Dibromo-BODIPY as an Organic Photocatalyst for Radical-Ionic Sequences.

A new dibrominated 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) is reported as a new metal-free photocatalyst. This BODIPY showed similar optoelectronic, electrochemical, and performance properties to those of Ru(bpy)3Cl2, one of the most common photocatalysts in a known radical-ionic transformation, such as the formation of 1,4-dicarbonyl compounds. Moreover, additional sequences in which the generated oxonium ion is trapped by an internal nucleophile were developed using this BODIPY photocatalyst. These new sequences allowed the straightforward preparation of γ-alkoxylactones, monoprotected 1,4-ketoaldehydes, and dihydrofurans. This new catalyst, the methodology, and the forged functional groups could be important tools in organic synthesis.

Extracurricular activities and group belonging as a protective factor in adolescence / Actividades extraescolares y pertenencia al grupo como factor protector en la adolescencia

In the transition into adulthood, family and school play a critical role protecting the adolescent from engaging in behaviors that could cause mental health problems. Nevertheless, there are other social groups and structured activities that have shown to act as an educational activity and as a protective factor as well. The aim of this study was to investigate the relationship between belonging to different types of social groups and the positive and negative mental health indicators of Mexican adolescents. Participants were 840 Mexican adolescents ranging between 12 and 17 years old. Results indicated that belonging to artistic and scout groups reported a statistically significant correlation with higher levels of emotional intelligence. Belonging to sport and artistic groups reported a statistically significant correlation with higher levels of resilience. No statistically significant results were found on anxiety, depression, and/or disruptive behaviors. Further research is needed, especially investigating possible predictive and moderating variables

En la transición a la vida adulta, la familia y la escuela juegan un papel protector decisivo para proteger al adolescente de comportamientos que podrían acarrearle problemas de salud mental. No obstante, hay otros grupos sociales y actividades estructuradas que han funcionado como actividades educativas además de como factores protectores. El objetivo de este trabajo ha sido investigar la relación entre la pertenencia a diferentes tipos de grupos sociales y los indicadores positivos y negativos de salud mental de adolescentes mexicanos. Los participantes eran 840 adolescentes mexicanos de edades comprendidas entre los 12 y los 17 años. Los resultados indican que la pertenencia a grupos artísticos y scouts correlacionaba significativamente con elevados niveles de inteligencia emocional. Pertenecer a grupos deportivos y artísticos correlacionaba significativamente con elevados niveles de resiliencia. No se dieron resultados estadísticamente significativos en ansiedad, depresión o conductas problemáticas. Se necesita continuar investigando, sobre todo en las posibles variables predictoras y moderadoras

Synthesis, photophysical, electrochemical and electrochemiluminescence properties of A2B2 zinc porphyrins: the effect of π-extended conjugation.

The synthesis of two A2B2 porphyrins, {5,15-bis-[4-(octyloxy)phenyl]-porphyrinato}zinc(ii) () and {5,15-bis-(carbazol-3-yl-ethynyl)-10,20-bis-[4-(octyloxy)phenyl]-porphinato}-zinc(ii) (), is reported. Their photophysical properties were studied by steady-state absorption and emission. Substituting the carbazolylethynyl moieties at two of the meso positions results in a large bathochromic shift of all the absorption bands, a notable increase in the absorption coefficient of the Q(0,0) band, and higher fluorescence quantum yield compared to porphyrin , with two unsubstituted meso positions. Cyclic voltammetry and digital simulation show that electrogenerated radical ions of are more stable than those of . The lack of substituents at the meso positions of leads to dimerization reactions of the radical cation. Despite this, the annihilation reaction of and produces very similar electrogenerated chemiluminescence (ECL) intensity. Spectroelectrochemical experiments demonstrate that the electroreduction of leads to a strong absorption band that might quench the ECL.

Phytotoxic Potential of Secondary Metabolites and Semisynthetic Compounds from Endophytic Fungus Xylaria feejeensis Strain SM3e-1b Isolated from Sapium macrocarpum.

