Characterization of humified substances in organic fertilizers by means of analytical electrofocusing (EF): A first approach

The objectives of the study were to test the electrofocusing technique to determine its suitability as a method for the characterization of organic fertilizers from a qualitative point of view and identification of the organic matrix in an unknown fertilizer; no laboratory methods for this purpose are presently available.Analytical electrofocusing (EF) is shown to fulfill these objectives and may be easily adopted as a routine manual procedure. A solution of sodium hydroxide was chosen as the extractant because it allows comparisons between various types of humified materials and permits the evolution of organic matter to be followed during maturation of the fertilizer itself. The organic fertilizers considered included many nitrogen-rich waste materials, mostly of animal origin. They are divided into different groups according to origin and EF profiles.     

Liquid Chromatography–Hybrid Linear Ion Trap–High-Resolution Mass Spectrometry (LTQ-Orbitrap) Method for the Determination of Glycoalkaloids and Their Aglycons in Potato Samples

Potatoes produce biologically active secondary metabolites like glycoalkaloids and their aglycons, which may have both adverse and beneficial effects in the diet. A new analytical method that uses liquid chromatography–mass spectrometry (LTQ-Orbitrap) has been developed for the analysis of glycoalkaloids and their aglycons in potato samples. Two glycoalkaloids, α-solanine and α-chaconine, and two aglycons, demissidine and solasodine, were quantified in potato samples. Samples were extracted using methanol, purified on an SPE Strata C₁₈ cartridge, and then analyzed in HPLC–mass spectrometry (LTQ-Orbitrap) with the FTMS operating in full scan at a resolving power of 30,000 (FWHM), enabling the detection and accurate mass measurement and with the ITMS mode operating in MRM (multiple reaction monitoring) for glycoalkaloids and their aglycons using the [M + H]⁺ ions and their optimized collision energies. After validation, the method was applied to screen different type of potatoes, and some cooking experiment were conducted.     

High Performance, Low-Dose Radiography Systems for Space and Remote Site Applications

Medical imaging applications using X- and gamma-rays have reached outstanding levels of complexity and performance, thanks to technology achievements in the fields of radiography, tomography and high resolution synchrotron devices. The operability of the related instrumentation resides in the availability of highly qualified specialists, as well as of medical doctors for diagnoses and treatment. This is a problem for personnel working in difficult ambient conditions as can be found in remote sites like Arctica, Antarctica and under-populated, desolated or mountainous regions on Earth. Astronauts, during long permanence at the Space Station or on future mission to Mars are potentially subject to risks such as traumas, fractures or diseases which would require semi-automated, easy-to-handle application of X-ray radiographic devices. For this purpose, the possible use of imaging instrumentation based on solid state detectors is discussed with special regard to CdZnTe pixel devices, now available with sub-mm resolution. The use of these semiconductor detectors will also allow to perform image diagnostics at much lower doses compared to the current plate-based radiographic techniques.     

Study of different nanostructured carbon supports for fuel cell catalysts

Pt clusters were deposited by an impregnation process on three carbon supports: multi-wall carbon nanotubes (MWNT), single-wall carbon nanohorns (SWNH), and Vulcan XC-72 carbon black to investigate the effect of the carbon support structure on the possibility of reducing Pt loading on electrodes for direct methanol (DMFC) fuel cells without impairing performance. MWNT and SWNH were in-house synthesised by a DC and an AC arc discharge process between pure graphite electrodes, respectively. UV-vis spectrophotometry, scanning and transmission electron microscopy, X-ray diffraction, and cyclic voltammetry measurements were used to characterize the Pt particles deposited on the three carbon supports. A differential yield for Pt deposition, not strictly related to the surface area of the carbon support, was observed. SWNH showed the highest surface chemical activity toward Pt deposition. Pt deposited in different forms depending on the carbon support. Electrochemical characterizations showed that the Pt nanostructures deposited on MWNT are particularly efficient in the methanol oxidation reaction.     

Adenosine receptor agonists: synthesis and biological evaluation of the diastereoisomers of 2-(3-hydroxy-3-phenyl-1-propyn-1-yl)NECA

Among the recently reported 2-(ar)alkynyl derivatives of 5'-N-ethylcarboxamidoadenosine (NECA), the (R,S)-2-(3-hydroxy-3-phenyl-1-propyn-1-yl)NECA [(R,S)-PHPNECA or SCH 59761] was found to be a very potent agonist at A1 and A2A receptor subtypes, with a Ki of 2.5 nM and 0.9 nM, respectively. Furthermore, this compound showed an inhibitory activity on platelet aggregation 16-fold higher than NECA, being the most potent anti-aggregatory nucleoside reported so far. Since this compound bears a chiral carbon in the side chain, the diastereoisomer separation was undertaken both by chiral HPLC and by a stereospecific synthetic method. Binding assays have shown that the (S)-diastereomer is about fivefold more potent and selective than the (R)-diastereomer as agonist of the A2A receptor subtype [(S)-PHPNECA, KiA2A = 0.5 nM; (R)-PHPNECA, KiA2A = 2.6 nM]. Functional studies indicated that (S)-PHPNECA possesses marked vasodilating activity and produces a relevant decrease in heart rate. Moreover, the (S)-diastereomer proved to be about ten times more potent than the (R)-diastereomer in inducing cardiovascular effects, in in vivo hemodynamic studies. However, the greatest difference between these two enantiomers resulted in the platelet aggregation test: in fact, the (R)-diastereomer displayed an inhibitory activity similar to that of NECA, whereas the (S)-diastereomer was 37-fold more active than NECA as an inhibitor of rabbit platelet aggregation, induced by ADP. These data suggest that (S)-PHPNECA could be a useful tool to investigate the mode of binding of agonists to the platelet adenosine receptor subtype.     

