Development of procedures for the triazole fungicides determination in fruits and liquid samples using microextraction techniques and chromatographic separation

Agricultural crops can be damaged by funguses, insects, worms and other organisms that cause diseases and decrease the yield of production. The effect of these damaging agents can be reduced using pesticides. Among them, triazole compounds are effective substances against fungus; for example, Oidium. Nevertheless, it has been detected that the residues of these fungicides in foods as well as in derivate products can affect the health of the consumers. Therefore, the European Union has established several regulations fixing the maximum residue of pesticide levels in a wide range of foods trying to assure the consumer safety. Hence, it is very important to develop adequate methods to determine these pesticide compounds. In most cases, gas or liquid chromatographic (GC, LC) separations are used in the analysis of the samples. But firstly, it is necessary to use proper sample treatments in order to preconcentrate and isolate the target analytes. To reach this aim, microextraction techniques are very effective tools; because allow to do both preconcentration and extraction of the analytes in one simple step that considerably reduces the source of errors. With these objectives, two remarkable techniques have been widely used during the last years: solid phase microextraction (SPME) and liquid phase microextraction (LPME) with its different options. Both techniques that avoid the use or reduce the amount of toxic solvents are convenient coupled to chromatographic equipments providing good quantitative results in a wide number of matrices and compounds. In this work simple and reliable methods have been developed using SPME and ultrasound assisted emulsification microextraction (USAEME) coupled to GC or LC for triazole fungicides determination. The proposed methods allow confidently determine triazole concentrations of μg L‐1 order in different fruit samples. Chemometric tools have been used to accomplish successful determinations. Firstly, in the selection and optimization of the variables involved in the microextraction processes; and secondly, to overcome the problems related to the overlapping peaks. Different fractional factorial designs have been used for the screening of the experimental variables; and central composite designs have been carried out to get the best experimental conditions. Trying to solve the overlapping peak problems multivariate calibration methods have been used. Parallel Factor Analysis 2 (PARAFAC2), Multivariate Curve Resolution (MCR) and Parallel Factor Analysis with Linear Dependencies (PARALIND) have been proposed, the adequate algorithms have been used according to data characteristics, and the results have been compared. Because its occurrence in Basque Country and its relevance in the production of cider and txakoli regional wines the grape and apple samples were selected. These crops are often treated with triazole compounds trying to solve the problems caused by the funguses. The peel and pulp from grape and apple, their juices and some commercial products such as musts, juice and cider have been analysed showing the adequacy of the developed methods for the triazole determination in this kind of fruit samples.

Children's Separation Anxiety Scale (CSAS): Psychometric Properties

This study describes the psychometric properties of the Children's Separation Anxiety Scale (CSAS), which assesses separation anxiety symptoms in childhood. Participants in Study 1 were 1,908 schoolchildren aged between 8 and 11. Exploratory factor analysis identified four factors: worry about separation, distress from separation, opposition to separation, and calm at separation, which explained 46.91% of the variance. In Study 2, 6,016 children aged 8–11 participated. The factor model in Study 1 was validated by confirmatory factor analysis. The internal consistency (α = 0.82) and temporal stability (r = 0.83) of the instrument were good. The convergent and discriminant validity were evaluated by means of correlations with other measures of separation anxiety, childhood anxiety, depression and anger. Sensitivity of the scale was 85% and its specificity, 95%. The results support the reliability and validity of the CSAS.

Direct catalytic macrolactonization and application of the phase separation strategy in complex molecule synthesis

Les macrolactones sont des squelettes structuraux importants dans de nombreuses sphères de l’industrie chimique, en particulier dans les marchés pharmaceutiques et cosmétiques. Toutefois, la stratégie traditionnelle pour la préparation de macrolactones demeure incommode en requérant notamment l’ajout (super)stœchiométrique d’agents activateurs. Conséquemment, des quantités stœchiométriques de sous-produits sont générées; ils sont souvent toxiques, dommageables pour l’environnement et nécessitent des méthodes de purification fastidieuses afin de les éliminer. La présente thèse décrit le développement d’une macrolactonisation efficace catalysée au hafnium directement à partir de précurseurs portant un acide carboxylique et un alcool primaire, ne générant que de l’eau comme sous-produit et ne nécessitant pas de techniques d’addition lente et/ou azéotropique. Le protocole a également été adapté à la synthèse directe de macrodiolides à partir de mélanges équimolaires de diols et de diacides carboxyliques et à la synthèse de dimères tête-à-queue de seco acides. Des muscs macrocycliques ainsi que des macrolactones pertinentes à la chimie médicinale ont pu être synthétisés avec l’approche développée. Un protocole pour l’estérification directe catalysée au hafnium entre des acides carboxyliques et des alcools primaires a aussi été développé. Différentes méthodes pour la macrolactonisation catalytique directe entre des alcools secondaires et des acides carboxyliques ont été étudiées. En outre, la stratégie de séparation de phase en macrocyclisation en débit continu a été appliquée lors de la synthèse totale formelle de la macrolactone ivorenolide A. Les étapes-clés de la synthèse incluent une macrocyclisation par le couplage d’alcynes de Glaser-Hay et une réaction de métathèse d’alcènes Z-sélective.

