Reactivity and selectivity of charged phenyl radicals toward amino acids in a Fourier transform ion cyclotron resonance mass spectrometer

The reactivity of 10 charged phenyl radicals toward several amino acids was examined in the gas phase in a dual-cell Fourier transform ion cyclotron resonance mass spectrometer. All radicals abstract a hydrogen atom from the amino acids, as expected. The most electrophilic radicals (with the greatest calculated vertical electron affinities (EA) at the radical site) also react with these amino acids via NH(2) abstraction (a nonradical nucleophilic addition-elimination reaction). Both the radical (hydrogen atom abstraction) and nonradical (NH(2) abstraction) reaction efficiencies were found to increase with the electrophilicity (EA) of the radical. However, NH(2) abstraction is more strongly influenced by EA. In contrast to an earlier report, the ionization energies of the amino acids do not appear to play a general reactivity-controlling role. Studies using several partially deuterium-labeled amino acids revealed that abstraction of a hydrogen atom from the α-carbon is only preferred for glycine; for the other amino acids, a hydrogen atom is preferentially abstracted from the side chain. The electrophilicity of the radicals does not appear to have a major influence on the site from which the hydrogen atom is abstracted. Hence, the regioselectivity of hydrogen atom abstraction appears to be independent of the structure of the radical but dependent on the structure of the amino acid. Surprisingly, abstraction of two hydrogen atoms was observed for the N-(3-nitro-5-dehydrophenyl)pyridinium radical, indicating that substituents on the radical not only influence the EA of the radical but also can be involved in the reaction. In disagreement with an earlier report, proline was found to display several unprecedented reaction pathways that likely do not proceed via a radical mechanism but rather by a nucleophilic addition-elimination mechanism. Both NH(2) and (15)NH(2) groups were abstracted from lysine labeled with (15)N on the side chain, indicating that NH(2) abstraction occurs both from the amino terminus and from the side chain. Quantum chemical calculations were employed to obtain insights into some of the reaction mechanisms.     

Theoretical and experimental investigations on the reactions of positively charged phenyl radicals with aromatic amino acids

The chemical behavior of positively charged phenyl radicals 3-dehydro-N-phenylpyridinium (a), N-(3-dehydro-5-chlorophenyl)pyridinium (b), and N-(3-dehydrophenyl)pyridinium (c) toward L-tyrosine, phenylalanine, and tryptophan was investigated in the gas phase both theoretically by performing molecular orbital calculations and experimentally by using FT/ICR mass spectrometry. All radicals react with phenylalanine and tryptophan nearly at the collision rate. The overall reactivity of the radicals toward tyrosine follows the order a > b > c, which is consistent with the electron affinity (EA) ordering of the radicals. The higher the electrophilicity (or EA) of the radical, the greater the reactivity. As expected, all radicals abstract a hydrogen atom from all of the amino acids. However, the most electrophilic radical a was also found to react with these amino acids via NH2 abstraction. A new reaction observed between radicals a-c and aromatic amino acids is the addition of the radical to the aromatic ring of the amino acid followed by Calpha-Cbeta bond cleavage, which leads to side-chain abstraction by the radical.     

The selectivity of charged phenyl radicals in hydrogen atom abstraction reactions with isopropanol

The vertical electron affinity is demonstrated to be a key factor in controlling the selectivity of charged phenyl radicals in hydrogen atom abstraction from isopropanol in the gas phase. The measurement of the total reaction efficiencies (hydrogen and/or deuterium atom abstraction) for unlabeled and partially deuterium-labeled isopropanol, and the branching ratios of hydrogen and deuterium atom abstraction, by using a Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer, allowed the determination of the selectivity for each site in the unlabeled isopropanol. Examination of hydrogen atom abstraction from isopropanol by eight structurally different radicals revealed that the preferred site is the CH group. The selectivity of the charged phenyl radicals correlates with the radical's vertical electron affinity and the reaction efficiency. The smaller the vertical electron affinity of a radical, the lower its reactivity, and the greater the preference for the thermodynamically favored CH group over the CH3 group or the OH group. As the vertical electron affinity increases from 4.87 to 6.28 eV, the primary kinetic isotope effects decrease from 2.9 to 1.3 for the CD group, and the mixture of primary and alpha-secondary kinetic isotopes decreases from 6.0 to 2.4 for the CD3 group.     

