Early coconut distillation and the origins of mezcal and tequila spirits in west-central Mexico

No evidence exists of distillation in Mexico before European contact. The Philippine people in Colima established the practice in the 16th Century to produce coconut spirits. Botanical, toponymic, archaeological, and ethnohistoric data are presented indicating that agave distillation began in Colima, in the lower Armería-Ayuquila and Coahuayana-Tuxpan river basins, using Agave angustifolia Haw. and through adaptation of the Philippine coconut spirits distillation technique. Subsequent selection and cultivation of agaves led to their domestication and diversification. This did not take place in the lower river basins, where agave populations tended to disappear. The distillation technique spread to the foothills of Colima volcanoes and from there to all of western Mexico, leading to creation of tequila and other agave spirits. Two factors aided producers in avoiding strict Colonial prohibitions and were therefore key to the diffusion and persistence of agave spirits production: (1) clandestine fermentation in sealed, underground pits carved from bedrock, a native, pre-European contact technique; and (2) small, easy-to-use Philippine-type stills that could be hidden from authorities and allowed use of a broad range of agave species. Dedicated to Henry Bruman in honor of his contribution to the understanding of coconut and agave genetic resources history in America.     

Phenolic constituents, furans, and total antioxidant status of distilled spirits.

The concentrations of 11 phenols and 5 furans were measured in 12 categories of distilled spirits by HPLC methodology, together with the total antioxidant status (TAS) of the same beverages. Ellagic acid was the phenol present in highest concentration in all beverages. Moderate amounts of syringaldehyde, syringic acid, and gallic acid, as well as lesser amounts of vanillin and vanillic acid, were measurable in most samples of whiskey, brandy, and rum but were largely undetectable in gin, vodka, liqueurs, and miscellaneous spirits. 5-(Hydroxymethyl)furfural was the predominant furan in the former three beverages, notably cognac, with 2-furaldehyde the next highest, but these were undetectable in most of the latter beverages. Highest TAS values were given by armagnac, cognac, and bourbon whiskey, all three of which tended toward the highest concentrations of phenols. Negative TAS values were exhibited by rum, vodka, gin, and miscellaneous spirits in line with the low or undetectable phenol concentrations in these beverages. Wood aging is the most likely source of phenols and furans in distilled spirits. Those beverages exposed to this treatment contain significant antioxidant activity, which is between the ranges for white and red wines, with the potential to augment the antiatherosclerotic functions attributable to the ethanol that they contain.     

Antioxidant activities and volatile constituents of various essential oils

Thirteen essential oils were examined for their antioxidant activity using three different assay systems. Jasmine, parsley seed, rose, and ylang-ylang oils inhibited hexanal oxidation by over 95% after 40 days at a level of 500 microg/mL in the aldehyde/carboxylic acid assay. Scavenging abilities of the oils for the 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical ranged from 39% for angelica seed oil to 90% for jasmine oil at a level of 200 microg/mL. The greatest inhibitory activity toward malonaldehyde (MA) formation from squalene upon UV-irradiation was obtained from parsley seed oil (inhibitory effect, 67%), followed by rose oil (46%), and celery seed oil (23%) at the level of 500 microg/mL. The main compounds of oils showing high antioxidant activity were limonene (composition, 74.6%) in celery seed, benzyl acetate (22.9%) in jasmine, alpha-pinene (33.7%) in juniper berry, myristicin (44%) in parsley seed, patchouli alcohol (28.8%) in patchouli, citronellol (34.2%) in rose, and germacrene (19.1%) in ylang-ylang.     

Antioxidant activity of Myristica malabarica extracts and their constituents

The 1,1-diphenyl-2-picrylhydrazyl (DPPH) assay of the ether, methanol, and aqueous extracts of the spice Myristica malabarica (rampatri) revealed the methanol extract to possess the best antioxidant activity. Column chromatography of the methanol extract led to the isolation of a new 2-acylresorcinol and four known diarylnonanoids of which the diarylnonanoid, malabaricone C, showed the maximum DPPH scavenging activity. Malabaricone C could prevent both Fe(II)- and 2,2'-azobis(2-amidinopropane)dihydrochloride-induced lipid peroxidation (LPO) of rat liver mitochondria more efficiently than curcumin. The anti-LPO activity of malabaricone C was attributed to its better radical scavenging and Fe(II) chelation capacities. The superior activity of malabaricone C was rationalized by a systematic structure-activity correlation of the results obtained with the structurally related diarylnonanoids and curcumin. Malabaricone C also prevented the gamma-ray-induced damage of pBR322 plasmid DNA in a concentration-dependent manner. The radioprotective activity was found to correlate with its (*)OH radical scavenging property, which matched well with that of d-mannitol.     

