17O and 1H relaxometric and DFT study of hyperfine coupling constants in [Mn(H2O)6]2+

[Abstract] Nuclear Magnetic Relaxation Dispersion (NMRD) profiles and 17O NMR chemical shifts and transverse relaxation rates of aqueous solutions of [Mn(H2O)6]2+ were recorded to determine the parameters governing the relaxivity in this complex and the 17O and 1H hyperfine coupling constants (HFCCs). The analysis of the NMRD and 17O NMR data provided a water exchange rate of kex298 = 28.2 × 106 s−1, and AO/ħ and AH/ħ hyperfine coupling constants of −34.6 and 5.4 rad s−1, respectively. DFT calculations (TPSSh model) performed on the [Mn(H2O)6]2+ and [Mn(H2O)6]2+·12H2O systems were used to evaluate theoretically the 17O and 1H HFCCs responsible for the 17O NMR chemical shifts and the scalar contributions to 17O and 1H NMR relaxation rates. The use of a mixed cluster–continuum approach with the explicit inclusion of second-sphere water molecules is critical for an accurate calculation of HFCCs of coordinated water molecules. The impact of complex dynamics on the calculated HFCCs was evaluated with the use of molecular dynamics simulations within the atom-centered density matrix propagation (ADMP) approach. These molecular dynamics simulations show that the Aiso values are critically affected by the distance between the oxygen atom of the coordinated water molecule and the MnII ion, as well as by the orientation of the water molecule plane with respect to the Mn–O vector. The substantial scalar contribution to relaxivity observed for [Mn(H2O)6]2+ is related to a combination of a slow water exchange rate and a slow electron spin relaxation.Xunta de Galicia; EM2012/08

Supramolecular hydrogels based on custom-made poly(ether urethane)s and cyclodextrins as potential drug delivery vehicles: design and characterization

The design of supramolecular (SM) hydrogels based on host-guest complexes represents an effective strategy to develop drug delivery systems. In this work, we designed SM hydrogels based on α-cyclodextrin and high-molar mass amphiphilic poly(ether urethane)s (PEUs, ) based on Poloxamer® 407 and differing in their chain extender. The successful formation of poly(pseudo)rotaxanes and their supramolecular interactions were chemically demonstrated. Then, self-healing (80-100% mechanical recovery) supramolecular hydrogels were developed by mixing PEU and α-cyclodextrin solutions at different concentrations. Stability in physiological-like environment and mechanical properties improved with increasing α-cyclodextrin content (9-10% w/v), meanwhile gelation time decreased. A synergistic effect of poly(pseudo)rotaxanes crystals and PEU micellar structures on gel properties was observed: the first were predominant at low PEU concentrations (1-5% w/v), while the latter prevailed at high PEU concentrations (7-9% w/v). Increasing PEU concentration led to gels with increased dissolution rate, not-fully developed networks and slight cytotoxicity, meanwhile residence time in aqueous media improved (>7 d). At low PEU concentrations (1-5% w/v), cytocompatible gels (100% cell viability) were obtained, which maintained their shape in aqueous medium up to 5 d and completely dissolved within 7 d. PEU chemical composition affected PEU/α-cyclodextrin interactions, with longer gelation time and lower mechanical properties in gels based on PEU with pendant functionalities. Gels progressively released a model molecule (fluorescein isothiocyanate-dextran) within 3-4 days with no initial burst release. We thus demonstrated the suitability of custom-made PEUs as constituent of SM hydrogels with α-cyclodextrin and the high potential of the resulting systems for drug delivery applications

Wine Traceability with Rare Earth Elements

The traceability of foodstuffs is now a relevant aspect of the food market. Scientific research has been devoted to addressing this issue by developing analytical protocols in order to find the link between soil and food items. In this view, chemical parameters that can act as soil markers are being sought. In this work, the role of rare earth elements (REEs) as geochemical markers in the traceability of red wine is discussed. The REE distribution in samples from each step of the wine making process of Primitivo wine (produced in Southern Italy) was determined using the highly sensitive inductively coupled plasma-mass spectrometry (ICP-MS) technique. Samples analyzed include grapes, must, and wine samples after every step in the vinification process. The resulting data were compared to the REE distribution in the soil, revealing that the soil fingerprint is maintained in the intermediate products up to and including grape must. Fractionation occurs thereafter as a consequence of further external interventions, which tends to modify the REE profile

Fingerprinting the Hydration Products of Hydraulic Binders Using Snapshots from Time-Resolved In Situ Multinuclear MAS NMR Spectroscopy

The very early hydration behavior of a hydraulic binder phase, ye'elimite, Ca4Al6O12SO4, in the absence and in the presence of calcium sulfate, has been investigated. A time-resolved in situ multin..