Hydrogen atom abstraction reactions of charged polyaromatic sigma-radicals related to the active intermediates of the enediyne antitumor drugs

Polar effects are demonstrated to play an important role in controlling the reactivity of polyaromatic sigma-radicals that are structurally related to the active intermediates of the enediyne anticancer type antibiotics. This was accomplished by measuring the rate constants of hydrogen atom abstraction for novel, charged dehydroquinolines, dehydroisoquinolines, dehydrobenzenes, and dehydronaphthalenes in the gas phase by using Fourier-transform ion cyclotron resonance mass spectrometry. The reactivity trends observed for these radicals upon hydrogen atom abstraction from tetrahydrofuran and 2-methyltetrahydrofuran, simple models of deoxyribose, do not reflect differences in reaction exothermicities, radical sizes, exact location of the radical site in the ring system, or heteroatom-radical site distances. However, the reactivity trends match the trend in the calculated electron affinities of the radicals. The radicals' different electrophilicities result in variations in the reaction barrier due to different extents of polarization of the transition state. Generally, the reaction efficiencies are the greatest when the formally charged heteroatom is contained within the same ring system as the radical site. In this case, polar effects have the greatest influence on radical reactivity. Hence, insertion of a basic heteroatom (which gets protonated in biological systems) into specific locations in the polyaromatic ring system of the sigma-biradicals, which ultimately cause cleavage of DNA exposed to the enediyne antitumor drugs, should allow tuning of the reactivity of these radicals.     

Reductive tert-Butylation of Anils by tert-Butylmercury Halides(1)

tert-Butyl radicals add to the carbon atom of benzylideneanilines to form anilino radicals, which are protonated in the presence of PTSA or NH(4)(+) in Me(2)SO. Reduction of the resulting aniline radical cations occurs readily by the ate complex, t-BuHgI(2)(-). In the absence of a proton donor, t-BuHgI will also transfer a hydrogen atom to the anilino radical to give the reductive alkylation product. Protonation can promote a free radical chain process involving electron transfer by substrate activation and/or by increasing the electron affinity of the intermediate radicals. Since the adduct radicals formed from benzylideneanilines are more easily protonated than the parent Schiff bases, PTSA but not NH(4)(+) demonstrates substrate activation, although both proton donors promote the free radical reaction.     

Reactivity of substituted charged phenyl radicals toward components of nucleic acids

Reactions of differently substituted phenyl radicals with components of nucleic acids have been investigated in the gas phase. A positively charged group located meta with respect to the radical site was employed to allow manipulation of the radicals in a Fourier-transform ion cyclotron resonance mass spectrometer. All of these electrophilic radicals react with sugars via exclusive hydrogen atom abstraction, with adenine and uracil almost exclusively via addition (likely at the C8 and C5 carbons, respectively), and with the nucleoside thymidine by hydrogen atom abstraction and addition at C5 in the base moiety (followed by elimination of (*)CH(3)). These findings parallel the reactivity of the phenyl radical with components of nucleic acids in solution, except that the selectivity for addition is different. Like HO(*), the electrophilic charged phenyl radicals appear to favor addition to the C5-end of the C5-C6 double bond of thymine and thymidine, whereas the phenyl radical preferentially adds to C6. The charged phenyl radicals do not predominantly add to thymine, as the neutral phenyl radical and HO(*), but mainly react by hydrogen atom abstraction from the methyl group (some addition to C5 in the base followed by loss of (*)CH(3) also occurs). Adenine appears to be the preferred target among the nucleobases, while uracil is the least favored. A systematic increase in the electrophilicity of the radicals by modification of the radicals' structures was found to facilitate all reactions, but the addition even more than hydrogen atom abstraction. Therefore, the least reactive radicals are most selective toward hydrogen atom abstraction, while the most reactive radicals also efficiently add to the base. Traditional enthalpy arguments do not rationalize the rate variations. Instead, the rates reflect the radicals' electron affinities used as a measure for their ability to polarize the transition state of each reaction.     

