Alliinase-independent Inhibition of Staphylococcus aureus B33 by Heated Garlic

ABSTRACT: Heated (121 °C) garlic extract in which alliinase was inactivated before crushing exhibited complete bacteriostatic activity at 15% against Staphylococcus aureus. Garlic heated for 45 min showed the highest antibacterial activity and the relative peak areas of 4-heptenal, methyl allyl disulfide, diallyl disulfide, 2-vinyl-4H-1,3-dithiin, and diallyl trisulfide (DATS) were highest at 45 min of heating. Other than 4-heptenal, all these compounds are known to possess different degrees of antibacterial activity. DATS was thought to be the primary antibacterial compound in heated garlic extract. It was tentatively concluded that antibacterial compounds were formed from alliin unreacted by alliinase by marked heating. Diallyl compounds with more than three sulfur atoms and the oxidized form of allicin were not detected.     

Characterisation of volatile sulphur-containing compounds generated in crushed leaves of Chinese chive (Allium tuberosum Rottler)

To characterise the composition of sulphur-containing constituents in Chinese chive (Allium tuberosum Rottler), GC–MS and HPLC analyses were carried out, using 12 varieties of Chinese origin, 4 varieties of Japanese origin and 6 commercially available cultivars. Five disulphides (dimethyl, allyl methyl, methyl 1-(E)-propenyl, diallyl, and allyl 1-(E)-propenyl), two trisulphides (dimethyl and allyl methyl), and two vinyldithiins (3-vinyl-[4H]-1,2- and 2-vinyl-[4H]-1,3-) were identified on the basis of their mass spectral and GC-retention data. Among the detected sulphur compounds, sulphides with a methyl group predominated over those with an allyl group. This was supported by the HPLC estimations, suggesting that all cultivars examined had much greater amounts of methiin than alliin. Also, two novel compounds were tentatively identified as [3H,4H]-1,2-dithiin and [2H,4H]-1,3-dithiin on the basis of their mass spectral features, GC-retention data, and some experimental results on their formation in reaction mixtures with different proportions of methiin and alliin. Their formation mechanism was proposed.     

Stability of Allicin in Garlic Juice

Stability of allicin in garlic juice was evaluated by gas chromatography (GC) and nonhealing HPLC. Allicin in garlic juice decreased to a nondetectable amount after 144 hr at 40°C. Because of heating effects, allicin, in GC analysis, was converted to 2-vinyl-[4H]-1,3-dithiin and 3-vinyl-[4H]-1,2-dithiin but not 3-vinyl-l,2-dithi-4-ene as reported by other investigators. Unheated garlic juice did not contain detectable amounts of 2-vinyl-[4H]-1,3-dithiin and 3-vinyl-[4H]-1,2-dithiin as shown by HPLC analysis.     

Inhibition of heterocyclic aromatic amine formation in fried ground beef patties by garlic and selected garlic-related sulfur compounds

The effects of garlic and selected organosulfur compounds (diallyl disulfide, dipropyl disulfide, diallyl sulfide, allyl methyl sulfide, allyl mercaptan, cysteine, and cystine) on the formation of heterocyclic aromatic amines (HAAs) in fried ground beef patties were evaluated. Minced garlic cloves (ca. 4.8 to 16.7%, wt/wt) or organosulfur compounds (0.67 mmol) were added directly to ground beef. Patties (100 g) were fried at 225 degrees C (surface temperature) for 10 min per side. Two patties were fried for each replication, and five replicates were analyzed for each treatment. For each replicate, four subsamples were analyzed (two unspiked subsamples for concentration and two spiked subsamples for the recovery of HAA standards). The volatile sulfur compounds significantly (P < 0.05) reduced concentrations of 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine by reductions of 46 to 81%, while average reductions of 35, 22, and 71%, were achieved with cystine, cysteine, and whole garlic, respectively. The volatile sulfur compounds reduced concentrations of 2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline by 34 to 67%, while reductions of 25, 19, and 63% (P < 0.05) were achieved with cystine, cysteine, and whole garlic, respectively. These studies confirm that garlic and some organosulfur compounds have the potential to reduce HAA formation incooked beef patties.     

