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101.
102.
Arjan J. H. Louter Philo A. Jones J. David Jorritsma Jolan J. Vreuls Udo A. Th. Brinkman 《Journal of separation science》1997,20(7):363-368
An automated system for derivaatization was coupled on-line with solid-phase extraction-gas-chromatography (SPE-GC). The system was optimized for the determination of phenol and chlorinated phenols in aqueous samples. The test analytes were acetylated with acetic anhydride; proper buffering of the sample was a critical factor. Next, the phenol acetates were enriched on a SPE cartridge and transferred to a GC; two appraoaches were studied. In the first approach, the derivatives were enriched on disposable C18 cartridges (ASPEC type) and desorbed with methylacetate. Aan aliquot of the final eluate was injected on-line the GC by means of a loop-type interface. In the second approach, trace enrichment was performed on 10 × 2 mm i.d. LC-type precolumn packed with polystyrenedivinylbenzene copolymer (PLRP-S) this precolumn was dried with a mitrogen purge and the phenol acetates were desorbed with ethyl acetate which was injectedon-line into the retention gap of the GC under partially concurrent solvent evaporation (PCSE) conditions. The Derivatization-SPE-GC system which was based on the loop-type interface has the advantage of simplicity and easy operation, the main drawback is the impossibility to determine phenol acetates which elute prior to trichlorophenol acetates. With the derivatization-SPE-GC approach using PCSE-based desorption, even the most volatile analyte of the test series, phenol acetate, can be determined successfully. The entire procedure, including the derivatization step, was fully automated and integrated in one set-up. The precision data for the integrated on-line derivatization-SP-FID system were fully satisfactory, with RSD values of 1–12 % at the 1 μg/1 level. When a sample volume of 2.2 ml was analyzed, The detection limits for the chlorinated phenol acetates were in the 0.1–0.3 μg/1 range. 相似文献
103.
Stress fields between interacting small particles ( approximately 100 nm) have been investigated by transmission electron microscopy. The background for these TEM observations is discussed in terms of adhesion stress fields (due to surface forces), the action of an applied point force, possibly magnetic, and dislocations or misfit strains due to an unfavorable matching of crystal lattices at the grain boundary. A further explanation might be sought along the line "squeezed-in oxide" which can be visualized as a coherent particle or a dislocation loop. Accompanying theoretical calculations have been performed and compared with the experimental results. 相似文献
104.
A benchtop high-resolution time-of-flight mass spectrometer (TOF MS) was evaluated for the determination of key organic microcontaminants. The major advantage of the TOF MS proved to be the high mass resolution of about 0.002 Da (10 ppm). Consequently, the detectability of polar pesticides, polynuclear aromatic hydrocarbons and polychlorinated biphenyls is excellent, and detection limits are in the order of 1–4 pg injected mass. Best mass spectral resolution was obtained for medium-scale peaks. It is a disadvantage that the calibration range is rather limited, viz. to about two orders of magnitude. The high mass spectral resolution was especially useful to improve the selectivity and sensitivity when analyzing target compounds in complex samples and to prevent false-positive identifications. 相似文献
105.
von Euler H Olsson JM Hultenby K Thörne A Lagerstedt AS 《Bioelectrochemistry (Amsterdam, Netherlands)》2003,59(1-2):89-98
INTRODUCTION: Electrochemical treatment (EChT) has been taken under serious consideration as being one of several techniques for local treatment of malignancies. The advantage of EChT is the minimal invasive approach and the absence of serious side effects. Macroscopic, histopathological and ultra-structural findings in liver following a four-electrode configuration (dog) and a two-electrode EChT design (dog and rat) were studied. MATERIALS AND METHODS: 30 female Sprague-Dawley rats and four female beagle dogs were studied with EChT using Platinum:Iridium electrodes and the delivered dose was 5, 10 or 90 C (As). After EChT, the animals were euthanized. RESULTS: The distribution of the lesions was predictable, irrespective of dose and electrode configuration. Destruction volumes were found to fit into a logarithmic curve (dose-response). Histopathological examination confirmed a spherical (rat) and cylindrical/ellipsoidal (dog) lesion. The type of necrosis differed due to electrode polarity. Ultra-structural analysis showed distinct features of cell damage depending on the distance from the electrode. Histopathological and ultra-structural examination demonstrated that the liver tissue close to the border of the lesion displayed a normal morphology. CONCLUSIONS: The in vivo dose-planning model is reliable, even in species with larger tissue mass such as dogs. A multi-electrode EChT-design could obtain predictable lesions. The cellular toxicity following EChT is clearly identified and varies with the distance from the electrode and polarity. The distinct border between the lesion and normal tissue suggests that EChT in a clinical setting for the treatment of liver tumours can give a reliable destruction margin. 相似文献
106.