Thermally activated mechanisms of hydrogen abstraction by growth precursors during plasma deposition of silicon thin films

Hydrogen abstraction by growth precursors is the dominant process responsible for reducing the hydrogen content of amorphous silicon thin films grown from SiH(4) discharges at low temperatures. Besides direct (Eley-Rideal) abstraction, gas-phase radicals may first adsorb on the growth surface and abstract hydrogen in a subsequent process, giving rise to thermally activated precursor-mediated (PM) and Langmuir-Hinshelwood (LH) abstraction mechanisms. Using results of first-principles density functional theory (DFT) calculations on the interaction of SiH(3) radicals with the hydrogen-terminated Si(001)-(2x1) surface, we show that precursor-mediated abstraction mechanisms can be described by a chemisorbed SiH(3) radical hopping between overcoordinated surface Si atoms while being weakly bonded to the surface before encountering a favorable site for hydrogen abstraction. The calculated energy barrier of 0.39 eV for the PM abstraction reaction is commensurate with the calculated barrier of 0.43-0.47 eV for diffusion of SiH(3) on the hydrogen-terminated Si(001)-(2x1) surface, which allows the radical to sample the entire surface for hydrogen atoms to abstract. In addition, using the same type of DFT analysis we have found that LH reaction pathways involve bond breaking between the silicon atoms of the chemisorbed SiH(3) radical and the film prior to hydrogen abstraction. The LH reaction pathways exhibit energy barriers of 0.76 eV or higher, confining the abstraction only to nearest-neighbor hydrogens. Furthermore, we have found that LH processes compete with radical desorption from the hydrogen-terminated Si(001)-(2x1) surface and may be suppressed by the dissociation of chemisorbed SiH(3) radicals into lower surface hydrides. Analysis of molecular-dynamics simulations of the growth process of plasma deposited silicon films have revealed that qualitatively similar pathways for thermally activated hydrogen abstraction also occur commonly on the amorphous silicon growth surface.     

Substituent effects on the nonradical reactivity of 4-dehydropyridinium cation

Recent studies have shown that the reactivity of the 4-dehydropyridinium cation significantly differs from the reactivities of its isomers toward tetrahydrofuran. While only hydrogen atom abstraction was observed for the 2- and 3-dehydropyridinium cations, nonradical reactions were observed for the 4-isomer. In order to learn more about these reactions, the gas-phase reactivities of the 4-dehydropyridinium cation and several of its derivatives toward tetrahydrofuran were investigated in a Fourier transform ion electron resonance mass spectrometer. Both radical and nonradical reactions were observed for most of these positively charged radicals. The major parameter determining whether nonradical reactions occur was found to be the electron affinity of the radicals--only those with relatively high electron affinities underwent nonradical reactions. The reactivities of the monoradicals are also affected by hydrogen bonding and steric effects.     

Reactivity of aromatic σ,σ-biradicals toward riboses

The gas-phase reactions of sugars with aromatic, carbon-centered sigma,sigma-biradicals with varying polarities [as reflected by their calculated electron affinities (EA)] and extent of spin-spin coupling [as reflected by their calculated singlet-triplet (S-T) gaps] have been studied. The biradicals are positively charged, which allows them to be manipulated and their reactions to be studied in a Fourier-transform ion cyclotron resonance mass spectrometer. Hydrogen atom abstraction from sugars was found to be the dominant reaction for the biradicals with large EA values, while the biradicals with large S-T gaps tend to form addition/elimination products instead. Hence, not all sigma, sigma-biradicals may be able to damage DNA by hydrogen atom abstraction. The overall reaction efficiencies of the biradicals towards a given substrate were found to be directly related to the magnitude of their EA values, and inversely related to their S-T gaps. The EA of a biradical appears to be a very important rate-controlling factor, and it may even counterbalance the reduced radical reactivity characteristic of singlet biradicals that have large S-T gaps.     