Volatile distribution in garlic (Allium sativum L.) by solid phase microextraction (SPME) with different processing conditions

Treatments of autoclaving, high temperature aging (aged-black garlic), crushing, and roasting at 100, 150, and 200°C were applied to alter the volatile profiles of garlic (Allium sativum L.). Headspace volatiles in samples were analyzed by a solid phase microextraction (SPME)-GC/MS. Total peak areas of crushed-raw garlic were the highest and those of aged-black garlic clove were the lowest. Crushing effects were clearly observed in raw garlic, aged-black garlic, and roasted garlic at 200°C for 60 min. Sulfur-containing volatiles including diallyl disulfide and diallyl trisulfide were major volatiles. Generally, peak areas of diallyl disulfide decreased when garlic received autoclaving and roasting treatment while diallyl trisulfide and allyl methyl trisulfide increased during heat treatment compared to raw garlic. Roasting at 200°C for 60 min caused the formation of pyrazines greatly in garlic. Principal component analysis (PCA) for the volatile profiles by SPME-GC/MS could discriminate types of processed garlic successfully.     

二次分子蒸馏提取与市售大蒜油的气质联用分析和比较

采用二次分子蒸馏技术提取大蒜中大蒜油,并运用气相色谱- 质谱联用分析,通过计算机检索与标准谱图对照,鉴定大蒜油中组分和主要化学成分,比较提取所得大蒜油与市售大蒜油的化学成分差异。结果表明：经分子蒸馏法所得大蒜油产物中主要含有二烯丙基一硫化物、二烯丙基二硫化物、甲基二硫化物、二烯丙基硫代亚磺酸酯及三硫醚等化合物,未检测出环状二硫醚和四硫醚化合物。     

气质联用法分析鱼香肉丝中的挥发性风味物质

应用顶空固相微萃取(SPME)—气相色谱和质谱联用(GC-MS)技术分析鱼香肉丝中的风味物质。建立鱼香肉丝中风味物质的萃取和分析条件,对鱼香肉丝在加工前后风味物质的变化进行比较。鱼香肉丝中主要挥发性风味物质有烯丙基硫醇、乙醇、己醛、3,3’-硫丙烯、桧烯、甲基-2-丙烯基-二硫化物、2-庚烯醛、二丙基-二硫化物、乙酸、2-呋喃甲醛、Z-柠檬醛、香叶醛、3,4-二氢-3-乙烯基-1,2-二硫化物。     

超临界CO2-分子蒸馏纯化蒜油与水蒸气蒸馏法制取蒜油挥发性成分分析

采用分子蒸馏技术(MD)将超临界CO2(SFE)萃取的蒜油进行纯化,以顶空固相微萃取气质联用技术(HSSPME-GC-MS)分析蒜油中的挥发性成分,确定最佳工艺：进样速度1 滴/s,蒸馏温度60℃,刮膜转速250r/min。纯化的蒜油挥发性成分仅有4 种,二烯丙基二硫醚和二烯丙基三硫醚、2- 乙烯基-1,3- 二硫杂-4- 环己烯和3- 乙烯基-1,2- 二硫杂-5- 环己烯;与水蒸气蒸馏法制得的新鲜蒜油(F-GO)比较,SFE 法是一种理想的制取蒜油的方法;蒜油放置30d(S-GO)后有效成分含量下降,导致品质下降。     

Chemical composition and classification of culinary and pharmaceutical garlic-based products

 Garlic Samples (n = 34) used as a spice and/or health preparations were analysed for their content of the major amino acid found in garlic, i. e. alliin and its five major decomposition products: 2-vinyl-[4H]-1,3-dithiin; 3-vinyl-[4H]-1,2-dithiin; diallyl disulphide; allylmethyl disulphide and diallyl trisulphide, using two high-performance liquid chromatographic methods. The obtained data were subjected to principal components analysis (PCA) which distinguished these samples into different individual categories according to the similarity of their chemical composition. The four distinguished groups were: fresh garlic bulbs, dry garlic products (powders, granulates and tablets), macerates in vegetable oils (salted garlic pastes, soups and bouillon cubes, which had a very similar chemical composition) and garlic essential oils. Received: 2 January 1996/Revised version: 18 March 1996     