Thiol-Ene Photo-Click Hydrogels with Tunable Mechanical Properties Resulting from the Exposure of Different -Ene Moieties through a Green Chemistry

Temperature and light responsiveness are widely exploited stimuli to tune the physico-chemical properties of double network hydrogels. In this work, new amphiphilic poly(ether urethane)s bearing photo-sensitive moieties (i.e., thiol, acrylate and norbornene functionalities) were engineered by exploiting the versatility of poly(urethane) chemistry and carbodiimide-mediated green functionalization procedures. Polymers were synthesized according to optimized protocols maximizing photo-sensitive group grafting while preserving their functionality (approx. 1.0 × 10E19, 2.6 × 10E19 and 8.1 × 10E17 thiol, acrylate and norbornene groups/gpolymer), and exploited to prepare thermo- and Vis-light-responsive thiol-ene photo-click hydrogels (18% w/v, 1:1 thiol:ene molar ratio). Green light-induced photo-curing allowed the achievement of a much more developed gel state with improved resistance to deformation (~60% increase in critical deformation, γL). Triethanolamine addition as co-initiator to thiol-acrylate hydrogels improved the photo-click reaction (i.e., achievement of a better-developed gel state). Differently, L-tyrosine addition to thiol-norbornene solutions slightly hindered cross-linking, resulting in less developed gels with worse mechanical performances (~62% γL decrease). In their optimized composition, thiol-norbornene formulations resulted in prevalent elastic behavior at lower frequency compared to thiol-acrylate gels due to the formation of purely bio-orthogonal instead of heterogeneous gel networks. Our findings highlight that exploiting the same thiol-ene photo-click chemistry, a fine tuning of the gel properties is possible by reacting specific functional groups

Condição de exportação e emprego formal na indústria brasileira, 2003-2008

 A recomposição da base produtiva brasileira, após a década 1990, ocorreu em um contexto de economia aberta e exposta à maior concorrência internacional, muitas vezes estabelecida em condições desfavoráveis, mas caracterizada por maior inserção externa da indústria brasileira. Este ensaio analisa os efeitos desse contexto econômico para a geração de empregos no setor industrial, segundo a condição de inserção das empresas no mercado internacional. Busca elucidar se a inserção externa das empresas está associada a perfis ocupacionais mais favoráveis em termos de qualificação e estabilidade do emprego. Os resultados confirmam que a continuidade da trajetória de crescimento com inserção externa representa um vetor relevante para maior qualificação da força de trabalho

Authentication and traceability study on barbera d\u2019asti and nizza docg wines: The role of trace-and ultra-trace elements

Barbera d\u2019Asti\u2014including Barbera d\u2019Asti superiore\u2014and Nizza are two DOCG (Denominazione di Origine Controllata e Garantita) wines produced in Piemonte (Italy) from the Barbera grape variety. Differences among them arise in the production specifications in terms of purity, ageing, and zone of production, in particular with concern to Nizza, which follows the most stringent rules, sells at three times the average price, and is considered to have the highest market value. To guarantee producers and consumers, authentication methods must be developed in order to distinguish among the different wines. As the production zones totally overlap, it is important to verify whether the distinction is possible or not according to metals content, or whether chemical markers more linked to winemaking are needed. In this work, Inductively Coupled Plasma (ICP) elemental analysis and multivariate data analysis are used to study the authentication and traceability of samples from the three designations of 2015 vintage. The results show that, as far as elemental distribution in wine is concerned, work in the cellar, rather than geographic provenance, is crucial for the possibility of distinction

Embedding Ordered Mesoporous Carbons into Thermosensitive Hydrogels: A Cutting-Edge Strategy to Vehiculate a Cargo and Control Its Release Profile

