Relationship between the bubble temperature and main oxidant created inside an air bubble under ultrasound

Numerical simulations of nonequilibrium chemical reactions in a pulsating air bubble have been performed for various ultrasonic frequencies (20 kHz, 100 kHz, 300 kHz, and 1 MHz) and pressure amplitudes (up to 10 bars). The results of the numerical simulations have indicated that the main oxidant is OH radical inside a nearly vaporous or vaporous bubble which is defined as a bubble with higher molar fraction of water vapor than 0.5 at the end of the bubble collapse. Inside a gaseous bubble which is defined as a bubble with much lower vapor fraction than 0.5, the main oxidant is H2O2 when the bubble temperature at the end of the bubble collapse is in the range of 4000-6500 K and O atom when it is above 6500 K. From the interior of a gaseous bubble, an appreciable amount of OH radical also dissolves into the liquid. When the bubble temperature at the end of the bubble collapse is higher than 7000 K, oxidants are strongly consumed inside a bubble by oxidizing nitrogen and the main chemical products inside a bubble are HNO2, NO, and HNO3.     

Multibubble Sonoluminescence from a Theoretical Perspective

In the present review, complexity in multibubble sonoluminescence (MBSL) is discussed. At relatively low ultrasonic frequency, a cavitation bubble is filled mostly with water vapor at relatively high acoustic amplitude which results in OH-line emission by chemiluminescence as well as emissions from weakly ionized plasma formed inside a bubble at the end of the violent bubble collapse. At relatively high ultrasonic frequency or at relatively low acoustic amplitude at relatively low ultrasonic frequency, a cavitation bubble is mostly filled with noncondensable gases such as air or argon at the end of the bubble collapse, which results in relatively high bubble temperature and light emissions from plasma formed inside a bubble. Ionization potential lowering for atoms and molecules occurs due to the extremely high density inside a bubble at the end of the violent bubble collapse, which is one of the main reasons for the plasma formation inside a bubble in addition to the high bubble temperature due to quasi-adiabatic compression of a bubble, where “quasi” means that appreciable thermal conduction takes place between the heated interior of a bubble and the surrounding liquid. Due to bubble–bubble interaction, liquid droplets enter bubbles at the bubble collapse, which results in sodium-line emission.     

Generation and consumption rates of OH radicals in sonochemical reactions

In this study, a KI aqueous solution or Methyl Orange (MO) aqueous solution was irradiated by an ultrasonic wave under the same experimental condition. The rates of oxidation of KI and MO by OH radicals differed by an order of magnitude. When the consumption of OH radicals by chemical reactions with species other than KI or MO is taken into account, numerical analysis of chemical kinetics model yields the same generation rate of OH radicals by the action of an ultrasonic wave for the experiments of KI and MO solutions.     

The range of ambient radius for an active bubble in sonoluminescence and sonochemical reactions

Numerical simulations of nonequilibrium chemical reactions inside an air bubble in liquid water irradiated by ultrasound have been performed for various ambient bubble radii. The intensity of sonoluminescence (SL) has also been calculated taking into account electron-atom bremsstrahlung, radiative attachment of electrons to neutral molecules, radiative recombination of electrons and ions, chemiluminescence of OH, molecular emission from nitrogen, etc. The lower bound of ambient radius for an active bubble in SL and sonochemical reactions nearly coincides with the Blake threshold for transient cavitation. The upper bound is in the same order of magnitude as that of the linear resonance radius. In actual experiments, however, the distribution of ambient radius for active bubbles may be narrow at around the threshold ambient radius for the shape instability. The threshold peak temperature inside an air bubble for nitrogen burning is higher than that for oxidant formation. The threshold peak temperatures depend on ultrasonic frequency and acoustic amplitude because chemical reactions inside a bubble are in nonequilibrium. The dominant emission mechanism in SL is electron-atom bremsstrahlung except at a lower bubble temperature than 2000 K, for which molecular emissions may be dominant.     