Bioactivity-directed fractionation of the combined culture medium and mycelium extract of the endophytic fungus Xylaria feejeensis strain SM3e-1b, isolated from Sapium macrocarpum, led to the isolation of three known natural products: (4S,5S,6S)-4-hydroxy-3-methoxy-5-methyl-5,6-epoxycyclohex-2-enone or coriloxine, 1; 2-hydroxy-5-methoxy-3-methylcyclohexa-2,5-diene-1,4-dione, 2; and 2,6-dihydroxy-5-methoxy-3-methylcyclohexa-2,5-diene-1,4-dione or fumiquinone B, 3. This is the first report of compound 3 being isolated from this species. Additionally, four new derivatives of coriloxine were prepared: (4R,5S,6R)-6-chloro-4,5-dihydroxy-3-methoxy-5-methylcyclohex-2-enone, 4; 6-hydroxy-5-methyl-3-(methylamino)cyclohexa-2,5- diene-1,4-dione, 5; (4R,5R,6R)-4,5-dihydroxy-3-methoxy-5-methyl-6-(phenylamino)cyclohex-2-enone, 6; and 2-((4-butylphenyl)amino)-5-methoxy-3-methylcyclohexa-2,5-diene-1,4-dione, 7. X-ray analysis allowed us to unambiguously determine the structures and absolute configuration of semisynthetic derivatives 4, 5, and 6. The phytotoxic activity of the three isolated natural products and the coriloxine derivatives is reported. Germination of the seed, root growth, and oxygen uptake of the seedlings of Trifolium pratense, Medicago sativa, Panicum miliaceum, and Amaranthus hypochondriacus were significantly inhibited by all of the tested compounds. In general, they were more effective inhibiting root elongation than suppressing the germination and seedling oxygen uptake processes as shown by their IC50 values.

Cambios en la percepción de la violencia y el comportamiento agresivo entre niños a partir de un programa de habilidades socioemocionales / Changes in the perception of violence and aggressive behavior among children based on a program of social and emotional skills

El objetivo de este trabajo fue medir el cambio en la frecuencia de victimización, comportamiento agresivo y comportamiento positivo de los niños, después de participar en el programa "Comunidades amigas de la infancia". Participaron 302 niños de entre 9 y 15 años, de quinto y sexto de primaria en dos escuelas públicas alta marginalidad en Guadalajara (México), que fueron evaluados con las escalas de victimización, agresión y conductas positivas de Orpinas (2009). Se observaron cambios en la percepción de la violencia de la cual son objeto los menores y un aumento en el reconocimiento de la agresión que ejercen hacia los compañeros en niños que inicialmente informaron no ser agresivos o que obtuvieron una puntuación baja en los niveles de agresión. Asimismo, aquellos niños que tienden a ser agresores mostraron una disminución significativa en la agresión, tanto directa como relacional, ejercida hacia sus iguales. Estos resultados sugieren que el programa "Comunidades amigas de la infancia" ayuda a disminuir la normalización de la violencia hacia los niños, así como los comportamientos agresivos hacia los compañeros

The aim of this research was to examine changes in the frequency of victimization, aggressive behavior and positive behavior among children after participating in the program "Child Friendly Communities". 302 children between 9 and 15 years of age participated; the children, who at the time of the intervention were completing the fifth and sixth grades of basic education in two public schools with high levels of marginalization, in the metropolitan area of Guadalajara (Mexico), were evaluated using Orpinas' (2009) scales of victimization, aggression and positive behaviors. We observed changes in their perception of the violence performed against them and a growing recognition of the aggression exercised by them against peers in those children who prior to the intervention reported not being aggressive or who obtained a low score on levels of aggression. Likewise, children who tend to be aggressors showed a significant decrease in aggression exerted against others, both direct and relational. Results suggest that the program Child Friendly Communities helps to decrease the normalization of violence against children as well as the aggressive behavior against peers

Mechanism of the OH radical scavenging activity of nordihydroguaiaretic acid: a combined theoretical and experimental study.

