Magnesium-Catalyzed Asymmetric Thia-Michael Addition to α,β-Unsaturated Ketones

We demonstrate the application of chiral magnesium complexes in an asymmetric carbon-sulfur bond-forming reaction. Enantioselective and cost-effective methodology under mild condition for the thia-Michael addition, utilizing an in situ generated chiral dinuclear magnesium-ProPhenol complex, has been developed. The versatility of this protocol is demonstrated with a broad range of thiol nucleophiles and a wide selection of enones. Enantioenriched β-ketosulfides are obtained in good to excellent yields and moderate to excellent enantioselectivity. The presented catalytic system exhibits excellent tolerance for structurally different substrates while maintaining high enantioselectivity. This observation aligns with proposed mechanism, wherein the sulfur atom coordinates to the catalyst in close proximity to the reaction center.     

Analysis of the Site-Specific Myoglobin Modifications in the Melibiose-Derived Novel Advanced Glycation End-Product

MAGE (melibiose-derived advanced glycation end-product) is the glycation product generated in the reaction of a model protein with melibiose. The in vivo analog accumulates in several tissues; however, its origin still needs explanation. In vitro MAGE is efficiently generated under dry conditions in contrast to the reaction carried in an aqueous solvent. Using liquid chromatography coupled with mass spectrometry, we analyzed the physicochemical properties and structures of myoglobin glycated with melibiose under different conditions. The targeted peptide analysis identified structurally different AGEs, including crosslinking and non-crosslinking modifications associated with lysine, arginine, and histidine residues. Glycation in a dry state was more efficient in the formation of structures containing an intact melibiose moiety (21.9%) compared to glycation under aqueous conditions (15.6%). The difference was reflected in characteristic fluorescence that results from protein structural changes and impact on a heme group of the model myoglobin protein. Finally, our results suggest that the formation of in vitro MAGE adduct is initiated by coupling melibiose to a model myoglobin protein. It is confirmed by the identification of intact melibiose moieties. The intermediate glycation product can further rearrange towards more advanced structures, including cross-links. This process can contribute to a pool of AGEs accumulating locally in vivo and affecting tissue biology.     

Congo Red as a Supramolecular Carrier System for Doxorubicin: An Approach to Understanding the Mechanism of Action

The uptake and distribution of doxorubicin in the MCF7 line of breast-cancer cells were monitored by Raman measurements. It was demonstrated that bioavailability of doxorubicin can be significantly enhanced by applying Congo red. To understand the mechanism of doxorubicin delivery by Congo red supramolecular carriers, additional monolayer measurements and molecular dynamics simulations on model membranes were undertaken. Acting as molecular scissors, Congo red particles cut doxorubicin aggregates and incorporated them into small-sized Congo red clusters. The mixed doxorubicin/Congo red clusters were adsorbed to the hydrophilic part of the model membrane. Such behavior promoted transfer through the membrane.     

ERAP/HLA-C and KIR Genetic Profile in Couples with Recurrent Implantation Failure

Proper embryo implantation depends on the tolerance of the maternal immune system to the fetus and its foreign paternal antigens. During implantation and early pregnancy, the dominant leukocytes in the uterus are uterine NK cells, expressing killer immunoglobulin-like receptors (KIR). KIRs recognize human leukocyte antigens (HLA-C) on the human trophoblast inherited from the father and mother. The antigenic peptides presented by the HLA are formed via their cleavage by endoplasmic reticulum aminopeptidases ERAP1 and ERAP2. The aim of this study was to assess the association of combined KIR genes and their HLA-C ligands, as well as ERAP1 and ERAP2 polymorphisms with recurrent implantation failure after in vitro fertilization (RIF). We tested 491 couples who underwent in vitro fertilization (IVF) and 322 fertile couples. Genotype CC rs27044 ERAP1 in female with a male’s HLA-C1C1 or HLA-C1C2 protected from RIF (p/p_corr. = 0.005/0.044, OR = 0.343; p/p_corr. = 0.003/0.027, OR = 0.442, respectively). Genotype TT rs30187 ERAP1 in female with a male’s HLA-C1C2 genotype increased the risk of RIF. Summarizing, in the combination of female ERAP1 and an HLA-C partner, the rs30187 C>T and rs27044 C>G polymorphisms play an important role in implantation failure.     

