Evaluacion termoquimica sobre la formacion de prehnita en las doleritas triasicas de EstopiÑan (Huesca, EspaÑa)

e ha realizado un estudio termodinámico sobre la formación de la prehnita en doleritas triásicas. A partir del diagrama establecido se propone que su formación es debida a una alteración hidrotermal, que ha afectado a las fracturas post-triásicas de la dolerita ya consolidada.

Lämmöntalteenottokattilan dynaaminen simulointimalli

Työssä mallinnettiin kombivoimalaitoksen lämmöntalteenottokattila Apros-simulointiohjelmalla. Simulointimalli valmistettiin vastaamaan Helsingin Energian Vuosaari B:n voimalaitoksen lämmöntalteenottokattilaa, joka toimii kahdella painetasolla. Kattila on Foster Wheelerin valmistama. Ennen mallinnuksen aloittamista tutustuttiin laitoksen termodynamiikkaan, jolloin saatiin riittävä teoreettinen tieto koko laitoksen toiminnasta. Kattilan reunaehtoina ovat kaasuturbiiniprosessi ja laitoksen höyrykierto. Kaasuturbiini korvattiin laskentayhtälöillä, jotka antavat alkuarvot mm. savukaasun massavirralle ja lämpötilalle ennen kattilaa kaasuturbiinin tehon funktiona. Kattila liitetään höyrykiertoon tuorehöyry- ja syöttövesilinjasta, jolloin reunaehtoina annetaan lämpötilat ja paineet massavirroille. Valmistettua mallia testattiin ylösajo- ja kuormanmuutostilanteessa. Ylösajotilanteessa saatuja laskentatuloksia verrattiin todellisen laitoksen mittaustuloksiin, jolloin varmistuttiin simulointimallin oikeasta fysikaalisesta toiminnasta. Kuormanmuutostilanteissa kaasuturbiinin tehoa muutettiin ja samalla seurattiin kattilan reagointia muutostilanteessa. Kuormanmuutosmittauksessa varmistettiin vielä, että kattila reagoi kuormanmuutokseen oikealla tavalla, eikä muutos aiheuta kattilan toiminnalle haitallista värähtelyä.

Selvityksiä reaktiokalorimetrin soveltuvuudesta hydrometallurgiaan

Tämän työn tavoitteena oli reaktiokalorimetrin käyttöönotto sekä sen käyttökelpoisuuden selvittäminen hydrometallurgisten sovellusten ja erityisesti sinkkisulfidin liuotuksen tutkimiseen. Työn kirjallisuusosassa on käsitelty yleisellä tasolla kalorimetrian ja reaktiokalorimetrian teoriaa, termodynamiikkaa sekä sinkkirikasteen liuotuksen kemiaa. Lisäksi työssä esitellään erilaisten kalorimetrien ja termoanalyyttisten mittauslaitteiden toimintaperiaatteita. Työn kokeellisessa osassa selvitettiin reaktiokalorimetrin mittaustulosten tarkkuutta vesi- kokeiden avulla. Laitteistolla määritettiin myös reaktiolämmöt sinkkisulfidin liukenemisreaktiolle sekä elohopeasuolan saostusreaktiolle. Lisäksi tutkittiin sekoitusnopeuden, lämpötilan ja kiintoainepitoisuuden vaikutusta mittaustuloksiin. Reaktiokalorimetrillä suoritettujen kokeiden perusteella havaittiin, että reaktiolämpöjen absoluuttisten arvojen määrittäminen laitteistolla on käytännössä vaikeaa. Koska reaktiokalorimetrillä pystytään määrittämään vain mittauksen aikana tapahtunut kokonaislämpömuutos, vaikuttavat mahdolliset faasimuutokset ja reaktorin lämpöhäviöt mittaustuloksiin. Näiden tekijöiden vaikutus on pyrittävä eliminoimaan tai niiden vaikutus on tunnettava tarkkaan, jos laitteella halutaan saada luotettavia reaktiolämpömittaustuloksia. Laitteiston mittaustarkkuus huononee huomattavasti, kun reaktorin lämpötila nousee yli 60 °C:een. Laitteistolla mitatut reaktiolämmöt poikkeavat huomattavasti vastaavista kirjallisuuden arvoista. Vedelle määritetyt ominaislämpökapasiteetit poikkeavat kirjallisuuden arvoista enintään 5 alle 90 °C:een lämpötilassa.

