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The adverse health effects of trans fatty acids (TFA) are well recognised. The Commission Regulation (EU) 2019/649 specifies that foods should not contain more than 2 g of industrially produced TFA (i-TFA) per 100 g of fat. This study aimed to investigate the fatty acid profile, with focus on TFA and i-TFA, of foods widely consumed in Greece that are purported to contain high TFA concentrations. Sweet and savoury (i.e. non-sweet), prepacked and non-prepacked (i.e. loose) processed foods (N = 140) were sampled. After lipid extraction, the fatty acid profile of each sample was determined by gas chromatography. Estimation of ruminant TFA (r-TFA) was based on butyric acid values. i-TFA was assessed after subtraction of r-TFA from total TFA. Both total and i-TFA contents of cakes, biscuits, croissants and doughnuts on average were low (

The 3D lanthanum-dicarboxylate MOF [La2(hex)3(H2O)4]3H2O, (1), (hex = trans,trans-muconic acid) has been obtained at 50 °C, in a silica gel column, either via in situ transformation of the 2D MOF [La2(hex)3(H2O)6]9H2O, (2), published previously, or directly. The structure is made up of metal–ligand layers pillared by a ligand dianion. The comparison of the crystal structures of the two MOFs allowed us to propose a possible mechanism of the 2D to 3D transformation. The presence of many short olefinic contacts allowed the formation of three photoproducts at different yields, the major one being the rtct isomer for the 3D MOF and the rttc one for the 2D MOF. In both cases, the three photoreactions proceed with the parallel reaction scheme. The comparison of the crystal structures of 1 and 2 allowed the photoreactivity differences observed to be explained.

A series of Lanthanide MOFs of hydromuconic acid (H2hymuc) with cations of different size (La3+, Ce3+, Gd3+, Y3+) were generated at room temperature, pH = 5.5–5.8, using water as solvent. Two microporous genuine supramolecular isomers were found for the larger cations (La3+, Ce3+) sustained either by discrete (H2O)18 clusters or by infinite water tapes, consisting of fused tetramers, pentamers and hexamers. The smaller cations (Gd3+, Y3+) produced a 2D phase, considered as catenane isomer of previously published lanthanide MOFs with adipic acid. MOFs obtained with Ce3+, Gd3+and Y3+ undergo irreversible solvent-mediated transformation, yielding isomorphous 3D two-fold interpenetrated MOFs. The close structural similarity between the 2D phase and the 3D interpenetrated one indicated a possible mechanism for this transformation.

A series of thiazolidine derivatives have been synthesized via tandem reaction of primary amines, isothiocyanates, and bis(imidoyl) chlorides in DMF at room temperature.

The sodium salt of methyl xanthate derives from the reaction of carbon disulfide and sodium hydroxide (1:1) in methanol. Addition of an acetonitrile solution of silver nitrate and tri-aryl-phosphine in 1:2 molar ratio, form the complexes with general formula [Ag(CH3OCS2)(Ar3P)2] (Ar3P = triphenylphosphine (tpp, 1), tri(p-tolyl)phosphine (tptp, 2) and tri(m-tolyl)phosphine (tmtp, 3)). The complexes have been characterized by melting point, FT-IR, UV–Vis, 1H, 31P NMR spectroscopic data and X-ray crystallography. The stability of the Ag–P bond in solution was determined by 31P NMR resonances signals. The photosensitivity of 1–3 against UVB radiation is studied by means of UV–Vis spectroscopy. The stronger photosensitivity is exhibited by 1. The LogP was calculated in order to correlate the influence of lipophilicity on biological activity. The steric demands of arylphosphine were assessed through determination of the cone angles, volumes and H-all atom contacts. Complex of tri(m-tolyl)phosphine exert the greatest steric repulsion (higher cone angle). Hirshfeld surface volumes (2 occupied the greatest space) were analyzed to clarify the nature of the intermolecular interactions. Complexes 1–3 were tested for their in vitro cytotoxic activity against human adenocarcinoma cancer cell lines: MCF-7 (breast, estrogen receptor (ER) positive), MDA-MB-231 (breast, estrogen receptor (ER) negative) and MRC-5 (normal human fetal lung fibroblast cells) with sulforhodamine B (SRB) colorimetric assay. Molecule 3 with the lower H-all atoms inter-molecular interactions exhibits the higher activity against MCF-7 cells. The results are correlated with those obtained from heteroleptic silver complexes of tri-aryl-phosphines and carboxylates analogs to 1–3 where the xanthate is replaced by carboxylates. The structure activity relationships (SAR) study underlines the significance of the ligand type on the bioactivity of these compounds.

