Influence of HZSM-5 catalyst on the thermal degradation of poly(vinyl chloride) in solution

The kinetics of thermal degradation of poly(vinyl chloride) (PVC) in solution was investigated at various temperatures (210-250degreesC). The degradation rate coefficients were determined from the time evolution of the molecular weight distribution (MWD). The energy of activation, determined from the temperature dependence of the rate coefficient, was 26.6 kcal/mol. The degradation of PVC was also studied in the presence of a catalyst (HZSM-5 zeolite). The results indicated that increase of the degradation rate of PVC is first order with the HZSM-5 concentration up to 50 g/L and zero order at higher concentrations. The thermal degradation kinetics of PVC in the presence of 50 g/L of the catalyst was studied at various temperatures. The temperature dependency of the rate coefficient was used to calculate the activation energy (21.5 kcal/mol). This is consistent with the observation that the presence of a catalyst generally decreases the activation energy and promotes degradation. (C) 2002 John Wiley Sons, Inc.

Ion beam processing of oriented CuO films deposited on (100) YSZ by laser ablation

A systematic study of Ar ion implantation in cupric oxide films has been reported. Oriented CuO films were deposited by pulsed excimer laser ablation technique on (1 0 0) YSZ substrates. X-ray diffraction (XRD) spectra showed the highly oriented nature of the deposited CuO films. The films were subjected to ion bombardment for studies of damage formation, Implantations were carried out using 100 keV Arf over a dose range between 5 x 10(12) and 5 x 10(15) ions/cm(2). The as-deposited and ion beam processed samples were characterized by XRD technique and resistance versus temperature (R-T) measurements. The activation energies for electrical conduction were found from In [R] versus 1/T curves. Defects play an important role in the conduction mechanism in the implanted samples. The conductivity of the film increases, and the corresponding activation energy decreases with respect to the dose value.

X-Ray structure of a ternary complex, copper(II)–lnosine 5-monophosphate–benzimidazole. The first example for the absence of direct metal–nucleotide interaction

The unprecedented absence of direct metal–nucleotide interaction has been observed in the X-ray structure of the ternary metal nucleotide system [Cu(bzim)(H2O)5]2+[IMP]2–·3H2O [IMP = inosine 5-monophosphate(2–), bzim = benzimidazole). The complex crystallizes in the space group P21 with a= 7.013(2), b= 13.179(9), c= 14.565(9)Å, = 94.82(4)°, and Z= 2. The structure was solved by the heavy-atom method and refined by full-matrix least squares on the basis of 1 761 observed (I? 3i) reflections to final R and R values of 0.034 and 0.036 respectively. The CuII has a distorted octahedral co-ordination with a nitrogen of the bzim ligand [Cu–N 1.947(5)Å] and three oxygens of water molecules in the basal plane [mean Cu–O 2.017(3)Å] and two more water oxygens at axial positions [Cu–O 2.194(6) and 2.732(5)Å]. The nucleotide base stacks with the bzim ligand at an average distance of 3.5 Å and an angle of 22°. In the lattice, N(7) of the base is linked to a lattice water through a hydrogen bond, while all the phosphate oxygens are involved in hydrogen bonds with co-ordinated as well as lattice water molecules. The co-ordination behaviour of IMP to CuII is compared in structures containing different -aromatic amines in order to assess the influence of the ternary ligand in complex formation. The present results indicate that, apart from the commonly observed phosphate binding, other modes of co-ordination are possible, these being influenced mainly by the -accepting properties of the ternary ligand.

The CaO-SrO-CuO-O-2 system: Phase equilibria and thermodynamic properties at 1123 K

Phase relationships in the CaO-SrO-CuO system in pure oxygen at 1.01 x 10(5) Pa pressure were determined by equilibrating different compositions at 1123 K for similar to 120 h and analyzing the phases present in the quenched samples using X-ray diffraction (XRD), optical and scanning electron microscopy, and energy dispersive analysis of X-rays (EDAX). Four solid solution series were observed in the system, The CawSr1-wO monoxide solid solution with rock-salt structure was found to exhibit an asymmetric miscibility gap, The mixing properties of the monoxide system were deduced using a subregular solution model, For the (CaxSr1-x)(2)CuO3 series, a complete solid solution range with orthorhombic space group Immm was obtained. Calcium substituted for strontium up to 68 at. % in SrCuO2+delta and 51.5 at. % in Sr14Cu24O41-delta. The tie lines between the solid solutions were determined accurately, The activity-composition relations in (CaxSr1-x)(2)CuO3, CaySr1-yCuO2+delta, and (Ca2Sr1-z)(14)Cu24O41-delta solid solutions were determined from experimental tie lines. Activities in the (CaxSr1-x)(2)CuO3 and CaySr1-yCuO2+delta series were close to the predictions of the Temkin model, The behavior of the (CazSr1-(z))(14)Cu24O41-delta solid solution was more complex, with the activity of SrCu(24/14)O-(41-delta/14) exhibiting both positive and negative deviations from ideality. Gibbs energy of formation of the CaCuO2+delta metastable phase at 1123 K was deduced from an analysis of the phase diagram.

