Zeolite-encapsulated Co(II), Ni(II) and Cu(II) complexes as catalysts for partial oxidation of benzyl alcohol and ethylbenzene

Co(II), Ni(II) and Cu(II) complexes of dimethylglyoxime and N,N-ethylenebis(7-methylsalicylideneamine) have been synthesized in situ in Y zeolite by the reaction of ion-exchanged metal ions with the flexible ligand molecules that had diffused into the cavities. The hybrid materials obtained have been characterized by elemental analysis, SEM, XRD, surface area, pore volume, magnetic moment, FTIR, UV-Vis and EPR techniques. Analysis of data indicates the formation of complexes in the pores without affecting the zeolite framework structure, the absence of any extraneous species and the geometry of encapsulated complexes. The catalytic activities for hydrogen peroxide decomposition and oxidation of benzyl alcohol and ethylbenzene of zeolite complexes are reported. Zeolite Cu(II) complexes were found to be more active than the corresponding Co(II) and Ni(II) complexes for oxidation reactions. The catalytic properties of the complexes are influenced by their geometry and by the steric environment of the active sites. Zeolite complexes are stable enough to be reused and are suitable to be utilized as partial oxidation catalysts.

Copper(II) complexes of embelin and 2-aminobenzimidazole encapsulated in zeolite Y-potential as catalysts

Copper(II) complexes of two biologically important ligands, viz., embelin (2,5-dihydroxy-3-undecyl-2,5-cyclohexadien 1,4-dione) and 2-aminobenzimidazole were entrapped in the cages of zeolite Y by the flexible ligand method. The capability of these compounds in catalyzing the reduction of oxygen (industrially known as deoxo reaction) was explored and the results indicate an enhancement of the catalytic properties from that of the simple copper ion exchanged zeolite. These point to the ability of the ligands in enhancing the oxygen binding capability of the metal ion. Elemental analyses, Fourier transform infrared (FTIR), diffuse reflectance and EPR spectral studies, magnetic susceptibility measurements, TG, surface area analyses and powder X-ray diffraction studies were used in understanding the presence, composition and structure of the complexes inside the cages. The study also reveals the increased thermal and mechanical stability of the complexes as a result of encapsulation.

Synthesis of High Coercivity Core–Shell Nanorods Based on Nickel and Cobalt and Their Magnetic Properties

Hybrid magnetic nanostructures with high coercivity have immense application potential in various fields. Nickel (Ni) electrodeposited inside Cobalt (Co) nanotubes (a new system named Ni @ Co nanorods) were fabricated using a two-step potentiostatic electrodeposition method. Ni @ Co nanorods were crystalline, and they have an average diameter of 150 nm and length of *15 lm. The X-ray diffraction studies revealed the existence of two separate phases corresponding to Ni and Co. Ni @ Co nanorods exhibited a very high longitudinal coercivity. The general mobility-assisted growth mechanism proposed for the growth of one-dimensional nanostructures inside nano porous alumina during potentiostatic electrodeposition is found to be valid in this case too

Effect of nickel nanofillers on the dielectric and magnetic properties of composites based on rubber in the X-band

Nickel–rubber nanocomposites were synthesized by incorporating ferromagnetic nickel nanoparticles in a natural rubber as well as neoprene rubber matrix. Complex dielectric permittivity and magnetic permeability of these composites were evaluated in the X-band microwave frequencies at room temperature using cavity perturbation technique. The dielectric loss in natural rubber is smaller compared to neoprene rubber. A steady increase in the dielectric permittivity is observed with increase in the content of nickel in both the composites. The magnetic permeability exhibits a steady decrease with increase in frequency and magnetic loss shows a relaxation at 8 GHz. The suitability of these composites as microwave absorbers is modeled based on the reflection loss which is dependant on the real and imaginary components of the complex dielectric permittivity and magnetic permeability.

Cure Characteristics and Mechanical Properties of Rubber Ferrite Composites Based on Nano-Nickel Ferrites

Ultra fine nickel ferrite have been synthesized by the sol-gel method. By heat treating different portions of the prepared powder separately at different temperatures, nano-sized particles of nickel ferrite with varying particle sizes were obtained. These powders were characterised by the X-ray diffraction and then incorporated in the nitrile rubber matrix according to a specific recipe for various loadings. The cure characteristics and the mechanical properties of these rubber ferrite composites (RFCs) were evaluated. The effect of loading and the grain size of the filler on the cure characteristics and tensile properties were also evaluated. It is found that the grain size and porosity of the filler plays a vital role in determining the mechanical properties of the RFCs

A prediction model for establishing the disability degree in adults with spinal cord injury: results based on WHO-DAS II perspective