Selection of ionic liquids to be used as separation agents for terpenes and terpenoids

In this work, ionic liquids are evaluated for the first time as solvents for extraction and entrainers in separation processes involving terpenes and terpenoids. For that purpose, activity coefficients at infinite dilution, γ13 ∞, of terpenes and terpenoids, in the ionic liquids [C4mim]Cl, [C4mim][CH3SO3], [C4mim][(CH3)2PO4] and [C4mim][CF3SO3] were determined by gas−liquid chromatography at six temperatures in the range 398.15 to 448.15 K. On the basis of the experimental values, a correlation of γ13 ∞ with an increase of the solubility parameters is proposed. The infinite dilution thermodynamic functions were calculated showing the entropic effect is dominant over the enthalpic. Gas−liquid partition coefficients give indications about the recovery and purification of terpenes and terpenoids from ionic liquid solutions. Presenting a strong innovative character, COSMO-RS was evaluated for the description of the selectivities and capacities, showing to be a useful tool for the screening of ionic liquids in order to find suitable candidates for terpenes and terpenoids extraction, and separation. COSMO-RS predictions show that in order to achieve the maximum separation efficiency, polar anions should be used such as bis(2,4,4-trimethylpentyl)phosphinate or acetate, whereas high capacities require nonpolar cations such as phosphonium.

An Acrostic Elegy by a Maronite Priest-Monk on the sorrow of the Virgin Mary at her separation from her Son

El propósito de este artículo es llamar la atención de los especialistas de la existencia de un hasta ahora desconocido e inédito poema acróstico árabe, que describe la aflicción y el dolor de la Virgen María en la separación de su amado Hijo. El texto de esta interesante pieza que se presenta aquí fue compuesta por un sacerdote maronita que residía en Roma.

An Afriat theorem for the collective model of household consumption

We provide a nonparametric 'revealed preference’ characterization of rational household behavior in terms of the collective consumption model, while accounting for general (possibly non-convex) individual preferences. We establish a Collective Axiom of Revealed Preference (CARP), which provides a necessary and sufficient condition for data consistency with collective rationality. Our main result takes the form of a ‘collective’ version of the Afriat Theorem for rational behavior in terms of the unitary model. This theorem has some interesting implications. With only a finite set of observations, the nature of consumption externalities (positive or negative) in the intra-household allocation process is non-testable. The same non-testability conclusion holds for privateness (with or without externalities) or publicness of consumption. By contrast, concavity of individual utility functions (representing convex preferences) turns out to be testable. In addition, monotonicity is testable for the model that assumes all household consumption is public.

Development of combined acidification and separation of slurry: effect on slurry fractions composition and gaseous emission

Doutoramento em Engenharia do Ambiente - Instituto Superior de Agronomia - UL

Carbon-supported ionic liquids as innovative adsorbents for CO2 separation from synthetic flue-gas

Fixed-bed thermodynamic CO2 adsorption tests were performed in model flue-gas onto Filtrasorb 400 and Nuchar RGC30 activated carbons (AC) functionalized with [Hmim][BF4] and [Emim][Gly] ionic liquids (IL). A comparative analysis of the CO2 capture results and N2 porosity characterization data evidenced that the use of [Hmim][BF4], a physical solvent for carbon dioxide, ended up into a worsening of the parent AC capture performance, due to a dominating pore blocking effect at all the operating temperatures. Conversely, the less sterically-hindered and amino acid-based [Emim][Gly] IL was effective in increasing the AC capture capacity at 353 K under milder impregnation conditions, the beneficial effect being attributed to both its chemical affinity towards CO2 and low pore volume reduction. The findings derived in this work outline interesting perspectives for the application of amino acid-based IL supported onto activated carbons for CO2 separation under post-combustion conditions, and future research efforts should be focused on the search for AC characterized by optimal pore size distribution and surface properties for IL functionalization.

