Polymer-assisted crystallization of low-dimensional lead sulfide particles

PbS micro- and nanoparticles were synthesized by a simple precipitation reaction of lead nitrate with thioacetamide in hydrosoluble polymer water solutions. The effects of four water soluble polymers: polyacrylamide (PAM), polyvinyl alcohol (PVA), polyethylene glycol (PEG) and poly-N-vinyl pyrrolidone (PVP) on the PbS crystallites morphology and structural properties were investigated by scanning electron microscopy (SEM) and X-ray diffraction (XRD). It was found that for the PbS particles obtained in the PVA, PEG and PVP, the (2 0 0) diffraction peak of the nanocrystals becomes dominant. The highest texture in the [2 0 0] direction was observed for the crystallites obtained in the presence of PVP. Polydisperse PbS particles with cubic morphology and size ranging from 100 nm to several microns are obtained in the case of PAM and PEG. Monodisperse cubic PbS crystallites with an average size of 200 nm are formed in the presence of PVA and PVP.     

Direct Evidence for a Peroxide Intermediate and a Reactive Enzyme–Substrate–Dioxygen Configuration in a Cofactor‐free Oxidase

Cofactor‐free oxidases and oxygenases promote and control the reactivity of O₂ with limited chemical tools at their disposal. Their mechanism of action is not completely understood and structural information is not available for any of the reaction intermediates. Near‐atomic resolution crystallography supported by in crystallo Raman spectroscopy and QM/MM calculations showed unambiguously that the archetypical cofactor‐free uricase catalyzes uric acid degradation via a C5(S)‐(hydro)peroxide intermediate. Low X‐ray doses break specifically the intermediate C5? OO(H) bond at 100 K, thus releasing O₂ in situ, which is trapped above the substrate radical. The dose‐dependent rate of bond rupture followed by combined crystallographic and Raman analysis indicates that ionizing radiation kick‐starts both peroxide decomposition and its regeneration. Peroxidation can be explained by a mechanism in which the substrate radical recombines with superoxide transiently produced in the active site.     

Study of mineral water resources from the Eastern Carpathians using stable isotopes

The Eastern Carpathians contain many mineral water springs that feed famous Romanian health resorts such as Borsec, Biborteni and Vatra Dornei. These waters have been used for their different therapeutic effects. In this work, mineral and spring waters from these Romanian regions were investigated by means of chemical and isotopic (δD and δ¹⁸O) analyses in order to understand the recharge mechanisms and also to determine their origins. Most of the investigated springs are of meteoric origin, having the average deuterium content of the local meteoric water. The higher ¹⁸O content with respect to the Meteoric Water Line (MWL) indicated an exchange reaction with crystalline igneous rocks at depth and with other rocks that the water encounters on its journey back to the surface. Copyright © 2009 John Wiley & Sons, Ltd.     

Quantification of Conversion Degree and Monomer Elution from Dental Composite Using HPLC and Micro-Raman Spectroscopy

The purpose of the study was to analyze the correlation between the quantity of eluted monomers from dental resin-based composite using reverse-phase HPLC and the degree of conversion (DC) using micro-Raman spectroscopy, and to evaluate the influence of the energy of polymerization delivered on the composite material and the applied resin layer thickness on these properties. There was direct proportion in degree of conversion and inverse proportion in monomer elution when the energy of light polymerization was increased from 20 to 40 J cm⁻²; however, further increase in energy density did not influence significantly the DC and the elution of monomers. Investigating the depth of cure significant differences could be measured both in DC and the elution of monomers. 1 mm layer increment up to 3 mm from the top led to 10 % decrease in DC and 30–35 % increase in monomer elution. Further increase in depth from 3 to 4 mm caused 30 % drop in DC and 55 % increase in the amount of leached monomers. The overall result of the findings indicates that direct correlation exists between DC of composite and the elution of unreacted monomers.

     

Obtaining of monodisperse particles through soap-free and seeded polymerization, respectively, through polymerization in the presence of C60

The present study reports on methods of synthesis of self-assembling monodisperse colloidal particles, obtained for the system styrene (St)–hydroxypropyl methacrylate, through emulsion polymerization, using no surfactant. The syntheses performed have led to the conclusion that the emulsion copolymerization in the presence of fullerene is responsible both for a significant decrease of the particles size as well as for a dimensional monodispersity of the system; the latter has been achieved also through seeded polymerization. The morphology and the size distribution of particles have been explored using scanning electron microscope and dynamic light scattering.     

