Electron impact and single photon ionization cross sections of neutral silver clusters

Neutral silver atoms and small clusters Ag _n (n=1...4) were generated by sputtering, i.e. by bombarding a polycrystalline silver surface with Ar⁺ ions of 5 keV. The sputtered particles were ionized by a crossed electron beam and subsequently detected by a quadrupole mass spectrometer. In alternative to the electron impact ionization, the same neutral species were also ionized by single photon absorption from a pulsed VUV laser (photon energy 7.9 eV), and the photoionization cross sections were evaluated from the laser intensity dependence of the measured signals. By in situ combining both ionization mechanisms, absolute values of the ratio σ _e (Ag _n )/σ _e (Ag) between the electron impact ionization cross sections of silver clusters and atoms could be determined for a fixed electron energy of 46 eV. These values can then be used to calibrate previously measured relative ionization functions. By calibrating the results using literature data measured for silver atoms, we present absolute cross sections for electron impact ionization of neutral Ag₂, Ag₃ and Ag₄ as a function of the electron energy between threshold and 125 eV.     

SynCar: an approach to automated synthesis

The automation of all aspects of manual solution-phase synthesis into one integrated, efficient, and reliable system could be regarded as something of an unmet challenge in organic chemistry. The requirements for modern solution-phase libraries in mainstream drug discovery is typically 50-250 high-purity compounds on a 10-100-mg scale, whether for target class libraries or lead optimization, and short cycle time in combination with high capacity is critical. To achieve these goals, in a codevelopment between Aventis and Accelab GmbH, Kusterdingen, Germany, we designed a completely novel system of independent workstations connected by a shuttle transfer system produced by Montech, Derendingen, Switzerland. Seven modular workstations process four reactions on each shuttle in parallel, with the ability to perform synthesis (temperature control and liquid reagent handling), filtration, liquid-liquid extraction, evaporation, weighing, solid-phase extraction, and HPLC/MS analysis. The modular design enables the continuous loading of shuttles at any time, and each shuttle can have its own workflow. The design also allows easy expansion for future needs. The result is a combination of high flexibility and high throughput.     

The bis-phenyltin-substituted, lone-pair-containing tungstoarsenate [(C(6)h(5)Sn)(2)as(2)W(19)O(67)(H(2)O)](8)(-)

The bis-phenyltin-substituted, lone-pair-containing tungstoarsenate [(C(6)H(5)Sn)(2)As(2)W(19)O(67)(H(2)O)](8)(-) (1) has been synthesized and characterized by multinuclear NMR, IR, and elemental analysis. Single-crystal X-ray analysis was carried out on (NH(4))(7)Na[(C(6)H(5)Sn)(2)As(2)W(19)O(67)(H(2)O)].17.5H(2)O (NH(4)(-1), which crystallizes in the monoclinic system, space group P2(1)/c, with a = 18.3127(17) A, b = 24.403(2) A, c = 22.965(2) A, beta = 106.223(2) degrees, and Z = 4. Polyanion 1 consists of two B-alpha-(As(III)W(9)O(33)) Keggin moieties linked via a WO(H(2)O) fragment and two SnC(6)H(5) groups leading to a sandwich-type structure with nominal C(2)(v) symmetry. Polyanion 1 is stable in solution as indicated by the expected 6-line pattern (4:4:4:4:2:1) in (183)W NMR and the expected (119)Sn, (13)C, and (1)H NMR spectra. Synthesis of 1 was accomplished by reaction of C(6)H(5)SnCl(3) and K(14)[As(2)W(19)O(67)(H(2)O)] in a 2:1 molar ratio in aqueous acidic medium (pH 2). In the solid-state structure of NH(4)(-1, neighboring polyanions are weakly bound via W-O-Na bonds leading to chains which interact with each other via the phenyl rings resulting in a 2-D assembly.     

Influence of moderate Joule heating on electroosmotic flow velocity, retention, and efficiency in capillary electrochromatography

The influence of Joule heating on electroosmotic flow velocity, the retention factor of neutral analytes, and separation efficiency in capillary electrochromatography was investigated theoretically and experimentally. A plot of electrical current against the applied electrical field strength was used to evaluate the Joule heating effect. When the mobile phase concentration of Tris buffer exceeded 5.0 mM in the studied capillary electrochromatography systems using particulate and monolithic columns (with an accompanying power level of heat dissipation higher than 0.35 W/m), the Joule heating effect became clearly noticeable. Theoretical models for describing the variation of electroosmotic flow velocity with increasing applied field strength and the change of retention factors for neutral analytes with electrical field strength at higher Tris buffer concentrations were analyzed to explain consequences of Joule heating in capillary electrochromatography. Qualitative agreement between experimental data and implications of the theoretical model analysis was observed. The decrease of separation efficiency in capillary electrochromatography with macroporous octadecylsilica particles at high buffer concentration can be also attributed to Joule heating mainly via the increased axial diffusion of the analyte molecules and dispersion of solute bands by a nonuniform electroosmotic flow profile over the column cross-section. However, within a moderate temperature range, the contribution of the macroscopic velocity profile in the column arising from radial temperature gradients is insignificant.     

