On the reduction of 4-oxo-4h-benzopyran-3-carbaldehydes : global and local electrophilicity patterns

The theoretical global and local electrophilicity patterns of substituted and chelated 4-oxo-4H-benzopyran-3-carbaldehydes (formylchromones) have been evaluated using the electrophilicity index proposed by Parr et al [J. Am. Chem. Soc. 1999, 121, 1922]. The complexation of formylchromones with aluminum predicts a strong electrophilic character of these compounds against nucleophiles. Local response at the active sites may also be assessed in terms of a global contribution described by the global electrophilicity, and a local contribution described by the variations in electrophilic Fukui function at those sites. The highest local electrophilicity is found at the formyl group of the chelated formylchromones, in spite of that, the highest positive charge is located on the pyrone carbonyl group. This result is consistent with the experimental observed reactivity displayed by 4-oxo-4H-benzopyran-3-carbaldehydes in the presence of 2-propanol and alumina

Tautomeric Equilibria Studies by Mass Spectrometry

Tautomerism in organic chemistry has been extensively studied in condensed phase by spectrometric methods, mainly by IR and NMR techniques. Mass spectrometry studies start 40 years ago but just recently it has been recognized the importance of the mass spectral data for the study of tautomerism in the gas phase.
Mass spectrometry can provide valuable information in regard to tautomeric equilibria when studying mass spectra among the members of different families of organic compounds.
The relevance of the mass spectral data resides on several facts but there are two that are of key importance:
1-	Mass spectral fragmentation assignments should be tautomer specific since the corresponding abundances ratios are supposed to be correlated to the keto/enol contents.
2-	Ionization in the ion source is supposed to have no effect on the position of the equilibrium so that the results reflect the tautomers content in the gas phase previous to ionization.
Some of the carbonylic compounds do not exhibit noticeable tautomerism so the fragment abundances assigned to the enol form is very low or not measurable. Since enolization is more noticeable in the case of thio-derivatives (which correlates adequately with the oxygenated analogues), the study of their mass spectra is an interesting choice to reach some degree of generalization. 
In addition, experimental findings are supported by semiempirical theoretical calculations, which probed to be adequate not only for supporting tendency correlations among the members of a compound family but also to calculate heats of tautomerization in gas phase.
Reports using mass spectrometry for tautomerism are becoming less common. One of the reasons is that now it would appear that the interpretation of MS results is not as straightforward as it was once believed, even though in a recent review it was written that: “Mass spectrometry is the most informative and practical method for studying and identifying tautomers in the gas phase” [1]. 
In fact, mass spectrometry seems to be very informative for studying and identifying tautomers, because in this case external factors like solvents, intermolecular interactions, etc., can be excluded by transferring the tautomeric system into gas phase, where the process becomes truly unimolecular [1].
This review covers the study of Tautomerism by Mass Spectrometry in the last four decades. 
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Supported internet-delivered cognitive behavioral therapy programs for depression, anxiety, and stress in university students: open, non-randomised trial of acceptability, effectiveness, and satisfaction

BACKGROUND: Many university campuses have limited mental health services that cannot cope with the high demand. One alternative is to use internet-delivered cognitive behavioral therapy (iCBT) as a way of tackling barriers such as lack of availability and scheduling issues. OBJECTIVE: This study aimed to assess feasibility, acceptability, effectiveness, and satisfaction of a supported iCBT intervention offering 3 programs on depression, anxiety, and stress to university students. The design was an open or nonrandomized feasibility trial. METHODS: Participants were recruited from 3 counseling centers at a large midwestern University in the United States. Those agreeing to take part chose 1 of 3 iCBT programs-Space from Depression, Space from Anxiety, or Space from Stress -all comprised 8 modules of media-rich interactive content. Participants were supported throughout the trial by a trained professional. The Patient Health Questionnaire 9 (PHQ-9), Generalized Anxiety Disorder 7 (GAD-7) questionnaire, and stress subscale of the Depression Anxiety and Stress Scale (DASS-21) were completed at baseline, 8 weeks, and 3-month follow-up. A Satisfaction With Treatment (SAT) questionnaire was completed at 8 weeks, and qualitative interviews were completed by a subsample of participants at 3 months. RESULTS: A total of 102 participants were recruited, with 52 choosing Space from Anxiety, 31 choosing Space from Depression, and 19 choosing Space from Stress. Mixed-effects models showed a significant decrease in symptoms of depression (F₄=6.36, P<.001), anxiety (F₄=7.97, P<.001), and stress (F₄=8.50, P<.001) over time across all 3 programs. The largest decreases in PHQ-9 scores at 8 weeks were among participants who chose the Space from Depression program (d=0.84); at 3 months, the largest decreases in PHQ-9 scores were among those who chose the Space from Stress program (d=0.74). The largest decreases in GAD-7 scores were among those who chose the Space from Anxiety program (d=0.74 at 8 weeks and d=0.94 at 3 months). The largest decrease in DASS-21 stress subscale scores was among those who chose the Space from Stress program (d=0.49 at 8 weeks and d=1.16 at 3 months). The mean time spent using the platform per session was 27.4 min (SD 33.8), and participants completed 53% (SD 37.6) of the total program content on average. Most (37/53, 69%) participants found the programs helpful or very helpful and liked the convenience and flexibility of the intervention. Qualitative interviews (n=14) indicated the intervention met students' expectations, and they saw it as a valuable complement to face-to-face treatment. CONCLUSIONS: The iCBT programs tested in our study appear to be feasible, acceptable, and effective in a university environment. Participants described the benefits of having a flexible, supported Web-based intervention available on campus. Larger trials should be conducted to further test the effectiveness of supported Web-based interventions that give students a choice of program depending on their symptom profile.Published versio

