Antonia Detomaso

Università degli Studi di Bari Aldo Moro, Bari, Apulia, Italy

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Publications (17)46.72 Total impact

  • [Show abstract] [Hide abstract]
    ABSTRACT: ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.
    ChemInform 10/2010; 24(40). DOI:10.1002/chin.199340119
  • [Show abstract] [Hide abstract]
    ABSTRACT: ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.
    ChemInform 07/2010; 29(27). DOI:10.1002/chin.199827096
  • [Show abstract] [Hide abstract]
    ABSTRACT: ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.
    ChemInform 04/2010; 26(15). DOI:10.1002/chin.199515289
  • [Show abstract] [Hide abstract]
    ABSTRACT: ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.
    ChemInform 03/2010; 28(10). DOI:10.1002/chin.199710178
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    Antonia Detomaso, Giuseppe Mascolo, Antonio Lopez
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    ABSTRACT: The structural elucidation of by-products arising from carbofuran photodegradation using a high-pressure UV lamp has been investigated by liquid chromatography/electrospray ionization tandem mass spectrometry (LC/ESI-MS/MS) employing a quadrupole time-of-flight mass spectrometer. Exact mass measurements of the [M + H]+ ions of the by-products and of product ions allowed the elemental formulae and related structures of seven photodegradation by-products (resulting, respectively, from photo-Fries rearrangement, hydroxylation of the benzene ring, oxidation of the 2,3-dihydrobenzofuran ring, cleavage of the carbamate group, hydrolysis of the ether group and the newly observed radical coupling and decarboxylation processes) to be determined confidently. Accurate mass measurements of product ions allowed ambiguities to be removed concerning neutral losses having the same nominal mass, namely CO and C2H4, allowing the fragmentation patterns to be rationalized.
    Rapid Communications in Mass Spectrometry 09/2005; 19(15):2193-202. DOI:10.1002/rcm.2036 · 2.64 Impact Factor
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    ABSTRACT: With the aim to evaluate the effect of temperature, 4-chloro-3-methyl phenol (CMP) degradation by Fenton's reagent was investigated at 25 and 70 degrees C under the following initial conditions: [CMP]0 = 10 mM, [Fe2+]0 = 0.5 mM; ([H2O2]0/[CMP]0) = 80, pH0 = 3. The results indicated that CMP degradation was strongly influenced by temperature. In fact, the maximum TOC removal, achieved after ca. 24h, was by far greater at 70 degrees C (85%) than at 25 degrees C (36%). The same happened for organic chlorine (TOX) conversion into inorganic chloride, i.e. 100%, after 3 h at 70 degrees C, and 87%, after 27 h at 25 degrees C. As the recorded trends of CMP removal and chloride formation were basically the same, hydroxy substitution (ipso-substitution) was hypothesised as one likely mechanism of CMP degradation. The higher level of mineralization recorded at 70 degrees C was ascribed to: (i) a greater *OH concentration; (ii) a consequently greater extent of CMP oxidation to organic acids; (iii) a higher decarboxylation rate of such acids. An interesting consequence of such extended organic acids decarboxylation was a pH increase up to 8 that, in turn, caused, in the treated mixture, the decomposition of excess H2O2 as well as the precipitation of iron ions. These two latter outcomes are technologically important considering that usually, before discharging Fenton treated wastewater, specific polishing steps are required just to remove iron ions, decompose excess hydrogen peroxide and neutralise the pH.
    Chemosphere 05/2005; 59(3):397-403. DOI:10.1016/j.chemosphere.2004.10.060 · 3.50 Impact Factor
  • G Mascolo, A Lopez, A Detomaso, G Lovecchio
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    ABSTRACT: End-product identification of organic pollutants during oxidation water treatments is of environmental concern due to their potential toxicity. In this work the coupling of ion chromatography (IC), equipped with a membrane ion suppressor, and electrospray ionization mass spectrometry (ESI-MS) has been successfully exploited for the identification of novel low molecular weight organic acids formed as final by-products of 2,4-dichloro-phenol (DCP) degradation by Fenton's reagent, an oxidation method widely employed to degrade recalcitrant organic pollutants in industrial wastewater. The IC-ESI-MS analytical set-up not only allowed the detection of known organic acids but also the identification of 13 new low molecular weight organic acids as a result of extensive oxidation of the parent organic pollutant. Some of the novel organic acids were shown to be chlorine containing by-products and, consequently, of environmental concern. The analytical set-up could be used for characterizing the unknown organic carbon fraction arising from oxidation water treatments.
    Journal of Chromatography A 04/2005; 1067(1-2):191-6. DOI:10.1016/j.chroma.2004.12.058 · 4.26 Impact Factor
