Bismuth modified carbon-based electrodes for the determination of selected neonicotinoid insecticides

Two types of bismuth modified electrodes, a bismuth-film modified glassy carbon (BiF-GCE) and a bismuth bulk modified carbon paste, were applied for the determination of selected nitroguanidine neonicotinoid insecticides. The method based on an ex situ prepared BiF-GCE operated in the differential pulse voltammetric (DPV) mode was applied to determine clothianidin in the concentration range from 2.5 to 23 μg cm?3 with a relative standard deviation (RSD) not exceeding 1.5%. The tricresyl phosphate-based carbon paste electrodes (TCP-CPEs), bulk modified with 5 and 20 w/w% of bismuth, showed a different analytical performance in the determination of imidacloprid, regarding the peak shape, potential window, and noise level. The TCP-CPE with 5% Bi was advantageous, and the developed DPV method based on it allowed the determination in the concentration range from 1.7 to 60 μg cm?3 with an RSD of 2.4%. To get a deeper insight into the morphology of the bismuth-based sensor surfaces, scanning electron microscopic measurements were performed of both the surface film and the bulk modified electrodes.     

In situ ATR FTIR monitoring of the formation of functionalized mono- and multilayers on germanium substrate: from 7-octenyltrichlorosilane to 7-carboxylsilane

The development and optimization of biomimetic surfaces required for biosensors and medical assays are made more efficient by quantitatively monitoring the surface chemical reactions in situ by means of attenuated total reflection (ATR) FTIR spectroscopy. single-beam-sample-reference (SBSR) ATR, as well as modulated excitation (ME), techniques have been applied to get physicochemical information on growth and structure of the surface layer. SBSR and ME methods result in optimum background compensation and signal-to-noise ratio. Surface modification was performed on a germanium multiple internal reflection element (Ge-MIRE). Activation of the surface resulted in free Ge-OH groups used for a spontaneous chemical reaction with 7-octenyltrichlorosilane (7-OTCS) in toluene. Formation of Ge-O-Si bonds was enabled by hydrolization of Si-Cl3 after partial elimination of a tightly bound thin water layer covering the MIRE. Unwanted side-reaction by hydrolization of Si-Cl3 in solution followed by polymerization paralleled this process. Steady growing of the silane layer to multilayer thickness with increasing time was observed in all experiments. Most unexpectedly, in some experiments the end-standing double bond of the silane layer was found to be partly oxidized even after being exposed only to toluene, probably because of catalysis by molecular sieve nanoparticles remaining in toluene after drying. Finally, theoretical means are presented enabling the calculation of the spectrum of dissolved 7-OTCS in toluene, a prerequisite for background compensation during in situ studies of the growing layer.     

Phenolic compounds of mountain tea from the Balkans: LC/DAD/ESI/MSn profile and content

Twenty-one samples of Sideritis species (S. scardica, S. raeseri, S. taurica, S. syriaca and S. perfoliata) from various locations on the Balkan Peninsula were evaluated for their chemical constituents. Chemical analyses were focused on secondary metabolites, particularly phenolic compounds, which have several roles in the plant physiological processes and have demonstrated significant health beneficial effects. The occurrence of hydroxycinnamic acids, phenylethanoid glycosides and flavonoids has been investigated in taxonomically related taxa of the genus Sideritis. A systematic method for phenolic compounds identification was developed using tandem mass spectrometry coupled to high performance liquid chromatography with diode array detection. Scanning for precursor ions of commonly found phenolics in Sideritis species using LC/MS11 with an ion trap instrument permitted the specific determination of hydroxycinnamic acid derivatives, and phenylethanoid and flavonoid glycosides. Further characterization of each phenolic compound was performed using MS/MS product-ion analysis and common-neutral-loss analysis. This on-line technique allowed identification of three hydroxycinnamic acid derivatives, eight phenylethanoid glycosides, and twenty-four flavonoid glycosides. All the taxa analysed produced very similar phenolic patterns characterized by the presence of 5-caffeoylquinic acid, lavandulifolioside, verbascoside, hypolaetin 7-O-[6'-O-acetyl]-allosyl(1-->2)glucoside, apigenin 7-(4"-p-coumaroylglucoside), 4'-O-methylisoscutellarein 7-O-[6'-O-acetyl]-allosyl(1-->2)glucoside, and minor amounts of isoverbascoside, apigenin 7-O-allosyl(1-->2)glucoside, isoscutellarein 7-O-allosyl-(1-->2)-[6"-O-acetyl]-glucoside, hypolaetin 7-O-allosyl-(1-->2)-[6"-O-acetyl]-glucoside and 4'-O-methylhypolaetin 7-O-[6'-O-acetyl]-allosyl-(1-->2)-[6"-O-acetyl]-glucoside. These results show that the investigated species are systematically very closely related. Phenylethanoid glycosides and flavonoid acetylglycosides are dominant and constitute 90% of the total phenolic compounds compared with hydroxycinnamic acid and flavonoid 7-O-glycosides. Principal component analysis (PCA) was performed for the nature and content of the different compounds to be correlated to the particular Sideritis species and also to the locations.     

