Microstructure and Rheological Properties of Composites of Potato Starch Granules and Amylose: A Comparison of Observed and Predicted Structures

Potato starch granules were gelatinised in amylose solution to study the effect of adding amylose to a highswelling granular starch system. The effects of varying the amount of potato starch from 1-10% , added to a solution of 2% amylose, were studied by means of dynamic viscoelastic measurements and light microscopy. The granules gelatinised in amylose solution had a lower degree of swelling than those gelatinised in water. The restricted swelling in amylose was reflected in a decrease in the complex shear modulus (G*) at 75\u27C. GeJatinisation in 2% amylopectin also caused a decrease in G*, but gelatinisation in 2% 0-glucose did not affect the rheological behaviour. Microstructural analysis showed that the added amylose was present outside the granules after swelling, whereas the inherent amylose from the potato starch seemed to have diffused main] y to the inner aqueous centre of the granules. The mixed potato starch/amylose systems showed a fast gelation comparable to that of cereal starch. The results were analysed by a model predicting the shear modulus of aqueous biphasic gels. When the system is regarded as a continuous network of added amylose with dispersed potato starch granules, the results from both microscopy and rheology are in excellent agreement with the model at potato starch concentrations below 6%. As the potato starch concentration was raised, the high swelling potential of the potato starch granules led to partial disruption of the continuous amylose network. The results imply that the inherent amylose from potato starch did not contribute to the gel strength caused by the added solubilised amylose

Many competing ceria (110) oxygen vacancy structures: from small to large supercells

We present periodic “DFT+U” studies of single oxygen vacancies on the CeO2(110) surface using a number of different supercells, finding a range of different local minimum structures for the vacancy and its two accompanying Ce(III) ions. We find three different geometrical structures in combination with a variety of different Ce(III) localization patterns, several of which have not been studied before. The desired trapping of electrons was achieved in a two-stage optimization procedure. We find that the surface oxygen nearest to the vacancy either moves within the plane towards the vacancy, or rises out of the surface into either a symmetric or an unsymmetric bridge structure. Results are shown in seven slab geometry supercells, p(2 × 1), p(2 × 2), p(2 × 3), p(3 × 2), p(2 × 4), p(4 × 2), and p(3 × 3), and indicate that the choice of supercell can affect the results qualitatively and quantitatively. An unsymmetric bridge structure with one nearest and one next-nearest neighbour Ce(III) ion (a combination of localizations not previously found) is the ground state in all (but one) of the supercells studied here, and the relative stability of other structures depends strongly on supercell size. Within any one supercell the formation energies of the different vacancy structures differ by up to 0.5 eV, but the same structure can vary by up to ∼1 eV between supercells. Furthermore, finite size scaling suggests that the remaining errors (compared to still larger supercells) can also be ∼1 eV for some vacancy structures

Correlations between magnetic properties and bond formation in Rh–MgO(001)

We present the results of first principles calculations for the magnetism of Rh adlayers on MgO (001), at three different adsorption sites and three different coverages, corresponding to 1, 1/2 and 1/8 monolayers. Finite magnetization is found in all cases except that of 1 Rh monolayer above the oxygen site, which is also the most stable. We examine how the magnetization changes as a function of the Rh-surface distance and relate this to changes in the real space charge density and in the density of states (DOS) as the Rh adlayer interacts with the surface. We find that increasing either the Rh-Rh interaction strength or the R h-surface interaction strength leads to reduced magnetization, while increasing the former drives a crossover from localized (atomic) to itinerant magnetism. Neither the magnetic transition itself, nor the localized-to-itinerant magnetism crossover, is found to be directly related to the formation of Rh- surface bonds. From a practical point of view, we predict that magnetism in the Rh-MgO(001) system is most likely to be found experimentally at reduced coverages and at low temperatures

