Regioselective Palladium-Catalyzed Cross-Coupling Reactions of 2,4,7-Trichloroquinazoline

The regioselective palladium-catalyzed cross-coupling reactions of 2,4,7-trichloroquinazoline with various aryl- and heteroarylboronic acids are reported. An efficient, sequential strategy was developed that provides access to novel, functionalized heterocycles.     

Representations of Clifford Algebras on Function Spaces on the Cantor Set

We give a representation of the (infinite-dimensional) complex Clifford algebra on the Hilbert space of square-integrable complexvalued functions on the Cantor set.     

Miscibility and morphology of poly(ethylhexylacrylate)/liquid crystal blends prepared under different conditions

A comparative study of the phase diagrams and morphology of blends of poly(2‐ethylhexylacrylate) and low molecular weight liquid crystals (LCs) prepared under different conditions is presented. Two LCs are used; one is the 4‐cyano‐4′‐n‐pentyl‐biphenyl and the other is the eutectic mixture of cyanoparaphenylenes known as E7. Two series of blends are prepared under different conditions. The first series is obtained by the polymerization induced phase separation (PIPS) process under UV‐curing starting from a monomeric mixture, while the second series is prepared by a combination of the solvent induced phase separation and the thermally induced phase separation process starting from a mixture containing a commercial polymer with known molecular weight. Using gel permeation chromatography, it is found that the polymer molecular weight of the UV‐cured systems decreases with the concentration of LC in the precursor mixture. The experimentally obtained phase diagrams of these two series of systems show a miscibility shift at the composition where the molar mass of the polymer in the PIPS/UV blend exceeds that of the commercial polymer. Data are rationalized in terms of the Flory‐Huggins theory of isotropic mixing and the Maier‐Saupe theory of nematic order. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 18–27, 2007     

Synthesis, characterization and thermal properties of cobalt(II), nickel(II) and copper(II) complexes of 2,6-bis(3,4,5-trimethyl-N-pyrazolyl)pyridine): the crystal structure of [Co(btmpp)(H2O)2(NO3)]NO3

Co(II), Ni(II) and Cu(II) nitrate complexes with btmpp, namely ([Co(btmpp)(H₂O)₂(NO₃)]NO₃ (1), [Ni(btmpp)(H₂O)(NO₃)]NO₃ (2) and [Cu(btmpp)(MeOH)(NO₃)]NO₃ (3), where btmpp = 2,6-bis(3,4,5-trimethyl-N-pyrazolyl)pyridine), have been synthesized and characterized by physicochemical and spectroscopic methods. The crystal structure of complex 1 has been determined by single crystal diffraction at 100K. In all the complexes, btmpp is coordinated in a tridentate mode through its nitrogen atoms. One of the nitrates in complex 1 is terminally bonded to the metal center through the oxygen atom, whereas the other one is out of the coordination sphere. The Co(II) atom in complex 1 is hexa-coordinated with a CoN₃O₃ distorted octahedral environment. Decomposition of three complexes was analyzed thermogravimetrically. All three complexes decompose similar to explosive material.     

Kinetic study of the reaction of dimethyl carbonate with trialkylamines

Quaternary ammonium compounds are produced worldwide in hundreds of millions of pound volume annually for a plethora of end‐uses from fabric‐care formulations to asphalt emulsifiers, typically from nongreen alkylating reagents. The kinetics of a reaction employing dimethyl carbonate (DMC) as a green alkylating agent was investigated using three trialkylamines (tributylamine, trihexylamine, and trioctylamine) at several temperatures. Arrhenius and Eyring analysis of the data showed that values of E_a (79 kJ/mol), ΔH^? (75 kJ/mol), and ΔS^? (220 J/(mol K)) were the same for all three amine reactants, consistent with a report that E_a is independent of alkyl chain length when the chain length is greater than three carbons. Although rates are significantly slower with DMC than with other alkylating reagents, the resulting methyl carbonate anion has advantages for clean anion metathesis, which is important for some applications, especially those involving ionic liquids. © 2010 Wiley Periodicals, Inc. Int J Chem Kinet 42: 221–225, 2010     

Experimental and computational investigations of a cadmium(II) mononuclear complex with 2,6-Bis(3,5-dimethyl-N-pyrazolyl)pyridine (bdmpp) and selenocyanate as ligands

