Effect of Ester Moiety on Structural Properties of Binary Mixed Monolayers of Alpha-Tocopherol Derivatives with DPPC

Phospholipid membranes are ubiquitous components of cells involved in physiological processes; thus, knowledge regarding their interactions with other molecules, including tocopherol ester derivatives, is of great importance. The surface pressure–area isotherms of pure α-tocopherol (Toc) and its derivatives (oxalate (OT), malonate (MT), succinate (ST), and carbo analog (CT)) were studied in Langmuir monolayers in order to evaluate phase formation, compressibility, packing, and ordering. The isotherms and compressibility results indicate that, under pressure, the ester derivatives and CT are able to form two-dimensional liquid-condensed (LC) ordered structures with collapse pressures ranging from 27 mN/m for CT to 44 mN/m for OT. Next, the effect of length of ester moiety on the surface behavior of DPPC/Toc derivatives’ binary monolayers at air–water interface was investigated. The average molecular area, elastic modulus, compressibility, and miscibility were calculated as a function of molar fraction of derivatives. Increasing the presence of Toc derivatives in DPPC monolayer induces expansion of isotherms, increased monolayer elasticity, interrupted packing, and lowered ordering in monolayer, leading to its fluidization. Decreasing collapse pressure with increasing molar ratio of derivatives indicates on the miscibility of Toc esters in DPPC monolayer. The interactions between components were analyzed using additivity rule and thermodynamic calculations of excess and total Gibbs energy of mixing. Calculated excess area and Gibbs energy indicated repulsion between components, confirming their partial mixing. In summary, the mechanism of the observed phenomena is mainly connected with interactions of ionized carboxyl groups of ester moieties with DPPC headgroup moieties where formed conformations perturb alignment of acyl chains, resulting in increasing mean area per molecule, leading to disordering and fluidization of mixed monolayer

Synthesis and Biological Evaluation of α-Tocopherol Derivatives as Potential Anticancer Agents

α-Tocopheryl succinate (α-TS) and α-tocopheryloxyacetic acid (α-TEA) are potent inducers of apoptosis in cancer cells and efficient suppressors of tumors in experimental model cancer cell lines. They exhibit selective cytotoxicity against tumor cells and very limited or no toxicity toward nonmalignant cells. In the present work, a series of new α-tocopherol derivatives were synthesized as analogs of α-TS and α-TEA. The cytotoxic activity of obtained compounds was tested using three human cancer cell lines, including chronic lymphoblastic leukemia (CEM), breast adenocarcinoma (MCF7), cervical adenocarcinoma (HeLa), and normal human fibroblasts (BJ). The introduction of an alkyl substituent into the ether-linked acetic acid moiety in α-TEA increased anticancer activity. α-Tocopheryloxy-2-methylpropanoic acid with two additional geminal methyl groups was more active against CEM cells compared to α-TEA and non-toxic to normal cells. In order to acquire a deeper understanding of the biological activity of synthesized compounds, a molecular docking study was also conducted. Our research confirmed that vitamin E derivatives are interesting and valuable compounds in terms of their potential therapeutic use as anticancer agents

Synthesis, DFT Calculations, and In Vitro Antioxidant Study on Novel Carba-Analogs of Vitamin E

Vitamin E is the most active natural lipophilic antioxidant with a broad spectrum of biological activity. α-Tocopherol (α-T), the main representative of the vitamin E family, is a strong inhibitor of lipid peroxidation as a chain-breaking antioxidant. Antioxidant and antiradical properties of vitamin E result from the presence of a phenolic hydroxyl group at the C-6 position. Due to stereoelectronic effects in the dihydropyranyl ring, the dissociation enthalpy for phenolic O–H bond (BDEOH) is reduced. The high chain-breaking reactivity of α-T is mainly attributed to orbital overlapping of the 2p-type lone pair on the oxygen atom (O1) in para position to the phenolic group, and the aromatic π-electron system. The influence of the O1 atom on the antioxidant activity of vitamin E was estimated quantitatively. The all-rac-1-carba-α-tocopherol was synthesized for the first time. Along with model compounds, 1-carba-analog of Trolox and its methyl ester were screened for their in vitro antioxidant activity by inhibition of styrene oxidation, and for the radical-reducing properties by means of 2,2-diphenyl-1-picrylhydrazyl free radical (DPPH) scavenging assay. To study the antioxidant activity, density functional theory (DFT) was also applied. Reaction enthalpies related to HAT (hydrogen atom transfer), SET–PT (sequential electron transfer—proton transfer), and SPLET (sequential proton loss—electron transfer) mechanisms were calculated

