Design and application of molecularly imprinted polymers (MIPs) for detection of veterinary residues and contaminants in food safety

The occurrence of residues and contaminants in food may be a health hazard for consumers as they can generate reactions in some cases and/or the emergence of bacterial resistance and toxicity, among others. In this research project, the selection of analytes of interest was carried out based on their frequency of use in livestock, both legal and fraudulent options, and based on the European Directive 96/22/EC. The first group was the group of corticosteroids, hormonal compounds frequently used in animal husbandry. The second group was the group of antibacterial substances, which consists of a wide range of molecules, both natural and synthetic. Amongst them, we selected two of the most important families: the beta-lactams and the amphenicols. Apart from residues of veterinary drugs, there is also the possibility of the unintentional presence of certain contaminants, such as fungal toxins. Within these mycotoxins, we selected the group of aflatoxins and patulin. The most unique and innovative aspect this thesis project lies in the development of molecular imprinted polymers (MIPs) to achieve the selective extraction of the analytes above mentioned, which could be found in food. These polymers are synthesized using different techniques and combined with various methods of detection

Special Issue: Infant and Child Nutrition and Foods

Milk is a natural fluid and as such contains small amounts of naturally occurring steroids. Human milk is recommended as the optimal source of nutrients for infants and young children, and it has been associated to several short- and long-term benefits. For this reason, its composition is used as a reference for designing infant formulas. However, the available information on the hormonal levels of these dairy products is scarce, and it is usually limited to estradiol and estrone. In the present study, six natural sex hormones (pregnenolone, progesterone, estrone, dehydroepiandrosterone, testosterone and androstenedione) have been extracted from sixteen milk-based infant formulas and analyzed with liquid chromatography tandem mass spectrometry (HPLC-MS/MS). The purpose of this research was to quantify natural steroid hormones in various infant formulas, to provide food and nutrition practitioners with information to estimate intakes in children. In addition, data found in the literature was used for comparison. The findings suggest that there are certain similarities between bovine milk and dairy products for infants. Furthermore, the detected levels were in general lower than those observed in human milk and/or colostrum. The reported results represent a valuable addition to the current knowledge on natural hormone content of infant foods

Magnetic molecularly imprinted stirring bar for isolation of patulin using grafting technique

The 19th International Electronic Conference on Synthetic Organic Chemistry session Polymer and Supramolecular ChemistryMycotoxins are low-molecular-weight natural products with great structural diversity produced as secondary metabolites by fungi. One of the principal toxic fungal metabolites is patulin (PAT), produced by over 30 genera of mold including species as Penicillium expansum or Penicillium griseofulvum, and normally related to vegetable-based products and fruit, mainly apple. These mold grow easily in damaged fruit or in derived-product as juices if storage conditions are deficient. Some of the most serious effects of PAT ingestion are agitation, convulsions, edema, ulceration intestinal, inflammation and vomiting. Thus, European Regulation 1881/2006 established a maximum content of 10 ppb in infant fruit juices, 50 ppb for fruit juices in adults and 25 ppb in fruit-derived products. Nowadays, the official analytical method for food adopted by AOAC International is HPLC with UV detection, using clean-up with ethyl acetate and sodium carbonate. However, the diverse drawbacks of this method (poor stability of PAT under alkaline extraction, poor resolution between PAT and co-extracted hydroxymethylfurfural) have originated interest in alternative options, such as LC methods coupled to mass spectrometry. In the last years, purification with molecularly imprinted polymers (MIP) started to be used, and are becoming promising materials for extracting different analytes present in food. Mycotoxins are too toxic or too expensive to be used as template molecules in MIP preparation. Template “bleeding” may be an additional problem, especially when dealing with very low detection levels. In the present work, a rapid and selective method based on magnetic molecularly imprinted stir-bar (MMIB) extraction has been developed for the isolation of PAT. A structural analogue, 2-oxindole, was used as dummy template. The polymer was grafted to the silanized glass surface of the stir ba

Riemann-Finsler geometry and Lorentz-violating kinematics

Effective field theories with explicit Lorentz violation are intimately linked to Riemann-Finsler geometry. The quadratic single-fermion restriction of the Standard-Model Extension provides a rich source of pseudo-Riemann-Finsler spacetimes and Riemann-Finsler spaces. An example is presented that is constructed from a 1-form coefficient and has Finsler structure complementary to the Randers structure.Comment: 19 page

Design of a molecularly imprinted stir-bar for isolation of patulin in apple and LC-MS/MS detection

Mycotoxins are a very diverse group of natural products produced as secondary metabolites by fungi. Patulin is produced by mold species normally related to vegetable-based products and fruit, mainly apple. Its ingestion may result in agitation, convulsions, edema, intestinal ulceration, inflammation, vomiting, and even immune, neurological or gastrointestinal disorders. For this reason, the European Commission Regulation (EC) 1881/2006 established a maximum content for patulin of 10 ppb in infant fruit juice, 50 ppb for fruit juice for adults and 25 ppb in fruit-derived products. In this work, a rapid and selective method based on magnetic molecularly imprinted stir-bar (MMISB) extraction has been developed for the isolation of patulin, using 2-oxindole as a dummy template. The final extraction protocol consisted of simply pouring in, stirring and pouring out samples and solvents from a beaker with the MMISB acting inside. The magnetic device provided satisfactory recoveries of patulin (60%–70%) in apple samples. The successful MMISB approach has been combined with high performance liquid chromatography coupled to tandem mass spectrometry (HPLC-MS/MS) to determine patulin.This research was supported by the project EM 2012/153 from Consellería de Cultura, Educación e Ordenacion Universitaria, Xunta de GaliciaS

