第四章 結果
三、 大蒜 30 個品種的含硫揮發性化合物變化
2. 大蒜 30 個品種之群聚分析
由所得之 17 種含硫揮發性化合物進行 30 個大蒜品種相似度估算，並由平均
連結法進行群聚分析及繪樹狀圖，如圖 7 所示， 30 個大蒜品種依照葉片揮發性 少了 peak No. 14（5-methyl-1,2,3-thiadiazole）。依化合物種類可分成 7 種成分的 一群，包括‘四川南蒜’和‘廣西仁東玉林’兩品種的化合物種類相同且相對含量相
片黑’多了 peak No. 3、4 及 10，peak No. 5 相對含量較第一及第二小群低，這 3 發性成分相似度高，分別為 0.9256、0.9995、0.9993 和 0.9976（見附 錄 45），
因此顯示台灣大蒜的含硫揮發性化合物組成與大陸品種的葉片組成相似。台灣四 成分分別可分別解釋的變異量為 38.86%、17.44%及 8.33%，共可解釋 64.63%。
第一個主成分之特徵向量及各性狀分量如表顯示，多數性狀與此主成分呈正相 關，其中以 peak No. 4、10、11、13 及 16 五種含硫揮發性化合物具有最高分量
值。第二主成分依各性狀分量顯示 peak No. 5、7、6、1 及 14 具較高分量值，即 以普通存在於大蒜的含硫化合物貢獻第二主成分，其中 peak No. 14 的影響與另 外四種含硫揮發性化合物呈現相反的趨勢。第三主成分 peak No. 16、11、25、5 和 21 五種含硫揮發性化合物有較高分量值，多數性狀與此主成分呈負相關，其
其中 peak No. 1、3、4、5、6、7、10、14、17、21 及 25 十一個成分為鱗莖共同 成分，每個品種中均有偵測到（表 27）。Peak No. 15 和 18 分別只於 8 個及 5 個 品種中偵測到，屬於不普遍的化合物。鱗莖所有的化合物種類較葉片多，且相對 量高，peak No. 15（unknown 3）、18（unknown 4）、23（unknown 9）和 24
（2-propenylthioacetonitrile）四種化合物只在鱗莖中有，但 peak No. 12 只於葉片 中有，鱗莖中並未偵測到。鱗莖中普遍含有 peak No. 3、4、10、11、13、16 及 25 等七種化合物，但在葉片中並不普遍。四個台灣品種中‘和美’和‘芳苑花蒜’的
含硫化合物種類最少（14 種），成分最相近，‘宜蘭白’的種類最多有 20 種，多
此群。 0.8691、0.8202、0.9905 和 0.9843（附 錄 62），顯示台灣大蒜鱗莖的含硫揮發 性化合物組成份與大陸品種相似度高，而‘宜蘭白’和‘越南’皆屬含硫揮發性化合 物含量最多之品種。台灣四個品種中，‘和美’和‘芳苑花蒜’、‘大片黑’的鱗莖含硫 揮發性化合物較為相似，而與‘宜蘭白’較不同；‘宜蘭白’和‘芳苑花蒜’的成分組成
較與‘大片黑’組成相似性高。
1（methyl 2-propenyl disulfide）、4（DADS）、5（allyl propyl disulfide）、7（AMTS）、
10 （ 3-vinyl-1,2-dithiacyclohex-4-ene ） 、 11 （ 5-methyl-1,2,3- thiadiazole ） 、 12
（3-vinyl-1,2-dithiacyclohex-5-ene）、16（unknown s5）、17（3-vinyl-4H -1,2-dithiin）
及 18（unknown s6）十個成分為葉片中主要成分，均有超過 25 個品種含有此成 分，其中peak No. 4、10、12、17 和 18 於每個品種中均有偵測到（表 29）。peak No. 2（unknown s1）、3（unknown s2）、6（C6H10S2）、8（unknown s3）、9
（4-methyl-1,2,3-trithia-cyclopentane）、13（2-vinyl-1,3-dithiane）和 14（DATS）
七種成分少品種有的化合物測得。溶劑萃取所得之化合物種類較SPME所得者 少，於溶劑萃取時無偵測到DAS、2-propenylthioacetonitrile及DATS（於SPME分 析中分別為peak No. 1、24 和 25）三種化合物，但 2-vinyl-1,3-dithiane和 3-vinyl-4H -1,2-dithiin（於溶劑萃取分析中分別為peak No. 13 和 17）僅於溶劑萃取中出現。
溶劑萃取中多數化合物的相對量大量降低，只有peak No. 10 和 12（於SPME中分
南昆明王旗營三瓣蒜’、‘蒼山蒲蒜’、‘彭州正月早’八個品種，都有 10 種同樣的 個化合物（peak No. 4、5、10、11、12、16、17 及 18）且含量低的 4 個品種聚 成一小群（包括兩個越南品種、‘雲南昆明瓣蒜’及‘北京新發地’），最後與化合 可解釋的變異量為 48.66%、12.94%及 10.44%，共可解釋 72.04%（表 30）。第一 個主成分之特徵向量及各性狀分量如表顯示，以 peak No. 17、18、12、4 及 13
表 2、30 個大蒜品種之植株性狀比較Z
Table 2. Comparison in field plant characters of 30 garlic cultivars.
假莖寬度 (cm) 假莖高度 (cm) 生長勢Y
All characters are examined from 3 plants labeled and grown in Taichung DAS from Oct. 15, 2007.
