Identification and determination of phase II nabumetone metabolites by high-performance liquid chromatography with photodiode array and mass spectrometric detection

Chromatographic analyses play an important role in the identification and determination of phase I and phase II drug metabolites. While the chemical standards of phase I metabolites are usually available from commercial sources or by various synthetic, degradation or isolation methods, the phase II drug metabolites have usually more complicated structures, their standards are in general inaccessible and their identification and determination require a comprehensive analytical approach involving the use of xenobiochemical methods and the employment of hyphenated analytical techniques. In this work, various high-performance liquid chromatography (HPLC) methods were employed in the evaluation of xenobiochemical experiments leading to the identification and determination of phase II nabumetone metabolites. Optimal conditions for the quantitative enzymatic deconjugation of phase II metabolites were found for the samples of minipig bile, small intestine contents and urine. Comparative HPLC analyses of the samples of above-mentioned biomatrices and of the same biomatrices after their enzymatic treatment using beta-glucuronidase and arylsulfatase afforded the qualitative and quantitative information about phase II nabumetone metabolites. Hereby, three principal phase II nabumetone metabolites (ether glucuronides) were discovered in minipig's body fluids and their structures were confirmed using liquid chromatography (LC)-electrospray ionization mass spectrometric (MS) analyses.     

Practical aspects of splitless injection of semivolatile compounds in fast gas chromatography

Possibilities and practical aspects of implementation of splitless injection of larger volumes for fast GC purposes utilizing narrow-bore column, hydrogen as carrier gas, fast temperature programming under programmed flow conditions and commercial instrumentation were searched. As a model sample semivolatile compounds of a broad range of volatility and polarity (7 n-alkanes and 19 pesticides) were chosen. Peak shapes, peak broadening and peak areas and its repeatability were evaluated under various experimental set-ups (liner/injection technique combinations). Various factors, such as liner design, injection technique, retention gap length, compound volatility and polarity, the solvent used, initial oven temperature influenced compound focusation and/or maximal injection volume. Combination of analytical column (CP-Sil 13 CB 25 m long, 0.15 mm i.d., film thickness 0.4 microm) with normal-bore retention gap (1 m long, 0.32 mm i.d.) allowed maximal injection volume 8 microl for 4 mm i.d. liner used without any peak distortion when solvent recondensation in the retention gap was employed.     

Formation of two isomeric closo-[(eta5-C5H5)FePC2B8H10] phosphadicarbaborane analogues of ferrocene via isolable eta1-bonded complexes of the [7-[(eta5-C5H5)Fe(CO)2]-(eta1-nido-PC2B8H10)] type

The reaction of nido-[7,8,9-PC(2)B(8)H(11)] (1) with [[CpFe(CO)(2)](2)] (Cp=eta(5)-C(5)H(5) (-)) in benzene (reflux, 3 days) gave an eta(1)-bonded complex [7-Fp-(eta(1)-nido-7,8,9,-PC(2)B(8)H(10))] (2; Fp=CpFe(CO)(2); yield 38 %). A similar reaction at elevated temperatures (xylene, reflux 24 h) gave the isomeric complex [7-Fp-(eta(1)-nido-7,9,10-PC(2)B(8)H(10))] (3; yield 28 %) together with the fully sandwiched complexes [1-Cp-closo-1,2,4,5-FePC(2)B(8)H(10)] 4 a (yield 30%) and [1-Cp-closo-1,2,4,8-FePC(2)B(8)H(10)] 4 b (yield 5%). Compounds 2 and 3 are isolable intermediates along the full eta(5)-complexation pathway of the phosphadicarbaborane cage; their heating (xylene, reflux, 24 h) leads finally to the isolation of compounds 4 a (yields 46 and 52%, respectively) and 4 b (yields 4 and 5%, respectively). Moreover, compound 3 is isolated as a side product from the heating of 2 (yield 10%). The structure of compound 4 a was determined by an X-ray structural analysis and the constitution of all compounds is consistent with the results of mass spectrometry and IR spectroscopy. Multinuclear ((1)H, (11)B, (31)P, and (13)C), two-dimensional [(11)B-(11)B]-COSY, and (1)H[(11)B(selective)] magnetic resonance measurements led to complete assignments of all resonances and are in excellent agreement with the structures proposed.     

