the RNA ends with a triazole linker. Both techniques are efficient and easy to perform. They should be useful in making stable, biologically relevant RNA constructs for structural studies. © The Author(s) 2017. Published by Oxford University Press on behalf of Nucleic Acids Research.

Controlling the growth of multiple ordered heteromolecular phases by utilizing intermolecular repulsion

NASA Astrophysics Data System (ADS)

Henneke, Caroline; Felter, Janina; Schwarz, Daniel; Stefan Tautz, F.; Kumpf, Christian

2017-06-01

Metal/organic interfaces and their structural, electronic, spintronic and thermodynamic properties have been investigated intensively, aiming to improve and develop future electronic devices. In this context, heteromolecular phases add new design opportunities simply by combining different molecules. However, controlling the desired phases in such complex systems is a challenging task. Here, we report an effective way of steering the growth of a bimolecular system composed of adsorbate species with opposite intermolecular interactions--repulsive and attractive, respectively. The repulsive species forms a two-dimensional lattice gas, the density of which controls which crystalline phases are stable. Critical gas phase densities determine the constant-area phase diagram that describes our experimental observations, including eutectic regions with three coexisting phases. We anticipate the general validity of this type of phase diagram for binary systems containing two-dimensional gas phases, and also show that the density of the gas phase allows engineering of the interface structure.

Shape-Persistent, Sterically Crowded Star Mesogens: From Exceptional Columnar Dimer Stacks to Supermesogens.

PubMed

Lehmann, Matthias; Maier, Philipp

2015-08-10

Hexasubstituted C3 -symmetric benzenes with three oligophenylenevinylene (OPV) arms and three pyridyl or phenyl substituents are shape-persistent star mesogens that are sterically crowded in the center. Such molecular structures possess large void spaces between their arms, which have to be filled in condensed phases. For the neat materials, this is accomplished by an exceptional formation of dimers and short-range helical packing in columnar mesophases. The mesophase is thermodynamically stable for the pyridyl compound. Only this derivative forms filled star-shaped supermesogens in the presence of various carboxylic acids. The latter do not arrange as dimers, but as monomers along the columnar stacks. In this liquid crystal (LC) phase, the guests are completely enclosed by the hosts. Therefore, the host can be regarded as a new LC endoreceptor, which allows the design of columnar functional structures in the future. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A new orthorhombic ground-state phase and mechanical strengths of ternary B2CO compound

NASA Astrophysics Data System (ADS)

Yan, Haiyan; Zhang, Meiguang; Wei, Qun; Zhang, Yun

2018-06-01

A novel orthorhombic oI16 structure, formed by strong covalent sp2-sp3 Bsbnd C and Bsbnd O bonds, was identified as to be the thermodynamic ground-state phase for B2CO compound by using an unbiased structure searching method. The energy of this new oI16 phase is considerably lower than all those of previously proposed candidates, and it is dynamically stable at atmosphere pressure through the phonon calculations. The evidences of the indirect semiconducting and chemical bonding nature are manifested by the electronic structure calculations and AIM analyses. The pronounced elastic anisotropy of oI16 structure has been revealed by the calculated distributions of elastic moduli along different crystal orientations. The calculated stress-strain relations of oI16 structure disclose its common hard nature but with an extended ductility.

Enamel-like apatite crown covering amorphous mineral in a crayfish mandible

PubMed Central

Bentov, Shmuel; Zaslansky, Paul; Al-Sawalmih, Ali; Masic, Admir; Fratzl, Peter; Sagi, Amir; Berman, Amir; Aichmayer, Barbara

2012-01-01

Carbonated hydroxyapatite is the mineral found in vertebrate bones and teeth, whereas invertebrates utilize calcium carbonate in their mineralized organs. In particular, stable amorphous calcium carbonate is found in many crustaceans. Here we report on an unusual, crystalline enamel-like apatite layer found in the mandibles of the arthropod Cherax quadricarinatus (freshwater crayfish). Despite their very different thermodynamic stabilities, amorphous calcium carbonate, amorphous calcium phosphate, calcite and fluorapatite coexist in well-defined functional layers in close proximity within the mandible. The softer amorphous minerals are found primarily in the bulk of the mandible whereas apatite, the harder and less soluble mineral, forms a wear-resistant, enamel-like coating of the molar tooth. Our findings suggest a unique case of convergent evolution, where similar functional challenges of mastication led to independent developments of structurally and mechanically similar, apatite-based layers in the teeth of genetically remote phyla: vertebrates and crustaceans. PMID:22588301

Hetero-junction photovoltaic device and method of fabricating the device

DOEpatents

Aytug, Tolga; Christen, David K; Paranthaman, Mariappan Parans; Polat, Ozgur

2014-02-10

A hetero-junction device and fabrication method in which phase-separated n-type and p-type semiconductor pillars define vertically-oriented p-n junctions extending above a substrate. Semiconductor materials are selected for the p-type and n-type pillars that are thermodynamically stable and substantially insoluble in one another. An epitaxial deposition process is employed to form the pillars on a nucleation layer and the mutual insolubility drives phase separation of the materials. During the epitaxial deposition process, the orientation is such that the nucleation layer initiates propagation of vertical columns resulting in a substantially ordered, three-dimensional structure throughout the deposited material. An oxidation state of at least a portion of one of the p-type or the n-type semiconductor materials is altered relative to the other, such that the band-gap energy of the semiconductor materials differ with respect to stoichiometric compositions and the device preferentially absorbs particular selected bands of radiation.

The ferromagnetic monolayer Fe(110) on W(110)

NASA Astrophysics Data System (ADS)

Gradmann, U.; Liu, G.; Elmers, H. J.; Przybylski, M.

1990-07-01

Ferromagnetic order in the pseudomorphic monolayer Fe(110) on W(110) was analyzed experimentally using Conversion Electron Mössbauer Spectroscopy (CEMS) and Torsion Oscillation Magnetometry (TOM). The monolayer is thermodynamically stable, crystallizes to large monolayer patches at elevated temperatures and therefore forms an excellent approximation to the ideal monolayer structure. It is ferromagnetic below a Curie-temperature T c,mono, which is given by (282±3) K for the Ag-coated layer, (290±10) K for coating by Cu, Ag or Au and ≈210 K for the free monolayer. For the Ag-coated monolayer, ground state hyperfine field B hf (0)=(11.9±0.3) T and magnetic moment per atom μ=2.53 μB could be determined, in fair agreement with theoretical predictions. Unusual properties of the phase transition are detected by the combination of both experimental techniques. Strong magnetic anisotropies, which are essential for ferromagnetic order, are determined by CEMS.

Recent Advances in the Theory and Simulation of Model Colloidal Microphase Formers.

PubMed

Zhuang, Yuan; Charbonneau, Patrick

2016-08-18

This mini-review synthesizes our understanding of the equilibrium behavior of particle-based models with short-range attractive and long-range repulsive (SALR) interactions. These models, which can form stable periodic microphases, aim to reproduce the essence of colloidal suspensions with competing interparticle interactions. Ordered structures, however, have yet to be obtained in experiments. In order to better understand the hurdles to periodic microphase assembly, marked theoretical and simulation advances have been made over the past few years. Here, we present recent progress in the study of microphases in models with SALR interactions using liquid-state theory and density-functional theory as well as numerical simulations. Combining these various approaches provides a description of periodic microphases, and gives insights into the rich phenomenology of the surrounding disordered regime. Ongoing research directions in the thermodynamics of models with SALR interactions are also presented.

Ultrasonic and spectral studies on charge transfer complexes of anisole and certain aromatic amines

NASA Astrophysics Data System (ADS)

Rajesh, R.; Raj Muhamed, R.; Justin Adaikala Baskar, A.; Kannappan, V.

2016-10-01

Stability constants of two complexes of anisole with aniline and N-methylaniline (NMA) are determined from the measured ultrasonic velocity in n-hexane medium at four different temperatures. Acoustic and excess thermo acoustic parameters [excess ultrasonic velocity (uE), excess molar volume (VE), excess internal pressure (πiE)] are reported for these systems at four different temperatures. The trend in acoustic and excess parameters with concentration in the two systems establishes the formation of hydrogen bonded complexes between anisole and the two amines. Thermodynamic properties are computed for the two complexes from the variation in K with temperature. The formation of these complexes is also established by UV spectral method and their spectral characteristics and stability constants are determined. K values of these complexes obtained by ultrasonic and UV spectroscopic techniques agree well. Aniline forms more stable complex than N-methylaniline with anisole in n-hexane medium.

Ground state intermolecular proton transfer in the supersystems thymine-(H2O)n and thymine-(CH3OH)n, n = 1,2: a theoretical study.

PubMed

Delchev, Vassil B; Shterev, Ivan G

2009-04-01

Twelve binary and eight ternary supersystems between thymine and methanol, and water were investigated in the ground state at the B3LYP and MP2 levels of theory using B3LYP/6-311 + + G(d,p) basis functions. The thermodynamics of complex formations and the mechanisms of intermolecular proton transfers were clarified in order to find out the most stable H-boned system. It was established that the energy barriers of the water/methanol-assisted proton transfers are several times lower than those of the intramolecular proton transfers in the DNA/RNA bases. The X-ray powder spectra of thymine, and this precrystallized from water and methanol showed that water molecules are incorporated in the crystal lattice of thymine forming H-bridges between thymine molecules.

Cubic martensite in high carbon steel

NASA Astrophysics Data System (ADS)

Chen, Yulin; Xiao, Wenlong; Jiao, Kun; Ping, Dehai; Xu, Huibin; Zhao, Xinqing; Wang, Yunzhi

2018-05-01

A distinguished structural characteristic of martensite in Fe-C steels is its tetragonality originating from carbon atoms occupying only one set of the three available octahedral interstitial sites in the body-centered-cubic (bcc) Fe lattice. Such a body-centered-tetragonal (bct) structure is believed to be thermodynamically stable because of elastic interactions between the interstitial carbon atoms. For such phase stability, however, there has been a lack of direct experimental evidence despite extensive studies of phase transformations in steels over one century. In this Rapid Communication, we report that the martensite formed in a high carbon Fe-8Ni-1.26C (wt%) steel at room temperature induced by applied stress/strain has actually a bcc rather than a bct crystal structure. This finding not only challenges the existing theories on the stability of bcc vs bct martensite in high carbon steels, but also provides insights into the mechanism for martensitic transformation in ferrous alloys.

Synthesis and bio-physicochemical properties of amide-functionalized N-methylpiperazinium surfactants.

PubMed

Chauhan, Vinay; Singh, Sukhprit; Mishra, Rachana; Kaur, Gurcharan

2014-12-15

Four new amide functionalized N-methylpiperazinium amphiphiles having tetradecyl, hexadecyl alkyl chain lengths and counterions; chloride or bromide have been synthesized and characterized by various spectroscopic techniques. These new surfactants have been investigated in detail for their self-assembling behavior by surface tension, conductivity and fluorescence measurements. The thermodynamic parameters of these surfactants indicate that micellization is exothermic and entropy-driven. The dynamic light scattering (DLS) and transmission electron microscopy (TEM) experiments have been performed to insight the aggregate size of these cationics. Thermal degradation of these new surfactants has also been evaluated by thermal gravimetric analysis (TGA). These new surfactants form stable complexes with DNA as acknowledged by agarose gel electrophoresis, ethidium bromide exclusion and zeta potential measurements. They have also been found to have low cytotoxicity by MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide) assay on the C6 glioma cell line. Copyright © 2014 Elsevier Inc. All rights reserved.

Peptide folding in the presence of interacting protein crowders

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bille, Anna, E-mail: anna.bille@thep.lu.se; Irbäck, Anders, E-mail: anders@thep.lu.se; Mohanty, Sandipan, E-mail: s.mohanty@fz-juelich.de

2016-05-07

Using Monte Carlo methods, we explore and compare the effects of two protein crowders, BPTI and GB1, on the folding thermodynamics of two peptides, the compact helical trp-cage and the β-hairpin-forming GB1m3. The thermally highly stable crowder proteins are modeled using a fixed backbone and rotatable side-chains, whereas the peptides are free to fold and unfold. In the simulations, the crowder proteins tend to distort the trp-cage fold, while having a stabilizing effect on GB1m3. The extent of the effects on a given peptide depends on the crowder type. Due to a sticky patch on its surface, BPTI causes largermore » changes than GB1 in the melting properties of the peptides. The observed effects on the peptides stem largely from attractive and specific interactions with the crowder surfaces, and differ from those seen in reference simulations with purely steric crowder particles.« less

The conformational flexibility of the carboxy terminal residues 105–114 is a key modulator of the catalytic activity and stability of Macrophage Migration Inhibitory Factor (MIF)†

PubMed Central

El-Turk, Farah; Cascella, Michele; Ouertatani-Sakouhi, Hajer; Narayanan, Raghavendran Lakshmi; Leng, Lin; Bucala, Richard; Hweckstetter, Markus; Rothlisberger, Ursula; Lashuel, Hilal A.

