Assessment of the Nd/U ratio for the quantification of neodymium in UO2

The secondary ion energy spectrum of uranium depends on the experimental conditions, which is a problem for the application of a relative sensitivity factor (RSF) procedure for the measurement of the Nd concentration in UO₂. This is interpreted as due to the dependence of the sputtering and ionisation yields of uranium on the oxidation state of the surface. Three experimental procedures are being tested to cope with this difficulty.     

High-performance liquid chromatographic analysis of cyclizine and its metabolite,norcyclizine in biological fluids using solid phase extraction

Summary A high-performance liquid chromatographic analysis of cyclizine and its metabolite, norcyclizine in biological fluids using protryptiline hydrochloride as internal standard is described. The drug and metabolite were extracted from the relevant biological matrix using a solid-phase extraction procedure combined with a simple phase separation step prior to chromatographic analysis. The separation was achieved on a reversed-phase C₁₈ column (10 μm) using acetonitrile — 0.05 M (pH=3) phosphate buffer (40:60), as the mobile phase with UV detection at 200 nm. Calibration curves were linear over the entire concentration range 5–100 ng/ml for cyclizine in serum and urine and for norcyclizine in urine. Precise quantitative analysis with relative standard deviations of <5 % was achieved.     

Determination of flumequine in channel catfish by liquid chromatography with fluorescence detection.

Rapid methods are described for determination of flumequine (FLU) residues in muscle and plasma of farm-raised channel catfish (Ictalurus punctatus). FLU residues were extracted from tissues with an acidified methanol solution, and extracts were cleaned up on C18 solid-phase extraction cartridges. FLU concentrations were determined by liquid chromatography (LC) using a C18 analytical column and fluorescence detection (excitation, 325 nm; emission, 360 nm). Mean recoveries of FLU from fortified muscle were 87-94% at 5 levels ranging from 10 to 160 ppb (5 replicates per level). FLU recoveries from fortified plasma were 92-97% at 5 levels ranging from 20 to 320 ppb. Limits of detection (signal-to-noise ratio, 3:1) for the method as described were 3 and 6 ppb for muscle and plasma, respectively. Relative standard deviations (RSDs) for recoveries were < or = 12%. Live catfish were dosed with 14C-labeled or unlabeled FLU to generate incurred residues. Recoveries of 14C residues throughout extraction and cleanup were 90 and 94% for muscle and plasma, respectively. RSDs for incurred FLU at 2 levels in muscle and plasma ranged from 2 to 6%. The identity of FLU in incurred tissues was confirmed by LC/mass spectrometry.     

The role of substituents on the addition of muonium to aromatics: As seen through muonium-radicals in allyl benzene compared to styrene,and from hammett parameters in aqueous solution

Muonium-radicals resulting from insertion into the benzene ring are found to be much more prevalent in allyl benzene (C₆H₅CH₂CH=CH₂) than in styrene (C₆H₅CH=CH₂). The salient implication of this comparison is that intramolecular rearrangements preceeded the μSR observation for the case of styrene. In turn, this suggests that muonium-containing free radicals, as seen directly by kilogauss transverse field μSR, are not necessarily theprimary radicals. Therefore, the elucidation of mechanism (and identification of the precursor) of Mu-radical formation is further complicated by the fact that the observations may refer to thermodynamically more stable secondary radicals-those resulting from a variety of intra-or inter-molecular relaxations or exchanges. Primary kinetic selectivities of thermalized muonium atom addition reactions can be determined, however, through the substituent effect on the Hammett linear free energy parameter in dilute solution. Results have been obtained for substituted benzenes and benzoic acids. Muonium apparently has a mild nucleophilic character. And, most interestingly, this is opposite to that of its heavy isotope hydrogen.     

Laser fluorescence on radio-active isotopes produced in very low yield

East particle-photon coincidence techniques, developed at Daresbury with strontium isotopes, allow ultrasensitive laser fluorescence spectroscopy of beams of radio-active isotopes which can only be produced in very low yields. The technique has now been applied to neutron-deficient barium isotopes down to¹²⁰Ba. From measured hyperfine splittings and isotope shifts, nuclear moments and changes in mean square radii have been determined. The work has revealed an abrupt increase in the mean square radius for¹²¹Ba large enough to disrupt the systematic staggering of nuclear size seen for the series. In a recent experiment an isomeric state of¹²⁷Ba with a half-life of about 2 seconds has been produced in a very low yield; nevertheless we have succeeded in obtaining a fluorescence spectrum.     