Objective: To establish a prediction model of the degree of disability in adults with Spinal CordInjury (SCI ) based on the use of the WHO-DAS II . Methods: The disability degree was correlatedwith three variable groups: clinical, sociodemographic and those related with rehabilitation services.A model of multiple linear regression was built to predict disability. 45 people with sci exhibitingdiverse etiology, neurological level and completeness participated. Patients were older than 18 andthey had more than a six-month post-injury. The WHO-DAS II and the ASIA impairment scale(AIS ) were used. Results: Variables that evidenced a significant relationship with disability were thefollowing: occupational situation, type of affiliation to the public health care system, injury evolutiontime, neurological level, partial preservation zone, ais motor and sensory scores and number ofclinical complications during the last year. Complications significantly associated to disability werejoint pain, urinary infections, intestinal problems and autonomic disreflexia. None of the variablesrelated to rehabilitation services showed significant association with disability. The disability degreeexhibited significant differences in favor of the groups that received the following services: assistivedevices supply and vocational, job or educational counseling. Conclusions: The best predictiondisability model in adults with sci with more than six months post-injury was built with variablesof injury evolution time, AIS sensory score and injury-related unemployment.

Complete filling of zeolite frameworks with polyalkynes formed in situ by transition-metal ion catalysts

We report the use of transition-metal-exchanged zeolites as media for the catalytic formation and encapsulation of both polyethyne and polypropyne, and computer modeling studies on the composites so formed. Alkyne gas was absorbed into the pores of zeolite Y (Faujasite) exchanged with transition-metal cations [Fe(II), Co(II), Cu(II), Ni(II), and Zn(II)]. Ni(II) and Zn(II) were found to be the most efficient for the production of poly-ynes. These cations were also found to be effective in polymer generation when exchanged in zeolites mordenite and beta. The resulting powdered samples were characterized by FTIR, Raman, diffuse reflectance electronic spectroscopy, TEM, and elemental analysis, revealing, nearly complete loading of the zeolite channels for the majority of the samples. Based on the experimental carbon content, we have derived the percentage of channel filling, and the proportion of the channels containing a single polymer chain for mordenite. Experimentally, the channels for Y are close to complete filling for polyethyne (PE) and polypropyne (PP), and this is also true for polyethyne in mordenite. Computer modeling studies using Cerius2 show that the channels of mordenite can only accept a single polymer chain of PP, in which case these channels are also completely filled.

Anion-directed synthesis of metal-organic frameworks based on 2-picolinate Cu(II) complexes: a ferromagnetic alternating chain and two unprecedented ferromagnetic fish backbone chains

Three new polynuclear copper(II) complexes of 2-picolinic acid (Hpic), {[Cu-2(pic)(3)(H2O)]ClO4}(n) (1), {[Cu-2(pic)(3)(H2O)]BF4}(n) (2), and [Cu-2(pic)3(H2O)(2)(NO3)](n) (3), have been synthesized by reaction of the "metalloligand" [Cu-(pic)(2)] with the corresponding copper(II) salts. The compounds are characterized by single-crystal X-ray diffraction analyses and variable-temperature magnetic measurements. Compounds 1 and 2 are isomorphous and crystallize in the triclinic system with space group P (1) over bar, while 3 crystallizes in the monoclinic system with space group P2(1)/n. The structural analyses reveal that complexes 1 and 2 are constructed by "fish backbone" chains through syn-anti (equatorial-equatorial) carboxylate bridges, which are linked to one another by syn-anti (equatorial-axial) carboxylate bridges, giving rise to a rectangular grid-like two-dimensional net. Complex 3 is formed by alternating chains of syn-anti carboxylate-bridged copper(II) atoms, which are linked together by strong H bonds involving coordinated nitrate ions and water molecules and uncoordinated oxygen atoms from carboxylate groups. The different coordination ability of the anions along with their involvement in the H-bonding network seems to be responsible for the difference in the final polymeric structures. Variable-temperature (2-300 K) magnetic susceptibility measurement shows the presence of weak ferromagnetic coupling for all three complexes that have been fitted with a fish backbone model developed for 1 and 2 (J = 1.74 and 0.99 cm(-1); J' = 0.19 and 0.25 cm(-1), respectively) and an alternating chain model for 3 (J = 1.19 cm(-1) and J' = 1.19 cm(-1)).

