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1.
A conventional solid-phase microextraction (SPME) method combined with liquid–liquid extraction was applied under equilibrium and nonequilibrium conditions to determine the partition coefficients (Kdoc) of 25 polychlorinated biphenyl congeners (PCBs) between Sigma–Aldrich humic acid (HA) and water. The values of log Kdoc determined with equilibrium SPME were linearly correlated with the logarithm of the octanol–water partition coefficients (Kow) for PCB congeners at log Kow < ∼7.2, but the trends were disrupted for log Kow from ∼7.2 to 8.18. In addition, short-term (5 min to 4 days) and long-term (5–44 days) uptake profiles of PCBs were established, from which a pseudo-equilibrium for sorption of PCBs was revealed at ∼4 days of extraction. To understand this phenomenon, the uptake profiles were fitted with two equations (one equation is often used for pure water samples and the other one is applicable for samples containing complex matrices) derived from a first-order kinetics model. Subsequently, Kdoc values obtained through kinetic approaches were compared with those acquired from equilibrium SPME. The comparison of Kdoc values indicated that the pseudo-equilibrium was caused by the slow desorption of PCBs from HA rather than the biphasic desorption mechanism.  相似文献   

2.
Solid-phase microextraction coupled with gas chromatography and mass spectrometry (SPME–GC–MS) was developed for the study of interactions between polycyclic aromatic hydrocarbons (PAHs) and dissolved organic matter (DOM). After the determination of the best conditions of extraction, the tool was applied to spiked water to calculate the dissolved organic carbon water distribution coefficient (KDOC) in presence of different mixtures of PAHs and Aldrich humic acid. The use of deuterated naphthalene as internal standard for freely dissolved PAH quantification was shown to provide more accuracy than regular external calibration. For the first time, KDOC values of 18 PAHs were calculated using data from SPME–GC–MS and fluorescence quenching; they were in agreement with the results of previous studies. Competition between PAHs, deuterated PAHs and DOM was demonstrated, pointing out the non-linearity of PAH–DOM interactions and the stronger interactions of light molecular weight PAHs (higher KDOC values) in absence of high molecular weight PAHs.  相似文献   

3.
A method is presented for the electroanalytical characterization of interactions of dsDNA with a drug, under conditions that both agents are dissolved in the phosphate buffer solution and both are electroactive. Normal pulse, square wave, differential pulse, and cyclic voltammetries were employed in the measurements of the drug and dsDNA oxidation signals at carbon electrodes. UV–Vis spectroscopy was used as a non-electrochemical method to support the electroanalytical data. An anticancer drug, C-1311 (5-diethylaminoethyl-amino-8-hydroxyimidazoacridinone), has been selected for the examination. Normal pulse voltammetry was particularly useful in showing that under the conditions employed neither dsDNA nor the drug were adsorbed at the electrode surface. Necessary conditions for the appearance of the well-defined dsDNA voltammetric signal (guanine peak) are: rigorous chemical and biological purity in the cell and appropriate purity of DNA. An analysis of the obtained results confirmed that there were two modes of interaction between C-1311 and dsDNA: by intercalation and electrostatically. In the presence of excess NaCl the electrostatic interactions deteriorate. The binding constants (K 1 and K 2, respectively) and the number (n) of nucleic base pairs (bp) and the number (m) of phosphate groups (pg) interacting with one molecule of drug have been determined. For strong interactions (intercalation) the values of the binding constant, K 1, and the binding-site size, n, equal 3.7 × 104 M−1 and 2.1, respectively. For the weak electrostatic interactions the K 2 and m parameters equal 0.28 × 104 M−1 and 4.7. The intercalation process is rather slow and its rate (the conditions of pseudo-first-order reaction) was estimated to equal 7 × 10−4 s−1. The possibility of independent determination of both interacting agents was very useful in the study. Figure Intercalation of C-1311 into a dsDNA fragment  相似文献   

