Synthesis and characterization of liquid crystalline tetra- and octa-substituted novel phthalocyanines

Methylene-bridged tetra- and octa-(13,17-dioxa nonacosane-15 sulfanyl)-substituted metal free- and Ni(II) phthalocyanines were synthesized from the corresponding phthalonitrile (3, 4) derivatives in the presence of the anhydrous metal salt (NiCl₂) or a strong organic base. The new compounds were characterized by elemental analyses, UV/Vis, IR, NMR and mass spectra. The mesogenic properties of these materials were studied by differential scanning calorimetry (DSC), optical microscopy and X-ray diffraction investigations. X-ray diffraction patterns of the mesophase confirm that tetra- and octa-substituted compounds (3a–b, 4a–b) form hexagonal columnar mesophases (Col_h). We indicated that addition of the methylene-bridged phthalocyanine (Pc) core can either decrease the liquid crystal phase transition temperatures or extend the liquid crystal temperature range to include room temperature. Also, the Pc compounds (3a, 3b, 4a and 4b) are liquid crystals at room temperature. These properties of the Pc complexes provide some advantages such as easily obtaining an ordered film for sensor applications. Computational modelling work was combined with X-ray diffraction investigation to validate the diameter of the phthalocyanine molecule (3b).     

The first bis(orotato–N,O) complex: Synthesis,crystal structure,spectroscopic and thermal characterization of (chaH)2[Cu(HOr–N,O)2(cha)] · 2H2O (cha = cyclohexylamine and HOr = orotate(2−))

The novel bis(cyclohexylaminium) cyclohexylaminebis(orotate–N,O)cuprate(II) dihydrate, (C₆H₁₅N)₂[Cu(C₅H₂N₂O₄)₂(C₆H₁₄N)] · 2H₂O, has been prepared and characterized by elemental analysis, magnetic measurements, FT-IR and UV–Vis spectroscopy, thermal analysis and X-ray diffraction. The Cu(II) complex crystallizes in the monoclinic space group P2₁/c. The copper atom in the five-coordinated (chaH)₂[Cu(HOr–N,O)₂(cha)] · 2H₂O is chelated by a deprotonated pyrimidine nitrogen atom and carboxylate oxygen atom as a bis(bidentate) ligand and the cyclohexylamine ligand completes the square-pyramidal coordination. The thermal decomposition of the complex has been predicted by the help of thermal analysis (TG, DTG and DTA).     

Diterpenoid Alkaloids of Delphinium buschianum Grossh.

From the aerial parts of Delphinium buschianum Grossh ., collected in Turkey, a new diterpenoid alkaloid 1 , named budelphine, was isolated along with the known diterpenoid alkaloids karakoline ( 2 ), 18‐hydroxy‐14‐O‐methylgadesine ( 3 ), delsoline ( 4 ), lapaconidine ( 5 ), columbianine ( 6 ), 14‐benzoylneoline ( 7 ), and hetisine ( 9 ). The structure of 1 was established on the basis of ¹H‐, ¹³C‐, DEPT, ¹H,¹H‐COSY, NOESY, HSQC, and HMBC NMR studies.     

Vitamin B13 Complexes of Nickel(II) and Copper(II) with Ethanolamine: Syntheses,Crystal Structures,Spectroscopic and Thermal Studies

Fac‐bis(ethanolamine)orotatonickel(II), [Ni(HOr)(ea)₂] and mer‐bis(ethanolamine)orotatocopper(II) dihydrate, [Cu(HOr)(ea)₂]· 2H₂O were synthesized and characterized by elemental analysis, FT‐IR, UV‐Vis Spectroscopy and thermal analysis. In addition, their solid‐state structures were determined by single crystal X‐ray diffraction studies. Both the fac‐[Ni(HOr)(ea)₂] (1) and mer‐[Cu(HOr)(ea)₂]·2H₂O (2) complexes are isomorphous and crystallize in the triclinic space group . The Ni²⁺ and Cu²⁺ ions are coordinated by two neutral ea ligands and one orotate dianion in a distorted octahedral fashion. The ea ligand acts as a bidentate donor through the amine N and hydroxyl O atoms, while orotate dianion is coordinated through deprotonated N3 pyrimidine atom and carboxylate oxygen atom as a bidentate ligand. Thermal decompositions of the complexes are studied in over the range 20–600 °C on heating in a static air atmosphere.     

