Environmental monitoring of the Capo Frasca military training site (West Sardinia): Operability and environmental protection balanced plan.

Military activities in training areas can contaminate soil and groundwater through different persistent pollutants. This article reports the design of the operating procedure to assess and monitor the environmental impact of training activities carried out at the Capo Frasca military firing range (PCF) on the west coast of Sardinia. The procedure includes two steps: (i) a baseline investigation of soil to detect the impact of previous training activities at PCF, and (ii) the development of a post-training monitoring plan.

Groundwater quality trend and trend reversal assessment in the European Water Framework Directive context: an example with nitrates in Italy.

Groundwater resources are of utmost importance in sustaining water related ecosystems, including humans. The long-lasting impacts from anthropogenic activities require early actions, owing to the natural time lag in groundwater formation and renewal. The European Union (EU) policy, within the implementation of the Water Framework Directive (WFD), requires Member States to identify and reverse any significant and sustained upward trend in the concentration of pollutants, defining specific protection measures to be included in the River Basin Management Plans (RBMP).

The Reaction of Thiyl Radical with Methyl Linoleate: Completing the Picture.

Cis lipids can be converted by thiols and free radicals into trans lipids, which are therefore a valuable tell-tale for free radical activity in the cell's lipidome. Our previous studies have shown that polyunsaturated lipids are isomerized by alkanethiyl radicals (S) in a cycle propagated by reversible double-bond addition and terminated by radical H-abstraction from the lipid. A critical flaw in this picture has long been that the reported lipid abstraction rate from radiolysis studies is faster than addition-isomerization, implying that the "cycle" must be terminating faster than it is propagating! Herein, we resolved this longstanding puzzle by combining a detailed product analysis, with reinvestigation of the time-resolved kinetics, DFT calculations of the indicated pathways, and reformulation of the radical-stasis equations.

Radical-based grafting of GMA on sutures of different nature.

Irradiation of a number of different sutures largely employed in the clinical practice with either high energy electrons or with γ-rays followed by quenching with glycidyl methacrylate (GMA) conveniently led to derivatization through a radical-based process. The radicals involved were detected by means of ESR spectroscopy and were characterized on the basis of their ESR spectral parameters which were also found to be consistent with the hfs constants predicted by DFT calculations. Evidence of the GMA derivatization of the sutures was obtained via(13)C CP-MAS NMR spectroscopy, while its extent was evaluated gravimetrically.

Radiation-induced formation of purine 5',8-cyclonucleosides in isolated and cellular DNA: high stereospecificity and modulating effect of oxygen.

The present work is aimed at gaining conclusive mechanistic insights into the radiation-induced formation of the 5'R and 5'S diastereomers of both adenine and guanine 5',8-cyclo-2'-deoxyribonucleosides, with emphasis on the delineation of the inhibitory effect of O(2) in isolated and cellular DNA. The levels of purine 5',8-cyclo-2'-deoxyribonucleosides as assessed by HPLC-MS/MS were found to decrease steadily with the increase of O(2) concentration, the 5',8-cyclo-2'-deoxyguanosine being produced more efficiently than the 5',8-cyclo-2'-deoxyadenosine for low O(2) concentrations. A high stereoselectivity was observed in the intramolecular addition of the C5' radical to the C8 of the purine leading, after the creation of the C5'-C8 bond and a subsequent oxidation step, to the predominant formation of the 5'R diastereomer for both purine 5',8-cyclonucleosides.

Hydrogen hyperfine splitting constants for phenoxyl radicals by DFT methods: regression analysis unravels hydrogen bonding effects.

DFT calculations using the B3LYP functional, medium-sized basis sets and empirical scaling of the results provide quantitative estimates of the hydrogen isotropic hyperfine splitting constants (hscs) in 2,6-di-alkyl phenoxyl radicals (1-11). Literature hscs for phenoxyl (12), 4-methylphenoxyl (13) and 4-methoxyphenoxyl (14) radicals, on the other hand, are poorly predicted by using this method. This different behaviour is explained considering that experimental hscs of 12-14 are influenced by H-bonds formed between phenoxyls and their parent phenols, usually present in large amounts in solution as radical precursors.

The reaction of spiro[indoline-naphthopyrans] with nitrogen oxides. Not a case of biradical double trapping.

The reactions of six differently substituted photochromic spiro[indoline-naphtopyrans] with .NO or .NO(2) under normal daylight conditions have been investigated by means of EPR spectroscopy along with those of three structurally related spiro[indoline-benzopyrans].

Comparison of isoelectronic 8-HO-G and 8-NH2-G derivatives in redox processes.

8-Oxo-7,8-dihydroguanine (8-oxo-G) is the major lesion of oxidatively generated DNA damage. Despite two decades of intense study, several fundamental properties remain to be defined. Its isoelectronic 8-aminoguanine (8-NH(2)-G) has also received considerable attention from a biological point of view, although its chemistry involving redox processes remains to be discovered.

