大蒜烯丙基硫化物的分离鉴定及抗氧化性

为了研究大蒜烯丙基硫化物的抗氧化活性,该文利用离子交换层析与制备液相技术从大蒜中分离得到S-烯丙基-L-半胱氨酸(S-allyl-L-cysteine,SAC)、S-烯丙基-L-半胱氨酸亚砜(S-allyl-L-cysteine sulfoxide,ACSO)和γ-谷氨酰-S-烯丙基-L-半胱氨酸(γ-L-glutamyl-S-allyl-L-cysteine,GSAC)3种水溶性烯丙基硫化物。分离产物利用高效液相色谱-电喷雾离子化串联质谱联用(high performance liquid chromatography-electrospray ionization-mass/mass spectrometry,HPLC-ESI-MS/MS)、核磁共振氢谱(proton nuclear magnetic resonance,1H NMR)和核磁共振碳谱(carbon-13 nuclear magnetic resonance,13C NMR)技术及比旋光度检测方法鉴定,并与合成标准品比对分析确定。同时,该文以具有半胱氨酸结构的还原型谷胱甘肽(glutathione,GSH)为参照测定了SAC、ACSO、GSAC的1,1-二苯基-2-三硝基苯肼(1,1-diphenyl-2-picrylhydrazyl,DPPH)自由基清除能力及铁离子螯合能力。结果表明,SAC和GSAC对DPPH自由基的清除率较高(73.55%,72.68%)且与GSH(71.14%)无显著性差异(P0.05);SAC和ACSO对铁离子的螯合率较高(81.21%,79.18%)且与GSH(78.13%)无显著性差异(P0.05),尤其是GSAC对铁离子螯合率(92.76%)显著性高于GSH(P0.05),证实了3种硫化物均具有很好的抗氧化性能。研究结果进一步解释和阐述大蒜硫化物的螯合能力,进而为大蒜硫化物以抗氧化为基础的其他功能活性研究提供参考。     

Identification of bitterness-masking compounds from cheese

Bitterness-masking compounds were identified in a natural white mold cheese. The oily fraction of the cheese was extracted and further fractionated by using silica gel column chromatography. The four fractions obtained were characterized by thin-layer chromatography and nuclear magnetic resonance spectroscopy. The fatty acid-containing fraction was found to have the highest bitterness-masking activity against quinine hydrochloride. Bitterness-masking activity was quantitated using a method based on subjective equivalents. At 0.5 mM, the fatty acid mixture, which had a composition similar to that of cheese, suppressed the bitterness of 0.008% quinine hydrochloride to be equivalent to that of 0.0049-0.0060% and 0.5 mM oleic acid to that of 0.0032-0.0038% solution. The binding potential between oleic acid and the bitter compounds was estimated by isothermal titration calorimetry. These results suggest that oleic acid masked bitterness by forming a complex with the bitter compounds.     

Allicin and allicin-derived garlic compounds increase breath acetone through allyl methyl sulfide: use in measuring allicin bioavailability

Progress in establishing systemic pharmacological effects for fresh, crushed garlic (Allium sativum L) in humans has been hindered by (1) the inability to measure allicin bioavailability, (2) lack of direct evidence that allicin has significant systemic activity at doses of garlic normally consumed, and (3) lack of a model for an acute effect. We have addressed these problems by quantifying the increases in breath acetone and breath allyl methyl sulfide (AMS). The area under the 48 h curve was measured in humans after consumption of standardized garlic preparations, allicin, and allicin-derived compounds, at the equivalent of 7 g of crushed garlic. It was shown that the allyl thiosulfinates (mainly allicin) are solely responsible for breath AMS and increased breath acetone. Diallyl trisulfide, diallyl disulfide, ajoene, and S-allylmercaptocysteine, at isomolar dithioallyl, showed the same quantitative effects as allicin. Consumption of AMS at isomolar allyl also gave the same effects as allicin, indicating that AMS is the main metabolite of allicin and is an active metabolite. In conclusion, allicin and allicin-derived compounds are rapidly metabolized to AMS, a compound which stimulates the production of acetone and which can be used to measure the bioavailability of allicin and, hence, the ability of garlic supplements to represent fresh garlic.     

