MII (M = Mn, Fe, Co, Ni and Cu) complexes with a chromone-derived neutral ligand: synthesis, structural characterization, photocatalytic and mycobacterial activity studies

The reaction of 2-(2-furyl)-3-hydroxychromone and nicotinoyl chloride produces a neutral ligand (L) which has nitrogen and oxygen donor atoms. Evidence of L polymorphism is discussed. The new molecule showed fluorescence...

Effect of Copper(II) Ion Binding by Porin P1 Precursor Fragments from Fusobacterium nucleatum on DNA Degradation

Fusobacterium nucleatum is one of the most notorious species involved in colorectal cancer. It was reported that numerous outer membrane proteins (OMP) are actively involved in carcinogenesis. In this paper, the structure and stability of certain complexes, as well as DNA cleavage and ROS generation by fragments of OMP, were investigated using experimental and theoretical methods. Mass spectrometry, potentiometry, UV-Vis, CD, EPR, gel electrophoresis and calculations at the density functional theory (DFT) level were applied. Two consecutive model peptides, Ac-AKGHEHQLE-NH2 and Ac-FGEHEHGRD-NH2, were studied. Both of these were rendered to form a variety of thermodynamically stable complexes with copper(II) ions. All of the complexes were stabilized, mainly due to interactions of metal with nitrogen and oxygen donor atoms, as well as rich hydrogen bond networks. It was also concluded that these complexes in the presence of hydrogen peroxide or ascorbic acid can effectively produce hydroxyl radicals and have an ability to cleave the DNA strands. Surprisingly, the second studied ligand at the micromolar concentration range causes overall DNA degradation.

Precursor Linear Self-Assembly Nonhydrolytic Sol-Gel Synthesis of Ba0.7Sr0.3TiO3 Ceramic Fibers

Ba0.7Sr0.3TiO3 ceramic fibers were synthesized via the precursor linear self-assembly nonhydrolytic sol-gel (NHSG) method, taking TiCl4 as the titanium source, anhydrous barium acetate and strontium acetate as the barium source and strontium source, anhydrous ethanol and glycol as the oxygen donor and solvent, respectively. The NHSG method promotes the formation of Ba–O–Ti and Sr–O–Ti through heterogeneous condensation. The bimolecular association structure of the reaction intermediate (chlorotitanium ethoxide) between ethanol and titanium tetrachloride facilitates the self-linear assembly of precursors. It also enables linear colloidal particle formation and excellent spinnability of the sol. The novel Ba0.7Sr0.3TiO3 ceramic fibers would promote the flexibility of electronic products.

Amine-modified silica for removing aspirin from water

The synthesis and structural characterisation (Fourier transform infrared, FTIR spectrometry, scanning electron microscopy, SEM and energy-dispersive X-ray, EDX) of amino-modified silicates (unloaded L1, and aspirin-loaded, L2) are reported. The optimal conditions for the extraction of aspirin from water by the modified silicate material were determined as a function of the mass of the extracting agent and the pH of the aqueous solution. The optimum mass was found to be 0.08–0.10 g with 99.9% removal of aspirin. Maximum extraction of aspirin by the material was observed at pH 4. The kinetics, the removal capacity of the material, as well as its recycling, were investigated. The results indicate that (i) the process is fast and (ii) the removal capacity for the drug is greater than that of previously reported materials and (iii)the modified silicate can be easily recycled. These data along with the low cost involved in the production of the material led to the conclusion that the modified silicate has the required potential for industrial use. Molecular simulation calculations suggest that one unit of aspirin interacts with one unit of the modified silicate L1 through hydrogen bond formation between the amine functional group of the silicate and the oxygen donor atoms of aspirin. Final conclusions are given.

BUTADIENE RUBBER: SYNTHESIS, MICROSTRUCTURE, AND ROLE OF CATALYSTS

ABSTRACT Butadiene rubber (BR) is one of the most useful and second most produced rubber worldwide. Polymerization of 1,3-butadiene (BD) is a highly stereospecific reaction that offers a wide variety of BR with different microstructures and influences the fundamental properties of the rubber. Since the first successful polymerization of conjugated diene using the Ziegler–Natta–based catalyst (TiCl4 or TiCl3 with aluminum alkyls) in 1954, the research on producing synthetic rubber with an appropriate catalyst system has been accelerated. Subsequently, various research groups are actively engaged in designing active catalyst systems based on a suitable combination of transition metal complexes with alkyl-aluminum and successfully using them in BD polymerization. Although various scientific inventions have proven their significance for the production of high-quality BR, with the rising demands in improving the quality of the product, research on developing new catalyst systems with enhanced catalytic activity and high stereoselectivity is still in progress. The present review focuses on the synthesis of BR using various transition metal catalysts and discusses their microstructures. The catalysts based on new-generation metal complexes with phosphorus, nitrogen, and oxygen donor ligands (e.g., phosphines, imines, 1,10-phenanthroline, and imino-pyridines) have been introduced. The role that catalysts play in the production of BR with different microstructures (i.e., high-cis, high-trans or low-cis, low-trans polybutadiene) has also been described. The combination of catalyst (transition metal complex) and suitable co-catalyst (alkyl-aluminum) is the major factor influencing the reaction and microstructure of the resulting polymer. This report focuses on the effect of transition metal catalysts (i.e., lithium [Li], titanium [Ti], zirconium [Zr], iron [Fe], cobalt [Co], nickel [Ni], and neodymium [Nd]) on the activity and stereoselectivity of polymers such as 1,4-cis-, 1,4-trans-, and 1,2-vinyl-polybutadiene.

