Ziegler-type hydrogenation catalysts made from group 8–10 transition metal precatalysts and AlR3 cocatalysts: A critical review of the literature

Ziegler-type hydrogenation catalysts (group 8–10 transition metal precatalysts plus AlR₃ cocatalysts) are one of the most important families of industrial hydrogenation catalysts, especially for polymer hydrogenation. Despite their ～40 year history of industrial use, there is a need for improved fundamental understanding in order to make further, rationally directed improvements in these catalysts. This review examines the existing literature on Ziegler-type hydrogenation catalysts, specifically: (i) the variables important to catalyst synthesis, (ii) the catalyst formation reaction mechanism, (iii) the compositional and structural nature of the active catalyst species, and (iv) the mechanism of catalytic hydrogenation. This review also (v) discusses the current approaches to the homogeneous versus heterogeneous catalysis question, with the goal of identifying if Ziegler-type hydrogenation catalysts are homogeneous (e.g., monometallic) versus heterogeneous (e.g., nanoclusters) as the true catalyst(s). A summary of the main insights from each section of the review is also given.     

Determination of mineral phosphate species in sedimentary phosphate rock in Mardin, SE Anatolia, Turkey by sequential extraction

The importance of the effect of phosphate rock depends on the chemical form of phosphorus in which this element is combined. The paper presents the results of inorganic and organic forms of phosphorus in the phosphate rock from Mazidag-Derik, Semikan deposit located at Mardin city at SE Anatolia of Turkey. Total phosphorus concentration in the rock is an average 18.5%. The inorganic phosphorus mean % contents were 99.98% for studied sedimentary phosphate rock. Speciation of inorganic phosphorus was carried out using a method based on sequential extractions of the sedimentary phosphate rock each releasing four forms of inorganic phosphorus: loosely sorbed phosphorus, phosphorus bound to aluminium (P-Al), phosphorus bound to calcium (P-Ca) and phosphorus bound to iron (P-Fe). Calcium bound phosphorus is the dominant form of inorganic phosphorus in the studied sedimentary phosphate rock. Aluminium bound phosphorus is the second, iron bound phosphorus is the third most prevailing form. Loosely bound phosphorus is present in the lowest amounts. Analyses of phosphorus forms in sedimentary phosphate rock using a UV spectrophotometric method and ICP-AES are reported here. For the phosphorus the two methods give the same results and the concentrations are in good agreement with the reference values.     

Low-threshold lasing eigenmodes of an infinite periodic chain of quantum wires

We study the lasing eigenvalue problems for a periodic open optical resonator made of an infinite grating of circular dielectric cylinders standing in free space, in the E- and H-polarization modes. If possessing a "negative-absorption" refractive index, such cylinders model a chain of quantum wires made of the gain material under pumping. The initial-guess values for the lasing frequencies are provided by the plane-wave scattering problems. We demonstrate a new effect: the existence of specific grating eigenmodes that have a low threshold of lasing even if the wires are optically very thin.     

MOL solution of DOM for transient radiative transfer in 3-D scattering media

A methodology based on the method of lines solution of discrete ordinates method for solution of the 3-D transient radiative transfer equation is introduced. The method is applied to the prediction of transient and steady state transmittances in a cubical enclosure containing purely scattering medium and validated against Monte Carlo solutions from the literature. The flexibility of the method for implementation of linear spatial differencing schemes, flux limiters and weighted essentially non-oscillatory methods is demonstrated. Van Leer flux limiter is found to provide stable, accurate and efficient solutions.     

The inhomogeneous quantum invariance group of commuting fermions

We consider a model of d fermions where creation and annihilation operators of different fermions commute. We show that this particle algebra is invariant under an inhomogeneous quantum group.      

