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Under base free and mild reaction conditions, 80.5% selectivity of lactic acid (LA) was achieved at 89.8% conversion of glycerol using a bifunctional Pt/Sn-MFI catalyst.
Solid sampling and analysis methods, such as laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), are challenged by matrix effects and calibration difficulties. Matrix-matched standards for external calibration are seldom available and it is difficult to distribute spikes evenly into a solid matrix as internal standards. While isotopic ratios of the same element can be measured to high precision, matrix-dependent effects in the sampling and analysis process frustrate accurate quantification and elemental ratio determinations. Here we introduce a potentially general solid matrix transformation approach entailing chemical reactions in molten ammonium bifluoride (ABF) salt that enables the introduction of spikes as tracers or internal standards. Proof of principle experiments show that the decomposition of uranium ore in sealed PFA fluoropolymer vials at 230 °C yields, after cooling, new solids suitable for direct solid sampling by LA. When spikes are included in the molten salt reaction, subsequent LA-ICP-MS sampling at several spots indicate that the spikes are evenly distributed, and that U-235 tracer dramatically improves reproducibility in U-238 analysis. Precisions improved from 17% relative standard deviation for U-238 signals to 0.1% for the ratio of sample U-238 to spiked U-235, a factor of over two orders of magnitude. These results introduce the concept of solid matrix transformation (SMT) using ABF, and provide proof of principle for a new method of incorporating internal standards into a solid for LA-ICP-MS. This new approach, SMT-LA-ICP-MS, provides opportunities to improve calibration and quantification in solids based analysis. Finally, looking forward, tracer addition to transformed solids opens up LA-based methods to analytical methodologies such as standard addition, isotope dilution, preparation of matrix-matched solid standards, external calibration, and monitoring instrument drift against external calibration standard
The confident identification of metabolites and xenobiotics in biological and environmental studies is an analytical challenge due to their immense dynamic range, vast chemical space and structural diversity. Ion mobility spectrometry (IMS) is widely used for small molecule analyses since it can separate isomeric species and be easily coupled with front end separations and mass spectrometry for multidimensional characterizations. However, to date IMS metabolomic and exposomic studies have been limited by an inadequate number of accurate collision cross section (CCS) values for small molecules, causing features to be detected but not confidently identified. In this work, we utilized drift tube IMS (DTIMS) to directly measure CCS values for over 450 small molecules including primary metabolites, secondary metabolites and xenobiotics. Since DTIMS measurements do not need calibrates, they avoid calibration errors which can cause CCS accuracy problems and difficulties identifying structurally similar molecules. Furthermore, all measurements were performed in triplicate in both positive and negative polarities with nitrogen gas and seven different electric fields, so that relative standard deviations (RSD) could be assessed for each molecule and structural differences studied. The primary metabolites selected for the database are from key metabolism pathways such as glycolysis, the pentose phosphate pathway, and the tricarboxylic acid (TCA) cycle, while the secondary metabolites consist of classes such as terpenes and flavonoids, and the xenobiotics represent a range of molecules from antibiotics to polycyclic aromatic hydrocarbons. Different CCS trends were observed for several of the diverse small molecule classes, allowing insight in their separations and a possible why of classifying unknowns. This CCS database and structural information are freely available for download at http://panomics.pnnl.gov/metabolites/ with new molecules being added monthly.
The relationship between noble metal phase particles and fission gas bubble production in used nuclear fuel is described. The majority of Te atoms within noble metal phase undergo radioactive decay to form stable Xe within a few hours after particle formation. This results in the production of clusters of Xe atoms contained within the solid metal matrix exhibiting an equivalent gas bubble pressure approaching 1 GPa. These high pressure bubbles are stabilized by the UO2 within the bulk of the fuel. However, when these bubbles form near the fuel / cladding interface, in combination with local and temporal damage caused by fission recoil, they are capable of overcoming the fracture strength of the UO2 and rupturing catastrophically. The force of the resulting bubble rupture is sufficient to eject noble metal phase particles several microns into the cladding. This proposed mechanism explains the observance of noble metal phase in cladding and is consistent with a host of morphological features found near the fuel / cladding interface.
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Temperature modulation was demonstrated as a novel way to control water partitioning during the reaction of silicate minerals with water-saturated supercritical carbon dioxide.
We demonstrate the potential of x-ray excited luminescence microscopy for full-field elemental and magnetic sensitive imaging using a commercially available optical microscope, mounted on preexisting synchrotron radiation (SR) beamline end stations. The principal components of the instrument will be described. Bench top measurements indicate that a resolution of 1 {mu}m or better is possible; this value was degraded in practice due to vibrations and/or drift in the end station and associated manipulator. X-ray energy dependent measurements performed on model solar cell materials and lithographically patterned magnetic thin film structures reveal clear elemental and magnetic signatures. The merits of the apparatus will be discussed in terms of conventional SR imaging techniques.