Antioxidant activity and constituents of propolis collected in various areas of Korea

Propolis is a resinous substance collected by honeybees from various plant sources. The composition of propolis depends on time, vegetation, and the area of collection. This study examined the antioxidant activity of propolis from various areas of Korea: Chilgok, Cheongju, Geochang, Muju, Pocheon, and Sangju. Ethanol extracts of propolis (EEP) were prepared and evaluated for their antioxidant activity by beta-carotene bleaching, 1,1-diphenyl-2-picrylhydrazyl free radical scavenging, and 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) radical cation decolorization assays. Furthermore, the major constituents in EEP were identified by high-performance liquid chromatography analysis with a photodiode array and mass spectrometric detection, and each component was quantitatively analyzed. EEP from Cheongju and Muju had relatively strong antioxidant activity accompanied by high total polyphenol contents. Propolis from Cheongju contained large amounts of antioxidative compounds, such as caffeic acid, kaempferol, and phenethyl caffeate. On the other hand, propolis from Pocheon had compounds not seen in propolis from other areas.     

Antioxidant activity of piper betel leaf extract and its constituents

The 1,1-diphenyl-2-picrylhydrazyl (DPPH) assay of the ethanol extracts of three varieties (Bangla, sweet, and Mysore) of Piper betel (pan) revealed the Bangla variety to possess the best antioxidant activity that can be correlated with the total phenolic content and reducing powers of the respective extracts. Column chromatography of the extract of the Bangla variety led to the isolation of chevibetol (CHV), allylpyrocatechol (APC), and their respective glucosides. The HPTLC analyses of the extracts revealed similar chemical profiles in all three P. betel varieties, although the concentrations of CHV and APC were significantly less in the sweet and Mysore varieties. Among the isolated compounds, APC showed the best results in all the in vitro experiments. It could prevent Fe(II)-induced lipid peroxidation (LPO) of liposomes and rat brain homogenates as well as gamma-ray-induced damage of pBR322 plasmid DNA more efficiently than CHV. The superior anti-LPO and radioprotective activities of APC vis-à-vis those of CHV could not be explained by their respective Fe(II) chelation and .OH radical scavenging capacities. The better ability of APC to scavenge O2-. radicals and H2O2 might account for the results.     

Antioxidant constituents in the fruits of Luffa cylindrica (L.) Roem

Hydrophilic antioxidant constituents in the fruits of the vegetable Luffa cylindrica (L.) Roem (sponge gourds) were separated by an antioxidant-guided assay to yield eight compounds: p-coumaric acid (1), 1-O-feruloyl-beta-D-glucose (2), 1-O-p-coumaroyl-beta-D-glucose (3), 1-O-caffeoyl-beta-D-glucose (4), 1-O-(4-hydroxybenzoyl)glucose (5), diosmetin-7-O-beta-D-glucuronide methyl ester (6), apigenin-7-O-beta-D-glucuronide methyl ester (7), and luteolin-7-O-beta-D-glucuronide methyl ester (8). The eight compounds were isolated by high-speed countercurrent chromatography and identified by electrospray ionization-mass spectrometry and NMR analysis, and the antioxidant activity was evaluated by the radical scavenging effect on the 1,1-diphenyl-2-picrylhydrazyl radical. High-performance liquid chromatography analysis showed that a total amount of the eight compounds in the dried gourds without skin was about 1%. The results demonstrate that the consumption of sponge gourds can supply some antioxidant constituents to human body.     

Antioxidant constituents of radish sprout (Kaiware-daikon), Raphanus sativus L

Methanol extracts of 11 kinds of commonly available vegetables were examined for hydroxyl radical scavenging potency using the bleomycin-Fe method. In this method, the iron ion and bleomycin in water form hydroxyl radicals, and the scavenging activity is monitored by the modified thiobarbituric acid method. All extracts showed scavenging capacity, even though the activity of some of them was lower than that of l-ascorbic acid. Those vegetables were classified into three groups according to their activity, groups showing strong activity, moderate activity, and weak activity, as compared to the activity of l-ascorbic acid at the same concentration. Among them, the methanol extract of radish sprout (Japanese name "kaiware-daikon") exhibited the highest potency (1.8 times as l-ascorbic acid). Then, we investigated the constituents of the methanol extract of radish sprout and the contribution to the overall activity of each compound by examining their activity. As the result, several kinds of sinapinic acid esters and flavonoids were isolated with high radical scavenging potency, which must contribute substantially to the activity.     

