Experimental and shell-model studies of the reactions 91Zr(d,p)92Zr and 90Zr(t,p)92Zr

The results of high-resolution studies of the ⁹¹Zr(d, p) reaction at E_d = 12 MeV and the ⁹⁰Zr(t, p) reaction at E_t = 11.85 MeV are presented. Absolute cross sections have been measured for both reactions and (d, p) spectroscopic factors determined. A comparison of these results with earlier data has been made, and although many of the previous assignments have been confirmed, many new features concerning the structure of ⁹²Zr have been discovered. Shell-model calculations have been performed for ⁹¹Zr and ⁹²Zr using a neutron space which includes the $\text{2}\text{d}{}_{\mathrm{<mtext>5</mtext><mtext>2</mtext>}}$, $\text{3}\text{s}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$, $\text{2}\text{d}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$, $\text{1}\text{g}{}_{\mathrm{<mtext>7</mtext><mtext>2</mtext>}}$ and $\text{1}\text{h}{}_{\mathrm{<mtext>11</mtext><mtext>2</mtext>}}$ orbits and a proton space comprising the $\text{1}\text{g}{}_{\mathrm{<mtext>9</mtext><mtext>2</mtext>}}$ and $\text{2}\text{p}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ orbits. Realistic proton-neutron and neutron-neutron interactions based on the Sussex matrix elements were used in the calculations. Spectroscopic factors have been calculated for the ⁹⁰Zr(d, p) and ⁹¹Zr(d, p) reactions and cross sections calculated for the ⁹⁰Zr(t, p) reaction. In general, good agreement between the theoretical and the experimental results has been obtained.     

First magnetic measurements of action currents in isolated cardiac Purkinje fibers

Summary We present the first measurements of the magnetic field associated with the action potential in a bundle of isolated cardiac Purkinje fibers. Our findings demonstrate the feasibility of using magnetic techniques to measure the axial current in a bundle of spontaneously active cardiac cells. Paper presented at the ≪IV International Workshop on Biomagnetism≫, held in Rome, September 14–16, 1982.     

Determination of ion mobility collision cross sections for unresolved isomeric mixtures using tandem mass spectrometry and chemometric deconvolution

Ion mobility (IM) is an important analytical technique for determining ion collision cross section (CCS) values in the gas-phase and gaining insight into molecular structures and conformations. However, limited instrument resolving powers for IM may restrict adequate characterization of conformationally similar ions, such as structural isomers, and reduce the accuracy of IM-based CCS calculations. Recently, we introduced an automated technique for extracting “pure” IM and collision-induced dissociation (CID) mass spectra of IM overlapping species using chemometric deconvolution of post-IM/CID mass spectrometry (MS) data [J. Am. Soc. Mass Spectrom., 2014, 25, 1810–1819]. Here we extend those capabilities to demonstrate how extracted IM profiles can be used to calculate accurate CCS values of peptide isomer ions which are not fully resolved by IM. We show that CCS values obtained from deconvoluted IM spectra match with CCS values measured from the individually analyzed corresponding peptides on uniform field IM instrumentation. We introduce an approach that utilizes experimentally determined IM arrival time (AT) “shift factors” to compensate for ion acceleration variations during post-IM/CID and significantly improve the accuracy of the calculated CCS values. Also, we discuss details of this IM deconvolution approach and compare empirical CCS values from traveling wave (TW)IM-MS and drift tube (DT)IM-MS with theoretically calculated CCS values using the projected superposition approximation (PSA). For example, experimentally measured deconvoluted TWIM-MS mean CCS values for doubly-protonated RYGGFM, RMFGYG, MFRYGG, and FRMYGG peptide isomers were 288.₈ Å², 295.₁ Å², 296.₈ Å², and 300.₁ Å²; all four of these CCS values were within 1.5% of independently measured DTIM-MS values.     

A collision cross-section database of singly-charged peptide ions

A database of ion-neutral collision cross-sections for singly-charged peptide ions is presented. The peptides included in the database were generated by enzymatic digestion of known proteins using three different enzymes, resulting in peptides that differ in terms of amino acid composition as well as N-terminal and C-terminal residues. The ion-neutral collision cross-sections were measured using ion mobility (IM) spectrometry that is directly coupled to a time-of-flight (TOF) mass spectrometer. The ions were formed by a matrix-assisted laser desorption ionization (MALDI) ion source operated at pressures (He bath gas) of 2 to 3 torr. The majority (63%) of the peptide ion collision cross-sections correlate well with structures that are best described as charge-solvated globules, but a significant number of the peptide ions exhibit collision cross-sections that are significantly larger or smaller than the average, globular mobility-mass correlation. Of the peptide ions having larger than average collision cross-sections, approximately 71% are derived from trypsin digestion (C-terminal Arg or Lys residues) and most of the peptide ions that have smaller (than globular) collision cross-sections are derived from pepsin digestion (90%).     

Application of Fragment Screening and Merging to the Discovery of Inhibitors of the Mycobacterium tuberculosis Cytochrome P450 CYP121

Pieces of the puzzle: The first fragment-based approach was used to target cytochrome?P450 enzymes (CYPs) for drug development. The experiments provide new insights into the binding site of the essential Mycobacterium tuberculosis CYP121 enzyme, and resulted in a promising novel lead compound based on fragment merging.     

