Synthetic studies with iron carbonyl complexes. Versatile synthesis of olefinic side-chains to a tricarbonyl(cyclohexadiene)iron(0) ring

Tricarbonyl(cyclohexadiene)iron(0) complexes bearing olefinic side-chains at the 2- or the 5-position have been prepared by a versatile route. Terminal olefins are isomerised to internal isomers. The presence of a methoxy substituent at the 2-position prevents isomerisation of the coordinated diene into conjugation with the olefin, so locking the side-chain at the 5-exo-position.     

Ion/Ion reactions for oligopeptide mixture analysis: application to mixtures comprised of 0.5–100 kDa components

Oligopeptide mixtures have been subjected to electrospray ionization, accumulated within a quadrupole ion trap, and subjected to ion/ion proton transfer reactions with anions derived from perfluoro-1,3-dimethylcyclohexane. Various mixtures were studied with approximate molecular weight ranges of 0.5–8.5, 12–30, 45–100, and 0.5–100 kDa. Mixtures of known composition were studied to evaluate the mixture complexity amenable to electrospray combined with ion/ion reactions to reduce spectral complexity associated with multiple charging. Mixture analysis with at least 40 components of low and medium molecular weight and roughly comparable solution concentrations appears to be straightforward. No matrix effects upon ionization were implicated in the data for the low and medium molecular weight mixtures but bovine albumin appeared to inhibit signals from bovine transferrin and chicken conalbumin in the high molecular weight mix. Furthermore, the presence of abundant low mass-to-charge ions appeared to inhibit signals from high molecular weight proteins (>40 kDa) in the 0.5–100 kDa mix. Such an observation is consistent with dynamic range limitations that can arise from discrimination based on ion space charge effects, although an ionization matrix effect could not be precluded from the data reported here. The results reported here indicate that the limitation to mixture complexity amenable to electrospray mass spectrometry imposed by spectral congestion associated with multiple charging can be significantly reduced via ion/ion reactions. The use of ion/ion reactions can therefore facilitate the study of other factors that can impose limitations to mixture analysis, such as matrix effects upon ionization and differences in ion transmission, accumulation, storage, and detection efficiencies.     

Decompositions of odd- and even-electron anions derived from deoxy-polyadenylates

Radical anions have been formed via electron transfer from multiply charged 5′-d(AAA)-3′ and 5′-d(AAAA)-3′ anions to CCl₃ ⁺. These ions have been isolated in a quadrupole ion trap operated with helium bath gas at a pressure of 1 mtorr and subjected to resonance excitation (i. e., conventional ion trap collisional activation). Collisional activation of the even-electron species of the same charge state formed directly via electrospray was also performed by using essentially identical conditions. The collisional activation data can be compared directly without ambiguity arising from differences in parent ion internal energies and/or dissociation time frames. Both the odd- and even-electron anions yield extensive sequence-informative fragmentation but show significant differences in the extent of nucleobase loss and in the relative contributions from the various sequence diagnostic dissociation channels. The results of this study indicate that radical anions derived from multiply deprotonated oligo-deoxynucleotides that survive the electron transfer process are stable with respect to fragmentation in the ion trap environment under normal storage conditions and that the unimolecular dissociation behavior of these ions differs from the even-electron anions of the same charge state. These findings suggest, therefore, that odd- and even-electron anions might be used to provide complementary sequence information in cases in which neither ion type provides the full sequence.     

