Miracle-dz/UniFAR-FTUs huggingface dataset:
An Advanced Tool for the Selection of Electrolyte Components for Rechargeable Lithium Batteries

The solid electrolyte interphase (SEI) plays a key role in lithium-metal, lithium-alloy, and lithium-ion batteries. The SEI on both lithium and carbonaceous electrodes consists of many different materials including LiF, Li{sub 2}CO{sub 3}, LiCO{sub 2}-R, Li{sub 2}O, lithium alkoxides, nonconductive polymers, and more. Close to the lithium or Li{sub x}C{sub 6} the SEI consists of the thermodynamically stable anions, such as O{sup 2{minus}}, S{sup 2{minus}}, and halides. Close to the solution the SEI also contains partially reduced materials such as polyolefins, semicarbonates, etc. These materials form simultaneously and precipitate on the electrode as a mosaic of microphases. These phases may, under certain conditions, form separate layers, but in general it is more appropriate to treat them as heteropolymicrophases. The SEI composition and properties depend strongly on electrolyte composition and on other factors. Rapid formation of the SEI is important in all lithium batteries, especially in the case of lithium-ion cells with graphite anodes. Hence SEI precursors must be selected from a group of materials that have high exchange current density (i{sub 0}) for reduction. As it is difficult to measure i{sub 0} on solid electrodes and only limited data, if any, are available, it is suggested to use the datamore » bank for the rate constant for the reduction of electrolyte components by hydrated electrons (e{sub aq}{sup {minus}}). The authors have demonstrated that the rate constants of the reactions of solvated electrons and electrolyte components and impurities correlate well with the formation voltage of SEI and with SEI composition. Thus, the rate constants (k{sub e}) for these reactions are proposed as a tool for the first screening of electrolyte components when a new electrolyte is designed. « less
Synthesis of Phthalic Anhydride: Catalysts, Kinetics, and Reaction Modeling

Abstract Information concerning the oxidation of o-xylene and naphthalene, the two main processes for producing phthalic anhydride, is updated and analyzed. New techniques for the preparation of catalysts, all based in the impregnation method and involving the control of parameters such as pH and ionic strength of solutions, are described; the performance of the resulting catalysts is compared with that of catalysts prepared by other methods. Sulfur-containing substances and promoters such as Ag, P, Nb, and Sb have been shown to enhance catalyst performance; studies of their effect on the surface area, acidic properties, and stabilization of the oxidation state of vanadium in supported V2O5 catalysts are described. The latest attempts to correlate the physicochemical characteristics of the catalysts with their catalytic features are analyzed. FTIR, Raman spectroscopy, adsorption of bases, 51V-NMR, XRD, XPS, SIMS, and electrical conductivity have been used in the study of V2O5/TiO2 catalysts, allowing furt.
Nanoparticle Assembly of Ordered Multicomponent Mesostructured Metal Oxides via a Versatile Sol−Gel Process

Multicomponent metal oxides have attracted attention for their potential use in electronic, (photo)catalytic, photovoltaic, and energy storage applications. The ability to simultaneously control the nanoscale structure and composition of such materials using simple and inexpensive routes is important for that potential to be realized. Here we introduce a simple and widely applicable methodology for the synthesis of multicomponent mesostructured metal oxides (MMMOs) from the combination of inexpensive and commercially available polymers with metal alkoxides solubilized in a sol−gel solution consisting of acetic acid, hydrochloric acid, and ethanol (AcHE). MMMOs obtained utilizing the AcHE system have tunable pore structures, a high degree homogeneity, and in certain cases thermal stability above 1000 °C. The ability to easily process these diverse MMMOs in the form of thin films, free-standing membranes, and monoliths provides distinct advantages over previously reported MMO synthesis proceduresespecially .
Controlled Transesterification and Its Effects on Structure Development in Polycarbonate–Poly(Butylene Terephthalate) Melt Blends