4.
The deuterium-isotope effects on the ionization constants of β-naphthol (2-naphthol) and boric acid, Δlog 10 K=[log 10 K D2O−log 10 K H2O], have been determined from measurements in light and heavy water at temperatures from 225 °C≤t≤300 °C and pressures near steam saturation. β-Naphthol is a thermally-stable colorimetric pH indicator, whose ionization constant lies close to that of H2PO4 (aq), the only acid for which Δlog 10 K is accurately known at elevated temperatures. A newly designed platinum flow cell was used to measure UV-visible spectra of β-naphthol in acid, base, and buffer solutions of H2PO4/HPO42− and D2PO4/DPO42−, from which the degree of ionization at known values of pH and pD was determined. Values of the ionization constants of β-naphthol in light and heavy water were calculated from these results, and used to derive a model for and over the experimental temperature range with an estimated precision of ±0.02 in log 10 K. The new values of K H2O and K D2O allowed us to use β-naphthol as a colorimetric indicator, to measure the equilibrium pH and pD of the buffer solutions B(OH)3/B(OH)4 and B(OD)3/B(OD)4 up to 300 °C, from which the ionization constants of boric acid were calculated. The magnitude of the deuterium isotope effect for H2PO4 (aq) is known to fall from Δlog 10 K=−0.62 to Δlog 10 K=−0.47, on the “aquamolal” concentration scale, as the temperature rises above 125 °C, but then remains almost constant. Although the temperature range is more limited, the new results for β-naphthol and boric acid appear to show a similar trend.  相似文献   

5.
A novel plastic material, poly(ethylene-co-vinyl acetate-co-carbon monoxide) (PEVAC), was evaluated as an absorptive passive equilibrium sampler for determination of the freely dissolved fraction of seven polar organic contaminants (POCs) in the presence of fulvic acid and sediment. The seven compounds selected were imidacloprid, carbendazim, metoprolol, atrazin, carbamazepine, diazinon and chlorpyrifos, i.e. a mixture of pharmaceuticals and pesticides having logarithmic octanol/water partition coefficients (log K OW) ranging from 0.2 to 4.77. The experiments demonstrated that the PEVAC sampler is well suited for determination of the freely dissolved fraction of chemicals in aquatic environments. Generally, the freely dissolved fraction of the POCs decreased with increasing hydrophobicity. However, strong interactions with functional groups of the organic matter seemed to dominate the partitioning for imidacloprid and carbendazim, having logarithmic dissociation partition coefficient log D < 1.47, and for metoprolol, which is positively charged at neutral pH.  相似文献   

6.
An aptamer-based label-free approach to hemin recognition and DNA assay using capillary electrophoresis with chemiluminescence detection is introduced here. Two guanine-rich DNA aptamers were used as the recognition element and target DNA, respectively. In the presence of potassium ions, the two aptamers folded into the G-quartet structures, binding hemin with high specificity and affinity. Based on the G-quartet–hemin interactions, the ligand molecule was specifically recognized with a K d ≈ 73 nM, and the target DNA could be detected at 0.1 μM. In phosphate buffer of pH 11.0, hemin catalyzed the H2O2-mediated oxidation of luminol to generate strong chemiluminescence signal; thus the target molecule itself served as an indicator for the molecule–aptamer interaction, which made the labeling and/or modification of aptamers or target molecules unnecessary. This label-free method for molecular recognition and DNA detection is therefore simple, easy, and effective. Figure A label-free approach to aptamer-based hemin recognition and DNA detection is introduced, which gives great potential for using a small molecule itself as the indicator for molecular recognition and DNA detection thereby avoiding any labeling or modification step  相似文献   

7.
Two kinds of Ca2+-regulated photoprotein obelin with altered color of bioluminescence were obtained by active-center amino acid substitution. The mutant W92F-H22E emits violet light (λmax = 390 nm) and the mutant Y139F emits greenish light (λ max = 498 nm), with small spectral overlap, both display high activity and stability and thus may be used as reporters. For demonstration, the mutants were applied in dual-color simultaneous immunoassay of two gonadotropic hormones—follicle-stimulating hormone and luteinizing hormone. Bioluminescence of the reporters was simultaneously triggered by single injection of Ca2+ solution, divided using band-pass optical filters and measured with a two-channel photometer. The sensitivity of simultaneous bioluminescence assay was close to that of a separate radioimmunoassay. Figure Two kinds of Ca2+-regulated photoprotein obelin with altered color of bioluminescence were obtained and applied in dual-color simultaneous immunoassay of two gonadotropic hormones.  相似文献   