Quantitative assessment of olfactory receptors activity in immobilized nanosomes: a novel concept for bioelectronic nose

We describe how mammalian olfactory receptors (ORs) could be used as sensing elements of highly specific and sensitive bioelectronic noses. An OR and an appropriate G(alpha) protein were co-expressed in Saccharomyces cerevisiae cells from which membrane nanosomes were prepared, and immobilized on a sensor chip. By Surface Plasmon Resonance, we were able to quantitatively evaluate OR stimulation by an odorant, and G protein activation. We demonstrate that ORs in nanosomes discriminate between odorant ligands and unrelated odorants, as in whole cells. This assay also provides the possibility for quantitative assessment of the coupling efficiency of the OR with different G(alpha) subunits, without the interference of the cellular transduction pathway. Our findings will be useful to develop a new generation of electronic noses for detection and discrimination of volatile compounds, particularly amenable to micro- and nano-sensor formats.     

l‐Isoleucyl‐l‐serine 0.33‐hydrate,l‐phenyl­alanyl‐l‐serine and l‐methionyl‐l‐serine 0.34‐hydrate

The structures of the title dipeptides, C₉H₁₈N₂O₄·0.33H₂O, C₁₂H₁₆N₂O₄ and C₈H₁₆N₂O₄S·0.34H₂O, complete a series of investigations focused on l ‐Xaa‐l ‐serine peptides, where Xaa is a hydro­phobic residue. All three structures are divided into hydro­philic and hydro­phobic layers. The hydro­philic layers are thin for l ‐phenyl­alanyl‐l ‐serine, rendered possible by an unusual peptide conformation, and thick for l ‐isoleucyl‐l ‐serine and l ‐methionyl‐l ‐serine, which include cocrystallized water mol­ecules on the twofold axes.     

Comparison and improvement of commonly applied statistical approaches for identification of plant species from IR spectra

Fourier transform infrared spectroscopy (FTIR) has been studied many times in the context of identification of plant, fungal and bacterial species. Infrared spectra are commonly analyzed using multivariate statistical methods such as cluster analysis (CA), principal component analysis (PCA), partial least squares analysis (PLS) and discriminant analysis (DA). In this study, a univariate statistical method for analysis of variance (ANOVA) was used to reduce the number of variables before applying the multivariate methods. Analyzing variables using ANOVA or a combination of ANOVA with CA produced better results. Here, experiments were carried out by performing ANOVA using the first derivative of the spectra instead of the original spectra or its second derivative because using the first‐derivative variables led to improved distinction between species. Different results were obtained by applying different validation methods. The leave‐one‐out validation method gave higher results than the validation‐with‐training and validation sample sets, thus indicating the non‐objectivity of the leave‐one‐out validation method. Copyright © 2010 John Wiley & Sons, Ltd.     