A series of 50:50 polycarbonate–poly(butylene terephthalate) (PC-PBT) blends were formed via reactive melt blending in a torque rheometer. A controlled degree of transesterification between the two homopolymers was initiated by the incorporation of an alkyl titanium catalyst during melt blending and finally quenched by the addition of a transesterification inhibitor. The resultant materials were characterized using differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA), Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). As the degree of transesterification increased, the composition of the blends became increasingly complex, comprising mixtures of the homopolymers and various AB-type copolymers of PC and PBT, resulting in significant changes in their thermal behavior. A corresponding transformation in the morphology of the blends was observed due to the formation of increasing concentrations of copolyesters. Thus, the initial coarse (>5 μm) bicontinuous morphology developed into a more finely dispersed submicron-scale structure, exhibited by blends containing significant volumes of interphase material; finally, at high degrees of transesterification, a homogeneous, amorphous material was formed.
High-affinity host–guest complex of cucurbit[7]uril with a bis(thiazolium) salt

A biologically- and pharmaceutically-relevant bis(thiazolium) dication model compound, α,α′-bis(thiazolium)-p-xylene (BTX2+), forms a strong 1 : 1 host–guest inclusion complex with cucurbit[7]uril (CB[7]). The complexation stoichiometry, binding affinity and geometry were studied via 1H NMR and UV-visible titrations, ESI-MS, and molecular modeling (ab initio calculations). The hydrogen/deuterium exchange reactions of the C(2)-proton of BTX2+ were conducted in the absence and presence of CB[7] in D2O at 25 °C and at an ionic strength of 0.20 M. The inhibition of C(2)-H/D exchange of the guest bis(thiazolium) dication upon complexation with CB[7] exhibited a second-order rate constant that decreased by more than four-fold in the presence of CB[7]. The supramolecular-controlled stability of thiazolium cations through complexation with CB[7] host molecules is anticipated to have applications for stability enhancement of thiazolium based drugs and to potentially draw interest in the application of CB[n] host molecules with regard to the formulation and delivery of these drugs.
Simultaneous HPLC determination of tocopherols, carotenoids, and chlorophylls for monitoring their effect on virgin olive oil oxidation

The oxidative stability of virgin olive oil is related to triacylglycerol composition and the presence of polar phenolic and other components. The present paper presents an HPLC methodology for the simultaneous determination of tocopherols, major carotenoids, and chlorophylls suitable to monitor their fate during virgin olive oil oxidation. The separation of the above classes of components was carried out using an n-hexane/2-propanol gradient within 20 min. Detection was accomplished using a UV detector in series with a diode array system. The method was validated and applied to oil samples subjected to autoxidation or photo-oxidation. The results indicated that the method could be used to highlight the effect of these components on virgin olive oil oxidative stability. Keywords: Virgin olive oil; HPLC; tocopherols; carotenoids; chlorophylls; oxidation
Study on Nucleation and Growth Rates of SiO₂ Particles in the Supersaturation Solution Produced by TEOS

Nucleation and growth of SiO2 particle in the SiO2 supersaturation solution, which was synthesized with TEOS by sol-gel method, were investigated. When the TEOS solution was fed into the semi-batch reactor containing the ammonia solution at constant flow rate, the concentration of silane produced by hydrolysis and condensation of TEOS and particle induction time were measured and then the supersaturation of SiO2 in the solution was estimated. For investigation of dependency of nucleation and growth rates of SiO2 particle on the supersaturation in the solution the concentration of the ammonia catalyst was varied. The reaction rates or hydrolysis and condensation of the TEOS was changed with the ammonia concentration and it resulted in variation of the supersaturation of SiO2 in the solution. The induction time and supersaturation was reduced with increase of the ammonia concentration due to facilitation of the hydrolysis and condensation reaction. Thus, the lower population density and larger size of final particles were obtained with the higher ammonia concentration. To predict the particle nucleation and growth rates from measurable variables of SiO2 supersaturation and particle induction time with change of TEOS reaction condition the model equations were suggested. From the comparison between experimental data and model prediction the exponential constant for particle nucleation rate was suggested as -634.02. This result meant that the particle nucleation rate was reduced with decrease of the induction time and the particles were induced at different supersaturation. In addition, the model prediction for the final mean particle size was well agreed with experimental data.
Effect of metal doping on the solvation of carbon nanotubes: a Monte Carlo simulation study