2-Alkynyl derivatives of adenosine-5'-N-ethyluronamide: selective A2 adenosine receptor agonists with potent inhibitory activity on platelet aggregation

A series of new 2-alkynyl and 2-cycloalkynyl derivatives of adenosine-5'-N-ethyluronamide (NECA) and of N-ethyl-1'-deoxy-1'-(6-amino-2-hexynyl-9H-purin-9-yl)-beta-D- ribofuranuronamide (1, HE-NECA), bearing hydroxy, amino, chloro, and cyano groups in the side chain, were synthesized. The compounds were studied in binding and functional assays to assess their potency for the A2 compared to A1 adenosine receptor. The presence of an alpha-hydroxyl group in the alkynyl chain of NECA derivatives accounts for the A2 agonist potency, leading to compounds endowed with sub-nanomolar affinity in binding studies. However, these analogues also possess good A1 receptor affinity resulting in low A2 selectivity. From functional experiments the 4-hydroxy-1-butynyl (6) and the 4-(2-tetrahydro-2H-pyranyloxy)-1-butynyl (16) derivatives appear to be very potent in inducing vasorelaxation without appreciable effect on heart rate. The new compounds were also tested as inhibitors of platelet aggregation induced by ADP. Introduction of an alpha-hydroxyl group in the alkynyl side chain caused a greater increase in antiaggregatory activity than either NECA or HE-NECA, resulting in the most potent inhibitors of platelet aggregation so far known in the nucleoside series. The presence of an alpha-quaternary carbon such as the 3-hydroxy-3,5-dimethyl-1-hexynyl (12) and the 3-hydroxy-3-phenyl-1-butynyl (15) derivatives markedly reduced the antiaggregatory potency without affecting the A2 affinity. The hydrophobicity index (k') of the new nucleosides barely correlated with the binding data, whereas high k' values were associated with increased A2 vs A1 selectivity but with reduced activity in all functional assays. Some of the compounds synthesized possess interesting pharmacological properties. Compounds having an appropriate balance between vasorelaxation and antiplatelet activity, if confirmed in vivo, deserve further development for the treatments of cardiovascular disorders.     

Electrochemical behaviour of metals in micellar medium and in water—tributylphosphate emulsions. Application to electrowinning of metals in waste water—I. Micellar medium

The inhibition of copper(II), nickel(II), cadmium(II), lead(II), cobalt(II), zinc(II) reduction by a non-ionic surfactant is studied in NaClO₄ as a non-complexing medium and in KSCN as a complexing medium. The magnitude of inhibition of these reactions appears very different according to pH in the perchlorate medium. In the thiocyanate medium, it seems that the stability of the complex has a very significant role in the inhibition process.     

Simultaneous determination of bisphenol A,octylphenol, and nonylphenol by pressurised liquid extraction and liquid chromatography–tandem mass spectrometry in powdered milk and infant formulas

A new analytical method, using pressurised liquid extraction (PLE) and liquid chromatography–tandem mass spectrometry (LC–MS/MS), was developed for the simultaneous determination of bisphenol A (BPA), octylphenol (OP) and nonylphenol (NP) in powdered infant formulas (IF) and powdered skimmed milk (PM). The analytes were extracted by PLE, using this optimised conditions: ethyl acetate as solvent, 70 °C of temperature, reversed-phase silica C₁₈ as dispersing agent and three cycles of extraction. The extracts were then injected in LC–MS/MS using a Gemini C₁₈ column and a mixture of 5% water and 95% methanol/acetonitrile, both with 0.1% ammonia, as a mobile phase. Recoveries at different fortification levels (0.5 and 0.05 mg kg⁻¹), were between 89% and 92% for BPA, 84 and 98% for OP, and 93% and 101% for NP. The method was applied to the analysis of samples of PM and IF, bought in Italian and Spanish markets. In positive samples, phenols concentration ranged from 0.07 to 1.29 mg kg⁻¹ for BPA, from 0.028 to 1.55 mg kg⁻¹ for OP and from 0.026 to 1.47 mg kg⁻¹ for NP.     

An enzymatic approach to the determination of the degree of stabilization of organic carbon in fertilizers

An enzymatic approach to assess the stability of organic matter extracted from organic fertilizers and amendments is proposed. The use of 0.1M NaOH plus 0.1M Na₄P₂O₇ previously suggested as a suitable extractant solution for soil organic matter was also found satisfactory for the extraction of organic matter from organic fertilizers and amendments, especially when the temperature was raised to 65°C. The presence of nonhumified compounds in the extracts from organic fertilizers may interfere considerably during fractionation of organic carbon. An enzymatic hydrolysis with lipase, lysozyme and pronase, added sequentially to the extracts, led to an appreciable reduction in the interference. The interference was further reduced by carrying out a successive acid hydrolysis with 3N H₂SO₄; in this case the DH values (percentage of humified fractions with respect to total extractable carbon) were reduced to less than 10% in all organic fertilizers, but remained higher than about 70% in organic amendments.