Physicochemical characterization of phosphinic pseudopeptides by capillary zone electrophoresis in highly acidic background electrolytes

Phosphinic pseudopeptides (i.e., peptide isosteres with one peptide bond replaced by a phosphinic acid moiety) were analyzed and physicochemically characterized by capillary zone electrophoresis in the pH range of 1.1-3.2, employing phosphoric, phosphinic, oxalic and dichloroacetic acids as background electrolyte (BGE) constituents. The acid dissociation constant (pK(a)) of phosphinate group in phosphinic pseudopeptides and ionic mobilities of these analytes were determined from the pH dependence of their effective electrophoretic mobilities corrected to standard temperature and constant ionic strength of the BGEs. It was shown that these corrections are necessary whenever precise mobility data at very low pH are to be determined. Additionally, it was found that the ionic mobilities of the phosphinic pseudopeptides and pK(a) of their phosphinate group are affected by the BGE constituent used. The variability of migration behavior of the pseudopeptides can be attributed to their ion-pairing formation with the BGE components.     

A two-step supercritical fluid extraction of polycyclic aromatic hydrocarbons from roadside soil samples

A two-step procedure for the supercritical fluid extraction (SFE) of polycyclic aromatic hydrocarbons from soil samples was developed. The procedure consists of a static supercritical fluid treatment in a closed extraction cell at a high temperature (T=250 or 340degreesC for 20 min) and an SFE with a solvent trapping. During the static phase, the sample is exposed to a supercritical organic solvent (methanol, toluene, dichloromethane, ACN, acetone, and hexane). The solvent penetrates particles of the matrix to substitute strongly bonded molecules and dissolves the analytes in the supercritical phase. At ambient temperature, supercritical fluids became liquid and lost their solvation abilities. Most of the analytes condense on the surface of the particles or on the extraction cell walls without forming strong bonds or penetrating deep into the matrix. Thus, the pretreatment liberates the analytes and they behave similar to those in freshly spiked samples. The common SFE with toluene-modified CO2 as an extraction fluid follows the static phase. With the use of the most suitable extraction phases (toluene, ACN), the extraction efficiency of the combined procedure is much higher (approximately100%). The results of the combined procedure are compared to the SFE procedure of the same untreated sample (difference less than 5%) and to the Soxhlet extraction. The extracts were analyzed using a GC with the flame ionization detection.     

Reactions of 3-formylchromone with active methylene and methyl compounds and some subsequent reactions of the resulting condensation products

This review presents a survey of the condensations of 3-formylchromone with various active methylene and methyl compounds, e.g. malonic or barbituric acid derivatives, five-membered heterocycles, etc. The utilisation of the condensation products for the synthesis of different heterocyclic systems, which is based on the ability of the gamma-pyrone ring to be opened by the nucleophilic attack is also reviewed. Finally, the applications of microwave irradiation as an unconventional method of reaction activation in the synthesis of condensation products is described and the biological activity of some chromone derivatives is noted.     

Particle and surface characterization of a natural illite and study of its copper retention

Illite clays are known to have a strong affinity for metallic pollutants in the environment and can be applied as low-cost adsorbents for industrial waste treatment. A crucial factor in the development of such applications, however, is the understanding of the chemical, mineralogical, and colloidal properties of these clays. It is also important to understand the mechanisms involved in the surface adsorption of metals by these adsorbants. In order to study the retention of transition metals on illite clays, we have applied surface characterization techniques such as FPIA, SEM-EDX, XRD, N2 (77 K) adsorption, and FTIR. In addition to these experimental techniques, we have also employed a theoretical model that accounts for the chemistry of transition metal ions, and considers the global retention process to be the sum of several single retention processes. This model adequately fits the experimental data and allows for the speciation of metal retention on illite surfaces. Between pH values of 2.53 and 3.01 the only adsorption processes are the electrostatic sorption of [Cu(H2O)6]2+, and the surface complexation of [Cu(H2O)6]2+ and [Cu(OH)(H2O)5]+ ions. Surface complexation of [Cu(OH)(H2O)5]+ ions increases with pH, overcoming [Cu(H2O)6]2+ retention, and thus contributing to the surface precipitation of Cu(OH)2.     