Aqueous nanomaterials have many applications in biotechnology, so creating stable solutions of nanotubes is an important problem. Structural compositions have an important role on the solvation of nanotubes in water. In this research, the solvation of alkali metal-doped carbon nanotubes is investigated in terms of solvation-free energy and compared with pure carbon nanotube. Herein it is reported the outcomes of Monte Carlo simulations of these nanotubes immersed in water to look at the effects of nanotube type on the solvation. The results indicate that carbon nanotube has poor solubility in water and metal doping increase the solvation-free energy of carbon nanotube. Oxygen radial density profiles inside and outside the nanotubes are also computed. The maxima density of water in carbon nanotube is located in the centre of nanotube far from the tube wall. Metal-doped carbon nanotubes have one maximum nearer to the wall respectively.
Poly(glycidyl methacrylate-co-3-thienyl-methylmethacrylate) based working electrodes for hydrogen peroxide biosensing

BACKGROUND: Hydrogen peroxide biosensors based on Poly(glycidyl methacrylate-co-3-thienylmethylmethacrylate)/ Polypyrrole [Poly(GMA-co-MTM)/PPy] composite film were reported. Poly(GMA-co-MTM) including various amounts of GMA and MTM monomers was synthesized via the radical polymerization. Enzyme horseradish peroxidase (HRP) was trapped in Poly(GMA-co-MTM)/PPy composites during the electropolymerization reaction between pyrrole and thiophene groups of MTM monomer, and chemically bonded via the epoxy groups of GMA. Analytical parameters of the fabricated electrodes were calculated and are discussed in terms of film electroactivity and mass transfer conditions of the composite films. RESULTS: The amount of electroactive HRP was found to be 1.25, 0.34 and 0.213 µg for the working electrodes of Poly(GMA30%- co-MTM70%)/PPy/HRP, Poly(GMA85%-co-MTM15%)/PPy/HRP and Poly(GMA90%-co-MTM10%)/PPy/HRP, respectively. Optimal response of the fabricated electrodes was obtained at pH 7 and an operational potential of − 0.35 V. It was observed that effective enzyme immobilization and electroactivity of the composite films could be changed by changing the ratios of GMA and MTM fractions of Poly(GMA-co-MTM) based working electrodes. CONCLUSION: The amount of electroactive enzyme increases with increasing MTM content of the final copolymer. High operational stabilities of the biosensors can be attributed to the strong covalent enzyme linkage via the epoxy groups of GMA due to preventing enzyme deterioration and loss. A more convenient microenvironment for mass transfer was provided for the electrodes by higher GMA ratios. It is observed that mass transfer is dominated by the mechanism of electron transfer to obtain effective sensitivity values. This work contributes to discussions clarifying the problems regarding the design parameters of biosensors. Copyright © 2011 Society of Chemical Industry
Simultaneous Detemination of Atorvastatin Calcium and Amlodipine Besylate by Spectrophotometry and Multivariate Calibration Methods in Pharmaceutical Formulations

Resolution of binary mixture of atorvastatin (ATV) and amlodipine (AML) with minimum sample pretreatment and without analyte separation has been successfully achieved using a rapid method based on partial least square analysis of UV–spectral data. Multivariate calibration modeling procedures, traditional partial least squares (PLS-2), interval partial least squares (iPLS) and synergy partial least squares (siPLS), were applied to select a spectral range that provided the lowest prediction error in comparison to the full-spectrum model. The simultaneous determination of both analytes was possible by PLS processing of sample absorbance between 220-425 nm. The correlation coefficients (R) and root mean squared error of cross validation (RMSECV) for ATV and AML in synthetic mixture were 0.9991, 0.9958 and 0.4538, 0.2411 in best siPLS models respectively. The optimized method has been used for determination of ATV and AML in amostatin commercial tablets. The proposed method are simple, fast, inexpensive and do not need any separation or preparation methods.
Experimental Gas Hydrate Dissociation Pressures for Pure Methane in Aqueous Solutions of MgCl2 and CaCl2 and for a (Methane + Ethane) Gas Mixture in an Aqueous Solution of (NaCl + MgCl2)

