Liquid chromatography/electrospray ionization/isotopic dilution mass spectrometry analysis of n-(phosphonomethyl) glycine and mass spectrometry analysis of aminomethyl phosphonic acid in environmental water and vegetation matrixes.

A liquid chromatography/electrospray/mass spectrometry (LC/ES/MS) method was developed for the analysis of glyphosate (n-phosphonomethyl glycine) and its metabolite, aminomethyl phosphonic acid (AMPA) using isotope-labelled glyphosate as a method surrogate. Optimized parameters were achieved to derivatize glyphosate and AMPA using 9-fluorenylmethyl chloroformate (FMOC-Cl) in borate buffer prior to a reversed-phase LC analysis. Method spike recovery data obtained using laboratory and real world sample matrixes indicated an excellent correlation between the recovery of the native and isotope-labelled glyphosate. Hence, the first performance-based, isotope dilution MS method with superior precision, accuracy, and data quality was developed for the analysis of glyphosate. There was, however, no observable correlation between the isotope-labelled glyphosate and AMPA. Thus, the use of this procedure for the accurate analysis of AMPA was not supported. Method detection limits established using standard U.S. Environmental Protection Agency protocol were 0.06 and 0.30 microg/L, respectively, for glyphosate and AMPA in water matrixes and 0.11 and 0.53 microg/g, respectively, in vegetation matrixes. Problems, solutions, and the method performance data related to the analysis of chlorine-treated drinking water samples are discussed. Applying this method to other environmental matrixes, e.g., soil, with minimum modifications is possible, assuring accurate, multimedia studies of glyphosate concentration in the environment and the delivery of useful multimedia information for regulatory applications.     

Die Bestimmung des Phosphors in Bronzen und anderen Legierungen

Ohne Zusammenfassung     

Multinuclear NMR spectroscopic studies of structure and dynamics in hydrous NaAlSi3O8 and Ca0.5AlSi3O8 glasses

We studied the local structure and dynamics of dissolved water in hydrous aluminosilicate glasses with the compositions NaAlSi₃O₈·0.3H₂O, NaAlSi₃O₈·1.3H₂O and Ca_0.5AlSi₃O₈·1.3H₂O by using multinuclear NMR spectroscopy. Glasses were produced by melting glass powders with deuterium oxide under high pressure and the resulting ²H/(¹H + ²H) ratio of the hydrous glasses was larger than 80%. NMR spectra reveal clear evidence for the presence of OH groups as well as of H₂O molecules. The motion of these water species in the time range from some μs to some ms was studied by ¹H NMR relaxation rates and the temperature dependence of the ²H NMR spectra. The motion is faster in the Ca-bearing glass than in the Na-bearing glass. The results are compared with those from quasi-elastic neutron scattering.     

Effect of temperature and chain length on the bimodal emission properties of single polyfluorene copolymer molecules

Fluorescence emission spectra were recorded for isolated polymer chains of the polyfluorene copolymer, F8BT [poly(9,9-di-n-octylfluorene-alt-benzothiadiazole)], at 298 and 20 K for two molecular weights (chain lengths). For long-chain F8BT at 298 K, the observed distribution of single-molecule emission maxima G(Emax) is bimodal, with peaks at approximately 2.35 eV ("blue") and approximately 2.25 eV ("red"). Previously, the red forms have been assigned to polymer chains that possess intrachain contacts, which lowers the local singlet exciton energy. At approximately 20 K, G(Emax) collapses into a single broad distribution centered at approximately 2.3 eV for long-chain F8BT. However, this distribution can be further divided into a high-energy edge that is dominated by the "blue" form, while the remainder of the distribution is composed of the "red" form. Low-molecular-weight F8BT samples emit exclusively from the blue form, and no shift in peak maxima with low temperature was observed. A Franck-Condon analysis reveals a decrease in emitting state displacements between spectra measured at 298 and 20 K, suggesting that temperature-induced structural displacements are responsible for the change in the bimodal emission.     