Y：生長勢 1 = 生長勢不良 2 = 生長勢中等 3 = 生長勢強 growth vigor 1: poor 2: medium 3: good
X：硬軟骨 h = 硬骨 s = 軟骨
Hard neck h: with flowering stalk Soft neck s: without flowering stalk
表 3、30 個大蒜品種之葉部性狀比較Z
Table 3. Comparison in leaf characters of 30 garlic cultivars.
葉色 葉數 葉長(cm) 葉寬 (cm) 葉姿 (度)
All characters are examined from 3 plants labeled and grown in Taichung DAS from Oct. 15, 2007.
表 4、30 個大蒜品種之鱗莖性狀比較Z
Table 4. Comparison in bulb characters of 30 garlic cultivars.
周徑 (cm) 重量 (g)
All characters are examined from 3 plants labeled and grown in Taichung DAS from Oct. 15, 2007.
Classes Classes 圖 1、供試 30 個大蒜品種之性狀調查
Fig. 1. The horticultural characters of 30 garlic cultivars studied.
Classes Classes 圖 1、續
Fig. 1. continued.
圖 2、以 12 個性狀分析 30 個供試大蒜品種
Fig. 2. The dengrogram of 30 tested garlic cultivars based on 11 horticulture characters.
表 5、30 種大蒜 12 個園藝性狀的主成分分析
Table 5. The three principal components for 12 characters of 30 garlic cultivars.
PC1 PC2 PC3
特徵值 5.99 1.87 1.35
變異數百分比 49.94% 15.62% 11.24%
累積百分比 49.94% 65.56% 76.79%
假莖寬度 0.3683 -0.1726 -0.1138
假莖長度 0.1905 0.5119 -0.3785
葉長 0.3426 -0.1485 -0.0051
葉寬 0.3347 -0.2860 -0.0063
葉色 0.1813 0.1779 -0.2787
葉數 0.2687 0.1506 -0.5003
生長勢 0.3550 -0.0140 -0.0813
葉姿 0.0356 0.5339 0.1502
鱗莖周徑 0.3327 -0.0269 0.4070
鱗莖重量 0.3535 0.0103 0.3448
蒜瓣數 0.0605 0.5137 0.4332
硬軟骨 0.3563 0.0004 0.1201
圖 3、以 12 個園藝性狀分析 30 個大蒜品種之主成分分析。（A）使用兩個主成分、（B）使用三 個主成分
Fig. 3. Principal component analysis of 30 garlic cultivars by 12 horticultural characters. (A) two principal components. (B) three principal components.
圖 4、含氘內標準品之結構式
Fig. 4. Chemical structures of deuterium-containing internal standards.
表 6、大蒜‘大片黑’葉片以固相微萃取法重複試驗所得之揮發性含硫化合物變異量
Table 6. Variation of abundance of volatile sulfur-containing compounds determined in replicated garlic
‘Large Black Leaf’ leaves by SPME-GC/MS.
重複(replicate)
I.S. I* 45,639,515 66,575,863 39,526,191 50,580,523 14,185,604 28.05%
5 63,625,372 53,466,182 89,011,377 68,700,977 18,308,101 26.65%
6 3,195,222 2,585,448 3,541,417 3,107,362 484,003 15.58%
7 8,077,692 8,181,843 14,661,104 10,306,880 3,771,228 36.59%
I.S. II 74,792,519 100,065,103 50,027,832 74,961,818 25,019,065 33.38%
14 536,498 70,590 151,816 252,968 248,880 98.38%
17 231,786 208,617 285,164 241,856 39,255 16.23%
22 325,663 398,216 209,898 311,259 94,982 30.52%
I.S. III 32,585,465 30,561,648 17,071,915 26,739,676 8,433,455 31.54%
*: I.S. I、II 及 III 分別為內標準品 1,4-dichlorobezene-d4、naphthalene-d8及 acenaphthene-d10
表 7、大蒜‘廣西崇左市扶綏縣’葉片以固相微萃取法重複試驗所得之揮發性含硫化合物變異量。
Table 7. Variation of abundance of volatile sulfur-containing compounds determined in replicated garlic
‘Guang-Shi Tsung-Tzo-Shr Fu-Suei-Shien’ leaves by SPME-GC/MS.
重複(replicate) 1 2,609,047 3,075,538 2,944,573 2,876,386 240,604 8.36%
I.S. I* 39,824,536 55,009,835 28,701,015 41,178,462 13,206,564 32.07%
5 65,235,651 54,476,106 94,636,126 71,449,294 20,788,550 29.10%
6 4,059,551 3,403,697 6,858,933 4,774,060 1,835,090 38.44%
7 9,493,919 8,741,407 21,052,298 13,095,875 6,900,730 52.69%
I.S. II 54,354,415 78,536,523 37,268,773 56,719,904 20,735,319 36.55%
17 170,315 111,682 234,888 172,295 61,626 35.77%
19 241,800 103,646 107,181 150,876 78,762 52.20%
22 157,160 213,229 172,270 180,886 29,010 16.04%
I.S. III 31,047,246 53,843,475 18,117,572 34,336,098 18,088,600 52.68%
*: I.S. I、II 及 III 分別為內標準品 1,4-dichlorobezene-d4、naphthalene-d8及 acenaphthene-d10
表 8、大蒜‘和美’蒜瓣以固相微萃取法重複試驗所得之揮發性含硫化合物變異量。
Table 8. Variation of abundance of volatile sulfur-containing compounds determined in replicated garlic
‘He-Mei’ cloves by SPME-GC/MS.
