New coating materials for hydrocarbon discrimination using a multisensor system and gas chromatography

Cobalt(II), nickel(II), and copper(II) stearates, their complexes with octadecylamine, and carbon nanotubes were used as coatings on chemical piezoquartz sensors for hydrocarbon vapors. The rapid and reliable identification of hydrocarbons and other volatile compounds is possible by combining an electric nose flow cell with eight piezoquartz sensors and an LKhM-80 gas chromatograph equipped with a short column (nose-chrom device). __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 41, No. 6, pp. 371–375, November–December, 2005.     

Miniaturized Verapamil Soild-State Potentiometric Sensors Based on Native Ionic Polymers

 Novel miniaturized carboxylated poly(vinyl chloride) and poly fluoro sulfonate (Nafion) matrix membrane sensors in an all-solid state graphite support were developed, electrochemically evaluated and used for the assay of verapamil drug. These sensors incorporate the native polymers without plasticizer and/or drug-ion pair complex. Upon soaking these sensors in verapamil test solution, electroactive self regenerated membranes are formed and a near-Nernstian potentiometric response is induced for verapamil over the concentration range 1×10⁻²–1×10⁻⁵ M with a cationic slope of 56–57 mV decade⁻¹ of concentration. Inherent advantages of these sensors include fast response (<10 s), long life time (>6 months), good thermal stability (up to 60 °C), high sensitivity (down to 1 μg ml⁻¹), extended working pH range (2–8) and reasonable selectivity. Verapamil could be determined in various dosage forms with an average recovery of 98.8% (st.dev. 0.8%) of the nominal concentration without any significant interferences from various excipients and diluents commonly used in drug formulations. Received August 17, 1998. Revision February 9, 1999.     

Changes of the Cu electrode real surface area during the process of electroless copper plating

The surface area (nanoscale roughness) of copper coatings deposited from electroless plating solutions containing Quadrol, L(+)- and DL(∓)-tartrate as Cu(II) ion ligands was measured using underpotential deposition thallium monolayer formation. Surface roughness of Cu coatings depends on the plating solution pH and the Cu(II) ligand, and varies over a wide range. In L(+)-tartrate and Quadrol solutions (pH 12.5–13.3) the roughness factor R _f is low and is equal to 2–3 and 4–6, respectively (substrate: electrodeposited Cu; R _f=2.2). Cu coatings of higher surface area are obtained in DL(∓)-tartrate (pH 12.3–12.7) and Quadrol (pH 12.0) solutions: R _f reaches 20–30. The correlation between R _f and Cu deposition rate was found in L(+)-tartrate solution. The Cu surface area changes are discussed in terms of partial electrochemical reactions of the autocatalytic Cu deposition process, and the decisive role of cathodic Cu(II) reduction from adsorbed Cu(II) complex species. Received: 2 November 1999 / Accepted: 22 February 2000     

Materials for capacitive carbon dioxide microsensors capable of operating at ambient temperatures

The responses of alkylamine functionalized organic bridged polysilsesquioxanes on chemicapacitive sensors to carbon dioxide (CO₂) are described operating at temperatures ranging from 15 to 50°C. These hybrid organic–inorganic network materials were synthesized by the sol–gel polymerization of a mixture of a matrix monomer and functional monomer at various ratios followed by aging and ink-jet deposition of the sol on each capacitive sensor. During exposure of the sensor to known concentrations of analyte, the material’s capacitance was measured. From these changes in capacitance, detection limits ranging from 40 to 100 ppm were calculated. Furthermore, a correlation was observed with increasing length of the alkyl chain in the amine monomer correlating with an increase in CO₂ sensitivity and a decrease in water sensitivity. These materials offer a new method for CO₂ detection for building control systems or other low-power applications using low operating temperatures.     