Marsupial chromosome DNA content and genome size assessed from flow karyotypes: invariable low autosomal GC content.

Extensive chromosome homologies revealed by cross-species chromosome painting between marsupials have suggested a high level of genome conservation during evolution. Surprisingly, it has been reported that marsupial genome sizes vary by more than 1.2 Gb between species. We have shown previously that individual chromosome sizes and GC content can be measured in flow karyotypes, and have applied this method to compare four marsupial species. Chromosome sizes and GC content were calculated for the grey short-tailed opossum (2n = 18), tammar wallaby (2n = 16), Tasmanian devil (2n = 14) and fat-tailed dunnart (2n = 14), resulting in genome sizes of 3.41, 3.31, 3.17 and 3.25 Gb, respectively. The findings under the same conditions allow a comparison between the four species, indicating that the genomes of these four species are 1-8% larger than human. We show that marsupial genomes are characterized by a low GC content invariable between autosomes and distinct from the higher GC content of the marsupial × chromosome

Interpreter Chart Diagram N-S

The team of researchers develops and implements technological resources focused on a methodological strategy that supports its use. Our investigation deals with the analysis beginner students’ competences attending the Analisis de Sistema career at the UNSa, in order to solve different computing problems such as the analysis of the design if the diagram N-S and the desktop test. This work describes the process undertaken by the educational software design called Diagramar. Its development and the searching activity are related to the adopted methodologies: the Extreme Programming and Investigation-Action. The pedagogical importance of Diagramar lies on finding an answer to students and teachers’ needs, providing a technological resource developed to fit these needs. It is mainly focused on the elaboration of the N-S diagrams. There are not many texts that provide an specification of algorithm and translate a methodological strategy able to support the staff of teachers from a continual investigation on its own practice.Presentado en el VIII Workshop Tecnología Informática aplicada en Educación (WTIAE)Red de Universidades con Carreras en Informática (RedUNCI

Analysis of the 40K contamination in NaI(Tl) crystals from different providers in the frame of the ANAIS project

NaI(Tl) large crystals are applied in the search for galactic dark matter particles through their elastic scattering off the target nuclei in the detector by measuring the scintillation signal produced. However, energies deposited in the form of nuclear recoils are small, which added to the low efficiency to convert that energy into scintillation, makes that events at or very near the energy threshold, attributed either to radioactive backgrounds or to spurious noise (non-bulk NaI(Tl) scintillation events), can compromise the sensitivity goals of such an experiment. DAMA/LIBRA experiment, using 250 kg NaI(Tl) target, reported first evidence of the presence of an annual modulation in the detection rate compatible with that expected for a dark matter signal just in the region below 6 keVee (electron equivalent energy). In the frame of the ANAIS (Annual modulation with NaI Scintillators) dark matter search project a large and long effort has been carried out in order to understand the origin of events at very low energy in large sodium iodide detectors and develop convenient filters to reject those non attributable to scintillation in the bulk NaI(Tl) crystal. 40K is probably the most relevant radioactive contaminant in the bulk for NaI(Tl) detectors because of its important contribution to the background at very low energy. ANAIS goal is to achieve levels at or below 20 ppb natural potassium. In this paper we will report on our effort to determine the 40K contamination in several NaI(Tl) crystals, by measuring in coincidence between two (or more) of them. Results obtained for the 40K content of crystals from different providers will be compared and prospects of the ANAIS dark matter search experiment will be briefly reviewed.Comment: Submitted to International Journal of Modern Physics

A Translational Murine Model of Sub-Lethal Intoxication with Shiga Toxin 2 Reveals Novel Ultrastructural Findings in the Brain Striatum