Synthesis and structure of La14V6CuO36.5: a transparent Cu(I) vanadate containing [OCuO](3-) sticks

The title compound, La14V6CuO36.5, was prepared from a stoichiometric mixture of La2O3,V2O5, and CuO at 1050-1080 degreesC. The compound forms transparent, pale green crystals and was characterized by wavelength dispersive spectroscopy and single crystal X-ray diffraction. The structure contains isolated VO43- tetrahedra and [OCuO](3-) sticks dispersed in a lanthanum oxide network. Films of La14V6CuO36.5 were grown on R-plane sapphire by using pulsed laser deposition. Rutherford backscattering spectroscopic and X-ray diffraction analyses of the films showed oriented growth of the title phase, a similar to5 eV optical band gap and n-type conductivity. The compound is an example of a transparent copper(I) oxide.

Thermodynamics of CuAlO2 and CuAl2O4 and phase equilibria in the system Cu2O CuO-Al2O3

The standard Gibbs free energies of formation of CuAlO2 and CuAl2O4 were determined in the range 700° to 1100°C, using emf measurements on the galvanic cells (1) Pt,CuO +] Cu2O/CaO-ZrO2/O2,Pt; (2) Pt,Cu +] CuAlO2+] Al2O3/CaO-ZrO2/ Cu +] Cu2O,Pt; and (3) Pt,CuAl2O4+] CuAlO2+]Al2O3/CaO-ZrO2/O2,Pt. The results are compared with published information on the stability of these compounds. The entropy of transformation of CuO from tenorite to the rock-salt structure is evaluated from the present results and from earlier studies on the entropy of formation of spinels from oxides of the rock-salt and corundum structures. The temperatures corresponding to 3-phase equilibria in the system Cu2O-CuO-Al2O3 at specified O2 pressures calculated from the present results are discussed in reference to available phase diagrams.

Completely random nanoporous Cu4O3-CuO-C composite thin films for potential application as multiple channel photonic band gap based filter in the telecommunication wavelengths

In 2003, Babin et al. theoretically predicted (J. Appl. Phys. 94:4244, 2003) that fabrication of organic-inorganic hybrid materials would probably be required to implement structures with multiple photonic band gaps. In tune with their prediction, we report synthesis of such an inorganic-organic nanocomposite, comprising Cu4O3-CuO-C thin films that experimentally exhibit the highest (of any known material) number (as many as eleven) of photonic band gaps in the near infrared. On contrary to the report by Wang et al. (Appl. Phys. Lett. 84:1629, 2004) that photonic crystals with multiple stop gaps require highly correlated structural arrangement such as multilayers of variable thicknesses, we demonstrate experimental realization of multiple stop gaps in completely randomized structures comprising inorganic oxide nanocrystals (Cu4O3 and CuO) randomly embedded in a randomly porous carbonaceous matrix. We report one step synthesis of such nanostructured films through the metalorganic chemical vapor deposition technique using a single source metalorganic precursor, Cu-4(deaH)(dea)(oAc)(5) a <...aEuro parts per thousand(CH3)(2)CO. The films displaying multiple (4/9/11) photonic band gaps with equal transmission losses in the infrared are promising materials to find applications as multiple channel photonic band gap based filter for WDM technology.

A New Method For The Generation Of 5,6-Quinolinedione 5-Methide .5. Synthesis Of Polycyclic Heteroaromatics

Reaction of 6-acetoxy-5-bromomethylquinoline (1c) and 2-bromomethyl-4-(2'-pyridyl)phenyl acetate (2b) with tetrachlorocatechol in acetone in the presence of anhydrous potassium carbonate resulted in the formation of diastereomeric products 3c, 3d, 4e and 4f.

Ethyl 1-(2-cyanoethyl)-3,5-dimethyl-1H-indole-2-carboxylate

The title compound, C16H18N2O2, is an important precursor in the synthesis of 1,2,3,4-tetrahydropyrazinoindoles, which show excellent antihistamine, antihypertensive and central nervous system depressant properties. The carbethoxy group attached to C2 and the planar cyanoethyl group attached to N1 make dihedral angles of 11.0(4) and 75.0(3)degrees, respectively, with the mean plane of the indole ring, The C-C=N chain is linear with a bond angle of 179.3 (4)degrees.

Dimethyl 2,2 `-[(4-oxo-2-phenyl-4H-chromene 5,7-diyl)dioxy]diacetate: a more densely packed polymorph

The title molecule, C21H18O8, crystallizes in two crystal polymorphs, see also Nallasivam, Nethaji, Vembu & Jaswant [Acta Cryst. (2009), E65, o314-o315]. The molecules of both polymorphs differ by the conformation of the oxomethylacetate groups. The title molecules are rather planar compared to the molecules of the other polymorph. In the title molecule, one of the oxomethylacetate groups is disordered (occupancies of 0.6058/0.3942). The structures of both polymorphs are stabilized by C-H center dot center dot center dot O and C-H center dot center dot center dot pi interactions. Due to the planarity of the title molecules and similar intermolecular interactions, the title molecules are more densely packed than those of the other polymorph.