重複(replicate) 1 28,941,916 76,971,381 28,548,217 44,820,505 27,844,172 62.12%
3 11,592,802 50,056,193 19,784,827 27,144,607 20,260,377 74.64%
4 2,318,853 7,431,031 3,022,646 4,257,510 2,770,787 65.08%
I.S. I* 60,631,298 31,772,657 70,569,546 54,324,500 20,152,703 37.10%
5 267,613,244 762,424,430 301,918,511 443,985,395 27,6309,206 62.23%
6 3,588,090 12,380,129 4,519,713 6,829,311 4,829,666 70.72%
7 7,177,999 32,091,348 5,782,501 15,017,283 14,803,028 98.57%
10 493,914 3,324,672 724,170 1,514,252 1,572,091 103.82%
11 218,544 1,620,150 302,576 713,757 786,084 110.13%
I.S. II 85,751,764 23,116,056 123,699,909 77,522,576 50,794,365 65.52%
13 1,574,841 3,616,189 1,542,164 2,244,398 1,188,118 52.94%
14 918,837 5,440,175 1,219,144 2,526,052 2,528,168 100.08%
17 3,819,144 23,775,569 3,606,703 10,400,472 11,583,661 111.38%
21 1,073,071 2,647,021 835,034 1,518,375 984,655 64.85%
22 350,766 263,751 212,636 275,718 69,838 25.33%
I.S. III 19,339,546 14,086,039 49,200,316 27,541,967 18,939,717 68.77%
25 1,354,284 4,238,331 1,143,472 2,245,362 1,729,177 77.01%
*: I.S. I、II 及 III 分別為內標準品 1,4-dichlorobezene-d4、naphthalene-d8及 acenaphthene-d10
表 9、大蒜‘大片黑’蒜瓣以固相微萃取法所重複試驗得之揮發性含硫化合物變異量。
Table 9. Variation of abundance of volatile sulfur-containing compounds determined in replicated garlic
‘Large Black Leaf’ cloves by SPME-GC/MS.
重複(replicate) 1 39,584,009 40,863,201 46,063,231 42,170,147 3,431,641 8.14%
3 9,121,710 16,218,758 17,908,852 14,416,440 4,662,588 32.34%
4 5,833,219 5,144,102 6,406,899 5,794,740 632,277 10.91%
I.S. I* 71,788,809 73,819,367 76,353,583 73,987,253 2,287,013 3.09%
5 436,516,382 446,909,366 496,812,185 460,079,311 32,233,237 7.01%
6 10,227,064 10,921,526 14,035,842 11,728,144 2,028,465 17.30%
7 29,692,097 26,593,297 34,140,924 30,142,106 3,793,883 12.59%
10 843,444 935,028 1,323,381 1,033,951 254,802 24.64%
11 822,481 657,851 926,503 802,279 135,460 16.88%
I.S. II 123,008,457 125,605,593 121,627,797 123,413,949 2,019,662 1.64%
13 3,800,388 2,975,828 4,007,729 3,594,648 545,849 15.19%
14 3,972,697 2,838,794 4,242,835 3,684,775 744,988 20.22%
16 2,334,169 1,340,896 2,497,936 2,057,667 626,119 30.43%
17 7,798,250 7,563,867 9,696,099 8,352,739 1,169,272 14.00%
19 1,371,435 1,604,521 1,088,388 1,354,781 258,469 19.08%
21 4,334,132 4,574,350 2,374,201 3,760,894 1,206,903 32.09%
22 404,431 403,154 265,484 357,690 79,855 22.33%
I.S. III 30,634,886 25,180,057 62,951,702 39,588,881 20,415,798 51.57%
25 5,341,307 6,362,117 3,333,119 5,012,181 1,541,087 30.75%
*: I.S. I、II 及 III 分別為內標準品 1,4-dichlorobezene-d4、naphthalene-d8及 acenaphthene-d10
表 10、大蒜‘宜蘭白’蒜瓣以固相微萃取法重複試驗所得之揮發性含硫化合物變異量
Table 10. Variation of abundance of volatile sulfur-containing compounds determined in replicated garlic ‘Yi-Lan White’ cloves by SPME-GC/MS.
重複(replicate) 1 32,555,928 53,587,678 36,744,727 40,962,778 11,132,277 27.18%
3 53,115,529 89,372,826 56,132,008 66,206,788 20,118,990 30.39%
4 8,734,921 14,655,442 12,898,767 12,096,377 3,040,726 25.14%
I.S. I* 31,948,451 22,946,798 25,745,718 26,880,322 4,606,836 17.14%
5 529,795,132 838,148,395 579,658,223 649,200,583 165,522,019 25.50%
6 10,923,854 17,772,814 8,403,311 12,366,660 4,848,521 39.21%
7 8,529,280 15,697,287 10,662,908 11,629,825 3,680,527 31.65%
10 5,861,867 10,726,061 11,807,807 9,465,245 3,167,143 33.46%
11 1,016,578 1,791,958 1,655,633 1,488,056 413,962 27.82%
I.S. II 69,246,714 48,219,799 52,087,134 56,517,882 11,191,802 19.80%
13 5,917,027 9,920,816 10,082,473 8,640,106 2,359,640 27.31%
14 8,423,819 14,235,333 15,307,611 12,655,588 3,703,828 29.27%
15 557,965 914,216 1,013,343 828,508 239,482 28.91%
16 4,767,831 6,090,461 6,070,002 5,642,765 757,784 13.43%
17 10,095,851 17,547,842 13,764,388 13,802,694 3,726,143 27.00%
18 209,412 366,334 204,591 260,113 92,022 35.38%
19 375,408 833,173 382,442 530,341 262,283 49.46%
21 8,708,847 17,179,893 10,140,908 12,009,883 4,534,254 37.75%
22 237,137 383,094 167,022 262,418 110,232 42.01%
23 530,038 1,330,199 555,629 805,289 454,766 56.47%
24 195,193 362,865 202,899 253,652 94,659 37.32%
I.S. III 28,786,761 17,291,179 30,723,918 25,600,619 7,261,077 28.36%
25 9,576,079 19,552,658 8,761,530 12,630,089 6,008,939 47.58%
*: I.S. I、II 及 III 分別為內標準品 1,4-dichlorobezene-d4、naphthalene-d8及 acenaphthene-d10
表 11、大蒜‘和美’蒜瓣以溶劑萃取法重複試驗所得之揮發性含硫化合物變異量
Table 11. Variation of abundance of volatile sulfur-containing compounds determined in replicated garlic ‘He-Mei’ cloves by solvent extraction-GC/MS.