High-level ab initio studies of hydrogen abstraction from prototype hydrocarbon systems

Symmetric and nonsymmetric hydrogen abstraction reactions are studied using state-of-the-art ab initio electronic structure methods. Second-order M?ller-Plesset perturbation theory (MP2) and the coupled-cluster singles, doubles, and perturbative triples [CCSD(T)] methods with large correlation consistent basis sets (cc-pVXZ, where X = D,T,Q) are used in determining the transition-state geometries, activation barriers, and thermodynamic properties of several representative hydrogen abstraction reactions. The importance of basis set, electron correlation, and choice of zeroth-order reference wave function in the accurate prediction of activation barriers and reaction enthalpies are also investigated. The ethynyl radical (*CCH), which has a very high affinity for hydrogen atoms, is studied as a prototype hydrogen abstraction agent. Our high-level quantum mechanical computations indicate that hydrogen abstraction using the ethynyl radical has an activation energy of less than 3 kcal mol(-1) for hydrogens bonded to an sp(2) or sp(3) carbon. These low activation barriers further corroborate previous studies suggesting that ethynyl-type radicals would make good tooltips for abstracting hydrogens from diamondoid surfaces during mechanosynthesis. Modeling the diamond C(111) surface with isobutane and treating the ethynyl radical as a tooltip, hydrogen abstraction in this reaction is predicted to be barrierless.     

Electron super-rich radicals in the gas phase. A neutralization-reionization mass spectrometric and ab initio/RRKM study of diaminohydroxymethyl and triaminomethyl radicals

Diaminohydroxymethyl (1) and triaminomethyl (2) radicals were generated by femtosecond collisional electron transfer to their corresponding cations (1+ and 2+, respectively) and characterized by neutralization-reionization mass spectrometry and ab initio/RRKM calculations at correlated levels of theory up to CCSD(T)/aug-cc-pVTZ. Ion 1+ was generated by gas-phase protonation of urea which was predicted to occur preferentially at the carbonyl oxygen with the 298 K proton affinity that was calculated as PA = 875 kJ mol-1. Upon formation, radical 1 gains vibrational excitation through Franck-Condon effects and rapidly dissociates by loss of a hydrogen atom, so that no survivor ions are observed after reionization. Two conformers of 1, syn-1 and anti-1, were found computationally as local energy minima that interconverted rapidly by inversion at one of the amine groups with a <7 kJ mol-1 barrier. The lowest energy dissociation of radical 1 was loss of the hydroxyl hydrogen atom from anti-1 with ETS = 65 kJ mol-1. The other dissociation pathways of 1 were a hydroxyl hydrogen migration to an amine group followed by dissociation to H2N-C=O* and NH3. Ion 2+ was generated by protonation of gas-phase guanidine with a PA = 985 kJ mol-1. Electron transfer to 2+ was accompanied by large Franck-Condon effects that caused complete dissociation of radical 2 by loss of an H atom on the experimental time scale of 4 mus. Radicals 1 and 2 were calculated to have extremely low ionization energies, 4.75 and 4.29 eV, respectively, which belong to the lowest among organic molecules and bracket the ionization energy of atomic potassium (4.34 eV). The stabilities of amino group containing methyl radicals, *CH2NH2, *CH(NH2)2, and 2, were calculated from isodesmic hydrogen atom exchange with methane. The pi-donating NH2 groups were found to increase the stability of the substituted methyl radicals, but the stabilities did not correlate with the radical ionization energies.     

