Metal-free, one-pot synthesis of 2-styrylquinolines via Friedländer annulation and sp3 C-H activation using 1,3-dimethylurea and L-tartaric acid (3:1) as deep eutectic solvent†

A simple, metal-free protocol is reported for the one-pot synthesis of 2-styrylquinolines using a combination of 1,3-dimethyl urea (1,3-DMU) and L-tartaric acid (LTA) (in 3:1 ratio) as deep eutectic solvent...

A Peridynamic Model for Crevice Corrosion Damage

A new peridynamic (PD) model for crevice corrosion damage is introduced and cross-validated with experimental results reported in the literature. The model defines a simple metal ion concentration-dependent corrosion rate along the metal-electrolyte interface. Crevice problems have ratios of gap-to-length of 1/100 or lower. To increase the computational efficiency when having a domain with an extreme aspect ratio, the PD formulation with spherical horizons is modified to accommodate arbitrary-shape horizons. The model is validated against experimental results on immersed bolted washers. The PD simulations predict the observed corrosion kinetics, and the deepest corrosion trenches form at a critical distance from the mouth of the crevice. The location of the most severe corrosion attack does not have to be specified as an input. Instead, it results directly from solving the problem with PD. The evolution of crevice corrosion damage is autonomous in PD, and only the geometry, initial, and boundary conditions control the evolution of the corrosion process.

Ionic Liquids based on the Concept of Melting Point Lowering due to Ethoxylation

Most of the commonly used Ionic Liquids (ILs) contain bulky organic cations with suitable anions. With our COMPLET (Concept of Melting Point Lowering due to Ethoxylation), we follow a different approach. We use simple, low-toxic, cheap and commercially available anions of the type Cx(EO)yCH2COO– to liquefy presumably any simple metal ion, independently of its charge. In the simplest case, the cation can be sodium or lithium, but synthesis of Ionic Liquids is also possible with cations of higher valences such as transition or rare earth metals. Anions with longer alkyl chains are surface active and form surface active ionic liquids (SAILs), which combine properties of ionic and nonionic surfactants at room temperature. They show significant structuring even in their pure state, i.e. in the absence of water or any other added solvent.

Smart Antibody-Conjugated Gold Nanoparticles for Bioengineered Polymers

Au and Ag nanoparticles (NP) were synthesized using a green method that allows control of both particle size and surface chemistry. The gold and silver nanoparticles were coated with a fluorescent goat anti-body IgG that chemically incorporated the nanoparticles and the internalization behavior was studied by phagocytosis in murine peritoneal macrophages. Despite that, in principle, the presence of a simple metal induces a greater degree of cell death following the particle uptake, our results suggest that a large part of the silver and gold nanoparticles enter cells by means other than endocytosis and phagocytosis, as truly intelligent nanoparticles. This represents a potential for immunotherapy and studies to modulate the innate immune response as truly smart nanoparticles.

Oxidation of Organic Compounds with Peroxides Catalyzed by Polynuclear Metal Compounds

The review describes articles that provide data on the synthesis and study of the properties of catalysts for the oxidation of alkanes, olefins, and alcohols. These catalysts are polynuclear complexes of iron, copper, osmium, nickel, manganese, cobalt, vanadium. Such complexes for example are: [Fe2(HPTB)(m-OH)(NO3)2](NO3)2·CH3OH·2H2O, where HPTB-¼N,N,N0,N0-tetrakis(2-benzimidazolylmethyl)-2-hydroxo-1,3-diaminopropane; complex [(PhSiO1,5)6]2[CuO]4[NaO0.5]4[dppmO2]2, where dppm-1,1-bis(diphenylphosphino)methane; (2,3-η-1,4-diphenylbut-2-en-1,4-dione)undecacarbonyl triangulotriosmium; phenylsilsesquioxane [(PhSiO1.5)10(CoO)5(NaOH)]; bi- and tri-nuclear oxidovanadium(V) complexes [{VO(OEt)(EtOH)}2(L2)] and [{VO(OMe)(H2O)}3(L3)]·2H2O (L2 = bis(2-hydroxybenzylidene)terephthalohydrazide and L3 = tris(2-hydroxybenzylidene)benzene-1,3,5-tricarbohydrazide); [Mn2L2O3][PF6]2 (L = 1,4,7-trimethyl-1,4,7-triazacyclononane). For comparison, articles are introduced describing catalysts for the oxidation of alkanes and alcohols with peroxides, which are simple metal salts or mononuclear metal complexes. In many cases, polynuclear complexes exhibit higher activity compared to mononuclear complexes and exhibit increased regioselectivity, for example, in the oxidation of linear alkanes. The review contains a description of some of the mechanisms of catalytic reactions. Additionally presented are articles comparing the rates of oxidation of solvents and substrates under oxidizing conditions for various catalyst structures, which allows researchers to conclude about the nature of the oxidizing species. This review is focused on recent works, as well as review articles and own original studies of the authors.

Predicting ligand removal energetics in thiolate-protected nanoclusters from molecular complexes

Density Functional Theory (DFT) calculations reveal that ligand removal energetics in thiolate-protected nanoclusters can be accurately predicted through simple metal–thiolate complex calculations.