Determination of the clean 4f peak shape in XPS for plutonium metal

Many of the interesting properties observed with plutonium are ascribed to the influence of 5f electrons, and to the degree of localisation observed within these electrons. Indeed, changes in 5f localisation are sensitively reflected in the final states observed in core-level photoemission measurements. However, when analysing the 4f manifold of elemental plutonium, it is essential to obtain spectra without the influence of oxidation, which can easily be misinterpreted as 5f localisation. The ideal method to extract elemental plutonium 4f spectra is to remove any influence of oxidation from the ‘clean’ plutonium data by careful measurement of the oxygen 1s region, and the subsequent subtraction of the unwanted oxide features. However, in order to achieve this objective it is essential to determine the relative sensitivity factor (RSF) for plutonium 4f and the precise shape of the 4f features from plutonium sesqui-oxide. In this paper, we report an experimental determination of the RSF for the plutonium 4f manifold using experimental data captured from two different Vacuum Generators spectrometers; an ESCALAB Mk II and an ESCALAB 220i.     

Molecular factor analysis applied to collections of NMR spectra

It is often useful to identify and quantify mixture components by analyzing collections of NMR spectra. Such collections arise in metabonomics and many other applications. Many mixtures studied by NMR can contain hundreds of compounds, and it is challenging to analyze the resulting complex spectra. We have approached the problem of separating signals from different molecules in complex mixtures by using self-modeling curve resolution as implemented by the alternating least-squares algorithm. Alternating least squares uses nonnegativity criteria to generate spectra and concentrations from a collection of mixture spectra. Compared to previous applications of alternating least squares, NMR spectra of complex mixtures possess unique features, such as large numbers of components and sample-to-sample variability in peak positions. To deal with these features, we developed a set of data preprocessing methods, and we made modifications to the alternating least-squares algorithm. We use the term "molecular factor analysis" to refer to the preprocessing and modified alternating least-squares methods. Molecular factor analysis was tested using an artificial data set and spectra from a metabonomics study. The results show that the tools can extract valuable information on sample composition from sets of NMR spectra.     

The Target Preparation Laboratory at Daresbury

The Target Preparation Laboratory at Daresbury Laboratory is described. This laboratory provides targets for the UK Nuclear Physics community whose experimental programme is performed in several laboratories worldwide. Details are given of its present capabilities and range of targets produced.     

Hybrids of gold nanoparticles and oligo(p-phenyleneethynylene)s end-functionalized with alkynylruthenium groups: Outstanding two-photon absorption in the second biological window

Oligo(p-phenyleneethynylene)s (OPEs) end-capped with (alkynyl)bis(diphosphine)ruthenium and thiol/thiolate groups stabilize ca. 2 nm diameter gold nanoparticles (AuNPs). The morphology, elemental composition and stability of the resultant organometallic OPE/AuNP hybrid materials have been defined using a combination of molecular- and nano-material chacterization techniques. The hybrids display long-term stability in solution (more than a month), good solubility in organic solvents, reversible ruthenium-centered oxidation, and transparency beyond 800 nm, and possess very strong nonlinear absorption activity at the first biological window, and unprecedented two-photon absorption activity in the second biological window (σ₂ up to 38,000 GM at 1,050 nm).

     

Chemical structure/property relationships in surfactants. 17. N-substituted-N-acyl glycinates in pure and synthetic hard river water

The surface properties [effectiveness of surface tension reduction (γ_CMC), critical micelle concentration (CMC), efficiency of surface tension reduction (pC ₂₀), maximum surface excess concentration (Γ_CMC), minimum area/molecule at the interface (A _min), and the CMC/C ₂₀) ratio] of well-purified N-substituted glycine derivatives, having the structural formula RC(O)N(R′)CH₂COONa, where RC(O)=lauroyl, myristoyl, or oleoyl, and R′=Et, Pr, Bu, CH₂CH₂OH or CH₂CH₂CH₂OCH₃, were investigated at 25°C in hard river water and distilled water. These surfactants show greater surface activity in hard river water than in distilled water. The effect of both the main alkyl chain R and the N-substituent R′ on surface properties was elucidated, the oleoyl group showing properties equivalent to that of a C₁₆ saturated acyl group. A linear relationship was observed between the pC ₂₀ or CMC values and the number of carbon atoms in the alkyl chain R or in R′ when it was alkyl. With increase in the number of carbon atoms in either R or the N-substituent R′ when it is alkyl, both pC ₂₀ and micelle-forming ability increase, although the effect of R′ on the foregoing two surface properties is lower than that of R. When R′ is (CH₂)₃OCH₃, however, the results suggest that R′ is only partly removed from contact with the aqueous phase either upon adsorption at the water/air interface or upon micellization. It increases A _min, is equivalent only to an ethyl group in its effect on pC ₂₀ and to a methyl group in its effect on CMC, and, in contrast to the effect of R′ when it is alkyl, produces no increase in the CMC/C ₂₀ ratio. As a result, γ_CMC increases with R when R′ is alkyl and decreases with R when R′ is (CH₂)₃OCH₃.     

