Domain wall dynamics in an optical Kerr cavity

An anisotropic (dichroic) optical cavity containing a self-focusing Kerr medium is shown to display a bifurcation between static --Ising-- and moving --Bloch-- domain walls, the so-called nonequilibrium Ising-Bloch transition (NIB). Bloch walls can show regular or irregular temporal behaviour, in particular, bursting and spiking. These phenomena are interpreted in terms of the spatio-temporal dynamics of the extended patterns connected by the wall, which display complex dynamical behaviour as well. Domain wall interaction, including the formation of bound states is also addressed.Comment: 15 pages Tex file with 11 postscript figures. Resubmitted to Phys. Rev.

Lanthanum-pyBOX complexes as catalysts for the enantioselective conjugate addition of malonate esters to beta-gamma-unsaturated alfa-ketimino esters

"This is an Accepted Manuscript of an article published by Taylor & Francis in Journal of Coordination Chemistry on 2018, available online: https://doi.org/10.1080/00958972.2018.1437422."[EN] In this paper, we report the application of chiral complexes of La(III) with pyBOX ligands as Lewis acid catalysts in the conjugate addition of malonic esters to N-tosyl imines derived from ß,gamma-unsaturated alfa-keto esters to give the corresponding chiral alfa,ß-dehydroamino esters. pyBOX complexes with La(III), Yb(III), Sc(III), and In(III) triflates were assessed in this reaction but only La(III) showed good activity and enantioselectivity, while Yb(III) provided the expected product with low yield and stereoselectivity, and the Sc(III) and In(III) complexes were completely inactive. The complex of La(OTf)3 with the diphenyl-pyBOX ligand prepared in situ provided the best results and allowed obtaining chiral ¿,ß-dehydroamino esters 3 with excellent yields, E:Z diastereomeric ratios (29:71-99:1) and high enantiomeric excesses (20-95%). The reaction could be applied to imines having a substituted aromatic ring or a heterocycle attached to the double bond, although the presence of electron-withdrawing groups on the aromatic ring was detrimental for stereoselectivity. The reaction products were obtained with the S configuration at the stereogenic center and the Z configuration at the enamine double bond as determined by NOESY experiments and X-ray analysis. Based on the experimental results a stereochemical model involving a nine-coordinate La(III) species has been proposed.This work was supported by the Ministerio de Economia y Competitividad (MINECO-Gobierno de Espana) [grant number CTQ2013-47494-P].Espinosa, M.; Blay, G.; Cardona, L.; Fernández, I.; Muñoz Roca, MDC.; Pedro, J. (2018). Lanthanum-pyBOX complexes as catalysts for the enantioselective conjugate addition of malonate esters to beta-gamma-unsaturated alfa-ketimino esters. Journal of Coordination Chemistry. 71(6):864-873. https://doi.org/10.1080/00958972.2018.1437422S864873716Yukawa, T., Seelig, B., Xu, Y., Morimoto, H., Matsunaga, S., Berkessel, A., & Shibasaki, M. (2010). Catalytic Asymmetric Aza-Morita−Baylis−Hillman Reaction of Methyl Acrylate: Role of a Bifunctional La(O-iPr)3/Linked-BINOL Complex. Journal of the American Chemical Society, 132(34), 11988-11992. doi:10.1021/ja103294aKodama, H., Ito, J., Hori, K., Ohta, T., & Furukawa, I. (2000). Lanthanide-catalyzed asymmetric 1,3-dipolar cycloaddition of nitrones to alkenes using 3,3′-bis(2-oxazolyl)-1,1′-bi-2-naphthol (BINOL-Box) ligands. Journal of Organometallic Chemistry, 603(1), 6-12. doi:10.1016/s0022-328x(00)00024-3De Bettencourt-Dias, A., Barber, P. S., & Bauer, S. (2012). A Water-Soluble Pybox Derivative and Its Highly Luminescent Lanthanide Ion Complexes. Journal of the American Chemical Society, 134(16), 6987-6994. doi:10.1021/ja209572mComelles, J., Pericas, À., Moreno-Mañas, M., Vallribera, A., Drudis-Solé, G., Lledos, A., … Roces-Fernández, L. (2007). Highly Enantioselective Electrophilic Amination and Michael Addition of Cyclic β-Ketoesters Induced by Lanthanides and (S,S)-ip-pybox:  The Mechanism⊥. The Journal of Organic Chemistry, 72(6), 2077-2087. doi:10.1021/jo0622678Sanchez-Blanco, A. I., Gothelf, K. V., & Jørgensen, K. A. (1997). Lanthanide-catalyzed endo- and enantioselective 1,3-dipolar cycloaddition reactions of nitrones with alkenes. Tetrahedron Letters, 38(45), 