A reevaluation of the ambident reactivity of the guanine moiety towards hydroxyl radicals.

Radically different: Contrary to previous proposals, the main reaction of the HO(*) radical with guanosine or 2'-deoxyguanosine is the hydrogen abstraction from the NH(2) moiety to give a guanyl radical. This radical, characterized by a broad band in the visible region (around 610 nm), undergoes tautomerization to the most stable isomer.

Reaction of hydrated electrons with guanine derivatives: tautomerism of intermediate species.

Here, we show that two tautomers are produced by the protonation of the guanine-electron adduct. The fate of electron adducts of a variety of substituted guanosines was investigated by radiolytic methods and addressed computationally by means of time-dependent DFT (TD-B3LYP/6-311G**//B1B95/6-31+G**) calculations. The reaction of e(aq-) with guanosine and 1-methylguanosine produces two transient species, whereas the reaction with N2-ethylguanosine and N2,N2-diethylguanosine produces only one.

On the actual EPR detection of thioacyl radicals.

The direct EPR detection of thioacyl radicals has been reported only once, while thioacyl nitroxides remain an elusive species. We failed to detect the thioacyl radicals from two thioaldehydes and from phosphoryldithioformates but have obtained EPR evidence that thioacyl radicals react with 2-methyl-2-nitrosopropane to give thiocarbonyloxyaminyls rather than thioacyl nitroxides. The results of DFT calculations support this unexpected reactivity of thioacyls, while making questionable their previous EPR identification.

One-electron reduction of 8-bromo-2-aminoadenosine in the aqueous phase: radiation chemical and DFT studies of the mechanism.

Two tautomeric forms of one-electron oxidized 2-aminoadenosine (2AA) have been produced by reactions of hydrated electrons (e aq-) with 8-bromo-2-aminoadenosine (8-Br-2AA) at natural pH, whereas only one tautomer is formed by oxidation of 2AA. Tailored experiments by pulse radiolysis and time-dependent DFT (TD-B3LYP/6-311G**//B1B95/6-31+G**) calculations allowed the definition of the reaction mechanism in some detail. The electron adducts of 8-Br-2AA protonated at C8 eject Br- and produce the two short-lived tautomers (8 and 9).

Ring opening of the cyclobutane in a thymine dimer radical anion.

The reactions of hydrated electrons (e(aq) (-)) with thymine dimer 2 and thymidine have been investigated by radiolytic methods coupled with product studies, and addressed computationally by means of BB1K-HMDFT calculations. Pulse radiolysis revealed that one-electron reduction of the thymine dimer 2 affords the radical anion of thymidine (5) with t(1/2)<35 ns. Indeed, the theoretical study suggests that radical anion 3, in which the spin density and charge distribution are located in both thymine rings, undergoes a fast partially ionic splitting of the cyclobutane with a half-life of a few ps.

Tautomerism in the guanyl radical.

Despite a few decades of intense study, a full description of tautomers of one-electron-oxidized guanine remains to be achieved. Here we show that two of these tautomers are produced by the protonation of an 8-haloguanine electron adduct. The rate constants for the reactions of hydrated electrons (e(aq)(-)) with a variety of 8-substituted guanine derivatives have been measured by a pulse radiolysis technique and correlated with both inductive and resonance components of the substituents.

Chemical radiation studies of 8-bromo-2'-deoxyinosine and 8-bromoinosine in aqueous solutions.

The reactions of hydrated electrons (e(aq) (-)) with 8-bromo-2'-deoxyinosine (8) and 8-bromoinosine (12) have been investigated by radiolytic methods coupled with product studies and have been addressed computationally by means of BB1K-HMDFT calculations. Pulse radiolysis revealed that one-electron reductive cleavage of the C--Br bond gives the C8 radical 9 or 13 followed by a fast radical translocation to the sugar moiety. Selective generation of a C5' radical occurs in the 2'-deoxyribo derivative, whereas in the ribo analogue the reaction is partitioned between the C5' and C2' positions with similar rates.

The kinetics of Z/E isomerization of methyl oleate catalyzed by photogenerated thiyl radicals.

The reaction of beta-mercaptoethanol with methyl oleate in tertbutyl alcohol was investigated under photochemical conditions. The time-dependent Z/E isomerization of the unsaturated moiety as well as the thiol-adduct formation were analyzed on the basis of radical generation rates and established rate constants. This provides precise room-temperature rate constants for the reversible thiyl radical addition to both Z and E isomers.

Redox and spin-trapping properties of phosphoryldithioacetates.