New Radical Borylation Pathways for Organoboron Synthesis Enabled by Photoredox Catalysis

Radical borylation using N‐heterocyclic carbene (NHC)‐BH₃ complexes as boryl radical precursors has emerged as an important synthetic tool for organoboron assembly. However, the majority of reported methods are limited to reaction modes involving carbo‐ and/or hydroboration of specific alkenes and alkynes. Moreover, the generation of NHC‐boryl radicals relies principally on hydrogen atom abstraction with the aid of radical initiators. A distinct radical generation method is reported, as well as the reaction pathways of NHC‐boryl radicals enabled by photoredox catalysis. NHC‐boryl radicals are generated via a single‐electron oxidation and subsequently undergo cross‐coupling with the in‐situ‐generated radical anions to yield gem‐difluoroallylboronates. A photoredox‐catalyzed radical arylboration reaction of alkenes was achieved using cyanoarenes as arylating components from which elaborated organoborons were accessed. Mechanistic studies verified the oxidative formation of NHC‐boryl radicals through a single‐electron‐transfer pathway.     

Nature of the chain propagation in the photostimulated reaction of 1-bromonaphthalene with sulfur-centered nucleophiles

The reactivity of -SC(NH)NH2 (1), MeCOS- (2), and PhCOS- (3) toward 1-naphthyl radicals was studied in DMSO. The photostimulated reaction of anions 1, 2, and 3 with 1-bromonaphthalene (4) after quenching with MeI renders 1-(methylthio)naphthalene (6) as a main product together with bis(1-naphthyl) sulfide (7) and naphthalene (5). The thioacetate ion (2) and thiobenzoate ion (3) were unreactive toward 4 as electron-donor under photostimulation; however, in the presence of potassium tert-butoxide anion (entrainment conditions), they gave the mentioned products 5, 6, and 7, after the addition of MeI. Quenching of the triplet state of 4 was assigned as the photoinduced initiation step, with a rate constant value of (4.6+/-0.5)x10(8) M-1 s-1 for tert-butoxide anion and a rough estimated value of (8+/-7)x10(7) M-1 s-1 for anion 1. By using hydrogen abstraction from DMSO as the competitive reaction, the absolute rate constants for the addition of anions 1, 2, and 3 to 1-naphthyl radicals have been determined to be 1.0x10(9), 1.2x10(9), and 3.5x10(9) M-1 s-1, respectively. This reactivity order is in agreement with the stability of the resulting radical anions (ArNu)*- (10-12)*-. The inhibition experiments of the photoinduced substitution reaction in the presence of radical scavengers and the global quantum yield higher than the unity are evidence of a radical chain mechanism for these substitution reactions by anions 1 and 2. Anion 3 adds to the 1-naphthyl radical, but is neither able to initiate nor to keep the propagation cycle. Evaluation of the electron-transfer driving forces for the reaction between (ArNu)*- and 4 together with the absence of a chain reaction for the anion 3 indicate that the propagation in the proposed mechanism is given by an acid-base reaction between the radical .C(O)Me or .C(NH)NH2 (13) and a base.     

Molecular description of indigo oxidation mechanisms initiated by OH and OOH radicals

In this work, we report a quantum chemistry mechanistic study of the hydroxyl (?OH) and hydroperoxyl (?OOH) radicals initiated oxidation of indigo, within the density functional theory framework. All possible hydrogen abstraction and radical addition reaction pathways have been considered. We find that the reaction between a free indigo molecule and an ?OH radical occurs mainly through two competing mechanisms: H-abstraction from an NH site and ?OH addition to the central C═C double bond. Although the latter is favored, both channels occur, the indigo chromophore group structure is modified, and thus the color is changed. This mechanism adequately accounts for the loss of chromophore in urban air, including indoor air such as in museums and in urban areas. Regarding the reactivity of indigo toward ?OOH radicals, only ?OOH-addition to the central double bond is thermodynamically feasible. The corresponding transition state free energy value is about 10 kcal/mol larger than the one for the ?OH initiated oxidation. Therefore, even considering that the ?OOH concentration is considerably larger than the one of ?OH, this reaction is not expected to contribute significantly to indigo oxidation under atmospheric conditions.     