Corrigendum to “The envelope theorem for multiobjective convex programming via contingent derivatives” [J. Math. Anal. Appl. 372 (1) (2010) 197–207]

The aim of this note is to formulate an envelope theorem for vector convex programs. This version corrects an earlier work, “The envelope theorem for multiobjective convex programming via contingent derivatives” by Jiménez Guerra et al. (2010) [3]. We first propose a necessary and sufficient condition allowing to restate the main result proved in the alluded paper. Second, we introduce a new Lagrange multiplier in order to obtain an envelope theorem avoiding the aforementioned error.

A natural extension of the classical envelope theorem in vector differential programming

The aim of this paper is to extend the classical envelope theorem from scalar to vector differential programming. The obtained result allows us to measure the quantitative behaviour of a certain set of optimal values (not necessarily a singleton) characterized to become minimum when the objective function is composed with a positive function, according to changes of any of the parameters which appear in the constraints. We show that the sensitivity of the program depends on a Lagrange multiplier and its sensitivity.

“Unintended effects”: A theorem for complex systems

Unintended effects are well known to economists and sociologists and their consequences may be devastating. The main objective of this article is to formulate a mathematical theorem, based on Gödel's famous incompleteness theorem, in which it is shown, that from the moment deontical modalities (prohibition, obligation, permission, and faculty) are introduced into the social system, responses are allowed by the system that are not produced, however, prohibited responses or unintended effects may occur.

Geochemical Assessment and Separation of Source Waters in the Upper Boulder River Watershed Near Boulder, MT

Environmental samples were collected at three surface water sites between 5/21/2011 and 11/21/2014 along the Upper Boulder River near Boulder Montana. The sites were located at Bernice (within the mountain block), near the High Ore drainage (near the mountain block/basin transition), and at the USGS Gauging Station near Boulder, Montana (within the basin). The parameters measured in the field were SC, temperature, and alkalinity with occasional pH measurements. We collected samples for anions, cations, and stable isotopes in the catchment. We identified endmembers by sampling snow and groundwater and determined from available data an approximate endmember for rain, snow, and groundwater. We used temporal and spatial variations of water chemistry and isotopes to generate an endmember mixing model. Groundwater was found to always be an important contributor to river flow and could increase by nearly an order of magnitude during large snowmelt events. This resulted in groundwater comprising ~20% of total river flow during snowmelt at all sites. At peak snowmelt we observed that near surface water contributions to the river were from a mixture of rain and snow. Soil water, though not sampled, was hypothesized to be an important part of the hydrologic story. If so, the endmember contributions determined in this study may be different. Groundwater may have the highest variation depending on water chemistry of shallow soil water.

Acoustic manipulation and alignment of particles for applications in separation, micro-templating and device fabrication

This dissertation studies the manipulation of particles using acoustic stimulation for applications in microfluidics and templating of devices. The term particle is used here to denote any solid, liquid or gaseous material that has properties, which are distinct from the fluid in which it is suspended. Manipulation means to take over the movements of the particles and to position them in specified locations. ^ Using devices, microfabricated out of silicon, the behavior of particles under the acoustic stimulation was studied with the main purpose of aligning the particles at either low-pressure zones, known as the nodes or high-pressure zones, known as anti-nodes. By aligning particles at the nodes in a flow system, these particles can be focused at the center or walls of a microchannel in order to ultimately separate them. These separations are of high scientific importance, especially in the biomedical domain, since acoustopheresis provides a unique approach to separate based on density and compressibility, unparalleled by other techniques. The study of controlling and aligning the particles in various geometries and configurations was successfully achieved by controlling the acoustic waves. ^ Apart from their use in flow systems, a stationary suspended-particle device was developed to provide controllable light transmittance based on acoustic stimuli. Using a glass compartment and a carbon-particle suspension in an organic solvent, the device responded to acoustic stimulation by aligning the particles. The alignment of light-absorbing carbon particles afforded an increase in visible light transmittance as high as 84.5%, and it was controlled by adjusting the frequency and amplitude of the acoustic wave. The device also demonstrated alignment memory rendering it energy-efficient. A similar device for suspended-particles in a monomer enabled the development of electrically conductive films. These films were based on networks of conductive particles. Elastomers doped with conductive metal particles were rendered surface conductive at particle loadings as low as 1% by weight using acoustic focusing. The resulting films were flexible and had transparencies exceeding 80% in the visible spectrum (400-800 nm) These films had electrical bulk conductivities exceeding 50 S/cm. ^

