Isotopic abundance measurements on solid nuclear-type samples by glow discharge mass spectrometry

A double-focusing Glow Discharge Mass Spectrometer (GDMS) installed in a glovebox for nuclear sample screening has been employed for isotopic measurements. Isotopic compositions of zirconium, silicon, lithium, boron, uranium and plutonium which are elements of nuclear concern have been determined. Interferences arising from the matrix sample and the discharge gas (Ar) for each of these elements are discussed. The GDMS results are compared with those from Thermal Ionization Mass Spectrometry (TIMS). For boron and lithium at g/g-ng/g levels, the two methods gave results in good agreement. In samples containing uranium the isotopic composition obtained by GDMS was in agreement with those from TIMS independently of the enrichment. Attempts for the determination of plutonium isotopic composition were also made. In this case, due to the interferences of uranium at mass 238 and americium at mass 241, the GDMS raw data are complementary with those values obtained from physical non-destructive techniques.     

A general synthetic route to 4-substituted-2,2′-bithiophenes

A new synthetic route to 4-substituted-2,2′-bithiophenes has been developed utilizing 4-bromo-2,2′-bithiophene ( 1 ). Formation of the bithienyllithium adduct via halogen-metal exchange was found to be problematic and resulted in complex mixtures of products. The Grignard reagent of 1 can be obtained easily via the “entrainment” method, allowing the production of 4-substituted-2,2′-bithiophenes (where sub-stituent = octyl, hydroxyethyl, hydroxymethyl, carboxy, carbomethoxy, acetoxyethyl, and acetoxymethyl).     

Fe-contacts on InAs(100) and InP(100) characterised by conversion electron Mössbauer spectroscopy

We have grown 4 nm thin films of ⁵⁷Fe on InAs(100) and InP(100) surfaces by use of MBE and studied the samples by ⁵⁷Fe conversion electron Mössbauer spectroscopy. In the case of InAs, the Mössbauer spectrum showed a sextet due to α-Fe and a further magnetically split component with slightly smaller hyperfine field, which is attributed to interface components. This result indicates that there is a relatively sharp interface between Fe and InAs. On the contrary, the spectrum of the InP sample showed a sextet with very broad lines and a smaller average hyperfine field. This suggests a strong chemical reaction between iron and the substrate, which results in the formation of a poorly crystalline phase.     

Approximating the permanent: A simple approach

In this article, we present an efficient and very simple unbiased estimator for the Permanent of square (0–1) matrices. As the main result, we prove that our estimator, even though its worst case behavior is provably very bad, runs in time polynomial in the size of the input matrix for almost all matrices. We also generalize our technique and apply it to another enumeration problem, that of counting Hamilton cycles in directed graphs. The ease with which this was done suggests that the basic technique may have wide applicability. © 1994 John Wiley & Sons, Inc.     

Mechanisms of radical removal by SO2

It is well established from experiments in premixed, laminar flames, jet-stirred reactors, flow reactors, and batch reactors that SO₂ acts to catalyze hydrogen atom removal at stoichiometric and reducing conditions. However, the commonly accepted mechanism for radical removal, SO₂ + H(+M) ? HOSO(+M), HOSO + H/OH ? SO₂ + H₂/H₂O, has been challenged by recent theoretical and experimental results. Based on ab initio calculations for key reactions, we update the kinetic model for this chemistry and re-examine the mechanism of fuel/SO₂ interactions. We find that the interaction of SO₂ with the radical pool is more complex than previously assumed, involving HOSO and SO, as well as, at high temperatures also HSO, SH, and S. The revised mechanism with a high rate constant for H + SO₂ recombination and with SO + H₂O, rather than SO₂ + H₂, as major products of the HOSO + H reaction is in agreement with a range of experimental results from batch and flow reactors, as well as laminar flames.     

On the bursting of linear polymer melts in inflation processes

Molten LLDPE and HDPE plates (thickness 2 mm) have been inflated into a circular cylinder (inner radius 31 mm) under isothermal conditions. Low deformation rates allow the plates to be inflated considerably into the cylinder, and at high inflation rates an early burst is observed.Axis-symmetric numerical simulation of the inflations have been performed, using a constitutive equation in the form of a separable memory integral where the strain dependence is described by the Linear Molecular Stress Function (L-MSF) model with dissipative convective constraint release. The material parameters in the constitutive model are obtained using liner viscoelastic (oscillatory shear) and uni-axial elongational measurements.The numerical simulations were performed for inflation of a flat plate and a perturbed plate, where a small circular cone was removed from the centre of the surface of the plate. This was done in order to investigate the stability of the inflations. It is shown that all of the inflations are hydrodynamically unstable, though the effect on the occurrence of the burst is limited. One exception is at slow inflation, where an unexpected burst may appear as a consequence of minute deviations from an ideal flat plate. All of the numerical calculations show quantitative agreement with the experiments for a wide range of experimental conditions. This strongly suggests that the initiation of the burst is a hydrodynamic phenomenon.The critical parameters in the inflation of molten linear polymers have been investigated using the Gel equation as a memory function (M(s)=Ans ^–(1+n)) and inflating the plate with a constant velocity for the top of the plate. The hydrodynamic burst in a linear polymer is mainly associated with the linear viscoelastic properties and only slightly with the non-linear strain dependence. Increased (linear) elasticity reduces the inflated volume, at the same inflation velocity, before the burst occurs. Furthermore, the critical parameter for the occurrence of the burst (whether or not the burst occurs) is related to the crossover point (G=G) in linear viscoelasticity.     

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.     

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.