Reactivity of Beer Bitter Acids Toward the 1-Hydroxyethyl Radical as Probed by Spin-Trapping Electron Paramagnetic Resonance (EPR) and Electrospray Ionization-Tandem Mass Spectrometry (ESI-MS/MS)

The iso-alpha-acids or isohumulones are the major contributors to the bitter taste of beer, and it is well-recognized that they are degraded during beer aging. In particular, the trans-isohumulones seem to be less stable than the cis-isohumulones. The major radical identified in beer is the 1-hydroxyethyl radical; however, the reactivity between this radical and the isohumulones has not been reported until now. Therefore, we studied the reactivity of isohumulones toward the 1-hydroxyethyl radical through a competitive kinetic approach. It was observed that both cis- and trans-isohumulones and dihydroisohumulones are decomposed in the presence of 1-hydroxyethyl radicals, while the reactivities are comparable. On the other hand, the tetrahydroisohumulones did not react with 1-hydroxyethyl radicals. The apparent second-order rate constants for the reactions between the 1-hydroxyethyl radical and these compounds were determined by electron paramagnetic resonance (EPR) spectroscopy and electrospray ionization-tandem mass spectrometry [ESI(+)-MS/MS]. It follows that degradation of beer bitter acids is highly influenced by the presence of 1-hydroxyethyl radicals. The reaction products were detected by liquid chromatography electrospray ionization-ion trap-tandem mass spectrometry (LC-ESI-IT-MS/MS), and the formation of oxidized derivatives of the isohumulones was confirmed. These data help to understand the mechanism of beer degradation upon aging.

Enzymatic Kinetic Resolution of tert-Butyl 2-(1-Hydroxyethyl)phenylcarbamate, A Key Intermediate to Chiral Organoselenanes and Organotelluranes

The enzymatic kinetic resolution of tert-butyl 2-(1-hydroxyethyl) phenylcarbamate via lipase-catalyzed transesterification reaction was studied. We investigated several reaction conditions and the carbamate was resolved by Candida antarctica lipase B (CAL-B), leading to the optically pure (R)- and (S)-enantiomers. The enzymatic process showed excellent enantioselectivity (E > 200). (R)- and (S)-tert-butyl 2-(1-hydroxyethyl) phenylcarbamate were easily transformed into the corresponding (R)and (S)-1-(2-aminophenyl)ethanols.

Superoxide Dismutase 1-mediated Production of Ethanol- and DNA-derived Radicals in Yeasts Challenged with Hydrogen Peroxide MOLECULAR INSIGHTS INTO THE GENOME INSTABILITY OF PEROXIREDOXIN-NULL STRAINS

Peroxiredoxins are receiving increasing attention as defenders against oxidative damage and sensors of hydrogen peroxide-mediated signaling events. In the yeast Saccharomyces cerevisiae, deletion of one or more isoforms of the peroxiredoxins is not lethal but compromises genome stability by mechanisms that remain under scrutiny. Here, we show that cytosolic peroxiredoxin-null cells (tsa1 Delta tsa2 Delta) are more resistant to hydrogen peroxide than wildtype (WT) cells and consume it faster under fermentative conditions. Also, tsa1 Delta tsa2 Delta cells produced higher yields of the 1-hydroxyethyl radical from oxidation of the glucose metabolite ethanol, as proved by spin-trapping experiments. A major role for Fenton chemistry in radical formation was excluded by comparing WT and tsa1 Delta tsa2 Delta cells with respect to their levels of total and chelatable metal ions and of radical produced in the presence of chelators. The main route for 1-hydroxyethyl radical formation was ascribed to the peroxidase activity of Cu, Zn-superoxide dismutase (Sod1), whose expression and activity increased similar to 5- and 2-fold, respectively, in tsa1 Delta tsa2 Delta compared with WT cells. Accordingly, overexpression of human Sod1 in WT yeasts led to increased 1-hydroxyethyl radical production. Relevantly, tsa1 Delta tsa2 Delta cells challenged with hydrogen peroxide contained higher levels of DNA-derived radicals and adducts as monitored by immuno-spin trapping and incorporation of (14)C from glucose into DNA, respectively. The results indicate that part of hydrogen peroxide consumption by tsa1 Delta tsa2 Delta cells is mediated by induced Sod1, which oxidizes ethanol to the 1-hydroxyethyl radical, which, in turn, leads to increased DNA damage. Overall, our studies provide a pathway to account for the hypermutability of peroxiredoxin-null strains.

