Analysis of Air Mean Temperature Anomalies by Using Horizontal Visibility Graphs

The last decades have been successively warmer at the Earth’s surface. An increasing interest in climate variability is appearing, and many research works have investigated the main effects on different climate variables. Some of them apply complex networks approaches to explore the spatial relation between distinct grid points or stations. In this work, the authors investigate whether topological properties change over several years. To this aim, we explore the application of the horizontal visibility graph (HVG) approach which maps a time series into a complex network. Data used in this study include a 60-year period of daily mean temperature anomalies in several stations over the Iberian Peninsula (Spain). Average degree, degree distribution exponent, and global clustering coefficient were analyzed. Interestingly, results show that they agree on a lack of significant trends, unlike annual mean values of anomalies, which present a characteristic upward trend. The main conclusions obtained are that complex networks structures and nonlinear features, such as weak correlations, appear not to be affected by rising temperatures derived from global climate conditions. Furthermore, different locations present a similar behavior and the intrinsic nature of these signals seems to be well described by network parameters.     

Evaluation of different extraction approaches for the determination of phenolic compounds and their metabolites in plasma by nanoLC-ESI-TOF-MS

Sample preparation is an important step for the determination of phenolic compounds in biological samples. Different extraction methods have been tested to determine phenolic compounds and their metabolites in plasma by nano-liquid chromatography coupled to electrospray ionisation-time-of-flight mass spectrometry (nanoLC-ESI-TOF-MS). The sample treatment optimisation was performed using commercial foetal bovine serum spiked with representative phenolic standards, namely naringenin, luteolin, verbascoside, apigenin, rutin, syringic acid and catechin. Different protein-precipitation conditions were evaluated as well as enzymatic digestion with trypsin and solid-phase extraction using different phases such as C-18, ABN and ENV+, working at different pH values. The optimum extraction procedure consisted of a previous protein-precipitation step using HCl 200?mmol/L in methanol for 2.5?h at 50?°C followed by a solid-phase extraction using C-18 cartridges at pH?2.5. This procedure was finally applied to the plasma of rats overfed with a phenolic-rich Lippia citriodora extract. These samples were analysed by nanoLC-ESI-TOF-MS, enabling the identification of five compounds previously found in the administered L. citriodora extract and one metabolite.     

Determination of total polyphenol index in wines employing a voltammetric electronic tongue

This work reports the application of a voltammetric electronic tongue system (ET) made from an array of modified graphite-epoxy composites plus a gold microelectrode in the qualitative and quantitative analysis of polyphenols found in wine. Wine samples were analyzed using cyclic voltammetry without any sample pretreatment. The obtained responses were preprocessed employing discrete wavelet transform (DWT) in order to compress and extract significant features from the voltammetric signals, and the obtained approximation coefficients fed a multivariate calibration method (artificial neural network-ANN-or partial least squares-PLS-) which accomplished the quantification of total polyphenol content. External test subset samples results were compared with the ones obtained with the Folin–Ciocalteu (FC) method and UV absorbance polyphenol index (I₂₈₀) as reference values, with highly significant correlation coefficients of 0.979 and 0.963 in the range from 50 to 2400 mg L⁻¹ gallic acid equivalents, respectively. In a separate experiment, qualitative discrimination of different polyphenols found in wine was also assessed by principal component analysis (PCA).     

Restricting the versatile metal-binding behaviour of adenine by using deaza-purine ligands in mixed-ligand copper(II) complexes

In order to deepen our understanding of the versatile behaviour of adenine (Hade) as ligand, we have synthesized four novel ternary copper(II) complexes having two deazaadenine ligands, namely 4-azabenzimidazole (H4abim) or 7-azaindole (H7azain) as N1,N6-dideazaadenine or N1,N6,N7-trideazaadenine, respectively. The related compounds were studied by thermal, spectral and single crystal X-ray diffraction methods. In [Cu(NBzIDA)(H4abim)]_n (1) the recognition between H4abim and the (N-benzyliminodiacetate)-copper(II) chelate only displays the formation of the Cu–N7(purine-like) bond, in contrast to Hade behaviour in [Cu(NBzIDA-like)(Hade)(H₂O)]·H₂O (Cu–N3(Hade) bond reinforced by N9–H···O(IDA-like) interaction). In [Cu(EIDA)(H7azain)(H₂O)] (2, EIDA = N-ethyliminodiacetate ligand), [Cu(NBzIDA)(H7azain)(H₂O)] (3) and [Cu(μ₂-SO₄)(H7azain)₂(H₂O)₂]_n (4), H7azain binds Cu(II) centre by the Cu–N3(purine-like) bond, reinforced by a N9–H···O(IDA-like or sulfate) intra-molecular interligand interaction.     