Chromenol Derivatives as Novel Antifungal Agents: Synthesis,In Silico and In Vitro Evaluation

Herein we report the synthesis of some new 1H-1,2,4-triazole functionalized chromenols (3a–3n) via tandem reactions of 1-(alkyl/aryl)-2-(1H-1,2,4-triazole-1-yl) with salicylic aldehydes and the evaluation of their antifungal activity. In silico prediction of biological activity with computer program PASS indicate that the compounds have a high novelty compared to the known antifungal agents. We did not find any close analog among the over 580,000 pharmaceutical agents in the Cortellis Drug Discovery Intelligence database at the similarity cutoff of 70%. The evaluation of antifungal activity in vitro revealed that the highest activity was exhibited by compound 3k, followed by 3n. Their MIC values for different fungi were 22.1–184.2 and 71.3–199.8 µM, respectively. Twelve from fourteen tested compounds were more active than the reference drugs ketoconazole and bifonazole. The most sensitive fungus appeared to be Trichoderma viride, while Aspergillus fumigatus was the most resistant one. It was found that the presence of the 2-(tert-butyl)-2H-chromen-2-ol substituent on the 4th position of the triazole ring is very beneficial for antifungal activity. Molecular docking studies on C. albicans sterol 14α-demethylase (CYP51) and DNA topoisomerase IV were used to predict the mechanism of antifungal activities. According to the docking results, the inhibition of CYP51 is a putative mechanism of antifungal activity of the novel chromenol derivatives. We also showed that most active compounds have a low cytotoxicity, which allows us to consider them promising antifungal agents for the subsequent testing activity in in vivo assays.     

MCM-41, MOF and UiO-67/MCM-41 adsorbents for pre-combustion CO2 capture by PSA: adsorption equilibria

Three different adsorbent materials, which are promising for pre-combustion CO₂ capture by a PSA (Pressure Swing Adsorption) process, are synthesized, pelletized and characterized. These materials are USO-2-Ni metal organic framework (MOF), mesoporous silica MCM-41 and a mixed material consisting of UiO-67 MOF bound with MCM-41. On these materials, equilibrium adsorption isotherms of CO₂ and H₂ are measured at different temperatures (25–140?°C) in a wide pressure range (up to 15?MPa). From the experimental data the parameters of different isotherm equations (Langmuir, Sips and Quadratic) are determined, together with the isosteric heats of adsorption. Binary adsorption of CO₂/H₂ mixtures on USO-2-Ni MOF is additionally measured and compared to predicted values using IAST (Ideal Adsorbed Solution Theory) showing a good agreement. The potential of the materials for the application of interest is evaluated by looking at their cyclic working capacity and compared to those of a commercial activated carbon. From this evaluation especially the USO-2-Ni MOF adsorbent looks promising compared to the commercial activated carbon. For the other two materials a smaller improvement, which is limited to lower temperatures, is expected.     

Comparison of salivary sodium and potassium concentrations measured by handheld ion-selective electrode meters and an automated biochemical analyser

Ion-selective electrode pocket meters available for use with saliva could be a convenient tool to assess how diseases, drugs, exercise or nutrition affect salivary composition. This study compared salivary sodium and potassium concentrations measured by handheld LAQUAtwin meters and a fully-automated biochemical analyzer. Agreement between two methods was assessed with Passing-Bablok regression and Bland-Altman plots. LAQUAtwin meters measured lower values of both analytes and provided repeatable though not accurate results. The meters may serve as an alternative to laboratory methods to gain insight into between-group differences in electrolyte concentrations, or a concentration change induced by an experimental procedure.     

The analysis of hardening of metal materials

There has been researched the interdependence of the process of microalloying, thermomechanical treatment and obtained mechanical characteristics of steel and AIMgSi alloys. There have been analyzed the hardening mechanisms of the mentioned alloys in correlation with grade, speed and temperature of strain. The achieved effects of alloys hardening are the consequences of combined operations of grain raffination, precipitation of dispersing particles of microalloying elements and increased density of dislocation.