Capillary-electrophoretic determination of zinc and cadmium ions in aqueous solutions with ion-exchange preconcentration

An approach to choosing analyte preconcentration conditions for the subsequent capillary electrophoresis (CE) analysis of the concentrate was substantiated using the simultaneous determination of zinc(II) and cadmium(II) trace concentrations as an example. A CE procedure was developed for the determination of Zn and Cd with the following characteristics: The time of the analysis, including analyte preconcentration from a 50-mL sample, was 30 min. The analytical ranges were 0.01–0.2 mg/L for cadmium(II) and 0.005–0.1 mg/L for zinc(II).     

On the relationships between molecular conformations and intermolecular contacts toward crystal self-assembly of mono-, di-, tri-, and tetra-oxygenated xanthone derivatives

Oxygenated xanthones have been extensively investigated over the years, but there are few reports concerning their crystal structure. Our chemical investigations of Brazilian plants resulted in the isolation of four natural products named 1-hydroxyxanthone (I), 1-hydroxy-7-methoxyxanthone (II), 1,5-dihydroxy-3-methoxyxanthone (III), and 1,7-dihydroxy-3,8-dimethoxyxanthone (IV). The structures of these compounds were established on the basis of single crystal X-ray diffraction. The xanthone nucleus conformation is essentially planar with the substituents adopting the orientations less sterically hindered. In addition, classical intermolecular hydrogen bonds (O–H···O) present in III and IV give rise to infinite ribbons. However, the xanthone I does not present any intermolecular hydrogen bonds, meanwhile the xanthone II presents only a non-classical one (C–H···O). The crystal packing of all xanthone structures is also stabilized by π–π interactions. The fingerprint plots, derived from the Hirshfeld surfaces, exhibited significant features of each crystal structures.     

Novel sol–gel reversible thermochromic materials for environmental sensors

Anhydrous cobalt(II) chloride has been encapsulated in several inorganic sol–gel matrices with different solvent/water ratios. Sols were cast into cuvettes and hermetically closed. Such sol–gel materials were found to be sensitive to temperature in the 10–50 °C range showing a change of colour. General characterisation of the sensitive materials was made by immersion into a thermostatic water bath and recording of the corresponding visible spectra. The optical response consisted of a change in colour from light pink to deep blue as the temperature increases. These temperature detectors behave as sensors showing good optical sensitivity in the range mentioned above and reversibility for more than 30 cycles. The sensors response time is at about 15 min and their lifetime is 2 months at least. These sol–gel materials have been designed to be applied for preservation and conservation purposes. High temperatures and cyclical temperature changes can yield severe consequences for the correct preservation of cultural heritage materials (textiles, archaeological ceramics and other remains, metallic objects and statues, stained glass windows, etc.) both in museums and outdoors.     

Potentiometric Determination of Menadione (Vitamin K3)

 The construction and electrochemical response characteristics of poly(vinyl) chloride matrix membrane sensors for menadione (vitamin K₃) are described. Membranes incorporating the ion association complexes of menadione anion with bathophenanthroline nickel(II) and iron(II) as electroactive materials show linear response for menadione over the range 10⁻¹–10⁻⁵ M with anionic slopes of 58.2–51.4 mV per concentration decade. Both sensors exhibit fast response time (20–30 s), low detection limit (2 × 10⁻⁵ M), good stability (4–6 weeks) and selectivity coefficient (10⁻¹–10⁻³). Direct potentiometric determination of menadione under static and hydrodynamic mode of operations shows average accuracies of 98.8 and 98.5% with relative standard deviations of 0.6% and 1.3%, respectively. Application of the method for the determination of menadione in human plasma gives favourable results compared with those obtained by the standard spectrophotometric method. Received February 26, 2001. Revision October 1, 2001.     