重複(replicate) 1 2,148,488 2,737,424 1,371,097 2,085,670 685,326 32.86%
2 265,039 250,444 230,257 248,580 17,466 7.03%
I.S. I* 4,711,829 3,633,720 4,013,046 4,119,532 546,886 13.28%
3 413,544 424,115 256,405 364,688 93,925 25.75%
4 5,575,129 6,970,880 4,032,184 5,526,064 1,469,962 26.60%
5 4,945,098 6,147,833 3,500,662 4,864,531 1,325,423 27.25%
6 157,254 155,467 33,902 115,541 70,707 61.20%
7 1,798,543 2,130,065 990,994 1,639,867 585,879 35.73%
9 314,304 331,907 248,106 298,106 44,186 14.82%
I.S. II 7,147,824 5,832,433 6,582,406 6,520,888 659,850 10.12%
10 32,017,694 37,341,751 23,928,871 31,096,105 6,753,764 21.72%
11 2,207,267 2,618,246 1,456,429 2,093,981 589,135 28.13%
12 7,622,686 8,478,135 6,320,602 7,473,808 1,086,444 14.54%
13 444,383 493,435 239,361 392,393 134,780 34.35%
14 228,177 254,075 108,265 196,839 77,792 39.52%
15 738,521 406,919 258,962 468,134 245,570 52.46%
16 1,620,276 1,176,997 827,763 1,208,345 397,185 32.87%
I.S. III 8,820,428 7,178,309 7,730,653 7,909,797 835,588 10.56%
I.S. IV 7,356,907 5,666,387 6,091,360 6,371,551 879,400 13.80%
17 11,162,990 12,774,278 7,833,300 10,590,189 2,519,800 23.79%
18 10,427,038 13,149,803 8,245,702 10,607,514 2,457,027 23.16%
I.S. V 4,847,180 3,465,612 3,700,056 4,004,283 739,323 18.46%
I.S. VI 3,265,427 2,268,212 2,320,940 2,618,193 561,141 21.43%
*: I.S. I、II、III、IV、V 及 VI 分別為內標準品 1,4-dichlorobezene-d4、naphthalene-d8、 acenaphthene-d10、anthracene-d10、chrysene-d12和 perylene-d12
表 12、大蒜‘大片黑’蒜球以溶劑萃取法重複試驗所得之揮發性含硫化合物變異量
Table 12. Variation of abundance of volatile sulfur-containing compounds determined in replicated garlic ‘Large Black Leaf’ cloves by solvent extraction-GC/MS.
重複(replicate)
2 328,289 448,932 446,635 407,952 69,000 16.91%
I.S. I* 4,110,087 4,178,414 4,574,547 4,287,683 250,770 5.85%
4 3,980,834 4,923,817 4,530,975 4,478,542 473,673 10.58%
5 1,979,701 3,874,105 3,525,219 3,126,342 1,008,226 32.25%
6 526,807 622,299 590,703 579,937 48,648 8.39%
7 295,814 519,426 503,847 439,696 124,848 28.39%
8 230,290 177,150 174,372 193,938 31,513 16.25%
9 252,965 674,749 651,512 526,409 237,094 45.04%
I.S. II 6,428,334 6,442,729 6,940,712 6,603,925 291,755 4.42%
10 29,274,178 37,171,984 35,181,601 33,875,921 4,107,607 12.13%
11 1,442,667 1,219,219 1,208,517 1,290,134 132,206 10.25%
12 7,527,410 8,340,992 7,788,966 7,885,789 415,343 5.27%
13 396,722 642,854 636,647 558,741 140,347 25.12%
15 436,692 659,202 859,337 651,743 211,421 32.44%
16 1,088,713 1,587,361 1,788,596 1,488,223 360,320 24.21%
I.S. III 7,746,914 7,914,189 8,614,774 8,091,959 460,431 5.69%
I.S. IV 6,253,184 6,486,808 7,063,922 6,601,305 417,320 6.32%
17 10,683,600 14,921,566 14,086,449 13,230,539 2,244,889 16.97%
18 10,589040 13,811,942 12,781,465 12,394,149 1,645,990 13.28%
I.S. V 3,929,327 4,103,850 4,552,908 4,195,362 321,705 7.67%
I.S. IV 2,567,039 2,744,892 2,982,480 2,764,804 208,435 7.54%
*: I.S. I、II、III、IV、V 及 VI 分別為內標準品 1,4-dichlorobezene-d4、naphthalene-d8、 acenaphthene-d10、anthracene-d10、chrysene-d12和 perylene-d12
表 13、使用‘宜蘭白’蒜球以溶劑萃取法重複試驗所得之揮發性含硫化合物變異量。
Table 13. ariation of abundance of volatile sulfur-containing compounds determined in replicated garlic
‘Yi-Lan White’ cloves by solvent extraction-GC/MS.
