Aspects of structural order in 209Bi-containing particles for potential MRI contrast agents based on quadrupole enhanced relaxation

ABSTRACT

Quadrupole relaxation enhancement (QRE) has been suggested as the key mechanism for a novel class of field-selective, potentially responsive magnetic resonance imaging contrast agents. In previous publications, QRE has been confirmed for solid compounds containing ²⁰⁹Bi as the quadrupolar nucleus (QN). For QRE to be effective in aqueous dispersions, several conditions must be met, i.e. high transition probability of the QN at the ¹H Larmor frequency, water exchange with the bulk and comparatively slow motion of the Bi-carrying particles. In this paper, the potential influence of structural order within the compounds (‘crystallinity’) on QRE was studied by nuclear quadrupole resonance (NQR) spectroscopy in one crystalline and two amorphous preparations of Triphenylbismuth (BiPh₃). The amorphous preparations comprised (1) a shock-frozen melt and (2) a granulate of polystyrene which contained homogeneously distributed BiPh₃ after common dissolution in THF and subsequent evaporation of the solvent. In contrast to the crystalline powder which exhibits strong, narrow NQR peaks the amorphous preparations did not reveal any NQR signals above the noise floor. From these findings, we conclude that the amorphous state leads to a significant spectral peak broadening and that for efficient QRE in potential contrast agents structures with a high degree of order (near crystalline) are required.     

Ionic Liquids [M3+][A−]3 with Three-Valent Cations and Their Possible Use to Easily Separate Rare Earth Metals

We introduce a simple way to liquify rare earth metals (REM) by incorporating the corresponding cations, in particular Eu³⁺, La³⁺, and Y³⁺, into polyvalent ionic liquids (ILs). In contrast to conventional methods, this is achieved not by transforming them into anionic complexes, but by keeping them as bare cations and combining them with convenient, cheap and commercially available anions (A) in the form [REM³⁺][A ⁻ ]₃. To do so, we follow the COncept of Melting Point Lowering due to EThoxylation (COMPLET) with alkyl polyethylene oxide carboxylates as anions. We provide basic properties, such as glass transition temperatures, viscosities, electrical conductivities, as well as water-octanol partition constants P and show that these ILs have remarkably different properties, despite the similarity of their cations. In addition, we show that the ionic liquids possess interesting luminescent properties as non-conventional fluorophores.     

Evaluation of Quality,Antioxidant Capacity,and Digestibility of Chickpea (Cicer arietinum L. cv Blanoro) Stored under N2 and CO2 Atmospheres

The aim of this work was to monitor the quality, antioxidant capacity and digestibility of chickpea exposed to different modified atmospheres. Chickpea quality (proximal analysis, color, texture, and water absorption) and the antioxidant capacity of free, conjugated, and bound phenol fractions obtained from raw and cooked chickpea, were determined. Cooked chickpea was exposed to N₂ and CO₂ atmospheres for 0, 25, and 50 days, and the antioxidant capacity was analyzed by DPPH (2,2′-diphenyl-1-picrylhydrazyl), ABTS (2,2′-azino-bis-[3ethylbenzothiazoline-6-sulfonic acid]), and total phenols. After in vitro digestion, the antioxidant capacity was measured by DPPH, ABTS, FRAP (ferric reducing antioxidant power), and AAPH (2,2′-Azobis [2-methylpropionamidine]). Additionally, quantification of total phenols, and UPLC-MS profile were determined. The results indicated that this grain contain high quality and high protein (18.38%). Bound phenolic compounds showed the highest amount (105.6 mg GAE/100 g) and the highest antioxidant capacity in all techniques. Cooked chickpeas maintained their quality and antioxidant capacity during 50 days of storage at 4 and −20 °C under a nitrogen atmosphere. Free and conjugated phenolic compounds could be hydrolyzed by digestive enzymes, increasing their bioaccessibility and their antioxidant capacity during each step of digestion. The majority compound in all samples was enterodiol, prevailing the flavonoid type in the rest of the identified compounds. Chickpea contains biological interest compounds with antioxidant potential suggesting that this legume can be exploited for various technologies.     

The Solid Solution Sr1−xBaxGa2: Substitutional Disorder and Chemical Bonding Visited by NMR Spectroscopy and Quantum Mechanical Calculations

Complete miscibility of the intermetallic phases (IPs) SrGa₂ and BaGa₂ forming the solid solution Sr_1?xBa_xGa₂ is shown by means of X‐ray diffraction, thermoanalytical and metallographic studies. Regarding the distances of Sr/Ba sites versus substitution degree, a model of isolated substitution centres (ISC) for up to 10 % cation substitution is explored to study the influence on the Ga bonding situation. A combined application of NMR spectroscopy and quantum mechanical (QM) calculations proves the electric field gradient (EFG) to be a sensitive measure of different bonding situations. The experimental resolution is boosted by orientation‐dependent NMR on magnetically aligned powder samples, revealing in first approximation two different Ga species in the ISC regimes. EFG calculations using superlattice structures within periodic boundary conditions are in fair agreement with the NMR spectroscopy data and are discussed in detail regarding their application on disordered IPs.     