A new cadmium (II) complex, [Cd(bdmpp)(SeCN)₂(H₂O)] (1) (where bdmpp = 2,6-bis(3,5-dimethyl-N-pyrazolyl)pyridine), has been synthesized and characterized by elemental and spectral (IR, ¹H-NMR and ¹³C-NMR, UV-Vis) analyses, differential scanning calorimetry, and single crystal X-ray diffraction studies. X-ray analysis showed that the structure was crystallized in the monoclinic space group Cc with a = 9.031(2), b = 13.884(3), c = 16.910(3) Å, and Z = 4. The geometry around the cadmium atom is distorted octahedral with a CdN₃Se₂O setup. The N atoms of the SeCN are engaged in two strong intermolecular H-bonding interactions forming a 3D supramolecular polymeric network. The geometry and vibrational frequencies of complex 1 computed with the DFT methods (BLYP, B3LYP, B3PW91, MPW1PW91) are in better agreement with experiment than those obtained with the ab-initio method except for the bond angles. The molecular orbital diagram has been also calculated and visualized at the B3LYP/LanL2DZ level of theory.      

Adsorption Equilibrium, Kinetics and Thermodynamics of α-Amylase on Poly(DVB-VIM)-Cu+2 Magnetic Metal-Chelate Affinity Sorbent

Designing an immobilised metal ion affinity process on large-scale demands that a thorough understanding be developed regarding the adsorption behaviour of proteins on metal-loaded gels and the characteristic adsorption parameters to be evaluated. In view of this requirement, interaction of ??-amylase as a model protein with newly synthesised magnetic-poly(divinylbenzene-1-vinylimidazole) [m-poly(DVB-VIM)] microbeads (average diameter, 53?C212???m) was investigated. The m-poly(DVB-VIM) microbeads were prepared by copolymerising of divinylbenzene (DVB) with 1-vinylimidazole (VIM). The m-poly(DVB-VIM) microbeads were characterised by N₂ adsorption/desorption isotherms, electron spin resonance, elemental analysis, scanning electron microscope and swelling studies. Cu²⁺ ions were chelated on the m-poly(DVB?CVIM) beads and used in adsorption of ??-amylase in a batch system. The maximum ??-amylase adsorption capacity of the m-poly(DVB?CVIM)?CCu²⁺ beads was determined as 10.84?mg/g at pH?6.0, 25?°C. The adsorption data were analyzed using three isotherm models, which are the Langmuir, Freundlich and Dubinin?CRadushkevich isotherm models. The pseudo-first-order, pseudo-second-order, modified Ritchie??s-second-order and intraparticle diffusion models were used to test dynamic experimental data. The study of temperature effect was quantified by calculating various thermodynamic parameters such as Gibbs free energy, enthalpy and entropy changes.     

Cytochrome c heme lyase can mature a fusion peptide composed of the amino-terminal residues of horse cytochrome c

It is shown that cytochrome c heme lyase (CCHL) attaches heme covalently to peptides composed of the N-terminal segment of cyt c fused to a non-heme containing protein, lending insight into the substrate specificity of CCHL and providing a new route to artificial heme proteins.     

Determination of traces of iron and lead in food and water samples after preconcentration on multiwalled carbon nanotubes

A new method using multiwalled carbon nanotubes as an SPE adsorbent was developed for the sensitive determination of trace iron and lead prior to flame atomic absorption spectrometry analysis. Iron and lead as 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline chelates were adsorbed quantitatively on multiwalled carbon nanotubes at a pH of 6.0 and easily eluted with 10 mL 1 M HNO3. The influences of matrix ions were also examined. The LOD values for iron and lead were calculated as 1.3 and 2.9 microg/L, respectively. Validation of the presented procedure was performed by the analysis of TMDA 54.4 fortified lake water and HR-1 Humber River sediment certified reference materials. The method was successfully applied to the determination of trace iron and lead in real environmental samples, and excellent results were achieved.     

Energies,Landé <Emphasis Type="Italic">g</Emphasis>-factors,and lifetimes for some excited levels of doubly ionized lanthanum

Using the relativistic Hartree-Fock (HFR) method developed by Cowan, we calculated the energy levels, Landé g-factors, and lifetimes for nd (n = 5–25), ns (n = 6–24), ng (n = 5–25), nf (n = 4–22), and np (n = 6–25) excited levels of doubly ionized lanthanum (La III, Z = 57). We compared the results with previously reported calculations and experiments.