Combining EXAFS and Computer Simulations to Refine the Structural Description of Actinyls in Water.

EXAFS spectroscopy is one of the most used techniques to solve the structure of actinoid solutions. In this work a systematic analysis of the EXAFS spectra of four actinyl cations, [UO2]2+, [NpO2]2+, [NpO2]+ and [PuO2]2+ has been carried out by comparing experimental results with theoretical spectra. These were obtained by averaging individual contributions from snapshots taken from classical Molecular Dynamics simulations which employed a recently developed [AnO2]2+/+ -H2O force field based on the hydrated ion model using a quantum-mechanical (B3LYP) potential energy surface. Analysis of the complex EXAFS signal shows that both An-Oyl and An-OW single scattering paths as well as multiple scattering ones involving [AnO2]+/2+ molecular cation and first-shell water molecules are mixed up all together to produce a very complex signal. Simulated EXAFS from the B3LYP force field are in reasonable agreement for some of the cases studied, although the k= 6-8 Å-1 region is hard to be reproduced theoretically. Except uranyl, all studied actinyls are open-shell electron configurations, therefore it has been investigated how simulated EXAFS spectra are affected by minute changes of An-O bond distances produced by the inclusion of static and dynamic electron correlation in the quantum mechanical calculations. A [NpO2]+-H2O force field based on a NEVPT2 potential energy surface has been developed. The small structural changes incorporated by the electron correlation on the actinyl aqua ion geometry, typically smaller than 0.07 Å, leads to improve the simulated spectrum with respect to that obtained from the B3LYP force field. For the other open-shell actinyls, [NpO2]2+ and [PuO2]2+, a simplified strategy has been adopted to improve the simulated EXAFS spectrum. It is computed taking as reference structure the NEVPT2 optimized geometry and including the DW factors of their corresponding MD simulations employing the B3LYP force field. A better agreement between the experimental and the simulated EXAFS spectra is found, confirming the a priori guess that the inclusion of dynamic and static correlation refine the structural description of the open-shell actinyl aqua ions.

A new machine learning approach for predicting the response to anemia treatment in a large cohort of End Stage Renal Disease patients undergoing dialysis.

Chronic Kidney Disease (CKD) anemia is one of the main common comorbidities in patients undergoing End Stage Renal Disease (ESRD). Iron supplement and especially Erythropoiesis Stimulating Agents (ESA) have become the treatment of choice for that anemia. However, it is very complicated to find an adequate treatment for every patient in each particular situation since dosage guidelines are based on average behaviors, and thus, they do not take into account the particular response to those drugs by different patients, although that response may vary enormously from one patient to another and even for the same patient in different stages of the anemia. This work proposes an advance with respect to previous works that have faced this problem using different methodologies (Machine Learning (ML), among others), since the diversity of the CKD population has been explicitly taken into account in order to produce a general and reliable model for the prediction of ESA/Iron therapy response. Furthermore, the ML model makes use of both human physiology and drug pharmacology to produce a model that outperforms previous approaches, yielding Mean Absolute Errors (MAE) of the Hemoglobin (Hb) prediction around or lower than 0.6 g/dl in the three countries analyzed in the study, namely, Spain, Italy and Portugal.

Multidisciplinary and biodanza intervention for the management of fibromyalgia.

OBJECTIVE: To evaluate and compare the effectiveness of a 16-week multidisciplinary (exercise plus psychological therapy) and biodanza intervention in women with fibromyalgia. PATIENTS AND METHODS: Thirty-eight women with fibromyalgia were distributed to a 16-week multidisciplinary (3-times/week) intervention (n=21) or Biodanza (1-time/week) intervention (n=17). We assessed tender point, body composition, physical fitness and psychological outcomes (Fibromyalgia Impact Questionnaire, the Short-Form Health Survey 36 questionnaire (SF-36), the Hospital Anxiety and Depression Scale, Vanderbilt Pain Management Inventory (VPMI), Rosenberg Self-Esteem Scale and General Self-Efficacy Scale). RESULTS: We observed a significant group*time interaction effect for the scales of SF-36 physical role (P=0.038) and social functioning (P=0.030) and for the passive coping scale in VPMI (P=0.043). Post hoc analysis revealed a significant improvement on social functioning (P=0.030) in the multidisciplinary group whereas it did not change in the Biodanza group. Post hoc analysis revealed a reduction in the use of passive coping (positive) (P less than 0.001) in the multidisciplinary group. There was no significant interaction or time effect in body composition and physical fitness. CONCLUSIONS: 16 weeks of multidisciplinary intervention induced greater benefits than a Biodanza intervention for social functioning and the use of passive coping strategies in women with fibromyalgia.

Expression of modified tocopherol content and profile in sunflower tissues.