Description of polarons in ceria using Density Functional Theory

The performance of various density functional theory (DFT) functionals in reproducing the localization of Ce4f electrons to form polarons in cerium dioxide (ceria) is studied. It is found that LDA+U with U=6eV provides the best description, followed by GGA+U with U=5 eV. Hybrids perform worse, with PBE0 better than HSE06 and HSE03. It is also demonstrated that the improvement in the description of the polarons obtained from LDA+U and GGA+U is due primarily to the effect the U has on the filled Ce4f states, but the improvement obtained using the hybrids is primarily due to their effect on the empty states. This difference can be expected to strongly impact some detailed predictions for the properties of ceria obtained using the two classes of functional

B3LYP calculations of cerium oxides RID C-3994-2009

In this paper we evaluate the performance of density functional theory with the B3LYP functional for calculations on ceria (CeO2) and cerium sesquioxide (Ce2O3). We demonstrate that B3LYP is able to describe CeO2 and Ce2O3 reasonably well. When compared to other functionals, B3LYP performs slightly better than the hybrid functional PBE0 for the electronic properties but slightly worse for the structural properties, although neither performs as well as LDA+U(U=6 eV) or PBE+U(U=5 eV).We also make an extensive comparison of atomic basis sets suitable for periodic calculations of these cerium oxides. Here we conclude that there is currently only one type of cerium basis set available in the literature that is able to give a reasonable description of the electronic structure of both CeO2 and Ce2O3. These basis sets are based on a 28 electron effective core potential (ECP) and 30 electrons are attributed to the valence space of cerium. Basis sets based on 46 electron ECPs fail for these materials

Cu-doped ceria: Oxygen vacancy formation made easy

DFT + U calculations of Cu-doped bulk ceria are presented. The first oxygen vacancy in Cu-doped ceria forms almost spontaneously and the second vacancy is also easily created. Whether zero, one or two oxygen vacancies, the Cu dopant is in the form Cu(+II), and prefers to be 4-coordinated in a close to planar structure. Charge compensation, structural relaxation and available Cu–O states all play roles in lowering the O vacancy formation energies, but to different degrees when the first and second oxygen vacancies are formed. The Cu-doped ceria(1 1 1) surface system behaves in a similar fashion

Immunotherapy with tolerogenic apolipoprotein B-100–loaded dendritic cells attenuates atherosclerosis in hypercholesterolemic mice

BACKGROUND: Atherosclerosis is a chronic inflammatory disease characterized by a massive intimal accumulation of low-density lipoprotein that triggers chronic vascular inflammation with an autoimmune response to low-density lipoprotein components. METHODS AND RESULTS: To dampen the inflammatory component of atherosclerosis, we injected hypercholesterolemic huB100(tg) × Ldlr(-/-) mice (mice transgenic for human apolipoprotein B100 [ApoB100] and deficient for the low-density lipoprotein receptor) intravenously with dendritic cells (DCs) that had been pulsed with the low-density lipoprotein protein ApoB100 in combination with the immunosuppressive cytokine interleukin-10. DCs treated with ApoB100 and interleukin-10 reduced proliferation of effector T cells, inhibited production of interferon-γ, and increased de novo generation of regulatory T cells in vitro. Spleen cells from mice treated with DCs plus ApoB100 plus interleukin-10 showed diminished proliferative responses to ApoB100 and significantly dampened T-helper 1 and 2 immunity to ApoB100. Spleen CD4(+) T cells from these mice suppressed activation of ApoB100-reactive T cells in a manner characteristic of regulatory T cells, and mRNA analysis of lymphoid organs showed induction of transcripts characteristic of these cells. Treatment of huB100(tg) × Ldlr(-/-) mice with ApoB100-pulsed tolerogenic DCs led to a significant (70%) reduction of atherosclerotic lesions in the aorta, with decreased CD4(+) T-cell infiltration and signs of reduced systemic inflammation. CONCLUSIONS: Tolerogenic DCs pulsed with ApoB100 reduced the autoimmune response against low-density lipoprotein and may represent a novel possibility for treatment or prevention of atherosclerosis.Swedish Research CouncilFoundation for Strategic ResearchVinnovaSwedish Heart-Lung FoundationEuropean Union (AtheroRemo integrated project)Stockholm County CouncilPublishe