The reaction of dialkyl acetylenedicarboxylates with 1-aryl-2-nitroethanones in the presence of pyridine leads to dialkyl 5-aryloyl-isoxazole-3,4-dicarboxylates through a novel mechanism, which involves a [2+2] cycloaddition/ring opening/cyclization sequence.

A simple one-pot synthesis of highly functionalized 1,2,4-diselenazolidines is described. Treatment of an acyl chloride with potassium selenocyanate in acetone gave an acyl isoselenocyanate and propane-2-selone, which both reacted with benzylamine or its derivatives to give the required products.

A novel iodine-mediated reaction of 2,6-dimethylquinoline with Knoevenagel condensation products of malononitrile with benzaldehydes, leading to a facile, one-pot synthesis of 2-aryl-3-(6-methylquinolin-2-yl)cyclopropane-1,1-dicarbonitriles, in moderate to good yields, is described.

A 2D lanthanum-dicarboxylate MOF of the formula [La2(hex)3(H2O)6]·9H2O (H2hex = trans,trans-hexadiendioic acid or trans,trans-muconic acid) has been synthesized by the silica gel technique. The structure consists of metal–organic layers separated by a 2D network of water molecules. The metal–organic layers are made up of La3+ arrays linked by the muconate ligands. Within a layer there is an infinite chain of short contacts between olefinic bonds allowing formation, upon UV irradiation, of three photoproducts. One of them was completely unexpected and its formation is explained by complex molecular movements in the solid state. The thermal instability of the MOF allowed isolation of five photochemically active lower hydrates. The rate constants of all hydrates were determined and show significant variations between them, attributable to structural rearrangements within the metal–organic layer brought about upon dehydration.

Treatment of a dimethylsulfoxide solution of 2-thioorotic acid (THO) with copper(I) halides unexpectedly results in the formation of the [Cu(L)(DMSO)2] complex, where L is the tetradentate N2O2-donor bis(4-carboxylato-6-oxo-pyrimidine-2-yl)sulfide dianion formed in situ by metal-assisted desulfurization of 2-thioorotic acid. The complex features a tetragonally distorted octahedral copper(II) center with two pyrimidine N atoms and two carboxylate O atoms of the ligand, forming a square plane, whereas two O atoms of DMSO solvate molecules occupy the axial positions. The molecular structure, electronic properties and the energetics of the metal–ligand interactions have been studied on the level of density functional calculations. The new compound was evaluated for its in vitro antibacterial activity, DNA degradation activity and for its efficacy as anticancer agent against different cancer and normal human and murine cell lines as well.

