The microscopic visualisation of the sonocrystallisation of ice using a novel ultrasonic cold stage

This work reports dynamic video images of the influence of ultrasonic cavitation on the sonocrystallisation of ice at a microscopic level. This has been achieved through the construction of a unique ultrasonic system for an optical microscope. The system consists of (1). an ultrasonic cold stage, (2). a temperature control system, and (3). a microscope and imaging setup. This allows the temperature of a sample to be systematically controlled while it is subjected to simultaneous excitation with alternating pressures in the ultrasonic frequency range. Both the amplitude of excitation and the frequency can be varied. Experiments on ice crystals in pure water and sucrose solutions were conducted. Three distinct phenomena were observed. Firstly, there is a tendency for cavitation bubbles to form at the grain boundaries between ice crystals. Secondly, there is a progressive melting of ice by cavitation bubbles which appear to eat their way into the ice phase. Thirdly, the dendritic ice structures may fragment under the influence of ultrasound, thus increasing the number of nuclei which may subsequently grow (secondary nucleation). These observations form the basis of a significantly enhanced understanding and exploitation of the sonocrystallisation of ice.     

Flow field analysis by large-area interrogation in particle image velocimetry

The evaluation of flow records obtained by particle image velocimetry (PIV) employs the interrogation of certain regions in the flow image. Basic relations are derived for the case that the velocity is not constant within the region of interrogation. The influence of a distribution of velocities on the Young's fringe system and its Fourier transform, the autocorrelation of the flow record, are discussed. The considerations show that there is an easy access to statistical parameters of the flow by carrying out large-field interrogation. The autocorrelation function will reproduce the probability density function of the velocity, and there is no need for a large number of time-consuming small-area interrogations. Furthermore, the effects of velocity variations in ordinary fringe analysis are discussed. Examples are given from synthetic PIV records and measurements in a wind tunnel.     

Lithium nickel oxide Li(Ni0.75Al0.17Co0.08)O2 as cathode material for lithium ion batteries

Al- and Co-substituted lithium nickel oxide of the nominal composition Li(Ni_0.75Al_0.17Co_0.08)O₂ was synthesised by a coprecipitation technique and by several solid state routes. Rietveld analysis of XRD profiles and galvanostatic cycling in glass cells were performed for structural and electrochemical characterisation. Depending on the reactivity of the respective precursor, there is in each case a minimal synthesis temperature, at which a single phase of the R layered structure could be obtained. The coprecipitation technique and solid state routes using pre-substituted nickel hydroxide are suitable for the synthesis of single phase Al- and Co-substituted lithium nickel oxide, even at rather low synthesis temperatures. The electrochemical performance of lithium nickel oxide Li(Ni_0.75Al_0.17Co_0.08)O₂ synthesised in air is poor due to an enhanced lithium nickel disorder. Synthesis in oxygen atmosphere seems to be required. Paper presented at the 6th Euroconference on Solid State Ionics, Cetraro, Calabria, Italy, Sept. 12–19, 1999.     

Global estimates of fundamental solutions for higher-order Schr?dinger equations

In this paper we first establish global pointwise time-space estimates of the fundamental solution for Schr?dinger equations, where the symbol of the spatial operator is a real non-degenerate elliptic polynomial. Then we use such estimates to establish related L ^p ?CL ^q estimates on the Schr?dinger solution. These estimates extend known results from the literature and are sharp. This result was lately already generalized to a degenerate case (cf. [4]).     

A Hydrocarbon-sensitized Argon Ionization Detector for the Detection of Inorganic Compunds

Noble gas ionization detectors make it possible to determine inorganie trace components in gases. Among the several modes of operation of these detectors the hydrocarbon-sensitized argon detector is a farourable compromise with regard to the relation of the expense to the attainable detection limit. The suitability of this detector for the determination of H₂, O₂, N₂, CH₄ and CO₂, in pure gases is shown.     

An economic¯X-chart approach to the joint control of the means of independent quality characteristics

Summary In controlling the mean of a multivariate normally distributed quality characteristic the main disadvantage of the globalT ²-control charts is that they don't indicate the component of the quality characteristic which gives rise to an alarm. To avoid this disadvantage the joint use of¯x-charts is proposed in this paper, where — for the sake of simplicity — the investigations are restricted to the case of independent components and to one-sided¯x-charts. On the basis of an economic objective function an approximation to the optimal design of the¯x-charts procedure is derived and discussed. It turns out that at least in the bivariate case the nearly optimal economic design is very close to the exact solution.Supported by the Deutsche Forschungsgemeinschaft (DFG).     