Assesment of dimethyl phthalate removal from aqueous phase using barium hexaferrite containing magnetic beads

The barium hexaferrite (BaFe(12)O(19)) containing magnetic poly (ethylene glycol dimethacrylate-vinyl pyridine; mag-poly [EGDMA-VP]) beads (average diameter=53-212 μm) were synthesized and characterized. Their use as an adsorbent in the removal of dimethyl phthalate (DMP) from an aqueous solution was investigated. The mag-poly (EGDMA-VP) beads were prepared by copolymerizing of 4-vinyl pyridine (VP) with ethylene glycol dimethacrylate (EGDMA). The mag-poly (EGDMA-VP) beads were characterized by N(2) adsorption/desorption isotherms (BET), vibrating sample magnetometer (VSM), X-ray powder diffraction (XRD), elemental analysis, scanning electron microscope (SEM), and swelling studies. At a fixed solid/solution ratio, the various factors affecting the adsorption of DMP from aqueous solutions such as pH, initial concentration, contact time, and temperature were analyzed. The maximum DMP adsorption capacity of the mag-poly (EGDMA-VP) beads was determined as 96.2 mg/g at pH 3.0, 25 °C. All the isotherm data can be fitted with both the Langmuir and the Dubinin-Radushkevich isotherm models. The pseudo-first-order, pseudo-second-order, Ritch-second-order, and intraparticle diffusion models were used to describe the adsorption kinetics. The thermodynamic parameters obtained indicated the exothermic nature of the adsorption. The DMP adsorption capacity did not change after 10 batch successive reactions, demonstrating the usefulness of the magnetic beads in applications.     

Degenerate molecular shuttles with flexible and rigid spacers

The preparation and dynamic behavior of degenerate rotaxane molecular shuttles are described in which a benzylic amide macrocycle moves back and forth between two naphthalimide-glycine units along a diphenylethyne spacer or an aliphatic spacer consisting of a C(9), C(12), or C(26) alkyl chain. Subtle differences in the (1)H NMR spectra of the rotaxanes can be related to the presence of conformers in which the macrocycle interacts simultaneously with both glycines, especially in the case of the C(9) spacer. The kinetic data of the shuttling behavior in the C(26) rotaxane were obtained from dynamic NMR spectroscopy. The Eyring activation parameters were found to be ΔH(?) = 10 ± 1 kcal mol(-1), ΔS(?) = -6.5 ± 2.0 cal mol(-1) K(-1), ΔG(?)(298) = 11.9 ± 0.2 kcal mol(-1). For the systems with the shorter spacers, the shuttling rates were higher. Also in the diphenylethyne, rotaxane shuttling is rapid on the NMR time scale, indicating that the rigid unit does not impose a large barrier to the translocation of the macrocycle.     

Electrokinetic properties of sepiolite suspensions in different electrolyte media

The present paper deals with the electrokinetic characterization of sepiolite. A series of systematic zeta potential measurements have been carried out to determine the isoelectric point (iep) and potential-determining ions (pdi), and the effect of mono-, di-, and trivalent electrolytes such as NaCl, KCl, LiCl, NaNO(3), NaCH(3)COO, MgCl(2), CaCl(2), BaCl(2), CoCl(2), CuCl(2), Pb(NO(3))(2), Na(2)CO(3), Na(2)SO(4), AlCl(3), FeCl(3), and Na(3)PO(4) on the zeta potential of sepiolite. Zeta potential has been calculated with the aid of Smoluchowski's equation. Sepiolite yields an isoelectric point at pH 6.6. The zeta potential for the sepiolite has ranged from +23.3 mV at pH approximately 2 to -22.4 mV at pH approximately 8 at 20 +/- 2 degrees C in water. The valency of the ions have proven to have a great influence on the electrokinetic behavior of the suspension. Monovalent cations were found to have a weak effect, while di- and trivalent cations made the zeta potential positive. Charge reversal was observed for divalent cations at 1 x 10(-2) M and for trivalent cations at 3 x 10(-4) M. As a result, it can be said that monovalent cations are indifferent ions when di- and trivalent cations are potential-determining ions.     