Identification of six phenylpropanoids from garlic skin as major antioxidants

The extract of garlic skins (peels) showed strong antioxidant activity, and some responsible constituents were isolated and identified. Garlic (Allium sativum L.) has been used as an herbal medicine, but there is no report on the health benefits of the skin or peel. In this study, the 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical scavenging activity of garlic skin extract was evaluated. Using chromatographic techniques, the active constituents were isolated and subsequently identified. Analyses by high-performance liquid chromatography coupled with a photodiode array detector (HPLC-PDA) suggested that these compounds were phenylpropanoids, which had a characteristic absorbance at 300-320 nm. Liquid chromatography-mass spectrometry (LC-MS) and nuclear magnetic resonance analyses allowed the chemical structures of the isolated constituents to be postulated. The proposed compounds were subsequently synthesized and compared with the constituents in the extract using HPLC-PDA and LC-MS. N-trans-Coumaroyloctopamine, N-trans-feruloyloctopamine, guaiacylglycerol-beta-ferulic acid ether, and guaiacylglycerol-beta-caffeic acid ether were identified as were trans-coumaric acid and trans-ferulic acid. Also, the antioxidant activities of these compounds were determined.     

Identification and quantification of zeaxanthin esters in plants using liquid chromatography-mass spectrometry

It has been suggested that lutein and zeaxanthin may decrease the risk for age-related macular degeneration. Surprisingly, oleoresins rich in zeaxanthin are not yet available on the market. Several authors have reported enhanced stability of esterified xanthophylls, so plants containing zeaxanthin esters were investigated to establish valuable sources for the production of durable oleoresins. Liquid chromatography-atmospheric pressure chemical ionization mass spectrometry [LC-(APCI)MS] was used to unequivocally identify zeaxanthin esters of a standard mixture and in several plant extracts. Zeaxanthin esters were quantified on the basis of their respective molecular masses using zeaxanthin for calibration; total zeaxanthin was determined after saponification of aliquots of the extracts. Thus, dried wolfberries (Lycium barbarum), Chinese lanterns (Physalis alkekengi), orange pepper (Capsicum annuum), and sea buckthorn (Hippophae rhamnoides) proved to be valuable zeaxanthin ester sources. The present LC-MS method allows for an even more detailed analysis of zeaxanthin esters than reported previously.     

基于主被动遥感数据和面向对象的大蒜识别

针对开封市大蒜种植破碎化程度高,光学数据难以高精度、快速提取问题.该研究基于谷歌地球引擎(Google EarthEngine,GEE)云平台、随机森林算法(Random Forest,RF)和面向对象方法,选择融合Sentinel-1卫星的后向散射系数与Sentinel-2卫星的光谱、光谱指数及纹理特征,分别应用10...     

Identification of a peptide in enzymatic hydrolyzate of cheese that inhibits ovalbumin permeation in Caco-2 cells

Because the first step in the triggering of food allergy is the permeation of the allergen through the intestine, enhancement of the intestinal barrier function is thought to be effective for preventing food allergy. In this study, a peptide that inhibits ovalbumin (OVA) permeation in an in vitro Caco-2 cell model was isolated from enzymatic hydrolyzate of cheese (EHC). Amino acid sequence analysis identified the active peptide as GPIVLNPWDQ, a sequence identical to amino acids 102-111 of alphas2-casein. The decapeptide significantly inhibited OVA permeation at a concentration of 10(-6) M. In addition, it was found that a pentapeptide half, NPWDQ, is essential for the inhibitory activity because NPWDQ but not GPIVL had nearly the same inhibitory activity as GPIVLNPWDQ. The possibility exists that EHC and/or peptides possessing the NPWDQ sequence can be practically applied to the prevention of food allergy.     