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    ABSTRACT: The reductive degradation of a chlorinated herbicide by iron powder was investigated at lab scale. The studied substrate was triallate (S-2,3,3-trichloroallyl di-isopropyl thiocarbamate) which contains a trichloroethylene moiety potentially reducible by zero-valent iron. Degradation reactions were carried out in batch, at 25 degrees C, in the absence of oxygen, by contacting electrolytic iron powder (size range: 20-50 microm) with a triallate aqueous solution (2.5 mgl(-1)). Herbicide decay, corresponding evolutions of TOC, TOX and chloride ion release were regularly monitored throughout the reactions. Furthermore, the main degradation by-products were identified by HPLC/MS. The results showed that, after 5 days, herbicide degradation extent was about 97% and that the reaction proceeded through the formation of a dechlorinated alkyne by-product (S-2-propinyl di-isopropyl thiocarbamate) resulting from the complete dechlorination of triallate. The subsequent reduction of such an alkyne intermediate gave S-allyl di-isopropyl thiocarbamate as main end by-product. The identified by-products suggested that dechlorination took place mainly via reductive beta-elimination. However, as traces of dichloroallyl di-isopropyl thiocarbamate were also detected, a role, although minor, was assigned even to hydrogenolysis in the overall dechlorination process.
    Chemosphere 12/2004; 57(7):579-86. DOI:10.1016/j.chemosphere.2004.06.040 · 3.50 Impact Factor
  • 01/2004: pages 313-319;
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    ABSTRACT: Chlorophenols (CPs) constitute a group of organic pollutants that are introduced into the environment as a result of several man-made activities, such as uncontrolled use of pesticides and herbicides, and as byproducts in the paper pulp bleaching. Promising removal technologies of chlorinated aromatics consist in the application of advanced oxidation processes (AOPs) that can provide an almost total degradation of a variety of contaminants. Among these, wide application find Fenton systems based on generation of reactive species having a high oxidizing power, such as hydroxyl radical HO*. Our objective was that of determining the overall degradation efficiency of the model compound 2,4-dichlorophenol (DCP) by thermal Fenton-type oxidation systems with a view toward defining in more details relevant process parameters, the effect of reaction temperature and of co-catalyst Cu2+. Reaction conditions were similar to those generally adopted as optimal in many practical applications, i.e. pollutant/Fe2+ (as FeSO4) ratio ca. 20, Fe2+/Cu2+ (co-catalyst) 2:1, pH adjusted and controlled at pH 3, and H2O2 in excess (up to four-fold over the stoichiometric amount required for complete mineralization). The results demonstrate that it is advantageous to carry out the reaction at a temperature markedly higher (70 degrees C) than ambient. The stepwise addition of H2O2 in aliquots yields an efficient transformation, while allowing a convenient control of the reaction exothermicity. Under these conditions, the essentially complete removal of the initial DCP is accomplished using just one equiv of H2O2 during 15 min; excess H2O2 (5 equivalents) yields extensive substrate mineralization. Also relevant, at 70 degrees C dechlorination of the initial DCP (and of derived reaction intermediates) is remarkably extensive (3-5% residual TOX), already with the addition of 1 equiv of H2O2. At the end of the reaction, IC and IC-MS analyses of the solution reveal that only low-molecular weight carboxylic acid (acetic, formic, oxalic, malonic, tartaric, etc.) contribute to the residual TOC. The whole of the results herein point to the advantage of performing the process at temperatures substantially higher than ambient (70 degrees C). Under the conditions adopted, almost complete degradation of the initial toxic compound can be achieved using hydrogen peroxide in fair excess (e.g., 3.5 equiv H2O2). In applying practical Fenton-type degradation systems to heavily polluted wastes, either for the pre-treatment of waters with a high COD value prior to biodegradation or for complete mineralization of pollutants, the set up of appropriate reaction conditions appears to be a key factor. Also, it is desirable to keep the concentration of iron salts within the lower limits in order to minimize the production and disposal of iron oxide sludges.
    Environmental Science and Pollution Research 02/2003; 10(6):379-84. DOI:10.1065/espr2003.06.155 · 2.76 Impact Factor
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    ABSTRACT: By employing either dimethyldioxirane or its trifluoromethyl analog, the direct, high-yield conversion of one cyclic and three open chain optically sec,sec-1,2-diols to the corresponding alpha-hydroxy ketones in high optical yield has been achieved.
    ChemInform 04/2002; 58(14). DOI:10.1021/jo00066a002