9siThe high drug loading capacity, cytocompatibility and easy functionalization of ordered mesoporous carbons (OMCs) make them attractive nanocarriers to treat several pathologies. OMCs’ efficiency could be further increased by embedding them into a hydrogel phase for an in loco prolonged drug release. In this work, OMCs were embedded into injectable thermosensitive hydrogels. In detail, rod-like (diameter ca. 250 nm, length ca. 700 nm) and spherical (diameter approximately 120 nm) OMCs were synthesized by nanocasting selected templates and loaded with ibuprofen through a melt infiltration method to achieve complete filling of their pores (100% loading yield). In parallel, an amphiphilic Poloxamer®407-based poly(ether urethane) was synthesized (Mn 72 kDa) and solubilized at 15 and 20% w/v concentration in saline solution to design thermosensitive hydrogels. OMC incorporation into the hydrogels (10 mg/mL concentration) did not negatively affect their gelation potential. Hybrid systems successfully released ibuprofen at a slower rate compared to control gels (gels embedding ibuprofen as such), but with no significant differences between rod-like and spherical OMC-loaded gels. OMCs can thus work as effective drug reservoirs that progressively release their payload over time and also upon encapsulation in a hydrogel phase, thus opening the way to their application to treat many different pathological states (e.g., as topical medications).openopenMonica Boffito; Rossella Laurano; Dimitra Giasafaki; Theodore Steriotis; Athanasios Papadopoulos; Chiara Tonda-Turo; Claudio Cassino; Georgia Charalambopoulou; Gianluca CiardelliBoffito, Monica; Laurano, Rossella; Giasafaki, Dimitra; Steriotis, Theodore; Papadopoulos, Athanasios; TONDA TURO, Chiara; Cassino, Claudio; Charalambopoulou, Georgia; Ciardelli, Gianluc

Antioxidant Composition of a Selection of Italian Red Wines and Their Corresponding Free-Radical Scavenging Ability

This study correlates the antioxidant composition profiles and the overall antioxidant capacities of 36 Italian red wine samples. The samples were fully characterized by chromatographic and spectrophotometric techniques. The overall antioxidant capacity was determined by titrating a solution of the semistable free radical DPPH (1,1-diphenyl-2-picrylhydrazyl) with each wine sample followed by Electron Paramagnetic Resonance (EPR) spectroscopy and then measuring the resulting decrease in DPPH-signal. The antioxidant activities of the samples were expressed as (+)-catechin equivalents and related to their antioxidant composition profiles. Samples with a high polyphenol content showed a high DPPH scavenging ability as well. Seven well-defined groups, mainly constituted by wines coming from the same cultivar, were evidenced by PCA analysis. Alcohol content and pH did not influence the wine DPPH scavenging ability. The most important variables contributing to the wines’ antioxidant power are total flavonoid, total phenol, and proanthocyanidin indices together with fertaric acid, trans-caftaric acid, trans-coutaric acid, and both quercetin glucoside and quercetin glucuronide. EPR is demonstrated to be faster than the other analytical methods (spectrophotometric and chromatographic analyses) to determine the wine overall antioxidant activity

Importance of outer-sphere and aggregation phenomena in the relaxation properties of phosphonated gadolinium complexes with potential applications as MRI contrast agents

[Abstract] A series composed of a tetra-, a tris- and a bisphosphonated ligand based on a pyridine scaffold (L4, L3 and L2, respectively) was studied within the frame of lanthanide (Ln) coordination. The stability constants of the complexes formed with lanthanide cations (Ln=La, Nd, Eu, Gd, Tb, Er and Lu) were determined by potentiometry in aqueous solutions (25.0 °C, 0.1 M NaClO4), showing that the tetraphosphonated complexes are among the most stable LnIII complexes reported in the literature. The complexation of L4 was further studied by different titration experiments using mass spectrometry and various spectroscopic techniques including UV/Vis absorption, and steady state and time-resolved luminescence (Ln=Eu and Tb). Titration experiments confirmed the formation of highly stable [LnL4] complexes. 31P NMR experiments of the LuL4 complex revealed an intramolecular interconversion process which was studied at different temperatures and was rationalized by DFT modelling. The relaxivity properties of the GdIII complexes were studied by recording their 1H NMRD profiles at various temperatures, by temperature dependent 17O NMR experiments (GdL4) and by pH dependent relaxivity measurements at 0.47 T (GdL3 and GdL2). In addition to the high relaxivity values observed for all complexes, the results showed an important second-sphere contribution to relaxivity and pH dependent variations associated with the formation of aggregates for GdL2 and GdL3. Finally, intravenous injection of GdL4 to a mouse was followed by dynamic MRI imaging at 1.5 T, which showed that the complex can be immediately found in the blood stream and rapidly eliminated through the liver and in large part through the kidneys.Torino. Compagnia di San Paolo; CSP-2012 NANOPROGL