The reaction of copper(I) halides with 2-thiouracil (TUC), 6-methyl-2-thiouacil (MTUC), and 4-methyl-2-mercaptopyrimidine (MPMTH) in the presence of triphenylphosphine (tpp) in a 1:1:2 molar ratio results in a mixed-ligand copper(I) complex with the formulas [Cu2(tpp)4(TUC)Cl] (1), [Cu2(tpp)4(MTUC)Cl] (2), [Cu(tpp)2(MPMTH)Cl]·(1)/2CH3OH (3), [Cu(tpp)2(MTUC)Br] (4), and [Cu(tpp)2(MTUC)I]·(1)/2CH3CN (5). The complexes have been characterized by FT-IR, (1)H NMR, and UV-vis spectroscopic techniques and single-crystal X-ray crystallography. Complexes 1 and 2 are binuclear copper(I) complexes. Two phosphorus atoms from tpp ligands are coordinated to the copper(I) ions, forming two units that are linked to each other by a deprotonated TUC or MTUC chelating ligand through a sulfur bridge. A linear Cu-S-Cu moiety is formed. The tetrahedral geometry around the metal centers is completed by the nitrogen-donor atom from the TUC or MTUC ligand for the one unit, while for the other one, it is completed by the chloride anion. Two phosphorus atoms from two tpp ligands, one sulfur atom from MPMTH or MTUC ligand, and one halide anion (Cl, Br, and I) form a tetrahedron around the copper ion in 3-5 and two polymorphic forms of 4 (4a and 4b). In all of the complexes, either mono- or binuclear intramolecular O-H···X hydrogen bonds enhance the stability of the structures. On the other hand, in almost all cases of mononuclear complexes (with the exception of a symmetry-independent molecule in 4a), intermolecular NH···O hydrogen-bonding interactions lead to dimerization. Complexes 1-5 were studied for their catalytic activity for the intermolecular cycloaddition of iodonium ylides toward dihydrofuran formation by HPLC, (1)H NMR, and LC-HRMS spectroscopic techniques. The results show that the geometry and halogen and ligand types have a strong effect on the catalytic properties of the complexes. The highest yield of dihydrofurans was obtained when "linear" complexes 1 and 2 were used as the catalysts. The activity of the metal complexes on the copper(I)-catalyzed and uncatalyzed intramolecular cycloaddition of iodonium ylide is rationalized through electronic structure calculation methods, and the results are compared with the experimental ones.

Olive mill wastewater (OMW) generated during the oil extraction from Olea europea L. var. koroneiki olives was sampled at the beginning, the middle and the end of the harvesting season for three successive crop production years, and from four olive mills. OMW samples were examined in respect to their physicochemical characteristics, fatty acid composition of the lipid fraction, and adverse effects on biomass production of nine white-rot fungi of the basidiomycetous genus Pleurotus . Total N, nitrogen species, potassium and phosphate concentrations as well as total phenolics content of OMW samples were influenced by the crop year but not from the harvest period (albeit higher values for nitrate, nitrite, phosphate and potassium as well as total phenolics contents were obtained during ripening of olives), whereas protein concentration, total organic carbon and total solids were not significantly affected by the crop year or the harvest period. In addition, fatty acids composition, i.e. nC14:0, nC16:1Δ9cis, nC17:1Δ10cis, nC18:0, nC18:1Δ9cis, nC22:0 and nC24:0 varied significantly during different crop years and harvest periods. Olive fruits maturity and biannual alternate-bearing appear to play key-roles in the fatty acid variation detected in OMW samples. OMW toxicity as evaluated by the mycelium growth of Pleurotus strains was influenced significantly by the phenolic content of OMW samples obtained during three successive crop years; in contrast, the olives harvest period did not affect Pleurotus biomass production. Hence, experimental data indicated that selected Pleurotus strains could serve as bioindicators of OMW toxicity. Development of viable OMW detoxification processes as well as the exploitation of the effluent’s fertilizing value are discussed in the light of the above findings.

Ten mixed-ligand Co(II) compounds with 2-hydroxy-benzophenones(ketones) and neocuproine(neoc) were synthesized and characterized by physicochemical and spectral (IR, UV–Vis) data. The cyclic voltammetry study in CH3CN gave all the expected waves for the redox processes of the metal Co(II) and the studied ligands. The X-ray diffraction study of two representative compounds proved the two different geometries, octahedral for [Co(2-hydroxy-benzophenone)2(neoc)] (3) and trigonal bipyramidal for [Co(2-hydroxy-4-methoxybenzophenone)(neoc)Br] (10). Additionally, the precursor compound [Co(neoc)Br2]·CH3OH·H2O (11) was proved by (X-ray) to posses tetrahedral geometry. The molecular structure and the possible isomers of the trigonal bipyramidal complex 10 were studied by means of density functional calculations (DFT). The thermal stability was investigated by means of simultaneous TG/DTG–DTA technique in nitrogen atmosphere up to 1000 °C, where metallic cobalt was found as the solid residue.

