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91.
Validation of a confirmatory method for lipophilic marine toxins in shellfish using UHPLC-HR-Orbitrap MS 总被引:1,自引:0,他引:1
Gabriel Orellana Julie Vanden Bussche Lieven Van Meulebroek Michiel Vandegehuchte Colin Janssen Lynn Vanhaecke 《Analytical and bioanalytical chemistry》2014,406(22):5303-5312
Lipophilic marine toxins are produced by harmful microalgae and can accumulate in edible filter feeders such as shellfish, leading to an introduction of toxins into the human food chain, causing different poisoning effects. During the last years, analytical methods, based on liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS), have been consolidated by interlaboratory validations. However, the main drawback of LC-MS/MS methods remains the limited number of compounds that can be analyzed in a single run. Due to the targeted nature of these methods, only known toxins, previously considered during method optimization, will be detected. Therefore in this study, a method based on ultra-high-performance liquid chromatography coupled to high-resolution Orbitrap mass spectrometry (UHPLC-HR-Orbitrap MS) was developed. Its quantitative performance was evaluated for confirmatory analysis of regulated lipophilic marine toxins in shellfish flesh according to Commission Decision 2002/657/EC. Okadaic acid (OA), dinophysistoxin-1 (DTX-1), pectenotoxin-2 (PTX-2), azaspiracid-1 (AZA-1), yessotoxin (YTX), and 13-desmethyl spirolide C (SPX-1) were quantified using matrix-matched calibration curves (MMS). For all compounds, the reproducibility ranged from 2.9 to 4.9 %, repeatability from 2.9 to 4.9 %, and recoveries from 82.9 to 113 % at the three different spiked levels. In addition, confirmatory identification of the compounds was effectively performed by the presence of a second diagnostic ion (13C). In conclusion, UHPLC-HR-Orbitrap MS permitted more accurate and faster detection of the target toxins than previously described LC-MS/MS methods. Furthermore, HRMS allows to retrospectively screen for many analogues and metabolites using its full-scan capabilities but also untargeted screening through the use of metabolomics software. Figure
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92.
93.
We report a study of the peak-effect phase diagram of a strongly disordered type-II superconductor V-21 at. %Ti using ac magnetic susceptibility and small-angle neutron scattering (SANS). In this system, the peak effect appears only at fields higher than 3.4 T. The sample is characterized by strong atomic disorder. Vortex states with field-cooled thermal histories show that both deep in the mixed state, as well as close to the peak effect, there exist no long-range orientationally ordered vortex lattices. The SANS scattering radial widths reveal vortex states ordered in the sub-mum scale. We conjecture that the peak effect in this system is a remnant of the Bragg glass disordering transition, but occurs on submicron length scales due to the presence of strong atomic disorder on larger length scales. 相似文献
94.
Li Q Gray KE Zheng H Claus H Rosenkranz S Ancona SN Osborn R Mitchell JF Chen Y Lynn JW 《Physical review letters》2007,98(16):167201
Contrary to conventional wisdom, our purified La 2-2x Sr 1+2x Mn2O7 crystals exhibit CE-type orbital and charge order as the low-temperature ground state for a hole doping level h=0.5. For small deviations from h=0.5, the high-temperature CE phase is replaced at low temperatures by an A-type antiferromagnet without coexistence. Larger deviations result in a lack of CE order at any temperature. Thus, small inhomogeneities in cation or oxygen composition could explain why others commonly see this reentrance with coexistence. 相似文献
95.
Akpa BS Holland DJ Sederman AJ Johns ML Gladden LF 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2007,186(1):160-165
PFG NMR methods are frequently used as a means of probing both coherent and incoherent molecular motions of fluids contained within heterogeneous porous media. The time scale over which molecular displacements can be probed in a conventional PFG NMR experiment is limited by the relaxation characteristics of (1)H - the nucleus that is typically observed. In multiphase systems, due to its sensitivity to susceptibility gradients and interactions with surfaces,(1)H signal is frequently characterized by rapid T(1) and T(2) relaxation. In this work, a heteronuclear approach to PFG NMR is demonstrated which allows the study of molecular displacement over extended time scales (and, consequently, length scales) by exploiting the longer relaxation time of (13)C. The method presented employs the DEPT technique of polarization transfer in order to enhance both the sensitivity and efficiency of (13)C detection. This hybrid coherence transfer PFG technique has been used to acquire displacement propagators for flow through a bead pack with an observation time of up to 35 s. 相似文献
96.