Deodorization of Garlic Breath Volatiles by Food and Food Components

The ability of foods and beverages to reduce allyl methyl disulfide, diallyl disulfide, allyl mercaptan, and allyl methyl sulfide on human breath after consumption of raw garlic was examined. The treatments were consumed immediately following raw garlic consumption for breath measurements, or were blended with garlic prior to headspace measurements. Measurements were done using a selected ion flow tube‐mass spectrometer. Chlorophyllin treatment demonstrated no deodorization in comparison to the control. Successful treatments may be due to enzymatic, polyphenolic, or acid deodorization. Enzymatic deodorization involved oxidation of polyphenolic compounds by enzymes, with the oxidized polyphenols causing deodorization. This was the probable mechanism in raw apple, parsley, spinach, and mint treatments. Polyphenolic deodorization involved deodorization by polyphenolic compounds without enzymatic activity. This probably occurred for microwaved apple, green tea, and lemon juice treatments. When pH is below 3.6, the enzyme alliinase is inactivated, which causes a reduction in volatile formation. This was demonstrated in pH‐adjusted headspace measurements. However, the mechanism for volatile reduction on human breath (after volatile formation) is unclear, and may have occurred in soft drink and lemon juice breath treatments. Whey protein was not an effective garlic breath deodorant and had no enzymatic activity, polyphenolic compounds, or acidity. Headspace concentrations did not correlate well to breath treatments.     

Effect of Milk on the Deodorization of Malodorous Breath after Garlic Ingestion

Abstract: The effect of milk and milk components on the deodorization of diallyl disulfide (DADS), allyl methyl disulfide (AMDS), allyl mercaptan (AM), allyl methyl sulfide (AMS), and methyl mercaptan (MM) in the headspace of garlic as well as in the mouth- and nose-space after garlic ingestion was investigated using selected ion flow tube-mass spectrometry (SIFT-MS). Fat-free and whole milk significantly reduced the head-, mouth-, and nose-space concentrations of all volatiles. Water was the major component in milk responsible for the deodorization of volatiles. Due to its higher fat content, whole milk was more effective than fat-free milk in the deodorization of the more hydrophobic volatiles diallyl disulfide and allyl methyl disulfide. Milk was more effective than water and 10% sodium caseinate in the deodorization of allyl methyl sulfide, a persistent garlic odor, in the mouth after garlic ingestion. Addition of milk to garlic before ingestion had a higher deodorizing effect on the volatiles in the mouth than drinking milk after consuming garlic. Practical Application: Ingesting beverages or foods with high water and/or fat content such as milk may help reduce the malodorous odor in breath after garlic ingestion and mask the garlic flavor during eating. To enhance the deodorizing effect, deodorant foods should be mixed with garlic before ingestion.     

Investigation of the volatile aroma components of garlic leaves essential oil. Possibility of utilization to enrich garlic bulb oil

The volatile aroma components of Egyptian green garlic leaves essential oil was investigated for the first time. After the utilization of garlic bulbs to prepare garlic oil or after drying the bulbs to produce garlic powder, garlic leaves are considered to be waste material, which is disposed of without any benefit. In this investigation, green garlic leaves were distilled and the essential oil was subjected to GC and GC-MS identification. The yield of the oil was 0.06% (based on wet weight of the leaves). The most prominent compounds of the essential oil were diallyl trisulfide (32.32%), followed by diallyl disulfide (31.35%) and methyl allyl trisulfide (11.40%); these compounds are the same as those found in garlic bulb oil. This means that garlic leaf oil is a rich, renewable and priceless source of garlic aroma compounds which could be utilized in fortification and enriching of garlic bulb essential oil to increase its quantity without changing the quality. Utilization of green garlic leaves for production of essential oil will also save, to some extent, the costs of disposing of large amounts of leaves in garlic possessing factories, transforming them into profits.     