Three natural basaltic samples were collected and used as efficient catalysts for the liquid‐phase synthesis of n‐butyl acetate. The samples were characterized by X‐ray fluorescence analysis (XRF), X‐ray diffraction (XRD), thermogravimetry (TG), differential thermal analysis (DTA), Fourier transform infrared (FT‐IR), scanning electron microscopy (SEM), and N2 sorption. The acidity of the samples was determined using isopropanol dehydration, and the strength of the acid sites was measured using chemisorption of basic probes. The catalytic activity of the samples towards the esterification of acetic acid with n‐butanol was extensively examined. The influence of different parameters, such as the reaction refluxing time, molar ratio, catalyst loading, reusability, and calcination temperature, on the esterification reaction was studied in detail. The results revealed that all samples had high catalytic activity with a selectivity of 100% to n‐butyl acetate formation. In addition, the sample obtained from the top hill of Volcano had the highest activity with a 80% yield of n‐butyl acetate. Moreover, the significant catalytic performances were well correlated with the acidity of the samples and to the reaction rate constants. 相似文献
107.
Guillaume Erbland Dr. Seifallah Abid Yohan Gisbert Nathalie Saffon-Merceron Yuichiro Hashimoto Leonardo Andreoni Théo Guérin Dr. Claire Kammerer Prof. Dr. Gwénaël Rapenne 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(71):16328-16339
The design and synthesis of two families of molecular-gear prototypes is reported, with the aim of assembling them into trains of gears on a surface and ultimately achieving controlled intermolecular gearing motion. These piano-stool ruthenium complexes incorporate a hydrotris(indazolyl)borate moiety as tripodal rotation axle and a pentaarylcyclopentadienyl ligand as star-shaped cogwheel, equipped with five teeth ranging from pseudo-1D aryl groups to large planar 2D paddles. A divergent synthetic approach was followed, starting from a pentakis(p-bromophenyl)cyclopentadienyl ruthenium(II) complex as key precursor or from its iodinated counterpart, obtained by copper-catalyzed aromatic Br/I exchange. Subsequent fivefold cross-coupling reactions with various partners allowed high structural diversity to be reached and yielded molecular-gear prototypes with aryl-, carbazole-, BODIPY- and porphyrin-derived teeth of increasing size and length. 相似文献
108.
The reaction of the metallocene dichlorides Cp2MCl2 (Cp = η5-C5H5; M = Ti, Zr, Hf, Mo, W) and Cp2′TiCl2 (Cp′ = η5-C5H4CH3) with equimolar amounts of dilithium-benzene-o-diselenolate, 1,2-(LiSe)2C6H4, gives the chelate complexes Cp2M(Se2C6H4) (M = Ti (I), Zr (II), Hf (III), Mo (IV), W (V)) and Cp2′Ti(Se2C6H4) (VI). CpTiCl3 reacts with 1,2-(LiSe)2C6H4 to give CpTiCl(Se2C6H4) (VII). The ring inversion activation parameters for I–VI can be determined by means of temperature-dependent 1H NMR spectroscopy in solution. The fragmentation behaviour of I–VII in the mass spectrometer has been investigated by pursuing metastable transitions, using linked-scan techniques. 相似文献
109.
Summary Comprehensive gas chromatography is an excellent technique for separating complex mixtures. If, however high-boiling compounds
such as polychlorinated biphenyls have to be analysed, proper adjustiment of the temperature of the modulator turns out to
be very important in maintaining the performance of the system. It is shown that miniaturisation of the column-to-modulator
coupling, adequate selection of the modulating conditions and, for halogenated compound mixtures, the use of a micro electron-capture
detector, can solve experimental problems previously encountered with high boilers. 相似文献
110.
The interaction of ethidium bromide (2,7-diamino-10-ethyl-9-phenylphenanthridinium bromide; EB) with double stranded (ds) calf thymus DNA and thermally denatured single stranded (ss) DNA was studied in solution and at the electrode surface by means of transfer voltammetry using a carbon paste electrode (CPE) as working electrode in 0.2 M acetate buffer, pH 5.0. As a result of intercalation of this dye between the base pairs of dsDNA, the characteristic peak of dsDNA, due to the oxidation of guanine residues, decreased and after a particular concentration of EB a new peak at +0.81 V appeared, probably due to the formation of a complex between dsDNA and EB. The non-intercalated EB gives another peak, but at an increased concentration of the dye. A similar behaviour was observed during the interaction of the dye with ssDNA.Furthermore, the interaction of EB with ds, ss and supercoiled (sc) DNA was studied at the hanging mercury drop electrode (HMDE) surface by means of alternating current voltammetry in 0.3 M NaCl and 50 mM sodium phosphate buffer (pH 8.5) as supporting electrolyte. dsDNA yields a smaller peak at −1.42 V (peak III) compared to the one yielded by ssDNA, since the latter is a relaxed and more accessible form. By addition of EB into the buffer solution an increase of peak III was observed in the dsDNA form as well as in ssDNA resulting from their interaction with EB. Furthermore, the appearance of peak III in covalently closed circular scDNA after exposure to increasing concentrations of EB is a result of the introduction of ‘free ends’ in DNA affecting its structural integrity. 相似文献