Photo-induced Fluorescence of Fluometuron in a Continuous-flow Multicommutation Assembly

This paper deals with the photo-induced fluorimetric determination of the herbicide Fluometuron with the aid of a continuous-flow assembly of the emergent and new methodology known as Multicommutation which was provided with an on-line photoreactor. Maximum fluorescence intensity was observed at basic pH solutions, 1×10⁻⁴ mol l⁻¹ NaOH, after 1.4 min of irradiation and being the maximum at λ_exc 247.0 nm and λ_em 325.0 nm. The influence of different experimental parameters either chemical (pH, surfactants presence, solvent polarity and temperature) or hydrodynamic (time of photo-degradation, size and number of different segments and flow-rate) was tested. The linear dynamic range was from 0.01 to 4.0 mg l⁻¹ of Fluometuron; the inter-day reproducibility (as R.S.D.) of the slope was 0.001% and 1.7% from the peaks intra-day reproducibility. A large series of potential interferents was studied and finally the method was applied to human urine, soil, formulation and water samples.     

Stability of AgIII towards Halides in Organosilver(III) Complexes

The involvement of silver in two-electron Ag^I/Ag^III processes is currently emerging. However, the range of stability of the required and uncommon Ag^III species is virtually unknown. Here, the stability of Ag^III towards the whole set of halide ligands in the organosilver(III) complex frame [(CF₃)₃AgX]⁻ (X=F, Cl, Br, I, At) is theoretically analyzed. The results obtained depend on a single factor: the nature of X. Even the softest and least electronegative halides (I and At) are found to form reasonably stable Ag^III−X bonds. Our estimates were confirmed by experiment. The whole series of nonradiative halide complexes [PPh₄][(CF₃)₃AgX] (X=F, Cl, Br, I) has been experimentally prepared and all its constituents have been isolated in pure form. The pseudohalides [PPh₄][(CF₃)₃AgCN] and [PPh₄][(CF₃)₃Ag(N₃)] have also been isolated, the latter being the first silver(III) azido complex. Except for the iodo compound, all the crystal and molecular structures have been established by single-crystal X-ray diffraction methods. The decomposition paths of the [(CF₃)₃AgX]⁻ entities at the unimolecular level have been examined in the gas phase by multistage mass spectrometry (MSⁿ). The experimental detection of the two series of mixed complexes [CF₃AgX]⁻ and [FAgX]⁻ arising from the corresponding parent species [(CF₃)₃AgX]⁻ demonstrate that the Ag−X bond is particularly robust. Our experimental observations are rationalized with the aid of theoretical methods. Smooth variation with the electronegativity of X is also observed in the thermolyses of bulk samples. The thermal stability in the solid state gradually decreases from X=F (145 °C, dec.) to X=I (78 °C, dec.) The experimentally established compatibility of Ag^III with the heaviest halides is of particular relevance to silver-mediated or silver-catalyzed processes.     

Diels-Alder reaction mechanisms of substituted chiral anthracene: A theoretical study based on the reaction force and reaction electronic flux

Quantum chemical calculations were used to study the mechanism of Diels-Alder reactions involving chiral anthracenes as dienes and a series of dienophiles. The reaction force analysis was employed to obtain a detailed scrutiny of the reaction mechanisms, it has been found that thermodynamics and kinetics of the reactions are quite consistent: the lower the activation energy, the lower the reaction energy, thus following the Bell-Evans-Polanyi principle. It has been found that activation energies are mostly due to structural rearrangements that in most cases represented more than 70% of the activation energy. Electronic activity mostly due to changes in σ and π bonding were revealed by the reaction electronic flux (REF), this property helps identify whether changes on σ or π bonding drive the reaction. Additionally, new global indexes describing the behavior of the electronic activity were introduced and then used to classify the reactions in terms of the spontaneity of their electronic activity. Local natural bond order electronic population analysis was used to check consistency with global REF through the characterization of specific changes in the electronic density that might be responsible for the activity already detected by the REF. Results show that reactions involving acetoxy lactones are driven by spontaneous electronic activity coming from bond forming/strengthening processes; in the case of maleic anhydrides and maleimides it appears that both spontaneous and non-spontaneous electronic activity are quite active in driving the reactions.     

On the strength of hydrogen bonding within water clusters on the coordination limit

Hydrogen bonds (HB) are arguably the most important noncovalent interactions in chemistry. We study herein how differences in connectivity alter the strength of HBs within water clusters of different sizes. We used for this purpose the interacting quantum atoms energy partition, which allows for the quantification of HB formation energies within a molecular cluster. We could expand our previously reported hierarchy of HB strength in these systems (Phys. Chem. Chem. Phys., 2016, 18 , 19557) to include tetracoordinated monomers. Surprisingly, the HBs between tetracoordinated water molecules are not the strongest HBs despite the widespread occurrence of these motifs (e.g., in ice I_h). The strongest HBs within H₂O clusters involve tricoordinated monomers. Nonetheless, HB tetracoordination is preferred in large water clusters because (a) it reduces HB anticooperativity associated with double HB donors and acceptors and (b) it results in a larger number of favorable interactions in the system. Finally, we also discuss (a) the importance of exchange-correlation to discriminate among the different examined types of HBs within H₂O clusters, (b) the use of the above-mentioned scale to quickly assess the relative stability of different isomers of a given water cluster, and (c) how the findings of this research can be exploited to indagate about the formation of polymorphs in crystallography. Overall, we expect that this investigation will provide valuable insights into the subtle interplay of tri- and tetracoordination in HB donors and acceptors as well as the ensuing interaction energies within H₂O clusters.     