Gas hydrate dissociation pressures along the hydrate−liquid−gas equilibrium line in the temperature range (273 to 292) K and for pressures up to 23 MPa have been determined for methane in aqueous unsaturated magnesium chloride solutions w = (1, 5, 10, and 15) % of MgCl2, in a calcium chloride solution w = 17.05 % of CaCl2, and for a (methane + ethane) mixture in an aqueous solution of sodium chloride and magnesium chloride w(NaCl) = 5 % + w(MgCl2) = 6.09 % applying an isochoric method. For the methane system, it is shown that considerable deviation from “ideal” behavior occurs at high MgCl2 concentrations. A gas hydrate calculation model has been applied being able to reproduce the experimental dissociation pressures to within ± 2 % as well as efficiently predicting the dissociation pressures and the inhibiting effects of various other electrolyte solutions for gas hydrate systems with pure gases and gas mixtures.
Investigation of Lignosulphonate Mannich Bases as Corrosion Inhibitors

To seek for new acidic corrosion inhibitor, this work used aliphatic amine, formaldehyde and sodium lignosulphonate as the raw materials to prepare new Mannich bases as eco-friendly corrosion inhibitors. The inhibition of these Mannich bases for mild steel corrosion in 2M HCl solution was investigated by weight loss technique. Through the single factor experiments, the optimal mole ratio was determined. Meanwhile, the influences of temperature and inhibitor dosage on the corrosion inhibition performance of the products were studied. The adsorptions on the surface of mild steel and inhibition mechanism were also discussed. Potentiodynamic polarization studies indicate that extracts are mixed-type inhibitors.
Control of electrons through patterning of superstructures in sodium cobaltate

Sodium Cobaltate (NaxCoO2) has emerged as a material of exceptional scientific and technological interest since it is among the best P-type thermoelectric materials. The superstructures in pure NaxCoO2 templates the Coulomb landscape on the Co layers and is found to control the physical properties. The combination of the high electrical conductivity in the Co layers with the low thermal conductivity due to the rattling of sodium ions in cages, are the precise conditions for thermoelectric materials with high figures of merit. Replacing Na by divalent ions was reported to lead to a dramatic improvement in thermoelectric performance. The superstructures of NaxCayCoO2 and NaxSryCoO2 have been determined by Laue diffraction using neutrons on SXD at ISIS and x-rays at Royal Holloway. Reverse Monte-Carlo methods were used to determine Na ion patterning including the locations of the divalent ions. Co and O displacements were also determined that show buckling following the Na structure. In the doped systems we find completely new multi-vacancy clusters. Di-vacancies form in Ca doped systems where the divalent ion sits at the central site. In the Sr doped systems two new superlattices are observed, explained by the clustering of separated Sr ions with associated vacancies. Multiple valence states have been detected by NMR, which is a local probe, but spatial charge ordering in the cobalt layer has not previously been observed. We report new measurements using Resonant X-ray Scattering on the Materials and Magnetism beamline I16 at Diamond. We find resonant x-ray scattering with the same periodicity as the sodium superstructure, directly demonstrating that the electronic ordering in these cobalt layers is controlled by the sodium ordering. We are able to reproduce the energy, polarisation and azimuthal dependencies of the resonant x-ray scattering in calculations using the FDMNES code.
Spring thaw and growing season N2O emissions from a field planted with edible peas and a cover crop