Evaluation of Antihyperglycemia and Antihypertension Potential of Native Peruvian Fruits Using In Vitro Models

Local food diversity and traditional crops are essential for cost-effective management of the global epidemic of type 2 diabetes and associated complications of hypertension. Water and 12% ethanol extracts of native Peruvian fruits such as Lucuma (Pouteria lucuma), Pacae (Inga feuille), Papayita arequipena (Carica pubescens), Capuli (Prunus capuli), Aguaymanto (Physalis peruviana), and Algarrobo (Prosopis pallida) were evaluated for total phenolics, antioxidant activity based on 2, 2-diphenyl-1-picrylhydrazyl radical scavenging assay, and functionality such as in vitro inhibition of alpha-amylase, alpha-glucosidase, and angiotensin I-converting enzyme (ACE) relevant for potential management of hyperglycemia and hypertension linked to type 2 diabetes. The total phenolic content ranged from 3.2 (Aguaymanto) to 11.4 (Lucuma fruit) mg/g of sample dry weight. A significant positive correlation was found between total phenolic content and antioxidant activity for the ethanolic extracts. No phenolic compound was detected in Lucuma (fruit and powder) and Pacae. Aqueous extracts from Lucuma and Algarrobo had the highest alpha-glucosidase inhibitory activities. Papayita arequipena and Algarrobo had significant ACE inhibitory activities reflecting antihypertensive potential. These in vitro results point to the excellent potential of Peruvian fruits for food-based strategies for complementing effective antidiabetes and antihypertension solutions based on further animal and clinical studies.

EVALUATION OF RED CURRANTS (RIBES RUBRUM L.), BLACK CURRANTS (RIBES NIGRUM L.), RED AND GREEN GOOSEBERRIES (RIBES UVA-CRISPA) FOR POTENTIAL MANAGEMENT OF TYPE 2 DIABETES AND HYPERTENSION USING IN VITRO MODELS

Red currants (Ribes rubrum L.), black currants (Ribes nigrum L.), red and green gooseberries (Ribes uva-crispa) were evaluated for the total phenolics, antioxidant capacity based on 2, 2-diphenyl-1-picrylhydrazyl radical scavenging assay and functionality such as in vitro inhibition of alpha-amylase, alpha-glucosidase and angiotensin I-converting enzyme (ACE) relevant for potential management of hyperglycemia and hypertension. The total phenolics content ranged from 3.2 (green gooseberries) to 13.5 (black currants) mg/g fruit fresh weight. No correlation was found between total phenolics and antioxidant activity. The major phenolic compounds were quercetin derivatives (black currants and green gooseberries) and chlorogenic acid (red currants and red gooseberries). Red currants had the highest alpha-glucosidase, alpha-amylase and ACE inhibitory activities. Therefore red currants could be good dietary sources with potential antidiabetes and antihypertension functionality to compliment overall dietary management of early stages of type 2 diabetes.

Isoflavones and antioxidant capacity of Peruvian and Brazilian lupin cultivars

Seed coats, cotyledons and hypocotyls from six Peruvian (Lupinus mutabilis Sweet) and two Brazilian (Lupinus albus and Lupinus angustifolius) lupin cultivars were assessed regarding their content of isoflavones and antioxidant capacity. Genistein and a genistein derivative were detected in seed coats and cotyledons from Peruvian cultivars. Total isoflavones ranged from 9.8 to 87, 16.1 to 30.8 and 1.3 to 6.1 mg/100 g of sample in fresh weight (expressed as genistein) in seed coat, cotyledon and hypocotyl fractions, respectively, from mutabilis species, whereas no isoflavones were detected in L. angustifolius and L. albus. A significant correlation (r = 0.99) was found between the total isoflavone levels and the antioxidant capacity measured by the 2,2-diphenyl-1-picrylhydrazyl radical-scavenging method in all fractions of Peruvian samples. No condensed tannins were detected in any of the lupin cultivars. The H-6 Andean cultivar is promising for its high isoflavone content and antioxidant capacity. Insights from this study indicate that lupin cultivars of the mutabilis species have similar isoflavone profiles and that isoflavones are more concentrated in the cotyledon seed fraction than in the seed coat or hypocotyl fractions. (C) 2008 Elsevier Inc. All rights reserved.