Dynamic Visualization of Free Radicals at Single Oxygen Bubbles using Chemiluminescence

The generation of free radicals is a key process in the formation and the collapse of the bubbles in water, however, the direct and dynamic observation of the radicals in this process at single bubbles has never been achieved. Here, the hydroxyl (OH^.) and oxygen (O₂^.−) radicals at single oxygen bubbles are continuously traced using chemiluminescence (CL), in which these radicals at the bubble react with the surrounding luminol in the solution emitting the light. Varied increase trends of luminescence are observed in the generation of a bubble, floating, short parking at the water/air interface and the final explosion, revealing the complexity in the distribution of radicals at the bubble unprecedentedly. Despite more radicals are observed at the bubble generated at a deep position under the water for the stabilization, almost the same amount of radicals are included in the bubbles that is independent on the water pressure during the production of the bubble. This rich information collected from the dynamic study of bubbles illustrates the complicated generation and distribution process of radicals at the bubbles, and will facilitate the understanding of the function about the bubbles.     

Mechanism of Pt(IV) sonochemical reduction in formic acid media and pure water

Sonochemical synthesis of platinum nanoparticles (Pt?NPs) in formic acid solutions and pure water was investigated using a 20?kHz ultrasonic irradiation. The obtained results gave new insights on the underneath Pt(IV) reduction mechanism in formic acid media under argon and in pure water under Ar/CO atmosphere. It was shown that in pure water sonochemical reduction of platinum ions occurs by hydrogen issued from homolytic water molecule split. Pt(IV)?ion reduction appears to be a very slow process under argon atmosphere in pure water due to formation of oxidizing species like OH radicals and H(2)O(2) leading to reoxidation of intermediate Pt(II) ions. Sonochemical reduction is accelerated manifold in the presence of formic acid or Ar/CO gas mixture. Solution and gas-phase analyses reveal that both CO and HCOOH act as OH(.) radical scavenger and reducing agent under ultrasonic irradiation. Their ability to reduce platinum ions at room temperature is enhanced due to the local heating in the liquid shell surround the cavitation bubble. An innovative synthesis route for monodispersed Pt?NPs in pure water without any templates or capping agents in the presence of Ar/CO gas mixture is then proposed. Obtained Pt?NPs within the range of 2-3?nm exhibited a strong stability towards sedimentation in water. Since Ar/CO atmosphere is the only restriction of the process, this procedure can be applied in various media and is also compatible with a large array of experimental conditions.     

Insights in the laser-induced breakdown spectroscopy signal generation underwater using dual pulse excitation — Part I: Vapor bubble,shockwaves and plasma

Plasma and vapor bubble formation and evolution after a nanosecond laser pulse delivered to aluminum targets inside water were studied by fast photography. This technique was also applied to monitor the plasma produced by a second laser pulse and for different interpulse delays. The bubble growth was evident only after 3 μs from the first laser pulse and the bubble shape changed during expansion and collapse cycles. The evolution and propagation of the initial shockwave and its reflections both from the back sample surface and cell walls were detected by Schlieren photography. The primary plasma develops in two phases: violent particle expulsion and ionization during the first μs, followed by slow plasma growth from the ablation crater into the evolving vapor bubble. The shape of the secondary plasma strongly depends on the inner bubble pressure whereas the particle expulsion into the expanded bubble is much less evident. Both the primary and secondary plasma have similar duration of about 30 μs. Detection efficiency of the secondary plasma is much reduced by light refraction at the curved bubble–water interface, which behaves as a negative lens; this leads to an apparent reduction of the plasma dimensions. Defocusing power of the bubble lens increases with its expansion due to the lowering of the vapor's refraction index with respect to that of the surrounding liquid (Lazic et al., 2012 [1]). Smell's reflections of secondary plasma radiation at the expanded bubble wall redistribute the detected intensity on a wavelength-dependent way and allow gathering of the emission also from the external plasma layer that otherwise, would not enter into the optical system.     

Mechanisms of formation of 8-oxoguanine due to reactions of one and two OH* radicals and the H2O2 molecule with guanine: A quantum computational study

