Alba Pusino

Stability and structure of copper(II) complexes with 2-amino-2-deoxy-D-mannose and some derivatives thereof

Abstract Potentiometric and spectroscopic studies indicate that 2-amino-2-deoxy- d -mannose (ManN), its methyl α-glycopyranoside, and methyl 2-amino-2-deoxy-α,β- d -galactopyranoside are good chelating agents for cupric ions. The stability constants for the complexes with the manno compounds are higher than those of 2-amino-2-deoxy- d -galactose (GalN) and 2-amino-2-deoxy- d -glucose (GlcN). The primary binding site is the amino group and the most effective secondary site in the manno compounds is HO-3. Comparison of the co-ordination abilities of GalN, GlcN, ManN, and their methyl glycopyranosides indicates that various hydroxyl groups can be involved in the binding of metal ions. The stability constants of the Ni(II) and Co(II) complexes with ManN are also presented.

Photodegradation of herbicide triasulfuron

Triasulfuron was degraded in aqueous solution by ultraviolet irradiation to yield 2-chloroethoxybenzene and (4-methoxy-6-methyl-1,3,5-triazin-2-yl)urea. The reaction followed first-order kinetics. In sunlight, the reaction was slower and afforded these two photoproducts together with 2-amino-4-methoxy-6-methyltriazine and 2-(2-chloroethoxy)benzenesulfonamide. The latter compounds arise from hydrolytic cleavage of the sulfonylurea bridge of triasulfuron because of the acidity of the reaction medium due to the loss of sulfur dioxide. A mechanism which accounts for the formation of the photoproducts is proposed.

Interaction of transition-metal ions with polygalacturonic acid: A potentiometric study

Abstract The complexes formed by polygalacturonic acid (PGA) with Mn2+, Co2+ and Ni2+ were investigated by potentiometric titration of the polyelectrolyte in presence of varying amounts of metal ions. Formation functions, evaluated from the titration data and analyzed according to the Bjerrum plot method, were interpreted as evidence of: 1) the involvement of two carboxylate groups in the complex formation; 2) very little difference in preference for the binding of all the three ions by PGA. By taking into account Potentiometric and spectroscopic results (the latter reported elsewhere), an outer-sphere electrostatic structure is suggested for all the complexes. The relevance of this type of interaction in soil biochemistry is discussed.

Sorption behavior of sulfamethazine on unamended and manure-amended soils and short-term impact on soil microbial community

In this study we investigated the sorption of sulfamethazine (SMZ) in two soils with different physico-chemical properties and the sulfonamide short-term influence on the microbial community structure and function. The presence of manure increased the SMZ sorption, the uppermost level being measured on soil with the lower pH and the higher manure content allowed by the Italian regulation. The sulfonamide desorption was hysteretic on both soils. SMZ addition to soil at the concentration of 53.6 μg/g had a significant short-term negative impact on readily culturable bacteria, potential metabolic activity (Biolog CLPP) and soil enzyme activity. Moreover, a shift of the culturable microbial populations towards a lower bacteria/fungi ratio was observed after SMZ addition. Despite the observed SMZ effects disappeared almost completely after 7 day, structural changes of microbial communities were still present in SMZ-treated soils. The results presented are remarkable since previous studies addressing the SMZ impact on soil microbial parameters failed to highlight any significant effect of the sulfonamide on microbial abundance and diversity.

ADSORPTION AND DEGRADATION OF TRIASULFURON ON HOMOIONIC MONTMORILLONITES

The adsorption and degradation of the herbicide triasulfuron [2-(2-chloroethoxy)-N-[[(4-methoxy-6-methyl-l,3,5-triazin-2-yl)amino]carbonyl]benzenesulfonamide] (CMMT) on homoionic Fe3+-, Al3+-, Ca2+-, or Na+-exchanged montmorillonite in aqueous medium were studied. Ca- and Na-exchanged montmorillonite were ineffective in the adsorption and degradation of triasulfuron. The adsorption on Fe-and Al-exchanged montmorillonite was rapid, and equilibrium was attained after 5 min. Degradation of the herbicide was slow and the type of the degradation products depended on the nature of the exchangeable cations. In the presence of Fe3+-rich montmorillonite, the metabolites 2-(2-chloro-ethoxy)benzenesulfonamide (CBSA), 2-(2-chloroethoxy)-N-[[(4-hydroxy-6-methyl-l,3,5-triazin-2-yl)amino]carbonyl]benzenesulfonamide (CHMT), and l-[2-(2-chloroethoxy)benzene-l-sulfonyl]-7-acetyl-triuret (CBAT) were the only identified products, whereas 2-amino-4-methoxy-6-methyltriazine (AMMT), CBSA, CHMT, and CBAT were the primary metabolites for the Al3+-rich montmorillonite. A Fourier transform infrared (FT-IR) study of montmorillonite samples after the interaction with triasulfuron in organic solution suggests that the hydrolysis mechanism involves the adsorption of the herbicide on the 2:1 layers.

Direct and indirect photolysis of two quinolinecarboxylic herbicides in aqueous systems

The photodegradation of two quinolinecarboxylic herbicides, 7-chloro-3-methylquinoline-8-carboxylic acid (QMe) and 3,7-dichloroquinoline-8-carboxylic acid (QCl), was studied in aqueous solution at different irradiation wavelengths. The effect of sunlight irradiation was investigated also in the presence of titanium dioxide (TiO(2)). UV irradiation degraded rapidly QMe affording 7-chloro-3-methylquinoline (MeQ) through a decarboxylation reaction. The reaction rate was lower in the presence of dissolved organic carbon (DOC) because of the adsorption of the herbicide on the organic components. Instead, QCl was stable under both UV light and sunlight irradiation. The irradiation of QMe or QCl solutions with simulated sunlight in the presence of TiO(2) produced the complete mineralization of the two herbicides.

