Diastereoselective synthesis of cularine alkaloids via enium ions and an easy entry to isoquinolines by aza-Wittig electrocyclic ring closure

In preliminary communications, we reported the diastereoselective synthesis of cularine and sarcocapnine via the intramolecular ring closure of nitrenium and oxenium ions, a new highly diastereoselective reductive methylation with (+)-8-phenylmenthyl chloroacetate followed by reduction with sodium borohydride, and a facile entry to the isoquinoline precursors by aza-Wittig electrocyclic ring closure. We now report the full details of the syntheses of (+)-O-demethylcularine, (+)-cularine, (+)-sarcocapnidine, (+)-sarcocapnine, and (+)-crassifoline and describe different methods of synthesis of their precursors.     

Sol-gel ZrO2 coatings for chemical protection of stainless steel

ZrO₂ coatings deposited on 316 L stainless steel sheets were synthesized by sol-gel method using Zr(OC₃H₇)₄ as precursor and isopropanol, glacial acetic acid, and water as solvents for application with ultrasounds. Different solutions for dip-coating were prepared with compositions varying between 0.025 and 0.9 mol/dm³ of ZrO₂. X-ray diffraction shows that the films densified at 800°C are crystalline with a tetragonal structure. The thickness of the coatings varied from 0.35–0.75 m. The influence of the ZrO₂ coatings on the corrosion behavior of stainless steel substrates in aqueous NaCl was studied through potentiodynamic polarization curves at 1 mV/s. The values of the electrochemical parameters allow for an explanation of the role of the films in the increased resistance of steel against corrosion in moderately aggressive environments.     

Copper determination in biological materials by ETAAS using W-Rh permanent modifier

A tungsten-rhodium treatment on the integrated platform of a transversely heated graphite atomiser was used as a permanent chemical modifier for the determination of copper in biological materials by using digested samples as well as slurry sampling in electrothermal atomic absorption spectrometry. The W-Rh permanent modifier was as efficient as Pd+Mg(NO(3))(2) conventional modifier for obtaining good Cu thermal stabilisation in the digested and slurry samples. The permanent W-Rh modifier remained stable by approximately 300 and 250 firings when 20 mul of digested sample and 20 mul of slurry were delivered into the atomiser, respectively. In addition, the permanent modifier increased the tube lifetime up to 1370 and 744 analytical measurements in the digested and slurry samples, respectively. Also, when the W-Rh permanent modifier was employed, there was less variation of the slope of the analytical curves during the total atomiser lifetime, resulting in a decreased need of re-calibration during routine analysis, increasing the sample throughput, and consequently diminishing the variable analytical costs. Detection limits obtained with W-Rh permanent modifier were 0.64 and 0.33 mug g(-1) Cu for digested (dilution factor 100 ml g(-1)) and 1.0% m/v slurries of biological materials, respectively. Results for the determination of copper in the samples were in agreement with those obtained with decomposed sample solutions by using Pd+Mg(NO(3)), since no statistical differences were found after applying the paired t-test at the 95% level.     

Penetration and interactions of the antimicrobial peptide, microcin J25, into uncharged phospholipid monolayers

Microcin J25 forms stable monolayers at the air-water interface showing a collapse at a surface pressure of 5 mN/m, 220 mV of surface potential, and 6 fV per squared centimeter of surface potential per unit of molecular surface density. The adsorption of microcin J25 from the subphase at clean interfaces leads to a rise of 10 mN/m in surface pressure and a surface potential of 220 mV. From these data microcin appears to be a poor surfactant per se. Nevertheless, the interaction with the lipid monolayer further increase the stability of the peptide at the interface depending on the mode in which the monolayer is formed. Spreading with egg PC leads to nonideal mixing up to 7 mN/m, with hyperpolarization and expansion of components at the interface, with a small excess free energy of mixing caused by favorable contributions to entropy due to molecular area expansion compensating for the unfavorable enthalpy changes arising from repulsive dipolar interactions. Above 7 mN/m microcin is squeezed out, leaving a film of pure phospholipid. Nevertheless, the presence of lipid at 10 and 20 mN/m stabilize further microcin at the interface and adsorption from the subphase proceeds up to 30 mN/m, equivalent to surface pressure in bilayers.     

Oxidation of Methanol on Pt,Pt–Ru,and Pt–Ru–Mo Electrocatalysts Dispersed in Polyaniline: An in situ Infrared Reflectance Spectroscopy Study

The electrochemical oxidation of methanol was investigated on a Pt–Ru–Mo catalyst with an in situ infrared reflectance spectroscopy. The electrocatalysts were prepared by an electrochemical deposition and dispersed in a conducting three-dimensional matrix of polyaniline (PAni). We observed that CO₂ is produced from methanol oxidation at 350 mV vs. RHE on PAni/Pt–Ru–Mo, which is 100 mV less negative than on PAni/Pt–Ru and 200 mV less than on PAni/Pt. The results suggest that Pt–Ru–Mo is less sensitive to CO_ADS poisoning than Pt–Ru and much more sensitive than Pt. Large differences are observed concerning the average wavenumber of _ADS between Pt–Ru–Mo, Pt–Ru, and Pt.     

