Laser ablation synthesis of new gold phosphides using red phosphorus and nanogold as precursors. Laser desorption ionisation time-of-flight mass spectrometry

Gold phosphides show unique optical or semiconductor properties and there are extensive high technology applications, e.g. in laser diodes, etc. In spite of the various AuP structures known, the search for new materials is wide. Laser ablation synthesis is a promising screening and synthetic method. Generation of gold phosphides via laser ablation of red phosphorus and nanogold mixtures was studied using laser desorption ionisation time-of-flight mass spectrometry (LDI TOFMS). Gold clusters Au(m)(+) (m?=?1 to ~35) were observed with a difference of one gold atom and their intensities were in decreasing order with respect to m. For P(n)(+) (n?=?2 to ~111) clusters, the intensities of odd-numbered phosphorus clusters are much higher than those for even-numbered phosphorus clusters. During ablation of P-nanogold mixtures, clusters Au(m)(+) (m?=?1-12), P(n)(+) (n?=?2-7, 9, 11, 13-33, 35-95 (odd numbers)), AuP(n)(+) (n?=?1, 2-88 (even numbers)), Au(2)P(n)(+) (n?=?1-7, 14-16, 21-51 (odd numbers)), Au(3)P(n)(+) (n?=?1-6, 8, 9, 14), Au(4)P(n)(+) (n?=?1-9, 14-16), Au(5)P(n)(+) (n?=?1-6, 14, 16), Au(6)P(n)(+) (n?=?1-6), Au(7)P(n)(+) (n?=?1-7), Au(8)P(n)(+) (n?=?1-6, 8), Au(9)P(n)(+) (n?=?1-10), Au(10)P(n)(+) (n?=?1-8, 15), Au(11)P(n)(+) (n?=?1-6), and Au(12)P(n)(+) (n?=?1, 2, 4) were detected in positive ion mode. In negative ion mode, Au(m)(-) (m?=?1-5), P(n)(-) (n?=?2, 3, 5-11, 13-19, 21-35, 39, 41, 47, 49, 55 (odd numbers)), AuP(n)(-) (n?=?4-6, 8-26, 30-36 (even numbers), 48), Au(2)P(n)(-) (n?=?2-5, 8, 11, 13, 15, 17), A(3) P(n)(-) (n?=?6-11, 32), Au(4)P(n)(-) (n?=?1, 2, 4, 6, 10), Au(6)P(5)(-), and Au(7)P(8)(-) clusters were observed. In both modes, phosphorus-rich Au(m)P(n) clusters prevailed. The first experimental evidence for formation of AuP(60) and gold-covered phosphorus Au(12)P(n) (n?=?1, 2, 4) clusters is given. The new gold phosphides generated might inspire synthesis of new Au-P materials with specific properties.     

Endomorphismen von ebenen Viergeweben (Beitrag zu einem Problem von J. Aczél)

Ohne Zusammenfassung     

Dilute solution properties of poly(dimethyldiallylammonium chloride) in aqueous sodium chloride solutions

MW fractions of poly(dimethyldiallylammonium chloride) (PDMDAAC) were prepared by preparative size-exclusion chromatography and characterized by static and dynamic light scattering, viscometry, size-exclusion chromatography, and electrophoretic light scattering, in 0.50M NaCl solution. The behavior of fractions with MW < 2 × 10⁵ was as expected for a strong polyelectrolyte in a good solvent, with a Mark-Houwink exponent of ca. 0.8, and MW-dependencies of the hydrodynamic radius and the radius of gyration of corresponding magnitude. At higher MW, curvature appears in the MW-dependencies, which can be best explained by the presence of branching. While this notably lowers the intrinsic viscosity at high MW, the electrophoretic mobility is unchanged regardless of molar mass. Thus, the branched polymers display the electrophoretic free-draining behavior characteristic of linear polyelectrolytes. ©1995 John Wiley & Sons, Inc.     

Spectrophotometric determination of rare earth elements by flow injection analysis based on their reaction with xylenol orange and cetylpyridinium bromide

Individual rare earth elements (REE) and their mixtures were determined by a FIA method based on the reaction with Xylenol Orange (XO) in the presence of cetylpyridinium bromide (CPB). Volumes of 30 microl of 2.5-25 microM REE solutions were injected into a carrier stream of 0.1M acetate buffer of pH 4.5 or 5.5 that was 0.06 mM in XO and 0.6 mM in CPB. At 1.8 ml/min flow rate, a sampling frequency of up to 100 samples per hour was achieved. The detection limits were in the range of 0.1-0.4 microg/ml REE and relative standard deviation of the measurement was 0.88% rel.     

6-Substituted 2-(2-benzothiazolyl) [1, 2, 3] benzotriazol-1-oxides and the kinetics of their formation

6-Substituted 2-(2-benzothiazolyl) [1, 2, 3] benzotriazol-1-oxides were prepared by a base catalyzed cyclization reaction of 2-(4-substituted 2-nitrophenylhydrazino) benzothiazoles. Influence of substitution in position 4 on the cyclization reaction rate was followed and correlated with Hammett constants.     

Capillary zone electrophoretic (CZE) study of uranium(VI) complexation with humic acids

The interaction of UO₂ ²⁺ with various humic acids (HA's) has been studied by capillary zone electrophoresis (CZE). The experiments were done in 10 mM acetate buffer with pH 3.3 and 4.0, to avoid hydrolysis of uranium. It was found that in slightly acidic media and low HA concentration (<3 mM), two complexes with uranium(VI) are formed by fast kinetics and uranyl migrates as cationic species. Electrophoretic mobilities are decreasing with the increasing HA/uranium ratio and a low soluble neutral compound is also formed. In addition, it was found that at HA concentrations higher than 3 mM negatively charged species are formed. Similar results were obtained for HA's of different origin (soil, peat, coal derived, IHSS standards). Conditional stability constants of the complexes UO₂ ²⁺-HA for Fluka I HA, were estimated to be log ₁ = 4.18±0.06 and log ₂ = 7.28±0.18.     

Highly reproducible capillary zone electrophoresis of humic acids in cyclodextrin- or oligosaccharide-modified background electrolytes

Capillary zone electrophoresis has been used for the characterization and separation of humic acids. It was found that addition of saccharides like alpha-, beta-, gamma-cyclodextrins, maltose, hydroxyethylcellulose or dextran sulfate in the background electrolyte (50 mM Na2 B4 O7, pH 9.6) yields better separation patterns and highly reproducible electropherograms. Electropherograms with higher numbers of peaks and high reproducibility were obtained with alpha- and beta-cyclodextrins or with a mixture of alpha- + gamma-cyclodextrin-modified background electrolytes. Separation was carried out with the cathode at the detector end of the column. Adsorption of humic acids to the capillary wall was diminished using an epoxy-coated capillary tube.