Investigation of the interaction between Co sulfide coatings and Cu(I) ions by cyclic voltammetry and XPS

The interaction between the Co sulfide coating formed on a glassy carbon electrode and Cu(I)-ammonia complexes solution was investigated by cyclic voltammetry in 0.1 M KClO₄, 0.1 M NaOH and 0.05 M H₂SO₄ solutions. It was determined that, after treating the cobalt sulfide coating formed by two deposition cycles with Cu(I)-ammonia complexes (0.4 M, pH 8.8–9.0, τ=180 s, T=25±1°C), an exchange occurs between the coating components and Cu(I). Copper(I) substitutes 75% of the Co(III) compounds present in the coating (~1.81×10^–7 mol cm^–2) because of Cu₂O (1.36×10^–7 mol cm^–2) formation. The rest of the Co(II) and Co(III) sulfide compounds are also replaced by copper with formation of Cu_{2– x} S with a stoichiometric coefficient close to 2 (~1.9). After modifying the cobalt sulfide coatings with Cu(I) ions, the total amount of metal (Co+Cu) increases, owing to the sorption of Cu(I) compounds. In addition, the number of deposition cycles decreases from 3 to 1.5 [1 cycle involves cobalt sulfide layer formation and 0.5 cycle is attributed to modifying by Cu(I) ions]. The coatings modified in the above-mentioned manner may be successfully used for plastic electrochemical metallization as Cu_{2– x} S coatings formed by three deposition cycles. Electronic Publication     

Extraction-photometric determination of <Emphasis Type="Italic">N</Emphasis>′,<Emphasis Type="Italic">N</Emphasis>′-dialkylbenzhydrazides as its complexes with copper

A procedure for extraction-photometric determination of N′,N′-dialkylbenzhydrazides has been proposed; the procedure is based on the formation of its colored complex with copper (II) followed by extraction with p-xylene and absorbance measurements at 460 nm (0.1–0.4 mmol of analyte in the sample) or at 330 nm (0.005–0.025 mmol of analyte in the sample).     

Adsorption of Cu(II), Cd(II), Pb(II), Cr(VI) by double hydroxides on the basis of Al oxide and Zr, Sn, and Ti oxides

It was studied the equilibrium adsorption and adsorption kinetics of Cu(II), Cd(II), Pb(II), and Cr(VI) by composite hydroxides formed by Me _x O _y · nH₂O and Me_0.4–0.7Al_0.6–0.3O _y · nH₂O, where Me = Zr, Sn and Ti. It was estimated the values of the diffusion coefficients of adsorbed ions Cu(II) and Cr(VI) from kinetic values. It was established that the estimated diffusion coefficients of adsorbed ions Cu(II) are in the range 0.4 × 10⁻¹²–2.5 × 10⁻¹² m²/s for individual hydroxides and 1.2 × 10⁻¹²–2.8 × 10⁻¹² m²/s for double hydroxides. The obtained values of diffusion coefficients Cr (VI) for double hydroxides are 0.1 × 10⁻¹⁰–0.4 × 10⁻¹⁰ m²/s.     

Capillary gas chromatography of metal chelates of diethyl dithiocarbamates

Summary Capillary GC of metal chelates of diethyl dithiocarbamate (DDTC) was examined on a methylsilicone DB-1 column, (25 meter, 0.2 mm. i.d) with a film thickness of 0.25 μm. Elution was carried out at the initial column temperature of 180°C and programmed at 5°C min⁻¹ to 260°C. Detection was by FID or ECD. Symmetrical peaks with base line separation were obtained with the metal chelates of copper(II), nickel(II), cobalt(III), manganese(II) and chromium(III). The ECD gave better sensitivity than the FID with a linear calibration range of 5–50 μg mL⁻¹ and detection limits 2.0–6.0 μg mL⁻¹, corresponding to 111–333 pg of metal ion reaching the detector. The method was applied to the determination of metal ions in water and pharmaceutical preparations with a coefficient of variation (CV) within 4.0%. When compared with a standard flame AAS method the results revealed no significant difference.     