Effect of PNA backbone modifications on cyanine dye binding to PNA-DNA duplexes investigated by optical spectroscopy and molecular dynamics simulations

Optical spectroscopy and molecular dynamics simulations have been used to study the interaction between a cationic cyanine dye and peptide nucleic acid (PNA)-DNA duplexes. This recognition event is important because it leads to a visible color change, signaling successful hybridization of PNA with a complementary DNA strand. We previously proposed that the dye recognized the minor groove of the duplex, using it as a template for the assembly of a helical aggregate. Consistent with this, we now report that addition of isobutyl groups to the PNA backbone hinders aggregation of the dye when the substituents project into the minor groove but have a weaker effect if directed out of the groove. UV-Visible and circular dichroic spectroscopy were used to compare aggregation on the different PNA-DNA duplexes, while molecular dynamics simulations were used to confirm that the substituents block the minor groove to varying degrees, depending on the configuration of the starting amino acid. In addition to a simple steric blockage effect of the substituent, the simulations suggest that directing the isobutyl group into the minor groove causes the groove to narrow and the duplex to become more rigid, structural perturbations that are relevant to the growing interest in backbone-modified PNA for applications in the biological and materials sciences.     

ABC‐type hetero‐arm star terpolymers through “Click” chemistry

Hetero‐arm star ABC‐type terpolymers, poly(methyl methacrylate)‐polystyrene‐poly(tert‐butyl acrylate) (PMMA‐PS‐PtBA) and PMMA‐PS‐poly(ethylene glycol) (PEG), were prepared by using “Click” chemistry strategy. For this, first, PMMA‐b‐PS with alkyne functional group at the junction point was obtained from successive atom transfer radical polymerization (ATRP) and nitroxide‐mediated radical polymerization (NMP) routes. Furthermore, PtBA obtained from ATRP of tBA and commercially available monohydroxyl PEG were efficiently converted to the azide end‐functionalized polymers. As a second step, the alkyne and azide functional polymers were reacted to give the hetero‐arm star polymers in the presence of CuBr/N,N,N′,N″,N″‐pentamethyldiethylenetriamine ( PMDETA) in DMF at room temperature for 24 h. The hetero‐arm star polymers were characterized by ¹H NMR, GPC, and DSC. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5699–5707, 2006     

Ultrasonic destruction of bisphenol-A: the operating parameters

Degradation of bisphenol-A (BPA) by ultrasonic irradiation at 300 kHz was investigated at varying substrate concentrations, pH, hydroxyl radical scavengers and sparge gases. It was found that increases in BPA initial concentration slowed down the reaction rate, but enhanced the sonochemical product yield. Both the rate of reaction and the product yield were adversely affected by pH elevation above the neutral level. The degree of BPA decay was fastest in the presence of air due to the formation of acids and excess radicals, and slowed down as the gas was replaced by argon and oxygen. The impact of large concentrations of hydroxyl radical scavengers such as carbonate and t-butanol was to decrease the rate of degradation, particularly when the scavenger concentration was considerably larger than that of BPA, and the deceleration was more remarkable in the presence of t-butanol than in that of carbonate.     

Determination of lead separated selectively with ion exchange method from solution onto BCW in Sirnak, East Anatolia of Turkey

There are approximately 82 million of tons asphaltites reserves in ?irnak, East Anatolia of Turkey. The present study was investigated to employ ashes of S?rnak BCW (burned coal waste) as an ion exchange in removal of important toxic metal, Lead (Pb), in high yields by adsorption. The ion exchange characteristics of lead onto BCW from aqueous solution were investigated with respect to the changes in pH of solution, adsorbent dosage, initial metal ion concentration, contact time and temperature of solution. For the adsorption of lead, the Langmuir isotherm model fitted to equilibrium data better than the Freundlich isotherm model. Thermodynamic functions, the change of free energy (ΔG°), enthalpy (ΔH°) and entropy (ΔS°) of adsorption were also calculated for lead. These parameters showed that the adsorption was feasible, spontaneous and exothermic at 293–333 K. Experimental data were also evaluated in terms of kinetic characteristics of adsorption. The batch kinetic data were correlated to the pseudo-first order and pseudo-second order models. The data fitted better to the pseudo-second order equation. The activation energy of systems was determined. Experimental data have shown that BCW that was used in unmodified form; as low cost, readily available ion exchange; can be used for removal of lead from industrial waste waters. Analysis was determined using Flame Atomic Absorption Spectrometry (FAAS).