Probing the Binding Region of the Single-Stranded DNA-Binding Domain of Rat DNA Polymerase β Using Nanosecond-Pulse Laser-Induced Cross-Linking and Mass Spectrometry

In recent years, there has been a significant number of studies in which UV light has been used as a reagent to induce cross-links in nucleic acid-protein complexes. An area of considerable interest among those interested in structural biology is the garnering of information about the sites of cross-linking within the protein and nucleic acid members of photolinked conjugates, under the assumption that such knowledge should lead to identification of contact regions or sites within the native complexes. In this paper, we present our results from a photocross-linking study of the complex of the single-stranded DNA-binding domain of rat DNA polymerase β (pol β-ss) with the oligonucleotide d(ATATATA). In this study, we have used single nanosecond laser pulses as the cross-linking reagent and matrix-assisted laser desorp-tion/ionization-time of flight mass spectrometry as an analytical tool to identify cross-linked peptides purified from proteolytic digests of the cross-linked complex. Six cross-linked peptides have been identified in tryptic digests of the protein-oligonucleotide conjugates that result from irradiation of the pol β-ss-d(ATATATA) complex with a single laser pulse. Comparisons with NMR data in the literature for the same complex show that each of the cross-linked peptides contains amino acids that are in contact with the nucleic acid component of the complex.     

Reaction of nitric oxide at the beta-carbon of enamines. A new method of preparing compounds containing the diazeniumdiolate functional group

The reaction of nitric oxide (NO) with enamines has been investigated. Unlike previously reported reactions of NO as a free radical with alkenes, the electrophilic addition of NO to the beta-carbon of enamines results in the formation of compounds containing the diazeniumdiolate functional group (-[N(O)NO](-)). This reaction between NO and enamines has been shown to be quite general and a variety of enamine-derived diazeniumdiolates have been isolated and characterized. While enamines derived from aldehydes and ketones whose structures allow for sequential multiple electrophilic additions tended to undergo overreaction leading to unstable products, it has been shown that this complication may be overcome by suitable choice of reaction solvent. The products obtained may exist as zwitterionic iminium salts or as neutral species depending upon the structure of the parent enamine. The diazeniumdiolate derived from 1-(N-morpholino)cyclohexene is unique among the new compounds in that it spontaneously releases NO upon dissolution in buffered aqueous solution at pH 7.4 and 37 degrees C. While the total quantity of NO released by this material (ca. 7% of the theoretical 2 moles) is apparently limited by a competing reaction in which it hydrolyzes to an alpha-diazeniumdiolated carbonyl compound and the parent amine, this feature may prove to be of great value in the development of multiaction pharmaceuticals based upon this new type of NO-releasing compound. Reports of enzymatic (oxidative) release of NO from previously known carbon-bound diazeniumdiolates also suggest that analogues of these compounds may be useful as pharmaceutical agents. This new method of introducing the relatively rarely studied diazeniumdiolate functional group into organic compounds should lead to further research into its chemical and biological properties.     

Cymantrene radical cation family: spectral and structural characterization of the half-sandwich analogues of ferrocenium ion

The anodic one-electron oxidation of three members of the half-sandwich family of piano-stool compounds MnCp (gamma)(CO) 3, where Cp (gamma) is a generic cyclopentadienyl ligand, has been studied in a CH 2Cl 2/[NBu 4][TFAB] electrolyte (TFAB = [B(C6F5) 4] (-)). The long-sought 17 e (-) radical cation of the parent complex MnCp(CO) 3 (cymantrene, 1, E 1/2 = 0.92 V vs ferrocene) has been shown to be persistent in solutions that use weakly coordinating anions in place of more nucleophilic traditional electrolyte anions. Spectroscopically characterized for the first time, 1 (+) was shown to absorb in the visible (530 nm), near-IR (2066 nm), and IR (2118, 1934 cm (-1)) regions. It was ESR-active at low temperatures (g parallel = 2.213, g perpendicular = 2.079, A parallel (Mn) = 79.2 G, A perpendicular (Mn) = 50 G) and NMR active at room temperature (delta = 22.4 vs TMS). The radical cations of the Cp-functionalized analogues, Mn(eta (5)-C5H 4NH2)(CO) 3, 2, E 1/2 = 0.62 V, and MnCp*(CO) 3 (Cp*= eta (5)-C 5Me 5, 3), E 1/2 = 0.64 V, were generated electrochemically as well by the chemical oxidant [ReCp(CO) 3] (+). The structures of 2 (+) and 3 (+) were determined by X-ray crystallographic studies of their TFAB salts. Compared to the structures of the corresponding neutral compounds, the cations showed elongated Mn-C(O) bonds and shortened C-O bonds, displaying the effect of diminished metal-to-CO backbonding. The bond-length changes in the Mn(CO) 3 moiety were much larger in 3 (+) (avg changes, Mn-C(O) = + 0.142 A, C-O = -0.063 A) than in 2 (+) (avg changes, Mn-C(O) = + 0.006 A, C-O = -0.003 A). Although there were only minor changes in the metal-to-center ring distances upon oxidation of either 2 or 3, there was decidedly less bending of the C(N) atom out of the cyclopentadienyl plane in 2 (+) compared to 2. The optical, vibrational, and magnetic resonance spectra of radicals 2 (+) and 3 (+) were also observed. The spectral data argue for the SOMOs of the 17-electron species being largely located on the Mn(CO) 3 moiety, having 40-50% Mn d-orbital character, with the ground states of the radicals, most likely (2)A', lying close in energy (within about 6000 cm (-1)) to excited states that are responsible for their rapid electronic relaxations. The cymantrenyl moiety is proposed as an anodic redox tag (or label) having physical and chemical properties that are significantly different from those of its ferrocenyl analogue.