Electrochemical Measurements of Optogenetically Stimulated Quantal Amine Release from Single Nerve Cell Varicosities in Drosophila Larvae

The nerve terminals found in the body wall of Drosophila melanogaster larvae are readily accessible to experimental manipulation. We used the light‐activated ion channel, channelrhodopsin‐2, which is expressed by genetic manipulation in Type II varicosities to study octopamine release in Drosophila. We report the development of a method to measure neurotransmitter release from exocytosis events at individual varicosities in the Drosophila larval system by amperometry. A microelectrode was placed in a region of the muscle containing a varicosity and held at a potential sufficient to oxidize octopamine and the terminal stimulated by blue light. Optical stimulation of Type II boutons evokes exocytosis of octopamine, which is detected through oxidization at the electrode surface. We observe 22700±4200 molecules of octopamine released per vesicle. This system provides a genetically accessible platform to study the regulation of amine release at an intact synapse.     

Chemometric study on the TiO2-photocatalytic degradation of nitrilotriacetic acid

A chemometric study on the TiO2-photocatalytic degradation of nitrilotriacetic acid (NTA) in aqueous media under UV radiation has been carried out taking into account the multiple variables that take part in the system. To save redundant number of experiments, the system has been managed under chemometric techniques for several variables as NTA and TiO2 concentrations, pH and irradiation time. Multiple-way analysis of the variance (MANOVA) has been applied to find the statistically significant variables. An artificial neural network (ANN) has been used to build an empirical model of the system. All measurements have been driven under experimental designs: a full-factorial design (FFD) was used to analyze significant factors through MANOVA, and a Doehlert design, which was modified by spatial rotation, was applied in order to have a satisfactory number of levels for the factor time to be able to train the ANN. The study allows the knowledge and prediction of the behavior of the system as well as to work out kinetic parameters and to optimize their variables. The results of kinetic parameters obtained with the neural network agreed with independent experimental results, confirming a Langmuir-Hinshelwood kinetic regime. The difference between NTA and ethylenediaminetetraacetic acid (EDTA), which has been previously studied, is also established.     

TiO2−CeOx−Pt Hollow Nanosphere Catalyst for Low-Temperature CO Oxidation

TiO₂−CeO₂−Pt hollow nanospheres (1 wt-% Pt) are realized using a liquid-phase strategy using NaCl as a template. The NaCl template is first coated with TiO₂ and thereafter with CeO₂ via the hydrolyzation of TiCl(OiPr)₃ and Ce(OiPr)₄ as suitable alkoxides. Finally, the NaCl template is removed by washing with water. The resulting @TiO₂−CeO₂ hollow nanospheres (□: inner cavity) exhibit an outer diameter of 140–180 nm, a wall thickness of 30–40 nm, an inner cavity of 80–100 nm, a specific surface area of 210 m²/g, a pore volume and area of 0.08 cm³/g and 191 m²/g, mainly with micropores ≥5 Å and ≤14 Å. The hollow nanosphere support is impregnated with Pt nanoparticles, using two different methods – a wet-chemical deposition (Pt(ac)₂, acetone, 25 °C) and a supercritical fluid reactive deposition (SFRD) process ([Pt(COD)Me₂], supercritical CO₂, 80 °C, 15.6 MPa) resulting in an uniform size distribution with Pt nanoparticles 2.5±0.1 nm (TiO₂−CeO₂−Pt_WCD) and 2.3±0.1 nm (TiO₂−CeO₂−Pt_SFRD) in size. The catalytic properties of the TiO₂−CeO₂−Pt hollow nanospheres are evaluated for CO oxidation between 50 and 500 °C. A promising catalytic activity and stable light-out/light-off temperatures are observed especially for the TiO₂−CeO₂−Pt_SFRD sample, indicating the suitability of hollow nanospheres as high-porosity catalyst material.     

Fluctuations in a general preferential attachment model via Stein's method

We consider a class of dynamic random graphs known as preferential attachment models, where the probability that a new vertex connects to an older vertex is proportional to a sublinear function of the indegree of the older vertex at that time. It is well known that the distribution of a uniformly chosen vertex converges to a limiting distribution. Depending on the parameters, the tail of the limiting distribution may behave like a power law or a stretched exponential. Using Stein's method we provide rates of convergence to zero of the total variation distance between the finite distribution and its limit. Our proof uses the fact that the limiting distribution is the stationary distribution of a Markov chain together with the generator method of Barbour.     

Two-phase Flow Dynamics at the Interface Between GDL and Gas Distributor Channel Using a Pore-Network Model

Transport in Porous Media - For improved operating conditions of a polymer electrolyte membrane (PEM) fuel cell, a sophisticated water management is crucial. Therefore, it is necessary to...