The antioxidant nordihydroguaiaretic acid (NDGA) is a plant phenolic lignan originally isolated from the creosote bush (Larrea tridentata). It has been shown that NDGA scavenges efficiently hydroxyl radicals ((*)OH). In the present paper the mechanism by which NDGA scavenges (*)OH is addressed performing a combined experimental and theoretical investigation. We found that NDGA protects, in a concentration-dependent way, bovine serum albumin and DNA from the damage induced by (*)OH generated by the Fenton reaction. In addition, the NDGA + (*)OH reaction is predicted to be diffusion-controlled. The first step of this reaction is proposed to occur mainly by a sequential electron proton transfer from NDGA to (*)OH generating a neutral radical of NDGA, which after a second oxidation step gives a diradical that after a cascade sequential complex reaction produces a cyclic compound. This cyclic product is predicted to have a UV-vis spectrum very similar to that of NDGA, making its identification by this technique very difficult. The electrochemical studies performed in water support the formation of a cyclic compound (C2) as the main product of the reaction. It is concluded that NDGA can scavenge at least two (*)OH.

Electrochemical and chemical oxidation of dithia-, diselena-, ditellura-, selenathia-, and tellurathiamesocycles and stability of the oxidized species.

The diverse electrochemical and chemical oxidations of dichalcogena-mesocycles are analyzed, broadening our understanding of the chemistry of the corresponding radical cations and dications. 1,5-Diselenocane and 1,5-ditellurocane undergo reversible two-electron oxidation with inverted potentials analogous to 1,5-dithiocane. On the other hand, 1,5-selenathiocane and 1,5-tellurathiocane undergo one-electron oxidative dimerization. The X-ray crystal structures of the Se-Se dimer of the 1,5-selenathiocane one-electron oxidized product and the monomeric two-electron oxidized product (dication) of 1,5-tellurathiocane are reported. 1,5-Dithiocanes and 1,5-diselenocanes with group 14 atoms as ring members undergo irreversible oxidation, unlike the reversible two-electron oxidation of the corresponding silicon-containing 1,5-ditellurocanes. These results demonstrate the chemical consequences of the dication stabilities Te(+)-Te(+) > Se(+)-Se(+) > S(+)-S(+), as well as Se(+)-Se(+) > Se(+)-S(+) and Te(+)-Te(+) > Te(+)-S(+).

Electron transfer and structural change: distinguishing concerted and two-step processes.

In electron-transfer reactions accompanied by structural changes, the structural change can be concerted with electron transfer or can occur in a separate reaction either preceding or following the electron-transfer step. In this paper we discuss ways of distinguishing concerted reactions from the latter two-step type. Included are recent examples in which no intermediates have been detected in the reactions, thus precluding the direct assignment to the two-step category. In these cases, other means are used to build support for the two-step mechanism with respect to the concerted process. These include an example of structural change preceding electron transfer, a demonstration that the current models of concerted reactions cannot fit the voltammetric data, and a case in which an independent measure of the inner reorganization energy was used to show that the reaction could not be a concerted electron transfer and structural change.

Quantitative evaluation of the mechanism of electroreduction of benzoyl cyanides.

The mechanism of reduction of benzoyl cyanide, 6, p-methoxybenzoyl cyanide, 7, and p-chlorobenzoyl cyanide, 8, has been studied in acetonitrile (6 and 7), N,N-dimethylformamide (6), and acetonitrile containing water (all three compounds). The reaction proceeds by initial reduction to form the anion radical followed by dimerization to produce an intermediate dianion, the dianion of the dicyanohydrin of benzil. The latter loses cyanide to give the anion of the monocyanohydrin of benzil, which undergoes two parallel reactions: expulsion of cyanide to give the corresponding benzil and rearrangement to the monoanion of mandelonitrile benzoate. The addition of water brings about an increase in the dimerization rate constant and an associated increase in the amount of benzil that is produced. The standard potentials for the initial reduction step have been evaluated, and their dependence on the substituent is discussed. The dimerization rate constants have also been evaluated.

Electron-transfer reactions with significant changes in structure. Unsymmetrical crowded ethylenes.

