Oxidation of organic sulfides by vanadium haloperoxidase model complexes

In addition to halide oxidation, the vanadium haloperoxidases are capable of oxidizing sulfides to sulfoxides. Four vanadium complexes with tripodal amine ligands, K[VO(O(2))(heida)] (1), VO(2)(bpg) (2), K[VO(2)(ada)] (3), and K(2)[VO(O(2))(nta)] (4), previously shown to perform bromide oxidation (Colpas, G. J.; Hamstra, B. J.; Kampf, J. W.; Pecoraro, V. L. J. Am. Chem. Soc. 1996, 118, 3469-3477), have now been shown to oxidize aryl alkyl sulfides to the corresponding sulfoxides. The oxidation was observed by the disappearance of thioanisole's ultraviolet absorption at 290 nm, by the change in the aromatic region of the (1)H NMR spectrum of the sulfides, and by changes in the complexes' (51)V NMR spectra. The amount of methyl phenyl sulfide oxidized in 3 h was 1000 equiv (per metal complex). The oxidation product is almost exclusively sulfoxide, with very little sulfone (less than 3% over a 3 h experiment) formed. This is consistent with an electrophilic oxidation mechanism, as had been proposed for oxidation of bromide by 1-4. The rate was found to be first order in substrate concentration, similar to the rate law observed for bromide oxidation. Unlike the bromide oxidation, the equivalent of acid required for peroxovanadium complex activation is not consumed. The complexes 1-4 are not reactive with styrene or cyclooctene. The relevance of these reactions to the mechanism of the vanadium haloperoxidases and, more generally, peroxovanadium oxygenation of sulfides will be discussed.     

Low-mass ions observed in plasma desorption mass spectrometry of high explosives

The low-mass ions observed in both positive and negative plasma desorption mass spectrometry (PDMS) of the high explosives HMX, RDX, CL-20, NC, PETN and TNT are reported. Possible identities of the most abundant ions are suggested and their presence or absence in the different spectra is related to the properties of the explosives as matrices in PDMS. The detection of abundant NO+ and NO2- ions for HMX, RDX and CL-20, which are efficient matrices, indicates that explosive decomposition takes place in PDMS of these three substances and that a contribution from the corresponding chemical energy release is possible. The observation of abundant C2H4N+ and CH2N+ ions, which have high protonation properties, might also explain the higher protein charge states observed with these matrices. Also, the observation of NO2-, possibly formed by electron scavenging which increases the survival probability of positively charged protein molecular ions, completes the pattern. TNT does not give any of these ions and it is thereby possible to explain why it does not work as a PDMS matrix. For NC and PETN, decomposition does not seem to be as pronounced as for HMX, RDX and CL-20, and also no particularly abundant ions with high protonation properties are observed. The fact that NC works well as a matrix might be related to other properties of this compound, such as its high adsorption ability.     

Stochastic simulation of reactive separations in capillary electrophoresis

A stochastic (Monte Carlo) simulation is used to investigate thermodynamic and kinetic contributions from the reversible A <--> B reaction in capillary electrophoresis (CE). The effects of equilibrium constant, rate constant, and electrophoretic mobility on the molecular zone profiles and the corresponding statistical moments are evaluated. As the reaction approaches steady state, the velocity of the zone is governed by the equilibrium constant and the electrophoretic mobilities of the reacting molecules. When the equilibrium constant is less than unity, the mean zone velocity is more similar to that of the reactant A. Conversely, when the equilibrium constant is greater than unity, the velocity is more similar to that of the product B. The extent of zone-broadening and asymmetry at steady state is dependent upon the equilibrium constant, the characteristic reaction lifetime, and the electrophoretic mobility difference between reacting molecules. If all other parameters are held constant, the plate height is greatest and skew is least when the equilibrium constant is unity. The plate height increases linearly with the characteristic reaction lifetime and electrophoretic mobility difference, whereas the skew is independent of these parameters. These conclusions have important implications for the elucidation of thermodynamic and kinetic information from experimental data.     

Diverse redox-active molecules bearing O-, S-, or Se-terminated tethers for attachment to silicon in studies of molecular information storage

A molecular approach to information storage employs redox-active molecules tethered to an electroactive surface. Attachment of the molecules to electroactive surfaces requires control over the nature of the tether (linker and surface attachment group). We have synthesized a collection of redox-active molecules bearing different linkers and surface anchor groups in free or protected form (hydroxy, mercapto, S-acetylthio, and Se-acetylseleno) for attachment to surfaces such as silicon, germanium, and gold. The molecules exhibit a number of cationic oxidation states, including one (ferrocene), two [zinc(II)porphyrin], three [cobalt(II)porphyrin], or four (lanthanide triple-decker sandwich compound). Electrochemical studies of monolayers of a variety of the redox-active molecules attached to Si(100) electrodes indicate that molecules exhibit a regular mode of attachment (via a Si-X bond, X = O, S, or Se), relatively homogeneous surface organization, and robust reversible electrochemical behavior. The acetyl protecting group undergoes cleavage during the surface deposition process, enabling attachment to silicon via thio or seleno groups without handling free thiols or selenols.     

Reactivity of peroxo forms of the vanadium haloperoxidase cofactor. A DFT investigation

Density functional theory has been used to investigate structural, electronic and reactivity properties of complexes related to the peroxo forms of vanadium haloperoxidases (VHPO). In particular, the reactivity of the cofactor as a function of protonation state and environment, which are two factors thought to be crucial in modulating the activity of the enzyme, has been examined. In full agreement with experimental data, results highlight the role of protonation in the activation of the peroxo-vanadium complexes and show that the oxo-transfer step involves the unprotonated axial peroxo oxygen atom, which is easily accessible to substrates in the peroxo form of the enzyme. The role of Lys353, which in the X-ray structure of the peroxide-bound form of vanadium chloroperoxidase is hydrogen bonded to the equatorial oxygen atom of the peroxo group, has been also explored. It is concluded that Lys353 can play a role similar to a H+ in the activation of the peroxo form of the cofactor.