From Simple Palladium(II) Monomers to 2D Heterometallic Sodium-Palladium(II) Coordination Networks with 2-Halonicotinates.

The 2D heterometallic sodium-palladium(II) coordination polymers with 2-halonicotinates [2-chloropyridine-3-carboxylate (2-chloronicotinate), 2-Clnic- and 2-bromopyridine-3-carboxylate (2-bromonicotinate), 2-Brnic-], {[Na2(H2O)2(µ-H2O)4PdCl2(µ-2-Clnic-N:O')2]}n (1), and {[Na2(H2O)2(µ-H2O)4PdBr2(µ-2-Brnic-N:O')2]·2H2O}n (2) were prepared in aqueous solutions under the presence of NaHCO3, while palladium(II) monomers with the neutral 2-chloronicotinic and 2-bromonicotinic acid ligands, [PdCl2(2-ClnicH-N)2]·2DMF (3) and [PdCl2(2-BrnicH-N)2]·2DMF (4), were prepared in DMF/water mixtures (DMF = N,N'-dimethylformamide). The zigzag chains of water-bridged sodium ions are in turn bridged by [PdCl2(2-Clnic)2]2- moieties in 1 or by [PdBr2(2-Brnic)2]2- moieties in 2, leading to the formation of the infinite 2D coordination networks of 1 or 2. The DFT calculations showed the halosubstituents type (Cl vs Br) does not have an influence on the formation of either trans or cis isomers. The trans isomers were found in all reported compounds; being more stable for about 10 to 15 kJ mol-1. The 2D coordination networks 1 and 2 are more stabilized by the formation of Na-Ocarboxylate bonds, comparing to the stabilization of palladium(II) monomers 3 and 4 by hydrogen-bonding with DMF molecules. The difference in DFT calculated energy stabilization for 1 and 2 is ascribed to the type of halosubstituents and to the presence/absence of lattice water molecules in 1 and 2. The compounds show no antibacterial activity toward reference strains of Escherichia coli and Staphylococcus aureus bacteria and no antiproliferative activity toward bladder (T24) and lung (A549) cancer cell lines.

The effect of Artemisia annua L. extract on microbiologically influenced corrosion of A36 steel caused by Pseudomonas aeruginosa.

The protective effect of A. annua against microbiologically influenced corrosion (MIC) of A36 steel caused by P. aeruginosa (PA) in a simulated marine environment was investigated using electrochemical, spectroscopic, and surface techniques. PA was found to accelerate the local dissolution of A36 which led to the formation of a porous α-FeOOH and γ-FeOOH surface layer. 2D and 3D profiles of treated coupons, obtained by optical profilometer, revealed the formation of crevices in the presence of PA. On the contrary, adding A. annua to the biotic medium led to the formation of a thinner, more uniform surface without significant damage. Electrochemical data showed that the addition of A. annua prevented the MIC of A36 steel with an inhibition efficiency of 60%. The protective effect was attributed to the formation of a more compact Fe3O4 surface layer, as well as the adsorption of phenolics, such as caffeic acid and its derivatives on the A36 steel surfaces, as detected by FTIR and SEM-EDS analysis. ICP-OES confirmed that Fe and Cr species more readily diffuse from A36 steel surfaces incubated in biotic media (Fe; 1516.35 ± 7.94 µg L-1 cm-2, Cr; 11.77 ± 0.40 µg L-1 cm-2) compared to the inhibited media (Fe; 35.01 ± 0.28 µg L-1 cm-2, Cr; 1.58 ± 0.01 µg L-1 cm-2).

Surfactant-Free Microemulsions in Fragrance Tinctures.

Tinctures are alcoholic or hydroalcoholic solutions prepared from vegetable or chemical substances. The concentration of the solute varies up to a maximum of 50%, e.g., vanilla tincture. Tinctures are very useful in the perfume industry because they contain ethanol, which can dissolve molecules such as fragrant molecules, and consequently form hydroalcoholic formulations together. Recently, we have shown that nanostructures exist in the monophasic water-ethanol-citronellol system, and it is therefore a question whether such nanostructures exist in a system where a perfume molecule of citral is present as the oil component instead of citronellol. In this study, the single-phase region was mapped conductometrically and then measured by Dynamic Light Scattering (DLS) and UV/Vis spectroscopy to determine the presence of nanostructures similar to classical microemulsions.

Synthesis and crystal structure of a 6-chloro-nicotinate salt of a one-dimensional cationic nickel(II) coordination polymer with 4,4'-bi-pyridine.