Dimepiperate adsorption and hydrolysis on Al (super 3+) -, Fe (super 3+) -, Ca (super 2+) -, and Na (super +) -montmorillonite

The adsorption of the herbicide dimepiperate S-(α;α-dimethylbenzyl)-1-piperidinecarbothioate on homoionic Fe3+-, Al3+-, Ca2+-, and Na+-montmorillonite was studied in aqueous medium. The adsorption is described well by the Freundlich equation. The adsorption capacity decreases in the order Fe3+ > Al3+ > Ca2+ > Na+ clay. The dimepiperate adsorption from chloroform solution was also investigated by analytical, spectroscopic, and X-ray powder diffraction techniques. IR results suggest that the adsorption involves the interaction of the thioester carbonyl group of dimepiperate possibly with the surrounding water of metal ions. On Al3+ and Fe3+ clays, this interaction leads to hydrolysis of the thioester bond and formation of the thiol and carbamic acid derivatives that yield α-methylstyrene and piperidine, respectively.

Interaction of the herbicide acifluorfen with montmorillonite; formation of insoluble Fe (super 3+) , Al (super 3+) , Cu (super 2+) , Ca (super 2+) complexes

Analytical, spectroscopic, and X-ray powder diffraction techniques were used to investigate the adsorption of the herbicide sodium acifluorfen (acifluorfen = 5-[2-chloro-4-(trifluorornethyl)phenoxy]-2-nitrobenzoic acid) from aqueous solution onto Cu2+-, Al3+-, Fe3+-, and Ca2+-saturated montmorillonite. As indicated by infrared and electron spin resonance spectra, which are coincident with those of the corresponding solid metal complexes, and by the basal spacings, which are the same for all the samples, acifluorfen extracted the exchangeable ions from the clay interlayer and precipitated them on external surfaces. The process involved the replacement of sodium as the saturating ion and was due to the formation of insoluble complexes between the herbicide and polyvalent metal ions.

ADSORPTION OF TWO QUINOLINECARBOXYLIC ACID HERBICIDES ON HOMOIONIC MONTMORILLONITES

The adsorption of the herbicides quinmerac 7-chloro-3-methylquinoline-8-carboxyl ic acid (QMe) and quinclorac 3,7-dichloroquinoline-8-carboxylic acid (QCl) on homoionic Fe3+-, Al3+-, Cu2+-, Ca2+-, K+- and Na+-exchanged montmorillonite was studied in aqueous solution. Adsorption data were fitted to the logarithmic form of the Freundlich equation. Ca- and Na-exchanged montmorillonites were ineffective in the adsorption of QMe. On the other hand, the QMe adsorption on Fe-exchanged montmorillonite was rapid and the equilibrium was attained after 15 min. An H-type isotherm was observed for the QMe adsorption on Fe-clay, indicating a high affinity of the solute for the sorption sites and almost complete adsorption from dilute solution. On the other hand, the adsorption isotherm of QMe on Al- and K-clay was of the S-type. This shape suggests that the solvent molecules may compete for the sorption sites. A Fourier transform infrared (FTIR) study suggested that the adsorption mechanism of QMe on Fe-, Al- and K-clay involves the protonation of QMe molecule due to the acidic water surrounding the saturating cations. The greater acidity of Fe-clay compared with Al- and K-clay explains both the lower QMe adsorption observed on Al and K systems and the lack of adsorption on Na and Ca systems. In contrast, the formation of a Cu complex permitted QMe to be adsorbed to a large extent to Cu-clay as shown by FTIR analysis. The QCl was adsorbed only by Fe-clay and the adsorption isotherm of QCl on Fe clay was of the S-type. This finding is consistent with the lower basic character of the QCl molecule nitrogen. In fact, the replacement of the electron-releasing methyl group in QMe with an electron-withdrawing Cl atom to form QCl makes the nitrogen lone-pair electrons of the quinoline ring unavailable for either protonation or complexation.

ADSORPTION MECHANISMS OF IMAZAMETHABENZ-METHYL ON HOMOIONIC MONTMORILLONITE

The adsorption of the herbicide imazamethabenz-methyl, a mixture of the two isomers methyl (±)-2-[4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1 H-imidazol-2-yl]-4-methylbenzoate para isomer) and methyl (±)-2-[4,5-dihydro-4-methyl-4-(l-methylethyl)-5-oxo-1 H-imidazol-2-yl]-5-methyl-benzoate (meta isomer), from water onto Al3+, Fe3+-, Ca2+-, K+- and Na+-montmorillonite was studied by analytical (HPLQ methods. The adsorption from an organic solvent was also investigated by spectroscopic (IR) and X-ray diffraction measurements. It was observed that, depending on the acidic properties of the exchangeable cations, two different mechanisms may take place. The first one, acting on Fe3+- and Al3+-clays, involves the protonation of the more basic nitrogen atom of imidazolinone ring of the herbicide because of a proton transfer from the acidic metal-bound water, followed by adsorption on the clay surfaces. In this case, the clay surfaces have greater affinity for the meta than the para isomer, due to the extra-stabilization of the meta protonated form by resonance. The second mechanism, taking place on Ca2+-, K+- and Na+-clays, is hydrogen-bond formation between the ester carbonyl group of the herbicide and hydration water metal ions and is not affected by the structure of the isomers.