The phenomenon of conglomerate crystallization. Part 40: The crystallization behavior oftrans- Co(III) amines (+)546-trans-[Co(3,2,3-tet)(NO2)2]Cl·3H2O (I), (−)589 -trans-[Co(3,2,3-tet)Cl2]NO3 (II), and of (+)546-trans-[Co(3,2,3-tet)(NO2)2]NO3 (III)

A racemic solution of (I) crystallizes as a conglomerate from which a crystal we selected was found to be (+)₅₄₆-trans-[Co(3,2,3-tet)(NO₂)₂]Cl·3H₂O (I), CoClO₇N₆C₈H₂₈. It crystallizes in the enantiomorphic space groupP2_l2_l2_l, with lattice constantsa=18.501(15) å,b=14.433(2) å, andc=6.441(3) å;V=1720.07 å³ andd(calc. M.W.=414.73,Z=4)=1.601 g cm^?3. A total of 2305 data were collected over the range of 4?≤2θ ≤55?; of these, 1724 (independent and withI > 3σ(I)) were used in the structural analysis. Data were corrected for absorption (Μ=11.920 cm^?1), and the relative transmission coefficients ranged from 0.8258 to 0.9565. Refinement was carried out for both lattice enantiomorphs, and at this stage theR(F) andR _w (F) residuals were, respectively, 0.0381 and 0.0479 for (+ + +) and 0.0448 and 0.0532 for (? ? ?). Thus, the former was selected as correct for our specimen, and the final cycle of refinement with the (+ + +) model converged toR(F) andR _w (F) of 0.0315 and 0.0365. A racemic solution of (II) crystallizes as a conglomerate from which a crystal we selected was found to be (?)₅₈₉-trans-[Co(3,2,3-tet)Cl₂]NO₃ (II), CoCl₂O₃N₅C₈H₂₂. It crystallizes in the enantiomorphic space groujp,P2_l with lattice constantsa=6.395(2) å,b=8.886(2) å,c=13.185(2) å, andΒ=99.24(2)?;V=739.59 å³ andd(calc. M.W.=366.14,Z=2)=1.646 g cm ^?3. A total of 2912 data were collected over the range of 4?<2θ<64?; of these, 2147 (independent and withI≥3σ(I)) were used in the structural analysis. Data were corrected for absorption (Μ =15.424 cm^?1), and the relative transmission coefficients ranged from 0.9632 to 0.9985. Refinement was carried out for both lattice enantiomorphs, and the finalR(F) andR _w (F) residuals were, respectively, 0.0326 and 0.0328 for (+ + +) and 0.0347 and 0.0348 for (? ? ?). Thus, the (+ + +) was selected as correct for our specimen. A racemic solution of (III) crystallizes as a conglomerate from which a crystal we selected was found to be (+)₅₈₉-trans-[Co(3,2,3-tet)(NO₂)₂]NO₃ (III), CoO₇N₇C₈H₂₂. It crystallizes in the enantiomorphic space group,P2_l with lattice constantsa=6.295(1) å, b=15.108(3) å,c=8.029(1) å, andΒ=100.28(2)?;V=751.35 å³ andd(calc. M.W.=387.24,Z=2)=1.712 g cm^?3. A total of 2393 data were collected over the range of 4?≤2θ≤60?; of these, 1869 (independent and withI≥3σ(I)) were used in the structural analysis. Data were corrected for absorption (Μ=11.859 cm^?1), and the relative transmission coefficients ranged from 0.8814 to 0.9976. Refinement was carried out for both lattice enantiomorphs and the finalR(F) andR _w (F) residuals were, respectively, 0.0463 and 0.0482 for (+ + +) and 0.0441 and 0.0442 for (? ? ?). Thus, the latter was selected as correct for our specimen, and the final cycle of refinement with the (? ? ?) model converged toR(F) andR _w (F) of 0.0436 and 0.0421. For all three compounds, the six-membered rings are chairs; the secondary nitrogens are chiral centers, and the five-membered rings are ordered and conformationally dissymmetric, as expected. Coincidentally, in (I), (II), and (III) the central rings are right-handed helices withδ(+50.0?),δ(+53.3?), andδ(+48.3?), respectively. Thus, the secondary nitrogens of all three cations are (R), rendering the cations chiral. The incidence of conglomerate crystallization intrans coordination compounds is rare, and those known are asymmetrically substituted (see Ref. 4 for the four known cases). Thus, the incidence of such crystallization mode in a new series of [trans- Co(amine ligands)X₂]⁺ cations bearing symmetrical pairs oftrans ligands was an unexpected and welcomed event. In all three cases, the counteranions are bonded to the hydrogens of the terminal -NH₂ moieties, thus forming an overall entity which resembles a macrocycle. In fact, parallels between the crystallization behavior of our compounds and that of macrocycles bearing related fragments is discussed. Finally, in the three compounds, homochiral cations are linked into infinite strings by hydrogen bonds between the axial ligands and amino hydrogens on adjacent cations of the string. In turn, strings are stitched together by the counteranions which form bonds with amino hydrogens on cations of adjacent strings.     

