Analysis of high-molecular-weight fructan polymers in crude plant extracts by high-resolution LC-MS

The main water-soluble carbohydrates in temperate forage grasses are polymeric fructans. Fructans consist of fructose chains of various chain lengths attached to sucrose as a core molecule. In grasses, fructans are a complex mixture of a large number of isomeric oligomers with a degree of polymerisation ranging from 3 to >100. Accurate monitoring and unambiguous peak identification requires chromatographic separation coupled to mass spectrometry. The mass range of ion trap mass spectrometers is limited, and we show here how monitoring selected multiply charged ions can be used for the detection and quantification of individual isomers and oligomers of high mass, particularly those of high degree of polymerization (DP > 20) in complex plant extracts. Previously reported methods using linear ion traps with low mass resolution have been shown to be useful for the detection of fructans with a DP up to 49. Here, we report a method using high-resolution mass spectrometry (MS) using an Exactive Orbitrap MS which greatly improves the signal-to-noise ratio and allows the detection of fructans up to DP = 100. High-sugar (HS) Lolium perenne cultivars with high concentrations of these fructans have been shown to be of benefit to the pastoral agricultural industry because they improve rumen nitrogen use efficiency and reduce nitrous oxide emissions from pastures. We demonstrate with our method that these HS grasses not only contain increased amounts of fructans in leaf blades but also accumulate fructans with much higher DP compared to cultivars with normal sugar levels.     

Relaxation oscillations in spruce–budworm interactions

We review and complement the study of the mathematical properties of the predator–prey dynamical system for spruce–budworm interactions studied in Ludwig et al. [D. Ludwig, D. Jones, C.S. Holling, Qualitative analysis of insect outbreak systems: the spruce budworm and forest, Journal of Animal Ecology 47 (1978), 315–332]. We use the singular perturbation method to identify parameter regimes which permit relaxation oscillations. The leading order contribution to the period of these oscillations is computed by means of this method and compared with the outcome of direct numerical simulations.     

Vibrational Spectra of Ethylenediamine Salts. I. Tentative Assignments of Infrared and Far Infrared Spectra

Abstract

We wish to report on some hitherto partly unnoticed and unexplained features in the infrared spectra of hydrogen halides of ethylenediamine. We have prepared normal, C-, N-, and perdeuterated ethylenediammonium chlorides and bromides and measured their infrared spectra in the range 4000–10 cm^?1.     

Scars of discrete rotational bands in hot nuclei

Rotational motion loses its coherence as a function of the nuclear internal excitation energy. The damping process does not proceed in a continuous fashion and scars of discrete rotational bands are found, inbedded in a background of damped rotational states, regardless whether the calculations are carried out using effective or “random” forces. The complexity of the damping mechanism is revealed in the lineshape of the ridges in the γ-γ correlation spectrum.     

Collective bands in 104,106,108Mo

We have used our analysis of γ-γ-γ data (5.7 × 10¹¹ triples and higher folds) taken with Gammasphere from prompt γ rays emitted in the spontaneous fission of ²⁵²Cf to study the collective bands in ^104,106,108Mo. The one-phonon and two-phonon γ-vibrational bands and known two-quasiparticle bands in neutron-rich ^104,106Mo were extended to higher spins. The one-and two-phonon γ-vibrational bands have remarkably close energies for transitions from the same spin states and identical moments of inertia. Several new bands are observed and are proposed as quasiparticle bands in ^104,106Mo, along with the first β-type vibrational band in ¹⁰⁶Mo. The quasiparticle bands have essentially constant moments of inertia near the rigid-body value that indicate blocking of the pairing interaction. Candidates for chiral doublet bands in ¹⁰⁶Mo are strong. These are the first reported chiral vibrational bands in an even-even nucleus. The text was submitted by the authors in English.     

Students' Retention of Mathematical Knowledge and Skills in Differential Equations

This study investigates students' retention of mathematical knowledge and skills in two differential equations classes. Posttests and delayed posttests after 1 year were administered to students in inquiry‐oriented and traditional classes. The results show that students in the inquiry‐oriented class retained conceptual knowledge, as seen by their performance on modeling problems, and retained equal proficiency in procedural problems, when compared with students in the traditionally taught classes. The results of this study add additional support to the claim that teaching for conceptual understanding can lead to longer retention of mathematical knowledge.     

The Morphology of Liquid-Crystalline Polymers and the Possible Consequences for their Rheological Behaviour

Polymer liquid crystals can occur as polydomain materials where the domain size may be tens of microns. While the material within each domain may be characterized by a common order parameter, the directors of the domains can be more or less randomly distributed. Since the transition from polydomain to monodomain material only involves the removal of grain boundaries and the alignment of directors, the free energy change must necessarily be small. Such a transition can readily be achieved, therefore, by the action of any external field: electrical, magnetic, stress or surface. In this work optical photomicrographs of polymeric liquid crystals with widely varying and in some cases well controlled morphologies are presented. Probable dependence of rheological behaviour on morphology is also discussed. Such dependence is expected to be considerable under certain conditions. Due to experimental and sample limitations, however, direct correlations of rheology and morphology are sparse. Morphological consequences for the rheology of liquid-crystalline materials can be exemplified by the following possibilities. In contrast to the case of isotropic melts, wall effects can be non-negligible. Zero shear rate rheological parameters are not expected to be uniquely defined quantities since the domain sizes are large and the director may not be effectively averaged over typical sample dimensions. Non-zero shear-rate measurements of rheological parameters is effected by the propensity of: (1) individual domain directors to align under the influence of a stress field and (2) flow alignment to dominate surface-induced alignment above some critical shear rate. The effects might be manifested by a non-newtonian regime as well as yield stress behaviour and thixotropy. The kinetics of relaxation from mono- to poly-domain material has implications for the dynamic response and rheological hysterises of the material.     

On the calculation of the structure of tris-(tert-butyl)-methane

A simple potential energy function developed on unstrained molecules and containing only 16 parameters can account for the unusually long C-C bonds and high C-H stretchings in highly strained tris-(tert-butyl)methane. On average, the structural deviations from experimental data are smaller than for some recently reported potential energy functions with 20–29 parameters. The success is thought to be due to fortunate handling of nonbonded interactions which include Coulomb terms.