Switchable Cycloadditions of Mesoionic Dipoles: Refreshing up a Regioselective Approach to Two Distinctive Heterocycles.

Mesoionic rings are among the most versatile 1,3-dipoles, as witnessed recently by their incorporation into bio-orthogonal strategies, and capable of affording unconventional heterocycles beyond the expected scope of Huisgen cycloadditions. Herein, we revisit in detail the reactivity of thiazol-3-ium-4-olates with alkynes, leading to thiophene and/or pyrid-2-one derivatives. A structural variation at the parent mesoionic dipole alters sufficiently the steric outcome, thereby favoring the regioselective formation of a single transient cycloadduct, which undergoes chemoselective fragmentation to either five- or six-membered heterocycles. The synthetic protocol benefits largely from microwave (MW) activation, which enhances reaction rates. The mechanism has been interrogated with the aid of density functional theory (DFT) calculations, which sheds light into the origin of the regioselectivity and points to a predictive formulation of reactivity involving competing pathways of mesoionic cycloadditions.

What functional proteomic and biochemical analysis tell us about animal stress in beef?

Animal management practices may influence the animal's susceptibility to stress, with detrimental effects on the ultimate meat quality. In this field, proteomics is a promising tool that reveals the biological pathways underpinning the effect of animal's pre-slaughter stress (PSS) on the ultimate meat quality. The objective of this work was to study the effect of a pre-slaughter procedure that may promote stress, such as mixing unfamiliar animals during the transport and lairage period, on the post-mortem muscle proteome of young bulls reared under two different farm management systems (Intensive or Extensive). Comparative proteomics and biochemical analysis reveal the effect of PSS on biochemical pathways involved in the meat colour development, muscle redox status, energy metabolism and autophagy. This work highlights the potential of some muscle proteins such as Beclin-1 (autophagy marker), CKM (biomarker of energy transduction) and proteins of the energy metabolism (ALDOA, PYGM, PGM1, PKM, GPI) as potential biomarkers to discriminate beef samples according to the incidence of PSS. SIGNIFICANCE: Meat scientists are interested in the study of individual animal-based measurements that allow the detection of stress situations which could have negative effects on meat quality. In this context, the mechanisms underlying the adverse effects of pre-slaughter stress on the post-mortem muscle metabolism need to be elucidated in order to understand how animal stress may influence the conversion of muscle into meat. In this work, the study of proteome changes in the post-mortem muscle has allowed the identification of significant biomarkers of these processes that could be used as tools for detecting inappropriate strategies that may induce increased animal stress and, in consequence, may compromise the ultimate beef quality.

Evaluación de la publicidad alimentaria del canal de televisión infantil Boing en España en 2016 / Evaluation of the food advertisements broadcast in the Boing children's television channel in Spain, 2016

INTRODUCCIÓN: dada la relación entre el marketing de alimentos poco saludables y la obesidad infantil, el propósito de este estudio fue evaluar el uso de técnicas de marketing (persuasivo y nutricional), su nivel de cumplimiento del nuevo Código PAOS y el perfil nutricional de los alimentos y bebidas anunciados en Boing. MATERIAL Y MÉTODOS: estudio descriptivo de una muestra de anuncios de alimentos y bebidas emitidos en 2016 por Boing, el canal de televisión infantil con publicidad de mayor audiencia en España. La información nutricional de los productos se obtuvo del etiquetado de estos y se clasificaron en más o menos saludables, según el perfil nutricional de la Organización Mundial de la Salud. Se analizó la presencia de las técnicas de marketing persuasivo y nutricional y su adecuación a las normas del nuevo Código PAOS. RESULTADOS: durante las 13,5 horas de emisión se emitieron 111 anuncios, correspondientes a 20 productos, 17 alimentos y 3 bebidas, con una tasa de 8,2 anuncios por hora. El 100% de los productos utilizaron alguna de las técnicas de marketing analizadas y resultaron no saludables, según el modelo de la Organización Mundial de la Salud. El 73,9% de los anuncios incumplieron alguna norma del código PAOS. CONCLUSIONES: los alimentos y bebidas anunciados fueron no saludables e hicieron un uso generalizado de técnicas de marketing nutricional y persuasivo. Tres de cada cuatro infringieron el código PAOS vigente en España, que se revela ineficaz, recomendándose sustituirlo por una regulación que proteja eficazmente a los menores de la publicidad de alimentos y bebidas no saludables