The enthalpies of combustion and formation of <Emphasis Type="Italic">L</Emphasis>-α-glutamic and 6-aminohexanoic acids

Summary The energies of combustion of crystalline L-α-glutamic and 6-aminohexanoic acids were measured in a static bomb adiabatic calorimeter, in pure oxygen at 3040 kPa. Corrections were made for the heats due to the ignition of sample and for the nitric acid formation. The derived enthalpies of formation for L-α -glutamic and 6-aminohexanoic acids are Δ_fH_cr⁰= -1002.6±1.1 kJ mol^-1and Δ_fH_cr⁰= -641.6±1.2 kJ mol^-1, respectively. The data of enthalpy of formation are compared with literature values and with estimated values by means of group additivity, using parameters recommended by Domalski and Hearing.     

Synthesis,structural, spectral,thermal and comparative biological activity studies of [V<Subscript>2</Subscript>O<Subscript>2</Subscript>(SO<Subscript>4</Subscript>)<Subscript>2</Subscript>(H<Subscript>2</Subscript>O)<Subscript>6</Subscript>]

The hydrothermal reaction of a mixture of V₂O₅, VCl₃, 2,5-pyridinedicarboxylic acid and diluted H₂SO₄ for 68 h at 180°C gives a blue colored solution which yields prismatic blue crystals of IV ₂ ^IV O₂(SO₄)₂(H₂O)₆] (1) in 32% yield (based on V). Complex 1 was investigated by means of elemental analysis (C, H and S), TGA, FT-IR, manganometric titration, Single Crystal X-ray Diffraction Methods and also comparative antimicrobial activities. Crystal data for the compound: monoclinic space group P2₁/c and unit cell parameters are a = 7.3850(12) Å, b = 7.3990(7) Å, c = 12.229(2) Å, β = 108.976(12)° and Z = 2. Although structure of 1 as a natural mineral has been previously determined, this work covers new preparation method and full characterization of 1 along with comparison of antibacterial activity between 1 and the commercial vanadium(IV) oxide sulfate hydrate compounds, VOSO₄ · xH₂O (Riedel-de Haën and Alfa Aesar brand names). 1 was evaluated for the antimicrobial activity against gram-positive, gram-negative bacteria, yeasts and mould compared with the commercial VOSO₄ · xH₂O compounds. 1 showed weak activity against bacteria Bacillus cereus, Nocardia asteroides and yeast Candida albicans. A good antimicrobial activity was recorded against Cirtobacter freundii (15 mm). There are only a few reproducible well-defined vanadium(IV) starting materials to use for exploring the synthesis of new materials. VCl₄, VO(acac)₂, VOSO₄ · xH₂O and [V(IV)OSO₄(H₂O)₄] · SO₄ · [H₂N(C₂H₄)₂NH₂] are common starting materials for such applications. In addition to these compounds, 1 can be used as an oxovanadium precursor.     

In vivo biodistribution of <Superscript>131</Superscript>I labeled bleomycin (BLM) and isomers (A2 and B2) on experimental animal models

Bleomycins (BLMs; BLM, A2, and B2) were labeled with ¹³¹I and radiopharmaceutical potentials were investigated using animal models in this study. Quality control procedures were carried out using thin layer radiochromatography (TLRC), high performance liquid chromatography (HPLC), and liquid chromatography (LC/MS/MS). Labeling yields of radiolabeled BLMs were found to be 90, 68, and 71%, respectively. HPLC chromatograms were taken for BLM and cold iodinated BLM (¹²⁷I-BLM). Five peaks were detected for BLM and three peaks for ¹²⁷I-BLM in the HPLC studies. Two peaks belong to isomers of BLM. The isomers of BLM were purified with using HPLC. Biological activity of BLM was determined on male Albino Wistar rats by biodistribution and scintigraphic studies were performed for BLMs by using New Zelland rabbits. The biodistribution results of ¹³¹I-BLM showed high uptake in the stomach, the bladder, the prostate, the testicle, and the spinal cord in rats. Scintigraphic results on rabbits agrees with that of biodistributional studies on rats. The scintigraphy of radiolabeled isomers (¹³¹I-A2 and ¹³¹I-B2) are similiarly found with that of ¹³¹I-BLM.