Imidoyl chlorides (generated from isocyanides and acyl chlorides) reacts with triisopropyl phosphite, in a Perkow-type reaction, to produce 1-alkoxycarbonyl-2-(alkylimino)vinyl diisopropyl phosphate, which undergo a smooth reaction with bidentate nucleophilic intermediates obtained from the reaction between malononitrile and heterocumulenes, such as arylisothiocyanates or carbon disulfide to produce polarized olefins containing 2-dicyanomethylene-2,3-dihydrothiazole and 2-dicyanomethylene-1,3-dithiole moieties.

A synthesis of cis-3-aryl-3a,8b-dihydro-3a,8b-dihydroxy-1-phenylindeno[1,2-c]pyrazol-4(1H)-ones in good yields from the sequential reaction between benzaldehydes, phenylhydrazine, and indan-1,2,3-trione in MeCN is described (Scheme"…1). Helvetica Chimica Acta

The crystal structure and packing of a series of six nearly tetrahedral organic compounds 1– 6, of general formula PhNH-CAr 1Ar 2Ar 3 [ 1(Ph, Ph, Ph), 2(Ph, Ph, 2-Py), 3(Ph, Ph, 3-Py), 4(Ph, Ph, 4-Py), 5(Ph, 2-Py, 2-Py), and 6(2-Py, 2-Py, 2-Py)], were investigated by X-ray crystallography and supported, in some cases, by ab initio calculations, IR spectroscopy, and 1H NMR. All molecules have in common an aniline group, but they differ in the number of phenyl groups that are replaced by pyridyl ones ( 1, 2, 5, 6) or the position of the nitrogen heteroatom at the pyridyl ring ( 2– 4). Purely van der Waals solids are obtained when the molecule can form an intramolecular N−H···N hydrogen bond ( 2, 5, 6), and, in this case, a correlation between melting point and structure was attempted. However, when intermolecular N−H···N bonds were established, helices ( 4) or tetrameric (two organic molecules + two solvent molecules) molecular complexes ( 3) were obtained.

The reaction of dialkyl acetylenedicarboxylates with 1-aryl-2-nitroethanones in the presence of pyridine leads to dialkyl 5-aryloyl-isoxazole-3,4-dicarboxylates through a novel mechanism, which involves a [2+2] cycloaddition/ring opening/cyclization sequence.

[Cd(phen)2(CA)]n (I, where phen is 1,10-phenanthroline and CA2− is the dianion of 3,6-dichloro-2,5-dihydroxy-1,4-benzoquinone) has been synthesized and its crystal structure has been determined by single-crystal X-ray diffraction at room temperature. The crystal of I is built from infinite chains of chloranilate-bridged cadmium(II) leading to a zig-zag structure, with the phenanthroline ligands being stacked between the chains. These interactions assist the formation of a closely packed 3D structure. The coordination environment of cadmium(II) – very scarce in its chemistry – is square antiprismatic. The polymer was also characterized with spectroscopic (IR, Raman, DRS) and thermogravimetric (TG, DTA) techniques.

Reaction of 4-formylantipyrine with thiosemicarbazide, N(3)-methylthiosemicarbazide and N(3)-ethylthiosemicarbazide produced the expected thiosemicarbazones, 1, 2 and 3. The three thiosemicarbazones were then reacted with K2PdCl4 to produce [Pd(NS)2] complexes, 4, 5, and 6, respectively, with coordination by the imine nitrogen and thiolate sulfur of the anionic thiosemicarbazone moiety. The thiosemicarbazones and their palladium complexes have been characterized by spectral IR, UV–Vis and 1H, 13C NMR and electrochemical techniques. The crystal structure of 6 has been obtained and found to be highly symmetrical with a trans arrangement of the two bidentate ligands.

