Flavone as a novel matrix for the matrix‐assisted laser desorption/ionisation analysis of lanthanide and transition metal salts

The mass spectral analysis of metal salts, especially lanthanide and transition metal salts, can be challenging. Although getting information on the metal present is usually straightforward, obtaining information on the correct oxidation state and anion composition is challenging. Many ionisation techniques have some redox component to the ionisation process, which commonly results in changing the oxidation state of the metal and the associated loss of ligand and anion information. We present here a simple method for negative ion matrix‐assisted laser desorption/ionisation mass spectrometry using the non‐acidic flavonoid flavone as a novel matrix. This results in reliable information on the oxidation state of the metal as spectra are dominated by anion adduct ions with very little (typically no) redox processes occurring.     

The S.M.A.R.T. (small mass,affordable, rapid,transfer-less) digestion method for heavy metal determinations

The S.M.A.R.T. (small mass, affordable, rapid, transfer-less) digestion method was developed to determine heavy metal concentrations in small sample masses. The S.M.A.R.T. digestion method is a hot water bath digestion where sample digestion and dilution are performed in the original sample tube. This method is faster than the typical methods used and reduces potential sources of error. Masses as small as 0.01 g have been digested and analysed using this method. The preparation and digestion time is reduced from 10 h to less than 4 h. Acid volumes are reduced from millilitres to microlitres and the only disposable supplies needed are sample tubes and pipette tips. Method accuracy was determined by digesting seven replicates of two standard reference materials using the S.M.A.R.T. method and analysing samples by inductively coupled plasma mass spectrometry. The S.M.A.R.T. digestion method was found to provide excellent recoveries for Al (76 ± 2.7%), Mn (99 ± 11%), Co (92 ± 17%), Ni (93 ± 28%), Cu (109 ± 33%), Zn (97 ± 7.1%), As (108 ± 20%), Sr (90 ± 12%), Mo (84 ± 23%), Ag (91 ± 1.8%), Cd (95 ± 6.2%), Sn (139 ± 52%) and Pb (95 ± 22%). This study has successfully developed an efficient and reproducible digestion method for heavy metal determination in limited biomass samples.     

Division closed partially ordered rings

Fuchs called a partially-ordered integral domain, say D, division closed if it has the property that whenever a > 0 and ab > 0, then b > 0. He showed that if D is a lattice-ordered division closed field, then D is totally ordered. In fact, it is known that for a lattice-ordered division ring, the following three conditions are equivalent: a) squares are positive, b) the order is total, and c) the ring is division closed. In the present article, our aim is to study \({\ell}\)-rings that possibly possess zerodivisors and focus on a natural generalization of the property of being division closed, what we call regular division closed. Our investigations lead us to the concept of a positive separating element in an \({\ell}\)-ring, which is related to the well-known concept of a positive d-element.     

Photoelastic tests on complex intersections of reinforced thin-shell cylinders

This paper presents the three-dimensional photoelastic analyses accompanied by extensive finite-element studies of several thin-shell pressure vessels with various cylindrical intersections. The models consisted of right circular cylindrical shells with diameter-to-thickness ratios of 220, reinforced with circumferential, longitudinal and diagonal T-stiffeners. The cylindrical shells and stiffeners were intersected by various smaller cylinders producing complex intersection joints which included radial and angular fillets. Each of the models was constructed from 80 to 150 parts prepared from flat sheets, “contour-cast” shells, and milled machined parts. The model techniques as well as the machining, assembling and testing methods of the pressure vessels are presented.     

Fracture energy for three-point-bend tests on single-edge-notched beams

Three test series of single-edge-notched beams in three-point bending are conducted to evaluate the fracture energy of concrete. The fracture energy is determined from the area under the complete load: load-point deflection diagram. The nonlinear fictitious crack model is implemented in a finite-element analysis showing good agreement with the experimental data. By varying the notch depth and the beam depth it is shown that the fracture energy, traditionally presented as a material property, depends upon the specimen size and configuration. This is atributed to the energy dissipation in the process zone which is not accounted for in the analytical model.     

New concepts for radiometric measurements of environmental samples

The Radiation Detection and Nuclear Sciences Group at Pacific Northwest National Laboratory has a long history in conducting measurements of radioisotopes for various applications. This experience includes ultra-low background measurements, arrays of germanium detectors, automated sampling and measurement systems and coincidence measurement systems. A recent lab-supported effort has been studying how these capabilities, both in terms of hardware and experience, can be leveraged to enable environmental sampling measurements. One area of interest is the release of fission products and actinides into the environment from a reactor incident. While the initial survey of this area is still under way, one isotope of interest that surfaced early in the study is ²³⁸Pu. Existing techniques to assay this isotope suffer from measurement challenges. In alpha counting, there can be significant interference with ²⁴¹Am, while in mass spectrometry, there can be interference with ²³⁸U. The authors are developing the concept for a detector that through coincidence counting techniques can distinguish ²³⁸Pu and ²⁴¹Am. In addition, we will design the system to conduct radiometric measurements of other plutonium isotopes to enable a direct comparison of those isotopes. We will present our concept of the detector system for ²³⁸Pu, as well as discuss other radiometric measurements of fission products and actinides with which we intend to advance the state of the art for environmental measurements.     

Synthesis and Structures of Stable PtII and PtIV Alkylidenes: Evidence for π-Bonding and Relativistic Stabilization

Isolable cationic Pt^II and Pt^IV alkylidenes, proposed intermediates in catalytic organic transformations, are reported. The bonding in these species was probed by experimental, structural, spectroscopic, electrochemical and computational methods, providing direct evidence for π-bonding, the often-theorized relativistic stabilization of these species, and the influence of oxidation state.     

Optimal learning for sequential sampling with non-parametric beliefs

We propose a sequential learning policy for ranking and selection problems, where we use a non-parametric procedure for estimating the value of a policy. Our estimation approach aggregates over a set of kernel functions in order to achieve a more consistent estimator. Each element in the kernel estimation set uses a different bandwidth to achieve better aggregation. The final estimate uses a weighting scheme with the inverse mean square errors of the kernel estimators as weights. This weighting scheme is shown to be optimal under independent kernel estimators. For choosing the measurement, we employ the knowledge gradient policy that relies on predictive distributions to calculate the optimal sampling point. Our method allows a setting where the beliefs are expected to be correlated but the correlation structure is unknown beforehand. Moreover, the proposed policy is shown to be asymptotically optimal.