Mass spectrometry of heterocyclic compounds—II: Electron-impact induced fragmentation of 3,5-diphenyl-1,2,4-oxadiazole

The electron-impact induced fragmentation of 3,5-diphenyl-1,2,4-oxadiazole has been investigated by labelling experiments, defocused metastable ion detections and high resolution mass measurements. The main fragmentation process suggests heterocyclic cleavage at the 1 to 5 and 3 to 4 bonds confirming our previous interpretation. The structure of the major fragment ion [C₇H₅NO]⁺· has been interpreted as being represented by the isomeric benzonitrile oxide and phenylisocyanate structures, the latter isomerising irreversibly from the former. The benzonitrile oxide structure is consistent with [C₇H₅NO]⁺· formation by cleavage of the 1 to 5 and 3 to 4 bonds.     

Sviluppo delle funzioni implicitamente definite da un sistema di equazioni nel campo reale

Sunto Per la funzione reale del punto P(x, y): F[ξ(P), η(P)], ove u=ξ(P), v=η(P) sono implicitamente definite nel campo reale dal sistema delle due equazioni u−x+ϕ(u, v)=0, v−y+φ(u, v)=0 si dà uno sviluppo che estende quello ottenuto dalLevi-Civita per la funzione F[y(x)], ove y(x) è definita dalla equazione y−x+ϕ(y)=0. Ad Antonio Signorini nel suo 70^mo compleanno.     

On Some Noncoercive Variational Inequalities

We study existence and regularity of solutions of noncoercive variational inequalities.     

Hammett correlations in the photosensitized oxidation of 4-substituted thioanisoles

Singlet oxygen is quenched by a series of 4-substituted thioanisoles (methoxy to nitro), with rate constant k(t) = 7 x 10(4) to 7 x 10(6) M(-)(1) s(-)(1), close to the value observed for the myoglobin-catalyzed sulfoxidation of the same sulfides. Correlations with sigma (rho = -1.97) and with E(ox) (slope -3.9 V(-)(1)) are evidence for an electrophilic mechanism. In methanol sulfoxides are formed (85%) via an intermediate quenched by diphenyl sulfoxide; competing minor paths lead to arylthiols, arylsulfenic acid, and aryl sulfoxides. In aprotic solvents, the sulfoxidation is quite sluggish, but carboxylic acids (mostly 100. The protonated persulfoxide is formed in this case and acts as an electrophile with sulfides, again with a rate constant correlating with sigma (rho = -1.78).     

Gas-phase ion chemistry in the ternary silane-propyne-phosphine system

The gas-phase ion chemistry of propyne-phosphine and silane-propyne-phosphine mixtures was studied by ion trap mass spectrometry. For the binary mixture, the effect of different partial pressures of the reagents on the yield of C and P-containing ions was evaluated. Reaction sequences and rate constants were determined and reaction efficiencies were calculated from comparison of experimental and collisional rate constants. In the ternary silane-propyne-phosphine systems, the reaction pathways leading to formation of Si(m)C(n)P(p)H(q) (+) ions were determined and the rate constants of the most important steps were measured. For some ion species, selected by double isolation procedures (MS/MS), the low ion abundances prevented determination of the reaction rate constants. Si, C and P-containing ions are mainly produced in reactions of Si(m)P(p)H(q) (+) ions with propyne, while the reactivity of the Si(m)C(n)H(q) (+) ions towards PH(3) and of the C(n)P(p)H(q) (+) ions towards SiH(4) is very low. The formation of hydrogenated Si--C--P ions is interesting for their possible role as precursors of amorphous silicon carbides doped with phosphorus, obtained in a single step, by deposition from properly activated silane-propyne-phosphine mixtures.     