Nitrous oxide emissions are highly episodic and to accurately quantify them annually, continuous measurements are required. A tower-based micrometeorological measuring system was used on a commercial cattle farm near Co teau-du-Lac, (QC, Canada) during 2003 and 2004 to quantify N2O emissions associated with the production of edible peas. It was equipped with an ultrasonic anemometer and a fast-response closed-path tunable diode laser. Continuous measurements of N2O fluxes were made during the spring thaw following corn cultivation in summer 2002, then during an edible pea growing season, followed by cattle manure application, cover crop planting and through until after the next spring ploughing. The cumulative N2O emissions of 0.7 kg N2O-N ha-1 during the initial snowmelt period following corn harvest were lower than expected. Sustained and small N2O emissions totalling 1.7 kg N2O-N ha-1 were observed during the growing season of the pea crop. Solid cattle manure applied after the pea harvest generated th.
Private Computing : The Trusted Digital Assistant

Het proefschrift is goedgekeurd door prof. dr. This dissertation was typeset with L A T E X in Charter and Euler, with symbols from A M S. The simple figures were drawn, then scanned at 1200 dpi, and converted to JPG with GIMP. The complicated once were programmed in METAPOST. The cover was drawn by Marianne Kulø. The dissertation was in its entirety written and typeset using NetBSD. ii Preface Over the last 10 years, I have continously been working on projects related to private computing. The projects to which I have been affiliated have varied in focus, in size and in scope. This dissertation reports from the various projects, and thus represents a decade of research. Over the years, I have had the pleasure of working with quite a few people. Fortunately, not all of them have let me be solely in control of our joint projects. In fact, some have put up quite some resistance when I have tried to lead the project in the direction I believed was best. Today, I believe this stubborn resistance benefited not only the projects per se, but probably also, in the end, this dissertation. The price to pay for cooperation is that I am not the sole author of every single publication this dissertaion is based on. However, I am the first author on all but one. On that last one, the authours are in alphabetic order. Thus, my claim is that this dissertation reports from my contributions. My ambition has been to present only work that has been validated by peer review. To that end, at the very beginning of each chapter there is a section identifying the underlying publication(s). All chapters , except those in the introduction (Chapters 1 – 3) and Chapter 7, are based on articles that has been published. A few of them has simply been printed, but most have been published. Because I report from a decade of continous work, some of the results presented here are quite dated. However, at the time they were published, they were not.
A study of molecular adsorption and transport at cell membrane and biologically relevant surfaces by Second Harmonic Generation

Most of the biological processes in living systems involve molecular adsorption and transport at biomembranes. It is highly desired to study the time-resolved transport kinetics through living cell membranes. In this thesis, an experimental means based on a nonlinear optical phenomenon, Second Harmonic Generation (SHG) has been demonstrated to detect the molecular adsorption and transport through living cell membranes in real time and to evaluate the salt ion effects on adsorption processes in biologically relevant colloidal systems. In the case of gram-negative bacteria, E.coli, a hydrophobic cation, Malachite Green (MG) has been observed to adsorb onto the cell surface and then sequentially transport across the double bilayer structures, the bacterial outer membrane and the cytoplasmic membrane. The adsorption characteristics as well as the transport rate constant at each of the membranes have been determined. In contrast to the prokaryotic E.coli cell, the molecular ion can adsorb onto the eukaryotic Murine Erythroleukemia (MEL) cell but cannot penetrate its membrane which has no hydrophobic ion permeable channels and is more tightly packed. MG cation has been used as a SHG indicator to probe the effects of solvent ionic strength and ion specificity on molecular adsorption at model protein systems. Polystyrene sulfate (PSS) microspheres and polystyrene carboxyl (PSC) microspheres have been examined. The electrostatic force dominated molecule-surface interaction between MG cations and the sulfate terminations at PSS surface is largely affected by the ionic strength of the solution but is not sensitive to the ion identity. On the other hand, the hydrophobic force dominated molecule-surface interaction between hydrophobic regions of the MG dye and PSC microsphere shows pronounced specific ion effects but is less affected by ionic strength of the solution. Degree Type Dissertation Degree Name Doctor of Philosophy (PhD) Graduate Group Chemistry First Advisor Hai-Lung Dai