8.
The effects of NaBr on the adsorption of alkanediyl-bis-(dimethyl dodecyl- ammonium bromide) (referred to as C12-s-C12 2Br) at the air/water interface and on the micellization in the solution have been investigated by surface tension and fluorescence techniques. The results showed that the addition of NaBr greatly enhances their efficiency and effectiveness in surface tension reduction as well as the ability of micellization, even induces strong premicellar aggregation before the cmc. These were attributed to the unique molecular structure of gemini surfactant, where the flexible polymethylene chain was the spacer linking the two quaternary ammonium heads. By a short spacer, the charges of the two quaternary ammonium head groups are concentrated. Even for a long spacer (s = 12), since it is bent toward the alkyl tails, the similar effect is also produced. This results in the high sensitivity of their ionic head groups to salt. Besides, the addition of salt also effectively promotes the hydrophobic interaction between the alkyl tails of gemini surfactants. The addition of NaBr strongly promotes the adsorption of quaternary ammonium gemini surfactants C12-s-C12 2Br at the air/water interface and the micellization in the solution.  相似文献   

9.
Enzyme-linked immunosorbent assay (ELISA), horseradish peroxidase (HRP)-catalyzed fluorescent reaction, and oxalate chemiluminescence imaging analysis have been combined to develop a sensitive, simple, and rapid method for analysis of interferon alpha (α-IFN) in human serum samples. A typical “sandwich type” immunoassay was used. Reaction of o-phenylenediamine (OPD) with hydrogen peroxide (H2O2), catalyzed by HRP, produced 2,3-diaminophenazine (PDA), which was detected by chemiluminescence imaging analysis with the bis(2,4,6-trichlorophenyl)oxalate (TCPO)–H2O2–glyoxaline–PDA chemiluminescent system. The TCPO chemiluminescent imaging system is more sensitive and the chemiluminescence quantum yield is at least five times higher than for the luminol–H2O2–HRP–PIP (p-iodophenol) chemiluminescent imaging system. The results showed there was a very good linear correlation between response and amount of α-IFN in the range 1.3–156.0 pg mL−1 (R = 0.9991) and the detection limit was 0.8 pg mL−1 (S/N=3). The relative standard deviation (n = 9) was 4.7%. The proposed method has been used for successful analysis of the amount of α-IFN in human serum. The results obtained compared well with those obtained by conventional colorimetric ELISA and luminol chemiluminescent ELISA. Figure Procedures of the proposed method  相似文献   

10.
Three hundred and thirty two bacterial colonies were isolated from soil contaminated by an oil spill. All the bacteria were cultured in a liquid medium individually, and the surface tensions of the media were compared. The bacterium whose culture medium had the lowest surface tension was identified as Pseudomonas sp. G11. A biosurfactant was produced by cultivation of the Pseudomonas sp. G11 in the LB media. For extraction of the biosurfactant, two solvent systems were used (n-hexane and a 2:1 (v/v) mixture of chloroform/MeOH), and the results were compared. Various experimental conditions (solvent composition, flow rate, etc.) were tested to optimize the analysis of the biosurfactant by asymmetrical flow field-flow fractionation (AsFlFFF). The biosurfactant was successfully separated from the culture medium by AsFlFFF when pure water was used as the carrier. From the retention data, the hydrodynamic diameter (d H) and molecular weight (M) of the biosurfactant were determined by AsFlFFF. The molecular weight was determined by using pullulans as the calibration standards. The d H and M were 49 nm and 2.3 × 105 Da when extracted with n-hexane, and 39 nm and 1.13 × 105 Da when extracted with the 2:1 mixture of chloroform/MeOH, respectively. Figure Separation of biosurfactant from its culture medium by flow FFF  相似文献   