By employing the vacuum ultraviolet (VUV) laser velocity-map imaging photoelectron (VUV-VMI-PE) method, we have obtained a vibrationally resolved photoelectron spectrum of gaseous propargyl radical [C{sub 3}H{sub 3}(X{sup 2}B{sub 1})] in the energy range of 0-4600 cm{sup -1} above its ionization energy. The cold C{sub 3}H{sub 3} radicals were produced from a supersonically cooled radical beam source based on 193 nm ArF photodissociation of C{sub 3}H{sub 3}Cl. The VUV-VMI-PE spectrum of C{sub 3}H{sub 3} thus obtained reveals a Franck-Condon factor (FCF) pattern with a highly dominant origin band along with weak vibrational progressions associated with excitations of the C-C {nu}{sub 5}{sup +}(a{sub 1}) and C{identical_to}C {nu}{sub 3}{sup +}(a{sub 1}) symmetric stretching modes and the CCH {nu}{sub 7}{sup +}(b{sub 1}) out-of-plane bending mode of C{sub 3}H{sub 3}{sup +}(X{sup 1}A{sub 1}). The {nu}{sub 5}{sup +}(a{sub 1}) vibrational frequency of 1120 cm{sup -1} determined in the present study is lower than the value deduced from the recent Ar-tagged infrared photodissociation study by 102 cm{sup -1}, confirming the highly accurate vibrational frequency predictions obtained by the most recent state-of-the-art ab initio quantum calculations. The observation of the FCF disallowed {nu}{sub 7}{sup +}(b{sub 1}) mode is indicative of vibronic interactions. The discrepancy observed between the FCF pattern determined in the present study and that predicted by a recent high-level quantum theoretical investigation can be taken as evidence that the potential energy surfaces used in the latter theoretical study are in need of improvement in order to provide a reliable FCF prediction for the C{sub 3}H{sub 3}/C{sub 3}H{sub 3}{sup +} photoionization system.
Real time grazing incidence small angle x-ray scattering and x-ray fluorescence (XRF) are used to elucidate nanodot formation on silicon surfaces during low energy ion beam irradiation of ultrathin iron-coated silicon substrates. Four surface modification stages were identified: (1) surface roughening due to film erosion, (2) surface smoothing and silicon-iron mixing, (3) structure formation, and (4) structure smoothing. The results conclude that 2.5 Multiplication-Sign 10{sup 15} iron atoms in a 50 nm depth triggers surface nanopatterning with a correlated nanodots distance of 25 nm. Moreover, there is a wide window in time where the surface can have correlated nanostructures even after the removal of all the iron atoms from the sample as confirmed by XRF and ex-situ x-ray photoelectron spectroscopy (XPS). In addition, in-situ XPS results indicated silicide formation, which plays a role in the structure formation mechanism.
We have developed a nanoparticle (NP) printing technique using Ni thin film lift-off from glass substrates after ultrafast irradiation in air. Unique interactions of ultrafast laser pulses with thin films allow for control over NP faceting and size distributions. Control is achieved by changing the laser fluence, film thickness, and film-substrate distance. We demonstrate 20 nm Ni film removal from substrates and rapid NP printing, with size distributions centered at a 6 nm diameter. When the Ni film thickness is lowered to 10 nm, NPs are printed with distributions peaked at a 2 nm diameter.
The soft x-ray diagnostic is suitable for monitoring plasma activity in the tokamak core, e.g., sawtooth instability. Moreover, spatially resolved measurements can provide information about plasma position and shape, which can supplement magnetic measurements. In this contribution, fast algorithms with the potential for a real-time use are tested on the data from the COMPASS tokamak. In addition, the soft x-ray data are compared with data from other diagnostics in order to discuss possible connection between sawtooth instability on one side and the transition to higher confinement mode, edge localized modes and productions of runaway electrons on the other side.
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Producing an overdense background plasma for neutralization purposes with a density that is high compared to the beam density is not always experimentally possible. We show that even an underdense background plasma with a small relative density can achieve high neutralization of intense ion beam pulses. Using particle-in-cell simulations, we show that if the total plasma electron charge is not sufficient to neutralize the beam charge, electron emitters are necessary for effective neutralization but are not needed if the plasma volume is so large that the total available charge in the electrons exceeds that of the ion beam. Several regimes of possible underdense/tenuous neutralization plasma densities are investigated with and without electron emitters or dense plasma at periphery regions, including the case of electron emitters without plasma, which does not effectively neutralize the beam. Over 95% neutralization is achieved for even very underdense background plasma with plasma density 1/15th the beam density. We compare results of particle-in-cell simulations with an analytic model of neutralization and find close agreement with the particle-in-cell simulations. Further, we show experimental data from the National Drift Compression experiment-II group that verifies the result that underdense plasma can neutralize intense heavy ion beams effectively.
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Thermoelectric coolers based on the Peltier effect have been utilized to control temperature gradient to study thermal effects in both bulk and thin film samples. The temperature gradient is controlled by two coolers and the polarity of the thermal gradient can be reversed by reversing an electric driven voltage. With appropriate controlled thermal gradient using this technique, the Nernst and the Seebeck effects can be measured in both bulk and thin film samples free of spurious contributions. In an arbitrary direction of thermal gradient, the Seebeck and the Nernst components can be decomposed from the measured signal based on the symmetry of the effects in a magnetic field.