超临界二氧化碳萃取蒜汁中大蒜油的研究

利用超临界二氧化碳对蒜汁中大蒜油的萃取进行了研究,结果表明：萃取釜中添加填料可以大大提高萃取速度;一次压榨汁大蒜素含量高,萃取速度快,但通过延长萃取时间,两次压榨汁可以得到较高的萃取率;超临界CO₂萃取蒜汁中大蒜油的最佳萃取条件为萃取压力15 MPa,萃取温度40℃,CO₂流量11 kg/h。该方法得到的大蒜油成分与从破碎大蒜固体中萃取得到的大蒜油成分基本相同,大蒜素含量在40%以上。     

Determination of natamycin in cheese and cheese rind: interlaboratory collaborative study

A collaborative test on the determination of natamycin in cheese and cheese rind was conducted. Participants were from 37 laboratories in 13 countries. Eight samples, consisting of 4 duplicates, were investigated by a spectrometric method and a liquid chromatographic (LC) method. The spectrometric method gave good results (coefficient of variation [CV] = 12%) and the LC method with ultraviolet detection gave reasonable results (CV = 25%) for levels down to 15 mg/kg (0.9 mg/dm2). For very low levels, a preconcentration step is necessary, but even then quantitation is poor (CV = 35-37%) for both methods at 1.7 mg/kg, although the presence of natamycin can be detected qualitatively. For a level of 0.3 mg/kg, quantitation is poor (CV = 39%) for the LC method and impossible (CV = 60%) for the spectrometric method.     

Identification of synthetic regioisomeric lutein esters and their quantification in a commercial lutein supplement

Synthetic mixtures of 24 mono- and diesters of the asymmetric hydroxylated carotenoid lutein with lauric, myristic, palmitic, and stearic acids were analyzed by liquid chromatography-ultraviolet/visible spectroscopy (LC-UV-vis) and characterized by LC-mass spectrometry (MS) and nuclear magnetic resonance spectroscopy (NMR). These compounds were then used for identifying the composition of a commercial lutein supplement. This is the first report of chromatographic separation of mixed fatty acid lutein diesters. Preferential MS loss of fatty acids or water occurred initially at the 3'-hydroxy position in the epsilon-ionone ring and subsequently at the 3-hydroxy position in the beta-ionone ring. This selective fragmentation leads to facile assignment of the specific fatty acids to the appropriate regioisomeric ionone ring. A commercial lutein supplement contained low levels of two pairs of regioisomeric monoesters and nearly equal levels of three homogeneous diesters and five pairs of mixed diesters. Palmitic acid was the predominant fatty acid, with lower amounts of myristic, stearic, and lauric acids.     

Spectrometric and liquid chromatographic determination of natamycin in cheese and cheese rind

Methods for determining natamycin content of cheese rind and cheese are presented. Cheese and rind samples are extracted with methanol and the fat precipitated by cooling the sample solution in methanol-water at -15 to -20 degrees C for ca 1 h. Natamycin levels are measured by UV spectrometric detection at absorbance minimum 311 nm, maximum 317 nm, and at exactly 329 nm, or by LC separation over Lichrosorb RP-8 column with detection at 303 nm. For measuring low levels, a concentration step is provided. The method is applicable to natamycin in cheese rind and in the interior of the cheese. Detection limit is 0.5 mg/kg. The method is suitable for controlling a maximum tolerance of natamycin on the cheese rind, at a level of 1 mg/dm2, and for detecting migration of natamycin into the cheese.     

Identification of two novel pigment precursors and a reddish-purple pigment involved in the blue-green discoloration of onion and garlic

