The tube electrode and e.s.r.

The convective diffusion equation for the downstream distribution of products and intermediates produced on a tube electrode under conditions of laminar flow is solved. For distances which are large compared to the thickness of the electrode, an analytical solution in real space can be found. The solution of the equation has been applied to an apparatus in which the intermediates and products are detected by e.s.r. The species are transported by laminar flow from the electrode through an e.s.r. cavity. Results are presented for two systems and are found to be in good agreement with the theory.     

A family of polynuclear cobalt and nickel complexes stabilised by 2-pyridonate and carboxylate ligands

The synthesis and structural characterisation of a series of cobalt and nickel cages are reported. Eight of these structures contain a [M10(mu3-OH)6(eta2, mu3-xhp),(eta2, mu2-O2CR)6]2+ core (where M = Co or Ni; xhp = 6-chloro- or 6-methyl-2-pyridonate: R = Me, Ph, CHMe2, CH2Cl, CHPh2 or CMe3), where the ten metal atoms describe a centred-tricapped-trigonal prism (ttp). The cage contains six hydroxide ligands around the central metal, and the exterior is coated with pyridonate and carboxylate ligands. For four of the cages additional metal centres are found attached to the upper and/or lower triangular faces of the trigonal prism, generating dodeca- and undecanuclear cages. Three further cages are reported that contain a metal core based on an incomplete centred-tetraicosahedron. These cages involve trimethylacetate as a ligand in company with either 6-methyl-2-pyridonate or 6-chloro-2-pyridonate. Comparison of these latter structures with the trigonal prisms reveal that they can be described as a pentacapped-trigonal prism missing one edge. Magnetic studies of three of the nickel cages with trigonal prismatic cores show spin ground states of S = 8, 4 and 2 for Ni12, Ni11 and Ni10 cages, respectively.     

Resolution limitations from detector pulse width and jitter in a linear orthogonal-acceleration time-of-flight mass spectrometer

Recent and ongoing advances in timing electronics together with the development of ionization techniques suited to time-of-flight mass spectrometry (TOF-MS) have contributed to renewed interest in this method of mass analysis. Whereas low resolving powers (m/?m < 500) were once an almost unavoidable drawback in TOF-MS, recent developments in instrument geometries have produced much higher resolving powers for many ion sources. The temporal width of detector pulses and jitter in timing electronics, however, lead to contributions to peak widths that are essentially independent of the mass-analyzer ion optics. The effective detector pulse width (?t _d ≈ 1–10 ns typically) can be a limiting factor in the development of high resolution time-of-flight (TOF) instruments with modest drift lengths (～1 m), It also reduces the mass resolution more seriously for light ions. This article presents a method for distinguishing the instrumental “ion arrival-time” resolution (R _o) of a linear TOF mass analyzer from that which is locally measured at a particular mass, limited by the broadening of the detector pulse width and electronics. The method also provides an estimate of ?t _d, that is useful in determining the temporal performance of the detection system. The model developed here is tested with data from a recently constructed orthogonal-acceleration TOF mass spectrometer equipped with a commercially available transient recorder (a LeCroy 400-Msamplejs digital oscilloscope) from which we obtained R _o = 4240 ± 100 [full width at half maximum (FWHM)) and ?t _d = 3.0 ± 0.1 ns (FWHM).     

New bis-, tris- and tetrakis(pyrazolyl)borate ligands with 3-pyridyl and 4-pyridyl substituents: synthesis and coordination chemistry

The new ligands dihydrobis[3-(4-pyridyl)pyrazol-1-yl]borate [Bp(4py)]-, hydrotris[3-(4-pyridyl)pyrazol-1-yl]borate [Tp(4py)]-, tetrakis[3-(4-pyridyl)pyrazol-1-yl]borate [Tkp(4py)]-, dihydrobis[3-(3-pyridyl)pyrazol-1-yl]borate [Bp(3py)]-, hydrotris[3-(3-pyridyl)pyrazol-1-yl]borate [Tp(3py)]- and tetrakis[3-(3-pyridyl)pyrazol-1-yl]borate [Tkp(4py)]- are derivatives of the well known bis-, tris- and tetrakis-(pyrazolyl)borate cores, bearing 4-pyridyl or 3-pyridyl substituents attached to the pyrazolyl C3 positions. These pyridyl groups cannot chelate to the metal ions in the poly(pyrazolyl) cavity but are externally directed. Structural studies on a range of metal complexes show how, in many cases, coordination of these pendant pyridyl groups to the M(pyrazolyl)n core of an adjacent metal complex fragment results in formation of coordination oligomers or polymeric networks. [Tl(Bp(3py))], [Tl(Bp(4py))] and [Tl(Tp(4py))] form one-dimensional polymeric chains via coordination of one of their pendant pyridyl units to the Tl(I) centre of an adjacent complex fragment; in contrast, in [Tl(Tp(3py))] coordination of all three pendant pyridyl units to separate Tl(I) neighbours results in formation of a two-dimensional polymeric sheet. In [Tl(Tkp(3py))] and [Tl(Tkp(4py))] the Tl(I) is coordinated by two or three of the four pyrazolyl arms, respectively; bridging interactions of pendant 4-pyridyl groups with adjacent Tl(I) centres result in a two-dimensional sheet forming in each case. In Ag(Tkp(4py)) each Ag(I) ion is coordinated by two pyrazolyl rings, and two bridging pyridyl ligands from other complex units, resulting in a one-dimensional chain consisting of pairs of cross-linked zigzag chains. In contrast to these polymeric coordination networks, the structures of [Cu(Tp(4py))] and [(Tp(3py))Cd(CH3CO2)] are dimers, with a pendant pyridyl residue from the first metal centre attaching to a vacant coordination site on the second, and vice versa; these dimers are stabilised by pi-stacking interactions between sections of the two ligands. [Ni(Tp(3py))2] is monomeric, with an octahedral coordination geometry arising from two tris(pyrazolyl)borate chelates; the array of pendant 3-pyridyl groups is involved only in intramolecular hydrogen-bonding. [(Tp(4py))Re(CO)3] is also monomeric, with a facial arrangement of three pyrazolyl ligands and three carbonyls, with the pendant 4-pyridyl groups not further coordinated. [(Tp(2py))Re(CO)3], based on the related ligand hydrotris[3-(2-pyridyl)pyrazol-1-yl]borate, has a similar fac-(CO)3(pyrazolyl)3 coordination geometry.     