The redox properties of ethyl diethoxyphosphoryldithioacetate (1), methyl diethoxyphosphorylfluorodithioacetate (2) and methyl diethoxyphosphoryldifluorodithioacetate (3) were measured by cyclic voltammetry. Addition of free radicals to the three dithioesters led to the detection of the ESR spectra of the spin adducts only with the last two compounds. Based on the reduction potentials of the three dithioacetates, this may be explained by capto-dative stabilization of the adducts.

Water effect on the o-h dissociation enthalpy of para-substituted phenols: a DFT study.

The effect of water on the O-H bond dissociation enthalpy (BDE) of para-substituted phenols has been investigated by means of DFT calculations. It is shown that the experimental BDE values are fairly well-reproduced by simple B3LYP/6-31G* calculations carried out on the phenol/phenoxyl-water complexes taking into account only hydrogen-bonding (HB) interactions of water molecules with molecular sites (HB model). On the contrary, the BDE values computed with the polarizable continuum model (PCM/B3LYP/6-31G*)8 are overestimated by about 3-4 kcal/mol.

Selective generation and reactivity of 5'-adenosinyl and 2'-adenosinyl radicals.

The reaction of hydrated electrons (e(-)(aq) with 8-bromoadenosine 7 has been investigated by radiolytic methods coupled with product studies. Pulse radiolysis revealed that one-electron reductive cleavage of the C-Br bond gives the C8 radical 8 followed by a fast radical translocation to the sugar moiety. The reaction is partitioned between C5' and C2' positions in a 60:40 ratio leading to 5'-adenosinyl radical 9 and 2'-adenosinyl radical 11.

A critical evaluation of the factors determining the effect of intramolecular hydrogen bonding on the O-H bond dissociation enthalpy of catechol and of flavonoid antioxidants.

New experimental results on the determination of the bond dissociation enthalpy (BDE) value of 3,5-di-tert-butylcatechol, a model compound for flavonoid antioxidants, by the EPR radical equilibration technique are reported. By measurement of the equilibrium constant for the reaction between 3,5-di-tert-butylcatechol and the 2,6-di-tert-butyl-4-methylphenoxyl radical, in UV irradiated isooctane solutions at different temperatures, it has been shown that the thermodynamic parameters for this reaction are DeltaH degrees = -2.8+/-0.

Electron transfer and singlet oxygen mechanisms in the photooxygenation of dibutyl sulfide and thioanisole in MeCN sensitized by N-methylquinolinium tetrafluoborate and 9,10-dicyanoanthracene. The probable involvement of a thiadioxirane intermediate in electron transfer photooxygenations.

Photooxygenations of PhSMe and Bu2S sensitized by N-methylquinolinium (NMQ+) and 9,10-dicyanoanthracene (DCA) in O2-saturated MeCN have been investigated by laser and steady-state photolysis. Laser photolysis experiments showed that excited NMQ+ promotes the efficient formation of sulfide radical cations with both substrates either in the presence or in absence of a cosensitizer (toluene). In contrast, excited DCA promotes the formation of radical ions with PhSMe, but not with Bu2S.

Radical ions from 3,3''',3''''-tris(butylsulfanyl)- 2,2':5',2'':5'',2''',5''',2'''':5'''',2'''''-sexithiophene: an experimental and theoretical study of the p- and n-doped oligomer.

The 3,3''',3'''''-tris(butylsulfanyl)- 2,2':5',2'':5'',2''',5''',2'''':5'''',2'''''-sexithiophene 1 was investigated through spectroscopic (NMR, EPR, UV/Vis-NIR), electrochemical, spectroelectrochemical and theoretical (DFT) studies. The charged species obtained upon its oxidation and reduction were characterised, showing that 1 can exist in at least five different oxidation states, that is, a neutral species, a radical cation, a dication, a radical anion, and a dianion. The long term stability of the radical cation 1+.

Antitumor agents 4. Characterization of free radicals produced during reduction of the antitumor drug 5H-pyridophenoxazin-5-one: an EPR study.

5H-Pyridophenoxazin-5-one (PPH), a new anticancer iminoquinone, is able to inhibit a large number of lymphoblastoid and solid tumor-derived cells at submicromolar concentrations. Molecular modeling calculations indicated that this compound might intercalate into the DNA double strand. This was also supported by nuclear magnetic resonance studies.

Hydrogen-bonding effects on the properties of phenoxyl radicals. An EPR, kinetic, and computational study.

The effect of 1,1,1,3,3,3-hexafluoropropan-2-ol (HFP) on the properties of phenoxyl radicals has been investigated. HFP produces large variations of the phenoxyl hyperfine splitting constants indicative of a large redistribution of electron spin density, which can be accounted for by the increased importance of the mesomeric structures with electric charge separation. The conformational rigidity of phenoxyl radicals with electron-releasing substituents is also greatly enhanced in the presence of HFP, as demonstrated by the 2 kcal/mol increase in the activation energy for the internal rotation of the p-OMe group in the p-methoxyphenoxyl radical.