All-solid-state potentiometric sensors for ascorbic acid by using a screen-printed compatible solid contact

The development of all-solid-state potentiometric ion selective electrodes for monitoring of ascorbic acid, by using a screen-printed compatible solid contact is described. The applied methodology is based on the use of PVC membrane modified with some firstly-tested ionophores (triphenyltin(IV)chloride, triphenyltin(IV)hydroxide and palmitoyl-l-ascorbic acid) and a novel one synthesized in our laboratory (dibutyltin(IV) diascorbate). Synthesis protocol and some preliminary identification studies are given. A conductive graphite-based polymer thick film ink was used as an internal solid contact between the graphite electrode and the PVC membrane. The presence and the nature of the solid contact (plain or doped with lanthanum 2,6-dichlorophenolindophenol (DCPI)) seem to enhance the analytical performance of the electrodes in terms of sensitivity, dynamic range, and response time. The analytical performance of the constructed electrodes was evaluated with potentiometry, constant-current chronopotentiometry and electrochemical impedance spectroscopy (EIS). The interference effect of various compounds was also tested. The potential response of the optimized Ph₃SnCl-based electrode was linear against ascorbic acid concentration range 0.005-5.0 mM. The applicability of the proposed sensors in real samples was also tested. The detection limit was 0.002 mM ascorbic acid (50 mM phosphate, pH 5 in 50 mM KCl). The slope of the electrodes was super-Nernstian and pH dependent, indicating a mechanism involving a combination of charge transfer and ion exchange processes. Fabrication of screen-printed ascorbate ISEs has also been demonstrated.     

Steroidal thiazoles,isothiazoles, thiazolines and thiazolidines

In order to discover new useful steroids in which the cyclopentanoperhydrophenanthrene system is condensed with various heterocyclic rings, many new compounds are continually being synthesized and tested for physiological action. The thiazole, isothiazole, thiazoline and thiazolidine ring condensed on several positions of the steroidal skeleton, has shown great interest due to the physiological properties. Literature coverage for this review includes publications which appear from 1946 to the 1980′s.     

Kinetic-potentiometric assay of formaldehyde in pharmaceutical and industrial samples, monitored by copper solid ion selective electrode, after its reaction with the copper(II)-bis-(ethylenediamine) complex

A kinetic-potentiometric method is described for the quantitative assay of formaldehyde (HCHO) in pharmaceutical and industrial preparations. It is based on the reaction of HCHO with (ethylenediamine)-Cu(II)-sulfate [Cu(CH₂NH₂)₂(H₂O)₂] · SO₄. The changes in potential, resulting from the release of the Cu(II) cations, are monitored with a Cu(II)-ion selective electrode. The calibration curve for the HCHO is linear in the concentration range 50–250 mg L⁻¹, with a limit of detection of 8.5 mg L⁻¹. The method shows very good reproducibility with an RSD of 2.6% for successive injections (n = 5) of 150 mg L⁻¹ HCHO primary solution, while it is interference free. The method was successfully tested in various industrial and pharmaceutical preparations.     

Beckmann rearrangement of 3-aza-a-homo-4α-androsten-4,17-dione oxime and 3-oxo-13α-amino-13,17-seco-4-androsten-17-oic 13,17-lactam oxime

Rearrangements of 3-aza-A-homo-4α-androsten-4, 17-dione oxime produced a mixture of the normal lactam product and the product of a “second order” cleavage, an unsaturated nitrile. The lactam 3, 17α-di-aza-A, D-bishomoandrost-4α-ene-4, 17-dione was also obtained from the rearrangement of the syn-3-oxo-13α-amino-13, 17-seco-4-androsten-17-oic-13, 17-lactam oxime. The resolution of syn- and anti-isomers of VIII was effected by column chromatography and their structure was determined by spectral data.     

Experimental study of flame stabilization in low Reynolds and Dean number flows in curved mesoscale ducts

Flame stabilization during non-premixed combustion in curved ducts with a diameter of the order of magnitude of the premixed flame thickness of the reactants was investigated experimentally, since it has been established that this is a configuration with potential advantages in the context of “micro”-combustion. It was shown that, in such “mesoscale” tubes, a stable flame oscillation including extinction/re-ignition phenomena can be established for steady boundary conditions. These oscillations lead, under appropriate conditions, to sound emission in the 50–350 Hz range. This was a mode of stabilization in addition to the “classical” steady flamelet, stabilized through thermal losses to the duct walls at higher values of the Reynolds number. Curvature of the duct was shown to have minimal effect on reactant mixing, which was diffusion-controlled, but significantly affected flame thickness and stabilization. To probe the fuel-oxidizer mixing in the U-shaped, optically accessible tubes, laser induced fluorescence of acetone fuel dopant was used, and the flame structure was studied using OH PLIF. The various stabilization regimes are discussed in terms of the Reynolds and Dean numbers of the tube flow.     