Correlation between chemical composition and antibacterial activity of essential oils from fifteen Eucalyptus species growing in the Korbous and Jbel Abderrahman arboreta (North East Tunisia)

The essential oils of fifteen Eucalyptus species harvested from the Jbel Abderrahman and Korbous arboreta (North East Tunisia) were screened for their antibacterial activities by the agar disc diffusion method. Eighteen major components as identified by GC/FID and GC/MS were selected for a study of the chemical and biological activity variability. The main one was 1,8-cineole, followed by spathulenol, trans-pinocarveol, α-pinene, p-cymene, globulol, cryptone, β-phellandrene, viridiflorol, borneol, limonene and isospathulenol. The chemical principal component analysis identified five species groups and subgroups, where each group constituted a chemotype, however that of the values of zone diameter of the inhibition (zdi) identified six groups of Eucalyptus oils, characterized by their antibacterial inhibition ability. The strongest activity was shown by E. platypus oil against Enterococcus faecalis and by E. lamannii oil against Staphylococcus aureus, Pseudomonas aeruginosa and Escherichia coli. A correlation between the levels of some major components and the antibacterial activities was observed.     

End-to-end single cyanato and thiocyanato bridged Cu(II) polymers with a new tridentate Schiff base ligand: crystal structure and magnetic properties

A new tridentate Schiff base ligand HL (L = C14H19N2O), derived from the condensation of benzoylacetone and 2-dimethylaminoethylamine in a 1:1 ratio, reacts with copper(ii) acetate and cyanate, thiocyanate or azide, to give rise to several end-to-end polymeric complexes of formulae [CuL(mu(1,3)-NCO)]n 1, [CuL(mu(1,3)-NCS)]n 2 and the complex 3 has two crystallographically independent units of formula [CuL(N3)] in the asymmetric unit cell. Complex 3 exists in dimeric form rather than as a polymeric chain. Compound 1 is the first report of a singly end-to-end cyanate bridged polymeric chain of Cu(II) with a Schiff base as a co-ligand. There are many examples of double NCS bridged polymeric chains, but fewer singly bridged ones such as compound 2. We have characterized these complexes by analytical, spectroscopic, structural and variable temperature magnetic susceptibility measurements. The coordination geometry around the Cu(II) centers is distorted square pyramidal for 1 and 2 and square planar for complex 3. The magnetic susceptibility data show slight antiferromagnetic coupling for the polymers having J values -0.19 and -0.57 cm(-1) for complexes 1 and 2 respectively. The low values of J are consistent with the equatorial-axial disposition of the bridges in the polymers.     