Erbium. fumarate [Er-2(fum)(3)(H2O)(4)].8H(2)O, 1, (fum = fumarate dianion) crystallizes at room temperature in a silica gel column. The structure is three-dimensional and consists of layers of erbium fumarate pillared by fumarate dianions acting in the bis-chelating mode. The layers contain arrays of erbium cations bridged by fumarate dianions acting in the bis-bidentate bridging mode. The relatively large channels formed in the direction of the a and c axes are filled by water molecules that form a hydrogen bonded layer, comprising cyclic hexamers with both boat and chair conformations and cyclic decamers with boat-chair-boat conformation. The water molecules are reversibly removed at 90 degreesC. The evacuated metal-organic framework, 2, is stable up to 400 degreesC. Both compounds 1 and 2 exhibit weak antiferromagnetic interactions. Crystal Growth & Design

Silver(I) chloride reacts with 2-mercapto-nicotinic acid (H(2)mna, C6H5NO2S) in the presence of an excess of triethylamine in DMSO to form a hexanuclear, water soluble, cluster of formula {[Ag-6(mu(3)-Hmna)(4)(mu(3)-mna)(2)](2-) (.)[(Et3NH)(+)](2)(.)(DMSO)(2)(.)(H2O)} (1). The complex 1 was characterized by elemental analyses, and FT-IR, UV-Vis and H-1 NMR spectroscopy. Crystal structures of complex 1 and the ligand, 2-mecapto-nicotinic acid (2), have been determined by X-ray diffraction. Compound 1, C52H68Ag6-N8O15S8, is monoclinic with a space group P2(1)/c (No. 14) and a = 11.7080(10), b = 16.2920(10), c = 18.3010(10) Angstrom, beta = 91.350(10)degrees, Z = 4. The entire molecule is ionic and consists of a double anionic hexa-nuclear cluster and two protonated triethylamine counter cations while it is solvated by two DMSO and one water molecule. The 2-mercapto-nicotinic acid (2), C6H5NO2S, is orthorhombic (space group Pna2(1) (No. 33), a = 8.3910(10), b = 13.2720(10), c = 5.892 Angstrom, Z = 4). An extended inter-molecular hydrogen bonding via (OH)-H-...-N contacts (O(1)H-...(5)[N(5)] = 1.8998, O(1)N-...(5) = 2.8049 Angstrom) links the molecules forming a supramolecular two-dimensional network. Complex 1, was evaluated for anti-HIV-RT activity. It was found to inhibit the human immunodeficiency viral replication reverse transcriptase (HIV-RT) with calculated inhibiting concentration (IC50) 0.01275 +/- 0.00115 mg ml(-1). (C) 2002 Elsevier Science B.V. All rights reserved. Inorganica Chimica Acta

Single crystals of [Cd(terephthalate)(H2O)3].4H2O (1), triaquo(1,4-benzenecarboxylato-κO)cadmium tetrahydrate, are grown in a silica gel column. Crystal structure analysis shows that (1) is a polymer with metal-organic chains stacked along the a axis forming layers parallel to the ab plane. These layers are linked by an unusual hydrogen-bonded network formed by the water molecules (both `free' and coordinated ones) and the carboxylate O atoms. This network comprises tridymite-like O8 cages which `propagate' in the direction of the a axis, mimicking the way they `propagate' along the c axis in hexagonal ice.

The structure and dehydration behavior of the porous 3D coordination polymer {[La2(adipate)3(H2O)4]6H2O}n are described. Each La3+ is coordinated by nine oxygen atoms belonging to five carboxylate ...

The conformation of title compounds has been determined in the solid state by X-ray crystallography and in solution by nmr spectroscopy. MM2 and molecular dynamics calculations were used to determine the conformation of one of these compounds in vacuo and in solution