Proton radiography of a laser-driven implosion

Protons accelerated by a picosecond laser pulse have been used to radiograph a 500 microm diameter capsule, imploded with 300 J of laser light in 6 symmetrically incident beams of wavelength 1.054 microm and pulse length 1 ns. Point projection proton backlighting was used to characterize the density gradients at discrete times through the implosion. Asymmetries were diagnosed both during the early and stagnation stages of the implosion. Comparison with analytic scattering theory and simple Monte Carlo simulations were consistent with a 3+/-1 g/cm3 core with diameter 85+/-10 microm. Scaling simulations show that protons>50 MeV are required to diagnose asymmetry in ignition scale conditions.     

Search for the Theta+ Pentaquark in the gammad--> DeltanK+ reaction measured with the CLAS spectrometer

For the first time, the reaction gammad-->DeltanK+ has been analyzed in order to search for the exotic pentaquark baryon Theta+(1540). The data were taken at Jefferson Laboratory, using the Hall-B tagged-photon beam of energy between 0.8 and 3.6 GeV and the CEBAF Large Acceptance Spectrometer (CLAS). No statistically significant structures were observed in the nK+ invariant-mass distribution. The upper limit on the gammad-->DeltaTheta+ integrated cross section has been calculated and found to be between 5 and 25 nb, depending on the production model assumed. The upper limit on the differential cross section is also reported.     

Isotope ratio monitoring gas chromatography/Mass spectrometry of D/H by high temperature conversion isotope ratio mass spectrometry

Of all the elements, hydrogen has the largest naturally occurring variations in the ratio of its stable isotopes (D/H). It is for this reason that there has been a strong desire to add hydrogen to the list of elements amenable to isotope ratio monitoring gas chromatography/mass spectrometry (irm-GC/MS). In irm-GC/MS the sample is entrained in helium as the carrier gas, which is also ionized and separated in the isotope ratio mass spectrometer (IRMS). Because of the low abundance of deuterium in nature, precise and accurate on-line monitoring of D/H ratios with an IRMS requires that low energy helium ions be kept out of the m/z 3 collector, which requires the use of an energy filter. A clean mass 3 (HD(+.)) signal which is independent of a large helium load in the electron impact ion source is essential in order to reach the sensitivity required for D/H analysis of capillary GC peaks. A new IRMS system, the DELTA(plus)XL(trade mark), has been designed for high precision, high accuracy measurements of transient signals of hydrogen gas. It incorporates a retardation lens integrated into the m/z 3 Faraday cup collector. Following GC separation, the hydrogen bound in organic compounds must be quantitatively converted into H(2) gas prior to analysis in the IRMS. Quantitative conversion is achieved by high temperature conversion (TC) at temperatures >1400 degrees C. Measurements of D/H ratios of individual organic compounds in complicated natural mixtures can now be made to a precision of 2 per thousand (delta notation) or, better, with typical sample amounts of approximately 200 ng per compound. Initial applications have focused on compounds of interest to petroleum research (biomarkers and natural gas components), food and flavor control (vanillin and ethanol), and metabolic studies (fatty acids and steroids). Copyright 1999 John Wiley & Sons, Ltd.     

Synthesis of Delta(1)-1,2-diazetines via a Diels-Alder cycloaddition approach

[reaction: see text] A novel method for the synthesis of Delta(1)-1,2-diazetines is presented. Diels-Alder cycloaddition of dienophile 4 with five dienes afforded cycloadducts in good to excellent yields. Four of the obtained cycloadducts were converted to the corresponding diazetines.     

A Practical Titanium-Catalyzed Synthesis of Bicyclic Cyclopentenones and Allylic Amines

A practical titanium-catalyzed synthesis of bicyclic cyclopentenones and allylic amines is described. The process converts enyne substrates to iminocyclopentenes using 10 mol % of the air- and moisture-stable precatalyst Cp(2)TiCl(2) in the presence of n-BuLi and triethylsilyl cyanide. The resulting iminocyclopentenes can be hydrolyzed to cyclopentenones in good yields or reduced to allylic silylamines with Red-Al or DIBALH. Treatment of the crude silylamines with acetyl chloride allows isolation of allylic amides in excellent yields.     