INTRODUCTION: given the link between marketing of unhealthy foods and childhood obesity, the aim of our study was to assess the use of persuasive and nutritional marketing strategies; the level of compliance in the use of these strategies the new PAOS code for self-regulation of food advertising targeting children aged less than 12 years; and the nutrient profile of the foods and beverages advertised on Boing TV. MATERIAL AND METHODS: descriptive study of a sample of food and drink advertisements broadcast in 2016 by Boing, the leading children's commercial TV channel in Spain. We obtained information on the nutritional composition of products from their labelling, based on which we classified them as healthy or unhealthy applying the WHO nutrient profile model. We analysed the use of persuasive and nutritional marketing strategies and their compliance with the standards set by the new PAOS code. RESULTS: the 13.5 hours of broadcasting analysed included 111 advertisements, at a rate of 8.2 commercials per hour. All of the products were advertised with some of the marketing strategies included in the analysis, and all were classified as unhealthy based on the WHO nutrient profile model. Also, 73.9% of the advertisements were contravened 1 or more PAOS code standards. CONCLUSIONS: the advertised foods and beverages were unhealthy, and their marketing involved the generalised use of nutritional and persuasive strategies. Three out of four commercials violated the PAOS code currently active in Spain, which proved ineffective and should therefore be replaced by regulation that can effectively protect children from the marketing of unhealthy foods and beverages

On the asymmetric autocatalysis of aldol reactions: The case of 4-nitrobenzaldehyde and acetone. A critical appraisal with a focus on theory.

Under neutral conditions, spontaneous mirror symmetry breaking has been occasionally reported for aldol reactions starting from achiral reagents and conditions. Chiral induction might be interpreted in terms of autocatalysis exerted by chiral mono-aldol or bis-aldol products as source of initial enantiomeric excesses, which may account for such experimental observations. We describe here a thorough Density Functional Theory (DFT) study on this complex and otherwise difficult problem, which provides some insights into this phenomenon. The picture adds further rationale to an in-depth analysis by Moyano et al, who showed the isolation and characterization of bis-aldol adducts and their participation in a complex network of reversible steps. However, the lack of enantiodiscrimination (ees vanish rapidly in solution) suggests, according to the present results, a weak association in complexes formed by the catalysts and substrates. The latter would also be consistent with almost flat transition states having similar heights for competitive catalyst-bound transition structures (actually, we were unable to locate them at the level explored). Overall, neither autocatalysis as once conjectured nor mutual inhibition of enantiomers appears to be operating mechanisms. Asymmetric amplification in early stages harnessing unavoidable enantiomeric imbalances in reaction mixtures of chiral products represents a plausible interpretation.

Evaluation of compliance with the Spanish Code of self-regulation of food and drinks advertising directed at children under the age of 12 years in Spain, 2012.

OBJECTIVE: To evaluate compliance levels with the Spanish Code of self-regulation of food and drinks advertising directed at children under the age of 12 years (Publicidad, Actividad, Obesidad, Salud [PAOS] Code) in 2012; and compare these against the figures for 2008. STUDY DESIGN: Cross-sectional study. METHODS: Television advertisements of food and drinks (AFD) were recorded over 7 days in 2012 (8am-midnight) of five Spanish channels popular to children. AFD were classified as core (nutrient-rich/low-calorie products), non-core (nutrient-poor/rich-calorie products) or miscellaneous. Compliance with each standard of the PAOS Code was evaluated. AFD were deemed to be fully compliant when it met all the standards. RESULTS: Two thousand five hundred and eighty-two AFDs came within the purview of the PAOS Code. Some of the standards that registered the highest levels of non-compliance were those regulating the suitability of the information presented (79.4%) and those prohibiting the use of characters popular with children (25%). Overall non-compliance with the Code was greater in 2012 than in 2008 (88.3% vs 49.3%). Non-compliance was highest for advertisements screened on children's/youth channels (92.3% vs. 81.5%; P < 0.001) and for those aired outside the enhanced protection time slot (89.3% vs. 86%; P = 0.015). CONCLUSIONS: Non-compliance with the PAOS Code is higher than for 2008. Given the lack of effectiveness of self-regulation, a statutory system should be adopted to ban AFD directed at minors, or at least restrict it to healthy products.

Intense PEGylation of Enzyme Surfaces: Relevant Stabilizing Effects.