A 6-chloro-nicotinate (6-Clnic) salt of a one-dimensional cationic nickel(II) coordination polymer with 4,4'-bi-pyridine (4,4'-bpy), namely, catena-poly[[[tetra-aqua-nickel(II)]-µ-4,4'-bi-pyridine-κ2 N:N'] bis-(6-chloro-nicotinate) tetra-hydrate], {[Ni(C10H8N2)(H2O)4](C6H3ClNO2)2·4H2O} n or {[Ni(4,4'-bpy)(H2O)4](6-Clnic)2·4H2O} n , (1), was prepared by the reaction of nickel(II) sulfate hepta-hydrate, 6-chloro-nicotinic acid and 4,4'-bi-pyridine in a mixture of water and ethanol. The mol-ecular structure of 1 comprises a one-dimensional polymeric {[Ni(4,4'-bpy)(H2O)4]2+} n cation, two 6-chloro-nicotinate anions and four water mol-ecules of crystallization per repeating polymeric unit. The nickel(II) ion in the polymeric cation is octa-hedrally coordinated by four water mol-ecule O atoms and by two 4,4'-bi-pyridine N atoms in the trans position. The 4,4'-bi-pyridine ligands act as bridges and, thus, connect the symmetry-related nickel(II) ions into an infinite one-dimensional polymeric chain extending along the b-axis direction. In the extended structure of 1, the polymeric chains of {[Ni(4,4'-bpy)(H2O)4]2+} n , the 6-chloro-nicotinate anions and the water mol-ecules of crystallization are assembled into an infinite three-dimensional hydrogen-bonded network via strong O-H⋯O and O-H⋯N hydrogen bonds, leading to the formation of the representative hydrogen-bonded ring motifs: tetra-meric R 2 4(8) and R 4 4(10) loops, a dimeric R 2 2(8) loop and a penta-meric R 4 5(16) loop.

The first coordination compound of 6-fluoro-nicotinate: the crystal structure of a one-dimensional nickel(II) coordination polymer containing the mixed ligands 6-fluoro-nicotinate and 4,4'-bi-pyridine.

A one-dimensional nickel(II) coordination polymer with the mixed ligands 6-fluoro-nicotinate (6-Fnic) and 4,4'-bi-pyridine (4,4'-bpy), namely, catena-poly[[di-aqua-bis-(6-fluoro-pyridine-3-carboxyl-ato-κO)nickel(II)]-µ-4,4'-bi-pyri-dine-κ2 N:N'] trihydrate], {[Ni(6-Fnic)2(4,4'-bpy)(H2O)2]·3H2O} n , (1), was prepared by the reaction of nickel(II) sulfate hepta-hydrate, 6-fluoro-nicotinic acid (C6H4FNO2) and 4,4'-bi-pyridine (C10H8N2) in a mixture of water and ethanol. The nickel(II) ion in 1 is octa-hedrally coordinated by the O atoms of two water mol-ecules, two O atoms from O-monodentate 6-fluoro-nicotinate ligands and two N atoms from bridging 4,4'-bi-pyridine ligands, forming a trans isomer. The bridging 4,4'-bi-pyridine ligands connect symmetry-related nickel(II) ions into infinite one-dimensional polymeric chains running in the [10] direction. In the extended structure of 1, the polymeric chains and lattice water mol-ecules are connected into a three-dimensional hydrogen-bonded network via strong O-H⋯O and O-H⋯N hydrogen bonds, leading to the formation of distinct hydrogen-bond ring motifs: octa-meric R 8 8(24) and hexa-meric R 8 6(16) loops.

The first coordination compound of deprotonated 2-bromo-nicotinic acid: crystal structure of a dinuclear paddle-wheel copper(II) complex.

A copper(II) dimer with the deprotonated anion of 2-bromo-nicotinic acid (2-BrnicH), namely, tetrakis(µ-2-bromonicotinato-κ2 O:O')bis[aquacopper(-II)](Cu-Cu), [Cu2(H2O)2(C6H3BrNO2)4] or [Cu2(H2O)2(2-Brnic)4], (1), was prepared by the reaction of copper(II) chloride dihydrate and 2-bromo-nicotinic acid in water. The copper(II) ion in 1 has a distorted square-pyramidal coordination environment, achieved by four carboxyl-ate O atoms in the basal plane and the water mol-ecule in the apical position. The pair of symmetry-related copper(II) ions are connected into a centrosymmetric paddle-wheel dinuclear cluster [Cu⋯Cu = 2.6470 (11) Å] via four O,O'-bridging 2-bromo-nicotinate ligands in the syn-syn coordination mode. In the extended structure of 1, the cluster mol-ecules are assembled into an infinite two-dimensional hydrogen-bonded network lying parallel to the (001) plane via strong O-H⋯O and O-H⋯N hydrogen bonds, leading to the formation of various hydrogen-bond ring motifs: dimeric R 2 2(8) and R 2 2(16) loops and a tetra-meric R 4 4(16) loop. The Hirshfeld surface analysis was also performed in order to better illustrate the nature and abundance of the inter-molecular contacts in the structure of 1.