Development of a novel molecularly imprinted stir-bar for isolation of aflatoxins

The 19th International Electronic Conference on Synthetic Organic Chemistry session Polymer and Supramolecular ChemistryMycotoxins are natural substances produced as secondary metabolites by a wide variety of different species of filamentous fungi. One of the most important groups in terms of occurrence and toxicity, is the group of aflatoxins (AFs). The major members of this group are aflatoxin B1, B2, G1, G2, M1 and M2. Exposure to AFs can cause chronic and acute toxic effects or death, as they can be carcinogenic, mutagenic, teratogenic and immunosuppressive. AFB1 is considered as the strongest carcinogen of natural origin and it is normally predominant in crops as well as in food products. Aflatoxin M1 is a major metabolite of aflatoxin B1 in humans and animals and it may be present in milk from animals fed with contaminated feed. Although the toxicity of M1 is about ten times lower than B1, it is known for its hepatotoxic and carcinogenic effects. Solid phase extraction (SPE) or the clean-up with organic solvents or immunoaffinity columns (IAC) have been frequently applied in the analysis of mycotoxins from cereals and/or milk. IAC in combination with HPLC are increasingly used as reference method due to their high selectivity and good elimination of matrix interferences. However, the cost of analysis is usually high. In recent years, molecularly imprinted polymers (MIP) have been become very popular and promising materials for extracting different analytes. AFs are too toxic to be used in MIP preparation and template bleeding may be an additional problem, especially when dealing with very low levels. For this reason, a dummy template was preferred for MIP synthesis. A rapid and selective extraction method based on magnetic MIP (MMIP) has been developed for the isolation of aflatoxins (B1, B2, G1, G2, M1) using a combination of imprinted polymer and magnetite. The successful MMIP stirring “cake” (used as a stir-bar) has been combined with HPLC-MS/MS for the determination of AFM1 in milk powder (infant formulas) to demonstrate its applicability to real sample

Inhomogeneous Magnetism in La-doped CaMnO3. (II) Mesoscopic Phase Separation due to Lattice-coupled FM Interactions

A detailed investigation of mesoscopic magnetic and crystallographic phase separation in Ca(1-x)La(x)MnO3, 0.00<=x<=0.20, is reported. Neutron powder diffraction and DC-magnetization techniques have been used to isolate the different roles played by electrons doped into the eg level as a function of their concentration x. The presence of multiple low-temperature magnetic and crystallographic phases within individual polycrystalline samples is argued to be an intrinsic feature of the system that follows from the shifting balance between competing FM and AFM interactions as a function of temperature. FM double-exchange interactions associated with doped eg electrons are favored over competing AFM interactions at higher temperatures, and couple more strongly with the lattice via orbital polarization. These FM interactions thereby play a privileged role, even at low eg electron concentrations, by virtue of structural modifications induced above the AFM transition temperatures.Comment: 8 pages, 7 figure

Nature of ege_g Electron Order in La1−x_{1-x}Sr1+x_{1+x}MnO4_4

Synchrotron x-ray scattering measurements of the low-temperature structure of the single-layer manganese oxide La$_{1-x}$Sr$_{1+x}$MnO$_4$, over the doping range $0.33 \le x \le 0.67$, indicate the existence of three distinct regions: a disordered phase ($x < 0.4$), a charge-ordered phase ($x \ge 0.5$), and a mixed phase ($0.4 \le x 0.5$, the modulation vector associated with the charge order is incommensurate with the lattice and depends linearly on the concentration of $e_g$ electrons. The primary superlattice reflections are strongly suppressed along the modulation direction and the higher harmonics are weak, implying the existence of a largely transverse and nearly sinusoidal structural distortion, consistent with a charge density wave of the $e_g$ electrons.Comment: 4 pages, 4 figure

Theory and phenomenology of two-Higgs-doublet models

We discuss theoretical and phenomenological aspects of two-Higgs-doublet extensions of the Standard Model. In general, these extensions have scalar mediated flavour changing neutral currents which are strongly constrained by experiment. Various strategies are discussed to control these flavour changing scalar currents and their phenomenological consequences are analysed. In particular, scenarios with natural flavour conservation are investigated, including the so-called type I and type II models as well as lepton-specific and inert models. Type III models are then discussed, where scalar flavour changing neutral currents are present at tree level, but are suppressed by either specific ansatze for the Yukawa couplings or by the introduction of family symmetries. We also consider the phenomenology of charged scalars in these models. Next we turn to the role of symmetries in the scalar sector. We discuss the six symmetry-constrained scalar potentials and their extension into the fermion sector. The vacuum structure of the scalar potential is analysed, including a study of the vacuum stability conditions on the potential and its renormalization-group improvement. The stability of the tree level minimum of the scalar potential in connection with electric charge conservation and its behaviour under CP is analysed. The question of CP violation is addressed in detail, including the cases of explicit CP violation and spontaneous CP violation. We present a detailed study of weak basis invariants which are odd under CP. A careful study of spontaneous CP violation is presented, including an analysis of the conditions which have to be satisfied in order for a vacuum to violate CP. We present minimal models of CP violation where the vacuum phase is sufficient to generate a complex CKM matrix, which is at present a requirement for any realistic model of spontaneous CP violation.Comment: v3: 180 pages, 506 references, new chapter 7 with recent LHC results; referee comments taken into account; submitted to Physics Report