2013-01-01

Macrophage migration inhibitory factor (MIF) is a multifunctional protein and a major mediator of innate immunity. Although X-ray crystallography revealed that MIF exists as a homotrimer, its oligomerization state in vivo as well as the factors governing its oligomerization and stability remain poorly understood. The C-terminal region of MIF is highly conserved and participates in several intramolecular interactions that suggest a role in modulating the stability and biochemical activity of MIF. To determine the importance of these interactions, point mutations (A48P, L46A), insertions (P107) at the monomer-monomer interfaces, and C-terminal deletion (Δ110-114NSTFA and Δ105–114NVGWNNSTFA) variants were designed and their structural properties, thermodynamic stability, oligomerization state, catalytic activity and receptor binding were characterized using a battery of biophysical methods. The C-terminal deletion mutants ΔC5 huMIF1-109 and ΔC10 huMIF1-104 were enzymatically inactive and thermodynamically less stable than wild type MIF. Analytical ultracentrifugation studies demonstrate that both C-terminal mutants sediment as trimers and exhibit similar binding to CD74 as the wild type protein. Disrupting the conformation of the C-terminal region 105–114 and increasing its conformational flexibility through the insertion of a proline residue at position 107 was sufficient to reproduce the structural, biochemical and thermodynamic properties of the deletion mutants. P107 MIF forms an enzymatically inactive trimer and exhibits reduced thermodynamic stability relative to the wild type protein. To provide a rationale for the changes induced by these mutations at the molecular level, we also performed molecular dynamics simulations on these mutants in comparison to the wild type MIF. Together, our studies demonstrate that inter-subunit interactions involving the C-terminal region 105–114, including a salt-bridge interaction between Arg73 of one monomer and the carboxy terminus of a neighbouring monomer, play critical roles in modulating tertiary structure stabilization, enzymatic activity, and thermodynamic stability of MIF, but not its oligomerization state and receptor binding properties. Our results suggest that targeting the C-terminal region could provide new strategies for allosteric modulation of MIF enzymatic activity and the development of novel inhibitors of MIF tautomerase activity. PMID:18795803

Biophysical Optimization of a Therapeutic Protein by Nonstandard Mutagenesis

PubMed Central

Pandyarajan, Vijay; Phillips, Nelson B.; Cox, Gabriela P.; Yang, Yanwu; Whittaker, Jonathan; Ismail-Beigi, Faramarz; Weiss, Michael A.

2014-01-01

Insulin provides a model for the therapeutic application of protein engineering. A paradigm in molecular pharmacology was defined by design of rapid-acting insulin analogs for the prandial control of glycemia. Such analogs, a cornerstone of current diabetes regimens, exhibit accelerated subcutaneous absorption due to more rapid disassembly of oligomeric species relative to wild-type insulin. This strategy is limited by a molecular trade-off between accelerated disassembly and enhanced susceptibility to degradation. Here, we demonstrate that this trade-off may be circumvented by nonstandard mutagenesis. Our studies employed LysB28, ProB29-insulin (“lispro”) as a model prandial analog that is less thermodynamically stable and more susceptible to fibrillation than is wild-type insulin. We have discovered that substitution of an invariant tyrosine adjoining the engineered sites in lispro (TyrB26) by 3-iodo-Tyr (i) augments its thermodynamic stability (ΔΔGu 0.5 ±0.2 kcal/mol), (ii) delays onset of fibrillation (lag time on gentle agitation at 37 °C was prolonged by 4-fold), (iii) enhances affinity for the insulin receptor (1.5 ± 0.1-fold), and (iv) preserves biological activity in a rat model of diabetes mellitus. 1H NMR studies suggest that the bulky iodo-substituent packs within a nonpolar interchain crevice. Remarkably, the 3-iodo-TyrB26 modification stabilizes an oligomeric form of insulin pertinent to pharmaceutical formulation (the R6 zinc hexamer) but preserves rapid disassembly of the oligomeric form pertinent to subcutaneous absorption (T6 hexamer). By exploiting this allosteric switch, 3-iodo-TyrB26-lispro thus illustrates how a nonstandard amino acid substitution can mitigate the unfavorable biophysical properties of an engineered protein while retaining its advantages. PMID:24993826

Synthesis and Thermodynamic Stability of Ba2B‧B″O6 and Ba3B*B″2O9 Perovskites Using the Molten Salt Method

NASA Astrophysics Data System (ADS)

Meng, Wei; Virkar, Anil V.

1999-12-01

A number of mixed perovskites of the types Ba2B‧B″O6 (BaB‧1/2B″1/2O3) and Ba3B*B″2O9 (BaB*1/3B″2/3O3) where B‧=Gd, La, Nd, Sm, or Y; B″=Nb and B*=Ca were synthesized by a conventional calcination process, as well as by the molten salt method. The former consists of calcining appropriate mixtures of oxide or carbonate precursors in air at elevated temperatures (∼1250°C). The latter method consists of adding appropriate mixtures of oxide or carbonate precursors to a molten salt bath at relatively low temperatures (on the order of 300 to 500°C) so that the requisite compound is formed by dissolution-reprecipitation. X-ray diffraction confirmed the formation of a single-phase perovskite in each case with calcination at 1250°C. In a molten salt bath, however, all except Ba2LaNbO6 and Ba2NdNbO6 formed the perovskite structure. On the contrary, powders of Ba2LaNbO6 and Ba2NdNbO6 formed by a high-temperature calcination process readily decomposed when introduced into the molten salt bath. The formation of the requisite perovskite at a temperature as low as 350°C in a molten salt suggests that: (a) The perovskite is stable at 350°C. (b) The molten salt exhibits sufficient precursor solubility for the dissolution-reprecipitation process to occur in a reasonable time. Similarly, the decomposition of Ba2LaNbO6 and Ba2NdNbO6 in a molten salt bath shows that these materials are thermodynamically unstable at the temperature of the molten salt bath.

Estimation of thermodynamic parameters for Au- and Mg-based metallic glasses

NASA Astrophysics Data System (ADS)

Gaur, Jitendra; Mishra, R. K.

2017-10-01

The study of temperature dependent thermodynamic parameters; Gibb's free energy difference (ΔG), entropy difference (ΔS) and enthalpy difference (ΔH) between the undercooled liquid and the corresponding equilibrium solid phases has been proved to be extremely advantageous in the study of the thermodynamic behaviour of Metallic glass (MG) forming melts. In last two decades, Au- and Mg-based alloys were found to form glass phases. In present study, the three thermodynamic parameters viz., ΔG, ΔS and ΔH are calculated theoretically in the entire temperature range Tm (melting temperature) to Tg (glass transition temperature) for both Au- and Mg-based five samples of MGs; Au77Ge13.6Si9.4, Au53.2Pb27.5Sb19.3, Au81.4Si18.6, Mg85.5Cu14.5 and Mg81.6Ga18.4 on the basis of Taylor's series expansion. A relative study is also made between the present result and the result obtained experimentally as well as on the basis of expressions projected by the earlier researchers. An attempt is also been made to narrate the reduced glass transition temperature with glass forming ability for all five MGs.

Quantum Rényi relative entropies affirm universality of thermodynamics.

PubMed

Misra, Avijit; Singh, Uttam; Bera, Manabendra Nath; Rajagopal, A K

2015-10-01

We formulate a complete theory of quantum thermodynamics in the Rényi entropic formalism exploiting the Rényi relative entropies, starting from the maximum entropy principle. In establishing the first and second laws of quantum thermodynamics, we have correctly identified accessible work and heat exchange in both equilibrium and nonequilibrium cases. The free energy (internal energy minus temperature times entropy) remains unaltered, when all the entities entering this relation are suitably defined. Exploiting Rényi relative entropies we have shown that this "form invariance" holds even beyond equilibrium and has profound operational significance in isothermal process. These results reduce to the Gibbs-von Neumann results when the Rényi entropic parameter α approaches 1. Moreover, it is shown that the universality of the Carnot statement of the second law is the consequence of the form invariance of the free energy, which is in turn the consequence of maximum entropy principle. Further, the Clausius inequality, which is the precursor to the Carnot statement, is also shown to hold based on the data processing inequalities for the traditional and sandwiched Rényi relative entropies. Thus, we find that the thermodynamics of nonequilibrium state and its deviation from equilibrium together determine the thermodynamic laws. This is another important manifestation of the concepts of information theory in thermodynamics when they are extended to the quantum realm. Our work is a substantial step towards formulating a complete theory of quantum thermodynamics and corresponding resource theory.

Correlations in quantum thermodynamics: Heat, work, and entropy production

PubMed Central

Alipour, S.; Benatti, F.; Bakhshinezhad, F.; Afsary, M.; Marcantoni, S.; Rezakhani, A. T.

2016-01-01

We provide a characterization of energy in the form of exchanged heat and work between two interacting constituents of a closed, bipartite, correlated quantum system. By defining a binding energy we derive a consistent quantum formulation of the first law of thermodynamics, in which the role of correlations becomes evident, and this formulation reduces to the standard classical picture in relevant systems. We next discuss the emergence of the second law of thermodynamics under certain—but fairly general—conditions such as the Markovian assumption. We illustrate the role of correlations and interactions in thermodynamics through two examples. PMID:27767124

Generation of hydrate forms of paroxetine HCl from the amorphous state: an evaluation of thermodynamic and experimental predictive approaches.

PubMed

Pina, M Fátima; Pinto, João F; Sousa, João J; Craig, Duncan Q M; Zhao, Min

2015-03-15

In this study, we evaluate the use of theoretical thermodynamic analysis of amorphous paroxetine hydrochloride (HCl) as well as experimental assessment in order to identify the most promising approach to stability and dissolution behaviour prediction, particularly in relation to stoichiometric and nonstoichiometric hydrate formation. Differential scanning calorimetry, thermogravimetric analysis, Fourier transform infrared and X-ray diffraction techniques were used. Parameters including heat capacity, configurational thermodynamic quantities, fragility and relaxation time classified amorphous paroxetine HCl as a moderate fragile glass with a considerable degree of molecular mobility. Solubility studies indicated little advantage of the amorphous form over the crystalline due to conversion to the hydrate Form I during equilibration, while the dissolution rate was higher for the amorphous form under sink conditions. A marked difference in the physical stability of amorphous paroxetine HCl was observed between dry and low humidity storage, with the system recrystallizing to the hydrate form. We conclude that, in this particular case (amorphous conversion to the hydrate), water may be playing a dual role in both plasticizing the amorphous form and driving the equilibrium towards the hydrate form, hence prediction of recrystallization behaviour from amorphous characteristics may be confounded by the additional process of hydrate generation. Copyright © 2015 Elsevier B.V. All rights reserved.

First-principles studies of chromium line-ordered alloys in a molybdenum disulfide monolayer

NASA Astrophysics Data System (ADS)

Andriambelaza, N. F.; Mapasha, R. E.; Chetty, N.

2017-08-01

Density functional theory calculations have been performed to study the thermodynamic stability, structural and electronic properties of various chromium (Cr) line-ordered alloy configurations in a molybdenum disulfide (MoS2) hexagonal monolayer for band gap engineering. Only the molybdenum (Mo) sites were substituted at each concentration in this study. For comparison purposes, different Cr line-ordered alloy and random alloy configurations were studied and the most thermodynamically stable ones at each concentration were identified. The configurations formed by the nearest neighbor pair of Cr atoms are energetically most favorable. The line-ordered alloys are constantly lower in formation energy than the random alloys at each concentration. An increase in Cr concentration reduces the lattice constant of the MoS2 system following the Vegard’s law. From density of states analysis, we found that the MoS2 band gap is tunable by both the Cr line-ordered alloys and random alloys with the same magnitudes. The reduction of the band gap is mainly due to the hybridization of the Cr 3d and Mo 4d orbitals at the vicinity of the band edges. The band gap engineering and magnitudes (1.65 eV to 0.86 eV) suggest that the Cr alloys in a MoS2 monolayer are good candidates for nanotechnology devices.

Infrared Multiple-Photon Dissociation Action Spectroscopy of the b2 + Ion from PPG: Evidence of Third Residue Affecting b2 + Fragment Structure

NASA Astrophysics Data System (ADS)

Poutsma, John C.; Martens, Jonathan; Oomens, Jos; Maitre, Phillipe; Steinmetz, Vincent; Bernier, Matthew; Jia, Mengxuan; Wysocki, Vicki

2017-07-01

Infrared multiple-photon dissociation (IRMPD) action spectroscopy was performed on the b2 + fragment ion from the protonated PPG tripeptide. Comparison of the experimental infrared spectrum with computed spectra for both oxazolone and diketopiperazine structures indicates that the majority of the fragment ion population has an oxazolone structure with the remainder having a diketopiperazine structure. This result is in contrast with a recent study of the IRMPD action spectrum of the PP b2 + fragment ion from PPP, which was found to be nearly 100% diketopiperazine (Martens et al. Int. J. Mass Spectrom. 2015, 377, 179). The diketopiperazine b2 + ion is thermodynamically more stable than the oxazolone but normally requires a trans/cis peptide bond isomerization in the dissociating peptide. Martens et al. showed through IRMPD action spectroscopy that the PPP precursor ion was in a conformation in which the first peptide bond is already in the cis conformation and thus it was energetically favorable to form the thermodynamically-favored diketopiperazine b2 + ion. In the present case, solution-phase NMR spectroscopy and gas-phase IRMPD action spectroscopy show that the PPG precursor ion has its first amide bond in a trans configuration suggesting that the third residue is playing an important role in both the structure of the peptide and the associated ring-closure barriers for oxazolone and diketopiperazine formation.

Trace Water as Prominent Factor to Induce Peptide Self-Assembly: Dynamic Evolution and Governing Interactions in Ionic Liquids.

PubMed

Wang, Juan; Yuan, Chengqian; Han, Yuchun; Wang, Yilin; Liu, Xiaomin; Zhang, Suojiang; Yan, Xuehai

2017-11-01

The interaction between water and biomolecules including peptides is of critical importance for forming high-level architectures and triggering life's functions. However, the bulk aqueous environment has limitations in detecting the kinetics and mechanisms of peptide self-assembly, especially relating to interactions of trace water. With ionic liquids (ILs) as a nonconventional medium, herein, it is discovered that trace amounts of water play a decisive role in triggering self-assembly of a biologically derived dipeptide. ILs provide a suitable nonaqueous environment, enabling us to mediate water content and follow the dynamic evolution of peptide self-assembly. The trace water is found to be involved in the assembly process of dipeptide, especially leading to the formation of stable noncovalent dipeptide oligomers in the early stage of nucleation, as evident by both experimental studies and theoretical simulations. The thermodynamics of the growth process is mainly governed by a synergistic effect of hydrophobic interaction and hydrogen bonds. Each step of assembly presents a different trend in thermodynamic energy. The dynamic evolution of assembly process can be efficiently mediated by changing trace water content. The decisive role of trace water in triggering and mediating self-assembly of biomolecules provides a new perspective in understanding supramolecular chemistry and molecular self-organization in biology. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thermodynamic parameters of U (VI) sorption onto soils in aquatic systems.

