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酱肉加工工艺及挥发性风味物质研究
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摘要
酱肉是我国传统肉制品,风味独特,深受人们喜爱。传统酱肉需经过干腌、自然发酵干燥,加工周期长;而湿腌、人工接种发酵和干制可以明显的缩短加工周期。酱肉的研究主要集中在安全卫生、保鲜及质量控制等方面,关于风味物质的研究较少。研究酱肉风味物质不但可以防止不良风味产生,还对工艺的优化和风昧的调配提供理论依据。
     本研究以猪肉和甜面酱为主要原料加工酱肉,应用正交试验设计等方法对风味配方、腌制条件和干制条件等工艺参数进行了优化;研究了不同加工工艺产品理化指标的变化;采用顶空固相微萃取-气相色谱-质谱联用仪对不同加工工艺的酱肉及其原料的挥发性风味物质进行了分析。主要研究结论如下:
     1.传统酱肉加工工艺:原料肉→清洗→腌制→上酱→自然风干→成品。配方:10%甜面酱,4%食盐、1%白糖、0.3%花椒、0.5%曲酒。
     传统酱肉加工中理化特性变化如下:(1)pH值变化:瘦肉pH值在5.80左右波动。肥肉pH值由6.70下降到5.89。(2)水分含量变化:肥肉、瘦肉的水分含量下降显著。(3)脂肪含量变化:肥肉的脂肪含量缓慢上升,由81.10%上升到93.59%,而瘦肉基本不变。(4)蛋白质含量变化:瘦肉中蛋白质含量呈现上升趋势,肥肉的蛋白质含量在3.98%和1.02%之间,变化不显著。(5)食盐含量变化:腌制阶段,食盐含量上升显著。风干时,瘦肉食盐含量呈现缓慢上升趋势,而脂肪含量低于1%。(6)过氧化值变化:腌制、上酱时,过氧化值比较低,风干前期剧烈上升,风干后期基本不变。(7)酸价变化:加工中由0.85 mg(KOH)/g上升到2.14 mg(KOH)/g。(8)丙二醛含量变化:在腌制阶段丙二醛含量变化不大;上酱和风干时,丙二醛含量缓慢上升。
     2.新工艺未发酵组酱肉加工工艺:原料肉→清洗→腌制→干制→包装→成品。配方:10%甜面酱、3%食盐、1%白糖、0.3%花椒、0.5%曲酒、0.013%亚硝酸钠、0.07%异抗坏血酸钠、0.1%复合磷酸盐。
     新工艺发酵组酱肉加工工艺:原料肉→清洗→腌制→发酵→干制→包装→成品。配方:10%甜面酱、3%食盐、1%白糖、0.3%花椒、0.5%曲酒、0.013%亚硝酸钠、0.07%异抗坏血酸钠、0.1%复合磷酸盐、2%发酵剂。
     新工艺酱肉加工中理化特性变化:(1)pH值变化:未发酵产品肥肉pH值在腌制前期下降迅速,从6.71降到6.58,腌制后期和干制过程无显著变化。未发酵瘦肉pH值先升后降。发酵产品肥肉以及添加发酵剂前的瘦肉的变化趋势和未发酵组相似,瘦肉发酵过程中pH值下降0.27,干制过程中降低趋势变缓。(2)水分含量变化:未发酵酱肉水分呈下降趋势,肥肉由13.54%到5.50%,而瘦肉从74.15%到48.69%,其中腌制前期和干制过程下降显著。(3)脂肪含量变化:肥肉脂肪含量缓慢的上升,瘦肉脂肪含量在3.00%上下波动。(4)蛋白质含量变化:瘦肉中蛋白质含量呈上升趋势,肥肉蛋白质含量处在2.26%与2.98%之间。(5)食盐含量变化:食盐含量呈现上升趋势。成品肥肉食盐含量为0.96%,瘦肉约为5.90%。(6)过氧化值变化:加工中逐渐变大。未发酵产品由1.5meq/kg上升到7.94meq/kg。发酵产品由1.5meq/kg上升到11.31meq/kg。(7)酸价变化:加工中呈现上升趋势。未发酵产品由0.85mg(KOH)/g上升到1.48mg(KOH)/g。发酵组产品由0.85mg(KOH)/g上升到1.31mg(KOH)/g。(8)丙二醛含量:新工艺酱肉丙二醛变化趋势与传统产品相似,但是含量较传统产品的低。
     3.实验建立了分析酱肉及其原料中挥发性风味物质的方法。采用固相微萃取装置,60℃下用75μm CAR/PDMS萃取头静态顶空萃取挥发性香气成分30min,250℃解吸5min。GC/MS分析条件为:岛津气相色谱质谱联用仪(GCMS-QP2010),DB-5ms柱。GC:程序升温,初温40℃,保留5min,以4℃/min的升温速率升温至120℃,再以12℃/min升温到250℃,保持10min。进样口温度250℃。载气He,流速1mL/min,分流比15:1。MS:接口温度250℃,离子源温度230℃,扫描质量范围35-500amu,电离方式为EI,电子能量70 eV,扫描速率0.5s/scan,四极杆质量分析器。谱库:NIST05和NIST05s。在此分析条件下能够较好的完成对酱肉及其原料中挥发性风味物质的分离和分析。
     4.通过HS-SPME-GC-MS,共从甜面酱、鲜肉、新工艺未发酵酱肉、新工艺发酵酱肉和传统酱肉等5个样品中检测出226种化合物,其中醇类49种,醛类27种,酸类13种,酮类15种,酯类27种,烃类38种,含氧杂环及含硫含氮化合物50种,醚类1种,其他6种。
     总离子流图中峰面积:甜面酱>新工艺发酵酱肉>传统酱肉>新工艺未发酵酱肉>鲜肉。由此推出甜面酱的挥发性风味物质最大,新工艺发酵酱肉次之,传统酱肉居第三,新工艺未发酵酱肉第四,鲜肉最小。
     确定了酱肉及其原料中主体风味物质:甜面酱中的主体风味物质包括3-甲基丁醛、2-甲基丁醛、呋喃醛、5-甲基-2-呋喃甲醛、苯甲醛、苯乙醛、2,3-丁二醇、3-甲基丁醇、2-呋喃甲醇、2-辛烯-1-醇、2-呋喃甲基酮、3-乙酰基4-羟基-6-甲基呋喃-2-酮、醋酸乙酯、醋酸。酱肉中的主体风味物质包括3-甲基丁醛、2-甲基丁醛、己醛、庚醛、辛醛、壬醛、沉香醇、2-辛烯-1-醇、3-甲基丁醇、薄荷烯酮、醋酸乙酯、醋酸、β-月桂烯。
     5.综合酱肉产品的风味、安全性以及检测出的挥发性香气成分的种类、含量,新工艺发酵酱肉产品品质最好,新工艺未发酵酱肉和传统酱肉次之。