Deodorization of Garlic Breath by Foods,and the Role of Polyphenol Oxidase and Phenolic Compounds

Garlic causes a strong garlic breath that may persist for almost a day. Therefore, it is important to study deodorization techniques for garlic breath. The volatiles responsible for garlic breath include diallyl disulfide, allyl mercaptan, allyl methyl disulfide, and allyl methyl sulfide. After eating garlic, water (control), raw, juiced or heated apple, raw or heated lettuce, raw or juiced mint leaves, or green tea were consumed immediately. The levels of the garlic volatiles on the breath were analyzed from 1 to 60 min by selected ion flow tube mass spectrometry (SIFT‐MS). Garlic was also blended with water (control), polyphenol oxidase (PPO), rosemarinic acid, quercetin or catechin, and the volatiles in the headspace analyzed from 3 to 40 min by SIFT‐MS. Raw apple, raw lettuce, and mint leaves significantly decreased all of the garlic breath volatiles in vivo. The proposed mechanism is enzymatic deodorization where volatiles react with phenolic compounds. Apple juice and mint juice also had a deodorizing effect on most of the garlic volatiles but were generally not as effective as the raw food, probably because the juice had enzymatic activity but the phenolic compounds had already polymerized. Both heated apple and heated lettuce produced a significant reduction of diallyl disulfide and allyl mercaptan. The presence of phenolic compounds that react with the volatile compounds even in the absence of enzymes is the most likely mechanism. Green tea had no deodorizing effect on the garlic volatile compounds. Rosmarinic acid, catechin, quercetin, and PPO significantly decreased all garlic breath volatiles in vitro. Rosmarinic acid was the most effective at deodorization.     

Reduction of Heterocyclic Aromatic Amine Formation and Overall Mutagenicity in Fried Ground Beef Patties by Organosulfur Compounds

ABSTRACT: The effects of several organosulfur compounds on heterocyclic aromatic amine (HAA) formation and overall mutagenicity in fried ground beef patties were evaluated. The greatest inhibition of total HAA formation was achieved with diallyl disulfide (78%) and dipropyl disulfide (70%); these compounds also reduced overall mutagenicity by 75 and 65%, respectively. The addition of diallyl sulfide, allyl methyl sulfide, and allyl mercaptan also significantly ( p < 0.05) reduced mutagenicity, with reductions of 56, 43, and 30%, respectively. The addition of cysteine and cystine, however, did not reduce the mutagenicity of cooked meat, an observation confirmed by the relatively small reductions in HAA concentrations.     

Odor Components of Human Breath After the Ingestion of Grated Raw Garlic

The major odor components of finely grated, raw garlic in the air of the human mouth have been studied. Immediately after garlic ingestion, tests of the mouth air of six subjects revealed two major peaks that were positively identified as being allyl mercaptan and diallyl disulfide; these findings are based on an evaluation of the fragment patterns of a GC-MS analysis and from the actual retention times of these authentic compounds. The allyl mercaptan level was higher than the level of diallyl disulfide, although both compounds smell like garlic. Our results suggest that after garlic ingestion, allyl mercaptan is the major garlic-smelling compound in human mouth air, and diallyl disulfide is secondary.     

同时蒸馏萃取- 气质联机分析腌渍野韭菜花香成分

以乙醚为溶剂,采用同时蒸馏萃取法提取腌渍野韭菜花精油,提取率0.29%。用气相色谱- 质谱法结合气相色谱保留指数定性方法,从腌渍野韭菜花精油中鉴定出37 种挥发性成分,占精油总成分的95.75%。主要成分为二甲基三硫醚(28.18%)、二甲基二硫醚(18.13%)、甲基丙烯基二硫醚(14.24%)、甲基烯丙基三硫醚(4.89%)、甲基烯丙基二硫醚(3.19%)、甲基甲硫基甲基二硫醚(3.10%)、4- 乙烯基愈创木酚(2.93%)、二烯丙基二硫醚(2.71%)、二甲基四硫醚(2.67%)、3- 羟基-2- 丁酮(2.42%)、2- 乙烯基-2- 丁烯醛(1.54%)、2,5- 二甲基-1,3,4- 五硫三环(1.45%)、苯甲醇(1.31%)和甲硫基甲磺酰基甲烷(1.28%)等。其中硫醚和多硫醚类成分11 种,相对含量79.99%,是腌渍野韭菜花的特征香气成分。     

