Assessing the activity coefficients of water in cholinium-based ionic liquids: experimental measurements and COSMO-RS modeling

The vapor liquid-equilibrium of water + ionic liquids is relevant for a wide range of applications of these compounds. It is usually measured by ebulliometric techniques, but these are time consuming and expensive. In this work it is shown that the activity coefficients of water in a series of cholinium-based ionic liquids can be reliably and quickly estimated at 298.15K using a humidity meter instrument. The cholinium based ionic liquids were chosen to test this experimental methodology since data for water activities of quaternary ammonium salts are available in the literature allowing the validation of the proposed technique. The COSMO-RS method provides a reliable description of the data and was also used to understand the molecular interactions occurring on these binary systems. The estimated excess enthalpies indicate that hydrogen bonding between water and ionic liquid anion is the dominant interaction that governs the behavior of water and cholinium-based ionic liquids systems, while the electrostatic-misfit and van der Walls forces have a minor contribution to the total excess enthalpies.

Development of methods for the determination of cadmium and thallium in oil shale by-products with graphite furnace atomic absorption spectrometry using direct analysis.

2014

Golf course irrigation and self-sufficiency water in Southern Spain

During the first decade of the 21st century, many golf courses were developed in the Southeast of Spain, which greatly increased the number of these facilities. Almost all of these golf courses have been accompanied by large residential developments composed of thousands of dwelling units. This article seeks to identify the factors that influence golf courses’ water consumption and estimate the number of dwelling units that an associated residential development needs to have to provide the effluent necessary to fully meet the irrigation needs of a golf course. The study indicates that private golf courses achieve greater levels of irrigation efficiency than public golf courses and that the golf courses associated with residential developments subject the irrigation needs of the grassland to the sale requirements of the real estate properties. The study also estimates that a golf course requires approximately 3000 dwelling units with an average annual occupancy of 33% to achieve self-sufficiency for irrigation.

Monodisperse W/O/W emulsions encapsulating L-ascorbic acid: Insights on their formulation using microchannel emulsification and stability studies

Stabilizing l-ascorbic acid is a challenge for food industries. The present study aimed to formulate monodisperse food-grade water-in-oil-in-water (W/O/W) emulsions containing a high concentration of l-ascorbic acid in an inner aqueous phase using homogenization and subsequent microchannel emulsification (MCE). The microchannel (MC) array plate used here was a silicon asymmetric straight-through MC array that consists of numerous 10. μm. ×. 100. μm microslots with a 30. μm depth, each connected to a 10. μm-diameter circular MC with a 70. μm depth. Water-in-oil (W/O) emulsions contained a soybean oil solution with 4-8% (w/w) tetraglycerin condensed ricinoleic acid ester as a continuous phase and an aqueous solution with 10-30% (w/v) l-ascorbic acid, 1% (w/w) magnesium sulfate, and 1% (w/v) gelatin as an inner aqueous phase. The W/O emulsion droplets formulated using a rotor-starter homogenizer had average droplet diameters of 2.6-2.9. μm and coefficients of variation (CVs) of 13-17%. MCE was performed using a dispersed W/O emulsion phase and a 5. mM phosphate buffer containing 1% (w/w) decaglycerol monolaurate and 10-30% (w/v) D(+)-glucose as an outer aqueous phase. Monodisperse W/O/W emulsions containing W/O droplets with average diameters of 26.0-31.5. μm and CVs below 10% were successfully formulated via an asymmetric straight-through MC array at a low hydrophobic emulsifier concentration, regardless of l-ascorbic acid concentration. The W/O droplets dispersed in these monodisperse W/O/W emulsions were physically stable in variation of average diameter and CV for more than 10d of storage at 4. °C. The monodisperse W/O/W emulsions also exhibited l-ascorbic acid retention exceeding 80% during storage.

Do increases in oil prices precede U.S. recessions?

This thesis examines the relationship between oil prices and economic activity, and it attempts to address the question: do increases in oil prices (oil shocks) precede U.S. recessions? This paper also applied macroeconomics, either through the direct use of a macroeconomic point of view or using a combination of mathematical and statistical models. Two mathematical and statistical models are used to determine the ability of oil prices to predict recessions in the United States. First, using the binary cyclical (Bry-Boschan method) indicator procedure to test the turning point of oil prices compared with turning points in GDP finds that oil prices almost always turn five month before a recession, suggesting that an oil shock might occur before a recession. Second, the Granger causality test shows that oil prices change do Granger cause U.S. recessions, indicating that oil prices are a useful signal to indicate a U.S. recession. Finally, combining this analysis with the literature, there are several potential explanations that the spike in oil prices result in slower GDP growth and are a contributing factor to U.S. recessions.

