Alkali halide nanocrystal growth and etching studied by AFM and modeled by MD simulations

NaCl hillocks have been grown on the NaCl(100) monocrystalline surface by simply making the tip of an atomic force microscope cantilever interact with the surface. A quantitative discussion about the hillock dissolution process as well as physical stability of these ionic surfaces has been made. Molecular dynamics simulations helped us to interpret the experimental data. An explanation for the hillock formation and dissolution phenomena is also discussed.     

A comparison of extraction chromatography TEVA? resin and MRT AnaLig? Tc-02 methods for 99Tc determination

Two commercial products??molecular recognition technology (MRT) product AnaLig^?Tc-02 gel and extraction chromatography TEVA^? resin were successfully tested for the separation of ⁹⁹Tc. The results obtained for both procedures were compared in terms of activities and recoveries. The demonstrated linear model clearly proves that the residua fulfill the Gaussian model, without any autocorrelation and trend for NPL Alpha?CBeta high 2003 intercomparison reference sample.     

Enhanced Photostability of a Ruthenium(II) Polypyridyl Complex under Highly Oxidizing Aqueous Conditions by Its Partial Inclusion into a Cyclodextrin

The complex [Ru(bpy)₂L]²⁺, where bpy=2,2′‐bipyridine, L=4‐(phenylethynyl)‐2,2′‐bipyridine, was prepared in its racemic and resolved forms (Δ and Λ). The phenylethynyl unit on the bipyridine for the complex acts as a binding site for α‐cyclodextrin in water (1:1 complex, K=3390 L mol^?1) or β‐cyclodextrin (2:1 complex, K₁=887 L mol^?1, K₂=8070 L mol^?1). The presence of the cyclodextrin provides partial protection to the complex under light‐activated water oxidation conditions.     

Study on the hydrolytic degradation of the segmented GL-b-[GL-co-TMC-co-CL]-b-GL copolymer with application as monofilar surgical suture

The hydrolytic degradation of Monosyn™, a segmented copolymer derived from glycolide, trimethylene carbonate and ε-caprolactone, has been evaluated in buffered aqueous media at different pH and temperature. Degradation processes have been followed by considering mass loss and molecular weight profiles as well as the changes on ¹H NMR and FTIR spectra, morphology and both calorimetric and mechanical properties during exposure to the selected media and temperature.     

NMR study of the gelation of a designed gelator

The gelation of a designed gelator was investigated by different NMR methods, which showed a clear thermal hysteresis. Two very simple approaches for the NMR determination of the gelation point are suggested. One involves the observation of the NMR integral, and the other records the ratio of the diffusion coefficients between the gelator and the solvent. Differential behavior of the gelator protons are interpreted as a hint that a part of the gelator molecule might still be flexible as in the dissolved state.     

Metallacarboranes as building blocks for polyanionic polyarmed aryl-ether materials

Polyanionic species have been obtained in high yield by a new route in the ring-opening reaction of cyclic oxonium [3,3'-Co(8-C4H8O2-1,2-C2B9H10)(1',2'-C2B9H11)] (2) by using carboxylic acids, Grignard reagents, and thiocarboranes as nucleophiles. The crystal structures of Na3(H2O)(C2H5OH)[1',3',5'-{3,3'-Co(8-O(CH2CH2O)2-1,2-C2B9H10)(1',2'-C2B9H11)}3-C6H3] and Na(H2O)[3,3'-Co(8-O(CH2CH2O)2C(O)CH3-1,2-C2B9H10)(1',2'-C2B9H11)] show that the chain contributes three or two oxygen atoms for coordination to Na(+), and interestingly, the [3,3'-Co(1,2-C2B9H11)2](-) moiety provides extra B-H coordination sites. These B-H...Na interactions in the solid state have also been confirmed by dynamic NMR studies in solution. These new polyanionic compounds that contain multiple carborane or metallacarborane clusters at their periphery may prove useful as new classes of boron neutron capture therapy compounds with enhanced water solubility and as a core to make a new class of dendrimers.     

Structural characterization of flexible proteins using small-angle X-ray scattering

Structural analysis of flexible macromolecular systems such as intrinsically disordered or multidomain proteins with flexible linkers is a difficult task as high-resolution techniques are barely applicable. A new approach, ensemble optimization method (EOM), is proposed to quantitatively characterize flexible proteins in solution using small-angle X-ray scattering (SAXS). The flexibility is taken into account by allowing for the coexistence of different conformations of the protein contributing to the experimental scattering pattern. These conformers are selected using a genetic algorithm from a pool containing a large number of randomly generated models covering the protein configurational space. Quantitative criteria are developed to analyze the EOM selected models and to determine the optimum number of conformers in the ensemble. Simultaneous fitting of multiple scattering patterns from deletion mutants, if available, provides yet more detailed local information about the structure. The efficiency of EOM is demonstrated in model and practical examples on completely or partially unfolded proteins and on multidomain proteins interconnected by linkers. In the latter case, EOM is able to distinguish between rigid and flexible proteins and to directly assess the interdomain contacts.     

Impact of Zeolite Framework Composition and Flexibility on Methanol-To-Olefins Selectivity: Confinement or Diffusion?

The methanol-to-olefins reaction catalyzed by small-pore cage-based acid zeolites and zeotypes produces a mixture of short chain olefins, whose selectivity to ethene, propene and butene varies with the cavity architecture and with the framework composition. The product distribution of aluminosilicates and silicoaluminophosphates with the CHA and AEI structures (H-SSZ-13, H-SAPO-34, H-SSZ-39 and H-SAPO-18) has been experimentally determined, and the impact of acidity and framework flexibility on the stability of the key cationic intermediates involved in the mechanism and on the diffusion of the olefin products through the 8r windows of the catalysts has been evaluated by means of periodic DFT calculations and ab initio molecular dynamics simulations. The preferential stabilization by confinement of fully methylated hydrocarbon pool intermediates favoring the paring pathway is the main factor controlling the final olefin product distribution.     

Determination of 99Tc in evaporator concentrates using solid phase extraction techniques

This paper describes a simple and rapid method of ⁹⁹Tc pre-concentration, separation and purification by using AnaLig^? Tc02 gel in two stages or AnaLig^? Tc02 gel in a first stage and TEVA^? resin in a second stage, which are commercially available from IBC advanced technologies, Inc. and Eichrom technologies, Inc., respectively. The method is suitable for analyzing large volume concentrate samples in a relatively short time. The use and effectiveness of AnaLig^? Tc02 and Eichrom’s TEVA^? resin were successfully tested by analysis of evaporator concentrate samples which belong to the class of most difficult matrices to analyze.