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941.
The construction of a new solid-phase microextraction/surfaced enhanced laser desorption/ionization-ion mobility spectrometry (SPME/SELDI-IMS) device is reported here. A polypyrrole (PPY) coated SPME/SELDI fiber was employed as the extraction phase and SELDI surface to introduce analytes into the IMS. Analytes were directly ionized from the PPY coated fiber tip by a Nd:YAG laser without the addition of a matrix. Optimal experimental parameters, such as extraction conditions and laser parameters, were investigated. The use of a SPME/SELDI fiber simplified the sampling and sample preparation for IMS. Verapamil could be directly extracted from urine sample and analyzed by IMS without any further sample cleanup. This technique could be used for the analysis of drugs and other non-volatile compounds. 相似文献
942.
Walasek J 《The Journal of chemical physics》2007,127(4):044901
The system of linear polymer liquid crystal (PLC) macromolecules, each modeled by semiflexible chain of alternate connected flexible and stiff rodlike sequences, is externally deformed. As a result, two orientation phases for hard rods are generated. One of them is nematic N+ with orientation parameter s>0; this has the place in monomer liquid crystal (MLC) systems and in PLCs. The nematic N- phase with s>0 appears in deformed PLCs only. This causes the fact that orientation of PLC chains, as a whole, is generated also by the system deformation. A discussion of that effect is the main goal of this article. The change of orientation is also discussed dependent on changes of the system temperature and parameters of the chain structure, such as the liquid crystal component concentration, contour lengths of stiff and flexible parts, and internal interactions parameters. Average shape of PLC chain and the shape anisotropy are calculated and discussed. 相似文献
943.
An analytical method for the determination of volatile and semi-volatile compounds representing various chemical groups in ice wines was developed and optimized in the presented study. A combination of the fully automated solid-phase microextraction (SPME) sample preparation technique and gas chromatographic-mass spectrometric (GC-MS) system to perform the final chromatographic separation and identification of the analytes of interest was utilized. A time-of-flight mass spectrometric (TOF-MS) analyzer provided very rapid analysis of this relatively complex matrix. Full spectral information in the range of m/z 35-450 was collected across the short GC run (less than 5 min). Divinylbenzene/Carboxen/Polydimethylsiloxane (DVB/CAR/PDMS) 50/30 microm fiber performed best during the optimization experiments and it was used in the headspace SPME mode to isolate compounds from ice wine samples, consisting of 3 mL wine with 1g salt addition. After the sample incubation and extraction (both 5 min at 45 degrees C), analytes were thermally desorbed in the GC injector for 2 min (injector maintained at 260 degrees C) and transferred into the column. The MS data acquisition rate of 50 spectra/s was selected as optimal. The optimized analytical method did not exceed 20 min per sample, including both the isolation and pre-concentration of the analytes of interest, the final GC-TOF-MS analysis and the fiber bake-out. Both a linear temperature-programmed retention index (LTPRI) method using C(8)-C(20) alkanes loaded onto the fiber and a mass spectral library search were employed to identify the target compounds. The repeatability of the developed and optimized HS-SPME-GC-TOF-MS method for ice wine analysis, expressed as relative standard deviation (RSD, %, n=7), ranged from 3.2 to 9.0%. 相似文献
944.
In this paper, we present results for the on-line determination of semivolatile organic compounds (SVOCs) in air using membrane
extraction with a sorbent interface–ion mobility spectrometry (MESI-IMS) system with a preheated carrier (stripping) gas.
The mechanism of the mass transfer of SVOCs across a membrane was initially studied. In comparison with the extraction of
volatile analytes, the mass transfer resistance that originated from the slow desorption from the internal membrane surface
during the SVOC extraction processes should be taken into account. A preheated carrier gas system was therefore built to facilitate
desorption of analytes from the internal membrane surface. With the benefit of a temperature gradient existing between the
internal and external membrane surfaces, an increase in the desorption rate of a specific analyte at the internal surface
and the diffusion coefficient within the membrane could be achieved while avoiding a decrease of the distribution constant
on the external membrane interface. This technique improved both the extraction rate and response times of the MESI-IMS system
for the analysis of SVOCs. Finally, the MESI-IMS system was shown to be capable of on-site measurement by monitoring selected
polynuclear aromatic hydrocarbons emitted from cigarette smoke.