Integration of spore-based genetically engineered whole-cell sensing systems into portable centrifugal microfluidic platforms

Bacterial whole-cell biosensing systems provide important information about the bioavailable amount of target analytes. They are characterized by high sensitivity and specificity/selectivity along with rapid response times and amenability to miniaturization as well as high-throughput analysis. Accordingly, they have been employed in various environmental and clinical applications. The use of spore-based sensing systems offers the unique advantage of long-term preservation of the sensing cells by taking advantage of the environmental resistance and ruggedness of bacterial spores. In this work, we have incorporated spore-based whole-cell sensing systems into centrifugal compact disk (CD) microfluidic platforms in order to develop a portable sensing system, which should enable the use of these hardy sensors for fast on-field analysis of compounds of interest. For that, we have employed two spore-based sensing systems for the detection of arsenite and zinc, respectively, and evaluated their analytical performance in the miniaturized microfluidic format. Furthermore, we have tested environmental and clinical samples on the CD microfluidic platforms using the spore-based sensors. Germination of spores and quantitative response to the analyte could be obtained in 2.5–3 h, depending on the sensing system, with detection limits of 1 × 10⁻⁷ M for arsenite and 1 × 10⁻⁶ M for zinc in both serum and fresh water samples. Incorporation of spore-based whole-cell biosensing systems on microfluidic platforms enabled the rapid and sensitive detection of the analytes and is expected to facilitate the on-site use of such sensing systems.     

Aqueous Equilibrium and Solution Structural Studies of the Interaction of N,N′-bis(4-imidazolymethyl)etylenediamine with Ca(II), Cd(II), Co(II), Cu(II), Mg(II), Mn(II), Ni(II), Pb(II) and Zn(II) Metal Ions

Divalent metal complexes of N,N′-bis(4-imidazolymethyl)etylenediamine (EMI) have been studied using potentiometric and spectroscopic techniques (UV-Vis and NMR methods) in aqueous 0.1 mol⋅L⁻¹ KCl supporting electrolyte at 25 °C. Final models and overall stability constants for the complexes of Ca(II), Cd(II), Co(II), Cu(II), Mg(II), Mn(II), Ni(II), Pb(II) and Zn(II) have been established by potentiometry for all M(II)–EMI systems, except for Co(II)–EMI. The data revealed that EMI forms ML complexes with all M(II)–EMI systems, which is the dominant species over a wide range of pH except for the Ca(II)–EMI and Mg(II)–EMI systems. Formation of the MnHL complex was also found for Mn(II)–EMI solutions. In addition, the UV-Vis and ¹H NMR results allowed us establish the coordination modes for the metal complexes between EMI with Cd(II), Cu(II), Ni(II) and Zn(II).     

Host-molecule-coated quantum dots as fluorescent sensors

“Host” molecules, containing a binding site that is highly specific for an analyte “guest,” are used as sensors to register analyte binding through a variety of mechanisms such as colorimetric, fluorescent, or electrochemical signals. There is increasing interest in the host–guest chemistry on the surface of quantum dots (QDs) and in the changes that it produces in the luminescent properties of QDs. The bulk of this study focuses on those QDs with bound host molecules (crown ether, cyclodextrin, calixarene, and porphyrin) and the selectivity they display toward metal ions and small organic molecules.     

Complexes of Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) with 4-chloro-2-methoxybenzoic acid anion

