油菜籽加工工艺的初步探讨——芥子甙在各主要加工过程中的分解

本文通过对菜籽加工工艺中蒸炒,预榨和浸出脱溶三个主要加工阶段的芥子甙分解产物的提取,纯化,色谱分析以及质谱分析,鉴定出样品中芥子甙分解产物主要有四种腈,预期的芥子甙分解产物ITC和OZT却没有发现。色谱分析的峰面积表明:在菜耔的这些加工阶段中,腈的含量是不同的,以脱溶液中的含量为最高,由所得结果可以推测,现行加工工艺条件有利于芥子甙的热分解的腈类的生成,因而在菜籽粕中主要的分解产物是腈类化合物。     

Detoxification of commercial united kingdom rapeseed meal by glucosinolate hydrolysis with exogenous myrosinase and the extractability of the aglucones by aqueous industrial methylated spirits

The aims of this study were to investigate the detoxification of United Kingdom commercial rapeseed meal by alcoholic extraction of aglucones released after treatment with mustard seed myrosinase. Aglucones released from the commercial rapeseed meal were compared with those resulting from autolysis of laboratory-defatted rapeseed. 3-Butenyl isothioc yanate, 5-vinyl-oxazolidene-2-thione (VOT) and 1-cyano-2-hydroxy-3-butene were detected in commercial rapeseed meal after glucosinolate hydrolysis. In comparison, autolysis of rapeseed at 5°C gave VOT, 1-cyano-2-hydroxy-3-butene and epithionitriles, but at 60°C epithionitrile release was significantly reduced. In addition, 1-cyano-3,4-epithiobutane was detected in the autolysed samples. Aglucones released at 40°C from commercial rapeseed meal by mustard seed myrosinase were 85% extractable in 60–90% (v/v) aqueous industrial methylated spirits. Extraction was significantly higher than previously reported for the intact glucosinolate. Double extraction of the myrosinase-treated meal with 80 % (v/v) aqueous industrial methylated spirits gave a meal with no detectable intact glucosinolate or aglucone content.     

双低油菜籽油脂加工副产品的研究现状与发展趋势

双低油菜籽油脂加工过程中的副产品具有广阔的应用前景.着重介绍了其主要副产品菜籽粕的营养成分及其营养价值,并对芥子碱、单宁、植酸和硫代葡萄糖甙等有毒有害成分的抗营养作用以及副产品中一些活性物质和天然抗氧化性物质的开发利用进行了讨论.     

Antinutritional effects of the rapeseed meals,darmor and jet neuf,and progoitrin together with myrosinase,in the growing rat

The antinutritional effects of rapeseed meals from cvs Darmor (‘low’ glucosinolate) and Jet Neuf (‘high’ glucosinolate), both fed for 30 d, and of the purified rapeseed glucosinolate, progoitrin (fed for 23 d), have been examined in rats, with and without the glucosinolate-degrading enzyme, myrosinase. With all of the experimental diets, feed intake was significantly reduced, the effects being more pronounced in the final period of the experiment. Both types of rapeseed meal significantly reduced live weight gain, and addition of myrosinase enhanced this effect during the second half of the experiment. Organ weights were usually increased in animals fed the experimental diets. The diet containing progoitrin and myrosinase increased liver weight by 58%. In agreement with other workers, thyroid weights were found to be greatly increased by the feeding of rapeseed meals or progoitrin together with myrosinase, although large increases in the size of this organ are also observed in the absence of this enzyme. The major antinutritional effects observed in this study became evident after 10-15 d, explaining the lack of such effects in earlier, short-term experiments. The results support the view that progoitrin is a major factor limiting the more extensive use of rapeseed as an animal feedingstuff.     

