Mario Benassi

Ambient mass spectrometry: bringing MS into the "real world".

AbstractMass spectrometry has recently undergone a second contemporary revolution with the introduction of a new group of desorption/ionization (DI) techniques known collectively as ambient mass spectrometry. Performed in an open atmosphere directly on samples in their natural environments or matrices, or by using auxiliary surfaces, ambient mass spectrometry (MS) has greatly simplified and increased the speed of MS analysis. Since its debut in 2004 there has been explosive growth in the applications and variants of ambient MS, and a very comprehensive set of techniques based on different desorption and ionization mechanisms is now available. Most types of molecules with a large range of masses and polarities can be ionized with great ease and simplicity with the outstanding combination of the speed, selectivity, and sensitivity of MS detection. This review describes and compares the basis of ionization and the concepts of the most promising ambient MS techniques known to date and illustrates, via typical analytical and bioanalytical applications, how ambient MS is helping to bring MS analysis deeper than ever into the “real world” open atmosphere environment—to wherever MS is needed. FigureSchematic of EASI

Catalase vs Peroxidase Activity of a Manganese(II) Compound: Identification of a Mn(III)―(μ-O)2―Mn(IV) Reaction Intermediate by Electrospray Ionization Mass Spectrometry and Electron Paramagnetic Resonance Spectroscopy

Herein, we report reactivity studies of the mononuclear water-soluble complex [Mn(II)(HPClNOL)(eta(1)-NO(3))(eta(2)-NO(3))] 1, where HPClNOL = 1-(bis-pyridin-2-ylmethyl-amino)-3-chloropropan-2-ol, toward peroxides (H(2)O(2) and tert-butylhydroperoxide). Both the catalase (in aqueous solution) and peroxidase (in CH(3)CN) activities of 1 were evaluated using a range of techniques including electronic absorption spectroscopy, volumetry (kinetic studies), pH monitoring during H(2)O(2) disproportionation, electron paramagnetic resonance (EPR), electrospray ionization mass spectrometry in the positive ion mode [ESI(+)-MS], and gas chromatography (GC). Electrochemical studies showed that 1 can be oxidized to Mn(III) and Mn(IV). The catalase-like activity of 1 was evaluated with and without pH control. The results show that the pH decreases when the reaction is performed in unbuffered media. Furthermore, the activity of 1 is greater in buffered than in unbuffered media, demonstrating that pH influences the activity of 1 toward H(2)O(2). For the reaction of 1 with H(2)O(2), EPR and ESI(+)-MS have led to the identification of the intermediate [Mn(III)Mn(IV)(mu-O)(2)(PClNOL)(2)](+). The peroxidase activity of 1 was also evaluated by monitoring cyclohexane oxidation, using H(2)O(2) or tert-butylhydroperoxide as the terminal oxidants. Low yields (<7%) were obtained for H(2)O(2), probably because it competes with 1 for the catalase-like activity. In contrast, using tert-butylhydroperoxide, up to 29% of cyclohexane conversion was obtained. A mechanistic model for the catalase activity of 1 that incorporates the observed lag phase in O(2) production, the pH variation, and the formation of a Mn(III)-(mu-O)(2)-Mn(IV) intermediate is proposed.

Recognition and Resolution of Isomeric Alkyl Anilines by Mass Spectrometry

Two MS techniques have been used to recognize and resolve a representative isomeric pair of N-alkyl and ring-alkyl substituted anilines. The first technique (1) uses MS/MS to perform ion/molecule reactions of structurally-diagnostic fragment ions (SDFI) whereas the second (2) uses traveling wave ion mobility spectrometry (TWIMS) of the pair of protonated molecules followed by on-line collision-induced dissociation (CID), that is, MS/TWIMS-CID/MS. Isomeric C7H7N+ ions of m/z 106 (1′ from 4-butylaniline and 2 from N-butylaniline) are formed as abundant fragments by 70 eV EI of the anilines, and found to function as suitable SDFI. Ions 1′ and 2 display nearly identical unimolecular dissociation chemistry, but contrasting bimolecular reactivity with ethyl vinyl ether, isoprene, acrolein, and 2-methyl-1,3-dioxolane. Ion 2 forms adducts to a large extent whereas 1′ is nearly inert towards all reactants tested. The intact protonated anilines are readily resolved and recognized by MS/TWIMS-CID/MS in a SYNAPT mass spectrometer (Waters Corporation, Manchester, UK). The protonated N-butyl aniline (the more compact isomer) displays shorter drift time and higher lability towards CID than its 4-butyl isomer. The general application of SDFI 1′ and 2 and other homologous and analogous ions and MS/TWIMS-CID/MS for absolute recognition and resolution of isomeric families of N-alkyl and ring-alkyl mono-substituted anilines and analogues is discussed.