The complexes of 4-chloro-2-methoxybenzoic acid anion with Mn²⁺, Co²⁺, Ni²⁺, Cu²⁺ and Zn²⁺ were obtained as polycrystalline solids with general formula M(C₈H₆ClO₃)₂·nH₂O and colours typical for M(II) ions (Mn – slightly pink, Co – pink, Ni – slightly green, Cu – turquoise and Zn – white). The results of elemental, thermal and spectral analyses suggest that compounds of Mn(II), Cu(II) and Zn(II) are tetrahydrates whereas those of Co(II) and Ni(II) are pentahydrates. The carboxylate groups in these complexes are monodentate. The hydrates of 4-chloro-2-methoxybenzoates of Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) heated in air to 1273 K are dehydrated in one step in the range of 323–411 K and form anhydrous salts which next in the range of 433–1212 K are decomposed to the following oxides: Mn₃O₄, CoO, NiO and ZnO. The final products of decomposition of Cu(II) complex are CuO and Cu. The solubility value in water at 293 K for all complexes is in the order of 10^–3 mol dm^–3. The plots of χ_M vs. temperature of 4-chloro-2-methoxybenzoates of Mn(II), Co(II), Ni(II) and Cu(II) follow the Curie–Weiss law. The magnetic moment values of Mn²⁺, Co²⁺, Ni²⁺ and Cu²⁺ ions in these complexes were determined in the range of 76−303 K and they change from: 5.88–6.04 μ_B for Mn(C₈H₆ClO₃)₂·4H₂O, 3.96–4.75 μ_B for Co(C₈H₆ClO₃)₂·5H₂O, 2.32–3.02 μ_B for Ni(C₈H₆ClO₃)₂·5H₂O and 1.77–1.94 μ_B for Cu(C₈H₆ClO₃)₂·4H₂O.     

Thermal, spectral and magnetic behaviour of 2,3,4-trimethoxybenzoates of Mn(II), Co(II), Ni(II) AND Cu(II)

Four new complexes of 2,3,4-trimethoxybenzoic acid anion with manganese(II), cobalt(II), nickel(II) and copper(II) cations were synthesized, analysed and characterized by standard chemical and physical methods. 2,3,4-Trimethoxybenzoates of Mn(II), Co(II), Ni(II) and Cu(II) are polycrystalline compounds with colours typical for M(II) ions. The carboxylate group in the anhydrous complexes of Mn(II), Co(II) and Ni(II) is monodentate and in that of Cu(II) monohydrate is bidentate bridging one. The anhydrous complexes of Mn(II), Co(II) and Ni(II) heated in air to 1273 K are stable up to 505–517 K. Next in the range of 505–1205 K they decompose to the following oxides: Mn₃O₄, CoO, NiO. The complex of Cu(II) is stable up to 390 K, and next in the range of 390–443 K it loses one molecule of water. The final product of its decomposition is CuO. The solubility in water at 293 K is of the order of 10^–3 mol dm^–3 for the Mn(II) complex and 10^–4 mol dm^–3 for Co(II), Ni(II) and Cu(II) complexes. The magnetic moment values of Mn²⁺, Co²⁺, Ni²⁺ and Cu²⁺ ions in 2,3,4-trimethoxybenzoates experimentally determined in the range of 77–300 K change from 5.64–6.57 μB (for Mn²⁺), 4.73–5.17 μB (for Co²⁺), 3.26–3.35 μB (for Ni²⁺) and 0.27–1.42 μB (for Cu²⁺). 2,3,4-Trimethoxybenzoates of Mn(II), Co(II) and Ni(II) follow the Curie–Weiss law, whereas that of Cu(II) forms a dimer.     

Phytoestrogen biomonitoring: an extractionless LC-MS/MS method for measuring urinary isoflavones and lignans by use of atmospheric pressure photoionization (APPI)