Structural and catalytic properties of bis(guanidine)copper(I) halides

The neutral, bicyclic guanidine 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine (hppH) coordinates to Cu(I) halides via the imine nitrogen, and the complexes are stabilized by intramolecular NH...X interactions (X = Cl, Br) or are partially dissociated (X = I) in the solid state; in all cases, fluxional behavior is observed in solution. Selected complexes have been tested as catalysts for the polymerization of methyl methacrylate.     

Application of the high-speed channel flow cell to reactive chemistry at solid surfaces

A high-speed channel flow cell is used to study the reaction of solid p-chloranil with basic aqueous solutions. Dissolution of the solid is shown to be induced by reaction of OH⁻ ions at the solid/liquid interface and appropriate kinetic parameters are reported. Received: 1 September 1998 / Accepted: 2 November 1998     

Spatial Regression Models for Extremes

Meteorological data are often recorded at a number of spatial locations. This gives rise to the possibility of pooling data through a spatial model to overcome some of the limitations imposed on an extreme value analysis by a lack of information. In this paper we develop a spatial model for extremes based on a standard representation for site-wise extremal behavior, combined with a spatial latent process for parameter variation over the region. A smooth, but possibly non-linear, spatial structure is an intrinsic feature of the model, and difficulties in computation are solved using Markov chain Monte Carlo inference. A simulation study is carried out to illustrate the potential gain in efficiency achieved by the spatial model. Finally, the model is applied to data generated from a climatological model in order to characterize the hurricane climate of the Gulf and Atlantic coasts of the United States.     

High-frequency sonoelectrochemical processes: mass transport, thermal and surface effects induced by cavitation in a 500 kHz reactor

The use of high frequency ultrasound in electrochemical systems is of major interest for the optimisation of electrosynthetic and electroanalytical procedures, especially when the strong mechanical effects of 20 kHz ultrasound are detrimental. The characterisation of a 500 kHz ultrasound reactor for sonoelectrochemical experiments by voltammetric and potentiometric measurements revealed the presence of considerable thermal, as well as mass transport, effects depending on geometric parameters and the material used for the construction of the working electrode. Micromixing and cavitation processes govern the mass transport to and from the electrode surface and are shown by atomic force microscopy (AFM) to cause erosion on the electrode surface. Electrochemically active films of Prussian blue are shown to be gradually removed by cavitation erosion. Degassing the solution prior to sonication increases the efficiency of cavitation processes.     

Reactivity of Sodium Pentaphospholide Na[cyclo-P5] towards C≡E (E=C,N, P) Triple Bonds

A diglyme solution of Na[cyclo-P₅] ( 1 ) reacts with alkynes and isolobal nitriles and phosphaalkynes to afford the otherwise elusive (aza)phospholide anions 2 a – c , 4 a,b , and 6 . The reaction of Na[cyclo-P₅] with alkynes and nitriles was studied by means of DFT methods, which suggested a concerted mechanism for the formation of 2 a and 4 b . The anions 2 a – c , 4 a,b , and 6 coordinate in an η⁵-fashion towards Fe^II to give the sandwich (aza)phosphametallocenes 3 a – c , 5 a,b and 7 in moderate to good yields. The new compounds were characterized by means of multinuclear NMR spectroscopy, single-crystal X-ray diffraction and cyclic voltammetry.     

Fluorescent dye guest-host effects in advanced ferroelectric liquid crystals

Previous work has shown that guest-host ferroelectric systems incorporating dichroically absorbing dyes are suitable for use in colour display applications. These utilize either the dichroic absorption of a conventional dye, or the emission of a fluorescent dye. We present here the electrooptical properties of several advanced ferroelectric liquid crystals doped with a new fluorescent dye, coloured blue in emission. The data consists of measurements of tilt angle, response time, spontaneous polarization, and rotational viscosity, from which we conclude that certain hosts are not adversely affected by the fluorescent dopants. These results are then discussed in connection with the use of these mixtures in two novel colour display configurations, which are also presented, utilizing either the dichroic absorption or the polarized fluorescence of the fluorophore guests.