Antioxidant activity of trans-resveratrol toward hydroxyl and hydroperoxyl radicals: a quantum chemical and computational kinetics study

In this work, we have carried out a systematic study of the antioxidant activity of trans-resveratrol toward hydroxyl ((?)OH) and hydroperoxyl ((?)OOH) radicals in aqueous simulated media using density functional quantum chemistry and computational kinetics methods. All possible mechanisms have been considered: hydrogen atom transfer (HAT), proton-coupled electron transfer (PCET), sequential electron proton transfer (SEPT), and radical adduct formation (RAF). Rate constants have been calculated using conventional transition state theory in conjunction with the Collins-Kimball theory. Branching ratios for the different paths contributing to the overall reaction, at 298 K, are reported. For the global reactivity of trans-resveratrol toward (?)OH radicals, in water at physiological pH, the main mechanism of reaction is proposed to be the sequential electron proton transfer (SEPT). However, we show that trans-resveratrol always reacts with (?)OH radicals at a rate that is diffusion-controlled, independent of the reaction pathway. This explains why trans-resveratrol is an excellent but very unselective (?)OH radical scavenger that provides antioxidant protection to the cell. Reaction between trans-resveratrol and the hydroperoxyl radical occurs only by phenolic hydrogen abstraction. The total rate coefficient is predicted to be 1.42 × 10(5) M(-1) s(-1), which is much smaller than the ones for reactions of trans-resveratrol with (?)OH radicals, but still important. Since the (?)OOH half-life time is several orders larger than the one of the (?)OH radical, it should contribute significantly to trans-resveratrol oxidation in aqueous biological media. Thus, trans-resveratrol may act as an efficient (?)OOH, and also presumably (?)OOR, radical scavenger.     

Photoredox chemistry of AOT: electron transfer and hydrogen abstraction in microemulsions involving the surfactant

Time-resolved magnetic resonance experiments (TREPR and CIDNP) are used to investigate previously unobserved redox chemistry of the surfactant dioctyl sulfosuccinate ester (AOT) using the photoexcited triplet state of anthraquinone 2,6-disulfonate (3AQDS*). Several different free radicals resulting from two independent oxidation pathways (electron transfer and hydrogen abstraction) are observed. These include the radical ions of AQDS and sulfite from electron-transfer processes, carbon-centered radicals from H-atom abstraction reactions, and an additional carbon-centered radical formed by electron transfer from the AOT sulfonate head group followed by the loss of SO3. The radicals exhibit intense chemically induced dynamic electron spin polarization (CIDEP) in their TREPR spectra. The intensity ratios of the observed TREPR signals for each radical depend on the water pool size and temperature, which in turn affect the predominant CIDEP mechanism. All signal carriers are accounted for by simulation, and CIDNP results provide strong supporting evidence for the assignments.     

羟基自由基和鸟嘌呤-胞嘧啶碱基对反应的密度泛函理论研究

为了解决年龄衰老、基因突变和癌症等问题, 理解DNA的氧化损伤机理非常重要. 本文利用密度泛函方法和极化连续介质模型在液相条件下研究了羟基自由基夺取鸟嘌呤-胞嘧啶(GC)碱基对上5 个氢原子的反应机理. 研究结果表明, 所有的脱氢反应路径都是放热过程, 热力学上五个脱氢反应路径形成自由基的稳定性顺序是(H2b-GC)^·>(GC-H4b)^·>(GC-H6)^·>(GC-H5)^·~(H8-GC)^·, 其中H2b反应路径的能量变化最大, 说明该反应平衡时的转化率最高. 动力学上, 相对于反应复合物的局部反应能垒大小顺序是H2b     

Evidence for glycosidic bond rotation in a nucleobase peroxyl radical and its effect on tandem lesion formation

Nucleobase peroxyl radicals are the major reactive intermediates formed in DNA when the biopolymer is exposed to gamma-radiolysis under aerobic conditions. The major reaction pathways for the peroxyl radical (1) derived from 5,6-dihydro-2'-deoxyuridin-6-yl involve pi-bond addition to or hydrogen atom abstraction from the adjacent nucleotides to produce tandem lesions. The ability to independently generate 1 at a defined site in DNA enabled us to probe its reactivity by varying the local DNA structure. The effect of DNA structure variation reveals that 1 reacts from its syn- and anti-conformations in competition with trapping by thiol. These experiments also reveal that tandem lesions will be produced as a mixture of diastereomers, which could impact their biological effects.     