The electrochemical reduction mechanisms of xanthylideneanthrone, 6, thioxanthylideneanthrone, 7, 10-(diphenylmethylene)anthrone, 8, and 9-(diphenylmethylene)-9H-fluorene, 9, have been studied in dimethylformamide. The reduction of the first two compounds proceeds from folded forms of the neutral to twisted forms of the anion radical according to a square scheme. The data for reduction of 8 can be well accounted for by the same square scheme. However, one-step reduction with concerted electron transfer and structural change cannot be ruled out. Compound 9, whose fluorene ring system cannot fold, exists only in twisted forms in the neutral, anion radical, and dianion. Consequently, there are no major changes in structure upon reduction, and the compound is reduced in two reversible steps with the second complicated by rapid loss of the dianion that is probably due to protonation by components of the medium.

Studies of potential inversion in an extended tetrathiafulvalene.

Electrochemical oxidation of the extended tetrathiafulvalene 9,10-bis(1,3-dithiole-2-ylidene)-9,10-dihydroanthracene (2) was studied in N,N-dimethylformamide. A single, two-electron oxidation peak occurs, and on the return sweep of a cyclic voltammogram, a two-electron reduction peak is seen. The oxidation of 2 to its cation radical and dication occurs with potential inversion (i.e., removal of the second electron occurs more easily than removal of the first). The extent of potential inversion was estimated by cyclic voltammetry to be 0.28 V by analysis of the process in terms of concerted structural change and electron transfer. Failure to detect the cation radical by EPR of an equimolar mixture of neutral 2 and the dication is consistent with this value. The inner reorganization energy of the cation radical was determined by gas-phase photoelectron spectroscopy (PES) to be 0.31-0.35 eV. Calculations, consistent with earlier experimental data, show rather large changes in structure associated with the oxidation processes. These large structural changes contrast with the relatively small inner reorganization energy found by PES. This observation prompted an analysis of voltammetry in terms of two-step processes, with structural change either preceding or following electron transfer. Agreement of simulations based on this mechanism with experimental voltammograms was equally as good as with the concerted mechanism. Notably, the two-step mechanism produced more realistic values of the transfer coefficient and electron-transfer rate constant for the first step of oxidation.

Change in reaction pathway in the reduction of 3,5-di-tert-butyl-1,2-benzoquinone with increasing concentrations of 2,2,2-trifluoroethanol.

The electrochemical reduction of 3,5-di-tert-butyl-1,2-benzoquinone, 1, has been studied in acetonitrile with added 2,2,2-trifluoroethanol, 2. At low concentrations of 2 the reaction proceeds by the following pathway: reduction of the quinone (Q) to its anion radical (Q*-) followed by complexation of the anion radical with 2 (HA) and the further reduction of the hydrogen-bonded complex (Q*- (HA)) to form HQ- and A-. The latter reaction is a concerted proton and electron- transfer reaction (CPET). At higher concentrations of 2, the pathway changes. The first steps remain the same, but now Q*- (HA) is reduced to HQ- via a disproportionation reaction with Q*- along with proton transfer from HA to Q*- to form HQ* which is reduced to HQ-. The only mechanism that could be found which would account for all of the data involves proton transfer to Q*- occurring within a higher complex, Q*-(HA)3.

Reduction of diesters of 1,2-diols. Regioselective C-O bond cleavage of the anionic forms.

The electrochemical reduction of benzoate diesters of glycols has been studied in acetonitrile and N,N-dimethylformamide as solvents. The reductions occur in two closely spaced one-electron steps, and it was found that the dianion diradicals decompose by one of two routes, depending on the substituents on the ethylene moiety: cleavage of two benzoates to produce alkene or formation of benzil by way of a postulated cyclic intermediate to produce also the dianion of the diol. These correspond to cleavage of the R-OC(O)Ar bonds and the RO-C(O)Ar bonds, respectively. When the radical formed by the former cleavage is a primary or secondary radical, the reaction is too slow to compete with the latter reaction that produces benzil. However, when that radical is either tertiary or benzylic, the former cleavage reaction is fast and no benzil is detected. The dianions of p-cyano- and p-nitrobenzoate esters are rather stable on the voltammetric time scale. However, the addition of lithium ions results in detectable formation of 4,4'-dicyanobenzil from four different p-cyanobenzoate diesters.