Anticarcinogenic properties of garlic: a review

Garlic is a popular spice added to several edible preparations and is a remedy for a variety of ailments. Epidemeological as well as laboratory studies have shown that garlic consumption reduces certain cancer incidences in the stomach, colon, mammary, cervical, etc. This article focuses on the general chemistry, metabolism, anticarcinogenic properties, mechanism of action behind the anticarcinogenic effects, functional foods based on garlic; and future areas of research. Garlic has been shown to metabolized into N-aceryl-S-allyl cysteine, allyl mercaptan, diallyl disulfide, diallyl sulfide, diallyl sulfoxide, diallyl sulfone, and allyl methyl sulfide. Garlic has been thought to bring about its anticarcinogenic effect through a number of mechanisms, such as the scavenging of radicals, increasing gluathione levels, increasing the activities of enzymes such as glutathione S-transferase, catalase, inhibition of cytochrome p4502E1, DNA repair mechanisms, prevention of chromosomal damage etc. Future research should standardize the dosage of garlic and type, ie., whether it should be taken fresh, cooked, or aged. The formulation of odorless functional foods with the retention of anticarcinogenic activity should be further studied.     

大蒜素和有机溶剂对蒜氨酸酶活性及大蒜油组成的影响

大蒜油具有重要的生物活性和调味功能。本文以化学合成的蒜氨酸为原料在蒜酶的催化下制备大蒜油,研究中间产物大蒜素、萃取溶剂对蒜酶活性的影响,以及溶剂对大蒜油组成成分的影响。结果显示:大蒜素在一定程度上会抑制蒜酶的活性,但不会导致蒜酶的完全失活;有机溶剂对蒜酶的影响比较复杂,其中氯仿、二氯甲烷使蒜酶活性完全丧失,而正己烷、正戊烷对蒜酶的活性影响则不明显。采用气质联用、核磁共振二维谱表征了不同溶剂下大蒜油的组成。用氯仿、正己烷等非极性溶剂萃取大蒜素,得到的大蒜油以3-乙烯基-1,2-二硫环己-4-烯(4X)和3-乙烯基-1,2-二硫环己-5-烯(5X)为主;而用乙酸等质子溶剂萃取,则大蒜油成分以二烯丙基三硫醚(DATS)、二烯丙基二硫醚(DADS)为主。     

新鲜蒜黄香气活性成分分析鉴定

为分析鉴定新鲜蒜黄的香气活性成分,将新鲜蒜黄加水和二氯甲烷匀浆后进行溶剂辅助蒸发处理,获得风味萃取物。风味萃取物采用气-质联机分析检测出39个挥发性化合物,采用稀释法/气相色谱-嗅闻分析检测出35个气味活性区。根据质谱、保留指数、嗅闻的气味、相关文献,鉴定出35个香气活性化合物,其中3-乙烯基-1,2-二硫环己-4-烯、2-乙烯基噻吩、2,3-二甲基噻吩、二甲基三硫醚、二烯丙基二硫醚、1-氧-4,6-二氧杂环辛烷-5-硫酮、2-甲基二氢-3(2H)噻吩酮具有极高稀释因子(log₃FD ≥ 6),表明对新鲜蒜黄风味贡献大。本实验样品处理条件温和,最大化保持了新鲜蒜黄的风味,研究结果可为蒜黄的贮藏加工及开发利用提供指导。     

泰安大蒜与金乡大蒜挥发性风味物质成分分析

采用自动化静态顶空与气质联用的方法分析对比金乡大蒜与泰安大蒜的挥发性成分,通过GC-MS分析和NIST质谱库计算机检索,对样品进行定性分析,并采用面积归一化法进行定量分析。检测结果表明,不同产地的大蒜中的挥发性风味物质种类略有差别,金乡大蒜中含硫化合物总量高于泰安大蒜,并且,新鲜大蒜含硫化合物含量高于贮藏大蒜,存在显著差异。金乡大蒜和泰安大蒜检出的风味物质种类略有差别,地域性差别对大蒜风味物质种类影响不大,但是,在大蒜风味物质中起决定性作用的1,3-二噻烷、烯丙基三硫化物、烯丙基二硫化物以及而烯丙基四硫醚,在含量上金乡大蒜明显高于泰安大蒜。同时,研究表明,静态顶空与气质联用能够快速、简便、高效、准确地对大蒜中的挥发性风味物质进行组分分析以及鉴定。