We present here a high-performance liquid chromatography−tandem mass spectrometry (LC-MS/MS) method for quantifying phytoestrogenic isoflavones (daidzein, equol, genistein, and O-desmethylangolensin) and lignans (enterodiol and enterolactone) in urine without the use of extraction or the preconcentration techniques inherent in existing methods. The development of this concept was made possible by use of atmospheric pressure photoionization (APPI); an ionization technique that we found to improve analyte sensitivity relative to electrospray ionization and atmospheric pressure chemical ionization for this particular group of compounds. The analytical performance of this method was equal to or exceeded that of comparable methods. Between-run coefficients of variation (CVs) across three quality control (QC) pool levels analyzed in duplicate over 20 days were 3.1–5.8% CV; within-run CVs were 2.3–6.0%. Accuracy, as determined by average spike recovery in QC pools, was generally within ±10% of being quantitative (100%). Relative limits of detection were 0.04–0.4 ng/mL urine, with absolute detection limits as low as 0.1 pg. This method was applied to the analysis of >2,500 urine specimens for the 2005–2006 Centers for Disease Control and Prevention’s National Health and Nutrition Examination Survey (NHANES). The method was capable of quantifying these compounds in 95–100% of study samples. This work is the first ever report of using APPI for the LC-MS/MS determination of these compounds in urine. It is also the first method of its kind to do so without any need for analyte extraction or preconcentration prior to analysis.     

Spectrophotometric Microdetermination of Some Pharmaceutically Impor tant Aminoquinoline Antimalarials, as Ion-Pair Complexes

 A simple, rapid, accurate and sensitive spectrophotometric method for the microdetermination of some pharmaceutically important aminoquinoline antimalarials, namely amodiaquine dihydrochloride (I), chloroquine phosphate (II) and primaquine phosphate (III) is described. The method is based on the interaction of these drugs with calmagite indicator to give highly coloured ion-pair complexes which exhibit maximum absorption at 663, 665 and 666 nm, respectively, Beer’s law is obeyed in the concentration ranges 1.0–25.0, 1.0–28.0 and 1.0–33.0 μg/ml for the drugs I, II and III, respectively. For more accurate analysis, the Ringbom optimum concentration ranges are 2.5–22.5, 2.0–26.0 and 3.0–30.0 μg/ml, respectively. The apparent molar absorptivities were calculated. Statistical treatment of the experimental results indicates that the method is sufficiently accurate and precise. The accuracy of the method is indicated by the recovery (99.8±1.4%) and the precision by the relative standard deviation (>1.5%). The proposed method has been applied to the determination of these drugs in certain formulations, with results that compared favourably with those obtained by the official methods. Received November 2, 1998. Revision February 29, 2000.     

Optimization of solid-phase microextraction procedures for the determination of tricyclic antidepressants and anticonvulsants in plasma samples by liquid chromatography

Simple, sensitive, and reproducible off-line solid-phase microextraction and liquid chromatography (SPME/LC) methods are described for the determination of seven anticonvulsants and tricyclic antidepressants in human plasma. Factorial design and simplex methodology were applied in the optimization of the SPME procedure for tricyclic antidepressants analyses. Important factors in the SPME efficiency are discussed, such as the fiber coatings (both lab-made and commercial), extraction time, pH, ionic strength, influence of plasma proteins, and desorption conditions. The development of the lab-made fiber coatings, namely, octadecylsilane, aminosilane, and polyurethane, are further described and applied to anticonvulsants analyses. The investigated plasmatic range for the evaluated anticonvulsants, using CW-TPR fiber, were the following: phenylethylmalonamide (3.00–40.0 μg mL⁻¹), phenobarbital (5.00–40.0 μg mL⁻¹), primidone (3.00–40.0 μg mL⁻¹), carbamazepine and carbamazepine-epoxide (2.00–24.0 μg mL⁻¹), phenytoin (2.00–40.0 μg mL⁻¹), and lamotrigine (0.50–12.0 μg mL⁻¹). The antidepressants’ linear plasmatic concentration ranged from 75.0 to 500 ng mL⁻¹ for imipramine, amitriptyline, and desipramine, and from 50.0 to 500 ng mL⁻¹ for nortriptyline, being in all cases, the limit of quantification represented by the lowest value. The precision (interassays) for all investigated drugs in plasma sample spiked with different concentrations of each analyte and submitted to the described procedures were lower than 15%. The off-line SPME/LC methodologies developed allow anticonvulsants and antidepressants analyses from therapeutic to toxic levels for therapeutic drug monitoring.