Figure Schematic of the MESI-IMS preheating carrier (stripping) gas system 相似文献
945.
Shcharbin D Mazur J Szwedzka M Wasiak M Palecz B Przybyszewska M Zaborski M Bryszewska M 《Colloids and surfaces. B, Biointerfaces》2007,58(2):286-289
Binding of Cd2+ by PAMAM 4.5 dendrimer was studied by equilibrium dialysis, isothermal titration calorimetry and zeta-potential measurement. The following binding parameters were obtained: n = 23.8 ± 9.5, Kb = 4.7 ± 0.9 × 103 in water; and n = 41.3 ± 13.4, Kb = 2.1 ± 0.8 × 103 in 0.15 mol/l phosphate-buffered saline. The location of the bound Cd2+ is discussed. The interactions between bovine serum albumin, PAMAM 4.5 dendrimer and cadmium were analyzed using fluorescence and equilibrium dialysis. The competition between Cd2+ binding to BSA and PAMAM 4.5 dendrimer was investigated. It is proposed that PAMAM 4.5 dendrimer could be successfully used for extracting Cd2+ from aqueous solutions (environmental protection). 相似文献
946.
Dabrowski JM Pereira MM Arnaut LG Monteiro CJ Peixoto AF Karocki A Urbańska K Stochel G 《Photochemistry and photobiology》2007,83(4):897-903
A water-soluble halogenated porphyrin, namely 5,10,15,20-tetrakis(2-chloro-3-sulfophenyl)porphyrin (TCPPSO(3)H), was prepared and evaluated as sensitizer for photodynamic therapy (PDT). Photophysical properties of TCPPSO(3)H, such as high photostability, long triplet lifetime and high singlet oxygen quantum yield suggest high effectiveness of this class of halogenated porphyrins in PDT. TCPPSO(3)H is non-toxic in the dark and causes a significant photodynamic effect examined against MCF7 (human breast carcinoma), SKMEL 188 (human melanoma) and S91(mouse melanoma) cell lines upon red light irradiation (cutoff < 600 nm) at low light doses. Time-dependent cellular uptake of TCPPSO(3)H reached plateau at 120 min and was the highest for S91, 20% lower for MCF7 and 70% lower for SKMEL 188. Our results show that this halogenated water-soluble porphyrin is an efficient photosensitizer and reveal the potential of this class of compounds as PDT agents. 相似文献
947.
Ezel Boyacı Chris Sparham Janusz Pawliszyn 《Analytical and bioanalytical chemistry》2014,406(2):409-420
The dual nature of the quaternary ammonium compounds, having permanently charged hydrophilic quaternary ammonium heads and long-chain hydrophobic tails, makes the sample preparation step and analysis of these compounds challenging. A high-throughput method based on thin-film solid-phase microextraction (SPME) and liquid chromatography mass spectrometry was developed for simultaneous quantitative analysis of nine benzylic and aliphatic quaternary ammonium compounds. Chromatographic separation and detection of analytes were obtained in reverse-phase mode in 8 min using a triple quadrupole mass spectrometer. Hydrophilic lipophilic balance particle-coated blades were found to be the most suitable among the different coatings tested in terms of recoveries and carryover on the blades. For desorption solvents, 70/30, v/v (A/B) with 0.1 % formic acid (where A is 10 mM ammonium acetate in acetonitrile/water (95/5?, v/v) and B is 0.1 %? (v/v) formic acid in isopropyl alcohol) was shown to be the most efficient solvent for the desorption of the analytes from the SPME sorbent. The SPME method was optimised in terms of extraction, pH, and preconditioning, as well as extraction and desorption times. Optimum conditions were 45 min of extraction time and 15 min of desorption time, all with agitation. The extraction was found to be optimum in a range of pH 6.0 to 8.0, which is consistent with the natural pH of water samples. Wide linear dynamic ranges with the developed method were obtained for each compound, enabling the application of the method for a wide range of concentrations. The developed method was validated according to the Food and Drug Administration criteria. The proposed method is the first SPME-based approach describing the applicability of the high-throughput thin-film SPME in a 96-well system for analysis of such challenging compounds. 相似文献
948.