The Nanostructure Studies of Surfactant-Free-Microemulsions in Fragrance Tinctures.

As it was shown recently that nanostructures can exist in water-ethanol-citronellol tinctures, a deeper investigation of these media was performed using conductivity, UV-Vis and FT-IR spectroscopy techniques. Different regimes of conductivity, depending on the water content, an increase of the polarity of the polar pseudo-phase with increasing water content, and even the presence of free water molecules at higher water content are observed, just as in classical surfactant-based microemulsions. The percolation model, generally used to fit conductivity data in surfactant based microemulsion having a weak interfacial film, can be used to fit our conductivity data below a critical water content Φ(p)(w) with a critical exponent typical of dynamic percolation. In presence of higher water contents, superior to Φ(p)(w), obtained conductivity data cannot be fitted neither with a static nor a dynamic percolation model. As in surfactant-based microemulsions, an increase of polarity of the microenvironment with increasing water content can be postulated using respectively the UV-Vis wavelength absorption band (λ(max)) of methyl orange and performing FT-IR spectra.

THE ROLE OF LOW MOLECULAR WEIGHT HEPARIN IN WOMEN WITH HEREDITARY THROMBOPHILIA FOR GOOD PERINATAL OUTCOME.

The aim of the study was to establish the importance of low molecular weight heparin (LMWH) treatment for good pregnancy outcome in patients with hereditary thrombophilia. This retrospective study included 70 patients with inherited thrombophilia who gave birth at Zagreb University Hospital Center in the period from January 2014 to January 2015. Fifty-seven women were treated and 13 women were not treated with LMWH. Perinatal outcome was significantly better in women with hereditary thrombophilia who were treated with heparin during pregnancy as compared with women without LMWH (p=0.006). Regardless of heparin therapy, patients with hereditary thrombophilia alone had a significantly better perinatal outcome as compared with women who, along with hereditary thrombophilia, had a history of habitual abortions (p=0.035) or intrauterine fetal death (p=0.033). Women treated with heparin had better perinatal outcome if they were without a history of recurrent or non-recurrent fetal loss (p=0.088). In the group without LMWH, perinatal outcome was significantly better in women with no history of habitual abortions as compared with women with recurrent miscarriages (p=0.047). Administration of LMWH is justified in women with hereditary thrombophilia and a history of adverse perinatal outcome.

Weak Micelle-Like Aggregation in Ternary Liquid Mixtures as Revealed by Conductivity, Surface Tension, and Light Scattering.

A very small concentration of NaBr is added to ternary, transparent, and thermodynamically stable mixtures of water, ethanol, and octanol. Measuring the electrical conductivity along lines with constant water to ethanol ratios reveals remarkable composition dependencies similar to those found in classical surfactant-based microemulsions. Indeed, light-scattering experiments along the same composition lines and additional surface tension measurements confirm the onset of aggregation and possibly direct, bicontinuous, and reversed structures in these surfactant-free systems such as in classical microemulsions.

Preventative valve-sparing aortic root replacement and pregnancy outcome in Marfan syndrome.

In Marfan syndrome, with dilatation of the aortic root secondary to an underlying connective tissue defect, pregnancy can cause hemodynamic stress leading to the development of an aortic aneurysm and even a fatal aortic dissection. In the presence of existing aortic root enlargement and a family history of aortic dissection, preventative elective surgery is suggested. Aortic root replacement with or without a valve-sparing procedure is superior to total aortic root replacement with prosthetic valve/tube graft. It provides excellent survival with low rates of aortic - valve related complications.

Ion-Association Reaction of Rb+ and Br- in 2-Methylpropan-2-ol + Water Mixtures.

The molar conductivity of RbBr solutions in 2-methylpropan-2-ol (tert-butanol) + water mixtures at alcohol mass fractions of 0.70, 0.80 and 0.90 was measured at temperatures from 288.15 to 308.15 K at 5 K intervals. The limiting molar conductivity (Δo) and the ion-pair formation constant (KoA) were determined by the Lee-Wheaton conductivity equation. Thermodynamic quantities, Gibbs energy (ΔGo), enthalpy (ΔHo) and entropy (ΔSo), for the ion-association reaction were derived from the temperature dependence of KoA; the activation energy of the ionic movement (ΔH*) was derived from the temperature dependence of Λo. These values were compared with those obtained earlier for HBr and NaBr in the same mixtures.