Determination of 25 elements in the complex oxide mineral zirconolite by analytical electron microscopy

In this paper we describe a technique for the determination of 25 elements in natural zirconolite using energy-dispersive analytical electron microscopy (AEM). The method presented here allows one to quantitatively investigate the chemistry of submicron-scale zones in complex oxide minerals. The effects of electron channeling, thickness variability and variations in detector resolution were minimized by using a controlled set of operating procedures and instrument parameters. To provide a high level of accurayy, k_ATI-factors were determined from standards for most of the 25 elements of interest, including all of the major elements. Each analytical spectrum is reduced to a set of raw peak counts (and errors) using a digital top-hat filter to suppress background followed by multiple least squares fitting of reference spectra. Counting times of 12–15 min per analysis were required to provide suitable counting statistics. Results are presented for zirconolite samples from the contact metamorphic aureole of the Bergell granodiorite intrusion, Switzerland-Italy. A comparison of 43 AEM analyses with 15 analyses obtained by wavelength-dispersive electron probe microanalysis (EPMA) shows that there is excellent agreement between the two data sets in the amounts of individual elements present, chemical trends and overall stoichiometry. An assessment of the combined data set shows that the major substitution mechanisms in the Bergell samples are coupled substitutions involving the M5,6- and M8-sites of the zirconolite structure: ^M8Ca²⁺ + ^M5,6Ti⁴⁺→^M8REE³⁺ + ^M5,6(Al,Fe)³⁺ and ^M8Ca²⁺ + ^M5,6Ti⁴⁺→^M8(Th,U)⁴⁺ + ^M5,6 (Mg,Fe)²⁺.     

Building the Additive Utility Functions for CAD-UFRJ Evaluation Staff Criteria

This paper presents an application of the UTA method for building utility functions for the evaluation criteria defined by the Staff Evaluation Commission (CAD) of the Rio de Janeiro Federal University (UFRJ). Every year, the CAD-UFRJ gives the staff evaluation results for each Postgraduate Engineering Programme. However, the method used to generate the staff evaluation is assumed unknown. Trying to find the CAD-UFRJ preference structure, the evaluation results supplied by CAD-UFRJ are used to apply the UTA method. Some additional information obtained from the CAD-UFRJ data is incorporated in the optimal solutions analysis.     

Solid phase synthesis of 5-aminopyrazoles and derivatives

The development of a novel solid phase synthesis of some 5-aminopyrazoles and derivatives is described. Reaction of hydrazines with solid supported β-keto-nitrile (1) affords 5-aminopyrazoles (2) the amino group of which is readily acylated or sulphonylated. Generation of the solid supported β-keto-nitrile (1) is non trivial and represents a key step in the overall synthesis.     

Synthesis and characterization of thermoresponsive amphiphilic block copolymers incorporating a poly(ethylene oxide‐stat‐propylene oxide) block

Amphiphilic BuO‐(PEO‐stat‐PPO)‐block‐PLA‐OH diblock and MeO‐PEO‐block‐(PEO‐stat‐PPO)‐block‐PLA‐OH triblock copolymers incorporating thermoresponsive poly(ethylene oxide‐stat‐propylene oxide) (PEO‐stat‐PPO) blocks were prepared by ring‐opening polymerization of lactide (LA) initiated by macroinitiators formed from treating BuO‐(PEO‐stat‐PPO)‐OH and MeO‐PEO‐block‐(PEO‐stat‐PPO)‐OH with AlEt₃. MeO‐PEO‐block‐(PEO‐stat‐PPO)‐OH was prepared by coupling MeO‐PEO‐OH and HO‐(PEO‐stat‐PPO)‐OH, followed by chromatographic purification. The cloud points of 0.2% aqueous solutions are between 36 and 46 °C for the diblock copolymers that contain a 50 wt % EO thermoresponsive block and 78 °C for the triblock copolymer that contains a 75 wt % EO thermoresponsive block. Variable temperature ¹H NMR spectra recorded on D₂O solutions of the diblock copolymers display no PLA resonances below the cloud point and fairly sharp PLA resonances above the cloud point, suggesting that desolvation of the thermoresponsive block increases the miscibility of the two blocks. Preliminary characterization of the micelles formed in aqueous solutions of BuO‐(PEO‐stat‐PPO)‐block‐PLA‐OH conducted using laser scanning confocal microscopy and pulsed gradient spin echo NMR point to significant changes in the size of the micellar aggregates as a function of temperature. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5156–5167, 2005     

Rate enhancement of PFP sulfonate ester aminolysis by chloride salts in organic and aqueous media

We report here, a method of accelerating the rate of aminolysis of PFP sulfonates to yield sulfonamides using tetrabutylammonium salts. We have previously explored the utility of employing PFP sulfonates in the formation of sulfonamides; however we demonstrate here the advantages of combining the existing methodology with a revised protocol which allows the diversity within both the sulfonate ester and the amine to be extended.     

Cooperative Lewis Pairs Based on Late Transition Metals: Activation of Small Molecules by Platinum(0) and B(C6F5)3

A Lewis basic platinum(0)–CO complex supported by a diphosphine ligand and B(C₆F₅)₃ act cooperatively, in a manner reminiscent of a frustrated Lewis pair, to activate small molecules such as hydrogen, CO₂, and ethene. This cooperative Lewis pair facilitates the coupling of CO and ethene in a new way.     

Extreme red shifted SERS nanotags

Surfaced enhanced Raman scattering (SERS) nanotags operating with 1280 nm excitation were constructed from reporter molecules selected from a library of 14 chalcogenopyrylium dyes containing phenyl, 2-thienyl, and 2-selenophenyl substituents and a surface of hollow gold nanoshells (HGNs). These 1280 SERS nanotags are unique as they have multiple chalcogen atoms available which allow them to adsorb strongly onto the gold surface of the HGN thus producing exceptional SERS signals at this long excitation wavelength. Picomolar limits of detection (LOD) were observed and individual reporters of the library were identified by principal component analysis and classified according to their unique structure and SERS spectra.     

A prochelator peptide designed to use heterometallic cooperativity to enhance metal ion affinity

A peptide has been designed so that its chelating affinity for one type of metal ion regulates its affinity for a second, different type of metal ion. The prochelator peptide (PCP), which is a fusion of motifs evocative of calcium loops and zinc fingers, forms a 1 : 2 Zn : peptide complex at pH 7.4 that increases its affinity for Zn²⁺ ∼3-fold in the presence of Tb³⁺ (log β₂ from 13.8 to 14.3), while the 1 : 1 luminescent complex with Tb³⁺ is brighter, longer lived, and 20-fold tighter in the presence of Zn²⁺ (log K from 6.2 to 7.5). This unique example of cooperative, heterometallic allostery in a biologically compatible construct suggests the possibility of designing conditionally active metal-binding agents that could respond to dynamic changes in cellular metal status.