PubMed

Kumar, Ajay; Rout, Sabyasachi; Ghosh, Malay; Singhal, Rakesh Kumar; Ravi, Pazhayath Mana

2013-01-01

The thermodynamic parameters viz. the standard free energy (∆Gº), Standard enthalpy change (∆Hº) and standard entropy change (∆Sº) were determined using the obtained values of distribution coefficient (kd) of U (VI) in two different types of soils (agricultural and undisturbed) by conducting a batch equilibrium experiment with aqueous media (groundwater and deionised water) at two different temperatures 25°C and 50°C. The obtained distribution coefficients (kd) values of U for undisturbed soil in groundwater showed about 75% higher than in agricultural soil at 25°C while in deionised water, these values were highly insignificant for both soils indicating that groundwater was observed to be more favorable for high surface sorption. At 50°C, the increased kd values in both soils revealed that solubility of U decreased with increasing temperature. Batch adsorption results indicated that U sorption onto soils was promoted at higher temperature and an endothermic and spontaneous interfacial process. The high positive values of ∆Sº for agricultural soil suggested a decrease in sorption capacity of U in that soil due to increased randomness at solid-solution interface. The low sorption onto agricultural soil may be due to presence of high amount of coarse particles in the form of sand (56%). Geochemical modeling predicted that mixed hydroxo-carbonato complexes of uranium were the most stable and abundant complexes in equilibrium solution during experimental.

Computer programs for thermodynamic and transport properties of hydrogen

NASA Technical Reports Server (NTRS)

Hall, W. J.; Mc Carty, R. D.; Roder, H. M.

1968-01-01

Computer program subroutines provide the thermodynamic and transport properties of hydrogen in tabular form. The programs provide 18 combinations of input and output variables. This program is written in FORTRAN 4 for use on the IBM 7044 or CDC 3600 computers.

Electronic and Electrochemical Properties of Li 1–x Mn 1.5 Ni 0.5 O 4 Spinel Cathodes As a Function of Lithium Content and Cation Ordering

DOE PAGES

Moorhead-Rosenberg, Zach; Huq, Ashfia; Goodenough, John B.; ...

2015-10-05

The electronic and electrochemical properties of the high-voltage spinel LiMn 1.5Ni 0.5O 4 as a function of cation ordering and lithium content have been investigated. Conductivity and activation energy measurements confirm that charge transfer occurs by small polaron hopping and the charge carrier conduction is easier in the Ni:3d band than in the in Mn:3d band. Seebeck coefficient data reveal that the Ni 2+/ 3+. and Ni 3+/ 4+ redox couples are combined in a single,3d band, and that maximum charge carrier concentration occurs where the average Ni oxidation state is close to 3+, corresponding to x = 0.5 inmore » Li Li 1-xMn 1.5Ni 0.5O 4. Furthermore, maximum electronic conductivity is found at x = 0.5, regardless of cation ordering. The thermodynamically stable phases formed during cycling were investigated by recording the X-ray diffraction (XRD) of chemically delithiated powders. The more ordered spinels maintained two separate two-phase regions upon lithium extraction, while the more disordered samples exhibited a solid-solubility region from LiMn 1.5Ni 0.5O 4 to Li 0.5Mn 1.5Ni 0.5O 4. The conductivity and phase-transformation data of four samples with varying degrees of cation ordering were compared to the electrochemical data collected with lithium cells. Only the most ordered spinel showed inferior rate performance, while the sample annealed for a shorter time performed comparable to the unannealed or disordered samples. Our results challenge the most common beliefs about high-voltage spinel: (i) low Mn 3+ content is responsible for poor rate performance and (ii) thermodynamically stable solid-solubility is critical for fast kinetics.« less

Reactivity of Hydrogen and Methanol on (001) Surfaces of WO3, ReO3, WO3/ReO3 and ReO3/WO3

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ling, Sanliang; Mei, Donghai; Gutowski, Maciej S.

2011-05-16

Bulk tungsten trioxide (WO3) and rhenium trioxide (ReO3) share very similar structures but display different electronic properties. WO3 is a wide bandgap semiconductor while ReO3 is an electronic conductor. With the advanced molecular beam epitaxy techniques, it is possible to make heterostructures comprised of layers of WO3 and ReO3. These heterostructures might display reactivity different than pure WO3 and ReO3. The interactions of two probe molecules (hydrogen and methanol) with the (001) surfaces of WO3, ReO3, and two heterostructures ReO3/WO3 and WO3/ReO3 were investigated at the density functional theory level. Atomic hydrogen prefers to adsorb at the terminal O1C sitesmore » forming a surface hydroxyl on four surfaces. Dissociative adsorption of a hydrogen molecule at the O1C site leads to formation of a water molecule adsorbed at the surface M5C site. This is thermodynamically the most stable state. A thermodynamically less stable dissociative state involves two surface hydroxyl groups O1CH and O2CH. The interaction of molecular hydrogen and methanol with pure ReO3 is stronger than with pure WO3 and the strength of the interaction substantially changes on the WO3/ReO3 and ReO3/WO3 heterostructures. The reaction barriers for decomposition and recombination reactions are sensitive to the nature of heterostructure. The calculated adsorption energy of methanol on WO3(001) of -65.6 kJ/mol is consistent with the previous experimental estimation of -67 kJ/mol. This material is based upon work supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences.« less

Progress in the development and optimization of polyoxometalate delignification systems

Treesearch

R.H. Atalla; I.A. Weinstock; J.S. Bond; R.S. Reiner; E.L. Springer; C.G. Hill; Yu. Geletii; V.A. Grigoriev; A.J. Bailey; L. Delannoy; C.L. Hill

2002-01-01

We have reported the use of polyoxometalates (POMs) as selective, regenerable delignification agents that are inherently thermodynamically stable, and self-buffering. The re-activation with oxygen is under conditions that mineralize the organic byproducts of the delignification process. Thus, the POMs provide the basis for a closed bleach plant wherein the consumable...

Progress in the development and optimization of polyoxometalate delignification systems

Treesearch

R.H. Atalla; I.A. Weinstock; R.S. Reiner; E.L. Springer; C.G. Hill

2003-01-01

We have reported the use of polyoxometalates (POMs) as selective, regenerable delignification agents that are inherently thermodynamically stable, and self-buffering. The re-activation with oxygen is under conditions that mineralize the organic byproducts of the delignification process. Thus, the POMs provide the basis for a closed bleach plant wherein the consumable...

Development of Silica Fibers and Microstructures with Large and Thermodynamically Stable Second Order Nonlinearity

DTIC Science & Technology

2011-06-22

high degree of symmetry directly leads to a symmetry-enforced selection rule that can produce quantum entanglement [21, 22]. This report is organized...page.) Then, using a Matlab program, we converted the microscope image to a binary bitmap, from which we extract fiber radius at any given location

String mediated phase transitions

NASA Technical Reports Server (NTRS)

Copeland, ED; Haws, D.; Rivers, R.; Holbraad, S.

1988-01-01

It is demonstrated from first principles how the existence of string-like structures can cause a system to undergo a phase transition. In particular, the role of topologically stable cosmic string in the restoration of spontaneously broken symmetries is emphasized. How the thermodynamic properties of strings alter when stiffness and nearest neighbor string-string interactions are included is discussed.

Stochastic approach to equilibrium and nonequilibrium thermodynamics.

PubMed

Tomé, Tânia; de Oliveira, Mário J

2015-04-01

We develop the stochastic approach to thermodynamics based on stochastic dynamics, which can be discrete (master equation) and continuous (Fokker-Planck equation), and on two assumptions concerning entropy. The first is the definition of entropy itself and the second the definition of entropy production rate, which is non-negative and vanishes in thermodynamic equilibrium. Based on these assumptions, we study interacting systems with many degrees of freedom in equilibrium or out of thermodynamic equilibrium and how the macroscopic laws are derived from the stochastic dynamics. These studies include the quasiequilibrium processes; the convexity of the equilibrium surface; the monotonic time behavior of thermodynamic potentials, including entropy; the bilinear form of the entropy production rate; the Onsager coefficients and reciprocal relations; and the nonequilibrium steady states of chemical reactions.

Chemical thermodynamic data. 1. The concept of links to the chemical elements and the historical development of key thermodynamic data [plus Supplementary Electronic Annex 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wolery, Thomas J.; Jove Colon, Carlos F.

Chemical thermodynamic data remain a keystone for geochemical modeling and reactive transport simulation as applied to an increasing number of applications in the earth sciences, as well as applications in other areas including metallurgy, material science, and industrial process design. The last century has seen the development of a large body of thermodynamic data and a number of major compilations. The past several decades have seen the development of thermodynamic databases in digital form designed to support computer calculations. However, problems with thermodynamic data appear to be persistent. One problem pertains to the use of inconsistent primary key reference data.more » Such data pertain to elemental reference forms and key, stoichiometrically simple chemical species including metal oxides, CO 2, water, and aqueous species such as Na + and Cl -. A consistent set of primary key data (standard Gibbs energies, standard enthalpies, and standard entropies for key chemical species) for 298.15K and 1 bar pressure is essential. Thermochemical convention is to define the standard Gibbs energy and the standard enthalpy of an individual chemical species in terms of formation from reference forms of the constituent chemical elements. We propose a formal concept of “links” to the elemental reference forms. This concept involves a documented understanding of all reactions and calculations leading to values for a formation property (standard Gibbs energy or enthalpy). A valid link consists of two parts: (a) the path of reactions and corrections and (b) the associated data, which are key data. Such a link differs from a bare “key” or “reference” datum in that it requires additional information. Some or all of its associated data may also be key data. In evaluating a reported thermodynamic datum, one should identify the links to the chemical elements, a process which can be time-consuming and which may lead to a dead end (an incomplete link). The use of two or more inconsistent links to the same elemental reference form in a thermodynamic database will result in an inconsistency in the database. Thus, in constructing a database, it is important to establish a set of reliable links (generally resulting in a set of primary reference data) and then correct all data adopted subsequently for consistency with that set. Recommended values of key data have not been constant through history. We review some of this history through the lens of major compilations and other influential reports, and note a number of problem areas. Finally, we illustrate the concepts developed in this paper by applying them to some key species of geochemical interest, including liquid water; quartz and aqueous silica; and gibbsite, corundum, and the aqueous aluminum ion.« less

Chemical thermodynamic data. 1. The concept of links to the chemical elements and the historical development of key thermodynamic data

NASA Astrophysics Data System (ADS)

Wolery, Thomas J.; Jové Colón, Carlos F.

2017-09-01

Chemical thermodynamic data remain a keystone for geochemical modeling and reactive transport simulation as applied to an increasing number of applications in the earth sciences, as well as applications in other areas including metallurgy, material science, and industrial process design. The last century has seen the development of a large body of thermodynamic data and a number of major compilations. The past several decades have seen the development of thermodynamic databases in digital form designed to support computer calculations. However, problems with thermodynamic data appear to be persistent. One problem pertains to the use of inconsistent primary key reference data. Such data pertain to elemental reference forms and key, stoichiometrically simple chemical species including metal oxides, CO2, water, and aqueous species such as Na+ and Cl-. A consistent set of primary key data (standard Gibbs energies, standard enthalpies, and standard entropies for key chemical species) for 298.15 K and 1 bar pressure is essential. Thermochemical convention is to define the standard Gibbs energy and the standard enthalpy of an individual chemical species in terms of formation from reference forms of the constituent chemical elements. We propose a formal concept of "links" to the elemental reference forms. This concept involves a documented understanding of all reactions and calculations leading to values for a formation property (standard Gibbs energy or enthalpy). A valid link consists of two parts: (a) the path of reactions and corrections and (b) the associated data, which are key data. Such a link differs from a bare "key" or "reference" datum in that it requires additional information. Some or all of its associated data may also be key data. In evaluating a reported thermodynamic datum, one should identify the links to the chemical elements, a process which can be time-consuming and which may lead to a dead end (an incomplete link). The use of two or more inconsistent links to the same elemental reference form in a thermodynamic database will result in an inconsistency in the database. Thus, in constructing a database, it is important to establish a set of reliable links (generally resulting in a set of primary reference data) and then correct all data adopted subsequently for consistency with that set. Recommended values of key data have not been constant through history. We review some of this history through the lens of major compilations and other influential reports, and note a number of problem areas. Finally, we illustrate the concepts developed in this paper by applying them to some key species of geochemical interest, including liquid water; quartz and aqueous silica; and gibbsite, corundum, and the aqueous aluminum ion.

Chemical thermodynamic data. 1. The concept of links to the chemical elements and the historical development of key thermodynamic data [plus Supplementary Electronic Annex 2

DOE PAGES

Wolery, Thomas J.; Jove Colon, Carlos F.

