Low temperature matrix-isolation and solid state vibrational spectra of tetrazole

Infrared spectra of tetrazole (CN isolated in an argon matrix (T \10 K) and in the solid state (at room 4H2) temperature) were investigated. In the crystalline phase, tetrazole exists in its 1H-tautomeric form and new assignments of the vibrational spectra (both infrared and Raman) of this phase are presented. The infrared spectrum of the matrix-isolated monomeric form of tetrazole is now reported and assigned for the Ðrst time, showing essentially the expected signature of the 2H-tetrazole tautomer. From relative intensities of the infrared bands ascribable to the two tautomers, the amount of the 1H-tautomer in the argon matrix was estimated to be ca. 10% of the most stable tautomer. Assuming that gas-phase relative populations of the two tautomers could be efficiently trapped in the argon matrix during deposition, the energy di erence between 1H- and 2H-tetrazole (*E was then obtained. The experimental value, kJ mol~1, 1Hh2H) *E1Hh2H\6.95^1.50 now determined for the Ðrst time, compares fairly well with the theoretical predictions for the molecule in vacuum (e.g., the zero point vibrational energy corrected energy di erence obtained at the B3LYP/6È31G* level of theory is 9.96 kJ mol~1)

Characterization of several hazelnut (Corylus avellana L.) cultivars based in chemical, fatty acid and sterol composition

Nineteen cultivars of hazelnuts (Corylus avellana L.) collected during the 2001 crop, from Vila Real, Portugal, were analysed for chemical composition, including moisture, total oil content, crude protein, ash, carbohydrates and nutritional value. Fat was the predominant component, ranging from 59.3 to 69.0%. Total oil was extracted and analysed for fatty acid and sterol compositions and oxidative stability. Fatty acid and sterol compositions were determined by Gas–Liquid Chromatography coupled to a Flame Ionisation Detector (GLC/FID). Monounsaturated fatty acids, particularly oleic acid, were predominant (78.7–84.6%). Total phytosterol content ranged from 133.8 to 263.0 mg/100 g of oil. Among the nine sterols identified and quantified, β-sitosterol was the major one with a mean percentage of 83.6%, while Δ5-avenasterol and campesterol were the second and the third components of the group with mean values of 6.1 and 5.8%, respectively. Since hazelnut oil can be used in olive oil adulteration, the values obtained were compared with published mean values of olive oils from different geographical origins

Low temperature matrix-isolation and solid state vibrational spectra of 5-chlorotetrazole

The vibrational spectra of 5-chlorotetrazole (CN4HCl) isolated in an argon matrix (T ¼ 8.5 K) and in the solid state (at room temperature) were studied. The infrared spectrum of monomers of 5-chlorotetrazole isolated in an argon matrix agrees well with the spectrum predicted theoretically (DFT(B3LYP)/6-31G*) for the 2Htautomer of the compound. The bands assigned to the 1H-tautomer appear in the experimental spectrum as very low intensity features. Based on the relative intensities of the bands in the spectra of the 1H- and 2Htautomers, the relative amount of the first tautomer in this matrix can be estimated as 1%. Three matrixes were deposited with different nozzle temperatures and the enthalpy difference between the tautomers DH ¼ 8.0 kJ mol 1 was estimated using the Van’t Hoff relation. The internal energy difference between the two tautomers was predicted theoretically (DFT B3LYP/6-31G*) as 12.6 kJ mol 1. This is in reasonable agreement with experimental observations. In the crystalline phase, this compound exists in its 1H-tautomeric form. Accordingly, the IR spectrum of polycrystalline 5-chlorotetrazole is well reproduced by the spectrum predicted theoretically for the 1H- tautomer

Mitochondrial Preconditioning: A Potential Neuroprotective Strategy

Mitochondria have long been known as the powerhouse of the cell. However, these organelles are also pivotal players in neuronal cell death. Mitochondrial dysfunction is a prominent feature of chronic brain disorders, including Alzheimer's disease (AD) and Parkinson's disease (PD), and cerebral ischemic stroke. Data derived from morphologic, biochemical, and molecular genetic studies indicate that mitochondria constitute a convergence point for neurodegeneration. Conversely, mitochondria have also been implicated in the neuroprotective signaling processes of preconditioning. Despite the precise molecular mechanisms underlying preconditioning-induced brain tolerance are still unclear, mitochondrial reactive oxygen species generation and mitochondrial ATP-sensitive potassium channels activation have been shown to be involved in the preconditioning phenomenon. This review intends to discuss how mitochondrial malfunction contributes to the onset and progression of cerebral ischemic stroke and AD and PD, two major neurodegenerative disorders. The role of mitochondrial mechanisms involved in the preconditioning-mediated neuroprotective events will be also discussed. Mitochondrial targeted preconditioning may represent a promising therapeutic weapon to fight neurodegeneration

Trehalose alleviates the phenotype of Machado–Joseph disease mouse models

Machado-Joseph disease (MJD), also known as spinocerebellar ataxia type 3, is the most common of the dominantly inherited ataxias worldwide and is characterized by mutant ataxin-3 aggregation and neuronal degeneration. There is no treatment available to block or delay disease progression. In this work we investigated whether trehalose, a natural occurring disaccharide widely used in food and cosmetic industry, would rescue biochemical, behavioral and neuropathological features of an in vitro and of a severe MJD transgenic mouse model.This work was funded by BioBlast Pharma, the ERDF through the Regional Operational Program Center 2020, Competitiveness Factors Operational Program (COMPETE 2020) and National Funds through FCT (Foundation for Science and Technology) - SFRH/BD/87404/2012, BrainHealth2020 projects (CENTRO-01-0145-FEDER-000008), ViraVector (CENTRO-01-0145FEDER-022095), CortaCAGs (POCI-01-0145-FEDER-016719), SpreadSilenc‑ing POCI-01-0145-FEDER-029716 and POCI-01-0145-FEDER-007440, as well as the SynSpread, ESMI and ModelPolyQ under the EU Joint ProgramNeurodegenerative Disease Research (JPND), the last two co-funded bythe European Union H2020 program, GA No. 643417; by National Ataxia Foundation (USA), the American Portuguese Biomedical Research Fund (APBRF) and the Richard Chin and Lily Lock Machado–Joseph Disease Research Fund.info:eu-repo/semantics/publishedVersio