11.
A new method for chemical analyses of nitride-based hard coatings is presented. Raman band shifts in the spectra of Al x Cr1−x N coatings, deposited by physical vapour deposition from Al x Cr1−x targets with x T,Al = 0, 0.25, 0.50, 0.70 and 0.85, are calibrated using compositional data of the coatings derived by elastic recoil detection analysis (ERDA) and electron probe micro-analysis (EPMA). Inserting the composition-dependent Raman shift of a combinatorial acoustic-optic lattice mode into an empirically derived equation allows the determination of Al/Cr ratios of the coating with an accuracy of about ±2%. Spot, line and area analyses of coated cemented carbide and cold work steel samples by using a computer-controlled, motorized x,y-stage are demonstrated and the most important errors influencing precision and accuracy are discussed. Figure Raman map of a coated cold-work steel sample  相似文献   

12.
A capacitive biosensor for the detection of bacterial endotoxin has been developed. Endotoxin-neutralizing protein derived from American horseshoe crab was immobilized to a self-assembled thiol layer on a biosensor transducer (Au). Upon injection of a sample containing endotoxin, a decrease in the observed capacitive signal was registered. Endotoxin could be determined under optimum conditions with a detection limit of 1.0 × 10−13 M and linearity ranging from 1.0 × 10−13 to 1.0 × 10−10 M. Good agreement was achieved when applying endotoxin preparations purified from an Escherichia coli cultivation to the capacitive biosensor system, utilizing the conventional method for quantitative endotoxin determination, the Limulus amebocyte lysate test as a reference. The capacitive biosensor method was statistically tested with the Wilcoxon signed rank test, which proved the system is acceptable for the quantitative analysis of bacterial endotoxin (P < 0.05). Figure The flow-injection capacitive biosensor system and the capacitive properties of the transducer surface, where CSAM is the capacitance change of the self-assembled thiol monolayer, CP is the capacitance change of the protein layer, Ca is the capacitance change of the analyte layer and CTotal is the total capacitance change measured at the working electrode/solution interface (modified from Limbut et al., 2006. Biosens Bioelectron 22: 233-240)  相似文献   

13.
The effect of dissolved humic acids on the recovery of PAHs from water samples has been investigated using a commercially available humic acid preparation as colloid model and a mixture containing the 16 EPA PAHs. The presence of humic acid reduced the extraction efficiency down to between 10 and 75%. An analytical protocol was therefore developed for the accurate determination of PAHs in the presence of humic acids based on isotope dilution mass spectrometry. The procedure compensates for losses due to sorption of PAHs and can be used for the determination of the total PAH concentration in water, i.e. dissolved PAHs plus PAHs adsorbed on colloids. To obtain reliable estimates it is essential to allow a certain time for equilibration between the isotope spike and the aqueous matrix which may vary between 5 and 24 h, in correlation with the water solubility of PAHs. The protocol allows one to recover the 16 PAHs studied at 94 to 105%. The expanded uncertainty of the measurements was 5–7% for all PAHs. Liquid–liquid extraction and solid-phase extraction in combination with the developed isotope dilution protocol performed equally well for the quantification of PAHs from water samples rich in colloidal material.   相似文献   

14.
The protonation constants of 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin, H2tpps4−, were determined in water–ethanol and water–methanol mixed solvents, using a combination of spectrophotometric and potentiometric methods at 20 °C and 0.1 mol⋅dm−3 sodium perchlorate as supporting electrolyte. Two protonation constants, K 1 and K 2, were characterized and were analyzed in various media in terms of the Kamlet, Abboud and Taft (KAT) parameters. Single-parameter correlations of the protonation constant K 1 versus α (hydrogen-bond donor acidity) and π * (dipolarity/polarizability) are poor in all solutions, but dual-parameter (α and π *) correlation represents a significant improvement with regard to the single- and multi-parameter models. However, the single-parameter correlation of log 10 K 2 in terms of β (hydrogen-bond acceptor basicity) shows a better result than dual- and multi-parameter correlations. Linear correlation is observed when the experimental log 10 K 1 and log 10 K 2 values are plotted versus the calculated ones when the KAT parameters are considered. To evaluate the protonation constants of H2tpps4−, the Yasuda-Shedlovsky extrapolation is used to obtain the log 10 K 1 and log 10 K 2 values at zero percent organic solvent. Finally, the results are discussed in terms of the effect of the solvent on protonation.  相似文献   