A pointwise constrained version of the Liapunov convexity theorem for vectorial linear first-order control systems

We generalize the Liapunov convexity theorem's version for vectorial control systems driven by linear ODEs of first-order p = 1 , in any dimension d ∈ N , by including a pointwise state-constraint. More precisely, given a x ‾ ( ⋅ ) ∈ W p , 1 ( [ a , b ] , R d ) solving the convexified p-th order differential inclusion L p x ‾ ( t ) ∈ co { u 0 ( t ) , u 1 ( t ) , … , u m ( t ) } a.e., consider the general problem consisting in finding bang-bang solutions (i.e. L p x ˆ ( t ) ∈ { u 0 ( t ) , u 1 ( t ) , … , u m ( t ) } a.e.) under the same boundary-data, x ˆ ( k ) ( a ) = x ‾ ( k ) ( a ) & x ˆ ( k ) ( b ) = x ‾ ( k ) ( b ) ( k = 0 , 1 , … , p − 1 ); but restricted, moreover, by a pointwise state constraint of the type 〈 x ˆ ( t ) , ω 〉 ≤ 〈 x ‾ ( t ) , ω 〉 ∀ t ∈ [ a , b ] (e.g. ω = ( 1 , 0 , … , 0 ) yielding x ˆ 1 ( t ) ≤ x ‾ 1 ( t ) ). Previous results in the scalar d = 1 case were the pioneering Amar & Cellina paper (dealing with L p x ( ⋅ ) = x ′ ( ⋅ ) ), followed by Cerf & Mariconda results, who solved the general case of linear differential operators L p of order p ≥ 2 with C 0 ( [ a , b ] ) -coefficients. This paper is dedicated to: focus on the missing case p = 1 , i.e. using L p x ( ⋅ ) = x ′ ( ⋅ ) + A ( ⋅ ) x ( ⋅ ) ; generalize the dimension of x ( ⋅ ) , from the scalar case d = 1 to the vectorial d ∈ N case; weaken the coefficients, from continuous to integrable, so that A ( ⋅ ) now becomes a d × d -integrable matrix; and allow the directional vector ω to become a moving AC function ω ( ⋅ ) . Previous vectorial results had constant ω, no matrix (i.e. A ( ⋅ ) ≡ 0 ) and considered: constant control-vertices (Amar & Mariconda) and, more recently, integrable control-vertices (ourselves).

Synthesis, Modification and Characterization of Polymeric Membranes for CO2 Separation

This doctorate focused on the development of dense polymeric membranes for carbon capture, mostly in post combustion applications, and for natural gas sweetening. The work was supported by the European Project NANOMEMC2 funded under H2020 program. Different materials have been investigated, that rely on two main transport mechanisms: the solution-diffusion and the facilitated transport. In both cases, proper nano-fillers have been added to the matrix, in order to boost the mechanical and permselective properties of the membranes. Facilitated transport membranes were based on the use of was polyvinylamine (PVAm), as main matrix with fixed-site carriers, and L-Arginine as mobile carrier; the filler, used mostly as reinforcer, was carboxymethylated nanocellulose (cNFC). Humid test showed interesting results, and especially the blend made of PVAm/cNFC/Arg in weight ratio 27,5/27,5/45 crossed the Robeson CO2/N2 upper bound, representing current state of the art membranes, with a CO2 permeability of 271 Barrer and CO2/N2 selectivity of 70. Solution diffusion membranes were based on Pebax®2533 matrix which was added with three different graphene oxide (GO)-based materials, namely pristine GO, Porous Graphene Oxide (PGO) and a GO functionalized with polyetheramine (PEAGO). All of them provided a modest but clear increment of permeability of the Pebax matrix, from plus 2% (GO) to plus 8% (PGO), with no change in selectivity. The gas tested with this type of composites were CO2 and N2, for Post combustion capture applications. Pebax®2533 was also chemically modified, obtaining the product called “Benzoyl-P2533”, that was fully characterized, and tested in term of permeation using five gas: CO2, N2, CH4, O2, and He. Modified material showed an increment of the overall permeability of the material of a fair 10% for all gases tested, apart from helium, that increased of almost 50%.