Model Compounds for Iron Proteins. Structures and Magnetic, Spectroscopic, and Redox Properties of Fe(III)M(II) and [Co(III)Fe(III)](2)O Complexes with (&mgr;-Carboxylato)bis(&mgr;-phenoxo)dimetalate and (&mgr;-Oxo)diiron(III) Cores

A series of heterobimetallic complexes of the type [Fe(III)M(II)L(&mgr;-OAc)(OAc)(H(2)O)](ClO(4)).nH(2)O (2-5) and [{Fe(III)Co(III)L(&mgr;-OAc)(OAc)}(2)(&mgr;-O)](ClO(4))(2).3H(2)O (6) where H(2)L is a tetraaminodiphenol macrocyclic ligand and M(II) = Zn(2), Ni(3), Co(4), and Mn(5) have been synthesized and characterized. The (1)H NMR spectrum of 6 exhibits all the resonances between 1 and 12 ppm. The IR and UV-vis spectra of 2-5 indicate that in all the cases the metal ions have similar coordination environments. A disordered crystal structure determined for 3 reveals the presence of a (&mgr;-acetate)bis(&mgr;-phenoxide)-Ni(II)Fe(III) core, in which the two metal ions have 6-fold coordination geometry and each have two amino nitrogens and two phenolate oxygens as the in-plane donors; aside from the axial bridging acetate, the sixth coordination site of nickel(II) is occupied by the unidentate acetate and that of iron(III) by a water molecule. The crystal structure determination of 6 shows that the two heterobinuclear Co(III)Fe(III) units are bound by an Fe-O-Fe linkage. 6 crystallizes in the orthorhombic space group Ibca with a = 17.577(4) ?, b = 27.282(7) ?, c = 28.647(6) ?, and Z = 8. The two iron(III) centers in 6 are strongly antiferromagnetically coupled, J = -100 cm(-1) (H = -2JS(1).S(2)), whereas the other two S(1) = S(2) = (5)/(2) systems, viz. [Fe(2)(III)(HL)(2)(&mgr;-OH)(2)](ClO(4))(2) (1) and the Fe(III)Mn(II) complex (5), exhibit weak antiferromagnetic exchange coupling with J = -4.5 cm(-1) (1) and -1.8 cm(-1) (5). The Fe(III)Ni(II) (3) and Fe(III)Co(II) (4) systems, however, exhibit weak ferromagnetic behavior with J = 1.7 cm(-1) (3) and 4.2 cm(-1) (4). The iron(III) center in 2-5 exhibits quasi-reversible redox behavior between -0.44 and -0.48 V vs Ag/AgCl associated with reduction to iron(II). The oxidation of cobalt(II) in 4 occurs quasi-reversibly at 0.74 V, while both nickel(II) and manganese(II) in 3 and 5 undergo irreversible oxidation at 0.85 V. The electrochemical reduction of 6 leads to the generation of 4.     

Upper semicontinuous fuzzy sets and applications

Let (X, τ) be a generalized topological space of type $\text{V}$_α (see A. Appert and K. Fan, “Espaces topologiques intermédiares,” Herman, Paris, 1951) and (L, ?) be a complete Brouwerian lattice such that the dual lattice of (L, ?) is also Brouwerian. We prove that every upper semicontinuous L-fuzzy subset of X can be represented by a τ-closed random set. As an important application we obtain a fuzzification of measurable spaces as well as of topological spaces. In particular a concept of measurable (open) L-fuzzy sets is developed.     

A measurement of the lifetimes of Ξ0 and Λ hyperons

The mean lifetimes of the Λ and Ξ⁰ hyperons have been measured in a short neutral beam at the CERN Proton Synchrotron. Λ and Ξ⁰ decays have been identified by measuring their decay products in a magnetic spectrometer and in a lead glass hodoscope. The experimental results, based on 53 000 Λ decays and 6300 Ξ⁰ decays are

From the result for τ_Ξ⁰ together with existing data on τ_Ξ^? we obtain a violation of the $\text{ΔI =}\text{1}\text{2}$ rule in non-leptonic Ξ decays.     

Mechanical Properties of Organic-Inorganic Hybrid Materials Determined by Indentation Techniques

The mechanical properties of hybrid materials consisting of polystyrene (PS), which was cross-linked with different proportions of the multifunctional cluster Zr₆O₄(OH)₄(methacrylate)₁₂ (Zr6) were investigated. With the help of (micro)indentation and scratch testing, the influence of the Zr6 clusters on mechanical properties, such as hardness, stiffness, creep, craze initiation, and scratch resistance was shown. There was only a slight increase in hardness and in indentation modulus with higher cluster loadings. While this observation was in agreement with the compression behaviour of the materials, the tensile properties showed a much stronger dependence on the Zr6 content. With increasing cluster loading, an increase of craze initiation stress, as determined by ball indentation experiments, was found. Performing scratch testing with constant load, a reduction of pile-up and a stronger recovery were observed for the hybrid materials compared to the neat PS. Scratch tests with a constant increase of load showed an increase of the critical load for crack opening during scratching.     

Critical evaluation of additivity schemes for estimating heats of atomization

Additivity schemes for estimating heats of formation and heats of atomization of alkanes and halo- alkanes are scrutinized. A least squares analysis of the heats of atomization of alkanes leads to a revision of the values of the parameters. The improvement in the estimated heats of atomization over the values obtained with parameters previously suggested amounts to at least 100%. The reasons for the deviations from the experimental values are discussed. These parameters can be transfered to haloalkanes. Additional parameters necessary for estimating heats of atomization of haloalkanes are also obtained through least squares analyses.