Mechanisms of formation of the mutagenic product 8-oxoguanine (8OG) due to reactions of guanine with two separate OH* radicals and with H2O2 were investigated at the B3LYP/6-31G, B3LYP/6-311++G, and B3LYP/AUG-cc-pVDZ levels of theory. Single point energy calculations were carried out with the MP2/AUG-cc-pVDZ method employing the optimized geometries at the B3LYP/AUG-cc-pVDZ level. Solvent effect was treated using the PCM and IEF-PCM models. Reactions of two separate OH* radicals and H2O2 with the C2 position of 5-methylimidazole (5MI) were investigated taking 5MI as a model to study reactions at the C8 position of guanine. The addition reaction of an OH* radical at the C8 position of guanine is found to be nearly barrierless while the corresponding adduct is quite stable. The reaction of a second OH* radical at the C8 position of guanine leading to the formation of 8OG complexed with a water molecule can take place according to two different mechanisms, involving two steps each. According to one mechanism, at the first step, 8-hydroxyguanine (8OHG) complexed with a water molecule is formed ,while at the second step, 8OHG is tautomerized to 8OG. In the other mechanism, at the first step, an intermediate complexed (IC) with a water molecule is formed, the five-membered ring of which is open, while at the second step, the five-membered ring is closed and a hydrogen bonded complex of 8OG with a water molecule is formed. The reaction of H2O2 with guanine leading to the formation of 8OG complexed with a water molecule can also take place in accordance with two different mechanisms having two steps each. At the first step of one mechanism, H2O2 is dissociated into two OH* groups that react with guanine to form the same IC as that formed in the reaction with two separate OH* radicals, and the subsequent step of this mechanism is also the same as that of the reaction of guanine with two separate OH* radicals. At the first step of the other mechanism of the reaction of guanine with H2O2, the latter molecule is dissociated into a hydrogen atom and an OOH* group which become bonded to the N7 and C8 atoms of guanine, respectively. At the second step of this mechanism, the OOH* group is dissociated into an oxygen atom and an OH* group, the former becomes bonded to the C8 atom of guanine while the latter abstracts the H8 atom bonded to C8, thus producing 8OG complexed with a water molecule. Solvent effects of the aqueous medium on certain reaction barriers and released energies are appreciable. 5MI works as a satisfactory model for a qualitative study of the reactions of two separate OH* radicals or H2O2 occurring at the C8 position of guanine.     

Pulsed Electrical Discharges in Water: Can Non-volatile Compounds Diffuse into the Plasma Channel?

The objective of this research effort is to develop a more comprehensive understanding of how molecules get degraded in plasma during an electrical discharge in water. The study correlates the intensity of hydroxyl (OH) radicals in the plasma and physicochemical properties of aqueous solutions of methanol, ethanol, acetonitrile, acetone, dimethyl sulfoxide (DMSO), dimethyl formamide (DMF), phenol, hydroquinone, caffeine, and bisphenol A (BPA). To determine the tendency of the used compounds to penetrate the plasma, their vapor pressures, Henry’s constants, aqueous solubilities, reaction rate constants with OH radicals, and octanol–water partition coefficients are compared and correlated with plasma spectroscopic and hydrogen peroxide (H₂O₂) measurements. OH radicals are precursors to the formation of hydrogen peroxide and any compound that diffuses into the plasma will react with and lower the intensity of OH radicals and therefore the concentration of hydrogen peroxide in the bulk liquid. Optical emission spectroscopy (OES) reveals that all the used compounds diffuse inside the plasma channel regardless of their vapor pressure where they get oxidized (primarily by OH radicals) and thermally degraded. Results also indicate that hydrophobicity (i.e., octanol–water partition coefficient) is the most important property that determines a compound’s tendency to diffuse inside the plasma channel; hydrophobic compounds readily penetrate the plasma whereas hydrophilic compounds tend to stay in the bulk liquid. The rate of formation of hydrogen peroxide is independent of the type of the compound present in the bulk liquid which confirms that this molecule is formed at the plasma interface.     

Time-domain calculations of the polarized Raman spectra, the transient infrared absorption anisotropy, and the extent of delocalization of the OH stretching mode of liquid water

The polarized Raman spectrum and the time dependence of the transient infrared (TRIR) absorption anisotropy are calculated for the OH stretching mode of liquid water (neat liquid H2O) by using time-domain formulations, which include the effects of both the diagonal frequency modulations (of individual oscillators) induced by the interactions between the dipole derivatives and the intermolecular electric field, and the off-diagonal (intermolecular) vibrational coupling described by the transition dipole coupling (TDC) mechanism. The IR spectrum of neat liquid H2O and the TRIR anisotropy of a liquid mixture of H2O/HDO/D2O are also calculated. It is shown that the calculated features of these optical signals, including the temperature dependence of the polarized Raman and IR spectra, are in reasonable agreement with the experimental results, indicating that the frequency separation between the isotropic and anisotropic components of the polarized Raman spectrum and the rapid decay (approximately 0.1 ps) of the TRIR anisotropy of the OH stretching mode of neat liquid H2O are mainly controlled by the resonant intermolecular vibrational coupling described by the TDC mechanism. Comparing with the time evolution of vibrational excitations, it is suggested that the TRIR anisotropy decays in the time needed for the initially localized vibrational excitations to delocalize over a few oscillators. It is also shown that the enhancement of the dipole derivatives by the interactions with surrounding molecules is an important factor in generating the spectral profiles of the OH stretching Raman band. The time-domain behavior of the molecular motions that affect the spectroscopic features is discussed.     