Zur volumetrischen Bestimmung des Zinks

Ohne Zusammenfassung     

A complexity approach to sustainability – Stafford Beer revisited

There is wide acceptance of the need for a more holistic approach to sustainability. However, practical solutions remain elusive and tend to exhibit underlying conflicts between different paradigms and their associated methodologies. This paper argues the need to wield analytical tools that themselves embody the principles of systemic, ecological thinking. We present here a theoretical framework based on complexity science – focused on organisational and second order cybernetics – that highlights our understanding of the concept of sustainability. The paper goes on to reflect upon how current practice would benefit from such an approach.     

On-line nuclear orientation and relaxation studies of Cs isotopes

The hyperfine field of CsFe has been measured to be (+)40.8(0.7)T, using the technique of on-line low temperature nuclear orientation. The time dependent relaxation of¹²¹Cs^m Fe has also been investigated using a new technique, giving a Korringa constant C_k of 0.059 (15) sK. From this, an effective relaxation time of 3.0 (0.8)s can be deduced for the short lived¹¹⁸Cs^m(T_1/2=17s). This value has then been used to extract the magnetic moment of¹¹⁸Cs^m to be |μ|=5.4 (1.1) nm.     

A parallel acquisition charged particle energy analyser using a magnetic field

A new form of charged particle energy analyser is proposed. It is broadly based on the 180° magnetic spectrograph, but is intended to detect charged particles moving out of the dispersion plane with a helical motion. The analyser has the capability to acquire charged particle energy spectra over a large energy range, similar to those acquired in Auger electron spectroscopy, ca. 2500 eV and large angular range, up to 90°, in parallel. These conditions are more favourable for surface analysis by electron spectroscopy at high vacuum, where for example an electron energy resolution of 0.2% to 0.5% is typical. Expressions showing how the landing positions of the charged particles on the detector vary as a function of energy and polar take off angle are determined as well as the conditions for optimum energy resolution at a range of polar take off angles. The equations reveal that in general, the device obtains the highest resolution at angles of revolution greater than 180°. The design is simple and could be easily put into practice using available material and technologies and be used to analyse the energies of electrons emitted from a sample placed in a scanning electron microscope. It can be made to function with a primary electron beam of any desired energy and could fit in to the small space between the sample and the end of an electron column. However, the device is difficult to retrofit into existing SEMs and ideally an SEM column needs to be designed to work in association with the analyser. The direction of the magnetic field of the analyser is coincident with the axis of the electron gun so that the primary beam is little influenced by the magnetic field and symmetry can be maintained in the primary beam electron column. Because the device is intended to acquire electron spectra in parallel, any movement of the primary beam on the sample because of a ramping field in the analyser is avoided. The field of view and the effect of the analyser upon the operation of the SEM are discussed. Spectra including elastic and Auger peaks reveal an energy resolution of ~4 eV at 900‐eV electron energy. Copyright © 2016 John Wiley & Sons, Ltd.     

Comprehensive comparison of liquid chromatography selectivity as provided by two types of liquid chromatography detectors (high resolution mass spectrometry and tandem mass spectrometry): “Where is the crossover point?”

The selectivity of mass traces obtained by monitoring liquid chromatography coupled to high resolution mass spectrometry (LC-HRMS) and liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) was compared. A number of blank extracts (fish, pork kidney, pork liver and honey) were separated by ultra performance liquid chromatography (UPLC). Detected were some 100 dummy transitions respectively dummy exact masses (traces). These dummy masses were the product of a random generator. The range of the permitted masses corresponded to those which are typical for analytes (e.g. veterinary drugs). The large number of monitored dummy traces ensured that endogenous compounds present in the matrix extract, produced a significant number of detectable chromatographic peaks. All obtained chromatographic peaks were integrated and standardized. Standardisation was done by dividing these absolute peak areas by the average response of a set of 7 different veterinary drugs. This permitted a direct comparison between the LC-HRMS and LC-MS/MS data. The data indicated that the selectivity of LC-HRMS exceeds LC-MS/MS, if high resolution mass spectrometry (HRMS) data is recorded with a resolution of 50,000 full width at half maximum (FWHM) and a corresponding mass window. This conclusion was further supported by experimental data (MS/MS based trace analysis), where a false positive finding was observed. An endogenous matrix compound present in honey matrix behaved like a banned nitroimidazole drug. This included identical retention time and two MRM traces, producing an MRM ratio between them, which perfectly matched the ratio observed in the external standard. HRMS measurement clearly resolved the interfering matrix compound and unmasked the false positive MS/MS finding.