Validation of a method for determination of phospholipase A2 and melittin in bee venom preparations by capillary electrophoresis

A method was validated for the determination of the 2 main components of bee venom, phospholipase A2 and melittin, by capillary electrophesis (CE). Optimum resolution and selectivity were attained with a running electrolyte of 150 mM phosphoric acid, pH 1.8. The repeatability and day-to-day reproducibility of the migration times were better than 0.36 and 2.8%, respectively. The repeatability and day-to-day reproducibility of the normalized peak areas were better than 1.3 and 2.6%, respectively. The response of the UV detector at 190 nm was linear over < 2 concentration decades, from 0.05 to 1.5 mg/mL, with correlation coefficients of 0.9994 for phospholipase A2 and 0.9997 for melittin. The limits of detection and quantitation were 4.5 and 15 microg/mL, respectively, for phospholipase A2 and 1.6 and 6 microg/mL, respectively, for melittin. The reproducibility of the measurements with 2 different CE instruments was satisfactory; the mean concentration and relative standard deviation (RSD) values for phospholipase A2 and melittin were 14.4% (RSD, 1.3%) and 51.4% (RSD, 1.1%), respectively, with instrument I; the corresponding values with instrument II were 14.5% (RSD, 2.8%) and 52.3% (RSD, 2.2%). The accuracy was estimated by comparison with a liquid chromatographic (LC) method. Differences between the CE and LC measurements were attributed to irreversible adsorption of the analytes on the LC column. The recoveries of phospholipase A2 and melittin with the CE method were 98.8 and 101.7%, respectively.     

Motion planning and actuator specialization in the control of active-flexible link robots

Trajectory planning is a well-known open-loop control strategy to minimize residual vibrations in point-to-point tasks of systems featuring mechanical flexibility. However, the major drawback of open-loop control is its limitation in coping with modeling uncertainty. In this paper a novel approach to trajectory planning based on LQR theory is proposed and applied to a single flexible link robot. To improve performance under parameter uncertainty the strategy is combined with collocated vibration control through piezoelectric actuation of the link. This combination raises the issue of the roles and the contribution of each actuator type to the overall performance of the maneuver. An actuator specialization is proposed where the joint controller is responsible for the gross vibrationless motion of the link, while the link actuators are expected to deal only with residual vibrations that may arise from modeling errors. Simulation and experimental results validate the trajectory planning methodology and the combination of the open-loop strategy with collocated vibration control.     

Electrochemical characterization of core@shell CoFe2O4/Au composite

Quantum dots (QDs) have received considerable attention due to their unique optical and electrical properties. Although substantial research has focused on the potential applications and toxicological impacts of QDs, far less effort has been directed toward understanding their fate and transport in the environment. In this work, the effect of four coatings, polyethylene glycol functionalized polymer (PEGP), carboxyl derivatized polymer (COOHP), linoleic acid (LA), and polyacrylic acid-octylamine (PAA-OA), on the transport and retention of QDs in porous media were evaluated under environmentally relevant conditions. Aqueous QD suspensions (ca. 10 nM) were introduced into water-saturated columns packed with 40–50 mesh Ottawa sand at a pore-water velocity of 7.6 m/day. At an ionic strength (IS) of 3 mM and pH of 7, PEGP-coated QDs were completely retained within the column, while more than 60 % of COOHP-coated QDs were transported through a column run under identical conditions. When PAA-OA and LA were used as coatings, effluent QD recoveries increased to more than 65 and 89 % of the injected mass, respectively. Additionally, a decrease in pH from 9.5 to 5.0, or an increase of IS from 0 to 30 mM reduced the eluted mass of PAA-OA-coated QDs by more than 2 and 15 times, respectively. The relative mobility of coated QDs (LA > PAA-OA > COOHP > PEGP) was consistent with total interaction energy profiles between QDs and sand surfaces calculated based on Derjaguin–Landau–Verwey–Overbeek (DLVO) theory. At an IS of 3 mM (NaCl) and pH 7, a linear correlation was obtained between the fraction of eluted QDs and the magnitude of the primary interaction energy barrier. These findings demonstrate the strong dependence of QD transport on coating type and indicate that interaction energies based on DLVO theory can be used to predict the relative mobility of QDs in porous media.