Construction of Recurrence Relations for the Jacobi Coefficients, Using Maple

Introduction In the field of numerical analysis, one frequently needs to determine the coefficients a (ff;fi) k [f ] in the expansion of a given function f into a uniformly convergent series of Jacobi polynomials, f(x) = 1 X k=0 a (ff;fi) k [f ] P (ff;fi) k (x) (\Gamma1 x 1); (1) where P (ff;fi) k (x) (ff; fi ? \Gamma1) is the usual notation for the kth Jacobi polynomial (cf. [2], Vol. II, x10.8, or [5], Vol. I, Ch. 8). The particular case of ff = fi = \Gamma 1 2 is c

Studying road restraint systems to develop new guidelines

Key to understanding the needs and tools of road infrastructure management for preventing run-off-road crashes or minimising their consequences, is to identify the hazards and sources of hazards caused by wrong or improper use of road safety devices and identify errors in the design, structure, construction and operation of road safety devices. Studying such an extended scope of the problem required fieldwork and surveys with road authorities, designers, road safety auditors and road maintenance services. An outline of new guidelines could only be developed after understanding the effects of restraint systems, the design, additional elements, type of road and safety barrier location on a road or engineering structure and the road and traffic conditions on their functionality and safety. The paper will present the preliminary results of this research (research project – ROSE). After an in-depth study of the literature, a comparative analysis was made of selected guidelines and principles of using road safety devices in nearly 40 countries from different continents. The parameters which were identified to influence the choice of safety barriers were divided into thematic groups. Two main categories were identified based on the theory of risk: probability and consequences. Probability included factors which, if present in the road cross-section, may make an accident more likely. Consequences included factors which increase the severity and consequences of an accident. One way to understand the functionality of road safety devices is to build numerical models and conduct simulation tests of virtual crash tests. While the literature on numerical road safety device studies includes plenty of detailed works, there are no cross-cutting papers to summarise the partial results of the work of many research teams and condense the theoretical formulations and numerical implementations for the purposes of crash test analysis. The paper will present a proposed approach to such work along with preliminary results of numerical studies for selected problems using road safety devices such as safety barriers on horizontal curves, the effect of kerbs on bridges or the location of obstacles within the barrier’s working width. The paper will discuss assumptions to a methodology of numerical models, calculations and automated processing of data to help with assessing the functionality of the devices. The paper will outline the design of the method for selecting optimal road safety devices. This will be based on device selection factors, fieldwork, surveys and simulations. The models and procedures used in the method will help to identify and link different sources of hazard when using road safety devices to tackle a specific event and will help to identify the weaknesses in the safe use of types of road safety devices. The method will take account of the effect of different factors on optimising device selection. They are: types of hazard sources, road class and its parameters, road traffic parameters (volume, structure, speed). The method will be further developed in new research

The effects of vehicle restraint systems on road safety

Key to understanding the needs and tools of road infrastructure management for preventing runoff-road crashes or minimising their consequences, is to identify the hazards and sources of hazards caused by wrong or improper use of road safety devices and identify errors in the design, structure, construction and operation of road safety devices. Studying such an extended scope of the problem required fieldwork and surveys with road authorities, designers, road safety auditors and road maintenance services. An outline of new guidelines could only be developed after understanding the effects of restraint systems, the design, additional elements, type of road and safety barrier location on a road or engineering structure and the road and traffic conditions on their functionality and safety. The paper will present the preliminary results of this research (research project – ROSE). One way to understand the functionality of road safety devices is to build numerical models and conduct simulation tests of virtual crash tests. The article presents the scope of work conducted as part of an effort to develop new vehicle restraint system guidelines

Paramagnetism of cobalt-doped ZnO nanoparticles obtained by microwave solvothermal synthesis

Zinc oxide nanopowders doped with 1–15 mol % cobalt were produced by the microwave solvothermal synthesis (MSS) technique. The obtained nanoparticles were annealed at 800 °C in nitrogen (99.999%) and in synthetic air. The material nanostructure was investigated by means of the following techniques: X-ray diffraction (XRD), helium pycnometry density, specific surface area (SSA), inductively coupled plasma optical emission spectrometry (ICP-OES), extended X-ray absorption fine structure (EXAFS) spectroscopy, scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS) and with magnetometry using superconducting quantum interference device (SQUID). Irrespective of the Co content, nanoparticles in their initial state present a similar morphology. They are composed of loosely agglomerated spherical particles with wurtzite-type crystal structure with crystallites of a mean size of 30 nm. Annealing to temperatures of up to 800 °C induced the growth of crystallites up to a maximum of 2 μm in diameter. For samples annealed in high purity nitrogen, the precipitation of metallic α-Co was detected for a Co content of 5 mol % or more. For samples annealed in synthetic air, no change of phase structure was detected, except for precipitation of Co3O4 for a Co content of 15 mol %. The results of the magentometry investigation indicated that all as-synthesized samples displayed paramagnetic properties with a contribution of anti-ferromagnetic coupling of Co–Co pairs. After annealing in synthetic air, the samples remained paramagnetic and samples annealed under nitrogen flow showed a magnetic response under the influences of a magnetic field, likely related to the precipitation of metallic Co in nanoparticles