Modelling the curing process in magneto-sensitive polymers: Rate-dependence and shrinkage

This paper deals with a phenomenologically motivated magneto-viscoelastic coupled finite strain framework for simulating the curing process of polymers under the application of a coupled magneto-mechanical road. Magneto-sensitive polymers are prepared by mixing micron-sized ferromagnetic particles in uncured polymers. Application of a magnetic field during the curing process causes the particles to align and form chain-like structures lending an overall anisotropy to the material. The polymer curing is a viscoelastic complex process where a transformation from fluid. to solid occurs in the course of time. During curing, volume shrinkage also occurs due to the packing of polymer chains by chemical reactions. Such reactions impart a continuous change of magneto-mechanical properties that can be modelled by an appropriate constitutive relation where the temporal evolution of material parameters is considered. To model the shrinkage during curing, a magnetic-induction-dependent approach is proposed which is based on a multiplicative decomposition of the deformation gradient into a mechanical and a magnetic-induction-dependent volume shrinkage part. The proposed model obeys the relevant laws of thermodynamics. Numerical examples, based on a generalised Mooney-Rivlin energy function, are presented to demonstrate the model capacity in the case of a magneto-viscoelastically coupled load.

Thermodynamic stability of nanosized multicomponent bubbles/droplets: The square gradient theory and the capillary approach

Formation of nanosized droplets/bubbles from a metastable bulk phase is connected to many unresolved scientific questions. We analyze the properties and stability of multicomponent droplets and bubbles in the canonical ensemble, and compare with single-component systems. The bubbles/droplets are described on the mesoscopic level by square gradient theory. Furthermore, we compare the results to a capillary model which gives a macroscopic description. Remarkably, the solutions of the square gradient model, representing bubbles and droplets, are accurately reproduced by the capillary model except in the vicinity of the spinodals. The solutions of the square gradient model form closed loops, which shows the inherent symmetry and connected nature of bubbles and droplets. A thermodynamic stability analysis is carried out, where the second variation of the square gradient description is compared to the eigenvalues of the Hessian matrix in the capillary description. The analysis shows that it is impossible to stabilize arbitrarily small bubbles or droplets in closed systems and gives insight into metastable regions close to the minimum bubble/droplet radii. Despite the large difference in complexity, the square gradient and the capillary model predict the same finite threshold sizes and very similar stability limits for bubbles and droplets, both for single-component and two-component systems.

Nuclear expansion with excitation

The expansion of an isolated hot spherical nucleus with excitation energy and its caloric curve are studied in a thermodynamic model with the SkM∗ force as the nuclear effective two-body inter-action. The calculated results are shown to compare well with the recent experimental data from energetic nuclear collisions. The fluctuations in temperature and density are also studied. They are seen to build up very rapidly beyond an excitation energy of ∼9 MeV/u. Volume-conserving quadrupole deformation in addition to expansion indicates , however, nuclear disassembly above an excitation energy of ∼4 MeV/u.

Cluster glasses of ultrasoft particles

We present molecular dynamics (MD) simulations results for dense fluids of ultrasoft, fully penetrable particles. These are a binary mixture and a polydisperse system of particles interacting via the generalized exponential model, which is known to yield cluster crystal phases for the corresponding monodisperse systems. Because of the dispersity in the particle size, the systems investigated in this work do not crystallize and form disordered cluster phases. The clusteringtransition appears as a smooth crossover to a regime in which particles are mostly located in clusters, isolated particles being infrequent. The analysis of the internal cluster structure reveals microsegregation of the big and small particles, with a strong homo-coordination in the binary mixture. Upon further lowering the temperature below the clusteringtransition, the motion of the clusters" centers-of-mass slows down dramatically, giving way to a cluster glass transition. In the cluster glass, the diffusivities remain finite and display an activated temperature dependence, indicating that relaxation in the cluster glass occurs via particle hopping in a nearly arrested matrix of clusters. Finally we discuss the influence of the microscopic dynamics on the transport properties by comparing the MD results with Monte Carlo simulations.