Lipase-mediated production of defensive toxins in the marine mollusc Oxynoe olivacea

Metabolites related to caulerpenyne (1), a toxic sesquiterpene featured by two enol-acetate residues, play a major role in the chemical defence of both algae of the genus Caulerpa and a few molluscs of the order Sacoglossa. Here we report the direct evidence that cell-free preparations of Oxynoe olivacea, a Mediterranean sacoglossan, transform efficiently the algal metabolite 1 to oxytoxin-2 (3), the main defensive metabolite of the mollusc. The process implies two distinct hydrolytic activities, here named LIP-1 and LIP-2, able to operate either hydrolysis of the acetyl residue at C-1 or concerted elimination of the acetyl groups at C-4 and C-13. Incubation experiments with tissue homogenates of O. olivacea or with commercially available lipases suggest a two-step mechanism that involves, in vitro, an unstable metabolite characterized as preoxytoxin-2 (4). The course of the entire process can be easily monitored by reverse phase HPLC/ESI-MS, as well as by NMR measurements, which provides direct evidence of the enzymatic mechanism leading to the formation of this last compound (4). In agreement with the literature, both fresh and frozen tissues of Mediterranean Caulerpa prolifera also have the capability to transform 1 into aldehydic derivatives, namely oxytoxin-1 (2) and oxytoxin-2 (3), through hydrolysis of the acetyl groups. However, differently from experiments with mollusc homogenates, the conversion is not complete and caulerpenyne (1) can be detected in the algal suspension for a few hours. HPLC/ESI-MS monitoring of this transformation suggests that the hydrolytic route involves different activities in the mollusc and seaweed.     

The influence of the boat-to-chair conversion on the demetallation of the nickel(II) complex of an open-chain tetramine containing a piperazine fragment

The nickel(II) complex with an open chain tetramine containing a piperazine fragment (1) displays an unusual resistance to demetallation in acidic solution and exhibits a lifetime of about five minutes in a solution 0.1 M in HClO4 and 7.0 M in NaClO4. Sluggishness with respect to the demetallation is ascribed to the occurrence of the boat-to-chair conformational conversion of the piperazine fragment, which implies the passage through the highly energetic half-boat transition state. The use of a high concentration of the inert electrolyte induces a 'salting out' effect on both thermodynamics (stability of metal complexes is enhanced) and kinetics (resistance to demetallation is increased).     

Electron transfer vs. proton transfer within radical-cation clusters of guanosine and deoxyguanosine with substituted naphthalenes and sinapinic acid

Guanosine (G) and deoxyguanosine (dG) radical cations can be generated in the gas phase by single electron transfer (SET) within nucleoside-dimethoxynaphthalenes (1-2) electron-bound heterodimers produced by fast atom bombardment in a four sector mass spectrometer. The nucleobase guanine is much more easily oxidized when it is linked to a ribose moiety. The radical cation dimers formed by G and dG with sinapinic acid behave as proton-bound heterodimers. The experiments mimic to some extent the migration of radical sites within stacking bases which causes DNA damaging through depurination processes.     

Model for single-particle dynamics in supercooled water

We analyze a set of 10 M-step molecular dynamics (MD) data of low-temperature SPC/E model water with a phenomenological analytical model. The motivation is twofold: to extract various k-dependent physical parameters associated with the single-particle or the self-intermediate scattering functions (SISFs) of water at a deeply supercooled temperature and to apply this analytical model to analyses of new high resolution quasielastic neutron scattering data presented elsewhere. The SISF of the center of mass computed from the MD data show clearly time-separated two-step relaxations with a well defined plateau in between. We model the short time relaxation of the test particle as a particle trapped in a harmonical potential well with the vibrational frequency distribution function having a two-peak structure known from previous inelastic neutron scattering experiments. For the long time part of the relaxation, we take the alpha relaxation suggested by mode-coupling theory. The model fits the low-temperature SISF over the entire time range from 1 fs to 10 ns, allowing us to extract peak positions of the vibrational density of states, the structural relaxation rate 1/tau of the cage (the potential well) and the stretch exponent beta. The structural relaxation rate has a power law dependence on the magnitude of the wave vector transfer k and the stretch exponent varies from 0.55 at large k to unity at small k.     

Focal loci of families and the genus of curves on surfaces

In this article we apply the classical method of focal loci of families to give a lower bound for the genus of curves lying on general surfaces. First we translate and reprove Xu's result that any curve on a general surface in of degree has geometric genus . Then we prove a similar lower bound for the curves lying on a general surface in a given component of the Noether-Lefschetz locus in and on a general projectively Cohen-Macaulay surface in .