固态发酵法脱除菜籽饼粕中总酚及芥子碱的工艺研究

筛选出能高效降解菜粕中总酚及芥子碱的菌株,并进行混合发酵,研究了不同菌株、不同菜粕原料、不同接种量、不同发酵时间、不同营养源及不同金属离子对总酚及芥子碱降解率的影响。结果表明:酿酒酵母、纳豆芽孢杆菌及枯草芽孢杆菌B4以8%的总接种量,等比例接种到添加了5%糖蜜和0.05%的硫酸铜及硫酸亚铁的菜籽饼粕(含水量为50%)中,发酵72h,菜粕中的总酚和芥子碱降解率可达到70.72%及80.06%。     

油菜籽中多酚的分布及加工过程对菜籽多酚含量的影响

对油菜籽壳粕和脱壳后的菜籽肉粕中提取液的总酚含量、对DPPH 自由基清除能力以及FRAP 抗氧化能力进行比较,并采用液质联用法对提取液中的主要成分进行鉴定,对其中的芥子酸和芥子碱进行定量分析。结果表明：菜籽肉粕提取液中的总酚含量、对DPPH 自由基清除能力以及FRAP 抗氧化能力约为菜籽壳粕中的两倍,芥子酸和芥子碱的含量分别为菜籽壳粕中的约2.5 倍和1.5 倍。通过对实验室溶剂除油的菜籽粕与工业高温粕比较发现,高温榨油过程会使菜籽的总酚含量、抗氧化性、芥子酸和芥子碱含量有所下降,其中总酚含量下降了12.06%,DPPH 自由基和FRAP 抗氧化值分别降低10.0% 和5.6%,芥子酸和芥子碱含量分别下降了5.6% 和21.12%。     

一株高效降解菜籽饼粕中硫苷的枯草芽孢杆菌基因组鉴定及功能分析北大核心CSCD

为筛选可高效降解菜籽饼粕中硫苷的细菌,给硫苷降解基因工程菌的构建提供实验数据,以堆放菜籽饼粕的土壤为分离源,通过硫苷选择培养基筛选及硫苷降解率测定,获得一株硫苷降解率最大的菌株C1,采用16S rRNA基因序列进行种属鉴定,通过第3代Illumina NovaSeq PE150测序,获得其基因组完成图并进行功能注释,借助比较基因组学探究C1降解硫苷的机制。结果表明:菌株C1为枯草芽孢杆菌(Bacillus subtilis),其硫苷降解率为(68.98±4.74)%;C1菌株的基因组染色体全长为4 139 381 bp,鸟嘌呤和胞嘧啶含量为43.88%,编码区总长度占全基因组的比例为89.14%;C1菌株能编码大量的功能蛋白,主要涉及氨基酸转运与代谢;比较基因组学分析确认,C1与枯草芽孢杆菌的模式菌株(NC000964.3)共线性高,序列中未见大片段易位和倒置的区域,但C1序列中2.7 Mb处出现一个小片段的插入,2.1~2.4 Mb处出现小片段缺失,分别涵盖了2条黑芥子酶的相关基因,推测C1的硫苷降解机制为其可高效分泌黑芥子酶。C1菌株能够高效降解菜籽饼粕中的硫苷,是构建硫苷降解基因工程菌的可选材料。     

Improving the nutritive value of rapeseed meal, using production process principles

With regard to studies on production process variants designed to improve the nutritive value of rapeseed meal, the authors describe the principles underlying the modified diffusion extraction procedures used (with and without rapeseed husking). Furthermore, they briefly outline the chemical methods applied to the determination of the nutrient composition and glucosinolate content of rapeseed meal variants as well as the methodology of their feeding and nitrogen balance experiments on growing albino rats and broilers. The results obtained with 13 analytical variants and 8 biological variants confirm once more the beneficial nutritive effects obtained with the reduction of the glucosinolate content of rapeseed meal in monogastric animal species. However, these results do not permit to appraise unequivocally the repercussion of rapeseed husking on the diminution of the content of paraplastic substances in rapeseed meal. The diffusion techniques used for reducing the glucosinolate content in rapeseed meal have been found to be effective.     

Influence of glucosinolates and a tentative high-molecular detrimental factor on the nutritional value of rapeseed meal

Feeding experiments with mice suggest that high-molecular weight compounds in rapeseed meal without direct relationship to glucosinolates have a detrimental effect on the nutritional value of the meal. This effect is precluded by treatment with ethanol or upon heating. Ethanol extraction improves the nutritional value of the residue as a result of the removal of non-essential nitrogenous compounds. The nutritional value of the seed meal of the cultivar Bronowski was superior to that of the high-glucosinolate meal. A freeze-dried ethanol extract of the high-glucosinolate cultivar Sv Rigo was toxic to mice, especially when fed in combination with myrosinase, in contrast to ethanol extract from the low-glucosinolate cultivar Bronowski. A decrease of the glucosinolate content to a level below that of Bronowski did not effect the growth response of mice.     