2016-09-26

Chemical thermodynamic data remain a keystone for geochemical modeling and reactive transport simulation as applied to an increasing number of applications in the earth sciences, as well as applications in other areas including metallurgy, material science, and industrial process design. The last century has seen the development of a large body of thermodynamic data and a number of major compilations. The past several decades have seen the development of thermodynamic databases in digital form designed to support computer calculations. However, problems with thermodynamic data appear to be persistent. One problem pertains to the use of inconsistent primary key reference data.more » Such data pertain to elemental reference forms and key, stoichiometrically simple chemical species including metal oxides, CO 2, water, and aqueous species such as Na + and Cl -. A consistent set of primary key data (standard Gibbs energies, standard enthalpies, and standard entropies for key chemical species) for 298.15K and 1 bar pressure is essential. Thermochemical convention is to define the standard Gibbs energy and the standard enthalpy of an individual chemical species in terms of formation from reference forms of the constituent chemical elements. We propose a formal concept of “links” to the elemental reference forms. This concept involves a documented understanding of all reactions and calculations leading to values for a formation property (standard Gibbs energy or enthalpy). A valid link consists of two parts: (a) the path of reactions and corrections and (b) the associated data, which are key data. Such a link differs from a bare “key” or “reference” datum in that it requires additional information. Some or all of its associated data may also be key data. In evaluating a reported thermodynamic datum, one should identify the links to the chemical elements, a process which can be time-consuming and which may lead to a dead end (an incomplete link). The use of two or more inconsistent links to the same elemental reference form in a thermodynamic database will result in an inconsistency in the database. Thus, in constructing a database, it is important to establish a set of reliable links (generally resulting in a set of primary reference data) and then correct all data adopted subsequently for consistency with that set. Recommended values of key data have not been constant through history. We review some of this history through the lens of major compilations and other influential reports, and note a number of problem areas. Finally, we illustrate the concepts developed in this paper by applying them to some key species of geochemical interest, including liquid water; quartz and aqueous silica; and gibbsite, corundum, and the aqueous aluminum ion.« less

Necessary conditions for the emergence of homochirality via autocatalytic self-replication

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stich, Michael; Ribó, Josep M.; Blackmond, Donna G., E-mail: blackmond@scripps.edu

We analyze a recent proposal for spontaneous mirror symmetry breaking based on the coupling of first-order enantioselective autocatalysis and direct production of the enantiomers that invokes a critical role for intrinsic reaction noise. For isolated systems, the racemic state is the unique stable outcome for both stochastic and deterministic dynamics when the system is in compliance with the constraints dictated by the thermodynamics of chemical reaction processes. In open systems, the racemic outcome also results for both stochastic and deterministic dynamics when driving the autocatalysis unidirectionally by external reagents. Nonracemic states can result in the latter only if the reversemore » reactions are strictly zero: these are kinetically controlled outcomes for small populations and volumes, and can be simulated by stochastic dynamics. However, the stability of the thermodynamic limit proves that the racemic outcome is the unique stable state for strictly irreversible externally driven autocatalysis. These findings contradict the suggestion that the inhibition requirement of the Frank autocatalytic model for the emergence of homochirality may be relaxed in a noise-induced mechanism.« less

Growth far from equilibrium: Examples from III-V semiconductors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kuech, Thomas F.; Babcock, Susan E.; Mawst, Luke

The development of new applications has driven the field of materials design and synthesis to investigate materials that are not thermodynamically stable phases. Materials which are not thermodynamically stable can be synthesized and used in many applications. These materials are kinetically stabilized during use. The formation of such metastable materials requires both an understanding of the associated thermochemistry and the key surface transport processes present during growth. Phase separation is most easily accomplished at the growth surface during synthesis where mass transport is most rapid. These surface transport processes are sensitive to the surface stoichiometry, reconstruction, and chemistry as wellmore » as the growth temperature. The formation of new metastable semiconducting alloys with compositions deep within a compositional miscibility gap serves as model systems for the understanding of the surface chemical and physical processes controlling their formation. The GaAs{sub 1−y}Bi{sub y} system is used here to elucidate the role of surface chemistry in the formation of a homogeneous metastable composition during the chemical vapor deposition of the alloy system.« less

Interacting hadron resonance gas model in the K -matrix formalism

NASA Astrophysics Data System (ADS)

Dash, Ashutosh; Samanta, Subhasis; Mohanty, Bedangadas

2018-05-01

An extension of hadron resonance gas (HRG) model is constructed to include interactions using relativistic virial expansion of partition function. The noninteracting part of the expansion contains all the stable baryons and mesons and the interacting part contains all the higher mass resonances which decay into two stable hadrons. The virial coefficients are related to the phase shifts which are calculated using K -matrix formalism in the present work. We have calculated various thermodynamics quantities like pressure, energy density, and entropy density of the system. A comparison of thermodynamic quantities with noninteracting HRG model, calculated using the same number of hadrons, shows that the results of the above formalism are larger. A good agreement between equation of state calculated in K -matrix formalism and lattice QCD simulations is observed. Specifically, the lattice QCD calculated interaction measure is well described in our formalism. We have also calculated second-order fluctuations and correlations of conserved charges in K -matrix formalism. We observe a good agreement of second-order fluctuations and baryon-strangeness correlation with lattice data below the crossover temperature.

First-principles investigation of the structural characteristics of LiMO2 cathode materials for lithium secondary batteries

NASA Astrophysics Data System (ADS)

Kim, Yongseon

2015-11-01

The structural features related to the defects of LiMO2 (M = Ni, Co, Mn) cathode materials for lithium secondary batteries were investigated by a simulation of phase diagrams based on first-principle calculations. Crystal models with various types of point defects were designed and dealt with as independent phases, which enabled an examination of the thermodynamic stability of the defects. A perfect phase without defects appeared to be the most stable for LiCoO2, whereas the formation of Li vacancies, O vacancies, and antisites between Li and Ni was thermodynamically unavoidable for LiNiO2. The introduction of both Co and Mn in LiNiO2 was effective in reducing the formation of point defects, but increasing the relative amount of Mn was undesirable because the antisite defect remained stable with Mn doping. The simulation showed good agreement with the experimental data and previous reports. Therefore, the method and the results of this study are expected to be useful for examining the synthesis, structure and related properties of layer-structured cathode materials.

Vibrational spectra, DFT quantum chemical calculations and conformational analysis of P-iodoanisole.

PubMed

Arivazhagan, M; Anitha Rexalin, D; Geethapriya, J

2013-09-01

The solid phase FT-IR and FT-Raman spectra of P-iodoanisole (P-IA) have been recorded in the regions 400-4000 and 50-4000 cm(-1), respectively. The spectra were interpreted in terms of fundamentals modes, combination and overtone bands. The structure of the molecule was optimized and the structural characteristics were determined by ab initio (HF) and density functional theory (B3LYP) methods with LanL2DZ as basis set. The potential energy surface scan for the selected dihedral angle of P-IA has been performed to identify stable conformer. The optimized structure parameters and vibrational wavenumbers of stable conformer have been predicted by density functional B3LYP method with LanL2DZ (with effective core potential representations of electrons near the nuclei for post-third row atoms) basis set. The nucleophilic and electrophilic sites obtained from the molecular electrostatic potential (MEP) surface were calculated. The temperature dependence of thermodynamic properties has been analyzed. Several thermodynamic parameters have been calculated using B3LYP with LanL2DZ basis set. Copyright © 2013 Elsevier B.V. All rights reserved.

Quantum corrections to the stress-energy tensor in thermodynamic equilibrium with acceleration

NASA Astrophysics Data System (ADS)

Becattini, F.; Grossi, E.

2015-08-01

We show that the stress-energy tensor has additional terms with respect to the ideal form in states of global thermodynamic equilibrium in flat spacetime with nonvanishing acceleration and vorticity. These corrections are of quantum origin and their leading terms are second order in the gradients of the thermodynamic fields. Their relevant coefficients can be expressed in terms of correlators of the stress-energy tensor operator and the generators of the Lorentz group. With respect to previous assessments, we find that there are more second-order coefficients and that all thermodynamic functions including energy density receive acceleration and vorticity dependent corrections. Notably, also the relation between ρ and p , that is, the equation of state, is affected by acceleration and vorticity. We have calculated the corrections for a free real scalar field—both massive and massless—and we have found that they increase, particularly for a massive field, at very high acceleration and vorticity and very low temperature. Finally, these nonideal terms depend on the explicit form of the stress-energy operator, implying that different stress-energy tensors of the scalar field—canonical or improved—are thermodynamically inequivalent.

Thermodynamics of Sultana-Dyer black hole

DOE Office of Scientific and Technical Information (OSTI.GOV)

Majhi, Bibhas Ranjan, E-mail: bibhas.majhi@mail.huji.ac.il

The thermodynamical entities on the dynamical horizon are not naturally defined like the usual static cases. Here I find the temperature, Smarr formula and the first law of thermodynamics for the Sultana-Dyer metric which is related to the Schwarzschild spacetime by a time dependent conformal factor. To find the temperature (T), the chiral anomaly expressions for the two dimensional spacetime are used. This shows an application of the anomaly method to study Hawking effect for a dynamical situation. Moreover, the analysis singles out one expression for temperature among two existing expressions in the literature. Interestingly, the present form satisfies themore » first law of thermodynamics. Also, it relates the Misner-Sharp energy (Ē) and the horizon entropy ( S-bar ) by an algebraic expression Ē = 2 S-bar T which is the general form of the Smarr formula. This fact is similar to the usual static black hole cases in Einstein's gravity where the energy is identified as the Komar conserved quantity.« less

Thermodynamic scaling of glassy dynamics and dynamic heterogeneities in metallic glass-forming liquid

NASA Astrophysics Data System (ADS)

Hu, Yuan-Chao; Shang, Bao-Shuang; Guan, Peng-Fei; Yang, Yong; Bai, Hai-Yang; Wang, Wei-Hua

2016-09-01

A ternary metallic glass-forming liquid is found to be not strongly correlating thermodynamically, but its average dynamics, dynamic heterogeneities including the high order dynamic correlation length, and static structure are still well described by thermodynamic scaling with the same scaling exponent γ. This may indicate that the metallic liquid could be treated as a single-parameter liquid. As an intrinsic material constant stemming from the fundamental interatomic interactions, γ is theoretically predicted from the thermodynamic fluctuations of the potential energy and the virial. Although γ is conventionally understood merely from the repulsive part of the inter-particle potentials, the strong correlation between γ and the Grüneisen parameter up to the accuracy of the Dulong-Petit approximation demonstrates the important roles of anharmonicity and attractive force of the interatomic potential in governing glass transition of metallic glassformers. These findings may shed light on how to understand metallic glass formation from the fundamental interatomic interactions.

First-Principles Thermodynamics Study of Spinel MgAl 2 O 4 Surface Stability

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cai, Qiuxia; Wang, Jian-guo; Wang, Yong

The surface stability of all possible terminations for three low-index (111, 110, 100) structures of the spinel MgAl2O4 has been studied using first-principles based thermodynamic approach. The surface Gibbs free energy results indicate that the 100_AlO2 termination is the most stable surface structure under ultra-high vacuum at T=1100 K regardless of Al-poor or Al-rich environment. With increasing oxygen pressure, the 111_O2(Al) termination becomes the most stable surface in the Al-rich environment. The oxygen vacancy formation is thermodynamically favorable over the 100_AlO2, 111_O2(Al) and the (111) structure with Mg/O connected terminations. On the basis of surface Gibbs free energies for bothmore » perfect and defective surface terminations, the 100_AlO2 and 111_O2(Al) are the most dominant surfaces in Al-rich environment under atmospheric condition. This is also consistent with our previously reported experimental observation. This work was supported by a Laboratory Directed Research and Development (LDRD) project of the Pacific Northwest National Laboratory (PNNL). The computing time was granted by the National Energy Research Scientific Computing Center (NERSC). Part of computing time was also granted by a scientific theme user proposal in the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL), which is a U.S. Department of Energy national scientific user facility located at PNNL in Richland, Washington.« less

Thermodynamic Behavior Research Analysis of Twin-roll Casting Lead Alloy Strip Process

NASA Astrophysics Data System (ADS)

Jiang, Chengcan; Rui, Yannian

2017-03-01

The thermodynamic behavior of twin-roll casting (TRC) lead alloy strip process directly affects the forming of the lead strip, the quality of the lead strip and the production efficiency. However, there is little research on the thermodynamics of lead alloy strip at home and abroad. The TRC lead process is studied in four parameters: the pouring temperature of molten lead, the depth of molten pool, the roll casting speed, and the rolling thickness of continuous casting. Firstly, the thermodynamic model for TRC lead process is built. Secondly, the thermodynamic behavior of the TRC process is simulated with the use of Fluent. Through the thermodynamics research and analysis, the process parameters of cast rolling lead strip can be obtained: the pouring temperature of molten lead: 360-400 °C, the depth of molten pool: 250-300 mm, the roll casting speed: 2.5-3 m/min, the rolling thickness: 8-9 mm. Based on the above process parameters, the optimal parameters(the pouring temperature of molten lead: 375-390 °C, the depth of molten pool: 285-300 mm, the roll casting speed: 2.75-3 m/min, the rolling thickness: 8.5-9 mm) can be gained with the use of the orthogonal experiment. Finally, the engineering test of TRC lead alloy strip is carried out and the test proves the thermodynamic model is scientific, necessary and correct. In this paper, a detailed study on the thermodynamic behavior of lead alloy strip is carried out and the process parameters of lead strip forming are obtained through the research, which provide an effective theoretical guide for TRC lead alloy strip process.

There and back again: Two views on the protein folding puzzle.

PubMed

Finkelstein, Alexei V; Badretdin, Azat J; Galzitskaya, Oxana V; Ivankov, Dmitry N; Bogatyreva, Natalya S; Garbuzynskiy, Sergiy O

2017-07-01

The ability of protein chains to spontaneously form their spatial structures is a long-standing puzzle in molecular biology. Experimentally measured folding times of single-domain globular proteins range from microseconds to hours: the difference (10-11 orders of magnitude) is the same as that between the life span of a mosquito and the age of the universe. This review describes physical theories of rates of overcoming the free-energy barrier separating the natively folded (N) and unfolded (U) states of protein chains in both directions: "U-to-N" and "N-to-U". In the theory of protein folding rates a special role is played by the point of thermodynamic (and kinetic) equilibrium between the native and unfolded state of the chain; here, the theory obtains the simplest form. Paradoxically, a theoretical estimate of the folding time is easier to get from consideration of protein unfolding (the "N-to-U" transition) rather than folding, because it is easier to outline a good unfolding pathway of any structure than a good folding pathway that leads to the stable fold, which is yet unknown to the folding protein chain. And since the rates of direct and reverse reactions are equal at the equilibrium point (as follows from the physical "detailed balance" principle), the estimated folding time can be derived from the estimated unfolding time. Theoretical analysis of the "N-to-U" transition outlines the range of protein folding rates in a good agreement with experiment. Theoretical analysis of folding (the "U-to-N" transition), performed at the level of formation and assembly of protein secondary structures, outlines the upper limit of protein folding times (i.e., of the time of search for the most stable fold). Both theories come to essentially the same results; this is not a surprise, because they describe overcoming one and the same free-energy barrier, although the way to the top of this barrier from the side of the unfolded state is very different from the way from the side of the native state; and both theories agree with experiment. In addition, they predict the maximal size of protein domains that fold under solely thermodynamic (rather than kinetic) control and explain the observed maximal size of the "foldable" protein domains. Copyright © 2017 Elsevier B.V. All rights reserved.

