Combined Application of Picosecond Transient Absorption and Emission Measurements in Studies of Radical-Ion Pair Dynamics

Abstract— Much of the emphasis in the development of methods for time-resolved measurements is on increasing experimental time resolution. Equally important, however, is the establishment of methods to apply existing techniques to problems of increasing complexity. Here we describe the application of a combination of picosecond absorption and emission measurements to solve a complex kinetic problem in organic photophysics, namely, the dynamics of interconverting radical-ion pairs. Although fairly routine, the emission measurements require higher time resolution and the absorption measurements require higher signal-to-noise ratios than are often achieved. In the first part of this paper we describe the ways in which these experimental requirements have been met. Next, the radical-ion pair kinetic problem and its solution are described. Finally, we discuss some future directions for the techniques as they relate to studies of radical-ion pair dynamics.     

Synthesis and Diels-Alder Reactions of a New Kind of Chiral Dienophiles: Cyclic Vinyl-p-tolylsulfilimines

A new kind of chiral dienophiles, cyclic vinyl-p-tolylsulfilimines (2a and 2b), were obtained from the corresponding (Z)-sulfinylacrylonitriles with HBF(4) and methanol. The asymmetric Diels-Alder reaction of optically pure 2a with cyclopentadiene under mild thermal or catalyzed conditions afforded only the endo-4a adduct with complete endo and pi-facial selectivities. The ability of the sulfilimine moiety to enhance the dienophilic reactivity of the double bond is similar to that of the sulfinyl group.     

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     

Analysis of amino acids in latent fingerprint residue by capillary electrophoresis‐mass spectrometry

The analysis of the chemical composition of fingerprints is important for the development and improvement of existing fingerprint enhancement techniques. This study demonstrates the first analysis of a latent fingerprint sample, using an optimized CE‐MS method. In total 12 amino acids were detected in the fingerprint sample. MS/MS fragmentation was used to provide additional identity confirmation, for which eight of the twelve detected amino acids generated confirmatory product ions. Nine amino acids were quantified and their relative abundances were consistent with previous studies with serine and glycine being the most abundant. The successful detection of amino acids from latent fingerprints demonstrates that CE‐MS is a potential future technique for further study of such compounds in fingerprint samples.     

Eine Methode zur Bestimmung von Salizylaten

Ohne Zusammenfassung     

Liquid ammonia as a dipolar aprotic solvent for aliphatic nucleophilic substitution reactions

The rate constants for the reactions of a variety of nucleophiles reacting with substituted benzyl chlorides in liquid ammonia (LNH(3)) have been determined. To fully interpret the associated linear free-energy relationships, the ionization constants of phenols ions in liquid ammonia were obtained using UV spectra. These equilibrium constants are the product of those for ion-pair formation and dissociation to the free ions, which can be separated by evaluating the effect of added ammonium ions. There is a linear relationship between the pK(a) of phenols in liquid ammonia and those in water of slope 1.68. Aminium ions exist in their unprotonated free base form in liquid ammonia and their ionization constants could not be determined by NMR. The rates of solvolysis of substituted benzyl chlorides in liquid ammonia at 25 °C show a Hammett ρ of zero, having little or no dependence upon ring substituents, which is in stark contrast with the hydrolysis rates of substituted benzyl halides in water, which vary 10(7) fold. The rate of substitution of benzyl chloride by substituted phenoxide ions is first order in the concentration of the nucleophile indicative of a S(N)2 process, and the dependence of the rate constants on the pK(a) of the phenol in liquid ammonia generates a Br?nsted β(nuc) = 0.40. Contrary to the solvolysis reaction, the reaction of phenoxide ion with 4-substituted benzyl chlorides gives a Hammett ρ = 1.1, excluding the 4-methoxy derivative, which shows the normal positive deviation. The second order rate constants for the substitution of benzyl chlorides by neutral and anionic amines show a single Br?nsted β(nuc) = 0.21 (based on the aqueous pK(a) of amine), but their dependence on the substituent in substituted benzyl chlorides varies with a Hammett ρ of 0 for neutral amines, similar to that seen for solvolysis, whereas that for amine anions is 0.93, similar to that seen for phenoxide ion.     

Copper(I)-catalyzed amination of aryl halides in liquid ammonia

The amination of aryl halides in liquid ammonia (LNH(3)) is catalyzed by a copper(I) salt/ascorbate system to yield primary aromatic amines in good to excellent yields. The low concentrations of catalyst required and the ease of product isolation suggest that this process has potential industrial applications. Commonly used ligands for analogous metal-catalyzed reactions are not effective. The rate of amination of iodobenzene in liquid ammonia is first order in copper(I) catalyst concentration. The small Hammett ρ = 0.49 for the amination of 4-substituted iodobenzenes in liquid ammonia at 25 °C indicates that the C-I bond is not significantly broken in the transition state structure and that there is a small generation of negative charge in the aryl ring, which is compatible with the oxidative addition of the copper ion being rate limiting.     

Measurements of magneto-Rayleigh-Taylor instability growth during the implosion of initially solid Al tubes driven by the 20-MA, 100-ns Z facility

The first controlled experiments measuring the growth of the magneto-Rayleigh-Taylor instability in fast (～100 ns) Z-pinch plasmas are reported. Sinusoidal perturbations on the surface of an initially solid Al tube (liner) with wavelengths of 25-400 μm were used to seed the instability. Radiographs with 15 μm resolution captured the evolution of the outer liner surface. Comparisons with numerical radiation magnetohydrodynamic simulations show remarkably good agreement down to 50 μm wavelengths.