Investigating the transformations of polyoxoanions using mass spectrometry and molecular dynamics

The reactions of [γ-SiW10O36]8– represent one of the most important synthetic gateways into a vast array of polyoxotungstate chemistry. Herein, we set about exploring the transformation of the lacunary polyoxoanion [β2-SiW11O39]8– into [γ-SiW10O36]8– using high-resolution electrospray mass spectrometry, density functional theory, and molecular dynamics. We show that the reaction proceeds through an unexpected {SiW9} precursor capable of undertaking a direct β → γ isomerization via a rotational transformation. The remarkably low-energy transition state of this transformation could be identified through theoretical calculations. Moreover, we explore the significant role of the countercations for the first time in such studies. This combination of experimental and the theoretical studies can now be used to understand the complex chemical transformations of oxoanions, leading to the design of reactivity by structural control

Adsorption of Direct Blue 78 using chitosan and cyclodextrins as adsorbents

The dyeing industry is one of the most polluting in the world. The adsorption of dyes by polymeric matrixes can be used to minimize the discharge of dyes into the environment. In the present study, chitosan-NaOH and β-cyclodextrin-epichlorohydrin polymers were used to remove the dye Direct Blue 78 from a wastewater model. To understand the adsorption behavior of Direct Blue 78 onto the polymers, adsorption rate and maximum adsorption capacity were calculated using kinetic tests and isotherm curves respectively. The kinetic data and mechanism of the adsorption process were analyzed by three models and the equilibrium data by three adsorption isotherms; also the different thermodynamic parameters were calculated. Results showed that the adsorption process follows pseudo-second-order kinetics in both polymers and the Langmuir isotherm best-fitted data for chitosan-NaOH polymer and the Freundlich isotherm for the β-CDs-EPI polymer. The adsorption process is exothermic in both cases and spontaneous for the β-CDs-EPI polymer to a certain temperature and not spontaneous for the chitosan-NaOH polymer and β-CDs-EPI polymer at higher temperatures. The complementary action of an advanced oxidation process eliminated >99% of the dye from water. The coupled process seems to be suitable for reducing the environmental impact of the dyeing industry.Ciencias de la Alimentació

Stability of microencapsulated strawberry flavour by spray drying, freeze drying and fluid bed

The main goal of this paper was to study the stability of a microencapsulated strawberry flavour using different encapsulating agents and drying techniques: spray drying, freeze drying and fluid bed. According to the quantification of volatile compounds, the blend MDs/Hi-Cap (9/1) at a fixed concentration of CDs (1.7%) was the most appropriate for microencapsulating the strawberry flavour. The best drying yield was observed in the case of freeze drying. In the case of the moisture content, spray drying samples presented the lowest values, followed by freeze drying and fluid bed. The study of stability at different temperatures and times revealed that the presence of CDs in the blend enabled a higher presence of volatile compounds in the powder than in its absence. Microphotographs showed smooth spherical particles in the case of spray drying, whereas the structure of the powder was amorphous, like glass, with freeze drying and irregular in the case of fluid bed.Ciencias de la Alimentació

El universo de Roald Dahl o como integrar diferentes asignaturas en un proyecto común

Memoria ID-0039. Ayudas de la Universidad de Salamanca para la innovación docente, curso 2015-2016

Synthesis of New Cyclodextrin-Based Adsorbents to Remove Direct Red 83:1

Two cyclodextrins (CDs), γ– and hydroxypropyl (HP)–γ–CDs were used to synthesize new adsorbents by using epichlorohydrin (EPI) as cross-linking agent in order to remove Direct Red 83:1 (DR) from water. Both polymers were characterized in terms of Fourier spectroscopy, nuclear magnetic resonance, particle size distribution and thermogravimetric analysis. Experimental data for both polymers were well fitted to the pseudo-second order and intraparticle diffusion model, indicating that in the adsorption both chemical and physical interactions are essential in the removal of DR. Three different isotherm models were analyzed, concluding that γ–CDs–EPI followed the Temkin isotherm and HP–γ–CDs-EPI the Freundlich isotherm, these results suggested that the adsorption was happening onto heterogeneous surfaces. The results of the Gibbs free energy showed that the adsorption was spontaneous at room temperature. In order to eliminate the remaining dye after the polymer treatment, and advanced oxidation process (AOP) was considered, achieving more than 90% of removal combining both mechanisms.European project “DYES4EVER” (Use of cyclodextrins for treatment of wastewater in textile industry to recover and reuse textile dyes, LIFE12 ENV/ES/000309) within the LIFE+ 2012 “Environment Policy and Governance project application” program.Ingeniería, Industria y Construcció

Is Routine Prophylaxis Against Pneumocystis jirovecii Needed in Liver Transplantation? A Retrospective Single-Centre Experience and Current Prophylaxis Strategies in Spain