Ion-ion proton transfer reactions of bio-ions involving noncovalent interactions: Holomyoglobin

Multiply protonated horse skeletal muscle holomyoglobin and apomyoglobin have been subjected to ion-ion proton transfer reactions with anions derived from perfluoro-1,3-dimethylcyclohexane in a quadrupole ion trap operated with helium as a bath gas at 1 mtorr. Neither the apomyoglobin nor holomyoglobin ions show any sign of fragmentation associated with charge state reduction to the 1 + charge state. This is particularly noteworthy for the holomyoglobin ions, which retain the noncovalently bound heme group. For example, no sign of heme loss is associated with charge state reduction from the 9 + charge state of holomyoglobin to the 1 + charge state despite the eight consecutive highly exothermic proton transfer reactions required to bring about this charge change. This result is consistent with calculations that show the combination of long ion lifetime and the high ion-helium collision rate relative to the ion-ion collision rate makes fragmentation unlikely for high mass ions in the ion trap environment even for noncovalently bound complexes of moderate binding strength. The ion-ion proton transfer rates for holo- and apomyoglobin ions of the same charge state also were observed to be indistinguishable, which supports the expectation that ion-ion proton transfer rates are insensitive to ion structure and are determined primarily by the attractive Coulomb field.     

New techniques for the analysis of fine-scaled clustering phenomena within atom probe tomography (APT) data.

Nanoscale atomic clusters in atom probe tomographic data are not universally defined but instead are characterized by the clustering algorithm used and the parameter values controlling the algorithmic process. A new core-linkage clustering algorithm is developed, combining fundamental elements of the conventional maximum separation method with density-based analyses. A key improvement to the algorithm is the independence of algorithmic parameters inherently unified in previous techniques, enabling a more accurate analysis to be applied across a wider range of material systems. Further, an objective procedure for the selection of parameters based on approximating the data with a model of complete spatial randomness is developed and applied. The use of higher nearest neighbor distributions is highlighted to give insight into the nature of the clustering phenomena present in a system and to generalize the clustering algorithms used to analyze it. Maximum separation, density-based scanning, and the core linkage algorithm, developed within this study, were separately applied to the investigation of fine solute clustering of solute atoms in an Al-1.9Zn-1.7Mg (at.%) at two distinct states of early phase decomposition and the results of these analyses were evaluated.     

Finite computable dimension and degrees of categoricity

We first give an example of a rigid structure of computable dimension 2 such that the unique isomorphism between two non-computably isomorphic computable copies has Turing degree strictly below ${\mathbf{0}}^{″}$, and not above ${\mathbf{0}}^{\prime }$. This gives a first example of a computable structure with a degree of categoricity that does not belong to an interval of the form $[{\mathbf{0}}^{(\alpha )},{\mathbf{0}}^{(\alpha +1)}]$ for any computable ordinal α. We then extend the technique to produce a rigid structure of computable dimension 3 such that if ${\mathbf{d}}_0$, ${\mathbf{d}}_1$, and ${\mathbf{d}}_2$ are the degrees of isomorphisms between distinct representatives of the three computable equivalence classes, then each ${\mathbf{d}}_i<{\mathbf{d}}_0\oplus {\mathbf{d}}_1\oplus {\mathbf{d}}_2$. The resulting structure is an example of a structure that has a degree of categoricity, but not strongly.     

First spin flipping of a stored spin-1 polarized beam

We recently studied spin flipping of a 270 MeV vertically polarized deuteron beam stored in the Indiana University Cyclotron Facility Cooler Ring. We adiabatically swept an rf solenoid's frequency through an rf-induced spin resonance and observed its effect on the deuterons' vector and tensor polarizations. After optimizing the resonance crossing rate and maximizing the solenoid's voltage, we measured a vector spin-flip efficiency of 94.2%+/-0.3%. We also found striking behavior of the spin-1 tensor polarization.     

Measurement of the absolute n p scattering differential cross section at 194 MeV

We describe a double-scattering experiment with a novel tagged neutron beam to measure differential cross sections for np backscattering to better than +/-2% absolute precision. The measurement focuses on angles and energies where the cross section magnitude and angle dependence constrain the charged pion-nucleon coupling constant, but existing data show serious discrepancies among themselves and with energy-dependent partial-wave analyses. The present results are in good accord with the partial-wave analyses, but deviate systematically from other recent measurements.