7923-7926. doi:10.1016/s0040-4039(97)10048-xDesimoni, G., Faita, G., Guala, M., & Pratelli, C. (2003). Different Lanthanide Ions and the Pybox Substituents Induce the Reverse of the Sense of Induction in the Enantioselective Diels−Alder Reaction between Acryloyloxazolidinone and Cyclopentadiene. The Journal of Organic Chemistry, 68(20), 7862-7866. doi:10.1021/jo034215dDesimoni, G., Faita, G., Filippone, S., Mella, M., Zampori, M. G., & Zema, M. (2001). A new and highly efficient catalyst for the enantioselective Mukaiyama–Michael reaction between ( E )-3-crotonoyl-1,3-oxazolidin-2-one and 2-trimethylsilyloxyfuran. Tetrahedron, 57(51), 10203-10212. doi:10.1016/s0040-4020(01)01055-9Sammis, G. M., Danjo, H., & Jacobsen, E. N. (2004). Cooperative Dual Catalysis:  Application to the Highly Enantioselective Conjugate Cyanation of Unsaturated Imides. Journal of the American Chemical Society, 126(32), 9928-9929. doi:10.1021/ja046653nJiang, J., Ma, Z., & Castle, S. L. (2015). Bulky α,β-dehydroamino acids: their occurrence in nature, synthesis, and applications. Tetrahedron, 71(34), 5431-5451. doi:10.1016/j.tet.2015.06.001Li, B., Cooper, L. E., & van der Donk, W. A. (2009). Chapter 21 In Vitro Studies of Lantibiotic Biosynthesis. Methods in Enzymology, 533-558. doi:10.1016/s0076-6879(09)04821-6M.A. Blaskovich. In Handbook on Syntheses of Amino Acids. General Route to Amino Acids, p. 225, ACS and Oxford University Press, New York (2010).Espinosa, M., García-Ortiz, A., Blay, G., Cardona, L., Muñoz, M. C., & Pedro, J. R. (2016). E,Z-Stereodivergent synthesis of N-tosyl α,β-dehydroamino esters via a Mukaiyama–Michael addition. RSC Advances, 6(19), 15655-15659. doi:10.1039/c5ra27354dEspinosa, M., Blay, G., Cardona, L., & Pedro, J. R. (2013). Corrigendum: Asymmetric Conjugate Addition of Malonate Esters to α,β-UnsaturatedN-Sulfonyl Imines: An Expeditious Route to Chiral δ-Aminoesters and Piperidones. Chemistry - A European Journal, 19(52), 17632-17632. doi:10.1002/chem.201304285X-ray data for compound 3bl: crystallized from hexane-EtOAc; C25H29SN1O8; Mr = 503.55; triclinic; space group = P1; a = 6.2550(2), b = 10.2870(4), c = 11.1380(5) Å; α = 69.333(2), β = 78.688(2), γ = 82.555(2)°; V = 656.11(5) Å3; Z = 1; ρcalcd = 1.274 Mg m−3; μ = 0.170 mm−1; F(0 0 0) = 266. A colorless crystal of 0.04 × 0.08 × 0.08 mm3 was used; 5797 [R(int) = 0.0682] total reflections were collected on a Enraf Nonius Kappa CCD equipped with a graphite monochromator and Mo Kα (λ = 0.71073 Å) radiation. The structures were solved by using direct methods with SHELXS-2014 and refined by using full matrix least squares on F2 with SHELXL-2014 [16]. Non-hydrogen atoms were refined anisotropically and hydrogens were obtained or placed in calculated positions refined by using idealized geometries (riding model) and assigned fixed isotropic displacement parameters. Final values were R = 0.0469 and ωR = 0.1054. CCDC-1581116 contains the supplementary crystallographic data for this compound. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.Parsons, S., Flack, H. D., & Wagner, T. (2013). Use of intensity quotients and differences in absolute structure refinement. Acta Crystallographica Section B Structural Science Crystal Engineering and Materials, 69(3), 249-259. doi:10.1107/s205251921301001

FITORREMEDIACIÓN AL PLOMO ASIMILABLE, UNA BIOTECNOLOGÍA PROMISORIA

La actividad minera, agrícola y otros, genera metales pesados como el plomo que pueden estar biodisponible ambientalmentey causar daño a los organismos vivos (biota)de los ecosistemas expuestos. El objetivo de la investigación es proponer una alternativa de mitigación al daño ambiental ocasionado por la hiperacumulación de plomo en el ser humano, debida a la actividad antropogénica a través de la fitorremediación del plomo asimilable, usado en países en vías de desarrollo como una tecnología tendiente a descontaminar el medioambiente. La fitorremediación se basa en la utilización de algas, plantas silvestres o introducidas, para la reducción, remoción, degradación o inmovilización de toxinas, descontaminando ecosistemas impactados. Por ello, se hace necesario indagar exhaustivamente más acerca de esta tecnología con el propósito de aplicar en nuestro medio, sus bondades y mitigar los problemas ambientales que vivimos actualmente en Moquegua