Dielectric relaxation spectroscopy in poly(hydroxyethyl acrylates)/water hydrogels

The electrical and dielectric properties of poly(hydroxyethyl acrylate), PHEA, hydrogels were studied by means of dielectric relaxation spectroscopy in wide ranges of frequencies (5–2 × 10⁹ Hz), temperatures (173–363 K) and water contents (0.065–0.46, g of water per gram of dry material). The secondary dipolar mechanisms (γ and β_sw) and the dc conductivity mechanism were studied in detail by analyzing the dielectric susceptibility data within the complex permittivity formalism, the modulus formalism, and the complex impedance formalism. For both mechanisms molecular mobility was found to increase with increasing temperature or increasing water content (T-f-h superposition principle). The energy parameters and the shape parameters of the response were determined for both mechanisms at several water contents and temperatures. The temperature dependence of dc conductivity was found to change from Vogel-Tamman-Fulcher (VTF) type to Arrhenius type at water contents of ca. 0.30. At water contents lower than about 0.30 the hydrogels are homogeneous whereas at higher water contents a separate water phase appears. In terms of the strong/fragile classification scheme our results suggest that the PHEA hydrogels are fragile systems. ©1995 John Wiley & Sons, Inc.     

A topological notion of boundedness

A topological boundedness notion is studied, which is proved to be productive. Classical theorems on compactness of Tychonoff, Alexander and Obreanu are generalized. A boundedness operator is defined and studied. Finally, a classification of all topological spaces is obtained according to boundedness criteria.The author is grateful to prof. N. Oeconomidis, who suggested the topic, for his continuous interest.     

Determination of carbofuran, carbaryl and their main metabolites in plasma samples of agricultural populations using gas chromatography–tandem mass spectrometry

A gas chromatography–tandem mass spectrometric (GC-MS/MS) method has been developed for the determination of carbofuran (2,3-dihydro-2,2-dimethylbenzofuran-7-yl methylcarbamate), carbaryl (1-naphthyl-N-methylcarbamate) and their main metabolites in human blood plasma. Optimization of the isolation of the compounds from plasma matrix included the precipitation, denaturation and digestion of plasma proteins. Derivatization was achieved by the use of trifluoroacetic acid anhydride and was optimized for temperature, time and volume of derivatization agent. In the proposed method, a mild precipitation technique was applied using β-mercaptoethanol and ascorbic acid in combination with solid-phase extraction technique using Oasis HLB (Hydrophobic Lipophilic Balance) cartridges for further clean up of samples. Carbamate linkage was not hydrolyzed to its phenol product, but both carbamate phenol and ketones were transformed into trifluoroacetyl derivatives in order to become volatile compounds and were determined using tandem mass spectrometry. The linearity of the method was shown for nine concentrations in the range of 0.50–250 ng mL⁻¹ in fortified plasma aliquots. Limits of detection (LODs) for all compounds ranged from 0.015–0.151 ng mL⁻¹. Inter-day and intra-day assays (RSD) for all compounds, at three concentration levels of 2.5, 25 and 100 ng mL⁻¹ (n=3) in fortified plasma samples were less than 18%. Accuracy (%E _r) was calculated at three concentration levels, 8, 80 and 160 ng mL⁻¹ (n=3), and ranged from −12.0 to 15.0%. Matrix effect was evaluated so mean recoveries were calculated for all compounds and ranged from 81–107%. Specificity for the use of this method to biological monitoring studies was achieved including four main metabolites of CF, 1-naphthol and 2-naphthol from the naphthalene metabolism pathways, and both the parent compound of carbofuran and carbaryl. The proposed method was applied to plasma samples of pesticide users.     

Disk-shaped Bose-Einstein condensates in the presence of an harmonic trap and an optical lattice

We study the existence and stability of solutions of the two-dimensional nonlinear Schrodinger equation in the combined presence of a parabolic and a periodic potential. The motivating physical example consists of Bose-Einstein condensates confined in an harmonic (e.g., magnetic) trap and an optical lattice. By connecting the nonlinear problem with the underlying linear spectrum, we examine the bifurcation of nonlinear modes out of the linear ones for both focusing and defocusing nonlinearities. In particular, we find real-valued solutions (such as multipoles) and complex-valued ones (such as vortices). A primary motivation of the present work is to develop "rules of thumb" about what waveforms to expect emerging in the nonlinear problem and about the stability of those modes. As a case example of the latter, we find that among the real-valued solutions, the one with larger norm for a fixed value of the chemical potential is expected to be unstable.