Recent Analytical Approaches for the Study of Bioavailability and Metabolism of Bioactive Phenolic Compounds

The study of the bioavailability of bioactive compounds is a fundamental step for the development of applications based on them, such as nutraceuticals, functional foods or cosmeceuticals. It is well-known that these compounds can undergo metabolic reactions before reaching therapeutic targets, which may also affect their bioactivity and possible applications. All recent studies that have focused on bioavailability and metabolism of phenolic and terpenoid compounds have been developed because of the advances in analytical chemistry and metabolomics approaches. The purpose of this review is to show the role of analytical chemistry and metabolomics in this field of knowledge. In this context, the different steps of the analytical chemistry workflow (design study, sample treatment, analytical techniques and data processing) applied in bioavailability and metabolism in vivo studies are detailed, as well as the most relevant results obtained from them.     

Code2vect: An efficient heterogenous data classifier and nonlinear regression technique

The aim of this paper is to present a new classification and regression algorithm based on Artificial Intelligence. The main feature of this algorithm, which will be called Code2Vect, is the nature of the data to treat: qualitative or quantitative and continuous or discrete. Contrary to other artificial intelligence techniques based on the “Big-Data,” this new approach will enable working with a reduced amount of data, within the so-called “Smart Data” paradigm. Moreover, the main purpose of this algorithm is to enable the representation of high-dimensional data and more specifically grouping and visualizing this data according to a given target. For that purpose, the data will be projected into a vectorial space equipped with an appropriate metric, able to group data according to their affinity (with respect to a given output of interest). Furthermore, another application of this algorithm lies on its prediction capability. As it occurs with most common data-mining techniques such as regression trees, by giving an input the output will be inferred, in this case considering the nature of the data formerly described. In order to illustrate its potentialities, two different applications will be addressed, one concerning the representation of high-dimensional and categorical data and another featuring the prediction capabilities of the algorithm.     

Recovery of Bioactive Ellagitannins by Ultrasound/Microwave-Assisted Extraction from Mexican Rambutan Peel (Nephelium lappaceum L.)

Rambutan (Nephelium lappaceum L.) is a tropical fruit from Asia which has become the main target of many studies involving polyphenolic analysis. Mexico produces over 8 million tons per year of rambutan, generating a huge amount of agro-industrial waste since only the pulp is used and the peel, which comprises around 45% of the fruit’s weight, is left behind. This waste can later be used in the recovery of polyphenolic fractions. In this work, emerging technologies such as microwave, ultrasound, and the hybridization of both were tested in the extraction of phenolic compounds from Mexican rambutan peel. The results show that the hybrid technology extraction yielded the highest polyphenolic content (176.38 mg GAE/g of dry rambutan peel). The HPLC/MS/ESI analysis revealed three majoritarian compounds: geraniin, corilagin, and ellagic acid. These compounds explain the excellent results for the biological assays, namely antioxidant activity evaluated by the DPPH, ABTS, and LOI (Lipid oxidation inhibition) assays that exhibited great antioxidant capacity with IC₅₀ values of 0.098, 0.335, and 0.034 mg/mL respectively, as well as prebiotic activity demonstrated by a µMax (maximum growth) of 0.203 for Lactobacillus paracasei. Lastly, these compounds have shown no hemolytic activity, opening the door for the elaboration of different products in the food, cosmetic, and pharmaceutical industries.     

Mineralogical analysis of auriferous ores from the El Diamante mine, Colombia

X-ray diffraction (XRD), Mössbauer spectrometry (MS), secondary ions mass spectroscopy (SIMS) and laser-ablation microprobe–inductively coupled plasma–mass spectrometry (LAM–ICP–MS) were used to study mineral samples of Colombian auriferous ores collected from the “El Diamante” mine, located in the municipality of Guachavez-Nariño, in Colombia. The samples were prepared as polished thin sections and polished sections. From XRD data, quartz, sphalerite and pyrite were detected and their respective cell parameters were estimated. From MS analyses, pyrite, arsenopyrite and chalcopyrite were identified; their respective hyperfine parameters and respective texture were deduced. Multiple regions of approximately 200 × 200 μm in each sample were analyzed with SIMS; the occurrence of “invisible gold” associated mainly with pyrite and secondarily with arsenopyrite could thus be assigned. It was also found that pyrite is of the arsenious type. Spots from 30 to 40 μm in diameter were analyzed with LAM–ICP–MS for pyrite, arsenopyrite and sphalerite; Au is “homogeneously” distributed inside the structure of the arsenious pyrite and the arsenopyrite (not as inclusions); the chemical composition indicates similarities of this “invisible gold”, forming a solid solution with arsenious pyrite and arsenopyrite. One hundred nineteen and 62 ppm of ‘invisible gold’ was quantified in 21 spots analyzed on pyrite and in 14 spots on arsenopyrite, respectively.     

Nanostructures in calcia stabilized hafnia thin films observed by PAC as a function of temperature

The hyperfine quadrupole interaction at Hf sites in films and powders of 14 mol% CaO–HfO₂ and 20 mol% CaO–HfO₂ has been determined as a function of temperature. Results indicate the formation of a cubic solid solution and other microstructures assigned to the ?₁ (CaHf₄O₉) and ?₂ (Ca₆Hf₁₉O₄₄) phases. Dynamical effects on the electric field gradient reveal the existence of oxygen vacancies movements in the solid solution. The thermal behavior of the relaxation constant observed in films allowed the determination of activation energies of 0.54 eV and 0.70 eV for the 14 mol% and 20 mol% CaO doped hafnias, respectively. The influence of the microdomains and the stability of the cubic solid solution are discussed.