Quantitative analysis of the main phenolics in rapeseed meal and oils processed differently using enzymatic hydrolysis and HPLC

Rapeseed meal is the dry residue of the rapeseed de-oiling process. It contains more phenolic compounds than any other oilseed meal. In analysis, rapeseed phenolic esters, mainly sinapine, are usually hydrolyzed to free phenolic acids, because sinapine is not available as a commercial standard. In this study, the efficiencies of different enzymes and enzyme preparations in hydrolyzing sinapine to sinapic acid were explored. The main phenolics in rapeseed meal were sinapine and sinapic acid. In rapeseed oil, the main phenolics were vinylsyringol, sinapine and sinapic acid. In hydrolyzing rapeseed meal, ferulic acid esterase and Ultraflo L were as effective in hydrolyzing sinapine as sodium hydroxide. Over 90% of sinapic acid derivatives were hydrolyzed to yield sinapic acid. Compared to base hydrolysis, enzyme treatment was not only as efficient but also less destructive to the liberated phenolics. Thus, enzymatic hydrolysis is a recommended procedure for optimal analysis of rapeseed phenolics. In rapeseed oils, hydrolysis was best applied in crude post-expelled rapeseed oils with high phenolic content.     

Effect of rapeseed meal on hepatic trimethylamine oxidase activity in the domestic fowl in relation to egg taint

Shaver 585 hens were classified as ‘tainters’ or ‘non-tainters’ according to their ability to produce eggs tainted with trimethylamine (TMA) when fed a diet containing 10% rapeseed meal (from Brassica napus). All were then fed this diet, or one containing an equivalent amount of soya-bean and fish meals for 16 weeks. Hepatic microsomal TMA oxidase activity was much lower in the rapeseed groups and was particularly low in the ‘tainters ’The apparent Michaelis constant of the enzyme was considerably higher in the rapeseed groups suggesting interference with the access or binding of the substrate. It was concluded that ‘tainters ’have an inherently low capacity for synthesising TMA oxidase and that the drastic reduction in its activity, which occurs when rapeseed meal is fed, allows TMA to pass into the egg. Preparations of the enzyme from ‘tainters ’and ‘non-tainters ’on the control diet were strongly and similarly inhibited by sinapine in vitro and their apparent Michaelis constants were increased about six-fold. Acetone and methanol extracts of rapeseed meal had a similar effect which was attributable to their sinapine content. Another inhibitor appeared to be present in a low sinapine fraction obtained by passing an aqueous solution of the methanol extract over a cation exchange resin.     

The role of water in the impact of high pressure on the myrosinase activity and glucosinolate content in seedlings from Brussels sprouts

In this study, it was shown that the amount of available water was found to influence the high pressure processing (HPP) effect on both myrosinase activity and total glucosinolate concentration in Brussels sprouts seedlings. Brussels sprouts seedlings with different water content (w_c = 4.8–89.4%) and water activity (a_w = 0.17–0.97) were pressurized at selected pressures between 200 and 800 MPa (5 °C and 3 min), thereby affecting pressure-induced enzyme denaturation, molecular diffusion, and cell permeability differently. The myrosinase activity and intact glucosinolate content in the dry seedlings (w_c < 14%) was not affected by the applied pressure treatments. Water adsorption (duration of 5 days) prior to HPP resulted in a decreased initial myrosinase activity due to changed plant cell permeability. Myrosinase was inactivated in seedlings with high water availability (w_c = 45–89%) after HPP, this inactivation is interpreted to be both pressure-induced and result from glucosinolate product catalyzed inactivation facilitated by enhanced cell permeability.Industrial relevanceHigh pressure processing (HPP) is increasingly applied in the food industry. The treatment is acknowledged for the ability to give products longer shelf life concomitant with a high nutritional quality and fresh appearance. Upon HPP of cruciferous plants it is important to have a special focus on the glucosinolate-myrosinase system, since sub-optimal pre-treatment and/or processing parameters can affect the food quality negatively. The present study provides valuable results regarding the significance of water content and activity on the sensitivity of the myrosinase-glucosinolate system in Brussels sprouts seedlings towards HPP. Thus, providing a tool for designing different types of HPP products with respect to levels of active myrosinase and intact glucosinolates by adjustment of water content, water activity and HPP level.     