BACKGROUND: Alpha-tocopherol is the predominant tocopherol form in sunflower seeds. Sunflower lines that accumulate increased levels of beta-, gamma- and delta-tocopherol in seeds as well as lines with reduced and increased total seed tocopherol content have been developed. The objective of this research was to evaluate whether the modified tocopherol levels are expressed in plant tissues other than seeds. RESULTS: Lines with increased levels of beta-, gamma- and delta-tocopherol in seeds also possessed increased levels of these tocopherols in leaves, roots and pollen. Correlation coefficients for the proportion of individual tocopherols in different plant tissues were significantly positive in all cases, ranging from 0.68 to 0.97. A line with reduced tocopherol content in seeds also showed reduced content in roots and pollen. CONCLUSION: Genetic modifications producing altered seed tocopherol profiles in sunflower are also expressed in leaves, roots and pollen. Reduced total seed tocopherol content is mainly expressed at the root and pollen level. The expression of tocopherol mutations in other plant tissues will enable further studies on the physiological role of tocopherols and could be of interest for early selection for these traits in breeding programmes.

Rapid determination of sterols in vegetable oils by CEC using methacrylate ester-based monolithic columns.

A method for the determination of sterols in vegetable oils by CEC with UV-Vis detection, using methacrylate ester-based monolithic columns, has been developed. To prepare the columns, polymerization mixtures containing monomers of different hydrophobicities were tried. The influence of composition of polymerization mixture was optimized in terms of porogenic solvent, monomers/porogens and monomer/crosslinker ratios. The composition of the mobile phase was also studied. The optimum monolith was obtained with lauryl methacrylate monomer at 60:40% (wt:wt) lauryl methacrylate/ethylene dimethacrylate ratio and 60 wt% porogens with 20 wt% of 1,4-butanediol (12 wt% 1,4-butanediol in the polymerization mixture). Excellent resolution between sterols was achieved in less than 7 min with an 85:10:5 v/v/v ACN-2-propanol-water buffer containing 5 mM Tris at pH 8.0. The limits of detection were lower than 0.04 mM, and inter-day and column-to-column reproducibilities at 0.75 mM were better than 6.2%. The method was applied to the determination of sterols in vegetable oils with different botanical origins and to detect olive oil adulteration with sunflower and soybean oils.

Classification of vegetable oils according to their botanical origin using sterol profiles established by direct infusion mass spectrometry.

A simple and quick method to classify vegetable oils according to their botanical origin, based on direct infusion of sterol extracts into a mass spectrometer, was developed. Using mass spectrometry (MS) with either an electrospray ionization or an atmospheric pressure photoionization source, followed by linear discriminant analysis of the mass spectral data, oil samples corresponding to eight different botanical origins were perfectly classified with an excellent resolution among all the categories. An excellent correlation between the sterol profiles obtained by MS and by the official gas chromatography (with flame ionization detection) method was obtained. Thus, the proposed method is a promising alternative for sterol fingerprinting of vegetable oils, with the advantage that prior chromatographic separation is not required.

Classification of vegetable oils according to their botanical origin using amino acid profiles established by direct infusion mass spectrometry.

Amino acid profiles, established by direct infusion mass spectrometry, have been used to classify vegetable oils according to their botanical origin. The proteins present in hazelnut, sunflower, corn, soybean, olive, avocado, peanut and grapeseed oils were precipitated with acetone, and the residue was hydrolyzed in acid medium, diluted in a hydrochloric acid/ethanol mixture, and infused into the mass spectrometer. The spectra of the hydrolyzed protein extracts showed [M+H]+ ions of the following amino acids: glycine, alanine, serine, proline, valine, threonine, cysteine, isoleucine + leucine, aspartic acid, lysine, glutamic acid, methionine, histidine, phenylalanine, arginine and tyrosine. These ions were used to construct linear discriminant analysis (LDA) models. The ratios of the ion signal intensities selected by pairs were used as predictors. With the sequential application of three LDA models, the eight botanical origin categories of the samples were well resolved.

Determination of tocopherols in vegetable oils by CEC using methacrylate ester-based monolithic columns.

The separation and determination of tocopherols (Ts) in vegetable oils by CEC using methacrylate ester-based monolithic columns has been developed. The effects of pore size of the monolithic columns were studied, and the composition of mobile phase was optimized. The optimal pore size of the monolith was obtained with 12 wt% 1,4-butanediol in the polymerization mixture. Excellent resolution between tocopherols was achieved within 10 min analysis time with a 99:1 v/v MeOH-aqueous buffer containing 5 mM tris(hydroxymethyl)aminomethane at pH 8.0. The LODs were lower than 2.3 microg/mL, and interday and column-to-column reproducibilities at 25 microg/mL were better than 5.6%. Using a 93:7 v/v MeOH-aqueous buffer, both tocopherols and tocotrienols (T(3)s) of grapeseed and palm oils were resolved. Application to the detection of olive oil adulteration with low-cost edible oils was demonstrated.