Pork cured with sweet soybean paste was a traditional meat product in China. After dry-salt, traditional pork cured with sweet soybean paste was fermented with microorganism coming from sweet soybean paste, then dried under natural environment. The processing period of traditional pork cured with sweet soybean paste processing was long, however wet salting, fermentation and drying technology could shorten the processing time. This studies about pork cured with sweet soybean paste were focused on safty, sanitary, preservation and quality control. The aspect of its flavor compounds was studied very little. Analysis of volatile flavor components of pork cured with sweet soybean paste could not only prevent the product of bad flavor, but also take a consult of improving flavor and production technique.
     Using pork and sweet soybean paste as the main materials, flavor additive, curing and drying conditions were optimized in this experiment. At the same time, changes of physicochemical indices during processing were studied. Furthermore this study had analyzed the volatile flavor components of porks cured with sweet soybean paste coming from different processing technology and its raw material with HS-SPME-GC-MS. The main conclusions were as follow.
     1. The processing technology of traditional pork cured with sweet soybean paste was cleanout, cure, brush sweet soybean paste and dryness. The preserving composition was sweet soybean paste10%, sodium chloride 4%, sugar 1%, zanthoxylum 0.3% and wine 0.5%.
     Changes of physicochemical indices of traditional pork cured with sweet soybean paste during processing: (1) Change of pH values: the pH values of muscle was floated around 5.8. The pH values of fat reduced from 6.70 to 5.89. (2) Change of water content: the change of water content presented obvious fall. (3) Change of fat content: the fat content of fat raised slowly, but muscle was almost unchanged. (4) Change of protein content: the protein content of muscle ascended, whereas the fat's was unchanged. (5) Change of sodium chloride content: the sodium chloride content went up sharply during curing. The sodium chloride content of muscle increased gradually during drying, whereas the fat's was below 1%. (6) Change of peroxide value: the POV was low when curing and brushing sweet soybean paste, then raised obviously in prophase of drying and was unchanged during the anaphase of drying. (7) Change of acid value: the AV was went up from 0.85 mg (KOH) / g to 2.14 mg (KOH) / g during processing. (8) Change of propyldialdehyde content: the propyldialdehyde content kept steady in curing, however it moved up slowly after curing.