15.
A new application of reversed-phase octadecyl (C18) solid phase extraction disks has been developed to separate the colloidally-associated polycyclic aromatic hydrocarbons (PAHs) from those that were truly dissolved in the samples of fresh water. A correction for the retention of small amounts of colloidal material on the C18 disks was required, which would have otherwise lead to minor underestimates in the degree of partitioning between the two phases. Using the humic substance Aldrich Humic Acid (AHA) as a model colloid and the 16 PAHs on the US Enrivonmental Protection Agency priority pollutant list, the partitioning coefficients of the PAHs between the colloidal and truly dissolved phases were shown to be proportional to the hydrophobicity of the PAHs, as measured by their octanol water partition coefficients (Kow). The values for the partition coefficients obtained (cKdoc′) were similar to those previously reported in the literature using alternative methods, confirming that the technique was producing acceptable results. The technique allows the in situ partitioning of PAHs between the truly dissolved and colloidal phases in fresh water bodies to be determined. It will provide an invaluable cross-check of the laboratory-based methods which often require substantial manipulation of the sample and potentially alter the partitioning between the phases.  相似文献   

16.
The discrimination and classification of allergy-relevant pollen was studied for the first time by mid-infrared Fourier transform infrared (FT-IR) microspectroscopy together with unsupervised and supervised multivariate statistical methods. Pollen samples of 11 different taxa were collected, whose outdoor air concentration during the flowering time is typically measured by aerobiological monitoring networks. Unsupervised hierarchical cluster analysis provided valuable information about the reproducibility of FT-IR spectra of the same taxon acquired either from one pollen grain in a 25 × 25 μm2 area or from a group of grains inside a 100 × 100 μm2 area. As regards the supervised learning method, best results were achieved using a K nearest neighbors classifier and the leave-one-out cross-validation procedure on the dataset composed of single pollen grain spectra (overall accuracy 84%). FT-IR microspectroscopy is therefore a reliable method for discrimination and classification of allergenic pollen. The limits of its practical application to the monitoring performed in the aerobiological stations were also discussed. Figure Traditional and innovative methods for the identification of airborne pollen grains  相似文献   

17.
Radix Scrophulariae (Xuanshen) is one of the famous Chinese herbal medicines widely used to treat rheumatism, tussis, pharyngalgia, arthritis, constipation, and conjunctival congestion. Harpagoside and cinnamic acid are the main bioactive components of Xuanshen. The purpose of this study was to develop an HPLC–UV method for simultaneous determination of harpagoside and cinnamic acid in rat plasma and investigate pharmacokinetic parameters of harpagoside and cinnamic acid after oral administration of Xuanshen extract (760 mg kg−1). After addition of syringin as internal standard, the analytes were isolated from plasma by liquid–liquid extraction. Separation was achieved on a Kromasil C18 column, and detection was by UV absorption at 272 nm. The described assay was validated in terms of linearity, accuracy, precision, recovery, and limit of quantification according to the FDA validation guidelines. Calibration curves for both analytes were linear with the coefficient of variation (r) for both was greater than 0.999. Accuracy for harpagoside and cinnamic acid ranged from 100.7–103.5% and 96.9–102.9%, respectively, and precision for both analytes were less than 8.5%. The main pharmacokinetic parameters found for harpagoside and cinnamic acid after oral infusion of Xuanshen extract were as follows: C max 1488.7 ± 205.9 and 556.8 ± 94.2 ng mL−1, T max 2.09 ± 0.31 and (1.48 ± 0.14 h, AUC0–24 10336.4 ± 1426.8 and 3653.1 ± 456.4 ng h mL−1, 11276.8 ± 1321.4 and 3704.5 ± 398.8 ng h mL−1, and t 1/2 4.9 ± 1.3 and 2.5 ± 0.9 h, respectively. These results indicated that the proposed method is simple, selective, and feasible for pharmacokinetic study of Radix Scrophulariae extract in rats. Figure Radix Scrophulariae  相似文献   

