Synthesis and characterization of poly(higher‐α‐olefin)s with a nickel(α‐diimine)/methylaluminoxane catalyst system: Effect of chain running on the polymer properties

Homopolymerization of octadecene‐1 at different reaction conditions has been studied. Significant chain running can be seen at higher polymerization temperatures. Interestingly, insertion of octadecene‐1 into a sterically hindered nickel‐cation/carbon (secondary) bond is observed. The microstructure of the polymer was established using NMR spectroscopy. The effects of chain running on polymer melting, crystallization behavior, and dynamic mechanical thermal properties were studied using DSC and DMTA. The extent of chain running (i.e., 2,ω‐, 1,ω‐enchainments) decreases with an increase in the carbon number of α‐olefins. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 191–210, 2007     

Nucleation and growth mechanism of Pd/Pt bimetallic clusters in sodium bis(2-ethylhexyl)sulfosuccinate (AOT) reverse micelles as studied by in situ X-ray absorption spectroscopy

We report in situ X-ray absorption spectroscopy (XAS) investigations on the formation of palladium-platinum (Pd/Pt) bimetallic clusters at the early stage within the water-in-oil microemulsion system of water/AOT/n-heptane. The reduction of palladium and platinum ions and the formation of corresponding clusters are monitored as a function of dosage of reducing agent, hydrazine (N(2)H(5)OH). Upon successive addition of the reducing agent, hydrazine (N(2)H(5)OH), five distinguishable steps are observed in the formation process of Pd/Pt clusters at the early stage. Both in situ X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) analysis for both the Pd K-edge and Pt L(III)-edge revealed the formation of Pd/Pt bimetallic clusters. A corresponding structural model is proposed for each step to provide a detailed insight into the nucleation and growth mechanism of Pd/Pt bimetallic clusters. We also discussed the atomic distribution of Pd and Pt atoms in Pd/Pt bimetallic clusters based on the calculated XAS structural parameters.     

Preparation of polymandelide by reaction of α-bromophenylacetic acid and triethylamine

Polymandelide was prepared in 77% yield by reaction of α-bromophenylacetic acid and triethylamine. The product was characterized by ¹H- and ¹³C-NMR and IR spectra and isolation and identification of mandelic acid from hydrolysis of the polymer. The NMR spectra indicate the presence of tacticity at CH in the polymer. Molecular weights were determined by GPC and viscosity measurements; n values of 12–20 are comparable to those reported for polymandelides prepared by other methods. The x-ray powder diffraction pattern showed the product to be completely amorphous. Thermal decomposition was studied using DSC.     

The influence of indoxyl sulfate and ammonium on the autofluorescence of human urine

Despite biological variability the spectral characteristics of undiluted human urine show relatively low autofluorescence at short UV (250-300 nm) excitation. However with dilution the fluorescence intensity remarkably increases. This paper examines the mechanisms behind this effect, by using excitation-emission matrices. Corrections for the inner filter effect were made for improved understanding of the spectral patterns. We focused on three major fluorophores (tryptophan, indoxyl sulfate and 5-hydroxyindole-3-acetate) that are excited at these wavelengths, and whose content in urine is strongly linked with various health conditions. Their fluorescence was studied both individually and in combinations. We also examined the effect of ammonium on the fluorescence of these major fluorophores individually and in combinations. Through these studies we have identified the leading effects that reduce the UV fluorescence, namely higher concentration of indoxyl sulfate producing the inner filter effect and concentration quenching and quenching of fluorophores by ammonium. This result will assist in broader utilisation of UV fluorescence in medical diagnostics.     

Accurate measurement of thermal expansion of solids between 77 K and 350 K by 3-terminal capacitance method

The construction of a three-terminal capacitance cell and a bath type cryostat to measure thermal expansion of solids in the temperature range 77 K to 350 K is described. Calculation of the thermal expansion coefficients by using spline approximation is discussed along with the various errors involved in the measurement. The capacitance cell is calibrated by using aluminium and germanium as standard reference materials. The cell has an accuracy of 4% in the measurement of thermal expansion coefficient and a resolution of 1 Å change in length of sample of length 1 cm.     

Expeditious,Nano-BF3 · SiO2-Catalyzed Michaelis–Arbuzov Reaction in an Ionic Liquid: Synthesis of Privileged Aryl/Heterocyclic Phosphonates

An expeditious, simple, and green method was developed for the synthesis of privileged aryl/heterocyclicphosphonates, 8(a–c) to 13(a–c) through Michaelis–Arbuzov reaction of aryl/heterocyclic halides (Br), 1–6, and trialkylphosphites, 7(a–c), in room-temperature ionic liquid [bbim]Br using heterogeneous Lewis catalyst, nano-silica-supported boron trifluoride (BF₃-SiO₂). The advantages of this protocol are simplicity, good yield of the products, less reaction time (20–38 min), mild reaction conditions, easy workup, and reusability of the catalyst and ionic liquid. It is demonstrated that nano-BF₃-SiO₂ is a recoverable and easy accessible catalyst for the formation of C(sp²)-P bond in an ionic liquid.     

Investigation of formation mechanism of Pt(111) nanoparticle layers grown on Ru(0001) core

A layer growth mechanism of Pt-Ru bimetallic nanoparticles has been proposed with supporting experiments and calculations by density functional theory (DFT). Elongated Pt atoms on Ru nanoparticles were synthesized via a two-step route, and their structural details were obtained by high-resolution transmission electron microscopy. Because of the intrinsic mismatch of lattice spacing between the two elements, such an unusual growth was analyzed with the DFT simulations to explore the mystery of the growth mechanism. Pt atoms would rearrange the packing order and adjust the Pt-Pt atomic distance, and so do the Ru nanoparticles in order to achieve the optimal energy status of the bimetallic system. The resultant Pt(111) layers could stack on top of the Ru(0001) core more tightly by fitting the pockets left between the Ru atoms. The findings give insight into the formation mechanism of the nanosized Pt-Ru bimetallic catalyst and pave the way for designing bimetallic catalysts with tailored properties at the atomic level.     

Elastic anomalies in strontium titanate

The anomalies of the second and third-order elastic constants have been considered for the phase transition of strontium titanate within the framework of Landau’s theory. All the anomalies of the second-order elastic constants have been obtained in a single formula using Kronecker delta functions and relations among them have been established. The real parts ofC*₁₁ andC*₄₄ decrease steeply across the transition temperature and thereafter flatly tend to their asymptotic values in the low temperature phase agreeing qualitatively with experimental observations. We have also derived expressions for the third-order elastic anomalies and discussed the temperature variation of the real part ofC*₁₁₁. We have derived expressions for the attenuation of the longitudinal and transverse waves along certain simple symmetry directions and have shown that there is nearly good agreement with experimental observations.