Nature of the Epidemic Threshold for the Susceptible-Infected-Susceptible Dynamics in Networks

We develop an analytical approach to the susceptible-infected-susceptible epidemic model that allows us to unravel the true origin of the absence of an epidemic threshold in heterogeneous networks. We find that a delicate balance between the number of high degree nodes in the network and the topological distance between them dictates the existence or absence of such a threshold. In particular, small-world random networks with a degree distribution decaying slower than an exponential have a vanishing epidemic threshold in the thermodynamic limit.

Effect of compressibility in bubble formation in closed systems

We analyze the stability of small bubbles in a closed system with fixed volume, temperature, and number of molecules. We show that there exists a minimum stable size of a bubble. Thus there exists a range of densities where no stable bubbles are allowed and the system has a homogeneous density which is lower than the coexistence density of the liquid. This becomes possible due to the finite liquid compressibility. Capillary analysis within the developed"modified bubble" model illustrates that the existence of the minimum bubble size is associated to the compressibility and it is not possible when the liquid is strictly incompressible. This finding is expected to have very important implications in cavitation and boiling.

Equilibrium of the simultaneous etherification ofisobutene and isoamylenes with ethanol inliquid-phase

The simultaneous etherification of isobutene and isoamylenes with ethanol has been studied using macroreticu-lar acid ion-exchange resins as catalyst. Most of the experiments were carried out over Amberlyst-35. In addition,Amberlyst-15 and Purolite CT-275 were also tested. Chemical equilibrium of four chemical reactions was studied:ethyl tert-butyl ether formation, tert-amyl ethyl ether formation from isoamylenes (2-methyl-1-butene and 2-methyl-2-butene) and isomerization reaction between both isoamylenes. Equilibrium data were obtained in a batchwisestirred tank reactor operated at 2.0 MPa and within the temperature range from 323 to 353 K. Experimental molarstandard enthalpy and entropy changes of reaction were determined for each reaction. From these data, the molarenthalpy change of formation of ethyl tert-butyl ether and tert-amyl ethyl ether were estimated. Besides, the chemical equilibrium between both diisobutene dimers, 2,4,4-trimethyl-1-pentene and 2,4,4-trimethyl-2-pentene, wasevaluated. A good agreement between thermodynamic results for the simultaneous etherification carried out in thiswork and those obtained for the isolated ethyl tert-butyl ether and tert-amyl ethyl ether systems was obtained.

CNDOL: A fast and reliable method for the calculation of electronic properties of very large systems. Applications to retinal binding pocket in rhodopsin and gas phase porphine.

Very large molecular systems can be calculated with the so called CNDOL approximate Hamiltonians that have been developed by avoiding oversimplifications and only using a priori parameters and formulas from the simpler NDO methods. A new diagonal monoelectronic term named CNDOL/21 shows great consistency and easier SCF convergence when used together with an appropriate function for charge repulsion energies that is derived from traditional formulas. It is possible to obtain a priori molecular orbitals and electron excitation properties after the configuration interaction of single excited determinants with reliability, maintaining interpretative possibilities even being a simplified Hamiltonian. Tests with some unequivocal gas phase maxima of simple molecules (benzene, furfural, acetaldehyde, hexyl alcohol, methyl amine, 2,5 dimethyl 2,4 hexadiene, and ethyl sulfide) ratify the general quality of this approach in comparison with other methods. The calculation of large systems as porphine in gas phase and a model of the complete retinal binding pocket in rhodopsin with 622 basis functions on 280 atoms at the quantum mechanical level show reliability leading to a resulting first allowed transition in 483 nm, very similar to the known experimental value of 500 nm of "dark state." In this very important case, our model gives a central role in this excitation to a charge transfer from the neighboring Glu(-) counterion to the retinaldehyde polyene chain. Tests with gas phase maxima of some important molecules corroborate the reliability of CNDOL/2 Hamiltonians.