Infection by Shiga toxin-producing Escherichia coli causes hemorrhagic colitis, hemolytic uremic syndrome (HUS), acute renal failure, and also central nervous system complications in around 30% of the children affected. Besides, neurological deficits are one of the most unrepairable and untreatable outcomes of HUS. Study of the striatum is relevant because basal ganglia are one of the brain areas most commonly affected in patients that have suffered from HUS and since the deleterious effects of a sub-lethal dose of Shiga toxin have never been studied in the striatum, the purpose of this study was to attempt to simulate an infection by Shiga toxin-producing E. coli in a murine model. To this end, intravenous administration of a sub-lethal dose of Shiga toxin 2 (0.5 ηg per mouse) was used and the correlation between neurological manifestations and ultrastructural changes in striatal brain cells was studied in detail. Neurological manifestations included significant motor behavior abnormalities in spontaneous motor activity, gait, pelvic elevation and hind limb activity eight days after administration of the toxin. Transmission electron microscopy revealed that the toxin caused early perivascular edema two days after administration, as well as significant damage in astrocytes four days after administration and significant damage in neurons and oligodendrocytes eight days after administration. Interrupted synapses and mast cell extravasation were also found eight days after administration of the toxin. We thus conclude that the chronological order of events observed in the striatum could explain the neurological disorders found eight days after administration of the toxin.Fil: Tironi Farinati, Alicia Carla Flavia. Universidad de Buenos Aires. Facultad de Medicina. Departamento de Ciencias Fisiológicas. Laboratorio de Fisiopatogenia; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Geoghegan, Patricia A.. Ministerio de Salud de la Nación. Administración Nacional de Laboratorios e Institutos de Salud; ArgentinaFil: Cangelosi, Adriana. Ministerio de Salud de la Nación. Administración Nacional de Laboratorios e Institutos de Salud; ArgentinaFil: Pinto, Alipio. Universidad de Buenos Aires. Facultad de Medicina. Departamento de Fisiología. Laboratorio de Neurofisiopatología; ArgentinaFil: Loidl, Cesar Fabian. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Instituto de Biología Celular y Neurociencias.;Fil: Goldstein, Jorge. Universidad de Buenos Aires. Facultad de Medicina. Departamento de Fisiología. Laboratorio de Neurofisiopatología; Argentin

Inside the adaptation process of Lactobacillus delbrueckii subsp. lactis to bile

Progressive adaptation to bile might render some lactobacilli able to withstand physiological bile salt concentrations. In this work, the adaptation to bile was evaluated on previously isolated dairy strains of Lactobacillus delbrueckii subsp. lactis 200 and L. delbrueckii subsp. lactis 200+, a strain derived thereof with stable bile-resistant phenotype. The adaptation to bile was obtained by comparing cytosolic proteomes of both strains grown in the presence or absence of bile. Proteomics were complemented with physiological studies on both strains focusing on glycolytic end-products, the ability to adhere to the human intestinal epithelial cell line HT29-MTX and survival to simulated gastrointestinal conditions. Protein pattern comparison of strains grown with and without bile allowed us to identify 9 different proteins whose production was regulated by bile in both strains, and 17 proteins that showed differences in their levels between the parental and the bile-resistant derivative. These included general stress response chaperones, proteins involved in transcription and translation, in peptidoglycan/exopolysaccharide biosynthesis, in the lipid and nucleotide metabolism and several glycolytic and pyruvate catabolism enzymes. Differences in the level of metabolic end-products of the sugar catabolism were found between the strains 200 and 200+. A decrease in the adhesion of both strains to the intestinal cell line was detected in the presence of bile. In simulated gastric and intestinal juices, a protective effect was exerted by milk improving the survival of both microorganisms. These results indicate that bile tolerance in L. delbrueckii subsp. lactis involves several mechanisms responding to the deleterious impact of bile salts on bacterial physiology. © 2010 Elsevier B.V.This work was supported by the following funds in Argentina: Programación CAI+D 2006 37-203 (Universidad Nacional del Litoral, Santa Fe, Argentina), Project PICT 2004 No. 09 20358 and PICT Jóvenes 2005 No. 32118 from the Agencia Nacional de Promoción Científica y Tecnológica (ANPCyT), and Project PIP 5321 from CONICET. The following Spanish funds are acknowledged: projects AGL2006-03336 and AGL2007-62736 from the Ministry of Science and Innovation. Patricia Burns received a 6-month grant from the Agencia Española de Cooperación Internacional for a research stay at IPLA (CSIC). Lorena Ruiz and Borja Sánchez were the recipients of a predoctoral I3P fellowship from CSIC and a postdoctoral Juan de la Cierva contract from the Spanish Ministry of Science and Innovation, respectively. Spanish and Argentinian groups shared a joint collaboration project CSIC–CONICET (reference 2005AR0047).Peer Reviewe