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    ABSTRACT: In applying dimethyldioxirane (la) and methyl(trifluoromethyl)dioxirane (Ib) to the oxyfunctionalization of vitamin D-3 and of its 3-acyl derivatives, remarkable selectivities could be attained. Thus, reaction of 3 beta-acetylvitamin D-3 (3a) and of 3 beta-(p-bromobenzoyl)vitamin D-3 (3b) with dioxirane 1b in CH2Cl2 at -40 degrees C displayed high diastereoselectivity, giving the corresponding all-R triepoxides 48 and 4b, in 85% and 83% isolated yield, respectively; X-ray crystallographic analysis allowed us to determine unambiguously the 5R,6R,7R,8R,10R stereochemistry of 4b. In reacting with 1b under the adopted conditions, vitamin D-3 itself (3c) also gave the corresponding all-R triepoxide 4c (72% isolated yield); here, chemoselectivity is demonstrated by the fact that the unmasked secondary alcohol moiety at C-3 was left unaffected. Steric effects and intermolecular dipolar directing effects, exercised over the incoming oxidant by the epoxide functionalities sequentially introduced, are thought to dictate the high diastereoselectivity observed in the formation of triepoxides 4a-c. By contrast, treatment of 3a with dimethyldioxirane (1a) at -40 OC gave just the corresponding 7,8-epoxide 5 as the major product (yield 60%). High site selectivity was achieved in the subsequent oxyfunctionalization of triepoxide 3a with excess methyl(trifluoromethyl) dioxirane (1b) in CH2Cl2 at 0 degrees C, which afforded the corresponding C-25 hydroxy derivative (6) in 82% isolated yield.
    Journal of the American Chemical Society 04/2002; 116(18). DOI:10.1021/ja00097a018 · 11.44 Impact Factor
  • Antonia Detomaso, Ruggero Curci
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    ABSTRACT: ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.
    ChemInform 05/2001; 32(18). DOI:10.1002/chin.200118168
  • Source
    Antonia Detomaso, Ruggero Curci
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    ABSTRACT: An efficient approach to the synthesis of N-hydroxyamino acids in high enantiomeric excess is described; this involves the high-yielding selective N-hydroxylation of N-Boc protected primary amino acid esters with methyl(trifluoromethyl)dioxirane under mild conditions.
    Tetrahedron Letters 01/2001; 42(4):755-758. DOI:10.1016/S0040-4039(00)02107-9 · 2.39 Impact Factor
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    ABSTRACT: Using dimethyldioxirane, the selective transformation of aldehyde N,N-dimethyl-hydrazones into the corresponding nitriles was achieved in high yield and under mild conditions. The detemination of the substituent effect on rates, along with an estimate of the primary kinetic isotope effect using PhCHNNMe2 and PhCDNNMe2 provided useful hints concerning the reaction mechanism. It was also observed that the nitrile products do not undergo further oxidation, even with excess dioxirane.
    Tetrahedron Letters 04/1998; 39(14):2009-2012. DOI:10.1016/S0040-4039(98)00118-X · 2.39 Impact Factor
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    ABSTRACT: Upon reaction with methyl(trifluoromethyl)dioxirane (1b) at −40 °C, vitamin D2 (2a) or its 3β-acetyl derivative (2b) give in high yield (78−80%) the corresponding tetraepoxide (3a,b) as a single diastereoisomer having the 5,6(β);7,8(β);10,19(α);22,23(pseudo-α) configuration. Transformation of tetraepoxide 3a into its 3β-(p-bromobenzoyl) derivative 3c allowed X-ray diffraction analysis; this permitted us to ascertain that the stereomeric tetraepoxide product has the R configuration at all of the seven newly generated stereocenters, i.e. 5R,6R;7R,8R;10R(19);22R,23R. The oxidation of 3β-acetyl vitamin D2 (2b) with the less powerful dimethyldioxirane (1a) led to the corresponding 5,6(β);7,8(β);10,19(α)-triepoxide 4 as the major product (62%), accompanied by tetraepoxide 3b (26%). Parallel to vitamin D3 triepoxide, remarkable site selectivity was monitored in oxyfunctionalization of 3β-acetyl vitamin D2 tetraepoxide (3b) at the side-chain tertiary C-25. Reaction of tetraepoxide 3b with the powerful dioxirane 1b at 0 °C left the epoxide groups and remaining C-H functionalities intact, affording the 25-hydroxy derivative 5 in good isolated yield (61%).
    Journal of the American Chemical Society 11/1996; 118(45). DOI:10.1021/ja9626300 · 11.44 Impact Factor
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    ABSTRACT: Isolated dimethyldioxirane (1a) and methyl(trifluoromethyl)dioxirane (1b) efficiently afford the conversion of bicyclic diols bicyclo [2.2.2]octane-1,2-diol (2) and (+)-pinane-2,3-diol (6), of tricyclic diols adamantane-1,2-diol (3), homoadamantane-3,4-diol (4), and of homopentaprismane-3,4-diol (5) into the corresponding α-hydroxy ketones in high yields and under mild conditions. In the oxidation of (+)-pinane-2,3-diol (6), (−)-2-hydroxy-3-pinanone (11) is obtained in optical yield > 97% with retention of configuration.
    Tetrahedron Letters 07/1993; 34(28):4559–4562. DOI:10.1016/0040-4039(93)88085-W · 2.39 Impact Factor

Publication Stats

160 Citations
46.72 Total Impact Points

Institutions

  • 2001–2010
    • Università degli Studi di Bari Aldo Moro
      • Department of Chemistry
      Bari, Apulia, Italy
  • 2004–2005
    • National Research Council
      • Institute of Water Research IRSA
      Roma, Latium, Italy
  • 1998
    • Politecnico di Bari
      Bari, Apulia, Italy