EFFECT OF GERMINATION TIME,TEMPERATURE AND MOISTURE ON MALTING OF SORGHUM

The effect of germination conditions on sorghum malt quality and malting loss was studied by germinating sorghum for different periods of time up to 6 days over a range of temperatures (24 to approximately 36°C) and moisture conditions. The moisture conditions varied from that sufficient to maintain green malt weight to that where surface moisture remained on the malt throughout germination. Germination time, temperature, moisture and the three possible pairwise interactions all had a highly significant effect on malt diastatic power, free α-amino nitrogen and extract. Malting loss was highly significantly affected by germination time and moisture and their pair-wise interaction. However, over the range examined, germination temperature had no significant effect on malting loss. In general diastatic power, free α-amino nitrogen, extract, and malting loss all increased with germination time. Germination temperatures of 24° and 28°C were both equally good for the development of diastatic power, free α-amino nitrogen and extract but higher temperatures were progressively worse. Distatic power, free α-amino nitrogen, extract and malting loss were, in general, all increased by high moisture during germination. However, high moisture and a negative effect on diastatic power towards the end of the germination period.     

ENDOSPERM BREAKDOWN IN DECORTICATED BARLEY GRAINS GROWN AT 25°C ON A WET SUBSTRATUM

When decorticated grains are grown at 25°C, in the dark and on a wet substratum the starchy endosperm is progressively dissolved and the residue is surrounded by a fluid filled space. The pattern of endosperm liquefaction is described. Attention is called to the important differences which exist between malted grains and those which have been grown ‘wet and warm’.     

DETERMINATION OF REPEATABILITY AND REPRODUCIBILITY OF A NEW RAPID ENZYME METHOD FOR THE DETERMINATION OF GLYCOSIDE NITRILE IN MALTED BARLEY

A new rapid method for the determination of malt glycosidic nitrile, using an enzymatic incubation with beta-glucosidase, was tested in an inter-laboratory collaborative trial. Repeatability (r₉₅) and reproducibility (R₉₅) values are reported. A limited comparison is made with the existing determination of malt combined nitrile using methods involving laboratory fermentations.     

Surface properties of linear alkyl benzene sulfonates in hard river water

Surface properties of a series of highly purified linear alkyl benzene sulfonates were extensively studied in hard river water. The effects of water hardness, alkyl chain length and position of the phenyl sulfonate group in the molecule on such surface properties as pC₂₀, critical micelle concentration (CMC), γ_CMC, CMC/C₂₀ ratio, and minimum area per molecule at the interface are discussed in detail. The position of phenyl sulfonate group in the molecule was found to have a pronounced effect on the CMC, γ_CMC value, CMC/C₂₀ ratio, and, to the contrary, a relatively small effect on the pC₂₀ value. The linear relationship between pC₂₀ or-log CMC, and m, the number of carbon atoms in the alkyl chain, was found for surfactants with the phenyl sulfonate group either at the terminal position or at the more central position in the molecule. γ_CMC decreases but the CMC value increases, when the position of phenyl sulfonate group moves from the terminal toward a more central position of the molecule, reflecting the “Hartley Effect” resulting from the branched alkyl chain.     

The Selective Oxidation of Methanol to Formaldehyde on Iron Molybdate Catalysts and on Component Oxides

The reaction of methanol with an industrial iron molybdate catalyst, and with Fe₂O₃ and with MoO₃, has been investigated with a pulsed flow reactor and temperature-programmed desorption (TPD). The molybdena-based samples show only formaldehyde in TPD as the carbon-containing product, arising from the decomposition of a surface methoxy species. In contrast, haematite yields no formaldehyde, only CO₂ and H₂, which evolve coincidently at 290 °C, and indicates the presence of a formate intermediate on the surface. In turn, the reactor work shows high selectivity to formaldehyde for the molybdate materials and zero for haematite. The iron molybdate sample is more active than the molybdena, conversion beginning at 150 °C for the former and 270 °C for the latter. These data are discussed in terms of a global mechanism for the reaction and a tentative reaction enthalpy profile is proposed. The main differences between the iron and molybdenum samples arise from the stronger binding of oxygen in the former and the higher concentration of cation sites.