Nitro-Oleic Acid-Mediated Nitroalkylation Modulates the Antioxidant Function of Cytosolic Peroxiredoxin Tsa1 during Heat Stress in Saccharomyces cerevisiae

This research was funded by ERDF grants co-financed by the Spanish Ministry of Economy and Competitiveness (Project PGC2018-096405-B-I00), the Junta de Andalucia (group BIO286), the I+D+I project within the framework Programme of FEDER Andalucia 2014-2020 (Reference 1380901), the grants for I+D+I projects, on a competitive basis, within the scope of the Andalusian plan for research, development and innovation (Junta de Andalucia, PAIDI 2020, Reference: PY20_01002), and the funding for the recruitment of researchers under Action 9 and 10 of the Research Support Plan of the University of Jaen (2019-2020, R.02/10/2020; 2020-2021, R.01/01/2022).Heat stress is one of the abiotic stresses that leads to oxidative stress. To protect themselves, yeast cells activate the antioxidant response, in which cytosolic peroxiredoxin Tsa1 plays an important role in hydrogen peroxide removal. Concomitantly, the activation of the heat shock response (HSR) is also triggered. Nitro-fatty acids are signaling molecules generated by the interaction of reactive nitrogen species with unsaturated fatty acids. These molecules have been detected in animals and plants. They exert their signaling function mainly through a post-translational modification called nitroalkylation. In addition, these molecules are closely related to the induction of the HSR. In this work, the endogenous presence of nitro-oleic acid (NO2-OA) in Saccharomyces cerevisiae is identified for the first time by LC-MS/MS. Both hydrogen peroxide levels and Tsa1 activity increased after heat stress with no change in protein content. The nitroalkylation of recombinant Tsa1 with NO2-OA was also observed. It is important to point out that cysteine 47 (peroxidatic) and cysteine 171 (resolving) are the main residues responsible for protein activity. Moreover, the in vivo nitroalkylation of Tsa1 peroxidatic cysteine disappeared during heat stress as the hydrogen peroxide generated in this situation caused the rupture of the NO2-OA binding to the protein and, thus, restored Tsa1 activity. Finally, the amino acid targets susceptible to nitroalkylation and the modulatory effect of this PTM on the enzymatic activity of Tsa1 are also shown in vitro and in vivo. This mechanism of response was faster than that involving the induction of genes and the synthesis of new proteins and could be considered as a key element in the fine-tuning regulation of defence mechanisms against oxidative stress in yeast.ERDF - Spanish Ministry of Economy and Competitiveness PGC2018-096405-B-I00Junta de Andalucia BIO286 PY20_01002I+D+I project within the framework Programme of FEDER Andalucia 2014-2020 1380901University of Jaen R.02/10/2020 R.01/01/202

Vinyl sulfone: a multi-purpose function in proteomics

The chapter is organized in three sections. In a first instance, a general overview of the vinyl sulfone chemistry in terms of the most relevant methods of synthesis and aspects of their reactivity will be followed by a discussion of the application of this chemical behaviour with proteins. Their advantages and disadvantages with other currently available methodologies to modify amine and thiol groups naturally present in proteins will be compared. In a second section the applications of vinyl sulfones to Proteomics will be enumerated. Finally, the wide scope of the vinyl sulfone chemistry in other omic sciences will be discussed.The authors acknowledge Dirección General de Investigación Científica y Técnica (DGICYT) (CTQ2008-01754) and Junta de Andalucía (P07-FQM-02899) for financial support

Reply: Response to Wilson et al. Comments on Lopez-Jaramillo et al. DivinylSulfone Cross-Linked Cyclodextrin-Based Polymeric Materials: Synthesis and Applications as Sorbents and Encapsulating Agents. Molecules, 2015, 20, 3565–3581

Reply: Response to Wilson et al. Comments on Lopez-Jaramillo et al. DivinylSulfone Cross-Linked Cyclodextrin-Based Polymeric Materials: Synthesis and Applications as Sorbents and Encapsulating Agents. Molecules, 2015, 20, 3565–3581The authors acknowledge the Ministerio de Ciencia and Innovacion for financial support (Grant CTQ2011-29299-CO2-01)

Fragmentation and low density as major conservation challenges for the southernmost populations of the European wildcat

