Characterization by three-dimensional representation of sequential transitions of metastable ions in a double focusing mass spectrometer

The ion currents due to products of selected ion reactions of toluene and 3-chlorophenol, occurring in the source or flight tube of a double focusing mass spectrometer for which the electric sector precedes the magnetic sector, have been represented by plotting them against two variables that reflect independently the effects of the sectors. The daughter ion produced from the molecular ion of 3-chlorophenol that decays by sequential losses of CO in the field free region preceding the electric sector and Cl˙ in the field free region preceding the magnetic sector gives rise to a peak with a distinctive shape on the resultant three-dimensional surface. A peak due to the daughter ion arising from the corresponding sequential losses of H˙ and C₂H₂ from the molecular ion of toluene could not be detected. A portion of the ion kinetic energy spectrum which would be recorded by a detector at the energy resolving slit is derived from the surface for 3-chlorophenol and is in satisfactory agreement with a published spectrum.     

Union of capillary high-performance liquid chromatography and microcoil nuclear magnetic resonance spectroscopy applied to the separation and identification of terpenoids

This paper describes the first coupling of a commercial capillary HPLC system with a diode array spectrophotometric detector and a custom-built nuclear magnetic resonance (NMR) flow microprobe. The eluent from a 3-microm diameter C18 HPLC column is linked to a 500 MHz 1H-NMR microcoil probe with an observe volume of 1.1 microl. The separation and structurally-rich detection of a mixture of terpenoids under both isocratic and gradient solvent elution conditions is presented. The lowest limits of detection yet reported for capillary HPLC on-line measurement (i.e., 37 ng for alpha-pinene) are achieved with this system. The complementary nature of diode array and NMR detection allows stopped-flow data collection from analytes which would otherwise go unnoticed in continuous-flow NMR. Moreover, stopped-flow NMR data is presented for the detection of a trace (sub-nmol) impurity in the sample mixture. Since NMR signals degrade and shift during solvent gradients, flow injection analysis studies are conducted with injected solvent plugs differing in mobile phase composition. The NMR signal degradation accompanying these injections is largely due to the variance in chemical shift with the solvent composition rather than to changes in magnetic susceptibility of the solvent. Characterization of such effects enables the development of improved NMR probes for the coupling of capillary HPLC and NMR.     

In-situ X-ray imaging of III-V strained-layer relaxation processes

The important value of the X-ray topography (XRT) technique for the investigation of III-V strained-layer relaxation processes is described. In addition to post-growth ex-situ XRT studies, a unique combined XRT/MBE growth facility has been constructed which allows the generation, motion and interaction of misfit dislocations to be monitored in-situ during epilayer growth, for the first time. The in-situ data already obtained for (100) InGaAs strained-layer growth on both Czochralski- and vertical-gradient freeze-grown GaAs substrates indicates technologically important differences in the initial relaxation process, including, in the latter case, the observation of a previously unreported secondary relaxation phase. Initial results relating to the influence of both post-growth annealing and the subsequent cool-down process are also described.     

Dipolar relaxations in the glass transition region and in the liquid crystalline phase of two side-chain liquid crystalline polysiloxanes

The molecular relaxation mechanisms in the glass transition region and in the liquid crystalline phase exhibited by two side-chain liquid crystalline polysiloxanes have been studied by Thermally Stimulated Discharge Currents. These results were compared with those previously obtained by dielectric relaxation spectroscopy. It was observed that two relaxation mechanisms were present in the liquid crystalline phase, and we suggest that these might correspond to the motions of the mesogenic moieties in the liquid crystalline phase. © 1996 John Wiley & Sons, Inc.     

The use of photoinitiated free-radical cyclopolymerization in the preparation of novel side-chain liquid-crystalline polydienes

The technique of photoinitiated free-radical cyclopolymerization has been used to produce a variety of novel side-chain liquid-crystalline (SCLC) polymers in which an alicyclic ring structure is incorporated into a polymer backbone. Most of the SCLC polymers gave glass transition temperatures (T_g) around room temperature and clearing points around 60–70°C. However, the poly(1,5-hexadiene) was the exception to this, exhibiting a T_g value of 14.5°C and a clearing point of 132.5°C. Confirmation of the structure of the alicyclic ring along the polymer backbone is extremely difficult to obtain, but evidence is given in the paper to support the ring structure.     

Crust density in bread baking: Mathematical modelling and numerical solutions

A model for the formation of a “crust” during bread baking is presented. The crust is the outermost part of the loaf where the final bread density is significantly higher than in the “crumb”, the interior of the loaf. The model is based on a collapse mechanism, whereby raised pressures due to thermal expansion and water evaporation squash bubbles in the bread as the dough sets and fractures; the latter process allows vapour within bubbles to escape.     

Directional tunneling escape from nearly spherical optical resonators

We report the surprising observation of directional tunneling escape from nearly spherical fused-silica optical resonators, in which most of the phase space is filled with nonchaotic regular trajectories. Experimental and theoretical studies of the dependence of the far-field emission pattern on both the degree of deformation and the excitation condition show that nonperturbative phase-space structures in the internal ray dynamics profoundly affect tunneling leakage of the whispering-gallery modes.     

The mass spectra of metal complexes of dibenzoylmethane

The mass spectra of a series of metal complexes of dibenzoylmethane have been rationalized. The paths of novel rearrangement reactions involving both hydrogen and oxygen migration may differ according to the type of metal atom in the complex. Further examples are proposed of the effect of metal valency changes in ion reactions.     

The lowest singlet state of dibenzofuran

The vapor absorption of dibenzofuran has been reexamined, and the spectrum and lifetime of the vapor fluorescence have been measured. Also measured were the polarized absorption in durene host and the depolarized absorption, fluorescence, and phosphorescence in cyclododecane host at 4 K. The fluoresecent state is that corresponding to the 3000 Å absorption in all media, and no evidence was found for a weak transition at 3175 Å as reported by Pinkham and Wait. The mixed crystal spectra are heavily perturbed, but from the polarizations observed in durene the 3000 Å transition is assigned as ${}^1\text{B}{}_2\text{←}{}^1\text{A}{}_1$ (long axis polarized).     

Solid-phase derivatization of tryptic peptides for rapid protein identification by matrix-assisted laser desorption/ionization mass spectrometry

Solid-phase sulfonation of tryptic peptides adsorbed to C18 muZipTips has been carried out to facilitate de novo sequencing with mass spectrometry. Peptides are reacted with the sulfonation reagent while they are still adsorbed to the solid phase. Excess reagent passes through the ZipTip to waste. Washing the products before subsequent elution from the mini-column also affords sample cleanup prior to analysis. Near quantitative N-terminal sulfonation can be achieved reliably at room temperature in only a few seconds. The method has been applied successfully to model peptides and to solution or in-gel digests of proteins. Current sequencing limits are about 100 fmol of protein. Multiplexed sample sulfonation reactions have been carried out with a manual 8-position micropipettor or using centrifugal force to reliably pass reagents and wash solutions over sample-loaded ZipTips. With multiplexing, overall preparation times have been reduced to about 1 min per sample. The solid-phase format facilitates efficient use of precious digest samples by enabling them to be recovered from the matrix-assisted laser desorption/ionization (MALDI) sample stage after mass fingerprinting, derivatized and re-analyzed by MALDI postsource decay mass spectrometry.