FITORREMEDIACIÓN AL PLOMO ASIMILABLE, UNA BIOTECNOLOGÍA PROMISORIA

La actividad minera, agrícola y otros, genera metales pesados como el plomo que pueden estar biodisponible ambientalmentey causar daño a los organismos vivos (biota)de los ecosistemas expuestos. El objetivo de la investigación es proponer una alternativa de mitigación al daño ambiental ocasionado por la hiperacumulación de plomo en el ser humano, debida a la actividad antropogénica a través de la fitorremediación del plomo asimilable, usado en países en vías de desarrollo como una tecnología tendiente a descontaminar el medioambiente. La fitorremediación se basa en la utilización de algas, plantas silvestres o introducidas, para la reducción, remoción, degradación o inmovilización de toxinas, descontaminando ecosistemas impactados. Por ello, se hace necesario indagar exhaustivamente más acerca de esta tecnología con el propósito de aplicar en nuestro medio, sus bondades y mitigar los problemas ambientales que vivimos actualmente en Moquegua

Biorefinery of biomass of agro-Industrial banana waste to obtain high-value biopolymers

On a worldwide scale, food demand is increasing as a consequence of global population growth. This makes companies push their food supply chains’ limits with a consequent increase in generation of large amounts of untreated waste that are considered of no value to them. Biorefinery technologies offer a suitable alternative for obtaining high-value products by using unconventional raw materials, such as agro-industrial waste. Currently, most biorefineries aim to take advantage of specific residues (by either chemical, biotechnological, or physical treatments) provided by agro-industry in order to develop high-value products for either in-house use or for sale purposes. This article reviews the currently explored possibilities to apply biorefinery-known processes to banana agro-industrial waste in order to generate high-value products out of this residual biomass source. Firstly, the Central and Latin American context regarding biomass and banana residues is presented, followed by advantages of using banana residues as raw materials for the production of distinct biofuels, nanocellulose fibers, different bioplastics, and other high-value products Lastly, additional uses of banana biomass residues are presented, including energy generation and water treatmen

Polymorphic appetite effects on waist circumference depend on rs3749474 CLOCK gene variant

Chronobiological aspects controlled by CLOCK genes may influence obesity incidence. Although there are studies that show an association between the expression of these genes and energy intake, waist circumference or abdominal obesity phenotypes, interactions with appetite have been insufficiently investigated in relation to chrononutrition. The objective was to identify interactions between CLOCK genetic variants involved in appetite status. A total of 442 subjects (329 women, 113 men; aged 18 to 65 years) were recruited. Anthropometric, dietary and lifestyle data were collected by trained nutritionists. Participants were classified according to their appetite feelings with a Likert scale. Multiple linear regression models were used to examine associations of the type genotype x appetite status on adiposity-related variables. p values were corrected by the Bonferroni method. A significant influence was found concerning the effects of appetite on waist circumference with respect to rs3749474 CLOCK polymorphism (p < 0.001). An additive model analysis (adjusted by age, gender, exercise and energy intake) showed that risk allele carriers, increased the waist circumference around 14 cm (β = 14.1, CI = 6.3–22.0) by each increment in the level of appetite. The effects of appetite on waist circumference may be partly modulated by the rs3749474 CLOCK polymorphism

An Indigenous Measure of Social Desirability Across Non-Western Countries

Cross-cultural differences in Social Desirability (SD) could be partly due to the nonequivalence of constructs, items, or other challenges of cross-cultural research. We tested to what extent a Mexican, indigenous scale of SD, capturing both positive and negative features of SD, would be useful in other countries. Data were collected in convenience samples in eight countries (Argentina, China, Colombia, Costa Rica, Lebanon, Mexico, Nicaragua, and Spain) in order to test the psychometric accuracy and invariance of the factor structure. Values of Tucker’s factor congruence coefficients (gauging invariance) and tests of the similarity of the cross-country similarity of Cronbach’s alpha (gauging internal consistency) revealed that SD, as measured by this indigenous list, is stable and comparable across cultures. The results are interpreted in a conceptual framework in which SD is viewed as a culturally embedded communication style that people use to integrate successfully into their groups

Promising 2,6,9-Trisubstituted Purine Derivatives for Anticancer Compounds: Synthesis, 3D-QSAR, and Preliminary Biological Assays