Maize open-pollinated populations physiological improvement: validating tools for drought response participatory selection

Participatory selection—exploiting specific adaptation traits to target environments—helps to guarantees yield stability in a changing climate, in particular under low-input or organic production. The purpose of the present study was to identify reliable, low-cost, fast and easy-to-use tools to complement traditional selection for an e ective participatory improvement of maize populations for drought resistance/tolerance. The morphological and eco-physiological responses to progressive water deprivation of four maize open-pollinated populations were assessed in both controlled and field conditions. Thermography and Chl a fluorescence, validated by gas exchange indicated that the best performing populations under water-deficit conditions were ‘Fandango’ and to a less extent ‘Pigarro’ (both from participatory breeding). These populations showed high yield potential under optimal and reduced watering. Under moderate water stress, ‘Bilhó’, originating from an altitude of 800 m, is one of the most resilient populations. The experiments under chamber conditions confirmed the existence of genetic variability within ‘Pigarro’ and ‘Fandango’ for drought response relevant for future populations breeding. Based on the easiness to score and population discriminatory power, the performance index (PIABS) emerges as an integrative phenotyping tool to use as a refinement of the common participatory maize selection especially under moderate water deprivationinfo:eu-repo/semantics/publishedVersio

Preserving the nutritional quality of crop plants under a changing climate: importance and strategies

Background: Global climate is changing more rapidly than ever, threatening plant growth and productivity while exerting considerable direct and indirect effects on the quality and quantity of plant nutrients. Scope: This review focuses on the global impact of climate change on the nutritional value of plant foods. It showcases the existing evidence linking the effects of climate change factors on crop nutrition and the concentration of nutrients in edible plant parts. It focuses on the effect of elevated CO2 (eCO2), elevated temperature (eT), salinity, waterlogging and drought stresses, and what is known regarding their direct and indirect influence on nutrient availability. Furthermore, it provides possible strategies to preserve the nutritional composition of plant foods under changing climates. Conclusions: Climate change has an impact on the accumulation of minerals and protein in crop plants, with eCO2 being the underlying factor of most of the reported changes. The effects are clearly dependent on the type, intensity and duration of the imposed stress, plant genotype and developmental stage. Strong interactions (both positive and negative) can be found between individual climatic factors and soil availability of nitrogen (N), potassium (K), iron (Fe) and phosphorous (P). The development of future interventions to ensure that the world's population has access to plentiful, safe and nutritious food may need to rely on breeding for nutrients under the context of climate change, including legumes in cropping systems, better farm management practices and utilization of microbial inoculants that enhance nutrient availability.info:eu-repo/semantics/publishedVersio

(2,2′-Bipyridine-κ2 N,N′)bromido(1,4,7-trithia­cyclo­nonane-κ3 S,S′,S′′)ruthenium(II) hexa­fluoridophosphate

The title compound, [RuBr(C10H8N2)(C6H12S3)]PF6 or [RuBr(bpy)([9]aneS3)]PF6 ([9]aneS3 is 1,4,7-trithia­cyclo­nonane and bpy is 2,2′-bipyridine), exhibits a very similar octahedral coordination geometry for the Ru2+ atom to that of its [RuCl(bpy)([9]aneS3)]+ analogue, with only the chloride ligand being substituted by a bromide ligand. The presence of a PF6 − anion (alongside with the coordinated bromide ligand) promotes the existence of an extensive network of weak C—H⋯X (X = F, Br) inter­actions

Design, synthesis and biologival evaluation of novel isoniazid derivatives with potente antitubercular activity

The disturbing emergence of multidrug-resistant strains of Mycobacterium tuberculosis (Mtb) has been driving the scientific community to urgently search for new and efficient antitubercular drugs. Despite the various drugs currently under evaluation, isoniazid is still the key and most effective component in all multi-therapeutic regimens recommended by the WHO. This paper describes the QSAR-oriented design, synthesis and in vitro antitubercular activity of several potent isoniazid derivatives (isonicotinoyl hydrazones and isonicotinoyl hydrazides) against H37Rv and two resistant Mtb strains. QSAR studies entailed RFs and ASNNs classification models, as well as MLR models. Strict validation procedures were used to guarantee the models' robustness and predictive ability. Lipophilicity was shown not to be relevant to explain the activity of these derivatives, whereas shorter N-N distances and lengthy substituents lead to more active compounds. Compounds I, 2, 4, 5 and 6, showed measured activities against H37Rv higher than INH (i.e., MIC <= 0.28 mu M), while compound 9 exhibited a six fold decrease in MIC against the katG (S315T) mutated strain, by comparison with INH (Le., 6.9 vs. 43.8 mu M). All compounds were ineffective against H37Rv(INH) (Delta katG), a strain with a full deletion of the katG gene, thus corroborating the importance of KatG in the activation of INH-based compounds. The most potent compounds were also shown not to be cytotoxic up to a concentration 500 times higher than MIC. (C) 2014 Elsevier Masson SAS. All rights reserved