INEPT Experiments Involving Quadrupolar Nuclei in Solids

Coherence transfer from quadrupolar²⁷Al (I= ) nuclei to³¹P (I= ) via INEPT experiments is investigated.²⁷Al →³¹P INEPT experiments on a (CH₃)₃P–AlCl₃complex in zeolite NaX are performed, and the results demonstrate that the³¹P INEPT signals strongly depend on whether or not the²⁷Al pulses are applied synchronously with the rotor period, and on the length of the²⁷Al pulses. A density-matrix calculation involving the use of the spin operators for spin and nuclei has been performed to help understand the evolution behavior of the density matrix under the influence of the quadrupolar interaction, the dipolar andJ-couplings, and the pulse lengths applied to the quadrupolar nuclei. The theoretical predictions obtained from these calculations are consistent with the INEPT experimental observations.     

Electronic transport at semiconductor surfaces––from point-contact transistor to micro-four-point probes

The electrical properties of semiconductor surfaces have played a decisive role in one of the most important discoveries of the last century, transistors. In the 1940s, the concept of surface states––new electron energy levels characteristic of the surface atoms––was instrumental in the fabrication of the first point-contact transistors, and led to the successful fabrication of field-effect transistors. However, to this day, one property of semiconductor surface states remains poorly understood, both theoretically and experimentally. That is the conduction of electrons or holes directly through the surface states. Since these states are restricted to a region only a few atom layers thick at a crystal surface, any signal from them might be swamped by conduction through the underlying bulk semiconductor crystal, as well as greatly perturbed by steps and other defects at the surface. Yet recent results show that this type of conduction is measurable using new types of experimental probes, such as the multi-tip scanning tunnelling microscope and the micro-four-point probe. The resulting electronic transport properties are intriguing, and suggest that semiconductor surfaces should be considered in their own right as a new class of electronic nanomaterials because the surface states have their own characters different from the underlying bulk states. As microelectronic devices shrink even further, and surface-to-volume ratios increase, surfaces will play an increasingly important role. These new nanomaterials could be crucial in the design of electronic devices in the coming decades, and also could become a platform for studying the physics of a new family of low-dimensional electron systems on nanometre scales.     

Resolving the different silicon clusters in Li12Si7 by 29Si and (6,7)Li solid-state NMR spectroscopy

Structural signatures: The analysis of Si-Si and Si-Li connectivities by solid-state NMR spectroscopy allows the different types of silicon clusters to be discriminated in the model lithium silicide compound Li(12)Si(7) (see picture, Si clusters red and blue, Li ions gray). The results provide new NMR spectroscopic strategies with which to differentiate and study the structures formed in silicon-based electrode materials.     

Pair Distribution Function Analysis and Solid State NMR Studies of Silicon Electrodes for Lithium Ion Batteries: Understanding the (De)lithiation Mechanisms

Lithium ion batteries (LIBs) containing silicon negative electrodes have been the subject of much recent investigation, because of the extremely large gravimetric and volumetric capacities of silicon. The crystalline-to-amorphous phase transition that occurs on electrochemical Li insertion into crystalline Si, during the first discharge, hinders attempts to link the structure in these systems with electrochemical performance. We apply a combination of local structure probes, ex situ (7)Li nuclear magnetic resonance (NMR) studies, and pair distribution function (PDF) analysis of X-ray data to investigate the changes in short-range order that occur during the initial charge and discharge cycles. The distinct electrochemical profiles observed subsequent to the first discharge have been shown to be associated with the formation of distinct amorphous lithiated silicide structures. For example, the first process seen on the second discharge is associated with the lithiation of the amorphous Si, forming small clusters. These clusters are broken in the second process to form isolated silicon anions. The (de)lithiation model helps explain the hysteresis and the steps in the electrochemical profile observed during the lithiation and delithiation of silicon.     

Using Stable Isotope Analyses to Identify Allochthonous Inputs to Lake Naivasha Mediated via the Hippopotamus Gut

Abstract

The hippopotamus grazes nocturnally on land and resides in water during the day. Much of the ingested material must therefore be defecated directly into the aquatic system and can thus be considered an allochthonous resource available to aquatic consumers. The utility of stable isotope analyses of carbon and nitrogen to distinguish hippo faecal matter from other potential basal resources was tested at Lake Naivasha, Kenya. Hippopotami proved faithful to a short grass diet although supplementary grazing of aquatic macrophytes was observed. The typical isotopic ratios of C4 grasses ingested were not altered substantially by gut processes, and were clearly distinct from algal and aquatic macrophyte isotopic ratios. However, marginal plants such as Cyperus papyrus exhibit C4 ratios, and so the technique is suitable only for use in localities where ‘contamination’ from such sources is negligible.