Colossal negative magnetoresistance from hopping in insulating ferromagnetic semiconductors

Ferromagnetic semiconductor Ga_1–xMn_xAs_1–yP_y thin films go through a metal–insulator transition at low temperature where electrical conduction becomes driven by hopping of charge carriers. In this regime, we report a colossal negative magnetoresistance (CNMR) coexisting with a saturated magnetic moment, unlike in the traditional magnetic semiconductor Ga_1–xMn_xAs. By analyzing the temperature dependence of the resistivity at fixed magnetic field, we demonstrate that the CNMR can be consistently described by the field dependence of the localization length, which relates to a field dependent mobility edge. This dependence is likely due to the random environment of Mn atoms in Ga_1–xMn_xAs_1–yP_y which causes a random spatial distribution of the mobility that is suppressed by an increasing magnetic field.     

Influence of oxide scales on heat transfer in secondary cooling zones in the continuous casting process,part 2: determination of material properties of oxide scales on steel under spray-water cooling conditions

In order to model heat transfer from the slab to the cooling agent in the continuous casting process the thermophysical properties of the surface layer must be taken into account. For this purpose thermal conductivities and thermal diffusivities of wustite as well as of two carbon steels were measured. The oxide scale growth for six steels was measured as a function of time and at temperatures between 900 and 1200°C in air and in steam. Complex heterogeneous oxide scales were examined by optical and scanning electron microscopy, by SIMS, as well as by Mössbauer spectroscopy. Segregation of alloying elements in the metal-oxide contact zone was found. Cracks due to thermal stresses result in spalling of the scale. Therefore, a straightforward use of the data for process modelling can principally not be recommended without restrictions.     

On reliability of a certain elementary safety system

The paper deals with the determination of reliability of an elementary safety system which consists of two identical elements used simultaneously (hot reserve) whereas for correct system operation is enough when one out of it is good. The operation time is so short that is assumed it is of zero length. Knowing the reliability of element, reliability of system is found.     

A three-prong strategy to develop functional food using protein isolates recovered from chicken processing by-products with isoelectric solubilization/precipitation

BACKGROUND: Skin‐on bone‐in chicken drumsticks were processed with isoelectric solubilization/precipitation to recover muscle proteins. The drumsticks were used as a model for dark chicken meat processing by‐products. The main objective of this study was conversion of dark chicken meat processing by‐products to restructured functional food product. An attempt was made to develop functional food product that would resemble respective product made from boneless skinless chicken breast meat. A three‐prong strategy to address diet‐driven cardiovascular disease (CVD)with a functional food was used in this study. The strategy included addition of three ingredients with well‐documented cardiovascular benefits: (i) ω‐3 polyunsaturated fatty acid‐rich oil (flaxseed‐algae, 9:1); (ii) soluble fiber; and (iii) salt substitute. Titanium dioxide, potato starch, polyphosphate, and transglutaminase were also added. The batters were formulated and cooked resulting in heat‐set gels. RESULTS: Color (L*a*b*), texture (torsion test, Kramer shear test, and texture profile analysis), thermal denaturation (differential scanning calorimetry), and gelation (dynamic rheology) of chicken drumstick gels and chicken breast gels were determined and compared. Chicken drumstick gels generally had comparable color and texture properties to the gels made from chicken breast meat. The endothermic transition (thermal denaturation) of myosin was more pronounced and gelation properties were better for the drumstick gels. CONCLUSION: This study demonstrated a feasibility to develop functional food made of muscle proteins recovered with isoelectric solubilization/precipitation from low‐value dark chicken meat processing by‐products. The functional food developed in this study was enriched with CVD‐beneficial nutrients and had comparable instrumental quality attributes to respective products made of chicken breast meat. Although the results of this study point towards the potential for a novel, marketable functional food product, sensory tests and storage stability study are recommended. Copyright © 2012 Society of Chemical Industry     

Dielectric and viscoelastic studies of curing epoxy-amine model systems

Summary The curing of different epoxy-amine model systems which present only gelification and/or vitrification processes has been followed with the evolution of their viscoelastic and electrical behaviours during the network formation. Some attempts are performed to correlate the significant evolution of the mechanical and electrical parameters with the physico-chemical changes of these well defined chemical systems during their hardening and complete curing.     

A numerical Hartree-Fock program for diatomic molecules

This paper describes an algorithm and a computer program which solves numerically (virtually exactly) equations of the restricted open-shell Hartree-Fock and Hartree-Fock-Slater model for diatomic molecules