Adding water to sugar: a spectroscopic and computational study of alpha- and beta-phenylxyloside in the gas phase

The gas phase structures of phenyl alpha- and beta-d-xylopyranoside (alpha- and beta-pXyl) and their mono-hydrates have been investigated using a combination of resonant two-photon ionization (R2PI), ultra-violet hole-burning and resonant infrared ion dip spectroscopy, coupled with density functional theory (DFT) and ab initio computation. The hole-burning experiments indicate the population of a single conformer only, in each of the two anomers. Their experimental and calculated infrared spectra are both consistent with a conformational assignment corresponding to the computed global minimum configuration. All three OH groups are oriented towards the oxygen atom (O1) on the anomeric carbon atom to form an all trans(ttt) counter-clockwise chain of hydrogen bonds. The mono-hydrates, alpha- and beta-pXyl(H(2)O) each populate two distinct structures in the molecular beam environment, with the water molecule inserted between OH4 and OH3 or between OH3 and OH2 in alpha-pXyl(H2O), and between OH2 and O1 in either of two alternative orientations, in beta-pXyl(H2O). In all of the mono-hydrated xyloside complexes, the water molecule inserts into the weakest link of the sugar molecules' hydrogen-bonded chain of hydroxy groups, creating a single extended chain, strengthened by co-operativity. The all-trans configuration of the xylose moiety is retained and the mono-hydrate structures correspond to those calculated to lie at the lowest relative energies.     

Molecular dynamics simulations of D2O ice photodesorption

Molecular dynamics (MD) calculations have been performed to study the ultraviolet (UV) photodissociation of D(2)O in an amorphous D(2)O ice surface at 10, 20, 60, and 90 K, in order to investigate the influence of isotope effects on the photodesorption processes. As for H(2)O, the main processes after UV photodissociation are trapping and desorption of either fragments or D(2)O molecules. Trapping mainly takes place in the deeper monolayers of the ice, whereas desorption occurs in the uppermost layers. There are three desorption processes: D atom, OD radical, and D(2)O molecule photodesorption. D(2)O desorption takes places either by direct desorption of a recombined D(2)O molecule, or when an energetic D atom produced by photodissociation kicks a surrounding D(2)O molecule out of the surface by transferring part of its momentum. Desorption probabilities are calculated for photoexcitation of D(2)O in the top four monolayers and are compared quantitatively with those for H(2)O obtained from previous MD simulations of UV photodissociation of amorphous water ice at different ice temperatures [Arasa et al., J. Chem. Phys. 132, 184510 (2010)]. The main conclusions are the same, but the average D atom photodesorption probability is smaller than that of the H atom (by about a factor of 0.9) because D has lower kinetic energy than H, whereas the average OD radical photodesorption probability is larger than that of OH (by about a factor of 2.5-2.9 depending on ice temperature) because OD has higher translational energy than OH for every ice temperature studied. The average D(2)O photodesorption probability is larger than that of H(2)O (by about a factor of 1.4-2.3 depending on ice temperature), and this is entirely due to a larger contribution of the D(2)O kick-out mechanism. This is an isotope effect: the kick-out mechanism is more efficient for D(2)O ice, because the D atom formed after D(2)O photodissociation has a larger momentum than photogenerated H atoms from H(2)O, and D transfers momentum more easily to D(2)O than H to H(2)O. The total (OD + D(2)O) yield has been compared with experiments and the total (OH + H(2)O) yield from previous simulations. We find better agreement when we compare experimental yields with calculated yields for D(2)O ice than when we compare with calculated yields for H(2)O ice.     

Investigating the Existence of Bulk Nanobubbles with Ultrasound

Nanobubbles are expected to dissolve in milliseconds. Experimental evidence of nanobubbles that were stable for days had thus been first received with circumspection. If the large number of experimental confirmations has now made clear that surface nanobubbles could exist, bulk nanobubbles are still subject to debate. When observations are reported, the main problem is to make sure the observed particles are really made of gas. We show that ultrasound is an ideal tool for investigating the existence of bulk nanobubbles: 1) it is sensitive to minute quantities of gas, 2) it allows one to determine the bubble size distribution, 3) it discriminates unambiguously between gaseous and solid/liquid inclusions. To illustrate the efficiency of ultrasonic detection, we performed size measurements of bubbles produced by a commercial nano‐/microbubble generator. No nanobubble was detected with this device. It would be insightful to use ultrasonic detection in experimental situations for which stable nanobubbles were reported.     