Knowledge of population dynamics of threatened species in the wild is key to effective conservation actions. However, at present, there are many examples of endangered animals for which their current situation is unknown, and not just in remote areas and less developed countries. We have explored this topic by studying the paradigmatic case of the European wildcat (Felis silvestris silvestris), an endangered small carnivore whose status has been subjectively established on the basis of non-systematic approaches and opportunistic records. Little is known about its demographic situation, prompting the need for information to improve conservation measures. However, the secretive behaviour of felines along with its low density in natural conditions have prevented the gathering of sufficient data. We developed a field sampling strategy for one of the largest populations (Andalusia, South Spain, 87,268 km2 ), based on a logistically viable systematic non-intrusive survey by camera-trapping. This study offers the first large-scale estimation for any European wildcat population, based on analytical approaches applied on Species Distribution Models. A hierarchical approach based on a Maxent model for distribution estimation was used, along with Generalised Linear Models for density estimation from explicit spatial capture-recapture data. Our results show that the distribution range is smaller and more highly fragmented than previously assumed. The overall estimated density was very low (0.069 ±0.0019 wildcats/km2 ) and the protected areas network seems to be insufficient to cover a significant part of the population or a viable nucleus in demographic terms. Indeed, the most important areas remain unprotected. Our main recommendations are to improve the protected area network and/or vigilance programs in hunting estates, in addition to studying and improving connectivity between the main population patches.The research was partially funded by the Consejería de Medio Ambiente y Ordenación del Territorio (www.juntadeandalucia.es > medioambiente > site > portalweb) through the European Union (FEDER Project http://www. juntadeandalucia.es/medioambiente/site/portalweb/ menuitem.6ffc7f4a4459b86a1daa5c105510e1c/? vgnextoid=05cf8706a8bb9510VgnVCM10000013 25e50aRCRD&vgnextchannel=05cf8706a8bb9510 VgnVCM1000001325e50aRCRD) and is part of the Global Change Observatory of Sierra Nevada (https://digibug.ugr.es/handle/10481/54686). J.M. G.-S. was supported by a Prometeo fellowship from the SENESCYT and the national agency for Education and Science of the Government of Ecuador (https://www.educacionsuperior.gob.ec/ prometeo/). There aren’t specific grant numbers or funding from commercial companies. The funders had no role in study design, data collection and analysis, decision to publish, or preparation of the manuscript

Turning carbon dots into selenium bearing nanoplatforms with in vitro GPx-like activity and pro-oxidant activity

Selenium (Se) has been defined as the “Janus element”, with one face showing antioxidant activity and the other pro-oxidant activity. The biological effect of Se depends on both dose and speciation. Se nanoparticles are attracting major interest, although their large-scale preparation for biomedical applications is not trivial. We hypothesize that acid anhydride-coated carbon dots (AACD) are an attractive platform for preparing nanoparticles containing chemically defined Se. The reaction of AA-CD with 3- selenocyanatopropan-1-amine yields carbon dots bearing selenocyanate and carboxylate groups (CD-SeCN) that allow for tuning the hydrosolubility. CD-SeCN has a Se content of 0.36 μmol per mg of nanoparticles, and they show the typical photoluminescence of carbon dots. The selenocyanate groups (SeCN) exhibited glutathione peroxidase-like activity and cytotoxicity. Data show that antioxidant behavior differs between normal and tumor cells, and the evaluation on HEK293 and A549 cells reveals that the toxicity of CD-SeCN depends on dose, time, and intracellular glutathione (GSH) content. The toxicity of CD-SeCN decreases with the time of incubation and the cell death mechanism switches from necrosis to apoptosis, indicating that CD-SeCN is neutralized. Additionally, high levels of intracellular GSH exert a protective effect. These results support a pharmacological potential in cancers with low levels of intracellular GSH. The use of AA-CD as nanoplatforms is a general strategy that paves the way for the engineering of advanced nanosystemsSpanish institution Ministerio de Ciencia, Innovacion y Universidades (No. CTQ2017- 86125-P)Unit of Excellence in Chemistry Applied to Biomedicine and the EnvironmentCentro de Instrumentacion Cientifica (Universidad de Granada)Universidad de Granada/CBUASpringer Natur