重複(replicate) 1 1,271,398 791,687 768,472 943,852 283,900 30.08%
I.S. I* 4,130,532 4,102,265 4,162,713 4,131,837 30,245 0.73%
3 306,832 182,479 146,083 211,798 84,290 39.80%
4 3,610,523 2,190,156 2,165,028 2,655,236 827,398 31.16%
5 3,832,748 2,442,494 2,413,887 2,896,376 811,048 28.00%
7 660,013 369,100 357,276 462,130 171,474 37.11%
8 170,170 63,845 62,475 98,830 61,786 62.52%
9 666,766 214,795 203,350 361,637 264,312 73.09%
I.S. II 6,446,755 6,601,928 6,612,729 6,553,804 92,864 1.42%
10 36,012,359 18,560,631 18,420,160 24,331,050 10,116,554 41.58%
11 1,688,445 649,138 666,478 1,001,354 595,102 59.43%
12 8,580,171 5,132,756 5,239,178 6,317,368 1,960,367 31.03%
13 399,877 157,077 152,592 236,516 141,493 59.82%
14 133,867 28,660 25,878 62,802 61,560 98.02%
15 801,277 325,157 322,668 483,034 275,610 57.06%
16 1,659,656 836,097 787,750 1,094,501 490,035 44.77%
I.S. III 7,867,297 7,816,022 7,811,562 7,831,627 30,972 0.40%
I.S. IV 6,470,948 6,400,968 6,402,037 6,424,651 40,098 0.62%
17 15,526,122 6,230,303 6,330,596 9,362,340 5,338,227 57.02%
18 13,968,519 6,804,265 6,691,796 9,154,860 4,169,130 45.54%
I.S. V 4,077,323 4,033,765 4,084,480 4,065,189 27,449 0.68%
I.S. IV 2,624,304 2,708,353 2,709,696 2,680,784 48,918 1.82%
*: I.S. I、II、III、IV、V 及 VI 分別為內標準品 1,4-dichlorobezene-d4、naphthalene-d8、 acenaphthene-d10、anthracene-d10、chrysene-d12和 perylene-d12
表 14、大蒜‘和美’蒜瓣中以溶劑萃取法所得之揮發性含硫化合物變異量。
Table 14. Variation of abundance of volatile sulfur-containing compounds determined in duplicated garlic ‘He-Mei’ cloves by solvent extraction.
重複(duplicate)
I.S. I* 4,449,991 4,516,522 4,464,747 4,477,087 34,939 0.78%
3 408,483 413,200 444,849 422,177 19,775 4.68%
I.S. II 6,774,187 6,896,994 6,792,661 6,821,281 66,217 0.97%
10 31,378,476 31,535,500 31,788,225 31,567,400 206,729 0.65%
11 2,150,532 2,150,205 2,127,446 2,142,728 13,235 0.62%
12 7,843,260 7,987,776 8,048,978 7,960,005 105,634 1.33%
13 418,234 456,828 450,715 441,926 20,744 4.69%
14 201,849 214,533 214,694 210,358 7,370 3.50%
15 803,829 757,066 737,182 766,026 34,215 4.47%
16 1,668,628 1,603,059 1,561,218 1,610,968 54,140 3.36%
I.S. III 8,312,309 8,523,436 8,332,053 8,389,266 116,613 1.39%
I.S. IV 6,795,100 6,986,716 6,894,298 6,892,038 95,827 1.39%
17 10,938,621 11,092,189 11,281,274 11,104,028 171,633 1.55%
18 10,539,996 10,835,240 11,203,713 10,859,650 332,531 3.06%
I.S. V 4,307,486 4,439,137 4,460,280 4,402,301 82,789 1.88%
I.S. VI 2,767,805 2,977,769 2,948,873 2,898,149 113,802 3.93%
*: I.S. I、II、III、IV、V 及 VI 分別為內標準品 1,4-dichlorobezene-d4、naphthalene-d8、 acenaphthene-d10、anthracene-d10、chrysene-d12和 perylene-d12
表 15、大蒜‘大片黑’蒜瓣中以溶劑萃取法所得之揮發性含硫化合物變異量。
Table 15. Variation of abundance of volatile sulfur-containing compounds determined in duplicated garlic ‘Large Black Leaf’ cloves by solvent extraction-GC/MS.