We designed, synthesized, and evaluated novel 2,6,9-trisubstituted purine derivatives for their prospective role as antitumor compounds. Using simple and efficient methodologies, 31 compounds were obtained. We tested these compounds in vitro to draw conclusions about their cell toxicity on seven cancer cells lines and one non-neoplastic cell line. Structural requirements for antitumor activity on two different cancer cell lines were analyzed with SAR and 3D-QSAR. The 3D-QSAR models showed that steric properties could better explain the cytotoxicity of compounds than electronic properties (70% and 30% of contribution, respectively). From this analysis, we concluded that an arylpiperazinyl system connected at position 6 of the purine ring is beneficial for cytotoxic activity, while the use of bulky systems at position C-2 of the purine is not favorable. Compound 7h was found to be an effective potential agent when compared with a currently marketed drug, cisplatin, in four out of the seven cancer cell lines tested. Compound 7h showed the highest potency, unprecedented selectivity, and complied with all the Lipinski rules. Finally, it was demonstrated that 7h induced apoptosis and caused cell cycle arrest at the S-phase on HL-60 cells. Our study suggests that substitution in the purine core by arylpiperidine moiety is essential to obtain derivatives with potential anticancer activityFinancial support was received from FONDECYT (Research Grant N◦ 1161816) and FONDEQUIP program CONICYT EQM 160042, Czech Science Foundation (19-09086S) and Palacky University (IGA_PrF_2019_013) and Xunta de Galicia (ED431C 2018/21) and European Regional Development Fund (Project ENOCH, N◦ CZ.02.1.01/0.0/0.0/16_019/0000868)S

The Absence of Caspase-8 in the Dopaminergic System Leads to Mild Autism-like Behavior

In the last decade, new non-apoptotic roles have been ascribed to apoptotic caspases. This family of proteins plays an important role in the sculpting of the brain in the early stages of development by eliminating excessive and nonfunctional synapses and extra cells. Consequently, impairments in this process can underlie many neurological and mental illnesses. This view is particularly relevant to dopamine because it plays a pleiotropic role in motor control, motivation, and reward processing. In this study, we analyze the effects of the elimination of caspase-8 (CASP8) on the development of catecholaminergic neurons using neurochemical, ultrastructural, and behavioral tests. To do this, we selectively delete the CASP8 gene in cells that express tyrosine hydroxylase with the help of recombination through the Cre-loxP system. Our results show that the number of dopaminergic neurons increases in the substantia nigra. In the striatum, the basal extracellular level of dopamine and potassium-evoked dopamine release decreased significantly in mice lacking CASP8, clearly showing the low dopamine functioning in tissues innervated by this neurotransmitter. This view is supported by electron microscopy analysis of striatal synapses. Interestingly, behavioral analysis demonstrates that mice lacking CASP8 show changes reminiscent of autism spectrum disorders (ASD). Our research reactivates the possible role of dopamine transmission in the pathogenesis of ASD and provides a mild model of autism.Ministerio de Economía y Competitividad RTI2018-098645-B-I00, PID2019-109569GB-I00, RTI2018-099778-B-I00Junta de Andalucía P18-RT-1372, US-1264806, PI-0080-2017, PI-0009-2017, PI-0134-2018, PEMP-0008-2020, P20_00958, CTS-510Instituto de Salud Carlos III PI18/01691Instituto de Investigación e Innovación en Ciencias Biomédicas de Cádiz-INiBICA LI19/06IN-CO22, IN-C09European Union 95568

Five microRNAs in Serum Are Able to Differentiate Breast Cancer Patients From Healthy Individuals

Breast cancer is the cancer with the most incidence and mortality in women. microRNAs are emerging as novel prognosis/diagnostic tools. Our aim was to identify a serum microRNA signature useful to predict cancer development. We focused on studying the expression levels of 30 microRNAs in the serum of 96 breast cancer patients vs. 92 control individuals. Bioinformatic studies provide a microRNA signature, designated as a predictor, based on the expression levels of five microRNAs. Then, we tested the predictor in a group of 60 randomly chosen women. Lastly, a proteomic study unveiled the overexpression and downregulation of proteins differently expressed in the serum of breast cancer patients vs. that of control individuals. Twenty-six microRNAs differentiate cancer tissue from healthy tissue, and 16 microRNAs differentiate the serum of cancer patients from that of the control group. The tissue expression of miR-99a, miR-497, miR-362, and miR-1274, and the serum levels of miR-141 correlated with patient survival. Moreover, the predictor consisting of miR-125b, miR-29c, miR-16, miR-1260, and miR-451 was able to differentiate breast cancer patients from controls. The predictor was validated in 20 new cases of breast cancer patients and tested in 60 volunteer women, assigning 11 out of 60 women to the cancer group. An association of low levels of miR-16 with a high content of CD44 protein in serum was found. Circulating microRNAs in serum can represent biomarkers for cancer prediction. Their clinical relevance and the potential use of the predictor here described are discussed