Separation and quantitation of monovalent anionic and cationic species in mainstream cigarette smoke aerosols by high-performance ion chromatography

A simple method has been developed to separate and quantitate monovalent ionic species in mainstream cigarette smoke aerosols based on ion chromatography (IC) with conductivity detection. The method entails collecting the smoke aerosol particulate phase by electrostatic precipitation, dissolving the smoke condensate in methanol (MeOH), and separating the ionic species on either a cation- or anion-exchange column. The method has been applied to the analysis of smoke aerosols from two cigarettes, 1R4F Kentucky Reference cigarettes and a new cigarette that heats but does not burn tobacco. The predominant cations in smoke aerosols from 1R4F Kentucky Reference and the new cigarettes are sodium (Na+), ammonium (NH4+), and potassium (K+) ions; the predominant anions are acetate (AcO-) and formate (HCOO-). Trace amounts of chloride (Cl-), nitrite (NO2-), and nitrate (NO3-) ions are also present.     

Investigations into the chromatographic behavior of a doxorubicin-peptide conjugate

HPLC impurity profile method development for a doxorubicin-heptapeptide conjugate included significant changes of the separation profile with diluent, eluent and pH. These separation variables were also temperature-dependent with a shift in retention from 35 to 45 degrees C. There was also a direct relationship of temperature with LC retention, and a pH minimum at 5.9. Atypical dependence of the impurity profile on diluent at a k' of 18 led to further investigation. A large change in retention by several minutes was a function of both the organic eluent composition and temperature between 15 and 30 degrees C. Several Van't Hoff temperature studies from 5 to 65 degrees C on several column types resulted in non-linear plots. Analysis of the molecular subunits suggested that the peptide portion of the analyte influenced the non-linear retention behavior. The stationary phase type was not a significant factor causing non-linearity. Circular dichroism-temperature studies indicated a notable transition in ellipticity for the amine regions (198-202 nm) that occurred between 39 and 44 degrees C. This transition temperature range coincided with the results of the Van't Hoff analysis, between 35 and 44 degrees C, to indicate that these effects were not primarily stationary phase induced.     

Hydrogen adsorption on the indium-rich indium phosphide (001) surface: a novel way to produce bridging In-H-In bonds

The indium phosphide (001) surface provides a unique chemical environment for studying the reactivity of hydrogen toward the electron-deficient group IIIA element, indium. Hydrogen adsorption on the In-rich delta(2 x 4) reconstruction produced a neutral, covalently bound bridging indium hydride. Using vibrational spectroscopy and ab initio cluster calculations, two types of bridging hydrides were identified, a (mu-H)In(2) and a (mu-H)(2)In(3) "butterfly-like" structure. These structures were formed owing to the large thermodynamic driving force for adsorption of H atoms on solid-state indium dimers.     

Quantized double-layer charging of highly monodisperse metal nanoparticles

We describe unprecedented resolution of electrochemically observed quantized double layer (QDL) charging, attained with use of reduced solution temperatures and with an annealing procedure that produces hexanethiolate monolayer protected gold clusters (C6 MPCs) with a high level of monodispersity in charging capacitance, C(CLU). The spacing DeltaV = e/C(CLU) on the electrochemical potential axis between one electron changes in the electronic charge of nanoscopic metal particles is determined by their effective capacitance C(CLU). The high monodispersity of the C6 MPCs with Au(140) cores facilitates (a) detailed rotated disk and cyclic voltammetric measurements, (b) simulation of QDL waveshapes based on assumed reversible, multivalent redox-like behavior, (c) determination of nanoparticle diffusion rates, and (d) observation of as many as 13 changes in the MPC charge state, from MPC(6-) to MPC(7+). The single electron QDL charging peaks are quite evenly spaced (DeltaV constant) at potentials near the MPC potential of zero charge, but are irregularly spaced at more positive and negative potentials. The irregular spacing is difficult to rationalize with classical double layer capacitance ideas and is proposed to arise from a correspondingly structured (e.g., not smooth) density of electronic states of the nanoparticle core, resulting from its small HOMO/LUMO gap and incipiently molecule-like behavior.