Molecular mechanism of a green-shifted, pH-dependent red fluorescent protein mKate variant.

Fluorescent proteins that can switch between distinct colors have contributed significantly to modern biomedical imaging technologies and molecular cell biology. Here we report the identification and biochemical analysis of a green-shifted red fluorescent protein variant GmKate, produced by the introduction of two mutations into mKate. Although the mutations decrease the overall brightness of the protein, GmKate is subject to pH-dependent, reversible green-to-red color conversion. At physiological pH, GmKate absorbs blue light (445 nm) and emits green fluorescence (525 nm). At pH above 9.0, GmKate absorbs 598 nm light and emits 646 nm, far-red fluorescence, similar to its sequence homolog mNeptune. Based on optical spectra and crystal structures of GmKate in its green and red states, the reversible color transition is attributed to the different protonation states of the cis-chromophore, an interpretation that was confirmed by quantum chemical calculations. Crystal structures reveal potential hydrogen bond networks around the chromophore that may facilitate the protonation switch, and indicate a molecular basis for the unusual bathochromic shift observed at high pH. This study provides mechanistic insights into the color tuning of mKate variants, which may aid the development of green-to-red color-convertible fluorescent sensors, and suggests GmKate as a prototype of genetically encoded pH sensors for biological studies.

Toward on-the-fly quantum mechanical/molecular mechanical (QM/MM) docking: development and benchmark of a scoring function.

We address the challenges of treating polarization and covalent interactions in docking by developing a hybrid quantum mechanical/molecular mechanical (QM/MM) scoring function based on the semiempirical self-consistent charge density functional tight-binding (SCC-DFTB) method and the CHARMM force field. To benchmark this scoring function within the EADock DSS docking algorithm, we created a publicly available dataset of high-quality X-ray structures of zinc metalloproteins ( http://www.molecular-modelling.ch/resources.php ). For zinc-bound ligands (226 complexes), the QM/MM scoring yielded a substantially improved success rate compared to the classical scoring function (77.0% vs 61.5%), while, for allosteric ligands (55 complexes), the success rate remained constant (49.1%). The QM/MM scoring significantly improved the detection of correct zinc-binding geometries and improved the docking success rate by more than 20% for several important drug targets. The performance of both the classical and the QM/MM scoring functions compare favorably to the performance of AutoDock4, AutoDock4Zn, and AutoDock Vina.

Fast generation of spin-squeezed states in bosonic Josephson junctions

We describe methods for the fast production of highly coherent-spin-squeezed many-body states in bosonic Josephson junctions. We start from the known mapping of the two-site Bose-Hubbard (BH) Hamiltonian to that of a single effective particle evolving according to a Schrödinger-like equation in Fock space. Since, for repulsive interactions, the effective potential in Fock space is nearly parabolic, we extend recently derived protocols for shortcuts to adiabatic evolution in harmonic potentials to the many-body BH Hamiltonian. A comparison with current experiments shows that our methods allow for an important reduction in the preparation times of highly squeezed spin states.

Antibioottien poisto vedestä adsorptiolla

Antibiootit ovat yleisessä käytössä olevia lääkeaineita, joilla on kyky hidastaa mikrobien kasvua. Osa lääkeaineesta poistuu elimistöstä muuntumattomana. Koska tavanomainen jäteveden käsittelyprosessi ei riitä poistamaan antibiootteja jätevedestä, ne päätyvät vesistöihin, joissa ne häiritsevät ekosysteemiä ja voivat aiheuttaa vastustuskykyisten bakteerikantojen muodostumisen. Antibiootit voitaisiin poistaa vedestä adsorptiolla. Työssä on esitelty antibioottien adsorptiomekanismeja, vedenkäsittelyssä käytettäviä adsorptioprosesseja ja adsorbentteja, jotka soveltuvat antibioottien erottamiseen vedestä. Lisäksi tarkastellaan yleisesti adsorption kinetiikkaa ja termodynamiikkaa sekä mallinnetaan panoskokeiden tulosten perusteella jatkuvatoimisen adsorptiokolonnin toimintaa.