Co(II)5(OH)6(SO4)2(H2O)4: the first ferromagnet based on a layered cobalt-hydroxide pillared by inorganic...OSO3-Co(H2O)4-O3SO..

The synthetic mineral Co(II)5(OH)6(SO4)2(H2O)4 (1), obtained by hydrothermal reaction of CoSO4.7H2O and NaOH at 165 degrees C and consisting of brucite-like Co4(OH)6O2 layers pillared by OSO3-Co(H2O)4-O3SO, is a ferromagnet (T(Curie)= 12 K, Hc= 580 Oe).     

Preparation and Characterization of Poly Vinyl Alcohol/Poly Vinyl Pyrrolidone/Clay Based Nanocomposite by Gamma Irradiation

A series of PVA/PVP/clay nanocomposite were prepared by gamma irradiation with different clay contents of (0.15, 0.3, 1, 1.5, 3 and 5 wt%). The gelation content and swelling behavior were investigated. The morphology and structure of PVA/PVP/clay nanocomposite and dispersion of the clay nanoparticles in the polymeric matrix were examined by infrared spectroscopy (FT-IR) and scanning electron microscopy (SEM). The introduction of clay into polymeric matrix was investigated by X-ray diffraction pattern (XRD) and Transmission electron microscope (TEM). It is observed that, the increase of the clay content causes a decrease in the swelling percent. The thermal stability studies confirmed that the introduction of clay lead to an increase in the thermal stability. The TEM results showed that the clay nanoparticles are interchelated or exfoliated in the polymeric matrix. Some desirable characteristics such as relatively good swelling and excellent barrier capability against microbe penetration suggested that PVA/PVP/clay nanocomposite can be a good candidate as a wound dressing.     

Solvent effects on the initial and transition states for the solvolysis of trans-dichlorobis-(N-methylethylenediamine) cobalt(III) complex in water–dimethyl sulfoxide mixtures

Solvent effects on the initial and transition states for the solvolysis of the trans-dichlorobis-(N-methylethylenediamine)cobalt(III), (meen), complex have been investigated in the 25–55 °C range in aqueous DMSO mixtures, of varying solvent composition up to 60% by vol. The log of the first order rate constant, k, varies non-linearly with the reciprocal of the dielectric constant at the same temperature, due to differential solvation of the initial and transition states. The changes in the enthalpy, H , and entropy, S , of activation with the mole fraction of the co-solvent show extrema at the composition range where the change in solvent structure occurs. The application of a free energy cycle to the process of the initial state going to the transition state suggests that the effect of solvent structure on the complex ion in the transition state dominates the initial state and that this effect increases as the mole fraction of co-solvent increases.     

Determination of Ciprofloxacin in Dried Blood Spots for Therapeutic Drug Monitoring

The use of blood spot collection cards is a simple way to obtain specimens for analysis of drugs for the purpose of therapeutic drug monitoring, assessing adherence to medications and preventing toxicity in certain groups of patients. We describe the development and validation of a microanalytical technique for the determination of ciprofloxacin from dried blood spots. The method is based on reversed phase liquid chromatography with fluorescence detection. Drug recovery in the developed method was found to be higher than 95%. The limits of detection and quantification were calculated to be to be 60 and 100 ng mL⁻¹, respectively. The intra- and inter-day precision (measured by CV%) was always less than 6% (13.07% at LOQ). The accuracy (measured by relative error, %) was always less than 8% (7.82% at LOQ). Stability analysis showed that ciprofloxacin is stable for at least 1 month when stored at −70 °C. The small volume of blood required (30 μL), combined with the simplicity of the analytical technique makes this method a potential procedure for monitoring ciprofloxacin concentrations in certain patient populations.

     

Officinalioside,a new lignan glucoside from Borago officinalis L.