重複(duplicate) 1 1,288,614 1,425,851 1,398,030 1,370,831 72,548 5.29%
2 496,587 506,228 517,673 506,829 10,556 2.08%
I.S. I* 4,574,547 4,410,688 4,289,868 4,425,034 142,881 3.23%
4 5,034,478 5,328,939 5,312,889 5,225,435 165,568 3.17%
5 3,923,586 4,165,346 4,161,527 4,083,486 138,491 3.39%
6 637,786 670,127 666,589 658,167 17,739 2.70%
7 548,293 563,535 565,613 559,147 9,457 1.69%
8 188,271 180,024 178,947 182,414 5,101 2.80%
9 703,442 825,803 639,071 722,772 94,855 13.12%
I.S. II 6,940,712 6,864,344 6,615,380 6,806,812 170,125 2.50%
10 37,985,792 39,371,169 40,109,255 39,155,405 1,078,049 2.75%
11 1,304,843 1,569,949 1,634,714 1,503,169 174,781 11.63%
12 8,273,008 8,922,430 9,187,071 8,794,169 470,336 5.35%
13 685,592 747,952 756,413 729,986 38,678 5.30%
15 927,831 973,983 977,196 959,670 27,620 2.88%
16 1,988,966 2,110,885 2,124,929 2,074,927 74,775 3.60%
I.S. III 8,627,851 8,350,695 8,015,110 8,331,219 306,834 3.68%
I.S. IV 7,097,723 6,868,582 6,607,924 6,858,076 245,068 3.57%
17 15,878,577 16,456,282 17,432,824 16,589,228 785,606 4.74%
18 14,330,967 15,266,594 15,180,212 14,925,924 517,055 3.46%
I.S. V 4,520,240 4,381,881 4,241,626 4,381,249 139,308 3.18%
I.S. VI 2,982,480 2,847,887 2,696,360 2,842,242 143,143 5.04%
*: I.S. I、II、III、IV、V 及 VI 分別為內標準品 1,4-dichlorobezene-d4、naphthalene-d8、 acenaphthene-d10、anthracene-d10、chrysene-d12和 perylene-d12
表 16、大蒜‘宜蘭白’蒜瓣中以溶劑萃取法所得之揮發性含硫化合物變異量。
Table 16. Variation of abundance of volatile sulfur-containing compounds determined in duplicated garlic ‘Yi-Lan White’ cloves by solvent extraction-GC/MS.
重複(duplicate)
I.S. I* 4,195,264 4,255,490 4,194,820 4,215,191 34,900 0.83%
3 159,739 168,943 170,522 166,401 5,823 3.50%
4 2,168,551 2,110,535 2,151,998 2,143,695 29,886 1.39%
5 2,433,467 2,407,552 2,421,480 2,420,833 12,970 0.54%
7 367,625 363,764 364,922 365,437 1,981 0.54%
8 49,541 45,690 51,215 48,815 2,833 5.80%
9 292,785 299,061 259,643 283,830 21,180 7.46%
I.S. II 6,702,520 6,781,928 6,726,470 6,736,973 40,733 0.60%
10 18,990,776 18,686,721 18,707,837 18,795,111 169,779 0.90%
11 718,641 673,699 671,280 687,874 26,673 3.88%
12 5,465,283 5,512,243 5,306,238 5,427,921 107,965 1.99%
13 158,828 160,365 158,351 159,181 1,052 0.66%
14 26,544 26,922 22,526 25,331 2,437 9.62%
15 330,975 318,704 328,971 326,217 6,583 2.02%
16 782,169 759,059 774,292 771,840 11,749 1.52%
I.S. III 7,798,485 7,934,649 7,851,678 7,861,604 68,623 0.87%
I.S. VI 6,472,941 6,579,232 6,451,441 6,501,205 68,423 1.05%
17 6,264,626 6,111,779 6,207,521 6,194,642 77,233 1.25%
18 6,622,488 6,496,334 6,471,956 6,530,259 80,797 1.24%
I.S. V 4,106,637 4,203,770 4,065,442 4,125,283 71,024 1.72%
I.S. VI 2,706,256 2,872,270 2,750,669 2,776,398 85,946 3.10%
*: I.S. I、II、III、IV、V 及 VI 分別為內標準品 1,4-dichlorobezene-d4、naphthalene-d8、 acenaphthene-d10、anthracene-d10、chrysene-d12和 perylene-d12
表 17、以固相微萃取法所得之大蒜揮發性含硫化合物及內標準品
Table 17. Identity of volatile sulfur-containing compounds in various garlic organs collected by SPME together with internal standards.
編號
Characteristic mass spectral ions (EI)
1 diallyl sulfide 7.11 114 45 41(81.40%), 73(80.50%), 39(61.90%) 2 3,4-dimethylthiophene 8.51 112 111 112(84.21%), 97(67.01%), 45(17.50%) 3 methyl 2-propenyl disulfide 8.88 120 41 120(97.80%), 45(83.70%), 39(81.50%) 4 unknown 1 10.24 103 102 103.95(58.16%), 44.95(33.84%), 39(14.69%) I.S. I* 1,4-dichlorobezene-d4 12.09 150 150 152(64.40%), 115(46.00%), 78(30.20%)
5 diallyl disulfide 14.49 146 41 39(37.70%), 45(28.20%), 73(20.70%) 6 allyl propyl disulfide 14.97 148 148 104(81.20%), 41(71.20%), 43(57.30%) 7 C6H10S2 15.20 146 73 146(98.99%), 81(78.99%), 41(56.99%) 8 trans-propenyl propyl disulfide 15.69 148 148 106(81.42%), 41(79.82%), 45(67.22%) 9 unknown 2 16.18 146 113 111(46.40%), 45.05(42.02%), 97.05(36.81%) 10 allyl methyl trisulfide 16.39 152 41 45(84.00%), 39(83.50%), 73(83.00%) 11 4-methyl-1,2,3-trithia-cyclopentane 16.87 138 41 45(69.00%), 138(64.00%), 73(58.00%) 12 3,4-dimethylisothiazole 17.54 113 113 71(52.91%), 72(43.00%), 45(27.00%) I.S. II naphthalene-d8 17.77 136 136 108(11.60%), 137(10.30%), 134(09.80%)
13 3-vinyl-1,2-dithiacyclohex-4-ene 17.94 144 111 144(82.70%), 97(68.90%), 103(50.20%) 14 5-methyl-1,2,3-thiadiazole 18.24 100 71 72(62.00%), 45(58.00%), 39(43.00%) 15 unknown 3 18.47 144 71 72(88.83%), 44.95(77.33%), 73(52.49%)
*: Internal Standard 內標準品
接上表
Characteristic mass spectral ions (EI)
16 3-vinyl-1,2-dithiacyclohex-5-ene 18.71 144 72 71(83.90%), 144(53.60%), 111(47.60%) 17 diallyl trisulfide 21.37 178 73 41(87.60%), 113(60.30%), 45(39.10%) 18 unknown 4 21.76 115 41 73(97.68%), 115.05 (79.17%), 39.1(59.67%) 19 unknown 5 22.15 178 73 45.05(46.33%), 41.1(43.43%), 114(34.90%) 20 unknown 6 22.56 152 152 150(82.45%), 41(53.62%), 73(47.36%) 21 unknown 7 23.17 170 169.95 41.1(51.58%), 63.95(49.23%), 127.9(47.41%) 22 unknown 8 23.32 172 140.15 138.05(30.62%), 122.05(27.97%), 172.15(27.39%) 23 unknown 9 23.66 184 41.1 39.1(49.69%), 45.05(49.69%), 78.9(45.51%) 24 2-propenylthioacetonitrile 25.39 113 41 45(70.31%), 39(57.91%), 73(50.21%) I.S. III* acenaphthene-d10 26.29 164 162 164(95.80%), 160(45.70%), 163(29.80%)
25 diallyl tetrasulfide 27.89 210 41 73 (36.90%), 39(30.90%), 146(27.10%)
*: Internal Standard 內標準品
圖 5、大蒜中揮發性含硫化合物結構式
Fig. 5. Chemical structures of volatile sulfur-containing compounds detected in garlic.