In liver transplant (LT) recipients, Pneumocystis jirovecii pneumonia (PJP) is most frequently reported before 1992 when immunosuppressive regimens were more intense. It is uncertain whether universal PJP prophylaxis is still applicable in the contemporary LT setting. We aimed to examine the incidence of PJP in LT recipients followed at our institution where routine prophylaxis has never been practiced and to define the prophylaxis strategies currently employed among LT units in Spain. All LT performed from 1990 to October 2019 were retrospectively reviewed and Spanish LT units were queried via email to specify their current prophylaxis strategy. During the study period, 662 LT procedures were carried out on 610 patients. Five cases of PJP were identified, with only one occurring within the first 6 months. The cumulative incidence and incidence rate were 0.82% and 0.99 cases per 1000 person transplant years. All LT units responded, the majority of which provide prophylaxis (80%). Duration of prophylaxis, however, varied significantly. The low incidence of PJP in our unprophylaxed cohort, with most cases occurring beyond the usual recommended period of prophylaxis, questions a one-size-fits-all approach to PJP prophylaxis. A significant heterogeneity in prophylaxis strategies exists among Spanish LT centres.Funding: This study was supported by the Health Research Institute Marqués de Valdecilla. IDIVAL. Santander. NEXT VAL17/07 grant to José Ignacio Fortea Ormaechea

Purification of Uranium-based Endohedral Metallofullerenes (EMFs) by Selective Supramolecular Encapsulation and Release

Supramolecular nanocapsule 1⋅(BArF) is able to sequentially and selectively entrap recently discovered U@C and unprecedented ScCU@C, simply by soaking crystals of 1⋅(BArF) in a toluene solution of arc-produced soot. These species, selectively and stepwise absorbed by 1⋅(BArF), are easily released, obtaining highly pure fractions of U@C and ScCU@C in one step. ScCU@C represents the first example of a mixed metal actinide-based endohedral metallofullerene (EMF). Remarkably, the host-guest studies revealed that 1⋅(BArF) is able to discriminate EMFs with the same carbon cage but with different encapsulated cluster and computational studies provide support for these observations

An Ultra‐Long‐Lived Triplet Excited State in Water at Room Temperature: Insights on the Molecular Design of Tridecafullerenes

Suitably engineered molecular systems exhibiting triplet excited states with very long lifetimes are important for high-end applications in nonlinear optics, photocatalysis, or biomedicine. We report the finding of an ultra-long-lived triplet state with a mean lifetime of 93 ms in an aqueous phase at room temperature, measured for a globular tridecafullerene with a highly compact glycodendrimeric structure. A series of three tridecafullerenes bearing different glycodendrons and spacers to the C60 units have been synthesized and characterized. UV/Vis spectra and DLS experiments confirm their aggregation in water. Steady-state and time-resolved fluorescence experiments suggest a different degree of inner solvation of the multifullerenes depending on their molecular design. Efficient quenching of the triplet states by O2 but not by waterborne azide anions has been observed. Molecular modelling reveals dissimilar access of the aqueous phase to the internal structure of the tridecafullerenes, differently shielded by the glycodendrimeric shell

Removing of Direct Red 83:1 using α- and HP-α-CDs polymerized with epichlorohydrin: Kinetic and equilibrium studies

The adsorption properties of two cyclodextrin-epichlorohydrin polymers to remove Direct Red 83:1 textile dye from wastewater solutions was evaluated. Adsorption studies were performed in a batch reactor, and the efficiency of the polymers under different parametric values such as contact time, adsorbent dosage, initial dye concentration, pH of initial solution and temperature was followed by spectrophotometry. Both Langmuir and Freundlich equations were used to fit the equilibrium isotherms and the kinetic data were analyzed by the pseudo-first-order and pseudo-second-order models. Adsorption process follows a pseudo-second-order kinetic and was influenced by intraparticle diffusion model, dye concentration and contact time, reaching equilibrium within the first 30 min. Experimental data were better fitted to Freundlich isotherm model than to Langmuir and Temkin isotherms. Since about 93% of dye removal was achieved under optimized conditions, the α-cyclodextrin-epichlorohydrin polymer seems to be a useful device for removing Direct Red 83:1 from aqueous solutions and industrial effluents.Ciencias Ambientale

Adsorption Properties of β- and Hydroxypropyl-β-Cyclodextrins Cross-Linked with Epichlorohydrin in Aqueous Solution. A Sustainable Recycling Strategy in Textile Dyeing Process

β-cyclodextrin (β-CD) and hydroxypropyl-β-cyclodextrin (HP-β-CD) were used to prepare insoluble polymers using epichlorohydrin as a cross-linking agent and the azo dye Direct Red 83:1 was used as target adsorbate. The preliminary study related to adsorbent dosage, pH, agitation or dye concentration allowed us to select the best conditions to carry out the rest of experiments. The kinetics was evaluated by Elovich, pseudo first order, pseudo second order, and intra-particle diffusion models. The results indicated that the pseudo second order model presented the best fit to the experimental data, indicating that chemisorption is controlling the process. The results were also evaluated by Freundlich, Langmuir and Temkin isotherms. According to the determination coefficient (R2), Freunlich gave the best results, which indicates that the adsorption process is happening on heterogeneous surfaces. One interesting parameter obtained from Langmuir isotherm is qmax (maximum adsorption capacity). This value was six times higher when a β-CDs-EPI polymer was employed. The cross-linked polymers were fully characterized by nuclear magnetic resonance (NMR), Fourier transform infrared spectroscopy (FTIR), thermal gravimetric analysis (TGA). Also, morphology and particle size distribution were both assessed. Under optimized conditions, the β-CDs-EPI polymer seems to be a useful device for removing Direct Red 83:1 (close 90%), from aqueous solutions and industrial effluents. Complementarily, non-adsorbed dye was photolyzed by a pulsed light driven advanced oxidation process. The proposed methodology is environmental and economically advantageous, considering the point of view of a sustainable recycling economy in the textile dyeing process.Ciencias Ambientale