Davies CJ Griffith JD Sederman AJ Gladden LF Johns ML 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2007,187(1):170-175
Analysis of diffusion measurements as a function of observation time (Delta), to calculate surface-to-volume ratios (S/V) and tortuosities (kappa), is a useful tool in the characterisation of porous media using NMR. However, using conventional pulsed field gradient (PFG) measurements, this requires long total experiment times (typically hours). Here, we show how the rapid diffusion measurement pulse sequence, Difftrain, can be used to provide the required experimental data much more rapidly (typically within minutes) with a consequential reduction in total experiment time of typically over an order of magnitude. Several novel modifications to the Difftrain pulse sequence are also presented to tailor it to this particular application; these include a variable delay between echoes (to ensure optimal echo position with respect to Delta) and a variable tip angle for the refocusing pulse (to ensure optimal use of available signal). Difftrain is applied to measure both S/V and kappa for a model glass bead pack; excellent agreement is found with both a conventional PFG measurement and with a bulk gravimetric measurement of S/V. 相似文献
97.
The core-shell structure of a range of acrylic-acrylic latexes has been investigated by combining different specimen preparation methods with transmission electron microscopy (TEM), dark-field scanning transmission electron microscopy (DSTEM) and low-voltage scanning electron microscopy (LV-SEM), including the first reported use of LV-SEM to observe composite latex particles at ambient and subambient temperatures. Spin-coating of liquid latex dispersions directly onto TEM grids or SEM stubs is shown to be a relatively straightforward mean of avoiding film formation during specimen preparation. In conjunction with double staining techniques, it has been found to be particularly convenient for characterizing the fine structure of particles with diameters down to below 100 nm. 相似文献
98.
Dr. Anna Pakhomova Birgit Fuchs Prof. Dr. Leonid S. Dubrovinsky Prof. Dr. Natalia Dubrovinskaia Prof. Dr. Hubert Huppertz 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(19):6007-6014
Based on the results from previous high-pressure experiments on the gadolinite-type mineral datolite, CaBSiO4(OH), the behavior of the isostructural borates β-HfB2O5 and β-ZrB2O5 have been studied by synchrotron-based in situ high-pressure single-crystal X-ray diffraction experiments. On compression to 120 GPa, both borate layer-structures are preserved. Additionally, at ≈114 GPa, the formation of a second phase can be observed in both compounds. The new high-pressure modification γ-ZrB2O5 features a rearrangement of the corner-sharing BO4 tetrahedra, while still maintaining the four- and eight-membered rings. The new phase γ-HfB2O5 contains ten-membered rings including the rare structural motif of edge-sharing BO4 tetrahedra with exceptionally short B−O and B⋅⋅⋅B distances. For both structures, unusually high coordination numbers are found for the transition metal cations, with ninefold coordinated Hf4+, and tenfold coordinated Zr4+, respectively. These findings remarkably show the potential of cold compression as a low-energy pathway to discover metastable structures that exhibit new coordinations and structural motifs. 相似文献
99.
Interpretation of NMR Relaxation as a Tool for Characterising the Adsorption Strength of Liquids inside Porous Materials
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Dr. Carmine D'Agostino Dr. Jonathan Mitchell Dr. Michael D. Mantle Prof. Lynn F. Gladden 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(40):13009-13015
Nuclear magnetic resonance (NMR) relaxation times are shown to provide a unique probe of adsorbate–adsorbent interactions in liquid‐saturated porous materials. A short theoretical analysis is presented, which shows that the ratio of the longitudinal to transverse relaxation times (T1/T2) is related to an adsorbate–adsorbent interaction energy, and we introduce a quantitative metric esurf (based on the relaxation time ratio) characterising the strength of this surface interaction. We then consider the interaction of water with a range of oxide surfaces (TiO2 anatase, TiO2 rutile, γ‐Al2O3, SiO2, θ‐Al2O3 and ZrO2) and show that esurf correlates with the strongest adsorption sites present, as determined by temperature programmed desorption (TPD). Thus we demonstrate that NMR relaxation measurements have a direct physical interpretation in terms of the characterisation of activation energy of desorption from the surface. Further, for a series of chemically similar solid materials, in this case a range of oxide materials, for which at least two calibration values are obtainable by TPD, the esurf parameter yields a direct estimate of the maximum activation energy of desorption from the surface. The results suggest that T1/T2 measurements may become a useful addition to the methods available to characterise liquid‐phase adsorption in porous materials. The particular motivation for this work is to characterise adsorbate–surface interactions in liquid‐phase catalysis. 相似文献
100.
Marcel Scheepstra Dr. Lidia Nieto Dr. Anna K. H. Hirsch Dr. Sascha Fuchs Dr. Seppe Leysen Chan Vinh Lam Leslie in het Panhuis Prof. Dr. Constant A. A. van Boeckel Dr. Hans Wienk Prof. Dr. Rolf Boelens Dr. Christian Ottmann Dr. Lech‐Gustav Milroy Prof. Dr. Luc Brunsveld 《Angewandte Chemie (International ed. in English)》2014,53(25):6443-6448