表 18、固相微萃取法所用之內標準品及其對應量之含硫揮發性化合物
Table 18. Volatile sulfur-containing compounds obtained and corresponding internal standards used in SPME-GC/MS.
內標準品 揮發性含硫化合物
1,4-dichlorobezene-d4 diallyl sulfide(peak No. 1), 3,4-dimethylthiophene(peak No.
2), methyl 2-propenyl disulfide(peak No. 3), unknown 1(peak No. 4), diallyl disulfide(peak No. 5), allyl propyl
disulfide(peak No. 6)
naphthalene-d8 C6H10S2(peak No. 7), trans-propenyl propyl disulfide(peak No. 8), unknown 2(peak No. 9), allyl methyl trisulfide(peak No. 10), 4-methyl-1,2,3-trithia-cyclopentane(peak No. 11), 3,4-dimethylisothiazole(peak No. 12), 3-vinyl-1,2- dithiacyclohex-4-ene(peak No. 13), 5-methyl-1,2,3-
thiadiazole(peak No. 14), unknown 3(peak No. 15), 3-vinyl- 1,2-dithiacyclohex-5-ene(peak No. 16), diallyl trisulfide(peak No. 17), unknown 4(peak No. 18), unknown 5(peak No. 19) acenaphthene-d10 unknown 6(peak No. 20), unknown 7(peak No. 21), unknown
8(peak No. 22), unknown 9(peak No. 23), 2-propenylthioacetonitrile(peak No. 24), diallyl tetrasulfide(peak No. 25)
表 19、以溶劑萃取法所得之大蒜揮發性含硫化合物及內標準品
Table 19. Identity of volatile sulfur-containing compounds in garlic bulbs collected by solvent extraction together with internal standards.
編號
Characteristic mass spectral ions (EI)
1 methyl 2-propenyl disulfide 8.58 120 41 120(97.80%), 45(83.70%), 39(81.50%) 2 unknown s1 12.43 112 79 112(83.33%), 96.95(77.36%), 83.95(67.69%) I.S. I* 1,4-dichlorobezene-d4 12.75 150 150 152(64.40%), 115(46.00%), 78(30.20%)
3 unknown s2 14.89 118 118 84.95(82.39%), 44.95(54.19%), 72(40.85%) 9 4-methyl-1,2,3-trithia-cyclopentane 20.65 138 41 45(69.00%), 138(64.00%), 73(58.00%) I.S. II naphthalene-d8 21.02 136 136 108(11.60%), 137(10.30%), 134(09.80%)
10 3-vinyl-1,2-dithiacyclohex-4-ene 21.38 144 111 144(82.70%), 97(68.90%), 103(50.20%) 11 5-methyl-1,2,3-thiadiazole 21.71 100 71 72(62.00%), 45(58.00%), 39(43.00%) 12 3-vinyl-1,2-dithiacyclohex-5-ene 22.58 144 72 71(83.90%), 144(53.60%), 111(47.60%) 13 2-vinyl-1,3-dithiane 22.94 146 146 74(67.21%), 72(44.10%), 45(43.10%) 14 diallyl trisulfide 26.87 178 73 41(87.60%), 113(60.30%), 45(39.10%) 15 unknown s4 27.59 144 111 144(72.09%), 45.05(47.69%), 96.95(32.46%)
*: Internal Standard 內標準品
接上表 編號 peak no.
化合物名稱
compound R.T.