Nickel(II) derivatives of N-benzyliminodiacetate(2−) ligands,with and without imidazole: Synthesis,crystal structure and properties

In an attempt to prepare binary and ternary compounds, we have obtained two molecular complexes [Ni(MEBIDA or MOBIDA)(H₂O)₃]·nH₂O (n = 0 or 1) and two iso-type salts [Ni(Him)₆][Ni(MEBIDA or MOBIDA)₂]·4H₂O [MEBIDA = N-(p-methylbenzyl)iminodiacetate(2−) and MOBIDA = N-(p-methoxybenzyl)iminodiacetate(2−) ligands, Him = imidazole]. Our results are discussed with regard to related copper(II) and nickel(II) compounds. The reasons for which these chelating ligands produce nickel(II) salts instead of ternary compounds remain unclear since other iminodiacetate-like ligands give true ternary Ni(II) compounds with imidazole and other N-heterocyclic ligands.     

Chelating ligand conformation driving the hypoxanthine metal binding patterns

The X-ray diffraction structural results of 23 ternary compounds, type M(II)(iminodiacetate-like)(hypoxanthine) [M = Co, Ni, Cu, or Zn], show that the iminodiacetate moiety conformation (mer-NO(2) or fac-NO(2)) is able to drive the M-hypoxanthine binding patterns displaying the M-N9 or M-N3 bond, cooperating with a N9-H···O intramolecular interaction, respectively.     

Disproportionation of O-methylhydroxylamine catalyzed by aquapentacyanoferrate(II)

The aquapentacyanoferrate(II) ion, [Fe(II)(CN)(5)H(2)O](3-), catalyzes the disproportionation reaction of O-methylhydroxylamine, NH(2)OCH(3), with stoichiometry 3NH(2)OCH(3) → NH(3) + N(2) + 3CH(3)OH. Kinetic and spectroscopic evidence support an initial N coordination of NH(2)OCH(3) to [Fe(II)(CN)(5)H(2)O](3-) followed by a homolytic scission leading to radicals [Fe(II)(CN)(5)(?)NH(2)](3-) (a precursor of Fe(III) centers and bound NH(3)) and free methoxyl, CH(3)O(?), thus establishing a radical path leading to N-methoxyamino ((?)NHOCH(3)) and 1,2-dimethoxyhydrazine, (NHOCH(3))(2). The latter species is moderately stable and proposed to be the precursor of N(2) and most of the generated CH(3)OH. Intermediate [Fe(III)(CN)(5)L](2-) complexes (L = NH(3), H(2)O) form dinuclear cyano-bridged mixed-valent species, affording a catalytic substitution of the L ligands promoted by [Fe(II)(CN)(5)L](3-). Free or bound NH(2)OCH(3) may act as reductants of [Fe(III)(CN)(5)L](2-), thus regenerating active sites. At increasing concentrations of NH(2)OCH(3) a coordinated diazene species emerges, [Fe(II)(CN)(5)N(2)H(2)](3-), which is consumed by the oxidizing CH(3)O(?), giving N(2) and CH(3)OH. Another side reaction forms [Fe(II)(CN)(5)N(O)CH(3)](3-), an intermediate containing the nitrosomethane ligand, which is further oxidized to the nitroprusside ion, [Fe(II)(CN)(5)NO](2-). The latter is a final oxidation product with a significant conversion of the initial [Fe(II)(CN)(5)H(2)O](3-) complex. The side reaction partially blocks the Fe(II)-aqua active site, though complete inhibition is not achieved because the radical path evolves faster than the formation rates of the Fe(II)-NO(+) bonds.     

Metathesis transformations of natural products: cross-metathesis of natural rubber and mandarin oil by Ru-alkylidene catalysts

This study reports on the degradation of natural rubber (NR) via crossmetathesis with mandarin oil and d-limonene, an abundant compound in essential oils; that were used as chain transfer agents (CTAs) and green solvents. Reactions were performed in the presence of the ruthenium-alkylidene catalysts (PCy?)?(Cl)?Ru=CHPh (I) and (1,3-dimesityl-4,5-dihydroimidazol-2-ylidene) (PCy?)Cl?Ru=CHPh (II), respectively. Catalyst II bears an N-heterocyclic carbene ligand (NHC) bounded to the ruthenium atom, which has a strong basic character; therefore it is more active toward trisubstituted olefins in comparison with catalyst I. In both cases, isolated monoterpene-terminated isoprene oligomers were obtained as products of the cross-metathesis degradation of NR. In the presence of catalyst II molecular weight values around M(n) × 102 and yields of 80% were obtained; whereas with catalyst I, the molecular weights of products were about M(n) × 10? with yields ranging 70 to 74%. The composition and yield of NR degradation products were determined by GC/MS (EI) analysis and it was found that the oligomers obtained have primarily one vinyl group and one terpene-monocyclic group at the chain end, with isoprene units A(m) = 2, 3 y 4.