Barbara Kubica Katarzyna Szarlowicz Marcin Stobinski Stefan Skiba Witold Reczynski Janusz Gołas 《Journal of Radioanalytical and Nuclear Chemistry》2014,299(3):1313-1320
The aim of the study is to present the results of determination of radioactivity of artificial 137Cs and natural 40K and certain heavy metals in soil samples collected from the eastern part of the Main Ridge of Carpathians, including the Beskid Niski Mts and the Bieszczady Mts. The evaluation of level of radionuclides was based on the bulk density analysis of the soil. A valuable finding of the study was a good linear correlation between the level of 137Cs concentration and bulk density of the soil as well as an inverse correlation between radioactivity of natural 40K and tested soil density. This might indicate though a high competitiveness of these elements between each other. Moreover, a good correlation between the concentrations of artificial element 137Cs and Pb has been also observed in soil samples collected from the Beskid Niski Mts. In most cases, the level of artificial 137Cs was lower comparing to an average 137Cs concentration established for soils in Poland. 相似文献
949.
In this publication, a novel solid phase microextraction (SPME) coating functionalized with a DNA aptamer for selective enrichment of a low abundance protein from diluted human plasma is described. This approach is based on the covalent immobilization of an aptamer ligand on electrospun microfibers made with the hydrophilic polymer poly(acrylonitrile-co-maleic acid) (PANCMA) on stainless steel rods. A plasma protein, human α-thrombin, was employed as a model protein for selective extraction by the developed Apt-SPME probe, and the detection was carried out with liquid chromatography/tandem mass spectrometry (LC–MS/MS). The SPME probe exhibited highly selective capture, good binding capacity, high stability and good repeatability for the extraction of thrombin. The protein selective probe was employed for direct extraction of thrombin from 20-fold diluted human plasma samples without any other purification. The Apt-SPME method coupled with LC–MS/MS provided a good linear dynamic range of 0.5–50 nM in diluted human plasma with a good correlation coefficient (R2 = 0.9923), and the detection limit of the proposed method was found to be 0.30 nM. Finally, the Apt-SPME coupled with LC–MS/MS method was successfully utilized for the determination of thrombin in clinical human plasma samples. One shortcoming of the method is its reduced efficiency in undiluted human plasma compared to the standard solution. Nevertheless, this new aptamer affinity-based SPME probe opens up the possibility of selective enrichment of a given targeted protein from complex sample either in vivo or ex vivo. 相似文献
950.
Krzysztof Durka Agnieszka Górska Piotr Jankowski Tomasz Kliś Marcin Kublicki Janusz Serwatowski Mateusz Urban Grzegorz Wesela-Bauman Krzysztof Woźniak 《Tetrahedron letters》2017,58(12):1185-1189
A one-pot protocol was developed for the synthesis of a series of luminescent heteroleptic diaryldiborinic complexes containing the central aryl ring bonded to two boron atoms substituted with pyrazole and complexed with 8-hydroxyquinoline. The luminescent properties of these compounds were measured. In dilute solutions they exhibited an emission at ca. 513 nm with quantum yields of 22–27% which are typical for borinic 8-hydroxyquinoline complexes. The only exception was the complex containing the bithiophene scaffold, for which no fluorescence was observed. The obtained pyrazole-based complexes show improved solubility and thermal stability with respect to their phenyl analogues. The experimental UV–vis absorption and emission data are supported by theoretical calculations of the frontier molecular orbitals, revealing the aromatic linker to quinolinato ligand excitation mechanism. 相似文献