Influence of oral fatty applications on biochemical indicators of inflammation and dysbiosis in the tissues of the rat mouth

Background. The negative impact on the body of high-fat nutrition largely depends on the fatty acid composition of edible fats and the presence of peroxidation products in them, which are formed during heat treatment. Despite the considerable number of studies on this issue, it remains unclear the nature of the influence of different dietary fats on the condition of the tissues of the oral cavity. The purpose of this study was to clarify this issue Methods. Ordinary (high-linoleic) sunflower oil, high-oleic sunflower oil and butter in the native state and after heat treatment were used. The experiments were carried out on 35 white rats with an average weight of 252±15 g, who were given oral applications of the above fats at a dose of 0.5 ml per rat for 3 days. After rat killing on the 4th day, the content of malondialdehyde (MDA), the activity of elastase, urease, lysozyme and catalase were determined in the cheek mucosa homogenate and in the gums. The degree of dysbiosis was calculated by the ratio of the relative activities of urease and lysozyme. The antioxidant-prooxidant API index was calculated from the ratio of catalase activity and MDA content Results. Oral applications of native and heat-treated oils cause a decrease in the MDA content in both tissues with the exception of heat-treated butter, applications of which do not reduce the MDA level. Applications of heat-treated oils increase the activity of elastase in the gums, and heat-treated sunflower oil in the cheek mucosa. Applications of native and heat-treated oils reduce the activity of catalase in the cheek and gums. The API index increases in the gums under the action of native oils and decreases under the action of thermally processed oils. Applications of butter (native and heat-treated) significantly reduce the activity of urease in the cheek mucosa. Sunflower and high-oleic sunflower oils tend to increase the activity of urease, the least pronounced for the latter. All oils except high-oleic sunflower, reduce the activity of lysozyme in both tissues and all oils increase the degree of dysbiosis (except butter in the cheek mucosa). The content of diene conjugates after heat treatment increased the most in butter, and the least in high-oleic sunflower oil. Conclusion. Oral applications of fats cause a decrease in the formation of active forms of oxygen in the tissues of the oral cavity, which causes the development of dysbiosis and inflammatory processes

In situ TEM observation of the Boudouard reaction: multi-layered graphene formation from CO on cobalt nanoparticles at atmospheric pressure

Using a MEMS nanoreactor in combination with a specially designed in situ Transmission Electron Microscope (TEM) holder and gas supply system, we imaged the formation of multiple layers of graphene encapsulating a cobalt nanoparticle, at 1 bar CO:N2 (1:1) and 500 °C. The cobalt nanoparticle was imaged live in a TEM during the Boudouard reaction. The in situ/operando TEM studies give insight into the behaviour of the catalyst at the nanometer-scale, under industrially relevant conditions. When switching from Fischer-Tropsch syngas conditions (CO:H2:N2 1:2:3 at 1 bar) to CO-rich conditions (CO:N2 1:1 at 1 bar), we observed the formation of multi-layered graphene on Co nanoparticles at 500 °C. Due to the high temperature, the surface of the Co nanoparticles facilitated the Boudouard reaction, causing CO dissociation and the formation of layers of graphene. After the formation of the first patches of graphene at the surface of the nanoparticle, more and more layers grew over the course of about 40 minutes. In its final state, around 10 layers of carbon capped the nanoparticle. During this process, the carbon shell caused mechanical stress in the nanoparticle, inducing permanent deformation. © The Royal Society of Chemistry 2017

Tailoring the oxidation state of cobalt through halide functionality in sol-gel silica

The functionality or oxidation state of cobalt within a silica matrix can be tailored through the use of cationic surfactants and their halide counter ions during the sol-gel synthesis. Simply by adding surfactant we could significantly increase the amount of cobalt existing as Co3O4 within the silica from 44% to 77%, without varying the cobalt precursor concentration. However, once the surfactant to cobalt ratio exceeded 1, further addition resulted in an inhibitory mechanism whereby the altered pyrolysis of the surfactant decreased Co3O4 production. These findings have significant implications for the production of cobalt/silica composites where maximizing the functional Co3O4 phase remains the goal for a broad range of catalytic, sensing and materials applications

Correlation between Fischer-Tropsch catalytic activity and composition of catalysts

This paper presents the synthesis and characterization of monometallic and bimetallic cobalt and iron nanoparticles supported on alumina. The catalysts were prepared by a wet impregnation method. Samples were characterized using temperature-programmed reduction (TPR), temperature-programmed oxidation (TPO), CO-chemisorption, transmission electron microscopy (TEM), field emission scanning electron microscopy (FESEM-EDX) and N2-adsorption analysis. Fischer-Tropsch synthesis (FTS) was carried out in a fixed-bed microreactor at 543 K and 1 atm, with H2/CO = 2 v/v and space velocity, SV = 12L/g.h. The physicochemical properties and the FTS activity of the bimetallic catalysts were analyzed and compared with those of monometallic cobalt and iron catalysts at similar operating conditions