By using a model reaction system representing blue-green discoloration that occurs when purees of onion (Allium cepa L.) and garlic (Allium sativum L.) are mixed, we isolated two pigment precursors (PPs) and a reddish-purple pigment (PUR-1) and determined their chemical structures. PPs were isolated from a heat-treated solution containing color developer (CD) and either l-valine or l-alanine, and their structures were determined as 2-(3,4-dimethylpyrrolyl)-3-methylbutanoic acid (PP-Val), and 2-(3,4-dimethyl-1H-pyrrolyl) propanoic acid (PP-Ala), respectively. Next, PUR-1 was isolated from a heat-treated solution containing PP-Val and allicin, and its structure was determined as (1E)-1-(1-((1S)-1-carboxy-2-methylpropyl)-3,4-dimethyl-1H-pyrrol-2-yl)-prop-1-enylene-3-(1-((1S)-1-carboxy-2-methylpropyl)-3,4-dimethyl-1H-pyrrol-2-ylidenium). The structure of PUR-1 suggested that PP molecules containing a 3,4-dimethyl pyrrole ring had been cross-linked by an allyl group of allicin to form conjugated pigments. While PUR-1 is a dipyrrole compound exhibiting a reddish-purple color, a color shift toward blue to green can be expected as the cross-linking reaction continues to form, for example, tri- or tetrapyrrole compounds.     

大蒜中主要功效成分分析研究进展

大蒜是一种重要的药食同源植物,含有丰富的功效成分.本文对大蒜及大蒜制品中主要的功效成分及其检测技术的研究进行了总结,并对大蒜生产和加工过程中主要功效成分研究的变化趋势进行了综述,最后对大蒜中攻效成分的研究发展方向进行了展望.     

Silicon alleviates mercury toxicity in garlic plants

Abstract

Silicon (Si) can increase plant stress tolerance. Mercury (Hg) is one of the major elements of heavy metal pollution. However, little attention has been paid to the possible effect of Si on Hg toxicity in plants. Here, the effects of Si on growth, photosynthesis, Hg accumulation and antioxidant defense were investigated in garlic grown in pots under Hg stress. Before sowing, Hg and Si were added at 3?mg Kg^?1 and 500?mg Kg^?1, respectively. The treatments included CT (control), Si, Hg and Hg?+?Si. The results showed that in non-stress conditions, added Si did not affect the garlic growth, photosynthetic gas exchange, malonaldehyde concentration or activities of antioxidant enzymes in leaves, except that it increased the superoxide dismutase activity. Under Hg stress, the garlic growth, leaf net photosynthetic rate, stomatal conductance, transpirational rate and superoxide dismutase activity in leaves were all inhibited, while the malondialdehyde concentration was increased; whereas these changes were all reversed in the presence of added Si. Added Si significantly decreased Hg concentrations in the root, bulb and shoot, and it also decreased exchangeable Hg level in the soil. These results suggest that Si could alleviate Hg toxicity in garlic through improving antioxidant defense ability, and decreasing Hg availability in soil and thus Hg uptake.     

Identification of the production chain of Asiago d'Allevo cheese by nuclear magnetic resonance spectroscopy and principal component analysis

In the present work, a rapid and simple NMR method to discriminate Asiago d'Allevo cheese samples from different production chains is described. A fast and reproducible extraction of the organic fraction was employed. By applying chemometric analysis to NMR data, it is possible to differentiate PDO Asiago cheese produced in alpine farms from that produced in lowland and mountain industrialized factories. PCA of both (1)H and (13)C NMR spectra showed a good separation of alpine farm products from the other ones, whereas the lowland and mountain industrialized cheeses are undistinguishable. The samples were differentiated on the basis of a higher content of unsaturated fatty acids, principally oleic, linoleic, linolenic, and conjugated linoleic acids for the alpine farm cheeses and a higher content of saturated fatty acids for the industrialized products. Conjugated linoleic acid and 1-pentene are also discriminating components.     

我国大蒜主产区大蒜根腐病病原真菌的分离及致病性初步研究

大蒜根腐病是我国大蒜主产区山东省金乡县及其周边地区大蒜的主要病害之一。采用常规组织分离法,从连续3 年采集的51 份大蒜根腐病根样品中分离纯化潜在大蒜根腐病病原菌真菌62 株,通过形态学和分子生物学对菌株进行鉴定,结果显示主要类群为镰刀菌属(Fusarium)和茎点霉(Setophoma);采用柯赫氏法则,明确镰刀菌属H9 为大蒜根腐病病原菌;采用温室水培试验,研究不同浓度大蒜根腐病病原菌H9 对大蒜幼苗的致病能力,结果显示致病能力与接种量呈正相关,接种孢子浓度2×109 cfu/mL、接菌量为100 和150 mL,40 d 后就可以导致大蒜幼苗产生严重的根腐病。综上,我国山东及周边地区大蒜主产区根腐病的主要病原真菌为镰刀菌属(Fusarium)和茎点霉属(Setophoma),为该地区大蒜根腐病的科学防治提供理论依据。     