Polymer organogels stabilized HIPE organogels and applications in oil fields

This research focuses on polymer stabilized high internal phase emulsions for oil spill recovery and oil safety.

Effect of chemical conjugation of L-leucine to chitosan on the dispersibility and drug release of a dry powder inhaler nanoparticle formulation

Purpose: This study investigated the effect of chemical conjugation of the amino acid L-leucine to the polysaccharide chitosan on the dispersibility and drug release pattern of a polymeric nanoparticle (NP)-based controlled release dry powder inhaler (DPI) formulation. Methods: A chemical conjugate of L-leucine with chitosan was synthesized and characterized by Infrared (IR) Spectroscopy, Nuclear Magnetic Resonance (NMR) Spectroscopy, Elemental Analysis and X-ray Photoelectron Spectroscopy (XPS). Nanoparticles of both chitosan and its conjugate were prepared by a water-in-oil emulsification – glutaraldehyde cross-linking method using the antihypertensive agent, diltiazem (Dz) hydrochloride as the model drug. The surface morphology and particle size distribution of the nanoparticles were determined by Scanning Electron Microscopy (SEM) and Dynamic Light Scattering (DLS). The dispersibility of the nanoparticle formulation was analysed by a Twin Stage Impinger (TSI) with a Rotahaler as the DPI device. Deposition of the particles in the different stages was determined by gravimetry and the amount of drug released was analysed by UV spectrophotometry. The release profile of the drug was studied in phosphate buffered saline at 37 ⁰C and analyzed by UV spectrophotometry. Results: The TSI study revealed that the fine particle fractions (FPF), as determined gravimetrically, for empty and drug-loaded conjugate nanoparticles were significantly higher than for the corresponding chitosan nanoparticles (24±1.2% and 21±0.7% vs 19±1.2% and 15±1.5% respectively; n=3, p<0.05). The FPF of drug-loaded chitosan and conjugate nanoparticles, in terms of the amount of drug determined spectrophotometrically, had similar values (21±0.7% vs 16±1.6%). After an initial burst, both chitosan and conjugate nanoparticles showed controlled release that lasted about 8 to 10 days, but conjugate nanoparticles showed twice as much total drug release compared to chitosan nanoparticles (~50% vs ~25%). Conjugate nanoparticles also showed significantly higher dug loading and entrapment efficiency than chitosan nanoparticles (conjugate: 20±1% & 46±1%, chitosan: 16±1% & 38±1%, n=3, p<0.05). Conclusion: Although L-leucine conjugation to chitosan increased dispersibility of formulated nanoparticles, the FPF values are still far from optimum. The particles showed a high level of initial burst release (chitosan, 16% and conjugate, 31%) that also will need further optimization.

Temperature-and pH-Sensitive Nanohydrogels of Poly(N-Isopropylacrylamide) for Food Packaging Applications: Modelling the Swelling-Collapse Behaviour

Temperature-sensitive poly(N-isopropylacrylamide) (PNIPA) nanohydrogels were synthesized by nanoemulsion polymerization in water-in-oil systems. Several cross-linking degrees and the incorporation of acrylic acid as comonomer at different concentrations were tested to produce nanohydrogels with a wide range of properties. The physicochemical properties of PNIPA nanohydrogels, and their relationship with the swelling-collapse behaviour, were studied to evaluate the suitability of PNIPA nanoparticles as smart delivery systems (for active packaging). The swelling-collapse transition was analyzed by the change in the optical properties of PNIPA nanohydrogels using ultraviolet-visible spectroscopy. The thermodynamic parameters associated with the nanohydrogels collapse were calculated using a mathematical approach based on the van't Hoff analysis, assuming a two-state equilibrium (swollen to collapsed). A mathematical model is proposed to predict both the thermally induced collapse, and the collapse induced by the simultaneous action of two factors (temperature and pH, or temperature and organic solvent concentration). Finally, van't Hoff analysis was compared with differential scanning calorimetry. The results obtained allow us to solve the problem of determining the molecular weight of the structural repeating unit in cross-linked NIPA polymers, which, as we show, can be estimated from the ratio of the molar heat capacity (obtained from the van't Hoff analysis) to the specific heat capacity (obtained from calorimetric measurements).