Quantification of selected volatile constituents and anions in Mexican Agave spirits (Tequila, Mezcal, Sotol, Bacanora)

A large collection (n = 95) of Mexican Agave spirits with protected appellations of origin (Tequila, Mezcal, Sotol, and Bacanora) was analyzed using ion and gas chromatography. Because of their production from oxalate-containing plant material, all Agave spirits contained significant concentrations of oxalate (0.1-9.7 mg/L). The two Tequila categories ("100% Agave" and "mixed") showed differences in the methanol, 2-/3-methyl-1-butanol, and 2-phenylethanol concentrations with lower concentrations in the mixed category. Mezcal showed no significant differences in any of the evaluated parameters that would allow a classification. Sotol showed higher nitrate concentrations and lower 2-/3-methyl-1-butanol concentrations. Bacanora was characterized by exceptionally high acetaldehyde concentrations and a relatively low ethyl lactate content. The methanol content was the most problematic compound regarding the Mexican standards: two Tequilas (4%), five Sotols (31%), and six Bacanoras (46%) had levels above the maximum methanol content of 300 g/hL of alcohol. In conclusion, the composition of Mexican Agave spirits was found to vary over a relatively large range.     

Antioxidant capacity of 26 spice extracts and characterization of their phenolic constituents

Total equivalent antioxidant capacity (TEAC) and phenolic content of 26 common spice extracts from 12 botanical families were investigated. Qualitative and quantitative analyses of major phenolics in the spice extracts were systematically conducted by reversed-phase high-performance liquid chromatography (RP-HPLC). Many spices contained high levels of phenolics and demonstrated high antioxidant capacity. Wide variation in TEAC values (0.55-168.7 mmol/100 g) and total phenolic content (0.04-14.38 g of gallic acid equivalent/100 g) was observed. A highly positive linear relationship (R2= 0.95) obtained between TEAC values and total phenolic content showed that phenolic compounds in the tested spices contributed significantly to their antioxidant capacity. Major types of phenolic constituents identified in the spice extracts were phenolic acids, phenolic diterpenes, flavonoids, and volatile oils (e.g., aromatic compounds). Rosmarinic acid was the dominant phenolic compound in the six spices of the family Labiatae. Phenolic volatile oils were the principal active ingredients in most spices. The spices and related families with the highest antioxidant capacity were screened, e.g., clove in the Myrtaceae, cinnamon in the Lauraceae, oregano in the Labiatae, etc., representing potential sources of potent natural antioxidants for commercial exploitation. This study provides direct comparative data on antioxidant capacity and total and individual phenolics contents of the 26 spice extracts.     

Comparison of the volatile constituents in cold-pressed bergamot oil and a volatile oil isolated by vacuum distillation

The vacuum distillation of bergamot peels furnishes a high-quality essential oil that is totally bergapten-free. This oil was compared with that produced by distillation of cold-pressed oils and those commercially available. The oil obtained by vacuum distillation of the bergamot vegetable matrix shows a composition quite similar to that of the cold-pressed oil. It also displays qualitative characteristics that are superior with respect to those normally observed for essential oils isolated by distillation of cold-pressed oils. Oils isolated by the method presented here can constitute ideal candidates in producing foods, for example, Earl Grey tea, and cosmetic preparations.     

Antioxidant phenolic constituents in roots of Rheum officinale and Rubia cordifolia: structure-radical scavenging activity relationships

The phenolic constituents in the roots of Rheum officinale and Rubia cordifolia were identified with the aid of high-performance liquid chromatography and liquid chromatography-mass spectrometry and by comparison with authentic standards. A total of 17 hydroxyanthraquinones, gallic acid, and tannins were separated, and 14 of them were identified, being the main phenolic constituents present. Their antioxidant activity (Trolox equivalent antioxidant capacity) was evaluated using the improved 2,2-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid)diammonium salt method. Hydroxyanthraquinones were the predominant antioxidant phenolic constituents in the roots of R. cordifolia, and tannins and gallic acid were the predominant antioxidant phenolic constituents in the roots of R. officinale. The structure-radical scavenging activity relationships of the tested hydroxyanthraquinones were systematically demonstrated as follows: Hydroxy groups on one benzene ring of the anthraquinone structure were essential for hydroxyanthraquinones to show activity, the ortho-dihydroxy structure in the hydroxyanthraquinone molecules could greatly enhance their radical scavenging effect, and glycosylation of the hydroxyanthraquinones reduced activity.     