Identification of fatty acid esters of pectenotoxin-2 seco acid in blue mussels (Mytilus edulis) from Ireland

Pectenotoxins from marine dinoflagellates of the genus Dinophysis are rapidly hydrolyzed by many shellfish to give pectenotoxin-2 seco acid, which isomerizes to 7-epi-pectenotoxin-2 seco acid. Three series of fatty acid esters of pectenotoxin-2 seco acid (PTX-2 seco acid) and 7-epi-PTX-2 seco acid were detected by LC-MS analysis of extracts from blue mussels (Mytilus edulis) from Ireland. The locations of the fatty acid ester linkages were identified by a combination of LC-MSn in positive- and negative-ion modes, LC-MS analysis of the products from reaction of the esters with sodium periodate, and NMR analysis of purified samples of the two most abundant ester derivatives. The 37-O-acyl esters of PTX-2 seco acid were the most abundant, followed by the corresponding 11-O-acyl esters, accompanied by low levels of the 33-O-acyl esters. The most abundant fatty acid esters in the fractionated sample were, in order, the 16:0, 22:6, 14:0, 16:1, 18:4, and 20:5 fatty acids, although a wide array of other PTX-2 seco acid fatty acid esters were also present at low levels.     

Phenolic esters in peat

The p-hydroxypropiophenone ester of stearic acid has been isolated sedge peat. This appears to be the first report of the ester as a natural product.     

Thin layer chromatographic determination of sterigmatocystin in cheese

A one-dimensional thin layer chromatographic method has been developed for determining sterigmatocystin in cheese. Cheese is extracted with acetonitrile-4% KCl (85 + 15). A simplified liquid-liquid partition cleanup is used, and the sample extract is passed through a cupric carbonate column for final purification. Sterigmatocystin is visualized by spraying the plate with aluminum chloride. The fluorescence of the spot is enhanced 10-fold by additional plate spraying with a silicone-ether mixture, enabling sterigmatocystin detection and quantitation at 2 and 5 micrograms/kg, respectively. Average recoveries were 88.3 and 86.4% at the 10 and 25 micrograms/kg levels, respectively.     

Optimization of fertilizer performances in long-term garlic cropping soils

Continuous cropping is a common pattern of modern agriculture that takes regional advantages for crop yield profits. Along the progress of mono-cropping continuously supported by intensive fertilizer inputs, such a cropping pattern often undergoes serious problems with low fertilizer use efficiencies and unsustainable crop production. In this study, we dealt with a > 25-year continuous garlic cropping system as an example for a problem-solving investigation. These garlic cropping soils underwent problems characterized by loss of soil organic matter, dramatic retention of NH⁺₄-N, and excess accumulation of phosphate and potash chemicals. Through hydroponic simulations, we revealed that the presence of NH⁺₄-N inhibited the root uptake of NH^-₃-N and K by 68% and 88%, respectively. Despite the traditionally emphasized importance of K, we observed the negative effect of high K on the growth of garlic roots. Further field experiments demonstrated that P and K applications can be reduced by 60% and 50%, respectively, without loss of yield. We thus developed a high-performance fertilization strategy by integrating a recomposed NPK fertilizer formulation to reduce unnecessary P and K inputs, a supplementary application of long-lasting C of woody peat to compensate for the soil C loss, and a foliar K approach to strengthen the stomatal function improvement with K. This strategy allowed a 15% increase of garlic yield and a seasonal soil C profit of ca. 1.8 Mg ha^-1 even at ca. 30% lower fertilizer cost. This study would be helpful in managing garlic fertilization and developing compound fertilizers, with broader significance for other long-term cropping soils.