Temperature-and pH-Sensitive Nanohydrogels of Poly(N-Isopropylacrylamide) for Food Packaging Applications: Modelling the Swelling-Collapse Behaviour

Temperature-sensitive poly(N-isopropylacrylamide) (PNIPA) nanohydrogels were synthesized by nanoemulsion polymerization in water-in-oil systems. Several cross-linking degrees and the incorporation of acrylic acid as comonomer at different concentrations were tested to produce nanohydrogels with a wide range of properties. The physicochemical properties of PNIPA nanohydrogels, and their relationship with the swelling-collapse behaviour, were studied to evaluate the suitability of PNIPA nanoparticles as smart delivery systems (for active packaging). The swelling-collapse transition was analyzed by the change in the optical properties of PNIPA nanohydrogels using ultraviolet-visible spectroscopy. The thermodynamic parameters associated with the nanohydrogels collapse were calculated using a mathematical approach based on the van't Hoff analysis, assuming a two-state equilibrium (swollen to collapsed). A mathematical model is proposed to predict both the thermally induced collapse, and the collapse induced by the simultaneous action of two factors (temperature and pH, or temperature and organic solvent concentration). Finally, van't Hoff analysis was compared with differential scanning calorimetry. The results obtained allow us to solve the problem of determining the molecular weight of the structural repeating unit in cross-linked NIPA polymers, which, as we show, can be estimated from the ratio of the molar heat capacity (obtained from the van't Hoff analysis) to the specific heat capacity (obtained from calorimetric measurements).

Development of functionalized terbium fluorescent nanoparticles for antibody labeling and time-resolved fluoroimmunoassay application

Silica-based functionalized terbium fluorescent nanoparticles were prepared, characterized and developed as a fluorescence probe for antibody labeling and time-resolved fluoroimmunoassay. The nanoparticles were prepared in a water-in-oil (W/O) microemulsion containing a strongly fluorescent Tb3+ chelate. N,N.N-1,N-1-12,6-bis(3'-aminomethyl-1'-pyrazolyl)phenylpyridine] tetrakis(acetate)-Tb3+ (BPTA-Tb3+), Triton X-100, octanol, and cyclohexane by controlling copolymerization of tetraethyl orthosilicate (TEOS) and 3-[2-(2- aminoethylamino)-ethylamino]propyl-trimethoxysilane (AEPS) with ammonia water. The characterizations by transmission electron microscopy and fluorometric quantum methods show that the nanoparticles are spherical and uniform in size, 45 +/- 3 nm in diameter, strongly fluorescent with fluorescence yield of 10% and a long fluorescence lifetime of 2.0 ms. The amino groups directly introduced to the nanoparticle's surface by using AEPS in the preparation made the surface modification and bioconjugation of the nanoparticles easier. The nanoparticle-labeled anti-human alpha-fetoprotein antibody was prepared and used for time-resolved fluoroimmunoassay of (x-fetoprotein (AFP) in human serum samples. The assay response is linear from 0.10 ng ml(-1) to about 100 ng ml(-1) with the detection limit of 0.10 ng ml(-1). The coefficient variations (CVs) of the method are less than 9.0%. and the recoveries are in the range of 84-98% for human serum sample measurements. (C) 2004 Elsevier B.V. All rights reserved.

Electrochemical and electrochemiluminescence study of Ru(bpy)(3)(2+)-doped silica nanoparticles with covalently grafted biomacromolecules

Spherical Ru(bpy)(3)(2+)-doped silica (RuSi) nanoparticles were prepared via a water-in-oil microemulsion approach. The electrochemical and electrochemiluminescent properties of the RuSi nanoparticles immobilized on an indium tin oxide (ITO) electrode were investigated. Further, electrochemiluminescence (ECL) of the RuSi nanoparticles with covalently coated biomacromolecules was studied. By covalent cross-linking with glutaraldehyde, gamma-(aminopropyl) triethoxysilane (APTES)-pretreated RuSi nanoparticles were coupled with different concentrations of bovine serum albumin (BSA), hemoglobin, and myoglobin, respectively.