There and back again: Two views on the protein folding puzzle

NASA Astrophysics Data System (ADS)

Finkelstein, Alexei V.; Badretdin, Azat J.; Galzitskaya, Oxana V.; Ivankov, Dmitry N.; Bogatyreva, Natalya S.; Garbuzynskiy, Sergiy O.

2017-07-01

The ability of protein chains to spontaneously form their spatial structures is a long-standing puzzle in molecular biology. Experimentally measured folding times of single-domain globular proteins range from microseconds to hours: the difference (10-11 orders of magnitude) is the same as that between the life span of a mosquito and the age of the universe. This review describes physical theories of rates of overcoming the free-energy barrier separating the natively folded (N) and unfolded (U) states of protein chains in both directions: ;U-to-N; and ;N-to-U;. In the theory of protein folding rates a special role is played by the point of thermodynamic (and kinetic) equilibrium between the native and unfolded state of the chain; here, the theory obtains the simplest form. Paradoxically, a theoretical estimate of the folding time is easier to get from consideration of protein unfolding (the ;N-to-U; transition) rather than folding, because it is easier to outline a good unfolding pathway of any structure than a good folding pathway that leads to the stable fold, which is yet unknown to the folding protein chain. And since the rates of direct and reverse reactions are equal at the equilibrium point (as follows from the physical ;detailed balance; principle), the estimated folding time can be derived from the estimated unfolding time. Theoretical analysis of the ;N-to-U; transition outlines the range of protein folding rates in a good agreement with experiment. Theoretical analysis of folding (the ;U-to-N; transition), performed at the level of formation and assembly of protein secondary structures, outlines the upper limit of protein folding times (i.e., of the time of search for the most stable fold). Both theories come to essentially the same results; this is not a surprise, because they describe overcoming one and the same free-energy barrier, although the way to the top of this barrier from the side of the unfolded state is very different from the way from the side of the native state; and both theories agree with experiment. In addition, they predict the maximal size of protein domains that fold under solely thermodynamic (rather than kinetic) control and explain the observed maximal size of the ;foldable; protein domains.

Theoretical investigation of M@Pb122- and M@Sn122- Zintl clusters (M = Lrn+, Lun+, La3+, Ac3+ and n = 0, 1, 2, 3).

PubMed

Joshi, Meenakshi; Chandrasekar, Aditi; Ghanty, Tapan K

2018-06-06

The positions of lawrencium (Lr), lutetium (Lu), actinium (Ac) and lanthanum (La) in the periodic table have been a controversial topic for quite some time. According to studies carried out by different groups with their justifications, these elements may potentially be placed in the d-block, p-block or all four in a 15 element f-block. The present work looks into this issue from a new perspective, which involves encapsulation of these four elements into Zintl ion clusters, Pb122- and Sn122-, followed by the determination of the structural, thermodynamic and electronic properties of these endohedral M@Pb122- and M@Sn122- clusters (M = Lrn+, Lun+ with n = 0, 1, 2, 3) using first principles based density functional theory (DFT). These parameters are compared with similar clusters encapsulated La3+ and Ac3+ ions in order to seek out similarities and differences to draw conclusions about their placement in the periodic table. For the first time the structural, energetic, and electronic properties of these metal atom/ion encapsulated Pb122- and Sn122- clusters have been investigated thoroughly. Structural parameters such as bond distances, geometry and symmetry, electronic properties viz. the density of states, the molecular orbital ordering, the electron localization function, bond critical point properties and charge distributions have been analyzed. Additionally, the thermodynamic property of the binding energy during the encapsulation process has also been calculated. All M@Pb12+ and M@Sn12+ (M = Lr and Lu) clusters form stable 18 bonding electron magic number systems with shell closing. They show negative values of binding energy and relatively large HOMO-LUMO energy gaps indicating the stability of such clusters. All the calculated parameters for Lr encapsulated clusters closely match with the corresponding calculated parameters of Lu encapsulated clusters, confirming the similarity between Lr and Lu metal atoms in various oxidation states, though their atomic ground state valence electronic configurations are different. The effect of spin orbit coupling has also been investigated using the ZORA approach. It is interesting to discover that La and Ac showed striking similarities to Lr and Lu with respect to all the properties investigated and have formed a stable 18-electron system.

Influence of polymorphism on the surface energetics of salmeterol xinafoate crystallized from supercritical fluids.

PubMed

Tong, Henry H Y; Shekunov, Boris Yu; York, Peter; Chow, Albert H L

2002-05-01

To characterize the surface thermodynamic properties of two polymorphic forms (I and II) of salmeterol xinafoate (SX) prepared from supercritical fluids and a commercial micronized SX (form 1) sample (MSX). Inverse gas chromatographic analysis was conducted on the SX samples at 30, 40, 50, and 60 degrees C using the following probes at infinite dilution: nonpolar probes (NPs; alkane C5-C9 series); and polar probes (PPs; i.e., dichloromethane, chloroform, acetone, ethyl acetate, diethyl ether, and tetrahydrofuran). Surface thermodynamic parameters of adsorption and Hansen solubility parameters were calculated from the retention times of the probes. The free energies of adsorption (- deltaG(A)) of the three samples obtained at various temperatures follow this order: SX-II > MSX approximately/= SX-I for the NPs; and SX-II > MSX > SX-I for the PPs. For both NPs and PPs, SX-II exhibits a less negative enthalpy of adsorption (deltaH(A)) and a much less negative entropy of adsorption (ASA) than MSX and SX-I, suggesting that the high -AGA of SX-II is contributed by a considerably reduced entropy loss. The dispersive component of surface free energy (gammas(D)) is the highest for MSX but the lowest for SX-II at all temperatures studied, whereas the specific component of surface free energy of adsorption (-deltaG(A)SP) is higher for SX-II than for SX-I. That SX-II displays the highest -deltaG(A) for the NP but the lowest gammasD of all the SX samples may be explained by the additional -AGA change associated with an increased mobility of the probe molecules on the less stable and more disordered SX-II surface. The acid and base parameters, K(A) and K(D) that were derived from deltaH(A)SP reveal significant differences in the relative acid and base properties among the samples. The calculated Hansen solubility parameters (deltaD, deltap, and deltaH) indicate that the surface of SX-II is the most polar and most energetic of all the three samples in terms of specific interactions (mostly hydrogen bonding). The metastable SX-II polymorph possesses a higher surface free energy, higher surface entropy, and a more polar surface than the stable SX-I polymorph.

Prediction of novel stable Fe-V-Si ternary phase

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nguyen, Manh Cuong; Chen, Chong; Zhao, Xin

Genetic algorithm searches based on a cluster expansion model are performed to search for stable phases of Fe-V-Si ternary. Here, we identify a new thermodynamically, dynamically and mechanically stable ternary phase of Fe 5V 2Si with 2 formula units in a tetragonal unit cell. The formation energy of this new ternary phase is -36.9 meV/atom below the current ternary convex hull. The magnetic moment of Fe in the new structure varies from -0.30-2.52 μ B depending strongly on the number of Fe nearest neighbors. The total magnetic moment is 10.44 μ B/unit cell for new Fe 5V 2Si structure andmore » the system is ordinarily metallic.« less

An automated and efficient conformation search of L-cysteine and L,L-cystine using the scaled hypersphere search method

NASA Astrophysics Data System (ADS)

Kishimoto, Naoki; Waizumi, Hiroki

2017-10-01

Stable conformers of L-cysteine and L,L-cystine were explored using an automated and efficient conformational searching method. The Gibbs energies of the stable conformers of L-cysteine and L,L-cystine were calculated with G4 and MP2 methods, respectively, at 450, 298.15, and 150 K. By assuming thermodynamic equilibrium and the barrier energies for the conformational isomerization pathways, the estimated ratios of the stable conformers of L-cysteine were compared with those determined by microwave spectroscopy in a previous study. Equilibrium structures of 1:1 and 2:1 cystine-Fe complexes were also calculated, and the energy of insertion of Fe into the disulfide bond was obtained.

Prediction of novel stable Fe-V-Si ternary phase

DOE PAGES

Nguyen, Manh Cuong; Chen, Chong; Zhao, Xin; ...

2018-10-28

Genetic algorithm searches based on a cluster expansion model are performed to search for stable phases of Fe-V-Si ternary. Here, we identify a new thermodynamically, dynamically and mechanically stable ternary phase of Fe 5V 2Si with 2 formula units in a tetragonal unit cell. The formation energy of this new ternary phase is -36.9 meV/atom below the current ternary convex hull. The magnetic moment of Fe in the new structure varies from -0.30-2.52 μ B depending strongly on the number of Fe nearest neighbors. The total magnetic moment is 10.44 μ B/unit cell for new Fe 5V 2Si structure andmore » the system is ordinarily metallic.« less

Theoretical analysis of co-solvent effect on the proton transfer reaction of glycine in a water–acetonitrile mixture

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kasai, Yukako; Yoshida, Norio, E-mail: noriwo@chem.kyushu-univ.jp; Nakano, Haruyuki

2015-05-28

The co-solvent effect on the proton transfer reaction of glycine in a water–acetonitrile mixture was examined using the reference interaction-site model self-consistent field theory. The free energy profiles of the proton transfer reaction of glycine between the carboxyl oxygen and amino nitrogen were computed in a water–acetonitrile mixture solvent at various molar fractions. Two types of reactions, the intramolecular proton transfer and water-mediated proton transfer, were considered. In both types of the reactions, a similar tendency was observed. In the pure water solvent, the zwitterionic form, where the carboxyl oxygen is deprotonated while the amino nitrogen is protonated, is moremore » stable than the neutral form. The reaction free energy is −10.6 kcal mol{sup −1}. On the other hand, in the pure acetonitrile solvent, glycine takes only the neutral form. The reaction free energy from the neutral to zwitterionic form gradually increases with increasing acetonitrile concentration, and in an equally mixed solvent, the zwitterionic and neutral forms are almost isoenergetic, with a difference of only 0.3 kcal mol{sup −1}. The free energy component analysis based on the thermodynamic cycle of the reaction also revealed that the free energy change of the neutral form is insensitive to the change of solvent environment but the zwitterionic form shows drastic changes. In particular, the excess chemical potential, one of the components of the solvation free energy, is dominant and contributes to the stabilization of the zwitterionic form.« less

The Gibbs Variational Method in Thermodynamics of Equilibrium Plasma: 1. General Conditions of Equilibrium and Stability for One-Component Charged Gas

DTIC Science & Technology

2018-04-01

systems containing ionized gases. 2. Gibbs Method in the Integral Form As per the Gibbs general methodology , based on the concept of heterogeneous...ARL-TR-8348 ● APR 2018 US Army Research Laboratory The Gibbs Variational Method in Thermodynamics of Equilibrium Plasma: 1...ARL-TR-8348 ● APR 2018 US Army Research Laboratory The Gibbs Variational Method in Thermodynamics of Equilibrium Plasma: 1. General

Prediction of the Iron-Based Polynuclear Magnetic Superhalogens with Pseudohalogen CN as Ligands.

PubMed

Ding, Li-Ping; Shao, Peng; Lu, Cheng; Zhang, Fang-Hui; Liu, Yun; Mu, Qiang

2017-07-17

To explore stable polynuclear magnetic superhalogens, we perform an unbiased structure search for polynuclear iron-based systems based on pseudohalogen ligand CN using the CALYPSO method in conjunction with density functional theory. The superhalogen properties, magnetic properties, and thermodynamic stabilities of neutral and anionic Fe 2 (CN) 5 and Fe 3 (CN) 7 clusters are investigated. The results show that both of the clusters have superhalogen properties due to their electron affinities (EAs) and that vertical detachment energies (VDEs) are significantly larger than those of the chlorine element and their ligand CN. The distribution of the extra electron analysis indicates that the extra electron is aggregated mainly into pseudohalogen ligand CN units in Fe 2 (CN) 5 ¯ and Fe 3 (CN) 7 ¯ cluster. These features contribute significantly to their high EA and VDE. Besides superhalogen properties, these two anionic clusters carry a large magnetic moment just like the Fe 2 F 5 ¯ cluster. Additionally, the thermodynamic stabilities are also discussed by calculating the energy required to fragment the cluster into various smaller stable clusters. It is found that Fe(CN) 2 is the most favorable fragmentation product for anionic Fe 2 (CN) 5 ¯ and Fe 3 (CN) 7 ¯ clusters, and both of the anions are less stable against ejection of Fe atoms than Fe(CN) n-x .

The Chemistry of Meteoric Iron

NASA Astrophysics Data System (ADS)

Self, D. E.; Plane, J. M. C.