Antioxidant capacity of the striped sunflower (Helianthus annuus L.) seed extracts evaluated by three in vitro methods

The antioxidant capacity of the striped sunflower seed cotyledon extracts, obtained by sequential extraction with different polarities of solvents, was evaluated by three different in vitro methods: ferric reducing/antioxidant power (FRAP), 2.2-diphenyl-1-picrylhydrazyl radical (DPPH) and oxygen radical absorbance capacity (ORAC) assays. In the three methods, the aqueous extract at 30 mu g/ml showed a higher antioxidant capacity value (FRAP, 45.27 mu mol; DPPH, 50.18%; ORAC, 1.5 Trolox equivalents) than the ethanolic extract (FRAP, 32.17 mu mol; DPPH, 15.21%; ORAC, 0.50 Trolox equivalents). When compared with the synthetic antioxidant butylated hydroxyl toluene, the antioxidant capacity of the aqueous extract varied from 45% to 66%, according to the used method. The high antioxidant capacity observed for the aqueous extract of the studied sunflower seed suggests that the intake of this seed may prevent in vivo oxidative reactions responsible for the development of several diseases, such as cancer.

Antioxidant properties in cashew apple byproduct (Anacardium occidentale L.): effect on lipoperoxidation and on the polyunsaturated fatty acids profile in rats

The cashew apple (Anacardium occidentale L.) contains phenolic compounds usually related with antioxidant properties. Then, the aim of this study was to investigate its antioxidant capacity. The antioxidant capacity of the hydroalcoholic extract of the cashew apple pulp (EHAlc.) was assessed for the scavenging of the 2,2-diphenyl-1-picrylhydrazyl radical (DPPH) by in vitro method and by an in vivo essay. For this essay a 30-day oral (gavage, EHAlc. 200 and 400 mg/kg) study was conducted in Wistar male rats, evaluating hepatic, plasma and brain tissues. In DPPH model, the extract demonstrated antioxidant activity of 95% (largest concentration, 1000 mu g/mL). There were found no relevant peroxidation comparing the treated animals with the control group. However, the treated group presented a lower level of brain lipoperoxidation. Also in the treated animals brain tissue was found the largest amount of polyunsaturated fatty acids (PUFA), mainly docosahexaenoic (DHA). Therqfore, the analyzed extract from cashew apple pulp clone CCP-76 contains effective natural antioxidants, responsible for free radical scavenging in vitro and also for decreasing the brain lipoperoxidation and keeping the PUFAS levels in Wistar rats.

Sugarcane spirit extracts of oak and Brazilian woods: antioxidant capacity and activity

Sugarcane spirit extracts of six different Brazilian woods for potential use in manufacturing aging casks were compared with similar extracts of five oak samples from different geographic origin and heat treatment regarding: (1) content of phenolics and copper; (2) radical reducing capacity and reactivity toward 2,2-diphenyl-1-picrylhydrazyl radical (DPPH center dot); and (3) effect on the rate of oxygen depletion rate in a peroxidating lipid model system. Total phenolic contents of the Brazilian wood extracts ranged from 0.65 (canela-sassafras) to 6.4 (jatoba) mmol(GAE) L(-1) and from 1.39 to 2.87 mmol(GAE) L(-1) for oak extracts. Flavonoids ranged from 1.54 x 10(-4) (ipe) to 6.5 x 10(-2) (oak) mmol(rutin) L(-1), and tannins from below the detection limit to 0.22 (jatoba) mmol(tannic acid) L(-1). Correlation was observed for the antioxidant capacity versus phenolics/flavonoids/tannins content, where oak extracts exhibit the highest radical scavenging capacity compared to Brazilian woods. Rate constant for radical scavenging by the extracts ranged from 4.9 x 10(3) M(-1) s(-1)(canela-sassafras) to 9.7 x 10(4) M(-1) s(-1) (oak). The oxygen consumption index showed the Brazilian woods amendoim and jatoba to be more efficient inhibitors than the oak extracts for lipid autoxidation initiated by metmyoglobin, despite that the oak extracts seem to be more efficient to scavenge DPPH center dot. No simple correlation with phenolics or copper content could be established, and a prooxidative tendency was observed for the extracts of canela-sassafras, castanheira, and louro-canela.