Direct comparison of solution and gas-phase reactions of the three distonic isomers of the pyridine radical cation with methanol

To directly compare the reactivity of positively charged carbon-centered aromatic σ-radicals toward methanol in solution and in the gas phase, the 2-, 3-, and 4-dehydropyridinium cations (distonic isomers of the pyridine radical cation) were generated by ultraviolet photolysis of the corresponding iodo precursors in a mixture of water and methanol at varying pH. The reaction mixtures were analyzed by using liquid chromatography/mass spectrometry. Hydrogen atom abstraction was the only reaction observed for the 3- and 4-dehydropyridinium cations (and pyridines) in solution. This also was the major reaction observed earlier in the gas phase. Depending on the pH, the hydrogen atom can be abstracted from different molecules (i.e., methanol or water) and from different sites (in methanol) by the 3- and 4-dehydropyridinium cations/pyridines in solution. In the pH range 1-4, the methyl group of methanol is the main hydrogen atom donor site for both 3- and 4-dehydropyridinium cations (just like in the gas phase). At higher pH, the hydroxyl groups of water and methanol also act as hydrogen atom donors. This finding is rationalized by a greater abundance of the unprotonated radicals that preferentially abstract hydrogen atoms from the polar hydroxyl groups. The percentage yield of hydrogen atom abstraction by these radicals was found to increase with lowering the pH in the pH range 1.0-3.2. This pH effect is rationalized by polar effects: the lower the pH, the greater the fraction of protonated (more polar) radicals in the solution. This finding is consistent with previous results obtained in the gas phase and suggests that gas-phase studies can be used to predict solution reactivity, but only as long as the same reactive species is studied in both experiments. This was found not to be the case for the 2-iodopyridinium cation. Photolysis of this precursor in solution resulted in the formation of two major addition products, 2-hydroxy- and 2-methoxypyridinium cations, in addition to the hydrogen atom abstraction product. These addition products were not observed in the earlier gas-phase studies on 2-dehydropyridinium cation. Their observation in solution is explained by the formation of another reactive intermediate, the 2-pyridylcation, upon photolysis of 2-iodopyridinium cation (and 2-iodopyridine). The same intermediate was observed in the gas phase but it was removed before examining the reactions of the desired radical, 2-dehydropyridinium cation (which cannot be done in solution).     

Trapping of the OH radical by alpha-tocopherol: a theoretical study

The antioxidant activity of alpha-tocopherol against the damaging hydroxyl radical was analyzed theoretically by hybrid density functional theory, following the direct dynamics method, where the thermal rate constants were calculated using variational transition-state theory with multidimensional tunneling. We found that the OH radical is only slightly or not at all selective, attacking by different mechanisms at several positions of the alpha-tocopherol molecule, giving competitive reactions. The most favorable pathways are the hydrogen abstraction reaction from the phenolic hydrogen and the electrophilic addition onto the aromatic ring. We propose a final rate constant, the sum of the competitive hydrogen abstraction and addition reactions, > or =2.7 x 10(8) M(-1) s(-1) at 298 K, where the hydrogen abstraction reaction represents only 20% of the total OH radical reaction. This result indicates that, molecule by molecule, in an apolar environment, alpha-tocopherol is less effective than coenzyme Q (which presents a rate constant of 6.2 x 10(10) M(-1) s(-1) at 298 K) as a scavenger of OH radicals. It was also found that both mechanisms are not direct but pass through intermediates in the entry channel, with little or no influence on the dynamics of the reactions. The hydrogen abstraction reaction also presents another intermediate in the exit channel, which may have a significant role in preventing the pro-oxidant effects of alpha-tocopherol, although less important than with free radicals other than OH.