About 120 tonnes of interplanetary dust enters the earth's atmosphere each day. Iron comprises a large fraction of this dust (12% by mass), and ablation of the particles gives rise to the layer of Fe atoms that occurs globally in the mesosphere around 85 km. Previous work in our laboratory has shown that Fe reacts rapidly with O3 to form FeO, which in turn reacts with O3, O2 and H2O to form FeO2, FeO3 and Fe(OH)2, respectively. The purpose of the present study was to determine which of these com- pounds provide stable reservoirs for iron below the atomic Fe layer, and hence form the "building blocks" of meteoric smoke particles which are implicated in phenomena lower in the atmosphere (e.g., noctilucent clouds and polar stratospheric ozone deple- tion). The reactions of these iron compounds were studied in a fast flow tube using the pulsed laser ablation of a rotating iron rod as the source of Fe atoms in the up- stream section of the tube. Iron compounds were produced by adding reactants further down the tube, and finally atomic O or H was added through a movable injector. At the downstream end of the tube, atomic Fe was detected by laser induced fluorescence at 248 nm. The following reactions were studied: FeO + O, FeO2 + O, FeO3 + O, FeO2 + O3, FeO3 + H2O, FeO3 + H, Fe(OH)2 + H, and FeOH + H. It is clear that the iron reservoir around 80 km is FeO3, which reacts very slowly with atomic O, in agreement with the requirements of a recent atmospheric model. However, Fe(OH)2 and FeO(OH), which are thermodynamically the most stable of these Fe species and eventually form from FeO3, are the likely building blocks of meteoric smoke.

Invited review: Caseins and the casein micelle: their biological functions, structures, and behavior in foods.

PubMed

Holt, C; Carver, J A; Ecroyd, H; Thorn, D C

2013-10-01

A typical casein micelle contains thousands of casein molecules, most of which form thermodynamically stable complexes with nanoclusters of amorphous calcium phosphate. Like many other unfolded proteins, caseins have an actual or potential tendency to assemble into toxic amyloid fibrils, particularly at the high concentrations found in milk. Fibrils do not form in milk because an alternative aggregation pathway is followed that results in formation of the casein micelle. As a result of forming micelles, nutritious milk can be secreted and stored without causing either pathological calcification or amyloidosis of the mother's mammary tissue. The ability to sequester nanoclusters of amorphous calcium phosphate in a stable complex is not unique to caseins. It has been demonstrated using a number of noncasein secreted phosphoproteins and may be of general physiological importance in preventing calcification of other biofluids and soft tissues. Thus, competent noncasein phosphoproteins have similar patterns of phosphorylation and the same type of flexible, unfolded conformation as caseins. The ability to suppress amyloid fibril formation by forming an alternative amorphous aggregate is also not unique to caseins and underlies the action of molecular chaperones such as the small heat-shock proteins. The open structure of the protein matrix of casein micelles is fragile and easily perturbed by changes in its environment. Perturbations can cause the polypeptide chains to segregate into regions of greater and lesser density. As a result, the reliable determination of the native structure of casein micelles continues to be extremely challenging. The biological functions of caseins, such as their chaperone activity, are determined by their composition and flexible conformation and by how the casein polypeptide chains interact with each other. These same properties determine how caseins behave in the manufacture of many dairy products and how they can be used as functional ingredients in other foods. Copyright © 2013 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Thermodynamic efficiency of learning a rule in neural networks

NASA Astrophysics Data System (ADS)

Goldt, Sebastian; Seifert, Udo

2017-11-01

Biological systems have to build models from their sensory input data that allow them to efficiently process previously unseen inputs. Here, we study a neural network learning a binary classification rule for these inputs from examples provided by a teacher. We analyse the ability of the network to apply the rule to new inputs, that is to generalise from past experience. Using stochastic thermodynamics, we show that the thermodynamic costs of the learning process provide an upper bound on the amount of information that the network is able to learn from its teacher for both batch and online learning. This allows us to introduce a thermodynamic efficiency of learning. We analytically compute the dynamics and the efficiency of a noisy neural network performing online learning in the thermodynamic limit. In particular, we analyse three popular learning algorithms, namely Hebbian, Perceptron and AdaTron learning. Our work extends the methods of stochastic thermodynamics to a new type of learning problem and might form a suitable basis for investigating the thermodynamics of decision-making.

CAP: A Computer Code for Generating Tabular Thermodynamic Functions from NASA Lewis Coefficients. Revised

NASA Technical Reports Server (NTRS)

Zehe, Michael J.; Gordon, Sanford; McBride, Bonnie J.

2002-01-01

For several decades the NASA Glenn Research Center has been providing a file of thermodynamic data for use in several computer programs. These data are in the form of least-squares coefficients that have been calculated from tabular thermodynamic data by means of the NASA Properties and Coefficients (PAC) program. The source thermodynamic data are obtained from the literature or from standard compilations. Most gas-phase thermodynamic functions are calculated by the authors from molecular constant data using ideal gas partition functions. The Coefficients and Properties (CAP) program described in this report permits the generation of tabulated thermodynamic functions from the NASA least-squares coefficients. CAP provides considerable flexibility in the output format, the number of temperatures to be tabulated, and the energy units of the calculated properties. This report provides a detailed description of input preparation, examples of input and output for several species, and a listing of all species in the current NASA Glenn thermodynamic data file.

CAP: A Computer Code for Generating Tabular Thermodynamic Functions from NASA Lewis Coefficients

NASA Technical Reports Server (NTRS)

Zehe, Michael J.; Gordon, Sanford; McBride, Bonnie J.

2001-01-01

For several decades the NASA Glenn Research Center has been providing a file of thermodynamic data for use in several computer programs. These data are in the form of least-squares coefficients that have been calculated from tabular thermodynamic data by means of the NASA Properties and Coefficients (PAC) program. The source thermodynamic data are obtained from the literature or from standard compilations. Most gas-phase thermodynamic functions are calculated by the authors from molecular constant data using ideal gas partition functions. The Coefficients and Properties (CAP) program described in this report permits the generation of tabulated thermodynamic functions from the NASA least-squares coefficients. CAP provides considerable flexibility in the output format, the number of temperatures to be tabulated, and the energy units of the calculated properties. This report provides a detailed description of input preparation, examples of input and output for several species, and a listing of all species in the current NASA Glenn thermodynamic data file.

Static heterogeneities in liquid water

NASA Astrophysics Data System (ADS)

Stanley, H. Eugene; Buldyrev, Sergey V.; Giovambattista, Nicolas

2004-10-01

The thermodynamic behavior of water seems to be closely related to static heterogeneities. These static heterogeneities are related to the local structure of water molecules, and when properly characterized, may offer an economical explanation of thermodynamic data. The key feature of liquid water is not so much that the existence of hydrogen bonds, first pointed out by Linus Pauling, but rather the local geometry of the liquid molecules is not spherical or oblong but tetrahedral. In the consideration of static heterogeneities, this local geometry is critical. Recent experiments suggested more than one phase of amorphous solid water, while simulations suggest that one of these phases is metastable with respect to another, so that in fact there are only two stable phases.

Design of nonimaging concentrators as second stages in tandem with image-forming first-stage concentrators

NASA Technical Reports Server (NTRS)

Winston, R.; Welford, W. T.

1980-01-01

The paper discusses the paraboloidal mirror as a tracking solar concentrator, fitting a nonimaging second stage to the paraboloidal mirror, other image-forming systems as first stages, and tracking systems in two-dimensional geometry. Because of inherent aberrations, the paraboloidal mirror cannot achieve the thermodynamic limit. It is shown how paraboloidal mirrors of short focal ratio and similar systems can have their flux concentration enhanced to near the thermodynamic limit by the addition of nonimaging compound elliptical concentrators.

Design of nonimaging concentrators as second stages in tandem with image-forming first-stage concentrators

NASA Astrophysics Data System (ADS)

Winston, R.; Welford, W. T.

1980-02-01

The paper discusses the paraboloidal mirror as a tracking solar concentrator, fitting a nonimaging second stage to the paraboloidal mirror, other image-forming systems as first stages, and tracking systems in two-dimensional geometry. Because of inherent aberrations, the paraboloidal mirror cannot achieve the thermodynamic limit. It is shown how paraboloidal mirrors of short focal ratio and similar systems can have their flux concentration enhanced to near the thermodynamic limit by the addition of nonimaging compound elliptical concentrators.

Langmuir-Gibbs Surface Phases and Transitions

NASA Astrophysics Data System (ADS)

Ocko, Benjamin; Sloutskin, Eli; Sapir, Zvi; Tamam, Lilach; Deutsch, Moshe; Bain, Colin

2007-03-01

Recent synchrotron x-ray measurements reveal surface ordering transitions in films of medium-length linear hydrocarbons (alkanes), spread on the water surface. Alkanes longer than hexane do not spread on the free surface of water. However, sub-mM concentrations of some anionic surfactants (e.g. CTAB) induce formation of thermodynamically stable alkane monolayers, through a ``pseudo-partial wetting'' phenomenon[1]. The monolayers, incorporating both water-insoluble alkanes (Langmuir) and water-soluble CTAB molecules (Gibbs) are called Langmuir-Gibbs (LG) films. The films formed by alkanes with n <=17 exhibit ordering transition upon cooling [2], below which the molecules are normal to the water surface and hexagonally packed, with CTAB molecules randomly mixed inside the quasi-2D crystal. Alkanes with n>17 can not form ordered LG monolayers, due to the repulsion from the n=16 tails of CTAB. This repulsion arises from the two chains' length mismatch. A demixing transition occurs upon ordering, with a pure alkane quasi-2D crystal forming on top of disordered alkyl tails of CTAB molecules. [1] K.M. Wilkinson et al., Chem. Phys. Phys. Chem. 6, 547 (2005). [2] E. Sloutskin, Z. Sapir, L. Tamam, B.M. Ocko, C.D. Bain, and M. Deutsch, Thin Solid Films, in press; K.M. Wilkinson, L. Qunfang, and C.D. Bain, Soft Matter 2, 66 (2006).

Silver ions-mediated conformational switch: facile design of structure-controllable nucleic acid probes.

PubMed

Wang, Yongxiang; Li, Jishan; Wang, Hao; Jin, Jianyu; Liu, Jinhua; Wang, Kemin; Tan, Weihong; Yang, Ronghua

2010-08-01

Conformationally constraint nucleic acid probes were usually designed by forming an intramolecular duplex based on Watson-Crick hydrogen bonds. The disadvantages of these approaches are the inflexibility and instability in complex environment of the Watson-Crick-based duplex. We report that this hydrogen bonding pattern can be replaced by metal-ligation between specific metal ions and the natural bases. To demonstrate the feasibility of this principle, two linear oligonucleotides and silver ions were examined as models for DNA hybridization assay and adenosine triphosphate detection. The both nucleic acids contain target binding sequences in the middle and cytosine (C)-rich sequences at the lateral portions. The strong interaction between Ag(+) ions and cytosines forms stable C-Ag(+)-C structures, which promises the oligonucleotides to form conformationally constraint formations. In the presence of its target, interaction between the loop sequences and the target unfolds the C-Ag(+)-C structures, and the corresponding probes unfolding can be detected by a change in their fluorescence emission. We discuss the thermodynamic and kinetic opportunities that are provided by using Ag(+) ion complexes instead of traditional Watson-Crick-based duplex. In particular, the intrinsic feature of the metal-ligation motif facilitates the design of functional nucleic acids probes by independently varying the concentration of Ag(+) ions in the medium.

From faceted vesicles to liquid icoshedra: Where topology and crystallography meet

DOE PAGES

Guttman, Shani; Ocko, Benjamin M.; Deutsch, Moshe; ...

2016-02-17

We study many common amphiphiles that spontaneously self-assemble in aqueous solutions, forming membranes and unilamellar vesicles. While the vesicular membranes are bilayers, with the hydrophilic moieties exposed to the solution, the structure formed by amphiphiles at the oil–water (i.e., alkane–water) interfaces, such as the surface of an oil droplet in water, is typically a monolayer. It has recently been demonstrated that these monolayers and bilayers may crystallize on cooling, with the thermodynamic conditions for this transition set by the geometry of the constituent molecules. While a planar hexagonal packing motif is particularly abundant in these crystals, a hexagonal lattice ismore » incompatible with a closed-surface topology, such as a closed vesicle or the surface of a droplet. Thus, (at least) 12 five-fold defects form, giving rise to a complex interplay between the stretching and the bending energies of these two-dimensional crystals; in addition, a central role is also played by the interfacial tension. This interplay, part of which has been theoretically studied in the past, gives rise to a range of unexpected and counterintuitive phenomena, such as the recently-observed temperature-tunable formation of stable liquid polyhedra, and a tail growing and droplet-splitting akin to the spontaneous emulsification effect.« less

Insights into molecular architecture of terpenes using small angle neutron scattering

NASA Astrophysics Data System (ADS)

Rai, Durgesh K.; Annamraju, Aparna; Pingali, Sai Venkatesh; O'Neill, Hugh M.; Mewalal, Ritesh; Gunter, Lee E.; Tuskan, Gerald A.

Understanding macromolecular architectures is vital to engineering prospective terpene candidates for advanced biofuels. Eucalyptus plants store terpenes in specialized cavity-like structures in the leaves called oil glands, which comprises of volatile (VTs) and non-volatile (NVTs) terpenes. Using small-angle neutron scattering, we have investigated the structure and phase behavior of the supramolecular assembly formed by Geranyl beta-D-glucoside (GDG), a NVT and compare the results with that of beta-octyl glucoside (BOG). The formation of micellar structures was observed in the concentration range of 0.5-5 v/v% in water using small angle neutron scattering (SANS) where Schultz sphere model was used in quantifying structural parameters of micelles. SANS studies determine that GDG and BOG behave like amphiphiles forming micellar structures in aqueous solution. The micelles swell upon addition of alpha-Pinene (AP) indicating partition to the core region of the micelles. The general behavior of the micellar growth after partitioning of AP to form thermodynamically stable sizes varies with the NVT concentration. Our studies reveal that the presence of steric hindrance in the GDG via the unsaturated bonds could help stabilize VTs inside the oil glands. LDRD project LOIS ID 7428, SNS, CSMB, HFIR, ORNL, DOE Office of Science User Facilities.