SPECTROSCOPIC AND MICROSCOPIC CHARACTERISTICS OF HUMAN SKIN AUTOFLUORESCENCE EMISSION

To improve the understanding of human skin autofluorescence emission, the spectroscopic and microscopic characteristics of skin autofluorescence were studied using a combined fluorescence and reflectance spectroanalyzer and a fiber optic microspectrophotometer. The autofluorescence spectra of in vivo human skin were measured over a wide excitation wavelength range (350–470 nm). The excitation–emission matrices of in vivo skin were obtained. An excitation–emission maximum pair (380 nm, 470 nm) was identified. It was revealed that the most probable energy of skin autofluorescence emission photons increases monotonically and near linearly with increasing excitation photon energy. It was demonstrated that the diffuse reflectance, R, can be used as a first order approximation of the fluorescence distortion factor f to correct the measured in vivo autofluorescence spectra for the effect of tissue reabsorption and scattering. The microscopic in vitro autofluorescence properties of excised skin tissue sections were examined using 442 nm He–Cd laser light excitation as an example. It was demonstrated that the fluorophore distribution inside the skin tissue is not uniform and the shapes of the autofluorescence spectra of different anatomical skin layers vary. The result of this study confirms that the major skin fluorophores are located in the dermis and provides an excellent foundation for Monte Carlo modeling of in vivo autofluorescence measurements.     

Thermotropic phase transition in soluble nanoscale lipid bilayers

The role of lipid domain size and protein-lipid interfaces in the thermotropic phase transition of dipalmitoylphosphatidylcholine (DPPC) and dimyristoylphosphatidylcholine (DMPC) bilayers in Nanodiscs was studied using small-angle X-ray scattering (SAXS), differential scanning calorimetry (DSC), and generalized polarization (GP) of the lipophilic probe Laurdan. Nanodiscs are water-soluble, monodisperse, self-assembled lipid bilayers encompassed by a helical membrane scaffold protein (MSP). MSPs of different lengths were used to define the diameter of the Nanodisc lipid bilayer from 76 to 108 A and the number of DPPC molecules from 164 to 335 per discoidal structure. In Nanodiscs of all sizes, the phase transitions were broader and shifted to higher temperatures relative to those observed in vesicle preparations. The size dependences of the transition enthalpies and structural parameters of Nanodiscs reveal the presence of a boundary lipid layer in contact with the scaffold protein encircling the perimeter of the disc. The thickness of this annular layer was estimated to be approximately 15 A, or two lipid molecules. SAXS was used to measure the lateral thermal expansion of Nanodiscs, and a steep decrease of bilayer thickness during the main lipid phase transition was observed. These results provide the basis for the quantitative understanding of cooperative phase transitions in membrane bilayers in confined geometries at the nanoscale.     

Intermolecular potential for thermal H2O-He collisions

Theoretical potentials for rotational excitation of H2O by He were constructed via several methods, all of which start with a large basis set SCF interaction. The semiempirical Hartree-Fock with damped dispersion (HFD) model adds a damped long-range attraction with parameters adjusted to fit experimental total differential cross sections. Purely ab initio potentials add correlation energies obtained via perturbation theory (MP2 and MP4) or a variational method (ICF1). Scattering calculations were performed on all surfaces to compare with available beam scattering and pressure broadening data and to assess sensitivity of state-to-state rates to uncertainties in the potential. From comparison with the limited experimental data, the ICF1 surface appears to be marginally better than the MP4 surface. Thermal rates calculated from this surface should be accurate to better than 50%, at least for the larger, more important rates.     

Atomic absorption with ultracold atoms

Recent advances in laser-atom cooling techniques and diode-laser technology now allow one to conduct an idealised atomic absorption experiment comprising a sample of ultracold, quasi-stationary absorbing atoms and a source of near-monochromatic resonant light. Under such conditions, the atomic absorption coefficient at line centre is independent of the oscillator strength of the atomic resonance line. This offers the prospect of ‘oscillator-strength-free’ atomic absorption spectroscopy in which the absorption signal is equally large for both strong and weak (closed) transitions of the same wavelength and in which absolute atomic absorption could be performed without knowledge of the oscillator strength. Moreover, the resolution and sensitivity for a given atom density are greatly enhanced, typically by approximately three orders of magnitude (and even more for weak transitions), compared with conventional flame or graphite-furnace atomic absorption. We describe an atomic absorption experiment based on samples of ultracold, laser-cooled caesium atoms and a narrow-bandwidth diode laser source that approximates the idealised conditions for oscillator-strength-free atomic absorption. The absorption measurements are used to determine the number density and temperature (approx. 6 μK) of the sample of ultracold atoms. Some of the technical obstacles that would have to be overcome before samples of ultracold atoms and diode laser sources could be used in analytical atomic absorption spectroscopy are discussed.     

Is N-protonated hydrogen isocyanide, H2NC+, an observable interstellar species?

Ab initio molecular orbital theory is used to examine the singlet and triplet potential energy surfaces for the CH2N+ system. The results confirm those of earlier studies which suggested that the singlet H2NC+ isomer could be formed via the corresponding triplet isomer. Also, it is shown that the reaction HCN+ + H2 might lead to this metastable isomer without invoking the triplet species. The best test of the hypothesis that this molecule can be formed by gas phase, ion molecule reactions and may be an important precursor in the interstellar synthesis of HCN and HNC is to search for it in space. To this end, theoretical predictions are made of its rotational frequencies and its vibrational frequencies and intensities to serve as a guide to laboratory spectroscopists and radioastronomers.