Dimethyl 2,2`-[(4-oxo-2-phenyl-4H-chromene-5,7-diyl)dioxy]diacetate:a less densely packed polymorph

The title molecule, C21H18O8, crystallizes in two crystal polymorphs,see also Nallasivam, Nethaji, Vembu & Jaswant [Acta Cryst. (2009),E65, o312-o313]. The main difference between the two polymorphs is in the conformation of the oxomethylacetate groups with regard to the almost planar [total puckering amplitude 0.047 (2) angstrom] chromene ring. In the title compound, the best planes of the oxomethylacetate groups through the non-H atoms are almost perpendicular to the chromene ring [making dihedral angles of 89.61 (6) and 80.59 (5)degrees], while in the second polymorph the molecules are close to planar. Both crystal structures are stabilized by C-H center dot center dot center dot O.

Synthesis of novel poly[(2,5-dimethoxy-p-phenylene)vinylene] precursors having two eliminatable groups: An approach for the control of conjugation length

Poly[(2,5-dimethoxy-p-phenylene)vinylene] (DMPPV) of varying conjugation length was synthesized by selective elimination of organic soluble precursor polymers that contained two eliminatable groups, namely, methoxy and acetate groups. These precursor copolymers were in turn synthesized by competitive nucleophilic substitution of the sulfonium polyelectrolyte precursor (generated by the standard Wessling route) using methanol and sodium acetate in acetic acid. The composition of the precursor copolymer, in terms of the relative amounts of methoxy and acetate groups, was controlled by varying the composition of the reaction mixture during nucleophilic substitution. Thermal elimination of these precursor copolymers at 250 degrees C, yielded partially conjugated polymers, whose color varied from light yellow to deep red. FT-IR studies confirmed that, while essentially all the acetate groups were eliminated, the methoxy groups were intact and caused the interruption in conjugation. Preliminary photoluminescence studies of the partially eliminated DMPPV samples showed a gradual shift in the emission maximum from 498 to 598 nm with increasing conjugation lengths, suggesting that the color of LED devices fabricated from such polymers can, in principle, be fine-tuned.

Thermodynamics of ligand (substrate end product) binding to endoxylanase from Chainia sp. (NCL-82-5-1): isothermal calorimetry and fluorescence titration studies

The binding of xylo-oligosaccharides to Chainia endoxylanase resulted in a decrease in fluorescence intensity of the enzyme with the formation of 1:1 complex. Equilibrium and thermodynamic parameters of ligand binding were determined by fluorescence titrations and titration calorimetry. The affinity of xylanase for the oligosaccharides increases in the order X-2 < X-3 < X-4 less than or equal to X-5. Contributions from the enthalpy towards the free energy change decreased with increasing chain length from X-2 to X-4, whereas an increase in entropy was observed, the change in enthalpy and entropy of binding being compensatory. The entropically driven binding process suggested that hydrophobic interactions as well as hydrogen bonds play a predominant role in ligand binding.

Adenosine-5'-carboxylic Acid

The two molecules in the asymmetric unit of adenosine-5'-carboxylic acid, C10H11N5O5, exist as zwitterions with N1 protonated and the carboxyl groups ionized. Both molecules are in an anti conformation with glycosyl torsion angles of -161.4(3) and -155.5(3)degrees. The ribose moieties adopt a C3-endo-C2-exo twist conformation. The pseudo-rotation parameters are P = 0.01(1) and 6.58(1)degrees, and tau(m) = 36.2(2) and 34.6(2)degrees, for molecules A and B, respectively. The carboxyl groups of A and B are not in the standard g(+), g(-) or t conformations. Both Watson-Crick sites, N1 and N6, of the adenine bases are involved in a pair of hydrogen bonds with the dissociated carboxyl groups, forming a cyclic tetramer. The adenine base of molecule A stacks on the ribose O4' atom of a symmetry-related B molecule at a distance of 2.88 Angstrom; the adenine base of B stacks in an analogous way at a distance of 2.91 Angstrom.

Bridged systems via radical cyclization reactions. Stereospecific synthesis of chiral tricyclo[6.2.1.0(1,5)]undecanes

The application of radical-mediated cyclizations and annulations in organic synthesis has grown in importance steadily over the years to reach the present status where they are now routinely used in the strategy-level planning.2 The presence of a quaternary carbon atom is frequently encountered in terpenoid natural products, and it often creates a synthetic challenge when two or more quaternary carbon atoms are present in a contiguous manner.3 Even though creation of a quaternary carbon atom by employing a tertiary radical is very facile, creation of a quaternary carbon atom (or a spiro carbon atom) via radical addition onto a fully substituted olefinic carbon atom is not that common but of synthetic importance. For example, the primary radical derived from the bromide 1 failed to cyclize to generate the two vicinal quaternary carbon atoms and resulted in only the reduced product 2.4 The tricyclic carbon framework tricyclo[6.2.1.01,5]undecane (3) is present in a number of sesquiterpenoids e.g. zizzanes, prelacinanes, etc.5