HPLC microfractionation of flavones and antioxidant (radical scavenging) activity of Saccharum officinarum L.

The antioxidant activity of sugarcane (Saccharum officinarum L.) juice towards DPPH reagent was determined (EC50) and the main compounds with radical scavenging activity in juice and leaves extracts were identified by HPLC-UV/PAD analysis combined with HPLC microfractionation monitored by TLC using β-carotene and DPPH as the detection reagents. In sugarcane leaves, luteolin-8-C-(rhamnosylglucoside) (1) was the most important compound with radical scavenging activity; in sugarcane juice, the flavones diosmetin-8-C-glucoside (2), vitexin (3) schaftoside (9), isoschaftoside (10) and 4',5'-dimethyl-luteolin-8-C-glucoside (11) were the most relevant compounds. The content of juice flavonoids (0.241 ± 0.001 mg total flavonoids/mL juice), comparable to other food sources of flavonoids, suggest the potential of sugarcane as a dietary source of natural antioxidants. However, the low antioxidant ability of sugarcane juice (EC50 = 100.2 ± 2.6 g L-1) also points to the need for further studies about the dietary intake of sugarcane flavonoids and its effects on human health.

Ergonomic Aspects Related to Surgeon Position in Laparoscopic Radical Prostatectomy

Purpose: The aim is to evaluate the level of inclination of the surgeon's spinal column (ISSC) while performing laparoscopic radical prostatectomy (LRP) when using one trocar on each side of the patient abdomen (""torero"" position) in two scenarios: With and without a thin head supporter adapted to the table. Materials and Methods: Based on trigonometric principles, we elaborated a formula to calculate the ISSC for a determined surgeon and surgical table while performing LRP in the torero position. The parameters considered were the width of the surgical table (m), the distance between the surgeon's anterior superior iliac spines (q), and the distance from the central point between the surgeon's anterior superior iliac spines to the surgeon's head (h). We used the formula alpha = 90 degree-cos(-1)(b/h) (where b = q/2 + m/2) in an Excel sheet to calculate the angle of inclination of the surgeon's spinal column. We applied the measures of 12 surgeons with different biotypes of our staff to calculate the ISSC with and without the thin head supporter. Results: The use of a thin head supporter reduced the mean ISCC in the torero position from 36.1 +/- 3.73 degrees (range 31.3 to 49.8 degrees) to 22.1 +/- 4.9 degrees (range 18.7 to 32.9 degrees), which corresponds to a reduction of 38.8% in the mean angle of inclination. This difference was statistically significant (P < 0.001). Conclusion: The use of a thin head supporter adapted to the surgical table objectively reduces lateral inclination of the surgeon's spinal column in the torero position, making LRP a more comfortable procedure.

Design of 1D and 2D molecule-based magnets with the ligand 4,5-dimethyl-1,2-phenylenebis(oxamato)