Absolute assignment of constitutional isomers via structurally diagnostic fragment ions: The challenging case of α- and β-acyl naphthalenes

A general mass spectrometric method is described for the absolute assignment of α- or β-acyl naphthalenes, via which the gaseous α- and β-naphthoyl cations of m/z 155 are used as structurally diagnostic fragment ions (SDFI). These stable acylium ions are common and normally abundant fragment ions of acylnaphthalenes in general. Using a pentaquadrupole mass spectrometer, CID experiments with argon and ion/molecule reactions with 2-methyl-1,3-dioxolane, isoprene, acetonitrile and propionitrile were performed but failed to distinguish the two SDFI. Reactions with ethyl vinyl ether and several homologues as well as ethyl vinyl thioether were, however, successful. In reactions with ethyl vinyl ether, the α-SDFI form a pair of diagnostic product ions of m/z 165 and m/z 181, which are absent in the corresponding spectrum of the β-SDFI. Methyl 4-(1-naphthyl)-2,4-dioxobutanoate was used as a test molecule for this class of constitutional isomers and absolute structural assignment as an α-acyl naphthalene was correctly performed via the characterization of its β-SDFI.

Recognition of Cyclic, Acyclic, Exocyclic, and Spiro Acetals via Structurally Diagnostic Ion/Molecule Reactions with the (CH3)2N-C+═O Acylium Ion

Reactions of the model acylium ion (CH3)2N-C(+)=O with acyclic, exocyclic, and spiro acetals of the general formula R(1)O-CR(3)R(4)-OR(2) were systematically evaluated via pentaquadrupole mass spectrometry. Characteristic intrinsic reactivities were observed for each of these classes of acetals. The two most common reactions observed were hydride and alkoxy anion [R(1)O(-) and R(2)O(-)] abstraction. Other specific reactions were also observed: (a) a secondary polar [4(+) + 2] cycloaddition for acetals bearing alpha,beta-unsaturated R(3) or R(4) substituents and (b) OH(-) abstraction for exocyclic and spiro acetals. These structurally diagnostic reactions, in conjunction with others observed previously for cyclic acetals, are shown to reveal the class of the acetal molecule and its ring type and substituents and to permit their recognition and distinction from other classes of isomeric molecules.

Exploring the intrinsic polar [4 + 2+] cycloaddition reactivity of gaseous carbosulfonium and carboxonium ions

Gas-phase reactions of model carbosulfonium ions (CH(3)-S(+)=CH(2;) CH(3)CH(2)-S(+)=CH(2) and Ph-S(+)=CH(2)) and an O-analogue carboxonium ion (CH(3)-O(+)=CH(2)) with acyclic (isoprene, 1,3-butadiene, methyl vinyl ketone) and cyclic (1,3-cyclohexadiene, thiophene, furan) conjugated dienes were systematically investigated by pentaquadrupole mass spectrometry. As corroborated by B3LYP/6-311 G(d,p) calculations, the carbosulfonium ions first react at large extents with the dienes forming adducts via simple addition. The nascent adducts, depending on their stability and internal energy, react further via two competitive channels: (1) in reactions with acyclic dienes via cyclization that yields formally [4+2(+)] cycloadducts, or (2) in reactions with the cyclic dienes via dissociation by HSR loss that yields methylenation (net CH(+) transfer) products. In great contrast to its S-analogues, CH(3)-O(+)=CH(2) (as well as C(2)H(5)-O(+)=CH(2) and Ph-O(+)=CH(2) in reactions with isoprene) forms little or no adduct and proton transfer is the dominant reaction channel. Isomerization to more acidic protonated aldehydes in the course of reaction seems to be the most plausible cause of the contrasting reactivity of carboxonium ions. The CH(2)=CH-O(+)=CH(2) ion forms an abundant [4+2(+)] cycloadduct with isoprene, but similar to the behavior of such α,β-unsaturated carboxonium ions in solution, seems to occur across the C=C bond.

Atribuição absoluta e geral de isômeros constitucionais por espectrometria de massas: o caso das metilpiperidinas

An absolute method is described via mass spectrometry (MS) for the structural assignment of isomers within the class of methylpiperidines. The method explores both the unimolecular and bimolecular gas phase behavior of structurally diagnostic fragment ions (SDFI). For the methylpiperidnes, the isomeric 2-methyl, 3-methyl and 4-methyl 2-azabutadienyl cations are found to function as SDFI. These fragment ions are expected to be formed from all members within the class, to be stable and to retain the structural information of the precursor molecule, and to not interconvert into one another. To characterize these SDFI, both the collision induced dissociation (CID) in argon and bimolecular ion/molecule chemistry with ethyl vinyl ether were compared.