This chapter describes the physicochemical coating of the surface of immobilized enzymes with a dense layer of polyethylene glycol (PEG) to improve enzyme stability. One hypothesis is that a dense, viscous, polar PEG layer around the enzyme would enhance enzyme thermal stability, while still providing access to the active site. PEG groups were attached by using aldehyde-dextran polymers, the dextran polymers are in turn attached to the enzyme surface that have been enriched with excess primary amino groups. The enzymes themselves were initially attached onto porous solids such that they may be separated easily from the reaction mixtures for easy downstream processing and that they may be recycled to reduce the cost of the biocatalyst. The hierarchical modification of enzyme surface with three different sublayers, under chemical design, provided a rational control at several structural levels. Few methods for increasing the number of amino groups on the surface of the enzyme are described: (a) chemical amination of carboxyl residues and (b) coating of the enzyme surface with cationic polymers containing a high percentage of primary amines. Reliable protocols for the PEGylation of four different enzymes are described here. For example, lipases from Thermomyces lanuginosa, Candida antarctica B, and Rhizomucor miehei attached to octyl sepharose and chemically modified via PEGylation are stabilized from 7- to 50-fold when compared to the stability of the corresponding unmodified enzyme. A derivative of endoxylanase from Trichoderma reesei, immobilized by multipoint covalent attachment on glyoxyl agarose, is stabilized by 50-fold. Very likely, the PEG layer generated a dense, high viscosity medium surrounding the enzyme surface and this increase in viscosity around the enzyme microenvironment resists distortion of enzyme structure by heat or other denaturing agents.

[Use of nutrition marketing in products advertised on TV in Spain]. / Uso del marketing nutricional en productos anunciados por televisión en España.

BACKGROUND: Nutrition marketing has generated a great amount of consumer interest; however, improper use of this type of marketing could mislead consumers. OBJECTIVES: To describe the frequency and proper use in Spain of nutrition marketing for products advertised on television while analyzing their nutrient profile for comparison. METHODS: Advertised food and drink products included in the study were selected after watching 80 hours of broadcasting of 4 Spanish television channels during May and June 2008. Upon purchase of the selected items, we estimated the frequency of use of the different nutrition marketing approaches, the proportion of nutritional and health claims meeting European regulations, and the proportion of less healthy products according to the United Kingdom Nutrient Profile Model UKNPM. RESULTS: Of the 88 products examined, 74% used nutrition marketing approaches. Half of the advertisements made nutrition claims and 42% health claims. The majority (89%) of the 83 nutrition claims met European regulations, with the category of "light products" being the least compliant with only 25% of products meeting regulations. Of the 37 product advertisements making health claims, 43% used authorized statements, of which, however, 75% also included unauthorized claims. Nutrient profile was less healthy in 55% of the products resorting to nutrition marketing. CONCLUSION: Lack of compliance with European regulations regarding nutrition and health claims, combined with the "less healthy" nutrient profile of many of the products marketed using these claims, may mislead Spanish consumers. To avoid this misinformation, it would be beneficial to: a) monitor level of adherence to regulations systematically; and b) introduce the use of nutrient profiles to approve these types of claims.

Síndrome paraneoplásico cerebeloso asociado con carcinoma de ovario / Paraneoplastic syndrome with cerebellar degeneration associated with ovarian carcinoma

Presentamos el caso de una paciente afectada de un síndrome paraneoplásico con degeneración cerebelosa, como primera manifestación de un tumor ovárico en la que todos los estudios resultaron normales, a excepción de la presencia de un autoanticuerpo anti-Yo, que reconoce antígenos citoplasmáticos de las células de Purkinje del cerebelo. La sospecha de un tumor ovárico fue confirmada microscópicamente tras la extirpación de los dos anejos. (AU)

Sindrome de dificultad respíratoria en el período neonatal: estudio del semestre noviembre 1987-abril 1988

Se estudian todos los recien nacidos vivos del semestre noviembre 1987 abril 1988 que fueron en total 1 817 niños, de los cuales 77 presentaron dificultad respiratoria, se investiga su asociación con factores como edad gestacional, peso al nacer y puntaje de Apgar, encontrándose relaciones significativas. Se describen además las causas más frecuentes que fueron: Pulmón húmedo (1 porciento), enfermedades del Sistema Nervioso Central (SNC) (8 porciento) y Enfermedad de la Membrana Hialina (EMH)(0,5 por ciento), los trastornos metabólicos secundarios (41,6 porciento) y las hemorragias intracraneales (10,4 porciento), constituyeron las complicaciones más frecuentes. Se evidenció en el trabajo la alta letalidad de la E.M.H. (44,5 porciento), observándose como el sindrome de dificultad respiratoria (S.D.R.) presenta un (0,4 porciento) de mortalidad de los cuales la mitad (0,2 porciento) está representado por la E.M.H. (AU)