Reaction of thianthrene and phenoxathiin cation radicals with 2,3-dimethyl-2-butene. Chemical and electrochemical studies.

Thianthrene cation radical tetrafluoroborate (Th*+ BF4-) has been found to add to 2,3-dimethyl-2-butene (DMB) at 0 degrees C and -15 degrees C. The adduct, 2,3-dimethyl-2,3-(5,10-thianthreniumdiyl)butane ditetrafluoroborate (12), was isolated at -15 degrees C, and its 1H NMR spectrum was recorded at that temperature. The adduct was stable in CD3CN solution at -15 degrees C but decomposed slowly at 0 degrees C and quickly at 23 degrees C, forming the salt of 2,4,4,5,5-pentamethyl-2-oxazoline (8) with loss of thianthrene (Th). These results explain why earlier attempts to prepare 12 and detect its formation at room temperature with NMR spectroscopy were not successful. Reaction of Th*+ with DMB was followed with cyclic voltammetry and was found to exhibit redox catalysis in which Th was regenerated. With the faster scanning techniques of cyclic voltammetry, the formation of 12 was detectable, with a reduction potential of about -1.0 V at 25 degrees C and 3 degrees C. The observed reduction potential was in harmony with reduction potentials of a number of other, stable monoadducts. Thus, the redox catalysis involved the rapid formation of 12 and its rapid decomposition into 8 and Th, the newly formed Th being responsible for the observed enhanced oxidation currents. In contrast, 8 appears to be formed directly by oxidation of DMB by PO*+PF6-.

Studies of the inner reorganization energies of the cation radicals of 1,4-bis(dimethylamino)benzene, 9,10-bis(dimethylamino)anthracene, and 3,6-bis(dimethylamino)durene by photoelectron spectroscopy and reinterpretation of the mechanism of the electrochemical oxidation of the parent diamines.

The inner reorganization energy of the cation radical of 1,4-bis(dimethylamino)benzene, 1, has been determined to be 0.72 +/- 0.02 eV by means of gas-phase photoelectron spectroscopy (PES). PES studies of 9,10-bis(dimethylamino)anthracene, 2, and 3,6-bis(dimethylamino)durene, 3, demonstrate that their reorganization energies are smaller than that of 1. The effect of lowering the inner reorganization energy on the rate constant for an electrochemical electron-transfer reaction is to increase the electron-transfer rate constant, k(s). However, voltammetric studies of the two-electron oxidation of 2 and 3 indicate that the values of k(s) for each step are smaller than those for 1, in contradistinction to the measured differences in reorganization energies. The voltammetric studies of 2 and 3 were reinterpreted according to a mechanism in which each step of oxidation was written as a two-step process, electron transfer with a small inner reorganization energy plus a chemical step of structural change. The agreement of simulations according to this mechanism with the experimental data was excellent. The new reaction scheme eliminated some suspicious features previously obtained with an analysis where electron transfer and structural change were considered to be concerted. In particular, all electron-transfer coefficients (alpha) were close to one-half, whereas the earlier treatment produced values of alpha much larger or smaller than one-half.

Studies of potential inversion in the electrochemical reduction of 11,11,12,12-tetracyano-9,10-anthraquinodimethane and 2,3,5,6-tetramethyl-7,7,8,8-tetracyano-1,4-benzoquinodimethane.