Interaction between OH radical and the water interface

Results from a theoretical study of the interactions of a OH radical on (H2O)20, (H2O)24, and (H2O)28 clusters used as a novel model of a water droplet are presented. This work shows that there is competition between OH radicals trapped on the surface and those encapsulated inside of a water cage. This is contrary to previous findings of HO2 radical interactions with water clusters. Natural bond orbital (NBO) analysis is used to analyze the bonding feature of OH to help explain the difference in behavior between OH and HO2 radicals toward a water surface.     

Insights in the laser induced breakdown spectroscopy signal generation underwater using dual pulse excitation — Part II: Plasma emission intensity as a function of interpulse delay

Influence of time delay between two laser pulses on the LIBS (laser induced breakdown spectroscopy) signal inside liquids was investigated and the results are compared with data from literature. Plasma was produced by laser ablation (LA) of aluminum inside water and its emission after the second laser pulse was characterized by spectrally and time resolved detection. Light propagation through the vapor bubble formed by the first laser pulse was studied by measurements of beam scattering and transmission. Optical absorption by the evolving bubble is not significant, but its growth is accompanied by lowering of its refraction index n_b with respect to surrounding liquid; this effect increases defocusing both of the incident beam and of the out-coming plasma radiation. Collection efficiency of the secondary plasma emission rapidly degrades with the cavity growth, but close to its full expansion the LIBS signal partially recovers through Snell's reflections at the liquid–vapor interface, which produce a bright spot close to the bubble center. Such a light redistribution allows detecting of the emission from external plasma volume, otherwise deflected out of the collection system. Except for strong line transitions from the main sample constituents, self-absorbed inside the high-pressure cavity, we observed the highest LIBS signal when sending the second pulse well before the bubble is fully expanded. Transitions of the pressure wave through the focal volume, formed by the first laser pulse and reflected from the cell's walls and sample back-plane, enhances the LIBS signal importantly. The measured lifetime of the secondary plasma rapidly decreases with the bubble expansion. Here, we also discuss the optimization of the optical collection system and some analytical aspects of double-pulse (DP) LIBS inside liquids.     

Gas-phase kinetics of hydroxyl radical reactions with C3H6 and C4H8: product branching ratios and OH addition site-specificity

Products of the reaction of OH radicals with propene, trans-2-butene, and 1-butene have been investigated in a fast flow reactor, coupled with time-of-flight mass spectrometry, at pressures between 0.8 and 3.0 Torr. The product determination includes H atom abstraction channels as well as site-specific OH addition. The OH radicals are produced by the H + NO(2) → OH + NO reaction or by the F + H(2)O → OH + HF reaction, the H or F atoms being produced in a microwave discharge. The gas mixture is ionized using single photon ionization (SPI at 10.54 eV), and products are detected using time-of-flight mass spectrometry (TOF-MS). The H atom abstraction channels are measured to be <2% for OH + propene, 8 ± 3% for OH + 1-butene, and 3 ± 1% for OH + trans-2-butene. Analysis of ion fragmentation patterns leads to 72 ± 16% OH addition to the propene terminal C atom and 71 ± 16% OH addition to the 1-butene terminal C atom. The errors bars represent 95% confidence intervals and include estimated uncertainties in photoionization cross sections.     

Bubble dynamics for broadband microrheology of complex fluids

Bubbles in complex fluids are often desirable, and sometimes simply inevitable, in the processing of formulated products. Bubbles can rise by buoyancy, grow or dissolve by mass transfer, and readily respond to changes in pressure, thereby applying a deformation to the surrounding complex fluid. The deformation field around a stationary, spherical bubble undergoing a change in radius is simple and localized, thus making it suitable for rheological measurements. This article reviews emerging approaches to extract information on the rheology of complex fluids by analysing bubble dynamics. The focus is on three phenomena: changes in radius by mass transfer, harmonic oscillations driven by an acoustic wave, and bubble collapse. These phenomena cover a broad range of deformation frequencies, from 10⁻⁴–10⁶ Hz, thus paving the way to broadband microrheology using bubbles as active probes. The outstanding challenges that need to be overcome to achieve a robust technique are also discussed.     