Determination of arsenic compounds in beverages by high-performance liquid chromatography-inductively coupled plasma mass spectrometry

Arsenic compounds including arsenous acid (As(III)), arsenic acid (As(V)), dimethylarsinic acid (DMA) and monomethylarsonic acid (MMA) were separated by high-performance liquid chromatography (HPLC) and detected by inductively coupled plasma mass spectrometry (ICP-MS). A Hamilton PRX-100 anionic-exchange column and a pH 8.5 K₂HPO₄/KH₂PO₄ 5.0 × 10⁻³ mol L⁻¹ mobile phase were used to achieve arsenic speciation. The separation of arsenic species provided peaks of As(III) at 2.75 min, DMA at 3.33 min, MMA at 5.17 min and As(V) at 12.5 min. The detection limits, defined as three times the standard deviation of the lowest standard measurements, were found to be 0.2, 0.2, 0.3 and 0.5 ng mL⁻¹ for As(III), DMA, MMA and As(V), respectively. The relative standard deviation values for a solution containing 5.0 μg L⁻¹ of As(III), DMA, MMA and As(V) were 1.2, 2.1, 2.5 and 3.0%, respectively. This analytical procedure was applied to the speciation of arsenic compounds in drinking (soft drink, beer, juice) samples. The validation of the procedure was achieved through the analysis of arsenic compounds in water and sediment certified reference materials.     

Performance of a sound card as data acquisition system and a lock-in emulated by software in capillary electrophoresis

The performance of fluorescence detectors in capillary electrophoresis is maximized when the excitation light intensity is modulated in time with optimal frequencies. This is especially true when photomultiplier tubes are used to detect the fluorescent light. The photomultiplier tube amplified raw output signal can in principle be captured directly by a personal computer sound card (PCSC) and processed by a lock-in emulated by software. This possibility is demonstrated in the present work and the performance of this new setup is compared with a traditional data acquisition system. The results obtained with this “PCSC and lock-in emulated by software” were of the same quality or even better compared to that obtained by conventional time integrators (Boxcars) and data acquisition boards. With PCSC the limits of detection (LOD) found for both naphthalene-2,3-dicarboxaldehyde-derivatized tyrosine and alanine were 3.3 and 3.5 fmol (injection of 5 nL of samples at 0.66 and 0.70 μmol/L), respectively. This is at least three times better compared to conventional systems when light emitting diodes (LEDs) are used as the excitation source in fluorescence detectors. The PCSC linear response range was also larger compared to conventional data acquisition boards. This scheme showed to be a practical and convenient alternative of data acquisition and signal processing for detection systems used in capillary electrophoresis.     

Development of a rapid and specific assay for detection of busulfan in human plasma by high-performance liquid chromatography/electrospray ionization tandem mass spectrometry

A sensitive and specific assay for detection of busulfan in human plasma was developed. The assay is based on rapid isolation of busulfan by liquid-liquid extraction with ethyl acetate, and detection by high-performance liquid chromatography with electrospray ionization and tandem mass spectrometry. 1,6-Bis(methanesulfonyloxy)hexane, a synthesized analogue of busulfan, was used as the internal standard (IS). The acquisition was performed in the multiple reaction monitoring mode; busulfan and the IS were detected with no interferences from plasma matrix. The method was linear over the range 5-2500 ng mL(-1), with r2 > 0.99 and a run time of only 3.5 min. The intra- and inter-assay precisions were in the ranges 2.1-11.9% and 3.2-10.1%, respectively, and the intra- and inter-assay accuracies were 92.2-107.6% and 94.7-104.1%, respectively. The absolute recoveries were 82.0% (20 ng mL(-1)), 90.6% (1000 ng mL(-1)) and 80.0% (2000 ng mL(-1)) for busulfan, and 89.1% for the IS (1000 ng mL(-1)). The limits of detection and quantification were 2 and 5 ng mL(-1), respectively. The validated method was successfully applied to analyze plasma samples obtained from six adults receiving doses of 1 mg kg(-1) in a conditioning regimen prior to bone marrow transplantation. A marked intra-patient variation in busulfan concentrations during the steady state was observed, which limits the application of pharmacokinetic modeling and suggests that continuous therapeutic monitoring is necessary for adequate individualized dosing. In this regard, the present assay brings important advantages relative to other methods described in the literature, i.e., it is highly specific and simple to perform, with a rapid chromatographic run time (3.5 min), and the whole procedure can be completed in 4-5 h, which would permit dose corrections after the third dose allowing earlier and better dosing adjustments towards the target level of busulfan.     

Counterions in poly(allylamine hydrochloride) and poly(styrene sulfonate) layer-by-layer films

The amount of counterions in layer-by-layer (LBL) films of poly(allylamine hydrochloride) (PAH) and poly(styrene sulfonate) (PSS) has been determined with X-ray photoelectron spectroscopy (XPS) for films prepared from solutions with various NaCl concentrations. Sodium and chloride counterions are present in LBL films produced from salt solutions, which are located at the surface and in the bulk of the films. The percentage of bulk counterions increases with the ionic strength of the polyelectrolyte before reaching a constant value. The bulk sodium/sulfur percentage ratios tend to 0.8 for samples washed with pure water and for samples washed with NaCl aqueous solutions, while the bulk chlorine/nitrogen percentage ratios tend to 0.5 for the same samples. The ratio between the percentages of polyelectrolyte ionic groups lies close to unity for all samples, indicating that counterions do not contribute to charge compensation in the polyelectrolyte during the adsorption process. The presence of counterions in LBL films is explained by Manning condensation near the polyelectrolyte ionic groups, leading to inter-polyelectrolyte ionic bondings via ionic networks. It is believed that condensation leads to the formation of NaCl crystallites in these LBL films, which was confirmed by X-ray diffraction measurements.