Navigating the Waters of Unconventional Crystalline Hydrates

PubMed Central

2015-01-01

Elucidating the crystal structures, transformations, and thermodynamics of the two zwitterionic hydrates (Hy2 and HyA) of 3-(4-dibenzo[b,f][1,4]oxepin-11-yl-piperazin-1-yl)-2,2-dimethylpropanoic acid (DB7) rationalizes the complex interplay of temperature, water activity, and pH on the solid form stability and transformation pathways to three neutral anhydrate polymorphs (Forms I, II°, and III). HyA contains 1.29 to 1.95 molecules of water per DB7 zwitterion (DB7z). Removal of the essential water stabilizing HyA causes it to collapse to an amorphous phase, frequently concomitantly nucleating the stable anhydrate Forms I and II°. Hy2 is a stoichiometric dihydrate and the only known precursor to Form III, a high energy disordered anhydrate, with the level of disorder depending on the drying conditions. X-ray crystallography, solid state NMR, and H/D exchange experiments on highly crystalline phase pure samples obtained by exquisite control over crystallization, filtration, and drying conditions, along with computational modeling, provided a molecular level understanding of this system. The slow rates of many transformations and sensitivity of equilibria to exact conditions, arising from its varying static and dynamic disorder and water mobility in different phases, meant that characterizing DB7 hydration in terms of simplified hydrate classifications was inappropriate for developing this pharmaceutical. PMID:26075319

First-principles calculations of the structural, elastic and thermodynamic properties of mackinawite (FeS) and pyrite (FeS2)

NASA Astrophysics Data System (ADS)

Wen, Xiangli; Liang, Yuxuan; Bai, Pengpeng; Luo, Bingwei; Fang, Teng; Yue, Luo; An, Teng; Song, Weiyu; Zheng, Shuqi

2017-11-01

The thermodynamic properties of Fe-S compounds with different crystal structure are very different. In this study, the structural, elastic and thermodynamic properties of mackinawite (FeS) and pyrite (FeS2) were investigated by first-principles calculations. Examination of the electronic density of states shows that mackinawite (FeS) is metallic and that pyrite (FeS2) is a semiconductor with a band gap of Eg = 1.02 eV. Using the stress-strain method, the elastic properties including the bulk modulus and shear modulus were derived from the elastic Cij data. Density functional perturbation theory (DFPT) calculations within the quasi-harmonic approximation (QHA) were used to calculate the thermodynamic properties, and the two Fe-S compounds are found to be dynamically stable. The isothermal bulk modulus, thermal expansion coefficient, heat capacities, Gibbs free energy and entropy of the Fe-S compounds are obtained by first-principles phonon calculations. Furthermore, the temperature of the mackinawite (FeS) ⟶ pyrite (FeS2) phase transition at 0 GPa was predicted. Based on the calculation results, the model for prediction of Fe-S compounds in the Fe-H2S-H2O system was improved.

Canonical fluid thermodynamics. [variational principles of stability for compressible adiabatic flow

NASA Technical Reports Server (NTRS)

Schmid, L. A.

1974-01-01

The space-time integral of the thermodynamic pressure plays in a certain sense the role of the thermodynamic potential for compressible adiabatic flow. The stability criterion can be converted into a variational minimum principle by requiring the molar free-enthalpy and temperature to be generalized velocities. In the fluid context, the definition of proper-time differentiation involves the fluid velocity expressed in terms of three particle identity parameters. The pressure function is then converted into a functional which is the Lagrangian density of the variational principle. Being also a minimum principle, the variational principle provides a means for comparing the relative stability of different flows. For boundary conditions with a high degree of symmetry, as in the case of a uniformly expanding spherical gas box, the most stable flow is a rectilinear flow for which the world-trajectory of each particle is a straight line. Since the behavior of the interior of a freely expanding cosmic cloud may be expected to be similar to that of the fluid in the spherical box of gas, this suggests that the cosmic principle is a consequence of the laws of thermodynamics, rather than just an ad hoc postulate.

Synthesis, chemical and biological studies on new Fe(3+)-glycosilated beta-diketo complexes for the treatment of iron deficiency.

PubMed

Arezzini, Beatrice; Ferrali, Marco; Ferrari, Erika; Frassineti, Chiara; Lazzari, Sandra; Marverti, Gaetano; Spagnolo, Ferdinando; Saladini, Monica

2008-11-01

A simple synthetic pathway to obtain glycosilated beta-diketo derivatives is proposed. These compounds show a good iron(III) affinity therefore we may suggest the use of their Fe(3+)-complexes as oral iron supplements in the treatment of anaemia. The glycosilated compounds (6-GlcH, 6-GlcOH and 6-GlcOCH(3)) are characterized by means of spectroscopic (UV, (1)H and (13)C NMR) and potentiometric techniques; they have a good water solubility, are kinetically stable in physiological condition (t(1/2)>100h) and show a low cytotoxicity also in high concentrations (IC(50)>400 microM). They are able to bind Fe(3+) ion in acid condition (pH approximately 2) forming complex species thermodynamically more stable than those of other ligands commonly used in the treatment of iron deficiency. The iron complexes show also a good kinetic stability both in acidic and physiological pH and have a good lypophilicity (logP>-0.7) that suggests an efficient gastrointestinal absorption in view of their possible use in oral therapy. In addition they demonstrate a poor affinity for competitive biological metal ion such as Ca(2+), and in particular 6-GlcOCH(3) is able to inhibit lipid peroxidation.

Study of iridium silicide monolayers using density functional theory

NASA Astrophysics Data System (ADS)

Popis, Minh D.; Popis, Sylvester V.; Oncel, Nuri; Hoffmann, Mark R.; ćakır, Deniz

2018-02-01

In this study, we investigated physical and electronic properties of possible two-dimensional structures formed by Si (silicon) and Ir (iridium). To this end, different plausible structures were modeled by using density functional theory and the cohesive energies calculated for the geometry of optimized structures, with the lowest equilibrium lattice constants. Among several candidate structures, we identified three mechanically (via elastic constants and Young's modulus), dynamically (via phonon calculations), and thermodynamically stable iridium silicide monolayer structures. The lowest energy structure has a chemical formula of Ir2Si4 (called r-IrSi2), with a rectangular lattice (Pmmn space group). Its cohesive energy was calculated to be -0.248 eV (per IrSi2 unit) with respect to bulk Ir and bulk Si. The band structure indicates that the Ir2Si4 monolayer exhibits metallic properties. Other stable structures have hexagonal (P-3m1) and tetragonal (P4/nmm) cell structures with 0.12 and 0.20 eV/f.u. higher cohesive energies, respectively. Our calculations showed that Ir-Si monolayers are reactive. Although O2 molecules exothermically dissociate on the surface of the free-standing iridium silicide monolayers with large binding energies, H2O molecules bind to the monolayers with a rather weak interaction.

Earth's oldest stable crust in the Pilbara Craton formed by cyclic gravitational overturns

NASA Astrophysics Data System (ADS)

Wiemer, Daniel; Schrank, Christoph E.; Murphy, David T.; Wenham, Lana; Allen, Charlotte M.

2018-05-01

During the early Archaean, the Earth was too hot to sustain rigid lithospheric plates subject to Wilson Cycle-style plate tectonics. Yet by that time, up to 50% of the present-day continental crust was generated. Preserved continental fragments from the early Archaean have distinct granite-dome/greenstone-keel crust that is interpreted to be the result of a gravitationally unstable stratification of felsic proto-crust overlain by denser mafic volcanic rocks, subject to reorganization by Rayleigh-Taylor flow. Here we provide age constraints on the duration of gravitational overturn in the East Pilbara Terrane. Our U-Pb ages indicate the emplacement of 3,600-3,460-million-year-old granitoid rocks, and their uplift during an overturn event ceasing about 3,413 million years ago. Exhumation and erosion of this felsic proto-crust accompanied crustal reorganization. Petrology and thermodynamic modelling suggest that the early felsic magmas were derived from the base of thick ( 43 km) basaltic proto-crust. Combining our data with regional geochronological studies unveils characteristic growth cycles on the order of 100 million years. We propose that maturation of the early crust over three of these cycles was required before a stable, differentiated continent emerged with sufficient rigidity for plate-like behaviour.

Quantum chemical calculation (electronic and topologic) and experimental (FT-IR, FT-Raman and UV) analysis of isonicotinic acid N-oxide

NASA Astrophysics Data System (ADS)

Karaca, Caglar; Atac, Ahmet; Karabacak, Mehmet

2015-04-01

In this work, the molecular conformation, vibrational and electronic analysis of isonicotinic acid N-oxide (iso-NANO) were presented in the ground state using experimental techniques (FT-IR, FT-Raman and UV) and density functional theory (DFT) employing B3LYP exchange correlation with the 6-311++G(d,p) basis set. The geometry optimization and energies associated possible two conformers (Rot-I and Rot-II) were computed. The vibrational spectra were calculated and fundamental vibrations were assigned on the basis of the total energy distribution (TED) of the vibrational modes, calculated with scaled quantum mechanics (SQM) method and PQS program. The obtained structures were analyzed with the Atoms in Molecules (AIMs) methodology. The computational results diagnose the most stable conformer of iso-NANO as the Rot-I form. Total density of state (TDOS) and partial density of state (PDOS) and also overlap population density of state (OPDOS) diagrams analysis for the most stable conformer (Rot-I) were calculated using the same method. Thermodynamic properties (heat capacity, entropy and enthalpy) of the title compound at different temperatures were calculated. As a result, the optimized geometry and calculated spectroscopic data show a good agreement with the experimental results.

Hydrophobic properties of a wavy rough substrate.

PubMed

Carbone, G; Mangialardi, L

2005-01-01

The wetting/non-wetting properties of a liquid drop in contact with a chemically hydrophobic rough surface (thermodynamic contact angle theta(e)>pi/2) are studied for the case of an extremely idealized rough profile: the liquid drop is considered to lie on a simple sinusoidal profile. Depending on surface geometry and pressure values, it is found that the Cassie and Wenzel states can coexist. But if the amplitude h of the substrate is sufficiently large the only possible stable state is the Cassie one, whereas if h is below a certain critical value hcr a transition to the Wenzel state occurs. Since in many potential applications of such super-hydrophobic surfaces, liquid drops often collide with the substrate (e.g. vehicle windscreens), in the paper the critical drop pressure pW is calculated at which the Cassie state is no longer stable and the liquid jumps into full contact with the substrate (Wenzel state). By analyzing the asymptotic behavior of the systems in the limiting case of a large substrate corrugation, a simple criterion is also proposed to calculate the minimum height asperity h necessary to prevent the Wenzel state from being formed, to preserve the super-hydrophobic properties of the substrate, and, hence, to design a robust super-hydrophobic surface.

Retention of intermediate polarization states in ferroelectric materials enabling memories for multi-bit data storage

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhao, Dong; Asadi, Kamal; Blom, Paul W. M.

A homogeneous ferroelectric single crystal exhibits only two remanent polarization states that are stable over time, whereas intermediate, or unsaturated, polarization states are thermodynamically instable. Commonly used ferroelectric materials however, are inhomogeneous polycrystalline thin films or ceramics. To investigate the stability of intermediate polarization states, formed upon incomplete, or partial, switching, we have systematically studied their retention in capacitors comprising two classic ferroelectric materials, viz. random copolymer of vinylidene fluoride with trifluoroethylene, P(VDF-TrFE), and Pb(Zr,Ti)O{sub 3}. Each experiment started from a discharged and electrically depolarized ferroelectric capacitor. Voltage pulses were applied to set the given polarization states. The retention wasmore » measured as a function of time at various temperatures. The intermediate polarization states are stable over time, up to the Curie temperature. We argue that the remarkable stability originates from the coexistence of effectively independent domains, with different values of polarization and coercive field. A domain growth model is derived quantitatively describing deterministic switching between the intermediate polarization states. We show that by using well-defined voltage pulses, the polarization can be set to any arbitrary value, allowing arithmetic programming. The feasibility of arithmetic programming along with the inherent stability of intermediate polarization states makes ferroelectric materials ideal candidates for multibit data storage.« less

Chemistry of atmosphere-surface interactions on Venus and Mars

NASA Astrophysics Data System (ADS)

Fegley, Bruce, Jr.; Treiman, Allan H.

Earth-based, earth-orbital, and spacecraft observational data are used in the present evaluation of Venus atmosphere-surface interactions to quantitatively characterize the reactions between C, H, S, Cl, F, and N gases and plausible surface minerals. Calculation results are used to predict stable minerals and mineral assemblages on the Venus surface, in order to ascertain which (if any) of the atmospheric gases are buffeted by mineral assemblages. Chemical equilibrium calculations using extant thermodynamic data on scapolite minerals predict that carbonate-bearing scapolite and sulfate meionite are unstable on the surface of Venus, while chloride-bearing scapolite is stable.

Universally stable black holes

NASA Astrophysics Data System (ADS)

Bueno, Pablo; Cano, Pablo A.

We argue that, when certain higher-curvature corrections are added to the four-dimensional Einstein-Hilbert action, black holes become stable below certain mass. We show this to be the case for an infinite family of ghost-free theories involving terms of arbitrarily high order in curvature. The thermodynamic behavior of the new black holes is universal for arbitrary values of the couplings, with the only exception of the Schwarzschild solution itself, which is recovered when all the couplings are set to zero. For this class of theories, the issue of non-unitary evolution is inexistent, as black holes never evaporate completely.

Opposite consequences of two transcription pauses caused by an intrinsic terminator oligo(U): antitermination versus termination by bacteriophage T7 RNA polymerase.

PubMed

Lee, Sooncheol; Kang, Changwon

2011-05-06

The RNA oligo(U) sequence, along with an immediately preceding RNA hairpin structure, is an essential cis-acting element for bacterial class I intrinsic termination. This sequence not only causes a pause in transcription during the beginning of the termination process but also facilitates transcript release at the end of the process. In this study, the oligo(U) sequence of the bacteriophage T7 intrinsic terminator Tφ, rather than the hairpin structure, induced pauses of phage T7 RNA polymerase not only at the termination site, triggering a termination process, but also 3 bp upstream, exerting an antitermination effect. The upstream pause presumably allowed RNA to form a thermodynamically more stable secondary structure rather than a terminator hairpin and to persist because the 5'-half of the terminator hairpin-forming sequence could be sequestered by a farther upstream sequence via sequence-specific hybridization, prohibiting formation of the terminator hairpin and termination. The putative antiterminator RNA structure lacked several base pairs essential for termination when probed using RNases A, T1, and V1. When the antiterminator was destabilized by incorporation of IMP into nascent RNA at G residue positions, antitermination was abolished. Furthermore, antitermination strength increased with more stable antiterminator secondary structures and longer pauses. Thus, the oligo(U)-mediated pause prior to the termination site can exert a cis-acting antitermination activity on intrinsic terminator Tφ, and the termination efficiency depends primarily on the termination-interfering pause that precedes the termination-facilitating pause at the termination site.