Effects of abscisic acid on glucosinolate content,isothiocyanate formation and myrosinase activity in cabbage sprouts

Effects of abscisic acid (ABA) on glucosinolate content, isothiocyanate formation and myrosinase activity in cabbage sprouts were investigated. Subsequently, their distributions in different organs were evaluated. ABA (50 μmol L^?1) significantly increased glucosinolate content, isothiocyanate formation and myrosinase activity by 72.65%, 268.15% and 67.69%, respectively, in 5‐day‐old sprouts. Application of ABA alleviated the decrease rate of glucosinolate content and increased the myrosinase activity during germination. Besides, isothiocyanate formation rapidly increased after germinating for 3 days. The glucosinolate content and isothiocyanate formation reduced by 46.51% and 38.01%, respectively, in fluridon (Flu)‐treated sprouts. Cotyledon of ABA‐treated sprouts had the highest glucosinolate content and isothiocyanate formation, indicating that ABA was necessary to enhance the isothiocyanate formation in cabbage sprouts by increasing glucosinolate content and myrosinase activity.     

Rapeseed meal and egg taint: Effects of B. campestris meals,progoitrin and potassium thiocyanate on trimethylamine oxidation

The inclusion of Candle (low glucosinolate) and Yellow Sarson (high glucosinolate) rapeseed meals in the diet of laying hens (100 g kg^?1 for 14 days) depressed the oxidation of trimethylamine (TMA) by about 34% and 77% respectively and raised the mean TMA content of their eggs to 0.56 and 1.47 μg g^?1. A dehulled, extracted Yellow Sarson meal had only a slight effect. A high glucosinolate B. napus meal suppressed TMA oxidation almost completely when fed for only 4 days. Differences in the tainting potential of the meals were related to their progoitrin contents. When fed alone this substance had a comparable effect on TMA oxidation which was due to the formation of goitrin in the gastrointestinal tract and its inhibition of TMA oxidase. Potassium thiocyanate (250 and 1000 mg kg^?1 diet for 14 days) had no effect on TMA oxidation. It is concluded that neither the breeding of low glucosinolate cultivars of rapeseed nor treatment of the meal is likely to provide a practicable solution to the taint problem and that the elimination of the tainting defect from commercial stock by selective breeding would be more effective.     

菜籽粕替代鱼粉对银鲫生长性能及饲料利用率的影响

为评估硬颗粒饲料和膨化饲料中菜籽粕替代鱼粉对银鲫生长及饲料利用率的影响,试验设计了4种等氮、等能的饲料,分别用菜籽粕替代饲料中0％(对照组)、25％、50％、75％的鱼粉,利用挤压膨化技术和环模制粒技术加工成4种膨化饲料和4种硬颗粒饲料,对银鲫进行为期50 d的饲养试验.结果显示:菜籽粕替代鱼粉饲喂银鲫后的生长性能及饲料利用率都呈现下降的趋势;相同饲料配方,饲喂膨化饲料的银鲫生长性能及饲料利用率优于饲喂硬颗粒饲料的银鲫.研究结果表明,菜籽粕替代银鲫饲料中适量的鱼粉是可行的,膨化饲料饲喂银鲫的效果优于硬颗粒饲料,利用膨化加工工艺可以显著提高银鲫饲料中菜籽粕对鱼粉替代量.     

Evaluation of rapeseed meals in broiler chicks: Effect of iodine supply and glucosinolate degradation by myrosinase or copper