18.
A microfluidic system incorporating chemiluminescence detection is reported as a new tool for measuring antioxidant capacity. The detection is based on a peroxyoxalate chemiluminescence (PO-CL) assay with 9,10-bis-(phenylethynyl)anthracene (BPEA) as the fluorescent probe and hydrogen peroxide as the oxidant. Antioxidant plugs injected into the hydrogen peroxide stream result in inhibition of the CL emission which can be quantified and correlated with antioxidant capacity. The PO-CL assay is performed in 800-μm-wide and 800-μm-deep microchannels on a poly(dimethylsiloxane) (PDMS) microchip. Controlled injection of the antioxidant plugs is performed through an injection valve. Of the plant-food based antioxidants tested, β-carotene was found to be the most efficient hydrogen peroxide scavenger (SA HP of 3.27 × 10−3 μmol−1 L), followed by α-tocopherol (SA HP of 2.36 × 10−3 μmol−1 L) and quercetin (SA HP of 0.31 × 10−3 μmol−1 L). Although the method is inherently simple and rapid, excellent analytical performance is afforded in terms of sensitivity, dynamic range, and precision, with RSD values typically below 1.5%. We expect our microfluidic devices to be used for in-the-field antioxidant capacity screening of plant-sourced food and pharmaceutical supplements. Figure Assembled PDMS microchip sandwiched between two glass plates with the top plate containing capillary reservoirs  相似文献   

19.
The use of olaquindox (OLA) as an additive in animal feedstuffs has been prohibited in the European Union and many other countries. In this study, a highly sensitive and specific indirect competitive enzyme-linked immunosorbent assay (ELISA) for determination of OLA in animal feed samples was developed. OLA was activated by NN-carbonyldiimidazole and coupled with bovine serum albumin (BSA) and ovalbumin (OVA). It was found that the sensitivity and specificity of the two antisera were very similar, with the IC50 values of 16 ng mL−1 and 19 ng mL−1, respectively. Cross-reactivity was less than 35% for four structurally related compounds and no recognition of five other antibiotics was observed. The better antiserum I was selected for further experiments, for example testing stability, solvent effect, accuracy, and precision. The IC50 value for eight standard curves was in the range 12–18 ng mL−1 and the LOD at a signal-to-noise ratio of 3 (S/N = 3) was 0.31 ± 0.11 ng mL−1. The ELISA tolerated 5% methanol without significant influence on IC50 value. The recoveries of spiked OLA in five different animal feed types including auxin, pig complex feed, fish complex feed, broiler concentrated feed, and pig premix feed were in the range 88.3–119.0% and the intra-assay relative standard deviation (RSD) was within 4.7–33.5% (n = 3). The ELISA for unspiked feed samples was confirmed by high-performance liquid chromatography (HPLC), with a high correlation coefficient of 0.9862 (n = 5). The proposed ELISA could be a feasible quantitative/screening method for OLA analysis in feed samples with the properties of high sensitivity, specificity, simplicity of sample pretreatment, high sample throughput, and low expense. Figure Polyclonal antibody based ELISA for detection of olaquindox  相似文献   

20.
A novel fluorescence quenching method for the determination of cationic surfactants (CS), specifically cetyltrimethylammonium bromide (CTAB), dodecyltrimethylammonium bromide (DTAB), and cetylpyridinium chloride (CPC), has been developed using water-soluble luminescent CdTe quantum dots (QDs) modified with thioglycolic acid (TGA). The possible interference from heavy and transition metals (HTM) has been efficiently eliminated through simple sample treatment with mercapto cotton made in-house. Under optimum conditions, the extent of fluorescence quenching of CdTe QDs is linearly proportional to the concentration of CS from 2.0 × 10−7 to 7.0 × 10−6 mol L−1 with a detection limit of 5.0 × 10−8 mol L−1. The relative standard deviation for 1.0 × 10−6 mol L−1 CTAB is 2.5% (n = 6). The proposed method exhibits high sensitivity and selectivity and furthermore avoided the use of toxic organic solvents and tedious solvent extraction procedures. It has been applied to the determination of trace CS in natural river water and commodity samples with satisfactory results. Potential interference from heavy and transition metals is eliminated during photoluminescence detection of CS through simple sample pre-treatment with mercapto cotton  相似文献   

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