Influence of Aluminum on the Formation Behavior of Zn-Al-Fe Intermetallic Particles in a Zinc Bath

NASA Astrophysics Data System (ADS)

Park, Joo Hyun; Park, Geun-Ho; Paik, Doo-Jin; Huh, Yoon; Hong, Moon-Hi

2012-01-01

The shape, size, and composition of dross particles as a function of aluminum content at a fixed temperature were investigated for aluminum added to the premelted Zn-Fe melt simulating the hot-dip galvanizing bath by a sampling methodology. In the early stage, less than 30 minutes after Al addition, local supersaturation and depletion of the aluminum concentration occurred simultaneously in the bath, resulting in the nucleation and growth of both Fe2Al5Zn x and FeZn13. However, the aluminum was homogenized continuously as the reaction proceeded, and fine and stable FeZn10Al x formed after 30 minutes. An Al-depleted zone (ADZ) mechanism was newly proposed for the "η→η+ζ→δ" phase transformations. The ζ phase bottom dross partly survived for a relatively long period, i.e., 2 hours in this work, whereas the η phase disappeared after 30 minutes. In the early stage of dross formation, both Al-free large particles as well as high-Al tiny particles were formed. The dross particle size decreased slightly with increased reaction time before reaching a plateau. The opposite tendency was observed when the Al content was 0.130 mass pct; with a relatively high Al content, the nucleation of tiny η phase dross was significantly enhanced because of the high degree of supersaturation. This unstable η phase dissolved continuously and underwent simple transformation to the stable δ phase. The relationship between nucleation potential and supersaturation ratio of species is discussed based on the thermodynamics of classical nucleation theory.

Binding thermodynamics discriminates fragments from druglike compounds: a thermodynamic description of fragment-based drug discovery.

PubMed

Williams, Glyn; Ferenczy, György G; Ulander, Johan; Keserű, György M

2017-04-01

Small is beautiful - reducing the size and complexity of chemical starting points for drug design allows better sampling of chemical space, reveals the most energetically important interactions within protein-binding sites and can lead to improvements in the physicochemical properties of the final drug. The impact of fragment-based drug discovery (FBDD) on recent drug discovery projects and our improved knowledge of the structural and thermodynamic details of ligand binding has prompted us to explore the relationships between ligand-binding thermodynamics and FBDD. Information on binding thermodynamics can give insights into the contributions to protein-ligand interactions and could therefore be used to prioritise compounds with a high degree of specificity in forming key interactions. Copyright © 2016 Elsevier Ltd. All rights reserved.

Thermodynamic stability of RNA structures formed by CNG trinucleotide repeats. Implication for prediction of RNA structure.

PubMed

Broda, Magdalena; Kierzek, Elzbieta; Gdaniec, Zofia; Kulinski, Tadeusz; Kierzek, Ryszard

2005-08-16

Trinucleotide repeat expansion diseases (TREDs) are correlated with elongation of CNG DNA and RNA repeats to pathological level. This paper shows, for the first time, complete data concerning thermodynamic stabilities of RNA with CNG trinucleotide repeats. Our studies include the stability of oligoribonucleotides composed of two to seven of CAG, CCG, CGG, and CUG repeats. The thermodynamic parameters of helix propagation correlated with the presence of multiple N-N mismatches within CNG RNA duplexes were also determined. Moreover, the total stability of CNG RNA hairpins, as well as the contribution of trinucleotide repeats placed only in the stem or loop regions, was evaluated. The improved thermodynamic parameters allow to predict much more accurately the thermodynamic stabilities and structures of CNG RNAs.

Thermodynamical Arguments against Evolution

ERIC Educational Resources Information Center

Rosenhouse, Jason

2017-01-01

The argument that the second law of thermodynamics contradicts the theory of evolution has recently been revived by anti-evolutionists. In its basic form, the argument asserts that whereas evolution implies that there has been an increase in biological complexity over time, the second law, a fundamental principle of physics, shows this to be…

Radioactivity and Environmental Security in the Oceans: New Research and Policy Priorities in the Arctic and North Atlantic

DTIC Science & Technology

1993-06-09

within the framework of an update for the computer database "DiaNIK" which has been developed at the Vernadsky Institute of Geochemistry and Analytical...chemical thermodynamic data for minerals and mineral-forming substances. The structure of thermodynamic database "DiaNIK" is based on the principles...in the database . A substantial portion of the thermodynamic values recommended by "DiaNIK" experts for the substances in User Version 3.1 resulted from

Silver(II) Oxide or Silver(I,III) Oxide?

ERIC Educational Resources Information Center

Tudela, David

2008-01-01

The often called silver peroxide and silver(II) oxide, AgO or Ag[subscript 2]O[subscript 2], is actually a mixed oxidation state silver(I,III) oxide. A thermochemical cycle, with lattice energies calculated within the "volume-based" thermodynamic approach, explain why the silver(I,III) oxide is more stable than the hypothetical silver(II) oxide.…

Reformulation of Nonlinear Anisotropic Crystal Elastoplasticity for Impact Physics

DTIC Science & Technology

2015-03-01

interest include metals, ceramics , minerals, and energetic materials . Accurate, efficient, stable, and thermodynamically consistent models for...Clayton JD. Phase field theory and analysis of pressure-shear induced amorphization and failure in boron carbide ceramic . AIMS Materials Science. 2014;1...of Nonlinear Anisotropic Crystal Elastoplasticity for Impact Physics by JD Clayton Weapons and Materials Research Directorate, ARL

Glass Formation, Phase Equilibria, and Thermodynamic Assessment of the Al-Ce-Co System Assisted by First-Principles Energy Calculations

NASA Astrophysics Data System (ADS)

Gao, Michael C.; Ünlü, Necip; Mihalkovic, Marek; Widom, Michael; Shiflet, G. J.

2007-10-01

This study investigates glass formation, phase equilibria, and thermodynamic descriptions of the Al-rich Al-Ce-Co ternary system using a novel approach that combines critical experiments, CALPHAD modeling, and first-principles (FP) calculations. The glass formation range (GFR) and a partial 500 °C isotherm are determined using a range of experimental techniques including melt spinning, transmission electron microscopy (TEM), electron probe microanalysis (EPMA), X-ray diffraction, and differential thermal analysis (DTA). Three stable ternary phases are confirmed, namely, Al8CeCo2, Al4CeCo, and AlCeCo, while a metastable phase, Al5CeCo2, was discovered. The equilibrium and metastable phases identified by the present and earlier reported experiments, together with many hypothetical ternary compounds, are further studied by FP calculations. Based on new experimental data and FP calculations, the thermodynamics of the Al-rich Al-Co-Ce system is optimized using the CALPHAD method. Application to glass formation is discussed in light of present studies.

Theoretical study of phonon dispersion, elastic, mechanical and thermodynamic properties of barium chalcogenides

NASA Astrophysics Data System (ADS)

Musari, A. A.; Orukombo, S. A.

2018-03-01

Barium chalcogenides are known for their high-technological importance and great scientific interest. Detailed studies of their elastic, mechanical, dynamical and thermodynamic properties were carried out using density functional theory and plane-wave pseudo potential method within the generalized gradient approximation. The optimized lattice constants were in good agreement when compared with experimental data. The independent elastic constants, calculated from a linear fit of the computed stress-strain function, were used to determine the Young’s modulus (E), bulk modulus (B), shear modulus (G), Poisson’s ratio (σ) and Zener’s anisotropy factor (A). Also, the Debye temperature and sound velocities for barium chalcogenides were estimated from the three independent elastic constants. The calculations of phonon dispersion showed that there are no negative frequencies throughout the Brillouin zone. Hence barium chalcogenides have dynamically stable NaCl-type crystal structure. Finally, their thermodynamic properties were calculated in the temperature range of 0-1000 K and their constant-volume specific heat capacities at room-temperature were reported.

Thermodynamic stability and kinetic inertness of a Gd-DTPA bisamide complex grafted onto gold nanoparticles.

PubMed

Mogilireddy, Vijetha; Déchamps-Olivier, Isabelle; Alric, Christophe; Laurent, Gautier; Laurent, Sophie; Vander Elst, Luce; Muller, Robert; Bazzi, Rana; Roux, Stéphane; Tillement, Olivier; Chuburu, Françoise

2015-01-01

Gold nanoparticles coated by gadolinium (III) chelates (Au@DTDTPA) where DTDTPA is a dithiolated bisamide derivative of diethylenetriamine-N,N,N',N'',N''-pentaacetic acid (DTPA), constituted contrast agents for both X-ray computed tomography and magnetic resonance imaging. In an MRI context, highly stable Gd(3+) complexes are needed for in vivo applications. Thus, knowledge of the thermodynamic stability and kinetic inertness of these chelates, when grafted onto gold nanoparticles, is crucial since bisamide DTPA chelates are usually less suited for Gd(3+) coordination than DTPA. Therefore, these parameters were evaluated by means of potentiometric titrations and relaxivity measurements. The results showed that, when the chelates were grafted onto the nanoparticle, not only their thermodynamic stability but also their kinetic inertness were improved. These positive effects were correlated to the chelate packing at the nanoparticle surface that stabilized the corresponding Gd(3+) complexes and greatly enhanced their kinetic inertness. Copyright © 2014 John Wiley & Sons, Ltd.

Amorphous and Crystalline Particulates: Challenges and Perspectives in Drug Delivery.

PubMed

Al-Obaidi, Hisham; Majumder, Mridul; Bari, Fiza

2017-01-01

Crystalline and amorphous dispersions have been the focus of academic and industrial research due to their potential role in formulating poorly water-soluble drugs. This review looks at the progress made starting with crystalline carriers in the form of eutectics moving towards more complex crystalline mixtures. It also covers using glassy polymers to maintain the drug as amorphous exhibiting higher energy and entropy. However, the amorphous form tends to recrystallize on storage, which limits the benefits of this approach. Specific interactions between the drug and the polymer may retard this spontaneous conversion of the amorphous drug. Some studies have shown that it is possible to maintain the drug in the amorphous form for extended periods of time. For the drug and the polymer to form a stable mixture they have to be miscible on a molecular basis. Another form of solid dispersions is pharmaceutical co-crystals, for which research has focused on understanding the chemistry, crystal engineering and physico-chemical properties. USFDA has issued a guidance in April 2013 suggesting that the co-crystals as a pharmaceutical product may be a reality; but just not yet! While some of the research is still oriented towards application of these carriers, understanding the mechanism by which drug-carrier miscibility occurs is also covered. Within this context is the use of thermodynamic models such as Flory-Huggins model with some examples of studies used to predict miscibility. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Total individual ion activity coefficients of calcium and carbonate in seawater at 25°C and 35%. salinity, and implications to the agreement between apparent and thermodynamic constants of calcite and aragonite

USGS Publications Warehouse

Plummer, Niel; Sundquist, Eric T.

1982-01-01

We have calculated the total individual ion activity coefficients of carbonate and calcium,  and , in seawater. Using the ratios of stoichiometric and thermodynamic constants of carbonic acid dissociation and total mean activity coefficient data measured in seawater, we have obtained values which differ significantly from those widely accepted in the literature. In seawater at 25°C and 35%. salinity the (molal) values of  and  are 0.038 ± 0.002 and 0.173 ± 0.010, respectively. These values of  and  are independent of liquid junction errors and internally consistent with the value . By defining  and  on a common scale (), the product  is independent of the assigned value of  and may be determined directly from thermodynamic measurements in seawater. Using the value  and new thermodynamic equilibrium constants for calcite and aragonite, we show that the apparent constants of calcite and aragonite are consistent with the thermodynamic equilibrium constants at 25°C and 35%. salinity. The demonstrated consistency between thermodynamic and apparent constants of calcite and aragonite does not support a hypothesis of stable Mg-calcite coatings on calcite or aragonite surfaces in seawater, and suggests that the calcite critical carbonate ion curve of Broecker and Takahashi (1978,Deep-Sea Research25, 65–95) defines the calcite equilibrium boundary in the oceans, within the uncertainty of the data.

Thermodynamics of transport through the ammonium transporter Amt-1 investigated with free energy calculations.

PubMed

Ullmann, R Thomas; Andrade, Susana L A; Ullmann, G Matthias

2012-08-16

Amt-1 from Archaeoglobus fulgidus (AfAmt-1) belongs to the Amt/Rh family of ammonium/ammonia transporting membrane proteins. The transport mode and the precise microscopic permeation mechanism utilized by these proteins are intensely debated. Open questions concern the identity of the transported substrate (ammonia and/or ammonium) and whether the transport is passive or active. To address these questions, we studied the overall thermodynamics of the different transport modes as a function of the environmental conditions. Then, we investigated the thermodynamics of the underlying microscopic transport mechanisms with free energy calculations within a continuum electrostatics model. The formalism developed for this purpose is of general utility in the calculation of binding free energies for ligands with multiple protonation forms or other binding forms. The results of our calculations are compared to the available experimental and theoretical data on Amt/Rh proteins and discussed in light of the current knowledge on the physiological conditions experienced by microorganisms and plants. We found that microscopic models of electroneutral and electrogenic transport modes are in principle thermodynamically viable. However, only the electrogenic variants have a net thermodynamic driving force under the physiological conditions experienced by microorganisms and plants. Thus, the transport mechanism of AfAmt-1 is most likely electrogenic.