The electrochemical reduction of the title compounds, 2a and 3a, and 7,7,8,8-tetracyanoquinodimethane, 1a, was studied in acetonitrile. The reduction of 1a shows normal ordering of potentials, i.e., the potential for insertion of the first electron, E degrees1, is more positive than the potential for the second step of reduction, E degrees2. Thus, E degrees1 - E degrees2 > 0. By contrast, 2a and 3a show inversion of potentials where introduction of the second electron occurs with greater ease than the first (E degrees1 - E degrees2 < 0). The extent of inversion has been determined by simulation of the cyclic voltammograms obtained at 298 and 257 K. Electron paramagnetic resonance measurements at room temperature of solutions containing equimolar mixtures of the neutral and dianion allow determination of the concentration of anion radicals from which the disproportionation equilibrium constant and E degrees1 - E degrees2 can be calculated. The results were in good agreement with the voltammetric determinations. Calculations were conducted to characterize the structural changes accompanying reduction to the anion radical and dianion forms. Fast scan experiments at low temperatures (up to 10 000 V/s at 257 K; 500 V/s at 233 K) were conducted in an attempt to detect intermediates in the reduction, but none was found. Thus, it is not possible to state whether structural change and electron transfer are concerted or occur in discrete steps.

2-[(R-phenyl)amine]-1,4-naphthalendiones as photosystem I electron acceptors: structure-activity relationship of m- and p-PAN compounds with QSAR analysis.

Nineteen 2-[(R-phenyl)amine]-1,4-naphthalendione derivatives (PAN) were tested on spinach thylakoids for their activity as electron acceptors. These molecules act as photosystem I electron acceptors in the micromolar range. AC(50) values varied from 5 nM to 24 microM. QSAR analysis revealed a linear correlation of the m-PAN derivative log [1/AC(50)] with the energy difference of the LUMO and HOMO orbitals. The biological activity of p-PAN derivatives correlates linearly with structural parameters. Electron affinity is being the most important. The half wave I potential values (E(1/2)) of PAN compounds (from -213 to -569 mV vs. NHE) match with the mid-point potentials of the A(0) to F(X) niche of PSI electron transport carriers. The logP values of PAN derivatives were 3.35 and 3.88, indicating that they are hydrophobic compounds. Therefore PAN compounds accept electrons at the hydrophobic A(0) to F(X) niche of PSI.

Time course study of oxidative and nitrosative stress and antioxidant enzymes in K2Cr2O7-induced nephrotoxicity.

BACKGROUND: Potassium dichromate (K2Cr2O7)-induced nephrotoxicity is associated with oxidative and nitrosative stress. In this study we investigated the relation between the time course of the oxidative and nitrosative stress with kidney damage and alterations in the following antioxidant enzymes: Cu, Zn superoxide dismutase (Cu, Zn-SOD), Mn-SOD, glutathione peroxidase (GPx), glutathione reductase (GR), and catalase (CAT). METHODS: Nephrotoxicity was induced in rats by a single injection of K2Cr2O7. Groups of animals were sacrificed on days 1,2,3,4,6,8,10, and 12. Nephrotoxicity was evaluated by histological studies and by measuring creatinine clearance, serum creatinine, blood urea nitrogen (BUN), and urinary excretion of N-acetyl-beta-D-glucosaminidase (NAG) and total protein. Oxidative and nitrosative stress were measured by immunohistochemical localization of protein carbonyls and 3-nitrotyrosine, respectively. Cu, Zn-SOD, Mn-SOD, and CAT were studied by immunohistochemical localization. The activity of total SOD, CAT, GPx, and GR was also measured as well as serum and kidney content of chromium and urinary excretion of NO2 -/NO3-. Data were compared by two-way analysis of variance followed by a post hoc test. RESULTS: Serum and kidney chromium content increased reaching the highest value on day 1. Nephrotoxicity was made evident by the decrease in creatinine clearance (days 1-4) and by the increase in serum creatinine (days 1-4), BUN (days 1-6), urinary excretion of NAG (days 1-4), and total protein (day 1-6) and by the structural damage to the proximal tubules (days 1-6). Oxidative and nitrosative stress were clearly evident on days 1-8. Urinary excretion of NO2-/NO3- decreased on days 2-6. Mn-SOD and Cu, Zn-SOD, estimated by immunohistochemistry, and total SOD activity remained unchanged. Activity of GPx decreased on days 3-12 and those of GR and CAT on days 2-10. Similar findings were observed by immunohistochemistry of CAT. CONCLUSION: These data show the association between oxidative and nitrosative stress with functional and structural renal damage induced by K2Cr2O7. Renal antioxidant enzymes were regulated differentially and were not closely associated with oxidative or nitrosative stress or with kidney damage. In addition, the decrease in the urinary excretion of NO2-/NO3- was associated with the renal nitrosative stress suggesting that nitric oxide was derived to the formation of reactive nitrogen species involved in protein nitration.