Divinyl Sulfone Cross-Linked Cyclodextrin-Based Polymeric Materials: Synthesis and Applications as Sorbents and Encapsulating Agents

The aim of this study was to evaluate the crosslinking abilities of divinyl sulfone (DVS) for the preparation of novel water-insoluble cyclodextrin-based polymers (CDPs) capable of forming inclusion complexes with different guest molecules. Reaction of DVS with native α-cyclodextrin (α-CD), β-cyclodextrin (β-CD) and/or starch generates a variety of homo- and hetero-CDPs with different degrees of crosslinking as a function of the reactants’ stoichiometric ratio. The novel materials were characterized by powder X-ray diffraction, electron microscopy and for their sorption of phenol and 4-nitrophenol. They were further evaluated as sorbents with phenolic pollutants (bisphenol A and β-naphthol) and bioactive compounds (the hormone progesterone and curcumin). Data obtained from the inclusion experiments show that the degree of cross-linking has a minor influence on the yield of inclusion complex formation and highlight the important role of the CDs, supporting a sorption process based on the formation of inclusion complexes. In general, the inclusion processes are better described by a Freundlich isotherm although an important number of them can also be fitted to the Langmuir isotherm with R2 ≥ 0.9, suggesting a sorption onto a monolayer of homogeneous sites

Evaluación del estado nutricional en población menor de 10 años de edad del municipio Pereira, Risaralda, Colombia, 2011. Segunda parte: Desnutrición crónica

La evaluación del estado nutricional en la población pediátrica es uno de los aspectos de mayor importancia en salud pública. Por estas razones se realizó un estudio para determinar la situación nutricional en menores de 10 años en el municipio Pereira, 2011. En este artículo se presenta la segunda parte de sus resultados para desnutrición crónica. Materiales y Métodos: Estudio de corte transversal, con una muestra probabilística, estratificada, evaluando el indicador Talla para la Edad en niños y niñas menores de 10 años del municipio Pereira (2011). La muestra fue recogida en colegios y en hogares familiares del municipio. Los resultados son comparados con los indicadores de los estudios de 2001 y 2008, con metodologías similares. Resultados: Para 2011 se aprecia una mejoría considerable en los niveles de desnutrición crónica, comparado con los resultados de 2001, con una reducción de 8,4% (de 41,1% a 32,7%). En los menores de 2 años, la prevalencia de desnutrición crónica fue de 35,4%, en tanto que los de 2 a 9,999 años fue de 32,09%. Discusión: Los presentes resultados deben orientar al diseño de políticas públicas que impulsen el avance del desarrollo social, el mejoramiento de las condiciones de vida, así como incidir en forma directa en la disponibilidad de alimentos y la educación nutricional en el Municipio a los fines de mejorar en forma integral las condiciones nutricionales que tiene la población infantil en Pereira. Para evaluar el impacto de dichas intervenciones especialmente en desnutrición crónica, deben mantenerse estudios periódicos de este tipo a mediano plazo para ver sus efectos y la tendencia en su reducción.Assessment of the nutritional state in pediatric population is one of the major issues of relevance in public health. For these reasons a study was made to determinate the nutritional state in children less than 10 years-old at the municipality of Pereira, 2011. in this article, the second part corresponding to chronic deficit malnutrition is presented. Materials and methods: a cross nutritional survey, with a probabilistic and stratified sample was made. This used the indicator Height for age in children less than 10 years-old of Pereira (2011). sample was collected at schools and family homes of the municipality. results are compared with indicators of 2001 and 2008 studies, with similar methodologies. results: For 2011 a considerable improvement in chronic deficit malnutrition, compared with 2001 results was observed, with a reduction of 8.4 percent points (from 41.1% to 32.7%) (20.4% of reduction). in those less than 2 years-old, prevalence was of 35.4% whilst in those 2-9.999 years-old was 32.09%. discussion: Present results should orient the design of public policies that promote the advance in social development, improvement of life conditions as well ways to impact in the availability of food and nutritional education in the municipality in order to integrally improve the nutritional conditions of the childhood population in Pereira. in order to assess the impact of those interventions, especially in chronic malnutrition, this kind of periodical studies should be done to see their effects and trends in its reduction.http://revistas.utp.edu.co/index.php/revistamedic