分子量 Mr
Base peak m/z (100%)
Characteristic mass spectral ions (EI)
16 unknown s5 28.23 144 111 144(78.09%), 45.05(49.81%), 77(30.20%) I.S. III* acenaphthene-d10 34.50 164 162 164(95.80%), 160(45.70%), 163(29.80%)
I.S. IV anthracene-d10 45.96 188 188 189(14.30%), 94(12.90%), 80(12.50%) 17 3-vinyl-4H-1,2-dithiin 52.12 144 45 111(89.00%), 144(73.00%), 39(57.00%) 18 unknown s6 52.21 216 111 216(51.89%), 116.95(50.54%), 45.05(49.57%) I.S. V chrysene-d12 67.07 240 240 236(24.60%), 241(17.30%), 120(10.90%) I.S. VI perylene-d12 77.53 264 264 260(24.30%), 265(22.10%), 132 (12.90%)
*: Internal Standard 內標準品
表 20、溶劑萃取法所用之內標準品及其對應量之含硫揮發性化合物
Table 20. Volatile sulfur-containing compounds obtained and corresponding internal standards used in solvent extraction-GC/MS.
內標準品 揮發性含硫化合物
1,4-dichlorobezene-d4 methyl 2-propenyl disulfide(peak No. 1), unknown s1(peak No. 2), unknown s2(peak No. 3), diallyl disulfide(peak No.
4), allyl propyl disulfide(peak No. 5)
naphthalene-d8 C6H10S2(peak No. 6), allyl methyl trisulfide(peak No. 7), unknown s3(peak No. 8), 4-methyl-1,2,3-trithia-cyclopentane (peak No. 9), 3-vinyl-1,2-dithiacyclohex-4-ene(peak No. 10), 5-methyl-1,2,3-thiadiazole(peak No. 11), 3-vinyl-1,2-
dithiacyclohex-5-ene(peak No. 12), 2 vinyl-1,3,-dithiane(peak No. 13), diallyl trisulfide(peak No. 14), unknown s4(peak No.
15)
acenaphthene-d10 unknown s5(peak No. 16), anthracene-d10
3-vinyl-4H-1,2-dithiin(peak No. 17), unknown s6(peak No.
18)
圖 6、大蒜‘和美’、‘大片黑’和‘宜蘭白’新葉標示後 20 天、40 天和 60 天之（A）葉長度及（B）
葉位變化。
Fig. 6. The change of (A) leaf length and (B) leaf position (from top view) of the leaf 20-days, 40-days, and 60-days after labeling on garlic cvs. ‘He-Mei’, ‘Large Black Leaf’, and ‘Yi-Lan White’.
表 21、‘和美’、‘大片黑’和‘宜蘭白’於葉齡 20、40 及 60 天葉片以 SPME-GC/MS 測定之葉身揮發性含硫化合物校正量z
Table 21. Calibrated abundance of volatile sulfur-containing compounds collected by SPME-GC/MS in leaf blade of garlic cvs. ‘He-Mei’, ‘Large Black Leaf’, and ‘Yi-Lan White’20, 40 and 60 days after labeling.
和美‘He-Mei’ 大片黑‘Large Black Leaf’ 宜蘭白‘Yi-Lan White’
編號x
5 11,894,132 78,848,247 16,822,937 34,242,047 74,212,224 28,565,549 31,229,843 26,172,776 17,040,018 6 678,072 4,640,087 716,090 2,459,633 2,640,539 833,496 1,674,789 2,117,976 787,628 7 3,274,034 16,018,584 2,585,510 19,008,335 6,664,399 3,080,661 9,296,084 9,562,682 3,528,665
10 - - - 305,291 - - 253,588 273856 - 22 209,386 174,768 148,679 345,205 254,576 157,922 288,028 249,844 164,105
z:田間各品種於種植後 80 天標示最上位新葉
y: Not detected
x: peak number and its corresponding compound are same as listed in Table 17
表 22、‘和美’、‘大片黑’ 和‘宜蘭白’之葉身、葉鞘和鱗莖以 SPME-GC/MS 測定之揮發性含硫化合物校正量z
Table 22. Calibrated abundance of volatile sulfur-containing compounds collected by SPME-GC/MS in leaf blade, leave sheath and cloves of garlic cvs. ‘He-Mei’, ‘Large Black Leaf’, and ‘Yi-Lan White’ 60 days after labeling.
和美‘He-Mei’ 大片黑‘Large Black Leaf’ 宜蘭白‘Yi-Lan White’ 5 15,834,260 18,453,951 119,675,460 23,825,103 29,769,570 40,988,014 13,040,168 17,136,898 70,008,601 6 616,440 2,522,183 5,601,162 653,315 4,107,380 1,788,926 1,527,982 1,126,420 4,934,371 7 2,225,713 11,699,665 41,479,403 2,414,698 24,892,778 16,376,249 2,729,883 11,774,400 33,854,282
8 - - - 402,700
x: peak number and its corresponding compound are same as listed in Table 17
接上表
和美‘He-Mei’ 大片黑‘Large Black Leaf’ 宜蘭白‘Yi-Lan White’
編號x
peak no. 葉身 葉鞘 鱗莖 葉身 葉鞘 鱗莖 葉身 葉鞘 鱗莖
19 - y 3,223,169 3,762,390 122,078 2,770,489 1,005,737 - 822,353 6,948,050
20 - - - - 227,464 51,976 - - 341,032
21 - 1,711,709 4,355,123 - 1,336,721 533,048 - 1,164,519 4,124,502 22 215,754 272,072 279,290 173,038 171,250 222,597 248,242 - 475,375
25 - - 707,826 - - - 615,754
z:田間各品種於種植後 80 天標示最上位新葉
y: Not detected
x: peak number and its corresponding compound are same as listed in Table 17
表 23、‘和美’和‘大片黑’之蒜皮和蒜瓣以 SPME-GC/MS 測定之揮發性含硫化合物校正量z
表 23、‘和美’和‘大片黑’之蒜皮和蒜瓣以 SPME-GC/MS 測定之揮發性含硫化合物校正量z