A new lignan glucoside, officinalioside (1), was isolated from n-BuOH fraction of the aerial parts of Borago officinalis L., together with four known compounds: actinidioionoside (2), roseoside (3), crotalionoside C (4) and kaempferol 3-O-β-D-galactopyranoside (5). The structure of the new compound was established by means of spectroscopic and chemical analyses. Compounds 1 and 2 showed a moderate DPPH radical scavenging activity (IC₅₀: 52.6 ± 1.70 and 41.3 ± 0.25 μM, respectively) comparable with that of the standard trolox (16.6 ± 2.2 μM) without any significant cytotoxicity towards human cell line A549 (IC₅₀ > 100 μM).     

Structural studies and biological evaluation of Co (II), Ni (II) and Cu (II) complexes of carbohydrazone derived from ethyl acetoacetate in addition to crystallographic description of La (III) or Sm (III) catalytic activity abnormal product

New carbohydrazone ligand derived from the condensation of carbohydrazide and ethyl acetoacetate, diethyl 3,3′‐(carbonylbis (hydrazin‐2‐yl‐1‐ylidene))(3E,3′E)‐dibutyrate (H₄EBC), and its divalent Co, Ni and Cu chelates have been isolated and characterized utilizing convenient methods. ¹H‐NMR spectrum of H₄EBC revealed the abundance of the enol isomer in solution, which was the opposite to what was shown by the solid IR. This was supported by comparing the theoretical IR of both keto and enol forms. In [Ni(H₄EBC)Cl₂(H₂O)]·2H₂O, H₄EBC acts as a neutral NON tridentate ligand via the (C=O)_carbonyl oxygen atom besides the two (C=N)_azomethine nitrogen atoms, while in [Co(H₄EBC)Cl₂(2H₂O)]·2H₂O, H₄EBC behaves as a neutral NN bidentate ligand through the two azomethine groups. Magnetic measurements inherent to their electronic spectra show that both Ni (II) and Co (II) chelates have octahedron coordination frameworks. On the other hand, the ligand behaves as a binegative tetradentate in [Cu₂(H₄EBC)Cl₂]·H₂O via the deprotonated (C=O)_carbonyl groups of the ethyl acetoacetate framework and the two (C=N)_azomethine groups. In the latter complex, the carbonyl group of the carbohydrazide moiety is converted to hydroxyl group. Cu (II) complex has a tetrahedral geometry according to ESR and electronic spectral data. The reaction of H₄EBC with SmCl₃·6H₂O or LnCl₃·7H₂O gave single crystals of abnormal product (C₁₆H₁₆N₄O₄). The packing diagram of this crystal has a chain structure. The photoluminescence spectra of [Cu ₂ (H ₄ EBC)Cl ₂ ]·H ₂ O , [Co(H ₄ EBC)Cl ₂ (H ₂ O) ₂ ]·2H ₂ O and [Ni(H ₄ EBC)Cl ₂ (H ₂ O)]·2H ₂ O display emission broad‐bands at 342, 321 and 337 nm, respectively. The microbial behavior of the synthesized moieties was investigated against various bacterial and fungal strains. [Cu₂(H₄EBC)Cl₂]·H₂O complex shows the same activity as ampicillin towards Escherichia coli and Staphylococcus aureus with inhibition zones of 26 and 22 mm, respectively. Antioxidant activity is determined using bleomycin‐dependent DNA damage assay besides erythrocyte hemolysis. Finally, in vitro cytotoxic activities against two different cell lines have been examined.     

Caracte´risation ete´tude structurale du bichromate mixte AgKCr2O7

The crystal structure of AgKCr₂O₇ has been determined by single crystal X-ray diffraction. The structure is orthorhombic, space groupPnam, with cell constantsa = 15.175(7),b = 7.414(4), andc = 6.014(2)A? forZ = 4. The structure was refined to a finalR of 0.072 for 934 reflections. The configuration of the dichromate ion, pseudo-C_2v, is similar to that found in most other dichromate structures. The potassium ion is surrounded by eight oxygen atoms and the silver ion has a square planar coordination.