Three new bimetallic oxamato-based magnets with the proligand 4,5-dimethyl-1,2-phenylenebis-(oxamato) (dmopba) were synthesized using water or dimethylsulfoxide (DMSO) as solvents. Single crystal X-ray diffraction provided structures for two of them: [MnCu(dmopba)(H(2)O)(3)]n center dot 4nH(2)O (1) and [MnCu(dmopba)(DMSO)(3)](n center dot)nDMSO (2). The crystalline structures for both 1 and 2 consist of linearly ordered oxamato-bridged Mn(II)Cu(II) bimetallic chains. The magnetic characterization revealed a typical behaviour of ferrimagnetic chains for 1 and 2. Least-squares fits of the experimental magnetic data performed in the 300-20 K temperature range led to J(MnCu) = -27.9 cm(-1), g(Cu) = 2.09 and g(Mn) = 1.98 for 1 and J(MnCu) = -30.5 cm(-1), g(Cu) = 2.09 and g(Mn) = 2.02 for 2 (H = -J(MnCu)Sigma S(Mn, i)(S(Cu, i) + S(Cu, i-1))). The two-dimensional ferrimagnetic system [Me(4)N](2n){Co(2)[Cu(dmopba)](3)}center dot 4nDMSO center dot nH(2)O (3) was prepared by reaction of Co(II) ions and an excess of [Cu(dmopba)](2-) in DMSO. The study of the temperature dependence of the magnetic susceptibility as well as the temperature and field dependences of the magnetization revealed a cluster glass-like behaviour for 3.

Single reaction interface flow system for chemiluminescent monitoring of mannitol based on its hydroxyl radical scavenger activity

A single reaction interface flow analysis (SIFA) system for the monitoring of mannitol in pharmaceutical formulations and human urine is presented. The developed approach takes advantage of the mannitol scavenger aptitude to inhibit the chemiluminescent reaction between luminol and myoglobin in the absence of H(2)O(2). The SIFA system facilitated the fully automation of the developed methodology, allowing the in-line reproducible handling of chemical species with a very short lifetime as is the case of the hydroxyl radical generated in the abovementioned luminol/myoglobin reaction. The proposed methodology allowed the determination of mannitol concentrations between 25 mmol L(-1) and 1 mol L(-1), with good precision (R.S.D. < 4.7%, n = 3) and a sampling frequency of about 60 h(-1). The procedure was applied to the determination of mannitol in pharmaceuticals and in human urine samples Without any pretreatment process. The results obtained for pharmaceutical formulations were statistically comparable to those provided by the reference method (R.D. < 4.6%); recoveries values obtained in the analysis of spiked urine samples (between 94.9 and 105.3% of the added amount) were also satisfactory. (C) 2008 Elsevier B.V. All rights reserved.

Solution Polymerization of N-vinylcaprolactam in 1,4-dioxane. Kinetic Dependence on Temperature, Monomer, and Initiator Concentrations

The kinetics of the solution free radical polymerization of N-vinylcaprolactam, in 1,4-dioxane and under various polymerization conditions was studied. Azobisisobutyronitrile and 3-mercaptopropionic acid were used as initiator and as chain transfer agent (CTA), respectively. The influence of monomer and initiator concentrations and polymerization temperature on the rate of polymerizations (R(p)) was investigated. In general, high conversions were obtained. The order with respect to initiator was consistent with the classical kinetic rate equation, while the order with respect to the monomer was greater than unity. The overall activation energy of 53.6 kJ mol(-1) was obtained in the temperature range 60-80 degrees C. The decreasing of the absolute molecular weights when increasing the CIA concentration was confirmed by GPC/SEC/LALS analyses. It was confirmed by UV-visible analyses the effect of molecular weights on the lower critical solution temperature of the polymers. It was also verified that the addition of the CTA influenced the kinetic of the polymerizations. (C) 2010 Wiley Periodicals, Inc. J Appl Polym Sci 118: 229-240, 2010

Synthesis of (Z)-1-Organylthiobut-1-en-3-ynes: Hydrothiolation of Symmetrical and Unsymmetrical Buta-1,3-diynes

Hydrothiolation of 1-organylbuta-1,3-diynes and 1,4-diorganylbuta-1,3-diynes with the sodium organylthiolate anions, which were generated in situ by reacting diphenyl and dibutyl disulfide with NaBH(4) in ethanol, results in the regio-, stereo-, and chemoselective formation of (Z)-1-organylthio-4-organylbut-1-en-3-ynes and (Z)-1-organylthio-1,4-diorganylbut-1-en-3-ynes, respectively.