Study on the lifetime of M-intermediate of bacteriorhodopsin film chemically modified with CeO2 nanoparticles

The characteristics of intermediates of bacteriorhodopsin (bR) can be verified by chemical modification of its surroundings. CeO2 nanoparticles, which were obtained using water-in-oil (W/O) microemulsion and calcined at various temperatures, were used as chemical additive for the modification of bR. X-ray diffraction (XRD) shows that the mean particle sizes for the samples calcined at 500 and 800 degrees C are approximately 10 and 30 nm, respectively. We prepared CeO2 nanoparticle modified poly(vinyl alcohol) (bR-PVA) films with an optical density of about 1.5 at the ground state. It is observed that the lifetime of the Wintermediate for the modified films is prolonged compared with that of the unmodified ones, and the lifetime increases with decreasing particle size. A probable mechanism, which is likely to involve effective molecular interactions between the CeO2 nanoparticles and the bR molecules, is discussed. The hydroxyl groups, which might arise from the interaction between the nanoparticles and the surrounding water molecules, help to lower the ability of the Schiff base of uptaking protons in the Wintermediate. The results indicate that controlling the interactions between biomolecules and various nanomaterials would enlarge the functionality and the range of the application of nanoparticles.

Synthesis and fluorescence of europium-doped barium fluoride cubic nanocolumns

Europium-doped barium fluoride cubic nanocolumns were synthesized from the quaternary water in oil reverse microemulsions In this process, the aqueous cores of water/cetyl trimethyl ammonium bromide (CTAB)/n-butanol/n-octane reverse microemulsions were used as microreactors for the precipitation of europium doped barium fluoride. XRD analysis shows that under the dopant concentration of 0.06% (molar fraction), the products are single phase. The result products are cubic column-like with about 30 similar to 50 nm edge length of cross section, and about 200 nm of length obtained from the transmission electron microscopy (TEM), and atomic force microscopy (AFM). Under the 0.06 % (molar fraction) of dopant concentration I the fluorescence of Eu2+ and Eu3+ under the 589 of excitation wavelength is observed.

Electrogenerated chemiluminescence sensing platform using Ru(bpy)(3)(2+) doped silica nanoparticles and carbon nanotubes

An effective electrogenerated chemiluminescence (ECL) sensor was developed by coimmobilization of the Ru(bpy)(2)(3+)-doped silica (RuDS) nanoparticles and carbon nanotubes (CNTs) on glassy carbon electrode through hydrophobic interaction. The uniform RuDS nanoparticles were prepared by a water-in-oil (W/O) microemulsion method and Ru(bpy)(3)(2+) doped inside could still maintain its high ECL efficiency. With such unique immobilization method, a great deal of Ru(bpy)(3)(2+) was immobilized three-dimensionally on the electrode , which could greatly enhance the ECL response and result in the increased sensitivity. On the other hand, CNTs played dual roles as matrix to immobilize RuDS nanoparticles and promoter to accelerate the electron transfer between Ru(bpy)(3)(2+) and the electrode. The as-prepared ECL sensor displayed good sensitivity and stability.

O princípio constitucional do desenvolvimento e a utilização de recursos hídricos na indústria de petróleo

As can be inferred by the title of its study The constitutional principle of sustainable development and the utilization of hidrical resources in the oil industry the transcribed pages are dedicated to the approach of the mentioned subjects which, despite being apparently different, will be shown intrinsically connected as goes by the study. The superation of this first step by the reader will lead to an important perception of the title: that the situation requires, urgently, a defined posture, a complete conduct change and, therefore, a modification of the paradigms currently establisheds. To brake barriers, modifying what is lived by, is the ultimate goal. For that, there is no unique path, linear, but there were broached the development themes, the hidrical resources theme and oil and natural gas industry at the necessary points to achieve, by the end, a comprehension for the Brazilian Federal Republic goals in the search for the application of these juridical norms. The ones whom lay down over this study shall notice that, more than a simple approach over these themes (which are still less worked and searched in Brazil), the heavy critic of an instituted and pacifically accepted reality, directly offensive of the constitutional principles. The debate evolves from punctual and specific aspects, it gains life, flies, searching how the juridical order equalizes the economic model to the environment defense. Standing by the possibility of conciliation among constitutional principles, the remodeling of an economic segment is defended, aligning it to the sustainable limits. Development, sustainable, becomes means and goals to the implementation of liberty, capacitating everyone to achieve their goals of life, their libertments, fruit of the inherent antagonism of the Constitution the sustainable development offers, while an axiological vector, a new reality to the economic order, turning it into a motriz element to the fortification of constitutional normative force and for the national development