In rapeseed meals (RSM) of a conventional (c) or a newly bred (n) variety 117 or 44 mmol glucosinolates and glucosinolate degradation products per kg dry matter were detected. Soaking meals in aqueous myrosinase or copper sulphate solution and subsequent drying reduced the content of antinutrients by more than 90%. Broiler chickens were fed (i) a glucosinolate-free diet, or this diet in which half the soybean meal was replaced by RSM of various origins and treatment; (ii) untreated cRSM; (iii) cRSM treated with myrosinase: (iv) cRSM treated with Cu (v) untreated nRSM; or (vi) nRSM treated with myrosinase. These diets were administered with or without supplementary iodine. Chickens receiving the iodine-deficient diets with myrosinase-treated RSM showed growth depression, incomplete feathering, leg injuries and severe goitre. In the serum T⁴ could not be detected. Giving myrosinase-treated RSM plus iodine, or giving other RSM diets irrespective of iodine administration, no growth depression was observed. RSM diets without iodine dosage markedly increased thyroid weight: there were no differences between the RSM variants. In contrast to the treatment with myrosinase, in the sera of the chickens fed on untreated RSM or RSM treated with copper T⁴ could be detected, suggesting that in iodine-deficient conditions differences in serum T⁴ concentration between RSM groups indicate a differing anti-thyroid activity. With iodine supplementation the RSM had a significant effect on thyroid weight. The largest thyroids (five-fold heavier) were in the animals with myrosinase-treated cRSM. The untreated cRSM and the nRSM trebled or doubled the thyroid weight, and the myrosinase-treated nRSM trebled it. The thyroid weight of chicks fed cRSM treated with copper did not differ significantly from the glucosinolate-free control. There was evidence that heating the myrosinase-treated RMS produced anti-thyroid compounds; these should be identified in further investigations.     

Rapeseed meal and egg taint: The role of sinapine

Neither the administration of sinapine bisulphate in the diet, nor the repeated intramuscular or intravenous injection of large doses of this substance, reduced the ability of chicks or laying hens to oxidise trimethylamine (TMA), as measured by the activity of TMA oxidase in hepatic microsomes or the amounts of ¹⁴C-TMA oxide that appeared in the plasma after the infusion of a standard dose of ¹⁴C-TMA. Thus, in contrast to its behaviour in vitro, sinapine did not produce significant inhibition of TMA oxidase under these conditions. Since the amount included in the diet was similar to that which would be provided by a diet containing 10% rapeseed meal, it was concluded that sinapine is not involved in the depression of TMA oxidation that occurs when the meal is fed and acts solely as a source of TMA in the consequent production of egg taint.     

A micromethod for the screening of individual seeds and cotyledons of Brassica napus and brassica campestris (rapeseed) for low sinapine content

The association of sinapine with the fishy or crabby odour present in eggs laid by certain brown egg laying hens when fed diets containing rapeseed meal indicates the desirability of removing sinapine from the original rapeseed. A method is presented whereby seeds and cotyledons of Brassica napus and B. campestris may be selected for low levels of sinapine. The method, based on microextraction, rapid chromatographic separation of sinapine and visual estimation of its fluorescence allows detection of 0.025 μg sinapine and enables 300-400 seed samples to be screened daily.     

Influence of glucosinolates and high-molecular factors on the nutritional value of low-glucosinolate rapeseed meal

In order to ascertain the reason for the prominent growth-inhibiting effect of unheated low-glucosinolate rapeseed meal, the nutritional value of various fractions of the meal was evaluated in growth experiments using mice. A meal containing myrosinase activity was not growth-inhibiting after the low-molecular compounds had been removed by dialysis. A hydrolysis of glucosinolates to isothiocyanates and oxazolidinethiones would probably not explain the marked antinutritional properties of the low-molecular fraction. Heat treatment after autolysis did not improve the nutritional value of the meal. The harmful factors present in an autolysed meal could be extracted with methylene chloride. This extract contained nitriles, but no isothiocyanates or oxazolidinethiones. Thus, together with other information, the results suggest that the growth-inhibiting effect of unheated, low-glucosinolate rapeseed meal is mainly due to the presence of factors that direct the hydrolysis of glucosinolates towards nitrile production.     

响应面法优化微波钝化玛咖黑芥子酶活

探讨微波处理在钝化玛咖黑芥子酶相对酶活研究中的应用。通过单因素试验考察微波强度、处理时间以及料液比3个主要因素对玛咖黑芥子酶相对酶活和芥子油苷的影响。以黑芥子酶相对酶活为响应值,进行响应面分析和优化,建立微波钝化玛咖黑芥子酶相对酶活的回归模型。结果显示：在微波强度14W/g、料液比2:1(g/mL)条件下对冰鲜玛咖处理60s,玛咖黑芥子酶相对酶活几乎完全丧失。与传统热水烫漂相比,在有效钝化黑芥子酶相对酶活的前提下,玛咖芥子油苷损失率下降28%,VC损失率下降21%,蛋白质含量无显著变化。