Vinyl sulfone silica: application of an open preactivated support to the study of transnitrosylation of plant proteins by S-nitrosoglutathione

Background S-nitrosylaton is implicated in the regulation of numerous signaling pathways with a diversity of regulatory roles. The high lability of the S-NO bond makes the study of proteins regulated by S-nitrosylation/denitrosylation a challenging task and most studies have focused on already S-nitrosylated proteins. We hypothesize that: i) S-nitrosoglutathione (GSNO) transnitrosylation is a feasible mechanism to account for the physiological S-nitrosylation of rather electropositive sulfur atoms from proteins, ii) affinity chromatography is a suitable approach to isolate proteins that are prone to undergo S-transnitrosylation and iii) vinyl sulfone silica is a suitable chromatographic bead.Results The combination of vinyl sulfone silica with GSNO yielded an affinity resin that withstood high ionic strength without shrinking or deforming and that it was suitable to isolate potential GSNO transnitrosylation target candidates. Fractions eluted at 1500 mM NaCl resulted in a symmetrical peak for both, protein and S-nitrosothiols, supporting the idea of transnitrosylation by GSNO as a selective process that involves strong and specific interactions with the target protein. Proteomic analysis led to the identification of 22 physiological significant enzymes that differ with the tissue analyzed, being regulatory proteins the most abundant group in hypocotyls. The identification of chloroplastidic FBPase, proteasome, GTP-binding protein, heat shock Hsp70, syntaxin, catalase I, thioredoxin peroxidase and cytochrome P450 that have already been reported as S-nitrosylated by other techniques can be considered as internal positive controls that validate our experimental approach. An additional validation was provided by the prediction of the S-nitrosylation sites in 19 of the GSNO transnitrosylation target candidates.Conclusions Vinyl sulfone silica is an open immobilization support that can be turned ad hoc and in a straightforward manner into an affinity resin. Its potential in omic sciences was successfully put to test in the context of the analysis of post-translational modification by S-nitrosylation with two different tissues: mature pea leaves and embryogenic sunflower hypocotyls. The identified proteins reveal an intriguing overlap among S-nitrosylation and both tyrosine nitration and thioredoxin regulation. Chloroplastidic FBPase is a paradigm of such overlap of post-translational modifications since it is reversible modified by thioredoxin and S-nitrosylation and irreversibly by tyrosine nitration. Our results suggest a complex interrelation among different modulation mechanisms mediated by NO-derived molecules.Financial Support was provided by Dirección General de Investigacion Cientıfica y Técnica (DGICYT) (CTQ2008-01754), Junta de Andalucía (P07-FQM-02899), Universidad de Jaén campus de Excelencia Internacional Agroalimentario ceiA3 and by ERDF-cofinanced grants from Ministry of Science and Innovation (BIO2012-33904) and Junta de Andalucía (research groups BIO286 and BIO192). We also acknowledge support of the publication fee by the CSIC Open Access Publication Support Initiative through its Unit of Information Resources for Research (URICI)

Study of Ionization Charge Density-Induced Gain Suppression in LGADs

Gain suppression induced by excess carriers in Low Gain Avalanche Detectors (LGADs) has been investigated using 3 MeV protons in a nuclear microprobe. In order to modify the ionization density inside the detector, Ion Beam Induced Current (IBIC) measurements were performed at different proton beam incidence angles between 0◦ and 85◦. The experimental results have been analyzed as a function of the ionization density projected on the multiplication layer, finding that the increase of ionization density leads to greater gain suppression. For bias voltages close to the gain onset value, this decrease in gain results into a significant distortion of the transient current waveforms measured by the Time-Resolved IBIC (TRIBIC) technique due to a deficit in the secondary holes component. For angles of incidence such that the Bragg peak falls within the sensitive volume of the detector, the formation of microplasmas modifies the behavior of the gain curves, producing an abrupt decrease in gain as the angle increases.Ministerio de Ciencia, Innovación y Universidades RTI2018-098117-B-C21, 10.13039/501100011033, ICTS-2020-02-US-4Junta de Andalucía US-1380791European Union FPA2017-85155-C4-1-R, FPA2017-85155-C4-2-