Antioxidant activity of prune (Prunus domestica L.) constituents and a new synergist

Ethanol extract of prune was separated into hexane-soluble and H(2)O-soluble fractions, and the H(2)O-soluble fraction was further separated into a methanol (MeOH) eluate and an H(2)O eluate by Diaion HP-20 column chromatography. The MeOH eluate exhibited the strongest antioxidant activity among the separated fractions evaluated by oxygen radical absorbance capacity (ORAC). Further purification of the MeOH eluate led to isolation of a novel compound, 4-amino-4-carboxychroman-2-one, together with four known compounds (p-coumaric acid, vanillic acid beta-glucoside, protocatechuic acid, and caffeic acid), structures of which were identified by NMR and MS analyses. The ORAC values of these isolated compounds showed 0.15-1.43 units (micromol of Trolox equiv)/micromol, and the new compound showed a remarkable synergistic effect on caffeoylquinic acid isomers. The antioxidant activity of the MeOH eluate was highly dependent on the major prune components, caffeoylquinic acid isomers, with a contribution from the new synergist.     

Spectrophotometric determination of urea in sugar cane distilled spirits

Urea is an important precursor in the formation of ethyl carbamate, a known carcinogen in alcoholic beverages. Ethyl carbamate has recently been detected at high concentrations in sugar cane distilled spirits, but little is known about the concentration of urea in these beverages. The objectives of this study were to validate methodology for the determination of urea in sugar cane distilled spirits, to determine the levels in 68 samples from different regions within the state of Minas Gerais, Brazil, and to examine the relationship between the concentrations of urea and ethyl carbamate. The method, based on the reaction of urea with 1-phenyl-1,2-propanodione-2-oxime and spectrophotometric quantification at 540 nm, provided linear response from 0.5 to 15.0 mg/L. No purification of the sample was required. The limits of detection and quantification were 0.1 and 0.5 mg/L, respectively. Urea was detected in 69% of the samples at levels varying from 0.50 to 5.10 mg/L. There was no significant difference on the levels of urea in samples from different regions of the state. No significant correlation between the levels of urea and ethyl carbamate was observed for the samples analyzed.     

Aromatic characterization of pot distilled kiwi spirits

This study contributes fundamental knowledge that will help to develop a distillate of kiwi wine, made from kiwis of the Hayward variety grown in the southwest of Galicia (Spain). Two yeast strains, L1 (Saccharomyces cerevisiae ALB-6 from the EVEGA yeast collection) and L2 (S. cerevisiae Uvaferm BDX from Lallemand) were assessed to obtain a highly aromatic distillate. The kiwi spirits obtained were compared with other fruit spirits, in terms of higher alcohols, minor alcohols, monoterpenols, and other minor compounds, which are relevant in determining the quality and taste of the kiwi spirits. It was found that the kiwi juice fermented with yeast L1 produced a more aromatic distillate. In addition, kiwi distillates produced with both yeasts had the same ratio of trans-3-hexen-1-ol and cis-3-hexen-1-ol, which is lower than that found in other fruit distillates.     

Antioxidant activity and characterization of volatile constituents of Taheebo (Tabebuia impetiginosa Martius ex DC)

Volatiles were isolated from the dried inner bark of Tabebuia impetiginosa using steam distillation under reduced pressure followed by continuous liquid-liquid extraction. The extract was analyzed by gas chromatography and gas chromatography-mass spectrometry. The major volatile constituents of T. impetiginosa were 4-methoxybenzaldehyde (52.84 microg/g), 4-methoxyphenol (38.91 microg/g), 5-allyl-1,2,3-trimethoxybenzene (elemicin; 34.15 microg/g), 1-methoxy-4-(1E)-1-propenylbenzene (trans-anethole; 33.75 microg/g), and 4-methoxybenzyl alcohol (30.29 microg/g). The antioxidant activity of the volatiles was evaluated using two different assays. The extract exhibited a potent inhibitory effect on the formation of conjugated diene hydroperoxides (from methyl linoleate) at a concentration of 1000 microg/mL. The extract also inhibited the oxidation of hexanal for 40 days at a level of 5 microg/mL. The antioxidative activity of T. impetiginosa volatiles was comparable with that of the well-known antioxidants, alpha-tocopherol, and butylated hydroxytoluene.     