The mechanism of the sonochemical degradation of benzoic acid in aqueous solutions

The sonolytic degradation of benzoic acid in aqueous solution was investigated at an ultrasonic frequency of 355 kHz. The degradation rate was found to be dependent upon the solution pH and the surface activity of the solute. The degradation rate was favoured at a solution pH lower than the pK _a of benzoic acid. At pH < pK _a, HPLC, GC and ESMS analysis showed that benzoic acid could be degraded both inside the bubble by pyrolysis and at the bubble/solution interface by the reaction with OH radicals. At higher pH (> pK _a) benzoic acid could only react with OH radicals in the bulk solution. During the sonolytic degradation of benzoic acid, mono-hydroxy substituted intermediates were observed as initial products. Further OH radical attack on the mono-hydroxy intermediates led to the formation of di-hydroxy derivatives. Continuous hydroxylation of the intermediates led to ring opening followed by complete mineralization. Mineralization of benzoic acid occurred at a rate of < 40μM/h.     

Dynamics of the gas-liquid interfacial reaction of O(1D) with a liquid hydrocarbon

The dynamics of the gas-liquid interfacial reaction of the first electronically excited state of the oxygen atom, O((1)D), with the surface of a liquid hydrocarbon, squalane (C(30)H(62); 2,6,10,15,19,23-hexamethyltetracosane) has been studied experimentally. Translationally hot O((1)D) atoms were generated by 193 nm photolysis of a low pressure (nominally 1 mTorr) of N(2)O a short distance (mean = 6 mm) above a continually refreshed liquid squalane surface. Nascent OH (X(2)Π, v' = 0) reaction products were detected by laser-induced fluorescence (LIF) on the OH A(2)Σ(+)-X(2)Π (1,0) band at the same distance above the surface. The speed distribution of the recoiling OH was characterized by measuring the appearance profiles as a function of photolysis-probe delay for selected rotational levels, N'. The rotational (and, partially, fine-structure) state distributions were also measured by recording LIF excitation spectra at selected photolysis-probe delays. The OH v' = 0 rotational distribution is bimodal and can be empirically decomposed into near thermal (~300 K) and much hotter (~6000 K) Boltzmann-temperature components. There is a strong positive correlation between rotational excitation and translation energy. However, the colder rotational component still represents a significant fraction (~30%) of the fastest products, which have substantially superthermal speeds. We estimate an approximate upper limit of 3% for the quantum yield of OH per O((1)D) atom that collides with the surface. By comparison with established mechanisms for the corresponding reactions in the gas phase, we conclude that the rotationally and translationally hot products are formed via a nonstatistical insertion mechanism. The rotationally cold but translationally hot component is most likely produced by direct abstraction. Secondary collisions at the liquid surface of products of either of the previous two mechanisms are most likely responsible for the rotationally and translationally cold products. We do not think it likely, a priori, that they could be produced in the observed significant yield via a statistical insertion mechanism for a molecule the size of squalane embedded in a surrounding liquid surface.     

A computational investigation on the geometries,stabilities, antioxidant activity,and the substituent effects of the L‐ascorbic acid and their derivatives

The geometries, stabilities, and antioxidant activities of L‐Ascorbic acid (1a), D‐erythroascorbate (2a), and D‐erythroascorbate glucoside (3a) as well as their sulfur and selenium derivatives are systematically investigated by using density functional theory. Emphasis is placed on studies of the two main mechanisms, that is, hydrogen atom donation and single‐electron transfer, and the O—H bond dissociation enthalpy and the ionization potential are computed in the gas phase and water solution. The calculated results indicate that the 2‐OH group in the five‐membered ring acts as an important H atom donor to free radicals. The 2‐OH radical spin density distribution shows that the unpaired electron is mostly located at the C3 atom of the five‐membered ring and partially at the vicinal O atoms, proving that a certain delocalization of the odd electron is effective in the five‐membered ring. In water aqueous solution, the antioxidant capacity and the electron donating ability are increased as the O atom in the five‐membered ring of 1a, 2a, and 3a is replaced by S and Se, respectively, in good agreement with experimental measurements; Furthermore, their antioxidant capacities are enhanced as compared with the standard antioxidant (resveratrol). © 2013 Wiley Periodicals, Inc.