Critical Grain Size of Fine Aggregates in the View of the Rheology of Mortar

The aim of this research was to investigate the validity of the Krieger-Dougherty model as a quantitative model to predict the viscosity of mortar depending on various aggregate sizes. The Krieger-Dougherty model reportedly predicted the viscosity of a suspension, which includes cement-based materials. Concrete or mortar incorporates natural resources, such as sand and gravel, referred to as aggregates, which can make up as much as 80% of the mixture by volume. Cement paste is a suspending medium at fresh state and then becomes a binder to link the aggregate after its hydration. Both the viscosity of the suspending medium and the characteristics of the aggregates, therefore, control the viscosity of the cement-based materials. In this research, various sizes and gradations of fine aggregate samples were prepared. Workability and rheological properties were measured using fresh-state mortar samples and incorporating the various-sized fine aggregates. Yield stress and viscosity measurements were obtained by using a rheometer. Based on the packing density of each fine aggregate sample, the viscosity of the mortar was predicted with the Krieger-Dougherty model. In addition, further adjustments were made to determine the water absorption of fine aggregates and was transferred from successful experiment to simulation for more accurate prediction. It was also determined that both yield stress and viscosity increase when the fine aggregate mean size decreases throughout the mix. However, when the mean size of the fine aggregates is bigger than 0.7 mm, the yield stress is not affected by the size of the fine aggregate. Additionally, if aggregate grains get smaller up to 0.3 mm, their water absorption is critical to the rheological behavior

Small Molecule Activation by Uranium Tris(aryloxides): Experimental and Computational Studies of Binding of N-2, Coupling of CO, and Deoxygenation Insertion of CO2 under Ambient Conditions

Previously unanticipated dinitrogen activation is exhibited by the well-known uranium tris(aryloxide) U(ODtbp)(3), U(OC6H3-Bu-2(t)-2,6)(3), and the tri-tert-butyl analogue U(OTtbp)(3), U(OC6H2-Bu-3(t)-2,4,6)(3), in the form of bridging, side-on dinitrogen complexes [U(OAr)(3)](2)(mu-eta(2):eta(2)-N-2), for which the tri-tert-butyl N-2 complex is the most robust U-2(N-2) complex isolated to date. Attempted reduction of the tris(aryloxide) complex under N-2 gave only the potassium salt of the uranium(III) tetra(aryloxide) anion, K[U(OAr)(4)], as a result of ligand redistribution. The solid-state structure is a polymeric chain formed by each potassium cation bridging two arenes of adjacent anions in an eta(6) fashion. The same uranium tris(aryloxides) were also found to couple carbon monoxide under ambient conditions to give exclusively the ynediolate [OCCO](2-) dianion in [U(OAr)(3)](2)(mu-eta(1):eta(1)-C2O2), in direct analogy with the reductive coupling recently shown to afford [U{N(SiMe3)(2)}(3)](2)(mu-eta(1):eta(1)-C2O2). The related U-III complexes U{N(SiPhMe2)(2)}(3) and U{CH(SiMe3)(2)}(3) however do not show CO coupling chemistry in our hands. Of the aryloxide complexes, only the U(OC6H2-Bu-3(t)-2,4,6)(3) reacts with CO2 to give an insertion product containing bridging oxo and aryl carbonate moieties, U-2(OTtbp)(4)(mu-O)(mu-eta(1):eta(1)-O2COC6H2-Bu-3(t)-2,4,6)(2), which has been structurally characterized. The presence of coordinated N-2 in [U(OTtbp)(3)](2)(N-2) prevents the occurrence of any reaction with CO2, underscoring the remarkable stability of the N-2 complex. The di-tert-butyl aryloxide does not insert CO2, and only U(ODtbp)(4) was isolated. The silylamide also reacts with carbon dioxide to afford U(OSiMe3)(4) as the only uranium-containing material. GGA and hybrid DFT calculations, in conjunction with topological analysis of the electron density, suggest that the U-N-2 bond is strongly polar, and that the only covalent U -> N-2 interaction is pi backbonding, leading to a formal (U-IV)(2)(N-2)(2-) description of the electronic structure. The N-N stretching wavenumber is preferred as a metric of N-2 reduction to the N-N bond length, as there is excellent agreement between theory and experiment for the former but poorer agreement for the latter due to X-ray crystallographic underestimation of r(N-N). Possible intermediates on the CO coupling pathway to [U(OAr)(3)](2)(mu-C2O2) are identified, and potential energy surface scans indicate that the ynediolate fragment is more weakly bound than the ancillary ligands, which may have implications in the development of low-temperature and pressure catalytic CO chemistry