Oxidation of Ethanol in Cu-Faujasites Studied by IR Spectroscopy

In this study, IR studies of the coadsorption of ethanol and CO on Cu+ cations evidenced the transfer of electrons from ethanol to Cu+, which caused the lowering of the frequency of the band attributed to CO bonded to the same Cu+ cation due to the more effective π back donation of d electrons of Cu to antibonding π* orbitals of CO. The reaction of ethanol with acid sites in zeolite HFAU above 370 K produced water and ethane, polymerizing to polyethylene. Ethanol adsorbed on zeolite Cu(2)HFAU containing acid sites and Cu+exch also produced ethene, but in this case, the ethene was bonded to Cu+ and did not polymerize. C=C stretching, which is IR non-active in the free ethene molecule, became IR active, and a weak IR band at 1538 cm−1 was present. The reaction of ethanol above 370 K in Cu(5)NaFAU zeolite (containing small amounts of Cu+exch and bigger amounts of Cu+ox, Cu2+exch and CuO) produced acetaldehyde, which was further oxidized to the acetate species (CH3COO-). As oxygen was not supplied, the donors of oxygen were the Cu species present in our zeolite. The CO and NO adsorption experiments performed in Cu-zeolite before and after ethanol reaction evidenced that both Cu+ox and Cu2+ (Cu2+exch and CuO) were consumed by the ethanol oxidation reaction. The studies of the considered reaction of bulk CuO and Cu2O as well as zeolites, in which the contribution of Cu+ox species was reduced by various treatments, suggest that ethanol was oxidized to acetaldehyde by Cu2+ox (the role of Cu+ox could not be elucidated), but Cu+ox was the oxygen donor in the acetate formation.

Crystal structures of zinc(II) complexes with β-hydroxypyridinecarboxylate ligands: examples of structure-directing effects used in inorganic crystal engineering

The coordination properties of four hydroxypyridinecarboxylates, designed for the treatment of iron-overloading conditions as bidentate O,O′-donor ligands, have been studied with ZnII in the solid state. The coordination compounds [Zn(A1)2(H2O)2] (1), [Zn(A2)2(H2O)] (2), [Zn(A3)2(H2O)]·2H2O (3) and [Zn2(B1)4(H2O)2]·4H2O (4), where the ligands are 1-methyl-4-oxidopyridinium-3-carboxylate (A1, C7H6NO3), 1,6-dimethyl-4-oxidopyridinium-3-carboxylate (A2, C8H8NO3), 1,5-dimethyl-4-oxido-pyridinium-3-carboxylate (A3, C8H8NO3) and 1-methyl-3-oxidopyridinium-4-carboxylate (B1, C7H6NO3), have been synthesized and analysed by single-crystal X-ray diffraction. The ligands were chosen to probe (i) the electronic effects of inverting the positions of the O-atom donor groups (i.e. A1 versus B1) and (ii) the electronic and steric effects of the addition of a second methyl group in different positions on the pyridine ring. Two axially coordinated water molecules resulting in a six-coordinated symmetrical octahedron complement the bis-ligand complex of A1. Ligands A2 and A3 form five-coordinated trigonal bipyramidal complexes with one additional water molecule in the coordination sphere, which is a rarely reported geometry for ZnII complexes. Ligand B1 shows a dimeric structure, where the two Zn2+ dications have slightly distorted octahedral geometry and the pyridinolate O atom of the neighbouring complex bridges them. The coordination spheres of the Zn2+ dications and the supramolecular structures are discussed in detail. The packing arrangements of 1–3 are similar, having alternating hydrophilic and hydrophobic layers, however the similarity is broken in 4. The obtained coordination geometries are compared with their previously determined CuII analogues. The study of the individual complexes is complemented with a comprehensive analysis of ZnII complexes with oxygen donor ligands with data from the Cambridge Structural Database.