Pyridine and phosphonate containing ligands for stable lanthanide complexation. An experimental and theoretical study to assess the solution structure

We report an experimental and theoretical study of the stability and solution structure of lanthanide complexes with two novel ligands containing pyridine units and phosphonate pendant arms on either ethane-1,2-diamine (L2) or cyclohexane-1,2-diamine (L3) backbones. Potentiometric studies have been carried out to determine the protonation constants of the ligands and the stability constants of the complexes with Gd(III) and the endogenous metal ions Zn(II) and Cu(II). While the stability constant of the GdL2 complex is too high to be determined by direct pH-potentiometric titrations, the cyclohexyl derivative GdL3 has a lower and assessable stability (log K(GdL3)=17.62). Due to the presence of the phosphonate groups, various protonated species can be detected up to pH approximately 8 for both ligands and all metal ions studied. The molecular clusters [Ln(L)(H2O)](3-).19H2O (Ln=La, Nd, Ho or Lu; L=L2 or L3) were characterized by theoretical calculations at the HF level. Our calculations provide two minimum energy geometries where the ligand adopts different conformations: twist-wrap (tw), in which the ligand wraps around the metal ion by twisting the pyridyl units relative to each other, and twist-fold (tf), where the slight twisting of the pyridyl units is accompanied by an overall folding of the two pyridine units towards one of the phosphonate groups. The relative free energies of the tw and tf conformations of [Ln(L)(H2O)]3- (L=L2, L3) complexes calculated in aqueous solution (C-PCM) by using the B3LYP model indicate that the tw form is the most stable one along the whole lanthanide series for the complexes of L3, while for those of L2 only the Gd(III) complex is more stable in the tf conformation by ca. 0.5 kcal mol-1. 1H NMR studies of the Eu(III) complex of L3 show the initial formation of the tf complex in aqueous solution, which slowly converts to the thermodynamically stable tw form. The structures calculated for the Nd(III) complexes are in reasonably good agreement with the experimental solution structures, as demonstrated by Nd(III)-induced relaxation rate enhancement effects in the 1H NMR spectra.     

Interpenetrative and transverse growth process of self-catalyzed ZnO nanorods

Beside longitudinal growth along the length, we show that ZnO nanorods also exhibit transverse growth, which is responsible for the formation of interpenetrative nanorods. The longitudinal growth is lead by the catalytically active Zn-terminated (0001) surface, while the oxygen-terminated surface is catalytically inactive, resulting in the formation of ‘pencil’ or ‘bullet’ shaped nanostructures.     

A Dynamic and Responsive Host in Action: Light‐Controlled Molecular Encapsulation

The rational design of a flexible molecular box, oAzoBox ⁴⁺, incoporating both photochromic and supramolecular recognition motifs is described. We exploit the E?Z photoisomerization properties of azobenzenes to alter the shape of the cavity of the macrocycle upon absorption of light. Imidazolium motifs are used as hydrogen‐bonding donor components, allowing for sequestration of small molecule guests in acetonitrile. Upon E→Z photoisomerization of oAzoBox ⁴⁺ the guest is expelled from the macrocyclic cavity.     

Design of a high-sensitivity negative ion source time-of-flight mass analyzer assembly created by cylindrical electrodes with a common axis

The new design incorporates the negative ion source and the mass analyzer, both constructed from cylindrical electrodes. The ion source is formed by three gridded cylindrical electrodes: a pulsed grid, the intermediate grid and the final accelerating grid. During a first time lapse, the electrons penetrate through the pulsed grid into the retarding field between this grid and the intermediate grid. The electrons are turning at some depth inside this intergrid space, where the attachment to neutral molecules most probably occurs. Next, the pulsed grid becoming strongly negative and ions are extracted towards the final acceleration grid. The ions from the cylindrical surface where they were created concentrate on the common axis of the electrodes (lateral focusing). The source lateral and time focus are coincident. A cylindrical electrostatic mirror is fitted to the source. The design, with a single stage, ensures also lateral focusing of the ions diverging from the common axis of the electrodes. The mirror electric and geometric parameters were selected to ensure both lateral and time focusing on the final detector with subsequent high luminosity. The basic parameters of the specific negative ion source time-of-flight mass analyzer design proposed here, are ion source final acceleration, intermediate, pulsed cylindrical grid radii 10, 20 and 30 mm, respectively, electrostatic mirror earthed grid and ion turning points surface radii 0.6 and 0.8 m, respectively. Ion packet smearing by the ion energy spread (resulting from the initial electron energy spread as electrons are turning at different depths inside the ionization region, from the moment when ions were created, being accelerated towards the pulsed grid during ionization) and by the turnaround time inside the cylindrical field was accounted for. Maintaining very high sensitivity, a resolution of the order of 100 is expected.