     2. The processing technology of unfermentation pork cured with sweet soybean paste was cleanout, cure, dryness and packaging. The preserving composition was sweet soybean paste 10%, sodium chloride 3%, sugar 1%, zanthoxylum 0.3%, wine 0.5%, sodium nitrite 0.013%, sodium isoascorbate 0.07%, multiple phosphate 0.1%.
     The processing technology of fermentative pork cured with sweet soybean paste was cleanout, cure, fermentation, dryness and packaging. The preserving composition was sweet soybean paste 10%, sodium chloride 3%, sugar 1%, zanthoxylum 0.3%, wine 0.5%, sodium nitrite 0.013%, sodium isoascorbate 0.07%, multiple phosphate 0.1%, starter 2%.
     Changes of physicochemical indices of new technics product during processing: (1) Changes of pH values: the pH values of fat from unfermentative product reduced quickly in the prophase of curing, however it decreased slowly during the anaphase of curing and drying. The pH values of muscle from unfermentative product ascended at first, then fell. The pH values of fat and the muscle in curing from fermentative product were siminar to unfermentative product, but the pH values of muscle in fermentation decreased sharply and the trend of change lessened on the process of drying. (2) Changes of water content: the change of water content of unfermentative product presented obvious fall, thereinto it fell dramatically during drying and the prophase of curing. Fermentative product went through the loss of water in curing, a improvement on fermentation and volatilization during drying. (3) Changes of fat content: the fat content of fat raised slowly, but the muscle's was floated around 3.00%. (4) Changes of protein content: the protein content of muscle ascended, whereas the fat's was between 2.26% and 2.98%. (5) Changes of sodium chloride content: the sodium chloride content showed a trend of rise. (6) Changes of peroxide value: the POV ascended steadily during processing. (7) Changes of acid value: the AV showed a tendency of rise. (8) Changes of propyldialdehyde content: the change of propyldialdehyde content to new technics product was siminar to traditional product, but the value was lower.
     3. The GC/MS method was: Shimadzu GCMS-QP2010 (Shimadzu, Japan.) was equipped with a capillary column: DB-5ms and a quadrupole mass filter. The volatile flavor compounds in pork cured with sweet soybean paste and its raw materials were isolated by solid phase microextraction at 60℃for 30min with the fiber of 75μm CAR/PDMS, then desorption in injection port of GC at 250℃for 5min. The split ratio was 15:1. The oven temperature was held at 40℃for 5 min and increase from 40℃to 120℃at the rate of 4℃min~(-1), from 120℃to 250℃at the rate of 12℃min~(-1), and the final temperature was maintained for 10min. The flow rate of helium, the carrier gas, was 1 mL min~(-1). The temperature of injector was 250℃; the ion source temperature and interfacetemperature were 230℃and 250℃, respectively. Other conditions were as follows: ionization energy, 70 eV; mass range 35-500 amu; and scanning rate 0.5 scans's~(-1).
     4. 226 species of volatile flavor compounds were identified from pork cured with sweet soybean paste and its raw material with HS-SPME-GC-MS. There were 49 alcohols, 27 aldehydes, 13 acids, 15 ketones, 27 esters, 38 hydrocarbons, 50 oxygen-, nitrogen- and sulfur-containing compounds, 1 aether, 6 others during those compounds.
     Sweet soybean paste owned the most of volatile flavor compounds, fermentative product was second, traditional product was third, nonfermentative product was fourth and the last is raw pork..
     The main aroma compounds of Sweet soybean paste were Butanal, 3-methyl-; Butanal, 2-methyl-; Furfural; 2-Furancarboxaldehyde,5-methyl-; Benzaldehyde; Benzeneacetaldehyde; 2,3-Butanediol; 1-Butanol, 3-methyl-; 2-Furanmethanol; 2-Octen-l-ol; Ketone,2-furyl methyl; 2H-Pyran-2-one, 3-acetyl-4-hydroxy-6-methyl-; Ethyl acetate and Acetic acid. The main aroma compounds of pork cured with sweet soybean paste were Butanal, 3-methyl-; Butanal, 2-methyl-; Hexanal; Heptanal; Octanal; nonanal; Linalyl alcohol;2-Octen-1-ol; 1-Butanol, 3-methyl-; Piperitone; Ethyl acetate; Acetic acid and .bata.-Myrcene.
     5. In conclution, the fermentative pork cured with sweet soybean paste was best.
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