Study of the effects of ion pairing and activity coefficients on the separation in standard potentials for two-step reduction of dinitroaromatics.

The electrochemical reduction of 9,10-dinitroanthracene, 1, and 3,6-dinitrodurene, 2, occurs with potential inversion. That is, the standard potential for formation of the anion radical is shifted in the negative direction from the standard potential for the anion radical/dianion couple. This behavior has been attributed to significant structural changes accompanying the reduction steps. In this work, an assessment was made of the magnitude of the effects of activity coefficients and ion pairing, two effects which contribute to potential inversion. 1,4-Dinitrobenzene, 3, and 2,5-dimethyl-1,4-dinitrobenzene, 4, were studied in acetonitrile and N,N-dimethylformamide with R(4)N(+) salts as electrolytes (R = CH(3)-, CH(3)CH(2)-, CH(3)(CH(2))(3)-, and CH(3)(CH(2))(7)-) at concentrations from 0.010 to 0.100 M. Significant ion pairing between the dianion, A(2-), and R(4)N(+) was found for (CH(3))(4)N(+) with both 3 and 4 while the effects of the other electrolytes were smaller. The data were successfully interpreted without recourse to other ion pairs, e.g., ion pairing between the anion radical and the electrolyte cation. Ion pair formation constants are reported along with the infinite-dilution values of the difference in the two standard potentials. The effects of activity coefficients and ion pairing at 0.10 M electrolyte do not exceed 100 mV for (CH(3)N(+)) and are only 20 to 60 mV for (CH(3))(4)N(+), a cation commonly used in studies of potential inversion. It is concluded that structural changes accompanying the reduction, rather than activity and ion pairing effects, are the dominant factors underlying potential inversion.

S-allylmercaptocysteine scavenges hydroxyl radical and singlet oxygen in vitro and attenuates gentamicin-induced oxidative and nitrosative stress and renal damage in vivo.

BACKGROUND: Oxidative and nitrosative stress have been involved in gentamicin-induced nephrotoxicity. The purpose of this work was to study the effect of S-allylmercaptocysteine, a garlic derived compound, on gentamicin-induced oxidative and nitrosative stress and nephrotoxicity. In addition, the in vitro reactive oxygen species scavenging properties of S-allylmercaptocysteine were studied. RESULTS: S-allylmercaptocysteine was able to scavenge hydroxyl radicals and singlet oxygen in vitro. In rats treated with gentamicin (70 mg/Kg body weight, subcutaneously, every 12 h, for 4 days), renal oxidative stress was made evident by the increase in protein carbonyl content and 4-hydroxy-2-nonenal, and the nitrosative stress was made evident by the increase in 3-nitrotyrosine. In addition, gentamicin-induced nephrotoxicity was evident by the: (1) decrease in creatinine clearance and in activity of circulating glutathione peroxidase, and (2) increase in urinary excretion of N-acetyl-beta-D-glucosaminidase, and (3) necrosis of proximal tubular cells. Gentamicin-induced oxidative and nitrosative stress and nephrotoxicity were attenuated by S-allylmercaptocysteine treatment (100 mg/Kg body weight, intragastrically, 24 h before the first dose of gentamicin and 50 mg/Kg body weight, intragastrically, every 12 h, for 4 days along gentamicin-treatment). CONCLUSION: In conclusion, S-allylmercaptocysteine is able to scavenge hydroxyl radicals and singlet oxygen in vitro and to ameliorate the gentamicin-induced nephrotoxicity and oxidative and nitrosative stress in vivo.