Potentiometric flow injection determination of glycerol in distilled spirits.

A single-line flow injection system including a tubular periodate-selective electrode without inner reference solution is proposed for glycerol determination in distilled spirits, based on oxidation of this polyol by periodate. Interferences due to 5.0 mg L(-1) Cu, 5000 mg L(-1) sucrose, and 3000 mg L(-1) fructose plus glucose were investigated. The procedure is characterized by a linear response for 20-500 mg L(-1) glycerol (r > 0.9999, n = 7), a relative standard deviation of results of <0.03, and an analytical throughput of 30 determinations per hour. Accuracy was assessed by applying the procedure to distilled spirits of sugarcane and grape already analyzed by HPLC; in addition, recoveries within 96 and 120% were obtained.     

Antioxidant constituents of almond [Prunus dulcis (Mill.) D.A. Webb] hulls

Almond hulls (Nonpareil variety) were extracted with methanol and analyzed by reversed phase HPLC with diode array detection. The extract contained 5-O-caffeoylquinic acid (chlorogenic acid), 4-O-caffeoylquinic acid (cryptochlorogenic acid), and 3-O-caffeoylquinic acid (neochlorogenic acid) in the ratio 79.5:14.8:5.7. The chlorogenic acid concentration of almond hulls was 42.52 +/- 4.50 mg/100 g of fresh weight (n = 4; moisture content = 11.39%). Extracts were tested for their ability to inhibit the oxidation of methyl linoleate at 40 degrees C. At an equivalent concentration (10 microg/1 g of methyl linoleate) almond hull extracts had higher antioxidant activity than alpha-tocopherol. At higher concentrations (50 microg/1 g of methyl linoleate) almond hull extracts showed increased antioxidant activity that was similar to chlorogenic acid and morin [2-(2,4-dihydroxyphenyl)-3,5,7-trihydroxy-4H-1-benzopyran-4-one] standards (at the same concentrations). These data indicate that almond hulls are a potential source of these dietary antioxidants. The sterols (3beta,22E)-stigmasta-5,22-dien-3-ol (stigmasterol) and (3beta)-stigmast-5-en-3-ol (beta-sitosterol) (18.9 mg and 16.0 mg/100 g of almond hull, respectively) were identified by GC-MS of the silylated almond hull extract.     

Assisted distillation cleanup of pesticide residues in animal fats: new beadless distillation tube

A new assisted distillation tube has been developed which contains no glass beads or glass wool. The sample is injected into the top of the tube, and a septum is not required. Large ground-glass joints (10/19) are used at the gas inlet and at the Florisil trap connection for maximum strength. Existing assisted distillation apparatus was easily modified to accept the new tubes. Recoveries of 9 organochlorine pesticides from butter and cattle fat ranged from 87 to 104% at a tube temperature of 230 degrees C and a nitrogen flow rate of 250 mL/min. No significant change occurred in recoveries of 8 of the 9 pesticides after 85 uses of the beadless tube. Only the recovery of HCB from butter decreased, from 95 to 80%, after 51 runs. The new tube was compared with the Unitrex glass bead-packed concentric tube at flow rates of 230, 400, and 600 mL nitrogen/min. Recoveries from the Unitrex tube were similar to those of the beadless tube for all pesticides except DDT which was significantly lower, indicating incomplete distillation at 250 mL/min and possible partial breakdown at 400 and 600 mL/min. A procedure is introduced for pressurized solvent washing of distillation tubes. This procedure is more efficient than vacuum washing.     

Production and composition of cider spirits distilled in "alquitara"

The capacity of alquitara (a traditional distillation system) to produce cider brandies is evaluated. To do so, the chemical composition of 12 fractions obtained during the distillation process and the cider brandies obtained from five ciders were analyzed (alcohol strength, methanol, volatile substances, furfural, and metals), taking into account European and Spanish legislation. During the course of distillation, an important increase in methanol, furfural, 2-phenylethanol, and metals in the last fractions was observed, while fusel oils were more abundant in the first fractions collected. Only acetaldehyde behaved differently, showing a minimum concentration in the middle fractions that might be explained by its formation on the surface of alquitara. On the other hand, the final distillates obtained by means of this method complied with the considered regulations. Worth highlighting in this regard are the low levels of a potential toxin such as methanol, as well as the detection of a constant ratio for methanol, ethanol, and fusel oil for the pairs of cider/spirits analyzed, which could be interpreted as an indication of good uniformity in the distillation system and method, thus guaranteeing product quality.