Design and theoretical study of nickel catalysts for syndiotactic polyolefins

A nickel catalyst was modeled with ligand L-2, [ NH = CH-CH = CH-O](-), which should have potential use as a syndiotactic polyolefin catalyst, and the reaction mechanism was studied by theoretical calculations using the density functional method at the B3LYP/ LANL2MB level. The mechanism involves the formation of the intermediate [(NiLMe)-Me-2](+), in which the metal occuples a T-shaped geometry. - This intermediate has two possible structures with the methyl group trans either to the oxygen or to the nitrogen atom of L-2. The results show that both structures can lead to the desired product via similar reaction paths, A and B. Thus, the polymerization could be considered as taking place either with the alkyl group occupying the position trans to the Ni-O or trans to the Ni-N bond in the catalyst. The polymerization process thus favors the catalysis of syndiotactic polyolefins. The syndiotactic synthesis effects could also be enhanced by variations in the ligand substituents. From energy considerations, we can conclude that it is more favorable for the methyl group to occupy the trans-O position to form a complex than to occupy the trans-N position. From bond length considerations, it is also more favoured for ethene to occupy the trans-O position than to occupy the trans-N position.

Palladium-coated nickel nanoclusters: new Hiyama cross-coupling catalysts

The advantages of bimetallic nanoparticles as C - C coupling catalysts are discussed, and a simple, bottom- up synthesis method of core - shell Ni - Pd clusters is presented. This method combines electrochemical and 'wet chemical' techniques, and enables the preparation of highly monodispersed structured bimetallic nanoclusters. The double- anode electrochemical cell is described in detail. The core - shell Ni - Pd clusters were then applied as catalysts in the Hiyama cross- coupling reaction between phenyltrimethoxysilane and various haloaryls. Good product yields were obtained with a variety of iodo- and bromoaryls. We found that, for a fixed amount of Pd atoms, the core - shell clusters outperform both the monometallic Pd clusters and the alloy bimetallic Ni - Pd ones. THF is an excellent solvent for this process, with less than 2% homocoupling by-product. The roles of the stabiliser and the solvent are discussed.

A global blended tropopause based on ERA data, Part II: trends and tropical broadening

A new tropopause definition involving a flow-dependent blending of the traditional thermal tropopause with one based on potential vorticity has been developed and applied to the European Centre for Medium-Range Weather Forecasts (ECMWF) reanalyses (ERA), ERA-40 and ERA-Interim. Global and regional trends in tropopause characteristics for annual and solsticial seasonal means are presented here, with emphasis on significant results for the newer ERA-Interim data for 1989-2007. The global-mean tropopause is rising at a rate of 47 m decade−1 , with pressure falling at 1.0 hPa decade−1 , and temperature falling at 0.18 K decade−1 . The Antarctic tropopause shows decreasing heights,warming,and increasing westerly winds. The Arctic tropopause also shows a warming, but with decreasing westerly winds. In the tropics the trends are small, but at the latitudes of the sub-tropical jets they are almost double the global values. It is found that these changes are mainly concentrated in the eastern hemisphere. Previous and new metrics for the rate of broadening of the tropics, based on both height and wind, give trends in the range 0.9◦ decade−1 to 2.2◦ decade−1 . For ERA-40 the global height and pressure trends for the period 1979-2001 are similar: 39 m decade−1 and -0.8 hPa decade−1. These values are smaller than those found from the thermal tropopause definition with this data set, as was used in most previous studies.

Synthesis, characterization, crystal structure, and DNA-binding of ruthenium(II) complexes of heterocyclic nitrogen ligands resulting from a benzimidazole-based quinazoline derivative

The reaction of cis-[RuCl2(dmso)(4)] with [6-(2-pyridinyl)-5,6-dihydrobenzimidazo[1,2-c] quinazoline] (L) afforded in pure form a blue ruthenium(II) complex, [Ru(L-1)(2)] (1), where the original L changed to [2-(1H-benzoimidazol-2-yl)-phenyl]-pyridin-2-ylmethylene-amine (HL1). Treatment of RuCl3 center dot 3H(2)O with L in dry tetrahydrofuran in inert atmosphere led to a green ruthenium(II) complex, trans-[RuCl2(L-2)(2)] (2), where L was oxidized in situ to the neutral species 6-pyridin-yl-benzo[4,5]imidazo[1,2-c] quinazoline (L-2). Complex 2 was also obtained from the reaction of RuCl3 center dot 3H(2)O with L-2 in dry ethanol. Complexes 1 and 2 have been characterized by physico-chemical and spectroscopic tools, and 1 has been structurally characterized by single-crystal X-ray crystallography. The electrochemical behavior of the complexes shows the Ru(III)/Ru(II) couple at different potentials with quasi-reversible voltammograms. The interaction of these complexes with calf thymus DNA by using absorption and emission spectral studies allowed determination of the binding constant K-b and the linear Stern-Volmer quenching constant K-SV